Você está na página 1de 6

Modelling, Control, and Optimisation of Membrane

Processes

Miroslav Fikar
Faculty of Chemical and Food Technology
Slovak University of Technology in Bratislava, Slovakia
Email: miroslav.kar@stuba.sk, URL: www.kirp.chtf.stuba.sk/kar

AbstractThis work deals with membrane processes that Suspended


stand for an emerging technology in chemical and bioprocess MF particles
industry used both in production and down-stream processing. Macro-
Membrane processes receive growing attention mainly due to UF molecules
reduced energy demands and higher efciency of the achieved
separation or processing goals. These systems, however, did not Dissociated acids
receive much attention from process optimization community and NF Divalent salts
that is why they provide many opportunities for development of Sugars
optimal operation design. Undisociated salts
RO Monovalent salts
Membrane processes, their common features, and principles
will be discussed in details. Mathematical models suitable for Water
modelling, simulation, and control will derived. The existing
industrial operation and control will be explained. Theory of Fig. 1. Classication of membranes with regard to pore size and lter-
automatic control will be employed to suggest improvements able/retained components.
over the existing state of control and to propose new control
strategies. Selected case studies will demonstrate the advantages
of the proposed approach. membrane separation processes which can be distinguished by
the actual type and pore size of a used membrane [7]. There are
I. I NTRODUCTION four categories of membrane ltration processes distinguished
Although membrane ltration is considered to be a mature at the level of pore size of employed membrane which are
technology, broad optimisation and innovation potential exists. schematically illustrated in Fig. 1:
Reducing operational costs is a key to exploit this technology microltration (MF),
and to make it competitive and sustainable for the future. This
paper presents overview of modelling, control, and optimi- ultraltration (UF),
sation of membrane processes that are designed to separate nanoltration (NF),
products from impurities.
reverse osmosis (RO).
Membrane processes have been integrated into large-scale
industrial processes since the last 50 years [19]. The main One can also distinguish between two main ways of
application areas are in the beverage, food industries, biotech- ltering a feed solution through the membrane: dead-end and
nology (e. g. [3], [6], [8], [12], [18], [24]). Some of the other cross-ow ltration. The dead-end ltration is limited to batch
important applications include, for example, virus harvest and processing due to necessity to repeatedly remove the ltration
purication [4], [21], desalination of various pigments [17] and cake. On the other hand, the cross-ow ltration is suitable
gelatin [20], purication of nanoparticles [2], [14], treatment for both continuous and discontinuous (batch) treatment of
of bleach plant efuents [13], or fruit juice clarication [23]. solutions and is generally more used in industry.

II. M EMBRANE S YSTEMS B. Process Congurations


A. Separation by Filtration The simplest in design are batch processing systems [22].
These are particularly suited to small-scale operations. Mi-
Membrane systems are used for ltration and purication
croltration systems usually operate with total recycle. On
of liquid or gas mixtures. A membrane acts as an incomplete
the other hand, UF applications prefer partial recycle with a
barrier between two uids. This structure is porous to allow
separate recirculation pump.
for passage of some uid from one side of the membrane
to the other one. Thus, it can be used for separation of An example of continuous processing systems are feed and
particles or chemicals. It prevents to pass the particles with size bleed systems. The feed is concentrated in the recirculation
bigger than the pores of the membrane, traditionally referred loop and the amount of feed added is balanced with the re-
as macro-solutes, and simultaneously it allows the particles tentate bleed. Single and multiloop congurations are possible.
of smaller size, typically denoted as micro-solutes, to get Typical applications include high purity water production using
through to permeate. This is a fundamental principle of all RO.

109
978-1-4799-3528-4/14/$31.00 2014 IEEE
diluant retentate permeate
u q 1
membrane C-CVD-C
module


feed tank C-VVD
VVD
0
time
Fig. 3. Representation of classical three-step processing (C-CVD-C), pre-
Fig. 2. Schematic representation of a generalised batch dialtration process. concentration combined with variable-volume dialtration (C-VVD), and
variable-volume dialtration (VVD) operation in terms of the function.

Dialtration systems add diluent to the retentate, thus alter


the concentration of solutes entering the membrane. It can where u represents ow-rate of the added diluant and V0 stands
be implemented for all ltration ranges (MF RO), as batch for the initial volume of the solution. According to Fig. 2, one
(Fig. 2) or continuous systems, as single or multiple (parallel, can write the balance of the ith component such that
series, counter-current) congurations.
d(ci V )
= cpi q, (2)
C. Materials and Modules dt
where cpi denotes concentration of a solute in the permeate
An ideal membrane should have a very low resistance to and ci the corresponding concentration in the retentate. These
solvent, good separation properties (to reject the macro-solute can be related via the rejection coefcient
maximally and to pass through micro-solutes). In addition, it cpi
should resist to fouling. Ri = 1 . (3)
ci
Most of membranes are produced from synthetic polymers
This yields
polysulphones, polyamides, polyacrylonitrile, polypropylene
as well as from ceramic materials. dci dV
V + ci = (1 Ri )ci q, (4)
A module, or a cartridge, provides a housing for the mem- dt dt
brane. The most common include at sheet and spiral wound which can be rewritten using (1) to
modules. Shell-and-tube modules, similar to heat-exchangers dci u q
are also used. Here, the feed enters through the tubes that are = ci + Ri ci , (5)
dt V V
porous. Individual tubes are packed together and xed by two
end plates. Let us dene dimensionless variable as a ratio of diluant
inow to membrane ux as
u
D. Fouling = . (6)
q
Membrane fouling is caused by deposition of particles
(emulsions) on the membrane surface. The processes that are The balance of each solute can then be written as
driving force of fouling are pore blocking, cake formation, dc1 c1 q
= (R1 ), c1 (t0 ) = c10 , (7a)
adsorption, etc. This phenomenon can be reversible or irre- dt V
versible. As such, it causes the permeate ux decline and dc2 c2 q
product quality losses. = (R2 ), c2 (t0 ) = c20 , (7b)
dt V
Therefore, membrane cleaning has to be performed periodi- and the volume balance as
cally. Acids are used to clean inorganic fouling, bases (caustic) dV
for organic of biologic fouling. = ( 1)q, V (t0 ) = V0 . (8)
dt
III. M ODELLING OF M EMBRANE P ROCESSES In general, rejection coefcients Ri and permeate ow q
can be functions of both concentrations c1 , c2 .
The subsequent sections will concentrate on one example
of membrane processes a batch membrane ltration plant (for
RO, UF, NF, or MF) with a given membrane area that operates IV. T RADITIONAL C ONTROL
under xed operating conditions (Fig. 2). The studied ltration The standard way of reaching the dual objective of frac-
system applies a cross-ow and pressure setpoint, and the tionation and concentration is to perform a multi-step process
permeate ows uncontrolled out of the membrane module. It including pre-concentration (C), constant-volume dialtration
is assumed that the system is well-mixed, and the introduction (CVD), and post-concentration steps. Other strategies include
of diluant causes no local concentration differences. variable-volume dialtration (VVD) [12], or a variation of
it, pre-concentration followed by variable-volume dialtration
Volume balance of the solution in the system can be stated
(C-VVD) [10]. These processes are best described with
as:
dV (i.e. the ratio of diluant ow to permeate ow) as a function
= u q, V (t0 ) = V0 , (1) of operation time as shown in Fig. 3.
dt

2014 15th International Carpathian Control Conference (ICCC) 110


V. P ROCESS O PTIMISATION Hamiltonian is afne in , its minimum is attained with
on its boundaries (bang-bang control) as
A. Problem Formulation 
0 if H > 0,
To optimise the process, one can formulate the cost = (14)
function which minimises a weighted objective consisting of if H < 0.
minimum time operation, minimum diluant operation, and If H = 0 then the Hamiltonian is singular and does not
minimum loss operation of the macro-solute with respect depend on . The fact that condition H = 0 implies the
to time-varying function (t). These are the most common derivatives of H with respect to time to be equal to zero.
objectives occurring in practice. The formulation is then as This yields a set of equations linear in
follows
 tf  tf H (x, ) = g T = 0, (15a)
J = min wT tf + wD q dt + wM (1 R1 )qc1 dt H (x, ) = hT = 0, (15b)
0 0
(9a) (x, , ) = (hx f f x h + (hx g g x h)) = 0,
H
s.t. (15c)
dc1 q where
= c1 (R1 ), c1 (0) = c1,0 , c1 (tf ) = c1,f (9b) hT (x)
dt V h(x) = g x f f x g, hx = . (16)
dc2 q x
= c2 (R2 ), c2 (0) = c2,0 , c2 (tf ) = c2,f (9c)
dt V
dV Let us also dene
= ( 1)q, V (0) = V0 , V (tf ) = Vf (9d)
dt q
[0, ]. qi = . (17)
(9e) ci
The non-negative weights wT 0, wD 0, and wM 0
represent weight of nal time, total diluant consumption, and C. Optimal Operation
minimum loss, respectively. Note that again both process Elimination of adjoint variables from the conditions (15)
differential equations and the cost function are afne in . results in the expression for singular surface in the state space
Pure dilution mode can be represented by . In this
step certain amount of diluant is added into the feed tank in S(c1 , c2 ) = wT R1 V q 3 (R1 R2 )(c1 q1 + c2 q2 + q)
one time instant. Hence that this step maintains the ratio of + wD R1 V q 5 (R1 R2 )
concentrations c1 and c2 .
= wT (q + c1 q1 + c2 q2 ) + wD q 2 = 0. (18)
It will be further assumed that the rejection coefcients
are constant, i.e. do not depend on concentrations. Although Several conclusions can be drawn from this expression:
this assumption is not valid in some cases, approximation by If minimum diluant case is considered (wT = wM =
constants simplies considerably the analysis and introduces 0) the singular operation should stay close to q = 0.
only a minor level of suboptimality. Note, that the condition q = 0 is unrealistic (cf. (7)),
the smallest possible permeate ow is desired.
B. Pontryagins Minimum Principle
The minimum time operation is characterised by the
To solve the problem (9) analytically, Pontryagins mini- singular state surface S(c1 , c2 ) of the form
mum principle [5], [16] will be used. The process differential
equations are afne in control. Hence they can be rearranged q + c1 q1 + c2 q2 = 0. (19)
as It can be easily shown that this equation can be
x = f (x) + g(x), (10) generalised for more than two components as
where x = (c1 , c2 , V )T . The Hamiltonian function can be then n

written as q+ ci qi = 0, (20)
T T i=1
H(x, , ) = 1 + f (x) + g (x)
= H0 (x, ) + H (x, ), (11) where n corresponds to the number of components.
The loss minimisation term does not contribute to
where = (1 , 2 , 3 )T is the vector of adjoint variables
the optimal concentration surface. This term can be
which are dened from
written in terms of initial and nal concentrations and
H
= = (f x + g x ), (12) volume of retentate
x  tf
where (1 R1 )qc1 dt = c1,0 V0 c1,f Vf . (21)
0
f T (x) g T (x)
f x (x) = , g x (x) = . (13) As shown in [15], the nal volume is xed by other
x x parameters and does not depend on actual control
According to Pontryagins minimum principle the optimal trajectory if the rejection coefcients are constant.
solution to (9) minimizes the Hamiltonian function. Since Therefore, this integral term cannot be optimised.

2014 15th International Carpathian Control Conference (ICCC) 111


The expression for singular control that will keep the This equation cannot be solved for c1 analytically and numer-
process at the optimal surface S(c1 , c2 ) = 0, can be obtained ical techniques have to be used.
by differentiating (18) again with respect to time. This yields
The corresponding control that will keep operation on the
S dc1 S dc2 singular curve is given from (24)
0= + , (22)
c1 dt c2 dt S S
S q S q c1 c1 R1 + c2 c2 R2
0= c1 (R1 ) + c2 (R2 ), (23) = S S
= R1 . (29)
c V c2 V c1 c1 + c2 c2
12 S
i=1 ci Ri
= 2 cS i
. (24) Applying = R1 to differential equation of macro-solute
i=1 ci ci conrms constant concentration operation
dc1 q
The optimal operation consists of three arcs and it is = c1 (R1 ) = 0. (30)
dened by the following feedback strategy: dt V

1) The control in the rst step is step is found from The optimal singular control mode is therefore VVD (or
 CVD if R1 = 1). Note also that the optimal operation does not
0 if S(c1,0 , c2,0 ) > 0,
= (25) depend on the value of rejection coefcient R2 of the micro-
if S(c1,0 , c2,0 ) < 0. solute.
It is applied until the condition S(c1 , c2 ) = 0 is met.
Let us demonstrate the optimal operation procedure on the
2) In the second step, the states reside on the singular
case when clim = 319 mol/m3 , k = 4.79 106 m/s, and
surface with singular control from (24).
A = 1 m. The goal is to process 0.1 m3 of solution from initial
3) The last step uses again either pure concentration
point [c1,0 , c2,0 ] = [10 mol/m3 , 31.5 mol/m3 ] to nal point
or dilution mode until the nal concentrations are
[c1,f , c2,f ] = [100 mol/m3 , 0.1 mol/m3 ]. Let us consider time
reached.
optimal operation and perfect rejection properties (R1 = 1,
The duration of the singular step is fully determined by the R2 = 0). The optimal trajectories are shown in Fig. 4 and the
last step and the nal conditions on concentrations. Therefore, nal time of time optimal operation is 4.88 h. The structure of
it is not determined in open-loop but can be implemented in a optimal operation of this process is = {0, 1, }, i.e. pre-
feedback fashion. More details on these results can be found concentration C, constant-volume dialtration CVD, and the
in [15]. nal dilution.
The actual process control will be implemented as follows:
VI. C ASE S TUDY
Consider the concentration polarisation model given by the 1) Calculate optimal singular concentration of the
permeate ow [9] macro-solute c1 from (28). Analytic solution exists
in this case and it is given as c1 = clim /e.
clim cp1
q(c1 ) = kA ln , (26) 2) Pre-concentration mode with = 0 until c1 = c1 .
c1 cp1 3) Variable volume dialtration mode with = R1 = 1
where cp1 is concentration of the macro-solute in the permeate until c1 /c2 = c1,f /c2,f .
and clim is the corresponding limiting (or wall) concentration, 4) Calculate the amount of water to be added based on
k is the transfer coefcient and A the membrane surface. If concentration c1 and volume V at the end of this
this solute is completely rejected (cp1 = 0), standard limiting stage as  
ux model [1] results. c1
Vw = V 1 . (31)
Recall that the rejection coefcient is dened as (3). c1,f
Therefore, the permeate ow can be written as 5) Remove the retentate from the membrane equipment
 
1 clim 1 R1 and dilute the nal solution with the calculated
q(c1 ) = kA ln . (27) amount of water.
R1 c1 R1

Optimal time operation with this model was studied in [9], The same parameters with the classical industrial operation
[11] with assumption that the optimal operation is a se- have been considered. The structure of operation is then
quence starting with pre-concentration, followed by constant = {0, 1} (pre-concentration followed by constant volume
volume dialtration, and optionally nished by another post- dialtration). Although the structure of operational mode is
concentration. The optimal dialtration concentration was different in optimal and this traditional case, the differences in
found to be a decreasing function of R1 with minimum at nal time are for the chosen values of parameters within 1%.
R1 = 1 being c1 = clim /e. It is therefore advisable to check the actual values of process
parameters to see if signicant improvement can be expected.
Following the derivation above one can notice that the
singular state curve (18) is a function of c1 only, and therefore Let us now consider the case with R1 = 0.8 and
constant R2 = 0.2. The structure of optimal operation of this process
  is = {0, R1 , }. One can see that the middle step of
1 clim 1 R1 clim
0 = ln . (28) optimal operation has changed from CVD to variable volume
R1 c1 R1 clim c1 (1 R1 ) dialtration (VVD).

2014 15th International Carpathian Control Conference (ICCC) 112


c2 [mol/m3 ]

c2 [mol/m3 ]
40 100 60 100

40

V [L]

V [L]
20 50 50
20

0 0 0 0
0 100 200 0 5 0 100 200 0 2 4
3 3
c1 [mol/m ] t [h] c1 [mol/m ] t [h]
40
1 1
40
Vw [L]

Vw [L]
0.5 20 0.5
20


0 0 0 0
0 5 0 5 0 2 4 0 2 4
t [h] t [h] t [h] t [h]

Fig. 4. Minimum time operation with R1 = 1, R2 = 0 and C/CVD optimal Fig. 6. Operation with C/CVD modes.
modes.
c2 [mol/m3 ]

60 100 The structure of operation of this process is = {0, 1, 0}.


The actual process control will be implemented as follows:
40
V [L]

50 1) Calculate optimal concentration of the macro-solute


20
c1 = clim /e.
0 0 2) Pre-concentration mode with = 0 until c1 = c1 .
0 100 200
3
0 2 4 3) Constant volume dialtration mode with = 1 until
c1 [mol/m ] t [h]
  R2
20
1 c2,f c1,f R1
= .
c2 c1
Vw [L]

10 0.5 4) Post-concentration mode with = 0 until c1 = c1,f .


0 0 The optimal trajectories are shown in Fig. 6 and the nal


0 1 2 3 0 1 2 3 time of time optimal operation is 3.24 h. One can observe that
t [h] t [h] the traditional operation results in considerably longer nal
time.
Fig. 5. Minimum time operation with C/VVD optimal modes.
Finally, let us mimic the optimal state diagram shown in
Fig. 4 where R1 = 1 and R2 = 0. Therefore, the structure
The optimal trajectories are shown in Fig. 5 and the nal of operation of this process is = {R2 , R1 , }. The actual
time of time optimal operation is 2.97 h. process control will be implemented as follows:

When compared with the state trajectories in Fig. 4 it can 1) Calculate optimal concentration of the macro-solute
be noticed that optimal operation shares the singular trajectory c1 = clim /e.
operation at constant c1 and therefore at constant permeate 2) Constant c2 concentration mode (VVD) with = R2
ow q. The third part of the trajectory is the same as well until c1 = c1 .
dilution by water. The rst part operates with increasing c2 3) Constant c1 concentration mode (VVD) with = R1
this is due to R2 > 0. until c2,f c1,f
= .
Consider again R1 = 0.8 and R2 = 0.2 but let us c2 c1
implement the traditional operation with pre-concentration and 4) Dilution mode with
constant volume dialtration. This is more complicated as the  
respective modes are no longer under constant concentrations. c1
Vw = V 1 . (34)
If constant is assumed division of the concentration material c1,f
balances in (9) yields
The trajectories are shown in Fig. 7 and the nal time of
dc1 c1 R2 such operation is the same as in the previous scenario (3.24 h).
= . (32) Again, this is suboptimal. However, compared to the optimal
dc2 c2 R1
operation, consumption of dialtration water has been reduced.
Integrating from an initial state to a nal state gives
 R 2  R 1 VII. C ONCLUSIONS
c2,f c1,f R 1 c1,f c2,f R 2
= or = , (33) This study considered membrane processes, their opti-
c2,0 c1,0 c1,0 c2,0
misation and control. As such membrane processing is a
if R1 = or R2 = , respectively. promising separation technology with many advantages over

2014 15th International Carpathian Control Conference (ICCC) 113


c2 [mol/m3 ]
40 100 [5] A. E. Bryson, Jr. and Y. C. Ho. Applied Optimal Control. Hemisphere
Publishing Corporation, 1975.

V [L]
[6] B. Cheang and A. L. Zydney. A two-stage ultraltration process for
20 50 fractionation of whey protein isolate. Journal of Membrane Science,
231(1-2):159167, 2004.
0 0 [7] M. Cheryan. Ultraltration and microltration handbook. CRC press,
0 100 200 0 2 4 Florida, USA, 1998.
c1 [mol/m3 ] t [h] [8] E. Drioli and A. Cassano. Separation, Extraction and Concentration
40 Processes in the Food, Beverage and Nutraceutical Industries, chapter
1 Advances in membrane-based concentration in the food and beverage
industries: direct osmosis and membrane contactors. Woodhead Publ
Vw [L]

20 0.5 Ltd, Cambridge, 2010.


[9] G. Foley. Minimisation of process time in ultraltration and continuous
dialtration: the effect of incomplete macrosolute rejection. Journal of
0 0 Membrane Science, 163(12):349355, 1999.
0 2 4 0 2 4
t [h] t [h] [10] G. Foley. Ultraltration with variable volume dialtration: A novel
approach to water saving in dialtration processes. Desalination, 199(1-
3):220221, 2006.
Fig. 7. Operation with constant concentration modes.
[11] G. Foley. Membrane Filtration. A Problem Solving Approach with
MATLAB. Cambridge University Press, Cambridge, UK, 2013.
other existing ones. Optimal control theory was employed to [12] M.Y. Jaffrin and J.Ph. Charrier. Optimization of ultraltration and
check suboptimality of existing operational practice and derive dialtration processes for albumin production. Journal of Membrane
Science, 97:7181, 1994.
analytical solution to a simple batch process.
[13] Ann-So Jonsson and Gun Tragardh. Ultraltration applications.
Although most of the material covers binary mixtures, it Desalination, 77:135 179, 1990. Proceedings of the Symposium on
is easy to extend the results to multicomponent mixtures of Membrane Technology.
to other process congurations. This opens a way to new [14] I. Limayem, C. Charcosset, and H. Fessi. Purication of nanoparticle
solutions involving a series of membrane processes, fractional suspensions by a concentration/dialtration process. Separation and
Purication Technology, 38(1):19, 2004.
operations, etc.
[15] R. Paulen and M. Fikar. Optimal Operation of Batch Membrane
Processes. Springer Verlag, 2014. (in preparation).
ACKNOWLEDGEMENTS
[16] L. S. Pontryagin, V. G. Boltyanskii, R. V. Gamkrelidze, and E. F.
The author acknowledges the contribution of the Scien- Mishchenko. The Mathematical Theory of Optimal Processes. Wiley,
tic Grant Agency of the Slovak Republic under the grant New York, 1962.
1/0053/13 and the Slovak Research and Development Agency [17] New Logic Research, Inc. VSEP for polymer dialtration. Technical
under the project APVV-0551-11. report, New Logic Research, Inc., Emeryville, CA 94608 USA, 2012.
[18] S. Schlosser. Engineering Aspects of Food Biotechnology, chapter
This publication is also the partial result of the Research & Membrane Filtration. CRC Press, 2014.
Development Operational Programme for the project Univer- [19] P. Schu and G. Mitra. Ultraltration membranes in the vaccine industry.
sity Scientic Park STU in Bratislava, ITMS 26240220084, In William K. Wang, editor, Membrane Separations in Biotechnology,
supported by the Research 7 Development Operational Pro- pages 225243. Marcel Dekker, Inc., New York, 2 edition, 2001.
gramme funded by the ERDF. [20] A. Simon, L. Vandanjon, G. Levesque, and P. Bourseau. Concentra-
tion and desalination of sh gelatin by ultraltration and continuous
R EFERENCES dialtration processes. Desalination, 144(1-3):313318, 2002.
[21] T. Vicente, C. Peixoto, M.J. Carrondo, and P.M. Alves. Purication of
[1] P. Aimar and R. Field. Limiting ux in membrane separations: A model recombinant baculoviruses for gene therapy using membrane processes.
based on the viscosity dependency of the mass transfer coefcient. Gene Ther, 16(6):766775, 2009.
Chem. Eng. Sci., 47(3):579586, 1992.
[22] D. Vidal-Brotons, M. L. Gras, E. Garcia-Castello, and P. Fito. En-
[2] E. Allemann, E. Doelker, and R. Gurny. Drug loaded poly(lactic acid) cyclopedia of Agricultural, Food, and Biological Engineering, chapter
nanoparticles produced by a reversible salting-out process: purication Membrane System Operation. Taylor & Francis, 2nd edition, 2011.
of an injectable dosage form. Eur. J. Pharm. Biopharm., 39:1318,
1993. [23] M. Yazdanshenas, A.R. Tabatabaeenezhad, R. Roostaazad, and A.B.
Khoshfetrat. Full scale analysis of apple juice ultraltration and
[3] M. T. Aspelund and C. E. Glatz. Purication of recombinant plant-made
optimization of dialtration. Separation and Purication Technology,
proteins from corn extracts by ultraltration. Journal of Membrane
47(12):5257, 2005.
Science, 353(1-2):103110, 2010.
[24] H. J. Zwijnenberg, A. J.B. Kemperman, M. E. Boerrigter, M. Lotz, J. F.
[4] J. Benavides, J. A. Mena, M. Cisneros-Ruiz, O. T. Ramrez, L. A.
Dijksterhuis, P. E. Poulsen, and G.-H. Koops. Native protein recovery
Palomares, and M. Rito-Palomares. Rotavirus-like particles primary
from potato fruit juice by ultraltration. Desalination, 144(1-3):331
recovery from insect cells in aqueous two-phase systems. Journal of
334, 2002.
Chromatography B, 842(1):4857, 2006.

2014 15th International Carpathian Control Conference (ICCC) 114

Você também pode gostar