Development of ion exchange membrane technology

DesGurtion.22(1977)495--504 QElheerscientiticPu~compaQy.

495 Amzterdarn - Printedin The h’eflmiands

DEVELOE?fEET OF IOB EXCUKGE

T. Seto,

El. Keuate

The 3rd &x&xls

Ion exchange

Pecbrane

vater.

sevage

of loa exchange

concentration

desallnatioa.

production,

uechrane

is briefly

by the cocpany

Asahi

Industry

Chedcal

kinds

tzmbranes

of ion exchange

high quaUty

have

membranes

The tocal

in the world

The Lou exchange

Kawasaki

* Present

have been

mu

exceeds

caustic

etc.

General

soda producapplLcetiou

is placed

fts developuentzl io 1950.

developed

conor

on large

applkations.

Since

research

Installed

of

electrochemCxl

by the ccmpany

ceters

ou

then, various

and these mzhranes of various

370,fXYO square

and

or 4.000.000

1. X977.

zaenbrane tnftfally

was started

developed

was s hozcogeous type uithout

techaology was established

in 1953.

The

ti 1956 for the teat operation of electro-

su 1960, a coamerdd

end its product

address:

posstble

CO the establishment

and the productlou

membrane productfop dialyters .

and other

seavater

of seawater

and a stress

area of the cmnbranea

appllcatious.

relrrforcewt

revfeved

used in the world

Besfdes

desalination,

Cob., Ltd. started

contributed

feet a5 of January

and currently

enrichment,

stage of

in 1950 and the total

desalinetton

and their applications

used currently square

&ey

uraniun

(Japau)

c?eveZoped for

In the early

I. 1977.

covers

presently

Tokyo

have been uainly

its research

as of January

cvrdule developed

ion exchange

started

Co.. Ltd..

in Japan

by the conpany

meters

the application

tion, adfponitrile

Industry

and its applicat1one

installed

370,OllO square

brackish

Che&caI

The coupany

area of the uecbrane

centration,

k&i

salt by seawater

development.

exceeds

TECEXOLOGY

and H. Komri* Mtiriou.

ma.mfacturFng their

HRLBMNE

nzedxane

plant

ups used for a brackish

l-2. Yurakucho

1-chope.

started water

up its productton

desalFParfDo

Chfyoda-‘ku. Tokyo

plant

at and

496

a salt rzimdactuzing

plant,

both of which were built the forloving year.

Nev types of ion exchange the technology

current

zppfication

since

problen

but also

vere

evailable.

higher mechanical strength tietedeveloped

Those new type

Luproved

Reinforced type &ranes

of electrodialysis.

chemical properties in 1972.

in 1965.

~2nufecturing

for salt

not only solved gypsrn scaling

efficiency

cou!zercial mzbranes

were developed for and introduced to the sea-

Uni-valent penzselective E&ranes water concentration of membranes

were required for the iqrovenzent of

rzebraes

or for oeu applLcations

the

which have

without degrading their electro-

Ion exchange

currently produced are

umzbranes

shoun in Table 1. TABLE 1 Ion exchmge

&ranes

E&zarks

Tyte

Major

K-101

Cation

Desalination

K-102

Cation

Salt Eznufacturing

K-301

Catfon

ADN production

K-401

Cation

Uraniln

A-1OL

Anion

DesalinatLon

A-102

Anion

A-201

Anion

A-211

Anion

Wney desalination

A-221

Anion

Nickel

Model

No.

Various

kinds

usage

Uni-vrlent

pemselective

Salt manufacturing

Uni-valent

penzselective

Desalination

Anti-organic fouling

reduction

recovery

of electrodialyzeti

aad

electtolyzers vere developed along

with the development of ion exchange mzzbranes. The first electrodialyzer vas made

using polysterene frame as its gasket ar?dthen

with plastic screen 2s spacers. me the perforrrance of the electrodialyzer distance

vas achieved

by utilizing

distance

for electrodialyzers

latter

rubber

coabinstion

because

the thinner

thrs cozblnation.

gaskets

were

used

sfgafficantly improved and uniform

The standard

Eterzbraae

mmbta.ne

is 0.75 ml and 0.5 cm thick gaskets are partially

utilized depending on applications, The low energy consurzptionLs expected the pwer consuqtion of electrodfalysfs depends on the electtic cell

because

resistance and the recirculating volume to the cell of The electrodialyzer.

497 The per

fLrst coxzercUl aad held

cell

A larger

node1 was

pairs of ubicb introduced Nosh&a

electrolyzer

plant

put into comercial the other

was

up to 1.800 ueubrane This mdel

in 1972 and was

Tuo types

m

excellent

uranitn

cell

also used

at

hzve

(Dylan 66 inter-

hother

process.

for the direct

meter

~a.5

of electrolyters

one is for adLponitrL.le

use:

is for chlor-dkdi

and it showed

of 1.0 square

a set of electrades.

per cell.

in Jrpan lacer.

used in a test program

@NC process)

meters

mea

between

f& 1972 am? it holds

area is 1.4 sqxare

desalination

production.

had ~II acttwe

cell patrs

for the salt modernization

been already

process

developed

active

sewater

mediate)

electkodlalyter

up to 1,5UO t!edxane

type of

purification

perfomance.

APPIJCATIOSS

use of ion exchjnge zenbtane in Japan was to coacentrate sca(13 when the mxbrane became couxercially available. salt

The m&or water Fig.

for manufacturing L shows

Shinnihon

a picture

Chenical

satisfactorily

of electrodialyzers

in 1961.

Ln operation

as the oldest

ables such as xcezbranes, gaskets, even

increased

other words, than

by twenty

basic

15 years

wfth

of a commercial

Ffg-

ones

spacers,

etc.

dE the

perforczmce

in Japan vith

salt plant

replaced

ELectmdfd$zers

capacity

is

of

technology

so far.

In

have

cm the actual

for seautter

consuz-

production

a life span of erore operatlng

experience

plant.

1

of

are still

Their

electrodlalyzers based

at Onahama

in the picture

perce d t by the irqrovPmPnt

coqonents steady

installed

tie electrodialyters

cmce=rtratiou

{1961)

Acid

I _

7

-

I

cx Pit

--

Dilutton

I

Eeadet

Filtered Seawater

S8Ud

Filter

fit Brine Pit

I

t

Seavatet

Fit

Intake

Evaporating

Crystallizer

Btucmetrfc

cunde;Lser

*Brine

I!. Deacrator

Fig.

2

Salt

Kauufac~uring

by Efectxmdtalysis

’

Pig. 2 shous

a typical

The systezz consists

crystallization. brine

system

process

is utFlfred

vhkch

feed

to heat

seavater

in vinter

tional

sand

and two Stage

in case of

used

for evaporatLng

Depending

its

seawater

seawater fs

a cbuven-

oay be chosen or tuo stage

generated

depading generatfon

by the turbiae

+ uhile

f;he lov pressure

stem

on the steady traditiona

solar

has been

had been

purposes.

Table

electrodialpsis

used

for sit

processes

as a gwemcental produced

process

in Japan had policy.

by electrodialysis

field is now used for industrtal

2 shows a LLst .of salt manufacturing

plams

and vast or cxnicLpa1

in Japan

i

process.

Salt nw.nufactur%nq

plants

in iapa.3

P-foductioa capacLty ketric ton-saltI'll>

of the compmy Chemfcal

Ind. Co,

ChenLcal

Naruto

Salt Mfg.

Naikai

SaLt Works

Co.

Ind. Co.

’

Technology AsahL

C?xemfcal

L75,OOO

AsaM

Cheah3.l

184,300

Aahf Asahf I Asuhi Asaizf

186,000

192,UOO

179,000

it vas

to He

As a ksult,

2

Ako Sea Water

is fs

is used

froa the turbine

the electrodfalysls

eoaporation

for food use in Japan

land vhich

of

petforezance

all

Shin Nihon

on

electrodialysis

turbine

Steam

d the electrkity

process

Yaw

stage

concentratton.

to rhe electrodialysls

TABLE

of

con-

of the seawater

by svitching

filtratfcm

Multi-

and the waste

by a barometric

collected

pretreat-t

in to produce

fron the brine.

The temperature

a single

svitched salt

is

sand

taken

crystallfzatlon~

that all

decided

I

for the system

for electrodialysts

used

Either sezuater

salt

is controlled

Ai typkal

of rav seawater.

czn be utflfzed generally

prokess

tnd suzxzet.

filtration

the qualLty

crystalltzer

and evaporattig

seawater

crystallization

for elebtrodialysis.

to the electrodfalysfs

source

concentrates crgat~~_Uires

I

by electrodialysis,

mazmfacturlng efectradLalysfs

for the evaporating

heat of the final evaporating denser

sections:

The Former p+cese

for the latter

effect

flc'yshaet of s&t

of tvo aaj$‘r

Chemical czfxex!lfc.2l Class Glass

sakito

salt Works

Kinkai.

Salt Hfg,

Co.

173.000

Tokuyan;a

Soda

santi

saltwg.

co.

172,700

Tokuyazra

Soda

usfng

500

Asahi Chzaical uade a cmtract Uls.=o,E&public

of

Korea.

and the plant will

dialysis

is

ta

will

aecbtanes

The

to btild a sjLt wufacturing

plant at

capacity is 150.000 u.etric ton of salt per year

be in operatloE

by the end of March,

stage

Tvo

1979.

electro-

be used and 21,600 cell pairs or t3,200 sheets of ion exchange

be installed.

Desalination technology;

The

major area of applications

is another

however, the de-d

first brackish

water

of

ion

exchange creobrane

for desalfaation plant is still Little in Japan.

desaliaation

plant

usiug

a Japanese technology w&s built

by Asahi chemical in 1961 at Webster, South Dakota, U.S.A.

(21

Hajor

four Islands

of Japan, which are Honshu, Hokkaido, Kyushu and Shikoku, are generally abunduat

in natural vater resources of hfgh quality. islands

have been

suffering

fron water

south of Tokyo is one of those isla.n& by electrodialysis electrodfzdysfs amount

was

of ion exchange

adopted

me&races

szaller than that for seawater

One signiffcant of Noshfoa sfully

in

seauater operation

event

for brackish used

for this

fn desalination

for three

desafiaation

voter

Since then,

desalination;

purpose

hovever,

in Japan

the

fs still much

by electrodialysis

was

plant in 1974. (3)(4) The plot

years

supplylng

the inhabitants

Seavater

dewllnation

unit

the start

up

has been succes-

of the islaud

Fig. 3 shows the electrodialyrer used

PCg. 3

plant

concentration.

desalination

fresh vater fron the sea.

Shfkinejina island located

and a brackish water

in 1970 for the first time.

installed

has been

On the other hand, uzmy mall

shortage.

for

uith

the plant.

Other

areas

cocnercially process, tion,

of

applicatians

established

acid

etc.

or alkali

The ioa

relatively

snail

Ion exchange

mesbrarte technology

desd.ination,

*ey m&brane

recovery

metal

adipanltrile

recovery,

exchange

although the amxmt

of

are:

production,

uhkh

are

from plating

chlor-aWall.

produc-

an inportant role in each process,

plays

of ion exchange mzubranes used in these applications are

conpared

to the predescribed

cajor

applications.

CKARACTERLSTICS 3F LAEGE WDULE of

The specifications wdel

manufactured

SS-0

by As&i

Koclel electrodialyter

ChemLcal is

Henbrane size :

wao

Actfve

area:

1.4 square

No. of

cell

No. of stacks:

L stacks

Flow:

Sheet

Press:

unit

of

crane

and

divided

is

into

its

vhen It

of

frequency

of

fs

systm

of higher grade

En electmdfatysh3 is

i.e.

strongly

for

or In place

procm3s

lqortant.

r

nininLzing

, quite

a high

underground vi11

be nuch

cleaning

follovfng

load

The

for easy hcmdling

factor

fitration

of

uill

the

be

has to be cleaned.

on the qualrty

vater

fs

of

the raw

adopted,

a

and twice to four tees

decreased,

if

2

ptetreatnent

is adopted.

or in other membrane The

mzters.

the doun tin=

vhen the stack depknds

Uhen sand

the preireatreat.

square

neebraue stacks,

necessary,

cleaning

is 2,520

area

qtickly

Therefore

The frequency

for seawater.

rate

type

the standard unit holds up to 1,800 cell

qkLte

is once a yeat

a year

reglacezeat

press

effective

replacEen

the stack

and the degree

typical

per stack

per press

portions,

is wde

necessary.

The stack

expected.

The frequency unter

is

tocel

several

and stack repLaceaent unit,

m3

Peters per cell

O-75 UD

As shoun in the speciflcatfon,

pairs

the standard

flav type

Filter distazxe:

Skmbrane

x,3(30

x

t22

\ipto 300 cell pairs

pairs:

is

as follaws:

pracesses,

is the actual

mual

the rzeiubrane membrane

502 rP,@dC~t

%XCS

at

the

PhIItS

USiUg

."ahf

1976.

Salt nanufactting:

less

tharr 10 percent

Bracktsh

water

less

than

Seawater

desalfmat~on:

There

a big

is

concentration application

desaltiation:

difference

to 3 H3/day water

(salt naufecturing)

accunrrlated

is

be eade

Ln

-&ranes

maxhize

the water

is becdng

recovery

a precious

electrodialysis

in achieving

dialysis

wotks

brine

Another

the river,

systm

vas

osmsis

process

resource

they are handled

it is very

because

even

shell

rate is

oanually.

wortant

to

the brackish

for fresh vatet.

Reverse

vater

osc!osls-

at Roswell, N.N., U.S.A. as a possible recovery. (5) In this cozzbined system. electrobecause

ft desalts

and returns

prucese

while

producfng

the relatively

desalted

concentrated

water

brine

to the feed

&s a final

for electrocUalys%a in the near future will be system. (6)(7) There are my cases in uhich the

or muiergrotmd

as to prevent

basin.

the contazzfcac5aa

If the plant

to tbe sda; hovever,

till be a btg problem. system

RspeELally

is used,

in the streaxz

hslp piping

to iacrease

or heat exchangers is an excelfat dectmlug

Rrocess the vote

Is located

when

a water

of brine utth

rzear the sea,

if it LE located

it 5s necessary

to keep the salt toxentratioo

at a low level uh5le

cleaning

the replaceaent

opportunity

in the closed

such as a cooling

electrodialysfs

frequent

of turbid

system.

be discharged

disposal

core

volme

2.5

of sea-

tested

has to be so treated l&e

can directly brine

osmosis

possible

waste water

zs possible,

water

as a dessltercoqxntrator

from the cabined

the application

water,

a high vater

from reverse

of the reverse waste

of brackish

BS mch

natural

cmhinatioa

approach

dilute

process

uhen

The

concentration,

larger

Therefore.

get d-es

the latter

than 0.4 H3/day

In other Gords,

concentration.

generally

In any desalination

Zess

although

applkation.

in seawater

the cell axtd as a result

in caSe of seawater

high because

desalination

than the foner

cell, while

desaltiation.

rates betveen seawater

replacezeut

as follows:

is fed to each

of seavater

1 percent

and seawater

experience

esplained

is fed in seawater

elements

in the annual

has less operating

d_%fference u.zy be partly

S percent

less t&m

iplad,

recirculntiaa

to blow dm

fn order

at L reasonable level ac,vhhh

aaticorrosivemzss.

to keep water

to

In thti case,

the concentration voluwz

it

the

fn the strem

sLgu.ffFcantly. I

503

DESALTED SEXHATER H3/br

2,382

O-37 eq/I Electrodialysis BXNE 118

H3Jht

3.2

Fig.

4

Mass balance of electrodfafysis in seawater (150,000 rzetric ton of saIt per year)

As shown in Fig. producing

4,

desalted

r=ezns that this some different

elect~dialyzers seavater

technology

produce

in the seavater can be applied

cancentratian

concentrated

concentration to s>stezs

may be necessary

pretreatrent

highly

eq/l

of cooling

depending

brine while

appllcatian. vater

on the water

It although

quality

of

the systw. Pig.

5 shows the pkture

SS-O electtodialyzers a desalination

process

cozzzercial applicetfon

for

of the latest

seawater

but also an excellent for years.

fnstalfation

concentration.

of

the largest

ELectrodielys~s

cancentwtfoa

process

node1

is not only proved

In

SS-O l&de1

electrodialyzers

BEFERENCES

(3)

(4)

(5) (6) (7)

for Pruducing Brine Concentrates fro3 Se* Tsunoda, Y.. "Electroditiysis water", First Laternational Syqosim on Water Desalination. U.S. Departnent of the Interior, October, 1965. Water Conversion-Electrodialysis DezanstraS&o, H., 'large Scale Bra&&h SyEpdSirn EIw Plam at Webster. South Dakota. U.S.A.", lst InrerQatlonnZ on Fresh Water frum the Sea, 1962. aad T. Miue, "Seavacer DesaliSeto, T., t. Ebara, R. Konori, A. Ymaguchi aatlon by Electrodialysis", St& lnternatfonal Symposirn cm Fresh Water fros the Sea, Hay 1976. Wwa, T., D. R, Jordan and W. l?. HcIlhenny, "SePtacer Desalting by Electrodialysis", First Desaltiation Congress of The Ametican CoritS.nent, IDEA, October, 1976. "Brine Ccncentratioa by Electro&alpsfs", report to the Office of Saliue Water, Dow Ch2mical Co.