ESL-IE-91-06-25

TREATMENT OF ORGANIC-CONTAMINATED WASTEWATER BY PERVAPORATION

J.G. WIJMANS
Research Director

J. KASCHEMEKAT
Design Engineer

R.W. BAKER
President

V.L. SIMMONS
Marketing Director

Membrane Technology and Research, Inc., Menlo Park, CA

ABSTRACT

The adoption of pervaporation as a viable, economical

industrial separation process has occurred fairly recently -
within the last ten years. Today pervaporation is used for a
number of liquid separations. The biggest current application is
the dehydration of 90% ethanol/water solutions to yield 99.5%
,2 This paper describes an emerging application
pure ethanol. 1,3
for pervaporation, the removal of organic solvents from dilute
aqueous streams. In this application, membranes more
!Jl>rmeable
permeable to organic compounds than to water are used. s -se

The removal and recovery of organic contaminants from

aqueous streams by pervaporation membrane systems is a viable
and economical treatment for many waste streams. Specific
opportunities for the technology are identified in this paper.
La~oratory and pilot system data are used
used! to develop system
desIgns and to calculate the cost of treating specific streams.
BACKGROUND

Hydrophobic. sparingly water-soluble. volatile solvents

are concentrated most efficiently by MTR's pervaporation
membranes. For example. I, I ,2-trichloroethane can be
concentrated 100- to 200-fold. Equally
Equal1y good separation is
obtained with other dissolved halocarbons or hydrocarbons,
such as benzene. toluene, etc. Sparingly soluble solvents such as
ethyl'ketone or ethyl acetate are also separated
butanol, methyl ethyl"ketone
well, and can be concentrated 40- to 6O-fold.
60-fold. Water-soluble
wel1,
solvents, such as alcohols, are concentrated less efficiently.
However, enrichments of 5- to 20-fold can be obtained even
with these solvents.

perm
Pervaporation is a membrane process in which a permselective membrane is used to separate mixtures of dissolved
solvents. A liquid mixture contacts one side of a membrane and
is removed as a vapor from the other side. Transport through
the membrane is induced by maintaining the vapor pressure on
the permeate side of the membrane lower than the vapor
pressure of the feed liquid. In the :Jaboratory,
laboratory, the low-pressure
permeate vapor pressure is most conveniently produced with a
vacuum pump. On a commercial scale, however, the vacuum
pumps required would be impossibly large. An attractive
I. is to
alternative to vacuum operations. illustrated in Figure I,
cool the permeate vapor, thus condensing it to a liquid. In this
process, the low pressure on the permeate side is maintained 'by
by
spontaneous condensation of the permeate vapor, and the
permeate vapor pressure is determined by the temperature of
the condensed liquid. This system is preferred in commercial
operations because the cost of providing cooling water for the
condenser is much less than the cost of a vacuum pump. Also, a
system using a condenser is inherently more reliable than one
which requires a vacuum pump.

Membrane and module design

economically viable pervaporation process requires
An economical1y
relatively thin membranes packaged in high-membrane-area
modules. When these requirements are met, high product flow
cost. The types of
rates are achieved at an economical cos\.
membrane and modules used in this work are illustrated in
Figu!e
Figufe 2. Composite membranes are made by coating a
relatively open microporous support membrane with a thin,
d~nse film.
dense

Purified
feed

The flat-sheet composite membranes are formed into

spiral-wound membranes modules similar to those used in
membrane reverse osmosis and gas separation systems.
However, in pervaporation modules more open permeate spacer
materials are used to minimize parasitic pressure drops on the
permeate (vapor) side of the membrane. Laboratory-scale
industrial
modules have a membrane area of 0.2-0.3 m 2 and industrial,call>
,cal" modules have a membrane area of 4-6 m 22.

Feed
liquid

_ _ Permselective layer
___
_ _ Microporous
support layer

Condensed
permeate
liquid

figure 2a. A cross-section of a multilayer composite

membrane. The permselective layer is
0.5-2.0-J,lm-thick and performs the
approximately 0.5-2.0-t'm-thick
separation. The microporous support provides
mechanical support for the selective layer.

03B-l
0381 S

Figure I. Schematic of the pervaporation process.

108
Proceedings from the 13th National Industrial Energy Technology Conference, Houston, TX, June 12-13, 1991

ESL-IE-91-06-25

MTR has constructed seven pervaporation pilot units

and has demonstrated the process on a wide range of aqueo;us
aqueo:us
organic waste streams. Industrial demonstration of the proce"
is \In,-!('rway.
un,-!('rway.

< 10 ppm benzene

.".~;:'::r~l:l:~:ugh / l........_ _o=>-=z=..,j

Membrane unit
n12
200 rrl2

1000 ppm
benzene
gallday
20,000 gal/day

m.mbt.l1.

2b. Composite membranes are formed into spiral-wound

Figure 2b.
pervaporatioll
modules. A typical industrial-sized pervaporation
module contains 405 m2 of membrane and produces
5-20 L of concentrated solvent permeate per hour
Applications

26% benzene
75 gal/day

_0.2% benzene
55 gal/day

pervaporati,,"
The opportunities for widespread use of pervaporatit"
to remove organic solvents from aqueous streams can be divl,;~L1
divl.;~L1
into l"ree
Three categories. listed helow
Poilu/ion cOn/rol.
con/rol. This category is characterized by
streams containing low concentrations of hydrophobic solvents.
The objective of the treatment is to lower the solvent
concentration to 10 ppm or less, so that the water can be
discharged or reused. A typical stream might come from a
contaminated surface water or the evaporator condensate from a
chemical plant.

:>99% benzene

20 gpl/day

Figure 3.
3.

Flow diagram of an MTR pervaporation system

systlm for
I
99% benzene removal.

recoYery. In this category, a typical stream

Sol Yen/ recoyery.
contains relatively high concentrations of a single solvent in
water. The objective is recovery of a concentrated solvent that
can be reused, and 90% solvent removal from the water stream
so that it can be discharged or further treated.

REFERENCES

mixed-so/Yent hazardous was/e

Volume reduction of mixed-solYen/
s/reams.
streams. Because this type of stream contains several solvents,
recycling a solvent concentrate back to the process is not usually
viable. However, the stream contains too much solvent to be
discharged. Currently, these waste streams would be trucked to
an incinerator or perhaps to a solvent reclaimer, both of which
are expensive alternatives. The objective of the pervaporation
process is to achieve 95-98% removal of solvent from the feed
stream so it can be discharged or reused, and to produce a
concentrated small-volume solvent stream that could be sent to
a reclaimer. Streams like this might be produced from a solvent
air scrubber or the regeneration cycle of a carbon adsorber.

As an example, consider a pervaporation system

designed for a pollution control application for the removal of
benzene from a process wastewater. Figure 3 is a flow diagram
of the system designed to remove 99% of the solvent from a
20,OOO-gpd stream containing 1,000 ppm benzene. The
concentration of the benzene is reduced to less than 10 ppm in
the final residue. This could be discharged, reused, or sent to a
final carbon adsorption polishing step. The pervaporation
system able to treat this benzene stream would have a membrane
area of 200 m 2 , producing a permeate with an average
concentration of 26%. Because benzene is relatively insoluble in
phase
water, permeate vapor of this concentration would phaseseparate on condensation to yield a pure benzene stream and a
small benzene-saturated aqueous stream, which would be
recycled to the feed. The operating costs of this system are
$14/1,000 gal of feed treated. This compares favorably to other
waste treatment methods, especially when the compact size,
simple operation and completeness of the separation are
considered.

I.
I.

H.E.A. Brlischke, "State of the Art of Pervaporation," in

on!
Proceedings of Third International Conference on:
Pervaporalion in the Chemical Industry, Nancy, France,
R. Bakish (ed), Bakish Materials, Englewood, NJ (1988).

2.
2.

G.F. Tusel and H.E.A. Brlischke, "Use of Pervaporation

Systems in the Chemical Industry," Desalination 52,
5~, 327
(1988).

3.
3.

I. Blume, J.G. Wijmans, and R.W. Baker, "The

Separation of Dissolved Organics from Water by
Pervaporation," J. Memb. Sci. 49, 253 (1990)

4.
4.

J. Kaschemekat, J.G. Wijmans, R.W. Baker and I.,

L
Blume, "Separation of Organics from Water Usin~
Pervaporation," in Proceedings of Third InternatiOnal
Internati~lPal
Bakish
Conference on Pervaporation, Nancy, France, R. 'Bakish
(ed.), Bakish Materials, Englewood, NJ (1988).

5.
5.

"Selbction
C.-M. Bell, F.-J. Gerner and H. Strathmann, "Selection
J, Memb.
Memb,
of Polymers for Pervaporation Membranes," J.
~,315 (1988).

6.
6.

C.A, Smolders,
Smolders
H.H. Nijhuis, M.H.V. Mulder and C.A.
Removal of
"Selection of Elastomeric Membranes for the Re~oval
Volatile Organic Components from Water," in
Proceedings of the Third International Conference on
Pervaporation in the Chemical Industry, Nancy, France,
R. Bakish (ed.), Bakish Materials, Englewood, NJ
(1988).

109
Proceedings from the 13th National Industrial Energy Technology Conference, Houston, TX, June 12-13, 1991