Escolar Documentos
Profissional Documentos
Cultura Documentos
www.elsevier.com/locate/ces
Received 8 August 2005; received in revised form 31 January 2006; accepted 6 March 2006
Available online 13 March 2006
Abstract
A complete breakthrough model is proposed and solved in this work to describe the removal of volatile organic compounds from a diluted
single-component gas stream passing through a microporous activated carbon fiber monolith (ACFM) under isothermal conditions. All significant
parameters are considered in the model, including type of adsorption isotherm, resistance to external gas diffusion, non-instantaneous adsorption
kinetics at the external surface and type of gas diffusion within the pore system. n-Butane was employed as the test compound for obtaining
the experimental breakthrough curves. The model including non-instantaneous adsorption at the external surface and surface pore diffusion
describes properly the experimental adsorption results.
䉷 2006 Elsevier Ltd. All rights reserved.
Keywords: Activated carbon; Carbon fibers; Volatile organic compounds; Adsorption; Mass transfer; Diffusion; Simulation; Modeling
1. Introduction VOCs (Centeno et al., 2003; Fuertes et al., 2003). However, the
use of granular packed beds has serious drawbacks, such as the
Low-density activated carbon fiber monoliths (ACFMs) have high pressure drop associated with the flow of gas through the
been developed recently (Burchell et al., 2000; Burchell and packed media, attrition of the granular material, channeling, gas
Judkins, 1997; Lee et al., 1997; Marbán et al., 2000; Vila- bypassing, etc. These disadvantages can be avoided with the
plana-Ortego et al., 2002) for several gas–solid applications utilization of ACFM that, in addition, exhibits a narrow poros-
due to their properties such as light-weight, high mechanical ity in the micropore range (< 2 nm). Micropores are primarily
strength and fast adsorption kinetics. The monolithic structure responsible for adsorption at low VOCs concentrations in am-
makes them easier to handle than packed beds and produces a bient air environments due to the overlapping of the attractive
low resistance to bulk gas flow. Thus, among the possible appli- forces of opposite pore walls (Derbyshire et al., 2001; Foster
cations, ACFMs are of interest for the adsorption and recovery et al., 1992). In many cases n-butane has been employed as
of organic vapors (Fuertes et al., 2003; Marbán and Fuertes, a reference molecule to compare the VOC adsorption capac-
2004), CO2 adsorption (Burchell et al., 1997; Burchell and Jud- ity of various materials (DeLiso et al., 1997; Gadkaree, 2001;
kins, 1997), as catalysts or catalyst support for the removal of Valdés-Solís et al., 2004).
SOx and NOx from flue gas (Marbán et al., 2003), water treat- The adsorption of VOCs in carbonaceous materials has
ment (Suzuki, 1991) and for CH4 storage (Muto et al., 2005). received increasing attention in recent years, and several at-
The removal of volatile organic compounds (VOCs), com- tempts to model the process have been published for granular
monly performed by adsorption, is of great interest for the air active carbon (Linders et al., 2001, 2003), ACF (Cheng et al.,
quality control. At a low-concentration level, adsorption on ac- 2004; Das et al., 2004) and carbon-coated ceramic monoliths
tive carbon is the most employed method for the removal of (Valdés-Solís et al., 2004). In general, the models found in liter-
ature include several simplifications; such as considering only
∗ Corresponding author. Tel.: +34 985 11 90 90; fax:+34 985 29 76 62. gas diffusion in the pores or assuming instantaneous adsorption
E-mail address: greca@incar.csic.es (G. Marbán). kinetics (Cheng et al., 2004; Linders et al., 2001, Valdés-Solís
0009-2509/$ - see front matter 䉷 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2006.03.008
G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772 4763
The textural properties (specific surface area and pore vol- 2.4. Dynamic adsorption experiments
ume) of the adsorbent material were evaluated by means of N2
adsorption isotherms (−196 ◦ C) obtained with a Micromerit- The adsorption chamber used for obtaining the breakthrough
ics ASAP 2010 analyzer, and by CO2 adsorption at 20 ◦ C with curves was a cylindrical pipe (7 mm i.d.) made of quartz. The
a thermogravimetric analyzer (TG CI Electronics). The results cylindrical ACFM was tightly fitted to the internal wall of the
obtained are presented in Table 1. Data on n-butane adsorption chamber by means of Teflon strips and vacuum grease (ther-
experiments performed with the TG system, including parame- mally stable up to 210 ◦ C). In this way gas bypassing was com-
ters for the Dubinin–Radushkevich isotherm (i.e., E0 ) are also pletely avoided. The bulk parameters of the ACFM used are
indicated in Table 1. shown in Table 1.
For the analysis of dynamic n-butane adsorption, the gas
2.3. TGA experiments mixture (500–2000 ppm in He; flow rate = 150 mL/ min) was
led into the adsorption chamber by means of a set of mass flow
A differential adsorption experiment was attempted in the controllers. The composition of the gases exiting the adsorp-
thermogravimetric analyzer at 30 ◦ C. In order to approach dif- tion chamber was analyzed continuously by a mass spectrom-
ferential conditions a very low sample weight (1.475 mg) and a eter (Baltzers, Omnistar model 300O) using mass fragments
high value of n-butane gas concentration (100 vol%) were used 18 for water and 58 for n-butane. The adsorbent temperature
at the maximum flow rate allowed by the experimental setup was measured by a thermocouple inserted into the adsorption
(82 mL/min, 1 atm). The crucible used for these experiments chamber. Prior to the adsorption experiments the adsorbent was
was specially fabricated with a wired mesh to assure fast ac- heated in He at 160 ◦ C for 30 min.
4764 G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772
y 1 y 1
Henry regime: < exp − 2 D.R regime: exp − 2
ys 2 ys 2
2
ys
1 y e = s exp − ln , (8)
e = s exp , (7) y
42 ys
2
je 2 y ys
je s 1 = 2
s
ln
s
exp − ln . (10)
= exp , (9) jy y y y
jy ys 42
The Sherwood number (Sh) is estimated here by the stan- In a similar way, the Darken equation can be applied to any
dard Ranz and Marshall correlation (Bird et al., 2002; Ruthven, kind of isotherm (e.g. Langmuir, Toth, etc.). Since adsorption
1984): is instantaneous:
Sh = 2 + 0.6Re1/2 Sc1/3 . (15) j 6b Sh C0
= (x − y=1 )
j Bo2 qe (C0 )
Although this correlation is valid for Re > 2, we have decided
= kext (x − y=1 ). (21)
to employ it because, according to Ruthven (Ruthven, 1984),
most correlations for Re < 2 usually underestimate the Sher- Combining (1) and (21):
wood number, and therefore it seems advisable to use a correla-
tion that yields the value of Sh=2 for the limiting case of Re=0 jx 1 j2 x 1 jx 1 − b
= − −
(infinite stagnant fluid around an isolated spherical particle). j P ep j2 j b
R2. Adsorption on highly dispersed microporous particles qe (C0 )
(i.e., fibrous monoliths): In this kind of systems it is assumed × kext (x − y=1 ). (22)
C0
that diffusion inside the fibers occurs via surface migration
along their small micropores. Different situations can be found: Coupling (17) and (21) we can obtain the border equation
that expresses the continuity between the axial and the radial
• R2.1: External mass transfer towards the external surface of profile:
the fibers, with instantaneous adsorption at the surface;
j kext
• R2.2: Resistance to adsorption at the external surface of the = (x − y=1 )
j =1 3
fibers (non-instantaneous adsorption).
DM Sh C0
= (x − y=1 ). (23)
It is desirable to use an expression for j/j that consider Dso 2 qe (C0 )
all the above resistances, following a similar formalism to that R2.2. Non-instantaneous surface adsorption: In this case the
used when modeling chemical processes. axial profile is expressed as in the former case by Eq. (22),
R2.1. Instantaneous surface adsorption: In this case, only the radial profile is calculated by the mass balance of Eq. (16)
external mass transfer and intraparticle diffusion control the and the external mass transfer resistance is given by Eq. (21),
process. The intraparticle diffusion resistance can be expressed whereas the resistance to external surface adsorption can be
by the following mass balance: accounted by the following equation, which assumes Lang-
j j j muir kinetics and resembles that used in the old Thomas model
= 2 2 (Thomas, 1944, 1948):
j j j
2
j 2 1 j j j j =1
= + + . (16) = ka t0 C0 y=1 (s − =1 ) − . (24)
j2 j j j j Ka
Similar to Eq. (2) we can integrate (16) to obtain By considering the equilibrium isotherm, constant Ka can
be removed from Eq. (24), which turns into
j j
= 3 . (17)
j j =1 j =1
= ka t0 C0 s y=1 1 − , (25)
j e,=1
The dimensionless surface diffusivity now depends on the
instantaneous adsorption and can be evaluated by the thermo- where e,=1 is the dimensionless adsorbed amount in equi-
dynamic relation expressed by the Darken equation: librium with y=1 . By equaling (21) and (25) and removing
d Ln(x) y=1
= . (18)
d Ln() j kext ka t0 C0 s (1 − =1 /e,=1 )x
= . (26)
Thus, application of the Darken equation to the D–R isotherm j kext + ka t0 C0 s (1 − =1 /e,=1 )
gives
1 1
Henry regime: < exp − 2 D.R regime: exp − 2
s 4 s 4
1
= 1, = ,
2[Ln(s /)]1/2
j j 1
= 0, (19) = [Ln(s /)]−3/2 . (20)
j j 4
4766 G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772
2
e,=1 ys
e,=1 y=1 1 = exp − ln . (28)
= exp , (27) s y=1
s ys 42
C Table 3
1.0 Expressions of evaluated by the Darken equation for different isotherms
A,D
Isotherms (Ds /Dso )
0.8 B
θ [x for curve A]
1
Freundlich isotherm (42)
Table 2 n(1 − /s )
Parameter values of simulation curves plotted in Fig. 1 (square n-butane (n = 0.6 for calculations)
concentration steps)
6 -12
Co= 1x10 Co= 1x106 Dso= 1.50x10 ka = 0.1
1.0 1.0 Dso= 1.50x10-12
ka ≥ 10
0.8 0.8
0.6 0.6
D.R.
θ
Co= 1x106 Co= 1x106
θ
1.0
Square step
0.8 ka . As observed, at high values of gas concentration (106 ppm),
(ka=∞)
the resistance to external surface adsorption exerts no effect
on the model results for values of ka over 10 m3 mol−1 s−1 ,
0.6
Dso=1.50×10-12 whereas for low values of gas concentration (500 ppm) clear
D.R.
differences are observed between the curves corresponding to
θ
Dso=2.00×10-12
0.4 Langmuir
-12 ka = 20 m3 mol−1 s−1 and ka = ∞ (dashed curves in Fig. 3).
Freundlich Dso=2.75×10
Dso=3.50×10-12
This fact has a clear mathematic explanation since parameter
Toth
0.2 Co=1×106 ppm C0 is multiplying ka in the equation that expresses the adsorp-
Yang Dso=9.50×10-12
Co=500 ppm
tion resistance (Eq. (33)). Due to the microporous character of
Constant Dso=1.60×10-12
0.0
ACFM adsorbents, they are thought to have excellent perfor-
0.0 0.5 1.0 1.5 2.0 2.5 3.0 mance in the removal of contaminants at low concentration.
(b) time (s) Therefore, according to the results shown in Fig. 3, any possible
external adsorption resistance will be detrimental at these spe-
Fig. 2. Application of the model at differential conditions for: (a) different cific conditions, whereas it can be unnoticed in environments
adsorption isotherms at a given value of Dso (C0 = 106 ppm); (b) different with a high concentration of the adsorptive.
adsorption isotherms at different values of Dso and C0 .
Since adsorption at the external surface and surface diffusion
inside the pores of the fibers are serial processes, the external
of Dso . This is appreciated in Fig. 2b, in which values of Dso adsorption resistance has a less marked effect on the model
were found in such a way that all expressions of yielded an results for lower values of surface diffusivity, as can be clearly
almost identical curve (solid lines for C0 = 106 ppm). However, observed in Fig. 3. Finally, from the modeling point of view,
when using a much lower gas concentration (C0 =500 ppm), the it is not possible to find a combination of [Dso , ka ] values that
same values of Dso produced very different curves, as indicated produces the same curve as that obtained under instantaneous
by dashed lines in Fig. 2b. Under dynamic conditions, before adsorption and, therefore, the existence of non-instantaneous
the breakthrough is attained, the gas phase inside the monolith adsorption is a clear modeling issue that can eventually be used
may present values from C = 0 to C0 . Therefore, it is obvious to improve the curve fitting of the breakthrough profile.
that the breakthrough profiles will be affected by the associated
differences in adsorption at varying values of gas concentration 4.2. Breakthrough profiles
(Fig. 2b) which permits to conclude that selection of the cor-
rect expression for the isotherm to be employed in the model is Fig. 4 shows the results of applying the model to ACFM
a key modeling issue. In this work the D–R isotherm was used (C0 = 500 ppm) under two different gas diffusion models. As
for fitting the experimental breakthrough profiles. The values of expected (see previous section), the curve corresponding to
the parameters of the D–R equation (Table 1) were determined gas phase diffusion inside the micropore system (regimen R1)
gravimetrically in specific experiments of n-butane adsorption. cannot reproduce the experimental results. Changing the effec-
A second observation, already pointed when commenting tive diffusivity to lower values, apart from lacking of physical
curves A and D of Fig. 1, refers to the effect of external adsorp- significance since Eq. (11) is not accomplished any more, nei-
tion resistance in the shape of the plot of versus time. Fig. 3 ther permitted to simulate the actual shape of the experimental
shows the simulated curves obtained by applying the model un- breakthrough profile. The other simulated curve displayed
der differential conditions for different values of C0 , Dso and in Fig. 4 was obtained by considering surface diffusion
G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772 4769
xξ=1
0.6 Co= 500 ppm
0.4 Deff=1.38x10-8m2s-1
ka=∞ Dso=1.5×10-12m2s-1
0.4
0.2 s
Co=500 ppm Experimental
0.0 0.2 Experimental
700 900 1100 1300 1500 Model
0.0
time (s)
700 900 1100 1300 1500
Fig. 4. Experimental and simulated breakthrough profiles obtained for different (a) time (s)
diffusion models (gas phase diffusion and surface diffusion).
1.2
Dso=1.5×10-12m2s-1
Co=500 ppm 0.4
0.4
s ka=∞
0.2 ka Experimental
0.2 Experimental
Model
Model
0.0
0.0
250 300 350 400 450 500
700 900 1100 1300 1500
(b) time (s)
(a) time (s)
Fig. 6. Experimental and simulated breakthrough profiles obtained at different
values of ka : (a) for C0 = 500 ppm; and (b) for C0 = 2000 ppm.
Dso=7.0×10-13m2s-1 Dso
1.0
Dso =1.0×10-12m2s-1
deal with the high-concentration gradient produced at the ex-
0.8 Dso=1.5×10-12m2s-1
ternal surface in such a way that the whole breakthrough curve
could be resolved in a reasonable time. Added to this, D–R
0.6
xξ=1
Experimental 5. Conclusions
Model
1.0
In this work a model to predict the breakthrough profile
0.8 of the adsorption n-butane by microporous fibrous adsorbents
Co = 2000 ppm
Co = 1500 ppm
Co = 1000 ppm
(ACFM) is proposed. The model includes non-instantaneous
Co = 500 ppm
0.6
xξ=1
0.0E+00
0 500 1000 1500 Notation
(b) time (s)
D v
Fig. 7. Experimental and best fitting simulated breakthrough profiles obtained
B0 Re Sc = DeqvM s , Bodenstein number according to
at different values of C0 : (a) Breakthrough profiles; and (b) breakthrough Levenspiel (Levenspiel, 1996)
rates. C adsorptive concentration in the gaseous bulk at
an axial position z in the monolith (0 < z < H ),
(i.e., Sherwood and Peclet numbers). Therefore, it was decided mol mgas−3
to make a survey on Dso and ka in an attempt to produce a C0 adsorptive concentration in the gaseous bulk at
better fitting of the upper zone of the breakthrough profile with −3
z < 0, mol mgas
the following conditions: (1) not to provoke a worsening of the Cp adsorptive concentration in the intraparti-
fitting in the lower zone of the breakthrough profile and (2) to cle gaseous phase at an absolute position
permit simultaneously a reasonable fitting of the breakthrough −3
(r, z)(0 < r < Deqv /2; 0 < z < H ), mol mgas
profiles obtained at higher n-butane concentrations in the inlet Cs saturation adsorptive concentration at
gas (1000, 1500 and 2000 ppm). −3
Tads , mol mgas
Fig. 5a shows that a decrease in the value of initial surface D monolith diameter, m
diffusivity allows the curve fitting to be improved in the upper Dax axial diffusivity, m2 s−1
zone of the breakthrough profile corresponding to the experi- Deff effective diffusivity in the pore system, m2 s−1
ment performed at C0 = 500 ppm, without provoking a signifi- Deqv equivalent diameter of the fibers = 1.5 × DF , m
cant worsening of the fitting for x=1 < 0.5. However, the same DF fiber diameter, m
procedure applied to the profile obtained at C0 = 2000 ppm DK Knudsen diffusivity, m2 s−1
produced a significant deterioration of the curve fitting in both DM molecular diffusivity, m2 s−1
zones of the profile (x=1 < 0.5 and x=1 > 0.5), as clearly ob- Dso surface diffusivity in the pore system at = 0,
served in Fig. 5b. m2 s−1
Introducing in the model some resistance to n-butane adsorp- E0 characteristic energy of the adsorbent, J mol−1
tion on the external surface of the fibers, or, in other words, H monolith height, m
decreasing the value of ka coefficient, also permitted to im- 3 m −3
K Henry constant, mgas part
prove the curve fitting in the upper zone of the breakthrough
ka external surface adsorption coefficient,
profile obtained at C0 = 500 ppm (Fig. 6a), but in this case the 3 mol−1 s−1
mgas
profiles obtained at higher values of C0 were also reasonably 3 m −2 s−1
well simulated (Fig. 6b). It was found in this way that values kext external mass transfer coefficient, mgas part
for Dso and ka of 1.5 × 10−12 m2 s−1 and 20 m3 mol−1 s−1 , MW adsorptive molecular weight, g mol−1
Deqv vs
respectively, produced a satisfactory fitting of the profiles ob- Pep Dax b , Bodenstein or particle Peclet number
tained at the different values of n-butane gas concentration, as according to CRC Handbook (CRC, 1984). Axial
shown in Fig. 7. It is worth noting that the time derivative of dispersion number according to Levenspiel
x=1 is also well reproduced by the model for the different val- (Levenspiel, 1996)
ues of C0 (Fig. 7b), which expresses the authentic goodness of q instantaneous amount of adsorbate, per adsorbent
−3
the curve fitting. volume, at an absolute position (r, z), mol mpart
G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772 4771
Linders, M.J.G., van de Broeke, L.J.P., Nijhuis, T.A., Kapteijn, F., Moulijn, Ruthven, D.M., 1984. Principles of Adsorption and Adsorption Processes.
J.A., 2001. Modelling sorption and diffusion in activated carbon: a novel Wiley, New York.
low pressure pulse-response technique. Carbon 39, 2113–2130. Suzuki, M., 1991. Application of fiber adsorbents in water-treatment. Water
Linders, M.J.G., Mallens, E.P.J., van Bokhoven, J.J.G.M., Kapteijn, F., Science and Technology 23, 1649–1658.
Moulijn, J.A., 2003. Breakthrough of shallow activated carbon beds under Thomas, H.C., 1944. Heterogeneous ion exchange in a flowing system. Journal
constant and pulsating flow. AIHA Journal 64, 173–180. of the American Chemical Society 66, 1664–1666.
Marbán, G., Antuña, R., Fuertes, A.B., 2003. Low-temperature SCR of NOx Thomas, H.C., 1948. Chromatography—a problem in kinetics. Annals of the
with NH3 over activated carbon fiber composite-supported metal oxides. New York Academy of Sciences 49, 161–182.
Applied Catalysis B: Environmental 41, 323–338. Valdés-Solís, T., Linders, M.J.G., Kapteijn, F., Marbán, G., Fuertes, A.B.,
Marbán, G., Fuertes, A.B., 2004. Co-adsorption of n-butane/water vapour 2004. Adsorption and breakthrough performance of carbon-coated ceramic
mixtures on activated carbon fibre-based monoliths. Carbon 42, 71–81. monoliths at low-concentration n-butane. Chemical Engineering Science
Marbán, G., Fuertes, A.B., Nevskaia, D.M., 2000. Dry formation of low- 59, 2780–2791.
density Nomex(TM) rejects-based activated carbon fiber composites. Vilaplana-Ortego, E., Alcañiz-Monge, J., Cazorla-Amorós, D., Linares-Solano,
Carbon 38, 2167–2170. A., 2002. Activated carbon fibre monoliths. Fuel Processing Technology
Muto, A., Bhaskar, T., Tsuneishi, S., Sakata, Y., 2005. Activated carbon 77–78, 445–451.
monoliths from phenol resin and carbonized cotton fiber for methane Wakao, N., Smith, J.M., 1962. Diffusion in catalyst pellets. Chemical
storage. Energy & Fuels 19, 251–257. Engineering Science 17, 825–834.