Sei sulla pagina 1di 2

TREATMENT TREATMENT OF OF ORGANIC-CONTAMINATED ORGANIC-CONTAMINATED

WASTEWATER WASTEWATER

J.G. J.G. WIJMANS WIJMANS

Research Research Director Director

J.

J. KASCHEMEKAT

KASCHEMEKAT

R.W. R.W. BAKER BAKER

Design Design Engineer Engineer

President President

ESL-IE-91-06-25

BY BY PERVAPORATION PERVAPORATION

V.L. V.L. SIMMONS SIMMONS

Marketing Marketing Director Director

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

ABSTRACT ABSTRACT

The The removal removal and and recovery recovery of of organic organic contaminants contaminants from from

aqueous streams by pervaporation membrane systems

is a viable

aqueous streams by pervaporation membrane systems is a viable

and and economical economical treatment treatment for for many many waste waste streams. streams.

opportunities for the technology are identified in this paper.

for the technology are identified in this paper.

opportunities

La~oratoryand La~oratoryand pilot pilot system system data data are are used used! to to develop develop system system

desIgns and to calculate the cost of treating specific streams.

desIgns and to calculate the

Specific Specific

cost of treating specific streams.

BACKGROUND BACKGROUND

Pervaporation Pervaporation is is a a membrane membrane process process in in which which a a perm- perm­

selective selective membrane membrane is is used used to to

solvents. solvents.

is is removed removed as as a a vapor vapor from from the the other other side. side.

the membrane

the membrane is induced by maintaining the vapor pressure on

the the permeate permeate side side of of the the membrane membrane lower lower than than the the vapor vapor

pressure pressure of of the the feed feed liquid. liquid.

is most conveniently produced with a

permeate vapor pressure is most conveniently produced with a

vacuum vacuum pump. pump.

permeate vapor pressure

is induced by maintaining the vapor pressure on

separate separate mixtures mixtures of of dissolved dissolved

A A liquid liquid mixture mixture contacts contacts one one side side of of a a membrane membrane and and

Transport Transport through through

In In the the :Jaboratory, laboratory, the the low-pressure low-pressure

On On a a commercial commercial scale, scale, however, however, the the vacuum vacuum

pumps pumps required required would would be be impossibly impossibly large. large.

alternative to vacuum operations. illustrated in Figure

alternative to vacuum operations. illustrated in Figure I, is to

cool cool the the permeate permeate vapor, vapor, thus thus condensing condensing it it to to a a liquid. liquid.

is maintained 'by

process, the low pressure on the permeate side is maintained by

spontaneous spontaneous condensation condensation of of the the permeate permeate vapor, vapor, and and the the

permeate vapor pressure

permeate vapor pressure is determined by the temperature of

This This system system is is preferred preferred in in commercial commercial

the the condensed condensed liquid. liquid.

operations operations because because the the cost cost of of providing providing cooling cooling water water for for the the

condenser condenser is is much much less less than than the the cost cost of of a a vacuum vacuum pump. pump.

system system using using a a condenser condenser is is inherently inherently more more reliable reliable than than one one

which which requires requires a a vacuum vacuum pump. pump.

An An attractive attractive

I. is to

In In this this

process, the low pressure on the permeate side

is determined by the temperature of

Also, Also, a a

Feed

liquid liquid

Feed

Purified Purified

feed

feed

a a Feed liquid liquid Feed Purified Purified feed feed Condensed C o n d e

Condensed Condensed

permeate

liquid liquid

permeate

03B-l S

038·1 S

of the pervaporation process.

Figure I. Schematic

Figure I. Schematic of the pervaporation process.

The The adoption adoption of of pervaporation pervaporation as as a a viable, viable, economical economical

industrial industrial separation separation process process has has occurred occurred fairly fairly recently recently ­ -

within within the the last last ten ten years. years.

number number of of liquid liquid separations. separations.

the the dehydration dehydration of of 90% 90% ethanol/water ethanol/water solutions solutions to to yield yield 99.5% 99.5%

Today Today pervaporation pervaporation is is used used for for a a

The The biggest biggest current current application application is is

pure ethanol.

of organic solvents from dilute

for pervaporation, the removal of organic solvents from dilute

aqueous aqueous streams. streams.

!Jl>rmeable to organic compounds than to water are used. s -

permeable to organic compounds than

pure

ethanol. 1 ,3

1

,2 This paper describes an emerging application

This paper describes an emerging application

for pervaporation, the removal

In In this this application, application, membranes membranes more more

to water are used. s

-

e

s

Hydrophobic. Hydrophobic. sparingly sparingly water-soluble. water-soluble. volatile volatile solvents solvents

are are concentrated concentrated most most efficiently efficiently by by MTR's MTR's pervaporation pervaporation

membranes. membranes.

concentrated 100- to

concentrated 100- to 200-fold.

obtained obtained with with other other dissolved dissolved halocarbons halocarbons or or hydrocarbons, hydrocarbons,

such

such as benzene. toluene, etc.

butanol, methyl

40- to 60-fold.

wel1, and can be concentrated 40- to 6O-fold.

solvents, such as alcohols, are

solvents, such as alcohols, are concentrated

well, and can be concentrated

butanol, methyl ethyl"ketone

For For

example. example.

I, I, I I ,2-trichloroethane ,2-trichloroethane

can can be be

200-fold.

Equally Equal1y good good separation separation is is

as benzene. toluene, etc.

Sparingly Sparingly soluble soluble solvents solvents such such as as

Water-soluble Water-soluble

concentrated less efficiently.

less efficiently.

ethyl'ketone or ethyl acetate are also separated

or ethyl acetate are also separated

However,

However, enrichments of 5- to 20-fold can be obtained even

with with these these solvents. solvents.

enrichments of 5- to 20-fold can be obtained even

Membrane Membrane and and module module design design

An An economical1y economically viable viable pervaporation pervaporation process process requires requires

relatively thin membranes packaged in

relatively thin membranes packaged

modules. modules.

rates rates are are achieved achieved at at an an economical economical cos\. cost.

membrane membrane and and modules modules used used in in this this work work are are illustrated illustrated in in

Figu!e

Figufe 2.

relatively relatively open open microporous microporous support support membrane membrane with with a a thin, thin,

dense d~nse film. film.

high-membrane-area

in high-membrane-area

When When these these requirements requirements are are met, met, high high product product flow flow

The The types types of of

Composite Composite membranes membranes are are made made by by coating coating a a

2.

The The flat-sheet flat-sheet composite composite membranes membranes are are formed formed into into

108 108

spiral-wound spiral-wound membranes membranes modules modules similar similar to to those those used used in in

membrane membrane reverse reverse osmosis osmosis and and gas gas separation separation systems. systems.

However, However, in in pervaporation pervaporation modules modules more more open open permeate permeate spacer spacer

materials materials are are used used to to minimize minimize parasitic parasitic pressure pressure drops drops on on the the

permeate (vapor) side

of the membrane.

permeate (vapor) side of the membrane.

modules have a a membrane area of 0.2-0.3 m 2 and industrial-

modules have

,call> ,cal" modules modules have have a a membrane membrane area area of of 4-6 4-6 m m

Laboratory-scale Laboratory-scale

2

and industrial­

2 2

. .

membrane area of 0.2-0.3 m

2 and industrial­ 2 2 . . membrane area of 0.2-0.3 m Permselective Permselective layer layer

Permselective Permselective layer layer

Microporous Microporous

support support layer layer

figure figure 2a. 2a.

A A cross-section cross-section of of a a multilayer multilayer composite composite

membrane. membrane.

approximately approximately 0.5-2.0-t'm-thick 0.5-2.0-J,lm-thick and and performs performs the the

The The permselective permselective layer layer is is

separation. separation.

mechanical

mechanical support for the selective layer.

support for the selective layer.

The The microporous microporous support support provides provides

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

o
o

Figure Figure 2b. 2b.

.".~;:'::r~l:l:~:ugh /l

m.mbt.l1.

o=>-=z=

,j

Composite Composite membranes membranes are are formed formed into into spiral-wound spiral-wound

modules. modules.

module contains 405 m 2 of membrane and produces

5-20 5-20 L L of of concentrated concentrated solvent solvent permeate permeate per per hour hour

module contains 405 m

A A typical typical industrial-sized industrial-sized pervaporatioll pervaporation

2

of membrane and produces

Applications Applications

The The opportunities opportunities for for widespread widespread use use of of pervaporatit·" pervaporati,,"

to remove organic solvents from aqueous streams can be divl.;~L1

solvents from aqueous streams can be divl,;~L1

to remove organic

into into l"ree Three categories. categories. listed listed helow helow

Poilu/ion cOn/rol.

Poilu/ion con/rol.

This This category category is is characterized characterized by by

containing low concentrations of hydrophobic solvents.

streams

streams containing low concentrations of hydrophobic solvents.

The The objective objective of of the the treatment treatment is is to to lower lower the the solvent solvent

concentration concentration to

10 ppm or less, so that the water can be

to 10 ppm or less, so that the water can be

discharged discharged or or reused. reused.

surface water or the evaporator condensate from a

contaminated surface water or the evaporator condensate from a

contaminated

chemical chemical plant. plant.

A A typical

typical stream might come from a

stream might come from a

Sol Yen/

Sol Yen/

recoYery.

recoyery.

In In this this category, category, a a typical typical stream stream

contains relatively high concentrations of a single solvent in

contains relatively high

water. water.

can can be be reused, reused, and and 90% 90% solvent solvent removal removal from from the the water water stream stream

so so that that it it can can be be discharged discharged or or further further treated. treated.

concentrations of a single solvent in

The The objective objective is is recovery recovery of of a a concentrated concentrated solvent solvent that that

Volume reduction of mixed-so/Yent hazardous was/e

Volume reduction of mixed-solYen/ hazardous was/e

s/reams.

streams.

recycling recycling a a solvent solvent concentrate concentrate back back to to the the process process is is not not usually usually

viable. viable.

discharged. discharged.

an

an incinerator or perhaps to a solvent reclaimer, both of which

are are expensive expensive alternatives. alternatives.

process

process is to achieve 95-98% removal of solvent from the feed

stream so it can be discharged or reused, and to produce a

it can be discharged or reused, and to produce a

stream so

is to achieve 95-98% removal of solvent from the feed

Because Because this this type type of of stream stream contains contains several several solvents, solvents,

However, However, the the stream stream contains contains too too much much solvent solvent to to be be

Currently, Currently, these these waste waste streams streams would would be be trucked trucked to to

incinerator or perhaps to a solvent reclaimer, both of which

The The objective objective of of the the pervaporation pervaporation

concentrated small-volume solvent stream that could be sent to

small-volume solvent stream that could be sent to

concentrated

a reclaimer.

a reclaimer. Streams like this might be produced from a solvent

produced from a solvent

air air scrubber scrubber or or the the regeneration regeneration cycle cycle of of a a carbon carbon adsorber. adsorber.

Streams like this might be

As As an an example, example, consider consider a a pervaporation pervaporation system system

control application for the removal of

designed for a pollution

designed for a pollution control application for the removal of

benzene benzene from from a a process process wastewater. wastewater.

of of the the system system designed designed to to remove remove 99% 99% of of the the solvent solvent from from a a

20,OOO-gpd

20,OOO-gpd stream containing 1,000 ppm benzene.

concentration concentration of of the the benzene benzene is is reduced reduced to to less less than than 10 10 ppm ppm in in

the the final final residue. residue.

final carbon adsorption polishing step.

final carbon adsorption polishing

system able to treat this benzene stream would have a

system able to treat this benzene stream would have a membrane

membrane

area of 200 m

area

concentration

concentration of 26%.

a a

Figure Figure 3 3 is is a a flow flow diagram diagram

The The

or sent

The The pervaporation pervaporation

stream containing 1,000 ppm benzene.

2

m 2

step.

to

This could be discharged, reused, or sent to

This could be discharged, reused,

of

200

, , producing producing a a permeate permeate with with an an average average

of 26%.

Because Because benzene benzene is is relatively relatively insoluble insoluble in in

water, water, permeate permeate vapor vapor of of this this concentration concentration would would phase- phase­

separate separate on on condensation condensation to to yield yield a a pure pure benzene benzene stream stream and and a a

small small benzene-saturated benzene-saturated aqueous aqueous stream, stream, which which would would be be

recycled recycled to to the the feed. feed.

$14/1,000 $14/1,000 gal gal of of feed feed treated. treated.

waste waste treatment treatment methods, methods, especially especially when when the the compact compact size, size,

simple operation and completeness

simple operation and completeness of the separation are

considered. considered.

The The operating operating costs costs of of this this system system are are

This This compares compares favorably favorably to to other other

of the separation are

ESL-IE-91-06-25

MTR MTR has has constructed constructed seven seven pervaporation pervaporation pilot pilot units units

109 109

and and has has demonstrated demonstrated the the process process on on a a wide wide range range of of aqueo:us aqueo;us

organic organic waste waste streams. streams.

is is \In,-!('rway. un,-!('rway.

Industrial Industrial demonstration demonstration of of the the proce" proce"

1000 1000 ppm ppm

benzene benzene

20,000 20,000 gallday gal/day

< < 10 10 ppm ppm

benzene benzene

26% benzene 75 gal/day
26% benzene
75 gal/day

200 n12

200 rrl2

Membrane Membrane unit unit

_0.2% _0.2%

benzene benzene

55 55 gal/day gal/day

:>99% benzene

:>99% benzene

20 20 gpl/day gpl/day

Figure

Figure 3.

3.

Flow Flow diagram diagram of of an an MTR MTR pervaporation pervaporation system systlm for for

99% 99% benzene benzene removal. removal.

I

REFERENCES REFERENCES

I. I.

2. 2.

3. 3.

4.

4.

5. 5.

6. 6.

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

Proceedings of Third International Conference on!

Proceedings

Pervaporalion in the Chemical Industry, Nancy, France,

Pervaporalion in the

R. R.

Bakish Bakish (ed), (ed), Bakish Bakish Materials, Materials, Englewood, Englewood, NJ NJ (1988). (1988).

of Third International Conference on:

Chemical Industry, Nancy, France,

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

Chemical Industry," Desalination 52, 327

Systems in the

Systems in the Chemical Industry," Desalination 5~, 327

(1988). (1988).

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

Separation Separation of of Dissolved Dissolved Organics Organics from from Water Water by by

Pervaporation," Pervaporation," J. J. Memb. Memb. Sci. Sci. 49, 49, 253 253 (1990) (1990)

J.

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

Blume, "Separation of Organics from Water Usin~

"Separation of Organics from Water Usin~

Blume,

Pervaporation," Pervaporation," in in Proceedings Proceedings of of Third Third InternatiOnal Internati~lPal

Conference Conference on on Pervaporation, Pervaporation, Nancy, Nancy, France, France, R. R. 'Bakish Bakish

(ed.), (ed.), Bakish Bakish Materials, Materials, Englewood, Englewood, NJ NJ (1988). (1988).

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

C.-M. C.-M. Bell, Bell, F.-J. F.-J. Gerner Gerner and and H. H. Strathmann, Strathmann, "Selbction "Selection

of of Polymers Polymers for for Pervaporation Pervaporation Membranes," Membranes," J. J, Memb. Memb,

~,315 ~,315 (1988). (1988).

H.H. H.H. Nijhuis, Nijhuis, M.H.V. M.H.V. Mulder Mulder and and C.A. C.A, Smolders, Smolders

"Selection

"Selection of Elastomeric Membranes for the Removal of

Volatile Volatile Organic Organic Components Components from from Water," Water," in in

Proceedings of the Third International Conference on

of the Third International Conference on

Proceedings

Pervaporation Pervaporation in in the the Chemical Chemical Industry, Industry, Nancy, Nancy, France, France,

R. R.

(1988). (1988).

of Elastomeric Membranes for the Re~ovalof

Bakish Bakish (ed.), (ed.), Bakish Bakish Materials, Materials, Englewood, Englewood, NJ NJ

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