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2. The influence of temperature and inlet velocity on cyclone pressure drop: a CFD study
Pages 7-12
Jolius Gimbun, T. G. Chuah, A. Fakhrul-Razi and Thomas S. Y. Choong
12. On-line dynamic optimization and control strategy for improving the performance of
batch reactors
Pages 101-114
A. Arpornwichanop, P. Kittisupakorn and I. M. Mujtaba
13. Synthesis of nano-sized particles from metal carbonates by the method of reversed
mycelles
Pages 115-119
Christo Karagiozov and Dafina Momchilova
14. Mechanism of mass transfer from bubbles in dispersions: Part II: Mass transfer
coefficients in stirred gasliquid reactor and bubble column
Pages 121-130
V. Linek, M. Korda and T. Moucha
3. Influence of the particle diameter and density in the gas velocity in jet spouted beds
Pages 153-157
Mara J. San Jos, Sonia Alvarez, Alvaro Ortiz de Salazar, Martn Olazar and Javier Bilbao
18. Using statistical moments to describe grinding in a ball mill for industrial-scale
process
Pages 263-266
Andrzej Heim, Tomasz P. Olejnik and Agnieszka Pawlak
22. Application of a vertical venturi separator for improved recycling of automotive tires
Pages 287-291
W. McBride and S. Keys
27. Controlling dust emissions and explosion hazards in powder handling plants
Pages 323-326
Peter Wypych, Dave Cook and Paul Cooper
Received 30 June 2003; received in revised form 29 July 2003; accepted 8 March 2004
Available online 24 April 2004
Abstract
This paper describes the production of anhydrous puffed borax from borax pentahydrate (BPH) in a batch calcinator. The calcination of
BPH is incomplete since agglomeration starts at 300 C. In order to avoid agglomeration at temperatures higher than 300 C, the surface of
BPH particles have been covered with a CaO layer in aqueous media having a higher melting point than pure BPH. To investigate the effect
of this CaO layer on the calcination of BPH, the samples were fed into the batch calcinator. During the calcination process, quantities such as
the bulk density value, particle size distribution, sodium borate and calcium content of anhydrous borax have been determined as a function
of temperature. It was found that the anhydrous borax can be obtained by calcination of BPH particles covered with CaO in 50, 20 and 5 min
time intervals at a temperature range of 300, 400 and 500 C, respectively. As a result, puffed anhydrous borax of 99% purity with bulk density
of 0.082 g cm3 and containing 0.670% Ca2+ has been produced by this method in 5 min interval at 500 C.
2004 Elsevier B.V. All rights reserved.
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doi:10.1016/j.cep.2004.03.004
2 . Sahin et al. / Chemical Engineering and Processing 44 (2005) 16
ticles during removal of water. In a fluidized bed, the calci- cation of this BA reaction has been the production of sodium
nation of BPH cannot exceed 300 C at the earlier stage of borohydride. Sodium borohydride which is used as a hydro-
the process. At this temperature, it turns into an amorphous gen storage medium can also be synthesized by the reaction
form of BA and softens easily. Softening of the particles of BA, with MgH2 through ball milling at room temperature
cause agglomeration, which disturbs the fluidization condi- as shown the following reaction [9]:
tion in the fluidized bed calcinator [6].
BPH can be calcined to BA without puffing by at least 8MgH2 +Na2 B4 O7 +Na2 CO3 4NaBH4 + 8MgO + CO2
two-stage calcination which each needs at long time interval The obtained anhydrous borax is very fragile, thus it can be
in fluidized bed [7]. As a result, the calcination of BPH in easily converted to powder form by grinding. This operation
fluidized bed have some problem such as stage-wise, puffing, increases the bulk density of BA.
agglomeration and needed long time.
Thus, a considerable number of attempts have been made
to develop a new method for production anhydrous borax 2. Experiments
from BPH. As it is known the calcination of BPH cannot
be conducted above agglomeration temperature of 300 C in The calcination of BPH to BA was carried out in a batch
fluidized bed. At temperatures higher than 300 C, the amor- calcinator (thermolyne 6000 furnace) which is heated to a
phous BA particles which soften readily adhere strongly to predetermined calcination temperature (Fig. 1). During con-
each other since BPH dissolves in their water. This prob- stant temperature experiments, particles were fed into the
lem has been solved in our system by covering the particles calcinator, which was in thermal equilibrium at the experi-
with a material that has a higher melting point than the fi- mental temperature. At a predetermined time interval, sam-
nal agglomeration temperature. For this propose, the surface ples were withdrawn using a vacuum sampling tube. Titri-
of BPH was covered with Ca(OH)2 layer in aqueous me- metric method was used to determine the Na2 B4 O7 content
dia. The presence of Ca(OH)2 prevents the agglomeration of of sample [10]. The Ca2+ content of samples was determined
BPH particles up to 500 C, since it controls the acceleration by Jenway PFP 7 model flame photometer. Bulk density of
of water vapor on the surface of BPH particles. Using this BA was measured by a standard method [11].
method BPH can be converted to puffed BA containing 99% The particle size of BPH used in the experiments was
Na2 B4 O7 in a 5-min interval at the temperature of 500 C. chosen in the range 630 + 450 m and bulk density was
The degree of puffing is very high, thus the calcination was determined as 0.91 g cm3 . Technical grade BPH obtained
carried out in an oven. from ETIHOLDING (Kirka, Turkey) was used in the ex-
The only disadvantage of this method is that the ob- periments. Original Na2 B4 O7 content of samples was deter-
tained product (BA) has a lower bulk density. Such a puffed mined as 69.95% by titrimetric method [10].
product, with large quantities of liquids and gas, can be Each series of experiments carried out with 10 g of BPH
loaded onto the expanded borax. For example, organic such washing 20 ml Ca(OH)2 solution with predetermined con-
as trichloroethylene, cyclohexanone and pentachlorophenol centration during 1 min. This washed BPH particles were
can be loaded at very high percentages onto the puffed bo- then dried at 65 C in an oven for 5 h. In another series of
rax, as can non-ionic and anionic surfactants, with the prod- experiments, a mixture containing BPH and 2, 4, 5, 7, 10,
uct retaining its free-flowing characteristics. This renders 17 and 34 wt.% CaO were fed into the calcinator at the tem-
the puffed borax very useful in such diverse compositions perature of 500 C for 10 min.
as dairy cleaners, fabric softeners and bath additives [8]. The other series of experiments, particles covering with
In addition, this puffed BA having large surface area can different Ca(OH)2 fed into the calcinator to investigate the
be used for solidgas reactions. Recently, one popular appli- thermal decomposition behavior in the calcinator at 300,
400, 500 C. At each temperature samples was taken at 3, In the first group of experimental work, mixtures contain-
5, 10, 20, 45 and 60 min intervals to determine the degree ing BPH and 2, 4, 5, 7, 10, 17 and 34 wt.% CaO were fed
of calcination. into the batch calcinator for 10 min at 500 C. At the end
of this kind of calcination, the conversion of BPH to BA is
found as about 99.6%. But, the BPH samples containing 2
3. Results and discussion and 4 wt.% CaO agglomerated slightly. However, agglomer-
ation was not observed at the concentration of CaO higher
The main aim of this study is that the calcination of BPH than 5 wt.%. Table 1 shows the values found at the end of
to BA is performed without agglomeration at higher temper- this group. As can be seen from this table, the maximum
ature than 300 C at which dehydration and decomposition content of Ca2+ in BA particle was found in the particle size
steps of it take place very fast. Normally, particles of BPH smaller than 315 m. The particle size of BA is expanded
dissolve their water and stick to each other to give agglom- about twice higher than used for BPH particles at the begin-
eration. ning of experiment by thermal shock. The result obtained
In this study, agglomeration was prevented by both cov- at the end of this step shows that the agglomeration can be
ering the surface of BPH particles in Ca(OH)2 aqueous so- prevented in presence of CaO. However, the obtained prod-
lution and BPHCaO mixture in solid state. uct (BA) at the end of this kind of operation contains high
Table 1
The effect of different BPHCaO mixture on the calcination of BPH particles at 500 C at the end of 10 min
Particle size (m) %CaO
5 10 17
+1250 40.517 0.51 0.0583 31.609 0.69 0.0612 39.931 1.40 0.0635
+1000 30.747 0.35 30.172 0.69 16.319 0.38
+800 6.897 0.12 10.632 0.35 6.597 0.12
+630 1.724 0.03 2.010 0.06
+560 0.287
+450
+315
315 20.115 4.05 25.287 5.21 18.942 10.16
Fig. 2. TG curves for BPH both in pure and containing 2.46 wt.% Ca2+ .
4 . Sahin et al. / Chemical Engineering and Processing 44 (2005) 16
100
95
90
%Na2B4O7
85 300 C
400 C
80
500 C
75
70
0 10 20 30 40 50
time(min.)
Fig. 3. Changes of calcination time with temperature for the BPH samples containing about 2.5 wt.% Ca2+ .
Table 2
Properties of dehydrated BPH covering with 2.5 wt.% Ca2+ layer
Particle size (m) 300 C 400 C 500 C
% fraction Ca2+ % (g cm3 ) % fraction Ca2+ % (g cm3 ) % fraction Ca2+ % (g cm3 )
+1250 96.407 1.01 0.0552 90.998 1.00 0.0312 81.344 1.00 0.0589
+1000 8.927
+800 0.638
+630
+560
+450
+315
315 3.593 1.88 9.002 1.361 9.009 1.50
values of CaO which is not suitable for industrial applica- crystal water and some structure water dehydrated quickly
tions. caused agglomeration. Thus, the mass transfer in this step
In the second group of experiment, the surface of BPH looked as the constant rate period where moisture movement
particle were covered with Ca(OH)2 in aqueous solution. within the solid is sufficiently rapid to maintain a saturated
TG analysis of the BPH both in pure state and covered with condition at the surface. In the case of dehydration of BPH
2.46 wt.% Ca2+ were performed under nitrogen atmosphere particles covered with Ca(OH)2 layer to increase the mass
at 10 C/min heating rate. Fig. 2 shows the results of TG transfer resistance between the particles and hot carrier gas,
analysis. As can be seen from Fig. 2, the covered BPH par- the calcination is mainly controlled by the Ca(OH)2 layer.
ticles with Ca(OH)2 dehydrate slowly with respect to pure Fig. 3 illustrates the Na2 B4 O7 content of the samples
state. This phenomena involves the simultaneous transfer of containing about 2.50 wt.% Ca2+ taken from the batch cal-
heat to evaporate the liquid and transfer of vapor within the cinator at different stages during isothermal decomposition
solid and vapor from the surface into the hot carrier gas. In conducted at various temperatures. The total Na2 B4 O7 con-
the case of pure BPH at temperature higher than 300 C, all tent of samples increased with increasing calcination tem-
Table 3
Properties of dehydrated BPH particles containing about 0.670 wt.% Ca2+
Particle size (m) 300 C 400 C 500 C
+1250 33.463 0.201 0.0727 61.318 0.170 0.044 28.940 0.210 0.0824
+1000 39.779 26.689 38.607
+800 18.739 5.574 22.708
+630 4.013 3.482
+560
+450
+315
315 4.006 0.467 6.419 0.498 6.263 0.471
. Sahin et al. / Chemical Engineering and Processing 44 (2005) 16 5
peratures. The BA contains some CaO, hence the conver- thick and homogenous cover on the surface of the anhy-
sion percentages of BA never attained 100% as seen from drous borax. The thickness of CaO layer controls the trans-
Fig. 3. The conversion of BPH to BA takes place in two fer rate of liberated water from borax pentahydrate to air.
stages namely dehydration and calcination [7]. But dehy- The sieve analysis, bulk density and Ca2+ content of BA
dration stage cannot be observed in Fig. 3 because of rapid obtained at the end of operation having different tempera-
dehydration of BPH. Fig. 3 illustrates that the calcination
of BPH to BA at 300 C completed in 50 min, whereas the
same degree of calcination realized in 5 min at the temper-
ature of 500 C. The Ca2+ content, bulk density and sieve
analysis of BA obtained at the end of this group of exper-
iments are illustrated in Table 2. As can be seen from this
table, the Ca2+ content of calcination realized at 300, 400
and 500 C is about 2.5 Ca2+ wt.%. The chosen particle size
range of BPH before calcination was 630 + 450 m and
the particle size of almost nine to ten part of calcines was
increased to +1210 m shown in Table 2. Thus, it can be
said that puffing is more effective in cause size increment
with respect to shrinking and fragmentation of puffed parti-
cles. The operation of covering BPH particles with Ca(OH)2
can not be attained at the temperature higher than 500 C
because of agglomeration. It is interesting to see that the
bulk density increased from 0.0317 to 0.0599 g cm3 with
increasing the temperature from 400 to 500 C. This behav-
ior of BPH can be easily explained by increasing sintering
effect which depends on the increasing temperature. In the
light of above results, it can also be concluded that better
operation could be possible from the second group of ex-
periment by decreasing the Ca2+ layer on the surface of
BPH particles. Thus, a third group of experiments were car-
ried out using very low Ca(OH)2 aqueous solution to cover
the BPH particles surface. The changes of Na2 B4 O7 con-
tent of samples containing about 0.60 wt.% Ca2+ with time
in this group are given in Fig. 4 at various constant temper-
atures. The Na2 B4 O7 content of the samples increases with
increasing calcination temperature. The calcination rate of
this group is higher than the previous group given in Fig. 3.
This behavior may be attributed to the fact that increas-
ing the percentages of additive caused the formation of a
100
95
90
%Na2B4O7
85
300 C
400 C
80 500 C
75
70
0 10 20 30 40 50
time (min.)
Fig. 4. Effect of temperature on the calcination of BPH samples containing Fig. 5. Microscopic photographs of borax pentahydrate: (a) pure, (b)
about 0.67 wt.% Ca2+ . containing 0.67 wt.% Ca2+ and (c) containing 2.5 wt.% Ca2+ .
6 . Sahin et al. / Chemical Engineering and Processing 44 (2005) 16
tures are given in Table 3. As can be seen in this table, parti- Ca(OH)2 to control the transport rate of liberated water
cle size shows a distribution which is attributed to the Ca2+ from inside BPH particle to air. By this method, the
content and temperature. In addition, the particles smaller content of BPH can be decreased up to about 0.68 wt.%
than 315 m contain twice higher Ca2+ than all other parti- Ca2+ .
cle sizes contained. Microscopic photographs of borax pen- (d) Calcination of BPH covered with Ca(OH)2 to BA re-
tahydrate in pure, containing 0.67 wt. and 2.5 wt.% Ca2+ alized in 50, 20 and 5 min intervals at 300, 400 and
are given in Fig. 5, respectively. In pure state, the surface 500 C, respectively. This result shows that at temper-
of BPH particles are smooth whereas the quality of par- atures higher than 400 C, the puffed anhydrous borax
ticles are decreased with increasing Ca2+ quantity on the can be obtained by continuous operation. Also, the high
surface. bulk density may be obtained by crashing puffed borax.
(e) The obtained low bulk density puffed borax is preferred
priority in some chemical process such as solid state
4. Conclusion reaction, adsorption and high temperature application
of BA.
In order to obtain anhydrous borax with low bulk den-
sity by calcination in batch calcinator, particular attention is
paid to cover BPH surface with Ca(OH)2 layer. The follow- References
ing conclusion can be withdrawn from the results obtained
during the calcination of covered BPH particles in a batch [1] R.P. Douglas, F.G. Donald, Refinement of the structure of tincal-
calcinator: conite, Acta Cryst. C47 (1991) 22792282.
[2] G. Nencetti, A. Pennacchi, Chim. Ind. Milan 46 (5) (1968) 518525.
(a) The calcination of BPH with single stage cannot be [3] Kirk-Othmer, Enc. Chem. Thech., 4 ed., vol. 4, 1992, p. 388.
carried out at the temperature higher than 300 C since [4] O. Sahin, A.N. Bulutcu, Turk. J. Chem. 26 (2002) 8996.
[5] S. Kocakusak, K. Akcay, T. Ayok, H.J. Koroglu, O.T. Savasc, R.
agglomeration is started. The calcination of BPH to BA
Tolun, Ind. Eng. Chem. Res. 35 (1996) 14241428.
also takes longer at around 300 C. [6] O. Sahin, U.G. Beker, A.N. Bulutucu, Int. J. Storing Handl. Process.
(b) BPH can be transformed to BA without agglomeration Powder 7 (1995) 165167.
by mixing CaO with BPH in solid state at temperature [7] O. Sahin, A.N. Bulutucu, Chem. Eng. Process. 41 (2002) 135141.
range 300500 C. In this case, the content of CaO in [8] T.E. Raymond, US Patent 4 412 978 (1983).
[9] Z.P. Li, N. Morigazaki, B.H. Liu, S. Suda, J. Alloys Compd. 349
BA must be higher than 7%.
(2003) 232236.
(c) Covering the BPH particles with Ca(OH)2 aqueous [10] D.F. Snell, C.L. Hilton, Encyclopedia of Industrial Chemical Anal-
solution also prevented the agglomeration in tempera- ysis, vol. 7, Wiley, New York, 1968, pp. 373384.
ture range 300500 C. In this kind of operation, the [11] ISO 3424, Sodium perborate for industrial use-determination of bulk
BPH particle surface was covered with a thin layer of density.
Chemical Engineering and Processing 44 (2005) 712
Received 16 February 2004; received in revised form 22 March 2004; accepted 22 March 2004
Available online 18 May 2004
Abstract
This work presents a computational fluid dynamics (CFD) calculation to predict and to evaluate the effects of temperature and inlet velocity
on the pressure drop of gas cyclones. The numerical solutions were carried out using spreadsheet and commercial CFD code Fluent 6.1. This
paper also reviews four empirical models for the prediction of cyclone pressure drop, namely [Air pollution control: a design approach, in: C.
David Cooper, F.C. Alley (Eds.), Cyclones, second ed., Woveland Press Inc., Illinois, 1939, p. 127139] [Chem. Eng. (1983) 99] [Doctoral
Thesis, Havarad University, USA, 1988], and [Chem. Eng. Progress (1993) 51]. All the predictions proved to be satisfactory when compared
with the presented experimental data. The CFD simulations predict excellently the cyclone pressure drop under different temperature and inlet
velocity with a maximum deviation of 3% from the experimental data. Specifically, results obtained from the computer modelling exercise
have demonstrated that CFD is a best method of modelling the cyclones operating pressure drop.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.005
8 J. Gimbun et al. / Chemical Engineering and Processing 44 (2005) 712
Table 1
Cyclone geometry used in this simulations
Geometry a/D b/D De /D S/D h/D H/D B/D Da
Stairmand high efficiency 0.5 0.2 0.5 0.5 1.5 4 0.375 0.305
Bohnet [2] 0.533 0.133 0.333 0.733 0.693 2.58 0.333 0.15
a Unit in meters.
J. Gimbun et al. / Chemical Engineering and Processing 44 (2005) 712 9
for inlet velocity ranging from 4.62 to 14.16 m/s by Bohnet Fig. 3. Evolution of pressure drop with inlet velocity. Comparison between
[2], and from 5.1 to 25 m/s by Griffiths and Boysan [8]. data presented by Bohnet [2], the predictions of CFD and four empirical
The numerical calculation was made with a fine numerical models (P = 1 bar, T = 293 K, D = 150 mm, geometry Bohnet [2]).
10 J. Gimbun et al. / Chemical Engineering and Processing 44 (2005) 712
2500
Dirgo
2000 CFD RSM
Pressure Drop (Pa)
1600
2500 CFD RSM
1400
Dirgo
CFD RNG k- CFD RSM
2000 1200
Pressure Drop (Pa)
1000
Pressure Drop (Pa)
200
Casal & Martinez
500 Casal & Martinez
0
Dirgo
0 200 400 600 800 1000 1200
Coker
0 Temperature (K)
5 10 15 20 25
Velocity (m/s) Fig. 8. Evolution of pressure drop with operating temperature. Compar-
ison between data presented by Bohnet [2], the predictions of CFD and
Fig. 5. 2D and 3D map of static pressure of Bohnet [2] cyclone for inlet four empirical models (Q = 80 m3 /h, T = 2931123 K, D = 150 mm,
velocity of 4.62 m/s and temperature 293 K. geometry Bohnet [2].
Fig. 6. 3D map of static pressure of Stairmand cyclone for inlet velocity Fig. 9. 3D Map of static pressure of Bohnet [2] cyclone for inlet velocity
of 20 m/s and temperature 293 K. of 11.48 m/s and temperature 850 K.
J. Gimbun et al. / Chemical Engineering and Processing 44 (2005) 712 11
performance for various operating conditions using a general soft- [8] W.D. Griffiths, F. Boysan, Computational fluid dynamics (CFD) and
ware, Chem. Eng. Process. 43 (2004) 511522. empirical modelling of the performance of a number of cyclone
[2] M. Bohnet, Influence of the gas temperature on the separation effi- samplers, J. Aerosol Sci. 27 (1996) 281304.
ciency of aerocyclones, Chem. Eng. Process. 34 (1995) 151156. [9] A. Ogawa, Separation of particles from air and gasses, vols. 1 and
[3] J. Casal, J.M. Martinez, A better way to calculate cyclone pressure 2, CRC Press, Boca Raton, Florida, USA, 1984.
drop, Chem. Eng. 90 (1983) 99. [10] M. Reddy, Fluent India, personal communication, 2003, mxr@
[4] A.K. Coker, Understand cyclone design, Chem. Eng. Progr. 28 (1993) fluent.co.in.
5155. [11] C.B. Shepherd, C.E. Lapple, Air pollution control: a design approach.
[5] J. Dirgo, Relationships between cyclone dimensions and performance. In: C.D Cooper, F.C. Alley (Eds.), Cyclones, second ed., Woveland
Doctoral Thesis, Havarad University, USA, 1988. Press Inc., Illinois, 1939, pp. 127139.
[6] T. Fraser, personal communication, 2003. fraserta1@cf.ac.uk, http:// [12] P.D. Silva, C. Briens, A. Bernis, Development of a new rapid method
www.cfd-online.com. to measure erosion rates in laboratory and pilot plant cyclones,
[7] C. Fredriksson, Exploratory experimental and theoretical studies of Powder Technol. 131 (2003) 111119.
cyclone gasification of wood powder. Doctoral Thesis, Lulea Uni- [13] M. Slack, Cyclonic separator, QNETCFD application Challenge,
versity of Technology, Sweden, 2003. http://www.qnet-cfd.net, Accessed on 8th August 2003.
Chemical Engineering and Processing 44 (2005) 1321
Received 20 January 2003; received in revised form 18 March 2004; accepted 26 March 2004
Available online 18 May 2004
Abstract
An algorithm for waste and pollutants reduction in reactor design is presented in this paper. This algorithm use potential environmental
impact balance (PEI) and PEI rate-law expression to track the generated PEI throughout reaction process within a reactor; and study how
reaction conditions (temperature, pressure, concentration, etc.) and various engineering factors (heat and mass transfer, and back-mixing and
so on) affect process environmental performance. The form of PEI rate-law expression should be consistent with the method for calculating
the overall PEI of mixtures of chemicals inside reactors. The algorithm can be used as a tool to aid in designing chemical reactors with
environmentally friendliness processes. The use of the methodology is illustrated with the reaction system of allyl chloride production.
2004 Elsevier B.V. All rights reserved.
Keywords: Reactor design; Potential environmental impact; Chemical reaction engineering; Impact analysis
Abbreviations: CSTR, continuous stirred-tank reactor; EIM, environ- 2. The potential environmental impact of a
mental impact minimization; NP, non-products; PEI, potential environ-
mental impact; PFR, plug-flow reactor
chemical process
Corresponding author. Tel.: +86-29-82668980;
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.006
14 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321
is defined as the effect that this material and energy would conditions and engineering factors and the like on the gen-
have on the environment if they were to be emitted into the eration of waste or pollutant is very important. However,
environment. For a steady-state process, the balance equa- studying each of wastes and pollutants within reactor is
tion is as follows: time-consuming and cost-consuming and the results may be
conflicting or competing, that is to say that reducing one pol-
Iin Iout + Igen = 0 (1)
lutant or waste may increasing the others. In addition, this
where Iin and Iout are the input and output rates of PEI, research method does not address the impact of the pollu-
respectively, and Igen denotes the PEI generation rate inside tion generated within a reactor. For example, reactor A may
the processes. produce 50 kg/h of pollutants while reactor B may produce
(in) 100 kg/h. However, the pollutants generated within reactor
Iin = mj xkj k + (2) A may be much more environmentally unfriendly than those
j k generated within reactor B. Thus, the strategies for reduc-
(out)
ing pollutants and wastes generated from reaction process
Iout = mj xkj k + (3) should be studied through their PEI rather than their mass
j k or concentrate, the results would be, then, scientific and be-
(in) (out) yond conflicting.
where mj is the mass flow rate of input stream j, mj Traditionally, the foundation of reactor design is the equa-
the mass flow rate of output stream j, xkj the mass fraction tions such as reaction rate equation, mass, energy and mo-
of chemical k in stream j, and k the overall potential envi- mentum balances as well as the model describing the fluid
ronmental impact (PEI) of chemical k. flow within reactors. With these equations, reactor designers
k = l kl
s
(4) can track compositions of chemicals, pressure and tempera-
l
ture throughout reaction process and discover the effects of
reaction conditions as well as engineering factors on these
where kls is the specific potential environmental impact of
parameters, and then, an appropriate reactor with profitable
chemical k for environmental impact category l, in units of processes can be designed. Nevertheless, this kind of design
PEI/kg of chemical k. Details of the method for calculat- method does not consider environmental perspective of pro-
ing kl
s appeared in reference [7]. The impact categories in-
cesses effectively.
volved in this theory fall into two general area concerning If the PEI generated within reactors could be tracked
with four categories in each area: throughout the process, the influence of reaction conditions
(1) The global atmospheric categories: and engineering factors on the generated PEI could also
Global warming potential (GWP). be clarified, and then reactors that generate the minimum
Ozone depletion potential (ODP). amount of PEI would be easily obtained. The above thinking
Acidification and acid-rain potential (AP). can be implemented by using the PEI balance and the PEI
Photochemical oxidation or smog formation potential rate-law expression in reactor design. In this way, the design
(PCOP). method is similar to the traditional reactor design method
based on balance equation and reaction rate equation.
(2) The local toxicological impact categories:
Human toxicity potential by ingestion (HTPI).
Human toxicity potential by either inhalation or der- 3.1. PEI rate-law expression
mal exposure (HTPE).
Aquatic toxicity potential (ATP). The PEI transformation rate of chemical k can be defined
Terrestrial toxicity potential (TTP). as:
Such an expression, which shows how the rate depends on changing of PEI throughout reactors; using Eq. (8) combin-
the concentrations of reactants, is called PEI rate-law expres- ing with other rate equations, the influence of operation pa-
sion. Note, PEI rate-law expression should be consistent with rameters such as temperature, concentration, pressure and
the method for calculating the overall PEI in Eqs. (2) and reaction time, etc. on environmental metrics of a chemical
(3), which ignore the combinational impacts that could be process could be analyzed facilely, and then, reactors gen-
associate with mixtures of chemicals which accounts for the erating a minimum of PEI could be designed easily.
additional terms not included into those equations. It should
be realized that if the method for calculating the overall PEI
of mixtures in reactors improve or adopt other method, the 4. Case study
form of the PEI rate-law expression should be adjusted ac-
cordingly. In this case study, we use the environmental impact indices
Obviously, rPEI can be expressed in terms of reaction tem- below, which can be derived from Eq. (1), to characterize
perature and concentration or partial pressure of chemicals environmental performance of reaction processes [7,8]:
and so on. Therefore, the PEI rate-law expression can be
(1) Potential environmental impact generation rate by non-
helpful to analyze the effect of concentrations and temper-
products Igen
NP .
ature on the PEI transformation rate, rPEI , and to study the
(2) Specific potential environmental impact due to non-
influence of back-mixing on process environmental perfor-
products PEI .
mance. At least, the PEI rate-law expression can reveal the
factors that control the transformation rate of PEI, so as to Igen
NP
provide guidance for the selection of reactor type and opera- PEI = (9)
p pp
tion conditions, and the inner structure of the reactor, which
produce desired products while creating minimum undesired where pp is the mass flow rate of product p, and PEI has
potential environmental impact. units of potential environmental impact per mass of prod-
ucts. Obviously, the smaller the values of Igen NP and
PEI ,
3.2. PEI balance the more environmental friendly the process, and all others
factors such as economics being equal, the more desirable.
Since desired products are the substance we desire and the Igen
NP would be useful in comparing different designs on an
objective of this paper is to present a methodology of waste absolute basis, while PEI would be useful in comparing
reduction, that is the primary concern is reducing the impact different designs independently of plant size [8].
and the amount of the non-products, the k of the desired These indices characterize some aspects of the genera-
products is not considered in PEI balance. This insures that tion of PEI within a reaction process. They are very useful
the user or producer is not directly penalized for producing in addressing questions related to the ability of the reactor
a chemical that has a high PEI value. Auxiliary materials to produce desired products while creating a minimum of
(catalyst, solvent and so on) used in reaction processes must undesired potential environmental impact.
leave the production process completely as waste or emis- To illustrate the use of the algorithm, a case of allyl chlo-
sion [10], so the PEI of the auxiliary materials should be ride manufacturing was used. Allyl chloride is manufactured
considered. Raw materials that if possible shall be entirely by means of non-catalytic chlorination of propylene. Con-
processed into the desired product are not as a rule com- sider the following reaction system.
pletely converted into the product. The losses that arise are The principle reaction is:
the cause of generated waste and emission [10], thus their Cl2 + CH2 =CHCH3 CH2 =CHCH2 Cl + HCl (10)
potential environmental impact should be taken into account.
To sum up, the PEI balance of reaction system under steady The main secondary reaction is further chlorination of allyl
state is: chloride to 1,3-dichloropropene:
Igen
NP
= Iout
NP
Iin
NP
(7) Cl2 + CH2 =CHCH2 Cl ClCH=CHCH2 Cl + HCl (11)
where the superscript NP represents materials except de- Another important side-reaction is the additive chlorination
sired products, that is, non-products. Iout
NP and I NP are input
in of propene to 1,2-dichloropropane:
and output rates of PEI caused by non-products, and Igen NP
Cl2 + CH2 =CHCH3 CH2 ClCHClCH3 (12)
the rate at which impact is generated in a reactor.
For a differential flow reactor, dV, we write a PEI balance This reaction system is a kind of complex van de vusse
equation over the reactor: reaction, a typical reaction process involving consecutive
and parallel reactions. It is, therefore, sufficiently complex
dIgen = rPEI dV (8)
to illustrate the algorithm. Due to the limit to the space of
With PEI balance Eq. (7), combining with other equations, the article, we only select temperature, concentration and
designers can reveal how PEI change with reaction time or back-mixing to be the object of research to illustrate the use
axial and radial direction inside reactors, i.e. can track the of the algorithm.
16 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321
The following calculations and curves drawing can be ac- respectively.The differential PEI balance of PFR reactors
complished by mathematical software such as Mathcad2000 is:
or Matlab.
dIgen = rPEI dV (19)
4.1. Preconditions Dividing Eq. (18) by Eq. (17), then integrate, we obtain:
Table 1
The specific potential environmental impact values for each category for the chemicals used in this case study [9]
Compound HTPI HTPE ATP TTP GWP PCOP AP
A 0 5.4 104 22 0 0 0 0
B 0 0 3.1 102 0 0 2.1 0
C 0.51 5.4 104 0.10 0.51 0 0 0
D 0.78 2.3 104 4.6 104 0.78 0 0 0.86
E 1.1 0 0.014 1.1 0 0 0
F 0.61 0 0.0059 0.61 0 0 0
Values are in PEI/kg.
Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321 17
rPEI has units of PEI/(L s). The value of rPEI is negative be-
cause the overall PEI of the reactant A is far greater than that
of each reaction products, in addition, the PEI of product C Fig. 1. Curves of rPEI /rB vs. CB , rPEI /rB in units of PEI/mol. The solid
curve is for PFR, the dashed for CSTR.
is not considered. Suppose reaction temperature T = 530 K,
and at the outlet of reactor, CB,out = 0.007 mol/L. Substi-
4.3.1.2. Not considering PEI of A. To illustrate the use of
tute Eqs. (20) and (26) into rPEI /rB , respectively, and then
the algorithm effectively, suppose A = 0 PEI/kg, and the
graph them in Fig. 1, respectively.
weighting factor for each impact type is likewise 1, and the
rPEI 1.6k1 + 1.5k3 + 1.2k2 (CC /CB ) PEI of each non-product except Cl2 is also considered. Note
= (28)
rB k1 + k 3 that this case is probably impractical in real manufacturing
processes. The PEI rate-law expression, rPEI , in units of
According to Eq. (25), Igen of CSTR is: PEI/(L s), is:
Fig. 2. Curves of rPEI /rB vs. CB of PFR ignoring the overall PEI of A. rPEI /rB in units of PEI/mol. The numbers 17 denote the reaction temperatures
of 450, 470, 490, 500, 510, 520 and 530 K, respectively.
18 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321
Fig. 3. Curves of rPEI /rB vs. CB of CSTR ignoring the overall PEI of A. rPEI /rB in units of PEI/mol. The numbers 17 denote the reaction temperatures
of 450, 470, 490, 500, 510, 520 and 530 K, respectively.
PFR equals the area of the shaded region multiplied by v0 . 4.4. The effect of temperature on environmental
From Eq. (25), Igen of CSTR is the product of v0 and the performance
area of the corresponding rectangle in Fig. 3. For example,
when reaction temperature is 450 K, Igen of CSTR equals 4.4.1. The effect on Igen
the area of the rectangle in Fig. 3 multiplied by v0 . In such When l = 1, from Eq. (27), it can be seen easily that the
case, the value of Igen is positive number. Comparing Fig. 2 value of rPEI decreases (its absolute value increase) as the
with Fig. 3, it can be found that lower Igen will be obtained if reaction temperature rises, that is, Igen can be lowered by
we adopt PFR and lower reaction temperature. For example, increasing reaction temperature. For example, when reaction
when reaction temperature is 500 K, and v0 is 325 L/s, Igen temperature increases from 500 to 600 K, and the outlet
of PFR is 4.8 101 PEI/h, while for CSTR, Igen = 1.1 concentration CB,out = 0.007 mol/K, and v0 is also 325 L/s,
103 PEI/h, which is 2.3 times that of PFR. Igen of PFR and CSTR would decrease from 3.2104 and
3.5104 to 3.7104 and 4.2104 PEI/h, respectively.
4.3.2. The effect on PEI The effect of reaction temperature on Igen can also be found
From Eqs. (9), (21) and (25), we obtain the formulas for from Figs. 2 and 3.
calculating PEI . Suppose v0 is 325 L/s, then for PFR: When not considering the PEI of Cl2 , from the PEI
Igen 13.0 CB rPEI rate-law expression, expressed in Eq. (29), we can find that
PEI = = dCB (31) in the initial stage of the reaction, the determining part
v0 CC,out MC 103 CC,out CB,0 rB
in the right side of Eq. (29) is 1.1 103 k1 CA CB +
for CSTR: 0.049k3 CA CB , due to the concentration of C is very low
Igen 13.0 rPEI while the concentrations of A and B are relatively high.
PEI = = (CB CB,0 ) Comparing the magnitudes of the two activation energies
v0 CC,out MC 103 CC,out rB
in the two terms, we conclude that the value of this part
(32)
decreases as the reaction temperature increases. Thus, in
where CC,out is the outlet concentration of C. the early stage of this reaction process, to lower the value
According to Eqs. (31) and (32), using the curves about of rPEI , the reactor should operate at relatively high tem-
rPEI /rB versus CB and corresponding area, the superior- perature. As the reaction proceeds, the concentration of C
ity in environmental index PEI about PFR and CSTR is increasing while CA and CB is decreasing, so that the
can be discovered. When l = 1, the outlet concentration influences of the third term, 0.33k2 CA CC , is becoming sig-
CC,out = 0.011 mol/L and reaction temperature T = 500 K, nificant. Since the magnitude of activation energy in this
using CSTR will obtain lower PEI than using PFR. In term is the maximum, operating at relatively low temper-
this case, for CSTR, PEI = 31 PEI/kg; for PFR, PEI = ature would result in a relatively low value of rPEI in this
26 PEI/kg. Nevertheless, if not considering A , for the stage. Accordingly, for the reaction system in this case, a
same CC,out and T, using PFR will obtain lower PEI PFR operating at higher temperature first and then lower
than using CSTR, for PFR, PEI = 0.30 PEI/kg, while for temperature must generate lower value of Igen than that sim-
CSTR, PEI = 0.80 PEI/kg, which is 2.6 times that of PFR. ply operating at a corresponding uniform temperature. The
Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321 19
curves in different temperature in Fig. 2 intersect each other, the total PEI per mass of product streams leaving the system,
this fact also indicate this result. For example, when the inlet Iout , are another category of indices to characterize some
and outlet concentrations of B are 0.024 and 0.007 mol/L, aspects of emission of PEI from a manufacturing process.
respectively, and v0 is 325 L/s, for PFR operating at reaction According to Eq. (1):
temperature of 450K, Igen = 3.9 101 PEI/h, and for PFR
Iout = Iin + Igen (33)
at 530 K, Igen = 6.7 101 PEI/h. While for a two-stage
PFR, in which the first stage operates at 530 K, and the Iout is obtained by dividing Iout by the output of products to
second stage operates at 450 K, the inlet concentration of B give:
of the second stage is 0.018 mol/L, Igen = 3.4 101 PEI/h.
Iout Iin + Igen
Obviously, it is 13% lower than that of the PFR simply Iout = = (34)
operating at reaction temperature of 450 K, and 49% lower p p p p
than that of the PFR simply operating at 530 K.
Substituting Eq. (9) into Eq. (34), we obtain:
4.4.2. The effect on PEI Iin
Iout = + PEI (35)
Known from Eqs. (31) and (32), rPEI /rB can be used to p p
study the effect of the reaction temperature. When l = 1,
it is not difficult to find that increasing reaction temperature For the case study, it is not difficult to obtain that Iin =
would decrease the values of rPEI /rB , accordingly the value 4.6 104 PEI/h, i.e. Iin is a constant. Therefore, when the
of PEI also decreases. For example, for CSTR operating at feed condition of a reaction process is fixed, back-mixing
500 K, if its outlet concentration CC,out = 0.011 mol/L, and and reactiontemperature affect Igen and Iout in the same
v0 is 325 L/s, the value of PEI is 31 PEI/kg, while for way. Since p p = v0 CC,out MC 103 , it is not difficult
CSTR operating at 530 K and with the same CC,out , the value to find that, when the feed condition and CC,out are spec-
of PEI is 36 PEI/kg, that is, this CSTR reduced the value ified, back-mixing and reaction temperature influence Iout
of PEI by 16%. Similar to this example, for the case of not and PEI in the same way, too.
considering the potential environmental impact of Cl2 , one Thus, in Section 4.3, when l = 1 and the reaction pro-
can also conclude the effect of temperature on PEI . cess is operated in the specified conditions, the results that
Igen and PEI of CSTR are less than those of PFR indicate
4.5. The effect of concentration on environmental that using CSTR can obtain lower Iout and Iout than us-
performance ing PFR. That means at the given conditions, back-mixing
make the emission of potential environmental impact de-
We here only study the effect of concentration on PEI . crease. By contrast, when not considering the PEI of A, the
Similar to previous method in Section 4.4.2, one can also use results are converse, i.e. using PFR would gain lower PEI
rPEI /rB to study the effect of concentration. From Eqs. (31) generation rate than using CSTR; and the value of PEI of
and (32), it can be found that for a particular outlet concen- CSTR that operate at reaction temperature 500 K and out-
tration of C the value of PEI would be decreased by in- let concentration CC,out = 0.011 mol/L is 2.6 times that of
creasing the value of rPEI /rB . When l = 1, from Eq. (28), PFR. The results indicate that at the given reaction condi-
the value of rPEI /rB can be increased by augmenting CC and tions, back-mixing will increase the emission of potential
decreasing CB within a reactor. Since C is a product whereas environmental impact of the reaction processes, accordingly,
B is a reactant, using CSTR will lead to higher CC and lower reactor designers should try to avoid it in such case.
CB within a reactor than using PFR. Therefore, in this case, In Section 4.4, when l = 1, the results show that a higher
using CSTR would result in lower value of PEI than using reaction temperature is favorable for the decrease of Igen
PFR operating at the same reaction conditions. When not and PEI in the giving conditions. Therefore, increasing the
considering the potential environmental impact of Cl2 , from reaction temperature will lead to the decrease of Iout and
Eq. (30), decreasing CC and increasing CB within a reactor Iout . When not considering the PEI of Cl2 , PFR operating
will increase the value of rPEI /rB , accordingly, using PFR at a high temperature in the first section and low tempera-
would result in lower PEI than using CSTR. These results ture in the remainder section can result in lower generation
are also concluded in Section 4.3.2. and emission of PEI than that operating at a corresponding
uniform temperature.
To study the effects of concentration on environmental
5. Discussion performance of reaction processes, two analyses are intro-
duced in Section 4.5. The results show that when l = 1,
In the case study, the indexes involved are Igen and PEI . operating at relatively low concentration of B and high
However, these two indexes only express the situation of concentration of C is favorable for decreasing the poten-
PEI generation within processes. The environmental perfor- tial environmental impact created in manufacturing a unit
mance of a process also relates to its emission of PEI. There- mass of the product C. This also is true for total PEI leav-
fore, in the WAR algorithm, the output rate of PEI, Iout , and ing the system per mass of product streams according to
20 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321
the relations about these two categories of indexes. By into this methodology as they become available. It is suggest
contrast, when neglecting the PEI of Cl2 , the results are that either the WAR algorithms assessment method and the
converse. PEI indexes, another similar method and indexes, or even a
In the cases study, we have only studied the effects of more sophisticated and comprehensive method and indexes
back-mixing on the environmental performance. Whereas be used to this pollution reduction methodology.
the phenomena of back-mixing is only one of engineering In the case study, the calculations of the impact indexes
factors, which still involve pre-mixing, heat and mass trans- should be accurate to no more than one significant figure
fer, thermostability and so on. However, the effects of those [12]. But two significant figures are used in order to allow
engineering factors not involved in the case study on envi- readers to reproduce the calculations if necessary. It is also
ronmental performance can also be simulated and therefore worth noting that, even being accurate to one significant
well studied through a combination of reactor mathematical figure, one can still discern significant differences in the
model, which relates to corresponding engineering factors, index between different cases.
with PEI balances. As for the effects of other reaction con-
ditions not involved in the case study, such as space time,
pressure, compositions of feeds and so on, which may af- 6. Conclusions
fect the environmental performance of reaction processes
significantly in some cases, can also be studied with the To perform pollution prevention in the process of reac-
help of corresponding PEI balances and the PEI rate-law tor design, studying the effects of reaction conditions such
expressions, because we can ultimately simulate the change as temperature, pressure and concentration as well as vari-
of the environmental indexes with these reaction conditions ous engineering factors on environmental performance of a
through PEI balance and PEI rate-law expression. reaction process is very important. In this paper, potential
The reaction system involved in the case studied is a kind environmental impact balance and PEI rate-law expression
of relatively complex van de vusse reaction, nevertheless the are proposed as a tool to be used to carry out this work. The
reaction system in real manufacturing process may involve form of PEI rate-law expression should be consistent with
more reaction types and, therefore, is more complex than the method for calculating the overall PEI of mixtures of
that one. One can, however, simulate the change of envi- chemicals inside reactors. The effectiveness of the method
ronmental indexes within a reactor by combining traditional has been demonstrated through the reaction of allyl chlo-
reactor mathematical model with the PEI balance, and may ride production. From the processes of the analyses in the
also discover the effects of reaction conditions and engineer- case study, analyzing with PEI balance and PEI rate-law ex-
ing factors on environmental performance by PEI rate-law pression combining with other corresponding equations and
expression and/or combinations it with other reaction rate some mathematic knowledge can give important insights
equations as well as other related equations in reactor math- into how reaction conditions as well as engineering factors
ematical models. affect the environmental performance of reaction processes.
Note that assuming l = 1 and not considering the PEI of This kind of study is one of the bases for developing chem-
Cl2 are just for illustrating the algorithm, these assumptions ical reactors with environmental benign processes.
may be inappropriate for a real reactor design. Other users of
this methodology may choose to weight effects differently
to reflect local needs and polices where the plants locate [8]. Acknowledgements
In the case study, the quantitative environmental impact
assessment and the PEI indexes are cited from the WAR al- Financial support provided by the National Natural Sci-
gorithm, it is worth noting that, however, quantitative impact ence Foundation of China under Grant No. 20176405 and
assessment and environmental indexes are likely to improve the Major State Basic Research Development Program un-
with time, and that these improvements can be incorporate der Grant No. G2000026307 is gratefully acknowledged.
Appendix A. Nomenclature
Greek letters
l weighting factor for impact category l
PEI generated PEI per unit mass of all desired products (PEI/kg)
kl
s the specific PEI of chemical k for environmental impact category l (PEI/kg of chemical k)
k overall PEI of chemical k (PEI/kg of chemical k)
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94 (320) (1998) 117121. chemical process simulator: the generalized waste reduction (WAR)
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design and operation, Chem. Eng. Prog. 94 (2) (1998) 6166. algorithm: environmental impacts, energy consumption, and engi-
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process is green, how do you known? Using principles of sustain- [10] W. Schramm, New findings on the generation of waste and emissions,
ability to determine what is greena corporate perspective, Green and a modified cleaner production assessment approachillustrated
Chem. 3 (2001) 16. by leather production, J. Cleaner Prod. 5 (4) (1997) 291300.
[5] H. Cabezas, J.C. Bare, S.K. Mallick, Pollution prevention with chem- [11] B. Pahor, Z. Kravanja, N.I. Bedenik, Synthesis of reactor networks
ical process simulator: the generalized waste reduction (WAR) algo- in overall process flowsheets within the multilevel MINLP approach,
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minimizing waste production in manufacturing process, J. Air Waste methodology for chemical process simulator, Ind. Eng. Chem. Res.
Manage. Assoc. 44 (1994) 13031308. 35 (11) (1996) 41284138.
Chemical Engineering and Processing 44 (2005) 2332
Received 28 April 2003; received in revised form 12 April 2004; accepted 13 April 2004
Available online 17 June 2004
Abstract
The combined uptake of Cu2+ and Zn2+ by activated sludge (biomass) was investigated at steady state in an activated sludge process (ASP)
without recycle (namely, once-thro ASP), for different values of influent metal concentrations and hydraulic residence time in the range of
2.540 h. The experiments were performed at a constant pH of 7 and temperature of 25 C. The results showed that the percentage removal of
both copper and zinc by activated sludge increased with the increasing residence time; moreover, the percent metal uptakes were higher for
both metals at the low level of influent metal concentrations [(Cu2+ ) = 1.5 mg/L and (Zn2+ ) = 9 mg/L], than those at the higher level of
concentrations [(Cu2+ ) = 4.5 mg/L and (Zn2+ ) = 27 mg/L]. The least represented forms of both Cu2+ and Zn2+ in activated sludge were
their sulfides, and the dominant metal forms were found to be organically bound for both of the metals, Zn2+ and Cu2+ .
2004 Elsevier B.V. All rights reserved.
Keywords: Biosorption; Activated sludge process; Removal of heavy metals; Sequential extraction of metals; Metal uptake
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.004
24 T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332
samples from the reactor were analyzed for substrate, S, and Secondly, concentrations of the HMs associated with the
biomass, X, concentrations. MLSS concentration was used solution, and solid phases of the effluent were determined.
as the primary indicator for steady state conditions. At each Two of 50 mL aliquots were collected from the effluent of
residence time, steady state was reached when the effluent the reactor, centrifuged at 1300 rpm for 15 min, by using
S (COD) and X (MLSS) concentrations remained constant a RC5C type Dupont centrifuge, to separate the solution
with respect to time. and solid phases, and the supernatants transferred to sam-
Experiments with HMs were performed at two concentra- ple tubes. Then, supernatants and the residual solid phase
tion levels of each metal (low levels: (Cu2+ ) = 1.5 mg/L were acidified by adding 10 mL concentrated HNO3 to each
and (Zn2+ ) = 9 mg/L; high levels: (Cu2+ ) = 4.5 mg/L sample tube. Samples were then analyzed by AAS after per-
and (Zn2+ ) = 27 mg/L, for different values of HRT in the forming the necessary dilutions to the sensitivity range of
range of 240 h using the same synthetic WW having the the instrument as explained above. The average of the results
composition given in Table 1. In these experiments, 1.8 L from the two samples were recorded as CS (metal concen-
of synthetic WW was inoculated with 0.2 L of acclimated tration in the solution phase), and CA (metal concentration
seed MOs in the activated sludge reactor, and the system in the solid phase) values for each HM.
was operated in batch mode for almost 72 h to ensure the The distribution of different metal forms in the sludge
growth of biomass by observing the increase in measured was determined by using the sequential extraction pro-
turbidities of the samples from the reactor. Then, the con- cedure [25]. Activated sludge mixed liquor of 1.5 L,
tinuous operation was started by feeding the reactor with corresponding to 0.2500.100 g of sludge, was collected
synthetic WW containing copper and zinc ions at the de- from the outlet of the reactor at the steady state. In order
sired inlet concentrations. Influent flow rate was adjusted to separate the sludge and supernatant, centrifugation at
in order to provide a required HRT. Samples were taken 1300 rpm for 15 min was carried out using a RC5C type
from the effluent stream at different times in order to deter- Dupont centrifuge. Then the extraction process was started
mine the effluent S and X concentrations until steady state by adding the reagents of KNO3 , KF, Na4 P2 O7 , EDTA
was reached. Then, a sample of 1.5 L from effluent stream (ethylene-diamine-tetraacetic-acid) and HNO3 on the con-
was collected for the metal analyses, and the operation was centrated sludge (order of addition given in Table 2), which
stopped. are capable of extracting exchangeable, adsorbed, organi-
cally bound, carbonates, and sulfides forms of the metals
2.3. Analytical methods in the sludge sample, respectively. To provide complete
extraction, samples were shaken on a platform shaker, then
Substrate concentrations were determined in centrifuged centrifuged at 1300 rpm for 15 min, and supernatants were
sample aliquots by standard COD analysis, and gravimet- decanted into separate tubes. Between each extraction, the
ric method was used to measure the biomass concentrations sludge residue was washed with 50 mL of de-ionized water
[24]. Analyses were repeated at least twice with the sam- by shaking for 30 min, and the samples centrifuged again
ples under the same experimental conditions and the average under the same conditions. Both supernatants from the ex-
values were obtained. traction and washing were combined and acidified with two
drops of 5 M HNO3 before metal analysis, in order to pre-
2.3.1. Distribution of metals among the constituents of serve the solutions. All metal concentrations were measured
activated sludge mixed liquor as before and conversions were made to obtain the concen-
Since metals were distributed between the two phases of trations of each form of each metal as mg metal/ kg sludge,
mixed liquor in the reactor, namely solution and biomass, the for which the metal concentration as mg/L was divided by
amounts of copper and zinc associated with these phases and the dried MLSS concentration (kg TSS/L), determined at
the forms of these metals in the biomass were determined the steady state. The same procedure was followed for the
at steady state condition for each HRT. other reagents, the only exception being that double extrac-
Firstly, the concentrations of HMs in effluent were de- tion was performed with EDTA and supernatants pooled
termined. At least three samples of 40 mL were acidified before the metal analyses. The remaining solid residue in
with 10 mL of concentrated HNO3 to decompose MOs.
These samples were diluted to the sensitivity range of the
atomic absorption spectrophotometer (AAS) (Model: Philips Table 2
9200X-AAS) (diluted 5 times for Cu2+ analysis, and 25 Details about sequential extraction process parameters [25]
times for Zn2+ analysis) and then analyzed. The average of Reagents Molarity pH Extraction (Solution/solids)
these measurements yielded the total HM concentration in (M) time (h) ratio
the effluent, CT (mg/L), for that specific experimental run. KNO3 1 24 50/1
To convert (mg metal/L) to (mg metal/kg sludge), the mea- KF 0.5 6.5 24 80/1
sured metal concentration (as, mg metal/L) at each HRT Na4 P2 O7 0.1 24 80/1
was divided by the steady state MLSS concentration (as, kg EDTA 0.1 6.5 224 80/1
HNO3 1 24 50/1
TSS/L).
26 T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332
the sample tube, at the end of the extraction procedure, was Table 6
decomposed with 5 mL of concentrated HNO3 in order to Material balance on zinc at the influent concentration of (Zn2+ )
= 27 mg/L
determine the levels of metals not extracted by the protocol.
h (h) CT CS CA [(CS + CA ) CT ]
100/CT
3. Results and discussion 40 29.20 29.14 0.72 +2.26
20 27.13 26.23 0.65 0.92
10 29.69 28.75 0.63 +1.04
Two phases exist in the activated sludge reactor; the liq- 5 28.38 27.68 0.52 0.63
uid phase consists of water, soluble ions and soluble sub- 2.5 28.88 28.52 0.44 +0.28
strate while the solid phase (biomass or sludge) has settleable
waste materials, dead and alive MOs in it. Metals associated
with these phases were investigated in this study. The ma- being (Cu2+ ) = 4.5 mg/L, (Zn2+ ) = 27 mg/L. It is seen
terial balance for the metals at the steady state is defined as in these tables that the total metal concentration in the ef-
follows: fluent is greater than that in the influent to the reactor at the
CT = CA + CS (1) steady state due to the experimental error occurred in the
determination of these concentrations in very small amounts
where CT is the total HM concentration in effluent (mg/L), of sludges produced. In spite of this, the obtained results are
CA is the HM concentration taken up by the sludge (mg/L) consistent as indicated by the small differences between the
and CS is the heavy metal concentration in the solution two sides of the material balance at each run, the maximum
(mg/L). This balance was applied to each run using HMs. In percent experimental error being within 5%.
Tables 36, material balance results for copper and zinc are Fig. 1 shows the percent metal removals. Small percentage
presented for two sets of experiments (in the first set, influ- removals (up to 10%) are because only small amounts of
ent HM concentrations being (Cu2+ ) = 1.5 mg/L, (Zn2+ ) biomass were produced in the system under the experimental
= 9 mg/L, and in the second set, influent HM concentrations conditions used. This is expected in a system where toxic
Table 3
Material balance on copper at the influent concentration of (Cu2+ ) 12
= 1.5 mg/L
h (h) CT CS CA [(CS + CA ) CT ]
100/CT
10
17.18 1.47 1.38 0.15 +1.04 Cu: 1.5 mg/L
14.68 1.61 1.42 0.12 4.35 Cu: 4.5 mg/L
9.22 1.63 1.60 0.09 +3.68 Zn: 9 mg/L
5.12 1.63 1.58 0.06 +0.61 Zn: 27 mg/L
3.75 1.43 1.43 0.02 +1.40 8
percent metal removal
Table 4
Material balance on zinc at the influent concentration of (Zn2+ ) = 9 mg/L
6
h (h) CT CS CA [(CS + CA ) CT ]
100/CT
17.18 11.13 10.32 0.54 2.43
14.68 10.57 10.70 0.55 +6.43 4
9.22 10.68 10.70 0.44 +4.31
5.12 9.88 9.09 0.39 4.05
3.75 9.79 9.83 0.29 +3.37
2
Table 5
Material balance on copper at the influent concentration of (Cu2+ )
= 4.5 mg/L
h (h) CT CS CA [(CS + CA ) CT ] 0
100/CT 0 10 20 30 40
40 5.24 4.88 0.22 2.67 residence time (h)
20 4.68 4.53 0.18 +0.64
Fig. 1. Percent removal of each metal [(CA /CT ) 100] in the ex-
10 4.27 4.23 0.13 +1.02
periments of Set-1 (influent concentrations: (Cu2+ ) = 1.5 mg/L,
5 4.20 4.19 0.08 +1.67
(Zn2+ ) = 9 mg/L) and Set-2 (influent concentrations:
2.5 4.58 4.57 0.04 +0.66
(Cu2+ ) = 4.5 mg/L, (Zn2+ ) = 27 mg/L).
T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332 27
Exchangeable 180
800 Adsorbed
Exchangeable
Organically bound Adsorbed
Carbonates 160 Organically bound
700 Sulfides Carbonates
140 Sulfides
mg metal removed / kg sludge
600
120
mg metal removed / kg sludge
500
100
400 80
300 60
40
200
20
100
0
0 2 4 6 8 10 12 14 16 18
2 4 6 8 10 12 14 16 18 residence time (h)
residence time (h)
Fig. 5. Distribution of Cu2+ among its forms in the sludge using the data
Fig. 3. Distribution of Zn2+ among its forms in the sludge using the data of Set-1 experiments.
of Set-1 experiments.
as a result of this, a more hydrophobic (larger contact angle) than the amount of organically removed copper at a HRT of
and less negatively charged floc surface was observed [28]. 40 h, while it was lower than that of organically bound cop-
The present OTASP was operated at high F/M ratios [23]; per at a HRT of 20 h. Therefore, it is shown in Fig. 2 that
although no data were obtained about the concentration and the copper uptake at a HRT of 40 h is less than that at 20 h.
the composition of EPS produced in this work, it might be The copper uptake is probably less at a HRT of 40 h due to
predicted from the available literature that the protein con- the effect of changing metabolic activity of microbial flocs
tent of the produced EPS in the flocs was low; thus the set- and the solubility constant of copper carbonate complex in
tling ability of the resulting sludge, most probably with a the medium at the prevailing conditions. The desorption of
high value of SVI was not good. Actually, low settlability of copper into the solution might have occurred due to the sol-
the produced sludge was observed in the experiments. The ubility constant of this complex.
effect of operational conditions on EPS composition will be
the subject of a future study in which it will be investigated
in an ASP with recycle to compare the effects of sludge 4. Conclusions
residence time (SRT), HRT, EPS and F/M ratio on the set-
tlability of produced sludge and metal uptake. In this study, The effect of hydraulic residence time (in the range of
the change in bacterial profile of the MLSS with metal con- 2.540 h) on the removal of Zn2+ and Cu2+ ions by acti-
centration was not followed, but it was reported in the lit- vated sludge was investigated in a once-thro activated sludge
erature [34] that many different species of bacteria isolated process (OTASP) at a constant pH of 7 and temperature of
from activated sludge were shown to produce EPS. These 25 C. It was found that the percentage removals of both cop-
polymers might be in the form of loose slime or capsules per and zinc by activated sludge increased with the increas-
adhered to the cell wall. In activated sludge, slime polymers ing residence time due to the increasing amounts of sludge
remained in the dissolved and colloidal phases of an efflu- produced with time. Higher percent removal of zinc at the
ent, while capsular polymers remained attached to the flocs low level of influent concentrations of both the copper and
and hence settled with the sludges. Some activated sludge zinc, (Cu2+ ) = 1.5 mg/L and for (Zn2+ ) = 9 mg/L, due
bacteria did not produce capsules or extracellular material. to the higher inlet concentration of zinc over that of copper
In these bacteria, metals might be accumulated either in the was replaced by the higher percent removal of copper at the
cytoplasm or by adsorption on to the cell wall. Some re- high level of influent concentrations of each metal, (Cu2+ )
searchers [35] concluded that only the half of the observed = 4.5 mg/L and for (Zn2+ ) = 27 mg/L, although copper is
metal uptake could be attributed to EPS and that cell itself known to be more toxic to the microorganisms than zinc.
played a role in accumulating metals. In another work [36], This suggested that the lower toxicity of zinc at its low con-
EPS were extracted, cells were broken up using ultrasound centration level is compensated by another factor such as
and cell envelopes were sedimented by centrifugation. Only the removal of both metals by precipitation also contribut-
small quantities of copper were found in the cytoplasm, but ing to the removal process. However, it was not possible
substantial amounts of copper were bound to cell envelopes to differentiate between the percent removals of each metal
and EPS. The metabolism of elements occurred in many by biosorption or by precipitation in OTASP. The previous
species of bacteria. It was also reported that four major types study [16] cannot render this information due to the presence
of metal transformation in organisms occurred [37], these of a third metal ion such as Ni2+ in the system. Therefore, a
being chelate formation by the binding of metals to organic further study is required in an activated sludge system with
ligands, shifts in metal valencies, substitution of one metal recycle which will differentiate the percent removals of each
for another and biomethylation of metals to microorganisms. metal by precipitation and biosorption clearly. In this study,
When metals were chelated to substrate molecules, the ad- at short residence times (a range of 2.55 h), the percent-
sorption of these molecules might represent a means of accu- age of zinc bound to the biomass is higher than for copper
mulating metals within a cell. These metabolic transforma- due to the dominating effect of lower toxicity of zinc; this
tions of metal ions by bacteria were different for each metal is also shown by the sequential extraction results yielding
and for different combinations of metals in the medium. the dominant form of both Zn2+ and Cu2+ as organically
Therefore, in such a dynamic system as is ASP, it is not bound indicating that both types of ions are removed by
plausible to use metal uptake as a measure of EPS content. biosorption rather than by precipitation due to the lower de-
As it is seen in Fig. 2, the copper uptake increases with the gree of inhibition of MOs at small sludge ages or HRTs in
HRT up to 20 h then it shows a slight decrease between 20 OTASP. This point can be clarified by investigation in an
and 40 h. This can be explained with the change in the given activated sludge process with recycle. It is also found that
ranking in Fig. 6. The chemical speciation and distribution the least represented forms of both the copper and zinc ions
of copper in an activated sludge slurry can be quantified in the sludge are their sulfides. A further study is under-
using an equlibrium constant approach including complex- way to investigate the effect of operational conditions on the
ation with inorganic and organic ligands and adsorption by composition of extracellular polymer substances in an ASP
activated sludge solids [38]. It can be observed in Fig. 6 that with recycle to compare the effects of sludge residence time,
the amount of copper carbonate per kg of sludge is higher hydraulic residence time, EPS and food to microorganism
T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332 31
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Chemical Engineering and Processing 44 (2005) 3339
Received 17 February 2004; received in revised form 11 March 2004; accepted 7 April 2004
Available online 1 June 2004
Abstract
The catalyst intraparticle reaction-diffusion process of parallel, equilibrium-restrained reactions for the methanation system was studied. The
non-isothermal one-dimensional and two-dimensional reaction-diffusion models for the key components have been established, and solved
using an orthogonal collocation method. The simulation values of the effectiveness factors for methanation reaction CH4 and shift reaction CO2
are fairly in agreement with the experimental values. CH4 is large, while CO2 is very small. The shift reaction takes place as direct and reverse
reaction inside the catalyst pellet because of the interaction of methanation and shift reaction. For parallel, equilibrium-restrained reactions,
effectiveness factors are not able to predict the catalyst internal-surface utilization accurately. Therefore, the intraparticle distributions of the
temperature, the concentrations of species and so on should be taken into account.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.003
34 G. Yu et al. / Chemical Engineering and Processing 44 (2005) 3339
2. Reaction system and fundamental data under the reaction conditions at 400600 C. The equilib-
rium constant of the WGSR is small and varies insignif-
With the reducing supply of low sulfur petroleum, the icantly with temperature. Due to the water formation and
demand for residual oil and coal with high-sulfur con- the concentration variations in carbon monoxide and hydro-
tent is increasing. The development and application of gen, which are consequences of the methanation reaction,
sulfur-resisting catalysts have received great attention. The the overall WGSR occurs both as the direct and reverse re-
KD306-type sulfur-resisting methanation catalyst, a sulfide action at internal surface of the catalyst. So, the fundamental
catalyst such as Mo and W of group VIB as the primary features of this reaction system are equilibrium-restrained,
species and Fe, Co, Ni of group VIII as the indispens- namely reversible, parallel reactions.
able promoters, can be used in methanation reaction with
sulfur-containing syngas as the reactants at high reactivity 2.1. Reaction kinetics [9]
and selectivity. The cylindrical catalyst pellets (diameter
= 5.422 mm, length = 4.327 mm) were prepared by com- The intrinsic kinetics was measured in an isothermal in-
pressing particles. tegrated reactor and the reaction rate equations in terms of
Methanation reaction and watergas shift reaction power function have been established
(WGSR), which are chosen as the examples for presenta-
46 944
tion, are expressed as follows: (rCH4 )w = 3.8333 106 exp
RT
0.58 P 0.52 mol s1 kg1
CO + 3H2 = CH4 + H2 O, H 298 = 206 kJ/mol PCO H2
CO + H2 O = CO2 + H2 , H 298 = 41 kJ/mol (rCO2 )w = 4.1089 105 exp
58 349
RT
The former is a volume-decreasing reaction, while the PCO0.58 P 0.98 (1 ) mol s1 kg1
H2 O
latter is not. Both reactions are exothermic. Methanation
is a deep hydrogenation reaction for carbon monoxide and where = JP /KP .
WGSR is a complete oxidation reaction in which carbon The macrokinetics were measured in a gradientless reac-
monoxide is oxidized into carbon dioxide and water is re- tor.
duced with the formation of hydrogen. As in the preparation
of methane, other hydrocarbons, low alcohols and particu- 2.2. Effective diffusivity DeffA [10]
larly, carbon dioxide and water are formed. Because of the
presence of water, WGSR always occurs in the methana- Mass transport inside the catalyst has been usually de-
tion process, which reduces the selectivity and yield of the scribed by applying the Fick equation, by means of an effec-
desired product. tive diffusivity DeffA . Based on properties of the interface
Fig. 1 shows reaction equilibrium constants of the metha- and neglecting the composition effect, composite diffusivity
nation reaction and the WGSR [12]. The mole composition of the multi-component gas mixture is calculated through
of town gas is: CO 20%, H2 40%, CO2 10%, H2 O the simplified Wilke model [13]. The effect of pore-radius
0%, N2 the rest. Methanation reaction is almost irreversible distribution on Knudsen diffusivity is taken into account.
The effective diffusivity DeffA is given by
16 1
N
10000 rmax 1 yj 1
DeffA = + f(r) dr
rmin 1 yA DAj DAk (r)
j=A
12 where is the tortuosity factor of the KD306 catalyst, which
1000
was measured using single pellet string reactor technique.
Kp,methanantion,atm -2
Kp,shift
The assumptions made for the reaction-diffusion models 4R2p Deff,CO2 (dCCO2 /dR)s
are as follows: CO2 =
(4/3)R3p p (rCO2 )w,s
(1) parallel, equilibrium-restrained reactions occur (namely,
methanation reaction is irreversible, while WGSR is re- the effectiveness factors for the catalyst pellet can be calcu-
versible); lated from
(2) non-first order reactions; N+1
(3) non-isothermal; 3 j=1 AN+1,j CCO2 ,j
CO2 = ,
(4) quasi-homogeneous; (Rp /Deff,CO2 )p (rCO2 )w,s
2
(5) only key components are considered (methane and car-
3 N+1
j=1 AN+1,j CCH4 ,j
bon dioxide). CH4 =
(R2p /Deff,CH4 )p (rCH4 )w,s
3.1. One-dimensional model
3.2. Two-dimensional model
Commonly [17], when the length-to-diameter ratio of a
cylindrical catalyst is close to 1, the cylindrical catalyst can RP and HP are the radius and semi-length of cylindri-
be simplified as a sphere, the radius of which, Rp , is calcu- cal catalyst, respectively. Assume a cylindrical ring element
lated by 3Vp /Sp . The one-dimensional, key-component based with the length dH and the radial thickness dR at the axial
reaction-diffusion models of methanation system are as fol- position H and the radial position R in the 2D cylindrical
lows: system. Introducing the dimensionless variables
d2 CCH4 2 dCCH4 R2p
+ = (rCH4 )w p R H
dx2 x dx Deff,CH4 x= , z=
Rp Hp
d2 CCO2 2 dCCO2 R2p
+ = (rCO2 )w p The species (methane and carbon dioxide) mass balance
dx2 x dx Deff,CO2
and energy conservation in the cylindrical ring element at
d2 T 2 dT R2p
+ = p [(rCH4 )w (HCH4 ) steady state lead to the following 2D partial differential equa-
dx2 x dx eff tions:
+ (rCO2 )w (HCO2 )]
2 2
Boundary conditions 2 CCH4 1 CCH4 Rp CCH4
+ +
x2 x x Hp z2
r
x= = 1, CCH4 = (CCH4 )s , CCO2 = (CCO2 )s , Rp2
Rp = p (rCH4 )w
T = Ts Deff,CH4
2 2
dCCH4 dCCO2 dT 2 CCO2 1 CCO2 Rp CCO2
x = 0, = 0, = 0, =0 + +
dx dx dx x2 x x Hp z2
R2p
Applying orthogonal collocation method, the above equa- = p (rCO2 )w
tions become Deff,CO2
2 2
2 T 1 T Rp T
N+1
2
R2p + +
Bjk + Ajk CCH4 ,k = (rCH4 )w,j p x 2 x x Hp z2
x Deff,CH4 Rp2
k=1
= p [(HCH4 )(rCH4 )w + (HCO2 )(rCO2 )w ]
N+1
2
R2p eff
Bjk + Ajk CCO2 ,k = (rCO2 )w,j p
x Deff,CO2
k=1 with the associated boundary conditions
N+1
2
R2p
Bjk + Ajk Tk = p [(rCH4 )w,j (HCH4 ) CCO2 CCH4 T
x eff x = 0, = = =0
k=1 x x x
+ (rCO2 )w,j (HCO2 )] CCO2 CCH4 T
z = 0, = = =0
The solutions of the above non-linear equations can be ob- z z z
tained using the Broyden quasi-Newton method [18]. Based x = 1 or z = 1, CCO2 = CCO2 ,s , CCH4 = CCH4 ,s , T = Ts
on the mass balance, the concentrations of other component,
such as CO, H2 , H2 O and so on, can be calculated from the Each item of the model at collocation point (I, J) may be
key components [9]. expressed as
36 G. Yu et al. / Chemical Engineering and Processing 44 (2005) 3339
F = CCO2 F = CCH4 F =T
N+1
N+1 N+1
N+1
N+1
N+1
2j2 2j2 2j2
(F)I,J aij xI2i2 zJ bij xI2i2 zJ cij xI2i2 zJ
j=1 i=1 j=1 i=1 j=1 i=1
N+1
N+1
N+1
N+1
N+1
N+1
F 2j2 2j2 2j2
(2i 2)aij xI2i3 zJ (2i 2)bij xI2i3 zJ (2i 2)cij xI2i3 zJ
x I,J j=1 i=1 j=1 i=1 j=1 i=1
N+1
N+1
N+1
N+1
N+1
N+1
2 F 2j2 2j2 2j2
(2i 2)(2i 3)aij xI2i4 zJ (2i 2)(2i 3)bij xI2i4 zJ (2i 2)(2i 3)cij xI2i4 zJ
x2 I,J j=1 i=1 j=1 i=1 j=1 i=1
N+1
N+1
N+1
N+1
N+1
N+1
2 F 2j4 2j4 2j4
(2j 2)(2j 3)aij xI2i2 zJ (2j 2)(2j 3)bij xI2i2 zJ (2j 2)(2j 3)cij xI2i2 zJ
z2 I,J j=1 i=1 j=1 i=1 j=1 i=1
where, I = 1, 2, . . . , NR + 1, J = 1, 2, . . . , NA + 1.
We obtain
NX +1 NX +1 2 N Z +1
1 Rp R2p p
BXIk CCH4 ,kJ + AXIk CCH4 ,kJ + BZJk CCH4 ,kI = (rCH4 )w,IJ
xI Hp Deff,CH4
k=1 k=1 k=1
NX +1 NX +1 2 N Z +1
1 Rp R2p p
BXIk CCO2 ,kJ + AXIk CCO2 ,kJ + BZJk CCO2 ,kI = (rCO2 )w,IJ
xI Hp Deff,CO2
k=1 k=1 k=1
NX +1 NX +1 2 N Z +1
1 Rp R2p p
BXIk TkJ + AXIk TkJ + BZJk TkI = [(HCH4 )IJ (rCH4 )w,IJ + (HCO2 )IJ (rCO2 )w,IJ ]
xI Hp eff
k=1 k=1 k=1
Table 1
Simulation results of one-dimensional and two-dimensional models by orthogonal collocation method
Number T (K) P (atm) Interface composition CH4 ,e CO2 ,e CH4 ,cone CO2 ,cone CH4 ,ctwo CO2 ,ctwo
yCH4 yCO
1 703.45 7.91 0.1774 0.1773 0.9277 0.0440 0.6699 0.0090 0.7192 0.0699
2 702.65 14.22 0.2508 0.1672 0.6992 0.0084 0.6128 0.0098 0.6696 0.0926
3 704.35 10.28 0.2739 0.1499 0.6679 0.0255 0.6490 0.0183 0.7022 0.0824
4 703.15 11.86 0.2816 0.1446 0.8273 0.0198 0.6351 0.0163 0.6901 0.0816
5 738.35 12.05 0.2836 0.1560 0.5774 0.0151 0.5558 0.0085 0.5832 0.0428
6 738.55 8.30 0.2330 0.1730 0.6665 0.0082 0.6081 0.0134 0.6513 0.0727
Table 2
One-dimensional parameter distribution within catalyst pellet for Number 1 (T = 703.45 K, P = 7.91 atm)
x yCO2 yCH4 yCO T (K) rCH4 103 mol s1 kg1 rCO2 103 mol s1 kg1
0.0000 0.1944 0.3443 0.0427 703.79 0.2620 5.4989
0.2154 0.1902 0.3392 0.0486 703.78 0.2862 0.1375
0.4206 0.1846 0.3236 0.0590 703.74 0.3391 0.1907
0.6063 0.1736 0.2977 0.0781 703.69 0.4319 0.3417
0.7635 0.1558 0.2634 0.1066 703.62 0.5625 0.4908
0.8851 0.1330 0.2256 0.1411 703.55 0.7124 0.7889
0.9653 0.1137 0.1935 0.1704 703.48 0.8398 2.3307
1.0000 0.1118 0.1774 0.1773 703.45 0.8905 18.9060
core center. The direct WGSR dominates between the men- not imply that WGSR hardly occurs in the catalyst pellet due
tioned above regions but its rate is low. The region of direct to internal diffusion. WGSR occurs remarkably at all sites of
reaction is big, while the region of reverse reaction is small. catalyst pellet, and the reaction rate of each site is not equal
Internal diffusion is not the major factor leading to low CO2 . to zero. As a result of the existence of direct and reverse
The existence of regions of the direct and reverse WGSR reaction of WGSR, and also the volume-decreasing metha-
contributes to a greater extent to low CO2 , which in turn nation reaction, there is small variation of carbon dioxide
causes the low net reaction rate. This low reaction rate does concentration due to the site change in the pellet.
It is shown in Tables 2 and 5 that the methanation reac-
tion takes place as a direct reaction throughout the whole
Table 3
Two-dimensional parameter distribution within catalyst pellet for No.
internal-surface of the pellet. Carbon monoxide, which is
3-yCH4 (T = 704.35 K, P = 10.28 atm) the product of the reverse WGSR, promotes the methanation
reaction. The interaction between the methanation reaction
z x
and the WGSR enhances the methanation reaction and also
0.0000 0.2390 0.5262 0.7639 0.9275 1.0000 improves CH4 . Internal diffusion also affects the methana-
0.0000 0.4220 0.4183 0.4002 0.3615 0.3085 0.2739 tion reaction.
0.2390 0.4175 0.4141 0.3969 0.3597 0.3081 0.2739 To put it briefly, the effectiveness factors for parallel
0.5262 0.3967 0.3942 0.3809 0.3504 0.3053 0.2739 equilibrium-restrained reactions cannot describe the utiliza-
0.7639 0.3561 0.3548 0.3474 0.3289 0.2981 0.2739 tion degree of catalyst internal-surface accurately. Therefore,
0.9275 0.3052 0.3051 0.3027 0.2966 0.2852 0.2739
the intraparticle distributions of the temperature, the concen-
1.0000 0.2739 0.2739 0.2739 0.2739 0.2739 0.2739
trations of species and so on should be taken into account.
Table 4 Table 5
Two-dimensional parameter distribution within catalyst pellet for No. Two-dimensional parameter distribution within catalyst pellet for No.
3-rCO2 103 (T = 704.35 K, P = 10.28 atm) 3-rCH4 103 (T = 704.35 K, P = 10.28 atm)
z x z x
0.0000 0.2390 0.5262 0.7639 0.9275 1.0000 0.0000 0.2390 0.5262 0.7639 0.9275 1.0000
0.0000 18.909 9.619 8.904 8.136 9.467 52.009 0.0000 0.1672 0.1891 0.2690 0.4486 0.7055 0.8575
0.2390 10.049 0.155 0.206 0.557 0.812 52.009 0.2390 0.1922 0.2129 0.2889 0.4617 0.7112 0.8575
0.5262 9.140 0.306 0.333 0.641 0.767 52.009 0.5262 0.2844 0.3015 0.3621 0.5058 0.7256 0.8575
0.7639 8.375 0.687 0.678 0.905 0.604 52.009 0.7639 0.4739 0.4849 0.5206 0.6098 0.7616 0.8575
0.9275 10.533 16.161 1.648 1.513 3.006 52.009 0.9275 0.7212 0.7260 0.7378 0.7682 0.8251 0.8575
1.0000 52.009 52.009 52.009 52.009 52.009 52.009 1.0000 0.8575 0.8575 0.8575 0.8575 0.8575 0.8575
38 G. Yu et al. / Chemical Engineering and Processing 44 (2005) 3339
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Eng. Progr. 46 (1950) 95. Institute of Science and Technology Press, Shanghai, 1990 (in Chi-
[14] W. Woodside, J.H. Messmer, Thermal conductivity of porous nese).
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1688. problem. Diffusion and reaction, Chem. Eng. Sci. 6 (1957) 262.
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Chemical Engineering and Processing 44 (2005) 4149
Received 19 December 2003; received in revised form 18 February 2004; accepted 1 April 2004
Available online 18 May 2004
Abstract
Proportional integral derivative (PID) controllers are extensively used in the process industry. As a result a large number of general purpose
tuning methodologies are available. These tuning methodologies can offer initial estimates of the parameters of the PID controllers. However,
the design objectives used for the development of these tuning methods can be quite different from the performance objectives specific to a
process under investigation. As a result, the control engineer often needs customized tuning methods in order to speed up or even eliminate the
retuning procedure, and thus, minimize the time and effort needed to design a satisfactory closed loop system. This paper presents a general
mathematical programming formulation for the development of customized PID controller tunings. A reformulation of the mathematical
formulation is proposed that transforms the initially nonlinear formulation to a linear one that can be solved to global optimality. A number
of case studies are presented to clarify the proposed methodology.
2004 Elsevier B.V. All rights reserved.
Corresponding author. Tel.: +44-1612004346; fax: +44-1612004399. In this work we consider single-input, single output
E-mail address: i.kookos@umist.ac.uk (I.K. Kookos). (SISO) linear time invariant (LTI) systems described by the
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.001
42 G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149
q
following discrete-time state space model
uk =
ek , k (8)
xk+1 = Axk + buk + Evk
(1)
=1
yk = Cxk + duk + Fvk
Finally, we define the variable E
,k to be equal to the product
where x is the n vector of state variables, u the input variable, of the binary variable
and the continuous variable ek , i.e.
v the m vector of disturbances, y the output variable, and
E
,k =
ek ,
, k (9)
k is the sampling time. First, we consider the general class
of proportional-only feedback controllers. In this case, the and Eq. (8) can be written in the following linear form
control moves are related to the deviation from the set point q
through the following: uk =
E
,k , k (10)
uk = kC ek , k (2)
=1
2.2. Tuning of proportional-integral (PID) controllers This is a nonlinear formulation due to the bilinear terms
involved in Eq. (17) and the (possibly) nonlinear objective.
The PID control law considered here contains the P, PI, Following the same procedure as in the previous subsection
PD, and PID control laws as special cases. The velocity form we can replace Eq. (17) by a set of linear inequalities.
of the discrete approximation of an ideal PID controller is We first assume that initial values of the controller param-
given by [2] eters have been obtained using any classical control tech-
nique. We then introduce tuning factors
P ,
I and
D as
S D 2D well as the binary variables P
, I
, and D
uk = kC 1 + + ek 1 + ek1
to denote the se-
I S S lection
-th term of the proportional, integral and derivative
D term of the PID controller, i.e.
+ ek2 (13)
S q
m
m
K =
m m
, m (20)
where S is the sampling time, kC the controller gain, I the
=1
integral time, and D is the derivative time. We define the
following variables: qm
m
= 1, m (21)
Pk = ek ek1 (14)
=1
Ik = S ek (15)
m = kC,0
m m
,
, m (22)
1
,k = P
Pk ,
, k (23)
Dk = (ek 2ek1 + ek2 ) (16)
S
O
,k = I
Ik ,
, k (24)
and Eq. (13) can be written as
,k = D
Dk ,
, k (25)
uk = KP Pk + KI Ik + KD Dk (17)
where m {P, I, D}. Eq. (17) can then be written in the
kC
K = kC ,
P
K = I
, K = kC D
D
(18) following linear form:
I
q
P q
I q
D
N
min = J[xk , uk ], P L P
,k P U P
KP ,KI ,KD ,
, k
k=0 Pk P U (1 P
) E
,k Pk P L (1 P
)
xk+1 = Axk + buk + Evk
(27)
yk = Cxk + duk + Fvk
I L I
O
,k I U I
ek = rk yk ,
, k
Ik I U (1 I
) O
,k Ik I L (1 I
)
uk = uk1 + uk (28)
uk = KP Pk + KI Ik + KD Dk
D L D U D
,k D
Pk = ek ek1 ,
, k
Dk DU (1 D
)
,k Dk D (1
)
L D
Ik = S ek (29)
s.t. (19)
S Dk = ek 2ek1 + ek2
Depending on the form of the objective function, the final
L
formulation obtained by replacing the nonlinear Eq. (17) by
yk yk yk
U
the set of linear inequalities corresponds to a MINLP (non-
uL u uU
k
linear objective), to a MIQP (quadratic objective) or to a
k k
MILP (linear objective). For the cases where the objective
u uk uU
L
function is linear, solution to global optimal solution is guar-
anteed using currently available software. The same holds
KP,L KP KP,U
true for the more general case where the objective function
KI,L KI KI,U is a convex function.
D,L The proposed formulation addresses the problem of PID
K KD KD,U controller design solely in the time domain. It is important to
44 G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149
[6]. -0.5
u(t)
-1
-2
In order to apply the proposed methodology the control 0 50 100 150
Time (min)
engineer needs to supply the model of the process under
investigation in discrete form (see Eq. (1)), an initial con- Fig. 1. Load response of the closed loop IPDT system (proposed: con-
troller tuning (that can be obtained using any classical tech- tinuous line, Luyben [10]: dotted line).
nique) and a performance criterion. Then, the optimization
problem can be solved using any commercial optimization
software. In this work GAMS [8] interface to CPLEX and Figs. 1 and 2 compare the closed loop behavior obtained
MINOS solvers was used to solve the proposed formulation. using the tuning proposed in this work and the tunings
All results were obtained on an Intel P4 2.66 GHz/512 Mb proposed by Tyreus and Luyben [10]. Fig. 1 shows that a
computer and the computational time was of the order of significant improvement in the closed loop load response is
few seconds. obtained when the proposed methodology is used. The value
of the objective function (Eq. (31)) is = 59.4 for the pro-
3.1. Control of integrating processes with time delay posed and = 197.7 for the Luybens tunings. Fig. 2 com-
(IPTD) pares the two methodologies for a unit step set point change.
The responses are comparable and the proposed method
Integrating processes with time delay are among the most results in = 28.6 while for Luybens tunings = 29.7.
commonly encountered processes. Liquid levels, for in-
stance, exhibit integrating behavior. A typical plant involves 3.2. Systems with inverse response and time delay
a large number of liquid level loops whose performance
affects strongly the overall performance of the regulatory Luyben [14] has recently investigated a class of mod-
control systems. The transfer function of an integrating els that involve both inverse response and time delay. More
process with time delay is the following: specifically he has considered the following type of pro-
kP ds cesses:
g(s) = e (30)
s
1 z s ds
PID controller tunings for this model have been given g(s) = kP e (33)
(1 + P s)2
by a number of researchers [913]. Chen and Fruehauf
[9] have given an industrial example of the level control that have a positive zero at s = +1/ z as well as time a
in a distillation column where the open loop dynamics delay d. Using the objective function given by Eq. (31) with
follows the IPTD model with parameters kP = 0.2 and = 1/ S and S = 0.1 we obtained
d = 7.4 min.
The proposed methodology has been applied using the KP = 0.356, KI = 0.154 (34)
following objective function:
N
for a hypothetical system with z = d = 1.6, kP = 1 and
min = S (|ek | + |uk |) (31) P = 1. A unit step disturbance at t = 0 min was assumed
KP ,KI followed be a unit step change in the set point at t = 50 min.
k=0
Fig. 3 compares the closed loop response obtained using the
where NS = f = 300 min. A unit step disturbance at t =
proposed tunings with the tunings given by Luyben [14].
0 min was assumed followed be a unit step change in the set
Luybens tunings correspond to = 19.5 while the ones
point at t = 150 min. The optimization problem was solved
proposed in this work to = 16.7. It is interesting to note
with = 1/ S and S = 0.2 min giving
that the proposed tunings result in improved load as well as
KP = 0.553, KI = 0.0178 (32) set point response.
G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149 45
1.5
y(t) 1
0.5
0
0 50 100 150
Time (min)
1
0.5
u(t)
0
-0.5
0 50 100 150
Time (min)
Fig. 2. Unit step set point response for IPDT system (proposed: continuous line, Luyben [10]: dotted line).
3.3. Control of integrating processes with time delay and In Figs. 4 and 5 the closed loop response obtained using
inverse response (IPTD&IV) the tunings proposed by Luyben (PI controller with kC =
0.854 and I = 23) is compared with the one obtained using
The open loop transfer function of an IPDT&IV process the criterion given by Eq. (31) (kC = 1.117 and I = 6.32)
is the following: with = 1/ S and S = 0.025 for the system:
1 z s ds 1 0.418s 0.1s
g(s) = kP e (35) g(s) = 0.457 e (36)
s(1 + P s) s(1 + 1.06s)
and combines the adverse effects associated with having a It is clear that for the set point change the two method-
right half plane zero at 1/ z , a pole at zero and a time delay ologies offer comparable performance ( = 7.4 for the
d. Recently, Luyben [15] proposed a successful and simple proposed and = 6.6 for Luybens method). However, as it
enough tuning techniques for PID controllers and IPDT&IV becomes clear from inspecting Fig. 4, the proposed method-
systems. ology offers massive improvement for the load response
0.5
y(t)
0 10 20 30 40 50 60 70 80 90 100
Time
0.5
u(t) 0
-0.5
-1
-1.5
0 10 20 30 40 50 60 70 80 90 100
Time
Fig. 3. Closed loop responsecase study 2 (proposed: continuous line, Luyben [14]: dotted line).
46 G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149
1.5 1.5
1
y(t) y(t) 1
0.5
0.5
0
0
-0.5 0 5 10 15 20 25 30 35 40 45 50
0 10 20 30 40 50 60 70 80 90 100
Time (min) Time (min)
0.5
1
0
-0.5 0.5
u(t) u(t)
-1
0
-1.5
-2 -0.5
0 10 20 30 40 50 60 70 80 90 100 0 5 10 15 20 25 30 35 40 45 50
Time (min) Time (min)
Fig. 4. Load response of the closed loop IPDT&IV system (proposed: Fig. 5. Unit step set point response for IPDT&IV system (proposed:
continuous line, Luyben [15]: dotted line). continuous line, Luyben [15]: dotted line).
case. The value of the objective function for the Luybens namics. They have, among other case studies, considered
method ( = 28.2) is 3.5 times the value of the objective the following system:
function obtained using the proposed method ( = 8.1). e0.5s
g(s) = (37)
(5s 1)(2s + 1)(0.5s + 1)
3.4. Control of an unstable process
and have demonstrated clearly the superiority of their
Most chemical processes exhibit stable open-loop behav- method over most of the available tuning techniques. The
ior. However, there are some important processes, such as same process was considered here with the objective func-
chemical and biological reactors, that might be operated tion given by Eq. (31) ( = 0.1 and S = 0.01) and the
around an unstable steady state. The tuning of PID controller proposed method gave the following tunings:
for unstable systems has recently attracted attention [1619]. KP = 6.905, K = 1.707, KD = 11.824 (38)
Lee et al. [18] have presented a powerful IMC-based tun-
ing methodology that appears to surpass most of available which are very close to the result reported by Lee et al.
tuning techniques for unstable systems with low order dy- [18]. In Fig. 6, the closed loop response obtained using the
0.2
0.15
0.1
y(t)
0.05
-0.05
0 2 4 6 8 10 12 14 16 18 20
Time
0
-0.5
u(t) -1
-1.5
-2
0 2 4 6 8 10 12 14 16 18 20
Time
Fig. 6. Load response of the open-loop unstable system (proposed: continuous line, Lee et al. [18]: dotted line).
G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149 47
0.8
0.6
y(t)
0.4
0.2
0
0 10 20 30 40 50
Time
0
-0.2
-0.4
u(t)
-0.6
-0.8
-1
0 10 20 30 40 50
Time
Fig. 7. Load response of the FOPTD/PI system (proposed: continuous line, Tang et al. [20]: dotted line).
0.8
0.6
y(t)
0.4
0.2
0
0 5 10 15 20 25 30
Time
0
-0.2
-0.4
u(t)
-0.6
-0.8
-1
0 5 10 15 20 25 30
Time
Fig. 8. Load response of the FOPTD/PID system (proposed: continuous line, Tang et al. [20]: dotted line).
48 G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149
1
0.8
0.6
y(t)
0.4
q =2 q =3 q =4 q =5
0.2
0
0 5 10 15 20 25 30
Time
0
-0.2
-0.4
u(t)
-0.6
-0.8 q =2 q =3 q =4 q =5
-1
0 5 10 15 20 25 30
Time
to control while when approaches or exceeds 1 then the Tang et al. [20] have also investigated the same case
corresponding system becomes progressively more difficult study. The closed loop performance obtained using the two
to control. A process with = 4 and unit gain is selected methodologies is compared in Fig. 7. A clear improvement
in this case study. The optimization problem (using the ob- in the performance is observed from Fig. 7 when the pro-
jective function given by Eq. (31)) was solved for a PI con- posed technique is used. In Fig. 8 the same comparison is
trol structure and a unit step load disturbance introduced at shown for the case of PID control.
t = 0. The solution obtained is FOPTD with large time delay systems is an important
class of systems for the process industries. A number of
KP = 0.42, KI = 0.163 (41) techniques are indeed available for tuning PID controllers
0.5
y(t)
0
-0.5
0 10 20 30 40 50 60
Time
0
-0.5
u(t)
-1
-1.5
0 10 20 30 40 50 60
Time
Fig. 10. Load response of the FOPTD/PID system using the proposed (continuous line), CM (dash dotted line), and the IMC method (dotted line) for
= 10.
G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149 49
that feature some form of predictive capability. However, a achieved by using the best available tunings for a number
limited number of tuning techniques are available for sim- of simplified but yet challenging process models.
ple PID controllers. The proposed mathematical formulation
was solved for a number of process models with [2, 5]
for unit load disturbances and the following tuning rules References
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Chemical Engineering and Processing 44 (2005) 5158
Received 19 May 2003; received in revised form 29 March 2004; accepted 30 March 2004
Available online 15 June 2004
Abstract
The pervaporation separation of acetic acidwater mixtures was performed over a range of 1090 wt.% acetic acid in the feed at temperatures
ranging 2550 C using acrylonitrile (AN) grafted poly(vinyl alcohol) (PVA) membranes. The permeation and separation characteristics of
PVA-g-AN membranes were studied as a function of membrane thickness, feed composition, operating temperature and pressure. When the
downstream pressure increased permeation rate increased with decreasing separation factor and at high acetic acid concentrations PVA-g-AN
membranes shows grater tendency for the separation of acetic acidwater mixtures. Depending on the membrane thickness, feed composition
and temperature PVA-g-AN membranes gave separation factors 2.314 and permeation rates 0.181.17 kg/m2 h. It was also determined that
PVA-g-AN membranes were found to have lower permeation rate and grater separation factors than PVA membranes.
2004 Elsevier B.V. All rights reserved.
Keywords: Membranes; Selectivity; Separations; Transport processes; Pervaporation; Acetic acidwater mixtures; Poly(vinyl alcohol) membranes; Graft
copolymerization
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.007
52 N. Alghezawi et al. / Chemical Engineering and Processing 44 (2005) 5158
2. Experimental
2.1. Materials
effective membrane area (m2 ) and operating time (h) respec- Table 2
Effect of membrane thickness on permeation rate and separation factor
tively.
Separation factor was calculated using: Thickness (m) Q (kg/m2 h)
Table 3
Comparison of PVA and PVA-g-AN membranes
T ( C) Q (kg/m2 h)
0.
8.0
permeation rate of grafted membranes at different grafting
0.2
ratio with respect to the feed composition was given. As it
6.0
seen from the graph although permeation rate decreases with
4.0 the amount of AN separation factors were almost the same.
0.1
2.0
3.4. Effect of temperature on pervaporation
0 0.0
0 10 30 50 70 90 100
The effect of temperature on the separation performance
CH3 COOH (wt %) of PVA-g-AN (PVA-2) membranes was studied in the tem-
perature range of 2550 C and the results were given in
Fig. 4. Effect of PVA:AN ratio on the permeation rate and separation
factor (T = 30 C): () (PVA-2); () Q (PVA-2); () (PVA-1);
Table 4. As it is reflected from the table, as the tempera-
() Q (PVA-1). ture increases permeation rate increases, however, separa-
tion factor stays constant above 30 C.
Table 4 Aminabhavi and Naik [37] obtained similar results in the
Effect of temperature on permeation rate and separation factor
pervaporation of acetic acidwater mixtures by using PVA
T ( C) Q (kg/m2 h) membranes. They reported that for 20 wt.% acetic acid so-
25 0.18 2.60 lutions separation factor stayed constant at 35 and 45 C al-
30 0.66 3.00 though permeation rate increased with temperature.
40 1.07 3.00 The permeation at various operating temperatures is
50 1.17 3.00
thought to be governed by three factors [7,23].
20 wt.% CH3 COOH; P = 23 Pa, t = 1.5 h.
1. Change in the free volume of the polymer membrane
swollen by pure components, which affects mainly per-
3.3. Effect of AN grafting on the performance of the PVA meation rates.
membranes 2. Change in the free volume due to the plasticizing effect.
3. Change in the interaction between permeants in the mem-
In order to understand the effect of grafting on the perfor- brane.
mance of PVA membranes, PVA-g-AN (PVA-2) membranes
were compared with the heat treated PVA membranes that According to the free volume theory as the temperature
were prepared by casting method from 7% (w/v) PVA solu- increase the frequency and amplitude of chain jumping (i.e.
tion (Table 3). thermal agitation) increase and the resulting free volumes
As it is reflected from the table that the presence of AN de- become larger. Increase in temperature also decreases the
creases the permeation rate while increasing the separation interaction between acetic acid and water molecules so it
factor. Increase in the separation factor is caused from the will be easy for both acetic acid and water molecules to
0. 5 16 .0
14 .0
0. 4
12 .0
0. 3 10 .0
Q (kg/m 2 h)
8. 0
0. 2 6. 0
4. 0
0. 1
2. 0
0. 0 0. 0
0 10 30 50 70 90 100
CH 3 COOH (wt %)
Fig. 5. Change of total permeation rate and separation factor with feed composition: () Q (30 C); () Q (40 C); () (30 C); () (40 C).
N. Alghezawi et al. / Chemical Engineering and Processing 44 (2005) 5158 55
0.4 5.0
4.0
0.3
2
Q(CH3COOH) (kg/m h)x10
Q (H2O) (kg/m h)
3.0
2
2
0.2
2.0
0.1
1.0
0 0.0
10 30 50 70 90
CH3COOH (wt %)
Fig. 6. Effect of feed composition on permeation rate of water and acetic acid: () Q (H2 O) (30 C); () Q (H2 O) (40 C); () Q (CH3 COOH) (30 C);
() Q (CH3 COOH) (40 C).
diffuse through the free volumes resulted by the increase crease steadily with the increase in acetic acid content of
in temperature. This situation leads to constant separation feed.
factors. Similar results were obtained in the pervaporation separa-
tion of acetic acidwater mixtures using blended polyacrylic
3.5. Effect of feed composition acidnylon 6 membranes [22], poly(4-vinylpyridine-co-
acrylonitrile) membranes [11] and in the permeation and
At 30 and 40 C the effect of feed concentration, in the separation of aqueous alcohol solutions through PVA-AN-
concentration range of 1090 wt.% of acetic acid solutions, HEMA latex membranes [5].
on the permeation rate and the separation factor was inves- However, in the studies of Huang and Yeom [23,24] using
tigated and the results were given in Fig. 5. From the figure chemically crosslinked PVA membranes, maximum perme-
it is clear that when acetic acid concentration in the feed so- ation rates were reported at low acetic acid concentrations
lution increases the permeation rate decreases, whereas the (10 wt.%).
separation factor increases. It can also be seen that the sep- Looking at the permeation rate of individual components
aration factors obtained at low temperatures are higher than (Fig. 6), the permeation rate of water component decreases
those obtained at high operating temperatures and they in- with the decrease in the water content of the feed solution
1.0
0.8
0.6
PSI
0.4
0.2
0.0
0 10 20 30 40 50 60 70 80 90
CH3COOH (wt%)
Table 5
Comparison of the performance of the membranes based on pva for the pervaporation separation of acetic acidwater mixtures
Polymer Temperature ( C) Mass % of acetic Permeation rate Separation factor () Ref. no.
acid in the feed (kg/m2 h)
PVA-g-PAAm 35 80 0.056 3.90 [45]
PVA/PAA (Blend membranes) 25 90 0.300 6.60 [46]
PVA/PHC 25 90 0.140 7.90 [46]
PVA/PVP 25 90 0.800 2.40 [46]
PVA 35 80 0.056 6.71 [37]
PVA 45 80 0.124 6.39 [37]
PVA-g-AAm (48%) 35 80 0.086 5.38 [37]
PVA-g-AAm (93%) 35 80 0.094 3.81 [37]
PVA-g-AN (52%) (PVA-2) 30 90 0.090 14.60 This study
PAAm, poly(acryl amide); PAA, poly(acrylic acid); PHC, poly(hydroxycarboxylic acid); PVP, poly(N-vinyl-2-pyrolidone); PVA, poly(vinyl alcohol); Aam,
acryl amide; AN, acrylonitrile.
and the permeation rate of water is higher than that of acetic the figure that PSI values of the membranes increases with
acid regardless of feed composition. These phenomena can the acetic acid concentration which shows that the perfor-
be explained in terms of plasticizing effect of water. As the mance of PVA-g-AN (PVA-2) membranes are good at high
water concentration in the feed is increased, the amorphous acetic acid concentrations
regions of the membrane becomes more swollen; hence the For comparison purposes several results regarding
flexibility of polymer chains increases the energy required the separation of acetic acidwater mixtures obtained
for diffusive transport through the membrane decreases. This by various authors with different type of membranes
could be the reason why low separation factors were ob- listed in Table 5. One can see that PVA-g-AN mem-
tained at low acetic acid concentrations. branes have high selectivity although they have almost the
Additionally in pervaporation separation follows the same permeation rate depending on the feed composition
solution-diffusion mechanism. Therefore the molecular size and temperature than the membranes studied up in the
of the permeating molecules becomes very important to table.
characterize the permeation behavior [43]. It is known that
acetic acid has larger molecular size (0.40 nm) than water 3.6. Effect of pressure on pervaporation
molecules (0.28 nm). As the amount of acetic acid increases
in the feed mixture it becomes difficult for acetic acid Effect of the down stream pressure on the permeation rate
molecules to diffuse through the less swollen membrane, so and the separation factor was shown in Fig. 8 for 20 wt.%
separation factor increases at high acid concentrations. acetic acid solution at 30 C. Permeation rate increases with
Pervaporation separation index values were calculated us- the pressure which complies well with theoretical prediction.
ing Eq. (3) and presented in Fig. 7. As it is reflected from However separation factor decreases as the down stream
0.6 4.0
3.0
0.4
Q (kg/m h)
2
2.0
0.2
1.0
0.0 0.0
2 4 6 8
-3
P (Pa x 10 )
Fig. 8. Effect of down stream pressure on the total permeation rate and separation factor (20 wt.% CH3 COOH; T = 30 C): () Q () .
N. Alghezawi et al. / Chemical Engineering and Processing 44 (2005) 5158 57
pressure increases. Similar results were also reported in the [10] H. Ohya, K. Matsumoto, Y. Negishi, T. Hino, H.S. Choi, The sepa-
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Acknowledgements
[17] H.C. Park, R.M. Meertens, M.H.V. Mulder, C.A. Smolders, Perva-
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Three of grateful to Gazi University Research Fund for branes of poly(acrylic acid) and poly(vinyl alcohol), J. Membr. Sci.
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Chemical Engineering and Processing 44 (2004) 5969
Received 21 July 2003; received in revised form 9 March 2004; accepted 25 March 2004
Available online 26 June 2004
Abstract
A newly developed -ray computed tomography scanner was implemented to study liquid flow distribution in a 30.48-cm-diameter column
packed with corrugated structure using countercurrent airwater flow. Validation experiments confirm that spatial resolution of 2.5 mm can
be achieved by the new CT unit.
Within the gas (010 cm/s superficial velocity) and liquid (0.62.5 cm/s superficial velocity) flow ranges investigated, a good liquid distri-
bution was observed at all conditions, as manifested by uniformity factor in excess of 70%. The liquid saturation increases with increasing
superficial liquid velocity as well as down the column height. Within the conditions studied, the effect of gas velocity was, in general, found
to be minimal.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.010
60 S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969
reactor (downflow of gas and liquid over randomly packed resolution of about 510% of the column diameter in the
particles). The apparatus was very similar to that being used measurement plane was claimed [912]. Mewes et al. [9]
in the Chemical Reaction Engineering Laboratory (CREL) used water which was introduced through a large number of
at Washington University in St Louis, albeit, with a higher injection nozzles into a 120 mm diameter reactor containing
number of detectors (32 of 1.27-cm-diameter BGO detectors monolith. With increasing liquid velocity, the liquid distri-
as against 9 of 5-cm-diameter Nal detectors) and increased bution improved. The authors did not demonstrate the effect
radioactive source strength (300 mCi as against 85 mCi). of gas velocity on the liquid distribution.
A comprehensive study was performed to quantify the error Toya et al. [13] used X-ray tomography to scan gas/liquid
associated with the measurements and the authors were able flow in a corrugated structured packing known as Sulzer
to detect solids holdup within 3% accuracy. The authors Mellapak 250 Y. The solids profile of the dry structured
also proposed a correlation to predict liquid holdup based packing was reproduced with fair accuracy. The scan was
on a force balance on liquid film and showed that tomog- performed in a 60-cm-diameter column. Very thin liquid film
raphy can reproduce the liquid holdup as predicted by the flowing past the structure at 0.006 m/s was also detected by
model for liquid flow rates up to 1.7 cm/s (no gas flowing). the tomography unit.
Yin et al. [15] investigated liquid distribution in a col- Iluita and Larachi [4] developed a hydraulic mechanistic
umn of 60 cm in diameter containing pall rings. The authors model for prediction of the irrigated pressure drop, liquid
found that the distributor type had a significant effect on the holdup and the effective interfacial area in the preloading
distribution, which was verified using computational fluid zone of structured packing operated in countercurrent flow
dynamics (CFD). of gas and liquid under partial wetting condition. The model
Examples of the use of tomographic techniques to deter- mimics the two phase flow situation by a network of double
mine gas/liquid distribution in structured packing is limited slits consisting of dry and wet slits. The model was success-
in the open literature. Mewes et al. [9] studied flow distribu- ful in predicting the irrigated pressure drop, liquid holdup
tion in monoliths using capacitance tomography. A spatial and effective interfacial area under various conditions.
Fig. 1. Schematic diagram of the experimental setup: (a) Process diagram (all dimensions in centimeter); (b) packing element; (c) liquid distributor. DP,
differential pressure transmitter; FI, flow indicator; TI, temperature indicator.
S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969 61
2. Experimental work
by 0.2 , thus producing large number of projections per some errors. In the new setup, the angular distance between
detector. two consecutive detectors is 0.2 , which is the same as
The new scanner introduced the following modifications the angle between two consecutive projections. Therefore,
(Fig. 3). there is no need to interpolate between the detector spaces
(Fig. 3b).
2.2.1. Collimator and detectors rotate simultaneously
In the old CT unit, the detectors are stationary in a partic- 2.2.3. Collimator slit width and radioactive source strength
ular view and the collimators move by a desired angle to ob- In order to achieve the best possible resolution, the thick-
tain projections for various chords. The intensity of radiation ness of the ray being attenuated should have infinitely small
as detected by the detectors is not uniform; it is maximum width. However, this is practically impossible since in that
when the collimator passes the center of the detector and case, we need to have an infinitely small slit width of the
minimum at the two edges. To overcome this non-uniformity detector collimator also. If the slit width is too small, the
in the new setup, the collimator position has been fixed at counts registered by the detectors will be very small, which
the center of the detector and the whole detectorcollimator in turn will affect the resolution. Generally, the maximum
rack is rotated (Fig. 3a). resolution that can be attained is equivalent to the slit width.
In the new setup, a collimator with a slit width of 2 mm is
2.2.2. Eliminating the need to interpolate between detectors used instead of 5 mm, which was the case in old CT unit.
In the old CT unit, the angular distance between two de- This is expected to result in a higher resolution of the order
tectors is 0.5 whereas a typical angle between two pro- of 2 mm (Fig. 3c).
jections is approximately 0.2 . Therefore, the source in- Moreover, the new CT along with all the associated elec-
tensity in the space between the detectors has to be in- tronics is mounted on wheels. Being completely made of
terpolated. Hence, two artificial projections are incorpo- aluminum instead of stainless steel, the whole assembly is
rated into the reconstruction process, which may lead to lightweight and can be moved around in different locations
Fig. 3. (a) New CT: the whole assembly moves; old CT: only the collimator rack moves; (b) new CT: no interpolation needed; old CT: interpolation
needed between detectors; (c) new CT: 2 mm collimator slit thickness; old CT: 5 mm collimator slit thickness.
S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969 63
Fig. 4. CT validation scan using: (a) jar filled with water; (b) cross-sectional attenuation profile of the liquid in the jar; (c) azimuthally averaged attenuation
in the radial direction (- actual attenuation, average attenuation).
for conducting holdup measurements at various experimen- by determining the solids fraction of the packing using com-
tal setups. puted tomography, which was compared to the one measured
The beam attenuation is measured along a number of by water displacement method.
beam paths through the column, which originate from dif- For the first case of a jar filled with water, the results are
ferent angles. Once a set of attenuation measurements is as follows.
completed, the density distribution image is reconstructed The collimator used in the present CT has an aperture of
by using the EstimationMaximization algorithm [5]. This 2 mm and therefore, theoretically, spatial resolution should
reconstruction algorithm is used, since it has the following be around 2 mm. In this test case, a 70 mm domain con-
advantages: (1) it accounts for statistical variations associ- taining 5.1 cm outer diameter glass jar filled with water was
ated with radiation measurements; (2) it readily incorporates reproduced (as shown in Fig. 4b). The diameter of the ob-
non-uniform beam effects; and (3) it ensures that the final ject obtained from CT was 5.3 cm, which indicates that we
reconstruction will contain positive values. To obtain statis- have a spatial resolution of 2 mm in this case. The attenua-
tically significant results, and to reduce the effect of position, tion in the water region should be uniform. In this case, the
the CT scans were obtained by scanning 360 around the scan gives a slightly non-uniform attenuation as shown in
column using a total scanning time of about five hours and Fig. 4c. The calculated error in the attenuation coefficient
collecting numerous beam path attenuations (approximately was found to be within 6.5%.
2500 projections). The final holdup distribution images are For the second case, a hollow ball was dipped inside a
obtained from the attenuation data using the relationships jar filled with water and scanned. The diameters of the ball
and the procedure developed by Chen et al. (2000) [6] for and jar were 6.98 and 18.95 cm, respectively, as shown in
packed bed. Fig. 5a. A scan area of 27 cm in diameter was reproduced
using the reconstruction algorithm. The dimensions of the
2.3. CT scan evaluation objects as reproduced by the scan were 6.97 and 19.20 cm,
respectively, as shown in Fig. 5b, which give a maximum
Since this was a new CT scanner developed to be used spatial error of about 2.5 mm. This is good enough to re-
for the first time, it was imperative to evaluate the perfor- solve relatively small maldistribution, if it exists, inside the
mance of the unit in terms of spatial and density resolution. 30.48-cm-diameter column used in this study. The figure
Two CT scans were performed to evaluate the system. In the shows that the overall error in the estimated total holdup is
first case, a 5.08 cm jar was filled with water and scanned within 12.8%.
(Fig. 4). In the second case, a hollow ball dipped in water It must be noted that the resolution changes with the size
was scanned and gas holdup was evaluated (Fig. 5). Further, of the object being scanned due to different attenuation of
a third validation, which will be discussed in the following the gamma rays. However, the obtained resolutions should
section of the Results and discussion, was also performed be adequate for a column of 30.5-cm-diameter.
64 S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969
Fig. 5. CT validation using: (a) hollow ball in water Jar; (b) density distribution of the object; (c) gas holdup profile of the system.
3. Results and discussion This overall average value is close to the values obtained
by CT scanning. Considering the error associated with the
3.1. Solids fraction of the packing measurement of small amount of the displaced water, this
indicates that CT provides adequate measurements of the
Solids fraction of the packing was first evaluated using CT solids distribution in the bed despite its small values.
at the same axial levels used for the actual flow scans, i.e.,
at 1.5, 2.5 and 3.5D, from the top packing surface, where 3.2. Liquid distribution in the bed of corrugated structured
D denote the diameter of the packing (30.48 cm). Fig. 6a packing
shows the solids distribution at those three axial positions.
The azimuthally averaged solids fraction is shown in Fig. 6b Fig. 7ac shows the time-averaged cross-sectional liquid
and is approximately equal to 2.5%. The solid fraction was saturation distribution in the column at superficial gas ve-
also measured experimentally by immersing the packing el- locities of 0, 5 and 10 cm/s, respectively. For each gas veloc-
ement in water-filled bath and measuring the volume of wa- ity, the liquid saturation distribution is shown at three axial
ter displaced, which was found to be approximately 3%. positions and three liquid velocities. Also provided are the
S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969 65
Fig. 6. Determination of solid distribution at three axial positions: (a) cross-sectional distribution; (b) azimuthally averaged solids holdup and (c) overall
solids holdup. The horizontal line indicates experimentally determined solids fraction.
time and cross-sectionally averaged liquid saturation values, liquid distributor design, which produces seven liquid jets
L , as well as the uniformity factor expressed as percentage at the top of the bed. These jets disperse while moving
f (discussed later). Liquid saturation is the ratio of liquid downward. At high liquid superficial velocity (2.17 cm/s),
volume to the bed void volume. It can be seen that, for the the uniformity factors are smaller than those obtained at
flow conditions used, as superficial liquid velocity increases, lower liquid superficial velocities, since, at this high liquid
the cross-sectional averaged liquid saturation increases. For velocity, the jets require longer bed length to disperse and
all the superficial gas and liquid velocities used, the liquid distribute.
saturation varies between 6 to 15%. Fig. 8 shows the time and azimuthally averaged radial
Fig. 7ac also illustrates the liquid saturation distribution liquid saturation profiles at varying superficial gas and liq-
along the length of the column. In general, it is observed uid velocities at the middle axial position (2.5D). The figure
that as the liquid moves downward, liquid saturation in- shows that liquid saturation is nearly flat, which suggests
creases. At all conditions studied, the uniformity factor a fair uniformity of liquid distribution. Moreover, with in-
shows that the liquid distribution improves at the bottom creasing liquid velocities, liquid saturation increases. Simi-
section of the bed (i.e. 3.5D). This could be due to the lar trends were obtained at all scan heights.
66 S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969
Fig. 7. Time averaged cross-sectional liquid saturation distribution in structured bed at (a) Ug: 0 cm/s; (b) Ug: 5 cm/s; (c) Ug: 10 cm/s. In the table, L
shows the liquid saturation and f % show uniformity factor percentage.
S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969 67
Fig. 7. (Continued ).
Fig. 8. Effect of superficial gas and liquid velocities on the liquid saturation Fig. 9. Effects of gas and liquid superficial velocities on the cross-
radial profile at axial position of 2.5D. sectionally averaged liquid saturation.
68 S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969
100 cm), and higher superficial gas velocity was used. Il- tributed domain would give a uniformity factor very close
liuta and Larachi [4] mentioned that gas flow rate had a to 0%.
marginal effect on liquid holdup, a fact reflected in this work The domain consisted of 60 by 60 pixels (3600) out of
as well. which 2936 pixels represent the actual cross-section of the
Experiments were also performed to compare the holdup column, and these are the pixels which represent the liquid
and flow distribution in a bed, randomly packed with 3 mm saturation distribution. Fig. 7ac show the uniformity factor
spherical alumina particle, under the same flow conditions in percentage (f %) for different liquid and gas superficial
as was done for structured packing. However, it was evident velocities for the scans performed in this work. In most of the
that the successful operating conditions for structured pack- cases, the uniformity factor is large (above 70%), suggesting
ing were too severe for random packed bed, due to very high a fairly uniform distribution of liquid achieved in the studied
pressure drop. For very low liquid velocity (1 mm/s) and setup.
no gas flow, when the experiment was possible, the liquid
distribution was poor as indicated by a low uniformity factor 3.4. Pressure drop in corrugated structured packing
(40%). However, this information is insufficient to com-
pare the distribution characteristics of structured and random The pressure drop across the length of the packing was
packings. extremely small and was beyond the detectable limit of the
available pressure gauges. The full scale of the available
3.3. Uniformity factor (f ) transducer (validyne differential transducer) was 200 units,
which correspond to a pressure drop of 1 cm of water. In
The uniformity of the liquid flow distribution across the our study, it was observed that the maximum pressure drop
column cross-section was quantified in this work. This is within the gas and liquid flow rates studied was about 1 mm
presented in Fig. 7ac in a tabular form along with time and of water (20 calibration units). A trend was seen wherein
cross-sectionally averaged liquid saturation values. Various the pressure drop increases with increasing gas and liquid
methods have been used in the literature to quantify the flow velocities.
uniformity across a column cross-section. Mercandelli et al.
[8] used a maldistribution factor, which was a variation of
the standard deviation among nine sectors that the flow do- 4. Final remarks
main was divided into. The factor varied between 0 and 1.
This method is suitable for flow domains, which are divided It was established that the newly developed CT unit has
into small number of sectors. For cases where large num- a spatial resolution of about 2 2.5 mm. This is quite ac-
ber of sectors are used (e.g. holdup obtained by tomography ceptable given the size of the column used in this study. The
where large number of pixels are used), the maldistribution solid fraction as determined by CT scan was about 2.5%,
values invariably give small values, thus making it impos- which was close to the value of 3% as determined by water
sible to ascertain the quality of distribution. Jiang proposed displacement method.
the relative standard deviation to quantify the uniformity of The liquid saturation increases with increasing superficial
flow [1]. However, since standard deviation can take values liquid velocity. Moreover, the liquid saturation increases as
up to infinity, this quantity will also not provide a proper the liquid phase moves downward. The liquid distribution
feel for the uniformity. was found to be fairly uniform in general as expressed by the
In the present work, the degree of uniformity is cal- uniformity factor which was relatively large, between 70 to
culated based on the t-test method. The circular domain 95%. Liquid distribution was better at the bottom of the bed,
representing the reactor is divided into several sub-domains, compared to the upper section. The effect of gas velocity,
each having a fixed number of pixels. In this work, 10 pix- was in general, found to be very small at the conditions used
els were arbitrarily taken. This constitutes several groups in this study.
of data points for liquid saturation; t-test was then carried
out between the group representing the overall averaged
cross-sectional distribution of liquid saturation and the av- Acknowledgements
erage of one sub-domain group. If the group passes the
t-test, this indicates that the null hypothesis is satisfied and The financial support provided by ABB Lummus Global,
the two groups are statistically the same. Then 1 is assigned Inc. is acknowledged which made this work possible.
to that pair. If the two groups are statistically not simi-
lar, then 0 is assigned. Uniformity factor is then defined
as the percentage number of groups that are statistically References
similar (i.e. passes the t-test) to the group representing the
whole cross-sectional distribution of liquid saturation and [1] Y. Jiang, Flow distribution and its impact on performance of
its average. In this method, a uniform distribution yields packed-bed reactors, Ph.D thesis, Washington University in St Louis,
a uniformity factor of 100%, and a completely maldis- Missouri, 2000.
S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969 69
[2] R. Krishna, Reactive Separation: a New Paradigm in an Old Bottle, [8] C. Marcandelli, A.S. Lamine, J.R. Bernard, G. Wild, Liquid distri-
Report from Chemical Engineering department, University of Ams- bution in trickle-bed reactor, Oil Gas Sci. Technol.-Rev IFP 55 (4)
terdam, 1999. (2000) 407415.
[3] G.G. Podrebarac, F.T.T. Ng, G.L. Rempel, The production of diace- [9] D. Mewes, T. Loser, M. Millies, Modeling of two-phase flow in
ton alcohol with catalytic distillation:part II. A rate-based catalytic packings and monoliths, Chem. Eng. Sci. 54 (21) (1999) 47294747.
distillation model for the reaction zone, Chem. Eng. Sci. 53 (3) [10] N. Reinecke, D. Mewes, Flow regimes of two phase flow in mono-
(1998) 1077. lith catalyst, in: Proceedings of 5th World Congress on Chemical
[4] I. Iliuta, F. Larachi, Mechanistic model for structured-packing con- Engineering, San Diego, CA, 1996.
taining columns: Irrigated pressure drop, liquid holdup and pack- [11] N. Reinecke, G. Petritsch, D. Schmitz, D. Mewes, Tomographic
ing fractional wetted area, Ind. Eng. Chem. Res. 40 (2000) 5140 measurement techniquesvisualization of multiphase flows, Chem.
5146. Eng. Technol 21 (1998) 718.
[5] S.B. Kumar, M.P. Dudukovic, Jamal Chaouki, Faical Larachi, Milorad [12] N. Reinecke, D. Mewes, Oscillatory transient two-phase flows in
P. Dudukovic, Computer assisted gamma and X-ray tomography: single channels with reference to monolithic catalyst supports, Int.
applications to multiphase flow systems, in: Non-Invasive Monit. J. Multiphase Flow 25 (67) (1999) 13731393.
Multiphase Flows, Elsevier, 1997, pp. 47103. [13] D. Toye, P. Marchot, M. Crine, M. Pelsser, G. LHomme, Local
[6] J. Chen, R. Novica, M.H. Al-Dahhan, M.P. Dudukovic, Study of measurements of void fraction and liquid holdup in packed columns
particle motion in packed/ebullated beds by computed tomography using X-ray computed tomography, Chem. Eng. Process. 37 (6)
(CT) and computer automated radioactive particle tracking (CARPT), (1998) 511520.
AIChE J. 47 (5) (2000) 9941004. [14] L. Spiegel, W. Meier, Distillation columns with structured packings
[7] C. Boyer, B. Fanget, Measurement of liquid flow distribu- in the next decade, Chem. Eng. Res. Des. 81 (A1) (2003) 3947.
tion in trickle bed reactor of large diameter with a new [15] F. Yin, A. Afacan, K. Nandakumar, K.T. Chuang, Liquid holdup
gamma-ray tomographic system, Chem. Eng. Sci. 57 (2002) 1079 distribution in packed columns: gamma ray tomography and CFD
1089. simulation, Chem. Eng. Process. 41 (5) (2002) 473483.
Chemical Engineering and Processing 44 (2005) 7179
Received 18 February 2004; received in revised form 7 May 2004; accepted 7 May 2004
Available online 1 July 2004
Abstract
Adsorbed natural gas (ANG) is an interesting opportunity for developing natural gas vehicles technology. In this case, adsorbents such as
activated carbons are used to store natural gas at moderate pressure, 3.5 MPa, compared to the high-pressure (20 MPa) required for current
compressed natural gas technology. Many studies are devoted to the elaboration of suitable adsorbent materials to optimise the methane storage
capacity. Nevertheless, since natural gas (NG) is composed of about 95% of methane mixed with other components, an important deterioration
of the storage performance is observed after successive cycles of an ANG system (filling and delivery). It is the result of adsorption of the
other components present in NG that are mainly higher molecular-weight hydrocarbons, carbon dioxide and nitrogen. In the present study,
the evolution of the storage capacity of a 2 l vessel cycled with NG is experimentally measured. As a function of the cycle number, the gas
composition at the outlet of the ANG system is determined using gas chromatography analysis.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.005
72 O. Pupier et al. / Chemical Engineering and Processing 44 (2005) 7179
0.02
2. Experimental
0.00
0 1 2 3 4
2.1. Experimental device and procedure
Pressure (MPa)
Fig. 1 shows the experimental laboratory device. A cylin- Fig. 2. Adsorption isotherm of methane in the activated carbon at 298 K.
drical stainless steel vessel of about 2 l (diameter: 110.3 mm;
length: 215 mm) equipped with a central gas diffuser was a constant volumetric flow rate equal to 25 sl min1 was in-
filled with the adsorbent packing. Four thermocouples were troduced into the vessel. Charge was considered over when
distributed radially throughout the vessel with a spacing of the pressure in the vessel was equal to 3.5 MPa and when the
11 mm and one on the reactor wall to evaluate the thermal difference between the mean temperature of the adsorbent
gradient during charge and discharge phases. Heat exchange minus the heat transfer fluid temperature was lower than
through the vessel wall took place with water at 298 K inlet 0.5 K. During each discharge, an almost constant volumet-
temperature flowing in a double casing around the reservoir. ric flow rate of 1 sl min1 was delivered at the outlet of the
Two mass flow controllers (MFC) recorded and controlled vessel. Every 4 min, the gas composition was measured with
the gas flow at the inlet and the outlet of the vessel. A pres- a micro-gas chromatograph. Discharge was considered over
sure transducer recorded the pressure in the vessel. At the when the pressure in the vessel was lower than 0.15 MPa
outlet of the vessel a micro-gas chromatograph allowed the and when the difference between the mean temperature of
analysis of the composition of the delivered gas during dis- the adsorbent minus the heat transfer fluid temperature was
charge. For safety reasons, a safety valve (SV) (calibrated at lower than 0.5 K. As soon as these conditions were reached
4.0 MPa) was on the top of the storage vessel, and the appa- a charge procedure happened.
ratus was placed in a ventilated safety closed room equipped
with gas detectors. 2.2. Preparation and characterisation of the adsorbent
The experimental procedure is described as follows. Be-
fore the start of the first run, the storage vessel was degassed A commercial activated carbon, manufactured by NORIT
during several hours at a temperature higher than 423 K at a was selected for the cycling operation. It is available in a
pressure lower than 10 Pa. Before the cycling operation, the grain form with particle sizes in the range of few millimetres.
data acquisition system was activated. During each charge, Fig. 2 presents the adsorption isotherm of pure methane at
micro-GC
P
MFC MFC
SV
T
T Micro-Computer
NG
Water
VESSEL
60
Qdd (V/V)
2
298 K measured with a high-pressure volumetric device [19] 45
under pressure up to 5 MPa.
From this raw material, a consolidated adsorbent com- 30
1
posite block was prepared following a procedure previously
15
detailed [10] in the case of Maxsorb like activated car-
bon (produced and sold by the Kansai Coke and Chemical 0 0
Company Ltd). First, the activated carbon crushed in powder 0 10 20 30
form with particle sizes around 100 m was coated with a Time (hours)
thermoplastic binder according to Boses patent [20]. Then,
Fig. 3. Cycling operation with pure methane: pressure profiles (continuous
it was mixed with expanded natural graphite (ENG) and line and left hand scale), adsorbed volume of methane per volume of
the obtained mixture was compressed directly in the storage composite block (symbol () and right-hand scale).
vessel and then heated up to the melting point of the me-
chanical binder. Thereafter, the vessel was air-cooled under
applied stress. The mechanical binder solidification ensures into the composite at 3.5 MPa is retained. This corresponds
all mechanical cohesion of the composite. ENG, which is to the difference between the delivered and the stored quan-
an excellent thermal binder ensures high values of the heat tity of methane. As expected, during cycling operation, the
transfer conductivity of the composite and of the heat ex- delivered quantity of methane is constant and is not influ-
change coefficient between the composite block and the wall enced by the number of cycles. This is the result of the
of the vessel. As discussed in previous papers [10,12], this reversible adsorption/desorption phenomena of a pure gas
procedure of preparation of composite block leads to two on an activated carbon. The experimental delivered quantity
main advantages. The density of the activated carbon in the (Fig. 3), directly obtained by the integration of the instanta-
composite is increased. The thermal properties are improved neous flow rate of methane at the outlet of the vessel is in
avoiding too much severe thermal limitation during dynamic agreement with the calculated one.
charge and discharge.
The two binders, the ENG and the thermoplastic polymer, 3.2. Cycling operation with natural gas
are inert concerning the methane adsorption. The methane
quantity delivered depends only on the activated carbon ad- Gaz De France provided natural gas. It is composed of
sorption isotherm and its apparent density in the adsorbent 92.2% of methane. The other components analysed with
composite block (Table 1). For pure methane, the quantity the micro-gas chromatograph are: CO2 , N2 , C2 H6 , C3 H8 ,
delivered at 298 K between 3.5 and 0.1 MPa is equal to 89 i-C4 H10 , n-C4 H10 , i-C5 H12 , n-C5 H12 and C6+ (Table 2).
(v/v).
3.2.1. Comparison of three typical cycles
Fig. 4 shows experimental profiles of the mean tempera-
3. Results and discussion ture, the pressure and the flow rate during charges of the cy-
cles 5, 100 and 700. Whatever the cycle, during the charge
3.1. Cycling operation with pure methane performed at high flow rate, the exothermic adsorption of
the different components of natural gas entails an increase
A preliminary cycling test was performed with pure of the mean temperature of the vessel (Fig. 4a). The range
methane. It is illustrated in Fig. 3. According to the de- in variation of the mean temperatures is the consequence
scribed experimental procedure, in the first cycle, the vessel of the coupling between the power delivered by the gas ad-
is charged from vacuum to 3.5 MPa at 298 K. During the sorption and the heat transfer inside the composite block.
first discharge, when the pressure decreases from 3.5 to The decrease of this range during the charge as a function of
0.1 MPa, around 20% of the total amount of gas adsorbed the cycle number is a first indication of the evolution of the
Table 2
Natural gas composition (mol%)
CH4 N2 CO2 C2 H6 C3 H8 i-C4 H10 n-C4 H10 i-C5 H12 n-C5 H12 C6+
92.18 1.82 0.75 4.23 0.78 0.13 0.09 0.012 0.006 0.002
74 O. Pupier et al. / Chemical Engineering and Processing 44 (2005) 7179
305 charges were realised for the same regulated flow rates at the
inlet of the vessel (Fig. 4c). The evolution of the duration
necessary for complete charge as well as the pressure pro-
file (Fig. 4b) demonstrate the decrease of the cycled mass
300 of natural gas at the vessel scale.
Fig. 5 presents in the case of the selected cycles, the
evolution of the molar ratio for three different components.
It is defined as follows,
295
Mi outlet
0 2 4 6 8 10 12 14
ri = ,
(a) Charge time (min) Mi inlet
where Mi outlet and Mi inlet are, respectively, the outlet and
4
the inlet molar percentage of the component i. While the
inlet molar percentage is constant (Table 2), the outlet mo-
lar percentage of each species was measured during the dis-
3 charges with the micro-gas chromatograph. Every 4 min, an
analysis was performed. In order to be able to compare these
Pressure (MPa)
3.0 Table 3
Evolution of the mean ratio (rm) during all the study
2.5 rmC2 H6 rmi-C4 H10 rmi-C5 H12
1.5
1.5
1.0
0.5
0.0
3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
(c) Pressure during desorption (MPa)
Fig. 5. Evolution of the ratio C2 H6 (a), i-C4 H10 (b), i-C5 H12 (c) at the
cycle numbers 5 (), 100 () and 700 ().
1.2
1.0
1.0
0.9
0.8
0.8
rmCO2
0.6
0.7
Carbon dioxide ( CO2 )
0.4
0.6
0.2
0.5
0.0
0 10 20 30 40 50 0 10 20 30 40 50
(a) Cycle number (b) Cycle number
Fig. 7. Relation between the mean ratio of CO2 in the gas at the outlet of the vessel (a) and the rate of variation of the efficiency (b).
equal to 83 (v/v), close to the delivered quantity of pure tween the cycles 10 and 30, a second rate of variation char-
methane. acterised by a second straight line can be drawn (Fig. 8b). As
First it is interesting to note the continuous decrease of for CO2 , as soon as the quantity of C2 H6 stored in the vessel
the efficiency. After 700 cycles, the steady state conditions at the end of the discharge phase does not change any more,
are not yet completely reached and the efficiency goes down another regime begins. Saturation of the vessel with propane
very slowly. At the end of the cycling operation, less than a that ends at cycle number 150 defines the third rate of vari-
half of the initial delivered quantity of gas is still cycled by ation (Fig. 9). Then, the evolution of the global efficiency is
the storage vessel. This is the result of the adsorption of the closely linked to the successive saturations of the activated
gases other than methane present in the mixture at low per- carbon with the different gases. At the end of the cycling op-
centage. Secondly, the rate of decrease is not constant and eration, the slow decrease of the efficiency is the result of the
depends on the number of cycles already performed. The slow accumulation of n-butane and gases with higher molec-
straight lines in Fig. 6 show that several rates of variation ular weight (cf. Appendix A). If the cycling operation had
can be drawn. These regimes are linked to the storage in the been continued, the last part of the efficiency profile (Fig. 6)
vessel of the different species that compose natural gas. It is should probably be decomposed with the different gases still
confirmed by the evolution of the mean ratios of the gas as a stored.
function of the number of cycles. The first rate of variation The global efficiency of the ANG process is influenced
corresponds to the progressive saturation of the adsorbent by greatly by the natural gas composition. Nevertheless, the
the carbon dioxide. During this step CO2 , like all the gases molar percentage of methane at the outlet of the vessel dur-
with a molecular weight higher than methane is stored in the ing discharge changes little during the cycling operation
vessel. As demonstrated by the Fig. 7a, at the scale of the (Fig. 10). It is a little bit higher than 0.92, the gas supply
vessel a steady state is reached for CO2 at a cycle number composition, during the first 50 cycles. Since nitrogen is not
around 10. As soon as the mean ratio of CO2 is equal to one, adsorbed at the working levels of pressure and temperature
the rate of variation of the efficiency changes (Fig. 7b). The (cf. Appendix A), this is the consequence of the storage of
second step corresponds to the number of cycle necessary CO2 and C2 H6 , the gas having the highest molar percent-
to reach the steady state for ethane (Fig. 8a), which is after ages in the gas feed. When this process is finished, because
methane, the lightest hydrocarbon in the gas mixture. Be- of the very low percentage of the others components of
1.2
1.0
1.0
0.9
0.8
rmC2H6
0.8
0.6 CO2
Ethane ( C2H6 ) 0.7
0.4
0.6
0.2
0.5
0.0
0 10 20 30 40 50 0 10 20 30 40 50
(a) Cycle number (b) Cycle number
Fig. 8. Relation between the mean ratio of C2 H6 in the gas at the outlet of the vessel (a) and the rate of variation of the efficiency (b).
O. Pupier et al. / Chemical Engineering and Processing 44 (2005) 7179 77
1.2
1.0
1.0
0.9
0.8
rmC3H8
0.8
0.6
Propane (C3H8) 0.7
0.4
0.6
0.2
CO2
0.0
0.5 C2H6
0 50 100 150 200 0 50 100 150 200
(a) Cycle number (b) Cycle number
Fig. 9. Relation between the mean ratio of C3 H8 in the gas at the outlet of the vessel (a) and the rate of variation of the efficiency (b).
4. Conclusion
Acknowledgements
The obtained experimental results display the great im-
pact of the gas composition on the performance of an ANG This work has been done with the financial support of
storage system. After 700 cycles, corresponding approxi- Gaz De France and ADEME.
mately to 250,000 km for a vehicle with a fuel tank allowing
400 km of autonomy, the efficiency of the storage system
falls down by 50%. The number of cycles necessary to reach Appendix A. Experimental profiles of the mean ratios
a steady state working mode, as well as the accurate value of for nitrogen, i-butane, n-butane, i-pentane, n-pentane,
the final performance, probably depends on the composition and the hydrocarbons with molecular weight higher
of natural gas and the dynamic working mode selected for than n-pentane (C6+ )
the cycling operation. Moreover, the microporous structure
of the activated carbon should influence the result. Never- For safety reasons, the cycling operation is interrupted
theless, basically, the final performance is the result of the during the weekend. After an interruption, always happening
multi-component adsorption equilibriums at a temperature at the end of a discharge phase, several cycles are necessary
of 298 K for the two characteristic working pressures, 3.5 to join the continuous curve representative of the evolution of
and 0.1 MPa. Gas chromatography analysis of the stream the behaviour of the tank. This phenomenon tends to demon-
composition at the outlet of the vessel shows that, as ex- strate the importance of the kinetics of the multi-component
pected, the different components contained in the natural adsorption equilibrium in the case of a complex mixture
gas, slowly obstruct the adsorption sites for methane. With of gas.
78 O. Pupier et al. / Chemical Engineering and Processing 44 (2005) 7179
O. Pupier et al. / Chemical Engineering and Processing 44 (2005) 7179 79
Received 12 March 2004; received in revised form 4 May 2004; accepted 5 May 2004
Available online 19 June 2004
Abstract
Small bubbles and flow uniformity are important for gasliquid and gasliquidsolid multiphase reactors. A reactor internal was designed
and installed in an external-loop airlift reactor (EL-ALR) to enhance bubble breakup and flow redistribution and improve reactor performance.
Hydrodynamic parameters, including local gas holdup, bubble rise velocity, bubble Sauter diameter and liquid velocity were measured. A
radial maldistribution index was introduced to describe radial non-uniformity in the hydrodynamic parameters. The influence of the internal
on this index was studied. Experimental results show that The effect of the internal is to make the radial profiles of the gas holdup, bubble
rise velocity and liquid velocity radially uniform. The bubble Sauter diameter decreases and the bubble size distribution is narrower. With
increasing distance away from the internal, the radial profiles change back to be similar to those before contact with it. The internal improves
the flow behavior up to a distance of 1.4 m.
2004 Elsevier B.V. All rights reserved.
Keywords: Airlift reactor; Internal; Radial profile; Gas holdup; Bubble size; Bubble breakup
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.003
82 T. Zhang et al. / Chemical Engineering and Processing 44 (2005) 8187
Fig. 3. Radial profile of the gas holdup at different axial positions. Fig. 5. Cross-sectional gas holdup at different axial positions.
84 T. Zhang et al. / Chemical Engineering and Processing 44 (2005) 8187
Fig. 10. Bubble Sauter diameter radial profile at different axial positions.
Fig. 8. Average bubble rise velocity as a function of the axial position.
Fig. 9. Axial change in the radial maldistribution index of the bubble rise
velocities. Fig. 11. Bubble size distribution at different axial positions.
86 T. Zhang et al. / Chemical Engineering and Processing 44 (2005) 8187
Received 23 May 2003; received in revised form 28 July 2003; accepted 31 March 2004
Available online 2 July 2004
Abstract
A multi-criteria synthesis strategy for heat-exchanger networks (HENs) simultaneously considering minimum utility consumption, max-
imum source-stream temperature flexibility, and even minimum number of matches is proposed. The flexible HEN synthesis problem is
formulated as a multi-objective mixed-integer linear programming (MO-MILP). For handling the multiple conflict design targets, a two-phase
fuzzy multi-criteria decision-making method is presented to attain a best compromised solution. Two numerical examples with flexibility pref-
erences in source-stream temperatures are supplied, demonstrating that the proposed strategy can provide definite and feasible compensatory
solutions for multi-criteria HEN synthesis problems.
2004 Elsevier B.V. All rights reserved.
Keywords: Heat-exchanger network; Synthesis; Flexibility; Superstructure; MILP; Multi-criteria decision-making; Fuzzy optimization
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.017
90 C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100
of the polyhedral region of uncertainty [10]. Under the as- then applied in phase II to simultaneously promote satisfac-
sumption of convexity, only the source-stream temperatures tion levels of all objectives with guaranteed least satisfaction
of the HENs are considered to be the uncertain input pa- value.
rameters. With this formulation, the standard definition of Two numerical examples with flexibility preference in
the HEN synthesis problem with minimal total utility con- source-stream temperatures is presented here to demonstrate
sumption and even minimum number of units is extended that the proposed interactive two-phase fuzzy optimization
to include a flexibility specification for the potential HEN method can provide a feasible and better compensatory so-
structure and can be stated as: given hot/cold streams to be lution for multi-objective HEN synthesis.
cooled/heated from nominal supply temperatures to speci-
fied target temperatures and hot/cold utility specifications,
synthesize a HEN such that it has minimal utility consump- 2. Model formulation
tion (considering nominal case or average of all vertical
operating points), minimal number of matches if desired, Consider the standard HEN synthesis problem with NH
and maximal flexibility for feasible operation. hot and NC cold process streams along with hot and cold
For handling the multiple and conflict design objectives, utilities. Since it is suitable for formulating the simultaneous
a fuzzy decision-making method is adopted to attain the solution which involving the consideration of both utility
compromised solution among all conflict objectives [11]. consumption and operational flexibility, the HEN superstruc-
Therein each design objective is treated as a fuzzy goal, ture proposed by [3,4] is applied for modeling the structure.
and a specific membership function is used to characterize Therein, the isothermal mixing assumption in the simplified
the transition from the numerical objective value to the de- superstructure eliminates the need for nonlinear/nonconvex
gree of satisfaction for the fuzzy objective. The final deci- energy balance. The minimum number of superstructure
sion, therefore, is interpreted as a fuzzy aggregation of these stages, NT , corresponds to max{NH , NC }, as suggested by
multiple objectives and measured by the overall degree of [3]. Fig. 1 illustrates a 2-hot/2-cold/2-stage superstructure.
satisfaction. And the best compromised solution is finally The mathematical programming formulation for minimizing
reached by maximizing the overall degree of satisfaction for utility consumption with specified uncertain source-stream
the decision. In the course of finding the solution, two pop- temperature ranges can be summarized as follows: [3,4,10]:
ular operators, the minimum and the average, are applied as (0)
(0)
the fuzzy intersection operators, the effects of which are ex- minJ (0) = qcui + qhuj (1)
x
i HP j CP
amined as well. We also proposed an interactive two-phase
fuzzy decision-making method by combining these two op-
zijk , zcui , zhuj ; tik , tjk ; dtijk , dtcui , dthuj ;
erators to take advantages of the both [11,12]. The minimum x qijk , qcui , qhuj ; (2)
operator is used in phase I to maximize the degree of satis-
i HP, j CP, k ST
faction for the worst objective, and the average operator is
(T in T out )FCpi =
qijk + qcui
i
i
kST jCP
overall heat balances
(T out T in )FCp =
j
j j qijk + qhuj
kST iHP
(tik ti,k+1 )FCpi =
q
ijk
jCP
stage heat balances
(tjk tj,k+1 )FCpj =
qijk
iHP
in(0) in(0)
ti,1 = Tiin {Ti
, Ti + }
uncertain inlet temperatures
t
in(0) in(0)
j,NT +1 = Tj {Tj , Tj + }
in
t t
ik
i,k+1
t t
jk
j,k+1
feasibility of temperatures
T out t
i
i,NT +1
out
Tj tj,1
(t
i,NT +1 Ti )FCpi = qcui
out
= x utility loads (3)
(Tjout tj,1 )FCpj = qhuj
qijk zijk 0
qcui zcui 0
logical constraints
qhuj zhuj 0
dt t t + (1 z )
ijk ik jk ijk
dt ti,k+1 t j,k+1 + (1 z )
ij,k+1 ijk
approach temperatures
dtcu t
i,NT +1 TCU + (1 zcui )
out
i
dthu j T out t
j,1 + (1 zhu j )
HU
(0)
dt T
ijk min
dtcu
(0)
T nominal approach temp. bounds
i min
dthu(0) Tmin
j
z + +
ijk zcu i zhu j MEU max
maximum exchanger units
i HP,j CP,k ST
i HP j CP
zijk , zcui , zhuj
{0, 1}
tik , tjk , dtijk , dtcui , dthuj , qijk , qcui , qhuj ;
0
i HP, j CP, k ST
or (n) (n)
Here, ri and rj are the vertex identifiers which take val-
ues of NV = 2(NH +NC ) combinations of +1 and 1, see
min J (ave)
xV V Table 1 in [10]. Therein, Eq. (4) considers nominal utilities
1 (n)
(n) and Eq. (5) takes into account the average of all vertical op-
= qcui + qhuj (5)
NV + 1 erating points.
n{0}VT iHP jCP
For the benchmark example mentioned in [10], a
(n) (n) (n)
2-hot/2-cold streams problem along with heating steam and
zijk , zcui , zhuj ; dtijk , dtcui , dthuj ;
cooling water, the maximal allowable variation of various
xV = (n) (n) (n) (n) (n)
tik , tjk ; q ijk , qcui , qhuj ;
(6) possible minimum-utility HEN structures is examined by
i HP, j CP, k ST, n {0} VT
(n)
(Ti
in(n)
Tiout )FCpi = qijk + qcui
(n)
k ST jCP
(n)
(n)
in(n)
(Tjout Tj )FCpj = qijk + qhuj
k ST iHP
(n)
(n) (n)
(tik ti,k+1 )FCpi = qijk
jCP
(n)
(n) (n)
(tjk tj,k+1 )FCpj = qijk
iHP
(n) (n)
Ti
in(n)
= (Ti
in(0)
+ ri ) = ti,1
in(n) in(0) (n) (n)
Tj = (Tj + rj ) = tj,NT +1
(n) (n)
tik ti,k+1
(n) (n)
tjk tj,k+1
(n)
Tiout ti,NT +1
(n)
Tjout tj,1
(n)
(ti,NT +1 Tiout )FCpi = qcui
(n)
V = xV (7)
out(n) (n) (n)
(Tj tj,1 )FCpj = qhuj
(n)
qijk zijk 0
(n)
qcui zcui 0
(n)
qhuj zhuj 0
(n) (n) (n)
dtijk tik tjk + (1 zijk )
(n) (n) (n)
dtij,k+1 ti,k+1 tj,k+1 + (1 zijk )
(n) (n)
dtcui ti,NT +1 TCU out + (1 zcu )
i
(n) (n)
dthuj THU tj,1 + (1 zhuj )
out
(0)
dtijk Tmin
(0)
dtcui Tmin
(0)
dthuj Tmin
zijk + zcui + zhuj MEUmax
iHP,jCP,k ST iHP jCP
zijk , zcui , zhuj {0, 1}
(n) (n) (n) (n) (n) (n) (n) (n)
tik , tjk , dtijk , dtcui , dthuj , qijk , qcui , qhuj 0
i HP, j CP, k ST, n {0} VT
C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100 93
Table 1
Problem data of example 1
Process streams and utilities Heat-capacity flow rate FCp (kW/K) Input temperature T in (K) Output temperature T out (K)
single objective. The minimum operator concentrates on im- The new feasible space guarantees the least degree
proving the worst scenario. However, the minimum operator of satisfaction for each fuzzy objective.
may result in multiple solutions since contribution of those
objectives with membership values greater than the mini-
mum one would not be cared. We thus combine these two 4. Numerical example
fuzzy intersection operators to take advantages of both and
propose a two-phase optimization procedure [11,12]. The Two numerical examples adapted from [4,10] are supplied
minimum operator is first used in phase I to find the least to demonstrate the efficacy of proposed HEN synthesis strat-
degree of satisfaction for the worst objective, then the aver- egy. To solve this MO-MILP for the HEN model, GAMS
age operator is applied in phase II to promote satisfaction [16] and CPLEX are used as the modeling environment and
levels of all objectives with guaranteed least membership the MIP solver, respectively. The computing machine is a
value. The merit of this method is that we can not only ob- personal computer with an Intel Pentium IV 2.26 GHz CPU.
tain the unique optimal solution by using average operator
but also guarantee each objective to go after their own max- Example 1. The 2-hot/2-cold streams example studied by
imum on the basis of taking the least degree of satisfaction [10], with problem data presented in Table 1, is illustrated.
as the lower-bound constraint. So, now we can summarize With these parameters, the multi-objective MILP formula-
the procedure of the two-phase fuzzy satisfying approach tion has 408 linear equality constraints, 760 linear inequal-
for the multi-criteria optimization problem. ity constraints, 12 binary variables, and 545 positive con-
tinuous variables. Notably, the restriction of MEUmax = 6
Step 1. For a function to be minimized, determine its ideal
in Eq. (7) will be removed should the minimum number of
solution and anti-ideal solutions by directly mini-
matches be simultaneously taken into account as one of the
mizing and maximizing the objective function.
design objectives.
min Js = J 1s According to the model formulation and the problem data,
xV V
(ideal solution ofJs , totally acceptable we solve the multi-criteria MILP synthesis problem by us-
ing the fuzzy optimization procedure discussed in Section
value) (19) 3. The ideal and anti-ideal solutions, obtained by sequen-
max Js = Js0 tially minimizing and maximizing each objective function,
xV V
are shown in Table 3. Within these lower/upper limiting val-
(anti ideal solution ofJs ,
ues, several preference intervals are subjectively selected to
unacceptable value) (20) establish linear membership functions for the fuzzy objec-
Notably, direct maximization and minimization tives. In implementing the two-phase fuzzy optimization, we
should be taken for a maximizing objective to firstly use the minimum operator to maximize the degree of
obtain the ideal and anti-ideal solutions. satisfaction for the worst target, min . The average operator
Step 2. Based on the importance of different objective func- is then applied to optimize the aggregated objectives with
tions and the acceptable ranges for objective val- guaranteed level of satisfaction.
ues, subjectively select suitable lower/upper bounds, At first, only two conflict objectives are considered: the
J 1s Js1 Js0 Js0 for minimizing objective and minimal utility consumption and the maximal flexibility to
J 0s Js0 Js1 Js1 for maximizing objective. De- all source-stream temperatures. And then the third objective,
membership functions for multiple fuzzy ob-
fine the minimal number of matches, would be appended. Results
jectives as given in Eqs. (12) and (13). of two-phase fuzzy optimization with preference intervals of
Step 3. (Phase I). Use the minimum operator to find the [2550, 12750] or [2550, 8850] for utility, [0, 150], [40, 90]
maximal degree of satisfaction for the worst objec- or [40, 70] for flexibility, and [4, 7] for unit numbers, along
tive, min . with either or not considering restrictions on heat loads at
extreme operating points, are listed in Table 4. The resulting
max D = max
xV V xV V (21) HEN structures are also depicted in Fig. 2. Notably, the re-
min(J1 , . . . , JS ) = min duced range of flexibility, [40, 90], implies that the required
minimum tolerance for temperature deviation is at least 40 K
Step 4. (Phase II). Use the average operator to simultane-
and a tolerance of maximum temperature deviation for 90 K
ously promote satisfaction levels of all objectives
with new constraints of guaranteed minimal degree
Table 3
of satisfaction.
The ideal/anti-ideal solutions of various objectives of example 1
J1 + + JS
max D = max (22) Objective function Ideal solution J 1i Anti-ideal solution Ji0
+
xV V +
xV V S
(0)
J1 utility (kW) 2550 12750
where J2 flexibility (K) 150 0
+ J3 units 4 12
V = V {Js min , s S} (23)
96 C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100
Table 4
Results of HEN synthesis for example 1 using two-phase optimization when simultaneously considering minimal utility and maximal flexibility (cases
IIV), and additional objective of minimal units (cases V and VI) with different preference intervals, and with or without considering restriction on heat
loads at vertices ( = = 0.6)
Case Preference intervals Heat load Phase Minimum utility Maximum flexibility Minimum units
Table 7
Results of HEN synthesis for example 2 using two-phase optimization when simultaneously considering minimal utility, maximal flexibility and minimal
units with different preference intervals, and with or without considering restriction on heat loads ( = = 0.6)
Case Preference intervals Heat load Phase Minimum utility Maximum flexibility Minimum units
Hot Cold Total Satisfaction Flexibility Satisfaction Units Satisfaction
Observing the results shown in Table 4, we also discover in Table 5. The number of superstructure stages is set as
that the integrated two-phase method can bring the merits of NT = 5. With these parameters, the MO-MILP formulation
the minimum and average operators together. The minimum has 3510 linear equality constraints, 8026 linear inequality
operator maximize the degree of satisfaction for the worst constraints, 31 binary variables, and 5981 positive continu-
objective, and can result in a harmonious solution with ous variables. The ideal and anti-ideal solutions are shown
satisfaction levels for objective functions that are equal or in Table 6. Various preference intervals are sequentially se-
close to each other. The average operator, on the other hand, lected for defining the membership functions, as shown in
can sometimes promote satisfaction levels for other objec- Table 7.
tives with guaranteed minimum value, such as Cases II, V,
and VI. Owing to these advantages, the two-phase method We directly use the ideal/anti-ideal solutions as the pref-
can thus provide the best compromised HEN configuration. erence intervals in Case I. The acceptable utility range is
reduced from [3780,9860] to [3780,4930] in Case II. With
Example 2. This problem consists of five hot streams and such a smaller allowance interval, the resulting utility con-
one cold stream, (NH = 5, NC = 1), along with steam and sumption will be reduced slightly from 3793 to 3660 at the
cooling water as utilities [3]. The problem data are listed expense of unit numbers increased from 8 to 10. In Case III,
C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100 99
the maximum allowable unit number is changed from 31 to NC number of cold streams
12. The resulting HEN structure is slightly different to that NH number of hot streams
of Case I, but the required unit numbers, utilities, and flexi- NT number of superstructure stages
bility are the same as Case I. In Case IV, when the minimum NV number of vertices, = 2N
flexibility requirement is upgraded from 0 to 10, the same qijk heat exchanged between stream i and j in stage k
HEN structure of Case I results with the same levels of util- qcui heat exchanged between stream i and cold utility
ity, flexibility and unit numbers. Cases VVIII give similar qhuj heat exchanged between stream i and hot utility
results with additional heat-load restrictions ( = = 0.6) r directional identifier for vertices
on various vertical operating points. With such additional ST index set of superstructure stages
constraints, the HEN structures use similar levels of utilities S number of objectives
and unit numbers, but the flexibility levels are dramatically Tmin minimum approach temperature
reduced. The resulting HEN structures are depicted in Fig. 3. tik temperature of stream i at hot end of stage k
tjk temperature of stream j at hot end of stage k
T temperature
5. Conclusion VT index set of vertices
x, xV vector of variables
In this paper, we use the fuzzy multi-criteria optimization zijk binary variable for existence of unit for match i
approach to synthesize the heat-exchanger network where and j in stage k
some conflict design objectives such as the total utility zcui binary variable for existence of unit for match i
consumption, the flexibilities to source-stream temperature and cold utility in stage k
variations, and even the total number of heat exchange units zhui binary variable for existence of unit for match j
can be considered simultaneously. Such a flexible HEN and hot utility in stage k
synthesis problem can be formulated as a multi-objective
mixed-integer linear programming (MO-MILP). For han- Greek letters
dling the multiple conflict design objectives, a two-phase , parameters used for restriction of heat-load
fuzzy optimization method is proposed to attain the best deviations
compromised solution. The attractive features of the pro- flexibility index
posed MO-MILP model are that it not only considers the flexibility index (scalar)
trade-off among the utility consumption, the source-stream Js membership function for Js
temperature flexibility, and even the number of matches, Js a fuzzy goal
but also avoids the determination of structural boundaries, S index set of multiple objectives
as discussed in [10]. Two numerical examples with various D a fuzzy set
cases are studied, demonstrating that the proposed strat- D degree of satisfaction
egy can provide a feasible compensatory solution for the upper bound for temperature difference
multi-criteria HEN synthesis problem. upper bound for heat exchange
the feasible searching region
Acknowledgements Superscripts
in inlet
(n) identifier for vertices
This work is supported by the National Science Council
out outlet
(ROC) under Contract NSC91-ET-7-002-004-ET. Partial fi-
(0) identifier for nominal operating condition
nancial support of Ministry of Economic Affairs under grant
92-EC-17-A-09-S1-019 is also acknowledged.
Subscripts
CU cold utility
Appendix A. Nomenclature HU hot utility
i index for hot process streams
CP index set of cold process stream j index for cold process streams
dtijk temperature approach for match i and j in stage k k index for superstructure stages
dtcui temperature approach for match i and cold utility s index for objectives
dthuj temperature approach for match j and hot utility
FCp heat capacity flowrate References
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Chemical Engineering and Processing 44 (2005) 101114
Received 23 December 2002; received in revised form 25 August 2003; accepted 28 April 2004
Available online 2 July 2004
Abstract
Since batch reactors are generally applied to produce a wide variety of specialty products, there is a great deal of interest to enhance batch
operation to achieve high quality and purity product while minimizing the conversion of undesired by-product. The use of process optimization
in the control of batch reactors presents a useful tool for operating batch reactors efficiently and optimally. In this work, we develop an approach,
based on an on-line dynamic optimization strategy, to modify optimal temperature set point profile for batch reactors. Two different optimization
problems concerning batch operation: maximization of product concentration and minimization of batch time, are formulated and solved using
a sequential optimization approach. An Extended Kalman Filter (EKF) is incorporated into the proposed approach in order to update current
states from their delayed measurement and to estimate unmeasurable state variables. A nonlinear model-based controller: generic model
control algorithm (GMC) is applied to drive the temperature of the batch reactor to follow the desired profile. A batch reactor with complex
exothermic reaction scheme is used to demonstrate the effectiveness of the proposed approach. The simulation results indicate that with the
proposed strategy, large improvement in batch reactor performance, in term of the amount of a desired product and batch operation time, can
be achieved compared to the method where the optimal temperature set point is pre-determined.
This paper gathers and integrates efficient well-known methodologies such as EKF, GMC and on-line optimization together, resulting in
an applicable, reliable and robust control technique for batch reactors.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.010
102 A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114
provides challenging and interesting problems. This is mined and then the model is updated, the optimization is
mainly due to the inherent complexity of the batch reac- performed on-line to generate a new optimal input profile.
tors which can be characterized by (i) highly nonlinear With the modified optimal profile, a designed controller is
behavior resulting from the dependence of reaction rates on used to control the system to follow this profile until the
concentrations and temperature, (ii) time-varying system; new one is available.
the process variables (e.g. concentration, temperature) and Apart from specifying the optimal set point profile, a con-
parameters change with time, (iii) no steady state operating trol system used to implement such a profile is another im-
condition, (iv) imperfect model; complex kinetic reactions portant issue to be considered. This is because the deviation
occurring within batch reactors are rarely well understood from the desired profile may cause an off-spec product. How-
that leads to an inaccuracy in developing the system model, ever, since it is well known that the control of batch reactors
and (v) lack of measurement information; the product is difficult due to the inherently nonlinear behavior, the use
qualities or key properties to be controlled (e.g. molecular of a linear control technique may give a poor performance.
weight) cannot be measured until the end of batch run or For this reason, many advanced control techniques have been
even if they can be measured sometime (e.g. concentration), developed and applied to the control of batch reactor. These
there is a significant time delay. Only a few of physical include, for example, nonlinear feedforward-feedback con-
quantities such as temperature and pressure are available trol [7], generic model control [8], adaptive control [1], glob-
for direct on-line measurement. That makes direct con- ally linearizing control [9], dynamic matrix control [10],
trol of product properties difficult [2]. Although, in recent linear model predictive control [11], or inverse model con-
years there have been significant advances in developing trol [12]. Reviews on the progress in control techniques that
new sensors for measuring these product properties, they have been applied to the control of batch reactors as well as
have rarely been used in industrial processes due to high their importance and performance are given by [13]. Among
operating cost and expensive investment on the measure- these advanced control methods, a generic model control
ment devices. Thus, the usual practice is to control other (GMC) technique is one of the most studied control algo-
variables that can be measured rapidly in order to obtain rithm. This is because nonlinear process models can be in-
desired product properties instead. terpreted straightaway in the GMC control algorithm so that
In general, optimal batch reactor operation can be car- they do not need to be linearized. Furthermore, its implemen-
ried out by two-step approach; firstly, determining an opti- tation is relatively easy when compared to other model-based
mal set point profile of key operating process variables such control methods; consequently, the application of this con-
as temperature [3]and secondly, tracking the desired profile trol technique appears in many chemical processes.
by a control system [4]. The optimal profile can usually be In this work, an approach based on an on-line dynamic op-
determined off-line by solving an optimal control problem. timization strategy to modify optimal temperature set point
However, as mentioned above, because of the complexity profile is developed for improving batch operation perfor-
of chemical reaction schemes, modeling errors are always mance. To demonstrate the effectiveness of the developed
present and in addition, process disturbances can occur dur- approach, the batch reactor studied by [8], where two paral-
ing the process operation. Due to the existence of this error lel exothermic reactions occur, is chosen here as a case study.
and disturbance, the final product may significantly differ For solving the on-line optimization problem, it needs the
from the desired value, even though the pre-specified opti- knowledge of the current states of the system. Although most
mal profile is tracked perfectly [5]. To realize this fact, it physical quantities (e.g. temperature, flowrate) can be mea-
is necessary to recalculate the optimal profile as an on-line sured frequently and are available as on line measurement,
optimization strategy whenever new feedback information some other properties (e.g. concentration) are measured in-
is available. This strategy could compensate the modeling frequently with time delay. To overcome this difficulty, the
error leading to process operation improvement. Extended Kalman Filter (EKF) is incorporated into the pro-
In order to perform the on-line optimization strategy, the posed strategy in order to estimate the concentrations from
knowledge of current state variables and/or parameters in their delayed measurements. The resulting optimal control
the process models is required. Due to the fact that some of problem is solved by the sequential solution and optimiza-
these variables cannot be known exactly or sometime can tion method which is often referred to as the control vector
be measured with time delay, it is essential to include an parameterization (CPV) method. Once the optimal tempera-
on-line estimator to estimate these process variables using ture profile is modified, a controller based on generic model
available process measurements as well. The sequence of control algorithm (GMC) is applied to control the batch re-
an estimation and optimization procedure is known as an actor temperature following the desired profile. In the GMC
estimation-optimization task [6]. As in several estimation formulation, the EKF is also used to estimate the heat re-
techniques, an Extended Kalman Filter (EKF) has become leased from the chemical reactions. It should be noted that
increasingly popular because it is relatively easy to imple- the proposed strategy would be one of several strategy stud-
ment. It has been found that the EKF can be applied to a ied to promote the applicability of on-line dynamic opti-
number of chemical process applications with great success. mization with set point tracking for improving a batch pro-
Once the estimate of unknown process variables is deter- cess; the aim of this work is to integrate efficient methods
A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114 103
including the EKF and GMC and on-line optimization lead- with
ing to an applicable, reliable and successful strategy for an
k12
actual implementation. k1 = exp k11
Tr + 273.15
2. Batch reactor k22
k2 = exp k21
Tr + 273.15
A reactor system considered by [8] which consists of a
batch reactor and jacket cooling system is chosen here as W = MWA MA + MWB MB + MWC MC + MWD MD
a case study. The typical diagram of this system is shown M r = MA + M B + M C + M D
in Fig. 1. It is assumed that two parallel highly exothermic
reactions are carried out in the reactor (CpA MA + CpB MB + CpC MC + CpD MD )
Cpr =
k1 Mr
A + B
C
Qr = H1 (k1 MA MB ) H2 (k2 MA MC )
k2
A + C
D Qj = UA(Tj Tr )
0.2 min is used for temperature measurements. It is noted the more efficient approach to obtain a maximum yield in a
that measurement noise is also included in the temperature minimum time or minimum cost and also to reach the spe-
sensors having Gaussian noise with zero mean and 1 C stan- cific final conditions of the products in terms of quality and
dard deviation. In addition, it was assumed that the concen- quantity.
tration (amount of mol) of reactants in the reactor is mea- In general, an objective function in the optimization prob-
sured infrequently and has a sampling time and measure- lem can be chosen, depending on the nature of the problem.
ment delay of 10 min. Here, two practical optimization problems related to batch
operation: maximization of product concentration in a fixed
batch time and minimization of batch operation time given
3. On-line dynamic optimization strategy amount of desired product, are considered to determine an
optimal reactor temperature profile. The first problem for-
The aim of a dynamic optimization problem is to deter- mulation is applied to a situation where we need to increase
mine a control profile minimizing (or maximizing) a given the amount of desired product while batch operation time is
objective function subject to process constraints. With the fixed. This is due to the limitation of complete production
optimal control policy, the controlled system is driven from line in a sequential processing. However, in some circum-
the initial state to a final desired state in an optimal way. stances, we need to reduce the duration of batch run to allow
However, in the presence of modeling error, the pre-specified the operation of more runs per day. This requirement leads
control profile may lose its optimal character [2]. For this to the minimum time optimization problem. These problems
reason, an on-line optimization strategy through a receding can be described in details as follows.
horizon scheme is employed in this work to compensate
such an error. The basic concept is to compute the optimal 3.1.1. Maximum product concentration problem (P1)
control profile based on current feedback information. How- In this type of problem, the objective is to compute the
ever, only the initial value of the optimal trajectory is sent optimal temperature policy maximizing the amount of a de-
to the system as a set point for the controller. After new sired product concentration for a given fixed batch time sub-
information of states is available from either measurement ject to bounds on the reactor temperature. The problem can
or estimation, the optimization is repeated again to generate be written mathematically as
updated optimal set point profile at the next time interval.
The method proposed for improving the batch operation max J = X(tf )
T(t)
can be divided into two phases: on-line modification of the
reactor temperature trajectory and on-line tracking of the de- subject to
sired temperature trajectory. The first phase involves deter- x = f(x(t), T, p, t) process model
mining an optimal temperature set point profile by solving
the on-line dynamic optimization problem and will be de- x(t0 ) = x(0) initial conditions
scribed in this section. The other phase involves designing a
TL T TU
nonlinear model-based controller to track the obtained tem-
perature set point and will be presented in the next section. tf = tf
Since both the on-line dynamic optimization and the
model-based control strategy rely on process models, the where X is the amount of the desired product at a given final
knowledge of current states and/or model parameters is batch time, x is the vector of state variables, x is the derivative
required. However, in most industrial processes, state vari- of x with respect to time (t), T is the reactor temperature, p
ables are not all measurable and some parameters are not are process parameters, tf is the fixed batch time, and TL and
known exactly. As a consequence, there is a need for es- TU are lower and upper bounds of the reactor temperature.
timating these states and parameters. In this work, two
Extended Kalman Filters (EKF) are implemented. The first 3.1.2. Minimum batch time problem (P2)
one is applied to predict the reactant concentration, which The purpose of this optimization problem is to determine
will be used for on-line dynamic optimization, from its the optimal temperature profiles to achieve the desired fi-
delayed measurement. The other one is applied to esti- nal product concentration in minimum batch time, thus the
mate the unknown heat of reaction, which will be used performance index is the final time whereas the desired pro-
for model-based controller, from the frequently available duction concentration is defined as a terminal constraints.
measurements of temperature. The formulation of the minimum batch time problem can be
shown as
3.1. Problem statements min J = tf
T(t)
As a batch reactor is utilized for the production of a wide subject to
variety of high value products, an optimization of batch op-
erating conditions, e.g. temperature, operating time, etc. is x = f(x(t), T, p, t) process model
A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114 105
x(t0 ) = x(0) initial conditions sideration, this approach can be divided into two categories:
sequential and simultaneous strategy.
TL T TU In the sequential strategy, a control (manipulated) variable
X(tf ) = X profile is discretized over a time interval. The discretized
control profile can be represented as a piecewise constant,
where X is the desired product concentration at the end of a piecewise linear, or a piecewise polynomial function. The
batch run and tf is final batch time. parameters in such functions and the length of time subin-
terval become decision variables in optimization problem.
3.2. Solution of dynamic optimization problems This strategy is also referred to a control vector parameter-
ization (CVP).
Computational techniques for the solution of a dynamic One advantage in the sequential approach is that only the
optimization problem as formulated above have been an ac- parameters that are used to discretize the control variable
tive area of research. There are a number of different tech- profile are considered as the decision variables. The opti-
niques that have been proposed in the literature to solve this mization formulated by this approach is a small scale NLP
class of problems. In general, they are mainly classified into that makes it attractive to apply for solving the optimal con-
three classes. trol with large dimensional systems that are modeled by a
The first one is based on a classical variation method. large number of differential equations. In addition, this ap-
This approach is also known as an indirect method as it proach can take the advantage of available IVP solvers. How-
focuses on obtaining the solution of the necessary conditions ever, the limitation of the sequential method is a difficulty
rather than solving the optimization directly. Solution of to handle a constraint on state variables (path constraint).
these conditions often results in a two-point boundary value This is because the state variables are not directly included
problem (TPBVP), which is accepted that it is difficult to in NLP.
solve [15]. Although several numerical techniques have been In contrast to the sequential solution method, the simul-
developed to address the solution of TPBVP, e.g. control taneous strategy solves the dynamic process model and the
vector iteration (CVI) and single/multiple shooting method, optimization problem at one step. This avoids solving the
these methods are generally based on an iterative integration model equations at each iteration in the optimization algo-
of the state and adjoint equations and are usually inefficient rithm as in the sequential approach. In this approach, the dy-
[16]. Another difficulty relies on the fact that it requires an namic process model constraints in the optimal control prob-
analytical differentiation to derive the necessary conditions. lem are transformed to a set of algebraic equations which
The second class of solutions is based on dynamic pro- is treated as equality constraints in NLP problem [20]. To
gramming. Unlike the variation method, this approach apply the simultaneous strategy, both state and control vari-
applies the principle of optimality to formulate an op- able profiles are discretized by approximating functions and
timization problem, leading to the development of the treated as the decision variables in optimization algorithms.
HamiltonJacobiBellman partial equations that determine The main advantage of the simultaneous approach is a ca-
the solution of the optimal control problem. However, pability in handing constraints on the state variables. This
this approach is quite limited to a simple control prob- is because these constraints can be dealt with by including
lem [17] because of a difficulty in obtaining the solution them directly in the NLP as additional constraints. However,
of the optimality equations. [18] extended the idea of the due to the discretization on both state and control variables,
optimality principle to develop an alternative technique, this leads the simultaneous approach to a large scale opti-
named as iterative dynamic programming (IDP). Although mization problem consisting of a large set of algebraic con-
the implementation of the IDP for solving many optimal straints and decision variables and needs a special solution
control problems can be found in the literature, it is known strategy.
that the IDP algorithm would be slower than most other As the ability of the sequential approach to handle large
gradient-based algorithms [19]. systems without the need to solve excessively large opti-
The last one is based on discretization techniques, re- mization problem, this approach is utilized in this study to
ceived major attention and considered as an efficient solu- solve the optimal control problem. The formulation of the
tion method. The concept of this approach is to transform the optimal control problem as a nonlinear programming is de-
original optimal control problem into a finite dimensional scribed below.
optimization problem, typically a nonlinear programming
problem (NLP). Then, the optimal control solution is given 3.2.1. Sequential approach
by applying a standard NLP solver to directly solve the op- Consider a dynamic process model as in the form of an
timization problem. For this reason, the method is known as implicit function
a direct method. The transformation of the problem can be f(t, x(t), x(t), u(t), p) = 0 [t0 , tF ] (7)
made by using discretization technique on either only con-
trol variables (partial discretization) or both state and con- where x(t) is the set of all state variables, x denotes the
trol variables (complete discretization). Based on this con- derivative of x(t) with respect to time, u(t) is a vector of con-
106 A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114
trol variables, and p is a vector of time invariant parameters. Gears type method is used for solving the process model
The time interval of interest is [t0 , tF ] and the function f is which provides the value of the objective function and con-
assumed to be continuously differentiable with respect to all straints. Gradient information of the objective function and
its arguments. For given initial condition x(t0 ), the optimal constraints with respect to the decision variables is eval-
control of a dynamic process represented by Eq. (7) can be uated in an efficient way using adjoint variable approach.
determined by computing u(t) maximizing (or minimizing) Then, a NLP solver determines a new set of control param-
an objective function J of the form eters and sends it back to the model solver. This procedure
is repeated until the optimal value is found satisfying a
J = F(x(tF ); x(tF ); u(tF ); tF ) (8)
specified accuracy.
subject to bounds on u(t) and terminal constraints. To trans-
form such a dynamic optimization problem into a nonlin- 3.3. State and parameter estimation
ear programming problem via the sequential approach, the
control u(t) is approximated by a finite dimensional repre- The implementation of the on-line optimization strategy
sentation. The time interval [t0 , tF ] is divided into a finite requires the knowledge of current states and/or parameters in
number of subintervals (P). In each subinterval, the control nonlinear process models in order to modify a new optimal
u(t) is represented by a set of basis functions involving a profile defined as a set point for a controller. It is known
finite number of parameters that some measurements i.e. concentration are available at
low sampling rate with significant time delay. To overcome
u(t) = j (t, zj ), t [tj1 , tj ] with j = 1, 2, . . . , J this difficulty, state and parameter estimation is incorporated
(9) into the proposed on-line optimization algorithm.
In this work, an Extended Kalman Filter (EKF), an ex-
where tJ = tF . The control profile is defined by the param- tension of the Kalman Filter, is designed to reconstruct the
eters zj and switching times tj . In this study, the piecewise current state variables from the delayed state measurement.
constant control is assumed and used because the form of The advantage of the EKF is that it requires information only
the solution is ideally suited for implementation on a digital from the previous sampling time and allows prior knowledge
computer. Thus the set of decision variables for the nonlin- of a system via process models to be used for the estimation.
ear program can be written as The algorithm of the EKF can be seen in Appendix A.
y = {z1 , z2 , . . . , zJ , t1 , t2 , . . . , tJ } (10)
3.3.1. Application to the batch reactor
The resulting nonlinear programming problem of the form Since the concentrations of reactants (MA , MB , MC and
min(or max ) J(y) (11) MD ) in batch reactor are assumed to be measurable with a
y delay of one sampling time; that is, at time k of the reactor,
subject to equality constraints (process model), inequality only information at time k 1 is available. Thus, the EKF
constraints, bounds on control, etc. is solved using an effec- is applied to estimate the value of reactant concentration at
tive decomposition algorithm named the successive reduced current time k from their delayed measurements at sampling
quadratic programming developed by [21]. Computational time k 1. However, since it is expected to exhibit uncer-
procedure of the sequential approach for the optimization tainty in reaction rate constant (i.e. k21 and k22 ) in real plant,
problem (Eq. (11)) is illustrated in Fig. 2. With the initial the EKF is also used to estimate these uncertain parame-
guess of the decision variables (y), an integrator based on ters. The following equations, therefore, are appended for
parameter estimation
Set initial conditions dk21
Guess initial control parameters =0 (12)
dt
dk22
Model Solver =0 (13)
dt
Evaluate Eqs. (1)(4), (12) and (13) correspond to Eq. (A.1) in
Objective function the EKF algorithm. Based on the estimate of the current
Constraints
Gradient
information, the dynamic optimization problem is resolved
no
to generate a new optimal temperature trajectory.
Check
NLP
tolerance
jectory. It is accepted that the use of linear control techniques is negligible compared to the heat transferred in the reactor,
in highly nonlinear and time variant chemical processes (e.g. the energy balance equation becomes
batch reactors) is quite limited to their performances and Qr + Ur Ar (Tj Tr )
dTr
may give a poor control response. Therefore, in this work, = (18)
a nonlinear control technique based on generic model con- dt Wr Cpr
trol (GMC) algorithm is utilized. This model-based control where Ur is the heat transfer coefficient, Ar is the heat trans-
methodology has been received much interest during the last fer area, Wr is the mass of the reactor contents, Cpr is the
decade and a number of applications of GMC to the con- mass heat capacity of the reactor content, and Qr is the heat
trol of batch processes have been reported in the literature released by the reactions.
(e.g. [4,8,22,23], etc.). However, most of these works focus Rearranging the Eq. (18) as in the form of GMC algo-
on using the GMC to track the pre-determined optimal pro- rithm, the following functions, f, g, and h can be defined
file (off-line calculation) of a reactor temperature. No effort
Qr Ur Ar Tr
has been made to apply the GMC to implement an on-line f(x, p, t) = (19)
optimal set point profile. Therefore, in this work, the perfor- Wr Cpr
mance of the GMC controller with optimal temperature set Ur Ar
points determined by on-line optimization strategy is also g(x, t) = (20)
Wr Cpr
evaluated and compared to that of the GMC controller with
pre-determined set point. h(x) = Tr (21)
Initial
setpoint Tj Tjsp Tr(k) Tj(k)
Dynamic
GMC REACTOR
compensation
Mi (K-1)
Qr(k) EKF
with simplified
reactor model
EKF
Updated Mi (K)
Trsp (K)
On-line dynamic
optimization problem
New reactor
temperature setpoint
Fig. 3. The proposed strategy for on-line update and control of reactor temperature profile.
can be approximated by a first order model with time con- states as shown below is used instead.
stant ( j ) [25]. Consequently, the Tjsp (k) can be computed dTr Qr + Ur Ar (Tj Tr )
by = (25)
dt Wr Cpr
Tj (k) Tj (k 1) dTj Fj j Cpj (Tjsp Tj ) Ur Ar (Tj Tr )
Tjsp (k) = Tj (k 1) + j (24) =
t dt Vj j Cpj
(26)
Table 3 98
Parameters and initial conditions in EKF
Estimate Mi , k21 and k22 96
MA (0) = 12 kmol P = diag[100 10 100 100 100 2000] 5
MB (0) = 12 kmol Q = diag[100 1 100 1 500 5000]
MC (0) = 0 kmol R = diag[10 10 10 10] 94
Temperature (C)
MD (0) = 0 kmol
k21 (0) = 38.9057 4
k22 (0) = 17000 92
Estimate Qr
Tr (0) = 20 C P = diag[1 1 100 20 10] 90 3
Table 5
Comparisons of the results obtained from off-line and on-line optimization strategy with GMC controller (problem P1)
Case studies Product C (kmol)
Off-line On-line
1. Nominal case
All parameters specified correctly 6.9478 6.9584
2. Plants/model mismatch case
50% k0 of reaction 2 in plant model (k21 = 38.2125) 7.6751 7.8851
+20% Ea of reaction 2 in plant model (k22 = 20400) 8.5825 10.2131
50% k0 and +20% Ea of reaction 2 in plant model 8.5827 10.2137
Note: k0 = exp(k21 ) and Ea = (k22 )(R) where k0 is pre-exponential rate constant, Ea = activation energy, and R is ideal gas constant.
In the nominal case, the product obtained from the off-line ison of the actual and estimated heat released by reactions,
strategy (C = 6.9478) is close to that obtained by the on-line respectively. It can be seen that the EKF provides an excel-
strategy (C = 6.9584). Fig. 5(a) and (b) shows the response lent estimation of the heat released. With this heat released,
of GMC controller to track the reactor temperature trajectory the GMC controller gives very good temperature control.
that is pre-specified by off-line calculation, and the compar- Similarly, in the case that optimal temperature is modified
via the on-line optimization strategy based on the current in-
formation of Mi , k21 and k22 obtained from delayed measure-
ment of Mi , the GMC controller is able to successfully track
the reactor temperature (Fig. 6(b)). The performance of the
EKF to predict the amount of MA , MB , MC , and MD at cur-
rent time from their measurement with time delay of 10 min
is illustrated in Fig. 6(a). Also, the EKF gives good estima-
tions of k21 and k22 as shown in Fig. 6(c). It is interesting to
note that since the initial reactor temperature starts at 20 C
which is below the optimal temperature set point, the GMC
controller attempts to drive the reactor temperature from this
condition to the specified set point. However, due to the dy-
namics of the reactor temperature, the reactor temperature
differs from the optimal set point during the first 20 min,
causing that the amount of the product C obtained from the
on-line strategy with the GMC controller (C = 6.9584) is
less than that obtained from the off-line strategy with perfect
tracking (see Table 4 for P = 20, C = 7.0379)
For the mismatch in k21 , the value of the desired prod-
uct C = 7.8851 can be achieved at the end of batch for the
on-line optimization strategy which is higher than that ob-
tained from off-line strategy where the mismatch is not no-
ticed (C = 7.6751). Similar results can be observed under
the case of plant model mismatch in k22 as shown in Table 5.
These results indicate clearly that the performance of batch
reactor operation is improved via the proposed strategy. Due
to similarity in their control responses, only the result for
change in k21 is shown in Fig. 7.
Finally, with a change in both k21 (50% k0 ) and k22
(+20% Ea) in plant model, the results using the on-line opti-
mization strategy show that the GMC controller is able to ac-
commodate this change very well as can be seen in Fig. 8(a).
Fig. 8(b) presents the performance of the EKF for estima-
tion of k21 and k22 . Since the EKF estimates these parameters
close to the true values, the mismatch is eliminated. That
Fig. 5. (a) Control response (off-line, nominal case): Trsp (dash), Tr
leads to high product C obtained at the final batch time (C
(solid), Tj (dot). (b) Heat released (off-line, nominal case): actual (solid), = 10.2137) compared to the value of C = 8.5827 obtained
estimated (dot). from the off-line optimization strategy.
A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114 111
Fig. 6. (a) Product profile (on-line, nominal case): actual (solid), estimated (). (b) Control response (on-line, nominal case): Trsp (dash), Tr (solid), Tj
(dot). (c) Estimate of k21 and k22 (on-line, nominal case): actual (solid), estimated ().
Fig. 8. (a) Control response (on-line, mismatch in k21 and k22 ): Trsp (dash),
Tr (solid), Tj (dot). (b) Estimate of k21 and k22 (on-line, mismatch in k21
and k22 ): actual (solid), estimated ().
Fig. 10. Control response (on-line, mismatch in k21 , problem P2): Trsp
modification of temperature set point profile (tf = 49.4 min) (dash), Tr (solid), Tj (dot).
is shorter compared to the result with the off-line strategy (tf
= 64.8 min). This is because the EKF can acknowledge this point modification, as expected, GMC controller can also
parameter uncertainty, so that the temperature set point pro- control the reactor corresponding to the changes in temper-
file is updated corresponding to a modified parameter value ature set point as can be seen in Fig. 10
close to the actual value. Fig. 9 shows, for this mismatch, The results for the remaining case studies are summa-
the control response of GMC controller to deliver the reac- rized in Table 6. An important aspect obtained from these
tor temperature from initial condition to the temperature set results is that in all cases, the minimum batch time to obtain
point determined off-line. For the on-line temperature set the desired product concentration in the on-line set point
Table 6
Comparisons of the results obtained from off-line and on-line optimization strategy with GMC controller (problem P2)
Case studies Final time (min)/product C (kmol)
Off-line On-line
modification strategy decreases. This points out the effec- For nonlinear systems, the process model can be described
tiveness of the proposed method to improve the operation by differential equations
of batch reactor.
x = F(x(t), u(t), t) + (t) (A.1)
y = G(x(t)) + (t) (A.2)
6. Conclusions
where F is a vector of system function, G is a vector of
measurement function, is a zero mean Gaussian process
In this work, the method using an on-line dynamic opti-
noise with covariance Q, and is a zero mean Gaussian
mization and control strategy to enhance batch reactor oper-
measurement noise with covariance R.
ation has been proposed. The on-line dynamic optimization
The equations for the EKF are given by a set of correction
by the idea of receding horizon scheme is performed. The ap-
and prediction equations as shown in the following:
proach is based on the updated current information of states
Correction phase: Correct the prior estimates of state at
of the system which are estimated from the delayed mea-
k 1 and update the weighting matrix
surement of the amount of reactants in the reactor using an
Extended Kalman Filter (EKF) technique, at specified time Kk1 = Pk1/k2 Ck1 T [Ck1 Pk1/k2 Ck1 T + R]1
interval to provide a new updated optimal reactor temper-
(A.3)
ature set point profile. Two types of optimization formula-
tion related to batch operation (maximum concentration and
minimum time problem) were considered in the proposed xk1/k1 = xk1/k2 + Kk1 [yk1 Ck1 xk1/k2 ]
on-line set point modification strategy. The obtained reac- (A.4)
tor temperature set point was implemented using a generic
model control (GMC). The EKF was also incorporated into
the GMC algorithm in order to estimate the heat released by Pk1/k1 = [I Kk1 Ck1 ]Pk1/k2 [I Kk1 Ck1 ]T
reactions using the direct measurement of reactor and jacket + Kk1 RKTk1 (A.5)
temperature. A batch reactor with highly exothermic reac-
tions was used as a simulation case study to demonstrate the Prediction phase: Integrate the nonlinear state and co-
effectiveness of the proposed approach. Simulation studies variance equations from time k 1 to k in order to acquire
have been carried out in both nominal case and plant/model estimate xk/k1 and Pk/k1
x = F(x, u)
mismatch case and the results show that the performance of
(A.6)
the batch reactor in terms of the amount of a desired prod-
uct and batch operation time can be improved significantly P = Ak1 P + PATk1 + Q (A.7)
by the proposed strategy. In addition, they also clearly in-
dicate the capability of the GMC controller to control the where xk/k1 denotes the estimate of state x at t = k from
reactor temperature along the specified trajectory and that information at t = k 1, K is Kalman gain matrix, P is
of the EKF to estimate the states and parameters of the covariance matrix, and matrices
system.
F G
Ak1 = and C =
x xk1|k1 x xk1|k2
Acknowledgements are the Jacobians of function F and G with respect to the
state vector, respectively.
The financial support to A. Arpornwichanop through local
graduate scholarship from the national science and technol-
ogy development agency (NSTDA) is gratefully acknowl- Appendix B. Nomenclature
edged. A. Arpornwichanop also acknowledges the support
of the Department of Chemical Engineering, University of ki rate constant for reaction i (kmol1 /s)
Bradford, UK during his stay as a visiting researcher at the ki1 rate constant 1 for reaction i
University in 2000. ki2 rate constant 2 for reaction i
t time (min)
t sampling time (min)
Appendix A. The EKF algorithm u input variables
x state variables
Since in this work the process models used are in time y output variables
continuous form and measurements are in discrete form, the A heat transfer area (m2 )
EKF in discrete/continuous formulation [27] is used. The Cp mass heat capacity (kJ/(kg C))
basic algorithm of the EKF can be summarized as follows: Cpi molar heat capacity of component i (kJ/(kmol C))
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Chemical Engineering and Processing 44 (2005) 115119
Received 2 December 2003; received in revised form 30 April 2004; accepted 5 May 2004
Available online 25 August 2004
Abstract
The nano-sized particles of calcium carbonate and barium carbonate have specific characteristics. They are important materials for the
industry. The main object of this investigation is to obtain nanoparticles of calcium carbonate and barium carbonate by chemical reaction
carried out in microemulsion of water in oil. The nanoparticles obtained are spherical. Their sizes vary from 20 to 30 nm. The shape and size
of particles are determinated by electron microscopy.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.004
116 C. Karagiozov, D. Momchilova / Chemical Engineering and Processing 44 (2005) 115119
Table 1
Ratio of volumes of organic and inorganic phases
Experiment Inorganic Organic Volume of inorganic Volume of organic V1 /V2
no. phase phase phase V1 (ml) phase V2 (ml)
1 2 3 4 5 6
1 Ca(OH)2 n-C6 H14 5 45 0.111
2 Ca(OH)2 n-C6 H14 10 40 0.250
3 Ca(OH)2 n-C6 H14 15 35 0.429
4 Ca(OH)2 n-C6 H14 20 30 0.667
1 Ba(OH)2 n-C6 H14 30 20 1.5
2 Ba(OH)2 n-C6 H14 25 25 1
3 Ba(OH)2 n-C6 H14 20 30 0.667
4 Ba(OH)2 n-C6 H14 15 35 0.429
5 Ba(OH)2 n-C6 H14 35 15 2.333
7 Ba(OH)2 n-C6 H14 40 10 4
Note: 1. All the experiments were carried out under stirring for 60 min at 400 rpm, 2. CO2 bubbling time was 60 min.
C. Karagiozov, D. Momchilova / Chemical Engineering and Processing 44 (2005) 115119 117
interphase surface oil/water solution in the drops and then The size of the nanoparticles of BaCO3 obtained was
interacts with the inorganic phase present in them. Thus, about 2030 nm. Their specific area was calculated to be
a chemical reaction was initiated which gave slightly solu- from 6.82 107 to 4.55 107 m2 /kg. The particles with
ble products (CaCO3 and BaCO3 ). This hypothesis can be 20 nm sizes have specific area of 6.82 107 m2 /kg while
schematically represented as follows (Fig. 3). particles with 30 nm size 4.55 107 m2 /kg. Therefore, the
The summarized equation of the chemical reaction pro- specific area decreased with the increase of particle radius
ceeding between the corresponding hydroxide and CO2 is (Fig. 3).
For the microemulsion system inorganic solution/
Me(OH)2 + CO2 MeCO3 + H2 O (1)
n-C6 H14 , it is important to prove that the inorganic so-
The chemistry of the separate stages of the process within a lution was dispersed in the organic phase in the form of
droplet can be described by the following reactions: microdrops. To determine the distribution of the phases in
the microemulsion, the forces of surface tension for each
Me(OH)2 Me2+ + 2OH (2)
microdrop should be estimated, as well as the forces acting
CO2 + H2 O H2 CO3 (3) at the interphase surface.
Forces of surface tension act on the surface of the parti-
H2 CO3 HCO
3 +H
+
(4) cles in the liquid phase. It can be expressed as the work for
the formation of a unit of interphase surface under constant
CO2 + OH HCO
3 (5)
thermodynamic parameters of the state (temperature, pres-
HCO + 2
3 H + CO3 (6) sure, chemical potentials of the components). This process
is reversible and isothermal. The surface tension forces can
Me2+ + CO2
3 MeCO3 (7) be regarded also as free energy per unit area, i.e. specific
free energy (GS ). Then, the free energy per unit weight of
where Me = Ca, Ba. particles would be
The basic parameter characterizing nano-particles is their
specific area, which can be determined by the formula [15] GS = GS A (11)
A = 4r N(m /kg)
2 2
(8)
where A: specific area (m2 /kg), r: particles radius (m), N:
number of particles per unit of weight.
The number of particles can be calculated from
1
N= (9)
(4/3)r 3
Substituting Eq. (11) into Eq. (10) gives the following ex-
pression for calculation of the specific area:
3 2
A= (m /kg) (10)
r Fig. 3. Probable mechanism of contact between the reagents.
118 C. Karagiozov, D. Momchilova / Chemical Engineering and Processing 44 (2005) 115119
Assuming that GS is constant value, then free energy Its value was calculated to be 0 = 68.18 . At 0 < 90
GS should increase with the decrease of particle radius A (as is in this case), the process called limited wetting or
[16,17]. wetting with impregnation. Therefore, the change of the free
The surface tension of 0.02 N solution of Ba(OH)2 was energy per unit area can be found by the expression
determined by the formula [18] G = TB /T T/ (17)
Ba(OH)2 = 0 + 0.049(1 aW ) (12)
The interphase tension T1 /T2 corresponds to the so-called
where : surface tension of Ba(OH)2 (dyne/cm), 0 : sur- boundary coefficient of spreading Sk , after equilibrium was
face tension of water at 25 C. It is considered to be established at the interphase surface between the two liq-
71.97 dyne/cm [18], aw : activity of water in the solution. uids. The higher the coefficient of spreading is, the faster is
The water activity in the solution was determined by the the spreading of the wetting liquid. In the system studied,
well-known equation [18] T1 /T2 = Sk = 50.5 > 0. It means that the surface tension of
n-C6 H14 remained lower than that of the inorganic solution,
tmBa(OH)2 MBa(OH)2
ln aW = B1 + at + bt2 i.e. n-C6 H14 wetted the polar phase of aqueous solution of
55510RT
Me(OH)2 .
B2
+
1000 + MBa(OH)2 mBa(OH)2
1 4. Conclusions
mBa(OH)2 MBa(OH)2 + (13)
E
The following conclusions can be formulated on the basis
where R: universal gas constant = 8.314441 J/mol, T: tem- of the results obtained
perature (K), mi : solution molality (g/l), Mi : mole weight
(g/mol), B1 , a, b, B2 , E: coefficients calculated by mathe- 1. A technique and process for preparation of nano-sized
matical treatment of the experimental data for heat capacity. particles from alkali carbonates was developed on the
Value of the surface tension of Ba(OH)2 was calculated to basis of the method of reversed micelles and a probable
be 71.88 dyne/cm. Reference data showed that n-C6 H14 = mechanism was suggested.
32.21 [18]. The value of Ba(OH)2 surface tension was close 2. Nano-sized particles of barium and calcium carbonate
to that of water ( 0 ) since the concentration of Ba(OH)2 was were obtained by a chemical reaction in a microemulsion.
low and the solution was very diluted. The particles were studied by electron microscopy and
Forces of interphase tension T1 /T2 act at the contact sur- were found to possess spherical shape and diameters from
face between the two liquid phases of Ba(OH)2 (or Ca(OH)2 ) 20 to 30 nm.
and n-C6 H14 . The thermodynamic condition for a liquid to 3. The nano-sized particles were obtained at various ratios
spread over the surface of another liquid is [19] of the phases forming the microemulsion. They were
T2 / > T1 / + T1 /T2 (14) about the same size, which confirmed the advantage of
the method selected.
where T1 / , T2 / : surface tensions of the liquids related 4. The particles synthesized were observed to agglomer-
to their environment (dyne/cm), T1 /T2 : surface tension at ate, probably due to effects induced by the electron mi-
the interphase boundary between the liquids (dyne/cm). croscopy analysis.
The interphase tension at the phase boundary between an 5. The values of the surface tensions of the individual phases
inorganic solution and oil was assumed to be 50.5 dyne/cm, were calculated, as well as the value of the interphase
according to literary data [19]. The two phases are quite tension. The results confirmed that the inorganic phase
different by polarity. The basic process taking place at the was dispersed in the organic phase.
contact surface between them is the change of the total con-
tact surface area due to the decrease of the total energy of
the system, i.e. the conditions became suitable for process Appendix A. Nomenclature
of wetting to take place. The coefficient of spreading S can
be calculated from the values of the surface and interphase aw activity of water in the solution
tensions according to [20] mi solution molality (g/l)
S = T2 / T1 / T1 /T2 , S = 10.853 (15) r particles radius (m)
o oil
At S < 0, the wetting angle can be determined by the equa- w water
tion [20] A specific area (m2 /kg)
T22 / T22 / T21 /T2 B1 , a, b, B2 , E coefficients calculated by mathematical
cos 0 = (16) treatment of the experimental data for
2T1 / T2 /
heat capacity
i.e. cos 0 = 0.3717 G change of the free energy per unit area
C. Karagiozov, D. Momchilova / Chemical Engineering and Processing 44 (2005) 115119 119
Abstract
Experimental data on the average mass transfer liquid film coefficient (kL ) in an aerated tank stirred by Rushton turbine and in bubble
column are presented. Liquid media were used as 0.8 M sodium sulphite solution, pure or with the addition of Sokrat 44 (copolymer of
acrylonitrile and acrylic acid) or short-fiber carboxymethylcellulose (CMC) for the Newtonian and long-fiber CMC for the non-Newtonian
viscosity enhancement and ocenol (cis-9-octadecen-1-ol) or polyethylenglycol (PEG) 1000 for surface tension change. Volumetric mass
transfer coefficient (kL a) and specific interfacial area (a) were measured by the Danckwerts plot method. Coefficients kL measured by pure
oxygen absorption in pure sulphite solution and Newtonian viscous liquids are well fitted by the eddy model in the form of kL = 0.448
(ev/)0.25 (D/v)0.5 with a mean deviation of 20%. Surface-active agents (ocenol and PEG) and non-Newtonian additive (long-fiber CMC)
reduced kL value significantly but their effect was not described satisfactorily neither by surface tension nor by surface pressure. It is shown
that the decisive quantity to correlate kL in the stirred tank and bubble column is power dissipated in the liquid phase rather than the bubble
diameter and the slip velocity. Absorption of air did not yield correct kL data, which did not depend on or slightly decreased with increasing
power. This is due to the application of an improper gas phase mixing model for absorption data evaluation.
2004 Elsevier B.V. All rights reserved.
Keywords: Gasliquid contactor; Bubble column; Agitated vessel; Mass transfer coefficient; Viscosity; Surfactants
1. Introduction tial ones, affect the mass transfer. In any case, these motions
are much smaller in scale than the gas bubbles. As a result,
Mass transfer from swarm of bubbles into turbulent liq- the size of the gas bubble is not a very critical parameter for
uid controls the rate of many chemical and biochemical pro- the estimation of kL . They deduced [1] the following rela-
cesses. It is assumed that the mechanism of mass transport tion for kL :
in liquid phase is due to a renewal of the liquid at the bub- 0.25 0.5
ev D
ble surface. Models of the process differ in the scale of flow, kL = c1 (1)
v
which is responsible for the renewal.
The first group of models (eddy models) assumes that Different authors predict different values of the constant c1 :
the liquid renewal is due to small-scale eddies of the turbu- 0.301 [2], 0.4 [1], 0.531 [3], 0.592 [4] and 1.13 [5].
lent field. These models are based on idealized eddy struc- The second group of models (slip velocity models) as-
tures of turbulence in the bubble vicinity. Lamont and Scott sumes a gross mean flow of fluid relative to the bubble (slip
[1] have assumed that the small scales of turbulent motion, velocity) and a bubble surface mobility control of this re-
which extend from the smallest viscous motions to the iner- newal rather than the small-scale eddies of the turbulent
field. The model proposed by Calderbank and Moo-Young
[6] belongs to this group. They [6] have divided bubbles by
Corresponding author. Tel. +420 2 2435 3298; size into two categories: the small bubbles (d < 1 mm),
fax: +420 2 3333 7335. which behave always as a rigid sphere, and the large
E-mail address: linekv@vscht.cz (V. Linek). ones (d > 2.5 mm), which always have a completely mobile
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.009
122 V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130
surface. An expression for the calculation of kL for the The time mobile depends on bubble diameter and surfactant
large bubbles has been deduced from dimensionless analy- concentration.
sis of mass transfer from rising particle in gravitational field.
d 1/2 ln (d/ htrans )
mobile = k (8)
g 1/3 D 1/2 csurf
kL = 0.42 (2)
v where d is an average bubble diameter, k is an empirical con-
For the small bubbles, an expression for the calculation of stant related with surfactant properties, csurf is the concen-
kL has been obtained by the equation proposed by Frssling tration of surfactant and htrans is the bubble clean segment
[7] for dissolution of a rigid sphere. height at the transition point from mobile to rigid.
The main difference between the eddy and the slip
g 1/3 D 2/3 velocity models is in the influence of turbulence inten-
kL = 0.31 (3)
sity on mass transfer coefficient: the eddy models predict
an increase while the slip velocity models a decrease of
The transition between these two bubble categories was kL with increasing turbulence intensity, i.e. with increasing
unclear and strongly dependent on the presence of surfac- power dissipated in the liquid. This is due to the fact that
tants. An expression for calculation of the mass transfer kL from rigid bubbles is cca four times lower than from the
coefficients in this transition region was not given. ones with a mobile surface. The small bubbles, which ei-
Recently, Vasconcelos et al. [8] and Alves et al. [9] pro- ther have lower kL (according to Calderbanks conception)
posed another variant of the slip velocity model. Their or become rigid more quickly (according to Alves concep-
model is based on experimentally observed phenomena of tion, mobile diminishes with diminishing bubble diameter
an abrupt change of the dissolution rate of free-floating bub- d, see Eq. (8)), are generated in large amount just at higher
bles held stationary in a downward water flow. Starting from turbulence intensities. As a result, this leads to the decrease
these experiments, they have interpreted the mass transport of average mass transfer coefficient with increasing power
from bubbles in terms of bubble contamination kinetics, us- dissipated in the liquid. Literature data on kL in stirred tanks
ing a stagnant cap model, according to which bubbles sud- supporting both these models can be found.
denly change from a mobile interface to a rigid condition In dispersions with no mechanical agitation (bubble
when surface tension gradients, caused by surfactant accu- columns, air-lifts), the only source of energy is the expansion
mulation, balance out shear stress. The fresh bubble entering of the entering gas which gives the relation e = gvs . Reith
the dispersion has clean, completely mobile interface. For [10], Dillon and Harris [11], Kawase et al. [5] and Vzquez
the bubbles with completely mobile surface, kL is given by et al. [12] revealed strong dependence of liquid-side mass
the equation, which follows from the well-known penetra- transfer coefficient on gas flow rate in bubble columns:
tion model with exposition time equal to d/vsl : kL vs 0.25/0.5 . Slight dependence or independence of kL
vsl 1/2 on vs was found by Schumpe and Deckwer [13], Bouaifi
kLmobil = 1.13 D (4) et al. [14], Wongsuchoto et al. [15] and Vasconcelos et
d
al. [8]. The values of kL corresponded to values predicted
After some time ( mobile ), enough contaminant for transition by Calderbanks model for large bubbles. Values which
to rigidity is accumulated on the surface. For the rigid bub- correspond also to small bubbles were found by Vzquez
bles, an expression for the calculation of kL follows from et al. [12] and Vasconcelos et al. [8] only, who worked with
Frssling [7] equation. solutions of surfactants. Vasconcelos et al. [8] interpreted
their results in terms of bubble contamination kinetics.
rigid vsl 2/3 1/6
kL = 0.6 D v (5) In dispersions with mechanical agitation, following au-
d thors found an increase of kL with increasing energy dissi-
Gasliquid slip velocities vsl are assumed to be close to pation e: Prasher and Wills [4] (kL e0.25 ); Figueiredo and
single-bubble terminal velocities in still water, vt , on which a Calderbank [16] (kL e0.33 ); Bouaifi and Roustan [17] (kL
correction for turbulence is introduced, vsl = 0.65vt [9]. As- e0.22 ); Panja and Rao [18] (kL e0.15 ); and Linek et al.
suming monosized bubble dispersion and considering only [19] (kL e0.14 ). Power dissipated in the liquid by an agi-
rigid
two possible values of kL (kLmobil and kL , depending on tator is proportional to the third power of impeller rate (e
surface mobility), they deduced the following relation for f3 ). Thus, we can add the results of authors that presented kL
the average mass transfer coefficient: as a function of impeller rate f: Koetsier and Thoenes [20]
(kL f0.9 e0.3 ) and Yoshida and Miura [21] (kL f0.6
rigid
kmobil mobile + kL (R mobile ) e0.2 ). Robinson and Wilke [22] measured kL that did not
kL = L (6)
R depend on power dissipated and Hassan and Robinson [23]
obtained coefficients that decreased with increasing power
where R is the average bubble residence time. dissipated. It was shown [32] that the reported independence
VL on or the decrease of kL with increasing power dissipated
R = (7)
q(1 ) was a result of misinterpretation of kL a data.
V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130 123
Figueiredo and Calderbank [16] have analysed the suit- efficients in the stirred vessel has been analysed by Linek
ability of Calderbanks model [6] for small and large et al. [3]. Alves et al. [9] measured the overall volumetric
bubbles to the interpretation of mass transfer coefficients in mass transfer coefficients kL a by the peroxide decomposi-
stirred vessels. They analysed an effect of the gas phase mix- tion steady-state technique with air as a gas phase, show-
ing model used for kL a evaluation by the dynamic method ing that kL decreased slightly with power dissipated. Linek
based on the inlet gas exchange N2 /air. In their original et al. [25] showed, however, that the steady-state methods
work [6], the kL a evaluation assumed that the interchange with air absorption/desorption give substantially lower kL a
of the gases in gas hold-up is immediate (steady-state model values at high mixing intensities as compared to pure oxy-
of the gas phase). Corresponding kL values were indepen- gen absorption. If the coefficients kL a were measured by the
dent of power dissipated in the liquid by the agitator and non-problematic pressure dynamic method [26] with pure
matched the constant value of 4.03.104 m s1 as predicted oxygen absorption in the same apparatus as in Alves et al.
by Calderbanks model [6] for large bubbles (Eq. (2)). [9], the relevant kL data were well interpreted in terms of the
When the gas phase dynamics was taken into account (the eddy model (Eq. (1)) with c1 = 0.531 [3]. The corrected
flushing out of an old gas by a new one), the correspond- data have shown that the decisive quantity to correlate kL in
ing values of kL were higher and well fitted by the eddy stirred tanks is power dissipated in the liquid phase rather
model (Eq. (1)) with c1 = 0.5, see Fig. 1. (It was shown than the bubble diameter and their rigidity and that kL in-
by Linek et al. [24] that faulty sampling of liquid used by creases with increasing turbulence intensity.
Figueiredo and Calderbank [16] leads to considerably over- It seems from the literature survey that in mechanically
estimated kL a values for kL a > 0.1 s1 . Therefore, kL values agitated dispersions, the intensity of energy dissipation plays
corresponding to this range are not included in the figure.) a dominant role in the value of the mass transfer coefficient
They concluded [16] (in difference with the original work and that the successful applications of the slip velocity
[6]) that kL is dependent on the turbulent intensity expressed models in stirred tanks are probably only a result of errors
as a function of the power dissipated per unit volume and in evaluation of kL a. On the contrary, in dispersions with no
that the coefficient is considerably higher than would be mechanical agitation, both conceptions (eddy and slip
found for bubbles in free rise under gravitational force as velocity) are equally successful. This may indicate that the
given by the model of small and large bubbles. mechanism of mass transfer without mechanical agitation
Vasconcelos variant of the slip velocity model based differs from that in the presence of agitation, as was sug-
on bubble contamination kinetics, Eqs. (4)(8), was used gested by Bouaifi et al. [14]. The same indicate the results by
by Alves et al. [9] to interpret kL data in a double Rush- Lamont and Scott [1]. They compared rates of mass trans-
ton turbine-stirred tank. The application of Vasconcelos fer from turbulent liquid into bubbles flowing in vertical
model to the interpretation of unreliable mass transfer co- and horizontal tube where the bubbles can and cannot rise
Fig. 1. Effect of gas phase mixing model used for kL a evaluation; kL values calculated from kL a and a presented by Figueiredo and Calderbank [16].
124 V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130
freely through the turbulent liquid, respectively. If the bub- the model of gradual surface contamination (Eqs. (4)(8))
bles could rise freely through the liquid, the mass transfer using three empirical parameters: htrans , k/csurf and vt /vsl .
coefficient did not depend on intensity of turbulence at low The aim of this paper is to make measurements with liq-
Reynolds number. With increasing Re number, the role of uids of various physical properties in order to define the
the intensity increased and at high Re number, the dependen- effect of the liquid properties and operating conditions on
cies for both arrangements (with and without the free rise of the parameter kL and the limits of validity of the literature
bubbles) coincided. It means that both mechanisms operate models for the interpretation of mass transfer coefficients in
simultaneously but they apply at different extent, depending bubble dispersions. The method, which is used for the mea-
on intensity of turbulence. surements, was verified in Part I to minimize misinterpreta-
Surface-active substances reduce the mass transfer coef- tions.
ficient markedly in gasliquid dispersions. Although a con-
siderable effort was made to identify the mechanism of mass
transfer in the presence of surfactants, no consistent conclu- 2. Experimental
sion had been drawn. Two possibilities were offered [27]:
surfactant molecules affect mass transfer via hydrodynam- The experiments were performed in a flat-bottomed
ics effects or via the formation of an interfacial barrier layer. cylindrical vessel with internal diameter 0.19 m, equipped
The barrier effect is due to a monolayer of the surfactants with standard Rushton turbine of 0.075 m in diameter lo-
formed at the interface, which can offer a resistance to be cated 0.08 m above the bottom. Four baffles (1/10 of the
crossed by the gas molecule. The resistance exerted by the vessel diameter width) were symmetrically mounted. A
monolayer is a complex phenomenon, possibly depending on membrane-covered polarographic oxygen probe was sit-
the effects of absorbing gassurfactantwater interactions, uated in the bottom to measure the equilibrium partial
which are related to the molecular structure of the surfac- pressure of oxygen in the bulk of liquid. Gas (pure oxygen
tant: the polarity of the hydrophilic group, the molecular or air) was taken from a pressure flask and introduced 2 cm
weight of the hydrophilic group, the hydrophilic chain length under the impeller through a tube of i.d. 4 mm. The bubble
and the orientation of the molecules at interface. Hydrody- column was realized by keeping zero rotational frequency of
namics effects are induced by the difference in composition the agitator. The experiments were performed with the same
and physical properties of the liquid at the interface and in solutions as those used in the kinetics measurement: 0.8 M
the bulk of liquid. Surfactants (but also electrolytes [28,29]) sodium sulphite solution, pure or with the addition of vis-
tend to create different spatially oriented structures in close cosity or surface tension-changing additives (see Table 1).
proximity of the interface and in bulk liquid and thus, their Physical properties of the solutions are given in Part I of
presence causes an energetic barrier for the surface renewal this work. The vessel was filled with liquid to the height of
due to additional requirements of reordering the liquid en- 226 mm, which amounts to 5.9 l. Superficial velocities of
tering or leaving the interface. For example, if the liquid aeration gas were 1.8, 3.6 or 5.4 mm s1 , which correspond
turbulent eddies penetrate to the interface, they would bring to volumetric flow rates 5.1 105 , 10.2 105 and 15.3
about an increase in the free energy per unit area of inter- 105 m3 s1 , respectively. The impeller rotational speeds
face due to the replacement of the interfacial liquid layer were 0, 5.5, 10, 14.33 and 18.83 l/s. Temperature was kept
by inner liquid of higher surface tension. This dampens the at 30 1 C by a cooling coil.
rejuvenation of the interfacial liquid by fresh bulk liquid, The specific power dissipated by agitators in the liquid,
renders mass transfer more difficult and lowers the value eagit , was measured by a strain gauge mounted on the im-
of mass transfer coefficient. Llorens et al. [27] decided the peller shaft. The total specific power e dissipated in the liq-
hydrodynamic effect to be the principal. They offered the uid by the agitator and the rising bubbles was calculated as
surface pressure (i.e. the difference in surface tension of e = eagit + gvs . The volumetric mass transfer coefficient
the solution without and with s , the surfactant) to rep- and interfacial area were measured by the Danckwerts plot
resent a measure of the additional work needed to replace method described in detail in Part I.
a surface element: (kL )s /kL = 1/(1.25 + 0.073 ) for 0.4 <
< 16 mN m1 and (kL )s /kL = 0.41 for > 16 mN m1 .
The form of the correlation did not depend on the type of 3. Results
surfactant. Zieminsky and Whittemore [28] offered the ionic
strength and Machon and Linek [29] the electrical surface 3.1. Volumetric mass transfer coefficient
potential to correlate the reduction of kL in electrolyte solu-
tions as measures of the additional work needed to replace a The overall volumetric mass transfer coefficients mea-
surface element in these solutions. Vzquez et al. [12] used sured by pure oxygen absorption were expressed as a func-
a simple correlation between the mass transfer coefficient tion of the total specific power dissipated in the liquid as
and surface tension of solution under the form kL 1.35 . follows:
Vasconcelos et al. [8] interpreted mass transfer coefficients
in air-lift and bubble columns with solution of surfactants by kL a = 1 e2 (9)
V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130 125
Table 1
Solutions used in this work and pertinent symbols and lines used in figures and parameters , and in correlations (9), (10) and (11) obtained by
regression of the experimental data
Solution Symbol Lines Parameter i =1 i =2 Mean Mean
deviation (%) deviationa
0.8 kmol m3 Na2 SO3 i 3.35 105 1.18 34 21
i 0.523 0.863 36 36
i 1.06 104 0.238 19 20
0.8 kmol m3 Na2 SO3 + Sokrat 44 (3 vol.%) i 3.26 105 1.16 44 43
i 0.507 0.913 40 43
i 6.70 105 0.243 11 11
0.8 kmol m3 Na2 SO3 + CMC TS.5 (0.2 wt.%)
i 3.65 105 1.08 30 29
i 1.21 0.632 33 49
i 1.04 104 0.276 25 26
0.8 kmol m3 Na2 SO3 + CMC TS.20 (0.6 wt.%) i 2.21 104 0.771 14 14
i 1.80 0.689 13 14
i 1.15 104 0.090 5 5
0.8 kmol m3 Na2 SO3 + ocenol (3 ppm by volume) + i 1.27 104 0.732 27 14
i 2.35 0.492 12 9
i 7.97 105 0.188 17 13
0.8 kmol m3 Na2 SO3 + PEG 1000 (100 ppm by mass) i 2.65 105 1.15 1
i 1.14 0.903 2
i 0.237 0.246 1
a Mean deviation when the gas flow rate vs is taken into account as an additional parameter (e.g., kL a = 1 e2 vs 3 ).
1, 2 values together with mean deviations of the data are of electrolyte solutions [24]. Marked reductions of kL a
given for all batches in Table 1. Taking into account gas are observed with ocenol (up to 10 times) and long-fiber
flow rate vs as additional independent parameter has not carboxymethylcellulose (CMC) TS.20 (up to four times).
improved fidelity of the correlation as follows from a com- The ocenol has a strong antifoaming effect that enhances
parison of the mean deviations of the relation (9) with and the coalescence rate of bubbles in dispersion. The resulting
without taking into account vs (see Table 1). Fig. 2 clearly coefficients are even lower than those predicted by a corre-
shows that kL a data for pure sulphite solution agree well lation suggested for coalescent batches like pure water [24].
with a recommended correlation for non-coalescent batches The reduction of kL a due to CMC TS.20 cannot be ascribed
Fig. 2. kL a/(vs )0.4 measured by pure oxygen absorption as a function of total power dissipated in the liquid, e. Symbols and lines (see Table 1).
126 V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130
Fig. 3. Interfacial area a measured by pure oxygen absorption as a function of total power dissipated in the liquid, e. Symbols and lines (see Table 1).
unequivocally to higher viscosity of the batch as the addi- pure oxygen absorption were expressed as a function of the
tion of Sokrat 44 (which increased the viscosity to the same total specific power dissipated in the liquid as follows:
extent as CMC) made no reduction in kL a.
kL = 1 e2 (11)
3.2. Specific interfacial area 1, 2 values together with mean deviations of the data are
given for all batches in Table 1. The results show clearly that
The specific interfacial areas measured by pure oxygen kL increases with increasing power dfissipated in the liq-
absorption were expressed as a function of the total specific uid with exponent 2 equal approximately to 0.25 in agree-
power dissipated in the liquid as follows: ment with the eddy model (1) (see Fig. 4). Exceptions
a = 1 e2 (10) are the solutions with the addition of long-fiber CMC TS.20
and ocenol. In these solutions, the coefficients increase with
1, 2 values together with mean deviations of the data are power but the exponent 2 is lower than 0.25 ( 2 = 0.09
given for all batches in Table 1. Taking into account gas and 0.188, respectively). The correlation (11) also fits well
flow rate vs as an additional independent parameter has not the data measured in the bubble column, which are repre-
improved fidelity of the correlation as follows from a com- sented by the points for e < 100 W m3 in Fig. 4. kL data
parison of the mean deviations of the relation (10) with and for all Newtonian batches without surface-active agents (i.e.
without taking into account vs (see Table 1). This agrees pure sulphite solution and with the addition of Sokrat and
with the finding of Westersterp et al. [30], who stated that short-fiber CMC) are well fitted by the equation
the interfacial area is independent of gas flow rate at im- 0.243
peller speeds higher than a critical one. The critical im- ev D
kL = 0.915 0.623 (12)
peller speed for Rushton turbine and sulphite solution equals v
9.4 s1 [29]. All but one of the impeller speeds used in this
with a mean deviation of 19%. If the theoretical value 0.25 of
work were higher than this critical value. The results given
the power exponent and 0.5 of Schmidt number exponent
in Fig. 3 show that ocenol and short-fiber CMC TS.5 pro-
are used, the equation changes to
duce a marked decrease of the interfacial area (up to five and
three times, respectively), and that a marked increase is pro- 0.25 0.5
ev D
duced by polyethylenglycol (PEG) (up to three times) and kL = 0.448 (13)
v
a smaller one by the addition of Sokrat (up to two times).
with a mean deviation of 20%. Since the deviation is prac-
3.3. Mass transfer coefficient tically the same as the deviations of correlation (11), cor-
relations (12) and (13) describe the effects of viscosity and
Mass transfer coefficients were calculated by the ratio diffusivity satisfactorily. Experimental and calculated values
kL a/a. The coefficients evaluated from the data measured by from Eq. (13) of kL are compared in Fig. 5.
V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130 127
Fig. 4. Liquid film mass transfer coefficient measured by pure oxygen absorption vs. total power dissipated in the liquid, e. Symbols and lines (see Table 1).
Fig. 8. Comparison of kL a, a and kL data measured by pure oxygen and air absorption in pure sulphite solution and with addition of ocenol. Air
absorption, filled symbols; oxygen absorption, hollow symbols; see Table 1.
V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130 129
Fig. 9. Comparison of mass transfer coefficients measured by air absorption in pure sulphite solution and in the solution with addition of ocenol with
Calderbanks model.
bubbles. (The average bubble diameter was calculated from be the result of interpretation of physically inconsistent kL
gas hold-up and interfacial area as d = 6/[(1)a].) The data.
data measured in solution with ocenol fall between the
values for large and small bubbles. This is usually
interpreted by partial contamination of bubble surface by Acknowledgements
surfactant, which shifts the transition between large and
small bubbles to higher bubble diameters. The decrease This work was supported by the Grant agency of Czech
of kL values with increasing stirring intensity (see Fig. 8 for Republic through the project no. 104/98/1126 and by Czech
ocenol) can be explained by an increasing amount of small Ministry of Education through the scientific project no.
bubbles. Such interpretation is frequently used in literature 223400007.
for the data measured by absorption of diluted gas.
Appendix A. Nomenclature
q volumetric gas flow rate, m3 s1 [13] A. Schumpe, W.D. Deckwer, Gas holdups, specific interfacial areas,
and mass transfer coefficients of aerated carboxymethyl cellulose
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vt single bubble terminal velocity in still water, m s1 706711.
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study of gas hold-up, bubble size, interfacial area and mass transfer
coefficients in gasliquid reactors and bubble columns, Chem. Eng.
Greek symbols
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gas hold-up tion and gas/liquid mass transfer in airlift contactors, Chem. Eng. J.
kinematics viscosity of the liquid phase, m2 s1 92 (2003) 8190.
=( s ), surface pressure, N m1 [16] M.M.L. Figueiredo, P.H. Calderbank, The scale-up of aerated mixing
vessels for specified oxygen dissolution rates, Chem. Eng. Sci. 34
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on liquid phase mass transfer in solutions of electrolytes, Chem.
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Chemical Engineering and Processing 44 (2005) 131137
Received 26 February 2004; received in revised form 4 May 2004; accepted 14 May 2004
Available online 2 July 2004
Abstract
In this article, a systematic study of the separation of the n-hexaneethyl acetate mixture with an entrainer by heterogeneous azeotropic
batch distillation is performed. Based upon the thermodynamic behaviour of the ternary mixtures, potential entrainers partially miscible with
one or two original azeotropic components are chosen. In all cases, the entrainer adds a heterogeneous binary or ternary azeotrope that is the
lowest boiling point in the ternary diagram. Therefore, it leaves the column by the overhead stream which is subcooled to get two liquid phases
in the decanter. The phase with the highest amount of the original component is removed as distillate product whereas the entrainer-rich phase
is continuously refluxed to the column. Considering methanol, acetonitrile, water and nitromethane as heterogeneous entrainers, screening was
performed based on the composition of the unstable heteroazeotropic mixture, the ratio of both liquid phases in the condensed top vapour and the
purity of the distillate product determined by the liquidliquid envelope at the decanter temperature. The process feasibility analysis is validated
by using rigorous simulation with the batch process simulator ProSimBatch. Simulation results are then corroborated in a bench experimental
column for the selected entrainer, showing several advantages of heterogeneous batch distillation (HBD) compared to homogeneous systems.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.006
132 I. Rodriguez-Donis et al. / Chemical Engineering and Processing 44 (2005) 131137
by homogeneous azeotropic batch distillation [1]. In con- ponents are selected. From the analysis of residue curve map
trast to batch homogeneous distillation processes, studies features, in particular the decanter phases composition and
on heterogeneous batch distillation (HBD) were scarce the distillation region separatrices curvature, the sequence of
[24] until a new method for the synthesis of heterogeneous products to be drawn from the rectifier column can be pre-
distillation in a batch rectifier was defined and a complete dicted. The number of distillation tasks in the whole process
set of rules for the selection of heterogeneous entrainers for is set by the products targeted purity.
the separation of non-ideal mixtures was established [5,6].
Simulation and experimental results have shown key dif-
ferences between homogeneous and heterogeneous batch 2. Selection of a suitable entrainer for the separation
distillation [6]. Indeed, some advantages of heterogeneous of n-hexaneethyl acetate mixtures by heterogeneous
batch processes compared to homogeneous systems are: (i) azeotropic batch distillation
more suitable candidate entrainers and hence, more design
alternatives for the separation of non-ideal mixtures, (ii) Liquidvapour equilibrium data for the binary mixture
simplified distillation sequences thanks to the liquidliquid n-hexaneethyl acetate have been scarcely reported in the
phase split occurring in some parts of the column and in the scientific literature [8]. Those authors reported a mini-
decanter, (iii) the addition of a smaller amount of entrainer to mum boiling temperature azeotrope with an average mole
the original mixture, (iv) the use of more flexible reflux poli- fraction of n-hexane equal to 0.6565 and a temperature
cies through any combination of the entrainer-rich phase and of 65.15 C at 101.3 kPa. A more detailed experimental
the distillate-rich phase, (v) the still path can cross unstable study, at atmospheric pressure, of liquidvapour equilib-
separatrices allowing the separation of components located rium was performed by Acosta et al. [9]. Their estimation
in different basic distillation regions. The overall cost re- of the azeotropic mixture corresponds to a temperature of
duction generated by these advantages makes heterogeneous 64.85 C with a molar fraction of n-hexane of 0.657 with
batch distillation an attractive option for the separation of an average experimental error for the temperature and com-
non-ideal mixture generated by specialty industries. position measurements of 0.02 C and 0.003 mole fraction,
The aim of this paper is to study the performance of het- respectively.
erogeneous batch distillation for the separation of the mix- The candidate homogeneous and heterogeneous en-
ture n-hexaneethyl acetate. This azeotropic mixture is often trainers are investigated applying the rules reported by
used in pharmaceutical industries for separating bioactive Rodriguez-Donis et al. [1,5]. The existence of binary and
substances by liquid chromatographic processes. The sepa- ternary azeotropes is sought by using literature data [8]
ration of this mixture by batch distillation was first studied and by simulating liquidvapour and liquidliquidvapour
by Rodriguez-Donis et al. [7], by using acetone as a homo- equilibrium by using the BibPhyAddIn Macro in an Excel
geneous entrainer. As the separation by using a single batch spreadsheet [10]. Confirming the need for a complex hybrid
distillation process with acetone was not possible, a hybrid process in case a homogeneous entrainer like acetone is
process was proposed involving a homogeneous azeotropic used [7], no homogeneous entrainer matching the reported
distillation column with acetone and a liquidliquid extrac- rules has been found whereas some suitable heteroge-
tion column with water. To circumvent this complex pro- neous entrainers have been identified; the composition and
cess, we propose in this paper a simpler process by using temperature of their azeotropic mixtures with the original
heterogeneous azeotropic batch distillation. Based on en- components are displayed in Table 1 [8].
trainer selection rules established by Rodriguez-Donis et al. As seen in Table 1, the boiling temperature of the pos-
[5], which consider the thermodynamic behaviour of mul- sible entrainers is either lower or higher than that of the
ticomponent mixtures, an initial list of potential entrainers original components. All candidates form a binary hetero-
partially miscible with one or both original azeotropic com- geneous azeotrope with n-hexane. Methanol and acetonitrile
Table 1
Potential heterogeneous entrainers for the separation of n-hexaneethyl acetate mixture with thermodynamics data from Gmehling et al. [8]
Entrainer bp Binary azeotrope with Binary azeotrope with Ternary azeotrope
n-hexane (68.7 C) ethyl acetate (77.1 C)
( C) xmolar a T ( C) xmolar a T ( C) xmolar a T ( C)
Table 2 Table 3
Binary interaction parameters for NRTL and UNIQUAC models Purity of n-hexane-rich phase (xI ) and entrainer-rich phase (xII ) at 25 C
Binary parameters Aij Aji aij Entrainer Binary azeotrope with Ternary azeotrope
Binary coefficients for NRTL model (cal/mol) n-hexane
n-Hexaneethyl acetate 720.731 33.844 0.1521 xnhexane
I xnhexane
II xI xII
n-Hexaneacetonitrile 924.616 1212.64 0.2000
Ethyl acetateacetonitrile 580.783 253.247 0.1997 Methanol 0.9152 0.1198 0.5346
Acetonitrile 0.9176 0.0605 0.3991
Binary coefficients for UNIQUAC model (cal/mol) Water 0.7028 0.2481 0.1265
n-Hexaneethyl acetate 371.892 133.73 0.1754 0.0324
n-Hexanemethanol 1451.225 7.831
Ethyl acetatemethanol 770.688 147.777 Nitromethane 0.9356 0.0893 0.2464 -
n-Hexanewater 2292.190 324.669
Ethyl acetatewater 768.058 214.271
n-Hexanenitromethane 1080.270 7.335 mixture n-hexaneethyl acetate-entrainer displayed in Fig. 1
Ethyl acetatenitromethane 181.416 42.973 indicate the temperature and the topological stability of all
singular points. As the heteroazeotropes are unstable nodes,
add a homogeneous minimum boiling azeotrope with ethyl they are recovered in the decanter where the phase rich in
acetate. Nitromethane forms a zeotropic mixture with ethyl one of the original components LW is removed as distillate,
acetate, whereas water is the only component that forms an whereas the other original component is retained into the
additional heterogeneous azeotrope with ethyl acetate and still at the process end. In some cases, the composition of the
also adds a heterogeneous ternary azeotrope to the result- phase rich in original component defined by the liquidliquid
ing mixture. Experimental liquidvapour equilibrium data equilibrium at the decanter temperature may not meet purity
are available for all binary entrainer- ethyl acetate mixtures requirements; then, further distillation tasks are needed.
[11]. However, for the binary system entrainer-n-hexane that One of the key thermodynamic parameter in heteroge-
exhibits a significant miscibility gap, the only experimental neous batch distillation is the decanter split ratio . It is de-
thermodynamic information is given in Table 1, except for fined by the position of the heteroazeotrope composition on
methanol for which liquidvapour equilibrium data were re- its liquidliquid tie line at the decanter temperature or alter-
ported by Gmehling et al. [11]. All previous experimental natively by the mole ratio of the entrainer-rich phase LR to
data are used to regress binary interaction parameters for the the overall liquid phase Lo into the decanter as follows:
UNIQUAC and NRTL models with ChemCAD IV minimiz- LR = Lo (1)
ing the mean square deviation between the experimental and
calculated mole fraction in the liquid-phase (Table 2). Then, Then, the molar quantity of entrainer-weak/original
ternary liquidliquidvapour equilibrium is determined by component-rich phase LW is given by equation (2):
using these binary coefficients with BibPhyAddIn [10]. As LW = (1 )Lo (2)
a result of the use of these binary interaction parameters
regressed on binary systems to predict the behavior of a As stated by Rodriguez-Donis et al. [6], the reflux policy
ternary system, we have detected the existence of the ex- to be used is strongly influenced by the split ratio at the
perimental heterogeneous ternary azeotrope in the mixture decanter. If the liquid reflux needed at the top of the column
n-hexaneethyl acetatewater, which has the lower boiling is lower than LR , then the distillation can be performed by
point in the system (unstable node). using only the reflux of entrainer-rich phase. Otherwise, the
For the synthesis of heterogeneous batch distillation separation of original components requires the reflux of a
the liquidliquid envelope at the decanter temperature is combination of both decanted phases.
considered in addition to the residue curve map. There- Nitromethane shows the simplest residue curve map with
fore, the binary interaction parameters used in predicting one unstable curved separatrix dividing the triangle in two
liquidliquid equilibrium are estimated from binary hetero- basic distillation regions. Methanol and acetonitrile give rise
geneous azeotrope or liquidliquid equilibrium data [8,10]. two binary azeotropic mixtures and three distillation regions
Table 3 shows the calculated purity of original compo- that are bounded by two unstable curved separatrices. Water
nents in each phase split at 25 C for all heterogeneous shows the most complicated residue curve maps, due to the
azeotropes reported in Table 1. The thermodynamic mod- presence of a ternary azeotrope and a miscibility gap with
els and binary coefficients used in the calculation of the both the n-hexane and the ethyl acetate component. In all
liquidliquidvapour equilibrium, liquidliquid equilibrium four cases, the heteroazeotrope (binary or ternary) has the
at 25 C and the separatrices are reported in Table 2. lowest boiling temperature of the system. As it can be seen in
From the thermodynamic information given in Tables 13, Table 3, all entrainers except water provide the n-hexane-rich
the residue curve maps are drawn in Fig. 1 for each entrainer phase LW as distillate product with a purity better than 0.91.
and the batch distillation task sequence required to perform Water is not a desirable entrainer because of the existence
the separation of the original components is deduced using of ternary azeotrope whose n-hexane-rich phase has a water
published rules [5]. The residue curve maps of the ternary purity much lower (0.70). Considering in Table 3 the split
134 I. Rodriguez-Donis et al. / Chemical Engineering and Processing 44 (2005) 131137
ratio at the decanter (inside the range 0.30.6) and the (MESH) equations which are solved for the whole column,
purity of both liquid phases at 25 C, methanol and acetoni- decanter included and taking into account the liquidliquid
trile are better entrainers than nitromethane. Methanol is a phase split. Numerical treatment of the Differential Alge-
light entrainer that would result in a ternary system with a braic Equation (DAE) system and discrete events handling is
low boiling temperature that in turn will likely increase the performed with DISCo, a numerical package for hybrid sys-
cost of the condenser cooling system and the make-up of tems with a DAE solver based on Gears method. The col-
fresh entrainer to be added in the next batch. Besides, the umn technical features and operating conditions are shown in
mole ratio of the product-to-be n-hexane in the methanol Table 4. A sequence of two operational batch steps, namely
II
rich phase (xnhexane in Table 3) is higher than the one cal-
culated for the acetonitrile. Therefore, acetonitrile seems the
best entrainer for the separation of n-hexaneethyl acetate Table 4
by heterogeneous azeotropic batch distillation. Operating conditions of heteroazeotropic batch distillation with acetonitrile
Parameters Value
Table 5
Simulation and experimental results (x1 : n-hexane; x2 : ethyl acetate; x3 : acetonitrile)
Simulation results Experimental results
unstable separatrix due to the recycle of both decanted liquid in the composition for all components are found to be 0.1
phases. The reason is that the liquid phase leaving the first and 0.3%, respectively.
tray of the column top has a composition (xT ) inbetween the As shown in Fig. 2, the still path obtained experimentally
heteroazeotrope and the acetonitrile-rich phase composition (circles) is in excellent agreement with the still trajectory
and is located in a distillation region (III) different from re- calculated by simulation. The selected reflux policy permits
gion (I) which contains the still composition at infinite reflux the still path to cross the separatrix into another distillation
FR . Consequently, the simulated still path crosses the un- region than the initial feed region. Hence, the still path is
stable separatrix separating distillation regions I and II (full able to reach the ethyl acetate vertex and this component re-
black line in Fig. 2). At the end of batch step 2, the still mains pure into the still at the end of the distillate removal
path reaches the ethyl acetate vertex when all n-hexane is step. Such a behavior is not possible with a homogeneous
drawn as distillate product. The operating parameters and entrainer that gives rise to a similar residue curve map be-
are set to obtain the binary heteroazeotrope at the column cause the distillation process is restricted to the distillation
top during the whole step 2. Therefore, the split ratio is region where the initial composition of the mixture is lo-
kept constant. The n-hexane-rich phase is drawn as distillate cated. In this case, ethyl acetate could not be obtained as an
product whereas the acetonitrile-rich phase can be recov- isolated product.
ered at the decanter at the end of the step 2. Table 5 reports Table 5 displays the quantity and composition of the main
the simulated purity and recovery yield of all components. streams of the process. n-Hexane is drawn of as distillate
Simulation computation time is typically less than 4 min on product with a molar purity of 96.8%. Another binary batch
a Pentium III-based computer. distillation step is required to obtain n-hexane with a high-
est purity. Ethyl acetate with 99.6% of purity is recovered in
the still at the end of the process, while the acetonitrilerich
4. Experimental verification of the separation of the phase obtained from decanter can be reused in the next batch
mixture n-hexaneethyl acetate by heteroazeotropic distillation process. The make-up of fresh entrainer for the
batch distillation in a bench scale rectification column next cycle of n-hexaneethyl acetate separation is approxi-
mately 52%.
The technical features of the column and the operating
conditions are similar for the experiments and the simula-
tions. The glass SCHOTT distillation column has a total 5. Conclusions
height of 1.7 m and an internal diameter of 0.026 m. The to-
tal height is packed with stainless steel wire mesh rings of Acetonitrile was chosen as a suitable heterogeneous
3 mm 3 mm. The total packed height is considered to be entrainer for the separation of the azeotropic mixture
equivalent to 45 theoretical plates and the total liquid hold n-hexaneethyl acetate by heteroazeotropic batch distil-
goes up of 52.5 ml. The condenser is subcooled at 25 C and lation from the comparison of the residue curve maps of
total liquid reflux is provided at the top of the column by a several candidate entrainers. We have confirmed the feasi-
solenoid valve. The open/close time of the solenoid valve is bility of the heteroazeotropic batch distillation via simula-
defined considering that 70% of the condensed vapour is re- tion and by experimentation in a bench batch distillation
turned to the column. The 30% remaining condensed vapour column. Good agreement was obtained between simulation
is collected into the decanter (70 ml) where the light phase and experimental results. The novel process with a single
is drawn as distillate (n-hexane-rich phase) whereas a por- heterogeneous distillation column shows a great potential
tion of the heavy entrainer-rich phase is recycled to the top over a reported hybrid process with a homogeneous distilla-
of the column with a peristaltic pump. tion column and a liquidliquid extraction column. Indeed,
Experiments taking into account these operating condi- the consumption of entrainer is low and the separation of
tions (Table 4) are carried out in the bench distillation col- all three components can be performed in a single batch
umn and the results are presented in Fig. 2 and Table 5. distillation step using the defined reflux policy. The ethyl
Analysis of the still composition is performed every 0.5 h. acetate purity is high enough to enable its recycling in a
The analysis of purity of the light and heavy phases in the chromatography process whereas the n-hexane-rich phase
decanter and of the distillate product is made at the end of must be purified in a simple non azeotropic batch distillation
the process (4.8 h). The acetonitrile, n-hexane and ethyl ac- process.
etate compositions are determined using a FISONS HRGC
chromatograph with a FID detector and with a column HP
INNOWax (30 m 0.53 mm, 0.25 m film). The injector
References
and detector temperature are held at 180 C while the col-
umn temperature is set equal to 65 C. Prior calibration is
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weighing on a SARTORIUS BP 211D balance with a pre- tures by homogeneous batch distillation, Ind. Eng. Chem. Res 40
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[4] S. Skouras, S. Skogestad, Separation of ternary heteroazeotropic liquid equilibrium of the ternary system ethyl acetate + hexane
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Chem. Eng. Proc. 43 (2004) 291304. 854.
[5] I. Rodriguez-Donis, V. Gerbaud, X. Joulia, Heterogeneous entrainer [10] S.A. ProSim, 2000, http://www.prosim.net, Reference Manual.
selection rules for the separation of azeotropic and close boiling [11] J. Gmehling, U. Onken, VapourLiquid Equilibrium Data Collection,
temperature mixtures by heterogeneous batch distillation, Ind. Eng. DECHEMA Chemistry Data Series, vol. 1, 12 parts, DECHEMA,
Chem. Res. 40 (2001) 49354950. Frankfurt am Main, 1982.
[6] I. Rodrguez-Donis, V. Gerbaud, X. Joulia, Feasibility of heteroge-
neous batch distillation, AIChE J. 48 (2002) 11681178.
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H. Schoenmakers, BASF AG, ZAT-L540, Ludwigshafen, Germany
S. Skogestad, Norwegian University of Science and Technology, Trondheim, Norway
A. Stankiewicz, DSM Research, The Netherlands
K. Sundmacher, Universitaet Magdeburg, Germany
J. Werther, Technische Universitat of Hamburg-Harburg, Hamburg, Germany
K.R. Westerterp, Twente University of Technology, Enschede, The Netherlands
*
1 The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper).
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Chemical Engineering and Processing 44 (2005) 139140
Editorial
Special issue on conveying and handling
of particulate solids
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.001
140 Editorial / Chemical Engineering and Processing 44 (2005) 139140
degradation (R.K. Sahoo and D. Roach, A. Heim et al., V. of fluidized bed process for photo-catalytic degradation of
Mizonov et al., and P.B. Kis et al.). Separation and classi- harmful gas components are described by T.H. Lim and S.D.
fication are inevitable processes in particle technology. M. Kim.
Shapiro and V. Galperin gave a review on various techniques We hope that this special volume offers a good cross-
of separation of particles. The paper of W. McBride and S. section on the professional work of the conference for the
Keys have applied vertical Venturi separator to improve re- readers, giving useful information on the results achieved
cycling of automotive tyres. recently in the field, and will also stimulate the participation
A worldwide revival of research activities nowadays on at the next event to be held in 2006 in Rome.
mixing, blending, homogenization processes of particulate April 2004.
solids is evidenced by three papers. A new pulsated bottom
mixer and its investigation were described by M. Nemenyi Janos Gyenis
and A.J. Kovacs. Process dynamics and homogenization ef- Research Institute of Chemical and Process Engineering
ficiency of mammoth silos were studied by D.L. Schott et University of Veszprem, P.O. Box 158
al. Assessment of homogeneity in powder mixtures by elec- Veszprem 8201, Hungary
trical capacitance measurement was proposed N. Ehrhardt Corresponding author. Tel.: +36 88 425 206
et al., as a good tool to examine segregation during particle fax: +36 88 424 424
flow or the efficiency of a mixer. E-mail address: gyenis@mukki.richem.hu
As a special topic, solids transport in a pilot-scale rotary (J. Gyenis)
kiln was studied and outlined in a paper of N. Descoins et al.
Avi Levy
Finally, two papers give examples on environmental aspects
Ben-Gurion University of the Negev
of this field. A nice overview on dust control and explosions
Beer-Sheva, Israel
in solids handling plants are given P. Wypych et al. with
description of some own experimental results. Application Available online 19 June 2004
Chemical Engineering and Processing 44 (2005) 141151
Abstract
Predrag Marjanovic was born on 1 May, 1951 in Belgrade, Yugoslavia, where he lived until November 1992. He moved with his wife
Mara and daughter Nevena to Glasgow, Scotland, where he continued to reside throughout his time in the UK. I was supervisor of his Ph.D.
programme and colleague in Glasgow for about 5 years. Predrags involvement in research covered a diverse range of topics, including
hydraulic transport, fluid mechanics, bulk material characterisation and hopper design. This review will mostly feature the work undertaken
for his Ph.D. and that associated with pneumatic conveying. A definitive list of Predrags references, however, is appended. Predrag died
suddenly on 14 September, 2001.
2004 Elsevier B.V. All rights reserved.
Keywords: Fluid mechanics; Hopper design; Vertical pipeline; Pneumatic conveying; Inclined pipeline; Pipeline bends; Rubber hose; Dense phase
Predrag obtained a 1st class Honours degree in Mechan- A high-pressure (7 bar gauge) top discharge blow tank
ical Engineering in 1975 from the University of Belgrade. having a 1 m3 capacity was made available and a pipeline
He then joined the Fluid Mechanics Department of the Uni- was built on the outside wall of the building, which allowed
versity of Belgrade as a teaching assistant, where he was a 17 m vertical rise. With a need to re-circulate materials for
employed for 18 years, rising to the position of Associate test purposes it was necessary to run the pipeline both up
Professor. During this time he obtained an M.Sc. with dis- and down the wall to complete the circuit. It was decided,
tinction in Process Engineering. His M.Sc. was on the Ex- therefore, to investigate pneumatic conveying performance
perimental Determination of GasSolids Friction Factors. In in both the vertically up and vertically down sections of the
these early years, he also published a number of papers on pipeline as it involved little additional effort in building and
hydraulic conveying with Professor M. Sasic. instrumenting the test facility for the added data. There was
I met Predrag in Belgrade in October 1979, being in- also a lot of interest at the time in the pneumatic conveying
troduced by Dr. Z. Bukerov from the University of Novi of various materials down vertical mine shafts. A sketch of
Sad. Predrag expressed the desire to undertake a Ph.D. pro- the test pipeline facility is provided in Fig. 1.
gramme on pneumatic conveying and particularly wanted Two pipelines, in fact, were built, one of 2 in. nominal
to investigate conveying vertically up in dense phase. There (53 mm actual) bore and another of 3 in. nominal (81 mm ac-
was the opportunity of undertaking such a programme of tual) bore. This was to allow the influence of pipeline bore to
research at Thames Polytechnic (now the University of be additionally investigated. The two pipelines ran alongside
Greenwich) in London, where I was a Senior Lecturer in one another and so the pipeline routing and geometry was
the Department of Mechanical Engineering, and Professor almost identical for the two pipelines. The pipelines were
Stan Mason was Head of Department. Predrag obtained built on the rear wall of the building and this had a fire escape
sabbatical leave from the University of Belgrade and came access with a large platform. As a consequence, because of
to London early in 1982. the convenience, it was decided to install sight glasses in the
two pipelines in both the vertically up and vertically down
sections. I had full video facilities available from the UK
Tel.: +44 1227 732493; fax: +44 1227 732504. Department of Trade and Industry for the research work.
E-mail address: drdavid.mills@btinternet.com (D. Mills).
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.002
142 D. Mills / Chemical Engineering and Processing 44 (2005) 141151
Fig. 5. Conveying characteristics for cement in 81 mm bore pipeline. Fig. 7. Pressure gradient for cement in 53 mm bore vertically up pipeline.
144 D. Mills / Chemical Engineering and Processing 44 (2005) 141151
Fig. 10. Pressure gradient for pulverised fuel ash in 81 mm bore vertically
Fig. 8. Pressure gradient for barytes in 81 mm bore vertically up pipeline.
down pipeline.
6. Pipeline bends
7. Pipeline material
8. Glasgow
9. Inclined pipelines
12. What could have come [15] D. Mills, J.S. Mason, P. Marjanovic, A comparison of pressure drops
in horizontal and vertical dense phase pneumatic conveying, Proceed-
ings of the 3rd International Conference on Pneumatic Conveying,
We are naturally left wondering what might have been Pecs, Hungary, March 1985.
achieved with so many more years that should have been his, [16] D. Mills, P. Marjanovic, J.S. Mason, An analysis of line pressure
to spend on the loves of his life: his family and his research gradient for dense phase vertical gassolids flow, Proceedings of the
work, and not forgetting the golf that he discovered in his GAMM Congress, Dubrovnik, Yugoslavia, April 1985.
new home in Scotland. Thank you for being such a valued [17] P. Marjanovic, D. Mills, J.S. Mason, An investigation of high con-
centration vertical pneumatic conveying, J. Procesna Tehnika, vol. 1,
colleague and friend. You will be long remembered by us
no. 2, Belgrade, Yugoslavia, December 1985, pp. 3949 (in Serbian).
all. [18] P. Marjanovic, On the choking velocity for vertical pneumatic con-
veying, Proceedings of the 17th Yugoslav Congress of Theoretical
and Applied Mechanics, Zadar, Yugoslavia, 1986 (in Serbian).
Further reading [19] P. Marjanovic, The design of vertical pneumatic conveying using
high-pressure blow tank system, Proceedings of the International
Colloquium on Modern Trends in the Development of Pneumatic
References and publications Conveying, Sarajevo, Yugoslavia, June 1986, pp. 4564.
[20] P. Marjanovic, D. Mills, J.S. Mason, A method of calculating
[1] P. Marjanovic, M. Sasic, Hydraulic transport of ash in thermo- flow parameters for pneumatic conveying in pipelines, Proceedings
power stations, Proceedings of the 4th Yugoslav Thermal Symposium, of the Pneumatech 3, PAC Conference, Jersey, UK, March 1987,
Belgrade, Yugoslavia, 1975 (in Serbian). pp. 143167.
[2] M. Sasic, P. Marjanovic, On the methods for calculation of hydraulic [21] P. Marjanovic, I. Vuskovic, L. Bodiroga, Hydraulic Transport of
transport and their reliability in practice. Part 1, Proceedings of the granular activated carbon in water refinery plant, Symposium on
5th International Conference on Hydraulic Transport of Solids in Water Supply, Belgrade, Yugoslavia, 1987 (in Serbian).
Pipes, vol. 1, Hanover, Germany, 1978, pp. A5:61A5:76. [22] P. Marjanovic. Bends in gassolids mixture flow in pipes a view to
[3] M. Sasic, P. Marjanovic, On the methods for calculation of hy- the prediction of pressure loss, GAMM Congress, Vienna, Austria,
draulic transport and their reliability in practice. Part 2, 5th Interna- 1988.
tional Conference on Hydraulic Transport of Solids in Pipes, vol. 2, [23] P. Marjanovic, Analysis of the change of flow parameters in dis-
Hanover, Germany, 1978, pp. X2X3. continuous pneumatic conveying systems, Proceedings of the 18th
[4] P. Marjanovic, Experimental determination of gassolids friction fac- Yugoslav Congress of Theoretical and Applied Mechanics, Vrnjacka
tor, M.Phil. Thesis, University of Belgrade, Yugoslavia, 1978 (in Banja, Yugoslavia, 1988, pp. 8992 (in Serbian).
Serbian).
[24] P. Marjanovic, Determination of performance characteristics of dilute
[5] M. Sasic, P. Marjanovic, Hydromechanics of gassolid systems, Jnl
phase pneumatic conveying system, Proceedings of the 3rd Sympo-
Tehnika-Masinstvo, no. 6, Belgrade, Yugoslavia, 1979, pp. 19 (in
sium of Process Industry Applications, Belgrade, Yugoslavia, 1988,
Serbian).
pp. 215223 (in Serbian).
[6] P. Marjanovic, J. Jovanovic, R. Askovic, Sur lecoulement dun
[25] P. Marjanovic, A comparison between pneumatic and hydraulic con-
liquide conducteur dans la region dentree un tube circulaire en
veying, Proceedings of the 19th Yugoslav Congress of Theoretical
presence dun champ magnetique. Publ. of Mathematical Institute
and Applied Mechanics, Ohrid, Yugoslavia, 1990, pp. 6166 (in Ser-
SANU, new series, vol. 3, no. 11, Belgrade, Yugoslavia, pp. 7580.
bian).
[7] M. Sasic, P. Marjanovic. One more general approach for investigation
[26] P. Marjanovic, D. Mills, J.S. Mason, The influence of bends on the
of hydro-mechanics of two-component systems, J. Powder Bulk
performance of a pneumatic conveying system, Proceedings of the
Solids Tech. 5 (1) (1981) 1319.
15th Powder and Bulk Solids Conference, Chicago, USA, June 1990,
[8] M. Sasic, P. Marjanovic, Non-isothermal compressible flow in pipes,
pp. 391399.
ZAMM 62 (1982) 226228.
[9] P. Marjanovic, A comparative study of performance characteristics for [27] P. Marjanovic, D. Mills, J.S. Mason, The influence of pipeline ma-
horizontal and vertical pneumatic conveying in pipelines, Proceedings terial on the performance of pneumatic conveying systems, Proceed-
of the Pneumatech 1. PAC Conference Stratford-upon-Avon, UK, ings of the Pneumatech 4, Glasgow, UK, June 1990, pp. 453464.
1982. [28] N. Barbalic, P. Marjanovic, E. Dzaferovic, Z. Mujcinovic, A. Cam-
[10] D. Mills, J.S. Mason, P. Marjanovic, Pneumatic conveying vertically para, Measurement of P.F. ash pneumatic conveying system parame-
down. Proceedings of the 8th Powder and Bulk Solids Conference, ters in thermo-power station Ugljevik-1, J. Procesna Tehnika, vol.
Atlanta, USA, May 1983, pp. 546557. 7, no. 1, Belgrade, Yugoslavia, 1991, pp. 2326 (in Serbian).
[11] D. Mills, J.S. Mason, P. Marjanovic, An analysis of the dense phase [29] P. Marjanovic, M. Stanojevic, B. Todorovic, A. Vlajcic, The influ-
pneumatic conveying of cement in vertical pipelines. Proceedings of ence of variable operating conditions on the design and exploitation
the 9th Powder and Bulk Solids Conference, Chicago, USA, May of air-slide systems in thermo-power stations, Proceedings of the
1984, pp. 125147. RelPowFlo 2, EFChE Publication Series no. 96, Oslo, Norway, 1993,
[12] D. Mills, J.S. Mason, P. Marjanovic, The influence of pipeline pp. 659671.
bore on dense phase pneumatic conveying in vertical pipelines. [30] P. Marjanovic, Modelling the transient behaviour of blow tank pneu-
Proceedings of the 16th Yugoslav Congress on Theoretical and matic conveying system. Powder handling and processing, Trans.
Applied Mechanics, Becici, Yugoslavia, May/June 1984, pp. 261 Tech. Pub. 5 (3) (1993) 219226.
269. [31] P. Marjanovic, Pneumatic conveying in an inclined pipeline: inappro-
[13] P. Marjanovic, An investigation of the behaviour of gassolids mix- priate, unfortunate or wrong concept? Proceedings of the 19th Powder
ture flow properties for vertical conveying in pipelines, Ph.D. Thesis, & Bulk Solids Conference, Chicago, USA, May 1994, pp. 235251.
CNAA, Thames Polytechnic, London, UK, 1984. [32] P. Marjanovic, D.J. Mason, Gassolid flows in an inclined pipeline,
[14] D. Mills, J.S. Mason, P. Marjanovic, The influence of product type Proceedings of the 1st International Particle Technology Forum, vol.
on dense phase pneumatic conveying in vertical pipelines, Proceed- 3, Denver, USA, August 1994, pp. 466471.
ings of the Pneumatech 2, Powder Advisory Centre Conference, [33] P. Marjanovic, Assessing the flow properties of powdered materials,
Canterbury, UK, September 1984, pp. 193210. IMechE Seminar on Hoppers and Silos, London, UK, 1994.
150 D. Mills / Chemical Engineering and Processing 44 (2005) 141151
[34] P. Marjanovic, V. Djordjevic, On the compressible flow losses through [52] T. Mooney, A. Levy, P. Marjanovic, D.J. Mason, An investigation
abrupt enlargements and contractions, J. Fluids Eng. Trans ASME of gassolids flow through inclined pipes, Proceedings of the 1997
116 (1994) 756762. Jubilee Research Event, vol. 1, Nottingham, UK, 1997, pp. 425428.
[35] P. Marjanovic, D. Geldart, J.L.R. Orband, T. Mooney, A comparative [53] P. Marjanovic, M.G. Jones, G. Welford, Pneumatic conveying of
analysis of two hopper design methods, Proceedings of the Interna- solids at high system pressures, J. Powder/Bulk Solids Technol. 1 (1)
tional Congress for Particle Technology PARTEC 95, Nrnberg, (1997) 37.
Germany, March 1995, pp. 6978. [54] P. Marjanovic, M. McGarvey, R.B. McKay, Development of lab-
[36] B. Armstrong, M.G. Jones, P. Marjanovic, G. Welford, P.J. Blenkin, oratory methodology to determine flow properties of organic pig-
R.G. Holder, An evaluation of the effects of high system pressure ment powders, Proceedings of the 2nd Israel Conference for Con-
on the performance of pneumatic coal conveyors, Proceedings of the veying and Handling of Particulate Solids, Jerusalem, Israel, 1997,
20th International Conference on Coal Utilization & Fuel Systems, pp. 2.282.33.
Clearwater, USA, 1995, pp. 393403. [55] A. Levy, T. Mooney, P. Marjanovic, D.J. Mason, Analytical, Nu-
[37] T. Mooney, P. Marjanovic, Bend pressure loss in a pneumatic con- merical and experimental investigations for gassolid flow through
veying system, Proceedings of the 20th Powder & Bulk Solids Con- straight pipe of different inclinations, Proceedings of the 2nd Is-
ference, Chicago, USA, May 1995, pp. 6173. rael Conference for Conveying and Handling of Particulate Solids,
[38] P. Marjanovic, G. Welford, M.G. Jones, Pneumatic conveying of coal Jerusalem, Israel, 1997, pp. 4.304.35.
against high back pressures, Proceedings of the 12th International [56] D.J. Mason, A. Levy, P. Marjanovic, The influence of bends on the
Pittsburgh Coal Conference, Pittsburgh, USA, September 1995. flow of gas-solids mixtures through pipelines, Proceedings of the
[39] M.G. Jones, P. Marjanovic, G. Welford, The prediction of pneumatic 2nd Israel Conference for Conveying and Handling of Particulate
conveying performance when conveying into back pressures up to Solids, Jerusalem, Israel, 1997, pp. 4.364.41.
20 bar, Proceedings of the 1st International Conference BULK ASIA, [57] P. Marjanovic, D.J. Mason, Gas solids flow in an inclined pipeline.
Singapore, 1995, pp. 107115. Powder handling and processing, Trans. Tech. Pub. 9 (3) (1997)
[40] R.J. Hitt, P. Marjanovic, A computer technique to develop a model 217220.
of vertical dense phase gassolids flow from experimental data. [58] A. Levy, T. Mooney, P. Marjanovic, D.J. Mason, A comparison of
Proceedings of the 1st International Symposium on Two-Phase Flow analytical and numerical models with experimental data for gassolid
Modelling and Experimentation, vol. 1, Rome Italy, October 1995, flow through a straight pipe at different inclinations, Powder Technol.
pp. 6774. 93 (1997) 253260.
[41] P. Marjanovic, M.G. Jones, Assessment of a new technique for [59] D.J. Mason, P. Marjanovic, A. Levy, A simulation system for pneu-
measuring flow properties of powdered materials stored in hoppers, matic conveying systems, Powder Technol. 95 (1998) 714.
IMechE J. Process. Mech. Eng. 210 (1996) 18.
[60] D.J. Mason, A. Levy, P. Marjanovic, The influence of bends on the
[42] P. Marjanovic, Theoretical and practical silo design, Seminar on
performance of pneumatic conveying systems, Adv. Powder Technol.
Storage and Transportation of Bulk Solids, Moreton-in-Marsh, UK,
9 (3) (1998) 197206.
March 1996.
[61] D.J. Mason, P. Marjanovic, Re-Visit of the fundamental definitions
[43] M.G. Jones, P. Marjanovic, Maintaining product quality in pneumatic
of fluid-solids flow properties in freight pipelines, Proceedings of
conveying, Proceedings of the Conveyorex 96 Seminar, Harrogate,
the 9th International Symposium on Freight Pipelines, Monterrey,
UK, April 1996.
Mexico, April 1998.
[44] P. Marjanovic, G. Welford, M.G. Jones, Pneumatic conveying of
[62] P. Marjanovic, A. Levy, D.J. Mason, An investigation of the flow
solids at high system pressures, Proceedings of the 21st Powder &
structure through abrupt enlargement of circular pipe, Proceedings
Bulk Solids Conference, Chicago, USA, May 1996, pp. 9198.
of the 9th International Symposium on Freight Pipelines, Monterrey,
[45] M.G. Jones, P. Marjanovic, The modification of material properties
Mexico, April 1998.
for improved flow characteristics, Proceedings of the Seminar on
Solving Problems in Hopper and Silo Systems, IMechE, London, [63] P. Marjanovic, M. McGarvey, R.B. McKay, Development of labora-
UK, June 1996. tory methodology to determine flow properties of organic pigment
powders. Powder handling and processing, Trans. Tech. Pub. 10 (2)
[46] P. Marjanovic, D.J. Mason, T. Mooney, The Performance of a pneu-
(1998) 151154.
matic conveying system which incorporates an inclined pipeline sec-
tion, Proceedings of the 1st International Conference on Pneumatic [64] M.G. Jones, P. Marjanovic, The influence of rotary valve air leakage
and Hydraulic Conveying Systems, Florida, USA, 1996. on pneumatic conveying system performance, Proceedings of the
[47] D.J. Mason, P. Marjanovic, A. Levy, A simulation system for pneu- 23rd Powder & Bulk Solids Conference, Chicago, USA, May 1998,
matic conveying systems, Proceedings of the 1st International Con- pp. 231239.
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[49] D.J. Mason, A. Levy, P. Marjanovic, Modelling the influence of bends [67] P. Marjanovic, D. Geldart, J.L.R. Orband, Techniques for assess-
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[50] A. Levy, P. Marjanovic, D.J. Mason, A Comparison of analytical the flow of gas-solids mixture trough pipelines, Proceedings of the
and numerical models for gas-solid flow through straight pipe of World Congress on Particle Techn 3, Brighton, UK, July 1998.
different inclinations with experimental data, Proceedings of the 12th [69] M.G. Jones, P. Marjanovic, D. McGlinchey, R. McLaren, Segregation
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Czech Republic, August 1996. 6th International Conference on Bulk Material Storage, Handling
[51] P. Marjanovic, Determination of bulk solids indices using the Johan- and Transportation, Wollongong, Australia, September 1998.
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Manchester, UK, December 1996, pp. 233238. tory methodology to determine flow properties of organic pigment
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London, UK, November 1998. fects in Pneumatic conveying, IMechE Conference Transactions, June
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of the 2nd International Conference on Pneumatic and Hydraulic Proceedings of the 16th International Conference on Material Flow,
Conveying Systems. UEF Conf. Davos, Switzerland, June 1999. Machines and Devices in Industry, Belgrade, Yugoslavia, December
[73] P. Marjanovic, E. McGee, Determination of powder flow properties 2000, pp. 2025.
using different shear cells, Proceedings of the RelPowFlo 3, Pors- [83] J.S. Xiang, P. Marjanovic, Modelling and simulation for pyroflow
grunn, Norway, August 1999, pp. 151158. type circulating fluidised bed boiler, Proceedings of the Interna-
[74] M.G. Jones, P. Marjanovic, D. McGlinchey, D. Morrison, Investiga- tional Congress for Particle Tech PARTEC 2001, Nrnberg, Ger-
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[75] P. Marjanovic, A. Levy, D.J. Mason, An investigation of the flow Bulk 2001 Technical Awareness Seminar, Manchester, UK, April
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[76] P. Marjanovic, M. McGarvey, R.B. McKay, Determination of the and uprating of discontinuous pneumatic conveying system perfor-
influence of surface coating and particle size on flow properties of mance through on-site measurement, Proceedings of the 6th World
organic pigment powders, Proceedings of the 3rd Israel Conference Congress of Chemical Engineering, Melbourne, Australia, September
for Conveying and Handling of Particulate Solids, Dead Sea, Israel, 2001.
vol. 1, May 2000, pp. 3.393.44. [86] J. Li, P. Marjanovic, J.S. Xiang, E.A. Knight, An experimental tech-
[77] M.G. Jones, P. Marjanovic, D. McGlinchey, An investigation of nique for the analysis of plugs travelling through pneumatic pipelines
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the 3rd Israel Conference for Conveying and Handling of Particulate Transportation, Newcastle, Australia, October 2001.
Solids, vol. 2, The Dead Sea, Israel, May 2000, pp. 10.9310.101. [88] J.S. Xiang, P. Marjanovic, Hydrodynamic model of gas-solid flow
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regation in pneumatic conveying lines, IMechE Conference Trans- Conference on Bulk Materials Storage, Handling and Transportation,
actions, June 2000, pp. 331340. Newcastle, Australia, October 2001, pp. 825832.
Chemical Engineering and Processing 44 (2005) 153157
Received 30 September 2003; received in revised form 25 February 2004; accepted 19 March 2004
Available online 20 June 2004
Abstract
A gas flow pattern in the regime of jet spouted bed (or dilute spouted bed) has been analyzed in conical spouted beds using materials of
different density and particle diameter. The experimental results have been fitted to an empirical equation for calculation of the interstitial
velocity at the contactor axis in jet spouted beds. The general equation proposed relates this property to the geometric factors of the contactor
(angle, ; and inlet diameter, Do ) and to the operating variables (particle size, dp ; particle density, s ; particle shape, ; stagnant bed height,
Ho ; and air relative velocity referred to that minimum spouting, uo /uoms ).
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.011
154 M.J. San Jose et al. / Chemical Engineering and Processing 44 (2005) 153157
2. Experimental
Table 1
Properties of the solids used
Material s dp o Geldart
(kg/m3 ) (mm) classification
Glass beads 2420 1.0 1 0.322 B
2420 2.0 1 0.328 D
2420 3.0 1 0.345 D
2420 3.5 1 0.351 D
2420 4.0 1 0.355 D
2420 5.0 1 0.358 D
Polypropylene 890 3.5 0.90 0.390 D
Extruded polystyrene 1030 1.0 0.80 0.395 B
1030 2.0 0.80 0.385 D
1030 3.5 0.80 0.380 D
Expanded polystyrene 65 3.5 0.95 0.507 D
Sawdust 242 1.0 0.90 0.324 B
242 1.5 0.90 0.328 D
242 2.0 0.90 0.330 D Fig. 4. Evolution with the dimensionless position in the bed, *, of the
vertical component of the gas interstitial velocity at the axis, uj (0), in jet
spouting regime. = 36 , Do = 0.04 m, Ho = 0.23 m for the different
materials of particle diameter dp = 3.5 mm.
Acknowledgements
Fig. 5. Map of gas interstitial velocity vector in jet spouting regime. Appendix A. Nomenclature
= 36 , Do = 0.04 m, Ho = 0.23 m and extruded polystyrene of particle
diameter dp = 3.5 mm.
Ar Archimedes number gdp3 g (s g )/2
As cross-sectional area of the spout (m2 )
36 , Do = 0.04 m, Ho = 0.23 m and extruded polystyrene dp particle diameter (m)
dp = 3.5 mm. The length of the arrows is proportional to Db , D c , D i , D o diameter of the upper level of the
the value of the corresponding velocity vector modulus. stagnant bed, of the column, of the bed
From the results it has been proven for all the experimen- base and of the inlet, respectively (m)
tal systems studied that the flow rate is constant along the g gravity constant (m s2 )
streamtubes defined in the annular zone, such as has been Hc , Ho height of the the conical section of the
proposed in the model. contactor, and of the stagnant bed,
In order to solve the model conservation equations, only respectively (m)
the knowledge of the average interstitial velocity in the r, z radial and longitudinal coordinates (m)
spout zone at each level, us , is required. This is calculated R contactor radius at z height (m)
as: (Reo )mj Reynolds modulus of minimum jet
1 1 Do /2 spouting referred to Do
us = u dAs = 2ur dr (7) u, uj (0), uj , uw vertical component of interstitial velocity,
As As 0
maximum velocity at the axis, at any
The values of us calculated using Eq. (7) are very similar position and at the contactor wall (m s1 )
(differ in less than 3%) to the values of velocity at the axis ur , us radial component of interstitial velocity
uj (0) for beds of sawdust and expanded polystyrene. Conse- and vertical component of the average
quently, the velocity profile in the spout zone is almost flat interstitial velocity in the spout at z level,
in beds of these solids. Nevertheless, for beds of glass beads respectively (m s1 )
and extruded polystyrene the velocity profiles in the spout u ratio between velocity and minimum
zone are more pronounced. spouting velocity, dimensionless
Greek letters
4. Conclusions o bed voidage of the static bed,
dimensionless
In jet spouted bed regime in conical spouted bed, the gas particle shape factor
interstitial velocity at the axis, uj (0), decreases as the dimen- contactor angle (deg)
sionless longitudinal position at the axis, , increases; be- viscosity (kg m1 s1 )
M.J. San Jose et al. / Chemical Engineering and Processing 44 (2005) 153157 157
, N , o longitudinal spherical coordinates, [10] J. Bilbao, M. Olazar, A. Romero, J.M. Arandes, Optimization of
the operation in a reactor with continuous catalyst circulation in the
maximum and minimum longitudinal
gaseous benzyl alcohol polymerization, Chem. Eng. Commun. 75
spherical coordinates (m) (1989) 121134.
g , s , v density of the gas, of the solid and of [11] O. Uemaki, T. Tsuji, in: K. Ostergaard, A. Sorensen (Eds.), Flu-
the glass beads, respectively (kg m3 ) idization V, Engineering Foundation, New York, 1986, p. 497.
dimensionless longitudinal spherical [12] O. Uemaki, T. Tsuji, in: Proceedings of the 41st Canadian Chem-
ical Engineering Conference, Vancouver, BC, CSChE Publications
coordinate, ( o )/(N o ) Department, Ottawa, Canada, 1991, pp. 117.
parameter of Eq. (2) (m). [13] T. Tsuji, T. Shibata, K. Yamaguchi, O. Uemaki, in: Proceedings of
International Conference on Coal Science, vol. I, 2327 October
1989, Tokyo, p. 457.
[14] J. Lede, H.Z. Li, J. Villermaux, Le Ciclon reactor. Partie I: measure
References directe de la distribution des temps de sjour de la phase Gaseuze-
Lois dExtrapolation, Chem. Eng. J. 42 (1989a) 3755.
[1] A. Markowski, W. Kaminski, Hydrodynamic characteristics of jet [15] J. Lede, K.B. Mathur, J. Villermaux, Le Ciclon reactor. Partie II:
spouted beds, Can. J. Chem. Eng. 61 (1983) 377381. measure directe de la distribution des temps de sjour de la phase
[2] M. Olazar, M.J. San Jos, A.T. Aguayo, J.M. Arandes, J. Bilbao, Solide-Lois dExtrapolation, Chem. Eng. J. 42 (1989b) 103117.
Stable operation conditions for gassolid contact regimes in conical [16] T.A. Gauthier, C.L. Briens, M.A. Bergougnou, P.A. Galtier, Distri-
spouted beds, Ind. Eng. Chem. Res. 31 (1992) 17841792. bution des temps de sejour du gaz dans un cyclone a co-courant,
[3] M. Olazar, M.J. San Jos, A.T. Aguayo, J.M. Arandes, J. Bilbao, Rcents Progrs en Gnie des Procds La Fluidisation 5 (1991)
Design factors of conical spouted beds and jet spouted beds, Ind. 185192.
Eng. Chem. Res. 32 (1993) 12451250. [17] R.K. Stoecker, A. Rastogi, L.A. Behie, W.Y. Svreck, M.A. Bergoug-
[4] M.J. San Jos, Operation regimes in conical spouted beds. Stability nou, A computer simulation of propane cracking in a spout-fluid bed
conditions and hydrodynamics, Ph.D. Dissertation, University of the reactor with draft tube, in: K. Ostergaard, A. Sorensen (Eds.), Flu-
Basque Country, Bilbao, Spain, 1991. idization V, Engineering Foundation, New York, 1986, pp. 465472.
[5] M.J. San Jos, M. Olazar, A.T. Aguayo, J.M. Arandes, J. Bilbao, [18] R.K. Stoecker, J.H. Eng, W.Y. Svreck, L.A. Behie, Ultrapyrolysis
Design and hydrodynamics of conical jet spouted beds, Rcents of propane in a spouted-bed reactor with a draft tube, AIChe J. 35
Progrs en Gnie des Procds, La Fluidisation 5 (1991) 146153. (1989) 16171624.
[6] M.J. San Jos, M. Olazar, A.T. Aguayo, J.M. Arandes, J. Bilbao, in: [19] D. Sonnet, S. Afara, C.L. Briens, J.F. Large, M.A. Bergougnou, 1988.
D. Behrens (Ed.), Gassolid contact regimes in conical spouted beds, Micromixing of particles in an ultra-rapid fluidized (URF) reactor,
Proceedings of the Fourth World Congress of Chemical Engineering, in: P. Basu, J.F. Large (Eds.), Circulating Fluidized Bed Technology
Fluidization Session, Chemische Technik und Biotechnologie e.V., II, Pergamon Press, Oxford.
Frankfurt am Main, Germany, 1991, pp. 9.513. [20] A. Tamir, Process and phenomena in impinging-stream reactors,
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Hydrodynamics correlations of conical jet spouted beds, in: O.E. [21] M.J. San Jos, M. Olazar, F.J. Peas, A.T. Aguayo, J.M. Arandes,
Potter, D.J. Nicklin (Eds.), Fluidization VII, Engineering Foundation, J. Bilbao, A model for gas flow in jet spouted beds, Can. J. Chem.
New York, 1992, pp. 831838. Eng. 71 (1993) 189194.
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(1993) 4552. 1986.
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of a jet spouted bed reactor with continuous catalyst feed in the benzil Bilbao, Correlation for calculation of the gas dispersion coefficient
alcohol polymerization, Ind. Eng. Chem. Res. 26 (1987) 12971304. in conical spouted beds, Chem. Eng. Sci. 50 (1995) 21612172.
Chemical Engineering and Processing 44 (2005) 159166
Received 23 June 2003; received in revised form 4 April 2004; accepted 15 April 2004
Available online 2 July 2004
Abstract
The aim of this work is to estimate more accurately fugitive dust emissions due to wind erosion of exposed aggregate storage piles. The
model constructed allows to quantify the temporal evolution in the mass flux when a bed of materials is exposed to a turbulent flow. It is based
on the interaction between particles take-off and wall turbulence. The model allows as well to take into account materials having a wide size
distribution, which is typical of materials such as coal or ore. Some experimental studies have shown a temporal decrease in the mass flux as
the bed contains a wide range of particle sizes. This decrease, due to large particles, is predicted by the model. The rate depends on the flow
velocity and the characteristics of the particles.
2004 Elsevier B.V. All rights reserved.
Keywords: Fugitive dust emissions; Wind erosion; Particle take-off; Mass flux
1. Introduction out in a wind tunnel with coal and ore, that the emitted mass
flux of particles decreases with time. He remarked the very
Atmospheric diffuse dust emissions constitute a pollution fast take-off of fine particles staying at the bed surface, then
source, which is difficult to be quantified. In fact, a diffuse the increasingly difficult take-off of the particles being be-
emission is defined as a polluting atmospheric flux which low. This can be explained by the presence of coarse par-
is spread out over a large area or which is not concentrated ticles close to the surface, which dont take-off because of
[1]. In the case of steelwork sites, diffuse dust emissions can their inertia. These large particles constitute a cover and this
represent many as 20% of airborne particle pollution, they phenomenon is called the pavement. The pavement of the
result from conveyances and handling of materials and from bed, which is inherent to the wide size distribution of parti-
wind erosion of exposed aggregate storage piles. This latter cles (especially to the presence of non-erodible particles at
category of emission source is widely predominant. the bed surface), generates a temporal decrease in emitted
The aims of the investigations presented in this paper are mass flux.
to estimate accurately fugitive dust emissions resulting from The temporal decrease in emitted mass flux in the case of
wind erosion. Thus, a model which allows to quantify emis- particles with a wide size distribution has been shown by a
sions resulting from an exposed particle bed to a turbulent few experimental studies [35]. These authors assume that
flow has been developed. Its originality is to take into ac- the temporal decrease in emitted flux is due to modifica-
count the wide particle size distribution of materials used, tion of soil surface during wind erosion. These experimen-
as example, at steelwork sites. Typically, the finer particles tal studies underline the importance to consider the tempo-
can have a size of about 10 m and the larger running to ral evolution of the emitted mass flux in order to accurately
centimetres. This characteristic is very important. In fact, estimate particles emissions with a wide size distribution.
Meunier [2] observed for various experimental tests carried The first part of the present work describes the wind ero-
sion model of a horizontal particle bed. A simple test of the
model is presented in the second part, which reports the in-
Corresponding author. Tel.: +33 3 2771 2379; fax: +33 3 2771 2915. fluence of a wide size distribution on the emitted mass flux
E-mail address: harion@ensm-douai.fr (J.-L. Harion). of particles.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.007
160 I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166
2. Wind erosion model of a particle bed the wall region of the turbulent boundary layer. Blackwelder
and Haritonidis [9] have shown that the average periodicity
2.1. Aerodynamic entrainment modelling of occurence is given by TB + 250 whose expression is:
TB u2
The modelling of aerodynamic entrainment is based on TB+ = (2)
the close link between particles take-off and turbulent co-
herent structures above the surface. In fact, some authors So the time step of the model is equal to TB .
[6,7] have experimentally observed that a particle take-off
can be associated to the ejection of fluid from the wall re- 2.2. The take-off criterion
gion due to the presence of streamwise counter rotating vor-
tices. If it is assumed that the presence of two streamwise Before the take-off criterion, a size range of representa-
counter rotating vortices produces only one ejection, each tive diameter Dp is selected randomly from the total number
pair of streamwise vortices is considered as a possibility that of size ranges of the particle size distribution. The take-off
a particle takes-off. Thus, for each of these possibilities, a criterion, which is established from the balance of forces
take-off criterion is tested. exerted on a particle lying at a flat surface, requires the
The vortex structures appear with statistical spatial peri- lift force from the flow to exceed the forces holding the
odicities, whose values are dependent on the flow properties particle down, namely the adhesive forces and the particle
and velocity, and on the presence or not of particles. Jimenez weight. The expression of the lift force used in the model
and Moin [8] have obtained, by numerical simulations, the is given by the experimental expression of Mollinger and
values of average spatial periodicities of appearing in the Nieuwstadt [10]. They have developed a new technique for
spanwise and streamwise directions of the flow which are measuring the lift force and its fluctuations. Consequently,
respectively, z + 100 and x + 250300. the instantaneous lift force value is equal to the sum of the
The periodicities are adimensionalized with the two scale ,
average lift force Faero and the fluctuating lift force Faero
parameters of the inner layer of the turbulent boundary, the which is selected randomly from its probability density func-
kinematic viscosity and the friction velocity u , by the tion which has been measured by Mollinger and Nieuwstadt
equation: [10]. In the same way, the adhesive force is selected ran-
u domly from its probability density function given by Zimon
+ = (1) [11].
The aerodynamic entrainment model is based on the com-
Although, these values are established in the case of a parison between the distributions of forces holding the par-
smooth wall, they will be considered in the first approxima- ticles on the bed and of the lift force exerted on the particles
tion like the spanwise and streamwise spatial periodicities by the flow. The expression of the take-off criterion is given
of the coherent structures over the particle bed. The parti- for each size range by:
cle bed is thus subdivided into boxes having spanwise and
streamwise sizes given by average spatial periodicities of Faero (Dp ) + Faero (Dp ) P(Dp ) + Fad (Dp ) + Fad (D)
the turbulent coherent structures. Particle take-off
Fig. 1 shows the number of taking-off possibilities over
the bed surface if it is assumed that each box, which contains The take-off test of the model developed in the present
an ejection, is associated with a possibility of taking-off. The study allows to simulate the stochastic nature of the phe-
numbers of possibilities of taking-off along the spanwise nomenon. The establishment of the take-off criterion is de-
and streamwise directions of the bed are equal respectively tailed more precisely in the thesis of Descamps [12].
to l/z and L/x . Consequently, they depend on the flow One of the characteristic parameters of particle take-off
velocity. is the threshold flow velocity, at which particles start to take
The frequency of the take-off criterion, which is tested for off. The threshold flow velocity can be defined from the
each box, is supposed to be equal to the burst frequency in take-off criterion.
Fig. 2 shows the take-off curve obtained by Foucaut [13]. The values of Dpref and Uref are, respectively, (2 / p g)1/3
It traces out the adimensionalized threshold friction velocity and ( p g)1/3 , where p = (p )/ [13]. The take-off
u according to the adimensionalized particle diameter Dp . curve allows to estimate by knowing the adimensional-
These two parameters are given by the following equations: ized friction flow velocity the granulometric slice liable to
take-off. In fact, the diameter noted Dpcrit1 is the diameter
Dp u
Dp = u = (3) from which the particles take-off and the diameter Dpcrit2
Dpref uref
Fig. 3. Integration of the effect of the pavement by diminishing by graduated steps the lift force exerted on a particle.
is the diameter from which the particles dont take-off be- The increment is given by:
cause of their inertia. Thus, if the value of Dpcrit2 is known,
the proportion of non-erodible particles can be determinate. Max pdf(Faeroinitial ) Min pdf(P + Fad )
F aero (Dp ) =
Nerosion (Dp )
2.3. Modelling of the pavement (7)
The temporal decrease in emitted mass flux can be ex- Fig. 3 shows schematically the modelling of the bed pave-
plained by the phenomenon of pavement, which is linked to ment.
the strong inertia particles, which cannot take-off and which This formulation allows to include in the model the lift
form a protection, called cover. It is supposed that these force influence decrease for particles which are in a deeper
non-erodible particles remain at the bed surface, and conse- position in the bed. When the erosion depth is attained, the
quently, overlay it completely from a certain depth, which take-off criterion can no more be respected. Indeed, the val-
is called erosion depth, Eerosion . From this depth, the vortex ues of the probability density functions of the instantaneous
structures bump only particles which they are not able to
entrain. No more take-off is possible.
In order to determinate the erosion depth, we assume that
the particles have a spatial uniform distribution along the
height H of the bed. For each size range, the number of layers
Nc (Dp ) including into the height of the bed is calculated by
dividing the height of the bed by the particle diameter. The
number of particles Npart (Dp ) of each size range, given by
the size distribution of beds particles, is distributed equally
on each layer of the bed:
Npart (Dp )
Np (Dp ) = (4)
Nc (Dp )
For each size range, the value of the lift force is then de-
creased as soon as all the particles of a layer have taken-off. Fig. 5. Algorithm of the model.
I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166 163
lift force are always smaller than the sum of the adhesion The input variables are:
and weight forces. In fact, the maximum of the probability
the exposition time to the turbulent flow, dexpo ;
density function of the lift force is lower than the minimum
the flow velocity, U ;
of the sum of the probability density function of the adhe-
the particles density, the representative diameters of the
sion force and the weight force.
size distribution and their mass percentages, the number
of size ranges and the value of their depth;
2.4. Synthesis and algorithm of the model
the adimensionnalized values of the streamwise, spanwise
and temporal appearing periodicities of coherent struc-
This part describes concisely the model presented in this
tures;
paper. The modelling is constituted of three parts (Fig. 4):
the sizes of the bed (height, width and length);
the aerodynamic entrainment of particles, which is based the kinematic viscosity and the density of the flow.
on the interaction between the coherent structures appear-
Afterwards, the modelling is divided into various parts:
ing at the bed surface and the particles take-off;
the definition of the take-off criterion which depends on the calculation of Npart (Dp ), Nc (Dp ) and Np (Dp );
the particles diameters and density for a given flow veloc- the establishment of Eerosion and Nerosion (Dp ),
ity; the calculation of Faero (Dp ) and of the average lift force,
the pavement modelling as a result of the presence of the standard deviation of the probability density function
coarser particles at the bed surface. of the lift force, the average adhesion force, the standard
deviation of the probability density function of the adhe-
The principle of the model is to scan the bed surface, sion force, the weight force,
which is subdivided into boxes whose the width and the the bed is scanned along width and length. The iterations
length are equal respectively to the spanwise and streamwise number is equal to the number of coherent structures ap-
statistical periodicities of appearing of the coherent struc- pearing along the width multiplied by the number of co-
tures. In fact, some authors have shown that the phenomenon herent structures appearing along the length multiplied by
of ejection in a turbulent boundary layer could be connected the ratio between the exposition period and the occurence
with the particles take-off. period of the vortex structures. The take-off criterion is
For each box, namely for each ejection, the criterion for tested for each iteration and the modelling of the pave-
taking-off is tested. Previously, it is necessary to determine ment is taken into account.
which particle, that is to say, which size range will be tested.
The size range of representative diameter Dp of the particle The results obtained by the model are the temporal varia-
likely to be carried away by the flow is selected randomly tion of the emitted mass and of the mass flux as well as the
from the size distribution. If all the particles of this size range temporal evolution of the surface size distribution and the
have taken-off, then an other size range is randomly selected. size distribution of eroded particles.
For each take-off, a particle is substracted from its size
range then it is counted in the emitted mass flux. Propor-
tionately to these takes-off, the flow has more and more dif- 3. Numerical results
ficulty to carry away particles, this difficulty is taken into
account by the modelling of the bed pavement. This part aims at showing that the model allows to
The model algorithm is showed on Fig. 5. estimate the temporal decrease of the emitted mass flux
observed in presence of non-erodible (relatively coarse) poral decrease and the initial percentage of the emitted mass
particles. flux increase.
A test has been investigated with a simple size distri- All these results can be deduced from the modelling of
bution constituted by a blend of erodible (60160 m) the wind erosion of the bed. The decrease rate goes higher,
and non-erodible sand particles (540640 m). The rate of when the cover rate, noted tdc, increases. This can be ex-
non-erodible particles, which is the cover rate noted tdc, plained by the modelling of the pavement, described in part
varies from 0 to 80%. Fig. 6 shows the size distributions 2.3. The reduction increment of the lift force is inversely
which are tested by the model. proportional to the erosion depth (Eq. (6)). According to the
The input variables are: definition of the erosion depth, the higher is the proportion
of non-erodible particles, the smallest is the erosion depth.
the exposition time to the turbulent flow, dexpo = 60 s,
Consequently, when the proportion of non-erodible particles
the flow velocity, U = 10 m/s,
is increased, the reduction increment becomes greater and
the particles density, p = 2500 kg/m3 , the representative
the temporal decrease is faster.
diameters of each size range, Dp , and the mass percentages
When the mass percentage of non-erodible particles
corresponding, Pmass , which are given by Fig. 6,
is greater, the emitted mass flux is lower. In fact, be-
the statistical spatial and temporal periodicities of appear-
fore the take-off criterion, a size range is randomly se-
ing of ejections x + =300, z + =100 and TB + = 250,
lected from the size distribution. So, the proportion of
the sizes of the bed H = 2.5 cm, L = 48.5 cm and l = 8.7
non-erodible particles is taken into account. When cover
cm.
rate is increased the chances that the particle is erodible are
Fig. 7 shows the results obtained by the model. The figure weaker.
traces out the evolutions of the mass flux in kg/m2 s according As flow velocity is increased, the emitted mass flux in-
to the time in s for a velocity of the flow equal to 10 m/s creases. In fact, the number of taking-off possibilities equals
and for various cover rates, tdc = 0, 20, 40, 60 and 80%. the number of boxes at the bed surface times the number
Several remarks can be made from the numerical results. of time step of the model. Moreover, the number of boxes
If the particles bed does not contain any non-erodible parti- at the bed surface multiplied by the number of time step is
cles, then the emitted mass flux is constant with time. When proportional to U 4 .
the particles bed contains non-erodible particles, the emitted When the takes-off are more numerous, the layers of par-
mass flux decreases with time. ticles are blown off faster. Consequently, the decrease of
Fig. 7 shows that the rate of the temporal decrease is emitted mass flux is greater.
higher when the initial percentage of large particles in- Fig. 7 also shows a temporal decrease in mass flux in
creases, which corresponds to experimental observations. graduated steps. The bound from one step to another is due
Moreover, the initial flux of particles decreases with the to the passage of one layer to another in the numerical model
presence of non-erodible particles. and consequently to the decrement of the probability density
Other tests, which are not represented in this paper, have function of the lift force. This is not directly representative of
shown that, when the velocity is higher, the rate of the tem- the reality. However, a general trend of the temporal decrease
Fig. 7. First results obtained by the model in the case of a wide size distribution: U =10 m/s; p =2500 kg/m3 ; tdc = 0, 20, 40, 60 and 80%.
I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166 165
Fig. 8. Interpolation of the temporal decrease in emitted mass flux obtained by the model: U =10 m/s; p =2500 kg/m3 ; tdc= 20, 40, 60 and 80%.
in the mass flux can be obtained by interpolating the data This study constitutes a first step on studying the mod-
by a negative exponential function. elling of wind erosion of multiple size grains bed.
In Fig. 8 it is observed that the temporal decrease of emit-
ted mass flux can be interpolated by an exponential negative
function: Acknowledgements
flux(t) = flux(tinitial )exp(kd t) (8) This work was carried out with the financial support
of ADEME (the French Agency for Environment and
kd is the decrease rate and flux(tinitial ) is the emitted mass Energy Management), ARCELOR Dunkerque and Fos-
flux at tinitial 0 s. sur-Mer (steelworks in France) and European Community
(FEDER).
4. Conclusions
Appendix A. Nomenclature
The pavement modelling allows to introduce into the
model the temporal evolution of the size distribution of Dp particle diameter (m)
materials at the bed surface. By a progressive decrease of Eerosion erosion depth (m)
the probability density function of the lift force, this model Fad adhesion force (N)
successfully predicts the temporal decrease in mass flux Faeroinitial initial instantaneous lift force (N)
that occurs with the presence of coarse particles at the sur- Faero mean lift force (N)
face. The rate of this decrease depends on the flow velocity F aero fluctuating lift force (N)
and the characteristics of the particles. In order to improve H bed height (m)
the accuracy of the estimation of fugitive particle emissions l bed width (m)
with a wide size distribution, it is necessary to take into L bed length (m)
account this temporal decrease. P particle weight (N)
An experimental study, whose aim is to measure the tem- Pmass mass percentage (%)
poral decrease in mass flux, is on running and will allow to t time (s)
compare the results obtained by the model with the measure- TB average periodicity of burst
ments. Thus, it will allow to adjust the numerical results. occurence (s)
Various improvements could be brought to the model. tdc cover rate: mass percentage of non-erodible
Another study, whose objective is to measure the statistical particles (%)
periodicities of the coherent structures on a rough wall, will TC size range cover rate (%)
allow to adjust the results obtained by the model with the u friction velocity (m s1 )
experimental results. U flow velocity (m s1 )
166 I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166
Greek letters [6] Schet, P., Contribution ltude des structures cohrentes en tur-
x + adimensionalized average streamwise bulence de paroi, De leur influence sur le transport des sdiments
dans le cas du charriage, Ph.D. Thesis, INPT, France,. 2000.
periodicity of appearing of vortex structure [7] Y. Nio, M.H. Garcia, Experiments on particle-turbulence interactions
z + adimensionalized average spanwise in the near-wall region of an open channel flow: Implications for
periodicity of appearing of vortex structure sediment transport, J. Fluid Mech. 326 (1996) 285319.
kinematic viscosity (m2 s1 ) [8] J. Jimenez, P. Moin, The minimal flow unit in near wall turbulence,
J. Fluid. Mech. 225 (1991) 213240.
[9] R.F. Blackwelder, J.H. Haritonidis, Scaling of the bursting frequency
in turbulent boundary layers, J. Fluid. Mech. 316 (1983) 285
References 306.
[10] A.M. Mollinger, F.T.M. Nieuwstadt, Measurement of the lift force
[1] R. Bouscaren, Emissions diffuses and fugitives in Journe dtudes on a particle fixed to the wall in the sublayer of a fully devel-
du CITEPA, 2002. oped turbulent boundary layer, J. Fluid. Mech. 316 (1996) 285
[2] M.A. Meunier, Envol et transport de particules en couche limite 306.
turbulente instationnaire, Ph.D. Thesis, University of Valenciennes, [11] A. Zimon, Adhesion of dust and powder, Plenum Publishing Corpo-
France, 1999. ration, 1982.
[3] L. Li, L.W. Martz, Aerodynamic dislodgement of multiple size grains [12] I. Descamps, Erosion olienne dun lit de particules large spectre
over time, Sedimentology 42 (1995) 683694. granulomtrique, Ph.D. Thesis, University of Valenciennes France,
[4] M.V. Lpez, Wind erosion in agricultural soils: an example of limited 2004.
supply of particles available for erosion, Catena 33 (1998) 1728. [13] J.M. Foucaut, M. Stanislas, Take-off threshold friction velocity of
[5] L.Y. Liu, P.J. Shi, X.Y. Zou, S.Y. Gao, H. Erdon, P. Yan, X.Y. Li, solid particles lying under a turbulent boundary layer, Exp. in Fluids.
Z.B. Dong, J.H. Wang, Short terms dynamics of wind erosion of 20 (1996) 377382.
three newly cultivated grasslands soils in Northern China, Geoderma [14] R. Kurose, S. Komori, Turbulence structure over a roughness, Int. J.
115 (2003) 5564. Mult. Pha. Flow. 27 (2001) 673683.
Chemical Engineering and Processing 44 (2005) 167173
Received 26 August 2003; received in revised form 4 December 2003; accepted 11 February 2004
Available online 25 September 2004
Abstract
Solids deposition in the horizontal pipeline of a pneumatic conveying system was studied both mathematically and experimentally. Math-
ematically modelled results using the coupled discrete element method (DEM) and computational fluid dynamics (CFD) approach have
demonstrated an intensive exchange of particles between the stationary layer (deposited particles) and the moving slug and a variation of
solids concentration and pressure and velocity distributions across the slug. Slug flows were also visualised experimentally through a glass
section and analysed by a high-speed video camera. The amount of particle deposition in the pipeline after a conveying was calculated
by controlling the solids feeding rate using a rotary valve and by monitoring the solids flow out of the system using dynamic load cells.
Experimentally generated data have quantitatively shown a tendency of more solids deposition with lower gas mass flow rate in slug flows
except that, below a certain amount of solids mass flow rate, the deposition becomes independent of gas flow rate.
2004 Published by Elsevier B.V.
Keywords: Pneumatic conveying; Slug flow; Solids deposition; CFD model; DEM simulation
1. Introduction system. To obtain an insight into the slug flow and solids de-
position characteristics, a coupled discrete element method
Low-velocity slug flow pneumatic conveying has become (DEM) and computational fluid dynamics (CFD) approach
more and more common in many industrial sectors ranging was used to simulate the solids and gas flows. Solids de-
across chemical, pharmaceutical and food industries, due to position in the horizontal section of the conveying system
its advantages over conventional high-velocity suspension was visualised through a glass section and recorded by a
flow in preventing product degradation and plant wear and high-speed video camera. The amount of particle deposition
in delivering high throughput and efficient power utilisation was calculated by closely monitoring the solids flow into
[1]. One of the distinguishing characteristics in such an op- and out of the system. Mathematically and experimentally
eration is the gravitational deposition of solid particles in generated data were analysed in order to develop a useful
pipelines, which is due to the low gas velocity used, usu- tool for the future prediction of solids deposition and slug
ally below the solids saltation velocity. A layer of particles flow behaviours in low-velocity pneumatic conveying.
at the bottom of the horizontal conveying line is commonly
seen in these systems and this solids deposition significantly
affects the transition and flow of slugs along the pipeline.
This paper presents mathematical and experimental stud- 2. Characteristics of slug flow - DEM modelling
ies of solids deposition characteristics in the horizontal
pipeline of a dense phase slug flow pneumatic conveying Although low-velocity slug flow pneumatic conveying has
been studied intensively in the past two decades [18], due
to the practical restrictions of applying modern measuring
Corresponding author. Tel.: +44 1236 878448; tools to gas and solids multiphase flows there is still a lack
fax: +44 1236 872837. of understanding of how gases and particles interact inside a
E-mail address: jintang.li@devro-casings.com (J. Li). moving slug and how these interactions affect the formation
169
170 J. Li et al. / Chemical Engineering and Processing 44 (2005) 167173
Fig. 4. Pressure drop along the pipeline DEM/CFD simulation (at 0.4 s).
Fig. 5. Gas velocity profile along the pipe DEM/CFD simulation (at 0.4 s).
J. Li et al. / Chemical Engineering and Processing 44 (2005) 167173 171
Fig. 6. Gas velocity profile in pipe cross section DEM/CFD simulation (at 0.4 s).
The gas velocity profiles may explain why a loose slug it comprises of a feed vessel, a receiving vessel, a 13 m
front is generated. That is particles in the front of the slug long conveying pipeline with interchangeable 5.1, 7.6 and
wave are pushed by the slug body and dragged ahead of 10.2 cm (i.e. 2, 3 and 4 in.) nominal bore pipes, a bank of air
the slug by the high local gas velocity at the top pipe cross supply nozzles, a variable speed rotary valve with dropout
section while being agitated through severe interactions in- box, an air filter unit, and connecting pipes and control
curred by the rising particles from the stationary layer be- valves. In the system, both gas and solids mass feeding
neath the slug front and floating over them. The agitated rates are closely controlled through the choked nozzle bank
particle layer underneath the slug front is actually acting as and the variable speed rotary valve. A set of three load cells
multiple fluidised rolling wheels for the slug, which greatly is mounted underneath the receiving vessel to monitor the
reduces the frictional forces comparing with a direct inter- weight of solids conveyed. This particular design allows the
action with the pipe bottom wall. In some cases, even an desired solids mass flow rate to be selected by adjusting
air pocket or a particle swirling flow is created between the the rotary valve speed while the actual conveying rate is
suspended loose slug front and the bottom particle layer, of calculated simultaneously from the load cell readings. Fig.
which the resulting mechanisms and its consequence on slug 8 shows a typical diagram of a non-suspension wave-like
flow need further studies. flow. Each step in the mass collected history is caused by
the arrival of a slug of solids. It is noticed that there is a
difference between the mass of solids flowing into and out
3. Experimental analysis of the system and the difference in the final masses is the
deposition of solids in the system, which usually forms a
Experiments were conducted to determine quantitatively particle layer in the pipeline at the end of conveying.
the amount of particle deposition in the pipeline of a spe- Different combinations of gas and solids flow rates were
cially designed pneumatic conveying system [17,18]. A tested in a 7.6 cm bore pipe with a common industrial gran-
schematic layout of the rig is shown in Fig. 7. Briefly ular material - polyethylene pellets. The pellets were spher-
Table 1
Solids deposition in a pneumatic conveying system
Ug (ca.) Mg (kg/s) Ms1 Ms2 Ms3 Ms4
(m/s)
Fixed Deposition Fixed Deposition Fixed SLR5 Deposition Fixed SLR10 Deposition
(kg/s) (kg) (kg/s) (kg) (kg/s) (kg) (kg/s) (kg)
25 0.1534 1.2270 0.00 0.6135 0.00 0.7669 0.00 1.5337 0.00
8 0.0491 1.2270 3.94 0.6135 9.35a 0.2454 11.35a 0.4908 9.51
6 0.0368 1.2270 6.28 0.6135 7.29 0.1840 9.18a 0.3681 5.43
4 0.0245 1.2270 6.05 0.6135 8.03 0.1227 8.33a 0.2454 8.05
2.6 0.0160 1.2270 9.79 0.6135 8.92 0.0798 11.70 0.1595 12.88a
a Large difference ( > 2 kg) of load cell readings occurred between repeated runs, which may be due to the unstable flow of slugs in these flow
conditions.
172 J. Li et al. / Chemical Engineering and Processing 44 (2005) 167173
ical in shape with an average diameter of 3 mm, a particle low gas velocity (< 10 m/s), a particle layer was built at the
density of 880 kg/m3 and an approximate bulk density of bottom of the pipeline after a slug passing and at the end of
550 kg/m3 . The experiments were started initially with high each test case. This solids deposition was assumed equiva-
superficial gas velocity at 25 m/s, in which very little particle lent to the difference of the final load cell readings between
deposition occurred (This was confirmed with visualisation the tested cases and that obtained using a high gas velocity
via a 3 m glass section in the conveying line). When using (25 m/s).
Received 22 July 2003; received in revised form 25 February 2004; accepted 19 March 2004
Available online 27 August 2004
Abstract
In the approach presented, attrition of bulk solids in pneumatic conveying is regarded as a result of a process function (stress conditions)
and a material function (influence of material properties). For dilute phase conveying the process function was determined by employing
computational fluid dynamics (CFD). Opposed to what was expected initially, the numerical simulations indicate that sliding friction apparently
is of importance in dilute phase conveying. This conclusion can be drawn from the low calculated impact angles in a pipe bend (rB /Dn = 5;
Dn = 80 mm) which lie between 5 and 35 . Consequently, the tangential impact velocity components ranging from 33 to 44 m/s are considerably
higher than the normal ones (525 m/s). These results were at first endorsed by observations made in experiments to determine the material
function. The relative attrition behavior of four different polypropylenes (PP) under pure sliding friction conditions closely resembles that
observed in attrition experiments carried out in a pipe bend of the above geometry, while differences are observed for normal impact conditions.
But further experiments with polymethylmethacrylates (PMMA) and polystyrenes (PS) showed that here the attrition behavior encountered
under normal impact conditions is similar to that observed in the pipe bend. With dynamic mechanical analysis (DMA) it was possible to
show that PP on one hand and PMMA and PS on the other are attrited by different mechanisms and that the glass transition temperature of
the polymers is a key factor in the determination of the prevailing attrition mechanism.
2004 Elsevier B.V. All rights reserved.
Keywords: Attrition; Pneumatic conveying; Polymers; Process function; Material function; Dynamic mechanical analysis (DMA)
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.012
176 L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185
Table 1
Overview of different material properties
Name Shape xp (mm) p (kg/m3 ) HV (MPa) E (MPa) y (MPa) JQd (kJ/m2 )
corresponds to the critical energy release rate Gc for materi- depending on the material vp,i ranged from 40.22 to 45 m/s.
als with a nonlinear deformation curve was measured at the The material properties required for the simulations were
Institute of Polymeric Materials, Martin-Luther University taken from Table 1.
Halle-Wittenberg by employing a modified Charpy notched In Fig. 2 the cumulative number distributions Q0 of im-
impact test. pact angles and impact velocity components are shown for
selected polymers. It can be observed that with 535 the
calculated angles are comparatively small. This results in
3. Comments on the process function low normal (525 m/s) and high tangential (3344 m/s) im-
pact velocity components which leads to the conclusion that
Since a detailed description of the determination of the not only impact stresses contribute to attrition in dilute phase
process function for dilute phase conveying has been given conveying but that sliding friction stresses might play an im-
elsewhere [12] only the main findings are presented here. portant role as well. The differences in the distributions of
The stress conditions were calculated by employing compu- the tangential velocity component can be mainly attributed
tational fluid dynamics (CFD). The fluid phase was modeled to the already mentioned slight variations in the initial par-
by using the Eulerian approach, i.e. the Reynolds averaged ticle velocities.
conservation equations for mass and momentum in conjunc- Since the results were unexpected, the particle wall im-
tion with the k- turbulence model while for the particulate pact locations were plotted from the data generated in the
phase the Lagrangian particle tracking as expressed in the simulations for a total of 2000 individual particles. They are
BassetBoussinesqOseen equation was applied. The parti- shown in Fig. 3 from two different angles. Due to the large
cles were modeled as being spherical, particle wall impacts particle diameters resulting in high inertia forces the parti-
as fully elastic and particle lift forces were neglected. cles do not follow the gas stream in the pipe bend, but pro-
The computational domain consisted of a straight pipe ceed directly to the outer bend wall. Only a slight sinking
with a diameter Dn of 80 mm and a length le of 2400 mm. caused by the gravity force can be observed. Since this be-
Proceeding the pipe is a bend. For the simulations different havior can be attributed to the high initial particle velocities,
rB /Dn ratios of 2, 5 and 10 corresponding to short, standard simulations varying these have been carried out. They lead
and long radius bends were used. Details on the geometry to changes in the respective number distributions of impact
can also be found in the experimental section, since an in- angle and velocity components, but did not have any effect
stallation possessing the above geometry of the straight pipe on the maximum angle. It can thus be concluded that not
in conjunction with a pipe bend of rB /Dn = 5 was con- only the bend geometry is of influence as simulations with
structed. Due to the fact that the simulations were intended varying rB /Dn ratio have shown but that the curvature of
to be as closely related to the experimental conditions as the pipe plays an important role for the impact conditions
possible, the gas and particle velocities measured in this in- as well. Although Fig. 3 clearly shows that the results are
stallations were used as boundary conditions for the simula- reasonable an experimental validation of the simulations is
tions. Thus the average gas entrance velocity normal to the nevertheless still necessary.
inlet face was set to vf,i = 40.77 m/s. The particle entrance For reasons of completeness, results for the determina-
velocities vp,i were intended to be equal to the gas velocity, tion of the process function for plug flow conveying shall
however due to experimental limitations it was not possible be stated briefly as well. Since in this case a two phase flow
to exactly match them with the gas velocity. Consequently, with high particle concentrations is regarded the options to
Fig. 2. Cumulative number distributions for wall impact angles and normal and tangential impact velocity components for one polymer of each class.
178 L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185
Fig. 3. Visualization of particle wall impact locations for 2000 particles of PP 1040 N with a diameter xp = 4 mm and initial gas and particle velocities
vx,i 41 m/s.
simulate this flow are very limited. Therefore, experimental same mode, q.v. [3]. Since under these circumstances the
results obtained by Mi and Wypych [13,14] were used to stress conditions are almost identical the significance of the
obtain at least a rough estimate of the stress conditions the material function becomes obvious. Unfortunately it is still
particles are subjected to. If it is assumed that the particles unknown which material properties determine the attrition
in a plug are at least for short times fixed relative to each behavior. In the case of polymers the identification is dif-
other, the highest relative velocities will occur between the ficult due to their viscoelastic nature. Thus the concept for
particles forming the outer layer of the plug and the pipe the determination of the material function shown in Fig. 4
wall. The stress mode in this case is sliding friction. From was developed.
measurements of the pressure exerted by a plug on the pipe The crucial point is to simulate the previously identified
wall and by applying the Hertzian equations for elastic con- basic stress modes impact and friction under well defined
tact, a contact pressure between a single particle and the stress conditions. This way, material properties can be re-
pipe wall of roughly 4 MPa is obtained. lated to attrition caused by these stress modes and the re-
spective attrition mechanisms in effect. For this purpose it
was chosen to perform single particle experiments in simple
4. The material function experimental setups to realize the defined stress conditions.
Details on these setups are given in the next section.
4.1. Concept for determination Ideally, the stress conditions obtained from the process
function are used as input parameters for the single particle
It is generally known that different bulk solids might ex- experiments. But due to practical reasons this is not always
hibit widely varying attrition rates even if conveyed in the possible, since a compromise between stress conditions
Fig. 4. General concept and experimental devices to determine the material function for attrition processes.
L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185 179
closely related to the conveying process and conditions F. Due to its shape a constant contact area of 16 mm2 and
where the attrition rates can be measured reliably has to thus a defined contact pressure pc is maintained throughout
be found. The knowledge gathered from the single particle the experiment. Due to sample geometry, the velocity over
experiments will be broadened by and compared to results the contact face varied by a maximum of 2.5% from the
of the defined stressing of a particle ensemble. For this median value. Through the number of revolutions n of the
purpose, experiments in a pipe bend are carried out to in- disc and the distance r between the particle and the disc axis,
vestigate the polymers under conditions closely related to the sliding velocity vs is adjusted. The sliding distance s
those in the conveying pipelines. results from the sliding velocity and the contact time tc . The
The results of the attrition experiments are compared to disc simulating the wall material can be changed to account
various material properties in order to identify those rele- for different materials and surface topographies conveying
vant for attrition. The long term goal is to develop a phys- pipelines might exhibit.
ical model of the attrition process which makes it possible The experimental parameters for the sliding friction ex-
to predict the amount of attrition that will be encountered periments, were chosen to simulate dense phase conveying
in a pneumatic conveying installation by knowledge of the conditions. Basically, two different sets of experimental pa-
process and material functions. rameters were used. The polypropylenes were tested against
different wall materials. Here, steel possessing different sur-
4.2. Experimental setup and parameters face roughness values was used. Since a sandblasted surface
lead to high attrition rates, a low contact pressure of 61 kPa
The experimental setups of two out of the three installa- as well as a long sliding distance of 1500 m were used. The
tions used to date are shown in Fig. 4. The installation on the sliding velocities ranged from 4 to 8 m/s. Based on the find-
left-hand side is used to stress single particles under normal ings from the process function for dense phase conveying,
impact loads. It was originally developed by Schnert and is a higher contact pressure of 0.61 MPa in conjunction with
described in Marktscheffel and Schnert [15]. The particles a lower sliding distance of 200 m was used for further ex-
are fed one by one into the center of a rotor (2) by means periments. To accomplish similar conditions to the experi-
of vibration (1). In the rotor, the particles are accelerated in ments in the pipe bend installation, here a steel disc with
radial channels and finally hit the impact ring (3) under an approximately the same roughness value as the pipe bend
impact angle of 90 . The impact velocity is determined by was installed. The parameters, especially the comparatively
the number of revolutions of the rotor. Particles and attri- high sliding distances had to be chosen in such a way, to
tion debris are collected in the impact chamber (4) and can make sure that reproducibly measurable attrition rates were
be discharged through a tube at the bottom of this chamber. obtained. As already mentioned, here the attrition rate was
The experiments were carried out under vacuum conditions determined according to Eq. (1) by weighing the single par-
to eliminate any effects due to viscous drag. ticles on a high precision scale.
For the attrition experiments approximately 25 g of poly- The third installation was constructed to conduct single
mer particles were used. After three, six and nine consec- particle attrition experiments under well defined stress con-
utive impacts with a velocity of 40 m/s, the attrition rate A ditions which are closely related to conditions in industrial
was determined as the relative loss of mass (see Eq. (1)). conveying installations. For this purpose a pipe bend was
This procedure was necessary since the attrition rates for chosen. The exact setup is given in Fig. 5. As it has already
some polymer classes were not measurable with satisfying been discussed, the geometry of this setup was used for the
accuracy for lower impact numbers. Since the attrition pro- simulations to determine the process function in dilute phase
cess is highly statistical, each experiment was repeated three conveying.
times. This also holds for the other experimental setups. In The installation was constructed as a negative pressure
the following diagrams, the median values of these three re- system with the blower being located downstream of the fil-
peated experiments are plotted with the standard deviations ter. This way a high flexibility in feeding the particles was
as error bars. For all experiments, the attrition rate A was
calculated according to Eq. (1), where Mi denotes the initial
particle mass. Ma is the mass of particles at the initial size
after the attrition experiment.
Mi Ma
A= (1)
Mi
The installation to simulate sliding friction shown on the
right-hand side of Fig. 4 was developed at our institute. In
design it resembles a classic pin-on-disc tribometer. Here,
a rectangular polymer particle cut from tensile bars with a
length of 10 mm, a width of 4 mm and a thickness of 4 mm
is pressed onto a rotating disc with a defined normal force Fig. 5. Design and dimensions of the pipe bend installation.
180 L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185
realized. For the experiments presented, the particles were and gas entrance velocities in the pipe bend installation were
fed into the pipe along its center axis by a specially designed approximately 41 m/s.
feeder in which they are accelerated with pressurized air to In the middle diagram, the error bars were omitted for
approximately 41 m/s prior to entering the pipe. The veloc- reasons of clarity. Although the attrition rates cannot be
ity of the particles was measured by photo-electric guards. compared directly due to the different stress conditions, it
The pipe has a diameter Dn of 80 mm and possesses the di- can be observed that the relative attrition behavior of the
mensions already presented in the process function section. polypropylenes in the sliding friction experiments is iden-
For separating the particles from the gas stream, a filter bag tical to that observed in the pipe bend experiments, i.e. in
was used. Particles and attrition debris are discharged at the both cases PP 2500 H is the least attrited material, while
bottom of the filter housing. With the blower, gas velocities PP 1148 RC is the most attrited one. For normal impacts,
in the pipe of up to 41 m/s are reached. They are measured considerable deviations from the results in the pipe bend are
and monitored with a Prandtls tube. found. This leads to the conclusion that attrition formation
Similar to the normal impact experiments, the attrition can be mainly attributed to sliding friction. This is in good
rates were determined after three, six and nine impacts. Here agreement with the findings from the process function for
it is assumed that only the first particle wall impact in the dilute phase conveying discussed earlier. In case of PMMA
pipe bend contributes significantly to attrition formation and and PS a different behavior is observed (see Fig. 7). Here,
that further impacts are of minor importance. Again 25 g the relative attrition behavior found for the normal impact
of the granular polymers were used. In order to maintain experiments corresponds to that in the pipe bend.
conditions close to those in conveying processes the particle These findings clearly show the significance of the ma-
velocity was set to be approximately equal to the gas velocity terial function, since the material reaction to similar stress
of 41 m/s. conditions in the pipe bend can vary greatly. In contrast to
PP, PMMA and PS apparently are attrited by the same mech-
4.3. Results of the single particle experiments anisms in effect under normal impact stress conditions. This
also clarifies that it is only possible to deduce the stress mode
The first results of the single particle experiments carried from the process function but that without knowledge of the
out for different polypropylenes have shown that the relative material function no conclusions concerning the governing
attrition behavior changes between the normal impact and attrition mechanisms can be drawn.
the sliding friction tests [12]. This was taken as a chance
to identify which attrition mechanism dominates in the pipe 4.4. Correlation between single particle experiments and
bend installation and thus presumably in dilute phase con- material properties
veying. In Fig. 6, a comparison of the results obtained for
the normal impact experiments, the sliding friction experi- One of the most important tasks in the determination of the
ments and the pipe bend installation is given. The normal material function is to identify those material properties rele-
impact velocity was 40 m/s. For sliding friction a vanadium vant to attrition formation. A comparison of the above results
steel disc possessing a sandblasted surface was used. The to classic mechanical material properties, e.g. Youngs mod-
contact pressure was 61 kPa, the sliding distance 1500 m and ulus E or Vickers hardness HV as given in Table 1 suggests
the sliding velocities ranged from 4 to 8 m/s. The particle that these are not suitable to describe attrition formation.
Fig. 6. Comparison of the attrition rates for different polypropylenes as obtained from experiments in the normal impact, sliding friction and pipe bend
experiments.
L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185 181
Fig. 7. Comparison of the attrition rates for different PMMA and PS granules as obtained from normal impact, sliding friction and pipe bend experiments.
This is due to the fact that the respective measurement pro- responding stress signal. For a fully elastic material, would
cedures for their determination do not take into account the be zero whereas it would be 90 for a fully plastic material.
dynamic nature of the attrition process. Therefore, in the With this phase lag, which is measured as well, the com-
present study dynamic mechanical analysis (DMA) was em- plex modulus of elasticity can be divided into the storage
ployed. modulus E and the loss modulus E .
For the measurements, the single cantilever flexure mode
E (, T) = |E | cos (3)
was chosen. For this, rectangular polymer samples of
32 mm 6 mm 2 mm had to be produced. This was done E (, T) = |E | sin (4)
by injection molding of the original polymers. Fig. 8 shows
the setup of a DMA-experiment in the single cantilever The storage modulus is proportional to the amount of
configuration. energy which is stored in the material elastically, whereas
Prior to the experiments, the polymer sample is fixed be- the loss modulus corresponds to the energy that is dissipated
tween two clamps and the sample dimensions are measured during one load cycle. Both quantities are combined in the
carefully. One of the two clamps is fixed, while the other damping factor tan which is defined as
can be moved up and down. To this clamp, a sinusoidal de- E
formation with an amplitude A and a frequency is ap- tan = (5)
E
plied and the corresponding force is measured, which can be
transferred into the stress A with the sample dimensions. After checking the influence of various experimental pa-
From these two quantities the complex modulus of elastic- rameters as well as the reproducibility of the measurements,
ity E is measured in dependence of sample temperature T a standard procedure was developed. The polymer samples
and oscillation frequency . are cooled quickly with liquid nitrogen to a temperature of
A 140 C. After an isothermal period of 1 min, a frequency
|E (, T)| = (2) sweep is carried out for 1, 3, 5, 10, 30, 40, 50 and 60 Hz with
A
a deformation amplitude of 20 m. Afterwards the temper-
The viscoelastic behavior of the polymers is reflected in ature is increased by 5 C and after another isothermal pe-
the phase lag between the deformation signal and the cor- riod of 1 min, the next frequency sweep is carried out. This
Fig. 9. Storage (E ) and loss (E ) modulus functions for different PP, PMMA and PS granules.
procedure is repeated until the value of the storage modu- methylmethacrylates/polystyrenes are reflected as well.
lus drops down to 10 MPa which was set as the criterion After the glass transition, the storage modulus reaches a
to end the measurement in time before melting of the sam- plateau for PP and PE due to the crystalline structures which
ple starts. The obtained storage and loss modulus functions do not change in stiffness significantly until melting. The
for the polymers are depicted in Figs. 9 and 10. The values amorphous polymers on the other hand fully soften during
given were obtained for a frequency of 10 Hz. glass transition leading to very low storage modulus values.
From the measurements the typical viscoelastic behavior In Table 2 the glass transition temperatures Tg as obtained
of the polymers becomes obvious. The polymer chains are from the storage and loss modulus values are given. For the
fixed relative to each other at low temperatures. Thus the storage modulus they were determined by using the inflec-
amount of energy that is stored elastically is high which is tion point method whereas for the loss modulus the peak
reflected in a high value of the storage modulus. The corre- maximum was used [16].
sponding values of the loss modulus are low. The mobility It can be observed that the agreement of the correspond-
of the polymer chains increases with increasing tempera- ing temperatures is quite well. As Ehrenstein et al. [16] point
ture and consequently the storage modulus decreases while out, this deviation is normal and usually Tg (E ) Tg (E )
the loss modulus increases. In the glass transition regime Tg (DSC) holds. The materials where a second temperature
the maximum of energy dissipation is reached (maximum value is given in italics do not only possess a glass transi-
of loss modulus) and the storage modulus falls rapidly. tion but also show a second order transition. For PP 2500 H,
The structural differences between the semicrystalline PMMA G7 and G55 these second order transitions which
polypropylenes/polyethylenes and the amorphous poly- are most likely caused by increased mobility of side-chains
Fig. 10. Storage (E ) and loss (E ) modulus functions for different PP and PE granules.
L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185 183
Fig. 11. Comparison of the attrition rates obtained from sliding friction experiments for 6 m/s, 0.61 MPa and 200 m against St-bend with storage (E ) and
loss modulus (E ) values measured at 10 Hz and 25 C.
or chain segments lie below their glass transition tempera- possible explanation for this behavior can be found in
tures. PE 2420 H and PE 5031 L on the other hand show the microscopic attrition mechanisms known from tribol-
their respective second order transitions above their glass ogy and was briefly discussed in [17]. As Fig. 11 shows,
transition temperatures (see Fig. 10). Here it is not quite PE 5031 L fits well into this tendency while PE 2420 H
clear what causes them. again does not. From the materials which are attrited by
If the ambient temperature at which the single particle ex- an impact mechanism, PMMA G7 and G55 also follow
periments were carried out is regarded as the macroscopic the above trend while the two polystyrenes do not. It is
stress temperature, it can be observed with respect to the currently under investigation how this observation can be
experimentally obtained attrition rates, that the polypropy- explained.
lenes which are attrited by sliding friction are stressed in If the above comparison is made for the attrition results
their glass transition regimes whereas the glass transition from the pipe bend installation, again a decrease in attrition
temperature of PMMA and PS lies well above the stress rate for the polypropylenes corresponds to decreasing E and
temperature. Obviously, the relation between the values of E values. Of course, the scatter gets larger since in this
the macroscopic stress temperature and the glass transi- installation although sliding friction is the most prominent
tion temperature can be used to evaluate which material attrition mechanism, impact also marginally contributes to
specific attrition mechanism impact or sliding friction overall attrition. Furthermore, PE 5031 L, PMMA G7 and
is dominating in attrition formation. This conclusion is PMMA G55 do not fit quite as well as for the sliding friction
also valid for PE 5031 L, while PE 2420 H which is a experiments while PE 2420 H, PS 144 C and PS 158 K
very soft material (see Youngs modulus in Table 1 or stor- shows the same discrepancies as before.
age modulus in Fig. 10) does not fit. In this case, addi- The results presented show that three levels have to be dis-
tional effects like adhesion are likely to play an important tinguished when investigating attrition processes. The first
role. one is the stress mode as derived from the process function
For PP it was furthermore found that the attrition rates which is essential to know if the attrition process is to be
observed in the sliding friction experiments decrease with simulated successfully in a simple experimental setup. The
decreasing values of both storage and loss modulus. A second point is the material reaction to this stress mode,
i.e. the material function which varies depending on mate-
rial properties like storage and loss modulus as measured
Table 2 by DMA. Finally, the microscopic attrition mechanisms (see
Glass transition temperatures as obtained from DMA measurements ( =
10 Hz)
[18] for impact and [19,20] for sliding friction) describing
the formation of attrition on a microscopic scale constitute
Name Tg (E ) ( C) Tg (E ) ( C) the bottom level.
PP 1040 N 17.54 15.08
PP 1100 RC 15.04 15.10
PP 1148 RC 15.16 15.08 5. Conclusions
PP 2500 H 37.33/12.43 34.88/9.99
PE 2420 H 122.32/12.02 114.82/9.62
PE 5031 L 107.31/45.03 109.81/55.12 In the present research project the problem of attrition
PMMA G7 45.07/107.69 29.90/110.20 in pneumatic conveying was addressed by regarding it as
PMMA G55 90.12 25.05/95.12 the result of a process and a material function. The process
PS 144 C 92.13 95.17 function summarizes the influence of all process parame-
PS 158 K 107.84 110.20
ters and as a result provides the stress conditions in terms
184 L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185
Received 5 August 2003; received in revised form 16 December 2003; accepted 11 February 2004
Available online 25 June 2004
Abstract
The Two-Fluid model has been used for modeling the flow of particulate materials through pneumatic dryer. The model was solved for
a two-dimensional steady-state condition and considering axial and radial profiles for the flow variables. A two-stage drying process was
implemented. In the first drying stage, heat transfer controls evaporation from the saturated outer surface of the particle to the surrounding
gas. At the second stage, the particles were assumed to have a wet core and a dry outer crust; the evaporation process of the liquid from a
particle assumed to be governed by diffusion through the particle crust and by convection into the gas medium. As evaporation proceeds, the
wet core shrinks while the particle dries.
Our developed model was applied to simulate drying process of wet sand in a pneumatic dryer. The numerical solutions were compared
with the results of independent numerical and experimental investigations. These comparisons are quite encouraging.
2004 Published by Elsevier B.V.
Blasco et al. [12] proposed two-dimensional mathemati- Non-slip and non-penetrating wall conditions.
cal model for the drying process of dense phase pneumatic Dispersed phase behavior like continuous phase.
conveying. However, heat and mass transfer were not consid- The particles are made from a substance containing solid
ered and therefore their model may be used for dense phase porous matrix and liquid or gas with liquid vapor.
pneumatic transport only. In their paper, both experimental The specific densities of the liquid and the solid, which
and numerical predictions for axial and radial profiles for compose the particle, are constants.
gas and solid velocity, axial profiles for solid concentration Mass, momentum and heat transfer occur only between
and pressure drop were presented. the two phases and not between the particles themselves.
Contrary to traditional one-dimensional models, two- The gas phase is a mixture of water vapor with air.
dimensional models are required for taking into consid- The gas behaves as ideal gas.
eration the effects of the radial distribution of the most Influence of gravity on gas phase is neglected.
influential thermophysical properties. As can be seen from Heat transfer can occur between the pipe wall and the
the above literature survey, not many studies have adopted continuous gas phase.
the two-dimensional approach for simulation the drying The acting forces per unit volume between the phases are
process in a vertical tube. In addition, their predictions were due to drag and virtual-mass.
not validated with experimental data and in some cases only At the first drying stage, the particle is isothermal and at
the momentum transfer was taken into account. the second drying stage the particle wet core temperature
In the present study, two-dimensional Two-Fluid Eulerian is different from that of dry crust.
model was used to describe the steady state, dilute phase flow The influence of the pressure gradient on the inertia of the
of a wet dispersed phase (wet solid particles) in a continuous solid particles is negligible in comparison to that of the
gas phase through a pneumatic dryer. The predictions of drag force.
the numerical solutions were compared successfully with Electrical and surface tension forces are neglected.
the results of other one-dimensional numerical solutions and
experimental data of Baeyens et al. [5] and Rocha [13]. Axial Based on the above-mentioned assumptions, the mass,
and the radial distributions of the characteristic properties momentum and energy balance equations for the gas and the
were examined. dispersed phases in two-dimensional, two-phase flow were
developed [14]. In order to solve the mass, momentum and
energy balance equations, several complimentary equations,
2. Theoretical model definitions and empirical correlations were required. These
were presented by [14]. In order to obtain the water vapor
A two-dimensional, Two-Fluid model has been developed distribution the gas phase the water vapor diffusion equa-
for modeling the steady-state flow of particulate materi- tion was added. During the second drying period, the model
als through vertical pneumatic dryer. Two-dimensional flow assumed that the particle consists of a dry crust surround-
field interpretations provide information about properties of ing a wet core. Hence, the particle is characterized by two
the continuous and dispersed phases at every point of the temperatures i.e., the particles crust and core temperatures.
flow field. Axial and radial profiles were obtained for the Furthermore, it was assumed that the heat transfer from the
flow variables. particles crust to the gas phase is equal to that transferred
The gas phase was treated as a mixture of gas and liquid from the wet core to the gas phase i.e., heat and mass cannot
vapor. The wet particle is made of porous solid structure be accumulated in the particle crust, since all the heat and
that contains saturated liquid. The drying model considered the mass is transferred by diffusion through the crust from
a two-stage drying process. In the first drying stage, heat the wet core to the surrounding gas. Based on this assump-
transfer controls evaporation from the saturated outer surface tion, additional heat balance equation was written.
of the particle to the surrounding gas. In the second stage, The mass transfer source term was obtained by multiply-
the particles are assumed to have a wet core and a dry outer ing the evaporation rate from a single particle by the total
crust. The evaporation of the liquid from a particle assumed number of particles per unit volume. Two-stage drying pro-
to be governed by diffusion through the particle crust and by cess was applied for calculating the mass transfer from a wet
convection into the gas medium. As evaporation proceeds, particle to the gas phase [6]. In the first drying period, the
the wet core shrinks as the particle dries. gas phase resistance controls the evaporation rate. When the
The developed model was solved numerically and applied liquid evaporated from the particle surface and fills all the
to simulate drying of wet sand in a laboratory-scale pneu- voids inside the porous particle, the second drying period
matic dryer. starts. During this drying period, the dry crust causes addi-
The drying model is based on the following assumptions: tional resistance to heat and mass transfer. This resistance,
which occurs between the outside diameter of the particle
Steady-state flow. and the diameter of the wet core is governed by a diffu-
The flow in the dryer is vertical, two-dimensional, sion process. The evaporation rate from a particle with a dry
non-rotational and axi-symmetrical. crust was expressed by Stephan-type diffusion rule [15]. The
I. Skuratovsky et al. / Chemical Engineering and Processing 44 (2005) 187192 189
Fig. 1. Comparison between the predictions of the present pneumatic drying model, DryPak model, Rocha in [20] and Levy and Borde [8] models and
the experimental data for (a) gas temperature, (b) solid temperature, (c) gas humidity and (d) particles moisture content along the dryer length.
mass transfer coefficient was calculated in analogy to the present two-dimensional model and the results of experi-
heat transfer coefficient from the Sherwood number, which mental data and one-dimensional models requires a repre-
is equivalent to the Nusselt number. It should also be noted sentation model for presenting the two-dimensional data in
that both the gas and the dispersed phases are mixtures, and one-dimensional terms. Thus, an averaging technique was
hence all their thermodynamic properties were calculated used to obtain the average values of the various solution
using the mixture theory. properties at the dryer cross-section. The average value of
a property, , at the dryer cross-sectional area was obtained
by mass weighted method and an average temperature of
3. Numerical simulations a phase was evaluated by the mean bulk temperature across
the tube.
The pneumatic drying model was solved numerically for R R
2 0 urdr 2 0 ucp Trdr
the drying processes of sand particles. The numerical proce- = R ; Tave = R (1)
dure includes discretization of the calculation domain into 2 0 urdr 2 0 ucp rdr
torus-shaped final volumes, and solving the model equa-
tions by implementation of the semi-implicit method for
pressure-linked equations (SIMPLE) algorithm [16]. The nu- 4. Numerical results and discussion
merical procedure also implemented the Interphase Slip Al-
gorithm (IPSA) of [17] in order to account the various cou- The predictions of the numerical simulations with
pling between the phases. The simulation stopped when the Baeyens et al.s [5] correlation for heat transfer were also
moisture content of a particle falls to a predefined value or compared with the experimental results of Rocha [13] (pre-
when the flow reaches the exit of the pneumatic dryer. sented by Silva and Correa [18]) that were obtained in a
In order to validate the theoretical model, the predic- 4-m high pneumatic dryer with diameter of 5.25 cm. In this
tions of the numerical simulations were compared with study, 380-m sand particles having density of 2622 kg/m3
experimental data. Comparison between the results of the and solid mass flow rate of 4.74 103 kg/s were dried
190 I. Skuratovsky et al. / Chemical Engineering and Processing 44 (2005) 187192
Fig. 2. The predictions of the pneumatic drying model for (a) gas phase velocity, (b) dispersed phase velocity, (c) gas phase temperature, (d) dispersed
phase temperature, (e) gas humidity, (f) particles moisture content and (g) particles diameter along stream lines and the dryer length.
I. Skuratovsky et al. / Chemical Engineering and Processing 44 (2005) 187192 191
with 3.947 102 kg/s air mass flow rate. Comparison ability to simulate and to predict drying processes in pneu-
between the predictions of the numerical simulations and matic dryer.
the experimental data for changes of gas temperature, solid
temperature, gas humidity and particles moisture content
with length under known wall temperature operating condi- Appendix A. Nomenclature
tions is presented in Fig. 1ad, respectively. When known
wall temperature operating conditions were simulated, it cp (J/kg K) specific heat of the gas
was assumed that in average the pipe wall temperature is R (m) radius of the pipe
just about the outlet air temperature and it is falling linearly Tave (K) average temperature
from 360 K at the inlet to 354 K at the outlet. In this way, T (K) temperature
heat losses from the dryer walls are considered indirectly. u (m/s) velocity
In these figures, the star symbols represent the experimen-
tal data of Rocha [13] that were published by Silva and Greek symbols
Correa [18] and the other curves and symbols represent the density
predictions of various models and numerical simulations. dummy property
Form these figures, it can be seen that the predictions of the
two-dimensional numerical simulations fit fairly well with
the experimental data and both one-dimensional DryPak
[19] and Levy and Borde [8] models. Detailed comparison References
between the various one-dimensional models can be found
at Levy and Borde [20]. Since the theoretical pneumatic [1] R.M. Bowen, in: A.C. Eringen (Ed.), Theory of Mixtures in Con-
tinuum Physics, Academic Press, NY, USA, 1976.
drying model and the numerical simulations done in the
[2] D. Gidaspow, Multiphase Flow and Fluidization, Academic Press,
course of this study predicted successfully the most impor- Boston, USA, 1994.
tant flow parameters (gas temperature, solid temperature, [3] P.A. Cundall, O.D. Strack, A discrete numerical model for granular
gas humidity and particles moisture content) of the drying assemblies, Geotechnique 29 (1979) 4765.
process, it was concluded that the presented model could [4] J. Andrieu, R. Bressat, Experimental, experimental & theoretical
study of a pneumatic dryer, Proc. 3rd Int. Drying Symp. 2 (1982)
be used for further investigations. The distributions of the
1019.
various flow properties along the dryer length for various [5] J. Baeyens, D. van Gauwbergen, I. Vinckier, Pneumatic drying: the
stream lines (i.e., fixed r/R) are presented in Fig. 2. use of large-scale experimental data in a design procedure, Powder
Form these figures, it can be seen that a fully developed Technol. 83 (1995) 139148.
flow was obtained after about 3 m from the dryer inlet. In [6] D. Levi-Hevroni, A. Levy, I. Borde, Mathematical modelling of
addition, various thicknesses of boundary layers were ob- drying of liquid/solid slurries in steady sate one-dimensional flow,
Drying Technol. 13 (5-7) (1995) 11871201.
tained for the various phases properties. This may influence [7] A. Levy, D.J. Mason, I. Borde, D. Levi-Hevroni, Drying of wet solids
the final product properties. particles in a steady-state one-dimensional flow, Powder Technol. 85
(1988) 1523.
[8] A. Levy, I. Borde, Steady-state one-dimensional flow for a pneumatic
5. Conclusions dryer, Chem. Eng. Proc. 38 (1999) 121130.
[9] Z. Mindziul, A. Kmiec, Modeling gas-solid flow in a pneumatic-flash
dryer, Drying96 Proc. 10th Int. Drying Symp. A (1996) 275
Two-Fluid, two-dimensional model was developed for 282.
modeling the dilute flow of particulate materials through [10] S.C.S. Rocha, A.E.A. Paixo, Pseudo two-dimensional model for a
pneumatic dryer. The model was solved for a steady-state pneumatic dryer, Drying96 Proc. 10th Int. Drying Symp. A (1996)
condition. Axial and radial profiles for the flow variables 340348.
[11] M.A. Silva, S.A. Nebra, Numerical simulation of drying in a cyclone,
were obtained. The developed model was applied to sim- Drying Technol. 15 (6-8) (1997) 17311741.
ulate the drying process of wet sand in a laboratory-scale [12] R. Blasco, R. Vega, P.I. Alvarez, Pneumatic drying with superheated
pneumatic dryer. The numerical solutions were compared steam: bi-dimensional model for high solid concentration, Drying
with the results of other numerical and experimental in- Technol. 19 (8) (2001) 20472061.
vestigations. The successful comparisons validate the theo- [13] S.C.S. Rocha, Contribution to the study of pneumatic drying: simula-
tion and influence of the gas-particle heat transfer coefficient, Ph.D.
retical and the numerical models. As demonstrated by the
Thesis, So Paulo University, So Paulo, Brazil, (in Portuguese),
two-dimensional numerical simulations, the radial distribu- 1988.
tion of the flow characteristics causes an uneven product [14] I. Skuratovsky, A. Levy, I. Borde, Two-fluid, two-dimensional model
quality. Thus in order to improve the drying process, a re- for pneumatic drying, Drying Technol. 21 (9) (2003) 16491672.
liable two-dimensional model is required. Further investi- [15] N. Abuaf, F.W. Staub, Drying of liquidsolid slurry droplets, Drying
86 Proc. 5th Int. Drying Symp. 1 (1987) 227248.
gations are needed in order to validate the two-dimensional
[16] S.V. Patankar, Numerical Heat Transfer and Fluid Flow, Hemisphere
distribution of the flow characteristic and to improve the Publishing Corporation, New York, USA, 1980.
model to account for particle circulation in the investigated [17] D.B. Spalding, Developments in the IPSA procedure for numeri-
domain. The present investigation significantly extends the cal computation of multiphase-flow phenomena with interphase slip,
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unequal temperatures, etc. in: Numerical Properties and Method- [19] Z. Pakowski, DryPak v.3, Program for psychometric and drying
ologies in Heat Transfer, Hemisphere, Washington, DC, 1983, computation, 1996.
pp. 421476. [20] A. Levy, I. Borde, Two-fluid model for pneumatic drying of
[18] M.A. Silva, J.L.G. Correa, Using DryPak to simulate drying process, particulate materials, Drying Technol. 19 (8) (2001) 1773
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Chemical Engineering and Processing 44 (2005) 193200
Received 25 August 2003; received in revised form 27 January 2004; accepted 11 February 2004
Available online 17 June 2004
Abstract
A systematic study of salting-out precipitation is carried out to obtain the operational limits within which this precipitation method can
be applied for the production of fines (mean particle size <10 m) with acceptable quality and productivity. The model substances: glycine
and sodium chloride are salted-out from their aqueous solutions by using ethanol as antisolvent. The main operational parameter is the initial
supersaturation of the solutions. It is shown that the smallest particles can be produced at the limits of the metastability domain determined by
three optional process parameters: the initial solution concentration, the equilibrium solubility and the operational time. The product quality
(crystallinity, polymorphic states, aggregation) and productivity considerably change with the operational conditions.
2004 Elsevier B.V. All rights reserved.
Keywords: Salting-out precipitation; Weimarn laws; Metastability; Initial supersaturation; Particle size
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.013
194 J. Toth et al. / Chemical Engineering and Processing 44 (2005) 193200
In the colloid chemistry practice the antisolvent precip- (quenching) before the particles could grow up their final,
itation is called Weimarns method. Weimarn published stable size.
his famous work The precipitation laws early in the past
century [4] but his statements seem to be still valid and
useful for reconsidering. His main conception was that the 3. Experimental
mean size of precipitates may change with the supersatura-
tion through a maximum. The maximum shifts up and left In the experiments analytical grade chemicals: glycine
with increasing time until the system reaches its stable state (purity 98.5%) or sodium chloride (99.5%), ethanol (99.8%)
where the precipitation process is completed. The principle and deionized water were used. The precipitation mode
of the Weimarn laws on precipitation is schematically shown was one-shot: at high supersaturations various amount (V0
in Fig. 1. According to the Weimarn laws, fine particles can = 0.00412 cm3 ) of saturated or undersaturated aqueous so-
be produced both at low and high supersaturation depending lutions of glycine (c0 = 20.000.50 g/100 g solution) were
on the time of crystallization and the solubility of the pre- added in one portion to 12 cm3 ethanol at ambient temper-
cipitate. Weimarn based his statements on his chemical pre- ature. At low supersaturations 12 cm3 saturated solutions of
cipitation experiences. What is the situation for salting-out glycine were added to various amount (Ve = 0.112 cm3 ) of
precipitation? It is not necessarily the same because there ethanol. Depending on the solution/antisolvent ratios, series
is a fundamental difference between the chemical- and salt- of initial supersaturations were created. In each case con-
ing out precipitation. In the first case the supersaturation centrated ethanol, saturated at 298 K (0.0037 g glycine/100 g
changes with the concentration of the reaction partners while solvent) was used. In the most cases the crystals appeared
the equilibrium concentration (solubility) remains constant, at once after the shots but 10 min stirring was applied ad-
but at salting-out processes both the supersaturation and the ditionally. No longer stirring time was allowed not to leave
equilibrium solubility change with the solution/antisolvent time for the polymorphic change. Some precipitation runs,
ratios, therefore, both can influence the particle size. together with the in-line particle size measurements, were
The relationship between particle size, solubility carried out directly in the 15 cm3 volume MALVERN cu-
and supersaturation is expressed by the well-known vette. When the suspension densities were higher than al-
GibbsThomson equation [5a]: lowed in direct CSD measurements by MALVERN 2600
c(r) 2V the samples were precipitated in an Erlenmeyer flask under
ln = ln S = , (1) stirring. In these cases the CSD measurements were possi-
c kTr
ble after the appropriate dilution of the slurry. The diluting
where c(r) is the solubility of the particles of size (radius) agent was the actual mother liquid or concentrated and satu-
r, c* is the normal equilibrium solubility of the substance, rated ethanol. For characterizing the particle size the volume
S is the supersaturation ratio, is the surface energy, V is mean diameter was used:
the molecular volume, k is the Boltzmann constant, T is the 4
absolute temperature. Eq. (1) does not consider the growth nd
d = 3 , (2)
process which follows the nucleation step. At precipitation, nd
in most cases, the growth process is rather an aggregation
step. When aiming fine crystals, the growth subprocess has to where n is the number of particles of equivalent diameter d.
be retarded, consequently, the precipitation has to be stopped For characterizing the particle size distribution the so called
span was used:
D90 D10
span = , (3)
D50
Mean size of crystalline individuals
stable state
where D10 , D50 , and D90 is the diameter below which 10,
50 and 90% of the volume of the particles lies.
The precipitates were separated by glass fibre filter,
washed by ethanol and air-dried. In some cases X-ray
diffraction (by Philips 3710) for polymorphism and SEM
unstable states
ity of sodium chloride, longer (60 min) additional stirring best fitted the whole range of solubilities have been found
was allowed. as follows:
for the glycinewaterethanol system:
y = 2.618 + 2.264 102 x
4. Experimental results and discussion
+ 23.17 exp(4.060 102 x), (5)
The main driving force of a salting-out precipitation pro- for the NaClwaterethanol system:
cess is the supersaturation generated by the different solubil-
ities of the solute in the solvent and antisolvent. The one-shot y = 24.91 4.348 101 x
mode generally means that the necessary amount of the an- + 18.66 exp[2.433 102 (100 x)], (6)
tisolvent is added in one portion to the initial solution (either where x is the mass percent of the ethanol, y is the equilib-
saturated or undersaturated) as it is schematically shown in rium concentration. In the range of 90100% ethanol con-
Fig. 2. In our cases the aqueous solution was added to the tent another type of equation was construed for the sake of
antisolvent. As a result of the antisolvent addition the orig- higher accuracy:
inal solubility of the substance will change until the new for the glycinewaterethanol system:
equilibrium solubility, ceq has been reached. To characterize
the supersaturation driving force in a precipitation system lg y = 2.656 9.476 102 x
the so called initial supersaturation, Si is used: + 1.363 103 x2 9.243 106 x3 , (7)
c0 for the NaClwaterethanol system:
Si = , (4)
ceq
lg y = 6.764 101 + 7.363 102 x 7.861 104 x2
i.e. it is a ratio between the initial concentration of the
(8)
solution to be crystallized (in this case the aqueous solu-
tion) and the equilibrium concentration (solubility) in the 25
solute-solvent-antisolvent system. In this way different val-
(a)
c0 (g glycine/100 g solution)
30
'one-shot' addition
C0- 25 (b)
c0 (g NaCl/100 g solution)
20
supersaturation driving
Solubility
0
0 20 40 60 80 100 0 20 40 60 80 100
antisolvent
Mass percent of the antisolvent Mass percent (g ethanol/100 g solvent), (%)
Fig. 2. The scheme of the one shot salting-out precipitation from the Fig. 3. Solubilities and applied supersaturation programmes for the
saturated and undersaturated solutions. glycinewaterethanol (a) and NaClwaterethanol (b) model systems.
196 J. Toth et al. / Chemical Engineering and Processing 44 (2005) 193200
The solubility curves (at 298 K) as well as the ways of cre- ture [8] where the unstable form is usually reported for
ating the different supersaturations are shown in Fig. 3, for waterethanol systems.
the glycinewaterethanol (a) and NaClwaterethanol (b) SEM micrographs were made on the representing samples
model systems, respectively. belonging to the points A, B, C in Fig. 4a, at the same time
The experiments with saturated aqueous solutions show XRD investigations were also carried out from these sam-
remarkable differences concerning the two model systems ples. At point A the polymorphic form is mainly (97%),
as it can be seen in Fig. 4, where the corresponding ini- the particles seem rather dendritic (Fig. 5). At point B the
tial supersaturation, Si and average particle size, d data of particles are pure with the signs of aggregation growth
glycine (a) and NaCl (b) are plotted, separately. When only (Fig. 6), while at point C the pure form was produced
a very small amount of glycine solution (0.004 cm3 ) was (Fig. 7). As a remarkable new experience: it was possible to
added to 12 cm3 of antisolvent the alcohol mass percent produce the pure form by precipitation.
was very high: 99.96% but surprisingly the particle size was Comparing the precipitation data of glycine and the refer-
not as small as expected, it was about 50 m. At somewhat ence non-polymorphic sodium chloride, the latter shows def-
lower Si and alcohol ratio a minimum occurred (point A in inite maximum in the Si d relation. It has to be mentioned
Fig. 4a). After the minimum the particle size approached that fine particles (d < 10 m) were produced even from sat-
to a plateau (point B in Fig. 4a) then a peak of 100 m, urated NaCl solutions (Fig. 4b). It is interesting since NaCl is
and finally decreased down to 20 m. These just mentioned better soluble in ethanol and longer operational time (60 min)
anomalies in the glycine particle size and Si relation can was allowed for its crystallization. But comparing the growth
be caused by several reasons (the change of the nucleation abilities of the two substances the linear growth rates are dif-
mechanism or polymorphic states, etc.). The polymorphic ferent at least in one magnitude: 108 ms1 for NaCl [5b]
change of glycine itself is already known from the litera- and for glycine 107 ms1 was found [9]. This case well
demonstrates the importance of the material properties.
The experiences with saturated solutions did not result in
acceptable small particle size for glycine and the particles
120 were more or less agglomerated. Not much improvement
(a) was achieved when some agglomeration retarding additives
Average particle size, d (mm)
Fig. 5. SEM micrograph on the glycine sample (mainly form) precipitated at high alcohol content and initial supersaturation (see point A in Fig. 4a).
represent the saturated initial solutions, while the lowest sibilities for the investigated model systems. Regarding the
ones belong to the less saturated solutions. At the same time formation of fine particles (d< 10 m) the following ten-
the lowest boundaries show the limits under which there dencies have been found: in the case of glycine, under the
was no crystallization within the applied operational time before mentioned experimental conditions, the desired small
(10 min for glycine and 60 min for NaCl). It means that the size was available only when undersaturated aqueous solu-
metastable limit must be not at a certain point but along a tions (c0 = 3.442.56 g/100 g solution) but high initial su-
rather broad operational area. persaturations (Si 800600) were applied. Because of the
By determining the boundaries of the whole operational low solubility at high ethanol content (at 99.6% ethanol ceq
field the precipitation area of the expected particle size can = 0.0041 g glycine/100 g solution) it was possible to cre-
be chosen within these limits. Fig. 8a and b show the pos- ate high supersaturations even in the originally undersat-
Fig. 6. SEM micrograph on the glycine sample ( form) precipitated at medium alcohol content and initial supersaturation (see point B in Fig. 4a).
198 J. Toth et al. / Chemical Engineering and Processing 44 (2005) 193200
Fig. 7. SEM micrograph on the glycine sample ( form) precipitated at low alcohol content and initial supersaturation (see point C in Fig. 4a).
urated solutions. In the case of NaCl the expected small the so called span see Eq. (3) as the measure of the
size was already obtained from saturated aqueous solution width of the particle size distribution. Having checked all
(c0 = 26.55 g NaCl/100 g solution) also at high supersatu- the particle size analysis data the characteristic value of span
ration (Si = 394). Decreasing the initial solution concentra- changed between 0.9 and 1.6 for glycine and between 0.9
tion down to 7.4 g NaCl/100 g solution (Si = 107, at 99.6%
ethanol content) the average particle size also decreased
down to 1 m.
When the goal is the production of fine particles it is
important to save the primary size of the crystals as they
appear first in the solution, i.e. the nucleation has to be pro-
moted over the growth and aggregation steps. In the case
of undersaturated, weak initial solutions the precipitation
takes place near the metastable region where the kinetic
processes are rather slow. For example, the induction time
which was necessary for crystallization in the weakest NaCl
solutions approaches to 60 min. Repeating the precipita-
tion (where the ethanol content was the same 99.6%) with
saturated aqueous solution there was no measurable induc-
tion time and the particle size changed considerably within
the applied 60 min operational time: the d was 4.41 m
after 10 min, 8.86 m at 20 min and finally16.27 m at
60 min. It is obvious that in the latter case not the small-
est available size was measured after 60 min, but for the
sake of comparison the same operational time had to be
applied.
Beside the average particle size, the size distribution is
also an important parameter of the product. Comparing the
obtained cumulative undersize distribution of the precipi-
tates it has been found that the ratio of the smallest parti-
cles (below 10 m) in the distribution was more than 50%
when d 10 m. In the other cases (d > 10 m) the ratio
was less than 50% and showed decreasing tendency with
increasing size. The Malvern 2600 size-analyzer calculates Fig. 8. The operational areas of the glycine (a) and NaCl (b) precipitation.
J. Toth et al. / Chemical Engineering and Processing 44 (2005) 193200 199
100
The productivity of a crystallization process is usually
expressed as the amount of the produced crystals in unit
80 volume of solution and unit time. The maximum available
amounts of the crystals produced from unit volume of solu-
60 tions, Q (g cm3 ) were calculated on the bases of the solu-
bility differences and shown as function of the average size
40 in Fig. 9a for glycine and Fig. 9b for NaCl. Although it is an
approximation especially for the weakest slurries, where the
20 measuring error would be also high, but in other cases it is
acceptable because the measured particle sizes were close to
0 their final, stable size. Taking the produced amounts of both
0 0.02 0.04 0.06 0.08 model materials as well as the operational time (10 min for
Q (gcm-3) glycine and 60 min for NaCl) into account the available pro-
Fig. 9. The relation between the average particle size, d and the maximum ductivities are between 1.66 106 1.82 104 g cm3 s1 ,
available amount of crystals, Q produced in unit volume of solution in or expressed in the usual industrial unit 6654 kg m3 h1 .
the glycinewaterethanol (a) and the NaClwaterethanol (b) systems The relatively low productivity is quite common in colloid
( refers to saturated initial solutions, refer to undersaturated systems or in nanoparticle formation. It is always a question
initial solutions).
of consideration to decide about what productivity is still
acceptable and on what expense, although there is a strong
and 1.8 for NaCl samples. These values are typical for the rule in the crystallization practice: the particle size and pro-
finest precipitates, too. ductivity cant be changed independently of each other.
Summarizing the experiences on the formation of fines In Fig. 10 the operational fields of the two model systems
by salting-out precipitation: the supersaturation has the are plotted together to make a comparison possible and assist
in the explanation of the experimental findings.
120
Average particle size d, (mm)
100 5. Conclusion
NaCl
80 A systematic study of the salting-out precipitation pro-
cess was made to obtain characteristic particle size and pro-
60 ductivity data within wide range of the initial supersatu-
rations. The appropriate supersaturations were created by
40 changing two independent parameters: the initial solution
glycine
metastability concentration and the solubility. The operational time was
20
domain fixed at a given system but in limited cases the effect of
the operational time on the particle size was also investi-
0
gated.
1 10 100 1000 10000
Initial supersaturation, Si () It has been concluded that the salting-out precipitation is
a flexible and acceptable process for producing fines but the
Fig. 10. The operational areas of the two systems studied. material properties (solubility, nucleation and growth ability)
200 J. Toth et al. / Chemical Engineering and Processing 44 (2005) 193200
may considerably limit the possibilities as it is well seen in d equivalent diameter of the particles (m)
Fig. 10. d average particle size (m)
The supersaturation particle size relations show definite Dx diameter below which x% of the volume of the
maximums just following the Weimarns statement in this particles lies (m)
respect. The metastable limit below which there is no crys- k Boltzmann constant (J K1 )
tallization within the applied batch time exists along the n the number of particles of equivalent diameter d ()
lower boundary of the operational field. The finest and ag- Q maximum available amount of crystals produced
glomeration free particles can be produced at the extremes, from unit volume of solution (g cm3 )
i.e. at the edges of the metastability domain determined by r particle radius (m)
changing three optional parameters: the initial solution con- S supersaturation ratio ()
centration, the solubility and operational time. Since the SEM scanning electron microscopy
particle size depends on the relative rate of the nucleation Si initial supersaturation ()
and aggregation growth kinetic processes the application of T absolute temperature (K)
growth retarding techniques (quenching) can be useful. The V molecular volume (m3 )
polymorphic state may change at the extremes: for example V0 volume of aqueous solutions (cm3 )
pure -glycine form was precipitated at low alcohol content Ve volume of ethanol antisolvent (cm3 )
although the form is more typical at salting-out precipita- XRD X-ray diffraction
tion. surface energy (J m2 )
Relatively low productivity can be expected when fines are
produced by salting-out process although it also depends on
the substance properties. The post-crystallization processing
(separation, concentration etc.) of very weak slurries may References
go according to the routines of colloid chemistry practice.
[1] The 15th Symp., Ind. Cryst., Sorrento, Italy, 2002.
[2] The 8th Conf., Colloid Chem., Keszthely, Hungary, 2002.
Acknowledgements [3] P.H. Karpinsky, Maneuvering through the Complexities of Batch
Precipitation, Proc. Int. Symp. Ind. Cryst., Tokyo, Japan, 1998,
The authors are very grateful to the University of pp. 1322.
[4] P.P. von Weimarn, The precipitation laws, Chem. Rev. 2 (1926) 217
Veszprm, Department of Silicate Chemistry and Material 242.
Sciences, Hungary for the XRD and SEM facilities. [5] (a) J.W. Mullin, Crystallization, third ed., Butterworh-Heinemann,
London, 1993. p. 102.;
(b) J.W. Mullin, Crystallization, third ed., Butterworh-Heinemann,
Appendix A. Nomenclature London, 1993, p. 222.
[6] A. Seidell, Solubilities of Organic Compounds, D. van Norstrand
Company Inc., New York, 1941, p. 124.
c(r) solubility of the particles of size (radius) r [7] H. Stephen, Solubilities of Inorganic and Organic Compounds, Perg-
(kmol m3 ) amon Press, 1964, pp. 102103.
c* normal equilibrium solubility of the substance [8] W. Hubig, ber die drei Formen des Glycins, Z. Naturforsch. 13b
(kmol m3 ) (1958) 633638.
[9] S. Halsz-Pterfi, Controlled Precipitation, CSc Thesis, Hung. Ac.
c0 initial concentration of aqueous solutions Sci., Budapest, 1994.
(g solute/100 g solution) [10] N. Garti, H. Zour, The effect of surfactants on the crystallization
ceq solubility of the substance (g solute/100 g solution) and polymorphic transformation of glutamic acid, J. Cryst. Growth
CSD crystal size distribution 172 (1997) 486498.
Chemical Engineering and Processing 44 (2005) 201207
Received 25 July 2003; received in revised form 15 February 2004; accepted 19 March 2004
Available online 24 June 2004
Abstract
A process using supercritical CO2 has been developed to produce form V crystals of cocoa butter. In this process, solid cocoa butter is put
in an autoclave in which supercritical carbon dioxide is then introduced. At high pressure, two liquid phases, one CO2 -rich and one cocoa
butter-rich are formed. Both of them can be sent to a depressurisation nozzle leading to particle formation in an expansion vessel. Moreover,
particles can also be formed in the first autoclave undergoing slower depressurisation. Both particle populations (upstream and downstream
the nozzle) have been characterised using calorimetric method (differential scanning calorimetry, DSC) and environmental scanning electron
microscopy (ESEM). The polymorphism of the particles produced as well as their size and morphology show that they are potentially usable
in the tempering step of the manufacturing process of chocolate.
2004 Elsevier B.V. All rights reserved.
1. Introduction end product. If the wrong type of fat is present the chocolate
may exhibit a white powdery surface called fat bloom which
1.1. Polymorphism of cocoa butter and chocolate tempering is to be avoided because of its unpleasant appearance. The
most desirable form is known as form V (or 2 ) having a
Cocoa butter, the fat of chocolate, is responsible for the melting temperature of 305307 K (3234 C). The transfer
pleasant melt in the mouth sensation given by chocolate. to the even more stable form VI is not desirable since it
It is a complex mixture of triacylglycerol (TAGs), which might lead to fat bloom as do the less stable forms.
melting points are in the good range (3135 C) to give The processing conditions determine which poly-
this feeling [1]. morph is formed. To obtain predominantly form V a
The most abundant are monounsaturated TAGs, the un- pre-crystallisation step also called tempering has been intro-
saturated fatty acid (very often oleic acid) being in the duced in the chocolate manufacturing process. It is aimed
2-position. 1-Palmitoyl-2-oleyl-3-stearoylglycerol (P-O-S), at the formation of form V seed crystals which in turn
P-O-P and S-O-S account for 3638, 1416 and 2328%, will force the bulk of the remaining fat to crystallise in
respectively of the total TAGs. It is these TAGs which are this stable form. Two main ways are used: (i) starting with
mainly responsible for the behaviour of chocolate when un- hot liquid chocolate 318323 K (4550 C) a succession
dergoing crystallisation [2]. of cooling to 300 K (27 C) in order to form both stable
There are six different ways for these TAGs to arrange and unstable crystals followed by re-heating to 303305 K
themselves when they crystallise. Six different polymorphs (3032 C) to melt only less stable crystals will lead to form
noted Ithe less stable with the lowest melting point 290 K V crystals which, in turn, will seed the mass of chocolate
(17 C)to VIthe most stable with the highest melting and (ii) seeding the mass of untempered chocolate by finely
point 308 K (35 C)can be obtained. The relative amount divided form V crystals of cocoa butter.
of these six polymorphs will condition several features of the
1.2. Crystallisation with supercritical processes
Corresponding author. Tel.: +33 563 493088; fax: +33 563 493025.
E-mail address: letourne@enstimac.fr (J.-J. Letourneau). Supercritical fluid (SCF) technology presents a new and
URL: http://wwww.enstimac.fr. interesting route for particle formation, which avoids most of
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.013
202 J.-J. Letourneau et al. / Chemical Engineering and Processing 44 (2005) 201207
the drawbacks of the traditional methods of milling/crushing with a maximum torque of 1.8 Nm and a flexible mantle
or liquid crystallisation. Supercritical processes are known heater.
to give micro- or even nano-particles with narrow size distri- The flow coming out this vessel is sprayed into the ex-
bution, and may allow the control of crystal polymorphism. pansion vessel (7) by means of a nozzle (6) (Spraydry
In addition, several other advantages inherent to these pro- SK-SIY80-SKY16, orifice insert diameter: 340 m, Spray-
cesses must be emphasised: they are single-step processes ing System). The powder formed is collected in a porous bag
with simplified downstream processing and they are envi- made of PTFE fibres. Then, CO2 is depressurised (10) and
ronmentally desirable since they avoid the use of organic can either be directed to the vent or purified and recycled.
solvents. Moreover, they allow the processing of thermola-
bile molecules and give high purity products [3]. 2.2. Cocoa butter particle generation
Although most of the applications of supercritical particle
formation are known in the pharmaceutical industry, some Pieces of solid cocoa butter are loaded in the vessel (5)
examples can be found with foodstuff. Cocoa butter a rela- equipped with a stirrer and this vessel is filled with CO2 .
tively high value product has been successfully micronised Then, the operating temperature and the stirrer speed are
using the PGSS (particles from gas-saturated solutions) pro- fixed by the controllers. Further addition of CO2 allows
cess [4]. In this paper we will investigate the production of reaching the operating pressure. The mixture thus obtained is
fine cocoa butter crystals in order to use them for the seed- stirred during a long enough period of time (at least 5 mn at
ing of chocolate. constant pressure and temperature) in order to reach the ther-
modynamic equilibrium. In particular if two liquid phases
are present, each of them is assumed to be saturated.
2. Material and methods The second vessel (7) is then filled with CO2 until reach-
ing the second operating pressure. This is the expansion
2.1. Experimental apparatus pressure at which the mixture is placed downstream of the
nozzle. This pressure is fixed during all the experiment with
The experiments were carried out in a versatile pilot plant a back-pressure regulator (10).
(Separex, France). A schematic diagram of the apparatus is The temperature of the CO2 upstream from the stirred
shown in Fig. 1. Carbon dioxide is cooled and stored in a liq- vessel is controlled by the heating device (4) and fixed to
uid CO2 storage tank (2). It can be circulated at a maximum be the same as the temperature of the mixture in the stirred
flow of 25 kg h1 by a membrane pump (Lewa, Germany) vessel.
(3). Compressed CO2 passes then through a heat exchanger During the experiments the valve between the two ves-
(4) and becomes supercritical. Some of the devices (1, 8, 9, sels is open. The saturated mixture sprayed into the expan-
13) shown in Fig. 1 are used for other experiments such as sion vessel via the nozzle, is subjected to a sudden drop
SAS or RESS with co-solvent. in pressure, resulting in supersaturated conditions and the
The vessel (5) (PARR Instrument, USA) is equipped crystallisation of the cocoa butter. This powder is collected
with three sapphire windows (16), a magnetic stirrer (15) in the bag inside the second vessel. This process is known
as RESS process (rapid expansion of supercritical solutions) agitation these two phases are mixed and the resulting fluid
[3]. appears (as seen through the windows) to be homogeneous
Two major types of experiments have been achieved: just like an emulsion.
The drop in pressure undergone by the mixture in the noz-
In the first one, the first vessel is let to slowly depres-
zle, leads also the temperature to fall and crystals of CO2
surise during its emptying through the nozzle. Therefore,
may appear (CO2 triple point: T = 216.6 K, P = 0.52 MPa).
particles of cocoa butter can also be formed in this vessel.
To prevent this solid CO2 formation, the pressure P7 in the
In the second, the membrane pump (3) feeds the vessel
expansion vessel must be kept beyond the triple point pres-
with CO2 in order to compensate the emptying via the
sure. But this does not always prevent the CO2 liquefaction
nozzle and to maintain a constant pressure.
if the temperature upstream the nozzle is not high enough.
Another refinement in the classification of types of ex- As an example shown in Fig. 2 (path A), the final tempera-
periments depends on the initial load of cocoa butter. For ture of pure CO2 at T = 333 K submit to an isenthalpic de-
small amounts, the mixture appears in a homogeneous single pressurization from P = 10 to 1 MPa is T = 233 K, which
phase. On the other hand, when the initial amount increases, is a point within the boundary of the liquidvapour region.
two phases are present. The presence of two phasesliquid and gasaround the
If the temperature is too low, the solid cocoa butter formed particles in formation could change the growth of the crys-
this second phase, but with higher temperatures two fluid tals and therefore their final morphology. The heating device
phases are in equilibrium: one is rich in CO2 and the other (17) is used to prevent the temperature T7 in the expansion
is rich in cocoa butter. Kokot et al. [5] showed that at 313 K vessel to be lower than the dew temperature of pure CO2 at
and 20 MPa, the mass fractions of CO2 for these two phases P7 . The theoretical path for the experiment #3 of Table 1 is
are 0.44 and 0.98. When working with two fluid phases shown in Fig. 2 (path B). For this experiment boiling water
and without stirring, the results of the experiments depend has been used in the heating device and the final tempera-
on the position of the outlet pipe of the first vessel: top or ture of the mixture at T = 373 K submit to a depressuriza-
bottom. If the fluid is extracted from the top of the vessel, tion from P = 20 to 1 MPa is T = 288 K. As it can be seen
the cocoa butter powder is produced from the richest phase this depressurization is almost isenthalpic.
in CO2 . Conversely, it is the cocoa butter rich phase which is The flowrate of CO2 is adapted to fit with the operating
extracted from the bottom. If the mixture is homogenised by conditions. It mainly depends on the characteristics of the
204 J.-J. Letourneau et al. / Chemical Engineering and Processing 44 (2005) 201207
Table 1
Experimental operating conditions
Experiment number Series Diam. (mm) M0 (g) V5 (cm3 ) P5 (MPa) T5 (K) P7 (MPa) T7 (K) Duration (min)
1 E-I 0.34 20.8 2000 20 313 0.6 288 23
2 E-I 0.34 30.6 2000 25 373 0.3 288 28
3 E-I 0.41 18.6 2000 20 318 1 288 22
4 E-I 0.41 36 2000 20 323 0.1 288 21
5 E-I 0.41 19.9 2000 30 313 0.9 288 21
6 E-II 0.41 20.6 2000 30 303 0.1 291 10
7 E-II 1.50 20.2 2000 25 303 0.1 293 6
8 E-III 0.41 19.9 2000 30 313 0.1 289 4
9 E-III 1.50 102.3 2000 31 298 0.1 292 3
10 E-IV 0.34 99.7 2000 20 293 0.7 291 7
11 E-IV 0.34 106.4 2000 27 305 0.4 288 24
12 E-IV 0.41 100.6 2000 20 313 0.2 288 14
13 E-IV 0.41 94.4 2000 32 313 0.3 288 15
14 E-V 0.34 128 1200 20 303 4 283 5
15 E-V 0.34 135 1200 25 308 2 283 5
Diam.: diameter of the nozzle orifice; M0 : initial mass of cocoa butter; V5 , P5 , T5 : volume, pressure and temperature of the tank (5), respectively; P7 ,
T7 : pressure and temperature of the tank (7), respectively.
nozzle and on the pressure difference P5 P7 between the 3. Results and discussion
two vessels. A typical flowrate value for the experiences
listed in Table 1 is about 20 kg h1 . 3.1. Particle formation experiments
The powder obtained in experiment 5 was collected in particles obtained in this vessel are made of a mixture of both
the vessel (5) and has the following characteristics: Tpeak forms IV and V. The faster the drop in pressure in this vessel,
= 300.5 K, Tend-set = 302.5 K for the first peak and: Tpeak the larger the quantity of form V powder obtained. A typical
= 303.7 K, Tend-set = 305.0 K for the second peak. All the example of this kind of particle is shown in Fig. 5. This
Fig. 4. ESEM picture of a cocoa butter particle obtained with experiment #15.
206 J.-J. Letourneau et al. / Chemical Engineering and Processing 44 (2005) 201207
Fig. 5. ESEM picture of a cocoa butter particle obtained with experiment #5.
powder is generally white, extremely light and sometimes 4. Perspectives and conclusion
pieces of original yellow cocoa butter can be found among
the particles. The best cocoa powders in terms of appearance, DSC,
reproducibility and shelf-stability are those of the E-V series.
3.2. Seeding of chocolate They have not been tested yet to seed chocolate and this will
be part of a future work.
The cocoa butter powder obtained by supercritical process High shear stresses are known to favour the most stable
was able to seed using the following conditions. forms of the cocoa butter. The same phenomenon is probably
At 306 K (33 C) and above, the seeding produced an also appearing in the supercritical generation of cocoa butter
under-tempered chocolate; at 304 K (31 C) and below, the particles: when the particles are generated in the expansion
chocolate was quickly over-tempered. However, at 305 K vessel with a huge drop in pressure through a small nozzle,
(32 C), good tempering conditions were obtained with less they are exclusively made of form Vwhen generated in the
than 0.3% of cocoa butter seeds. This is at least 2 C higher first vessel with a slow drop in pressure form IV is present
than common seeding and several degrees higher than most and even predominant. This is a track for further studies.
industrial tempering step. Therefore, the chocolate is very A major interest in using this new process [8] is the value
much thinner. of the temperature at which seeding can be done with the
The powder samples described in series E-I and E-IV cocoa butter particles supercritically generated. At 305 K
(obtained with the smallest nozzle) gave the best results. The the chocolate is less viscous, this is advantageous in term
seeding was carried out at 305 K (32 C) with a mass fraction of flowability and energy consumption. An additional ad-
of 0.10.2% and produced a well-tempered chocolate. At vantage lies in the fact that the time needed to obtain a
this high temperature, the stirrer velocity is a critical point well-tempered chocolate is shorter (about 5 min). Moreover,
as an excess of mechanical energy could melt the seeds, the overall quantity of seeds to temper the chocolate is very
but this has to be tested using an industrial scale tempering small. Therefore, a scaling-up of this process to an industrial
machine (batch or continuous). scale appears feasible.
J.-J. Letourneau et al. / Chemical Engineering and Processing 44 (2005) 201207 207
Received 26 August 2003; received in revised form 1 March 2004; accepted 19 March 2004
Available online 17 July 2004
Abstract
This paper highlights some of the outcomes from a EU Accompanying Measure focussing on food powders. The main goals of the work
were to outline the major industrial problems, knowledge barriers, and research challenges and opportunities in relation to food powders, and
to promote the creation of a sustainable network of excellence in the area of food powders. Food powders are powders first and foremost,
thus many of the research challenges and opportunities are similar to handling and processing of other powders. As a result, much can be
learned from other industries that deal with powders. What makes food powders different from many other powders is their composition,
which is mainly of biological origin, and that they are eventually consumed by people and animals. Consequently, stability of food ingredient
functionality and prevention of contamination are major issues right through from powder production to final application of the powder, which
is usually in the form of a wet formulation.
2004 Elsevier B.V. All rights reserved.
fax: +353 21 4270249. This paper summarises some of the key findings from the
E-mail address: j.fitzpatrick@ucc.ie (J.J. Fitzpatrick). strategic document for research in food powders [1].
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.014
210 J.J. Fitzpatrick, L. Ahrne / Chemical Engineering and Processing 44 (2005) 209214
1.2. Food powders what is special about them 1.3. Identification of problems, knowledge barriers and
research challenges and opportunities
The development of formulation engineering concepts in
food manufacturing and the demand for diversity in food When looking at the processes involved in going from
products has driven a substantial market increase for food powder production to its final application, they can be
ingredients. Most ingredients are supplied in powdered form broadly divided into the following two categories in Table 1.
and therefore powder technology is an increasingly impor- Category A processes have the dominant influence in cre-
tant issue both to food ingredient manufacturers and food ating the powder properties that influence the powders
producers. The two major aspects about food powders that final application. Category B processes may influence the
make them special are biological origin and the fact that powder properties by degrading them or by requiring cer-
they are ultimately consumed by humans and animals. tain properties to allow effective handling and transport. To
The major reason for production in powder form is sim- identify problems, knowledge barriers and research chal-
ply to prolong the shelf-life of the ingredient by reducing lenges and opportunities, it may be useful to look at these
water content, otherwise the ingredient will be degraded and categories separately and to generically investigate how
broken down in its natural biological environment. So, the research possibilities may come about as a result.
major function of the powder form is to maintain the sta- For example, for category A processes, it may be useful
bility of the ingredient functionality until it is required for to firstly look at the applications of the powder (how it is
utilisation, which is usually in some sort of wet formulation. finally applied) and work backwards to the production of
The major functionalities of food ingredients can be broadly the powder. There are not many food powders that are di-
classified as rectly consumed by the final consumer in powder form only.
Most are incorporated as ingredients into some sort of wet
formulation somewhere along the chain before being finally
physical/chemical: for example, gelation, emulsification,
ingested by the consumer. As a result, an important area is
foaming, pH control;
research into the technologies and processes involved in ad-
nutritional: for example, vitamins, nutraceuticals;
dition and mixing of powders to produce these wet formu-
organoleptic: for example, colour, taste, smell, texture.
lations. Allied to this, is the creation of powder properties
that enable these processes to function and that enhance pro-
There are a multitude of food ingredients available with a cess performance. From this, a major area of research is the
whole variety of different functions, and there is huge scope investigation of how powder properties influence their roles
for R&D into investigating new ingredients, and new and in forming wet formulations. Some of these properties may
improved functionalities. As the role of the powder form is be difficult to define and measure, thus definition and mea-
mainly to preserve this functionality over time and to deliver surement may become research areas that must be tackled
it when required, the focus of this work deals with the pow- before effective investigation of how the properties affect
der issues and not the different ingredient functionalities. application.
The major powder issue with regard to food ingredient pow- A further step back from application to powder produc-
ders is maintaining the stability of ingredient functionality tion is the processes that create the desired powder proper-
from production right through to final powder application. ties. Thus, another major area of research involves the study
Most food powders are not directly consumed by humans of these processes, and investigating how raw material vari-
and animals, they are usually mixed with water and other ables and process input variables affect the engineering of
liquids to produce wet formulations, which are further pro- the desired powder properties. Finally, as mentioned above,
cessed to produce products that are directly consumed. As a a very important aspect of research for food powders is
result of being ultimately consumed by humans and animals, component stability, all the way from powder production,
prevention of contamination of the powders with microor-
ganisms, viruses and undesirable chemical components is a
huge issue for food powder manufacturers and the food in- Table 1
Classification of powder processes
dustry in general. One major case of food poisoning linked
to a contaminated powder can be very detrimental to a pro- A. Processes that give B. Handling and
ducer. powder its properties transport processes
Other powder issues are also important in delivering the Powder production processes Storage (e.g. silos, IBCs, bags, cans)
food powder, and these include the ability to handle and Drying Transport (e.g. feeders and conveyers)
Comminution Packaging equipment
transport ingredient powders, dust problems, dust fire and Crystallisation/precipitation
explosion hazards, allergy problems, creation of desirable + drying
powder particle properties, and the ability to dissolve these Mixing
powders when required. Many of these issues are in com- Separation
mon with other powders and much can be learnt from other Agglomeration/granulation
Coating/encapsulation
industries dealing with powders.
J.J. Fitzpatrick, L. Ahrne / Chemical Engineering and Processing 44 (2005) 209214 211
through storage, handling and processing right through to fi- Research into agglomeration, coating, encapsulation, and
nal application of the powder. There are also holistic issues barrier technologies, to maintain component stability and
of importance for food powders, including health and food to provide smart composite powders for triggered re-
safety, fire and explosion hazards, energy efficiency and cost lease and targeted delivery.
of manufacture especially for basic food powders.
As a result of the above considerations, the following six 2.2. Prevention of contamination
sections were created to gain a more focused insight into
typical industrial issues and problems, knowledge barriers Contamination of a food powder with undesirable bio-life
and research opportunities in areas that have importance to forms and chemical components is a major concern due
food powders in particular, and which also are relevant to to direct impact on human and animal health. As a conse-
powders in general quence, one high profile case can cause major damage to
an individual company and a whole industrial sector. Be-
Quality and safety cause of its importance, a lot of work has already been done
Powder production processes to prevent contamination. There are plenty of methods and
Mixing and agglomeration procedures available to eliminate most contamination risks,
Other added-value technologies however the key to success requires constant monitoring and
Powder storage and transport strict implementation of current good manufacturing prac-
Characterisation of powders tices (cGMP). The EU hygienic engineering design group
These areas are explored in detail in the strategic docu- (EHEDG) has produced documentation on the hygienic de-
ment for research in food powders. Some of the major is- sign of food equipment, including those dealing with dry
sues that surface from these sections are presented in the particulate solids [2]. Problems still exist with dust forma-
following two sections. tion leading to powder settling on equipment, which may
provide a growth environment for microbes when contact
with moisture exists.
2. Powder issues of practical importance to food
powders 2.3. Dust prevention and control
2.1. Maintaining or stabilising the functionality of Dust generation can lead to a number of problems for food
ingredients powders. These can be summarised as follows: (i) health
problems, in particular allergy problems; (ii) contamination
This is a critical theme for food powder ingredients as and plant hygiene issues due to dust settling and sticking
many of them will be added to form wet formulations and onto equipment; and (iii) fire/explosion hazards. As a result,
they will be expected to perform. For example, will the egg improvement in dust measurement, prevention and control
white have the same functional performance when dried, is a major issue when dealing with food powders.
handled and rehydrated as it did before it was dried? How Due to their biological origin, there is always the pos-
can polyunsaturated fats be dried, stored and applied with- sibility that a food powder may contain biological active
out being readily oxidised and producing noxious odours? components, such as enzymes, that may be harmful and
What lactic acid culture activity will remain after it has been may produce allergy problems. Consequently, this may
dried, stored and rehydrated after 1 year? Thus, research into eventually lead to the imposition of stricter dust exposure
maintaining the stability of ingredient functionality during limits. Self-ignition of food powders that stick onto the
formulation prior to drying, drying, storage, handling, pro- drying chamber is still a big problem. The powder may
cessing and rehydration is key to food powder ingredients. be experiencing temperatures below its minimum igni-
Some examples of general research topics include tion temperature, however the temperature and moisture
content may be high enough to favour other exothermal
Research into formulation technology prior to drying and reactions, that may cause the product to heat up over time
the role of excipients in maintaining and enhancing com- until it reaches a temperature that can sustain combustion
ponent stability. reactions. At this stage, it will start to smoulder and then
Research into the mechanisms of small molecule stabili- it can start a fire or a dust explosion. This self-ignition
sation of biopolymers during the removal of water during scenario can also occur in other equipment, such as filter
drying. bag houses. There is a need for a greater understand-
Research into improved and alternative drying technolo- ing of these self-ignition mechanisms and how to prevent
gies that maintain the stability of components (e.g. low their occurrence. There is also a need for in-line sensors
temperature drying). that can detect volatiles coming from these reactions and
Research into factors that affect the destabilisation of the give early warning of self-ignition. Sensors for measuring
functionality of ingredients in powder form during stor- carbon-monoxide have been developed and are already in-
age, handling and rehydration. dustrially implemented in the dairy industry but sensors for
212 J.J. Fitzpatrick, L. Ahrne / Chemical Engineering and Processing 44 (2005) 209214
measuring other volatiles where CO is not given off are and do not appear to realise that solving these problems can
required. save a lot of headache and more importantly, bottom-line
cost. A major underlying problem is education insofar as
2.4. Stickiness many working in the food industry do not have an adequate
knowledge of powder science and technology to be able to
Occasionally during spray drying of many different prod- apply it effectively in the food industry.
uct formulations, there may be one formulation whereby the
powder starts sticking onto the wall of the drying chamber 2.7. Particle engineering
and coating it. In powder mixing where a small amount of
liquid ingredient is sprayed onto a powder, the powder may This involves the engineering of food powder ingredient
stick to the mixing chamber surface and form a crust over particles that can maintain ingredient stability and function-
time. Both these examples may appear mundane, however ality, that do not present dust formation problems, that do
they cause major problems when they occur, as the chamber not present difficult handling and transport problems, and
now needs to be cleaned. There is a need for testing that can can be readily rehydrated to deliver their required functional
predict the likelihood of a powder sticking onto a surface, performance in a wet formulation. The major limitation to
and how this is affected by the composition of the pow- this type of approach is the low value of food powders and
der and processing conditions. Furthermore, there is a need the low cost driven nature of food powder product that stunts
for determining approaches to overcoming these stickiness this type of innovation. On the other hand, particle engineer-
problems. ing is the key to the higher added value of food powders,
e.g. by producing products with excellent instant properties.
2.5. Segregation of food ingredient mixes
science and technology, which is definitely making progress In addition, there is potential for looking at alternative
with time. mechanisms that may result in more effective ways of doing
things that could lead to the development of new equipment
3.2. Transfer of existing knowledge into application in based on these new concepts. For example, the concepts
industry behind most present-day dry mixers have been around for
decades. Maybe, there are alternative approaches, such as
Much more attention should be paid to transfer of exist- the application of chaos in mixing that could lead to more
ing knowledge from universities, research centres and con- effective mixing with less energy requirement. Similar com-
sultancies into industry. In most cases, knowledge transfer, ments could be made for other processes, such as granula-
mainly in the form of innovative equipment and system de- tion, whereby a greater understanding of the fundamental
sign, is introduced to industry via powder equipment sup- science may lead to alternative approaches to granulation
pliers. Consequently, there is potential for greater synergy process design.
between these suppliers and centres of research.
Non-multinational companies/SMEs, in particular, can 3.5. On-line and in-line monitoring and control
use much more knowledge to escape from the trial and error
approach. There is an enormous amount of wasted time and This is very much in its infancy as applied to powder pro-
effort because the same mistakes and problems appear time cesses, and as a result, there is a lot of scope for work in
and time again throughout the process industries. There is this area. The advantages of improved monitoring and con-
a lot of wisdom scattered about that can be applied to solve trol are early warning of problems, reduced costs and more
many of these problems and prevent many of these mistakes. consistent product quality. Presently, there are a number of
However, the limiting steps are education and knowledge sensors that have potential for use on- or in-line, however
transfer, although the situation is gradually improving with there is scope for the development of on-/in-line versions
time and with more and more individuals promoting the of existing sensors and totally new sensors. The major chal-
importance of particle/powder science and technology. lenges for the application of existing sensors are either one
or a combination of the following: (i) reducing sensor cost;
3.3. Standardisation of powder property definition and (ii) improvement of sensor robustness for real-time opera-
measurement tion in a powder environment, and (iii) development of data
analysis technology that can filter the sensor output and con-
In the world of particles and powders, there are many vert it into useful information for control.
properties and there is a multitude of property definitions
and measuring techniques, which may even vary from one 3.6. Nanoparticle technology
industry to another. There is a need to standardise the defi-
nition and measurement of these properties. This will help Nanotechnology is gaining more and more popularity
streamline definitions and measurement techniques to those throughout industry. As a result, nanoparticle technology
that are most applicable. It will help in obtaining greater represents a new promising field of application to food pow-
reproducibility and also enable greater comparison of work ders, although current research and development is very
undertaken by different groups. much in its infancy.
Description and modelling of the fundamental mecha- Most powder processes, and in particular drying and com-
nisms that can be applied in the design of most powder pro- minution, are not very energy efficient. An improvement in
cesses is still very much at an early stage. It is comparable the fundamental science, modelling and application to de-
to the pre McCabe-Thiele era in distillation technology. This sign coupled with improved on- and in-line monitoring (e.g.
is particularly true for many common operations like dry model predictive control) will give opportunities to improve
powder mixing, mixing of powders and liquids, granulation energy efficiency while ensuring product quality.
and coating. Many of them have similar mechanisms taking
place, such as particle motion and particle/liquid contact,
thus there is potential for cross-fertilisation. There is much Acknowledgements
scope for progress in this area. Modelling techniques, such
as DEM and CFD, are trying to model particle/particle and We would like to acknowledge the five group leaders
particle/fluid motions and interactions, however it may take in the project for their valued contributions: Prof. Koen
many years before these techniques are useful for design in- Dewettinck, Ghent University, Belgium; Richard Farnish,
volving real powders, and some are dubious whether they Wolfson Centre for Bulk Solids Handling Technology, UK;
will ever be useful for real cohesive powders. The first step Prof. Peter Lillford, University of York, UK; Dr. Sivert Ose,
in the modelling of spray-drying has already been taken. POSTEC, Norway; and Prof. Karl Sommer, TU-Munich,
214 J.J. Fitzpatrick, L. Ahrne / Chemical Engineering and Processing 44 (2005) 209214
Received 1 August 2003; received in revised form 25 December 2003; accepted 11 February 2004
Available online 19 June 2004
Abstract
In this contribution a novel fluidized-bed coating process is introduced to encapsulate heat-sensitive materials with particle sizes below
100 m. Supercritical carbon dioxide is used as solvent for the coating material as well as carrier fluid for the core material. The behaviour
of the high pressure fluidized-bed was investigated for different process parameters and materials. It is shown that the fluidization starts at
lower fluid velocities if the pressure is increased and it was possible to fluidized particles with a mean size below 10 m. The coating of glass
beads with stearyl alcohol was carried out and layers with a thickness of 18 m were achieved.
2004 Elsevier B.V. All rights reserved.
1. Introduction density is like that of a fluid (thus they are effective solvents)
while their viscosity and diffusion coefficient are like that
Solid particles are encapsulated for use in various prod- of gases (thus they exhibit good mass transport behaviour).
ucts, including pharmaceuticals, processed food and fer- These properties make supercritical fluids effective as an
tilizers, and energetic materials. To encapsulate particles, extractant. Via the RESS process, particles and droplets in
a fluidized-bed coater equipped with a spray nozzle such the submicron range can be produced by atomizing a super-
as a Wurster Coater is commonly used [1]. Conventional critical solution through a nozzle. These fine droplets make
coating processes involve layering a liquid coating mate- it possible to improve the deposition onto the particles, so
rial usually in the form of atomized droplets through the that a thinner and more even coating layer can be achieved
nozzle onto a fluidized-bed of particles. After the atomized [4,5]. In addition, because the cohesion and adhesion forces
droplets of coating material come into contact with the are small compared to organic solvents, the capillary forces
core particles, the solvent must evaporate quickly. If excess are considerably reduced, making it possible to encapsulate
droplets are present in the bed, agglomeration takes place, particles smaller than 100 m without forming agglomer-
leading to particle growth and defluidization. Therefore, ates. In this process, the supercritical fluid is used both as
proper droplet atomization and drying are essential to avoid solvent for the coating material and as carrier fluid for the
unplanned agglomeration of solid particles. In case of fine formation of the fluidized-bed.
particles (<100 m), however, agglomeration becomes a
serious problem because of their strong cohesive forces.
The feed liquid acts as a binder for the fine particles. 2. Experimental
A novel fluidized-bed coating process using the rapid ex-
pansion of supercritical solutions (RESS) is described for 2.1. High pressure fluidized-bed device
the encapsulation of fine particles [2,3]. This process ex-
ploits the capability of supercritical fluids to act as a selec- The experiments were conducted in a laboratory scale de-
tive solvent. Supercritical fluids are noteworthy in that their vice. A schematic view of the high pressure fluidized-bed
coating apparatus is shown in Fig. 1. The apparatus consists
essentially of three subsections: the CO2 supply, the extrac-
Corresponding author. Tel.: +49 7214 640 350; tor (in which the CO2 becomes saturated with coating) and
fax: +49 7214 640 581. the high pressure reactor (where the coating takes place).
E-mail address: hartmut.kroeber@ict.fraunhofer.de (H. Krber). The maximum allowable pressure in the device is 30 MPa at
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.014
216 H. Krber, U. Teipel / Chemical Engineering and Processing 44 (2005) 215219
Table 1
Properties of the used core materials
Material Density (kg/m3 ) Mean particle size (m)
Assuming homogenous expansion of the fluidized-bed the for the calculation of the single particle collection efficiency
collection efficiency Eg may be calculated as a function of may be found in literature [4,15,16].
process parameters, for example the size of the collector
particle dP or the height of the fluidized-bed z as well as
the effective single particle collection efficiency and the 4. Results
porosity of the fluidized-bed :
4.1. Fluidization
mdep min mout 3 1
Eg = = = 1 exp z
min min 2 dP Before starting with the microencapsulation the fluid dy-
(3) namic of the high pressure fluidized-bed was investigated.
Fig. 3 shows the porosity (bed voidage; = Vspace /Vtotal
The collection efficiency Eg can be determined by mea- = 1Vparticle /Vtotal ) of the fluidized-bed (glass beads 3 are
suring the total mass of the coating deposited on the core used) at different pressures (corresponding to different fluid
particles (mdep ) by thermal gravimetric analysis (TGA) and densities). As expected the porosity increases if the fluid ve-
calculating the total mass of the coating reaching the reactor
(min ) from the phase equilibrium in the extractor (pextr , extr )
and from the mass flow of CO2 through the nozzle. This
mass flow rate can be calculated [7] and depends strongly
on the conditions before the nozzle (pN , N ) and the nozzle
diameter (dN ).
A successful coating process requires that the encapsu-
lation substance adheres sufficiently to the surface of the
fluidized-bed material. Of course, the adhesion also affects
the collection efficiency. In literature [4,8,9], the impact of
adhesion to the coating process is taken into consideration
by introduction of the adhesion coefficient . Thus effective
single particle collection efficiency may be formulated:
Fig. 3. Bed voidage of glass beads (mean particle size: 124.6 m) vs.
= (4) fluid velocity at different operating pressures (R = 328 K).
Fig. 6. SEM pictures of untreated glass beads (left) and with stearyl alcohol coated particles (right).
locity is increased. At low velocities a sharp increase of the showed that the droplet size of the aerosol of stearyl alcohol
porosity is seen. This point represents the transition between behind the nozzle is independent of the pressure before the
the fixed-bed and fluidized-bed regime. The minimum ve- nozzle [7].
locity which is necessary to fluidize the particles decreases SEM pictures of the encapsulated particles show that the
if the pressure is risen. At 2 and 8 MPa this velocity is 8 and coating layer is uniform and smooth. In Fig. 6 coated glass
2.9 cm/s, respectively. particle is presented and compared to untreated material.
The fluidization of smaller particles started at lower
velocities and the influence of the pressure on the min-
imum velocity was reduced. Using the glass beads 1 5. Conclusions
this velocity was 0.95 cm/s at 2 MPa and 0.67 cm/s at
6 MPa. Fig. 4 shows the influence of pressure on the A new fluidized-bed coating process (particle encapsula-
minimum fluidization velocity for the glass beads 1 tion with supercritical fluids; PESF process) was introduced
and 2. to encapsulate fine and heat-sensitive particles. It was shown
that the fluidization of particles under sub- or supercritical
conditions is different from that under atmospheric pressure.
4.2. Microencapsulation With increasing pressure the minimum fluid velocity which
is necessary to start the fluidization decreases. It was possible
In first coating experiments glass beads with a mean par- to fluidize glass beads with a mean particle size of 7.4 m.
ticle size of 70 m were encapsulated with stearyl alcohol. Stearyl alcohol was used for first coating experiments with
The layer thickness was measured at different coating times glass particles of a mean particle size of 70 m. Complete
by thermal gravimetric analysis. Fig. 5 presents these re- coatings with a layer thickness between 1 and 8 m can be
sults for different pressures before the nozzle. The condi- achieved depending on the coating time and process condi-
tion inside of the fluidized-bed reactor were constant (R tions.
= 328 K, pR = 8 MPa). As nozzle we used a 100 m Laval Further investigations of the particle coating in a high
nozzle which was heated up to 353 K. The extraction condi- pressure fluidized-bed will be carried out. Especially, vari-
tions were equal to them at the nozzle (353 K; 1619 MPa). ations of the particle and coating material as well as coat-
The velocity of the carrier fluid (carbon dioxide) through the ing conditions like pressure and temperature will be per-
fluidized-bed was twice of the minimum fluidization veloc- formed. The encapsulation of particles smaller than 10 m
ity. The coating thickness varies from 1 to 8 m, depend- with very thin layers without agglomeration is a challenge of
ing on the coating time, and that, at long times, the thick- this project. Therefore, the hydrodynamic of the high pres-
ness approaches a constant value. It is seen that at higher sure fluidized-bed has to be characterized by experiments as
pre-expansion pressure the layer thickness increases. One well as calculations.
reason for that is the higher solubility of stearyl alcohol An estimation of the single particle collection efficiency
if extraction pressure increases so that more coating mate- should be possible by measuring the collection efficiency
rial reaches the reactor. This tendency is supported by an Eg and the layer thickness. Using this estimation the time
increase of the mass flow rate of carbon dioxide through which is necessary to obtain a particular layer thickness can
the nozzle at elevated pressures. Furthermore, Krber et al. be predicted.
H. Krber, U. Teipel / Chemical Engineering and Processing 44 (2005) 215219 219
Received 30 August 2003; received in revised form 18 December 2003; accepted 11 February 2004
Available online 19 June 2004
Abstract
Formation of spherical, micron-sized ceramic particles was investigated in an RF thermal plasma reactor. It has been concluded that a
wide size distribution of feedstock powders gives rise to either excessive evaporation of smaller grains or insufficient melting of bigger ones.
Ceramic spheres with more or less voids inside can also be prepared starting from powders pretreated in special ways.
2004 Elsevier B.V. All rights reserved.
1. Introduction 2. Experimental
Spherical particles proved to be superior in several ap- The experimental apparatus consisted of a TEKNA-type
plications owing to their favorable properties. Thus, they induction plasma torch (PL-035LS) with a quartz confine-
are used in thermal spraying for their excellent flowabil- ment tube of 25 mm and a water cooled steel chamber con-
ity, in powder metallurgy because of their excellent repro- nected to a cyclone. The plasma plate power of 21 kW was
ducibility in manufacturing parts with controlled porosity provided by a four turn, water cooled induction coil from an
and as a filler material, as well. Metal microspheres can RF generator operating at an oscillator frequency of 3 MHz.
be easily produced by melt atomization. Similar method High purity argon was used both as plasma and sheath gas
in the case of ceramics is impractical. Micron-sized ce- with flow rates of 20 and 60 l min1 , respectively. In order
ramic particles, however, can be smelted by thermal plas- to raise the low enthalpy and heat conductivity of the argon
mas that provide exceptional conditions for spheroidization plasma gas, hydrogen was also mixed into the sheath gas
due to its high temperature. In terms of purity and resi- with a proportion of 10% (v/v).
dence time of the particles in the hot temperature core, RF The starting powders were fed with a PRAXAIR powder
plasmas provide better conditions as compared to arc plas- feeder through an injection probe to the top of the plasma
mas. flame by argon carrier gas (3 l min1 ) with a constant feed
The present report describes the preparation of spherical rate of 10 g min1 . The outlet of the quartz injection tube of
ceramic particles of different kind and of different size in an an inner diameter of 2 mm, was located 10 mm below the
inductively coupled RF thermal plasma reactor. The effect top of the induction coil.
of plasma gases and the type of the feedstock materials on Commercial alumina (ALO-Ex30 and ALO-GB1 from
the microstructure of the formed particles was studied in the AJKA Alumina Co. Ltd., Hungary), aluminum-hydroxide
experiments. and silica powders were investigated. Impurity levels of the
powders were below 0.5%. In some tests, minor amount of
NaNO3 and Na-silicates were, however, blended into the
silica aggregates. The sodium-silicates were used as binding
agents of primary particles, while NaNO3 was applied to
Corresponding author. Tel.: +36 1 325 7933x415;
release gas (O2 and N2 ) at temperatures higher than 720 C.
fax: +36 1 325 7892. Both the raw materials and the produced powders were
E-mail address: karoly@chemres.hu (Z. Karoly). characterized for density, particle size distribution, specific
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.015
222 Z. Karoly, J. Szepvlgyi / Chemical Engineering and Processing 44 (2005) 221224
surface area, phase composition (XRD) and microstructure particle size of the feedstock powder. Besides spheroidiza-
(SEM). Density was determined by means of picnometry. tion melting usually caused an increase in density that fell
The particle size distribution by volume of grains was de- close to the theoretical one ( = 2.32 g cm3 ) at silica pow-
termined by a Malvern Master Particle Sizer. The specific ders. However, the higher was the size of the feedstock par-
surface areas were measured with a conventional volumetric ticles, the density of products remained increasingly below
instrument by BET method. A Philips Xpert XRD appara- the theoretical one. This can be attributed to the fact, that
tus was used for X-ray diffraction measurements. Standard above a certain size particles have not got enough time to
X-ray powder techniques were used with Cu K radiations be melted on the whole. Thus, the core remains unaffected.
generated at 40 kV and 30 mA. The microstructural (SEM) Considerable changes in the size of silica after processing
investigations were performed on a JEOL JSN50A appara- cannot be observed (Fig. 3), whereas the specific surface
tus. Cross-section images of the particles were made by em- area of products was increased and it was higher with de-
bedding them into resin that was followed by their cutting creasing mean particle size of the feedstock. Particles below
by diamond blade. the mean size are prone to be evaporated completely to be
condensed again in the nanosize range in the cooler parts
of the plasma reactor. These nano-sized particles usually
3. Results and discussion cover the surface of bigger ones. Decreasing the power or
reducing the residence times would decrease evaporation
According to the scanning images of particles spheroidiza- rate, however, it would also jeopardize the spheroidization
tion took place effectively (compare Figs. 1 and 2). A of bigger particles.
spheroidization rate as high as 90% could be achieved. Spherical alumina can also be formed from commercial,
It was previously shown [1] that increasing feed rate en- low cost aluminum-oxides or even from aluminum-hydr-
tail declining spheroidization efficiency. This phenomenon, oxides. In the latter case energy of the plasma should provide
however, could not be experienced with increasing mean not only the enthalpy of melting but that of dehydration and
subsequent phase transformations of alumina as well. Under
the aforementioned conditions particles below 45 m have a
good chance to be spherodized. Presumably the wide particle
size distribution of starting gibbsite powder accounts for the
less spheroidization rate of 70%.
Application of agglomerated alumina powders as feed-
stock material gives rise to spheroidization too. Density of
product particles falls much below the theoretical one (th ,
Al2 O3 = 3.95 g cm3 ), while significant increase in the grain
size can be observed in case of alumina (Fig. 4). Scanning
images of these powders, however, show they mainly con-
sist of hollow particles. Formation of hollow particles and
the size enlargement can be attributed to the expansion of
gases located in the interior of melted droplets. The gases
Fig. 4. Comparison of the particle size distribution of feedstock material (straight line) and product (dashed line) ( represents apparent density).
4. Crystallinity
5. Conclusions
Received 27 August 2003; received in revised form 25 March 2004; accepted 15 April 2004
Available online 19 June 2004
Abstract
Steelmaking and plating industry generates large quantities of dusts and sludge. They are regarded as hazardous wastes because of the
leaching out of their toxic components. Therefore, particular wastes are stockpiled at high cost. Our work aimed at RF thermal plasma processing
of a steelmaking flue dust and sludge from the hot plating of steel products. Waste samples were treated in reducing atmosphere, respectively, to
produce fine metallic powders and in neutral/oxidizing atmosphere to synthesize zinc ferrite nanopowders. Starting powders and products were
characterized by their chemical (ICP-AES) and phase (X-ray diffraction, XRD) composition, particle size and morphology (scanning electron
microscopy, SEM). It was found that iron and zinc content of the particular wastes can be reduced to metals in the presence of hydrogen. In
neutral/oxidizing conditions spinel ferrites of variable composition were formed even during the very short residence time in the reactor.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.008
226 I. Mohai, J. Szepvlgyi / Chemical Engineering and Processing 44 (2005) 225229
Concentration (wt.%)
2. Experimental CFD 65.0 4.22 0.98 1.96 0.15 1.02 0
HPS 17.5 39.5 0.23 2.76 0.29 2.22 6.99
Two wastes, a converter flue dust (CFD) from the steel-
making process and a sludge from the hot plating of steel
products (hot plating sludge, HPS), were treated in a RF (SEM) analysis was performed by a JEOL JSN50A appara-
thermal plasma reactor (35 MHz, max, 35 kW plate power). tus.
Power of the generator was coupled to a TEKNA PL-35
torch which was connected to a water cooled plasma cham-
ber, a cyclone and a filter (Fig. 1). Temperature field in the 3. Results and discussion
torch and the reactor was calculated by a 2D mathemati-
cal model based on the continuity, momentum, energy and 3.1. Reduction of the converter flue dust and the hot
species conservation equations [6]. The highest gas temper- plating sludge
ature at the 24 kW plate power case was 11,500 K near to the
coil region [7]. The mean temperature of the plasma flame Both CFD and HPS samples had broad particle size dis-
was about 5000 K. tribution between 1 and 100 m with a mean particle size
Argon was used as the central plasma gas and as the of 29.5 and 37.2 m, respectively. The HPS had to be dried
sheath gas, as well. Reagent (H2 ) or auxiliary (O2 ) gases prior to the analysis and the plasma treatment. Its weight
were mixed to the sheath gas. Powders were injected axially loss on drying at 105 C was 60.8%.
into the hottest region of the plasma by a PRAXAIR powder Chemical compositions of the industrial samples are
feeder through a water cooled probe. Both the raw materials shown in Table 1. Iron and zinc have the highest concen-
and the products were characterized in terms of particle size, tration in both samples. Chlorine content of HPS (6.99%)
chemical and phase compositions. In each run products were is also worth mentioning. In addition to the data in Table 1
collected from the reactor wall (R), from the reactor bottom both CFD and HPS samples contained other components,
(RB) and the cyclone (C). such as Al, Cr, Ni, Mn, Cu, Cd, P and C in an amount of
Particle size distribution was measured by a Particle Size less than 1%.
Analyser (Malvern 2600C). For bulk chemical compositions The main crystalline phase of the CFD sample was mag-
samples were digested in diluted HNO3 solution using a netite (FeOFe2 O3 ) (Fig. 2). Traces of hematite (Fe2 O3 )
CEM microwave digestion system. Dissolved samples were were also detected. Although carbon content of the sample
analysed by ICP-AES technique (Labtest PSX7521). Phase was rather low (1.2 wt.%) intense reflection of the graphite
conditions were determined by X-ray diffraction analysis could be observed on the diffractogram. This can be ex-
(XRD, Philips PW 1710). Scanning electron microscopic plained by the strong orientation of the graphite particles to
the direction of the X-ray.
Main diffraction peaks of the HPS sample (Fig. 3) can be
Fe
G Sample C
Intensity (a.u.)
M
M W Sample RB
Fe
W W Sample R
M
M M+G Sample CFD
H
20 30 40 50 60
2 ()
Fig. 2. X-ray diffractogram of the converter flue dust (CFD) and the
plasma treated samples produced therefrom: sample Rfrom the reactor
wall, sample RBfrom the reactor bottom, sample Cfrom the cyclone.
Assignation of peaks: Fe, metallic iron; M, magnetite; W, wustite; H,
Fig. 1. Scheme of the experimental setup. hematite; G, graphite.
I. Mohai, J. Szepvlgyi / Chemical Engineering and Processing 44 (2005) 225229 227
Table 2
Conditions of reduction tests
Waste powder Flow rate of gases (l/min) Power (kW) Feed rate (g/min) Espec (kWh/g)
Fig. 4. Scanning electron micrographs of sample CFD and its reduction products.
indicated a lower agglomeration of the HPS particles com- and the particles O2 was mixed to the sheath gas. Al-
paring to the CFD starting material. High extent of the non- though during conventional ferrite production the starting
reacted simonkolleite in the plasma treated samples can be oxide mixture is heated for several hours above 1000 C,
traced back to the volatile content of the HPS sample: due in the RF plasma some milliseconds of residence time was
to thermal effect simonkolleite releases HCl and H2 O. A enough to produce fine ferrite powders from the waste
considerable part of the plasma energy may be lost on the mixture.
dissociation of these gases. Both powders collected from the reactor wall and from the
reactor bottom showed similar diffraction patterns (Fig. 5.)
3.2. Synthesis of zinc ferrites indicating the presence of spinel as the dominant phase
(amount of sample C was negligible in these experiments).
For the synthesis of zinc ferrite (ZnFe2 O4 ) of stoichio- Composition of the spinel phase was estimated from the
metric composition CFD and HPS samples were mixed lattice parameters (a), assuming, that the increase of lat-
in an appropriate ratio. From the chemical analysis the tice parameter due to Zn incorporation is proportional to
Fe/Zn molar ratio of the mixture was 2.18. To override the the Zn concentration. From these calculations the composi-
problem of the cooling effect of volatiles on the plasma tions of sample R and sample RB were Zn0.7 Fe2.3 O4 and
(mentioned above), prior to mixing HPS sample was pre- Zn0.4 Fe2.6 O4 , respectively. Consequently, some of the Zn
heated at 300 C to reduce its volatile (H2 O) content. Con- content of the starting mixture could not build into the spinel
ditions of the plasma treatments can be seen in Table 3. structure and left the system through the exhaust in the form
In order to improve heat transport between the hot gases of very fine ZnO powder.
Table 3
Conditions of the ferrite synthesis
Waste powder Flow rate of gases (l/min) Power (kW) Feed rate (g/min) Espec (kWh/g)
20 25 30 35 40 45 50
2 () Acknowledgements
Fig. 5. X-ray diffractogram of the zinc ferrite (ZF) synthetised from the
mixture of CFD and HPS samples. The authors are grateful for the financial support from the
National Scientific Research Fund OTKA T032272.
NiZn ferrites could also be synthesized in RF plasma
reactor from the CFD and HPS powders by admixing
References
Ni3 H4 CO7 4H2 O to the waste mixture. Molar ratio of the
metals was set for Ni/Zn/Fe = 0.4/0.6/2. XRD diffrac-
[1] A.L. Hare, in: J. Feinman (Ed.), Plasma Technology in Metallurgical
tograms of the products showed the complete transfor- Processing, ISS, Warrendale, PA, 1987, pp. 175187.
mation of the starting mixture to spinel phases. However, [2] R.C. Eshenbach, R.E. Haun, in: Proceedings Workshop on Industrial
in sample R spinel phase consisted of the mixture of Application of Plasma Chemistry, Drexel University Press, Minneapo-
Ni0.2 Zn0.5 Fe2.3 O4 and Ni0.6 Zn0.3 Fe2.1 O4 , while in sample lis, MN, 1995, p. 9.
RB for the composition of the spinel (in accordance with the [3] W. Hoffelner, R. Burkhard, V. Haefeli, H. Sun, in: Proceedings of the
13th International Symposium on Plasma Chemistry, Peking University
chemical analysis) Ni0.2 Zn0.5 Fe2.3 O4 could be estimated Press, Beijing, China, 1997, p. 1915.
from the lattice parameter. [4] E. Pfender, Thermal plasma technology: where do we stand and
where are we going, Plasma Chem. Plasma Proc. 19 (1999) 1
31.
4. Conclusions [5] I. Mohai, J. Szpvlgyi, I. Bertti, M. Mohai, J. Gubicza, T. Ungr,
Thermal plasma synthesis of zinc ferrite nanopowders, Solid State
Metallurgical waste powders containing iron and zinc ox- Ionics 141-142 (2001) 163168.
[6] A. Gaillat, R.M. Barnes, P. Proulx, M.I. Boulos, Computer modelling
ides and hydroxides can be reduced to metals in RF thermal of enclosed inductively coupled plasma discharges, Spectrochim. Acta
plasma in the presence of hydrogen. However, if the particles B-At. Spectrosc. 50 (10) (1995) 11871205.
are agglomerated they cannot be reduced due to the short [7] Z. Karoly, Project report F 029731 supported by the National Scientific
residence time in the hot plasma region. Thus, to achieve Research Fund, Hungarian, 2002.
Chemical Engineering and Processing 44 (2005) 231235
Received 3 October 2003; received in revised form 29 January 2004; accepted 11 February 2004
Available online 17 June 2004
Abstract
Thermal pyrolysis for upgrading plastic wastes is one of the better methods for recycling plastics in terms of its perspectives for industrial
implementation. The conical spouted bed reactor proposed in this paper may be a solution to the problems arising in fluidized beds handling
sticky solids, as particle agglomeration phenomena, which can cause defluidization. In order to avoid defluidization, experiments have been
carried out in batch mode in the temperature range of 450600 C. A good performance of the reactor is proven under the conditions of
maximum particle stickiness.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.016
232 R. Aguado et al. / Chemical Engineering and Processing 44 (2005) 231235
2. Experimental to a dilute spouted bed (or jet spouted bed, which is char-
acteristic of a conical contactor and in which bed voidage
The components of the pilot plant are described in a previ- is uniform and higher than 0.90) [9] and the gas residence
ous paper [6]. The hopper contains plastic particles of 1 mm, time decreases from a few seconds to approximately 20 ms.
which are driven forward its end by paddles attached to a As the plastic material is introduced into the reactor, it
shaft rotated by a motor. The hopper is sealed and has an N2 melts onto the sand particles and coats them. The vigorous
entry that allows for attaining the pressure required for in- cyclic movement of the particles can prevent agglomeration
troducing the feed into the reactor by means of a worm. The problems. Temperature is measured by means of three ther-
feed flow rate is regulated by means of a frequency shifter mocouples placed at different radial positions in the reactor
that actuates on the rotation speed of the worm. The tube for and provided with free vertical movement. Bed isothermic-
introducing the feed into the reactor, of 20 mm i.d., is made ity is noteworthy, which is attained due to the vigorous par-
up of two concentric tubes, and water circulates along the ticle circulation.
annular zone for cooling the feed and, consequently, avoid- Reaction temperature is attained by means of two electric
ing the melting of the plastic and the ensuing plugging of resistances covered with ceramic material. One resistance is
the reactor inlet. The feeding system is provided with free located within the tube for heating the inert gas prior to entry
vertical and horizontal movements, which permits the feeder into the reactor and the second one surrounds the conical
to be placed at the desired location on the upper surface of section of the reactor. Temperature in both these positions
the reactor. Previous experiments have shown that the more is measured by two thermocouples. The two heating zones
suitable locations for feeding the plastic are those over the are thermically insulated.
annular zone of the bed, preferably intermediate positions The runs have been carried out at 400, 500, 550 and 600 C
between the spout and the wall. by feeding 1 g of plastic material (with a particle size of
Fig. 1 shows a scheme of the reactor where its characteris- approximately 1 mm) and using 30 g of sand (with a size
tic dimensions are defined [8]: HT = 0.34 m; Hc = 0.205 m, between 0.63 and 1 mm).
= 28 ; Dc = 0.123 m; Di = 0.02 m; Do = 0.01 m. The materials used for pyrolyzing are: low density
When the inert gas flow rate is increased, the gassolid polyethylene (LDPE), high density polyethylene (HDPE)
contact regime evolves from the conventional spouted bed and polypropylene (PP) (supplied by Dow Chemical, Tar-
ragona, Spain). The properties of these materials are set out
in Table 1.
3. Results
Table 1
Properties of the materials studied
Material Molecular weight (g/mol) Polydispersity Density s (kg/m3 ) Heating value (MJ/kg) Pyrolysis heat (kJ/kg)
which the defluidization of the bed can be avoided: dilute spouted bed, as velocity is increased from 1.05 to
2.50 ums .
r m0
crit = exp 1 (8) In Fig. 3 it is observed that, for a given amount of sand
2 r2
in the reactor as gas velocity is increased, the amount of
Eq. (8) shows the dependency of the critical thickness plastic that may be fed increases almost linearly, which is a
with mass m, radius rp , and velocity o of the inert parti- consequence of particle velocity increase. Consequently, the
cles coated with plastic and with the viscosity of the mate- ratio of plastic/sand in the feed may be as high as 0.03 for
rial that coats the sand . For the experimental conditions the experimental reactor, which may treat 100 g of sand in a
(total mass of sand, 30 g; mass of plastic in the feed, 1 g; spouted bed regime and corresponds to 62 mm of stagnant
sand particle diameter, between 0.6 and 1.2 mm; sand den- bed height. Likewise, and taking into account the scaling
sity 2600 kg m3 , average velocity of the particles in the an- capacity of the conical spouted bed, a reactor with a stagnant
nular zones, 0.25 m s1 [7], the critical thickness predicted bed height of 430 mm (33.3 kg of sand) may treat 1 kg of
by Eq. (8) is 250 m. In this calculation, the viscosity of the plastic in batch operation.
plastic has been taken at its fusion temperature, 16 poises,
because it is in the initial step of fusion when the stickiness
of the plastic is maximum point. 4. Conclusions
In the fluidized bed, the velocity of the particles is of a
few cm s1 and the critical thickness of the fused plastic is The conical spouted bed reactor is especially suitable for
between 4 and 7 mm. A fact that should be taken into account avoiding agglomeration problems in the pyrolysis of poly-
is that, although gas velocity is increased, particle velocity olefins, even when the operation is carried out under the
hardly changes because most of the excess gas rises through conditions of maximum stickiness. In this reactor, the cyclic
the bed in the bubble phase. Nevertheless, in the conical movement of sand particles allows for their uniform coat-
spouted bed, particle velocity is increased by raising gas ing with fused plastic. Furthermore, the high velocity of
velocity up to the dilute spouted bed, in which bed voidage the particles generates collisions whose energy suffices to
is uniform (between 0.9 and 0.99) and the particle descent avoid their agglomeration. The critical thickness of the plas-
velocity is almost equal to the ascent velocity [9]. tic layer is an order of magnitude higher than that corre-
sponding to the fluidized bed, which gives way to a higher
3.3. Limit operating conditions for the equipment yield by reactor volume unit.
Appendix A. Nomenclature
ur , u z , horizontal and vertical components of [2] J.A. Conesa, R. Font, A. Marcilla, Comparison between the pyrolysis
gas velocity, respectively (m s1 )
of types of polyethylenes in a fluidized bed reactor, Energy Fuels
11 (1997) 126136.
Wp plastic mass (kg) [3] W. Kaminsky, Possibilities and limits of pyrolysis, Makromol. Chem.
Macromol. Symp. 57 (1992) 145160.
Greek symbols [4] W. Kaminsky, Chemical Recycling of Mixed Plastics by Pyrolysis,
stress angle Adv. Polym. Technol. 14 (1995) 337344.
[5] P.T. Williams, E.A. Williams, Fluidised bed pyrolysis of low density
crit critical thickness of the plastic layer (m) polyethylene to produce petrochemical feedstock, J. Anal. Appl.
shape factor Pyrolysis 51 (1999) 107126.
cone angle, radians [6] R. Aguado, M. Olazar, B. Gaisn, R. Prieto, J. Bilbao, Kinetic study
viscosity of the melted plastic of polyolefins pyrolysis in a conical spouted bed reactor, Ind. Eng.
(kg m1 s1 ) Chem. Res. 41 (2002) 45594566.
[7] M. Olazar, M.J. San Jos, S. Alvarez, A. Morales, J. Bilbao, Mea-
o average particle velocity in the annulus surements of particle velocities in conical spouted beds using an
(m s1 ) optical fibre probe, Ind. Eng. Chem. Res. 37 (1998) 45204527.
s , v density of the particle and of glass, [8] M. Olazar, M.J. San Jos, A.T. Aguayo, J.M. Arandes, J. Bilbao,
respectively (kg m3 ) Stable operation conditions for gas-solid contact regimes in conical
spouted beds, Ind. Eng. Chem. Res. 31 (1992) 17841792.
o , z horizontal and vertical components
[9] M.J. San Jos, M. Olazar, S. Alvarez, J. Bilbao, Local bed voidage
of particle velocity, respectively (m s1 ) in conical spouted beds, Ind. Eng. Chem. Res. 37 (1998) 25532558.
z (0) component of particle velocity in the [10] M.J. San Jos, M. Olazar, S. Alvarez, M.A. Izquierdo, J. Bilbao,
z direction along the axis of the Solid cross-flow into the spout and trajectories in conical spouted
contactor (m s1 ) beds, Chem. Eng. Sci. 53 (1998) 35613570.
[11] N. Epstein, J.R. Grace, Spouting of particulate solids, In: L. Otten,
M.E. Fayed (Eds.), Handbook of Powder Science and Technology,
2nd ed., Van Nostrand Reinhold, New York, 1997, pp. 532567
References (Chapter 10).
[12] U. Arena, M.L. Mastellone, Defluidization phenomena during the
[1] D.S. Scott, S.R. Czernik, J. Piskorz, A.G. Radlein, Fast pyrolysis of pyrolysis of two plastic wastes, Chem. Eng. Sci. 55 (2000) 2849
plastic wastes, Energy Fuels 4 (1990) 407411. 2860.
Chemical Engineering and Processing 44 (2005) 237243
Received 30 July 2003; received in revised form 10 December 2003; accepted 11 February 2004
Available online 19 June 2004
Abstract
Results of investigations of the effect of particle size composition of the raw material and the amount of wetting liquid supplied to the
bed on the energy needed for growth and consolidation of granules during wet drum granulation process are presented in the paper. Energy
consumption at subsequent stages of the granulation process was determined on the basis of the instantaneous values of torque recorded every
1 s on the granulator shaft.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.017
238 T. Gluba / Chemical Engineering and Processing 44 (2005) 237243
3. Experimental
3.1. Materials
Table 1
The physical properties of the raw materials
Material
D1 D2 D3 D4 D5
5
Granulation 1: Granulation 2 (w=0.147):
y = -2E-12x4 + 2E-08x3 - 8E-05x 2 + 0.147x - 96.7
Nu [ W/kg ]
y = 7E-05x + 4.2
D2
Wetting segment 2:
Wetting
3 y = 0.0011x + 3.76 w=0.147
w=0.155
w=0.160
Wetting segment 1: w=0.165
y = 0.025x + 2.07
2
Fig. 2. Schematic diagram of the equipment for granulation tests: (1)
0 1000 2000 3000 t[s] 4000
granulator drum, (2) pneumatic nozzles, (3) engine, (4) inverter, (5) tripod,
(6) rotameters, (7) water tank, (8) compressor, (9) tachometer, (10) torque tg [ s ]
0 1000 2000 3000
meter, (11) reader, and (12) computer.
Fig. 3. Change of power demand during granulation.
representative of the whole feed were taken at determined for the granulation stage:
time intervals. On this basis, progressions of product prop- M(t) Mi
Mu (t) = (4)
erties (granule size, porosity) were obtained. The first sam- mb
ple was taken immediately after wetting (granulation time tg
= 0) and the last one in the moment when water pressed out and then unit power demand Nu (t) from Eq. (5).
to the granule surface made them stick to the inner surface Nu (t) = Mu (t) (5)
of the drum preventing further processing in this way (tg
= tgmax ). This limiting (maximum) granulation time tgmax were calculated.
depended on the mean particle size of the raw material dm Diagrams representing changes in power demand in time
and feed moisture content w. For the whole process duration for the entire cycle of granulated material production (wet-
instantaneous values of torque on the granulator shaft were ting and granulation) are shown in Fig. 3.
recorded every 1 s. The relationships Nu (t) have a characteristic run. During
feed wetting, a rapid linear increase of power demand in the
initial period and then a slow-down of the growth rate could
be observed. In the initial period of the granulation stage,
4. Results
this relationship is linear too, while at the end some curving
is clearly visible. In the description of power changes on the
The results of investigation show that the particle size
particular stages, linear and polynomial functions were used.
distribution of the raw material and wetting of the bed had
Specific energy values Eu (t) (i.e. energy per unit mass of
a significant effect on the granulation process and proper-
the feed) were calculated by integrating the fitted equations
ties of the product obtained. Changes in the particle size
over their respective time intervals (Eq. (6)).
distribution of the raw material and feed moisture content t1
caused changes in dynamic parameters of the bed tumbling
Eu (t) = Nu (t) dt (6)
in the drum, and in parallel, affected the rate of changes t0
in product properties (particle size distribution, porosity
of granules), which finally determined the total energy Fig. 4 shows examples (for raw material D2) of the ef-
demand for processing the raw material into granulated fect of feed moisture content w on the energy necessary to
product of specific characteristics. The energy of bed pro- produce granulated material of specified mean particle di-
cessing was calculated taking instantaneous moments M(t) ameter.
measured on the granulator shaft and recorded in time in- It is apparent from Fig. 4 that the energy input required for
tervals equal to 1 s in the whole wetting and granulation agglomerate growth decreases as the amount of liquid sup-
period. plied to the bed during wetting is increased (in a determined
On the basis of the values of torque M(t), the instantaneous range). Already a small, below 1%, increase of the liquid
unit torque Mu (t) from Eqs. (3) and (4) supplied during wetting (particularly in the lower range of
moisture content) leads to a significant decrease of energy
for the wetting stage: demand (mainly due to a decrease of the required granula-
tion time).
M(t) Mi A significant effect of the amount of added binding liq-
Mu (t) = (3)
ms + Q w w t uid on the process of granulation was also shown by other
240 T. Gluba / Chemical Engineering and Processing 44 (2005) 237243
12
D2
dgm [ mm ]
w=0.147
8
w=0.155
w=0.160
w=0.165
0
0 4 8 12
Eu [ kJ / kg ]
the equation average bulk density b . After the wetting period, the bed
gb0 contains, beside granules, non-granulated material particles
m = 1 (9) whose mass depends on the amount of wetting liquid added.
(1 g0 )
Hence, spaces between the formed granules can be filled up
where: g0 , porosity of granules at the beginning of gran- partly with non-granulated raw material and partly with air.
ulation (tg = 0); and gb0 bulk density of granules at the The investigations proved that bulk density of the bed after
beginning of granulation (kg/m3 ). wetting (in dried state) was often lower than the density of
On the basis of the measurements, it was found that inner loose raw material.
porosity of granules obtained after wetting (tg = 0) did not It was assumed that intergranular porosity m for grain
depend on the amount of added wetting liquid and for a fraction i with narrow intervals did not change during
given raw material is similar to mean porosity of initial dry granulation and was constant for a given raw material:
material (Fig. 7).
This means that the density of particle packing in the mi = constant (10)
granules that were formed in the wetting period corresponds The porosity of granules of size 4 mm was determined
to the density of particle packing in the raw material of on the basis of mass and volume of a defined number of
granules from a given size fraction from the equation:
mg
g = 1 (11)
Vg
where: mg , mass of granules taken from a size fraction (kg);
and Vg = Vgi , total volume of taken granules (m3 )
The volume of single granules of shape close to spherical
was calculated on the basis of their dimensions in three main
directions, using the formula for ellipsoid. The volume of
granules of shape different from spherical was determined
by the pycnometric method.
On the basis of porosity determined for the granules from
particular size fractions of product samples taken from the
drum in a specific moment, mean porosity of granules was
calculated from the relation
i=max
g (t) = xi gi (t) (12)
i=1
Fig. 7. Comparison of porosity of granules formed after wetting g0 with where: g , mean porosity of granules at granulation time tg ;
mean porosity of raw material . and gi , porosity of granules from size fraction i at time tg .
242 T. Gluba / Chemical Engineering and Processing 44 (2005) 237243
5. Conclusions
tionally, an increase of liquid content in the granulated bed rotational speed of the granulator (1/s)
causes that the increment of granule size at the rapid growth mean particle consolidation in the granules
stage becomes more vehement, which can sometimes make
the process control difficult and consequently result in an
excessive growth of particles. As was shown in the investi- References
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[14] S.M. Iveson, J.D. Litster, Growth regime map for liquid-bound gran-
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Chemical Engineering and Processing 44 (2005) 245252
Received 22 July 2003; received in revised form 15 December 2003; accepted 11 February 2004
Available online 2 July 2004
Abstract
In product engineering of particulate systems, the property function relates the dispersity to the product properties, whereas the process
function shows how to produce the required dispersity. These principles are applied to the production of nanoparticles. Nanoparticles are
controlled by surface forces. Due to their high mobility nanoparticles are unstable and may coagulate rapidly if the particles are not stabilized.
Stabilization is achieved by tailoring the particulate surfaces, e.g. through repulsive double layer forces. Macroscopic properties are thus
controlled by microscopic control of the interfaces, i.e. we bridge the gap between the molecular level and material properties. These principles
are generally valid and are thus applied to precipitation and to nanomilling in stirred ball mills. The mean particle size in precipitation can be
controlled by either the mixing intensity or the surface charge density of the particles. In stirred media mills oxide particles as small as 10 nm
can be achieved by stabilizing the particles appropriately.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.018
246 W. Peukert et al. / Chemical Engineering and Processing 44 (2005) 245252
2. From particle surfaces to macroscopic properties of molecular interactions, described by classical force laws.
This theorem states that once the electron density distribu-
It is common to all nanoparticle applications that inter- tions have been determined the intermolecular interactions
facial and surface properties of the particles play a central can be calculated on the basis of classical electrostatics. The
role and that macroscopic properties can only be tailored by contact value theorem [3] is analogous: the force between
microscopic design of the interfaces. The ratio of adhesion two surfaces is determined by the density distribution of the
forces to particle weight scales with particle diameter x2 molecules and particles between them.
and it is for instance at 1 m in the order of 106 . Thus, in Depending on the application, particles have to be sta-
order to generate well-defined properties, particle interac- bilized against aggregation. In general, stabilization can be
tions have to be controlled carefully. Surface chemistry and achieved by tailoring the particleparticle interactions by
physics determine not only the particulate interactions with electrostatic or steric means. Whereas in the gas phase the
fluid or solid phases. These types of interactions are van der possibilities of stabilization are rather limited, a variety of
Waals forces, polar interactions, hydrogen or even chemical methods exists in the liquid phase. In liquids, particles of-
bonds. Particle interactions also control particle and struc- ten carry electrostatic charges which lead, in accordance
ture formation. For product engineering of nanoparticulate with the DLVO-theory, to repulsive interaction potentials be-
systems, the conceptual starting point is the particle surface tween the particles since they carry the same charges and
which transports the respective particle interactions, thus thus to stabilization. Aggregation and stabilization may also
leading to the desired structure. Vice versa, structure forma- be tailored by polymers. The adsorption of polymers on the
tion can only be understood by considering the relevant in- particles surfaces may either influence the surface charge or
teractions which are determined by the particle surface. This act as a steric barrier avoiding close contact of the particles
concept is illustrated in Fig. 1 for oxide particles in an aque- surfaces. The selection of the optimal polymer for a cer-
ous solution where particle interactions can be understood tain combination of particle and liquid is still accomplished
in the view of the well-known DLVO-theory as a superposi- empirically, although some guidelines have been formulated
tion of van der Waals and electrostatic double layer forces. based on polymer physics and chemistry [4]. Special effects
This approach is based on some wide-ranging precondi- like hydration forces, e.g. observed for silica [5], are not
tions. In order to bridge the gap between microscopic molec- considered in this paper.
ular nature of a particle surface and macroscopic properties,
a multi-scale approach covering several orders of magni-
tude of space and time is needed. On the most basic level 3. Modeling of population dynamics
quantum mechanics prevail. However, it is often possible by
using the HellmanFeynman theorem [3] to transfer the in- Aggregation kinetics depends on transport mechanisms
trinsic quantum mechanical nature of surfaces to the physics bringing the particles in contact and on particleparticle
interactions. Both aspects influence the kinetics (i.e. the re- above. Particleparticle interactions are not considered. As
sulting particle size distributions as a function of time) and particle density, the value of barium sulfate of 4500 kg/m3
the structure of the aggregates. The most important transport was used. It becomes evident from the results shown in Fig. 2
mechanisms are Brownian diffusion, laminar and turbulent that Brownian motion and turbulent shear at moderate shear
shear due to fluid motion and sedimentation. The follow- rates are the most important transport mechanisms not only
ing equations describe the collision kernels of these mech- for nanoparticles but also for submicron particles.
anisms: To additionally account for the effect of the aggregate
structure on the aggregation kinetics, a collision diameter xc
Brownian diffusion [6]:
is introduced which can be calculated based on the fractal
2kT 1 1 dimension DF of the aggregate (Eq. (5)).
0 = (x1 + x2 ) + (1)
3 x1 x2 6m 1/DF
xc = (5)
Sedimentation [7]: P
x1 2 x2 2 F In this equation m represents the mass of the aggregate and
0 = g + 1 P the density of the aggregate material. Recent small angle
2 2 P
neutron scattering (SANS) measurements have shown that
x1 2 x2 2 2P
(2) the fractal dimension of aggregates increases from 1.8 for
2 2 9 Brownian diffusion to values in the range of 2.2 when shear
Laminar shear [6]: forces prevail [9]. Thus, higher external forces lead to denser
aggregates (e.g. caused by compaction) and the aggregate
4 x1 x 2 3 structure depends on aggregation mechanism.
0 = + (3)
3 2 2 In order to take particleparticle interactions into account,
Turbulent shear [8]: a stability ratio W is included which relates the collision ker-
nel 0 to the aggregation kernel agg . The stability ratio W
8 x1 x2 3 F 1/2 depends on the interaction potential (r) and is defined as
0 = + (4)
15 2 2 ratio of the aggregation rate without to the rate with inter-
actions additional to the omnipresent van der Waals forces.
In these equations, x1 and x2 denote the particle sizes of the For Brownian motion as dominant reason for collisions, the
colliding particles, T the absolute temperature, k the Boltz- stability ratio W can be calculated according to Eq. (6) taken
mann constant, the dynamic viscosity of the fluid, F the from Fuchs [10]. In case of shear as aggregation mechanism,
density of the fluid, P the density of the particle, the lo- the force d/dr relative to the friction force should rather be
cal shear rate and the local mass-specific power input due considered instead of the ratio of interaction energy relative
to turbulence. to thermal energy.
Fig. 2 compares collision kernels calculated for a 250 nm 0 0
particle as function of the collision partner size for Brown- agg = = (6)
W x x (1/r )exp((r)/kT) dr
2
ian motion, laminar and turbulent shear flows as well as sed-
imentation at 25 C in water based on the equations given Particles can either be produced by bottom-up pro-
cesses (e.g. precipitation) or topdown approaches (e.g.
wet milling). In these processes particleparticle interac-
10-12 Brownian diffusion tions become relevant when the particle size is below 1 m.
sedimentation Engineering macroscopic product properties is then only
10-13 laminar shear (10 s-1)
collision kernel in m3s-1
which superposes the terms for nucleation, growth, grinding higher initial concentrations, smaller particles would result.
and aggregation. While nucleation and growth act as supersaturation sink,
mixing can be considered as supersaturation source. Con-
n(x) dn sequently, the time scale of mixing must fit the time scale
= Bhom (xn ) + G + Bagg (n, x) Dagg (n, x)
t
dx
nucleation
of particle formation, i.e. mixing must be at least as fast as
aggregation
growth precipitation, and thus highly turbulent mixing is required
xmax for nanoparticle generation.
S(x)n(x) + S(y)n(y)b(x, y) dy (7) The precipitation process was simulated based on the
x
population balance equation (Eq. (7) without the grinding
grinding
terms) coupled via mass and species balances with a mixing
In this equation Bhom represents the nucleation rate at which model based on the Engulfment model of micromixing by
nuclei of size xn are formed. G is the linear growth rate and Baldyga and Bourne [15]. The modifications of the mixing
Bagg as well as Dagg are the well-known expressions for the model are described in [14]. The particle formation is mod-
birth and death rate of aggregation [7], given below. Within eled through homogeneous nucleation based on the classical
Eq. (7) S(y) is the selection function describing the relative description and diffusion-controlled growth (for details see
amount of particles with size y breaking within a time step [16]). The aggregation of particles is modeled by Eqs. (4), (8)
dt. The breakage function b(x, y) describes the number of and (9). As solver for the population balance equation, the
fragments with size x produced per breaking particle y. commercial software PARSIVAL by CiT GmbH was used.
The implemented algorithm fits the particle size distribu-
Bagg (n, x) tion by polynomials based on a finite-element type Galerkin
h-p-method optimizing the number of variables (number of
x agg
3
x 3 3 , n x 3 n()
3 3
x2 polynomials, order of polynomials) and applies an adaptive
= d time discretization of Rothes type. Details on the simula-
2 0 (x3 3 )2/3
(8) tion algorithm can be found in [17]. Besides computational
speed, the main advantages of the Galerkin h-p-method are
that no assumptions concerning the shape of the particle
Dagg (n, x) = n(x) agg (x, )n() d (9)
0 size distribution are necessary and that the overall accuracy
can be estimated quantitatively from the mass defect during
The kinetics of stabilization must match the kinetics simulation. Simulations of the precipitation process includ-
of aggregation. While ion diffusion and adsorption is fast ing mixing are promising and the number-weighted mean
(electrostatic stabilization), the diffusion and adsorption of particle size can be predicted very well by taking into ac-
polymers (steric stabilization) is slow and may be a limit- count mixing, nucleation, particle growth and aggregation.
ing factor which can only be overcome by applying high It is currently worked at an advanced approach that com-
polymer concentrations. The stability of the electrostatic prises computational fluid dynamics (CFD) modeling cou-
stabilized suspension in moderately fast processes can for pled with mixing and the solution of the population balance
example be monitored and controlled in-line by modern accounting for nucleation, growth and aggregation in order
electro-acoustic techniques [13]. to improve the prediction of the width of the particle size
distribution.
Simulation results of a precipitation process as presented
4. Stabilization during precipitation in Fig. 3 clearly show the different time scales of mixing, par-
ticle formation and aggregation. Fig. 3 also shows the range
In the conducted experiments, barium and sulfate solu- of aggregation for the mentioned conditions and thus the
tions were mixed continuously in a T-mixer resulting in a possible range of particleparticle interactions. Depending
supersaturated mixture and consequently the formation of on stabilization conditions, i.e. for stability ratios W ranging
barium sulfate particles. Apart from educt concentrations it from 1 (no repulsive interaction) to infinity, very different
was found that the intensity of mixing has a strong influ- particle sizes (distributions) are obtained even at times in the
ence on the resulting particle size distribution [11,14] in the range of milliseconds. Thus, the aggregation of nanoparti-
nanometer range. The more intense the mixing, the smaller cles is a challenge to be met on time-scales of milliseconds
the particles. The reason for this behavior lies in the differ- when controlling or tailoring particle size distributions in
ent dependencies of nucleation and growth rates on super- precipitation. This is also depicted in Fig. 4, showing sim-
saturation, the thermodynamic driving force of solid forma- ulation results of the volume-weighted particle size for dif-
tion. With increasing supersaturation, the nucleation rate as ferent mixing and aggregation conditions. Since fast mixing
a highly non-linear function increases much stronger than requires highly turbulent flows, it comes along with signif-
the growth rate. As a consequence, considerably more parti- icant turbulent aggregation. In the presented calculations a
cles are formed at higher supersaturations. The increase is so constant stability ration of W = 1 and aggregation only in
strong that even if higher supersaturations were achieved by the mixer was considered (i.e. during the mean residence
W. Peukert et al. / Chemical Engineering and Processing 44 (2005) 245252 249
mean (volume) particle size in nm
1000
ng
e
particle
400 formation 40 800
particle size,
stabilization
no aggregation 600
200 20
range
(W)
400
0 0
10-6 10 -5
10 -4
10 -3
10 -2
10 -1 200
precipitation duration in s 0
100 101 102 103 104 105 106 107
Fig. 3. Time scales in precipitation calculated for BaSO4 precipitated from
0.5 m BaCl2 - and 0.33 m H2 SO4 -solutions at 25 C. To quantify mixing, mean specific power input in W/kg
a specific power input typical for the applied T-mixer ( = 103 W/kg)
was used. Fig. 4. Simulated influence of aggregation and stabilization in nanoparticle
precipitation.
time), which leads to a residence time effect (the faster the
flow through the mixer, the larger the specific power input cipitation. The theoretically calculated supersaturation (as-
but shorter the residence time). As can be seen, particle sizes suming ideal mixing) was kept constant in all experiments
well in the micrometer range can easily be reached within while the initial molar ratio R of barium to sulfate ions was
milliseconds and that the influence of turbulent aggregation altered. Operating parameters such as flow rate and mixer
can be controlled (besides stabilization) by the duration of geometry were kept constant. Thus, it can be assumed that
aggregation. Latter, however, only applies to turbulent aggre- mixing, the build-up of supersaturation and solid formation
gation. Aggregation due to Brownian motion must be con- were similar in all cases and that possible small variations
trolled by stabilization since the resulting aggregates would cannot account for the measured differences. Hence, the sig-
reach the micrometer range within seconds. nificant differences in particle size distributions are due to
Concerning aggregation kinetics and stabilization it was the altered particleparticle interactions and the resulting al-
found in case of barium sulfate that barium ions adsorb more tered stabilization. As the barium excess is increased, so
readily than sulfate ions [11]. Thus, increasing the ratio R of is the stability against aggregation. Thus, particle size and
barium to sulfate ions in the educt composition and thereby eventually aggregate structure of a precipitation process can
increasing the excess of barium ions after precipitation leads be adjusted to fit needs.
to high surface potentials and stabilization. Fig. 5 shows Recent investigations [18] to quantify stabilization were
measured particle size distributions of continuously precip- successful in correlating to observed stability of colloidal
itated barium sulfate, measured based on quasi-elastic light barium sulfate suspensions with the suspension compo-
scattering (UPA 150 by Microtrac) within 3 min after pre- sition and in particular the concentrations of Ba2+ - and
1.0
cumulative volume distribution
R = 10
R = 3.0
0.8 R = 2.0
R = 1.5
R = 1.2
0.6
R = 1.1
R = 1.0
0.4
excess of
barium ions out of
0.2
measurement
range
0.0
20 100 1000 6000
particle size in nm
Fig. 5. Measured particle size distributions of precipitated barium sulfate showing the influence of the barium to sulfate initial ratio R on stability and
aggregation, respectively.
250 W. Peukert et al. / Chemical Engineering and Processing 44 (2005) 245252
mean (volume) particle size in nm
400 1
R = 1.5 turbulent shear, = 400 W/kg
particle size x50,3 in m
D = 20
R = 1.3
300
D = 1.25
stability
0.1 factor
200 R = 2 R = 1.5
D = 80 D = 100 pH = 7.8
pH = 5.1
pH = 4.1
100 pure breakage
simulation
0.01
104 105
0 time in s
100 101 102 103 104 105 106
Fig. 7. Comparison of mean particle size obtained in a wet milling of
duration in s -alumina (cm = 0.2) with the results of a population balance model.
[14] H.C. Schwarzer, W. Peukert, Tailoring particle size through nanopar- [17] M. Wulkow, A. Gerstlauer, U. Nieken, Modeling and simulation of
ticle precipitation, Chem. Eng. Comm. 191 (2004) 580606. crystallization processes using Parsival, Chem. Eng. Sci. 56 (2001)
[15] J. Baldyga, J.R. Bourne, Turbulent Mixing and Chemical Reactions, 25752588.
John Wiley, Chichester, 1999. [18] H.C. Schwarzer, W. Peukert, Prediction of aggregation kinetics based
[16] A. Mersmann, Crystallization Technology Handbook, second ed., on surface properties of nanoparticles, Chem. Eng. Sci., in press.
Marcel Dekker, New York, 2001.
Chemical Engineering and Processing 44 (2005) 253261
Received 1 August 2003; received in revised form 25 December 2003; accepted 11 February 2004
Available online 25 June 2004
Abstract
Degradation characteristics of South Blackwater and Ensham coal from the stockpiles of Gladstone Port Authority were tested by using
a drop tests apparatus to minimise the fines generation during transport and handling through the Port Authoritys ship loading facilities.
Non-cushioned coal sample of both types of coal dropped on different impact surfaces produced higher percentage of fines than the sample
of cushioned coal, initial 10% fines, initial 30% fines and initial 50% fines. The effect of different types of surfaces onto which the coal was
dropped with initial fines was determined by dropping onto a steel surface, conveyor surface and coal surface (stockpile). The results showed
that the tests with initial 30% fines with lump coal has no significant difference of fines generation in between the three impact surfaces. Both
types of coal with initial 10% fines dropped on steel surface produced more fines than conveyor and coal surface. The cushioning effect of fines
on coal impact surface was least compare to other two impact surfaces. The degradation model was used satisfactorily for South Blackwater
coal on different impact surfaces.
2004 Elsevier B.V. All rights reserved.
Keywords: Cushioning effects; Degradation; Mean particle size; Types of impact surface
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.019
254 R.K. Sahoo, D. Roach / Chemical Engineering and Processing 44 (2005) 253261
horizontal steel plate, conveyor belt and coal stockpile. The Fig. 2. Cumulative percentage of 16.0 mm fines vs. number of drops of
dropped coal was sieved to remove the fines (16.0 mm five types of cushioning tests of South Blackwater coal on steel surface.
size). In this way the percentage of fines produced at each
drop were determined. The calculation methodology for
4. Results and discussion
fines percentage was given in Sahoo et al. [2].
Experiments were carried out to determine the reduction
4.1. Cushioning tests of two types of coal on three different
of lump coal degradation due to the presence of coal fines
impact surfaces
(16.0 mm) with the lumps at the different impact surfaces.
Cushioning effects of fines consists of five different types
4.1.1. Steel surface
of tests are as follows.
The cushioning effects of fines of South Blackwater and
Ensham coal tested on steel surface at 5 m drop height
3.1. Non-cushioned coal were shown in Figs. 2 and 3. Data for the Fig. 2 are given
in Table 2. The result of these figures shows that, there
Non-cushioned coal is a coal sample having an initial was a significant difference of fines percentage between the
size range 76.2 + 50.8 mm, which was used for repeated non-cushioned and cushioned coal sample. Non-cushioned
drops, and has the fines component (16.0 mm size fraction) coal sample of South Blackwater coal dropped on steel sur-
removed after each drop. face produced 12% more fines than a cushioned coal sam-
ple, 13.3% more fines than a sample of initial 10% fines,
27.5% more fines than a sample of initial 30% fines and
3.2. Cushioned coal 30.9% more fines than a sample of initial 50% fines at 30 m
total drops (six drops at 5 m) shown in Fig. 2.
Cushioned coal is a coal sample having initial size range At 5 m drop height non-cushioned coal sample of Ensham
76.2 + 50.8 mm, which was used for repeated drops, but coal dropped on steel surface produced 11% more fines than
does not remove the fines component after each drop. a cushioned coal sample, 15.7% more fines than a sample of
initial 10% fines, 26.3% more fines than a sample of initial
3.3. Initial 10% fines 30% fines and 29.8% more fines than a sample of initial
50% fines at 30 m total drops shown in Fig. 3.
It is a coal sample containing 90% mass of sample to be Fig. 2 shows that the cushioned coal sample of South
dropped of size range 76.2 + 50.8 mm and a 10% mass of Blackwater coal dropped on steel surface produced 1.3%
sample of fines of 16.0 mm size fraction.
50
Ensham Coal, Steel Surface
Cumulative percentage of fines
30 Non-cushioned coal
It is a coal sample containing 70% mass of sample to be
cushioned coal
dropped of size range 76.2 + 50.8 mm and a 30% mass of 20 initial 10% fines
sample of fines of 16.0 mm size fraction. initial 30% fines
10
initital 50% fines
Table 2
Cumulative percentage of 16.0 mm fines of five types of cushioning tests of South Blackwater coal dropped on steel surface from 5 m height
Number of drops Cumulative percentage of 16.0 mm fines of South Blackwater coal
Non-cushioned coal Cushioned coal Initial 10% fines Initial 30% fines Initial 50% fines
30
30
25
25
20 Cushioned coal
Initial 10% fines Cushioned coal
20
15 Initial 10% fines
Initial 30% fines
10 15 Initial 30% fines
5 10
0
5
0 1 2 3 4 5 6
Number of Drops 0
0 1 2 3 4 5 6
Fig. 4. Cumulative percentage of 16.0 mm fines vs. number of drops Number of Drops
of three types of cushioning tests of South Blackwater coal dropped on
conveyor surface. Fig. 5. Cumulative percentage of 16.0 mm fines vs. number of drops
of three types of cushioning tests of Ensham coal dropped on conveyor
surface.
more fines than a sample of initial 10% fines, 15% more
fines than a sample of initial 30% fines and 19% more fines
than a sample of initial 50% fines at 30 m total drops. The shown in Fig. 5. The data for the Figs. 4 and 5 are given in
cushioned coal sample of Ensham coal dropped on steel Table 3.
surface produced 5% more fines than a sample of initial 10%
fines, 16% more fines than a sample of initial 30% fines and 4.1.3. Coal surface
19% more fines than a sample of initial 50% fines at 30 m Fig. 6 shows that the cushioned coal sample of South
total drops shown in Fig. 3. Blackwater coal dropped on coal surface produced 1.3%
more fines than a sample of initial 10% fines and 4.3% more
4.1.2. Conveyor surface fines than a sample of initial 30% fines at 30 m total drops.
Fig. 4 shows that the cushioned coal sample of South The cushioned coal sample of Ensham coal dropped on coal
Blackwater coal dropped on conveyor surface produced surface produced 2% more fines than a sample of initial
0.5% more fines than a sample of initial 10% fines and 10% fines and 4.5% more fines than a sample of initial 30%
8.3% more fines than a sample of initial 30% fines at 30 m fines at 30 m total drops shown in Fig. 7. The data for the
total drops. At 5 m drop height the cushioned coal sample of Figs. 67 are given in Table 4.
Ensham coal dropped on conveyor surface produced 4.5% The results of cushioning effects of both types of coal in
more fines than a sample of initial 10% fines and 12% more Figs. 6 and 7 shows that the initial fines with lump coal does
fines than a sample of initial 30% fines at 30 m total drops not reduce much fines generation when dropped on coal
Table 3
Cumulative percentage of 16.0 mm fines of three types of cushioning tests of two types of coal on conveyor belt surface from 5 m height
Number of drops Percentage of 16.0 mm fines of South Blackwater coal Percentage of 16.0 mm fines of Ensham coal
Cushioned coal Initial 10% fines Initial 30% fines Cushioned coal Initial 10% fines Initial 30% fines
35 South Blackwater Coal, Coal Surface South Blackwater Coal, Cushioned Coal
40
Cumulative Percentage of Fines
30
25 30
Cushioned coal
20 Steel plate
Initial 10% fines
15 20 Conveyor belt
Initial 30% fines
Coal piles
10
5
10
0
0 1 2 3 4 5 6 0
0 1 2 3 4 5 6
Number of Drops
Number of Drops
Fig. 6. Cumulative percentage of 16.0 mm fines vs. number of drops
of three types of cushioning tests of South Blackwater coal dropped on Fig. 8. Comparison of percentage of fines generation of three impact
coal surface. surfaces of South Blackwater coal tested with cushioned coal sample.
30
25
30
20 Cushioned coal
Steel plate
Initial 10% fines
15 Conveyor belt
Initial 30% fines 20
10 Coal piles
5 10
0
0 1 2 3 4 5 6
0
Number of Drops 0 1 2 3 4 5 6
Number of Drops
Fig. 7. Cumulative percentage of 16.0 mm fines vs. number of drops of
three types of cushioning tests of Ensham coal dropped on coal surface. Fig. 9. Comparison of percentage of fines generation of three impact
surfaces of Ensham coal tested with cushioned coal sample.
impact surface. Hence, cushioning effects of fines on coal
surface is minimum compare to other two impact surfaces.
South Blackwater Coal, Initial 10% Fines
35
30
tested with three types of cushioning samples (Cushioned 25 Steel impact
coal, Initial 10% fines and Initial 30% fines) surface
20 Conveyor impact
surface
The comparison of three different impact surfaces tested 15 Coal impact
surface
with cushioned coal sample, initial 10% fines coal sample 10
produced 8.5% more fines than the drops onto a conveyor Number of Drops
surface and 13.4% more fines than a coal surface (coal stock- Fig. 10. Comparison of percentage of fines generation of three impact
pile) at 30 m total drops shown in Fig. 8. Similarly, En- surfaces of South Blackwater coal tested with initial 10% fines coal
sham coal produced 4.6% more fines on steel surface than sample.
Table 4
Cumulative percentage of 16.0 mm fines of three types of cushioning tests of two types of coal on coal stockpile surface from 5 m height
Number of drops Percentage of 16.0 mm fines of South Blackwater coal Percentage of 16.0 mm fines of Ensham coal
Cushioned coal Initial 10% fines Initial 30% fines Cushioned coal Initial 10% fines Initial 30% fines
30
30
cumulative percentage of fines
30
sults of these figures revel that different impact surface has
25 Steel impact
surface
different degradation characteristics which is opposite to the
20 results of Waters et al. [5].
Conveyor impact
15 surface Figs. 12 and 13 shows that there were no significant dif-
10 Coal impact ference of fines percentage in between three impact surfaces
surface
5
tested with sample of initial 30% fines of South Blackwater
and Ensham coal at 30 m total drops. The results of these
0
0 1 2 3 4 5 6 figures reveal that at higher percentage of initial fines the
Number of Drops cushioning effects of fines on different impact surfaces are
same.
Fig. 12. Comparison of percentage of fines generation of three impact
surfaces of South Blackwater coal tested with initial 30% fines coal
sample. 4.3. Comparison of two types of coal tested on three
surfaces
35 Ensham Coal, Initial 30% Fines When two types of coal are compared, the coal sample of
initial 10% fines of south Blackwater coal dropped on steel
Cumulative percentage of fines
30
surface produced 5% more fines than Ensham coal at 30 m
25
Steel impact total drops shown in Fig. 14 and there was no significant
surface
20 difference of fines percentage between two types of coal
Conveyor impact
15 surface
tested with initial 30% fines sample on steel surface shown
Coal impact in Fig. 14.
10
surface
Figs. 15 and 16 shows that, there was no significant dif-
5 ference of fines percentage between two types of coal tested
0 with initial 10% fines and initial 30% fines on conveyor sur-
0 1 2 3 4 5 6
face and coal surface at 30 m total drops.
Number of drops
30 South B.water
initial 10% fines
conveyor surface and 12.3% more fines than coal surface 25
Ensham initial 10%
shown in Fig. 9. 20 fines
At initial 10% fines of South Blackwater coal, the steel 15 South B.water
initial 30% fines
surface produced 8% more fines than conveyor surface and 10
Ensham initial 30%
13% more fines than coal surface at 30 m total drops (six 5 fines
35
Ensham initial (Cushioned Coal)
10 30
30% fines D'Model data
(Cushioned Coal)
5 25
Raw data (Initial
20 10% Fines)
0
D'Model data
0 1 2 3 4 5 6 15
(Initial 10% Fines)
Number of Drops 10 Rawa data (Initial
30% Fines)
5 D'Model data
Fig. 16. Comparison of percentage of fines generation of two types of
0 (Initial 30% Fines)
coal tested with initial 10% fines and 30% fines on coal surface.
0 1 2 3 4 5 6
Number of Drops
4.4. Degradation model of South Blackwater coal on three
Fig. 17. Comparison of raw data and model data of South Blackwater at
impact surfaces 5 m drop height. (D Model data = Degradation Model data).
Table 6
The value of parameters for the degradation model for both types of coal at 5 m drop heights
Types of coal Drop height (m) Cushioned parameter = cij (%) Surface parameter = sij (%)
Cushioned coal Initial 10% fines Initial 30% fines Conveyor Coal
[2] R.K. Sahoo, D.M. Weedon, D. Roach, Coal degradation Part-1: Proceedings of the Second International Conference on Bulk Material
factors affecting coal degradation during handling, BSH 22 (4) (2002) Storage, Handling and Transportation, Wollongong, Australia, 1986,
282288. pp. 2025.
[3] R.K. Sahoo, D.M. Weedon, D. Roach, Coal degradation, Part-2: [7] L.G. Austin, R.R. Klimple, P.T. Luckie, The process engineering of
experimental study of several factors affecting Gladstone Port size reduction, Ball Milling, SEM/AIME, New York, 1984.
Authoritys lump coal degradation, BSH 22 (5) (2002) 356361. [8] A.G. Waters, A. Vince, C.S. Teo, A technique for determining the
[4] B. Fagerberg, N. Sandberg, Degradation of lump ores in transport, resistance to shatter of lump materials, Proc. of CHEMECA, Mel-
in: Proceedings of the Second International Symposium on Transport bourne 2 (1987) 107.1107.8.
and Handling of Minerals, Rotterdam, The Netherlands, vol. 2, 1973, [9] C.S. Teo, A.G. Waters, The effect of drop height and particle size
pp. 28156. on the extent of degradation of agglomerates, in: Proceedings of
[5] A.G. Waters, A. Vince, M. Mahoney, An experimental investigation Australian Biocentennial International Conference for the Process
of some factors influencing the degradation of lump iron ore, in: Industries, CHEMECA88 Sydney, 1988 pp. 665670.
Proceedings of the Third International Conference on Bulk Materials, [10] A.A. Griffith, The phenomena of rupture and flow in solids, Philos.
Storage, Handling and Transportation, Newcastle, 1989, pp. 8488. Trans. R. Soc. London A221 (1920) 163198.
[6] T.E. Norgate, D.F. Tompsitt, R.J. Batterham, Computer simulation of [11] R.K. Sahoo, D. Roach, Degradation model of the dropped coal on
the degradation of lump ores during transportation and handling. in: different impact surfaces, BSH 23 (6) (2003) 6.
Chemical Engineering and Processing 44 (2005) 263266
Received 4 August 2003; received in revised form 17 December 2003; accepted 11 February 2004
Available online 2 July 2004
Abstract
The aim of the paper was to describe the process of grinding of raw materials used in the industrial-scale production of ceramic tiles, by
applying the theory of statistical moments. Grinding was performed in industrial ball mills in ceramic tile factories Ceramika Paradyz Ltd.
and Opoczno S.A. The ball mills operated in a batch mode. A mixture of feldspars and clay was comminuted. Its composition and fractions
depended on the conditions that should be satisfied by raw materials for the production of wall tiles (monoporosis and stoneware) and terracotta.
The ground material was subjected to a particle size analysis. Results of the analysis were used in the calculation of relationships applied in
the theory of statistical moments. The main parameters, i.e. zero moment of the first order and central moments of the third and fourth order
were determined. The values of central moments were used in the calculation of skewness and flatness coefficients. Additionally, changes of
mean particle size in time were determined.
2004 Elsevier B.V. All rights reserved.
2. Description of the model
Corresponding author. Tel.: +48 42 631 3713.
E-mail addresses: heim@wipos.p.lodz.pl (A. Heim),
tolejnik@mail.p.lodz.pl (T.P. Olejnik). In the classical theory of statistical moments they were
1 Tel.: +48-42-631-3713. determined by the formulae
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.020
264 A. Heim et al. / Chemical Engineering and Processing 44 (2005) 263266
m
Table 2
m1 = di w i (1) Feed composition for stoneware and terracotta at Opoczno [10]
i=1 Stoneware Terracotta
M3 Solid components (kg) 20000 20000
K1 = 3/2
(2) Including feldspar (kg) 6000 10000
M2
Clay (kg) 14000 10000
M4 Liquid components (kg) 1500 1500
K2 = 3 (3)
M22 Including water (kg) 1422 1422
Flumix (kg) 20 20
where the central moment of the k-th order is Water glass (kg) 68 68
m
Mk = (di m1 )k wi (4) Table 3
i=1 Feed composition for monoporosis and terracotta in Paradyz [11]
The zero moment of the first order m1 is identical to the Monoporosis Terracotta
mean grain size of the entire set.
Solid components (kg) 21300 22000
A common feature of the classical absolute measures of Including feldspar (kg) 3834 11660
skewness and flatness is that they do not have a finite numer- Clay (%) 11502 7700
ical interval which theoretically would include all possible Dolomite (%) 1704 1980
values. In order to interpret the coefficients of flatness and Calcium carbonate (%) 1704
skewness more easily, original modified forms presented by Raw crushed minerals (%) 660
Eqs. (5) and (6) were proposed. Liquid components (kg) 2100 2600
Including water (kg) 2051 2550
M4 (M2 )2 Trisodium polyphosphate (kg) 49 50
K1m = (5)
M4
M3 Table 4
K2m = (6) Ball size and weight in the mills in Ceramika Paradyz [11] and Opoczno
(M2 ) +M
3/2
3 S.A. [10]
A characteristic feature of these modified coefficients is that Ball diameter (m) Weight (kg)
their values are included always in the strictly determined
Ceramika Paradyz 0.025 4000
intervals: the value of modified skewness coefficient K2m is
0.030 8000
always in the interval 1, 1, while the value of the modified 0.040 8000
flatness coefficient K1m is always in the interval 0, 1. 0.045 6500
Ball diameter (inch) Weight (kg)
Table 5
Comparison of calculated mean particle size m1 , flatness coefficient K1m and skewness coefficient K2m . Terracotta grinding in the mill at Opoczno S.A.
Grinding time (min)
70
m 1 [ m]
60 Opoczno_terracotta
Parady _terracotta
50 Opoczno_stoneware
Parady _monoporosis
40
30
20
10
t [min]
0
0 200 400 600 800 1000
Fig. 1. Changes in the mean particle size m1 for raw materials ground at Opoczno and Paradyz.
360, 420, 480, 540, 600, 660, 720, 780, 840 and 900 of a mean particle size (zero moment m1 ) and modified
min; coefficients of skewness K2m and flatness K1m . Examples of
grinding at Opoczno S.A.: stoneware 15, 45, 75, 105, results obtained for one sample are given in Table 5.
135 and 175 min, terracotta 60, 120, 180, 240, 300, 360, Fig. 1 shows changes in the mean particle size m1 as a
420 and 480 min. function of time for raw materials ground in the mills at
Opoczno and Paradyz. In all cases, in the initial grinding
The samples were subjected to particle size analysis using period, an intensive change of the mean particle size m1
a laser analyser. Results obtained enabled the calculation takes place. For terracotta and silica ground at Opoczno,
1,2
K1m, K2m
0,8
0,6
K1m (Opoczno - stoneware)
.
K1m (Paradyz - monoporosis)
0,4 K1m (Opoczno - terracotta)
.
K1m (Paradyz - terracotta)
K2m (Opoczno - stoneware)
.
K2m (Paradyz - monoporosis)
0,2 K2m (Opoczno - terracotta)
.
K2m (Paradyz - terracotta) m1 [m]
0
0 10 20 30 40 50 60 70
Fig. 2. Dependence of the modified flatness coefficient K2m and skewness coefficient K1m on mean particle size m1 for raw materials being ground.
266 A. Heim et al. / Chemical Engineering and Processing 44 (2005) 263266
Received 15 July 2003; received in revised form 5 January 2004; accepted 11 February 2004
Available online 25 June 2004
Abstract
The objective of the study is to develop an effective and universal approach, based on the theory of Markov chains, to calculate the basic
parameters of the steady state regime of complex technological systems for processing granular materials. In particular, we focus on the
response of a complex milling system to fluctuations of the feed rate to the system. It is shown that depending on the characteristics of the
classifiers the fluctuations can grow unlimitedly, so that the stability of throughputs in the circuit can be lost.
2004 Elsevier B.V. All rights reserved.
1. Introduction During the last years, certain attention has been devoted
to the application of the theory of Markov chains to model
Application of complex technological systems in produc- complex technological systems as well as separate processes
tion of fine powders is a well known tendency in improve- of them [17]. This theory appears to be an effective and
ment of the production efficiency. In particular, complex universal mathematical tool also allowing the efficient com-
milling circuits allow reducing the specific energy, which is putational analysis with modern computers. An algorithm
necessary for grinding. This is due to the correspondence for modelling and calculation of steady-state parameters of
of the size of grinding bodies and that of current particles, circuits of arbitrary complexity was proposed in [8,9]. It is
and also to the evacuation of particles, which are already implicitly based on the Markov chain approach and uses its
ground enough, from the process. Application of networks basic ideas. The basic operator of the approach is the block
of classifiers allows obtaining very high sharpness of cut, matrix of a circuit, which is to be constructed (according
even though separate classifiers of the network could be to developed rules) of matrices of grinding and classifica-
fairly ineffective. A common feature of such circuits is the tion for mills and classifiers the circuit consists of. However,
use of recycling classifier-formed particle flows, formed by there is no clear correlation between the algorithm and the
a classifier, and directed to further grinding, or to repeated general strategy of building Markov chain models that does
classification. For instance, in particle size controlled pro- not allow developing it. Besides that, the approach deals
duction of flour, such networks can currently include more with state (throughput and fraction size distribution) inde-
than 50 mills and classifiers, while three stages containing pendent matrices, i.e., represents a linear model of the cir-
1520 hydrocyclones are needed in the paper pulp process- cuit. At the same time, the flow rate of the recycling particle
ing. However, this feature predetermines some difficulties in flow is not known in advance, as it will depend on the char-
the mathematical modelling of the circuits, as well as some acteristics of the classification which, in turn, depend on the
problems in their industrial operation. mass flow rate to the classifier. This may cause considerable
deviation of real throughputs from calculated ones even at a
Corresponding author. Present address: Centre Poudres et Procedes,
small fluctuation of the feed rate to the circuit for example.
The objective of the study is an attempt to estimate con-
Campus Jarland, Ecole des Mines dAlbi Carmaux, Albi Ct Cedex, Albi
81013, France. Fax: +33 5 63 49 30 25. ditions, under which a circuit has stable steady-state char-
E-mail address: berthiaux@enstimac.fr (H. Berthiaux). acteristics, as well as conditions, under which this stability
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.021
268 V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272
can be lost. For this, simulations based on the Markov chain (a)
formulation for calculating the transient behaviour a circuit,
B22
are performed. B23
1 2 3
B0 B11 B12=B21
2. Application of the theory of Markov chains to model (b)
steady-state parameters of complex circuits
B22
B23
The simplest technological systems with recycling flows 1 2 3
are shown schematically in Fig. 1. In this, the scheme (a) B0 B11 B13=B21
corresponds to a closed milling circuit, and the scheme (b) B12
to a network of classifiers, in which, the fine product of the
first classifier has the repeated classification in the second Fig. 1. Technological systems with recycling flows: (a) closed milling
circuit; (b) network of classifiers. (3-absorber of particles).
apparatus. These basic elements can be a part of more com-
plex circuits. First let us examine the closed circuit milling
system. ones standing for transitions among fractions, i.e., to grind-
The chain model corresponding to the closed circuit ing, horizontalfor transitions among elements of the cir-
milling system with localised models of all its elements is cuit. The matrix of transition probabilities has the following
presented in Fig. 2. It can be constructed in different ways, form:
but first let us examine the model shown in Fig. 2a. Every P 11 P 12 0
column of the set of cells corresponds to an element of P = P 21 P 22 0 (1)
the circuit: a mill; a classifier; or an absorber. The cells 0 P 31 I
within columns correspond to fraction numbers with the
total number of fractions equal to r. The fraction size de- where P is the block matrix consisting of smaller matrices of
creases with increasing fraction number. The state of the size r r. The matrices on the main diagonal describe transi-
system is characterised by the set of probabilities fij to tions among cells (rows) within the corresponding columns,
occupy the cells, every of which can be interpreted as the the matrices on the diagonals neighbouring to the main one
relative mass content of particles in the cell ij. In partic- describe forward (upper diagonal) and backward (lower di-
ular, the set fij , I = 1,2,. . . r, corresponds to the particle agonal) transitions between elements of the circuit, i.e., be-
size distribution in the hold-up of the jth element of the tween columns of cells. I is the identity matrix of the same
circuit. size as P ij , O is the zero matrix of the same size.
After a transition time t the state of the system changes, An example of the matrix P expressed in numbers is
and these changes occur due to transitions of particles among shown below. The total number of fractions, which are un-
the cells. The arrows show possible transitions, the vertical der observation, is taken equal to 3 (r = 3). The transition
(a) (b)
feed
11 12 13
Fraction number (size)
11 12 13 1r
21 22 23
Element of the circuit
feed
31 32 33 21 22 23 2r
r1 r2 r3
31 32 33 3r
Mill Classifier Absorber
fine
Fig. 2. Two variants of constructing the cell model of the closed circuit milling system.
V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272 269
q
probabilities are denoted as pp where p is the index of the with the probability to stay in it equal to zero, placed just
cell where the material transits to from the cell q. before the real absorber which is not included in the chain.
11 12
p11 0 0 p11 0 0 0 0 0
p11 p21
0 0 p22
0 0 0 0
21 21 21
p11 p21 p31 0 0 p32 0 0 0
31 31 31 31
p11 p12
12
0 0 0
12 0 0 0 0
P = 0 p21 0
0 p 22 0
0 0 0 (1a)
22 22
0 p31 0 p32 0 0 0
0 0
32
32
p13
12
1 0 0
0 0 0 0 0
0 0 0 0 p22 23 0 0 1 0
0 0 0 0 0 p33 32 0 0 1
The mass content of fractions in the cells is described by the
state vector F , which is the column block vector consisting In this case, the identity matrix I in (1) is to be replaced by
of vectors f j related to the jth column of the set of cells the zero matrix of the same size, and the matrix P becomes:
placed one after another: P 11 P 12 0
f1 P = P 21 P 22 0 , (6)
P 31
F = f2 (2) 0 0
f3 and the steady-state (asymptotic) distribution can be calcu-
lated by the formula:
where every vector f j has the size r 1, and consists of
elements fij , f2j , . . . , frj . F = (I P)1 F 0 , (7)
The feed vector F 0 is similar to F , and contains mass
which follows from the formula for the sum of the infinite
fractions, which are added to the circuit after every transi-
geometrical progression written in matrix notation.
tion. In the case shown in Fig. 2a, it contains only the first
After separating the vectors f i from F it becomes pos-
non-zero vector of the three, which is the fraction size dis-
sible to define fraction size distribution in every element
tribution f 0 in the feed to the circuit. The rest two vectors
of the circuit, and then, using (4) and (5)-throughputs and
are the zero vectors of the same size.
hold-ups in them.
If the transition time t is chosen, and matrices P ij are
The algorithm of the circuit matrix construction can be
defined, the matrix P can be constructed and successive
strongly simplified, if we suppose that, the particle flow in
evolution of the state vector F can be calculated as:
the mill can be presented as the perfect plug flow, and take
F n+1 = P(F n + F n0 ). (3) the transition time equal to the particle residence time in
the mill. In this case, the probability to stay within the cell
The hold-up in the jth element of the circuit and the total
presenting the mill is equal to zero. Since the residence time
flow rate from it to the pth apparatus of the circuit are:
for a mill is normally much longer than it is for a classifier,
r
the same holds true for the probability to stay in the cell
Mj = fij (4) presenting the classifier.
i=1 In this case, the constructing of the circuit matrix is more
r
convenient if the axes are directed as it is shown in Fig. 2b.
Bpj =
ij
fij pip (5) Under the above assumptions this matrix takes the form:
i=1
0 I C 0
j
where Bp is the mass flow rate from the jth to the pth element
P = G 0 0, (8)
ij
of the circuit, pip is the probability of transition of the ith 0 C 0
size fraction between these elements.
Under a continuous constant feed to the circuit there exists where G is the matrix of grinding in the mill related to the
a steady-state (asymptotic) regime of the circuit operation. transition time t, which is a lower triangle matrix of size r
However, this solution cannot be obtained with the matrix r (r is the number of fractions under observation) C, the ma-
(1) because it contains the absorbing state, the probability trix of classification, which is a diagonal matrix of the same
of which grows unlimitedly. In order to get round the size consisting of discrete values of a grade efficiency curve
difficulty, the absorbing cell can be presented not like the [8,9,11]. Substitution of the matrix (8) into Eq. (7) gives:
end of the chain, but as an intermediate element of the chain F = K1 F 0 (9)
270 V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272
is the final form of the matrix of the circuit, which can be 3.1. Closed circuit milling system
constructed on the basis of the following rule:
Let us turn back to the closed circuit milling system shown
The matrix K of the circuit is the block matrix of size
in Fig. 1a. The throughput dependent matrix of grinding was
m x m blocks, i.e., smaller matrices presenting processes
introduced as follows. For the fixed throughput Bs the ma-
in elements of the circuit, every of which has the size
trix P was constructed on the basis of the linear selection
r r, where m is the number of elements of the circuit
and homogeneous breakage functions [8,10]. It was sup-
(including the absorber), r is the number of fractions under
posed that the only result of the throughput change was the
observation.
variation of the mean residence time. Under the assumption
The main diagonal of K contains the identity matrices of
of a constant hold-up, it gives:
size r r with the sign minus.
Every column of K belongs to an element of the circuit. P(B) = P(Bs )tm /tms = P(Bs )(M/B)/(M/Bs ) = P(Bs )Bs/B
The matrix of the element is to be placed in the row of this
column, whose number is equal to the number of element, (12)
where the particle flow is directed. where, tm is the mean grinding time, M, the constant is the
This rule is universal and can be used for an arbitrary hold-up in the mill, and the subscript s indicates the reference
circuit. The vectors f i of the block vector F is the fraction regime of grinding.
size distribution in the particle flow before the ith element. The matrix of classification C was introduced on the basis
The matrix K for the network of classifiers shown in Fig. 1b of the formula by Molerus and Hoffmann [11] for the grade
has the following form: efficiency curve:
1
I I C2 0 qx = (13)
1 + x/xc exp((s/2)(1 x/xc ))
K = C1 I 0 (11)
0 C2 I where, x and xc is the current and cut size respectively, s
is the parameter related to the efficiency of classification.
where, the absorber for the coarse product from the first With s Eq. (13) gives the grade efficiency curve of
classifier is not included into the chain because information the perfect classifier with the cut size xc . The elements of
on the state is irrelevant to the objective of this study. C were calculated as Cjj = qx (xj /xc ) where, xj is the mean
It is necessary to note that the matrix K does not deal with size fraction.
the hold-ups at all. The same rule for its construction was When the throughput in a classifier is changed, both the
suggested in [8,9] on the basis of particle fractions flows bal- cut size xc and the parameter s can be changed. An increase
ance only, without referring to Markov chains models. Here of the throughput practically always leads to the decrease of
it was obtained as a particular case of the developed model, s (the efficiency decreases) but the cut size can both increase
which is presented by the matrix P and allows describing and decrease. Both parameters are changing the outflows
also the evolution of hold-ups in general case provided the of fine and coarse material, but it can be shown that the
smaller matrices of P are known. influence of the cut size is much stronger. That is why the
Once the types of equipment a circuit consists of have assumption that xc = xc (B), but s = s(B) was introduced.
been decided upon, we have the preliminary information Despite, the dependence of the cut size on the throughput
on the corresponding matrices, and can calculate the circuit can be very complex, as the first approximation it can be
using the algorithm described above. After calculating the taken as a linear one around the reference throughput:
throughputs, we can select sizes of the equipment chosen. xc (B) = xc (Bs ) k(B Bs ) (14)
Thus, we get the complete information on the circuit param-
eters, which are supposed to be reached in the real operation. where, xc (Bs ) is the cut size at the reference throughput,
If the matrices of the equipment are throughput independent, which was used to choose the classifier, k = (xc /B)B=Bs ,
small errors in describing them give also a small error in pre- and its positive value is assigned to the decreasing function
dicting the circuit parameters. However, if they are through- xc (B), which is being met more often for industrial classi-
put dependent, first, the error can become much larger, and fiers.
second, small variation of operating parameters of the circuit Investigation of transient processes after deviation of the
may cause large variation of throughputs, up to conditions feed rate was done as a numerical experiment according to
when the circuit fails to work. Further on, we will try to the following procedure. The basic value of the feed rate B0
V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272 271
Fig. 4. Areas of stable and unstable operation of the closed milling circuit Fig. 6. Areas of stable and unstable operation of the network of classifiers
(os = 5; s = 15). (os = 5, s = 15).
272 V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272
Received 2 September 2003; received in revised form 24 March 2004; accepted 15 April 2004
Available online 26 June 2004
Abstract
An optimising design method is presented for designing closed grinding circuits to meet the requirements for the particulate product
expressed as a combination of the mean value and standard deviation of the particle size. The grinding circuit is modelled by a discrete
mathematical model describing the axial mixing and breakage of particles in the mill and a possible time delay in the recycle line. The design
problem is formulated as a nonlinear programming task in which the convective flow velocity and the axial dispersion coefficient of the ground
material are selected as design variables.
The method proved to be a useful tool for optimising design of grinding systems, and can be applied as a decision aid for process engineers
to improve the efficiency of processes and maintaining the quality required for the particular products.
2004 Elsevier B.V. All rights reserved.
Keywords: Continuous grinding; Grinding mill-classifier circuit; Optimising design; Nonlinear programming; Simulation
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.009
274 P.B. Kis et al. / Chemical Engineering and Processing 44 (2005) 273277
in the form [8]: containing information about the average deviation of the
particle size from its mean. Following the model formed by
xi xi Eqs (1)(3), the mean particle size and the standard deviation
B(xk , xi ) = + (1 ) ,
xk xk of size at the outlet are computed as
xmin xi < xk xmax , 0 1. (5) I
(yJ , xi , tn )
x(tn ) = xi(1/2) I (6)
In expressions (4) and (5), , Ks , , and are consti-
i=1 i=1 (yJ , xi , tn )
tutive parameters. Based on these relations, we can precise
also functions pk,i in Eqs. (1)(3): pk,I = S(xk )[B(xk ,xi ) and
B(xk ,xi1 )], I = 1, 2, . . . , I; k = i, . . . , I.
I
(yJ , xi , tn )
Let us note that in order to have stable numerical scheme s(tn ) = xi(1/2) I
2 x(tn )2 (7)
in simulation the condition (Peh2y )/(2 + Pehy + i=1 i=1 (y J , xi , tn )
Peh2y S(xi(1/2) )) is required to be satisfied.
The first term on the right hand side of Eq. (1) gives where x denotes the mean particle size and s stands for
the amount of particles of ith size at the moment of time the standard deviation, being the positive square root of the
tn which neither moved forwards nor broke during one variance.
time step of simulation. The second term represents those Assuming now that the requirements for the quality of
particles of the same size that moved backwards from the the product are formulated in terms of prescribed mean size
second section. The third term expresses the amount of 0 and standard deviation 0 , the objective function for
particles that remained in the first section and have bro- choosing the design variables is formulated as
ken from some size higher than xi to that subinterval of Q(d) = w1 (xs (d) 0 )2 + w2 (ss (d) 0 )2 (8)
size. Term ai (tn ) denotes the amount of particles of the ith
size that freshly enters the system. Finally, the last term where w1 and w2 are weighing factors, expressing the
(VF VB )(xi(1/2) )(yJ , xi , tnd ) is the fraction of par- significance of the mean value and standard deviation terms,
ticles of the ith size that left the mill at the moment of time according to the requirements, xs (.) and ss (.), denote the
tnd and was classified by the classifier to recycle into the steady state values of the mean size and standard deviation,
mill for further grinding. Here, function i , 0 i = (xi ) respectively, computed by solving the set of Eqs. (1)(3),
1, describes the operation of the classifier, whilst parame- and d is the vector of the design variables.
ter d denotes the discrete time delay in the recirculation line. Based on these considerations, the purpose of optimisa-
The variation of the amounts of particles in the internal tion is to determine the values of the design variables d of
sections of the mill is described by Eq. (2). The first term on the grinding circuit to produce such particulate product that
the right hand side of Eq. (2) represents the fraction of par- the objective function be minimal.
ticles of the ith size that moved forwards from the previous In this formulation, precising the initial conditions for
column, while the third term gives that part of particles of the Eqs. (1)(3), this set of equations is solved recurrently in
same size that moved backwards from the next column. The time to generate the steady state values xs (.) and ss (.), pro-
second term expresses the amount of particles that have not vided the system parameters and the feed conditions are
changed at all. Finally, the last term describes the amount of given. This means that the set of Eqs. (1)(3) is solved in
those particles that remained in the section and has broken each step of searching the optimal solution, monitoring at
from some size larger than xi to the ith subinterval. the same time if the steady state was reached.
Finally, the size composition of particles in the last section
of the mill is described via Eq. (3). The first term on the
right hand side expresses the amount of those particles that 4. Results and discussion
moved forwards from the previous column. The second term
represents particles that have not changed at all, while the In the simulation runs, the design parameters were chosen
third term gives the amount of particles that remained in the as d = (u,D), i.e. the kinetic parameters of breakage and
last column and have broken from some size larger than xi the classification function were fixed. The size distribution
to the interval in question. of particles in the feed stream was constant, selecting 0 for
x = xmax /2 and 0.05 for x > xmax /2, while the initial size
distribution of the material in the mill was the same in each
3. Formulation of the optimisation problem run. The largest particle size was chosen xmax = 103 m,
and the values of the kinetic parameters were Ks = 104 ,
The particle size distribution of the product is one of the = 1.00, = 3.00, = 0.60, = 0.48. The classification
most important product characteristics of grinding circuits. function was a jump function of the form
Instead of the complete distribution, however, we are limited
0, i = 1, . . . , [I/2]
mostly to determining a few characteristic parameters of the i =
product size such as the mean particle size and the variance, 1, i = [I/2] + 1, . . . , I
276 P.B. Kis et al. / Chemical Engineering and Processing 44 (2005) 273277
Table 1
Values of the objective function in the environment of local minimum
Convective flow Axial dispersion coefficient, D (m2 /s)
velocity, u (m/s)
0.004 0.005 0.006 0.007 0.008 0.009
Appendix A. Nomenclature
Received 22 June 2003; received in revised form 14 January 2004; accepted 11 February 2004
Available online 1 July 2004
Abstract
An overview is given of modern air classification devices, their operation principles, features and parameters, as cut size, cleanness
and recovery. We outline the separation zones common to existing classifiers. In practice, various gravitational and centrifugal classifiers
are employed, including those with vertical and horizontal air streams, cascade classifiers, fluidized bed separators, inertial, vortex, rotor
classifiers, etc. Choice of the classifier type and designs is dictated by the technological requirements (throughput, cleanness, etc.) and the
properties of materials to be classified. Advantages and limitations of the classifiers and basic trends in their development are considered.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.022
280 M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285
= 0.5(c + f ). The above definitions of c , f are suitable cally all particles are separated due to unavoidable stochastic
when the cut size is given. Otherwise, c , f may be esti- factors.
mated by grade efficiency curves [1].
2.2. Gravitational-crossflow zone
2. Particle separation zones A horizontal air stream entering this zone expands within a
chamber and converges towards the outlet (Fig. 1b). Particles
An interior space of a classifying device, where solid fed in the chamber with zero velocity accelerate horizontally
particles interact with air stream, is the separation zone. by the drag force Fd and also fall down. At the end of the
Four basic separation zones are known, as described acceleration interval the horizontal velocity component vx of
by Rumpf [2], which include gravitational-counterflow, all particles almost reaches the are flow velocity u and they
gravitational-crossflow, centrifugal-counterflow and centri- do not separate in this direction. Separation occurs due do
fugal-crossflow zone. particles vertical motion across the air stream. Each particle
falls at its own terminal settling velocity. Accordingly, due
2.1. Gravitational-counterflow zone to the horizontal motion they land on the bottom at different
chamber locations: coarse-close to the inlet, smaller-close
The gravitational-counterflow zone exists in air stream ris- to the outlet. Coarse fraction is gathered on the bottom of
ing up with velocity u inside a vertical chamber with parallel the chamber, fines do not reach the bottom and are carried
walls (Fig. 1a). Particles experience gravity G and drag Fd away by the air flow through the outlet.
forces acting in opposite directions. Coarse particles, hav- Thus, in the gravitational-crossflow zone particle separa-
ing terminal settling velocity VTS larger than air flow ve- tion is a two-dimensional process, where their trajectories
locity, move downwards, against the air stream, and fines are in fact ballistic tracks. Unlike the counterflow zone, the
rise with the stream. The cut size d50 is calculated from the cut size depends not only on the particles terminal velocity,
equilibrium G = Fd combined with zero particles absolute but mainly on the chamber length and height. These param-
velocity, i.e. VTS = u. Theoretically, the cut size particles eters are chosen in such a way that particles with the cut
are indefinitely suspended in the separation zone. Practi- size land at the farthest point A of the bottom (Fig. 1b).
Fig. 1. Separation zones: (a) gravitational-counterflow zone, (b) gravitational-crossflow zone, (c) centrifugal-counterflow zone, (d) centrifugal-crossflow
zone.
M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285 281
2.3. Centrifugal-counterflow zone to the wall faster; smaller ones make it farther along the ax-
ial direction. The chamber is designed in such a way that
This separation zone is characterized by a flat air vortex the cut size particles reach the periphery at its edge (point
prevailing in a cylindrical chamber with tangential inlet and A). The separation process in the centrifugal-crossflow zone
central outlet (Fig. 1c). In this vortex air rotates and flows is similar to that in cyclones; so these devices have similar
radially towards the chamber centre. The radial air move- design principles.
ment (radial sink flow type) serves as the particles separa-
tion track.
Particles fed tangentially with air stream are involved in 3. Air classifiers types and designs
rotation. Due to the centrifugal (inertial) force Fc their tra-
jectories gradually deviate from the air streamlines. Sepa- Numerous air classifier designs are described in the
ration is governed by the balance between Fc and the drag literature [3,21]. No universal design method can be recom-
force component Fdr induced by the radial air movement. mended for separation of different materials, as each device
Coarse particles drift towards the chamber walls, where they type has its specific technical requirements and suitable
fall down to the outlet. Fines move towards the chamber for specific product. The separation zones described above
axis where they are eventually carried out by the air stream. serve as a basis for systematizing air classifiers, which
Particles with cut size theoretically move with zero radial may have several zones used in combination in the same
velocity, but practically go to one of the products. As the device.
centrifugal force depends on the radial position, so does the Air classifiers may have external or internal aerodynamic
cut size d50 . This distinguishes the separation process in the cycles. The former devices are constructed independently
centrifugal-counterflow zone from the separation occurring of dust collectors and fans and connected to them via
in the gravitational-counterflow zone. To keep the cut size pipelines. The internal-cycle (recirculating-air) devices
constant along the radial direction, the classifier should be contain these elements in a single unit, and hence need
designed to provide constant tangential air velocity. This less production area and normally require lower invest-
feature is characteristic of the Archimedean spiral or free ments. They have several technical shortcomings outlined in
vortex flow [2]. subsection 3.5.
Air classifiers may also be distinguished by method of
2.4. Centrifugal-crossflow zone powder feed. Particles may be fed either within air stream, or
separately by freely pouring them within the device. Other
This zone may be created in an air vortex for example systematizing may be done with respect to the air stream
in a cylindrical chamber with inlet and outlet placed on the form, classifier design features and operation mode (contin-
opposite sides of the chamber axis (Fig. 1d). The fed par- uous or batch).
ticles enter with the air stream through whirl blades, which Below we review principal schemes of most commonly
create a screw-type flow. The blade profiles should be de- used air classifiers to summarize the most important features
signed such that the radial component of the air velocity of their design and operation. Modern trends of classifier
everywhere vanishes. Particles rotate while drifting radially design account for stochastic nature of separation and aero-
towards the chamber walls with size-dependent velocities. dynamic parameters of equipment, creation of precise air
As they simultaneously proceed along the chamber axis they velocity field, repeated cleaning of both fractions, arrange-
reach the wall in different locations. Larger particles arrive ment of several classifying stages, etc.
Fig. 2. Cascade classifiers: (a) zigzag, (b) shelf classifier, (c) with horizontal scavenging.
282 M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285
3.1. Gravitational air classifiers These shortcomings prevail also in Shelf cascade classi-
fier [6], where instead of pipes, inclined shelves are mounted
3.1.1. Counterflow classifiers with vertical (rising) flows on the inner walls of a vertical vessel (Fig. 2b). Strong turbu-
Early classifiers of such type [3] were constructed as verti- lence prevailing under the shelves cause high pressure drops
cal chambers having within a rising air stream (Fig. 1a) with (of up to 45 kPa) and high energy consumption of these
particles fed from the top or from the side. Being inexpensive devices.
and simple in construction and maintenance, these devices Cascade principle was also combined with cross-count
have one important shortcoming. Namely, the fed particles horizontal scavenging [7] in a vertical vessel divided into
break air flow uniformity and create significant turbulence. separation and precipitation chambers, separated by a per-
As such, coarse particles prevent fines from rising with the meable grid with concave shelves (Fig. 2c). Particles fed
air stream. This in combination with the single-stage oper- from the top pour onto the upper shelf, glide down and fall
ation mode underlies low separation efficiency of counter- of its edge where they are scavenged by the cross-current
flow classifiers with rising flows. These classifiers are used stream. Part of fines is carried into the precipitation chamber
only for separation of coarse bulk materials, containing two and the rest of the mixture falls onto the next shelf for re-
types of particles of well differing sizes, e.g. coarse sand or peated separation. After multiple separations, coarse fraction
pebbles of 110 mm mixed with dust 0.10.2 mm. exits from the separation chamber and fines leave the pre-
cipitation chamber. The finest fraction exits with the stream
3.1.2. Crossflow classifiers with horizontal air stream and is collected in cyclones or filters.
Separation in these devices known as winnowing ma- This design practically or to a considerable extent elim-
chines [3], is achieved due to the difference between tra- inates particles collisions in the separation zone, which
jectories of coarse and fine particles in the separation zone sharpens separation. As the flow field in the chamber has no
(Fig. 1b). Their operation and efficiency are strongly af- inherent vortexes the device has lower air resistance and en-
fected by the stochastic factors of the process, in particular ergy consumption. Several prototypes of this classifier were
by uncertainties in feeding and particles aerodynamic inter- used in phosphate industry for separation of crushed phos-
actions. In most cases coarse particles prevent proper clas- phate ore at 1 mm cut size. One such plant with output of 25 t
sification of fines. Separation efficiency of these devices is per hour and pressure drop of 800900 Pa yielded 9698%
usually low. They are normally used for separation of solid cleanness of fines and 7885% of coarse fraction [8].
particles according to densities (e.g. grain from peel), rather
than by size. Sometimes crossflow separation in horizontal 3.3. Fluidized bed classifiers
streams is used in combination with other separation prin-
ciples. In these devices classification occurs in the space over
a fluidized bed from which fine particles are carried away
3.2. Cascade air classifiers with the air stream. The air velocity must essentially ex-
ceed the maximal fluidization velocity of fine fraction. These
These devices, known as Zigzag classifiers [4], are cas- classifiers operate on the gravitational counterflow separa-
cades of several inclined branch pipes of a rectangular cross tion principle with fluidized bed used to increase particles
section arranged to form a vertical zigzag channel (Fig. 2a). residence time in the separator. Coarse particles can move
Air flowing from below scavenges the particles fed from horizontally across the bed to the exit, which is another ad-
above in cross-current direction. The flow field within the vantage of this device.
chamber has vortexes in the turn points, where the fines are Fluidized bed classifiers may have straight or widening
dragged by the stream, and the coarse particles cross it to- forms. The latter (Fig. 3a) consist of a conical chamber with
wards the opposite wall and pour down. Separation occurs in a grid permeable for particles fed from below, inlet and
a cross-flow process. Sequential pipes arrangement enables outlet pipes and a branch for coarse product. Air velocity
multiple scavenging to improve the separation efficiency. in the holes is high so that all the particles move far up-
Several types of Zigzag classifier are produced by Alpine wards into the cone, where the stream expands and the par-
[5] for separation of ferruginous ore, fertilizers, plastic, ticles slow down. The coarse part returns to the grid and the
wooden dust, etc. at cut sizes ranging from 0.1 to 10 mm. fines are carried away. The cones upper diameter is cho-
The number of parallel chambers varies from one to 16 sen in such a way that the air velocity does not exceed the
with output ranging from 1 to 10 t/h. coarse particles terminal velocity. These particles exit from
Although multiple scavenging improves separation, a pseudo-boiling layer formed above the grid through the
coarse particles crossing the air stream on each cascade step outlet branch. Pass-through grids allow arranging several
collide and mix with fines. This precludes sharp separation cones one over another i.e. to design multi-stage classifiers
and decreases the efficiency. Another disadvantage of the (Fig. 3b). Each stage has its (coarse) product with size de-
device is its high aerodynamic resistance (pressure drop of pendent on the chamber diameter.
about 2.53.5 kPa), resulting from the vortexes formed in Classifiers with pass-through grids did not find wide use
cascades turn points. in practice mainly because of their big size. For example, a
M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285 283
Fig. 4. (a) Franken/Buell gravitational-inertial classifier, (b) Vortex classifier, (c) gravitationalcentrifugal classifier.
284 M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285
in the curvilinear chamber to mix with fed material. This with throughputs of up to about 20 t/h are widely used in
was eliminated by adding a branch pipe in the centre of the cement and coal milling plants [18].
curvilinear chamber to provide a separate exit of fines [16].
One such 20 t/h classifier was tested in phosphate works to 3.5.3. Rotor classifiers
separate 50400 m fraction from ground phosphorite. It Rotor classifiers utilize rotating blades for air circu-
had coarse product cleanness of 91% and recovery of 77%. lation. In one such classifier [19] (see Fig. 5a) particle
laden air enters from below and rises upward into a con-
3.5. Centrifugal air classifiers ical vessel, containing a drive-activated rotor with a cone
and rotating blades. These blades whirl the air to create a
Two main types of these classifiers are known, distin- centrifugal-counterflow separation zone in the upper part
guished by method of creating air rotation. In vortex clas- of the vessel. The cut size is controlled by adjusting the
sifiers the air is rotated by stationary vanes (or tangential drives rotational velocity. These devices with throughputs
pipes); in rotor classifiers this is done by rotating blades. The of up to 1.5 t/h are used for separation of fine quartz powder,
latter devices may have open or closed aerodynamic cycle. cement, ground limestone etc. at cut sizes of 20100 m
and coarse product recovery of 7080%. Similar classifiers
3.5.1. Vortex air classifiers were developed by Hosokawa Co. [17] for separation of
Vortex air classifiers have centrifugal-counterflow separa- ground coal, talc, aluminum oxide, etc. A variant of rotor
tion zone. Alpine A-G manufactures several such classifiers classifiers (Blade Classifier) [20] has profiled blades similar
on the basis of the Rumpfs developments. One device of to axial compressors (Fig. 5b). The space above the blades
this type (Fig. 4b) is designed as a flat horizontal cylinder is arranged to form a centrifugal-crossflow zone, (rather
containing a vortex chamber. Particle-laden air passes via in- than the counterflow zone, characteristic of the Hosokawa
clined vanes into the chamber, through which the air moves classifiers). In this zone particle separation occurs as de-
along a spiral trajectory, carrying the fines out. Coarse parti- scribed in Section 2.4. Among the various blade profiles
cles are drawn to the wall region and exit via a screw outlet. tested, the highest efficiency was registered for that pro-
These classifiers are used for separation of fine powders, e.g. viding the solid body air rotation. The blade classifiers
limestone, quartz, pigments, etc. at cut sizes of 5100 m allow separation 2060 m powders, e.g. quartz, pigments,
[1,17]. alumina with 7080% both products recovery.
Fig. 5. (a) Rotor classifier, (b) classifier with profiled blades, (c) circulating air classifier.
M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285 285
ing separated as in the centrifugal-crossflow separation zone [4] F. Kaiser, Der Zickzack-Sichter ein Windsichter nach neuen Prinzip,
(see Fig. 1d). When the air abruptly turns to the vanes, fines Chemie-Ing.-Techn. 35, 1963.
[5] Zerkleinerungsmaschinen, Windsichter, Extruder, Alpine Prospekt
proceed down to their exit. Air-particle motion within the 017/2R, 1968.
intermediate space is similar to that in cyclones. [6] M. Barsky, Powder Fractionation, Nedra, Moscow, 1980.
These classifiers may process up to 800 t/h of bulk solids [7] V. Galperin, et al., Device for Separating Bulk Materials, USSR
[22]. They have rather poor dust/air separation in the inter- Patent No. 1619535, 1984.
mediate zone, resulting in particle accumulation, which re- [8] V. Galperin, et al, Dry Classification of Phosphate Ore in Chilisai
Phosphate Field, Chem Industry, 12, Moscow, 1988.
duces their efficiency. Cut size control in these devices is [9] A. Vasilenchuk, et al., Gravitational Air Classifier with Fluidized
difficult. Bed, USSR Patent 228641, 1968.
[10] V. Galperin, et al., Industrial tests of the Air Classifiers with Flu-
idized Bed, Proceedings of Mines and Chemistry Institute for Raw
4. Conclusions Materials, issue 57, Moscow, 1985.
[11] V. Galperin, Gravitational Air Classifier with Fluidized Bed, USSR
Patent 1619535, 1984.
Choice of the classifier type is dictated by product re- [12] V. Galperin, M. Shapiro, Separation of Solid Particles in a Fluidized
quirements, technological and economic factors. Rational Bed Air Classifier, Powder Handling and Processing, 11, No. 2,
design and improving separation quality is done by creating AprilJune 1999.
a well-defined and stable air flow, reducing turbulence, elim- [13] J.F. Franken, Apparatus for Classifying Particulate Material, USA
Patent 3006470, 1961.
inating particles collisions, controlling feed and repeated [14] J.P. Vandenhoeck, Classifier with gas flow distributor, USA Patent
cleaning of both fractions. Among gravitational type clas- 3006470, 1961.
sifiers, fluidized-bed based devices provide stable operation [15] Buell, A Division of Fisher-Klosterman, Inc., http://www.fjinc.
and sharp separation in the cut size range of 501000 m. com/Buell/cat1.html 2003.
Smaller-size particles may be separated by rotor classifiers, [16] V. Galperin, et al., Air Classifier, USSR Patent 608568, 1978.
[17] Hosokawa, http://www.hosokawa.com.web/powderequip/
enabling easy cut-size control and providing products re- CLASSIFIERS/HTM, Powder and Particle Processing, 2003.
coveries up to 80%. [18] G.K. Smyshliaev, Air Classification in Mineral Processing, Nedra,
Moscow, 1969.
[19] V. Rybin, S. Bockshtein, Investigation of Impingement-Vortex Clas-
sifier, Proceedings of the Institute of Building Materials, Gosstrojiz-
References dat, 1960.
[20] M. Dubinsky, V. Galperin, Blade Air Classifier, USSR Patent 177766,
[1] H. Rumpf, Particle Technology, Chapman and Hall, London, 1990. 1965.
[2] H. Rumpf, Fortschritte und Probleme auf dem Gebiete der Wind- [21] I. Klumpar, et al., Air Classifiers, Chemical Engineering, 3 March,
sichtung, Staub, vol. 47, 1956. 1986.
[3] A. Taggart, Handbook of Mineral Dressing, John Willey & Sons, [22] Sturtevant Inc., Whirlwind Air Classifiers, http://www.sturtevant.com,
USA, 1950. 2003.
Chemical Engineering and Processing 44 (2005) 287291
Received 1 September 2003; received in revised form 6 January 2004; accepted 11 February 2004
Available online 19 June 2004
Abstract
This paper reports on the successful application of a large vertical venturi separator for the removal of tangled steel and rayon fibres from
crumbed rubber product as part of a tyre recycling process. This represents an advance over the other separation units encountered during this
project in cleaning efficiency and scalability. The venturi separator was able to unwind the synthetic fibres from the steel fibre by keeping the
agglomerate in a suspended state within the throat of the venturi. A chaotic particle motion was observed at the throat which aided in teasing
the synthetic away from the steel fibre. Overall the venturi separator offered far superior cleaning ability, suitable throughput rates and simple
construction/implementation. The concept could easily be applied to other industries where an aerodynamic classifier offering potentially
unlimited particle retention times may be beneficial.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.023
288 W. McBride, S. Keys / Chemical Engineering and Processing 44 (2005) 287291
To Filter
the mouth of the venturi. With the throat velocity set to
prevent the largest particles from exiting the venturi, an ex-
tremely fast and efficient cleaning was achieved (typically
less than 10 s of residence time). As the material fell down
Cone for material dispersion
into the throat it was progressively reacted on by the op-
posing air flow and accelerated back into the venturi dif-
fuser. A large degree of interparticle collision was evident
in the continuous falling/elevating process providing a ran-
dom or chaotic motion. This randomness tended to tease
the loose end of the synthetic fibre from the steel fibre.
Air flow
As the particle circulated the synthetic fibre was progres-
Fig. 1. Typical style fabric separator. sively pulled from the steel fibre. Once the steel fibre was
W. McBride, S. Keys / Chemical Engineering and Processing 44 (2005) 287291 289
Storage Fd
Hopper
V
Screw Feeder
Mg
Central Feed Tube To Filters
Fig. 3. Force balance on a particle: aerodynamic due to air flow (up) and;
gravity (down).
rp Vdz
2
Vdz
To Filters
Z
Butterfly valve to
dump product
V 2 = U 2 2aS. (4)
Screw Feeder
From the drag Eq. (1) and noting the F = MA then it can be
shown that the acceleration on a particle at some position
Z (Fig. 4) from the start of the converging section can be
determined by
3a Cd 2
ap = V (5)
8rs dz
Where ap is the particle acceleration of a particle with radius
r.
If the venturi is segmented into slices Z thick it can be
shown that the velocity exiting the slice is given by
seperator
(6)
Received 14 August 2003; received in revised form 2 February 2004; accepted 11 February 2004
Available online 28 July 2004
Abstract
Many bulk commodities, such as cereal grains loaded into a silo require active mixing during storage. A special pulsated bottom mixer was
patented at our university for gentle mixing of granular solids stored in large containers or silos. This work intended to reveal the fundamentals
in displacement of single particles mixed by different pulsation orders. A glass-walled simulator (filled with wooden cylinders) was build in
order to be able to follow particles inside the simulated mixer. Three pulsating pistons were attached to the bottom of the simulator. Their
movements provide the mixing effect. Selected cylinders (some with different densities and friction coefficients) were followed during mixing.
Their positions were recorded after certain pulsations. From the measurements the mixing velocity of cylinders was calculated. Examinations
were focused on to give restrictions of the mixing: density and friction of the particles in connection with the pulsation. No correlations were
found between the mixing velocity and density or friction of the particles.
2004 Elsevier B.V. All rights reserved.
1. Introduction the contact forces between two spheres and a particle and
wall, respectively [4,5]. The model considers among others,
Research on storage, mixing, and preservation techniques the stiffness, damping, and friction coefficients of the par-
of bulky materials has been initiated 15 years ago at the Uni- ticles. However, the results of modeling of pulsated bottom
versity of West Hungary, Faculty of Agricultural and Food mixer were inaccurate and did not follow exactly our mea-
Sciences, Institute of Agricultural, Food and Environmental surements. Therefore, examinations were set up to clarify
Engineering. A pilot size storage container was built with in- the principles.
flatable air tubes at the bottom of the bulk. Inflating and de- A laboratory glass-walled mixing simulator (dimensions:
flating them with compressed air enable to move and mix the 0.7 m 0.5 m 0.02 m) was built based on the pilot-scale
grain layers being placed above them [1]. Using this patented apparatus (Fig. 1). Three pulsating pistons were attached at
method the formation of rotting parts can be prevented and the bottom of the simulator. The circulation of the particles
the existing centers can be eliminated. On the other hand, is due to the sequence of the pulsation of the pistons. The
the mixing system with ventilation can increase the safety of pattern of motion using the pistons is similar to the motion
storage [2,3]. The investigations proved that this method is achieved by vibrating processes [6]. The difference between
also suitable for other granular materials than cereal grains. the two processes is that any kind of motion pattern can be
Based on the pilot scale measurements mathematical mod- acquired by using the pulsating mixer independently from
eling was started in order to describe the processes. Discrete the shape of vessel.
element method (DEM) was used to model the mixing. This Consequently, the direction of movement of particles with
was originated from a simple mechanical model to formulate different densities is independent in our system.
The basic aim of this examination was to find out the
effects of densities and friction coefficients of particles on
Corresponding author. Tel.: +36 96 566 635; fax: +36 96 566 641.
E-mail address: nemenyim@mtk.nyme.hu (M. Nemenyi). the velocities of movement and mixing.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.024
294 M. Nemenyi, A.J. Kovacs / Chemical Engineering and Processing 44 (2005) 293296
70.00 cm
particles
50.00 cm
42.50 cm vessel
4.00 cm
2 1 3
(a) 17.00 cm (b) pistons 7.00 cm
Fig. 1. Schematic diagram of the laboratory glass-walled mixing simulator of (a) cylinder in the middle move down; (b) cylinders in the middle move
upwards.
Fig. 2. Photo of the mixing simulator during measurement (1, 2, 3: selected cylinders; sequence: 2). (a) Before movement, (b) after 50 sequences, (c)
after 100 sequences, (d) after 150 sequences, (e) after 200 sequences, and (f) after 250 sequences.
M. Nemenyi, A.J. Kovacs / Chemical Engineering and Processing 44 (2005) 293296 295
Table 1
The sequences of the pistons (starting point: all three cylinders are down)
Steps Sequence 1 (Fig. 1a) Sequence 2 (Fig. 1b)
2. Material and methods mixer (Fig. 2). Each measurement was taken until 300500
sequences reached that is each selected cylinder rotated at
The simulator (Fig. 1) was filled with wooden cylin- least two times.
ders with the diameter of 20 mm and the length of 18 mm
( = 700 kg/m3 , = 0.25). The examined parameters
were: (i) mixing of particles inside the bulk; and (ii) 3. Results and discussions
moving (mixing) characteristics of selected cylinders with
different parameters. In each measurement three cylin- The evaluation of measurements was carried out using the
ders with the same properties were followed. Different MATLAB 6.5 software (Fig. 3). The path of the three se-
properties of cylinders were studied, such as: wooden lected cylinders visualized and the velocity of each cylinder
cylinders with coarse surfaces (coated with sandpaper): was calculated. The velocity of a cylinder was calculated
fine = 0.63; middle = 0.73; rough = 0.91; aluminum by dividing the sequences by the distance that the cylinder
cylinders ( = 0.24, = 2500 kg/m3 ); wooden cylinder drove. The velocities of three cylinders were averaged.
with meat insert ( = 1600 kg/m3 ); hollow metal cylin- Based on the measurements the following was established.
der ( = 0.25, = 6180 kg/m3 ). Figs. 1 and 2 show The velocity of cylinder is independent of the friction coef-
the diagram and picture of pulsated bottom mixer. The ficient (Figs. 4 and 5). This means that the smooth surfaced
lifting of a piston was taken by 0.5 s, and the lowering wooden or aluminum cylinders move with the same speed
was done by 0.1 s. Two moving sequences were utilized as the rough sand-paper covered one. Higher average veloc-
(Table 1). ities with 0.2 cm per movement was found in sequence 2
After 10 sequences the positions of the three selected (where the middle examined cylinder moves upward), than
cylinders were recorded and a photo was taken from the in sequence 1 (where a cylinder in the middle moves down).
0. 5
could be reached even under a significant density difference
0. 4 (1:10). It was also proved that the denser particles could be
0. 3 moved in any directions into the bulk.
0. 2 The results of the above measurements can be used for
Average: 0.59 improving the mathematical descriptions. However, in this
0. 1
kind of mixing a major revision and maybe simplification
0. 0
of the models seems to be suitable.
0. 0 0.2 0. 4 0.6 0. 8 1.0
Friction coefficient,
0. 1 Average: 0. 38
0. 0 Acknowledgements
0. 0 0.2 0. 4 0.6 0. 8 1.0
Friction coefficient, The authors express their thanks to Ms. Mrta Varga (Hun-
Fig. 5. Velocities of the selected cylinders with different friction coeffi- garian Academy of Sciences, Research Group of Process
cients; middle section moves upwards. Engineering of Agricultural Products) and Mr. Roland Pap,
Ph.D. students for their help; and the founder of Hungarian
0.7
Research Funds (OTKA) # T032666 and # F035247.
0.6 Middle pa rt do wn
[distance: cm/movement]
0.4
[1] M. Nemnyi, Z. Srkny, K. Kacz, Moving the cereal bulks by pneu-
0.3 matic system, Hung. Agric. Eng. 5 (1992) 2425.
[2] K. Kacz, Z. Srkny, Intensive mixing the cereal bulks by pneumatic
0.2 method during storage, Hung. Agric. Eng. 6 (1996) 5758.
aluminum
metal
wood+
met al
0.1
particles with special regard to grains in pulsated bottom mixer, in:
0 Proceedings of Third Israeli Conference for Conveying and Han-
0 0 4 6 8 10 dling of Particulate Solids, Dead Sea, Israel, 29 May1 June 2000,
De ns ity ratio [ / wo o d ] pp. 8.248.28.
[4] Zs. Ulbert, J. Szpvlgyi, J. Gyenis, Y. Tsuji, Modelling and simulation
Fig. 6. Velocities of the selected cylinders with different densities. of particle mixing in gravity and pneumatic mixing tubes containing
helicoidal mixer element, Recents Progres en Genie des Procedes 11
One of the reasons of this is that the distance of penetration (1997) 299306.
of pistons into the bulk was not the same on the sides than [5] P.A. Cundall, O.D.L. Strack, A discrete numerical model for granular
assemblies, Geotechnique 29 (1979) 4765.
in the middle (Fig. 1). [6] K. Erdsz, Vibrcis technika az lelmiszeriparban, Mezogazdasgi
The densities of cylinders also do not play a role in the Kiad, Budapest, 1984 (Vibration technique in food industry, Agri-
velocities according to our measurements (Fig. 6). It can cultural Press, Budapest).
Chemical Engineering and Processing 44 (2005) 297302
Received 26 August 2003; received in revised form 10 March 2004; accepted 19 March 2004
Available online 25 June 2004
Abstract
Previous publications of the authors introduced the homogenization theory of mammoth silos and process dynamics as an indicator of
the homogenization efficiency of mammoth silos. Here, it is shown that process dynamics can be used for estimating the homogenization
efficiency mainly for silos with a large H/D, given a negative exponential auto correlation function for modeling of the input properties. For
smaller silos with equal volume process dynamics underestimates the homogenization results, due to the existence of top and bottom cones.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.015
298 D.L. Schott et al. / Chemical Engineering and Processing 44 (2005) 297302
+(6Vci3 3Vs+r
2
Vci )ez /Vci
The homogenization process, existing out of a stacking A characteristic volume of the input property (Vci ) equal
and reclaiming process, is linear and due to constant stacking to 40 m3 means that the signal is very incoherent. This indi-
and reclaiming angles the system is time invariant as well. cates that homogenizing will improve the coherence of the
Applying s requires a continuous and linear time invariant signal and reduce the amount of fluctuations very well. Fig. 2
system, this first requirement is met by taking infinite thin shows the improvement of the auto correlation function de-
slices. How the auto covariance function of the output is pending on the stacking and reclaiming angles. The y-axis
obtained is in detail explained in previous publications of represents the auto correlation function as a function of
Gerstel and Schott [3,4], here only the result based on a the lag V on the x-axis. The plot on the left-hand side shows
first order negative exponential input correlation function the results of the homogenization process with a horizontal
(Eq. (2)) is presented in Eqs. (3)(5). stacking method, whereas the other plot shows the results
on the basis of inclined stacking ( = 30 ). The plots repre-
x () = e||/Vci (2) sent the correlation function of the input (solid line) and the
D.L. Schott et al. / Chemical Engineering and Processing 44 (2005) 297302 299
in = 10 in = 0 = 10
[-] = 0 = 20 = 30 [-] =30 = 20 = 30
1 1
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0 0
0 1 2 3 4 0 1 2 3 4
v x103 [m3] v x103 [m3]
Fig. 2. PD results: input and output auto correlation functions with Vci = 40 m3 .
in = 10 in = 0 = 10
[-] = 0 = 20 = 30 [-] =30 = 20 = 30
1 1
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0 0
0 1 2 3 4 0 1 2 3 4
v x103 [m3] v x103 [m3]
Fig. 3. PD results: input and output auto correlation functions with Vci = 400 m3 .
correlation functions of the output (dashed lines). The cor- The requirement for applying PD is that the system should
relation functions of the output differ since the reclaiming be a linear time invariant system. This is the case in the area
angle is different as indicated in the legend of the plot. where both the reclaiming and the stacking angles are con-
The improvement of the characteristic volume can be de- stant. This part is indicated by const in Fig. 5. The top and
rived from the figure. For example: the characteristic volume bottom cones are indicated by top and bottom respec-
of the output property (Vco ) is approximately 2000 m3 when tively. This notation is also used in the following tables.
the stacking is horizontally ( = 0 ) and the reclaiming an- The stacking method can be implemented in two ways;
gle = 20 . This improves to Vco 4000 m3 when the using an inclined conveyor (ic) and controlled dump (cd).
stacking angle = 30 and the reclaiming angle = 20 . The difference is shown in Fig. 4.
A better correlated input signal will leave less space for These tables show that the PD results match quite
improvement compared to the previous. Fig. 3 shows the well with the results of the constant part and the total
improvement of the auto correlation functions for Vci =
400 m3 . It follows that the characteristic volume of the output
property (Vco ) is just slightly higher compared to Vci =
40 m3 : Vco 3400 m3 versus Vco 3200 m3 for = 0
and = 30 .
Results of the reduction of the standard deviation obtained
from PD follow in the next subsection.
Table 1
Results of the reduction of the standard deviation from process dynamics and simulations for Vci = 40 m3 , H = 50 m and D = 32 m.
Vci = 40 m3 PD (y /x ) Average y /x of 400 simulations
Table 2
Results of the reduction of the standard deviation from process dynamics and simulations for Vci = 400 m3 , H = 50 m and D = 32 m
Vci = 400 m3 PD (y /x ) Average y /x of 400 simulations
CL
top
CL
constant
bottom
Table 5
Results of the reduction of the standard deviation from process dynamics and simulations for Vci = 400 m3 , H = 25 m, and D = 45 m
H= 25 m; D = 45 m; Vci = 400 m3 PD (y /x ) y /x simulations
Total Const Top Bottom
sult the estimation by PD is getting worse, but is at least vi,s volume of layer i in slice s (m3 )
an underestimation of the total homogenization results (see vj,s volume of layer j in slice s (m3 )
Table 5). vslice volume of a slice (m3 )
Vci characteristic volume of the input properties
(m3 )
5. Conclusions Vco characteristic volume of the output
properties (m3 )
With material properties modeled by a negative exponen- Vs+r volume of stacking + reclaiming cone (m3 )
tial auto correlation function we have seen that the estima-
tion by process dynamics is quite well for H = 50 m and D Greek letters
= 32 m. For silos with a smaller H/D the estimation is get- yy auto covariance function of the output
ting worse, because the volume where the process dynamics auto correlation function
can be applied is getting smaller and top and bottom cones x auto correlation function of the input x
dominate the results. Compared to tall silos, the homoge- x standard deviation of the input signal x
nization result in small silos with equal storage volume will
, z lag (m3 )
in general be better because the amount of material between
the first and last intersected layers in a slice is larger. Of
course this is valid for equal stacking and reclaiming meth-
ods. References
[1] D.L. Schott, A.W. Gerstel, L.A. van Wijk, Homogenization theory of
mammoth silos, in: Proceedings of the Seventh ICBMH, University
Appendix A. Nomenclature
of Newcastle, NSW, Australia, 2001, pp. 199208.
[2] D.L. Schott, L.A. van Wijk, C. Kraaikamp, Large scale homogeniza-
m number of slices tion in mammoth silos: importance of modeling input properties, Int.
ns number of layers intersected by slice s J. Miner. Process. 71 (14) (2003) 179199.
302 D.L. Schott et al. / Chemical Engineering and Processing 44 (2005) 297302
[3] A.W. Gerstel, D.L. Schott, Homogenisation in mammoth silos, in: [5] E.J. Oosterhuis, D.L. Schott, L.A. van Wijk, Reclaim screw in mam-
Proceedings of the Seventh ICBMH, University of Newcastle, NSW, moth silos operating on a free surface: comparison between horizontal
Australia, 2001, pp. 189198. and inclined operation on free flowing bulk solids, in: Proceedings of
[4] A.W. Gerstel, D.L. Schott, Upgrading of bulk material in mammoth the Fourth CHoPS, Budapest, Hungary, 2003.
silos, Port Technol. Int. 17 (2002) 109116.
Chemical Engineering and Processing 44 (2005) 303313
Received 27 August 2003; received in revised form 10 March 2004; accepted 19 March 2004
Available online 25 June 2004
Abstract
In this paper, we try to improve our comprehension of one of the most important challenge in the particulate solids industry: the assessment
of the homogeneity of powder mixtures. A two-electrode electrical capacitance method is used to measure the permittivity of mixtures while
flowing in a 1-D set up. An emphasis is placed on the possibility of following homogeneity evolution through permittivity measurement,
without the necessity to calculate the volumetric proportions of each component from an effective medium formulation. The methodology is
applied to examine segregation in a funnel, as well as the efficiency of a laboratory drum mixer.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.016
304 N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313
respect to the overall number of possible samples about the media (such as in classical ECT methods), but with the
one million. objective of obtaining a global dielectric information and
In other words, the technological improvement of the follow its variation while powder is flowing into the tube,
products does not guarantee the same progress at the man- with the aim to measure the composition of binary or ternary
ufacturing level at all, mostly because of a lack of instru- mixtures in the axial direction of the powder flow stream.
mentation and control of the processes, more deeply linked It is waited that this method will provide, through specific
to the lack of understanding and reliability of particle char- iterative algorithms, a quantitative and structural information
acterisation in general. If we except the mineral industry, about a binary mixture flowing out of a mixer (either batch
the industrial applications of particle control systems are or continuous) in relation with its own processing.
still scarce, the only well-known example being particle
size distribution measurement through LASER diffraction.
However, the situation is not so dramatic if we look at the 2. Theoretical and conceptual developments
progress made in the field of particulate instrumentation
research in the last decade, with a constant special insight 2.1. Powder blend homogeneity: macro and micro
provided by the international conference series Control of considerations
Particulate Processes [5].
Optical techniques were developed both in situ and on Homogeneity is a key concept for many chemical engi-
line over a broad range of applications and various types of neering applications, especially those in which a transforma-
light sources. Main examples are solids concentration mea- tion occur (precipitation, chemical reaction, grinding, . . . ),
surements in particle fluidisation [6,7], as well as gassolid because of the coupling between kinetics aspects and con-
flow [8], or sample composition in dry blending operations, tact time of the reagents due to the flow conditions. In
this latter beginning from the pioneering work of Harwood the field of powder mixing, in most cases, no transforma-
et al. [9] up to more recent advances in this scientific field tion takes place and the quality of the product is the fact
[1012]. The main interest of these techniques lays in the of the particulate flow dynamics itself. Also, the main dif-
fact that optical probes are easily available on the market, ference with fluid mixing lays in the fact that a perfect mix
so that qualitative monitoring of mixers is possible at an in- cannot be performed at a molecular scale, and is still diffi-
dustrial scale. However, these probes only provide local in- cult to assess at the scale of a particle. This is due to a wide
formation of the mixture (typically 1/40 of a tablet), so that variety of particleparticle interactions, resulting in a con-
in essence, they still sample the powder flow in a way that flict between mobility of single particles, which is essential
may be intrusive and not always representative of the overall to achieve a good mix, and resistance to segregation, which
stream. is a fact of the mixtures structure. In that sense, cohesive
Electrical capacitance tomography (ECT), as well as elec- particulate media (typically below 50 m) can be viewed as
trical resistance tomography (ERT) for liquidsolid systems, macrofluids, while free-flowing systems (typically supe-
experienced a flourishing development these recent years rior to 500 m) can be viewed as microfluids. Between
for a wide variety of applications [1318]. Their major these two extreme behaviours that sometimes may occur
advantage is that they provide, in a non-intrusive way, a in a single product (case of aerable powders) particle and
cross-sectional view of a stream that may contain at the particle packets trajectories and motion are both influenced
same time a liquid, a solid and a gas. In that sense, they by gravity and surface forces.
are able to give a radial image, which in turn, and through As felt above, the concept of powder blend homogene-
the help of other multiple electrode sensors in the axial di- ity cannot be dissociated from the scale at which a mixture
rection, can be reconstructed in three dimensions. However, is observed. For continuous mixers, homogeneity must be
this huge amount of information must be contrasted with the defined at the level of the blend flowing out of the vessel,
low resolution at which it is given. This has probably limited and falling down to a conveyor or any other transportation
the application of this technique to powder mixtures that re- equipment. In the case of a batch mixer, the mixture struc-
quire an analysis at a very fine scale. X-ray, -ray, as well ture can be particularly complex to define, but in practice
as magnetic resonance imaging (MRI), must also be cited and when the mixer is emptied, the content of the vessel
in the category of the tomographic techniques. They were is discharged through a pipe to a container or a tableting
mostly used to investigate fluidisation processes, but still machine. Hence, in both cases and if we take into account
seem difficult to employ at the level of a factory [1921]. the entire cross-section of the pipe, the mixture flow can be
LASER-induced fluorescence (LIF) technique must finally assimilated as a 1-D particle stream.
be cited, especially because some pharmaceutical ingredi- Thus, let us consider a powder mixture flow as a mono-
ents can naturally provide a signal when excited by the ad- dimensional layer divided into N consecutive elementary
equate beam [22]. samples. In a first approach, the size of these can be ar-
In this work, we develop an electrical capacitance sensor bitrary fixed, not too small to prevent from statistical er-
that consists of only two electrodes placed around a glass rors (inversely proportional to the square root of the par-
tube. This set up is considered not in the view of imaging ticle number) and not too large for ensuring the validity
N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313 305
Fig. 1. Two mixtures (a and b) of identical macromixing state can exhibit different micromixing structures that may result in products of different quality
and effects.
of the following analysis. From a global point of view, practical consequence: tablets should probably be produced
the distribution of the compositions is a first indicator of at this segregation scale to statistically ensure that these
the mixtures homogeneity, a perfect blend (at the scale of have the right (desired) composition. However, the figure
scrutiny of the samples size) corresponding to a peak cen- given here is still global, as we do not know anything about
tred on the mean value. Hence, the following standard de- the location and the distribution of the segregated zones in
viation (Eq. (1)) can be considered as a good macromixing the mixer, and also on zones of acceptable defaults. As a
index (the coefficient of variation can also be employed). consequence, the size of the tablets that corresponds to the
N segregation scale may be not so adequate as it is said to be.
i=1 (xi )
2
= (1) Nr
N (xi )(xi+r )
R(r) = i=1N (2)
i=1 (xi )
This latter formula, which is commonly used in the in- 2
dustrial practice, also holds for the case of an estimation of
the mixture quality using random sampling. However, the An illustrating example for this idea is provided in Fig. 2,
main problem in this global analysis lays in the well-known in which a series of consecutive elementary samples con-
(since the famous Danckwerts example in chemical reac- taining an active ingredient has been artificially generated.
tors [23]) fact that two different structures can correspond to One may easily find that the mean content is = 5%, while
the same intensity of segregation criteria. Fig. 1 illustrates the global standard deviation is = 1.34%. If we refer to
this idea, which has a very practical sense in the context of a pharmaceutical standard, this is not a good mixing, being
pharmaceutical blending. the corresponding coefficient of variation equal to 26%. As
In effect, let us assume that the two processes depicted it can also be seen from the data, an important deviation
here concern pharmaceutical tablets produced in packages from the mean occurs for sample nos. 11 and 12, which
containing six consecutive unit doses. These are of identi- have the particularity of being corrected at a small scale
cal macromixing state, as standard deviations are equal. But (sample nos. 13 and 14). From the point of view of mon-
in one case (namely Fig. 1a), a patient will take a slightly itoring of the mixing process, it is certainly interesting to
under-dosed treatment, and another one a slightly overdosed search for this local default that makes the overall mixture
treatment, while in the second possibility (Fig. 1b), an equi- probably inadequate, despite of the fact that other regions
librium of the dose will be reached after the second take. seem to be much better mixed.
Indeed, structure defaults can provoke negative therapeutic If we look at the variations of the corresponding auto-
effects that cannot be diagnosed with a macroscopic index correlation function (Fig. 3), the characteristic distance r0
of segregation intensity. covers between 1 and 2 elementary samples, which means
As introduced by Danckwerts in the mid-fifties [24,25], that these must be grouped two by two or three by three (for
and more recently reviewed by Gyenis [26], the mixing more security) to avoid any correlation. Doing so, six or ten
structure can be accounted for by the use of the autocorrela- tablets can be defined depending on the way the elementary
tion function R(r) (Eq. (2)). The distance r0 , corresponding ones were grouped together (see also Fig. 2). However, this
to the equation R(r) = 0, at which two sample compositions procedure did not really change the situation, as it gave rise
can be considered to be uncorrelated, is a main character- to an overdosed (no. 4) and an under-dosed tablet (no. 5) and
istic of the structure of the mixture and has an important four perfectly dosed tablets (nos. l3 and 6). This is due to
306 N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313
Fig. 2. Numerical example showing that a non-randomised structural default (heterogeneous zone between sample nos. 1114) cannot be cleared by
increasing sample size either by a factor 2 (top case) or 3 (bottom case).
the fact that this structural default induces segregation at a mixture, with the aim of disregarding samples of inadequate
relatively short scale, and cannot be adequately detected by composition rather than grouping them. For this reason, we
the criteria r0 . The reason for this failure is fundamentally derived another type of analysis, which we claim to be more
linked to the global (but structural) character of this crite- sensible to structural defaults and also easier to adapt to
rion that characterises homogeneity at the scale of all the on-line measurement of continuous processes in which the
N samples. In other words, this analysis would give a bet- series of data is, in principle, infinite. Let us first define a
ter result if the problematic elementary samples were not window that consists of n consecutive elementary sam-
placed coast to coast in the mixture, but dispatched along ples (of course n < N) placed at the beginning of the data
the whole data set. series. For this packet of samples, a mean 1,n and a stan-
dard deviation 1,n can be defined by the following Eqs. (3)
2.2. Methodology for detecting structural defaults and (4).
n
1
Because of the above-mentioned type of problem, it is ad- 1,n = xi (3)
n
visable to have a better insight on the local structure of the i=1
Fig. 3. Autocorrelogram corresponding to the present example, and indicating that a characteristic interval of two samples should be considered for
ensuring homogeneity.
N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313 307
n curve is the consequence of a good mixture achieved at a
i=1 (xi 1,n )2
1,n = (4) small scale, while a rough one corresponds to the existence
n of heterogeneous regions in the blend.
Let us further displace this window from one sample to From the graph, it is also possible to calculate the number
the right (of, say, Fig. 2), defining thus another mean 2,n of samples n0 that form part of the default, and should prob-
and another standard deviation 2,n . If the composition of ably be taken away from the production line. In effect, it is
the newly considered sample (number n + 1) is close to x1 , easy to demonstrate Eq. (7). In the present example, as np
then both 2,n and 2,n will be close to 1,n and 1,n , re- = 8 and n = 5, one will verify that the heterogeneous zone
spectively. In the contrary, if a small structural default ex- effectively covers four consecutive elementary samples.
ists, it will be detected by this analysis because the variation n0 = np n + 1 (7)
of the corresponding mean and standard deviation will be
important, even if it concerns segregation at a small scale.
Generalisation of Eqs. (3) and (4) for packets beginning with 3. Experimental set up development and methodologies
sample number k is obviously given by Eqs. (5) and (6).
n+k1 Like in any micromixing state consideration, the experi-
1
k,n = xi (5) mental illustration of the concept needs the development of
n a sensor. Because even slight structural defaults must be de-
i=k
tected, it can be felt that this technique may cover the fol-
n+k1 lowing properties:
i=k (xi k,n )2
k,n = (6)
n (1) Be adapted on-line: The three dimensional knowledge
of the repartition of the components in a vessel (as in
For the above example, one can observe that the seventh
a batch mixer) is generally of a few interest for the
packet first considers the small segregated region, while it is
practitioner, especially because an important disruption
not touched after the fourteenth if the size of the window is
of the mixture occurs when emptying the mixer.
equal to five samples. This results in a clearly marked peak
(2) Be non-intrusive: This is the better way to avoid any
on a graph representing the variation of these local variances
cutting error due to the insertion of a probe in the
with time, while the means are affected at a much lower
powder flow.
level (see Fig. 4).
(3) Be exhaustive: As all defaults are to be screened, no
The reason for this lays in the fact that even a small
partial sampling procedures that would induce a statis-
deviation in composition has a consequence on the standard
tical bias can be developed. For instance, the derivation
deviation value, so that the local standard deviations are as
of a certain part of the powder flow for analysis cannot
great as many samples in the packet demonstrate a deviation
be considered here.
from the mean. In our case, it can be seen that the number
(4) Have a good spatial and temporal resolution.
np of packets that are affected by the perturbation is equal to
8 out of 16, which also helps in magnifying the default. For On the other hand, as only the global content in the sam-
instance, it is felt that a smoothed local standard deviation ple is to be derived, imaging and tomographic techniques
Fig. 4. Evolution of the local means and standard deviations with the number of packet considered (packet width equal to five elementary samples),
magnifying the existence and the location of the heterogeneous zone.
308 N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313
that also provide spatial distributions are perhaps too pow- section of a glass tube of external diameter 12 mm (see Fig.
erful tools to be employed with respect to the information 5). A PVC screen allows isolating the electrodes from the
effectively needed. From the above-mentioned techniques, it aluminium full cylinder (of dimensions 40 mm 30 mm)
can be understood that the best method profile should com- that covers the overall measuring cell. This latter also pre-
bine the advantages of fibre-optics (flexibility, global infor- vents from external disturbances, as well as the coaxial
mation) and ECT (non-intrusive, no sampling) sensors. cables, making the liaison with the capacitance meter.
The sensor is connected to a capacitance meter consisting
3.1. Electrical capacitance set up of the electronic circuit depicted in Fig. 6, and further to a
computer through an analogic/numeric converter. Measure-
Classical ECT set ups are composed by a ring of elec- ments are taken at a frequency of 5000 scans per second
trodes (typically 12, see [27,28]), which is generally placed and the sensibility of the circuit is high enough (close to
around the external part of the pipe itself. The correlation 0.1 pF) to detect the capacity variations of some picofarads
between the dielectric measurements provided by the elec- provoked by changes in the composition of the measured
trodes allows for a tomographic mapping of the pipe in volume. Preliminary results also show that capacity and di-
the radial direction. In the present case and as commented electric permittivity could be linked to each other through a
above, the radial distribution of the components is of a few linear relation over the whole measuring range in which we
interest (at least in a first approximation) as we are only work. It must be stated that such a statement is only true if the
concerned with the overall composition in the measuring measured space between electrodes is fully filled with mate-
volume. For this reason, we developed a capacitance sensor rial. Otherwise, the measurements would show very strong
with the aim of measuring the variations of the global ca- non-linear character.
pacity of a mixture during its own flow. It thus consists of The calibration of the sensors is performed with a liquid
only two copper electrodes covering practically the whole (namely n-butyl acetate) of known dielectric permittivity,
particle segregation during transport, as well as ensuring (sugar at the bottom and SiC at the top). This preparation
mass flow of the blend. The particles are then falling at the flowed through the glass tube equipped by the first sensor
centre of a funnel (without accumulation) that is connected and then through a lower funnel equipped by the two other
to the glass tube surrounded by a first capacitive sensor (de- sensors at its outlet. The discharge profiles are represented
noted sensor H). At the end of the tube, a Sulzer static in Fig. 8.
mixer consisting of six mixing elements is placed. These The profile in the upper funnel clearly shows the step of
mainly allow for a radial motion of the particles and few permittivity applied to the system, whereas the profile after
axial mixing occurs in normal flow regime (see [31]). The the lower funnel is clearly spread. This shows us that the
mixture further flows by gravity to another funnel placed in
the upper part of another glass tube that supports the last two
sensors separated by a known distance (see Fig. 7). Assum-
ing mass flow in this last section, the correlation between
the responses of these sensors (denoted M and B) allows for
the calculation of the flow rate and the frequency to consider
avoiding any sample crossing.
For instance, the glass tube must always be full of solids
with a constant flow. To ensure this, the end of each tube
was squeezed and the bottom of these tubes were placed at
a short distance from a conveyor belt operating at constant
speed (5 m min1 ), thus gently deposing the mixture as a
layer onto the belt. This set up also allows a validation of the
method by comparing the sample compositions in the belt
to the compositions given by the closest sensor. With this
special set up, all particle flow rates become quickly equal
from the vibrating channel to the conveyor belt (in fact, the
amplitude of the vibrations can be adjusted for this task).
Fig. 10. View of the initial discharge profiles before and after the static mixer.
SiC is mixed with sugar at the beginning of the experiment 4.2. Kinetics of mixing in a laboratory drum mixer: the
because it flows preferentially in the middle of the funnel, Rotocube
whereas components situated near the walls are flowing at
the end. In this section, we apply the above methodology for the
We can also conclude that this experimental device gen- case of the Rotocube mixer (see Fig. 9), and in particular,
erates a high segregation by density difference that give rise we examine the influence of the number of revolutions at a
to a preferential flow in the centre of the funnel. It thus fixed rotational speed (30 rpm) on the mixture quality.
greatly perturbs the measures and the mixing process. In or- The first experiment was realised without any action of the
der to prevent from segregation, it is therefore particularly Rotocube and we just divided the initial preparation into
important not to fill the funnels, so that a solution could be three successive layers placed in a vibrating conveyor: the
to convey powders directly to the centre of it. lower one was constituted by half of sugar, the middle one
Fig. 11. Standard deviation of dielectric permittivity before and after the static mixer versus the number of revolutions in the Rotocube .
312 N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313
by all the SiC and the upper one by the rest of sugar. All the n0 number of samples that form part of the default
preparations constituted of 20% by mass of SiC and 80% by and should probably be taken away from the
mass of sugar. Fig. 10 clearly shows that this experimental production line
device prevents from segregation inference, even if there is np number of packets that are affected by the
still left some, probably due to the conveyors vibrations. It perturbation
must be commented that the nominal value in SiC content is N number of considered consecutive elementary
not reached because of the small thickness of the SiC layer samples into which the powder mixture flow
and of a slight phenomenon of mixing between SiC and is divided
sugar when passing from the first layer to the second one. Nc number of components in the powder mixture,
Experiments were then realised with several number of including the air trough the porosity of the medium
revolutions of the mixer. The entire mixture flowed through Pi volumetric proportion of the component i in the
the device and the standard deviation of the whole mixture powder mixture
(3600 samples) could be derived for each experiment. Fig. 11 r spatial (or temporal) variable corresponding to
shows the evolution of the standard deviation of the permit- the distance (or time elapsed) between two samples
tivity versus the number of revolutions. We can immediately r0 distance (or time elapsed) between two samples
see that the two plots are quite close, which shows that the corresponding to the equation R(r) = 0
static mixer mixes in a radial way, an effect that cannot be R(r) autocorrelation function
detected by the sensors we used. Concerning the shape of the xi weight composition in a key component in the
plots, it is clearly shown that the mixing quality is improved elementary sample i
by the Rotocube since the first revolution. Then, quality is
slowly bettered up to four revolutions and begins slowly to Symbols
decrease after four revolutions. This can be due to a change mean observed for the N consecutive samples
in the mixing mechanism in the Rotocube (passage from a standard deviation for the N consecutive samples
shearing mechanism to a diffusion one), which may change k,n mean for a packet of n samples beginning at
the mixing structure. Note that the presence of oscillations, sample number k
which are softened by the static mixer, may be due to seg- k,n standard deviation for a packet of n samples
regation in the Rotocube , but also in the vibrating system. beginning at sample k
i dense dielectric permittivity of the component
i in the powder mixture
5. Conclusions
m dielectric permittivity of the powder mixture
Hopefully, dielectric constants of current materials are
covering a wide range of values, which also means that such
a method can be applied in various industrial applications. References
This study has shown the possibility to measure segrega-
tion problems when discharging mixtures through a funnel. [1] F.J. Muzzio, T. Shinbrot, B.J. Glasser, Powder technology in the
It has also shown the effect of the number of drum revolu- pharmaceutical industry: the need to catch up fast, Powder Technol.
tions at a fixed speed on the quality of a mixture, as well as 124 (2002) 17.
the effect of a static mixer. The axial structure of the mix- [2] J. Berman, A. Schoeneman, J.T. Shelton, Unit dose sampling: a tale
tures through autocorrelation functions could also be stud- of two thieves, Drug Dev. Ind. Pharm. 22 (11) (1996) 11211132.
[3] F.J. Muzzio, P. Robinson, C. Wightman, D. Brone, Sampling practices
ied from these data, but this has not been reported here for in powder blending, Int. J. Pharm. 155 (1997).
clarity of the paper. In addition, it must be remembered that [4] S. Massol-Chaudeur, Caractrisation de ltat de mlange de poudres
we just studied the evolution of the dielectric permittivity, cas de mlanges faiblement doss, Ph.D. Thesis, INPL Nancy,
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[11] D. Steinmetz, B. Hocine, M. Poux, C. Lagurie, Analyse du mlange Technol. 120 (2001) 7075.
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spectroscopy, Powder Technol. 123 (2002) 185193. Real-time noninvasive monitoring of dry powder blend homogeneity,
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review, Powder Technol. 112 (2000) 174192. et fonctionnement des racteurs, Tec&Doc, Lavoisier ed, 1984,
[14] K.L. Ostrowski, S.P. Luke, M.A. Benett, R.A. Williams, Application p. 204.
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Chemical Engineering and Processing 44 (2005) 315321
Received 14 July 2003; received in revised form 18 December 2003; accepted 11 February 2004
Available online 26 June 2004
Abstract
Experiments for the investigation of the flow of granular solids in a pyrolysis pilot-scale rotary kiln are presented. These experiments
consisted first in measuring the volumetric filling ratio (steady-state experiences) for several operating conditions and second in recording the
exit flow rates after a positive or negative step in one of the operating parameters (dynamic experiences). A dynamical model computing the
evolution of the flow rate of granular solids through the kiln has been developed based on Saeman model [Chem. Eng. Prog. 47 (1951) 508].
The simulations are compared with experimental results; the model gives good results for the rolling mode, but for the slipping mode too.
2004 Elsevier B.V. All rights reserved.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.025
316 N. Descoins et al. / Chemical Engineering and Processing 44 (2005) 315321
used nowadays because of its good predictive ability and its Bulk density Diameter Dynamic angle Wall friction
simplicity. It is based on a geometrical analysis of the move-
(kg/m3) (mm) of repose (deg.) angle (deg.)
ment of one solid particle in the bed; the model assumes the
bed is in rolling motion. Some authors have developed para- (with the grid) (without the grid)
metric models based on the determination of experimental
residence time distributions [24]. More recent attempts to
improve the description of the solid phase motion exist but 873 1% [1 5] 33 2 21 2
the developed models tend to be rather complex to use [5,6].
Fig. 1. Physical properties of crushed rice.
The majority of the studies conducted are concerned with
steady-state studies [16] and there is little published work
dealing with the time dependent axial flow of a granular model presented in the next section. The angle of repose is
solid through an inclined rotating cylinder [7,8]. directly measured inside the kiln and reflects the bulk char-
This paper presents the first experimental results for the acteristics of solid bed in rolling mode; the rolling mode
solid motion inside a pilot-scale rotary kiln. Such data are has been obtained only for the experiments with the metal
useful to enable efficient pyrolysis reactions inside a rotary grid rolled inside the rotating kiln. The wall friction angle
kiln to be carried out, through the prediction of residence will be used for the slipping regime (i.e. cases without the
time and material hold-up, and the evaluation of different grid). The wall friction angle is measured according to this
surfaces and temperature profiles according to the operating procedure: the rice is laid on a metal plate (with the same
conditions. In the first part, the pilot-scale rotary kiln and the roughness of the wall kiln) and the wall friction angle is
principle of the experiments will be described. An original determined as the solids begin to fall along the tilted plate.
dynamic solid motion model will be presented in the second
part, this dynamic model is derived from the original static 2.3. Experimental methods
model of Seaman [1]. The static and dynamic experimental
results are finally compared with the simulated results. Measurements of volumetric filling ratio were carried out
for several operating conditions in stationary regime accord-
ing to the procedure explained in the following. The station-
2. Experimental ary regime was identified when the exit flow rate became
constant. An electronic balance allowed to measure the flow
2.1. Pilot-scale rotary kiln rate; the acquisition period was fixed in order to have an ab-
solute incertitude for the solid flow rate less than 2 kg h1
The pilot-scale pyrolysis reactor is an externally heated (5.6 104 kg s1 ).
rotary kiln. The kiln is an nickelchrome hollow cylinder 4 m The experimental method was the following one:
long with 0.21 m internal diameter. The cylinder is heated the rotation of kiln, the vibrating conveyor and the elec-
by five independent electric elements allowing a temperature tronic balance were switched on,
profile along the kiln to be prescribed. The pilot operates as soon as the exit solid flow rate was constant, the rotation
under a positive working pressure of nitrogen (30 mbar) and of kiln and the vibrating conveyor were switched off,
with a maximum temperature of 1000 C. Nitrogen is used as the balance was replaced by an empty container and the
a carrier gas for the vapours produced by pyrolysis reactions. rotation was restarted,
Nitrogen and solids can flow in counter-current or co-current when the kiln was empty then the total mass of solid in
way. Rotational speed is adjustable between 0.5 and 8 rpm the container was measured,
(8.3 103 and 0.13 tr s1 )and the cylinder can be tilted at the volumetric filling ratio was deducted from this mass
angles of up to 7 . The continuous feeding system consists (with an incertitude about 1%).
of a 30 dm3 hopper with a vibrating cylindrical conveyor;
solid feed rates are adjusted by a potentiometer between 10 Experiments were performed to measure the transient re-
and 80 kg h1 (2.8 103 and 2.2 102 kg s1 ). sponse of the exit flow rate after a positive or negative step
The inside wall of the rotating cylinder is smooth, so a change in the operating parameters (only experiments with
metal grid (netting with 2 cm mesh) has been rolled inside a step change in the rotation speed are presented here). The
the cylinder in order to artificially increase the roughness of step change was applied after the stationary regime was iden-
the wall for several experiments presented later. tified.
Fig. 2. Schemes of the rotary kiln with the main variables used in the equations.
Saeman [1]: Ss corresponds to the cross section of solid and can be ex-
pressed in function of the local bed height. The Eq. (1) can be
4 tan() dH(z) inserted in the above equation and finally a partial differen-
Qv (z) = nR3 + cot()
3 sin() dz tial equation can be derived for the computation of the transi-
3/2 tory profiles of bed (more details are given in Appendix A):
2H(z) H(z)2
(1)
R R2 1/2 H(z, t) UT tan() 1/2 H(z, t)
FH F (1 FH )1/2
t sin() H z
This equation gives the local volumetric solid flow rate (Qv )
UT 3/2 H(z, t)
according to the kiln radius (R), the different operating vari- = R cot FH with FH
ables (, n), the angle of repose of materials () and the local z 3 z
depth of the solid bed (H). The spatial variable (z) is defined 2H(z, t) H(z, t)2
from the kiln end; for example, H(z = 0) corresponds to the = and UT = 2nR (4)
R R2
depth of the solid bed at the exit of the kiln. Two views of Two boundary conditions are necessary. The first condition is
the kiln are presented in Fig. 2 with the main variables used always for the constant exit height (at z = 0) and the second
in the equations. one defines the continuity of the flow between the vibrating
The equation is obtained by a geometrical analysis of feeder and the kiln at the inlet of the kiln (at z = L):
the path that one particle follows in travelling through the
rotary kiln. For this analysis, the rolling regime is assumed, H(z = 0, t) = H S
i.e. particles roll down continually on the bed surface (the H(t)
active layer), then they enter the passive region where they z z=L
are carried upward by the rotating wall until they enter the 3/2
active layer again. The angle of repose is assumed to be 3QEv tan() 2H(z = L, t) H(z = L, t)2
=
constant all along the kiln. 2UT R2 R R2
In the stationary regime and for a non-reactive solid, the tan()
volumetric solid flow rate is constant and equal to the inlet
cos()
flow rate given by the vibrating feeder (QEv ). From Eq. (1),
the following ordinary differential equation is directly ob- (5)
tained and can be solved with a boundary condition (exit The initial profile is computed by the Saeman model
height fixed) in order to compute the bed profile along the (Eq. (1)). The inlet flow rate and/or the operating parame-
kiln: ters can be modified during the resolution of the dynamic
3/2 equation. Spurling et al. [7] give a similar equation, but the
dH(z) 3QEv tan() 2H(z) H(z)2 tan() computed variable is not the local height of the bed, but the
=
dz 4nR 3 R R 2 cos() maximum half angle subtended by the bed at the cylinder
(2) axis.
The dynamic model can simulate the filling phase of
The mass conservation equation is written for the transitory the kiln, provided there are some physical considerations.
regime and for a non reactive solid: In fact, the volumetric flow rate cannot be set to 0 in the
Ss (z, t) Qv (z, t) Saemans equation because a mathematical singularity oc-
= (3) curs. So the flow rate is set to a very low value, close to 0,
t z
318 N. Descoins et al. / Chemical Engineering and Processing 44 (2005) 315321
ent times (1600, 3200, 48,000, 6400 and 8000 s). The bed
depth profile computed by the dynamic model converges on
the profile computed by the steady state model with the final
value of rotational speed.
1 15 1.7 1 No 11 13 21
2 23 2.9 1 No 11 12 21
3 26 4.0 1 No 10 10 21
4 35 5.2 1 No 11 10 21
5 21 1.7 2 No 11 12 21
6 34 2.9 2 No 11 11 21
7 47 4.0 2 No 10 10 21
8 62 5.2 2 No 10 11 21
9 9 1.7 1 Yes 12 12 33
10 20 2.9 1 Yes 15 16 33
11 41 4.0 1 Yes 24 23 33
12 51 5.2 1 Yes 24 24 33
uated. The model gives rather good results for the simula- the wall [9]. An assumption of the model is to have a con-
tion of the subsequent transient phase; however, a slightly stant angle of repose.
tendency to overestimates the length of the transition phase
for the cases without grid can be observed. These overesti- 3.4. Dynamic results: transient response to a step in
mations can be perhaps explained from some visual obser- operating parameters
vations: for the slipping regime (cases without grid), some
small oscillations of the angle of repose have been observed In order to evaluate the quality of the developed model,
in course of the experiments. Mellmann called this type of new experiments have been carried out. These experiments
motion surging, which is characterised by periodic alter- consisted in fixing operating parameters (inclination angle,
nations between adhesive and kinetic friction of the bed on rotation speed, inlet flow rate), waiting for the steady state
Fig. 6. Experimental (markers) and simulated (lines) exit flow rates for a Fig. 7. Experimental (markers) and simulated (lines) exit flow rates for a
filling phase. Experiments without grid inside the kiln. filling phase. Experiments with a grid inside the kiln.
320 N. Descoins et al. / Chemical Engineering and Processing 44 (2005) 315321
4. Conclusion
Received 27 August 2003; received in revised form 2 January 2004; accepted 11 February 2004
Available online 17 July 2004
Abstract
This paper presents results from investigations into quantifying and modelling the dust generation and air entrainment mechanisms that
occur during free-falling streams of material. Emphasis is placed on the effects of drop height and product temperature. This information is
important for the efficient design and operation of dust control systems, as well as minimising the risk and severity of dust explosions.
2004 Published by Elsevier B.V.
Fig. 2. Dust generation and air entrainment for falling stream of material.
3. Previous research
are applied. This is a result of the inherent assumption that
The first serious attempt to predict the quantity of air the flow in the stream is made up of particles that act in-
entrained by a falling stream theoretically was that of dependently, whereas the reality is that: the stream of parti-
Hemeon [1]. Hemeon modelled the air entrainment process cles form a relatively coherent stream, Fig. 2; and particles
as one whereby the drag force exerted by each solid parti- within the stream interact with the quiescent ambient to a
cle was essentially equal to that of a single particle falling much lesser extent than if they were falling independently
through a quiescent fluid. He deduced that the induced through the fluid.
(entrained) air flow, Qind , is given by (converted here to SI
units):
1/3
0.66g m(hA)2 4. Experimental facility and results
Qind = m3 /s (1)
(dp p )
Two experimental rigs were used for this study. The first
where g = gravitational acceleration, m = mass flow rate of rig comprised a double-feed hopper arrangement to ensure
solids, h = drop height, A = cross-sectional area of material a virtually constant mass flow rate of powder during each
stream, dp = particle diameter and p = particle density. test. The hopper arrangement was mounted on a frame that
Tooker [2] then used this approach to formulate a means could be raised or lowered to change drop height and was
of calculating the extract air requirements for enclosures, suspended on cables connected to three load cells to en-
such as conveyor transfer stations. The equations of Hemeon able the mass flow rate to be recorded. The bulk material
[1] and Tooker [2], and variations thereon, are used widely dropped through a hole in a shelf above the stockpile and
in industry. However, they generally grossly over-predict the air was extracted from underneath the shelf at a rate such
rate of air entrainment unless empirical correction factors that the air pressure under the shelf was kept exactly equal
P. Wypych et al. / Chemical Engineering and Processing 44 (2005) 323326 325
Fig. 3. Experimental rig used to measure entrained air and dust generation.
Fig. 4. Specific air entrainment results of Smithers (x symbols) and Glutz
(
symbols) using alumina with drop heights of 625650 mm.
to that of the external ambient air, as shown in Fig. 3. A
pressure observation port between the space under the shelf
and outside allowed the pressure to be equalised between
the surrounding air and the underside of the shelf by smoke
visualisation. Under these conditions, the volume of air ex-
tracted from beneath the shelf was equal to the total vol-
ume of air and bulk material falling through the aperture.
A relatively inert and robust powder, alumina (median size
= 96 m, particle density = 2465 kg/m3 ; loose-poured bulk
density = 1010 kg/m3 ), was selected for testing.
The second rig involved the release of approximately 2 kg
of hot alumina from an electrically heated hopper in a sealed
box. The alumina was dropped onto a plate at the bottom
of the box and the dust liberated during the fall and subse-
quent impact was collected in petri dishes and weighed to
determine the specific dust generation rate G = (dust liber- Fig. 5. Dust generation from a falling stream of alumina as a function of
ated/mass of parent material). The motivation for this work temperature difference (drop height = 500 mm, mass = 2.0 kg).
came from the need to understand the fundamentals of dust
generation during hot solids handling processes, such as The results of the experiments to determine how the rate
those involved in cement and coke production. of dust generation is influenced by the temperature differ-
ence between the bulk material and the surrounding ambient
air are shown in Fig. 5 [6]. Clearly, temperature difference
has a very strong influence on dust generation rates for
5. Results and discussion
materials with a relatively high proportion of fines. For the
alumina used in these experiments a temperature difference
The volume of entrained air was found to be proportional
of 140 C results in an increase in dust generation rate
to the drop height raised to the power of approximately 5/3.
by approximately an order of magnitude. This could ex-
This is in contrast to Eq. (1) where the expected index is
plain the premature failure of dust filtration systems on hot
2/3 [3]. This is an important result and suggests that a better
processes, where existing design and selection techniques
approach to modelling of the air entrainment process might
could be grossly under-estimating actual dust loadings.
come from the use of a modified plume theory.
The specific air entrainment (i.e. air entrainment per unit
mass of parent bulk material) was found to decrease with
6. Dust explosion hazards
increasing mass flow rate of solids, Fig. 4. The solid line
correlates the results of Smithers [4] and Glutz [5] and shows
In many instances, it may be possible to reduce the risk
that specific air entrainment is proportional to m0.67 . If the
and severity of dust explosions by minimising the generation
particles in the falling stream behaved independently of one
and turbulence of dust. In a falling stream of material:
another, each interacting in the same way with the ambient
air, then the specific air entrainment would be constant with the main core of falling powder is surrounded by a tur-
respect to mass flow rate. The experimental results show that bulent layer of fine dust, which escapes easily into the
this is not the case. surrounding air, Fig. 2;
326 P. Wypych et al. / Chemical Engineering and Processing 44 (2005) 323326
air is entrained in the falling stream of dilating powder; Particle damage and dust generation are extremely low
the impact zone is a highly turbulent region where the en- and often unable to be detected (e.g. sugar crystals can be
trained air is ejected into the atmosphere at relatively high conveyed without even being scratched).
velocity and carries with it a large amount of fine dust; Electrostatic charge generation and risk of spark ignition
considerable reductions in dust concentration and turbu- are very low.
lence, as well as dust explosion risk and severity, can The concentration of particles inside the pipeline is ex-
be achieved by minimising drop height and hence, the tremely high and beyond the upper explosible limit (UEL).
amount of entrained air, as demonstrated previously. This forms a natural buffer zone or barrier for any
explosion that may occur in a vessel at either end of the
The situation depicted in Fig. 2 is exacerbated for pneu-
pipeline (i.e. flame propagation is unlikely). This could
matically filled bins. Here, the velocity at impact can be
avoid the need for explosion suppression and/or isolation,
quite high, especially when the material reaches high level.
which would be required normally for a dilute-phase or
Employing a large drop-out box or tee-bend can reduce
dust extraction system.
the extent and severity of dust generation. Further reductions
The frequency and turbulence of particles striking the filter
in dust loading, explosion risk and severity may be possible
elements are extremely low.
by using a tangential entry. For example, Hauert et al. [7]
Filtration requirements (e.g. filter surface area) also are
found that the reduced explosion pressures for the tangential
quite low.
pneumatic filling of wheat flour and corn starch were 35
times smaller than those obtained with central filling.
Significant increases in dust also can occur during 7. Conclusions
the dilute-phase transport (suspension flow) of granular
materials, such as sugar and wheat. The relatively high Free-falling bulk solids can produce large quantities of
transport velocities can cause particle attrition and a sig- fugitive dust and comprise core and boundary layer regions.
nificant increase in fines, as well as an increased level of Specific air entrainment increases with drop height, but de-
electrostatic charge generation and risk of spark ignition. creases with increasing solids mass flow rate. Higher temper-
Significant reductions in velocity are achieved by pursu- atures or transport velocities increase dust generation rates
ing the dense-phase (non-suspension) mode of flow. Here dramatically. Significant reductions in velocity and dust gen-
the particles are conveyed either in fluidised dense-phase eration are achieved by selecting the dense-phase mode of
(e.g. for air-retentive powders, such as flour and starch) or flow. Such findings should be considered for the efficient
low-velocity slug-flow (e.g. for granular products, such as design and operation of dust control and explosion control
wheat and sugar). The following typical operating condi- systems.
tions for wheat conveyed through a 105 mm 96 m long
pipeline demonstrate the possible (velocity) differences
between dilute-phase and dense-phase. References
Dilute-phase (suspension flow): solids mass flow
= 6 t h1 , air mass flow = 0.260 kg s1 , solids loading [1] W.D.L. Hemeon, Plant and Process Ventilation, Industrial Press, New
York, USA, 1963.
= 6, pipeline pressure drop = 30 kPa, transport velocity [2] G.E. Tooker, Bulk Solids Handling 12 (1992) 227232.
= 19.325.0 m s1 . [3] P. Cooper, P.C. Arnold, Air entrainment and dust generation from
Dense-phase (low-velocity slug-flow): solids mass flow a falling stream of bulk material, Kona Powder Particle 13 (1995)
= 6 t h1 , air mass flow = 0.065 kg s1 , solids loading 125134.
= 26, pipeline pressure drop = 120 kPa, air velocity = 2.9 [4] T. Smithers, Generation of Dust from a Falling Stream of Material, BE
to 6.3 m s1 .
Honours Thesis, Mechanical Engineering, University of Wollongong,
1994.
In addition to the obvious advantages of reduced air flow, [5] A. Glutz, Air Entrainment in Falling Streams of Material, BE Honours
Thesis, Mechanical Engineering, University of Wollongong, 1995.
velocity and hence, power, dense-phase offers the following [6] B. Perrin, Dust Generation from a Heated Bulk Solid, BE Honours
additional benefits. Thesis, Mechanical Engineering, University of Wollongong, 1999.
[7] F. Hauert, A. Vogl, S. Radandt, Dust cloud characterization and its
Particle velocity is controlled easily in the range influence on the pressure-time-history in silos, Process Safety Progress
0.252 m s1 . 15 (1996) 178184.
Chemical Engineering and Processing 44 (2005) 327334
Received 31 July 2003; received in revised form 12 December 2003; accepted 11 February 2004
Available online 25 June 2004
Abstract
The effects of the ratio of TiO2 /silica gel, superficial gas velocity (Ug ), solid circulation rate (Gs ), initial trichloroethylene (TCE) concen-
tration, wavelength of UV light, and concentrations of H2 O and O2 on photodegradation of TCE over TiO2 /silica gel have been determined
in a circulating fluidized bed (CFB) photoreactor. The TCE conversion decreases with wavelength of the UV light, the initial TCE and H2 O
concentrations in the CFB reactor. The optimum concentration of O2 for TCE degradation is found to be approximately 9 vol.% in the CFB
photoreactor. The CFB photoreactor is an effective tool for high TCE degradation with efficient utilization of photon energy.
2004 Elsevier B.V. All rights reserved.
Keywords: TiO2 /silica gel; Solid circulation rate and holdup; Circulation fluidized bed (CFB) photoreactor
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.027
328 T.H. Lim, S.D. Kim / Chemical Engineering and Processing 44 (2005) 327334
tor configuration provides both exposure of photocatalyst to (23 mm-i.d., Pyrex glass) and a solids feeding system. A
UV light and good penetration of the light into the photo- sintered metal plate was used as a gas distributor to provide
catalyst bed that allows more contact of photocatalyst and uniform fluidization of TiO2 /silica gel photocatalyst.
reactant gas [8]. Also, UV light can be more evenly dis- To improve sealing and the mechanical problems,
tributed within the given catalyst bed. Furthermore, a newly non-mechanical valves (loop-seal, L-, J-, and V-valve) are
developed circulating fluidized bed (CFB) photoreactor sys- commonly employed [10]. The present CFB photoreactor
tem enables remote delivery of UV light to the photocata- had a loop-seal for photocatalyst feeding and its flow rate
lyst, which is ideally suited to the gas remediation since it was varied by aeration rate at the bottom of the loop-seal.
provides good contact between UV light and photocatalyst The amount of the photocatalyst was 80 g for one batch op-
with reaction gas, higher reactant throughputs, reduces mass eration. During the operation, photocatalyst particles were
transport limitations [9] and lower pressure drops compared transported by up-flowing gas at the bottom of the riser.
to conventional bubbling fluidized beds [10]. Although the The transported particles from the riser were collected and
two-dimensional fluidized bed photocatalytic reactor system separated in a cyclone. The separated photocatalyst parti-
can be applied to water and gas treatments, a CFB photore- cles flow down into the downcomer. The powders in the
actor system for gas phase treatment has not been reported downcomer flow into the riser again through a loop-seal
yet. by adjusting aeration gas. The flow rate of reactant gases
In the present study, the effects of the initial TCE con- (548 ppmv TCE/N2 balance, 50 vol.% O2 /N2 balance, N2 )
centration, wavelength of the UV light, H2 O concentration, were regulated by a mass flow controller (MKS, USA) to
O2 concentration, the ratio of TiO2 /silica gel, superficial gas match suitable concentrations of TCE, O2 , and H2 O and in-
velocity (Ug ), solid circulation rate (Gs ) on photodegrada- troduced into the bottom of the CFB photoreactor. Concen-
tion of TCE have been determined in a CFB photoreactor tration of TCE was measured by online gas chromatography
system. equipped with ECD (HP 6890 II) and an auto-sampling
valve system (Valco instrument Inc., A60). The minimum
fluidization velocity (Umf ) of TiO2 /silica gel photocatalyst
2. Experimental was determined by the pressure drop and the expanded bed
height in the bed with variation of Ug [5,7].
2.1. Photocatalyst
2.3. The installation of the UV light lamp
In general, TiO2 powder is classified into Geldart C group
having a poor fluidization behavior [5,6]. Therefore, silica Photoillumination was provided with 15 germicidal
gel (Aldrich, USA) with size of 3060 mesh and surface area white and 15 fluorescent black light lamps (8 W, Sankyo
of 490 m2 g1 was used as a support to enhance fluidization Denki Japan, G8T8, F8T8). Wavelength of the white light
quality. This support is transparent to near UV light. Precur- lamp ranged from 200 to 300 nm with the maximum light
sor solutions for TiO2 coating on silica gel were prepared by intensity at 254 nm, wavelength of the black light lamp
using titanium ethoxide, ethanol, HCl, hexylene glycol and ranged 300400 nm with the maximum light intensity at
milli-Q water. Titanium ethoxide (5 g) and hexylene glycol 356 nm. The light intensity was measured by UV radiome-
(2.8 cc) were dissolved in ethanol (50 g). After mixing vig- ter (Cole-Parmer, VLX-3 W, USA). The UV light lamps
orously at room temperature for 90 min, water (0.4 cc) and was affixed at the outside of the CFB riser for effective UV
37 vol.% HCl (0.1 cc) were added to the solution. The molar light irradiation and aluminum foil surrounded the UV light
ratios of water and HCl to the titanium ethoxide were 1 and lamps to minimize loss of light irradiation and to improve
0.11, respectively. After mixing vigorously at room tempera- utilization of reflected and deflected lights.
ture for 90 min, silica gel was added to the aqueous colloidal
suspensions of TiO2 . Then, it was dried at 80 C for 24 h
and calcined at 450 C for 1 h. The composition of a crystal 3. Results and discussion
structure was verified by Rigaku RINT2000 HRXRD. The
amount of TiO2 coating on silica gel is found to be 0.3 g To determine the optimum content of TiO2 in silica gel
of TiO2 per gram silica gel. The BET surface area of the for maximum TCE conversion, the TiO2 /silica gel ratio was
silica/TiO2 catalyst is somewhat reduced to 404 m2 g1 due varied from 0.10 to 0.42 with variation of Ug (1.3, 1.5,
to pore plugging by the impregnated TiO2 . 1.7 m s1 ) as shown in Fig. 2. As can be seen, the conver-
sion increases gradually up to 80% at Ug = 1.5 m s1 with
2.2. Circulating fluidized bed (CFB) photoreactor increasing the TiO2 /silica gel ratio up to around 0.3. When
TiO2 /silica gel ratio is below 0.3, TiO2 content is not suffi-
A circulating fluidized bed (CFB) photoreactor and cient to decompose TCE by photocatalysis in the photore-
installation of the UV light lamps is shown in Fig. 1. actor. Thereafter, TCE conversion remains constant with a
The CFB photoreactor composed of a riser (13 mm-i.d. further increase in TiO2 /silica gel ratio due to the arrival of
1200 mm-high, Quartz glass), cyclone, downcomer sufficient participating reaction of TCE by the photodegra-
T.H. Lim, S.D. Kim / Chemical Engineering and Processing 44 (2005) 327334 329
dation. Therefore, it may be clamed that the optimum ratio sufficient mixing of reactant and catalyst at the optimum su-
of TiO2 /silica gel in the present CFB photoreactor is 0.3 at perficial gas velocity to provide the maximum contact be-
the given specific geometry of UV light irradiation. There- tween TiO2 /silica gel and TCE gas-UV light in the CFB
fore, the TiO2 /silica gel ratio of 0.3 was employed in all the photoreactor.
experimental conditions. The solid circulation rate (Gs , kg m2 s1 ) can be con-
The effect of Ug on photocatalytic activity of TiO2 /silica trolled by aeration gas in the loop-seal to adjust pressure
gel as a bed material in the CFB photoreactor is shown in balance in the CFB loop. Solid circulation rate is a unique
Fig. 3. As can be seen, TCE conversion over TiO2 /silica gel operating variable in the CFB system as a function of pres-
photocatalyst exhibits a maximum value at Ug = 1.5 m s1 sure drop across loop-seal of a CFB photoractor [10] and
where UV light transmission and mixing of TiO2 /silica gel directly related to solid holdup in the riser where the pho-
and TCE gas might be at the optimum condition. Thereafter, todegradation of TCE occurs.
TCE conversion decreases with a further increase in Ug due Solid holdup (s ), the volume fraction of solids, and
to bypassing of unreacted TCE gas and reduction of resi- Priser, pressure drop in the riser are defined as
dence time of TCE gas in the photoreactor [5,7]. Therefore,
it can be concluded that photo degradation of TCE requires s = 1 g (1)
330 T.H. Lim, S.D. Kim / Chemical Engineering and Processing 44 (2005) 327334
Fig. 2. Effect of TiO2 /silica gel ratio on TCE conversion with a variation
of Ug .
Fig. 4. Effect of solid circulation rate on TCE conversion with a variation
Priser of wavelength of UV light Ug .
= (1 g )(s g )g (2)
L
where, Priser , L, g , s , g are pressure drop across the riser
(PRB PRT ), length of the measuring height, gas holdup, Gs at the given wavelengths (254 and 365 nm). With the ger-
solid density and gas density, respectively. micidal white lamp at Gs = 9.2 kg m2 s1 (s = 0.018),
The TCE conversion with a variation of wavelength of UV more than 80% of TCE is degraded, and the TCE conversion
light as a function of Gs and s is shown in the Fig. 4. As can increases up to 90% with increasing Gs (15.4 kg m2 s1 )
be seen, TCE conversion increases linearly with increasing at s = 0.031. Therefore, it can be seen that solid holdup
(s ) affects the performance of CFB photoreactor since the
optimum s provides better contact between the catalyst
(TiO2 /silica gel) and the reactant gas (TCE) at the given
UV light irradiation as reported in the surface modifica-
tion of HDPE powders in a circulating fluidized bed reactor
[10].
The effect of initial TCE concentration on TCE conver-
sion in the CFB photoreactor is shown in Fig. 5 where the
conversion decreases linearly with increasing the initial TCE
concentration at the given Ug (1.3 and 1.5 m s1 ). It may in-
dicate that the limited and fixed amounts of active sites on
TiO2 /silica gel are present before degradation of TCE as ob-
served for decomposition of toluene and formaldehyde by
UV/TiO2 at the saturated adsorption with the fixed active
sites [1,7,11].
The effect of wavelength of the UV light (germicidal
white and fluorescent black lamps) on TCE conversion in
the CFB photoreactor is shown in Fig. 6. As can be seen,
the germicidal white lamp (254 nm) exhibits higher TCE
conversion than the fluorescent black lamp (365 nm). It has
been reported that variation of photon energy in excess of
band gap of TiO2 does not affect the product mixture from a
photocatalyst reactor [12]. The increase of TCE conversion
Fig. 3. Effect of Ug on TCE conversion with a variation of Gs . is caused by higher photon flux, rather than by increases
T.H. Lim, S.D. Kim / Chemical Engineering and Processing 44 (2005) 327334 331
in the energy of individual photons. Germicidal white wavelength light is adsorbed more strongly by TiO2 /silica
lamps are about 25% more efficient than fluorescent black gel than the longer one. Therefore, penetration distance
lights to producing photons with wavelengths less than of photons into TiO2 /silica gel is shorter and electrons
385 nm [11]. In addition, it has been reported that shorter and holes are formed closer to the surface of TiO2 /silica
gel. Therefore, photons take less time to migrate onto 9 vol.% for the maximum TCE conversion in the CFB
TiO2 /silica gel surface and hence have less time to par- photoreactor.
ticipate in energy wasting recombination reactions before The effect of H2 O concentration on the TCE conversion
useful surface (or near-surface) chemical reaction take place in the CFB photoreactor is shown in Fig. 8. As can be seen,
[5]. Therefore, the shorter wavelength (245 nm) irradiation TCE conversion decreases with H2 O concentration at the
is more effective to enhance photodegradation of TCE than given Ug (1.3, 1.5 m s1 ). The presence of H2 O could en-
the longer wavelength (365 nm) irradiation in the CFB hance or reduce the photocatalytic reaction rates that depend
photoreactor. on the reactant and H2 O concentrations [4]. The water vapor
The effect of O2 concentration on TCE conversion with in this study negatively affects the photocatalytic conversion
variation of Ug is shown in Fig. 7 where the TCE conversion of TCE as reported previously [13]. In general, the presence
increases with increasing O2 concentration up to 9 vol.% of water vapor in photocatalytic reactions is considered to be
and remains constant with a further increase in O2 con- favorable because water molecules react with valence band
centration. The role of molecular O2 in the photocatalytic holes to produce reactive hydroxyl radicals. Indeed, a small
gas-treatment is three-fold: (1) a conduction band for elec- amount of preadsorbed water is found to be essential in pho-
tron scavenger to reduce fast electronhole recombination, tocatalytic degradation of TCE [9]. Although no water was
(2) a precursor of active oxygen species (e.g. HO2 , HO, O) added in this study except when the effect of water vapor
that initiate decomposition reactions, and (3) a replenishing on the TCE conversion was determined, water molecules
source of the lattice oxygen that could be depleted during generated in situ from various reactions byproduct of TCE
the photocatalytic degradation [9]. Therefore, increasing photo-degradation seem to be a sufficient source of OH rad-
oxygen content up to 9 vol.% enhances TCE conversion. ical in the photoreaction of TCE. Also, TCE molecules are
Above 9 vol.% of O2 , TCE conversion remains constant oxidized through direct hole transfer pathway that does not
that may indicate a sign of O2 saturation. In the absence involve OH radical mediators [4]. It can be reasonably accept
of O2 at Ug = 1.5 m s1 , it can be noticed that the conver- that both the hydroxyl radical and the direct hole pathways
sion reaches 0.75 that may imply the lattice oxygen took are operating in the photocatalytic conversion of TCE. In ei-
part in the photocatalytic degradation of TCE [9]. From ther case, excess water molecules compete for active surface
this study, the optimum O2 concentration is approximately sites on TiO2 /silica gel photocatalyst with TCE molecules
T.H. Lim, S.D. Kim / Chemical Engineering and Processing 44 (2005) 327334 333
References
Acknowledgements
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The authors would like to thank for a grant in aid of re-
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search to Dr. S.D. Kim from the LG-Caltex Co. in the frame [2] J. Peral, X. Domenech, D. Ollis, Heterogeneous photocatalysis for
of the Brain Korea 21 Project. Also, this work was supported purification, decontamination and deodorization of Air, J. Chem.
by Korea Research Foundation Grant (KRF-2000-E00442). Technol. Biotechnol. 70 (1997) 117140.
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[3] P.L. Yue, F. Khan, Photocatalytic ammonia synthesis in a fluidized [9] W.Y. Choi, J.Y. Ko, H.W. Park, J.S. Chung, Investigation on
bed reactor, Chem. Sci. Eng. 38 (1983) 18931900. TiO2 -coated optical fibers for gas-phase photocatalytic oxidation of
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trichloroethylene in contaminated air streams, Environ. Sci. Technol. [10] S.H. Jung, S.H. Park, D.H. Lee, S.D. Kim, Surface modification
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*
1 The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper).
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