Reactive and Hybrid Separations: Incentives, Applications, Barriers

8
Reactive and Hybrid Separations:

Incentives, Applications, Barriers
Andrzej Stankiewicz
DSM Research, Geleen, The Netherlands
1. INTRODUCTION
Integration of various steps/operations presents one of the most promising ways
for intensifying (bio)chemical processes. It can be achieved either by combining
reaction and separation in a single reactive separation step or by combining two
(or more) separation techniques in a hybrid separation unit. Such an integration
may bring a number of advantages to the process under consideration, not just a
decrease in the size of equipment.
This chapter provides a general overview of the reactive and hybrid sep-
arations and discusses their place in the intensification of (bio)chemical processes.
Written from an industrial point of view, it focuses on the application aspects of
those integrative technologies. Potential application fields are reported, along
with already existing commercial-scale operations. Special attention is given to
the barriers that hamper a broader introduction of the reactive and hybrid separ-
ations into industrial practice and the ways to overcome those barriers. The mod-
eling and design aspects of three reactive separation methods (reactive
distillation, reactive absorption, and reactive extraction) are discussed in more
detail in Chapter 9.
Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

2. REACTIVE SEPARATIONS—WHY INTEGRATE?
In the simplest case, integration of reaction and separation may take place on the
purely equipment level, without introducing any new functional interrelations
between the operations involved—the reaction does not influence the separation,
nor has the separation process any effect upon the reaction. The aimed result of
such combination can be:
Lower investment costs (compact plant layout, integral design)
Smaller inventory (safety aspects)
Improved heat management/energy utilization.
The Urea 2000plus™ technology, developed by Stamicarbon B.V. (1) and
described further in Chapter 12, presents a typical example of such a “noninter-
relating” integration. The integration resulted here in a considerably smaller and
cheaper plant, with much less high-pressure equipment/piping needed and less
energy consumption. Yet the interrelations between the reaction and other oper-
ations remained basically the same as in the conventional technology.
In most cases, however, the reaction and separation are integrated in order
to benefit from the interaction effect between those two, for instance,
To improve yield/selectivity (e.g., via equilibrium shift)
To facilitate separation (e.g., azeotrope problems)
For other reasons, e.g., to extend the catalyst lifetime
One speaks in those cases about reactive separations or separative reactors.
The industrially important reactive separations include:
Reactive distillation
Membrane-based reactive separations
Reactive adsorption
Reactive absorption
Reactive extraction
Reactive crystallization
2.1. Reactive Distillation

In most industrial applications the reactive distillation is used to improve the
yield/selectivity of the required product. Figure 1 shows three examples of indus-
trial processes, in which combination of reaction and distillation shifts the equil-
ibrium of the reaction A B ↔ C D in the required direction (2). The length
of the reacting, distillation, and stripping zones as well as the positioning of the
reactant inlets vary in each particular case, depending on the process requirements.
On the other hand, in selective hydrogenations of dienes and aromatics (3), reactive
distillation is used to remove the single-hydrogenated product from the reaction

FIGURE 1 Examples of industrial processes employing reactive distillation:
(a) methyl tert-butyl ether (MTBE) from isobutene and methanol; (b) cumene
via alkylation of benzene with propylene; (c) ethylene glycol via hydration of
ethylene oxide.
zone, thus preventing its further hydrogenation and increasing its yield. In the
methyl acetate technology of Eastman Chemical, integration of reactive distillation
with extractive distillation in a single unit totally solved the azeotrope problem (4).
Reactive distillation can also be used as a powerful separation method in case
of mixtures containing reactive and inert components with close boiling points.
The method is schematically depicted in Figure 2. Here, a reactive entrainer is
introduced to the first reactive distillation column, to form an intermediate prod-
uct having a boiling point much more distant from the boiling point of the inert
components. In the first column, inert components are therefore easily separated,
while the intermediate product is fed to the second reactive distillation step,
where the reversed reaction takes place and the original reactive component is
recovered and separated from the entrainer. Stein et al. (5) investigated the appli-
cation of this principle to the separation of close-boiling i-butene and n-butene,
using methanol as a reactive entrainer.
Obviously, reactive distillation may lead to significant savings on energy.
Hydrolysis of methyl acetate presents an industrial example of such energy savings.

The heat requirements of the reactive distillation-based process are ca. 50% lower
than in the conventional technology. In the alkylation of benzene to cumene reac-
tive distillation effectively eliminated the hot spots and reduced the oligomeriza-
tion of propylene (6).
Table 1 gives an overview of the possible applications of reactive distillation
reported in the literature. Very few of them have been realized so far on the com-
mercial scale. One of the common factors that hinders a broader application of
reactive distillation is a small feasible operation window. The overlap region in the
pressure–temperature domain, in which chemical reaction and separation and appa-
ratus design are feasible, is usually quite narrow (see Figure 2 in Chapter 9). A
possible remedy for this limitation is sought in the development of new types of
catalysts that would allow one to significantly broaden the feasible operation win-
dow for chemical reaction.
2.2. Membrane-Based Reactive Separations

Sirkar et al. (64) give an interesting overview of various functions that a mem-
brane may play in a chemical reactor. Those functions are schematically shown
in Figure 3 and summarized in Table 2.
FIGURE 2 Separation of reactive and inert components with close boiling

points, facilitated by reactive distillation. (From Ref. 5.)

TABLE 1 Reported Existing and Potential Applications of Reactive
Distillation
Product/process Selected refs.
Butyl acrylate from butanol and acrylic acid 7

n-Butyl acetate from n-butanol and acetic acid 8
Ethyl acetate from ethanol and acetic acid 9,10
Methyl acetate from methanol and acetic acid 11,12
Hydrolysis of methyl acetate 13
2-Methylpropylacetate from 2-methylpropanol 14
and acetic acid
Amyl acetate from amyl alcohol and acetic acid 15
Ethyl pentenoate from ethanol and pentenoic acid 16
Esterification of fatty acids 17
Methylal from formaldehyde and methanol 18,19
TAME (tertiary amyl ether) 20–22
MTBE (methyl tert-butyl ether) 23,24
ETBE (ethyl tert-butyl ether) from ethanol and 25,26
isobutene
ETBE (ethyl tert-butyl ether) from bioethanol and 27
tert-butylalcohol
Diisopropyl ether from propene 28
TAA (tert-amyl alcohol) via hydration of isoamylene 29
Isopropanol via hydration of propene 30
Cyclohexanol via hydration of cyclohexene 31,32
Phenol from cumene 33
Ethylene glycol via hydration of ethylene oxide 34,35
Isobutene via dehydration of tert-butanol 36–38
Isoamylenes via dehydration of 2-methyl-1-butanol 39
Isophorone from acetone 40
MIBK (Methyl iso-butyl ketone) from acetone 41,42
Diacetone alcohol (DAA) and mesityl oxide (MO) via 43,44
aldol condensation of acetone
Acetone via dehydrogenation of propanol 45
Tetrahydrofuran from butanediol 46
Xylenes via toluene disproportionation 47
Hydrogenation of unsaturated hydrocarbons 48,49
Isomerization of C5-C6 paraffins 50
Isobutene via hydroisomerization of C4 alkenes 51
Cumene via alkylation of benzene with propylene 52
Ethylbenzene via alkylation of benzene with ethylene 53,54
Cyclopentane and/or cyclopentene from 55
dicyclopentadiene
Purification of hydrofluorocarbons 56

TABLE 1 (cont.)
Naphtha desulfurization 57
Dihydroxy polyether polyol via alkanolysis of 58
corresponding diesters
Glycine from glycinonitryle 59
DEC (diethylcarbonate) via carbonylation of ethanol 60
with dimethylcarbonate
Polyamides (e.g., Nylon 6) via hydrolytic 61
polymerization of amino nitriles
Nylon 66 via polycondensation 62
Propylene oxide from propylene chlorohydrin 63
and calcium hydroxide
Among all the membrane functions listed in Table 2, catalytic membranes

probably attract the most attention. The scientific literature on catalytic membrane
reactors is exceptionally rich and includes many interesting ideas, such as heat- and
mass-integrated combination of hydrogenation and dehydrogenation processes in
a single membrane unit. Yet practically no large-scale industrial applications of
catalytic membrane reactors have been reported so far, perhaps with the excep-
tion of the Russian vitamin K technology (65). The primary reason for this is the
relatively high price of membrane units, although other factors, such as low per-
meability, sealing problems, as well as mechanical and thermal fragileness of the
membranes, also play an important role. Further developments in the field of
material engineering will surely change this picture.
Possible application areas of catalytic membrane reactors include:
Dehydrogenations, e.g., ethane to ethene, ethylbenzene to styrene, methanol
to formaldehyde
Methane steam reforming
Water–gas shift reaction
Selective oxidations, e.g., propane to acroleine, butane to maleic anhydride,
ethylene to ethylene oxide
Oxidative dehydrogenations of hydrocarbons
Oxidative coupling of methane
Methane oxidation to syngas
An excellent review of all potential applications of catalytic membrane reactors
studied so far can be found in the 2002 book by Sanchez Marcano and Tsotsis (66).
On the other hand, membranes are frequently employed in combination with
a bioreactor, for instance, in enzymatic pharmaceutical processes. An example

of such an application of an ultrafiltration membrane-reactor system for the pro-
duction of s-ibuprofen is discussed further in Chapter 12.
2.3. Reactive Adsorption

The vast majority of possible applications of reactive adsorption aim at the improve-
ment of the product yield by shifting the equilibrium in the required direction. In
contrast to the nonreactive adsorption techniques, such as simulated moving beds
and pressure-swing adsorption, and despite its great potential [for example, a
12-fold higher conversion per pass in oxidative methane coupling (67)], the
FIGURE 3 Membrane functions in chemical reactor. (Reproduced with per-

mission from Sirkar et al. (64), copyright (1999) American Chemical Society.)

TABLE 2 Membrane Functions in Chemical Reactor Systems
Function Examples
Separation of products from In situ product removal from enzymatic

the reaction mixture reactor via a nanofiltration or
ultrafiltration membrane
Removal of selected enantiomer via
a liquid membrane
Removal of water in esterification
reactions via a pervaporation
membrane
Hydrogen removal in catalytic
dehydrogenation reactions
Separation of a reactant from Separation of oxygen from air for
a mixed stream for intro- oxidizing methane to syngas
duction into the reactor Separation of hydrogen from
dehydrogenation reaction to oxidize
it with oxygen on permeate side
Separation of organic priority
pollutants from wastewater for
biological purification
Controlled addition of one Controlled oxygen addition in partial
reactant or two reactants oxidation reactions (to increase
selectivity)
Controlled air introduction in oxidative
dehydrogenations
Nondispersive phase contacting, Emulsion-free enzymatic splitting of
with reaction at the phase fats
interface or in the bulk phases Bubble-free oxygen/ozone supply in
wastewater treatment via hollow-
fiber membranes
Segregation of a catalyst Segregation of enzymes with respect
(and cofactor) in a reactor to molecular weight on ultrafiltration
membranes
Immobilization of a catalyst Immobilization of enzymes or cells on
in (or on) a membrane polymeric membranes
Immobilization of metals (Pd, Pt) on
ceramic membranes
Membrane is the catalyst Cation exchange membranes for
esterification reactions
Palladium membranes for
hydrogenation/dehydrogenation
reactions

TABLE 2 (cont.)
Function Examples
Membrane is the reactor Reactions in flow-through membrane

systems (“pore flow-through
reactors”)
Solid electrolyte membrane Solid electrolyte membranes such as
supports the electrodes, H and O2 conductors in fuel cells
conducts ions, and achieves
the reactions on its surface
Transfer of heat Membranes coupling endo- and
exothermic reaction zones (e.g.,
hydrogenation–dehydrogenation)
Immobilizing the liquid Supported liquid membranes (SLM) for
reaction medium homogeneous catalytic processes
Source: Ref. 64.
industrial-scale applications of adsorptive reactors remain to be seen. Challenges

involve materials development of catalysts/adsorbents and matching of process
conditions (same temperature) for both reaction and adsorption so that high yields/
selectivities can be achieved. Reactive adsorption processes investigated in the
bench or pilot scale are numerous, as shown in Table 3.
One of the more promising types of adsorptive reactors is the so-called gas–
solid–solid trickle-flow reactor (GSSTFR), in which fine adsorbent trickles through
the fixed bed of catalyst (Figure 4), removing selectively in situ one or more of
the products from the reaction zone. In the case of methanol synthesis this led to
conversions significantly exceeding the equilibrium conversions under the given
conditions (98). The economics of the methanol process based on the gas–solid–
solid trickle-flow reactor was evaluated and compared with the conventional low-
pressure Lurgi process (99). For the production scale of 1000 tons per day, the new
technology offered considerable reductions in cooling water consumption (50%),
recirculation energy (70%), raw materials (12%), and catalyst amount (70%).
Further improvement of the GSSTFR concept could be seen in applying a mov-
ing bed of adsorbent through straight, parallel channels of a monolithic catalyst,
similar to the one shown in Figure 23 of Chapter 6.
2.4. Reactive Extraction

Similar to reactive adsorption, the reactive extraction can be applied primarily in
multireaction systems, for improvement in yields and selectivities to desired prod-
ucts. The combination of reaction with liquid–liquid extraction can also be used

TABLE 3 Processes Investigated in Reactive Adsorption Systems
Process Selected refs. Reactor type
Esterification of glycerin with acetic acid 68 Simulated moving bed chromatographic reactor
(SMBCR)
Methyl tert-butyl ether (MTBE) synthesis 69,70 SMBCR
Hydrolysis of methyl formate 71 Discontinuous chromatographic reactor
Oxidative coupling of methane 67,72 SMBCR
Enzymatic production of L-amino acids 73 Centrifugal partition chromatographic reactor
Oxidation of phenols 74 Chromatographic reactor
Ethyl acetate from ethanol and acetic acid 75 Chromatographic reactor
Enzymatic inversion of sucrose 76 SMBCR
77 Rotating cylindrical annulus chromatographic
reactor (RCACR)
Dehydroisomerization of n-butane 78 Chromatographic pulse reactor
to isobutene
Mesitylene hydrogenation 72 SMBCR
Hydrogenation of 1,3,5-trimethylbenzene 79,80 SMBCR
Biosynthesis of dextran polymer 81 Chromatographic pulse reactor
from sucrose
Dissociation of dicyclopentadiene 82,83 SMBCR
Dehydrogenation of cyclohexane 84 Chromatographic pulse reactor
85 RCACR
Ascorbic acid synthesis 86 SMBCR
Regioselective enzymatic 87 SMBCR
diol esterification
88 Batch and fixed-bed adsorptive
reactors

TABLE 3 (cont.)
Process Selected refs. Reactor type
Oxidation of lean VOC mixtures 89 SMBCR

Hydrolysis of methyl formate 90 RCACR
Enzymatic production of lactosucrose 91 SMBCR
from sucrose and lactose
Diethylacetal from ethanol and 92 Fixed-bed adsorptive reactor
acetaldehyde
Steam methane reforming 93 Pressure-swing adsorptive reactor (PSAR)
Propene metathesis to ethene 94 PSAR
and 2-butene
1-Butene dehydrogenation to 95 Rapid PSAR
1,3-butadiene
Sulfur from H2S (Claus process) 96 Reverse-flow adsorptive reactor
HCN from carbon monoxide 96 Reverse-flow adsorptive reactor
and ammonia
6-Aminopenicillanic acid from 97 Trickle-flow fluidized-bed reactor
penicillin G
Methanol synthesis 98,99 Gas–solid–solid trickle-flow reactor (GSSTFR)

FIGURE 4 Gas–solid–solid trickle-flow reactor. (From Ref. 98.)
for the separation of waste by-products that are hard to separate using conven-
tional techniques (100,101). An overview of processes studied in reactive extrac-
tion systems is shown in Table 4.
In 2002, an interesting concept was proposed for coupling a CO2-based
supercritical extraction with air oxidation in order to remove and decompose pol-
lutants from gases or liquids (134). An exemplary process scheme according to
this preliminary concept is shown in Figure 5. Possible (future) environmental
applications of such an integrated supercritical extraction-reaction system include
treatment of liquid effluents, regeneration of catalysts and adsorption materials,
and soil decontamination.

2.5. Reactive Crystallization/Precipitation
Reactive crystallization/precipitation plays a role in a number of industrially
relevant processes, such as liquid-phase oxidation of para-xylene to produce
technical-grade terephthalic acid, the acidic hydrolysis of sodium salicylate to
salicylic acid, and the absorption of ammonia in aqueous sulfuric acid to form
ammonium sulfate (135). Reactive crystallization/precipitation is also widely
applied in the pharmaceutical industry, to facilitate the resolution of the enan-
tiomers (diastereomeric crystallization). Here, the racemate is reacted with a spe-
cific optically active material (resolving agent) to produce two diastereomeric
derivatives (usually salts) that are easily separated by crystallization:
( DL )-A ( L )-〉 → ( D)-A ⋅ ( L )-〉 ( L )-A ⋅ ( L )-〉
racemate resolving agent n-salt p-salt
TABLE 4 Some Processes Studied in Reactive Extraction Systems

Penicillin G recovery 102–106

Downstream separation of 1,3-propanediol 107
Separation of lactic acid 108–111
Separation of organic acids from the products of 112
partial oxidation of paraffins
Separation of salicylic acid 113,114
Separation of D,L-phenylalanine 113,115
Separation of citric acid 116
Separation of aspartic acid 117
Cephalosporin C recovery 118
Separation of metals (e.g., zinc) 119–121
Phenolic wastewater treatment 122
Separation of dicarboxylic acids (e.g., oxalic, malonic, 123
succinic, adipic acid)
Recovery of gallium from coal fly ash 124
Recovery of palladium, platinum, rodium from 125
leaching solutions
Fractionation of amino acids 126
Recovery of 7-ACA (7-aminocephalosporanic acid) 127
Recovery of erythromycin 128
Removal of toxic heavy metals from wastewater streams 129,130
Production of dioxolane from aldehyde 131
Recovery of aldehydes and ketones from hydrocarbon 132
mixtures
Production of cyclic ester oligomers from linear polyesters 133

FIGURE 5 Countercurrent supercritical extraction coupled with air oxidation
to remove and decompose pollutants from gases and liquids. (From Ref.
134.)
Diastereomeric crystallization is commonly used in the production of a number

of pharmaceuticals, such as ampicillin, ethambutol, chloramphenicol, diltiazem,
fosfomycin, and naproxen (136).
Somewhat similar are the so-called adductive crystallization processes,
often (wrongly) called extractive crystallization, where reactions of complex/
adduct formation are used to separate compounds that are otherwise difficult to
separate. Examples of adductive crystallization include separation of p- and m-
cresols (137), separation of o- and p-nitrochlorobenzenes (138), separation of
quinaldine and isoquinoline (139), separation of nonaromatic compounds from
naphtha-cracking raffinate (140), and separation of p-cresol from 2,6-xylenol
(141). Other examples of reactive crystallization/precipitation reported in the lit-
erature are listed in Table 5.
Reactive crystallization/precipitation can also be conducted in high-gravity
(Higee) fields using rotating equipment. In China this technique has been used
successfully for the production of nano-size particles of CaCO3. Ultrafine particles

with the mean size of 15–40 nm and a very narrow size distribution were pro-
duced by carbonation of a lime suspension in a rotating packed-bed reactor (RPBR)
(158). The reaction times in RPBR were 4- to 10-fold shorter than the correspon-
ding reaction times in a conventional stirred-tank unit. A similar technique was
used for the production of nanofibrils of aluminum hydroxide with a diameter of
1–10 nm and 50–300 nm long as well as nanoparticles of SrCO3 with a mean size
of 40 nm (159).
2.6. Reactive Absorption/Stripping

Reactive absorption is very old as a processing technique and has been used for
production purposes in a number of classical bulk-chemical technologies, such as
nitric or sulfuric acid. The Raschig process for the production of hydroxylamine,
an important intermediate in classical caprolactam technologies (Stamicarbon,
Inventa), is also an example of a multistep reactive absorption process. Here,
water, ammonia, and carbon dioxide react together in an absorption column to
give a solution of ammonium carbonate, which subsequently forms an alkaline
TABLE 5 Examples of Reactive Crystallization/Precipitation

Selected
Product refs. Remarks
Calcium carbonate 142,143 Liquid–liquid and gas–liquid

reaction systems
Methyl -methoximino 144
acetoacetate
Magnesium hydroxide 145,146
Calcium phosphate 147,148
Magnesium ammonium 149 Removal of ammonium and
phosphate phosphate ions from
wastewater
Lead sulfate 150
Magnesium carbonate 151
Nickel hydroxide 152
Ziprasidone–HClH2O 153 Conducted in impinging
fluid jet stream system
Barium carbonate 154 To remove CO2 from waste
gas
Boric acid 155 Reaction of borax solution
with solid oxalic acid
Procaine benzylpenicillin 156
Sulfamic acid 157 From urea and fuming H2SO4

solution of ammonium nitrite by reactive absorption of nitrous oxide at low tem-
perature. In a further step, the ammonium nitrite is converted to hydroxylamine
disulfonate with sulfur dioxide. The hydroxylamine disulfonate solution is drawn
off and the salt is hydrolyzed and neutralized to give hydroxylamine sulfate and
ammonium sulfate as coproduct.
Carbon dioxide removal by reactive absorption in amine solutions is also
applied on the commercial scale, for instance, in the treatment of flue gas (see
later in this chapter). Another possible application field of the technique is gas
desulfurization, in which H2S is removed and converted to sulfur by means of
reactive absorption. Aqueous solutions of ferric chelates (160–162) as well as
tetramethylene sulfone, pyridine, quinoline, and polyglycol ether solutions of
SO2 (163,164) have been proposed as solvents. Reactive absorption can also be
used for NOx reduction and removal from flue or exhaust gases (165,166). The
separation of light olefins and paraffins by means of a reversible chemical com-
plexation of olefins with Ag(I) or Cu(I) compounds in aqueous and nonaqueous
solutions is another very interesting example of reactive absorption, one that
could possibly replace the conventional cryogenic distillation technology (167).
3. HYBRID SEPARATIONS
Generally speaking, hybrid separations can be described as processing methods that
integrate two or more different separation techniques in a single operation, making
use of the synergy between them. The industrially most important (or promising)
hybrid separations include:
Extractive distillation
Adsorptive distillation
Membrane distillation
Membrane absorption/stripping
Adsorptive membranes (membrane chromatography)
Membrane extraction
3.1. Extractive Distillation

Extractive distillation is probably the oldest and most widely applied type of
hybrid separation, particularly useful in close-boiling-point problems or in sys-
tems in which components form azeotropes. In the method, an extra component
(solvent) is added to the system, which does not form azeotropes with feed com-
ponents. The solvent alters the relative volatility of original feed components,
allowing one to distill overhead. The solvent leaves the column with the bottom
products and is separated in a binary column. Energy savings represent the most
important advantage of extractive distillation over the conventional (nonhybrid)
separation methods (168,169).

FIGURE 6 Scheme of aromatics separation via extractive distillation in the
BTX process of the GTC Technology Corp.
Originally, extractive distillation was limited to two-component problems.

However, recent developments in solvent technology enabled applications of
this hybrid separation in multicomponent systems as well. An example of such
application is the BTX process of the GTC Technology Corp., shown in Figure 6,
in which extractive distillation replaced the conventional liquid–liquid extraction
to separate aromatics from catalytic reformate or pyrolysis gasoline. This led to a
ca. 25% lower capital cost and a ca. 15% decrease in energy consumption (170).
Some other examples of existing and potential applications of the extractive dis-
tillations are listed in Table 6.
Solvents used for extractive distillation vary considerably, but in almost all
cases solvent selection presents a trade-off between its selectivity and solvency
(194). The effectivity of the solvent can sometimes be improved by the addition
of a salt (195).
3.2. Adsorptive Distillation

Although considered by some authors a “novel process,” adsorptive distillation is
a relatively old hybrid separation, originating in the early 1950s (196). It is a

TABLE 6 Reported (Potential) Applications of Extractive Distillation
Selected
Separation process refs. Remarks
High-purity cyclohexane 171 Close-boiling-point problem

from petroleum
Benzene and toluene 172,173 Close-boiling-point problem
from nonaromatics
Isopropyl ether from acetone 174 Azeotrope problem
Methyl acetate from 175 Azeotrope problem
methanol
Anhydrous ethanol from 176 Azeotrope problem
fermentation broth
Ethyl acetate from 177 Azeotrope problem
ethanol/water
Ternary acetate–alcohol–water 178 Azeotrope problem
systems (propyl, butyl,
amyl, hexyl)
m-Xylene from o-xylene 179 Close-boiling-point problem
MTBE from impurities 180 Close-boiling-point problem
Binary mixtures of 181 Close-boiling-point problem
lower-boiling alcohols
Binary mixtures of 182,183 Close-boiling-point problem
phenolic compounds
(chlorophenol, phenol,
cresol, xylenol)
Acetone from water 184 Azeotrope problem
Ethanol dehydration 185 Azeotrope problem
C2 alcohols from water 186 Azeotrope problem
Cyclohexane-cyclohexene- 187 Close-boiling-point problem
benzene
MTBE from ethanol 188 Azeotrope problem
Methylcyclohexane from 189 Close-boiling-point problem
toluene
Anhydrous ethanol recovery 190 Azeotrope problem
from wastewater streams
Propylene from propane 191 Close-boiling-point problem
1-Butene from 1,3-butadiene 192,193 Close-boiling-point problem
three-phase mass transfer operation in which distillation is carried in presence of

a solid selective adsorbent. The adsorbent usually consists of a fine powder (parti-
cle size in the 10-m range), fluidized and circulated by an inert carrier. The
process is typically carried in two columns: an adsorptive distillation column for
increasing separation ability, and a distillative desorption column for enhancing

the regeneration of the adsorbent. As in the case of extractive distillation, adsorp-
tive distillation also can be used for the separation of mixtures containing close-
boiling components or to bypass the azeotrope. Another interesting potential
application field is the removal of trace impurities in the production of fine chem-
icals. The simplest scheme of an adsorptive distillation system for separating a
binary mixture of azeotrope-forming components is shown in Figure 7. Here,
adsorbent S carried by an inert fluid carrier enters the adsorptive distillation col-
umn, selectively adsorbs component B from the feed, and flows to the desorption
(stripping) column, in which separation and enrichment of B takes place. Figure 8
shows another variant of adsorptive distillation, as proposed in a patent by Shell
(197), for improved separation of closely-boiling hydrocarbon mixtures. Here an
extra stripping medium (e.g., pentane) is used to remove the adsorbate in the
stripping column.
Despite an almost 50-year history, no large-scale commercial processes
using adsorptive distillation have been reported so far. Some potential application
fields for this hybrid separation are listed in Table 7.
FIGURE 7 Scheme of an adsorptive distillation system for the separation of

azeotrope-forming components A and B (S–adsorbent).

FIGURE 8 Simplified scheme of an adsorptive distillation–based separation
of closely boiling hydrocarbon mixtures. (From Ref. 197.)
3.3. Membrane Distillation

Membrane distillation is considered a promising separation method applicable pri-
marily in environmental technologies. In membrane distillation a microporous and
hydrophobic membrane separates aqueous solutions at different temperatures and
compositions, as shown in Figure 9. The temperature difference existing across the
membrane results in a vapor pressure difference. The molecules are transported
through the pores of the membrane from the high-vapor-pressure side to the low-
vapor-pressure side. At least one side of the membrane remains in contact with the
liquid phase. Benefits offered by membrane distillation include (202):
100% (theoretical) rejection of ions, macromolecules, colloids, cells, and
other nonvolatiles
Lower operating temperatures than conventional distillation
Lower operating pressures than conventional pressure-driven membrane
separation
Reduced chemical interaction between membrane and process solutions
Less demanding membrane mechanical property requirements
Reduced vapor spaces compared to conventional distillation

Membrane distillation systems may be classified into four different cat-
egories (203):
Direct contact membrane distillation (DCMD), in which the membrane is
in direct contact with the liquid phase on both sides
Air-gap membrane distillation (AGMD), in which an air gap is interposed
between the membrane and the condensation surface
Vacuum membrane distillation (VMD), in which the vapor phase is evacu-
ated from the liquid through the membrane and the condensation takes
place in a separate apparatus
Sweeping-gas membrane distillation (SGMD), in which a stripping gas,
instead of vacuum, is used as a carrier
Currently, the most important application area for membrane distillation is
water desalination technology. Figure 10 shows one of the water desalination
processes developed by a Japanese organization, the Water Re-Use Promotion
Center, in cooperation with Takenaka Corporation and Organo Corporation (204).
The process uses solar energy and can therefore be installed at locations without
an electricity supply. Other application areas for membrane distillation reported
in the literature are summarized in Table 8.
In 2002, the TNO Environment, Energy and Process Innovation institute
in the Netherlands developed a membrane-based distillation concept that radically
improves the economy and ecology of existing desalination technology for
TABLE 7 Potential Application Fields of Adsorptive Distillation Reported

in the Literature
Selected
System refs. Remarks
Toluene–methylcyclohexane 196 Suitable adsorbents: silica gel,

mixtures and other activated carbon, coconut
closely boiling charcoal, bauxite,
hydrocarbons activated alumina
Naphtha reformate and 197 Silica gel as adsorbent
other close-boiling
hydrocarbons
o-Xylene–m-xylene mixture 198 Modeling study
Ethanol–water and ethyl 199,200 Zeolite (4A molecular sieve)
acetate–water–n-butanol as adsorbent, glycol as
mixtures carrier
p-Xylene–m-xylene mixture 201 Zeolite (NaY molecular sieve)
as adsorbent, n-decane as
carrier

FIGURE 9 Scheme of a membrane distillation process.
seawater and brackish water. This so-called Memstill® technology (Figure 11a)
combines multistage flash and multieffect distillation modes into one membrane
module. Since the Memstill® module houses a continuum of evaporation stages
in an almost ideal countercurrent flow configuration, a very high recovery of the
evaporation heat is possible. The economic advantage of the Memstill® technol-
ogy, compared to the “classical” desalination techniques, is shown in Figure 11b.
An academic-industrial consortium is currently developing and improving the
Memstill® process concept and module design (226). The same TNO Institute
has also developed a concept of another membrane-based distillation technology
for fractionation of non-water-based systems (227). The technology, called
MEMFRAC, offers high energy efficiency in compact equipment. The study car-
ried out for fractionation of benzene from toluene showed that with MEMFRAC
technology a HETP between 5 and 10 cm could be obtained. Additional advan-
tages of the MEMFRAC technology include: lack of entrainment, flooding, foam-
ing, or channeling (due to indirect gas–liquid contact), independent gas/liquid
control, and the possibility for modular plant design. Such a modular MEMFRAC
distillation unit is schematically presented in Figure 12.
On the other hand, a pervaporation membrane can be coupled with a con-
ventional distillation column, resulting in a hybrid membrane/distillation process
(228,229). Some of the investigated applications of such hybrid pervaporation
membrane/distillation systems are shown in Table 9. In hybrid pervaporation/
distillation systems, the membrane units can be installed on the overhead vapor
of the distillation column, as shown in Figure 13a for the case of propylene/
propane splitting (234), or they can be installed on the feed to the distillation column,

FIGURE 10 Scheme of the demonstration test plant for water desalination using solar energy and membrane distillation.
(Courtesy: CADDET, Center for Renewable Energy, Harwell, UK).

TABLE 8 Application Areas of Membrane Distillation
Selected
System/process refs. Remarks
Concentration of H2SO4, 205–207

H3PO4, NaOH, HNO3, and
HCl solutions
Concentration of 2,3-butanediol 208 VMD process
from fermentation broths
Wastewater treatment in 209 Integrated reverse
the textile industry osmosis/membrane
distillation process
Radioactive wastewater 210 Integrated reverse
treatment osmosis/membrane
distillation process
Removal of benzene traces 211 VMD process
from water
Concentration of protein solutions 212
Removal of halogenated VOCs 213 VMD process
Concentration of oil–water 214
emulsions
Concentration of sugar/sucrose 215,216 DCMD and AGMD
solutions processes
Separation of water and glycols 217 DCMD process
Ethanol–water separation 218 AGMD process
Acetone and ethanol removal 219 AGMD process
from aqueous solutions
Propanone removal from 220 AGMD process
aqueous streams
Acetone–butanol–ethanol 221 AGMD process
(ABE) solvent recovery
Fermentative ethanol 222,223 Integration of MD in
production fermentation resulted
in ca. 2 increase of
production rate
Concentration and purification 224
of fluosilicic acid
Removal of trichloroethylene 225 VMD process

FIGURE 11 Memstill® technology of seawater desalination developed at the TNO institute: (a) principle of the
process; (b) cost comparison with other desalination techniques. (From Ref. 226.)

FIGURE 12 Scheme of a modular MEMFRAC distillation unit for fractionation
of non-water-based systems, developed at the TNO Institute. (From Ref. 227.)
as shown in Figure 13b for the case of aromatic/aliphatic hydrocarbon separation

(235). Shortcut design methods for hybrid pervaporation/distillation processes
can be found in Ref. 236.
3.4. Membrane Absorption/Stripping

Membrane absorption is one of the processes that Mother Nature had invented long
before engineers did. Human lungs and intestines present perfect examples of
membrane absorption systems. In the simplest case a gaseous component is selec-
tively transported via a membrane and dissolved in the absorbing liquid, as shown
in Figure 14. It is also possible to carry a membrane-based absorption-desorption
process, with two liquids on both sides of the membrane (237), or a membrane
stripping process, in which selected components are removed from the liquid phase
through the membrane by a stripping gas (238). An important characteristic feature

of membrane absorption is that it proceeds without creating a real gas–liquid inter-
face in the form of bubbles. Such a bubbleless gas–liquid mass transfer can be of
advantage in certain processes, for instance, in shear-sensitive biological systems.
One of the most important application areas of the membrane absorption is
the capture of CO2 from flue gas. Kværner has recently developed a membrane
absorption–based technology for the removal of CO2 from turbine exhaust gases in
offshore applications (239). The process, based on membrane-facilitated CO2
absorption in amine, followed by membrane-facilitated stripping with steam, is
schematically shown in Figure 15. The expected cost reduction, in comparison with
a conventional amine separation process, ranges between 30 and 40%, for both
investment and operating costs. The new membrane-based process also offers a very
significant reduction in the weight and size of equipment (70–75% and 65%, respec-
tively; see Figure 16), a great advantage in the case of offshore technology. Some
other possible applications of membrane absorption/stripping are shown in Table 10.
3.5. Membrane Chromatography (Adsorptive Membranes)

Membrane chromatography is a separation technique used almost exclusively in
the downstream processing of proteins. Traditionally, most chromatographic
purification steps in the downstream processing of proteins take place in columns
packed with bead-shaped particles. Membrane chromatography presents a hybrid
combination of liquid chromatography and membrane filtration based on micro-
porous or macroporous membranes that contain functional ligands attached to
their inner pore structure, which act as adsorbents. The main feature and advan-
tage of this technique, compared to the conventional ones, is the absence of pore
TABLE 9 Possible Applications of Hybrid Pervaporation/Distillation

Systems
System/process Selected
investigated refs. Remarks/effects
Benzene–cyclohexane 230 Combination of extractive distillation

separation and one-stage pervaporation;
high-purity (99.2–99.5%) products;
estimated cost savings of 20%
Ethanol dehydration 231 Simulation study; 50% cost
reduction in comparison with
conventional azeotropic distillation
Propylene/propane 232 Pilot-plant studies; 20–50% savings
splitting on operating costs
Propylene/propane 233 26–30% savings on capital
splitting investment

FIGURE 13 Combined distillation/pervaporation systems for (a) propylene/ propane splitting and (b) aromatic/aliphatic
hydrocarbon separation. (Part a from Ref. 234; part b from Ref. 235.)

FIGURE 14 Membrane absorption.
diffusion, which is the main transport resistance in traditional chromatography.

Dissolved molecules are carried directly to the adsorptive sites in the membranes
by convective flow (Figure 17), which increases the throughput of the process.
Membrane chromatography presents a process-intensive option for the protein A,
G, or L affinity chromatography (247–253), as well as for metal affinity, ion-
exchange, hydrophobic interaction or reversed-phase chromatography (254–258).
In recent years some new potential application fields for membrane chromato-
graphy have been demonstrated. Those are listed in Table 11.
FIGURE 15 Membrane absorption–based technology for removal of CO2

from turbine exhaust gases, developed by Kværner Process Systems.
(Courtesy: Kværner.)

FIGURE 16 Plant-size reduction in Kværner’s technology for CO2 removal
from exhaust gases: (a) conventional process; (b) membrane absorption
process. (Courtesy: Kværner.)
3.6. Membrane Extraction

In membrane extraction, the treated solution and the extractant/solvent are sep-
arated from each other by means of a solid or liquid membrane. The technique is
applied primarily in three areas: wastewater treatment (e.g., removal of pollutants
or recovery of trace components), biotechnology (e.g., removal of products from
fermentation broths or separation of enantiomers), and analytical chemistry (e.g.,
online monitoring of pollutant concentrations in wastewater). Figure 18a shows
schematically an industrial hollow fiber–based pertraction unit for water treat-
ment, according to the TNO technology (263). The unit can be integrated with a
film evaporator to enable the release of pollutants in pure form (Figure 18b).

Other more promising possible applications of membrane extraction, reported in
the literature, are listed in Table 12.
3.7. Other Hybrid Separations

In extractive crystallization (nonadductive), the driving force for the separation
process is created by altering the solid–liquid phase relationships via the addition
of a third component (usually liquid solvent) to the system. The solvent is chosen
in such a way that it binds strongly at the crystallization temperature but separates
easily at another temperature, where it is usually regenerated via distillation.
Examples of such defined extractive distillations include separation of m- and p-
cresols using acetic acid as the solvent (297), separation of o- and p-nitrochloro-
benzenes using p-dichlorobenzene (298), separation of lithium sulfate and lithium
formate using n-butanol or 2-propanol (299), and separation of p-xylene from
m-xylene using pentene (300).
TABLE 10 Reported Possible Applications of Membrane Absorption/

Stripping
System/process Selected
investigated refs. Remarks/effects
Ammonia absorption/ 240 Pilot-plant study in a polypropylene

desorption from hollow-fiber column; ammonia is
ammonia water absorbed in diluted sulfuric acid
CO2 and/or SO2 removal 241 Absorption in NaOH, K2CO3,
alkanolamines, and Na2SO3 using
hydrophobic microporous hollow-
fiber modules
Cyanide recovery from 242 Recovery via a gas-filled membrane
wastewater (GFM) placed between the waste-
water and a chemical stripping
solution
H2S removal from gas 243 Asymmetric hollow-fiber modules
streams coupled with concentrated
alkaline solution
CO2 production for the 244 Possible energy saving of more
horticultural industry than 30% reported
(greenhouses)
H2S and SO2 removal 245 Polyvinylidene fluoride (PVDF)
hollow fibers and concentrated
NaOH solution used
VOC removal from 246 Air stripping process via a
wastewater polypropylene hollow-fiber module

FIGURE 17 Comparison of transport mechanisms in (a) conventional chro-
matography and in (b) membrane chromatography.
Smith, Bryson, and Valsaray (301,302) investigated solvent sublation, an

adsorptive bubble process, combining the transport mechanisms of liquid/liquid
extraction and gas stripping. The technique exploits the surface-active nature of
organic compounds in their removal from water systems. The mechanism of solvent
sublation is shown in Figure 19a. Gas bubbles are used to transport adsorbed solute
from the bulk solution to the solvent layer. Solvent sublation is particularly prom-
ising in the removal of (hydrophobic) organic compounds from wastewater streams.
An exemplary process scheme is shown in Figure 19b. An important advantage of
the method is that the intimate contact between the extracting solvent and the waste-
water is prevented (no problem of residual solvent in the treated water).
Zeitsch (303) conducted a preliminary research on the removal of acetic
acid from the vapor stream of furfural reactors by means of extractive condensa-
tion. It is a hybrid vapor-phase extraction process, in which solvent (triethyl-
amine, TEA) forms a high-boiling complex with acetic acid. As a result, a “fog”

fraction is formed that can be separated via a coalescence filter or an electrostatic
separator. The technique is reported to be highly selective.
In 2002, Drioli and coworkers (304) investigated a process for obtaining
protein crystals by means of membrane crystallization, which actually combines
membrane distillation and crystallization techniques. The solvent evaporates at
the membrane interface, migrates through the pores of the membrane, and con-
denses on the opposite side of the membrane. The reported preliminary results
indicate interesting potentialities of this new method with respect to macromole-
cular crystallization.
4. BARRIERS AND FUTURE PROSPECTS

Despite many ongoing research activities in the field and a number of successful
commercializations, there still exist numerous technical and nontechnical barriers
that hinder a wider introduction of reactive and hybrid separations into industrial
practice. Two workshops held in 1998 by the Center for Waste Reduction
Technologies of AIChE (305) identified some of the barriers for reactive separ-
ations and divided them into three categories:
a. Technical gaps, such as lack of simulation and scale-up capability, lack
of validated thermodynamic and kinetic data, lack of materials (e.g.,
TABLE 11 Reported New Potential Applications of Membrane

Chromatography
Selected
System/process investigated refs. Remarks/effects
Separation of polynucleotides 259 Supercoiled plasmid DNA

investigated as model
Separation of oligonucleotides 260
and peptides
Separation of small 260 Benzene, toluene, homologues
hydrophobic molecules of 4-hydroxybenzoate
investigated
Enantiomeric separation 261 Racemic mixtures of
tryptophan and thiophenal
investigated in microfluidic-
based membrane
chromatography
Separation of trace metals 262 La-Ce-Pr-Nd-Sm separation
and Zr-Hf separation
investigated

FIGURE 18 Pertraction technology for wastewater treatment from the TNO
Institute: (a) scheme of the hollow-fiber pertraction unit; (b) integration of
pertraction with film evaporation. (Courtesy: TNO.)

TABLE 12 Reported Potential Applications of Membrane Extraction
R
Selected
System/process investigated refs. Remarks
Separation of acetic acid from aqueous solution 264 Microporous polypropylene membrane,
MIBK as solvent
Separation of (S)-naproxen from racemic 265 Reactive extraction via hollow-fiber
naproxen thioesters membrane
Separation of D,L-alanine and D,L-phenylalanine 266,267 Hollow-fiber zeolite membrane
racemic mixtures
Removal of sulfanilic acid from wastewater 268 Hollow-fiber modules
Lactic acid purification and concentration 269 Emulsion liquid membranes (ELMs)
Enrichment of bisphenol A 270 Liquid membrane
Phenol recovery from aqueous solutions 271,272 Various liquid and solid membranes
Zinc(II) recovery from HCl solution 273 Bulk liquid and hollow-fiber membranes
Hydrogen separation from methane steam 274 Palladium alloy membranes
conversion products
Separation of liquid olefin/paraffin mixtures 275 Nonporous polymeric membranes
Removal of 2-chlorophenol 276 Liquid membrane from aqueous solutions
Ethanol removal from aqueous solutions 277 Microporous polypropylene membrane
Separation of cephalosporin C from 278 Bulk and emulsion liquid membranes
fermentation broth
Separation of penicillin G 279 Supported liquid membrane
from aqueous streams (Amberlite LA-2)
Enrichment of amino acids 280 Supported liquid membrane (Aliquat 336)
Separation of cephalexin from a mixture of 7-ADCA 281 Supported liquid membrane (Aliquat 336)
Separation of butyric acid from fermentation broth 282 Liquid membrane
(continued)

TABLE 12 (cont.)
Selected
System/process investigated refs. Remarks
Separation of propionic and acetic acid from 283 Polymeric membranes

fermentation broth
Separation of citric acid from fermentation broth 284 Liquid membrane
Separation of lactic acid from fermentation broth 285 Emulsion liquid membrane
Production of acetone, butanol, and ethanol 286 Polypropylene membrane
(ABE) from potato wastes
Separation of long-chain unsaturated fatty acids 287 Microporous membrane, MeCN
and n-heptane as solvents
(Heavy) metals recovery from wastewater 288–292 Various membranes
Removal of organic contaminants from wastewater 293–296 Various membranes

FIGURE 19 Solvent sublation: (a) process mechanism and (b) an exemplary
process scheme. (From Refs. 301 and 302.)

integrated catalysts/sorbents, membrane materials), and lack of high-
level process synthesis methodology
b. Technology transfer barriers, such as lack of multidisciplinary team
approaches to process integration, lack of commonality of prob-
lems (technology is application-specific) and lack of demonstrations/
prototypes on a reasonable scale (reactive and hybrid separations are
still regarded more as a science than a technology)
c. General barriers, such as higher standards, to which new technologies
must be held, compared to conventional technologies, lack of informa-
tion on process economics (early economic and process evaluation),
and fear of risk in using new technologies.
Most of these barriers also hold for hybrid separations. Two more factors
that clearly play a hindering role in the commercial application of many reactive
and hybrid separations are: the already-mentioned small feasible operation win-
dows and the reduction of the degree of freedom caused by the integration of reac-
tion and separation or by the coupling of two separations in one processing unit.
Figure 20 shows an example of how the integration of reaction and membrane
separation reduces the degree of freedom in a membrane reactor, resulting in
decreased operational flexibility (306).
FIGURE 20 Degree of integration versus degree of freedom, in an example of

a membrane reactor. (From Ref. 306.)

Despite the existing barriers, the coming years are expected to bring a sig-
nificant increase in the number of industrially applied reactive and hybrid sep-
aration technologies. In particular, progress can be expected in the application of
reactive distillation, reactive adsorption, and membrane-based operations. In
hybrid separations, expansion of research activities on new product/process areas
has already been seen. Reactive and hybrid separations have enormous potential
for process intensification. Making full use of that potential will lead to substan-
tially smaller, cleaner, and more energy-efficient chemical and biochemical
plants.
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Reactive and Hybrid Separations: Incentives, Applications, Barriers

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Reactive and Hybrid Separations:

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2.1. Reactive Distillation

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2.2. Membrane-Based Reactive Separations

FIGURE 2 Separation of reactive and inert components with close boiling

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Product/process Selected refs.

Butyl acrylate from butanol and acrylic acid 7

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Among all the membrane functions listed in Table 2, catalytic membranes

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2.3. Reactive Adsorption

FIGURE 3 Membrane functions in chemical reactor. (Reproduced with per-

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Separation of products from In situ product removal from enzymatic

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Membrane is the reactor Reactions in ﬂow-through membrane

Source: Ref. 64.

industrial-scale applications of adsorptive reactors remain to be seen. Challenges

2.4. Reactive Extraction

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Oxidation of lean VOC mixtures 89 SMBCR

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TABLE 4 Some Processes Studied in Reactive Extraction Systems

Penicillin G recovery 102–106

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Diastereomeric crystallization is commonly used in the production of a number

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2.6. Reactive Absorption/Stripping

TABLE 5 Examples of Reactive Crystallization/Precipitation

Calcium carbonate 142,143 Liquid–liquid and gas–liquid

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3.1. Extractive Distillation

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Originally, extractive distillation was limited to two-component problems.

3.2. Adsorptive Distillation

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High-purity cyclohexane 171 Close-boiling-point problem

three-phase mass transfer operation in which distillation is carried in presence of

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FIGURE 7 Scheme of an adsorptive distillation system for the separation of

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3.3. Membrane Distillation

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TABLE 7 Potential Application Fields of Adsorptive Distillation Reported

Toluene–methylcyclohexane 196 Suitable adsorbents: silica gel,

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Concentration of H2SO4, 205–207

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

as shown in Figure 13b for the case of aromatic/aliphatic hydrocarbon separation

3.4. Membrane Absorption/Stripping

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

3.5. Membrane Chromatography (Adsorptive Membranes)

TABLE 9 Possible Applications of Hybrid Pervaporation/Distillation

Benzene–cyclohexane 230 Combination of extractive distillation