USOO681.

4865B1

(12) United States Patent (10) Patent No.: US 6,814,865 B1

Aminabhavi et al. (45) Date of Patent: Nov. 9, 2004

(54) ION EXCHANGE MEMBRANES, METHODS 5,137,925 A 8/1992 Hodgdon ..................... 521/27
AND PROCESSES FOR PRODUCTION 5,147,553 A * 9/1992 Waite ........ ... 210/654
THEREOF AND USES IN SPECIFIC s:
2- -- 12
A : 1. East - - - - - - 28's
allels . . . . . . . . . . . . . . . . . . . . . . .
APPLICATIONS 5,264,125 A 11/1993 MacDonald et al. ... 21.0/500.35
(75) Inventors: Tejraj Aminabhavi, Austin, TX (US); 3. A s1998 Altmeier - - - - - - - - - - - - - - - - 21.0/500.37
2- - - 2 /1999 Altmeier ...................... 521/32
Padmakar V. Kulkarni, Dallas, TX 6,045,694. A 4/2000 Wang et al. ........... 21.0/500.37
(US); Mahadevappa Y. 6,103,078 A 8/2000 Hitchems et al. ........... 204/296
Kariduraganavar, Pawate Nagar (IN)
FOREIGN PATENT DOCUMENTS
(73) Assignee: Seventy-Seventh Meridian IL 60843 10/1985 .............. CO8J/5/22
Corporation LLC, Dallas, TX (US) JP 58O93729 6/1983 .............. CO8JA5/22
c: - JP 62041234 2/1987 .............. CO8J/5/22
(*) Notice: Subject to any disclaimer, the term of this JP 63116708 5/1988 ........... B01D/13/02
patent is extended or adjusted under 35
U.S.C. 154(b) by 223 days. OTHER PUBLICATIONS
Toti et al., “Electrodialysis Membrane Technology for Puri
(21) Appl. No.: 10/007,442 fication of Brackish Ground Water.” Polymer News, 2000,
(22) Filed: Dec. 5, 2001 Vol. 25, 7 pages.
(51) Int. Cl." ................................................ B01D 71/00 cited by examiner
(52) U.S. Cl. ............................ 210/500.21; 210/500.27; Primary Examiner W. L. Walker
210/50028; 210/500.42; 210/502.1; 210/503; ASSistant Examiner-KS Menon
210/504; 210/649; 429/247; 429/248; 429/249; (74) Attorney, Agent, or Firm-Baker Botts L.L.P.
429/250; 204/296; 204/518; 204/520; 204/521;
204/522; 204/523; 204/524 (57) ABSTRACT
(58) Field of Search ....................... 210/500.21,500.27, The invention includes novel anion eXchange membranes
210/50028,500.42, 502.1, 503, 263, 735, formed by in Situ polymerization of at least one monomer,
736, 321.71, 660, 638, 641, 644, 649, 653; polymer or copolymer on a woven Support membrane and
204/296, 518, 520–524; 429/247-250, 12, their methods of formation. The woven support membrane is
41, 34, 44; 427/487, 491, 245, 246 preferably a woven PVC membrane. The invention also
(56) References Cited includes novel cation exchange membranes with or without
woven Support membranes and their methods of formation.
U.S. PATENT DOCUMENTS The invention encompasses a process for using the mem
branes in electrodialysis of ionic Solutions and in particular
3.945,927 A 3/1976 Imai et al. ............. 210/550 M industrial effluents or brackish water or seawater. The elec
3,947,351 A 3/1976 Asawa et al. ............. 210/22 R trodialysis proceSS need not include a step to remove exceSS
4,505,797 A 3/1985 Hodgdon et al. ........... 204/252 ions prior to electrodialysis and produces less waste
4,522,902 A 6/1985 Minchak et al. ............ 429/252 by-product and/or by-products which can be recycled.
4,608,393 A 8/1986 Hamano ...................... 521/27
4992,176 A 2/1991 Bartels ....................... 210/640
5,126,503 A 6/1992 Bartels ....................... 585/818 9 Claims, 7 Drawing Sheets

Hi-5. . . . Hish
ar
s
N4
CH5

HC-Car-OH
| H2
CH2
Cl
N
rs
---c
U.S. Patent Nov. 9, 2004 Sheet 1 of 7 US 6,814,865 B1

FIG. 1

th. . . . Fin
H2 H2 FIG 3
N 21

N1C N4
CH2 CH3
HC-C-OH
- H2
()--i, HC-C-OH
| H2
CH2
CI.N
21

N
ti-sh C-C
U.S. Patent Nov. 9, 2004 Sheet 2 of 7 US 6,814,865 B1

SO3H
FIG. 4 O O

N-R-N f

+a;-a-a-a-i-o-o: O O
+,-,---i-o-o: O
N-R-N O r

O O

SO3H

S03H
FIG. 5

+o-p-, +o, --
NH
CH2 NH

-HCH-CH2- . . . -th-o-;
U.S. Patent Nov. 9, 2004 Sheet 3 of 7 US 6,814,865 B1

CH=CH2 NH2
O
21 N BPO ROOM
| + h;6 -e-. - TEMPERATURE
NN H H2

{-6-6),
2 H2 H-6),
H2 H2
N 21 CHyl
2 N HEXANE
NC- N
CH2
HC-C-OH
--C-C--
H2 H2
. . . -C-C-
H2 H2
| H2
N 21
HC-C-OH 1 N
H2 N1C N4
CH2
Cl t CH3
21 HC-C-OH
- 2
S -a,
C-C HC-C-OH
t- Sh H2
C. t
N
N
FIG. 6
---
U.S. Patent Nov. 9, 2004 Sheet 5 of 7 US 6,814,865 B1

O O
THERMA
H3C-C-C-N-C-C-CH3 -- N-R-N POLYMERIZATION
H2 H2 H2 H2
O O
O O

C-C-C-N-C-C-C
H2 H2 H2 H2 H2 H2 N-R-N CURING -
f

O O

H CH 0 0
N-R-N
E.-----
2 H "29
H
NoO 0/ SULFONATION
E.-----
2
2

N-R-N r

SO3H O O
U.S. Patent Nov. 9, 2004 Sheet 7 of 7 US 6,814,865 B1
1.
1. C
til St
s
s ad U

Cl
S 3

2 ad E o - 9 c qo

-- -
r

Hee qu E O - O - as FC |
-- -H -H

2 u E O - to u

--

a 2 --
s
-- --
--

2 o' E O - O - us
 US 6,814,865 B1
1 2
ION EXCHANGE MEMBRANES, METHODS these products. Further, this results in high ratioS of recov
AND PROCESSES FOR PRODUCTION ered water. Water retrieved through electrodialysis is rela
THEREOF AND USES IN SPECIFIC tively clean and may be used or reused with little or no
APPLICATIONS further treatment. Electrodialysis processes using ion
eXchange membranes also represent an advantage over the
currently used reverse osmosis methods for recovery of
BACKGROUND OF THE INVENTION precious metals. Such as gold and Silver because reverese
oSmosis membranes are Susceptible to Scaling and Salt
The present invention relates to a new family of anion and deposition, known as membrane fouling. Electrodialysis
cation exhange membranes, methods of producing Such membranes can easily be washed with dilute acidic Solutions
membrances, and their uses. requiring minimum maintainance and also minimum waste
Uses of Ion Exchange Membranes is generated during the process.
Anion eXchange membranes having anion eXchange Another advantage lies in the properties of the membranes
groupS Such as quaternary ammonium groups or cation themselves. Electrodialysis membranes may be Synthesized
eXchange membranes having cation exchange groupS Such to be highly Specific, allowing the Separation of targeted ions
as Sulfonic acid groups or carboxylic acid groups have a 15
in the electrodialysis process. Ion eXchange membranes are
wide variety of applications including desalination, precious also capable of withstanding highly acidic Solutions, unlike
metal recovery, etc. Such ion eXchange membranes are membranes and materials used in other filtration processes.
If they are durable and Specific, ion eXchange membranes
critical components of advanced Separation Systems that may be cost effective even in Small-scale treatment.
may be used used in: However, these membranes remain most useful in removing
electrodialytic concentration or desalination of electrolyte Salts from water, Seawater, brackish water, including valu
Solutions, able metals from waste industrial Sources because utilizing
Separation of Specific ions from mixture of ionic Such membranes with large contact areas further reduces the
Solutions, cost of the process.
Current Techniques for Producing Ion Exchange Mem
processes Such as chlor-alkali production, where the branes
membranes are used as Separators for electrolysis, 25
Despite the great potential of ion eXchange membrane
recovery of acids or alkalis through ion eXchange mem electrodialysis applications, current techniques for produc
brane processes, ing Such membranes are inadequate or overly expensive.
concentration of Seawater to produce Sodium chloride, Most of the previously developed ion eXchange membranes
may be classified as either homogenous or heterogenous.
deminerlization of Saline water, and Heterogenous membranes are prepared by incorporating the
deSalination of cheese-whey products. ion exchange groups into the film-forming resins by (i) dry
In a more specific illustration, the excessive use of fer molding or calendering mixtures of the ion eXchange and
tilizerS has resulted in the excessive concentration of nitrate film-forming materials, (ii) dispersing the ion exchange
ions in ground water. This poses a Serious problem because material in a Solution of the film-forming polymer and then
concentrations of nitrate ions above 25 ppm are harmful to 35 casting films from the Solution and evaporating the Solvent,
human health. Similarly, concentrations of fluoride ions and (iii) dispersing the ion exchange material in a partially
significantly above the 0.5-1.5 ppm recommended level for polymerized film-forming polymer, casting films, and com
drinking water are harmful to human health. Excessive pleting the polymerization. FIG. 1 illustrates a current
fluoride intake may result in Skeletal or dental fluorosis. heterogenouse membrane as described in U.S. Pat. No.
Recent Studies have clearly shown a direct correlation 40
6,103,078 of Hitchems et al.
between the intake of nitrate and blue baby syndrome Homogenous ion eXchange membranes are better Suited
(resulting in infant mortality), cancer of the womb and other because the fixed ion charges are distributed homogenously
problems in pregnant women. Excessive chloride has also over the entire polymer matrix. In the past, a few homog
caused panic where young and capable people have Sud enous ion exchange membranes have been prepared by (i)
denly developed premature aging Symptoms requiring walk polymerization of mixtures of reactants that can undergo
ing sticks to move. Such health threats may be alleviated by 45 condensation polymerization (at least one of the reactants
removing excessive harmful ions from water using an anion must contain a group that can be made anionic or cationic)
eXchange membrane in appropriate combination with a or (ii) chain polymerization of mixtures of reactants (e.g.
cation eXchange membrane. styrene, Vinyl pyridine or divinylbenzene) that can polymer
The use of these anion and cation exchange membranes ize (at least one of the reactants must contain an anionic or
represents an advancement over the techniques used in the 50 cationic moiety). There is a current need for the develop
past, Such as reverse osmosis and ultrafiltration ment of ion eXchange membranes possessing a combination
(DeSalination, 121: 139 (1999)). More stringent regulations of both good electrochemical performance and high
designed to promote public health also make the removal of mechanical Strength that can be provided by the homog
these and harmful ions necessary for a wide range of enous membranes.
industrial applications. Electrodialysis represents the most 55 More Specifically, previously developed heterogenous ion
promising method to meet these regulatory requirements eXchange membranes are prepared by dispersing finely
through the development of nitrate and fluoride ion-Selective divided pulverized particles of ion eXchange materials in a
anion exchange membranes. polymeric binder. These membranes suffer from numerous
In fact, for treatment of a variety of industrial effluents, disadvantages arising from their macro-sized, non-uniform
elctrodialysis offerS Significant advantages over other tech 60
particle structure. Furthermore, it is extremely difficult to
niques (Pure and Applied Chemistry, 46: 213-220 (1976)). overcome this problem by uniformly dispersing the ion
One Such advantage lies in the fact that wastewater con eXchange materials in the polymer binder. Because of the
Stituents are neither destroyed nor chemically altered by persistence of this problem, membranes prepared in this
electrodialysis. This allows the recovery of valuable prod manner will contain Zones with higher or lower concentra
ucts Such as certain metal ions and other inorganic materials tion of the exchangeable ionic groups, leading to inequalities
which may then have further commercial applications. Such 65 in ion transport. This in turn results in interuptions in ionic
recovery is facilitated by the fact that electrodialysis pro conductance from one Side of the membrane to the other
duces a concentrated, low-volume waste Stream containing when employed in electrodialysis.
 US 6,814,865 B1
3 4
One type of heterogenous membrane, the composite ene. The ionic charges on the membranes were introduced
membrane, attempts to overcome these problems by using by using quaternary Salts like trimethylamine in the case of
thin adhesive layers for lamination of the cation or anion chloromethylstyrene and methyl iodide or, rarely, methyl
eXchange membranes. See FIG. 1. Although this type of bromide in the case of vinyl pyridine monomer. These
membrane is quite popular and exhibits tolerable Stability in membranes have shown low electrical resistivity and good
Some processes, it is entirely unsatisfactory in harsh envi mechanical Strength in addition to Satisfactory transport
ronments Such as those with high temperatures and Strong properties i.e. transport numbers exceeding 98% for the
oxidizing conditions. In these harsh environments, the thin corresponding anions Such as bromide, nitrate, chloride,
adhesive layer used to laminate the membrane Is not stable fluoride, Sulfate, etc.
and will peel off after eXtened use, destroying the membrane. Even though these membranes have reached commercial
Homogenous membranes have generally been prepared applications in electrodialysis, they leave ample room for
by casting homogenous Solutions of a film-forming polymer further improvement The primary problem with Such mem
or copolymer (e.g. polystyrene-butadiene) and a polyelec branes lies in the method of preparation. The method used to
trolyte (e.g. N-methyl4-vinyl pyridinium chloride polymer). prepare chloromethylstyrene is very hazardous because it
Although generally better than heterogenous membranes, necessitates the use of toxic compounds, Such as
even these membranes are unsatisfactory for a wide variety 15 chloromethylether, a known carcinogen which may even
of applications because the mixed polyelectrolyte is not become airborn during the preparation process. Moreover,
bound to the film-forming polymer. As a result, the poly chloromethylstyrene is usually not available in large quan
electrolyte is slowly extracted from the membrane during tities. Additionally, the use of divinyl benzene makes the
use, eventually resulting in a loSS of conductivity as well as preparation process very costly further leading to the
ion eXchange capacity. increased overall process cost.
Some of the more Successful ion eXchange membranes In other efforts, polysulfone and polyetherSulfone mem
have employed a wide range of Support materials. branes have been prepared (J. Membrane Science, 156:
Specifically, polyester (Dacron (R), polyamides (Nylon(R), 61-45 (1999)). These types of membranes show increased
acrylics (Orion(R), modacrylics (Dynel(R) or Kanecaron(R), mechanical Strength and increased facility in the fabrication
vinylidene chlorides (SarancB), tetrafluoroethylene process. However, membrane Synthesis nevertheless
(Teflon(R), glass (Fiberglas(R), rayons, polyvinyl chloride 25 requires the use of hazardous chloromethylether. Moreover,
(Teviron cloth), polypropylene and the like having a visibly these membranes exhibit transport numbers only in the
open Structure as found in woven type fabrics have been range of 77% to 87% (J. Membrane Science, Part B, 37:
used. 1773–1785 (1999)).
Radiation-induced grafting methods previously described A few attempts have been made to Synthesize anion
and widely investigated for the preparation of ion exchange eXchange membranes by copolymerizing 4-vinylpyridine
membranes have met with limited success. When practiced with divinyl benzene (Polymer, 40: 7243-7249 (1999)).
on a large scale, however, the levels of electrical power Radiation grafting of 4-vinylpyridine onto polyethylene thin
required to produce these membranes is economically or film as a Support have also been attempted (J. Polymer
physically impracticable (J. Applied Polymer Sci., 76: Science, Part B: 27: 2229–2241 (2000); J. Applied Polymer
220–227 (2000), J. Electrochemical Society, 142: 35 Science, 64: 1469–1475 (1997)). The electrochemical prop
3659–3663 (1995), J. Applied Polymer Sci., 64: 1469–1475 erties of these membranes are poor. U.S. Pat. No. 5,936,004
(1997)). To date, most of the commercially available ion was issued for the preparation of blend membranes of
eXchange membranes are prepared using the copolymers of epichlorohydrin and polyacrylonitrile in the presence of
styrene (St), chloromethylstyrene and divinylbenzene 1,4-diazobicyclo-(2,2,2)-octane in DMF as a quaternizing
(DVB), which are subsequently modified by the addition of 40
agent. See the chemical Structure given in FIG. 2 for an
ion exchange moieties (Reactive & Functional Polymers, illustration of this membrane. This method avoids the use of
46: 3947 (2000)). Since St-DVB copolymer is not easily toxic chloromethylether and the membranes appear to have
molded into a membrane of Sufficient mechanical Strength better transport properties than previously reported, but they
for most applications, St, DVB and other monomers are have not been commercially accepted for a variety of
often alternatively coated onto a Support membrane made of reasons. First, the membranes are formed Solely from the
polypropylene (PP) or polyvinyl chloride (PVC). Apart from 45 polymer itself and lack any additional Support Thus their
Styrene, polysulfones, polyether Sulfones or polyvinylpyri mechanical Stability is impaired, especially at larger Sizes.
dine have also been used as a matrix polymer. However, Second, the membranes are formed by Starting with halo
these materials are all difficult to shape into thin, flexible genated polyethers to produce polyethylene-based mem
layerS most useful as ion eXchange membranes. In addition, branes. Polyethylene is not as Strong as many other fibers
very toxic chemicals Such as chloromethyl ethers (a carci 50 and this contributes to further deficiencies in mechanical
nogenic compound) must be used to produce these poly strength. Therefore, the membranes of U.S. Pat. No. 5,936,
CS. 004 are limited in size and must be replaced frequently
Anion exchangers (e.g. DD 301 541) (J. Membrane because of their poor mechanical Stability.
Science, 179:101-117 (2000)) containing alkylidene Additionally, Such membranes are often unable to process
epoxides bound on a polyvinyl alcohol base and prepared 55 highly concentrated ionic Solutions. Therefore, a pretreating
from the reaction of epichlorohydrin with the secondary or process must be used to remove Some unwanted ions prior
tertiary amines have also been produced. These exchangers to treatment by electrodialysis. In the case of desalination,
have the drawback that they can only be produced as balls this requirement is set forth previously (Polymer News, 25:
and not as membranes. Additionally, their chemical Stability 80-86 (2000)), which describes a desalination technique
against acids and alkalis is unsatisfactory due to the pro 60
using State-of-the-art membranes. Because of the inherent
duction of polyhydroxylated polymers. limitations of these membranes, and the entire pretreatment
Presently, most Successful anion eXchange membranes System is required prior to electrodialysis, making the pro
have been prepared by copolymerizing chloromethylstyrene ceSS costlier and more cumberSome.
or Vinyl pyridine in the presence of divinyl benzene using Therefore, a need exists for the development of ion
benzoyl peroxide as an initiator (J. Membrane Science, Part eXchange membranes with good electrochemical properties
B, 37:1773–1785 (1999)). Membranes have also been pre 65 coupled with excellent chemical, mechanical and thermal
pared by copolymerization of Styrene and divinyl benzene or Stability that may be prepared with minimal usage of haz
butadiene or copolymerization of acrylonitrile and butadi ardous chemicals and that may be used in a wide variety of
 US 6,814,865 B1
S 6
applications and particularly in commercial applications or rohydrin monomer, and the crosslinking agent comprises
for concentrated ionic Solutions. aniline. All these chemicals are nonhazardous. The molar
ratio of 4-Vinyl pyridine:epichlorohydrin:aniline is prefer
SUMMARY OF THE INVENTION ably 1:1:0.5, 1:0.5:0.25, or 1:1:0.05.
The present invention meets the needs for improved ion In another preferred embodiment, a copolymer comprises
eXchange membranes and processes for their preparation 4-Vinylpyridine and another copolymer comprises
and use described above and presents other advantages as N-isopropylacrylamide, a monomer comprises an aliphatic
Summarized below. epichlorohydrin, the crosslinking agent comprises aniline,
One membrane of the present invention is a homogenous and polymerization is initiated using benzyl peroxide.
anion exchange membrane comprising of poly(4- In another preferred embodiment the proceSS is used to
vinylpyridine) crosslinked with epichlorohydrin and aniline produce a cation exchange membrane comprising a Sulfonic
on a woven Support membrane. In a preferred: embodiment, acid group. Following polymerization and crosslinking the
the woven support membrane is a woven PVC membrane membrane may be Subjected to a Sulfonating agent to
(more commonly Teviron cloth). produce ion exchange groups from previously unreacted
Another membrane of the present invention is a homog 15 polymers. The Sulfonating agent is preferably Sulfanylic acid
enous cation exchange membrane comprising crosslinked in dichloromethane. In a more preferred embodiment, one
N,N'-diallylaniline and a maleimide derivative on a woven copolymer is N,N'-diallylaniline and another copolymer is a
Support membrane. The woven Support membrane in a maleimide derivative. In another preferred embodiment, the
preferred embodiment of this membrane is also a woven polymer is a brominated polyvinyl alcohol.
PVC membrane (Teviron cloth). The invention also comprises a process for electodialysis
In another embodiment, a novel cation eXchange mem using the membranes. The process generally comprises
brane was developed by using polyvinyl alcohol, PVA (Mol. providing a Solution comprising ions to be removed, passing
Wt.=1,25,000). The process involves the bromination (0.5 N the Solution through a membrane Stack of alternating anion
bromine in acetic acid) of PVA followed by sulfonation in and cation exchange membranes while applying a current
25% aqueous solution of sulfanylic acid for 6 hours. The orthogonal to the membrane Surfaces, and withdrawing
Sulfonated membrane obtained was crosslinked with form
25 purified or concentrated Solution from alternating compart
aldehyde in concentrated Sulfuric acid for 30 minutes to ments of the membrane Stack The process may be used to
obtain a good cation eXchange membrane. treat industrial effluents, especially acqueous industrial efflu
ents. It may also be used to treat naturally occurring aqueous
The process of the present invention is for producing an Solutions Such as brackish water or Seawater. The desired
ion eXchange membrane through in Situ polymerization of at end product of treatment may be purified water and/or
least one monomer, comonomer, polymer or copolymer on recovered ions. Except in the case of extremely concentrated
a woven Support membrane. A thick Solution of the Solutions, there is no need to remove excess ions prior to
monomers, comonomers, polymers and/or copolymerS is electrodialysis. Finally, membranes may be constructed So
prepared and polymerization carried on the woven Support as to be selective in ion permeability to allow removal of
membrane. Polymerization in Situ requires the addition of a 35 primarily one or more particular types of ions.
catalyst. A polyelectrolyle may be produced during poly For a better understanding of the invention and its
merization or Subsequent to that Step. Additionally, the advantages, reference may be made to the following descrip
polymers may be crosslinked during polymerization or tion of exemplary embodiments, taken in conjunction with
Subsequent to that Step. In a preferred embodiment, the the accompanying drawings
woven support membrane is a woven PVC cloth. Crosslink
ing may be accomplished through the use of a crosslinking 40 BRIEF DESCRIPTION OF THE DRAWINGS
agent or by heat curing. After the membrane has been
formed and crosslinked, it may be Subjected to a reagent FIG. 1: FIG. 1 depicts a heterogenous membrane of the
capable of forming an ion exchange group from previously type described in U.S. Pat. No. 6,103,078.
unreacted portions of the monomer, comonomer, polymer FIG. 2: FIG. 2 depicts a homogenous membrane of the
and/or copolymer. 45 type described in U.S. Pat. No. 5,936,004.
In a preferred embodiment, the process is used to form an FIG. 3: FIG. 3 is an anion exchange membrane of the
anion eXchange membrane comprising a positively charged present invention.
organic molecule, a quaternary ammonium group, or another FIG. 4: FIG. 4 is a cation exchange membrane of the
alkaline group. At least one monomer, comonomer, polymer present invention.
or copolymer is preferably an aromatic nitrogen-containing 50 FIG. 5: FIG. 5 is another cation exchange membrane of
monomer, polymer and/or copolymer containing one or the present invention.
more tertiary amine groups. These tertiary amine group or FIG. 6: FIG. 6 is a preferred embodiment of the process
groups may be quaternized during or after polymerization to for producing anion exchange membranes.
produce a quaternary ammonium anion eXchange group. If FIG. 7: FIG. 7 is another preferred embodiment of the
quaternization is accomplished after polymerization and 55 process for producing anion exchange membranes.
crosslinking, a quaternizing agent should be used. This
quarternizing agent might be methyl chloride, methyl iodide, FIG. 8: FIG. 8 is a preferred embodiment of the process
methyl bromide, ethyl chloride, ethyl iodide, ethyl bromide, for producing cation exchange membranes.
propyl chloride, propyl iodide, or propyl bromide. FIG. 9: FIG. 9 is another preferred embodiment of the
Preferrably, it is methyl iodide in a hexane solvent to make process for producing cation exchange membranes.
the proceSS leSS toxic. 60 FIG. 10: FIG. 10 depicts the electrodialysis step of a
At least one of the monomers used in anion eXchange preferred embodiment of the desalination process of the
membrane formation is preferrably Selected from the group present invention.
consisting of tertiary Substituted acrylamides, methylacry DETAILED DESCRIPTION OF THE
late esters, methylacrylamides, acrylates, esters and alkyl INVENTION
Substituted tertiary amine groups. In a more preferred 65
embodiment, a polymer or copolymer comprises This invention relates to the development of new poly
4-Vinylpyridine, an aromatic monomer, an aliphatic epichlo meric membranes for the Separation of inorganic Salts from
 US 6,814,865 B1
7 8
their mixtures. The membranes may also be used for the purification of water for reuse in industrial applications
permeation of dissolved oxygen from water. The ion including electroplating, leather tanning, dying, Semi
eXchange membranes of this invention have good electro conductor manufacture, printed circuit board manufac
chemical properties and excellent chemical, mechanical and ture and mining,
thermal stability and can be used for the effective removal of deashing of Sugar cane juice for production of better
Salts from water from any Source. These membranes are quality Sugar and improved yield with reduced genera
useful for the removal of cations and anions of any Salts in tion of molasses;
water including fluoride, chloride, nitrate, phosphate, and purification of amino acids, Vitamins, enzymes, cheese
Sulfate. The membranes can be designed to possess high Salt and vaccines, and
selectivity and exhibit good electrical conductivity. The removal of excessive fluoride and arsenic from ground
methods used to produce these membranes are quite simple Water.
and leSS expensive than the presention exchange membrane Ion Exchange Membranes
production methods and thus contribute to the overall The ion eXchange membranes of the present invention are
economy of any process using these membranes. The inven homogenous membranes composed of polymer and poly
tion also encompasses the use of these membranes in a 15 electrolyte polymerized in Situ and crosslinked. Ion
variety of electrodialysis applications from desalination eXchange groups may be present immediately after poly
techniques for the recovery of heavy metals or even cyanide merization in Situ or may be formed by Subsequent treatment
ions from waste Streams from the metal plating and mining of the membrane.
industries.
One of the most desirable qualities of ion exhange mem
The anion eXchange membranes of the present invention branes is the ability to reduce the consumption of electric
include the positively charged organic molecules, quater power by incorporation of materials with low electrical
nary ammonium groups, or other alkaline groups. The cation resistance. Lower electrical resistance results in faster per
eXchange membranes include Sulfonic acid groups, carboxy meability of ions through the membrane when used in
lic acid groups, or other acidic groups. The membranes electrodialysis (J. Membrane Science, 181:167-178 (2001);
produced show good mechanical and chemical Stability J. Membrane Science, 179: 101-117 (2000)). The mem
coupled with excellent electrochemical properties, including 25 branes of the present invention exhibit relatively low elec
low AC electrical resistance resulting in greater conductiv trical resistance. For example, one anion exchange mem
ity. The membranes may be reinforced on a woven PVC brane was found to have a resistance of only 1.5 to 3.0, ohm
cloth to provide further mechanical Support and Stability. cm when equilibrated at room temperature in a salt
The conditions used in the present invention to produce Solution, a value that is most Satisfactory even when com
ion eXchange membranes are completely non-hazardous and pared to the presently used membranes.
do not require Sophisticated equipment or facilities in com In addition to low electrical resistance, ion eXchange
parison with the methodologies presently used. The cost of membranes require mechanical strength to withstand the
membrane production is considerably leSS and the manufac physical forces of electrodialysis. Many previous mem
turing process is environmentally cleaner when compared branes have either exhibited poor mechanical Strength or
with many available technologies. 35 have obtained it at the expense of desirable electrochemical
Electrodialysis units using these membranes are easy to properties. Crosslinking of the present membrane improves
operate, require less expensive maintenance, and consume its mechanical stability with little to no detriment to elec
less electricity when compared to units using conventional trochemical properties. Mechanical Strength is further
membranes. Further, the membranes may be used in a wide increased by the Support membrane upon which the ion
variety of electrodialysis application including, but not 40
eXchange membrane is polymerized. The Support membrane
limited to: is chosen So that it is neither Soluble nor Subject to Substan
removal of any Salts, cations, or anions including, but not tial Swelling in the Solvent or medium in which the polymer
limited to, nitrates, Sulfates, phosphates, chlorides, bro is found prior to in Situ polymerization. In a preferred
mides and fluorides from any Sources including ground embodiment of the present invention, PVC fabric (Teviron
water, brackish ground water, Surface water, brackish cloth, Teijin Co., Ltd., Minoamihonmachi, Chuuou-ku,
Surface water, Sea water and industrial waste water to
45 Osaka city, Japan) is used as a Support membrane. PVC is
produce potable or other less ionized water, the preferred material because it can form a microporous
concentration and recovery of Salts and metals from Structure and is resistant to a wide variety of chemicals.
One anion eXchange membrane of the present invention
industrial and mining effluents, and other Sources of may be produced by the polymerization of an aromatic
raw materials, including the production of Salt from 50 nitrogen-containing monomer, polymer, and/or copolymer
SeaWater, containing one to Several tertiary amine groups which is
removal of ionic Salts from waste water from any industial contemporaneously or Subsequently quaternized. The qua
process including chemical, food preparation, ternary ammonium anion eXchange group formed by direct
pharmaceutical, petroleum, metallurgical and synfuel addition thus creates a polymeric quaternary ammonium
related processes to produce water Suitable for reuse or 55 chloride. The membrane may also be crosslinked via poly
discharge, merization of its vinyl group in the presence of epichloro
concentration and removal of various acids Such as hydro hydrin and aniline using a catalyst under heat treatment. The
chloric acid, phosphoric acid, Sulfuric acid, chromic crosslinking Step helps to restrict water imbibition when
acid and hydrofluoric acid from industrial effluents and water is taken up or absorbed by the ion eXchange mem
any other Sources of these and other acids 60
brane. Membrane formation occurs in Situ after application
to a woven Support membrane, preferrably a PVC support
Separation of metallic and nonmetallic elements including membrane. See FIG. 3 for an illustration of one such
iodine, Strontium, uranium, and plutonium, whether membrane.
radioactive or non-radioactive, from nuclear waste Similarly, a cation eXchange membrane of the present
Sources as needed in nuclear waste processing, recy invention may be prepared by copolymerization of N,N'-
cling and disposal during dismantling of nuclear 65 diallylaniline with a maleimide derivative and then applied
weapons, or design and operation of nuclear power as a paste to a woven PVC Support for in Situ polymeriza
plants and in other facilities, tion. The polymer thus formed is further crosslinked by
 US 6,814,865 B1
9 10
thermal curing in order to increase the mechanical Strength accomplished using methyl iodide in a hexane Solvent. The
and chemical Stability. crossliniking reaction may be Successfully completed by
The membrane is then Subjected to Sulfonation using using mixture of 1:1:0.5 in the molar ratio of
chlorosulfonic acid in dichloromethane. This results in a 4-Vinylpyridine:epichlorohydrin:aniline. Similarly, mixture
high level of acidic groups dispersed throughout the mem ratios 1:0.5:0.25 and 1:0.1:0.05 may also be used. This
brane. Such a cation eXchange membrane is illustrated in procedure yields polymers with hydroxy-terminated groups
FIG. 4. to increase the Swelling of the membranes and thus increase
Another cation exchange membrane of the present inven the transport properties. Using this method, the number of
tion may be prepared using polyvinyl alcohol, PVA eXchangeable groups is increased for the better efficiency of
(preferrably, Mol. Wt.=1,25,000). The process involves bro the membrane due to increased flux.
mination of the PVA using a 0.5 N bromine in acetic acid The treatment of the membrane with an auxiliary quater
followed by sulfonation in 25% aqueous solution of sulfa nizing agent, used only to quaternize the unreacted tertiary
nylic acid for 6 hours. The sulfonated membrane may then amino monomers in the polymer, is effected by Simply
be crosslinked, preferrably with formaldehyde in concen Soaking the membrane in a Saturated Solution of the quat
trated Sulfuric acid for 30 minutes. This results in a cation ernizing agent in hexane or another Such similar Solvent. In
exchange membrane as illustrated in FIG. 5 with desirable 15 a preferred embodiment, methyl iodide is the quaternizing
electrochemical and mechanical properties. agent.
Production Process One process of the present invention is the two-step
The production process of the present invention involves procedure as follows. 4-Vinylpyridine is homopolymerized
the in Situ polymerization of at least one polymer or copoly with Simultaneous croSSlinking and quaternizing by addition
mer on a woven PVC support membrane to form an ion of epichlorohydrin and aniline. The reaction is carried out in
eXchange membrane. At least one polymer or copolymer a hot air oven on a PVC woven fabric support membrane at
should be capable of forming a polyelectrolyte during poly 80 C. In the second step, unreacted pyridine units of
merization and/or upon Subsequent treatment of the mem poly(4-vinylpyridine) are quaternized in hexane containing
brane to chemically alter unreacted groups of the polymer. methyl iodide to give a Strongly alkaline anion exchange
The process additionally includes crosslinking. The membrane. Variations in the process parameterS Such as
crosslinking may be accomplished in a single Step by adding 25
temperature, reaction time, extent of crosslinking and water
crosslinking agents before polymerization or as a Second content are likely to affect the quality of the membrane.
Step by application of the crosslinking agents to the poly Optimum water content is critical for a high quality
merized membrane or Subjecting of the polymerized mem membrane. In the present invention, the higher the
brane to conditions that induce crosslinking. This proceSS crosslinking, the lower the water content. Thus a membrane
represents a novel method of forming ion eXchange mem with low levels of crosslinked polymer will have higher
branes and also achieves Several advantages over the pre water content. The number of ion exhangeable groups is also
vious processes in terms of lower cost and reduction in the an important factor in membrane quality. Longer reaction
use of hazardous chemicals. times will increase the
Many efficiencies in the ion eXchange membrane produc Substitution of ion exchangeable groups. An increase in
tion process of the present invention result from the use of 35 reaction temperature up to 80° C. will also increase the
a woven Support membrane, Such as polyvinyl chloride introduction of ion exchangeable groups, thereby
(PVC) and the process of in situ polymerization on the increasing the electrochemical properties of the mem
woven membrane. Woven PVC membranes are the preferred branes. However, the durability of the membranes
Support membranes. PVC produces excellent ion exchange
membranes when polymerized because the PVC provides depends upon the environmantal conditions Such Scal
continuous micropores through which ions Smaller than the 40 ing etc. All these factors were considered during the
pore size can be selectively permeated. The use of PVC synthesis of the membranes. One skilled in the art,
membranes also results in a production cost reduction and based upon prior knowledge and the description pro
environmental benefits because the manufacturing proceSS vided above should easily determine the set of reaction
uses leSS hazardous materials. Specifically, the use of car parameters required to produce a membrane with any
cinogenic chloromethylether is avoided in the production 45 Specificly desired qualities.
process of this embodiment of the invention. Additionally, In two other related processes, anion exchange mem
unlike radiation grafting techniques, the present techniques branes may be produced by two different methods. In the
for membrane production do not require high-energy radia first method, membranes are prepared by dissolving poly(4-
tion Sources that can consume prohibitively expensive vinylpyridine) in ethyl alcohol and adding this Solution to an
amounts of electrical power. 50 epichlorohydrin and aniline mixture in relative amounts
In a preferred embodiment of the ion exchange membrane depending upon the extent of crosslinking to be achieved
production process of the present invention, a Support mem (greater crosslinking is observed if more epichlorohydrin
brane is coated with a polymerizing Solution containing a and aniline mixture is present). The resulting mixture is
polyelectrolyte, and ion eXchange groups are Subsequently pasted onto woven PVC Support and dried at room tempera
introduced during and/or after polymerization. 55 ture. The ion eXchange membrane thus obtained is washed
More specifically, anion eXchange membranes may be with diethyl ether and further quaternized with methyl
produced through a novel proceSS by preparing a paste of iodide.
4-Vinylpyridine polymer or copolymer and the aliphatic In order to avoid direct polymerization of 4-Vinylpyridine,
epichlorohydrin monomer in the presence of aniline and a a Second method may be used in which Simultaneous
catalyst. The paste is applied to a woven fabric membrane 60
polymerization and crosslinking are achieved. This differs
such as a PVC membrane and then heated to a high from the first process described above because in the Second
temperature. After polymerization, the polymer is washed method the polymerization Step is avoided. A reduction in
and further quaternized with methyl iodide to produce the one Step of the proceSS may be economical commercially. In
ion exchange membrane. See FIGS. 6 and 7. this method, membranes are produced by applying a mixture
Epichlorohydrin is used in this process along with of monomer, an initiator, and crosslinking agent onto woven
4-Vinylpyridine and aliline because of its Superior chemical 65 PVC support, then heating the mixture to 80 C. in a oven
Stability and crosslinkability. In the process, epichlorohydrin for 12 hours. The resulting membrane is then washed with
and aniline both act as crosslinking agents. Quaternization is diethyl ether to remove the unreacted monomers, dried at
 US 6,814,865 B1
11 12
room temperature, then dipped in a mixture of hexane and of Solid materials from wastes containing Solid, gaseous, or
methyl iodide for about 12 hours to achieve quaternization. liquid Suspension for industrial or military purposes, e.g.
The proceSS may be optimized So that the number of ion recovery of Silicates or other precious materials as well as
eXchangeable groups increases due to an increase in the removal of organics to be used in the production and
number of reactive groups per gram of polymer. This was fabrication of Semiconductors and other electronic devices
possible due to the fact that quaternization of aniline can common to the telecommunication, computer, and other
take place. In order to avoid evaporation of the monomer, the related industries, including products using nanotechnology.
film may be simply covered with polyester sheets and The membranes may also be used for the recovery of
pressed between iron plates. inorganic materilals whether in Solid, or liquid Suspension
For large-scale production, the Second method may be for research and development or production of pharmaceu
more desirable than the first because it consists of only one ticals or other products for activities related to biotechnol
Step. Thus, the Second process is less expensive than the first ogy and food industries. Finally, the ion eXchange mem
branes may also be used for recovery of Specific mineral
and its membranes may be easier to fabricate in production elements from the above described processes for further
run quantities. economic employment, whether Such recovery is intended to
An anion eXchange membrane formed from be primary or Secondary in nature, as allowed by appropriate
4-Vinylpyridine and an N-isopropylacrylamide copolymer 15
regulatory authority.
may also be produced using a Similar proceSS as illustrated Electrodialysis in the present invention may be accom
in FIG. 7. Variations of such a process similar to those plished using ion Selective membranes and the application of
described above in order to achieve similar objectives will an electric field orthogonal to the membranes. See FIG. 10.
be understood by one skilled in the art. The anion and cation Selective membranes are placed alter
In another preferred embodiment, a cation exchange natively between the anode and cathode. This results in the
membrane was prepared by copolymerization of N,N'- concentration or dilution of the Solution in neighboring
diallylaniline with maleimide derivative. The polymer comparments, leading to high water purity in alternating
obtained was precipitated in a nonsolvent (methanol, compartments. The cost of the process may be reduced by
acetone or ethanol). Next, it was dissolved in a minimum using the largest membrane Surface area possible. Thus,
amount of organic Solvent (chloroform or benzene) So as to electrodialysis is quite effective in the deionization of waste/
obtain a pasty mass, which was pasted on a woven PVC effluent from industrial Sources. Electrodialysis can concen
membrane. The polymer formed was further crosslinked by 25 trate an electrolyte to high levels, resulting in high water
thermal curing in order to increase the mechanical Strength recycling ratios and a Small waste Stream to dispose off. The
electrodialysis process of the present invention, unlike pre
and chemical stability. The membrane thus obtained was vious processes, may also be used to deionize highly acidic
Subjected to Sulfonation using chlorosulfonic acid in Solutions because the membranes of the present investiga
dichloromethane, thereby increasing the number of ion tion are resistant to highly acidic environments.
eXchange groups present. See FIG. 8 for an illustration of One water purification method of the present invention
this process. may be used in the desalination of brackish water or Sea
A Second novel cation eXchange membrane was prepared water and treatment of Seawater to recover Salt. In this
by brominating polyvinyl alcohol using the brominating method, an electrical potential gradient is applied acroSS an
mixture (i.e., 0.5 N bromine in acetic acid). The brominated ion eXchange membrane of the present invention in order to
membrane was treated with 25% solution of sulfanylic acid 35 Separate the Salt or other ions Such as poisonous arsenic and
in water in order to introduce the Sulfonic acid groups. Then fluoride from water. Unlike previous methods, in the method
the membrane was treated with formaldehyde in concen of the present invention, water is not pretreated with ion
trated sulfuric acid to crosslink it. See FIG. 9 for a depiction eXchange columns to remove the excessive Salt content. It
of this process. Membrane formation was confirmed by the may be passed through the ion exchange membrane Stack
FTIR data and the membrane was tested for its ion exchange module without any pretreatment because the Superior quali
properties. Ion exchange capacity is 2-2.5 meg of Sodium/g 40 ties of the membranes of the present invention allow them to
of the membrane. The Swelling of the membrane in water is withstand solutions with high ion content and to effectively
about 25 to 30% (a favorable condition for electrodialysis remove Such concentrated ions to produce water meeting the
World Health Organization impurity limit or other desirable
process). The resistance of the membrane is 34 ohm cm. purity limits.
AJI these properties are better than most of the presently Alternate Starting water for the above proceSS may be
used commercial membranes. 45
water from industrial effluents, Such as a waste water from
Processes Utilizing Ion Exchange Membranes the chemical, food processing, Semiconductor and metal
The present invention not only encompasses ion exchange processing or tannery industries. Even industrial effluents
membranes and processes for their production, but also should not require pretreatment to obtain water of acceptable
methods of using Such membranes. One group of Such purity. However, pretreatment of Some extremely concen
methods is water desalination through electrodialysis. Elec 50 trated Solutions, Such as extremely hard water may be
trodialysis may be used for purification or remediation of advisable even when using the membranes of the present
water containing Sewage or Similar contaminants, purifica invention. Even if pretreatment is included, the process of
tion or remediation of industrial discharges, including dis the present invention will Still represent cost Savings over
charges from mining, tannery, and other extractive industries previous methods because the ion concentration need not be
which may contain either organic or inorganic chemicals, lowered as much during pretreatment.
compounds, or mixtures, purification or remediation of
55 Although only preferred embodiments of the invention
irrigation water from return flows, or purification or reme are specifically described above and in the following
diation of water from whatever Source containing toxic examples, it will be appreciated that modifications and
Substances from either natural or human deposition. All Such variations of the invention are possible without departing
purification or remediation may be to Safety levels pre from the Spirit and intended Scope of the invention.
60 EXAMPLES
Scribed by any relevant regulatory authority. Similarly, the
ion exchange membranes of the present invention may be Example 1
used for desalination of Seawater, Surface water or ground Preparation of Anion EXchange Membrane Using
water containing Saline, or Surface water or groundwater
containing other minerals in Solution or Suspension to Safety 4-Vinylpyridine Crosslinked with Epichlorohydrin
levels prescribed by any relevant regulatory authority. 65 and Aniline
The ion eXchange membranes may also have applications One gram of 4-vinylpyridine was dissolved in 10 ml of
in the recovery of solids. They may be used for the removal ethyl alcohol and the mixture was polymerized in the
 US 6,814,865 B1
13 14
presence of a benzyl peroxide initiator (2 weight % relative the membrane is insoluble in water without causing the
to the vinyl monomer) for 6 hours at 80° C. in a 100 ml membrane to loose its flexibility. Depending upon the degree
round bottom flask. The polymer formed in solution was of crosslinking during its Synthesis, the membrane will
precipitated by the addition of 50 ml of water. The white naturally absorb a fixed quantity of water and become totally
colored Solid polymer was separated by filtration and ionically conductive when equilibrated in water.
washed repeatedly with distilled water to remove the low In other embodiments, Suitable aliphatic vinyl monomers
molecular weight polymers. About 4 g of polymer was or comonomers comprising covalently bonded tertiary
dissolved in 1000 ml of ethyl alcohol and to this solution, amine groups are: tertiary-Substituted acrylamides, methy
epichlorohydrin and aniline were added as crosslinking lacrylate esters, methacrylamides, acrylate, esters or alkyl
agents. The resulting mixture was poured onto woven PVC Substituted tertiary amine groups (Chem. Commun.,
membrane and the process of crosslinking was continued up 1303–1304 (1998)).
to 12 hours at room temperature. The membranes of this invention can be obtained by the
Subsequently, the PVC fabric with polymer was sand process of casting Solutions or pastes of the polymer or of
wiched between plastic lined glass plates and heated to 80 the mixtures of polymers in miscible common Solvents or in
C. for periods up to 12 hours to form the crosslinked 15 liquid comonomers, which are used to couple onto the
polymer membrane having quaternary ammonium groups woven PVC membrane. Here, the Solutions of desired
and reinforced with PVC support. These membranes exhib polymers or copolymers are usually prepared by dissolving
ited excellent mechanical properties (Muller burst strength each of the polymers in a common Solvent, followed by heat
of 4–5 kgf/cm) and, in particular, excellent resistance to polymerization with the added catalyst. The quaternization
aggressive chemicals were obtained. The unreacted pyridine and polymerization generally take place Simultaneously. The
units were quaternized using methyl iodide by placing the membrane obtained is then treated with alkyl halide. The
membrane in a mixture of hexane:methyl iodide in the molar preferred alkylating agent is methyl iodide. However, other
ratio of 6:4 at room temperature for 12 hours. The alkylated alkylating agents like methyl, ethyl, or propyl in the form of
membrane was washed with diethyl ether to remove any chloride, iodide or bromide may also be used.
residual methyl iodide and the membrane was dried under
Vacuum for 2 hours. 25 Example 2
The membrane thus produced exhibited electrical resis
tance of between 1.5 and 3.0 ohm cm as measured after Preparation of Anion EXchange Membrane Using
attainment of equilibration at 25 C. in 0.5 N sodium N-Isopropylacrylamide and 4-Vinylpyridine
chloride Solution. The instrument used for this measurement
was an APLAB Autocompute LCR-Sortester (Model 4912, The anion eXchange membrane was prepared by copoly
Serial No. 981/1 made in Mumbai) at the frequency of 1 kHz merizing 4-vinylpyridine and N-isopropylacrylamide using
using AC. The transport number was found to be >0.98 as benzyl peroxide as an initiator. The 4-vinylpyridine and
measured by electrodialysis of 0.5 NSodium chloride solu N-isopropylacrylamide (1 weight% to the vinyl monomer),
tion at the current density of 20 mA/cm. An indigeneously aniline and epichlorohydrin and the initiator were mixed in
built chronopotentiometry was also used to measure the 35
a 100 ml beaker. The resulting mixture was pasted onto
transport number. The ion eXchange capacity in woven PVC material and polymerized at 80 C. for 12 hours
milliequivalents/g of chloride ions from the dry membrane in an inert atmosphere. The polymer formed was washed
was found to be between 2.5 and 3.5. This is the useful range with diethylether to remove unreacted monomers. It was
of values for any commercial membrane for the intended further quaternized with methyl iodide in hexane as a
application of this embodiment. The thickness of the mem solvent for 12 hours at room temperature. See FIG. 7. The
branes as measured by micrometer Screw gauge was 40 polymer structure was confirmed as characterized by FTIR.
between 0.14 and 0.16 mm. Water content (wet mass/g of
chloride ion from dry membrane) i.e., equilibrium Swelling Example 3
was 15-20%. These data were obtained after attainment of
equilibrium Swelling of the membranes that are immersed in Preparation of N,N'-Diallylaniline-Based Cation
distilled water and also in 0.1 N Sodium chloride Solution. 45 Exchange Membranes
The wet mass was measured after equilibrium with 0.1 N One of the cation exchange membranes of the present
Sodium chloride Solution.
The membrane thus obtained was characterized by FTIR. invention was prepared by copolymerization of N,N'-
The peak observed at wavenumber 3406 cm' is due to diallylaniline with maleimide derivative in an Inert atmo
N-H and O-H bond indicating the reaction between 50
sphere at 80° C. for 12 hours. The polymer obtained was
epichlorohydrin and aniline. It also indicates the presence an precipitated in a nonsolvent (methanol, acetone or ethanol).
unreacted N-H group of aniline. The peak at 1597 cm is Next, it was dissolved in a minimum amount of organic
due to the N-H asymmetric bending of aniline. The peak at Solvent (chloroform or benzene) So, as to obtain a pasty
1424 cm is due to the O-H bending of the epichloro mass, which was then pasted on a woven PVC membrane.
hydrin indicating its ring opening for crosslinking. The The polymer formed was further crosslinked by thermal
C-N stretching frequencies appearing at 1504 cm indi 55 curing at 120° C. for 12 hours in an inert atmosphere in order
cates the reaction between aniline and epichlorohydrin. to increase the mechanical Strength and chemical Stability.
Thus, during polymerization by this method, the nitrogen The membrane thus obtained was subjected to Sulfonation
group of the Vinyl pyridine monomer couples directly with using chloroSulfonic acid in dichloromethane. The reaction
Scheme is shown in FIG. 8.
the alkyl group of the epichlorohydrin to from the quater
nary ammonium chloride groups. The tertiary amine vinyl 60
Example 4
monomers of the polymer attach themselves covalently to
the chain in this reaction forming part of the polymer Preparation of Cation Exchange Membrane Based
backbone as shown in FIG. 6.
on Polyvinyl Alcohol Followed by Sulfonation with
Further reaction of the coupled crosslinked polymer when Sulfanylic Acid
treated with hexane Saturated methyl iodide quaternizes the 65
tertiary amino group as shown above. The thus-formed A Second novel cation eXchange membrane was prepared
three-dimensional matrix Structure is Sufficient to ensure that by brominating polyvinyl alcohol in a brominating mixture
 US 6,814,865 B1
15 16
(i.e., 0.5 N bromine in acetic acid). This was treated with
25% solution of sulfanylic acid in water to introduce Sul --CH-CH2-------CH-CH2-),
fonic acid groups. The membrane was treated with formal
dehyde: in concentrated Sulfuric acid to obtain a crosslinked
membrane. This membrane was prepared without the use of 5 N 21
any support PVC membrane. The membrane formation was
confirmed by FTIR and tested for its ion eXchange capacity. 2 N
CI CI
See FIG. 9. Ion exchange capacity of this membrane is 2-2.5
med of Sodium/g of the membrane. The Swelling of the CH2 CH
membrane in water is in the range 25-30% (a favorable
condition for electrodialysis membrane). The resistance of CH-CH-OH
the membrane is 3-4 ohm cm°. | Cir
The FTIR data of the membranes indicate that the reaction -CH
scheme provided in FIG. 9 is acceptable. For example, the
peak at 3061 cm is due to the O-H and N-H streching 15
vibrations of polyvinyl alcohol and Sulfanylic acid. The
peaks at 1601 and 838 cm are attributed to the N-H
deformation as well as wagging of the Sulfanylic acid,
respectively. However, the peak at 1011 cm' is due to the
S=O streching of the sulfanylic acid.
Example 5
--CH-CH,-
Desalination of Brackish Water or Seawater Using
Anion and Cation Exchange Membranes
Brackish water or Seawater which may or may not be 25 4. The membrane of claim 1, wherein the membrane
chlorine-dosed is provided through a feed pipe to an elec comprise a compound of the following formula:
trodialysis unit. The water is obtained from a borewell or
intake pipe and may pass through a chlorine-dosing or other H H2 H H2 H2 H
treatment Station, but no pretreatment designed Solely to C-C -
X
---- C-C -
y
---- C -C X
remove exceSS ions occurs.
The electrodialysis unit is 600 mmx1,100 mmx800 mm N 21 =o
and houses at approximinately 120 pairs (or more depending NH
upon the type of water) of alternating cation and anion 2 N
exchange membranes which measure 500 mmx1,000 mm C C c1" YCH,
each and are separated by 880 mmx380 mm spacers. Each 35
CH2 CH
membrane is Sealed to the edges of the membrane region of H2
the electrodialysis unit by a 500 mmx1,000 mm gasket
around its perimeter. The entire unit is placed Securely
within the sturdy walls of the polyvinyl chloride sheets. This
prevents leakage of water around rather than filtration 40
through the membrane. An 880x380 mm precious metal
titanium anode is located at one end of the membrane Stack
while a stainleSS Steel cathode of the Same size is located at
the opposite end of the membrane Stack. The general con
figuration of the electrodialysis unit not drawn to Scale and 45
showing only a few representative membrane pairs may be
Seen in FIG. 10.
Power is Supplied to the anode and cathode using a 230
Volt D.C. power Supply with 15 amps capacity. Two pumps
of 0.5 HP capacity are used to circulate feed water into the
unit and to remove and/or recirculate the concentrated 50
wastewater from alternating Spaces between membranes. 5. A proceSS for electrodialysis comprising:
One pump of 0.25 HP capacity is used to remove and/or
recirculate the purified water. Water flow into the electrodi providing a Solution comprising ions to be removed;
alysis unit is indiated and controlled using a rotameter which passing the Solution through a membrane Stack compris
includes a Solenoid valve, ball valves, a pipe line and a panel 55
board. ing at least one anion exchange membrane prepared
We claim: using a method including:
1. A homogenous anion eXchange membrane prepared i) providing of 4-vinyl pyridine;
using a method comprising:
i) providing of 4-vinyl pyridine; 60
ii) in situ polymerization the 4-vinyl pyridine on a
ii) in Situ polymerization the 4-vinyl pyridine on a woven woven Support membrane; and
Support membrane; and iii) crosslinking with epichlorohydrin and aniline;
iii) crosslinking with epichlorohydrin and aniline. while applying a current orthogonal to the membrane
2. The membrane of claim 1 wherein the woven support Surfaces, and
membrane is a woven PVC membrane. 65
3. The membrane of claim 1, wherein the membrane withdrawing purified or concentrated Solution from alter
comprise a compound of the following formula: nating compartments of the membrane Stack.
 US 6,814,865 B1
17 18
6. The process of claim 5 wherein the solution is an 9. The process of claim 7, wherein the brackish water or
aqueous industrial effluent. Seawater is not treated to remove exceSS ions prior to
7. The process of claim 5 wherein the solution is a electrodialysis.
naturally occurring aqueous Solution.
8. The process of claim 7, wherein the solution is brackish
Water Or SeaWater. k . . . .