SEPARATION PROCESSES WITH MEMBRANE BASED HYBRID

SYSTEMS

Andrzej KOŁTUNIEWICZ

Wrocław University of Technology, Faculty of Chemistry, Department of Chemical

Engineering, Norwida Street 4/6, 50-373 Wroclaw

Separation processes are used to transform a mixtures of substances into two

or more compositionally-distinct products which are isolated in pure form when they
are valuable products. Separation processes are also used for recovery, reuse or
recycling some selected components e.g. water, solvents and chemical agents in
variety of clean technologies. The increased world-wide competitiveness in
production and also policy of sustainable development has attracted the industry
attention onto the exploration of novel concepts required for improve current process
designs. Membrane based hybrid processes have recently emerged as a category of
most effective separation processes. The Webster's Dictionary [1] defines two main
types of “hybrids,” i.e. “an offspring of two animals or plants of different races,
breeds, varieties, species, or genera,” and more general which can be used in
technology, i.e. “something that has two different types of components performing
essentially the same function” [2]. Lipnitzki and Field [3] defined a hybrid process
as a combination consisting of generally different, unit operations, which are
interlinked and optimized to achieve a predefined task. They distinguished two
different groups of hybrid processes, e.g.
1. Hybrid processes consisting of processes which are `essentially performing
the same function'. In this case all processes in the package would be
separation processes.
2. Hybrid processes which are an offspring of two different processes. In the
case of membrane based hybrid processes this group includes the
combination of membranes and a reactor.
This definition includes different unit processes such as extractive
distillation [4] but excludes in-series-processes like a cascade of the same units like
distillation columns or membrane units because the separation in principle could be
achieved in one unit. Hybrid processes are more than just integrated processes. A
true hybrid process take advantage from synergy of integration to solve technical
and economic limitations that apply to at least one of the component unit operations
and that could not be achieved either technically or economically alone'. Hybrid
processes can be easily optimized because they have higher degrees of freedom,
number of parameters and range of operation. Therefore integration of some
conventional processes with membrane separation technologies permits the
rationalization of direct and indirect energy consumption improving at the same time
the product quality and the process capacity and selectivity. The strategy of
introducing hybrid processes in the modern clean technologies is characterized by

32
advanced levels of automation capacity, modularity, and remote control. But it also
includes upgrading and retrofitting of an existing process, thus reducing energy
consumption and low costs, and could be regarded as one means of to form a both
technically and economically viable technologies. According to above mentioned
definitions, the membrane based hybrids can be divided onto the two main groups
including membranes combined with other separation processes [5] and membranes
combined with reactors. However, in practice there are four specific groups that
could be distinguished among membrane separation hybrid systems, e.g. such as
membranes combined with conventional unit processes [6], hybrid processes
combining only different membrane separation processes [7], membrane contactors
and membranes combined with some kind aggregation of separated substances.

MEMBRANE-BASED HYBRID SEPARATION PROCESSES

MEMBRANE + SEPARATION

MEMBRANE + REACTION

Membranes Membranes Membrane Membranes

+ contactors Aggregation
Unit
Process

Membranes+ PV Absorption Adsorption Reactors

Absorption RO Adsorption Ion exchange Photoreactors
Distillation ED Distillation Biosorption Bioreactors
Extraction NF Extraction Complexation Photo bioreactors
Flotation UF Micelles Photo oxidation
Centrifuges MF Flocculation Biooxidation
LM Precipitation Denitrification
Crystallization

Fig.1. Classification of membrane based hybrid processes

Membranes with conventional unit processes

The first known membrane-based separation process was combination of

pervaporation and distillation, being published for the dehydration of isopropanol+
ethanol mixtures by Binning and James [8] in 1958. It can overcome restrictions
encountered using distillation alone, like the addition of a solvent which is removed
in subsequent steps, pressure variations, and a high number of trays in the

33
distillation columns. The PV process is integrated into the distillation process to
reduce the number of trays by processing a side stream of the distillation column or
to split the azeotropes before distillation but also as a polishing step of either the top
or bottom product of the distillation column. Distillation/membrane hybrid processes
have a potential for energy savings and, under some circumstances, are superior to
the single separation processes, especially if high product purities are required.
Design methodology for a membrane/distillation column hybrid process has been
already evaluated [9-13].
Such systems are used for many applications such as: separation of
methanol/MTBE/C, mixture [14], aroma concentrate [15] dewatering of solvents
[16]. It was shown that pervaporation can easily be used to break the azeotrope of
methanol and TAME [17]. Integrated distillation with vapor permeation is used for
dehumidification of compressed air [18]. Distillation is also frequently coupled with
RO in hybrid systems for water desalination, which has been shown to be
technically and economically superior to nonintegrated MSF and RO systems [19]
by improving the performance reducing water cost but also the cost of materials of
construction, equipment, membranes, steam, energy, chemicals, etc. [20, 21]. A
hybrid process that combines a vapor permeation process with absorption and
stripping process was used for removal of volatile organic compounds (VOCs) from
gas streams [22, 23], acetone recovery with hybrid comprising PV and absorption
column [24], removal of VOCs from groundwater with PV and air stripping [25],
removal of acid gases from natural gas [26]. There are also other hybrids of
membranes with unit separation processes, such as systems combine ion-exchange
membranes with solvent extraction processes [27]. Membrane-adsorption hybrid
system may be also performed solely with adsorptive membranes [28]. Membrane
adsorbers are a hybrid synthesis of these two technologies, aiming at combining the
selectivity of chromatography resins with the high productivity associated with
filtration membranes. Like perfusion beads, membrane adsorbers were developed as
an alternative to conventional gel bead chromatography.

Membrane contactors form also the specific group of hybrids with high
level of integration between membranes and such separation processes as
distillation, extraction and absorption or adsorption. In the membrane contactor
these unit processes are performed directly in membrane module where the
membrane plays a role of artificial interface between two fluids with mass transfer
of separated component between them. This technique is performed by inserting a
microporous membrane wall between the feed phase and a stripping phase.
Referring to conventional unit separation processes performed in columns, many
advantages of the membrane contactors can be pointed out. There are no loading,
flooding or emulsification problems, except the pumping of the flowing phases, no
stirring nor is mixing needed. One drawback occurs when using a membrane as it
creates additional resistance that hinders diffusion from one phase to another, thus
slowing down the separation. In most cases, the large surface area per volume

34
offered by hollow fiber modules overcomes this disadvantage. In most cases, the
large surface area per volume offered by hollow fiber modules overcomes this
disadvantage.

Membrane with aggregation process involves bonding of the separated

species firstly to some special bonding agent and then separating the aggregates
from the stream by membrane separation processes. There are several ways of
binding that are used in practice such as adsorption on pulverized adsorbent,
biosorption on microorganisms or some biological materials, complexation [29],
chelating [30], binding on polymers, coagulation, flocculation, precipitation,
crystallization, micellar solubilization etc. Very promising way of the binding is
using ion exchange resins, molecularly imprinted materials, functionalized polymers
etc. It should be noted that several hybrid processes based on aggregation and other
separation processes such as flotation [31-33]or centrifugation [34].

Membrane reactors and membrane bioreactors and photoreactors belong to

the recent achievements in process engineering. Separation of undesired components
may be also carried out throughout their dematerialization by chemical conversion.
Combining a membrane with a chemical reaction has been shown to offer
advantages in a number of different instances [35], which can be performed in
membrane module integrated with reactor or solely in membrane. The catalytic
membrane enables an efficient three-phase contact between gaseous phase, liquid
phase, and the active surface. The pore size of the catalytic layer can be adjusted in
the mesoporous or macroporous range according to the needs of the reaction, with a
narrow pore size distribution. Moreover, the membrane catalyst concept allows a
tuning of the reaction rate by adjusting the pressure to suit variable operating
situations, i.e., different feed concentration, flowrate, and so on[36, 37]. One of
potentials application is the use of Pervaporation process to drive an equilibrated
reaction. Reviews of the literature concerning membrane reactors reveal that a very
large fraction of catalytic membrane reactor applications involves reversible
reactions, which reach a thermodynamically limited conversion level in a
conventional reactor [38-44]. By conducting, these reactions in a catalytic
membrane wherein one product can selectively permeate through the membrane and
out of the reaction zone, an overall conversion is attained which is much greater than
that realized in the conventional reactor [45-56].
The utilization of bioreactors [57] with enzymes or whole cells immobilized
is used in biotechnology and several research areas. The specially challenging task is
the separation of xenobiotic from water and air environment when they are present
even in much diluted form. The specific group comprise so called refractory
chemicals which are very resistant for decomposition. New methods, such as
photocatalytic reactions [58], allow in many cases a complete degradation of organic
pollutants in very small and harmless species, without using chemicals, avoiding
sludge production and its disposal. These processes are based on the electronic

35
excitation of a molecule or solid caused by light absorption (usually UV light) [59]
that drastically alters its ability to lose or gain electrons and promote decomposition
of pollutants to harmless by-products [60-63].

REFERENCES

1. P. B. Grove (Ed.), Webster's Third New International Dictionary of the English

Language, Merriam-Webster, Incorporated Springfield, MA, USA, 1993
2. N. H. Dickey (Ed.), Funk and Wagnalls New Encyclopedia, Funk & Wagnalls
Corporation, NY, USA, 1995
3. F. Lipnizki, R. W. Field, P.-K. Ten, J. Membr. Sci., 153(1999)183
4. A. Szanyi, P. Mizsey, Z. Fonyo, Chem. Eng. Process.,43(2004)327
5. X. Feng, C. Y. Pan, J. Ivory, D. Ghosh, Chem. Eng. Sci., Vol 53. No 9. DD 1689-
1698, 1998
6. J. K. Gienger, R. J. Ray, AIChE Symp. Ser. 84(261)(1988)168
7. R. Wodzki, G. Sionkowski, G. Pozniak, Sep. Sci. Technol., 34(1999)627
8. R. C. Binning, F. E. James, Pet. Renifer, 37(1958)214
9. W. Stephan, R. D. Noble, C. A. Koval, J .Membr. Sci., 99(1995)259
10.T. Pettersen, K. M. Lien, J. Membr. Sci., 99(1995)21
11.A. M. Eliceche, M. C. Daviou, P. M. Hoch, I. O. Uribe Computers Chem. Eng.,
26(2002)563
12.J. Bausa, W. Marquardt, AIChE Annual Meeting 1998, Miami, Florida,
November 16-21, 1998
13.T. Pettersen, K.M. Lien, J. Membr. Sci., 99(1995)21
14.Y. Lu, L. Zhang, H.-L. Chen, Z.-H. Qian, C.-J. Gao, Desalination, 149(2002)81
15.S. Alvarez et al., J. Food Eng., 46(2000)109
16.S. Sommer, B. Klinkhammer, T. Melin, Desalination, 149(2002)15
17.S. Marx, P. van der Gryp, H. Neomagus, R. Everson, K. Keizer, J. Membr. Sci.,
209(2002)353
18.Y. Wu, et al., J. Membr. Sci., 196(2002)179
19.E. El-Sayed, et al., Desalination, 128(2000)231
20.A. M. Helalet al., Desalination, 154(2003)43
21.E. El-Sayed et al. Desalination, 128(2000)231, E. Cardona et al., Desalination,
153(2002)167
22.T. K. Poddarl, K. K. Sirkar, J. Membr. Sci., 132(1997)229
23.D. Roizarda, V. Teplyakov, E. Favre, L. Fefilatiev, N. Lagunstsov, V.
Khotirnsky, Desalination, 162(2004)41
24.E. Marki, B. Lenti, Gy. Vatai, E. Bekassy-Molnar, Sep. Pur. Technol., 22-
23(2001)377
25.M. R. Shah, R. D. Noble, D. E. Clough, J. Membr. Sci., 241(2004)257
26.B. D. Bhide, A. Voskericyan, S. A. Stern, J. Membr. Sci., 140(1998)27
27.S. E. Kentish, G. W. Stevens, Innovations in separations technology for the
recycling and re-use of liquid waste streams
28.L. R. Castilho, F. B. Anspachl, W.-D. Deckwer, J. Membr. Sci., 207(2002)253

36
29.P Baticle, C. Kiefer, N. Lackhchaf, O. Leclerc, M. Persins, J. Sarrazin, Sep.
Purif. Technol., 18(2000)195
30.A. Kryvoruchko, L. Yurlova, B. Kornilovich, Desalination, 144(2002)243
31.C. Blocher et al., Water Res., 37 (2003)4018
32.V. Mavrov, T. Erwe, C. B1ocher, H. Chmiel, Desalination. 157(2003)97
33.N. K. Lazaridis, C. Blöcher, J. Dorda, K. A. Matis, J. Membr. Sci., 228(2004)83
34.E. Turano, S. Curcio, M. G. De Paola, V. Calabrò, G. Iorio, J. Membr. Sci.,
209(2002)519
35.Q. L. Liu, H. F. Chen, J. Membr. Sci., 196(2002)171
36.K. Daub, R. Dittmeyer, Proceedings of the 15th International Symposium on
Chem. React. Eng. (ISCRE 15), Newport Beach, CA, September 13–16, 1998
37.K. Daub, G. Emig, M.-J. Chollier, M. Callant, R. Dittmeyer, Chem. Eng. Sci.,
54(1999)1577
38.K. Mohan, R. Govind, AIChE J., 34(1988)1493
39.K. Mohan, R. Govind, AIChE J., 32(1986)2083
40.K. Mohan, R. Govind, Ind. Eng. Chem. Res., 27(1988)2064
41.N. Itoh, AIChE J., 33(1987)1576
42.Y. M. Sun, S. J. Khang, Ind. Eng. Chem. Res., 29(1990)232
43.Y. M. Sun, S. J. Khang, Ind. Eng. Chem. Res., 29(1990)232
44.S. Vemiya, N. Sato, H. Ando, E. Kikuchi, Ind. Eng. Chem. Res., 30(1991)585
45.I. K. Song, W. Y. Lee, Appl. Catal. A: Gen., 96(1993)53
46.H. Kita, K. Tanaka, K. Okamoto, M. Yamamoto, Chem. Lett., (1987)2053
47.M. O. David, Q. T. Nguyen, J. Neel, J. Membr. Sci., 73(1992)129
48.K. Okamoto, M. Yamamoto, Y. Otoshi, T. Semoto, J. Chem. Eng. Jpn.,
26(1993)475
49.H. Kita, S. Sasaki, K. Tanaka, K. I. Okamoto, M. Yamoto, Chem. Lett.,
(1988)2025
50.H. Kita, S. Sasaki, K. Tanaka, K. I. Okamoto, M. Yamoto, Chem. Lett.,
(1988)2025
51.X. Feng, R. Y. M. Huang, Chem. Eng. Sci., 51(1996)4673
52.L. Bagnell, K. Cavell, A. M. Hodges, A. W. H. Mau, A. J. Seen, J. Membr. Sci.,
85(1993)291
53.Q. Liu, P. Jia, H. Chen, J. Membr. Sci., 159(1999)233
54.M. O. David, R. Gref, Q. T. Nguyen, J. Neel, Trans. Inst. Chem. Eng.,
69(1991)335
55.M. O. David, R. Gref, Q. T. Nguyen, J. Neel, Trans. Inst. Chem. Eng.,
69(1991)341
56.Q. L. Liu, Y. S. Zhu, H. F. Chen, J. Chem. Eng. Chin. Univ., 11(1997)172
57.V. Calabrò, S. Curcio, G. Iorio, J. Membr. Sci., 206(2002)217
58.R. Molinari, L. Palmisano, E. Drioli, M. Schiavello, J. Membr. Sci.,
206(2002)399
59.H. Hyung, S. Lee, J. Yoon, C. Lee, Ozone Sci. Eng., 22(2000)637
60.K. Rajeshwar, Chem. Industry, 2(1996)135

37
61.M. Schiavello (Ed.), Photoelectrochemistry, Photocatalysis and Photoreactors,
Fundamentals and Developments, Reidel, Dordrecht, 1985
62.E. Pelizzetti, N. Serpone (Eds.), Photocatalysis. Fundamentals and Applications,
Wiley, New York, 1989
63.C. Regnault, I. Kano, D. Darbouret, S. Mabic, J. Chromatog. A, 1030(2004)289

38