MODERN CHLOR-ALKALI TECHNOLOGY

Volume 5
 MODERN
CHLOR-ALKALI
TECHNOLOGY

Volume 5

Edited by

T. C. WELLINGTON
Hays Chemical Distribution Ltd,
Sandbach, Cheshire, UK

Published for SCI

SCI
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WITH 48 TABLES AND 184 IlLUSTRATIONS

© 1992 SCI

British Library Cataloguing in Publication Data

Modem Chlor-alkali Technology. - Vol.5

I. Wellington, T. C.
665.83

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 v

CONTENTS

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . xi
1 The effect of green issues on the chlorine/caustic soda balance. 1
B. A. Friedfeld
Kline & Co.,
165 Passaic Avenue,
Fairfield,
New Jersey 07004,
USA
2 Changes in the chemical requirements of the bleached kraft pulp
industry. . . . . . . . . . . . . . . . . . . . . . . . . . . 13
D. A. Perham
Perhamconsult Ltd,
4 Deans Close,
Croydon,
CR05PU,
UK
3 ICI 'Hydecat' process for the catalytic destruction of hypochlorite
emuent streams . . . . . . . . . . . . . . . . . . . . 23
P. E. J. Abbott, M. Carlin, M. E. Fakley, F. E. Hancock,
F. King
ICI Kataico,
PO Box 1,
Billingham,
Cleveland TS23 lLB,
UK
4 Green aspects of chlorine bleach-approaches and national
characteristics. .... . . . . . . . . . . . . .. 35
J. P. Shields
Hays Chemical Distribution Ltd,
Bulk Products,
Sandbach,
Cheshire CWll 9PZ,
UK
 vi
5 Cyclochrome-The recycle of sodium dichromate in sodium chlorate
manufacture. . . . . . . . . . . . . . . . . . . . . . . . . 43
R. E. Alford
Chemetics International Co. Ltd,
Chemical Technology Division,
1818 Cornwall Avenue,
Vancouver,
British Columbia,
Canada V6J 1C7

6 The design and development of F1emion membranes 59

H. Miyake
Asahi Glass Co. Ltd,
1150 Hazawa-cho,
Kanagawa-ku,
Yokohama-shi 221,
Japan

7 Understanding membrane operating conditions. 69

J. T. Keating
E. I. du Pont de Nemours & Co., Inc.,
PO Box 80323,
Wilmington,
Delaware 19880-0323,
USA

8 Factors which influence the permselectivity of high performance

chior-alkali membranes . . . . . . . . . . . . . . . . . . . . 81
H. L. Yeager, A. A. Gronowski
Department of Chemistry,
The University of Calgary,
2500 University Drive N.W.,
Calgary,
Alberta,
Canada T2N IN4

9 Natural high flow rate recirculation: a highlight on De Nora

Technologies membrane electrolyzers. . . . . . . 93
O. Borrione, A. Ottaviani
Oronzio De Nora Technologies SpA,
Via Bristolfi 35,
20134 Milan,
Italy
 vii
10 Safety and economy of membrane cell electrolyzers. 105
K. Schneiders, B. Luke
Uhde GmbH,
Friedrich-Uhde-Strasse 15,
D-4600 Dortmund,
Germany

11 Recent development and operation dynamics of new ion exchange

membrane series Aciplex®-F from Asahi Chemical. . . . . . . . 117
H. Shiroki, T. Hiyoshi, T. Ohta
Asahi Chemical Industry Co. Ltd,
3-2 Yako 1-chome,
Kawasaki-ku,
Kawasaki,
Japan

12 Nafion® membranes for the 1990s 131

E. I. Baucom
E. I. du Pont de Nemours & Co.,
Fayetteville,
North Carolina 28302,
USA

13 A new improved method for the determination of sodium hydroxide

current efficiency in membrane cells . . . . . . . . . . . . . . 143
G. W. Cowell, A. D. Martin, B. K. Revill
ICI Chemicals and Polymers Ltd,
Research and Technology Department,
PO Box 7,
Winnington,
Northwich,
Cheshire CW8 4DJ,
UK

14 Advances in Flemion membranes for chlor-alkali production. 159

Y. Sajima, M. Nakao, T. Shimohira, H. Miyake
Asahi Glass Co. Ltd,
Chemical Engineering Division,
2-25-14 Kameido,
Koutou-ku,
Tokyo 136,
Japan
 viii

15 Mercury/membrane cens-when to change: a chlorine producer's

considerations elfecting the timing for this changeover . . . . . . 177
M. R. Marcan
Marcan van Gelder Ltd,
Givat Downs 33,
PO Box 7181,
Haifa 31071,
Israel

16 Issues involved in membrane conversion of a chlor-alkali business . 185

R. W. Curry
ICI Chemicals and Polymers Ltd,
Chlor Chemicals Group,
HQAnnex,
Runcorn,
Cheshire WA7 4QG,
UK

17 Production of 70% caustic soda directly from decomposer, an

elfective way to save energy . . . . . . . 199
A. J. Acioli, E. F. Powell, F. C. Viana
Companhia Quimica do Reconcavo,
Rua Oxigenio No. 765,
Area do Complexo Basico,
CEP4281O,
Camacari,
Brazil

18 PolyraJDix® Diaphragm-a commercial reality . . . . . . . . . . 209

T. F. Florkiewicz, L. C. Curlin
OxyTech Systems, Inc.,
100 Seventh Avenue,
Chardon,
Ohio 44024-1000,
USA

19 Chlorine vapor suppression tests-D.O.E. Nevada Test Site June

1990 . . . . . . . . . . . . . . . . . . . . . . . . . 223
J. R. Thomerson, D. E. Billings
Dow Chemical USA,
Texas Operations,
A-1230 Building,
Freeport,
Texas 77541,
USA
 IX

20 Chlorine safety. . . . . . . . . . . . . . . . . . . . . 233

Presented by Mr J. A. Walkier of AKZO,
On behalf of EURO CHLOR,
EURO CHLOR Secretariat,
Avenue E. Van Nieuwenhuyse 4,
Box 2,
1160 Brussels,
Belgium

21 Design and operation of emergency chlorine absorption systems . . 239

T. F. O'Brien
United Engineers and Constructors Inc.,
Catalytic Division,
Philadelphia,
USA
I. F. White
Badger Catalytic Ltd,
CI Tower,
St George's Square,
High Street,
New Malden,
Surrey KT3 4HH,
UK

22 Lurgi's experience with steel and Raney-nickel as cathode material. 257

R. Dworak, K. Lohrberg, R. Muller
Lurgi GmbH,
Lurgi Allee 5,
D-600 Frankfurt 11,
Germany

23 Improvement of electrode performance resulting from combined

optimization of coating composition and structural design 269
C. Traini, G. Meneghini
De Nora Permelec SpA,
Via Bistolfi 35,
20134 Milan,
Italy

24 Hydrogen evolution on oxide electrodes. . . . . . . . . . . . . 281

S. Trasatti
University of Milan,
Via Venezian 21,
20133 Milan,
Italy
 x
25 Impurity effects in chlorate plants . . . . . . . . . . . . . . 295
J. Wanngard
Eka Nobel,
Electrochemicals Division,
Box 13000,
S-850 13 Sundsvall,
Sweden

26 Caustic evaporator corrosion: causes and remedy. . . . . . . . . 307

T. V. Bommaraju, P. J. Orosz
Occidental Chemical Corporation,
Development Center,
PO Box 344,
Niagara Falls,
New York 14302,
USA

Index of Contributors 321

Subject Index 323

 XI

INTRODUCTION

The papers in this volume were presented at the 1991 London International
Chlorine Symposium held at the intercontinental Hotel from 5th-7th June.
This was the sixth symposium in a series organized by the Electrochemical
Technology Group of the SCI and held in London at intervals of three years.
A continued high level of interest in the proceedings was demonstrated by
offers of 40 papers, and of these 26 were selected for inclusion in the
programme. The conference intention was to reflect the developments in
chlorine technology hardware and software and to address the economic,
political, environmental and safety issues which are increasingly impacting on
the chlorine industry as the millennium approaches. In the event the five
sessions were broadly based on the following topic areas:
Chlorine and the Environment
Membranes 1
Membranes 2
Chlorine Safety
Electrodes/Electrode Reactions
Not unexpectedly, the importance of membrane technology to the industry
was reflected by the inclusion of 9 papers. However, the traditional diaphragm,
mercury and chlorate cell technologies were also represented.
The academic base of the organizing body was underlined by the selection of
papers from the Universities of Milan and Calgary, and by the opening and
closing remarks of the Chairman of the SCI Electrochemical Technology
Group, Frank Goodridge, Professor Emeritus of Newcastle University.
The opportunity was taken to present the SCI Castner Medal to Dr H.
Miyake of Asahi Glass Co. Ltd for his work on the design and development of
Flemion electrodes.
The conference was attended by 282 delegates from 31 countries with
representation from all 6 continents.
The Electrochemical Technology Group of the SCI would like to thank all of
the delegates whose participation was essential to the success of the event. In
particular, thanks are due to the following:

1. The contributors of the papers.

2. The session Chairmen:
Dr R. G. Smerko (The Chlorine Institute);
 xii
Dr B. S. Gilliatt (lCI Chemicals & Polymers Ltd);
Dr D. F. Turner (Roche Products Ltd);
Dr A. A. Seys (Eurochlor);
Dr J. P. Shields (Hays Chemical Distribution Ltd);
3. The Chlorine Institute and Eurochlor for assistance with printing costs.
4. Hays Chemical Distribution Ltd for secretarial support, assistance with
printing costs and hospitality.
5. The organizing committee:
Mr D. Bell (Hays Chemical Distribution Ltd);
Mr J. R. Cowling (Hays Chemical Distribution Ltd);
Mr B. Lott (The Associated Octel Co. Ltd);
Mr J. S. Moorhouse (RhOne Poulenc Chemicals);
Mr N. M. Prout (Rhone Poulenc Chemicals);
Dr J. P. Shields (Hays Chemical Distribution Ltd);
Dr D. F. Turner (Roche Products Ltd);
Dr R. A. Woolhouse (ICI Chemicals & Polymers Ltd).

T. C. WELLINGTON
Chairman-Organizing Committee
Hays Chemical Distribution Ltd
 1

THE EFFECT OF GREEN ISSUES

ON THE CHLORINE/CAUSTIC SODA BALANCE

Barry A. Friedfeld
Project Manager
Kline & Company
165 Passaic Avenue
Fairfield, NJ 07004
U.S.A.

ABSTRACT

There are a number of green issues affecting the future

consumption of chlorine in North America including the
following end-use applications:
- Bleaching kraft pulp
- Disinfecting drinking water
- Manufacturing chlorofluorocarbons
- Cleaning surfaces with chlorinated solvents

In order to protect the environment, the pulp and paper

industry is changing its kraft bleaching procedures. These
changes are resulting in methods which use chlorine
dioxide, oxygen, or other bleaching agents in place of
chlorine. Although chlorine can be used to generate
chlorine dioxide, most North American mills are selecting
other methods to generate chlorine dioxide.
Concern over the formation of trihalomethanes when
drinking water is disinfected with chlorine or sodium
hypochlorite is resulting in some municipalities con-
sidering other methods of disinfection. Chlorine dioxide,
hydrogen peroxide, and ozone appear to be the most likely
replacement products.
Another environmental issue affecting chlorine con-
sumption is depletion of the ozone layer. Alternatives
for chlorofluorocarbons and chlorinated solvents will
consume less chlorine than the current products.
 2

Combined, these environmental issues have reduced the

demand for chlorine for some key end-use applications in
North America. However, partially offsetting these
declines is the increased demand for chlorine to produce
VCM. While demand for chlorine is declining, demand for
caustic soda is increasihg. Further, Kline & Company sees
North America going from a net exporter of electrolytic
caustic soda to requiring additional caustic soda from
either imports or the conversion of either soda ash or
trona to caustic soda.

INTRODUCTION

Typically, chlorine and caustic soda are co-produced in an

electrochemical cell yielding 1. 0 parts of chlorine and
1.1 parts of caustic soda (ECU). It is important for
producers to have balanced markets for both products.
Several environmental issues are reducing the demand for
chlorine. However, demand for caustic soda is not
affected by environmental issues.

This paper explores the effect these environmental

issues will have on the demand for chlorine and the
chlorine/caustic soda balance. It reviews historical
consumption patterns for chlorine and caustic soda and the
factors leading to the current industry status. The effect
various environmental issues have on future chlorine demand
are discussed. Further, growth rates for chlorine and
caustic soda are projected to the year 2000. Lastly,
opportuni ties for soda ash to replace caustic soda as a
source of alkalinity are reviewed.
Historical consumption
Chlorine: Since 1975 when Kline & Company published
its first major study of the chloralkali industry, world
consumption of chlorine has increased 13.0 million tonnes
going from 24.5 million tonnes in 1975 to 37.5 million
tonnes by 1990. The region comprised of Asia, Africa, and
Oceania (excluding Japan) had the largest increase going
from 1. 0 million tonnes in 1975 to 5.6 million tonnes by
1990. This growth is the result of increased capacity and
production in such countries as China, Saudi Arabia, and
the Pacific Rim for petrochemical complexes which upgrade
basic chemical feedstocks into PVC. The balance of the
growth is accounted for in the other regions, as shown in
Figure 1.
 3

Figure 1
ESTIMATED HISTORICAL DEMAND FOR CHLORINE BY REGION
1975 TO 1990
Million tonn ••
40

30

20
R
D D
I I I
r:l I
i I I
10
I

1975 USO 11)S5 11)1)0

~ Europ. 0 North Am.rlca 0 A.la, Africa, ~ Latin Am.rlca
Oc.anla

During this period, consumption of chlorine has been

growing at a declining rate . Worldwide, the average rate
of growth for chlorine consumption declined from 4.7\ for
the period between 1975 and 1980 to 2.6\ for the period
between 1985 and 1990 . The rate of decline is greatest in
the industrialized regions of North America, Western
Europe, and Japan,as shown in Table 1 .

TABLE 1
Estimated historical average annual growth rates in
world demand for chlorine by region 1975 to 1990

Av~rgg~ g[Qwth rgt~. ?i/yr

Region 1975-1980 1980-1985 1985-1990

Europe 3 . 7\ 3.0\ 1.2\

North America 3.0 ( 1.1) 1.9
Asia, Africa, Oceania 22.0 5.3 9.9
Japan 2.9 (1. 4) 2.7
Latin America ~ .l.d. Q.....Q
Average J......1\ J........i\ ~\
 4

Caustic soda: During the period between 1975 and 1990,

world demand for caustic soda grew 13.5 million tonnes up
from 27.4 million tonnes in 1975 to 40.9 million tonnes by
1990. Demand for caustic soda in the regions of Europe
and North America has increased at a lower rate than what
has been available from the increased chlorine production.
Therefore, these regions have been the major net exporting
regions of caustic soda to Asia, Africa, and Oceania and
Latin America, as shown in Figure 2.
Figure 2
ESTIMATED HISTORICAL DEMAND FOR CAUSTIC SODA
BY REGION 1975 TO 1990
Million tonn ••
50 r------------------------------------------------,
40

30

11175 11180 11185 111110

E3 Europ. 0 North Am.rlc. 0 A.I., Afrlc., ~ L.ttn Am.rlc.
Oc •• nl.
Average annual growth rates for caustic soda have only
been in the 1.0% to 1.5% range in the industrialized
regions of North America, western Europe, and Japan. In
the other regions, the growth rates have been in the 2.0%
to 5.0%, as shown in Table 2.
TABLE 2
Estimated historical average annual growth rates for
caustic soda by region 1975 to 1990

Av~rage grQwth rat~. ?6Lyr

Region 1975-1980 1980-1985 1985-1990

Europe 3.6% 1. 6% 2.2%

North America 2.0 0.0 1.5
Asia, Africa, Oceania 20.6 3.3 3.7
Japan 1.4 (1. 4) 2.7
Latin America --L..Q !LJ!. .LA
Average -.L2% .L..l% ~%
 5

Since it is not practical to store large quantities of

chlorine, chloralkali plants are operated to satisfy
chlorine demand. In a balanced market, chlorine and
caustic soda are priced relatively equally. However,
prices of both chlorine and caustic soda fluctuate to
encourage consumption of the product which is out of
balance. At times in the early to mid 1980' s, the growth
rate of caustic soda was below that of chlorine resulting
in low caustic soda prices to encourage consumption of
caustic soda over soda ash as an alternative form of
alkali. As we enter the 1990's, this situation has
reversed.

ENVIRONMENTAL ISSUES
There are a number of green issues effecting the future
consumption of chlorine in North America including the
following end-use applications:
- Bleaching kraft pulp
- Disinfecting drinking water
- Manufacturing chlorofluorocarbons
- Cleaning surfaces with chlorinated solvents
Pulp bleaching
By 1987, a suspected link was established between the
formation of dioxin and kraft pulp bleached with chlorine.
Since then, a number of new regulations have been imposed
on the pulp and paper industry in both Canada and the
United States. These regulations are patterned after
those already enacted in Scandinavia, a leader in adopting
alternative bleaching systems.
In order to meet these regulations, the pulp and paper
industry is investigating a number of systems which do not
use chlorine including the following:
- Oxygen delignification
- Hypochlorous acid
- High rates of chlorine dioxide sUbstitution
- Oxygen and/or hydrogen peroxide extraction

Oxygen delignification reduces the amount of bleaching

agents required in the bleach plant. Oxygen delignifica-
tion is very capital intensive and is especially costly as
a retrofit into existing mills. Therefore, we expect
oxygen delignification to be primarily used in new grass
root mills.
 6

In the short term, hypochlorous acid appears to be the

least capital intensive method to reduce chlorine in pulp
bleaching. Some pulp and paper companies have installed a
hypochlorous acid system in the latter stages of their
bleach plants to replace chlorine dioxide. This chlorine
dioxide is then available to be added into the first stage
of the bleaching sequence in place of chlorine. However,
a number of pulp and paper companies have expressed a
concern of chloroform being formed when hypochlorous acid
is used.

High rates of substitution of chlorine dioxide for

chlorine in the first stage of the bleaching sequence is
the most popular method being chosen today by pulp mi lIs
to reduce the amount of chlorinated organic compounds in
the mill's effluent. Unlike chlorine, chlorine dioxide
does not readily form chlorinated organic compounds in the
bleaching of kraft pulp. Although there are a number of
systems to generate chlorine dioxide, the most popular
systems use sodium chlorate and produce sodium sulfate as
the by-product. These systems do not use chlorine or
hydrochloric acid. However, a membrane system is being
commercialized to convert this sodium sulfate to caustic
soda.
An integrated system, can use chlorine or hydrochloric
acid to generate chlorine dioxide from sodium chlorate and
produces by-product sodium chloride which is recycled to
the sodium chlorate cell. Although this type of system
uses chlorine, it has not been popular due to the high
capital and operating costs.
Oxygen and/or hydrogen peroxide extraction reduces the
amount of caustic soda required in the bleaching operation.
With declining consumption of chlorine and ·the resulting
high prices of caustic soda, all pulp and paper mills are
concerned about reducing their consumption of caustic soda.
By 1995, Kline & Company projects that approximately
50% of the chlorine used in pulp bleaching in 1990 will be
consumed in North America. Further, that by the year 2000,
less than 25% of the volume of chlorine consumed in 1990
will be consumed to bleach pulp in North America, as shown
in Figure 3.
High caustic soda prices have prompted the North
American pulp and paper industry to adopt processing
methods which require less caustic soda for each ton of
pulp produced. Even so, Kline & Company estimates that
North American caustic soda consumption by the pulp and
paper industry will increase from 2.B million tonnes in
1990 to 3.3 million tonnes by the year 2000. With the
reduction in chlorine consumption for pulp bleaching,
nearly 3 million tonnes of caustic soda for the pulp and
paper industry will be from additional caustic soda
purchases, as shown in Figure 4.
 7

Figure 3
FORECAST NORTH AMERICAN DEMAND FOR CHLORINE
BY THE PULP AND PAPER INDUSTRY 1990 TO 2000
Thousand tonn ••
1,600

1.400 l-
i
1,200 l- i

1,000
,
. I.
800
!
I
1
, I
I I
600 l- I
I ,
I I
400 I- !
I
I

I
200 l-

o I I t

1990 1995 2000

Figure 4
FORECAST NORTH AMERICAN DEMAND FOR CAUSTIC
SODA BY THE PULP AND PAPER INDUSTRY
1990 to 2000
Thou.andtonn ••
3 ,500 , - - - - - - - - - - - - - - - - -- --------,

3 ,000 I- x
2 ,500 I-

2 ,000 I-
~~ ~
~ ex:
1,500 I- I ~ R>~
IV'i ?Q< ><,NY
I t8&S8~
1,000 I- DC :X::XXX

500 I- .
1
O L----~-~--~-~-~----~-~-~_~
1990
I I I

1995
I

2000
o Balanc.d cau.tlc .od. ~ Additional c.u.tlc purch••••
 8

The Scandinavian pulp and paper industry has the same

environmental pressures on pulp bleaching as found in
North America. However, the industry is already using
high chlorine dioxide substitution in the first bleaching
stage and oxygen delignification is more commonly
practiced. Therefore, the effect on the chlorine/caustic
soda balance between now and the year 2000 will not be as
great in Scandinavia as in North America.

Water treatment

Concern over the formation of trihalomethanes when

drinking water is disinfected with chlorine or sodium
hypochlorite has resulted in some municipalities in the
Uni ted States to consider other methods of disinfection.
Chlorine dioxide, hydrogen peroxide, and ozone appear to
be the most likely replacement products. Other commun-
ities are using such purification methods as carbon adsorp-
tion to remove organic contaminants. Overall, it appears
that chlorine consumption for water treatment wi 11 stay
stagnant at about 5% of the North American consumption in
the 90' s. This lack of growth will further add to the
caustic soda imbalance.
Ozone depletion

Concern over the depletion of the ozone layer has lead to

the adoption of the Montreal Protocol. This document,
including additional amendments, calls for the phasing out
of chlorofluorocarbons (CFCs). Currently, the leading
global producers of CFCs are developing replacement pro-
ducts. These replacement products are hydrofluorocarbons
(HFCs) or hydrochlorofluorocarbons (HCFCs) . In both
cases, the ozone depletion potential of the HFCs and the
HCFCs is orders of magnitude less than the CFCs. However,
these replacement products are expected to be considerably
more expensive than the CFCs. Therefore, such applications
as foam blowing for seat cushions are/will be converting
to alternate foam blowing systems. This will result in a
reduction in the market for the replacement products for
the CFCs. Although some of these replacement products
will use more chlorine per molecule, since fewer molecules
will be sold, chlorine consumption to produce CFCs and the
replacement products will be reduced.

Surface cleaning

In addition to CFCs, l,l,l-trichloroethane (methyl chloro-

form) has also been linked to ozone destruction. A time
table has been proposed to discontinue the manufacture and
use of methyl chloroform for cleaning applications. Once
this ban is implemented, chlorine demand will be further
reduced. However, in anticipation of the ban, many
electronic manufacturing operations in the United States
are switching cleaning systems to aqueous or semi-aqueous
systems which do not use methyl chloroform.
 9

In addition, a number of chlorinated solvents have

already been replaced by such other solvents as acetone
and methylethyl ketone due to the health concerns of
chlorinated solvents. Further, improved solvent recovery
and solvent recycling programs will continue to reduce the
demand for virgin chlorinated solvents in many surface
cleaning applications.

Forecast Demand for Chlorine and Caustic Soda

Chlorine

Environmental issues will be responsible for significant

chlorine demand reductions in the pulp and paper industry,
the manufacture of CFCs, methyl chloroform, cleaning sol-
vents, and water treatment. Combined, these end uses are
projected to use 1. 0 million less tonnes of chlorine by
1995 than in 1990 in the United States, as shown in Table
3.

TABLE 3
Estimated chlorine demand reductions by 1995 in North
America due to environmental issues compared to 1990

Thousand
Application tonnes

Pulp bleaching 700

CFCs 150
Methyl chloroform ~
Total-a 1. 000

a- Such other applications as solvents and water

treatment are expected to be flat.

Partially offsetting these declines, is the rate of

growth of chlorine consumption for VCM. Demand of chlor-
ine for VCM in the United States has been growing at an
average annual rate of nearly 5%. This trend is expected
to continue to 1995 resulting in the consumption of an
additional 0.9 million tonnes chlorine. Essentially,
chlorine production in the united States is projected to
be flat between 1990 and 1995.
 10

After 1995, the majority of the environmental issues

affecting chlorine demand for CFCs and methyl chloroform
will have already occurred. Therefore, no further
decreases are expected for these end uses. However,
additional declines are expected in the pulp and paper
industry resulting in an average annual growth rate for
chlorine of 1 . 5% between 1995 and 2000 for the united
States. This growth rate assumes no additional by-product
HCI is recycled. If this assumption is not va 1 i~, U. S .
production of chlorine will remain flat to declining.
Chlorine production in Japan and Western Europe is
expected to have similar growth patterns as found in the
United States due to environmental pressures. However, in
regions with developing economies, the rate of growth of
chlorine production will be significantly higher resulting
in a forecast global average annual rate of growth for
chlorine of 1. 0% to 1. 5% between 1990 and 1995, as shown
in Figure 5 .

Figure 5
FORECAST WORLD DEMAND FOR CHLORINE 1990 TO 2000
MIllion tonne. BY REGION
50 r---------------------------------------------------,
40

"
30

20

1990 1995 2000

t2:l Europe-a 0 North America o A.'a, Africa,
Oceanla-b
~ Latin America

a- Include. Eaat Europe.

b- Include. Japan.
 11

caustic soda

Demand for caustic is not expected to be affected by

environmental issues. Therefore, demand for caustic soda
is forecast to continue to grow at an average annual
growth rate of 2.0\ to 2.5\ between 1990 and 2000. As
with chlorine, demand for caustic soda is growing at a
higher average annual rate in those regions with
developing economies, as shown in Figure 6.

Figure 6
FORECAST WORLD DEMAND FOR CAUSTIC SODA 1990 TO 2000
BY REGION
MIllion tonne.
60.---------------------------------------------~

50

40

30

20

10

neo 2000
~ Europe-. 0 North Amerlc. o A.I., Afrlc., ~ L.tln Amerlc.
Oce.nl.-b
.- Include. E•• t Europe.
b- Include. J.p.n.

Chlorine/caustic soda balance

Worldwide, supply and demand for caustic soda were about in
balance in 1990 even though many producers offered chlorine
at low prices to encourage higher overall production so
additional quantities of caustic soda would be produced and
offered at relatively high prices. However, with worldwide
demand for caustic soda growing at an average annual rate of
about 1% greater than that for chlorine, a shortage of 2.0
million tonnes of electrolytic caustic soda is expected by
1995. Further, this shortage is expected to increase to
about 5.0 million tonnes by the year 2000, as shown in
Figure 7 .
 12

Figure 7
FORECAST WORLD SUPPLY AND DEMAND FOR CAUSTIC SODA

MIllion tonn ••
52 .-------------------------------------------------~

50

48

46 ......
Supply-a..... ········
...........
44

42

40 ~--------~--------~--------~--------~--------~
1990 1992 1994 1996 1998 2000

a- Supply from electrolytic production.

There are a number of ways this potential shortfall of
caustic soda can be alleviated including:
- Direct sUbstitution of soda ash for caustic soda where
possible
- Conversion of soda ash to caustic soda
- Technological changes

Conclusions
Environmental pressures are reducing chlorine demand for a
number of end uses. Demand for VCM is the one area of
growth. Therefore, chlorine producers need to position
themselves to serve this segment of the industry in order to
keep their plants operating at capacity. Since this will
not always be possible, shutdowns of smaller, older plants
whose chlorine output is for the pulp and paper or CFC
markets are expected. The capacity loss of these plants
will be offset by newer plants designed to serve the VCM
market.
A shortfall of caustic soda is forecast between 1990 and
2000. Caustic soda prices should remain relatively high
between 1990 and 2000. This will encourage conversion of
soda ash to caustic soda to make up the shortfall. Large
users of caustic soda need to make long-range supply plans
and develop a long-range strategy in order to assure
themselves of adequate supply.
 13

CHAtaS IN TI£ CHEMICAL REQUIR9£NTS OF UE BLEACt£D KRAFT

Pll.P INDUSTRY
Donald A. Perham
Consultant
Croydon, England

ABSTRACT
The bleached kraft pulp industry is a significant consumer of
caustic soda, chlorine and sodium chlorate, the latter being
reduced to chlorine dioxide at site.
The industry is now under considerable environmental pressure
to reduce or eliminate its discharges of chlorinated ~rganic
compounds, including dioxins, which can be generated in the
bleaching process.
This paper discusses the changes that are occurring in the
industry in response to these pressures. It also analyzes the
process options and the comparative process economics of these.

INTROOUCTION
In the main bleached chemical pulp producing countries, the
industry is an important consumer of chlorine, caustic soda and
sodium chlorate, and changes in the pulp industry can affect
their demand and also the chlor-alkali ECU balance. In the
case of sodium chlorate, over 90% of world production is used
by the pulp industry to manufacture chlorine dioxide on-site
for bleaching.
The recent driving force for change has been concern for
the environment, in particular with the organically-bound
chlorinated compounds, which are expressed as total
organically-bound chlorine, TOCI or alternatively as adsorbable
organic halogen, AOX. These include chlorinated dioxins and
furans, some of which are highly toxic, in bleach plant
effluents, which has generated considerable concern.
 14

PROCESS CONSIDERATIONS
Pulp mills have been responding to increasing environmental
pressures by the introduction of extended delignification.
oxygen delignification. and increased chlorine dioxide
substitution. The first two of these reduce the bleach
chemicals demand and the last reduces the amount of chlorine
used per ton of pulp. New bleached kraft pulp mills
employing a combination of these technologies are now
setting the standard and will make compliance with the ever-
tightening effluent standards difficult for older mills. For
these mills. the easiest to implement is increased chlorine
dioxide substitution. which can reduce AOX discharges
significantly. A conservative correlation for estimation of
AOX is the following relationship.
AOX = 0.11 (C + 0.20) kg/AOMT pulp
where C = molecular chlorine consumption. and
o consumption of chlorine dioxide as
available chlorine.
As 1 kg of chlorine dioxide has the same oxidizing power
as 2.63 kg of chlorine. it can be readily seen from the above
relationship how bleach plant generation of AOX would be
considerably reduced by increasing chlorine dioxide
substitution.
A bleached kraft pulp mill. depending on which process is
used to generate chlorine dioxide. can generate much or all of
its requirements for chemical makeup for the digestion and
chemical recovery systems. The changes in bleaching chemicals.
resulting from the use of extended and oxygen delignification
and of more chlorine dioxide. have significant cost
implications for the pulp mills concerned. These matters are
also of considerable concern to those engaged in chlor-alkali
and sodium chlorate production.
Reduction in chlorine consumption without commensurate
reduction in caustic consumed contributes to imbalance for the
chloralkali industry. The U.S. bleached kraft pulp industry
consumes about 21_ of total domestic caustic soda production so
this trend has been causing the North American chlor-alkali
industry some concern. A consequence is that the North American
 15
chlor-alkali ~roducers are now imposing a price penalty for
the caustic soda purchased in excess of the ECU ratio.
During the last three years, considerable chlorine dioxide
capacity has been converted or added using the Albright &
Wilson ERCO Division R8 or the Eka Nobel SVP-MeOH processes,
which employ methanol for reduction of sodium chlorate to form
chlorine dioxide. For existing facilities using the common R3
or SVP sulphuric acid process, this enables an increase in
chlorine dioxide capacity to be achieved at a relatively low
additional capital cost. In addition, a number of integrated
process plants, which employ hydrochloric acid for reduction,
have been ordered. Both these options significantly change
pulp mill chemical makeup requirements.

ECONOMIC CONSIDERATIONS
Examination of the economics of the various process choices
have been examined using typical pulp mill balances for both

TABLE 1
Bleach Chemical Requirements in kg/AOMT pulp

Furnish -Active Chlorine- NaOH ----oxygen---- Bleach

Cl CI02 Total Cl D-stage E-stage sequence

SUbstitution Level - 10-15%

Softwood 30 45 20.9 100 40 n11 5 CO-EO-O-E-O
34/18 25 13.3 60 30 18 4 O-CO-EO-o-O
25/14 20 13.3 55 27 13 3 D-Co-Eo-D-O
Hardwood 20 30 17.1 75 35 n11 4 CO-EO-o-E-O
23/14 16 11.0 45 19 12 3.5 O-CO-Eo-O-O
16/10 15 9.5 40 18 8 2 O-CO-Eo-O

SUbstl tutlon Level - 50%

Softwood 30 25 28.5 100 35 n11 5 CO-EO-o-E-O
34/18 15 17.1 60 26 18 4 O-CO-EO-O-O
25/14 14 15.6 55 25 13 3 D-CO-EO-O-O
Hardwood 20 19 21.3 75 30 n11 4 CO-EO-O-E-O
23/14 11 12.9 45 16 12 3.5 D-CO-EO-D-O
16/10 10 11.4 40 15 8 2 D-CO-EO-O
 16

Furnish Kappa -Active Chlorine- NaOH ----Oxygen---- Bleach

No Cl Cl~ Total Cl o-stage E-stage Sequence

Substitution Level -100%

Softwood 30 n11 38.0 100 31 n11 5 CO-EO-o-E-O
34/18 n11 22.8 60 24 18 4 O-CO-EO-O-D
25/14 n11 20.9 55 22 13 3 O-CO-EO-o-O
HarctNood 20 n11 28.6 75 25 n11 4 CO-EO-O-E-O
23/14 n11 17.1 45 14 12 3.5 Q-CO-EO-O-O
16/10 n11 15.2 40 14 8 2 o-CO-EO-O

hardwood and softwood. For a mill seeking to increase chlor-

ination stage substitution, the choice of chlorine dioxide
system can be significant in terms of pulp mill chemical costs.
Table 1 above shows typical bleach chemical requirements
for both hardwood and softwood mills employing the different
delignification and bleach sequences required to achieve
production of market pulp with a brightness of 100% ISO. The
table shows how the quantities of chemicals required for
bleaching reduce as more de lignification is carried out. The
data are given for different amounts of chlorine dioxide
substitution, ranging from a minimum of 10-15% to 100%
substitution.

TABLE 2
Chlorine Oioxide Systems Unit Quantities
Quantities per unit weight chlorine dioxide

Raw Materials
Chlorate 1.66 1.66 1.7 1.66 1.64
Sodium chloride 0.95 0.2 n11 0.2 trace
Sulphuric acid 1.6 1.0 n11 0.2 1.0
Hydrochloric acid n11 0.5 1.3 n11 n11
Sulphur dioxide n11 nil n11 0.5 n11
Methanol nil nil nil nil 0.2
By-products
Chlorine 0.6 0.5 0.7 0.1 n11
Sodium sulphate 2.3 1.5 nil 1.4 1.4*
Sodium chloride nil n11 1.0 nil nil

* This is the equivalent as saltcake of the sodium

sesquisulphate produced by the R8 and SVP-MeOH processes.
 17

Tabl. 3 giv •• the unit co.ts used for the comparison of

the various chlorine dioxide processes, these are a selection
from actual costs at one mill site and those given in
reference [2].

TABLE :5
Unit Costs for Chemicals

Chemical Unit Delivered Cost

US$/MT

Chlorine MT no
Caustic soda MT 100" 275
NaOH ECU penalty MT 100" 25
Sodium chlorate MT 465
Salt included in chlorate cost
Sulphuric acid MT 100" 70
Methanol MT 105
Sulphur dioxide MT 275
Hydrochloric acid MT 100" 150
Oxygen MT 90
Magnesium sulphate MT 100" 600
Sodium sulphate MT 100
Catalyst $/ST CI02 6
Royalty $/ST CIO~
- R:5, R H, R5 26
- R7, R8 :54

These costs are typical for the South-Eastern United States.

The unit quantities given 1n table 2, taken from reference
[1), can be somewhat idealistic compared with mill experience,
particularly in regard to the amount of sodium chlorate used;
they are, however, suitable for this comparative exercise.
Figure 1 compares the total bleach and recovery chemicals
related direct costs for chemical balance models for softwood
pulp based on the previous data and also based on chemical
makeup requirements of 4 kg sulphur/ADMT and 9 kg sodium/ADMT
pulp. which reflect modern mill design practice. Figure 2
shows the corresponding total direct costs for hardwood pulp
production.
Where low consistency chlorination is used, the R:5/SVP
system, which employs sulphuric acid for chlorate reduction,
generally offers the lowest costs; th1s 1s not the case for
 60
SDFT'vIDDD 60
mil Conventional Dellgnlflca tlon SUBSTITUTION
55 ~\. 55
~ Extenoleol Dellgnlflcatlon
r;j"~h~}·~r5\·
~ ~ '\ ~
-.......,...,~~
..........
50 ~ Extenoleol + O-Dellgnlflcatlon 50

..9- 45 45
3
0-.-
40 40
I-
L ......
00
Q 35 35
<[

~ 30
" 30

25 25

20 L::1 t=1 t=1 t=1 t=1 t=1 t=1 t=1 t=1 t=1 CJ t=1 t=1 t=1 t=1 CJ CJ CJ t=1 c-, 20
R3/SVP R3H/SVP- R5/SVP- R7/SVP- RS/SVP-MeOH
Po.rtlo.l HCl Toto.l HCl MARS

Figure 1. Total direct bleach & recovery chemical costs for

softwood pulp.
 ~I HARDWOOD I~

50 I Conventlono.l Dellgnlf'ICo.-tlon 50
~ Extended Dellgnlf'lcatlOn SUBSTITUTION
45 ~\. 45
~ Extended + D-Dellgnlf'lco. tlon ,,'-,.t\.,.t\. ~\.
~ ~'V"''V~
0..40 -..,...,~-.,...,-...... 40
--'
3
a.. 35
35
I--
~ \0
~ 30 30 -
<l:

"""25 25

20 20

15 HHHH HHHH HHHH t=1t=1t=1t=1 t=1t=1t=1r=-1 15

R31SVP R3H/SVP- RS/SVP- R7ISVP- RB/SVP-MeOH
PQrtlo.l HCl TotQl HCl MARS

FIgure 2. Total dIrect bleach & recovery chemIcal costs for

hardwood pulp.
 20

high substitution levels with softwood as not all the by-

product saltcake can be utilized for makeup. The R3/SVP
process, with low chlorine dioxide substitution of around
10-15%, offers the opportunity of a good pulp mill chemical
balance, with chlorine and caustic soda in or close to the ECU
stoichiometic ratio. This option is no longer tenable except,
possibly, in the third world. Reference [3] discusses the
options open for on-site bleach chemical production for a mill
in the third world based on use of the R3 process and low
substitution. Reference [4] compares and discusses bleach
chemicals and other manufacturing costs for a swing mill
capable of producing both hardwood and softwood bleached kraft
pulps.
The methanol-based processes, R8 and SVP-MeOH, have
marginally higher chemical costs at lower substitution levels
than the R3H/Partial HCl process, which uses a mixture of
sulphuric and hydrochloric acids for reduction. At 100%
substitution the R8 and SVP-MeOH processes offer the lowest
costs for both hardwood and softwood mills; this ignores the
use of the R3/SVP process, which becomes impracticable at
higher substitution levels due to the amount of by-product
salt cake generated.
There is also the advantage of the methanol processes in
being able to increase output by up to 50%, with a relatively
low cost retrofit of an R3 or SVP plant.
As with on-site chlorate plant generation of R2 chlorate
solution for the R3/SVP process, it is practicable to produce a
chlorate solution suitable for the R8 or SVP-MeOH processes;
this may be as a 600 gpl NaCI03' 70 gpl NaCl solution
direct from the cellroom, or as a 600 gpl NaCI03 solution
with only a trace of NaCl with the incorporation of a
crystallizer in the chlorate plant. Use of a 600 gpl
NaCI03' 70 gpl NaCl solution results in the chlorine
dioxide plant operating in a mixed R3/R8 or SVP-MeOH mode, with
the production of more by-product salt cake and chlorine.
The R5/Total HCl and integrated processes, which all use
only hydrochloric acid for reduction, are more costly than
other alternatives such as the methanol-based processes and
 21

R3H/Partial HCl. This remains the case even where allowance is

made in assessment of ECU penalty for the caustic soda
equivalent to the hydrochloric acid required for the R5/Total
SVP process, as discussed in reference [5].
It should also be commented that, should a mill have a
suitable power balance to enable on-site sodium chlorate
production to be considered, it is not necessary to choose an
integrated process to use this power; the sodium chlorate can
be also be used in the other chlorine dioxide processes.
There can be cost disadvantages with integrated processes
due to their lower yield of chlorine dioxide, thus requiring
more electric power for chlorate production. They also produce
a chlorine dioxide solution of lower concentration and with
significantly more chlorine in solution than that produced by
the modern methanol-based processes, namely a minimum of 10 gpl
CI0 2 with only a trace of chlorine. This can be a
significant disadvantage for a bleach sequence with a medium
consistency chlorination stage; the accompanying chlorine is
also a serious disadvantage in the general movement away from
the use of elemental chlorine in bleaching.
The ranking of mill chemical costs for the different
chlorine dioxide processes is dependent on the degree of
delignification carried out before bleaching. As discussed in
reference [5], ECU caustic soda penalties do not alter the
cost-rankings given above for the chlorine dioxide process
alternatives.

CONCLUSIONS
Firstly, the chlorine consumption used for pulp bleaching will
continue to decline, with a corresponding increase in chlorine
dioxide being required.
For increased chlorine dioxide production, the comparisons
made show that the modern methanol processes offer the lowest
direct costs for a pulp mill choosing to operate at high levels
of chlorine dioxide substitution. This is likely to be the
industry norm for the foreseeable future. The hydrochloric
acid-based processes are significantly more costly; they also
have other technical disadvantages.
 22
Where a pulp mill has a favourable power balance and/or
tariff with the power utility, consideration may be given to
on-site manufacture of sodium chlorate without using one of the
integrated processes for the production of chlorine dioxide.
These comparisons are based on first half 1991 ~u~t~ fu[' ~

typical mill in the South-Eastern United States. Other mills

with significantly different unit costs may arrive at other
conclusions. In order to make an effective'/decision, a study
is required of existing facilities with cost evaluations being
carried out on the alternatives identified using, local cost
data.

REFERENCES
1. ERCO Chlorine Dioxide Processes, Toronto, 1989.

2. Chemical Marketing Reporter, May 6, 1991, 209(18).

3. Perham, D.A., Aspects of on-site generation of chemical

pulp mill bleaching chemicals.
Appita, 1986, 39(5), 391-396.

4. Perham, D.A., Calder, H.S. & Ryder, P.G.,

Comparative aspects of pulping E. globulus &
P. radiata in the same installation,
40th Appita Annual Conference, Auckland, April 1986.

5. Perham, D.A., Bleached Kraft Pulp Mill Chemical Costs,

Perhamconsult Ltd., Croydon, 1990, pp. 3.01-3.05.
 23

*
ICI 'HYDECAT' PROCESS FOR THE CATALYTIC DESTRUCTION OF
HYPOCHLORITE EFFLUENT STREAMS

PEJ ABBOTT, M CARLIN, M E FAKLEY** ,F E HANCOCK & F KING

ICI Katalco, P.O.Box I, Billingham,
Cleveland T523 lLB, U.K.

ABSTRACT

The concern about the environmental impact of chlorinated caustic effluent

streams and the problems associated with the removal of volatile organic
carbons from such effluents has encouraged ICI to research and develop
"HYDECAT " technology.

The paper will address the environmental impact of contaminated waste

hypochlorite, the chemistry of hypochlorite and the current international
legislative scene. The traditional methods employed for the destruction
of chlorinated caustic wastes will be critically reviewed in the light of
current practice and the likely impact of the restructuring of the
chlorine producing and consuming market.

The ICI "HYDECAT" process employs proprietary heterogeneous catalyst and a

unique reactor design to accelerate the decomposition of hypochlorite thus
producing oxygen gas and brine for disposal or recycle. A typical
"HYDECAT" hypochlorite destruction unit will be described and experience
to date reviewed. Developments to aid removal of low levels of volatile
organic carbons from such streams will be discussed. Advantages of the
new process include:

+ lower capital costs than conventional treatment

+ operational simplicity and reliability
+ low labour and maintenance costs
+ safer and cleaner operation
+ continuous oxygenation of the waste stream

The potential applicability of the "HYDECAT" process to major chlorine

utilising processes will be illustrated with references to vinyl chloride
monomer, titanium dioxide and organic chlorinations. The adoption of the
"HYDECAT " treatment process will strengthen the environmental
compatibility of the chlorine industry.

*
(**'HYDECAT' is a Trade Mark of ICI Chemicals & Polymers Ltd)
( indicates principal author)
 24
INTRODUCTION

Pure solutions of sodium hypochlorite make a vital contribution to health

and quality of life through applications in water treatment and
disinfection. However, the destruction of chlorinated caustic effluents
is a common unit operation associated with the electrolytic production of
chlorine and arises from the adsorption of chlorine containing vent-gases
in caustic scrubbing towers (1).

CAUSTIC - .......-l~---,r--------,

VENT --+--f

CHLORINE - ........- 1 - -

CHLORINATED
CAUSTIC

Figure 1. Caustic Scrubbing Tower

+ 20H > CI + OCI + K = 7.5 x 1015

Depending upon the industrial process constraints the levels of

hypochlorite in such effluents can range from less than 1% to above 10%.
There is no published figure for the total amount of chlorinated caustic
effluent produced annually but a conservative estimate of 1% of annual
chlorine production, i.e. currently 360 000 tonnes per annum as chlorine,
would correspond to 7.2 Mtpa of aqueous effluent containing 5% available
chlorine.

The challenge to develop a cost effective and environmentally satisfactory

hypochlorite destruction process using a heterogeneous catalyst has been
addressed by several groups of workers over the past two decades without
lasting success. The 'HYDECAT' Process is the successful result of ICI's
work to develop a practical hypochlorite destruction process which meets
the requirements of chlorine manufacturers and consumers.

ENVIRONMENTAL POSITION

The treatment of aqueous wastes which are high in Total Organic Carbon
with hypochlorite results in formation of only minute quantities of
haloforms (typically at the 5-10 ppb level), whereas, it is well known
that the chlorination of drinking water can give rise to higher levels of
haloforms (10-100 ppb) because of interaction between the residual
chlorine and naturally occurring organic acids. The major concern over
the discharge of industrial effluents containing hypochlorite stems from
the effect of concentrated hypochlorite on aquatic life and the possible
presence of red and/or black listed halogenated compounds in such
effluent streams (2).
 25

TABLE 1
Industries Requiring Chlorinated Caustic Effluent Destruction

a Chlorine I caustic soda a Pharmaceuticals

a Vinyl chloride monomer a Inorganic pigments

a Chlorinated solvents a Magnesium metal

a CFC replacements a Sodium metal

a Organic dyes

Chemical plants which use chlorine to produce chlorinated organics

inevitably produce chlorocarbon contaminated scrubber effluents and before
such chI oro-carbons can be recovered or treated the effluents must be
neutralised. At pH 9 hypochlorous acid formation begins and chlorine
liberation follows as the pH falls. Unless this process is controlled for
chlorine recovery there exists the possibility of subsequent chlorine
release downstream in the effluent treatment system.

C10 HOCl

HOCl + OCl

Biological treatment of aqueous wastes containing chlorinated organics is

a challenge in itself and is being addressed by several groups of workers.
The lethal dosage of hypochlorite for such organisms is thought to be 100
ppm free chlorine, depending upon the composition of the effluent stream.
Therefore it is increasingly important that the free chlorine level in
such effluents is reduced in a controlled manner rather than by trusting
the decomposition of hypochlorite to its light catalysed decomposition.
thermal disproportionation etc. in the waste management system.

The permitted levels for free chlorine discharges in aqueous industrial

effluents vary widely across the globe and depend markedly upon the water
quality at the final discharge point. For example. in-land disposal of
such wastes in Alberta. Canada is limited to streams containing 5-10 ppm
free chlorine. In some countries control is maintained by indirect
consents agreed with the local authorities - such as for colour. smell.
BOD. etc. In Japan this translates into target limits for aqueous
discharges of around 30 ppm free chlorine depending upon locale. The
aquatic toxicity limits for free and combined chlorine are such that the
target level for discharge into fresh water is now below 1 ppm in America
(3). However, to put this into context, it should be borne in mind that
the residual chlorine in tap-water is often around the 0.1-0.3 ppm level.

As we are all aware, the importance of chlorine and its derivatives to

health and the global quality of life is best supported by good
environmental practice at all stages in the production chain. The safe
and reliable control of chlorinated caustic wastes is but one part of this
important topic.
 26

TRADITIONAL TREATMENT OPTIONS

Most production processes using chlorine need chlorinated caustic effluent
destruction - the exact destruction capacity depending largely on the
composition of the waste and the degree of site integration. The largest
chlorine plants, where large quantities of spent acid are available (for
example spent sulphuric acid from chlorine drying), can often acidify and
recover the liberated chlorine. However if the stream is highly
contaminated with light gases, or organics, this option may not be open.

There are currently two methods of hypochlorite destruction widely

employed - chemical addition or heavy metal slurry catalytic destruction.

Chemical addition

The most general method of destroying hypochlorite is by chemical reaction

with a reducing agent in stirred tanks. Several reducing agents have been
employed - the choice being dominated by cost, availability and ease of
handling.

TABLE 2
Chemical Destruction Reactions

Sodium sulphide NaOGI + Na2S ~ NaGI + sulphur products

Sodium bisulphite NaOGI + NaHS0 3 ~ NaGI + NaHS04

Hydrogen peroxide

Other reducing agents employed include sulphur dioxide and granulated

activated carbon. The former is common in water treatment to correct over
chlorination. All the processes are exothermic and careful control of the
addition is required, particularly at high initial hypochlorite
concentrations. Sufficient residence time is required to allow all the
hypochlorite to be reduced. The process is very expensive due to its high
labour, transportation and chemical costs - the latter being considerable
when decomposing strong solutions of hypochlorite. All the reactions are
theoretically stoichiometric but it is found that over addition is
sometimes necessary to compensate for imperfect control and for kinetic
reasons (4). Over addition of reducing agent may generate a high chemical
oxygen demand (COD) for the hypo depleted stream. Chemical addition can
achieve reduction of free chlorine to very low levels but is expensive fa.
all but low hypo concentrations or very low and intermittent volumes of
effluent.
 27
TABLE 3
Chemical Costs

Chemical Chemical cost (£ per kilomole of OCn

o Sodium sulphide 8
o Sulphur dioxide 28
o Sodium bisulphite 35

(Assumes stoichiometric reaction)

Heavy metal slurry catalysis

The metal catalysed decomposition of sodium hypochlorite to sodium

chloride and oxygen has been known since 1834 and indeed forms the basis
of existing processes employing heavy metal catalyst slurries (or more
correctly suspensions) (1).

20CI > 2CI H = -15 kcal/mol

Figure 2. Hypochlorite Destruction Reaction

A catalytic destruction process based on this chemistry requires the

addition of metal salts to the effluent in tanks which are either stirred
or agitated via an external circulation loop. In practice either
solutions of nickel, iron + nickel, or cobalt salts are added as catalysts
which form a precipitate at the high pH of the effluent.

WAS11!
HYPOCK.OIIIIt
STOCK
TANK

_ _ _-" DISCHARGE

Figure 3. Slurry Catalyst

Hypochlorite Destruction (Schematic)

Since the rate of the catalytic destruction reaction is a function of

temperature, hypochlorite concentration, pH and catalyst concentration,
 28
care has to be exercised to avoid vigorous oxygen evolution or sluggish
destruction. Reaction times are variable but even more time is required
for the settling of the catalyst slurry prior 3to discharge of the
supernatant treated liquor. Typically a 40 m treatment volume may
require 24 hours reaction and 48-72 hours for the catalyst slurry to
settle. In practice, it is found that the activity of such catalyst
slurries decreases from batch to batch and addition of fresh metal salts
is necessary. Operators appear divided over whether declining activity is
due to the formation of a less active metal oxide phase or to loss of
metal from such systems. The discharging of heavy metal salts would be an
environmental concern in itself.

The recovery and recycle of the catalyst from processes of this type has
been described but substantially increases both capital and operating
costs. Furthermore the inherent complexity of such a system is
unattractive as an effluent treatment option - operators require a simple
and reliable process. Since the performance of such plants is at best
unreliable, chemical addition is sometimes included.

It is widely agreed across the chlorine utilising industry that existing

hypochlorite destruction processes are expensive to install and can be
troublesome to operate. Many of the chemicals involved are hazardous and
the effluent itself is extremely caustic and corrosive.

Heterogeneous Catalysts

All previous attempts to immobilise the slurry catalyst appear to have

floundered due to limitations in durability and efficiency of the catalyst
at high hypochlorite concentrations and high pH. Several patents claim
the invention of catalysts for the decomposition reaction. A system
offered by Dow using a supported cobalt oxide catalyst requires the
neutralisation of the hypochlorite streams to pH 8 prior to contact with
the catalyst (5). The destruction reaction thus becomes the decomposition
of hypochlorous acid which tends to lower the pH of the reacting solution:

2HOCl > + 2HCl

Since neutralisation of strong hypochlorite is practically difficult

and the spinel catalyst is intolerant of either low or high pH excursions,
the process appears not to have gained general acceptance.

A novel catalyst formulated as KYNAR encapsulated cobalt oxide

designed by Pennwalt (now Atochem) for the secondary dechlorination of
brine is reportedly unstable to high (> 2%) hypochlorite concentrations
and the high attrition losses coupled with the high catalyst cost rendered
its use uneconomic (6). No applications of this catalyst in chlorinated
waste treatment have been reported.

THE ICI 'HYDECAT' PROCESS

In the light of a changing chlorine industry, and the environmental

concerns being expressed about chlorinated caustic waste, ICI began a
programme of work in late 1986 to develop an active, robust, heterogeneous
catalyst for the hypochlorite destruction reaction. This in itself was a
considerable challenge in that the high pH levels and corrosive nature of
the effluents limit the selection of suitable catalytic materials - as
earlier workers had found. The performance target set for the catalyst
 29

was for at least one years continuous operating life without significant
decline in activity. Life-tests of the novel supported nickel catalyst
run at inlet pH 13-14, now exceed 16 000 hours duration with continued
high performance and demonstrate the robustness of the catalyst
formulation.

0.3
G.28
0.26
0.24

I
0.22
0.2
~ 0.18
~0 0.16
:cu 0.14
,..
&. 0.12
:c
0.1
~ 0.08
0.06
0.04
• •
0.02
0
,. • •
0 2 4 6 8 10 12
Hours on line (Thousands)

Figure 4. 'HYDECAT' Catalyst Performance v. Time

For the first time a supported nickel catalyst has been developed
which combines both the necessary activity and long life-time for the
destruction of hypochlorite under high pH conditions. However, in order
to offer an efficient and reliable industrial process which easily
integrates into any chlorine utilising plant, the supported catalyst must
be incorporated into a new reactor concept.

It is a consequence of the destruction reaction stoichiometry, and

the physical chemistry of the process itself, that up to 30 volumes of gas
are produced for every 1 volume of 10% sodium hypochlorite solution
reacted. The oxygen is saturated with water vapour and has to be
separated from the reacting solution without undue disruption of the
liquid plug flow. Surprisingly it is found that an important
consideration in the vessel design is the provision of adequate liquid
surface area for oxygen disengagement. Bubbles of oxygen, whose size is
governed by the liquid surface tension and local shear forces, form at the
catalyst pellet surface. The typical bubble diameter of 0.2 mm is much
less than that generally encountered in 3 phase reactors and means that
the bubble rise velocity is low. The use of deep, fixed-bed reactors is
undesirable, especially for the destruction of strong hypochlorite
effluents where gas voidages build up in the fluid and consequently reduce
the catalytic bed efficiency.
 30

OPTIOHAl
WAStE PRE-MEATER
HYPOCILORITE
S10CK
TANK

'HYDECAr
MOOULE
DISCHARGE

WASTE
TRANSFER
PUMP

Figure 5. 'HYDECAT' Process

Hypochlorite Destruction (Schematic)

Therefore a unique reactor has been designed in which the primary

liquid flow direction is horizontal and which allows ample time for
bubbles to rise through the catalyst bed and escape. The 'HYDECAT'
Process therefore employs a reactor in which the liquid cascades through a
series of beds under gravity flow, an arrangement which allows destruction
of strong hypochlorite (up to 15% available chlorine) to exit
concentrations reliably below 30 ppm - a destruction efficiency of
99.999%. To minimise maintenance, the system operates without moving
parts. The reactor is modular in concept - three sizes are currently
available.

TABLE 4
ICI 'HYDECAT' Module Sizes

Size Typical Maximum Treatment Volume Treatment Cost

(Based upon 10% inlet hypo at 30·C, (Module + catalyst)
10 ppm outlet hypo)

(Htres/hour) (m 3/day) (£/kmole OCr)

HM1 150 3.6 1.1
HM2 600 14.4 0.8
HM3 3000 70.0 0.6

The treatment costs are based upon a 3 year depreciation of the

module cost and a 3 year catalyst life-time. Larger treatment capacities
are achieved by combinations of modules piped to flow in parallel.
 31

Oxygen Gas

SOURCES OF CHI.ORIIIIATED
CAUSl1C EFFLUEJIT

CHLORINE PRODUCTION

VINYL ctl..ORIDE
~R PRODUCTION

TITANIUM DK>Xtoe
PlANTS

I
CHlOflO.ORGANK:S I
I
PlANTS Ca.D. DYES) I
I
I
I .--------,
... : ~.!
,,
I

,"
I • _____ ,

... ______ -1

Figure 6. 'HYDECAT' Installation (Schematic)

If the effluent contains no organics, then the modules may be

fabricated from glass fibre reinforced plastics. If organics are present
then other options for materials of construction are available. Given the
simplicity and size of the modules, titanium fabrication is possible and
in which case the treatment cost for HM3 increases from £0.6 to £0.9/kmole
OCI

Preliminary results indicate that a high proportion of any volatile

organic compounds (VOCs) are co-stripped from the effluent by the oxygen
evolution. The extent of such stripping varies from stream to stream as
it depends critically upon the volume of oxygen evolving, the effluent
temperature and the organic volatility. It is envisaged that the gaseous
stream will either be sent for VOC recovery within the host plant or for
incineration. The quantity of effluent which can be treated by a
'HYDECAT' module (i.e. catalyst performance) is a function of several
factors defined by the stream itself and the target for hypochlorite
removal.

TABLE 5
Factors Determining Size of a 'HYDECAT' Installation

0 Inlet hypochlorite concentration «15% available chlorine)

0 Outlet hypochlorite specification (typically < 30 ppm)

0 Inlet stream temperature « 6S·C)

0 Inlet stream alkalinity (> pH 8.5)

0 Effluent flow rate

 32

The UK 'HYDECAT' Pilot Unit has been in operation for nearly 2 years
and has successfully processed scrubber effluents containing hypochlorite
from a number of different processes, for example aromatic and aliphatic
chlorinations, inorganic pigments and metal processing. The nickel
catalyst does not suffer from poisoning to any appreciable extent
presumably because it operates in a high Ni(III) oxidation state and in an
oxidising solution where most of the traditional poisoning species are
also oxidised. The detailed reaction mechanism is still uncertain and ICI
is investigating the active species at the catalyst surface with the aim
of further improving catalyst performance.
100
•
99
•
98
•
97
c
0 •
Ic
0
96
•
U
95

94

93 •
92 45 55
15 25 35
Temperature (e)
Figure 7. Catalyst Conversion v. Temperature

Since, as indicated above, the catalytic reaction is exothermic, the

temperature rise in the reactor can be used to minimise the volume of
catalyst required and maintain the rate of reaction as the hypochlorite
concentration falls. Typically, residence times of 20 minutes are
employed. 100.-----------------------------------------,

Figure 8. Catalyst Conversion v. Flowrate

 33

The first commercial 'HYDECAT' unit has been constructed and is due
on-line at the ICI Runcorn site shortly. ICI Australia have been granted
a license for their newest chlorine plant at Yarwun in Australia. Other
units are at the planning stage and ICI Katalco has generated a kinetic
model which permits the calculation of the required catalyst volumes, that
is module sizes and combinations, for any effluent stream.

Calculations show that, depending upon the temperature of the inlet

stream, a 'HYDECAT' system (costed as the reactor module depreciated over
10 years and with a three year catalyst life-time) is cheaper than
chemical addition at hypochlorite concentrations above 0.2% (+/- 0.1%).
(This calculation is conservative as it ignores the capital cost of the
chemical addition equipment).

TABLE 6
The Advantages of the 'HYDECAT' Process

a Lower capital cost

a Lower cost per tonne hypochlorite destroyed
a Operational simplicity and reliability
a Automatable
a Low labour and maintenance costs
a Effluent stream is oxygen saturated
a Environmentally compatible

CONCLUSIONS

Caustic scrubbing of waste streams containing chlorine is a feature of the

chlorine producing and utilising industries. With the advent of smaller
chlorine plants, there will be the increased need for de-centralised
scrubber effluent treatment. The existing technologies suffer from a
number of practical disadvantages and are expensive to operate. In line
with developments elsewhere in the chemical industry, fixed bed catalytic
treatment of effluent streams proves cheaper and easier than chemical
dosing. ICI believes that the 'HYDECAT' Process satisfies the technical,
cost and environmental requirements of such a process. If necessary a
combination of 'HYDECAT' Technology with low level chemical dosing (as
practised in the potable water treatment industry) can cheaply and
effectively eliminate free chlorine from these effluents to any required
level.

The ICI 'HYDECAT' Process was awarded the 1990 Better Environment
Award for Industry in the Pollution Abatement Technology Category and is
being offered under license by ICI Katalco as the best option for the safe
destruction of chlorinated caustic effluents.
 34

ACKNOWLEDGEMENTS

The presenter is indebted to co-authors PEJ Abbott, M Carlin, F Hancock

and F King and their colleagues within ICI Chemicals & Polymers Ltd who
generated the results described above and to the company for permission to
present the paper.

REFERENCES

1. S.D. Gokhale and L.L. Frank, Hypochlorite waste management in

chlor-alkali industry. In Waste Treatment and Utilisation, ed. M.
MOO-Young, C.W. Robinson, and G.J. Farquhar, Pergamon Press, New
York, 1982, pp.347-367.

2. European Communities Directive 76/464

3. P.A. Taylor and A.J. Stewart, Evaluation of the Toxicity of Various

Forms of Chlorine to Ceriodaphnia, AICHE Summer National Meeting,
Session 78, Characterisation and Reduction of Wastewater Toxicity,
August 20, 1990, San Diego, California.

4. G.R. Helz, and L. Kosak-Channing, Environ. Sci. Technol., 1984,

18(2), pp48A-55A.

5. D.L. Caldwell, and R.J. Fuchs Jr., Catalytic decomposition of

hypochlorite using substituted cobalt oxide spinels, US patent
4,368,110, 1983.

6. A.L. Compere, and W.L. Griffith, Catalytic sodium hypochlorite

degradation using a Kynar stabilised catalyst, Oak Ridge National
Laboratory, Oak Ridge, Tennessee, USA, June 1987.
 35

GREEN ASPECTS OF CHLORINE BLEACH -

APPROACHES AND NATIOHAL CHARACTERISTICS

JAMES P SHIELDS
Technical/Engineering Director,
Hays Chemical Distribution Limited,
Sandbach, Cheshire, CW11 9PZ

ABSTRACT

The paper offers some premises for the growth of environmental

concern in general. It looks at the background of concern
about chlorine in particular, and then at chlorine bleach and
its green status in different countries. The chlorine bleach
issue in the United Kingdom since 1989 is examined and the
lessons from this period are presented.

The Growth of Enviro:n:men.tal Concern - Premises

The first premise may be viewed as somewhat cynical. It is
that selfishness is a greater motivator than altruism.
Pragmatically expressed it ,is that people are motivated by
self-interest. The basic sense of survival expressed simply
is that people do not want to die. As a minimum, the public
expects protection from sudden or acute safety lapses - a
toxic gas release or a liquid spillage on a person would
generate significant indignation. On a broader scale, the
public expects protection from illnesses which can be chronic
or acute such as emphysema, bronchitis or cancer. Indignation
generated by these illnesses, however, is often tempered by
the ambiguity of source and they may not be easily
attributable to, say, chlorine or the chemical industry. It
is arguable that public concern with the environment is not a
matter of the welfare of animal or plant life but the notion
that if pollution threatens those things, it will threaten
personal well-being also.
The second premise is that improvements in communications
have increased the market disproportionately. The public
thirst for information has outgrown the supply.
 36

Instantaneous newsworthy items from Capitol Hill, Westminster

or the Kremlin are delivered hot into lounges allover the
developed world. There has been an explosion of local
newspapers, local radio channels and cellular telephones. The
recent coverage of the Gulf War exemplifies the explosion of
and demand for information, where cameras were carried
initially on the fighter aircraft and subsequently on the
missiles themselves in order to carry the viewer to the point
of destruction.
The third premise is that to be newsworthy is to be
sensational. It was not newsworthy that refrigerants improved
the quality of life. It was newsworthy that they could cause
skin cancer. A threat tends to be newsworthy~ a benefit is
soon taken for granted.
Chlorine and the Chemical Industry
The combination of these and other features produces a
scenario where items can be made newsworthy by exaggeration to
the point of disinformation, pseudo-science and
misinterpretation. When these are allied to a conditioning of
the audience, we have the recipe for over-reaction. Two
examples of advertisements promoting over-reaction are shown
below:
DIAPER ADVERTISEMENT - "In our opinion, a nappy
can't hope to be environmentally friendly unless its
pulp is 100% non-chlorine bleached"

ARTICLE ON BLEACHED PRODUCTS IN THE NATIONAL

PRESS - "Chlorine is the main culprit here, for it
is used in massive quantities allover the world and
is a chemical linchpin in the formation of poisonous
dioxins and other lethal chemicals known as
organochlorines"
The third advertisement is a clear example of emotional
blackmail:
ADVERTISEMENT FOR A 'CARE' RANGE OF PRODUCTS -
"The stickleback is a freshwater fish ............ .
the poor little fellow has to make do with oxygen-
deficient, algae-infested or chemically-polluted
water .....•....... Two culprits in the kitchen are
chlorine and phosphates ..•........ The consequences
of chlorine in our water can be equally distressing
. . . . . . . . . . . .. Ultimately, it can react to release
traces of harmful chemical compounds, including
dioxins, which can affect all forms of aquatic life"
 37

The conditioning associated with chlorine and chemicals

in general is very evident in history. The preoccupation with
finding new outlets for chlorine during the first half of this
century knew no restrictions: new solvents, new pesticides,
plastics, refrigerants, all were hailed as major contributions
to quality of life, as indeed they proved to be. Rumblings in
the mid-sixties about non-degradabili ty of pesticides, and
speculations about the ozone layer, were the first signs of
preparation of the audience for a swing back against chlorine.
The focus on carcinogenic materials and the association of
chlorine with mercury were forerunners of the bad news.
Minimata, Seveso, Bhopal, the Rhine, Flixborough and Chernobyl
punctuated the next twenty years. Dioxin acquired a deadly
reputation in spite of evidence that exposure up to parts per
million produces no more than pimples. The reputation of
dioxin was sufficient to get the bleached disposable nappy
(diaper) to number six in the U.K. hit parade for green issues
in 1989. The CFC issue was, of course, an evergreen number
one throughout the whole of that year, bettering even the
durability of the hits of presley, the Beatles and Madonna.
Endemic in all of the developed world today is a low
regard for chemicals. The stigma acquired by chemicals and
the chemical industry must be recognised as our failure to
advertise the eradication of illnesses, the improvement in
life expectancy and the benefits to the quality of life,
brought about by chemicals. The basic failure of the chemical
industry to open its image to public scrutiny in proportion
with growing demand for information has made it easy prey for
radical environmental groups, who are themselves exploiting
the change.
Chlorine Bleach in Various Countries
By way of a case study I will refer to bleach or sodium
hypochlorite or chlorine bleach as it is currently being
termed. The environmental movements around bleach from 1989
to the present serve to illustrate the effects of pressure and
conditioning. Green Consumer Day in the UK took place in
September, 1989. A number of 'green ranges' of supermarket
products were launched against recent concerns about dioxins
in bleached materials. Prior to that date a number of us in
the UK industry had put our acts together and had decided to
promote the benefits of bleach in a public way, and to refute
disinformation about the use of bleach - disinformation which
was growing alarmingly. The status of a number of European
countries on bleach at this time makes for an interesting
comparison.
U.K. Growing environmental objections to chlorine bleach
on the back of hype about dioxin in cartons, coffee filter
papers, diapers, halomethanes in sewage; use in the home
largely confined to toilet.
 38

Germany. Chlorine bleach banned from domestic use, as a

result of two deaths associated with the use of hypochlorite
- one from ingestion and one from a heart attack during
exposure to chlorine gas resulting from misuse of
hypochlorite.
France. A proactive promotional exercise on bleach had
been under way for some ten years. The thrust of the
initiative had been personal hygiene and prevention of
infection. The oil crisis of the seventies had developed the
promotion of bleach with low temperature washing of clothes,
thus saving energy. The campaign had been further heightened
in 1989, the bicentenary of the French Revolution and also the
bicentenary of the discovery of bleach by Berthollet, who thus
revolutionised home hygiene. The anniversary was used to
extol the virtues of bleach with extensive use of the
technical press - medical and pharmaceutical, and female
fashion and health magazines. Translated quotations from the
French campaign are shown below:

JOURNAL DE LA MEDECINE PRATIQUE - "At low

concentrations (1/100), Chlorine Bleach is the best
antiseptic: wi thin 30 seconds, 99.9% of germs are
destroyed"
QUOTIDIEN DU MEDECIN - "Antibiotics and
vaccines are a valuable treatment against infectious
diseases, but they are unable to prevent the
infection as Bleach can"

QUOTIDIEN DU PHARMACIEN - "Chlorine Bleach: The

disinfectant giant"
JOURNAL DE L' AVANCEE MEDICALE - "Interesting
that Bleach suppresses cholera, given the fact that
cholera germs are resistant to common antibiotics"
INTERBLOC - "Due to vaccines and antibiotics,
strong diseases are disappearing but new infectious
diseases are appearing e.g. AIDS, against which
there are no vaccines. Therefore we must reinforce
preventive hygiene with Bleach which kills all known
germs"

Following a press conference in 1989 there were

publications in thirty-six magazines, all promoting the use of
bleach and carrying no defence. By 1990 advertisements on the
use of bleach were being displayed on prime-time television.
French concerns were around the household safety features of
hypochlorite. Environmental concerns were not evident. The
use in France focused on laundry and hygiene in the kitchen.
Household use was about twice the U.K. rate.
 39

Sweden and the Netherlands. Growing and mounting

enviroruneritaI-pressure-:---SIgniflcant pressure in Holland on
all disinfectants.
Spain and Portugal. Level of use in the household about
four times the U.K. rate; similar receptiveness as France to
bleach promotion; comparatively insignificant environmental
pressure.
Response to the Bleach Issue in the United. Kingdom

Producers and formulators initially tested each other's

experiences of environmental concerns. Al though there were
common threads running through the experiences, there was no
common language in the response to some of the concerns.
Consequently a number of companies took upon themsel ves to
produce question and answer documents. These were circulated
widely to salespeople, agents and customers. Common
environmental statements were agreed. Preparation was made
for a press conference. This would feature hygienists who
would discuss disinfection in the home. The panel would
include a spokesperson to respond to environmental enquiries,
and would be chaired by the Federation Chairman. The
Federation was to be used in order to detract from the charge
of vested interest. In a similar vein, a paper was to be
presented from an independent expert. The work of the Pasteur
Institute in France, as an independent source of expertise,
had been very valuable in that initiative. Examples of the
prevalent health issues were:
FOOD POISONING
* Latest UK figures show> 20,000 cases per year
and it is predicted that true figure is likely to
exceed 2 million.
* Considerable recent public awareness due to
press coverage on:
Listeria
Campylobacter
Salmonella
* Many parts of the home where an effective
disinfectant is required:
Toilet
Food preparation areas
Chopping boards
Dishcloths
Petfood bowls
Nappy buckets etc.
 40

GASTRO-ENTERITIS/DYSENTERY
* Infantile Gastro-Enteritis still very common.
Particularly dangerous in babies under 6 months old.

* Dysentry is also cause for concern as outbreaks

still occur in Day Nurseries/Infant Schools.
* Effective disinfection can help prevent cross
contamination.

Invitations were sent out to a wide targeted audience:

1) Women's magazines
2) National Press women's page editors
3) Environmental health groups
4) Health and hygiene groups.
There was a positive interest only from the environmental
groups. Mad Cow Disease at that particular time was firmly in
number one position in the hit parade. Media training was
undertaken by the projected panel, but the conference was
deferred, although the interest of the environmental health
group was addressed at a later date. By that time promotional
booklets had been developed by a number of companies, and the
group had spread its activities into a European group. Two
position papers were completed, one responsive and one
promotional, and were issued under the auspices of the
Federation. Similar promotional literature was released in
Spain and Portugal.
The Effects
Are we succeeding or failing? The non-chlorine bleaches are
less effective than hypochlorite in any case and the consumer
prefers chlorine bleach. Kitchen hygiene is a feature of the
position paper. The growth of reported food-poisoning cases
is shown in Figure 1. Products based on hypochlorite have
been launched to cover kitchen hygiene. People associated
with hypochlorite are more confident about response, but
really the environmental attack was not as severe as expected.
Margaret Thatcher announced that she did not use chlorine
bleach in Downing Street and did not survive the year. Prince
Charles is associated with similar remarks in his green video
with John Cleese. He is not yet King Charles. McDonald's
have announced that they clean lettuces with chlorine and use
chemicals extensively for kitchen hygiene.
 41

<!)
z
Z 60 ,000
0
en
00-
50,000
0
0
0 40,000
lI-
lI-
0
en 30,000
w
en
~
() 20,000
0
w
~
II: 10,000
0
0-
W
II: 0
1950 1955 1960 1965 1970 1975 1980 1985

YEARS

Figure 1. Fo~d poisoning: reported cases up to 1989

(Source: Communicable Disease Surveillance Centre)

Lessons
i) Talk to each other, to the workforce, salesforce,
customers, schools.

ii) Develop a common language.

iii) Develop response and promotional literature.
iv) Use Federation and non-company experts.
v) Have a package on file and an ability to mobilise people
and the package quickly.
vi) Minimise defence and maximise promotion.

vii) Follow the line:

a) Here is why the product is needed.

b) Here is the evidence that it solves the problem .

c) Here is the evidence that its deleterious

environmental impact is negligible .
 43

CYCWCHROME - THE RECYCLE OF SODIUM DICHROMATE

IN SODIUM CHWRATE MANUFACTURE

Dr. R.E. Alford,

Manager, Research & Technology Department
Chemetics International Company Ltd.
Vancouver, British Columbia, Canada

ABSTRACf

Sodium dichromate is used in the electrochemical manufacture of sodium chlorate to

both buffer the electrolyte and to minimize undesirable cathodic reactions.

Increasing quantities of chlorine dioxide are being produced from chlorate solutions
as the use of environmentally undesirable chlorine is reduced in pulp mill bleaching
operations. Such processes result in the contamination of mill effluents with
chromium species which cause environmental concerns.

Several processes are known for dichromate removal, but they are expensive to
operate. This paper will discuss a process utilizing ammonia and sodium hypochlorite,
both generally available at sodium chlorate producing plants, to recover dichromate
at a reagent cost less than the value of the recovered dichromate.

INTRODUCfION

Alkali metal chlorate salts are produced by electrolysis of chloride salts, generally in
an undivided cell, or via sodium chlorate so produced. The process dates back to
1802 when Risinger and Berzelius (1) electrolyzed sodium chloride. In 1851 Watt was
granted a patent (2) for a chlorate manufacturing process but it was not until the late
1800's that plants in Europe and America commenced industrial scale production.
 44

The electrochemical generation of sodium chlorate, in essence one of the simplest

electrochemical processes, is the second largest application of electrosynthesis. It has
been the subject of ongoing improvements and rapid growth; current world capacity
approaches 3,000,000 te per annum (see fig. (i». The bulk of sodium chlorate is used
in the pulp industry to produce chlorine dioxide for pulp bleaching, where it is
replacing chlorine to reduce the level of toxic chioro-organic compounds (produced
by chlorine bleaching), discharged with pulp mill effluents. In other areas the use of
sodium chlorate as a herbicide has decreased dramatically though its early use in
chlorate based explosives remains. A more exotic, explosives related, growth area is
fuel for the space programs, where ammonium perchlorate is produced by further
electrochemical oxidation and double decomposition from sodium chlorate.

The electrochemical generation of sodium chlorate has been studied extensively and
many reaction sequences advanced. In its most simple form the process may be
represented by:

(i)

However, this gives no insight to the significance of the process steps, not the least of
which is the relevance of chromium VI.

The anodic reactions will be familiar to those involved in both chlorine and chlorate
production viz:

Cl- -+ 1hC12 + e (ii)

6ClO- + 3H20 -+ 2CI03- + 4Cr + 6H+ + 3/2 O2 + 6e (iii)
2H20 -+ O2 + 4H+ + 4e (iv)
 fig . ( i)

Production
3.0 r....······....·..·..............·.......... ·· ..·· ......·........·....·....·......·...............................,
• Row
Sodium Chlorate .w. Eur~
• North America
2.5 ·~ ......·..·........ ··..................·........·........·..·..........·....·....- ..-

Technology
i
~ 2.
Unknown
~
c
,g 1.5
0
:J .j::..
VI
~
D-
IU 1.0
:J
C

End Use .!i

1960 1970 1980 1990

CYCLOCHROME [HEmEll[S
 46

Reactions (iii) and (iv) represent the electrochemical anodic inefficiencies and are
readily contained to acceptable limits by appropriate choice of reaction conditions,
notably operating temperature, reaction volume and the nature of the anode coating.

It is the cathodic processes which have been responsible for the use of chromium VI
in sodium chlorate production viz:

2HzO + 2e --. H2 + 20R- (v)

ClO- + HzO + 2e --. Ct + 20R- (vi)
Cl03- + 3HzO + 6e --. Cl- + 60R- (vii)

The cathodic inefficiency reactions (vi) and (vii), which would account for a very
significant decrease in current efficiency, are inhibited by the use of chromium VI
salts (or by the less satisfactory use of a divided cell). Inclusion of chromium salts
typically 2 - 7 giL (as sodium dichromate) is believed to result in a modification of
the electrode surface such that reduction of hypochlorite and chlorate is effectively
prevented (3).

The formation of sodium chlorate itself is principally achieved in solution, reaction

(iii) occurring to a negligible extent under normal operating conditions, as follows:

Clz + HzO --. HClO + HCI (viii)

HOCl ... ClO- + H+ (ix)
2HClO + ClO- --. Cl03- + 2Ct + 2H+ (x)

However, further to the electrochemical inefficiencies there is an additional

inefficiency, the decomposition of hypochlorite viz:

2ClO- (xi)
 47

Returning to the use of chromium VI salts, a further advantage, beyond that of

cathode surface modification, is its buffering action which facilitates control at the
appropriate pH for dismutation of hypochlorite to chlorate and chloride.

Environmental Aspects
The principal and growing use for sodium chlorate is the increasing substitution
of chlorine by chlorine dioxide in pulp bleaching. It is driven by environmental
concerns. (One being that the use of chlorine gives rise to dioxins in pulp mill
effluent which results in contamination and injury to aquatic life and in turn poses a
wider threat to the food chain. In addition chlorine bleaching gives rise to other
undesirable AOX compounds). However, the use of chlorate "cell liquor" results in
chromium salts being discharged with the pulp mill effluent.

Chlorine dioxide, at the industrial scale, is produced by acid reduction of

sodium chlorate using either hydrochloric acid (e.g. Chemetics' Integrated Process,
whereby the co-produced sodium chloride is electrochemically re-oxidized to sodium
chlorate and the co-produced chlorine reduced with hydrogen, co-produced from the
production of chlorate (reaction (i» viz:

2NaCI03 + 4HCI - 2CI02 + 2NaCI + Cl2 + 2H20 (xii)

2NaCI + 6HzO - 2NaCI03 + 6H2 (i)
Cl2 + H2 -2HCI (xiii)

The balance of the hydrochloric acid can be provided by reduction of brought in

chlorine with some of the excess hydrogen from chlorate production, the balance of
which can be used as a fuel. In this way chlorine and chlorate plants can be linked
to produce chlorine dioxide and sodium hydroxide from salt viz:

NaCI + 3H20 - ........................ - CI02 + NaOH + 2lhH2 (xiv)

 48

A related procedure is the reduction utilizing sulphuric acid and salt, which produces
undesirable sodium sulphate as a co-product viz:

(xv)

A modification to the acid reduction process utilizes methanol with coincident co-
production of formaldehyde.

Chlorate reduction, by either hydrochloric or sulphuric acid, is effected utilizing

either "cell liquor" or a sodium chlorate solution produced by dissolution of sodium
chlorate which was crystallized from "cell liquor".

In the latter case impurity levels build up within the electrolyte circuit of the
sodium chlorate producer, necessitating further electrolyte treatment or more
preferably a purge of electrolyte. Purged electrolyte is generally supplied to a pulp
mill for chlorine dioxide production.

The pulp mill use of "cell liquor", either as a main or partial feed to a chlorine
dioxide generator, results in the discharge of any chromium salts with the pulp mill
effluent.

A sodium chlorate plant exporting sodium chlorate as "cell liquor" exports some
2 to 10 kg of sodium dichromate with every tonne of sodium chlorate. Although the
sodium dichromate has no effect on chlorine dioxide production, other than in some
evaporative processes, the environmental impact of its discharge in the pulp mill
effluent needs to be noted. A 100,000 tepa sodium chlorate plant, producing 10% of
its product as cell liquor, would discharge the equivalent of some 20 - 100 tepa of
sodium dichromate.
 49

Chromate Remoyal
There are a number of methods of removing chromates from chlorate liquors.
These methods include reduction of the chromate to mixed chromous and chromic
salts with precipitation of the insoluble hydroxides where reduction may be effected
by: water soluble sulphides (4), hydrazine (5), hydroxylamine (6), sulphites (7) and
electrochemical means (8). Chromate may also be removed by ion exchange
techniques (9) and by precipitation, of which barium chromate is an obvious example.

Each of these processes present certain problems. Reduction by sulphide gives

rise to precipitated sulphur, any sulphide excess would give rise to hydrogen sulphide
on acidification and violent reaction with chlorine dioxide. Hydrazine or
hydroxylamine are expensive reagents, potentially cause chlorate reduction but most
particularly, have an undesirable reaction with chlorine dioxide. The use of sulphites
requires pH adjustment to values of 2 to 4 with potential preferential reduction of
chlorate. The electrochemical process is inefficient and does not effect quantitative
chromate removal. The ion exchange process is also inefficient with some deleterious
oxidation of the ion exchange resin being a further limitation.

Cyclochrome Process
The Chemetics Cyclochrome process was developed to essentially quantitatively
recover chromate from exported cell liquor using inexpensive reagents with recycle of
the recovered chromium.

The basic steps of the process involve the reduction of chromium VI to

chromium IT/ill, using sodium hypochlorite and ammonia, with separation and recycle
of the precipitated chromium hydroxide (see fig. (ii) & (iii».
I t I ~

I ill
I ',J

, "

;~ ,,
!I;

, I,

,-
 I'
I,! I
•..,11

lill
I! !II
!I
0TT

- - - ~- - - - - ---~ ~;~
 52

Sodium hypochlorite recovered from chlorine dioxide production or other

sources may be conveniently utilized. Ammonia is frequently used to dechlorinate cell
liquor prior to shipment or crystallization and is therefore also a familiar reagent.

The overall process may be represented by:

The individual process steps involve the following.

Reductant Production and Partial Chromate Reduction

Ammonia and chlorine are added to the chlorate liquor under alkaline
conditions maintaining a large ammonia excess. The excess ammonia is subsequently
recovered and recycled. The actual composition of the reductant is uncertain but the
process may be represented by the production and reaction of hydrazine or
hydroxylamine, though we have no evidence of either species being present, e.g.:

lONH3 + 5Clz -+ 5N2H 4 + lOHCI (xviii)

3N~Cr207 + 5N2H 4 -+ 2Cr30 4 + 5N2 + 7H20 + 6NaOH (xix)

Empirically we have found that the following conditions are most suitable:

NH3:NaOCI > 15:1 (mole ratio)

Reaction time > 5 minutes
Reaction temperature > 70°C
pHm > 10.5

The ammonia is preferably added to the chlorate liquor prior to addition of sodium
hypochlorite/chlorine and the reaction may be conducted in a conventional stirred
reactor or preferably an in-line mixer.
 53

Recycle of Ammonia Excess

Excess ammonia in the chlorate liquor, which contains partially reduced
chromium salts, may be removed by distillation, in many cases utilizing waste steam.

After distillation an ammonia concentration of less than 50 mg/L can easily be

attained. Continuous trials have been executed using a 3 m packed column with
preheating of the chlorate liquor fed to the top of the packed section. Experiments
have been executed with and without distillate reflux. Typical results are presented
in Table 1.

Table 1
Ammonia Recovery from Reduced Chromium Salt Chlorate Liquor by
Atmospheric Distillation without Reflux
NH3 Concentration
Liquor Feed Rate
m3/m2.h Feed Distillate Bottoms
% % mg/L
13.3 3.42 18.9 250
13.3 3.15 13.7 35
13.3 2.10 11.2 35
13.3 1.35 7.1 30
10.7 3.50 10.8 180
10.7 3.15 10.2 25

Residual ammonia levels of 200 mg/L have been shown to have no detrimental effect
on chlorine dioxide production and such ammonia levels are common in chlorate
liquors exported from plants using ammonia for hypochlorite destruction.
 54

Precipitation of Reduced Chromium

Final reduction of chromium and precipitation of the mixed hydrated oxide is
achieved by pH adjustment of the ammonia stripped solution using, for example,
hydrochloric acid.

At 80a C the reduced chromium is insoluble in the pH range of 6 to 7.7. At pH's

above this value chromium II/III salts remain in solution as anion complexes and
below as hydrated chromic and chromous ions. For operational purposes pH control
within the band of pHm 6 to 7.5 would be convenient. This would result in a soluble
chromium concentration of less than 0.2 mg/L (see Table 2), which is superior to that
generally applying for sodium chlorate crystal product.

Table 2
Effect of pH on Soluble Chromium Levels
for Precipitation at 800C from Typical
Cell Liquor
pHm Soluble Cr mg/L
8.0 24
7.7 < 0.2
7.5 < 0.2
7.0 < 0.2
6.5 < 0.2
6.0 < 0.2
 55

Separation of Reduced Chromium

The hydrated chromium oxide precipitate is exceedingly fine and light. It is not
conveniently separated by gravity settling and adding flocculants, which would be
recycled to the electrolysis plant, may present problems.

Of the many separation technologies which could be employed, including

enhanced gravity devices and the various forms of filtration, we have found cross flow
micro-filtration quite suitable. The hydrated chromium oxide can be conveniently
concentrated to at least the equivalent of 50 g chromium per litre of liquor using cross
flow filtration capable of operating in a back pulse mode. This technique can be used
to produce a solids free chlorate liquor, hence negating the requirement for a
polishing filter associated with gravity settling techniques. The slurry may then be
returned to the electrolysis plant with prior chromium oxidation if required.

Chromium Return
The concentrated hydrated chromium oxide suspension in chlorate liquor may
be returned directly to the cellroom or after a chromium 111m oxidation step to
chromium VI.

In the electrolyte circuit the chromium 111m would be oxidized to chromium

VI viz:

In Chemetics' technology the return of the chromium oxide suspension can be

to the chlorate reactor, degasifiers or cell feed whichever may be most convenient.

Oxidation of the suspension can alternatively be achieved prior to return to the

cell room by a variety of means, though the use of sodium hypochlorite is likely to be
 56

the most expedient, including that sourced from within the chlorate plant. Under
these conditions oxidation could be executed in a stirred reactor or in-line mixer or
a simple pipe mixer.

Rea&ent Economics
A range of reaction conditions have been evaluated from which the reagent
consumptions, see Table 3, have been determined. The analysis is based on a 100,000
tepa crystal sodium chlorate plant with a 10% purge operating with an equivalent
sodium dichromate in cell liquor of 5 gIL (Typical values range from 2 to 7 gIL).

Table 3
Chromium RecoveryIReagent Consumption
Basis: 100,000 tepa NaCI03 Plant
10% Purge on which Chromium Recovery is Effected
5 gIL NazCrz07
Material Quantity tepa Economics
Recovered Consumed Recovered Consumed Credit* Debit*
kC$ kC$
NazCr20 7 72.6 46.5
NH3 28.9 0.6
NaOCI 184 6.7
HCI 20.4 0.2
Totals 46.5 7.5
* Canadian West Coast

CONCLUSION

The production of chlorates may be conveniently achieved by electrolysis of chlorides

in an electrochemical cell where chromium VI is utilized to achieve high efficiency
production. The chromium VI may be recovered from the cell liquor and recycled
such that the exported cell liquor contains less than 0.2 mg/L chromium, utilizing
ammonia and a hypochlorite salt or chlorine.
 57

REFERENCES

1. Risinger & Berzelius, Neuses. Alg, J. Chem., 1115-149

2. British Patent 13,785 (1851)
3. Lindbergh & Simonsson Dept. of Applied Electrochemistry, Stockholm
4. U.S. Patent 3843759
5. U.S. Patent 4268486, Canadian Patent 1139090
6. German Patent 3032131
7. U.S. Patent 4259297
8. U.S. Patent 4699701
9. U.S. Patent 3835001
 59

The Design and Development of Flemion Membranes

Haruhisa Miyake
Research Center, Asahi Glass Co., Ltd.,
1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, 221 JAPAN

ABSTRACT
Salt brine electrolysis using perfluorinated ion exchange membranes is now
recognized worldwide as the most energy saving process for the production
of chlorine and caustic alkali. Membranes are based on perfluorinated
polymers having functional groups.
Asahi Glass succeeded in the development of new membranes through
the first successful synthesis of perfluorocarboxylated polymers. These
membranes achieved high permselectivity due to less water uptake of the
carboxylates as compared with the sulfonates. Currently, many commercial
membranes contain layers of both sulfonate and carboxylate
perfluoropolymers. This paper deals with synthetic methods for
fluorocarbon acid monomers and polymers, structure and properties of the
polymers and membranes made thereof, and industrial apphcations.

Introduction
ehlor-alkali process using ion exchange membranes is now recognized as the
most energy savin~ process for the production of chlorine and caustic alkali.
Particularly In Japan, the mercury process withered out by 1986,
having been converted mostly to the membrane process. During the course
of the conversion, the membrane process has demonstrated the ability to
attain drastic improvements not only in pollution control but also in
electrical power consumption.
The key of this technology is high performance membranes which are
made of perfluorinated polymers having functional groups.
Perfluorosulfonated membranes were first made by the du Pont
Company. Although they were originally developed for the use as a solid
polymer electrolyte in fuel cells, studies on application to a chlor-alkali
process were soon conducted worldwide. As the development proceeded,
sulfonated membranes were not always found to show sufficient
performance. High performance membranes were expected to appear.
Asahi Glass Company succeeded in the development of comrletely new
perfluorinated ionomer membranes based upon the first successfu synthesis
of carboxylated perfluoropolymers and has commercialized the membranes as
 60

Flemion. Due to less water uptake of the carboxylates, Flemion

membranes showed excellent permselectivity.
Currently, many commercial membranes used for chlor-alkali cells
contain layers of both sulfonate and carboxylate perfluoropolymers.
Preparation of polymers
Perfluorocarboxylated polymers which we
newly synthesized have general formulae
as shown below. These polymers are
copolymers of tetrafluoroethylene and
perfluorovinyl ether having carboxylated where m=O or 1, n=1-5
group instead of sulfonated group. X=COOH, SOlH or their derivatives
Typical functional monomers were
methy I perfluoro-5-oxa-6-heptenoate,
methyl perfluoro-6-oxa-7-octenoate and
y
S CF2=CFOCF2 FO(CF2)2S02F
CF3
methyl perfluoro-5,B-dioxa-6-methyl-9-
decenoate. Hereinafter, these monomers M, CF. =CFO(CF.J.COOCH.
are referred to as Mlo M2 and Ma, M. CF.=CFO(CF,J,COOCH.
respectively.
M. CF. =CFOCF, fFO(CF,J.COOCH.
CF.

A typical preparative route to carboxylated perfluorovinyl ethers is

shown here.

(x+l)HFPO

A
FOC(~FOCF2)x+lCF2CF2C02CH3 - - -.... CF 2 =CFO(CF2~FO)x(CF2)3C02CH3
CF 3 -COF 2 CF 3

(x- 0,1)

A cyclic lactone is formed in considerable yield (70-BO%) by the reaction

of 1,4-diiodo-perfluorobutane with oleum. The controlled addition of
methanol to the lactone gives selectively 3-methoxycarbonyl perfluoro-
propionyl fluoride, to which hexafluoropropylene oxide is added.
Finally, the acid fluoride group is converted to a perfluorovinyl group
by pyrolysis. An alternative pathway from the lactone to the vinyl ether
has been developed to improve the yield.
~CF2 4
C.r2 )F2 HFPO ... FOCyFO(CF2)3COF ... CF2 =CFO(CF2)3C02CH3
b-C=O CF 3 CH)OH

The molar ratio of functional perfluorovinyl ether to tetra-

fluoroethylene in copolymer is directly related to ion exchange capacity of
the resulting polymeric acid. This ratio can be controlled by monomer feed
 61

ratio in the copolymerization procedure. Since perfluorovinyl ethers have

been known to be radically active, copolymerization of tetrafluoroethylene
and functional perfluorovinyl ether was carried out by using a radical
initiator.
Fig.l shows the copolymer composition curve obtained for the
copolymerization of tetrafluoroethylene and functional monomers (M I and M3)
The curve in this figure clearly indicates that both monomers have
almost the same reactivity toward tetrafluoroethylene irrespective of the
difference of side chain length. The monomer reactivity ratios of
tetrafluoroethylene and functional vinyl ethers were calculated as 7.0 and
0.14, respectively, by using Fineman-Ross Method. From these reactivity
ratios, Q and e values of each monomer were derived by the Alfrey-Price
equation. Since Q and e values of tetrafluoroethylene are known to be
0.049 and 1.22, Q and e values of functional vinyl ethers were obtained as
0.0057 and 1.08, respectively. The much smaller Q value of these vinyl
ethers as compared with that of tetrafluoroethylene explains their lower
reactivity than that of tetrafluoroethylene.
Characterization
Characterization of polymers was carried out for copolymers of tetrafluoro-
ethylene and MI. Fig.2 shows a typical IR spectrum.
IOOr-------------------.

I I I
o 3200 2~OO 1800
M I or M 2 content In teed I mol -,.) Wove number (em-I)
'C2 F•• 7.00
rMI Of M]· 0.14 Fig.2 IR spectrum of copolymer
Fig.l Copolymer composition curve

The absorption at 2960 and 1780cm- 1 are due to carbon-hydrogen bond

and carbonyl bond in ester group, respectively. The absorption in the
range of 1l00-1300cm-1 are assigned to carbon-fluorine bonds, which appear
commonly in fluorocarbon polymers. The formation of copolymers was
also confirmed by fluorine NMR spectrum giving their characteristic peaks
as shown in Fig.3.
Whereas methyl ester type copolymers were insoluble in common
solvents, decyl ester type copolymers were soluble in fluorocarbon solvents
such as chlorbenzotrifluoride. Thus, molecular weights of copolymers were
measured by using an osmotic pressure method and found to be in the
range of 105-106. In FigA, molecular weight is plotted against TQ value
which is defined as the temperature at which the volumetric melt flow rate
of copolymer is 100mm3 / sec through the orifice of 1mm diameter and 1mm
length under the load of 30kg / cm2• As shown in this figure, logarithmic
molecular weight has good linear relationship with TQ value. Crystallinity
 62

CFl
10'
.,
.t:
.~ 5X 10$

CFlCOO "
~
:l
0
~

OCFl 0 10'
:2

I
~ 5X 10'
Me
-80 -120
150 200 250
8ppm from CFCl 3
Ta ee) Q= 100mm'/sec
Fig.3 19F_NMR spectrum of copolymer Fig.4 Molecular weight and TQ

III
.~ 10 5
o
c.

M,
...>-
Vl
o
.?> ~ 10 4
.;;; 5.6 .;;
]
C 12.6
...
C
III
1-
16.S CO

20.5 ~ 10 3
<I: L....a._ _ _--'-_ _ _...J.....J
31.2 10 10 2 103
5 15 25 Shear rate (5-1)
28 (degree)

F~g.5 X-ray spectra of copolymers

Fig.6 Melt flow behavior of polymer

100

\f\""~"'
3.0

Sodium type 80
2.5

'"E 60

\~\~35%NaOH
~ "'"."'
2.0
~
E.
~
.:;
1.5 40

1.0
20
_---------
.....
ESTER TYPE
0.5

2 3 4

50 100 150 200 250 300 2 9

Strain ,%, (degree)

Fig.8 Small angle X-ray scatterings of

Fig.7 Stress-strain curves of the membranes Na salt type membrane
 63

of copolymers was measured by the wide angle X-ray diffraction method as

shown in Fig.5. It decreased with increasing functional vinyl ether content
and the copolymer became almost amorphous above the vinyl ether content
of 20 mole%.
Furthermore, copolymers were melt processable as shown in Fig.6.
Properties
Copolymers are used in the field of ion permselective membranes by taking
advantage of ion exchange functions. Accordingly, properties as ion
exchange membranes are important from the practical point of view. Most
important and fundamental properties of membranes are mechanical
strength, ion permselectivity and conductivity. These properties strongly
depended upon the degree of dissociation of functional group and cohesive
forces of fluorinated polymer chains, which are related to the type of
functional groups and molecular structure of polymers, respectively.
Figure 7 shows stress-strain curves of the perfluorocarboxylated
membrane in the state of ester and sodium salt. The sodium type
membrane exhibited significant increase of tensile modulus and decrease of
elongation as compared with ester type one. This indicates the formation
of some kind of crosslinking structure by incorporation of ionic moieties.
Fig.S shows the small angle X-ray scattering pattern. The appearance of a
new peak in the sodium salt type membrane strongly suggests the ionic
cluster formation.
The shift of peaks to lower angle was observed by diluting the
concentration of the soaked solution. The formation of cluster in
perfluorinated ion exchange membranes was confirmed by several
researchers.
Table 1 shows the temperature Table 1 Ten,ile Strength or the Membrane.
dependence of tensile strength. The
sodium type membrane retains its high Temperature Tensile Strength (kg/mm')
strength even at a elevated temperature ee) Sodium Type Ester Type
of 90°C, although the ester type
membrane loses its strength with the rise 25 3.2 2.5
of temperature. These behaviors are also 50 2.5 0.4
explained by ionic clustering. 90 2.3 0.07
In the membrane, there exists a
fixed ion concentration which is defined as milliequivalent weight of
functional group per unit weight of water. Figure 9 shows the relationship
between ion exchange capacity and water content of different molecular type
of polymers including both perfluorocarboxylic and perfluorosulfonic acid
ones. It is shown that water content increases with the increase of ion
exchange capacity for each membrane. However, the slopes are much
smaller with carboxylic type membranes than that with sulfonic acid type
membranes and the former show lower water content than the latter.
Among carboxylated membranes, the one having shorter side chain length
exhibited much lower water content.
Since carboxylated membranes have low water content even with high
ion exchange capacity, they can attain considerably high fixed ion
concentration expressed as Aw.
Figure 10 shows fixed ion concentration of various membranes which
are soaked in caustic soda. As expected from the above facts,
perfluorocarboxylate membranes have higher fixed ion concentration than
perfluorosulfonate membranes, and the difference is remarkable particularly
in high caustic concentration range.
 64

50
C35SNaOH,90'C)
~

....
40
,I So,H TYPE ,"
:r Ml

... / <T

"
30
I:
!I: / E

,-
~
o <I: 20
U

___ ~ -~-A'-
R 0.82
,-' S03H TYPE
O.S 1.0 1.2 1.4 1.6 I.S 0L-----1~0~--~2~0----~3~0~---470~
Ion exchange capacity (meq/g-dry polymer)
eNaOH ("1
Fig.9 Dependence of water content upon ion exchange Fig.lO Influence of caustic concentration
capacity of membranes upon fixed ion concentration

100r-------------------------,

;;:/
6

::I"~
50:lH TYP! /
1.0

g, ~ 95

0
0
0.8
W
AR~/y
13
AA 1.36
~ 90 "/
0.6
,'if An 1.44 I
/M3
/ COOHTYPE
:I:
~ b MI All 1.21
0.4 / AR 1.21
_ _ _ _ ()-~, A' 1."
11) /
/ 0 _ _0__ 0::::=:. 85
~--~--~--~--~
0.2
".. . .-: o::::.--===~----·
;::::::.. MI All 1.23
20 40

10 20 30 40 Anolyte NaC12009/1

Caustic concentration (s) Temperalure

Flg.11 S value and caustic concentration Fig.12 Influence of caustic concentration upon
current efficiency

10. 1. - - - - - - - - - - - - - - - - , 10·'.--------------.
S03H eOOH 3.9."col/mol

...u
"0
C
"
o
U

....o
u

11>
W
1.0 1.5 2.0

Ion exchange capacity (moq!g-dry polymer) ,~"L---~20__-_,3~O---£~--J

C HaOH ey.)
Fig.l3 Conductivity of membranes against ion
Fig.14 Dependence of membrane condu-
exchange capacity
ctivity upon caustic concentration
 65

Figure 11 shows hydroxyl ion concentration in Donnan equilibrium in

membrane with that of outer caustic solution. As is clear in this figure,
perfluorocarboxylate membranes have lower value of Donnan hydroxyl ion
concentration than perfluorosulfonate membranes, because of the higher
fixed ion concentration of the former. These features of
perfluorocarboxylated membranes directly result in higher ion permselec-
tivity leading to the higher current efficiency than perfluorosulfonated
membranes when they are used in chlor-alkali electrolytic/rocess. Fig.12
shows current efficiency obtained with perfluorocarboxylate membrane in a
chlor-alkali cell.
Current efficiency as high as 95-97% is attained in high strength
caustic solution, whilst such a high current efficiency is never obtained with
perfluorosulfonated membrane.
Figure 13 shows the electrical conductivity for both carboxylic and
sulfonic acid membranes. Conductivity increases with the increase of ion
exchange capacity. At the same level of ion exchange capacity, carboxylic
acid membranes have lower conductivity than sulfonic acid ones, because
dissociation constant of carboxylic acid is lower than that of sulfonic acid.
However, carboxylic acid membranes can attain high conductivity by
increasing ion exchange capacity. In the meanwhile, conductivity was
affected not only by molecular structure but also by environmental
conditions in which membranes are soaked. Dependence of the conductivity
upon concentration of caustic soda at several temperatures is shown in
Fig.14 in case of perfluorocarboxylate membranes.
The conductivity is seen to be strongly affected by the caustic
concentration and the temperature. From the figure, the apparent
activation ener~ for the ionic conductance was calculated to be 3.9, 9.1 and
17.1kcal / mol In 14, 25 and 40wt% caustic solution, respectively. The
decrease of conductivity with the increase of caustic concentration is
ascribed to the decrease in ionic mobility, which is caused by the loss of
water in the membrane. The low value of the conductivity and the high
value of the activation energy in high caustic solutions implies that there
exists a strong interaction between counter ion and fixed ion in the
membrane.
On the other hand, high ion exchange capacity membranes can serve
as high conductive membranes even in high caustic concentrations.
Table 2 shows the activation energy and conductivity of membranes in
35% caustic solution against ion exchange capacity.
As is clear in this table, high ion exchange capacity can weaken the
ionic interaction effectively.
Diffusion of ions through perfluorocarboxylic acid membranes has been
studied. A measurement cell is divided by a membrane into two
compartments which are filled with caustic and sodium chloride solution
respectively. As shown in Fig.15 and Fig.16, apparent diffusion coefficients
of NaCI and NaOH depend strongly upon caustic concentration, while their
dependence upon NaCI concentration is smaller. When the concentration of
both solutions is equal, for example 3.5N, the apparent diffusion coefficient
of sodium hydroxide in the membrane is almost 5 times as large as that of
sodium chloride. In the meanwhile, diffusion coefficients of N aOH and
NaCI in aqueous solutions of the same concentration are almost the same
and are in the range of 10-5 cm2 / sec. This means that their diffusion
coefficients in membrane lower remarkably but that the coefficient of NaOH
is not affected so much as that of N aCl.
Meanwhile, there should be a correlation between conductivity and
diffusion coefficient, because both conductivity and diffusibility are based on
ionic mobility in a membrane_ Figure 17 presents a relationship between
 66
OO-'r-----------,
Table 2 Activation energy and ionic conductance
of membranes 351 NaOH

Ion Exchange capacity

1.2 1.4 1.7 1.9
(meq/gl

Ea (keal/mol) 15.3 14.4 12.0 10.4

3 ~rnol/l NoCl/membrane/NoOl-lICI
Temperature: SO"C

1O-cL.-~2"=0----}'0~--·.'-'0
Kx 10 4 (Q-lem-l) 2.3 8.5 87 300 Causlic concentration ('"/.)

Fig.iS Dependence of app4ren~ diffusion

coefficient upon NaOH concentration
10-·r---------~
10-'r--------~
Noel (eJ/membrane 135-;. NoOH
Temperature: 90·C

Ne... •____
u _,
-- 10 - D HooH
] .~
~ ."
~

c
~

o
~ rh-~ ______~D~N'~Cl~_
~
S~eci(ic conductivity, X (n-'em-')
IO-9~2- - - ! - - - - ! - - - - ! X: 35"/. NoOH, 90·C
0: 35 moUl Noel/membranel
Sodium chloride concenlration (mol/l) 35 "I. NoOH. 90"(
Fig.16 Dependence of diffusion coeffi- Fig.17 Correlation between diffusion
cient upon NaC! concentration coefficient and membrane conductivity

conductivity and diffusion coefficients of

electrolytes. Transfer of ions under
current passage is also important. 10
-.
Figure 18 shows flux of sodium chloride
with and without current passage.
The influence of current passage upon ~~
sodium chloride flux was noteworthy. , -, 0

The decrease in the flux is caused by

'-
"0 10

the draw-back of chloride anion to the

E
-.~
anode side. In this figure, the broken <.;:
line shows the value measured without Z
-,
current passage in which the flux of
-"
sodium chloride is 3-8 times as large as 10
2 3 4 5
that with current passage. The fact CNaCI (m/I)

that the flux of sodium chloride with e NaCI (cl/Membrane/NaOH 35 % e

current passage decreases wi th Current : O.2A/cm!l
increasing sodium chloride concentration Temperature : 90·C

indicates complexity of material Fig.lS Dependence of NaCl flux upon NaCl

transfer. concenCracion
 67

Application to the chlor-alkali process

The membrane permits only the passage of sodium ions from the anode
chamber to the cathode chamber and prevents the migration of hydroxyl
ions to the anode chamber, which would reduce the current efficiency if it
occurred.
The essential requirements for the membrane used in chlor-alkali cells
are high conductivity, selectivity and mechanical strength.
To achieve both high current efficiency and high conductivity, the
membranes are composed of at least two layers.
Perfluorosulfonated polymers or perfluorocarboxylated polymers having
high ion exchange capacity are used for the anode side layer, in order to
attain high conductivity. Perfluorocarboxylated polymers with low ion
exchange capacity are used for the cathode side layer in order to achieve
high current efficiency.
To endow the membranes with necessary strength, the membranes are
reinforced with polytetrafluoroethylene woven cloth. Furthermore, surfaces
of the membranes are coated with hydrophilic inorganic porous layer so as
to release gas bubbles being generated in electrolytic cells.
The maximum caustic soda concentration that can be obtained lies in
the range of 30-40% caustic. The current efficiency is 95-96% and an
interelectrode voltage of about 2.9volt is obtained at 35% caustic
concentration under a current density of 30 AI dm2 •
Energy consumption by the membrane process is now approximately
1000kwh I t lower than that of the mercury or the diaphragm process (30%
energy saving) .
Currently, Asahi Glass is developing an entirely new membrane that
is capable of directly producing 50% caustic soda without need of further
evaporation, based on a new design of membrane structure.
 69

UNDERST ANDING MEMBRANE OPERATING CONDITIONS

JAMES T. KEATING
E.I. du Pont de Nemours & Co., Inc.
Experimental Station
Wilmington, DE 19880-0323 USA

ABSTRACT

Operating conditions for membrane chloralkali electrolysis have been detennined by experiment
and experience in the more than ten years that membranes have been widely used by the
industry. In that time our understanding of how membranes operate has advanced. We now
can present a clear picture of why the operating conditions are what they are and describe the
consequences of operation outside the recommended range.

DISCUSSION

Membrane Structure
The ideal membrane for a chloralkali cell separates the electrolytes, and the chlorine and
hydrogen. It offers no resistance to passage of cations and infinite resistance to passage of
anions. It resists tearing and puncture and is chemically and dimensionally stable in the hot
caustic and chlorine environment (Figure I).

The real membrane is a fluorocarbon copolymer containing carboxylate and sulfonate

acid or salt groups, reinforced with fluorocarbon fabric. Figure 2A shows the cross section of
a typical membrane. This has been the basic structure of Nafion* membrane for over ten years.
The thicker sulfonate polymer on the alUJde side of the membrane provides high conductivity
and absorbs enough water to keep the membrane flexible and tough at all operating conditions.
The thinner carboxylate layer on the cathode side of the membrane has excellent anion rejection
and provides high caustic current efficiency.

*Du Pont's registered trademark/or its perjluorinated membranes.

 70

electrons

o o
o 0 M o 0

Chlorine o e 00 Hydrogen
o o o
o
Na+lwater -+~
~:....t-.... o
o o
o
o~CI _

Brine

Figure 1. The ideal membrane prevents mixing of chlorine and hydrogen and offers no
resistance to sodium ion transport while completely rejecting anion passage.

The soundness of this structure has been proved in plants all over the world.
Laboratory tests on Nafion® 90209 show current efficiencies of over 95% after 75 months in
commercial service. Original membrane is running in this plant seven years after installation.

Research by Yeager and Gronowski, published elsewhere in this volume, shows that
the membrane is capable of nearly perfect caustic current efficiency under specific but realistic
conditions. The polymer can stop substantially all hydroxide ion passage.

_I-
--
.....
•
-:----
III
iii
c:

---
o
:=
:::I
f/l

Reinforcement
-'---------
(A) (8)

Figure 2. (A) is a cross section of typical Nafion® membrane showing

fluorocarbon sulfonate and carboxylate layers.
(B) is a cross sectional representation of the membrane as a poly -
anion, composed of sulfonate and carboxylate groups.
 71

Figure 2B is a simplified picture of the membrane as a polymeric salt. The negative or

anionic groups are immobile because they are part of the polymer. The anionic groups are
neutralized by cations, sodium or potassium ion in chloralkali work, but other cations are
possible. Because cations are interchangeable, the membrane is called a cation exchange
membrane. The membrane is also a salt, having about the same strength as lOOg/1 brine.

The cations are mobile and move freely under the influence of electric fields,
concentrations, temperature, and other differences in free energy. Anions are repelled by the
membrane because of its fixed negative charges. This is the fundamental reason that the
membrane can transport cations with little resistance, and offer a nearly impassable barrier to
anions.

Because the membrane is a salt and an ion exchange polymer, it is important to use only
pure water and solutions to keep the membrane from absorbing impurities. Only corrosion-
resistant materials should be allowed in contact with the membrane. Solutions should be
alkaline to prevent the corrosion that can sometimes occur even with nickel cathodes during cell
assembly. The degree of corrosion is insignificant for the cathode, but the nickel absorbed by
the membrane can increase its electrical resistance.

Being a salt, the membrane absorbs water and electrolytes, and swells. The degree of
swelling is determined by the temperature and ionic strength of the solution. This dimensional
change must be considered in chloralkali cell operation, where it is important that the membrane
be flat and tight to prevent wrinkling, which impedes gas flow and can lead to abrasion of the
membrane by the electrodes. For this reason, membrane manufacturers provide detailed
instructions on how their membranes are to be treated before installation.

Mass Transport in Membrane

In chloralkali electrolysis, sodium ions carry most of the current through the membrane.
However, the membrane offers no resistance to any cation. Neutral species such as water and
silica, being uncharged, are also not repelled by the membrane, and can be carried in with the
convection caused by the cations. Even anions can enter the membrane because anion rejection
by the membrane is not perfect [1]. Problems occur when species entering the membrane
become insoluble as they proceed from the relatively acidic anolyte toward the strongly basic
catholyte [2] (Figure 3). Impurities are considered in detail in another paper [3].

If everything in the brine except sodium, chloride, and water is considered an impurity,
we can classify impurities as cationic (calcium, magnesium, aluminum, etc.), anionic (sulfate,
iodide), or neutral (silica). Not all impurities are harmful, and of those that are, not all affect the
membrane in the same way. Harmless impurities include those that pass through the membrane
without affecting it, potassium is an example, and those that do not enter the membrane at all,
as with iron.

Hannful impurities include the alkaline earth cations (magnesium, calcium, etc.). The
concentrations at which they become harmful to the membrane are related to the solubilities of
their hydroxides.
 72

pH >15

Anolyte o Catholyte
Mg++

N a+/n· H20 ---If----+........

Ca++
o
pH 2-4.5

Figure 3. Cross sectional representation of the membrane showing the change in pH across the
membrane thickness (150-200!J.m), and the different points of precipitation for calcium and
magnesium ions from the anolyte .

• Magnesium ion precipitates near the anode-side of the membrane, blocking sodium ion
transport. Resistance to sodium ion flow appears as higher voltage [4].

• Calcium hydroxide is more soluble than magnesium hydroxide and progresses farther
into the membrane before precipitating. The higher solubility leads to larger crystals and
these physically disrupt the polymer at the membrane-catholyte surface. The result is
lower current efficiency, in addition to higher voltage .

• Alkaline earth cations in the presence of iodide precipitate apparently as the periodates.
In the case of barium, barium periodate. Even substantial quantities of these precipitates
usually have little or no effect on the performance of membranes that have the structure
of the Nafion®.

Operating Conditions
Operating conditions for membrane chloralkali cells are shown in the Table. The principal aim
of these conditions is to keep the mass flow (sodium ions plus water) within the membrane's
capacity for mass transport. The mass flow at 3kA/m2 is about 200g/min/m2. This is typical,
but how much can the membrane transport?

The composition of the polymers that make up the membrane influence capacity, but
this inherent capacity is similar for most membranes. The effect of operating conditions on
membrane capacity can be determined from such fundamental measures as sodium ion
diffusion rates or conductivity. Both are related to the ease with which ions can pass through
the membrane.

Current Density: The upper limit of current density is related to membrane capacity, but
the membrane is only one factor determining the limit. Membrane operates successfully at
current densities >4kA/m2 in certain plants, and has run at much higher current densities
 73

TABlE
Typical Operating Conditions For Membrane Chloralkali Electrolysis

Current Density 1.5 - 4kA/m2

Temperature SO-95°C
Caustic Concentration 30- 35%
Anolyte Concentration 170g/l (minimum)

experimentally. At higher current densities, current distribution becomes more critical. This is
not the average current distribution but the actual current distribution as seen by the membrane
and includes temperature and electrolyte concentration profiles, and the gas fraction in the
electrolyzer, as well as current distribution in the electrodes.

The lower limit on current density is not set to protect the membrane. Even at very low
current densities the membrane functions nonnally, but diffusion plays a relatively much larger
part. Therefore current efficiency can decline at lower current density, and caustic purity may
be affected by increased chloride and chlorate. These effects are reversible, and performance
will recover at nonnal operating conditions. However, higher pH anolyte may affect anode life.

Temperature: The membrane is an electrolyte solution, and like electrolytes generally,

increases in conductivity with rising temperature. The dependence on temperature is strong, as
shown in Figure 4, the rate of diffusion of sodium ion through membrane. This is not a
question of a few percent variation over 10 Co. It is factors of three or more, approaching an
order of magnitude. Conductivity measurements show the same thing (Figure 5).

Membrane capacity does not determine the upper temperature limit. With higher
temperature membrane water content rises with the consequences already described. Also,
water vapor becomes a larger fraction of the gas volume, especially in the anolyte, which has a
boiling point of about 105°C. Gas disengagement becomes more difficult and electrolyte
resistance increases. If boiling should occur, the membrane could be affected if vapor pressure
within the membrane became great enough to form voids in the polymer.

Catholyte concentration: The capacity of the membrane is proportional to the membrane

water content. Water content is quite variable and is determined by the concentrations of the
anolyte and catholyte. The membrane in the electrolytic cell is an electrolyte solution separating
the catholyte and anolyte solutions. The available water will distribute itself among the three
electrolytes: sodium chloride, membrane, and sodium hydroxide.

The simple rule is the more water available, the greater the membrane capacity.
Catholyte is more concentrated than the anolyte (10 M versus 3-4 M) and therefore catholyte
concentration is more critical. Figures 4 and 5 show the magnitude of the effect
 74

10-7

8O"C

10-8

3.10-9 I - - - - - - - - + - - - - - - - + - - - - - - - - i
25 30 35 40
% NaOH

Figure 4. Dependence of sodium ion diffusion rate in carboxylate polymer on caustic

concentration and temperature [5].

1O-5 - t - - - - - - - t - - - - - - - t - - - - - - - i
25 30 35 40
% NaOH

Figure 5. Conductivity of carboxylate polymer: effect of temperature and caustic strength [6].

The lower concentration limit for caustic is established to ensure good performance.
With too much water in the membrane, excessive swelling can lead to wrinkling and
mechanical problems. Swollen membrane has poorer anion rejection and therefore lower
 75

current efficiency. In itself this does no harm to the membrane but can cause increased oxygen
and chlorate production and possibly reduced anode life.

Anolyte concentration: For anolyte, an upper concentration limit is not usually

specified, because of the lesser effect of brine on membrane water content and also because it is
not usually in the operator's interest to run at high anolyte strength. The lower concentration
limit is established because as the anolyte strength decreases, more water passes through the
membrane. Water transport is usually stated as moles of water per sodium ion (n'H20INa+) or
as moles of water per Faraday. Figure 6 shows the relationship of anolyte concentration to
water transport. The absolute values depend on the nature of the electrolyzer and the membrane
type, but the trend is typical. Since in operation we want to avoid exceeding membrane
capacity, and since the mass passing through the membrane includes water, the lower limit for
anolyte strength is established to limit the mass flow.

Nafion® 90209
~
5.
, ,
0..+
i '"
~... ~ ,
~ :i' 4.5 o 0....
, ,
0
'0
~
Nafion® 966
4.
' ' -...~8
3.5
10 11 12 13 14 15 16 17 18 19 20
Anolyte
Wt%

Figure 6. Water transport as a function of anolyte concentration and membrane type.

Electrolyzer design also affects water transport.

The lower limit includes a safety factor to allow for the possibility that at certain
locations in an electrolyzer there may be lower anolyte concentrations because of imperfect
mixing. At very low concentrations of anolyte, water electrolysis will increase, generating
protons, which can damage membrane. The mechanism of proton damage is discussed below.
 76

To summarize, membrane capacity for mass transport is reduced by:

• Increasing Catholyte Concentration

• Increasing Anolyte Concentration
• Decreasing Temperature

The mass load on the membrane is increased by:

• Increasing Current Density

• Decreasing Brine Concentration

Load Shedding
Power costs sometimes change with the time of day making it desirable or necessary for
chloralkali manufacturers to vary their power consumption. This variation is called load
shedding or cycling. For the membrane load shedding is change in mass transport. Flows and
amperage should be changed simultaneously and gradually to allow the membrane to respond

If power is varied without changing anything else, the lower amperage state will have
high anolyte concentration and lower temperature. Daily swings between relatively hot and
cold, concentrated and dilute states are not good for the membrane. It may not have time to
equilibrate and come to the optimum operating condition. Also, it should be clear from the
discussion of operating conditions that raising amperage from this state will put a strain on the
membrane by surging flow through it while it is relatively cold and dehydrated. The cumulative
effect of such repeated though small shocks may be to reduce performance.

Cell Start Up
Operating conditions are especially critical during cell start up with new membranes. The goal
is to maintain uniform membrane conductivity during start up. As shown above, conductivity
is directly related to temperature and inversely related to electrolyte strength. Another factor is
the rate of current rise. Gradual current rise is preferable.

The danger is that certain areas of the membrane will begin conducting before others.
They will heat and become more conductive and therefore heat further. These areas will carry
more and more of the current and eventually overload while other areas are still relatively
nonconductive. The overloaded areas will be damaged by excessive current, usually by being
blistered The basic cause is uneven current distribution and local overheating.

The most obvious symptom of poor startup is high voltage. When the voltage is
unusually high, damage can often be prevented or minimized by slowing or stopping the rate of
current rise, perhaps reducing it a little, and letting the membrane equilibrate and become
uniformly conductive. Then the current can be raised to the goal level.

Badly started membranes may also show poor current efficiency. Sometimes membrane
performance will improve even if nothing is done about operating conditions. Other times,
 77

performance will stabilize or decline. However, if poor current efficiency is seen after startup,
it is best to take action. It may be possible to improve current efficiency by lowering electrolyte
concentrations. This increases conductivity and hydrates the membrane, facilitating its
equilibration.

Brine Acidification
Brine feeds to electrolyzers are sometimes acidified to reduce oxygen generation, chlorate
formation, to improve anode life, or to consume hydrochloric acid. Anolyte pH should be ~2
to prevent damage.

Protons are better conductors than sodium ions [7]. At pH 2, about 1-2% of the current
will be carried by protons. As pH decreases, protons carry a greater fraction of the current. In
itself, this is no problem. Fuel cells operate this way. If the membrane is constructed of
sulfonate polymer exclusively, only caustic current efficiency will suffer. However, almost all
chloralkali membrane electrolyzers use carboxylate or sulfonate/carboxylate membranes.
Carboxylate, when protonated, becomes non-conductive, as shown in Figure 7. The diffusion
rate decreases by over 100 as the pH falls below 2. Note that the sodium ion concentration, a
measure of the degree of protonation of the membrane, is almost unchanged. This shows that
very little protonation is needed to steeply increase membrane resistance.

3.5
10-7
.. §
...8 3.0 .~

is
~ "<~ 2.5 8 ...
8.~
~ ~B 10-8 Concentration
us
Ii ..'
.'
......... __ ......... __ ...... -_........... . 2.0
-e
§ ~

rI)
10-9 .. 1.5
~
/
rI)

1.0

10-10 0.5
0 1 2 3 4 5 6 7 8
pH (25D C)

Figure 7. Decline in sodium ion diffusion through carboxylate polymer at pH <2.

Conditions: 5M brine, 800C. [5]
 78

As more and more protons stream into the membrane, resistance increases, voltage
rises, and eventually the resulting heat will cause blistering and permanent damage. If the
voltage rise is detected before any physical damage is done, stopping the acid feed will reverse
the effects, though it may take several days for the voltage to return to normal.

Hydrogen ion activity (pH), not acidity, is the critical factor in acidified anolyte. pH
must be measured. Acidity is easy to calculate but is an unreliable measure of activity.
Although pH and acidity have a simple relation in water

pH = -loglO(hydrogen ion concentration, moles/liter)

where hydrogen ion activity, the critical value, is close to the concentration, in brine the relation
is complex and depends on the brine concentration and composition. Figure 8 shows how, for
a particular brine, brine strength influences the relation of acidity to pH. Other factors that
affect the relationship of pH and acidity will be the primary treatment of the brine, especially
the excess carbonate and hydroxide, or if the brine receives no primary treatment, as is
sometimes the case with vacuum salt, and sulfate content.

Acidity and pH are discussed more completely in Bergner's paper [8].

'. X-
. '-.-- ---- --- --
. - .",:
. '-.
".-.... -. :-:-. - _ Brine (gil)

-- ---
""El _ _ .... -. - - 190
1 .• 240
---~ 280
310
O+-~~~~~~-+~~~~~~~r-~~~

o 0.2 0.4 0.6 0.8

Hel (gil)

Figure 8. At a given acidity, increasing brine concentration decreases brine pH. The precise
values depend on the brine composition.
 79

SUMMARY

Operating conditions for membrane reflect its chemical nature: it is a salt and an ion exchanger.
Care must be taken to prevent ionic impurities from contaminating the membrane and reducing
its capacity. Since expansion is critical to proper installation in electrolyzers, pretreatment of the
membrane is important to ensure it is flat and smooth during operation.

Brine purity is important to good performance and long life. Specific impurities and
certain combinations of impurities must be considered. The membrane supplier can give
guidance in the early stages of planning.

The membrane must transport sodium ions and water during electrolysis. Membrane
capacity for transport is directly related to temperature and water content. Catholyte and anolyte
concentration affect capacity, and the current density is a direct measure of the mass load on the
membrane. By current density is meant the actual current density, which is affected by the
current distribution, which is in turn a function of the electrolyzer design, and electrolyte
concentration and temperature uniformity.

The operating conditions are chosen by the membrane manufacturer to get the best
performance and lifetime from the membrane in all electrolyzers and with brine that meets
specified purity requirements. All factors are not equally important. The consequences of
operation outside of the recommended limits are not always instantaneous or immediately
serious or irreversible. On the other hand, the effects though small can be cumulative, and
may shorten the useful life of the membrane. Other factors beside the membrane are critical
too. The membrane manufacturer chooses conditions that will be safe for all users in all
situations. Different electrolyzers and regimes will make some of these factors less important,

This paper is intended to show that there are sound reasons for the conditions we
recommend to users of our chloralkali membranes. Users however, have experience of their
own which must also be considered. No one should change conditions that have proved
successful, even if these conditions do not agree with the points made here. If users have
questions about how they are operating now, or about how they would like to operate, they
should ask the membrane supplier and electrolyzer manufacturer.

REFERENCES

1. Under typical electrolysis conditions, about half the cations pass through the membrane.
Only about 1 in 10 000 chloride ions and 1 in 1000 sulfate ions enter the membrane and into
the caustic catholyte. See T. C. Bissot, Proceedings of the Symposium on Diaphragms,
Separators, and Ion-Exchange Membranes, PV 86-13, p. 42,1986, The Electrochemical
Society, Pennington, N.J.
 80

2. Y. Ogata, S. Uchiyama, M. Hayashi, M. Yasuda, and F. Hine, 1. Al1l1l. Electrochem.,

1990, 20, 555-558.

3. I.T. Keating and K.I. Behling "Brine, Impurities, and Membrane Chloralkali Cell
Perfonnance" in Modem Cblor-alkali TechnololO'. vol. 4, N.M. Prout, I.S. Moorhouse,
eds., Elsevier, New York, 1990, ch. 12. A revised and expanded version of this paper is
available from the authors.

4. T. Momose, N. Higuchi, O. Arimoto, and K. Yamaguchi, I. Electrochem. Soc., 1991,

138(3), 735-741.

5. Z. Twardowski, H.L. Yeager, and B. O'Dell, I. Electrocbem. Soc., 1982, 129(2), 328-
332.

6. H. Miyake, Y. Sugaya, and M. Yamabe, Rej)OI1s Res. Lab. Asahi Glass Co.. Ltd., 1987,
37(2),241-256.

7. I. O'M. Bockris, N. Bonciocat, and F. Gutmann, An Introduction to Electrochemical

~, Wykeham, London, 1974, p. 31.

8. D. Bergner, I. Apj!l. Electrochem., 1990,20,716-722.

 81

FACTORS WHICH INFLUENCE THE PERMSELECTIVITY OF

HIGH PERFORMANCE CHLOR·ALKALI MEMBRANES

HOWARD L. YEAGER and ADAM A. GRONOWSKI

Department of Chemistry
The University of Calgary
Calgary, Alberta, Canada, T2N IN4

ABSTRACT

Membrane current efficiencies have been determined in a laboratory chlor-alkali cell for
several test materials with similar polymer composition and different fabrication
features. Experiments were conducted as a function of solution mixing and membrane
electrode gap over a wide range of catholyte concentrations. The results show high
inherent rejection of hydroxide ion transport by the polymer film, and that this rejection
can be altered by the specifics of membrane design and cell geometry and operation. A
proposed explanation of the results focuses on the nature of hydroxide ion transport in
aqueous media, which involves quantum mechanical proton tunneling processes. The
large significance of the membrane's steady state water content in an operating cell as a
factor in the determination of membrane performance is discussed.

INTRODUCTION

High performance membranes for use in chlor-alkali cells represent a major success in
membrane technology. Membrane permselectivities of over 95% along with excellent
durability in the cell environment are now expected of commercial membranes. The
central reason for this success is found in the remarkable properties of the perfluorinated
ionomers which make up these membranes. Several manufacturers supply these
membranes, and the essential chemical and structural properties are fairly similar. Also,
several different membrane cell configurations are now in use, with various design
differences among them. Overall, membrane permselectivity is a complex function of
the exact polymer composition of the membrane as well as other details of membrane
fabrication, the membrane's conditions of use, and the details of cell design and
operation. Thus, it is difficult to develop simple and predictable models for
understanding membrane performance in a chlor-alkali cell, due to the number of
variables involved.
In part, the understanding of membrane performance is made more difficult due
to the fact that hydroxide ion is a charge carrier in the membrane. Hydroxide ion, like
hydrogen ion, can migrate under an electrical field involving quantum mechanical
tunneling of protons in an aqueous environment. This second mechanism of ion
transport complicates the prediction of membrane permselectivity based on the sorption
of ions into the membrane under specified conditions. This is because the degree of
 82

proton tunneling is very dependent on water activity and the physical state of water
molecules in the transporting medium.
This research was undertaken in order to develop insight into the relative
importance of some of these parameters on membrane permselectivity in chlor-alkali
electrolysis. The strategy has been to fix certain parameters and to systematically vary
others in order to their relative importance. Use has been made of radioisotope tracers
and automated experimental methods to facilitate the acquisition of the necessarily large
data sets for such a project. One important parameter was fixed for all experiments: the
polymer composition of the membrane. E.I. du Pont de Nemours & Company provided
several perfluorinated ionomer membranes for testing. Although each of these had
differences in the details of fabrication, the polymers in the membranes were all
essentially identical in composition. These sulfonate-carboxylate bilayer membranes are
typical of today's best high performance materials, and allow us to see how their
performance can be optimized by adjustment of particular membrane and cell variables.
The membrane parameters which were selected for evaluation are fabric
reinforcement, the use of sacrificial fibers in such fabrics, and the coating of the
catholyte surface of the membrane with hydrophilic particles for bubble release. In order
to accomplish this, four membrane samples were evaluated. First, a smooth surface
membrane bilayer film was used, containing layers of sulfonate and carboxylate
functionality. (The carboxylate side of the film is placed in contact with the catholyte to
ensure rejection of hydroxide ion transport through the bilayer.) Next, a fabric
reinforced version of this film membrane was studied. Also, the commercial membrane
Nafion R 90209 was evaluated. This membrane contains a fabric reinforcement with
some polyester threads that quickly dissolve in use. This ~roduces lateral channels in
the sulfonate portion of the bilayer. Finally, Nafion 954, another successful
commercial chlor-alkali membrane, was studied. This membrane also contains a
reinforcing fabric with sacrificial fibers, and in addition is surface coated. Thus, the
effects of these membrane design features can be evaluated by separate comparative
experiments with each material.
The electrolysis cell parameters which were selected for study are the rate of
solution mixing at the membrane surfaces and the spacing between the membrane and
the cathode, i.e. membrane-cathode gap. The first of these parameters is related to the
desirability of effective solution mixing over the entire surface of the membrane in the
cell. Through this study, some understanding of the effects of non-uniformity of solution
mixing within the cell can be gained. The membrane-cathode gap is another important
property. Modern membrane cells are operated either in the finite gap mode, with gaps
of at most a few millimeters, or in the zero gap mode where contact is made between the
membrane and the cathode. We evaluated the effects of these geometries by performing
experiments where the membrane-cathode gap was set at 2 mm, and where the cathode
was advanced to touch the membrane, leaving a 2 mm anode-membrane gap. Finally,
some experiments were conducted where both electrodes were placed 2 cm from the
membrane. Although this is an unrealistic geometry for an actual cell, it enables the
effects of solution mixing to be evaluated in the absence of bubble formation in the
vicinity of the membrane. Also, this configuration enables more uniform current density
to be attained.

EXPERIMENTAL
A computer controlled apparatus was constructed to perform radiotracer determinations
of membrane current efficiency. With this apparatus, sodium chloride anolyte and
sodium hydroxide catholyte solutions of fixed concentrations are selected under
computer control for introduction into the laboratory electrolysis cell, using a
pump/valve system constructed entirely of PTFE components. In addition to these
 83

solutions, separate containers are used for brine solutions which have identical
concentrations and are also doped with sodium-22 radiotracer. The computer also
controls temperature regulation, electrolysis current and duration, and sample collection.
In practice, the membrane is equilibrated with selected anolyte and catholyte solutions
for a period of several hours. Then, electrolysis is performed using fresh portions of
these solutions to further condition the membrane to these conditions. Finally, an
electrolysis is performed using radioactive brine. At the end of this electrolysis, a
sample of the anolyte and the entire catholyte solution are collected for radioactive
analysis. In this manner, the transport number of sodium ion can be determined. This
value, multiplied by 100, corresponds to the conventional caustic current efficiency.
A cross-sectional diagram of the electrolysis cell is shown in Figure 1. Each
half-cell is constructed in similar fashion, except that the total volume of circulated
anolyte solution (300 mL) is larger than that of the catholyte solution (225 mL). Certain
features of the cell design are omitted for the sake of clarity in Figure l. Solutions are
introduced into the conical half-cells through a port which is just above the membrane
face. This enables very efficient solution mixing to be achieved at the membrane
surfaces. The cell is shown in the wide electrode gap configuration, where
electrolytically generated chlorine and hydrogen bubbles form away from the membrane.
In the finite electrode gap configuration, the anode is advanced to touch the membrane,
and the cathode is advanced to a distance of 2 mm from the membrane surface. In the
zero gap configuration, the opposite electrode-membrane distances are arranged, so that
the membrane touches the cathode.

Anode
Compartment

Figure 1. Laboratory membrane electrolysis cell.

Other details of the cell construction which are shown include cartridge heaters
placed inside the hollow electrode holders, temperature sensors in housings near the rear
of each compartment, and Pt level sensors at the top of each compartment. Solutions are
circulated continuously during operations, to ensure temperature eqUilibrium, which was
stable to within 1 Co of the set point. The anode is a DSA expanded mesh electrode, and
the cathode is a coarse nickel metal mesh. Additional details of this apparatus can be
found elsewhere (1-3).
 84

All experiments were conducted at 90°C and at 3 leA m-2 membrane current
density. Brine anolyte solution concentrations were varied from 2.5 to 4.0 M (13 to 20
wt.%), and caustic catholyte solutions were varied from 22 to 45 wt.%. Results reported
here are for the middle brine concentration of 3.5 M (18 wt.%), which were fairly
representative of results for the other brine concentrations.

RESULTS
The effects of solution mixing are presented in Figures 2-5. Here good mixing refers to a
high degree of solution circulation in the space between the electrode and cathode. Poor
mixing refers to a rate of circulation which is 30 times slower than the well mixed case,
and which generates an essentially quiescent solution at the membrane faces.
Experiments were performed where the rates of anolyte and catholyte solution mixing
were individually varied; only catholyte stirring had a measurable effect on membrane
permselectivity. For subsequent experiments, anolyte solutions were well stirred while
the effect of catholyte stirring was evaluated.
Figure 2 shows the effect of solution mixing on the smooth bilayer film
membrane. This film actually yielded near perfect membrane current efficiency at its
peak of performance. The peak value was repeatably measured to be over 99%. This
suggests that this high performance polymer is inherently capable of quite high rejection
of hydroxide ion transport under selected conditions. This performance is degraded
somewhat far poor catholyee lOIuhon mixiIl,. The peak of perfOlD1llllCC is reduced and
shifted to lower caustic concenUlllioR.

-
~
~
>.
100
()
c: 95
(])
'0
:e 90

---
W
c:
(])
85

--
::J
()
80
()
75
ti::J •• - Good Mixing
as 70 - Poor Mixing
()

65
20 25 30 35 40 45 50
NaOH (wt %)
FiJUN 1. Cunat efficic8CJ of . . un-1dRfGIad ........ falm, wide elcarodc-
solution gaps.
 85

~ 100
>.
0 95
c:
Q)
·0
90

-
:E
w
c: 85
....
Q)
....
::J 80
0
0
:;:::; 75
!/) •• - Good Mixing
::J
as 70 - Poor Mixing
0
65
20 25 30 35 40 45 50
NaOH (wt %)
Figure 3. Current efficiency of the un-reinforced membrane film, finite cathode-
solution gap.

A somewhat similar change is seen for the finite cathode-membrane solution gap,
as shown in Figure 3, although again under conditions of good solution mixing, the
rejection of hydroxide ion transport is nearly complete at its peak of performance. The
behavior of the commercial NafionR 90209 is shown in Figure 4; again poor solution
mixing produces reduced membrane current efficiency although the position of the peak
maximum is only slightly shifted.

l>. 100
.......... -,
0
c: 95 ".
"."" ,,
Q)
·0
90 ._..... ",,'" \\

-
:E
w \
85
c: \
....
Q)
.... \
::J 80
0
0
:;:::; 75
!/) •• - Good Mixing
::J
as 70 - Poor Mixing
0
65
20 25 30 35 40 45 50
NaOH (wt %)
Figure 4. Current efficiency of Nafionl. 90209, fmite cathode-solution gap.
 86

Finally, the coated membrane NafionR 954 shows much less dependence on the
degree of solution mixing, as shown in Figure 5. Here, the layer of coated particles
might be expected to generate a much thicker un stirred solution layer at the membrane
surface compared to uncoated materials. This might explain its reduced dependence on
solution agitation. Comparison of Figures 4 and 5 reveals that the presence of a
membrane coating produces a lower peak current efficiency and also reduces the
influence of changing catholyte concentration on the membrane's current efficiency.

-
~
>.
100

u
---
c: 95
Q)
'0
m 85 90

-c:
Q)
~
~
::J 80
()
.~ 75
in ••• Good Mixing
::J
co 70 - Poor Mixing
()

65
20 25 30 35 40 45 50
NaOH (wt %)
Figure 5. Current efficiency of Nafion R 954, fmite cathode-solution gap.

The effects of reinforcing fabrics on membrane current efficiency are shown in

Figures 6 and 7 for the finite cathode-solution gap configuration with good solution
mixing. Figure 6 shows that the effect of an open weave PTFE reinforcing fabric is
quite minimal, although the minimum seen for the un-reinforced film at highest caustic
concentrations is lost when fabric reinforcement is added. When sacrificial fibers are
introduced however, there is a more pronounced change. Now, the maximum in current
efficiency is broadened to much higher catholyte concentrations. The presence of
sacrificial fibers has also been found to increase water transport through the membrane,
probably due to the general increase in water activity inside the membrane phase. These
results suggest that the fabric reinforcement increases the overall hydration of the
carboxylate layer as well, which reduces the loss in current efficiency with increasing
caustic strength.
 87

~ 100
>.
()
c 95
Q)
.(3
90

-
:t:
w
c 85
Q)
'-
'-
::J 80
0
()
+:: 75
(/) ••• Film
::J
co 70
0 - Reinforced Film

65
20 25 30 35 40 45 50
NaOH (wt %)
Figure 6. Current efficiency of the film membrane and the fabric reinforced version,
fmite membrane-cathode gap.

-?i 100 ....... -,

>.
()
c 95
~
~ '" \
Q)
.(3 ~ \
:t: 90 ~
\
w \
C
Q)
85 \
'-
'- \
0
::J 80
'- ~
.S2 75
ii5 ••• Reinforced Film
::J
co
0 70 - 90209
65
20 25 30 35 40 45 50
NaOH (wt %)
Figure 7. Current efficiency of the fabric reinforced membrane and N afion R 90209,
finite membrane-cathode gap.

Finally, the effects of zero membrane-cathode gap on these membranes are

shown in Figures 8 and 9. In general, current efficiency is reduced in all cases compared
to the finite gap geometry. There are further changes in membrane permselectivity as
well. Although the effect of sacrificial fibers remains the same at lower caustic
concentrations, their influence largely disappears at high caustic strengths, as seen in
Figure 8. The most notable difference is seen in Figure 9, where the influence of surface
 88

coating is seen. The N afionR 954 response is very similar to the finite gap case when
poor solution mixing is used, as shown in Figure 5. In contrast, NafionR 90209 actually
shows somewhat improved performance compared to the finite cathode gap case with
poor solution mixing. However, its performance over most of the concentration region is
not as high as that of the coated membrane.

~ 100
~
>.
u 95
c:
Q)

-C
.(3
;;:::: 90
W
85
....
Q)
....
:::J 80
0
u 75
~ - Reinforced Film
:::J
ttl
() 70 --- 90209

65
20 25 30 35 40 45 50
NaOH (wt %)
Figure 8. Current efficiency of the reinforced film membrane and NafionR 90209, zero
membrane-cathode gap.

~ 100
~
>.

,
u 95
c:
Q) ~
.(3
90
\
==
w
\
C 85
\
....
Q)
.... \
:::J 80 \
()
.~
\
ii5
75
--- 90209 \
:::J
ttl
() 70 -954 \
65
20 25 30 35 40 45 50
NaOH (wt %)
Figure 9. Current efficiency of NafionR 90209 and NafionR 954, zero membrane-
cathode gap.
 89

THE NATURE OF MEMBRANE PERMSELECTIVITY IN CHLOR-ALKALI

CELLS

These results clearly indicate that both membrane and cell variables significantly affect
the ability of the same polymer material to reject hydroxide ion transport under identical
conditions of solution concentration, current density, and temperature. Funher, the
interactions among these variables are complex, although certain trends are clearly
shown. One important question to be asked is why the membrane permselectivity
depends on caustic catholyte concentration in such a complex manner at all. A very
generalized diagram of membrane current efficiency versus catholyte concentration
under conditions such as those used in this work is shown in Figure 10.

100

95
>-
0
c 90
Q)
'0

-......
==
W
c
Q)
85

80
~
0

75
Region A B c D

70
0 5 10 15 20 25 30 35 40 45 50
Weight % NaOH

Figure 10. Generalized current efficiency dependence of a bilayer chlor-alkali

membrane versus catholyte concentration.

Four separate concentration regions are noted in the figure. Region A

corresponds to the concentration range in which Donnan exclusion of sorbed electrolyte
is overcome, and so current efficiency would be expected to decrease due to increasing
sorption by hydroxide ion. Region B cannot be interpreted in this way, because
hydroxide sorption continues to increase as solution concentration increases. Region C
is characterized by a subsequent drop in membrane permselectivity, sometimes to very
low levels. This is the more expected result, based on the relative concentrations of ions
in the membrane under these conditions. Finally, Region D depicts a final upturn in
membrane permselectivity for very high caustic concentrations. This upturn is only seen
in some cases, but is included here in the interests of generality. The results of the
present work indicate that this general curve can be shifted and the peak width affected
by alterations in these cell and membrane variables.
Mauritz and Gray have offered a reasonable explanation of the reasons behind the
differences seen for Regions A, B, and C in Figure 10 (4). It is focused on the
phenomenon of quantum mechanical proton tunneling in aqueous alkaline solution
 90

environments, which yields an enhanced effective mobility of hydroxide ion compared to

the other current carrier, sodium ion. The efficiency of proton tunneling events is
strongly affected by the state of surrounding water molecules, as depicted in Figure 11.

Proton Tunneling In Alkaline Aqueous Environments

H H H H
I I I I
O-H ... 0- of • 0-'·' H-O

Dilute solution
H H H H
I I I, I
Na+O-H ... 0- of • Na+O-··· H-O

Concentrated solution
H
I
"-"CF2-CF2 -COO-··· H-O Na+
Dehydrated carboxylate membrane

Figure 11. Proton tunneling in various aqueous alkaline media.

Hydrated hydroxide ions exchange protons among surrounding hydrogen bonded

water molecules through a tunneling process, in similar fashion to proton tunneling in
aqueous acidic media. This results in an effective increase in the mobility of hydroxide
ion, which generates a mobility enhancement of about a factor of three over ions of
similar size and charge density. The frequency of tunneling events for a
perfluorosulfonate ionomer membrane was monitored by Mauritz and Gray using
infrared spectroscopy. The membrane was first equilibrated in sodium hydroxide
solutions of successively increasing concentration before measurement. Their results
showed that the extent of proton tunneling events increased, decreased, and then
increased again with increasing caustic solution concentration. The respective
concentration regions correlate reasonably well with Regions A, Band C in Figure 10 as
well. We have repeated some of these measurements for a perfluorocarboxylate film,
with similar findings; correlation of the respective concentration regions with those
shown in Figure 10 are improved from the sulfonate case (5).
Thus, there is evidence that the complicated behavior'of these membranes with
increasing caustic strength is related to the extent and nature of water sorption in the
permselective carboxylate layer of each membrane. While the change in current
efficiency in Region A is attributable to the onset of sorption of (tunneling) hydroxide
ions into the polymer, the behavior of Region B may be due to the decrease in the
frequency of tunneling events which would remove the non-classical transport
mechanism of hydroxide ion. This may be due to the removal of the symmetry of the
tunneling event in media of low water content, as diagrammed in Figure 10. Eventually,
the last water molecules in the now severely dehydrated membranes exist between
 91

sodium ions and exchange sites. This situation would appear to again increase the
probability of tunneling events, which would account for the behavior in Region C.
Finally Region D, which is only seen in some instances, seems to be one in which proton
tunneling is again reduced somewhat. Although interpretation is highly speculative, this
may occur only for very dehydrated membranes which contain minimal amounts of
water.
If this interpretation of the concentration dependence of membrane
permselectivity is essentially correct, the extent of electro-osmotically transponed water
would be of great imponance in establishing membrane current efficiency, as would the
extent to which equilibrium is attained between the carboxylate layer and the catholyte
solution to which it is exposed in individual cases. The ratio of water to sodium ion
which is transponed through the membranes under study varies from about 3.5 to 5.5,
depending on brine and caustic concentrations and the nature of the membrane. This
range of water to sodium ion corresponds to a caustic solution concentration range from
29 wt.% to 39 wt.%. Note that this is generally the range in which membrane
permselectivity can vary dramatically, as seen in Figure 10.
This view of the nature of permselectivity as a function of caustic concentration
is generally consistent with many of the results shown in Figures 2 to 9, although
detailed interpretation is difficult without extensive water transpon information.
Nevenheless, it would appear that this interpretation is valuable in terms of
understanding the influence of various membrane and cell parameters on membrane
permselectivity.

CONCLUSIONS
Several conclusions can be drawn from this research. First, the polymer bifilm which
was used for each of these membranes is capable of yielding essentially perfect rejection
of hydroxide ion under cenain conditions in a chlor-alkali cell. Next, fabric
reinforcement does not significantly affect membrane performance. However, sacrificial
fibers which may be present in some reinforcing fabrics will shift the concentration
dependence of membrane current efficiency to higher caustic strengths. Poor solution
mixing at the membrane-catholyte interface is generally detrimental to membrane
current efficiency, with the least effect seen with coated membranes. Finally, the
membrane-cathode gap can have a significant effect on membrane performance,
although the magnitude of the effect depends on various membrane design parameters.
It would seem desirable to consider this latter point along with the influence of electrode
gap on the voltage performance of an operating cell, in order to evaluate the overall
effects of cell geometry on power consumption of a given membrane and cell design.

ACKNOWLEDGEMENT

The authors would like to express their appreciation to E.I. du Pont de Nemours & Co.
for supplying the membranes which were used in this study, and for financial suppon of
this research. Also, we wish to thank Dr. James Keating of Du Pont for many useful
discussions about the nature of membrane performance in the chlor-alkali cell
environment.
 92

REFERENCES
1. H.L. Yeager and I.D. Malinsky, U.S. Patent No. 4,545,863, (1985).

2. H.L. Yeager and I.D. Malinksy, in Coulombic Interactions in Macromolecular

Systems, A. Eisenberg and F. E. Bailey, eds., ACS Symposium Series No. 302,
Chap. 11, American Chemical Society, Washington, D.C. (1986).
3. A.A. Gronowski and H.L. Yeager, I. Electrochem. Soc., in press.

4. K.A. Mauritz and C.L. Gray, Macromolecules, 16,1279-1286 (1986).

5. Unpublished results.
 93

NATURAL HIGH FLOW RATE RECIRCULATION : A HIGHLIGHT ON

DE NORA TECHNOLOGIES MEMBRANE ELECTROL'fZERS

PIERLUIGI BORRIONE
ORONZIO DE NORA TECHNOLOGIES S.p.A.
P.za Repubblica lIlA - 20124 Milan - ITALY

ANGELO OTTAVIANI
S.E.R.E. S.r.l. - ORONZIO DE NORA GROUP
Via Bistolfi 35 - 20134 Milan - ITALY

ABSTRACT

The present paper is intended to illustrate the main characteristics of

ORONZIO DE NORA TECHNOLOGIES last generation membrane electrolyzers and
the relevant advantages such as :
- natural gas-lift recirculation of both the anolyte and the catholyte;
high flow rate of brine recirculation such as to provide for the most
complete uniformity in temperature, pH, concentration in any cell of the
electrolyzer stack;
possibility to add hydrochloric acid to each electrolyzer in order to
attain a tailored individual pH regulation of the anolyte, depending on
the life and thus on the efficiency of the membranes;
high hold-up of liquid provided by large volume gas disengagers.

INTRODUCTION

At the last SCI Meeting the electrode geometry and features of the
mechanical hardware of ODNT membrane electrolyzers were illustrated (1)
and particular consideration was given to the high uniformity of current
density on the active membrane area provided by this type of design.
This paper is directed toward providing a highlight on the eharacter-
istics of the natural recirculation system designed into ODNT
electrolyzers as well as on the optimized process conditions enabled
thereby.
Homogeneous and stable conditions, pertaining to current density,
temperature, electrolyte concentration and gas void fraction, are the key
variables to be controlled in order to achieve high current efficiencies
and long membrane life.
Natural recirculation technology is an effective and economical means
for attaining such conditions in a membrane cell.
 94
NATURAL GAS LIFT RECIRCULATION WITH CHLORINE AND HYDROGEN

The operating principle of natural gas lift recirculation is illustrated

in Fig. 1.

B
.
C
lJ h

..
LIQUID o o · w.
COLUMN TIIO LPHASES
GAS LIQUID
. COLUI1H
•
. .
0

- ~ SECTION A

PRESSURE BALANCE ON SECTION A

I fl h = fa, h + l>.P
'I . '.p .AVERAGE DENSITY OF
LIQUID AND 2-PHASE COLUMNS
~P • PRESSURE DROP OF RECYCLE LOOP

Figure 1. Gas Lift Recirculation

A pressure balance on section A shows that the weight of the liquid

column B is balanced by the sum of the weight of the 2-phase, gas and
liquid column C and the pressure losses caused by recirculation flow
inside the whole loop (2).
The average density of the gas-liquid mixture will result from an
integration along height "h" of the local density which is a function of
the density of the liquid and the local void fraction. The latter is a
complex function of the gas and liquid properties as well as of their
respective velocities (3).
The ODNT natural gas recirculation design takes into consideration
both theoretical as well as practical parameters deriving from specifical-
ly designed experimental work carried out by ODNT.

RECIRCULATION LOOP OF THE ELECTROL'lZERS

Figure 2 shows how liquid and gas flow along the surface of a monopolar
anodic element of a typical ODNT electrolyzer.
 95

Figure 2. Monopolar anodic element of ODNT electrolyzer

When fresh brine is fed through a T-nozzle into the anolyte downcomer
at a minimum flow ratio of 1:10, an efficient mixing is provided both by
the 90 0 angle injection tube and the length of the downcomer. The
down comer enters a lower manifold having a suitable cross-section for
ensuring uniform distribution to each element and thus to each anode
compartment.
The chlorine produced at the anode rises together with the anolyte
forming a 2-phase mixture which is released from the top of the anode
compartment through a connecting flexible Teflon joint to the gas
disengager where the gas is separated.
The level in the gas disengager is properly maintained by a suitable
overflow which discharges a minor amount of depleted anolyte while the
greater portion enters through the downcomer.
The scheme of the catholyte recirculation is basically the same as
that of the anolyte. This arrangement allows water to be fed through
the downcomer into the cathode compartments without causing local dilution
which would damage the membranes. As a matter of fact, feed water is
mixed with the recycled catholyte in a typical ratio of 1:100.
Figure 3 is an exploded view of a DD 175 monopolar electrolyzer,
comprising:
- the current distributing structure of the monopolar element
- the gaskets and membrane assembly
- the cathodic terminal elements and the clamping means including tie-rods
and springs
 96
- copper flexible electrical connections
- supporting frames and electrical insulators
- the recirculation loop made of large volume titanium and large volume
nickel gas disengagers positioned along the length of the electrolyzer,
collecting gases and electrolytes, connected to the elements by double
Teflon joints, visual inspection glasses on the gas disengagers,
down comers from the gas disengagers to the lower feed manifolds, and
connections of the same to the inlet nozzles of the elements by double
Teflon joints.

Figure 3. Exploded view of DD 175 electrolyzer

As aforesaid, the recirculation rate, both on anodic and cathodic

compartments, is extremely high, ranging from 0.4 to 0.8 m3/h per square
meter of membrane: these values correspond to about 10 to 20 times the
fresh brine flow and to about 100 to 200 times the water feed flow.
Consequently, an electrolyzer rated 240 kA at 4 kA/m2 affords a
natural recirculation flow of about 36 m3/h (0.6 m3/h.m2 of membrane) and
in a plant with a capacity of 165,000 ton/year of NaOH on 100% basis the
total recirculation flow rate for each electrolyte amounts to 2200 m3/h.
This volume is attained just by using the gas lift effect thus avoiding
the economic penalty sustained if pumps with such a high flow rate
capacity had to be installed.
 97

DESIGN OF NATURAL RECIRCULATION

Assuming the minimum value for the recirculation flow rate as the design
condition, the gradients of concentration (delta-C) and temperature
(delta-T) through each single cell are as follows:
- anode delta-C < 10 gpl as NaCl
delta-T < 3 °C
- cathode delta-C < 0.3\ by weight as NaOH
delta-T < 0.5 °C
The maximum void fraction at the top of the cell is less than 60% on
the anodic side and 45\ on the cathodic side, whereas it may reach respec-
tively more than BO% and 60% in electrolyzers based on a once-through
flow.
These results are very important for the long-term integrity of the
membrane because wrinkles, caused by overswelling due to an anomalous
depletion of the anolyte as well as salt blisters induced by chlorine
stagnation, are avoided.
The diagram of Fig. 4 illustrates the recirculation flow rate as a
function of the current density:
- at 500 A/m2 a value of 0.4 m3/h.m2 of membrane is found which means that
even at an extremely low current density the recirculation is already
effective
- between 500 and 1500 A/m2 the flow rate is increased by 25%
between 1500 and 4000 A/m2 a nearly linear increase of about B% is
observed for each 1000 A/m2, up to 0.6 m3/h.m2 of membrane, which is
about 15 times the fresh brine flow .

...
0,55

0,5

0,45

0,4

0.35

0,3
5110 1000 I5l1O Z500 300D 3500 400D
UmJt Deasily (A/IIl)

Fig. 4. Recirculation vs current density - 34 DD 175 electrolyzer

This diagram applies within a large range around the typical average
operating conditions (85°C, 33% NaOH and 210 gpl NaCl). Both theoretical
calculation and test cell results demonstrate that the recirculation flow
rate is negligibly affected even with variations of the temperature within
soc or of the NaOH concentration within 3%.
 98
The length of the electrolyzers, that is the number of unitary cells,
does not affect the recirculation flow rate, as shown in Fig. 5.

1 Specfa: Flow" (1db2)

OJ

OJ

0.7

OJ

u.s

Fig. 5. Recirculation vs length of electrolyzer (at 3.5 KA/m2)

The distribution of the electrolyte flow to each compartment is

extremely uniform (Fig. 6), the maximum deviation being about 2.0% less
and about 1% higher than the average value for the first and for the last
compartment, respectively.

10
DevillioD frolilverage ('II)

:r :r :I: :r x x I
:r :r :I:
0 X I
:r x
:I: :r
-2 •

...
-6

.
·10
10 12 14 1& 11 20 22 24 2& 21 30 32 34
Unitary Cen Number

Fig. 6. Flow distribution along 34DD175 electrolyzer

 99

Suitable simulation tests with a transparent backwall have been

performed both to confirm the absence of permanent gas pockets and the
optimal design of the outlet nozzle geometry to minimize pressure fluctua-
tions even with such a large two-phase gas liquid flow.

ACID ADDITION TO REDUCE ANODIC BY-PRODUCTS

For many producers, the produced chlorine should meet high purity
specifications as to oxygen content. This may be achieved by adding
hydrochloric acid to the anolyte so that the chlorine may be directly
utilized in downstream user plants, producing products such as
dichloroethane (OCE), without intermediate purification by liquefaction.
As is well known, oxygen, hypochlorous acid and chlorate are the
anodic by-products and their build-up depends on the membrane current
efficiency (eE), which is directly related to the quantity of hydroxyl
ions which back-migrate from the cathode compartment.
Fig. 7 shows the reactions most likely to occur when the pH in the
anodic chamber ranges around 4, a normal value without acid addition (4).

(E1) 2H20 - 4e- -, 02 • 4H •

• 40H- -, 4H20
(E2) C12. H20 -, HCIO • CI- • H•
• OH- -, H20
(ES) HCIO. H2O - 2e- -, 02 • CI- • SH+
• SOH- -, 8H20
(E4) 8HCI0 • SH20 - 8.- -, 81202 • 12H+ • 4CI- • 2CI03-
• 120H- -, 12H20

Note· OH- from Inefficiency pf the membrane

Figure 7. Anodic by-product formation

Equation E1 is the typical water electrolysis reaction in competition

with chlorine evolution at the anode, its importance is strongly influ-
enced by the anolyte pH and by the type of anodic coating. With a low
oxygen coating, the oxygen produced according to E1 amounts to about 25%
of the total oxygen contained in chlorine. Equation E2 represents the
disproportionation of chlorine to give hypochlorous acid and hydrochloric
acid, the neutralization of the acidity due to the hydroxyl ions back-mi-
grated through the membrane shifts the equilibrium towards a high concen-
tration of hypochlorous acid which in turn enhances the further formation
of oxygen and chlorate according to reactions E3 and E4. It is therefore
clear that the addition of hydrochloric acid to the anolyte counter-bal-
ances the flow of back-migrating hydroxyl ions and decreases the formation
of by-products.
The ratio among these by-products may vary according to the type of
technology and during the membrane lifetime. Typical average results
without acid addition on commercial plants, using low oxygen anode coating
and neutral fresh brine feed, are reported in Fig. 8. These values may
be reduced by acid addition, to attain values as low as 0.5 % by volume
for oxygen, 0.25 CE (%) for hypochlorous acid and 0.1 CE (%) for chlorate.
 100

MEMBRANE EFFICIENCY 98 94 92
CE (t.)

OXYGEN CONTENT 1.5 2.3 3.2

IN CHLORINE
't. by vol)

OXYGEN PRODUCED 2.9 4.4 5.8

I . CE 't.)

HCIO PRODUCED 1.8 2.5 3.0

•• CE 't.)

NaCI03 PRODUCED 0.20 0.35 0.70

a. CE (t.)

Figure 8. Average anodic by-product formation from commercial plants

without acid addition

The quantity of acid, which may even be a remarkably large amount, is

a function of the membrane efficiency, for example with a membrane current
efficiency of 92\, an amount of about 70 llh of 32\ hydrochloric acid
solution should be added to a 240 kA electrolyzer, which corresponds to
about 7\ of current efficiency.
It is the high rate recirculation loop that allows for the injection
of such large amounts of hydrochloric acid directly into the chlorine
gas disengager (Fig. 9), without decreasing the pH to a value lower than
2.0 which could damage the membranes.

Figure 9. ODNTElectrolyzer schematic

 101

On the contrary, all technologies which do not provide for a recircu-

lation loop exhibit a substantially lower anolyte flow rate and conse-
quently the injection of large volumes of hydrochloric acid would lower
the pH down to unacceptable values.
As a matter of fact, when the anolyte pH is less than 2 the electric
current transport in the membrane by the H+ becomes competitive to the
Na+. Migrating protons will acidify the membrane carboxylic layer hinder-
ing conductivity. This resistance increase will result in overheating and
permanent damage of the membrane. The m1n1mUID limit of pH = 2 and the
rather modest flow, typical of the once-through electrolyzer without
external recirculation, enable one to introduce only minimum amounts of
Hel which are not at all sufficient to reduce by-product formation.

LARGE LIQUID HOLD-UP GAS DISENGAGERS

A large liquid hold-up volume in the gas disengagers not only ensure
efficient separation even in the presence of foam but further provides for
the following advantages:
- in the case of sudden shutdowns, such as those caused by total loss of
electric power, the high hold-Up of liquid, due to the large dimensions
of the gas disengager, allows the liquid to cover the membrane even when
the gas fraction has become completely separated (Fig. 10).

Figure 10. Normal operation vs sudden shut-down

It is known that the presence of gas pockets may lead to dangerous

mixing of hydrogen and chlorine. This is most likely to happen when the
membrane is defective.
- In the case of abnormally low feed rates, enough time is left to take
appropriate steps to correct the anomaly without any need to shut the
electrolyzer down. Fig. 11 shows the anolyte concentration shift after
a complete failure of fresh brine feed. The concentration remains over
100 gpl for 20 minutes, while the liquid level is kept well above the
membranes upper edge.
 102

150 Liquid Iml it the modie gas diseagager (DUD)

140
130
120
110
100
90
10
70
10
50
40
30
20
10
O+----r----r----r---,----~--~----r_--_.--~r___,

o 2 4 6
• 10 12 14 16
TUIe (minuteS)
18 20

Fig. 11. Feed brine failure - 34DD175 electrolyzer - 210 KA

- The membrane undergoes smooth physical changes as far as temperature and

electrolyte concentrations are concerned even during uncontrolled
transients.

90
Tellperm ("C)

85

x • •
• x x J:

• •
10

~+---~--~--~--,---'---'---.---.----r---r---r--~

o 10 20 40 50 10 70 10 90 100 110 120

TIIIIt (minutes)
• Alodie X CaIIIodic: I
Fig. 12.a Instantaneous load start-up
 103

32
Caustic Strength (NaOH %wgt)

31

30

29

21

o 10 20 30 50 60 70 10 90 100 110 120

TJIIIe (miDdcs)
Fig. 12.b Instantaneous load start-up

300
Anolyle ConcemtioD (gpl NICQ
290

210

260

250

2«1

230

220

210

o 10 20 30 50 60 70 80 90 100 110 120

TUIIt (miauteS)
Fig. 12.c Instantaneous load start-up

COMPUTER SIMULATION OF ELECTROLYZER BEHAVIOUR

The transients are critical situations for the membranes to sustain as

such perturbances may negatively affect the membrane performance. A
computerized mathematical model, which reproduces the operation of a
commercial electrolyzer, has been optimized through experimental studies
both on pilot and industrial electrolyzers.
 104

Fig. 12 shows the computer simulation of the start-up conditions for

a single monopolar electrolyzer when 100\ load is instantaneously switched
on. The model allows for the optimization of the operating parameters
such as initial temperatures of electrolytes, flow rate of brine feed,
time interval between switching on the load and beginning of water feed.

CONCLUSIONS

The technology presented in this paper illustrates the characteristics and

the operating conditions of a natural recirculation electrolyzer provided
with a high hold-up obtained by the generous dimensioning of the gas
disengagers. The characteristics and advantages are summarized as
follows:
- high recirculation flow rate, equal to 0.6 mJ/h.m2 of membrane, this
amounts to a total of 36 m3/h, in the case of a 240 kA electrolyzer;
- remarkable homogeneity of the preferred operating parameters, such as
electrolyte concentrations and temperatures, as found through every
single cell of each electrolyzer;
- providing flexibility for adding large quantities of hydrochloric acid
as required for decreasing the oxygen content in the chlorine, without
lowering the pH in the anode compartment to levels dangerous to the
membrane integrity;
- certainty of keeping the electrolyte level always above the membrane
upper edge during every operating condition including instantaneous
total loss of power;
- slow shift of the preferred operating conditions even in the case of
abnormally low feeding rates where enough time is yet available on the
electrolyzer to correct the anomaly and to avoid production losses.

REFERENCES

1. G.J. Morris, Improving Membrane Cell Operation. Modern ehlor-Alkali

'Technology. Vol. 4. Elsevier Applied Science Publishers, New York,
1990, pp. 197-213.
2. J.G. Collier, Convective Boiling and Condensation. McGraw-Hill,
Maidenhead, 1972.
3. G. Govier, K. Aziz, The Flow of Complex Mixtures in Pipes. Van
Nostrand Reinhold, New York, 1972.
4. S. Kotowski, B. Busse, The oxygen side reaction in the membrane cell.
Modern ehlor-Alkali Technology. Vol. 3. K. Wall. Ellis Horwood,
Chichester, 1986, pp 310-323.
 105

SAFETY AND ECONOMY OF MEKBRAHE CELL ELECTROLYZERS

K. Schneiders, B. Luke,
Uhde GmbH,
Friedrich-Uhde-Str. 15, 0-4600 Dortmund, Germany

ABSTRACT

Low investment cost, low running cost by low power

consumption and low personnel requirements are the targets
for any new chlor-alkali plant project.
According to these economic priorities technologies will be
selected either for grass root plants or for conversions of
mercury or diaphragm cell rooms.

However, in addition the requirements of safety become more

and more important not only in Europe but also worldwide.
This paper deals with the safety and economics of Hoechst-
Uhde membrane cell electrolyzers and it is structured as
follows:
1. General aspects of safety and economics
2. Improvements in safety and economics in cell room
configuration and electrolyzer design
3. Examples for occurrences and system reaction

GENERAL ASPECTS OF SAFETY AND ECONOMY

Chlorine, caustic and also hydrogen are products of high

value. They are made by the use of much electrical energy,
best materials of construction and highly qualified
personnel.
On the other hand chlorine and caustic are hazardous
chemicals. Their production, transport and storage are to be
secured by intensive efforts.
 106

Chlorine and hydrogen are produced together side by side and

can lead, if mixed, to significant explosions. Therefore,
special care is to be taken to keep these chemicals apart
from each other.

ELECTROLYSIS

/
SAFETY ECONOMY

J
ENVIRONMENT AVAILABILITY

Figure 1. Objective
Under these conditions chlor-a1kali electrolysis takes place
(Fig. 1). These conditions describe the background, on which
the objectives for the design of chloralkali electrolysis
are defined:
Firstly the safety:
There are two kinds of safety, which need to be realized:
One is the safety which protects the people within the
plant, the population and the environment in the
surroundings from the hazardous chemicals and from possible
explosions.
The other one is the safety which insures a permanent online
supply of the products to the consumers.
If this safety is provided, transport and storage of
chlorine and caustic are reduced to a minimum, which in turn
increases safety and economy.
Secondly the economics:
The highest priority for reduction of operating cost is of
course to save energy. This matter has put already the
membrane process into a leading position against the mercury
and diaphragm process. In addition to that much effort is to
be spent for reduction of investment and personal
requirements without any loss of safety.
Two further items have a great influence on the overall
economy of a membrane cell plant. These are the electrode
coatings and ion exchange membranes, which are very costly
ini tially and even more so if they are to be replaced.
 107

DESIGN OF HOECHST· UHDE • ELECTROLVZER

/
EXTERNAL
\INTERNAL

j j
INTERGRAnON INTO ELECTROLVZER
CELL ROOM ITSELF

Figure 2. Solution

The design of Hoechst-Uhde electrolyzers should incorporate

both safety and €conomy (Fig. 2).
It is not only the electrolyzer itself, its internal
components, which have to have these particular properties.
Also external factors mean the integration into a cell room
either designed for grass root plants or for the conversion
of mercury or diaphragm cell rooms is of major importance.

ITEMS TO PROVE SAFETY AND ECONOMY

It is not intended presently to detail the design of

Hoechst-Uhde electrolyzers. This has been done on earlier
occasions.
Therefore, some items will be picked out of the design
concept, which highlight in particular the implementation of
safety and economy.
These items are structured as follows:
1. The configuration of Hoechst-Uhde electrolyzers into a
cell room layout.
• typical electrical circuit
• instrumentation
• interlocking system
 108

2. The electrolyzer design itself comprising:

• single element
• monitoring
• electrical insulation
• materials used
Cell room configuration
Fig. 3 shows the arrangement of electrolyzers containing 120
Hoechst-Uhde single elements. The single elements are
connected in series and result in a total voltage of
approximately 380 V. Typical for this bipolar arrangement is
the low current of 11 kA, which passes through each
electrolyzer. One of these units produces 15,000 tpy caustic.
A plant with a capacity of 120,000 tpy NaOH would need 8
electrolyzers and a total current of only 85 kA. The same
plant equipped with 120 monopolar cells would need 170 kA.
This ratio is applicable to all sizes of plants.

I
;; 85 KA
380 V

1 2. 3 8

Figure 3. Electrolyzer Configuration

The economical aspect of this arrangement is low investment in

rectifier and busbars due to the small current, a minimum of
space required, low cost DC switches for only 11 kA each and
less cost for instrumentation and piping because of the low
number of electrolyzers.
The same arrangement comprises a significant contribution
towards safety. Due to the low number of electrolyzers per
plant a maximum of instrumentation can be installed per
electrolyzer without effecting the overall economy.
 109

IIIII£
8 Df.JR1I£
~
IHl.YlE

El...ECTRtl.Y2ER
FI

•
CN.BTIC HYIJl!XIN
CA1IIl.YlE

I®I®I

Figure 4. Instrumentation and Interlocking System

Fig. 4 shows the instrumentation which is installed around

each electrolyzer. The following values are continuously
monitored and transmitted to the control room:
brine and caustic flow
anolyte and catholyte temperature
current
electrolyzer voltage difference between two symmetric
sections (SU = U1 - U2 )
single element voltage
All data obtained by the transmitters are fed into a
electrolyzer monitoring and interlocking system.

The two voltages U1 and U2 of each electrolyzer are

permanently compared and under normal conditions the SU is
maintained zero. If there is an upset in one element the
element voltage rises. The upset will be indicated, because
SU rises simultaneously.

If one or more of the values exceed their fixed limits the

system can act automatically in three different directions:
 110

The DC switches open and isolate the electrolyzer

completely from the busbar system.

Polarization current is put on, thus maintaining the

electric field to prevent any hypo movlng into the
catholyte under hot electrolyte conditions for protection
of cathode coating and crystal formation in membranes.
Additionally the polarisation of the electrolyzer avoids
any reverse current.
The main rectifier reduces load to maintain constant
current density for the remaining electrolyzers.
The electrolyzers are put immediately into stable condition.
The problem can be analyzed carefully and a restart carried
out with short down time. Any short circuiting is avoided with
remaining busbar potential. The local DC switches are
permanently available in comparison to jumper switches, which
have to be positioned which takes time. It is also a matter of
safety to be able to disconnect an electrolyzer completely
from the busbar system, when maintenance is to be done, to
safeguard personnel.
Local pressure indicators and safety valves are installed on
anolyte!Cl2 and catholyte!H2 headers of each electrolyzer. The
very sensltive safety valves ensure that the differential
pressure is never greater than 200 mbar across the membrane
and the absolute pressure never higher than 300 mbar in the
electrolyzer to prevent any mechanical damage.

This is of major importance as long as the electrolyzer is

under shut down or start-up operation. Under this condition
the electrolyzer is cut off from the safety, which is provided
by the pressure control system of the plant.
These safety devices, which are provided for each Hoechst-Uhde
electrolyzer, are common for any reactor in the chemical
industry, 50 why not for electrolyzers? However, most of the
electrolyzers in the market are small and their number per
plant too big to afford a safety system for each of them.
Therefore, a certain risk is taken into consideration.

Electrolyzer design
Safety and economy are not only to be implemented into
electrolyzer configuration with instrumentation and
interlocks. They should be realized in each single element.
Fig. 5 shows a typical Hoechst-Uhde single element. Numbers of
these units are arranged in series to form packages of maximum
20 in one compression. Up to 6 packages are connected to build
one electrolyzer.
 111

CONNECTION IN SERIES ~ r---- CELL VOLTAGE

VISIBLE GASKETS

OPEN CONTACTS ---It+t7"''IIf-,c:-f." ~111:::

=~ CONTACT VOLTAGE

TIGHTNESS

lARGE ELECTROLYTE VOLUME

TRANSPARENT HOSES
FLOW

VISIBLE GASKETS TIGHTNESS

PROPERTY ANOL YTE CATHOL YTE

OBSERVATION
CI I HI

Figure 5. Single element

The picture summarizes the properties of a single element,

which make observations possible, to ensure the perfect
function of each single unit. For the earlier any
abnormality is detected the longer lifetime of the equipment
is ensured.
For example a prolongation of membrane lifetime from the
expected 2, to for example 4 years, effects a reduction of 5
$ per ton of product, which is a significant improvement in
economics.
The features of the single element, which allow the
desirable observations are:
The connection of the single elements in series, ensures the
same current passing through each element, enables the
operator to measure the particular voltage of each element
or allows connection directly to a distributed control
system (DeS). The cell voltage is a very valuable
measurement because it indicates any deviation of
• current distribution
• electrolyte concentration by flow changes
• temperature
• gas hold ups etc.
The open contacts between two adjacent elements can be
checked also by easy voltage measurement from anode to
 112

cathode across the contact. Any deviation can be rectified

early and easily by detaching the elements and cleaning of
contact surfaces. Because ' the voltage from anode pan to
anode pan is transferred to the DeS the contact voltage is
included into the monitoring system.

Each single element is sealed individually by flanges and

bolts, which are visible from outside and easily accessible.
The tightness is ensured for a long time with 4 years proven
to date and at least 6 years expected.
Inlet and outlet hoses are provided for each element. They
are also sealed individually with good visibility and access
for retightening, if necessary. The hoses are translucent,
so that the flow can be observed. This is important mainly
during start-up to ensure right from the beginning the
proper function of the element. It is actually possible to
distinguish under low load condition between green outlet of
anolyte (normal) and white, when all chlorine is absorbed by
the alkaline brine caused by a hole in the membrane.
The electrolyte volum~s of the elements ~re comparatively
large: approx: 40 11m anolyte and 30 11m catholyte. This
provides a relatively long reaction time for the operators
to rectify disturbances of inlet flow, concentration and
temperature .
Another important aspect of safety in designing an
electrolyzer is the electrical insulation and personal
protection from any electrical shocks. A Hoechst-Uhde
electrolyzer has a total v~ltage of approximately 400 V
under full load and 4 kA/m . This means ± 200 V towards
ground, which is comparable to other cell rooms equipped
with 120 monopolar membrane cells, diaphragm cells or
mercury cells.

I I
po
"""
H fo-
,
t>
""" ,
cru. RAO<

-- --
~

~I _ INSULAT ORS

, ~I
Joo '
~ ..
Joo
PERSONAL PROTECTION

f:::-- - 1=

Figure 6. Electrical insulation

 113

However, the Hoechst-Uhde electrolyzers are provided with a

double insulating system against ground. In Fig. 6 one can see
primarily the single elements itself insulated between their
supports and the cell rack. The busbars and the compression
devices for maintaining contact pressure are also insulated
against the cell rack as to be seen on the left side of the
drawing. The cell rack itself is secondarily insulated against
ground by big insulators placed below the 4 posts of the cell
rack. By this system any grounding and leaking current is
safely avoided.
To which danger are people exposed working with this type of
electrolyzer?
One case could be that one electrolyzer is shut down, while
the neighbouring one is under operation. One person could
touch the end of the operating electrolyzer and simultaneously
some electrolyte (the only grounded material) of the shut down
one. The maximum voltage difference could be 200 V.
Or if somebody spreads his arms, his span width may be 1.5 m,
and touches operating elements of one electrolyzer, he could
be exposed to a maximum of 60 V between his hands, which is
still under any dangerous limit.
However, all these possibilities should be prevented.
Therefore, each electrolyzer, in operation, is covered by
transparent polycarbonate sheets, avoiding any personal
contact, but maintaining full visibility for monitoring (see
Fig. 6).
The last item of safety and economy implementation into
electrolyzer design is the selection of materials for
construction.

The safety, which is provided by high quality and costly

materials can be compensated by the achievement of long
component lifetime.
For example the selection of the gasket material:
A PTFE based gasket individually sealed prevents the hazardous
chemicals from leaking out of the containment. The same
gasket, which is surely more expensive than any rubber based
gasket, helps to prolong membrane lifetime by not being the
limiting factor for replacement.
Another example is nickel as the preferred material for
cathode construction. Because of the fact that an element
should remain closed and untouched for periods of at least 4
years, all items to be changed for replacement, like gaskets,
anode coating, membrane, and cathode coating should have
lifetimes of 4, 8 or 12 years to fit into a economical
replacement schedule. If cathode material like stainless steel
would also be an item of regular replacement (e.g. 10 years)
it would make the schedule more difficult and replacements
more expensive, if one item could not reach it's full
 114

lifetime. The unlimited durability of nickel does not

interfere with the replacement schedule of coatings and
membranes and therefore improves economy. Also caustic
leakages through cathode pans are prohibited by nickel as the
material of construction to insure the safety.

EXAMPLES FOR OCCURRENCES AND SYSTEM REACTION

If we would ask membrane plant operators, which occurrence

they consider as the most severe, they will mention the
explosion of hydrogen-chlorine first with the comment that
these gases are only separated by a thin sheet of "cloth"
instead of a thick metal "wall". And in fact explosions have
taken place in all technologies.

However, if these cases are analyzed, two statements can be

made:

• most of the explosions took place during shut down and

start up operation
• explosions are consequences of previous occurrences or
maloperations, which could have been prevented

The philosophy followed in the Hoechst-Uhde single element

technology towards safety and economy is the set up of a
preventive system, which detects malfunction or maloperation
at the earliest, minimizes the damages and makes replacements
easy at low cost.

PLANT OCCURRENCE MEASUREMENT REACTION

CONDITIONS
START UP ELECTROLYZER FILLING PRESSURE HIGH PRESSURE RELEASE
WITH CLOSED VENT VALVES BY SAFETY VALVES

START UP PINHOLE IN MEMBRANE LOW ELEMENT VOLTAGE LEAK TEST OF MEM-

AT LOW LOAD BRANE ~ REPLACEMENT

INCREASE OF LOAD COOLING OF ELECTRO- ANOLYTE I CATHOLYTE AUTOMATIC SWITCH OFF

LYTES NOT STARTED TEMPERATURE HIGH OF ELECTROLZER
ABOVE 92·C

NORMAL OPERATION LOSS OF FLOW TO LOW FLOW INDICATION AUTOMATIC SWITCH OFF
ONE ELECTROLYZER OF ELECTROLYZER AFTER
ELECTROLYZER VOLTAGE 5 MIN. OF LOW FLOW INDIC.
HIGH
AUTOMATIC SWITCH OFF
ANOLYTE I CATHOLYTE AFTER TEMP. > 92·C
TEMPERATURE HIGH

NORMAL OPERATION LOSS OF FLOW TO ONE SINGLE ELEMENT VOL- AUTOMATIC SWITCH OFF
SINGLE ELEMENT TAGE HIGH OF ELECTROLVZER AFTER
SINGLE ELEMENT VOLTAGE
NO OVERFLOW VISIBLE > 200 mV THAN AVERAGE

Table 1. Examples for occurrences and system reactions

 115

With this background five occurrences and the according

reactions will be discussed: (Table 1)

1. Before electrolyzers are taken in line they are to be

filled with electrolytes and heated up. During this
period the electrolyzer is cut off from all peripheral
safety systems. If somebody starts filling without
opening of any anolyte, catholyte, or vent valves, head
tank pressure (approx. 1 bar) will be applied to the
electrolyzer either to one or both sides of the membrane.
Damage to membranes and structure will follow. To prevent
this the safety valves installed in each electrolyzer
will open and release the pressure to a separate header
system. The valves are designed to take liquid and gas
without excessive built up of pressure.
2. The highest probability that membranes get punctures or
pinholes is during handling and assembly of the single
elements. Therefore, each membrane will be carefully leak
tested prior to installation. However, during start up
operation a final cross check can be performed. Directly
after taking load under low current condition elements
with a damaged membrane show a significant lower voltage
(approx. 500 mV) than the others. This is caused by the
fact that caustic has leaked into the anolyte compartment
effecting a very alkaline anolyte. Therefore, oxygen is
produced preferably at low voltage. This observation can
be only done with elements connected in series ("bipolar"
type) and a voltage monitoring system provided for each
single element. If such an element is found during start
up, a leak test can be repeated inside the electrolyzer
and if necessary replaced quickly.

3. During increase of the load the setpoints for control of

cell temperature have to be adjusted manually, also
heaters are to be changed to coolers. If such an
operation is missed or carried out too late, the
catholyte and anolyte temperature increase quickly.
Boiling electrolytes and pressure built up inside the
elements by the discharge of the huge vapour volume are
the consequences. Membranes and structure may get
damaged.
However, anolyte and catholyte temperature are recorded
for each electrolyzer. A value above 92 DC will take each
electrolyzer and probably the whole cell room off line.
The inlet temperature can be adjusted and the plant
restarted quickly.
4. A major danger is the loss of electrolyte flow to the
electrolyzers. The loss of flow to all electrolyzers is
easily interlocked by the low level of head tank with the
main rectifier. However, the electrolyte flow to a single
electrolyzer may be interrupted or reduced by blockage of
an inlet strainer. Loose particles from failing rubber
 116

lining or other inliners may be the cause for that. In

such a case the flow indicator to the electrolyzer
affected will show low flow and after 5 minutes - this is
the time to correct maloperated valve positions - the
electrolyzer will be taken off line automatically.
Even if this indication would have failed, the
electrolyzer will be either by the signal "high voltage"
or "high anolyte/catholyte temperature" taken off line.
Cleaning of strainers is a quick action. After a period
of less than one hour an electrolyzer can be restarted.
5. In general it is also possible that one single element
suffers from low flow or even non flow. In such a case
the voltage of the element will rise slowly, if the inlet
hose is choked, and quickly, if an inlet hose breaks and
the electrolytic area is reduced by the falling level.
This voltage rise of a single element will be noticed by
the voltage monitoring system in such a way, that the
voltage difference between the two sections increases
simultaneously. The electrolyzer will be taken off line
as soon as a value of 200 mV is exceeded. This is a very
sensitive adjustment. Even if this system would fail, the
big electrolyte volume of a single element and the small
inlet nozzle, through which draining may take place,
provide a long time to react to the operator. Therefore,
up to now none of the 4400 Hoechst-Uhde elements, which
are on line presently, were damaged by such an
occurrence.

Anyway, repair is easily done and also in such a case

downtime is only one hour and major damage is prevented.
These 5 cases are only examples for many cases, which could
prove the implementation of safety and economy into the
Hoechst-Uhde electrolyzer design.
 117

RECENT DEVELOPMENT AND OPERATION DYNAMICS OF

NEW ION EXCHANGE MEMBRANE SERIES ACIPLEX@-F FROM ASAHI CHEMICAL

HIROYUKI SHIROKI, TATSUO HIYOSHI, TETSURO OHTA

Asahi Chemical Industry Co., Ltd.
3-2, Yako l-chome, Kawasaki-ku, Kawasaki, Japan

ABSTRACT

The characteristics and operation dynamics of the new series Aciplex-F recently developed
by Asahi Chemical, as observed in their stable performance in extensive operation world-
wide, are described together with the development status of the most recent grade in the
series, the F-5000 membranes for heightened membrane performance, and that of membranes
for direct production of 50 % caustic soda. Also reported are new findings on the influence
of brine impurities on ion exchange membrane performance.

INTRODUCTION

The world's first ion exchange membrane process plant for commercial chlor-alkali produc-
tion began operation at Asahi Chemical in 1975 [1]. With the continuing advances in
membrane and membrane process technology in the sixteen years since then, and its inherent
advantages as a non-polluting, energy efficient process with high product quality, the number
of chlor-alkali plants utilizing the ion exchange membrane process has increased rapidly,
both through new plant construction and expansion and through conversion of existing
plants from the mercury and the diaphragm processes. Advances by Asahi Chemical, in
membranes, electrolyzers, anodes, activated cathodes, and the electrolytic process, have
contributed constantly to this growth [2-5J. The capacity of chlor-alkali plants worldwide
currently using the Asahi Chemical ion exchange membrane process has now grown to 1.5
million tons of caustic soda per year.
Key performance criteria for salt electrolysis by the ion exchange membrane process
 118

are high membrane current efficiency, low electrolytic voltage, high product (caustic soda
and chlorine) purity, and stable maintenance of these high performance levels in long-term
operation. With the new series Aciplex-F membranes, it is possible to fully meet all of these
requirements, as shown here by their long-term performance in both electrolytic experiments
and commercial electrolyzers. Also described here is the Aciplex F-5000, currently under
development for a further heightening of membrane performance levels.
We also describe the effects of various brine impurities on stable performance, and
progress in the development of membranes for direct production of 50 % caustic soda by the
ion exchange membrane process.

CHARACTERISTICS AND PERFORMANCE OF NEW SERIES ACIPLEX-F MEMBRANES

Characteristics
The new series Aciplex-F membranes, perfluoro carboxylic membranes based on many years
of technological development and extensive experience in commercial application of ion
exchange membrane salt electrolysis, are characterized essentially by the following.
(1) High cation permselectivity.
(2) High electrical conductivity.
(3) High product (caustic soda and chlorine) quality.
(4) High, stable chemical resistance and mechanical strength.
(5) Ease of handling and use.
The membranes are composed of polymeric layers with the chemical structures shown
in Fig. I. The weakly acidic carboxylic layer provides superior barrier properties and
heightened cation permselectivity, and serves to ensure high-quality, high-purity product
caustic soda. The strongly acidic sulfonyl layer provides superior electrical conductivity and
heightened physical strength with a minimal increase in ohmic drop, and makes possible the
production of high-purity chlorine. PTFE reinforcement in the membrane provides high
durability in operation and prevents tear propagation. Where necessary, a hydrophilic layer
containing inorganic particles is incorporated onto the membrane surface, to prevent evolv-
ing gas bubble adhesion.

Performance and operation dynamics

The operating characteristics of a membrane are generally affected by the electrolytic
conditions, and most essentially by the electrolyte concentrations, electrolytic temperatlJre,
and current density. Fig. 2 shows the NaCI content in product caustic soda, cell voltage, and
current efficiency with the Aciplex F-4100 under various electrolytic conditions. As indicat-
ed, this membrane exhibits a current efficiency of more than 95 % under a broad range of
electrolytic conditions.
 119

-(CF2 -CF 2 )x CF 2 -CF---+ -(CF 2 -CF 2 )x CF2 -CF---I-

gF2 )
(CF-CF gF2 )
(CF-CF
m 3 m 3
o o
(CF2 )n (CF2 )n
COO-Na+ S03-Na+
m=0-2, n=1-4 m=0-2, n=1-4
carboxylic sulfonic

Figure 1. Aciplex-F membrane polymer structures.

>36~
g 3:2
~ 34
______
3.0 ----- ,/ --
--- ---
I
0

50~
z'"I

~
~

o~E
c.
o c.
L!) ~
........
(3 , ,
o
, ,

z'" 25 30 35 2 3 4 2 4 6 80 85 90
NaOH (%) NaCI (N) C.D. (KA/m') Temp. (OC)

Figure 2. Electrolysis conditions and Aciplex F-4100 performance.

Base conditions: NaOH, 30.5% ; NaCI, 3.35N ; C.D., 4KA/m 2 ; temp., 8YC.

The new series Aciplex-F membranes in currently available standard grades provide
excellent performance for caustic soda concentrations ranging from 20 % to 35 % through
optimization of the ion exchange capacity and other properties.
The relationship between the Aciplex F-4100 performance and the anolyte acidity is
shown in Fig. 3. As indicated by these curves, the oxygen content in the product chlorine
gas can be reduced to a very low value without affecting the current efficiency, cell voltage,
or NaCI content of the product caustic soda, by adjusting the anolyte acidity with HC!.
In general, the concentration of oxygen in product chlorine gas tends to vary with the
anode composition and configuration and the pressure difference between the anolyte and
catholyte compartments. The surface of Aciplex-F membranes facing the anode is uniquely
textured, for maximum effect from HCl addition, and makes it practical to obtain product
chlorine with an oxygen content of less than 0.5 vo!' % in commercial chlor-alkali plants
under standard operating conditions.
 120

98

Q o o
o
~

\ ~30
S 96
W
cJ d'(
o
......
In
94 C3
~ '0
~--O.~OO-'-------O.~O'-------O~.-, ~-O.~O-O'------O-.~O'-------O~.,---

1.0
3.5
~
......
"0 N

C3
> 3.3 ';;.0.5
o

3.' ~----:-O-!.O-:-O'--------:O~.O-'-------O~.l-
0.' ~----L_ _ _ _ _ _ _ _L.-_ _ _ _""':""...L..-_

0.'
Anolyte acidity (N) Anolyte Acidity (N)

Figure 3. Anolyte acidity and Aciplex F-4100 performance.

Base conditions: NaOH, 30.5%; NaCl, 3.35N ; C.D., 4KA/m 2 ; temp., 90T.

Stability and reproducibility

Electrolyzer operation invariably involves departures from the designed operating condi-
tions, due to current load changes, shutdown and startup, electrolyte concentration changes,
abnormalities, and other factors. It is therefore important that the ion exchange membrane
exhibits performance stability and performance recovery with good reproducibility under
changing conditions.
Fig. 4 shows the results of a pilot-scale test with the Aciplex F-4100, in which the
caustic soda concentration, electrolytic temperature, and current density were varied substan-
tially. The accompanying changes in membrane performance were small, and practically
complete recovery was observed following the restoration of the operating conditions.
Variations in startup conditions have little or no influence on the performance of the
Aciplex-F membrane following the establishment of normal conditions, as indicated by the
results of laboratory-scale trials shown in Fig. 5. With startup conditions in the range of
50-90°C, 23-40 % caustic soda in the cathode compartment, and 2.7-5.0 N NaCI in the anode
compartment, no observable difference in current efficiency or electrolytic voltage was
observed after normal conditions were obtained. Even after a startup at 50°C, subsequent
performance was normal and no abnormality was found in the membrane upon examination
at the end of the trial.
 121

NaOH~ 33% -30-·-- 33 ---'35-33-

Temp ""=------
85"C -------. 90--80-·--- 85
C . D . I - - - - - - - 4KA/m' - - - - - - . - 2 - 4 -

:~t
96
95
3.4
3.2
...
~
"0 3.0
>
2.8
::c
0
III
Z
I ~

o~E
c.
oLl")~ c. SOf
.......
(3
z
III
o ::
0
:- j::
5
~::'::: ~
10 15 20
DOL
Figure 4. Performance reproducibility with Aciplex F-4100 in commercial-size cell.

startup

I
98 ~ 90"(; i
*~
W 94 it ..
U 90 ~ temp.90"C (a)
~ 3.6 :

; ~:! ~~i=H~~=O
* 98133~%
94
:£~,*.,.", ~l1'll'jjo.,.
40%:
DOL

~ 90 I
(a) Temperature test
(b) Caustic strength test
36 ~ 23% ! NaOH 33% (b)
~.~
(c) Bri ne strength test
g~:! ~"iIl"'£I>4"',"*~:!M>8'i9>8"..fI~~e'H:!'18'''''''''' membrane: Aciplex F-4IOO
after startup normal conditions:
I

o 5 10 15 20 NaOH, 33%; NaCI, 3.35N; temp.,90·C.

DOL
Figure 5. Reproducibility with Aciplex F-4100 from various start-up conditions.
Base conditions: NaOH, 33%; NaCI, 3.35N ; C.D., 4KA/m 2 ; temp., 90"C.
 122

The high-level stability and reproducibility of the Aciplex-F membranes indicated by

these trials, under a broad range of startup conditions and various operating conditions, has
now been confirmed in extensive utilization of the membranes in commercial plants
worldwide.

Performance in commercial utilization

New series Aciplex-F membranes have consistently exhibited stable, high-level performance
in the many commercial chlor-alkali plants where they have been installed in the course of
the past three years, as indicated by Fig. 6 and 7. The performance of the Aciplex F-4100,
for 30 % and 33 % caustic soda production, is shown in Fig. 6. The current efficiency was
determined from the caustic soda production rate. Cell voltage was determined in operation
with a current density of 4 KA/m 2 , a temperature of 90T, and an activated cathode
developed by Asahi Chemical. Fig. 7 shows similar performance and stability by the Aciplex
F-2200 in the commercial production of 23 % caustic soda, using a mild steel cathode.
In all cases, cell voltage was highly stable, with little variation among cells, electrol-
yzers, or plants, and the NaCI content in the product caustic soda was consistently low.
Current efficiency was also high at all plants, but with some difference among the plants in
its tendency over time, which was apparently attributable to differing feed brine impurities,
as described below.

- [', - Nobeoka Plant 33% -u- C Plant]

- 0 - Nobeoka Plant ] D Plant 30%
-0- A Plant 30% E Plant
- 0- B Plant
9S C .E. (%)

97~~~~_~~
96 tr~--"'""I.ft:-.:--t.... . . . ~ /_o~'" -;-6+---6- b----~
95 \o---~~-,-:::---- ~__ -_-O------_=-_:~-u-----:---ty---- "~
94 ''*----,-41 -.--..cr.---

Cell Volt (Vat 4KAlm', 90'C) 6- Cathode: Activated

3.3 t;;,.----b----_-O'-- _ _ _ -.6_ _ _ .=-=-~_;::---- .... -- -------1' _____ ----l> _ _ ~--- - & - - - - - 6
3.2 "(T'- p' -~-~ ---.- ------0-----,,--- __ 0 ________ - 0 ·
0- _________ :. ______

I
3.1

60 NaCI/50%-NaOH (ppm)

:g :~.~?~_~~~:.~;~~-::~~:-=~~~~~------~---u--o-------uo ,
o 5 10 15 20 25 30 35 40 45
MOL

Figure 6. Operational results with Aciplex F-4100 in 30% and 33%

caustic soda commercial plants.
 123

_C
C.E. (%) -",,- Nobeoka plant -6- B plant
plant
!lf~=,:,,*~;;;?,=~~~~~A~ P": ~ ~c=

II r-=:.?~~''<~'~;:c,~==~~-~~ -, ~'.--'-~'- _.
Cell Volt (Vat 4KA/m', 90'(;) Cathode: Mild Steel
I

5 10 15 20 25 30 35
MOL

Figure 7. Operational results with Aciplex F-2200 in 23% caustic soda commercial plants.

Electrolyzer amenability
The new series Aciplex-F membranes are appropriate for a broad range of electrolyzers.
Although all of the above results were obtained in finite-gap electrolyzers with bipolar
configuration, Aciplex-F membranes also provide superior performance and stability in
zero-gap electrolyzers. As shown in Fig. 8, the Aciplex F-4200 exhibits decreasing cell
voltage with decreasing inter-electrode distance in the cell, in contrast to the Aciplex F-4100,
and is thus highly appropriate for use in zero-gap cells. The stable, high-level performance
of the Aciplex-F membranes has been shown in their operation in various finite- and
zero-gap electrolyzers with monopolar configuration other than those of the Asahi Chemical
process as indicated in Fig. 9 to II.

4.0
---p
C)
3.8
en

E
.......
« 3.6
::.::: F-4100
"""
+J
co 3.4
~
.....
(5
> 3.2
Q)
u 3.0 F-4200

0 1.0 2.0 3.0

Electrode distance (mm)

Figure 8. Electrode distance and cell voltage with Aciplex F-4200 and F-4100.
Conditions: NaOH, 33%; NaCl, 3.35N ; C.D., 4KA/m 2 ; temp., 90·C
 124

98
97
96
95

NaCI/31-32% NaOH (ppm)

40
30
20
o
"0 ,~o
_0_0_0_0- o~o,
'"
o-o~o-o-o_o
o "'-
o
o 5 10 15
MOL

Figure 9. Performance of Aciplex F-4100 in user's finite-gap cell.

Conditions: NaOH, 31-32%; NaCI, 200gpl; C.D., 2.5-3.0KA/m 2 ; temp., 75-8S'C.

99
98
~
97
w 96
cj
Electrolyzer-A -0-
95 II -B -e-
94 1/ -C -6,-

.:::::
.!:9 220 240~
U 200
z'"
180

:c
o
z'" ::~
32 0 5 10 1'5
,
20
MOL

Figure 10. Performance of Aciplex F-4200 in user's zero-gap cell.

Conditions: C.D., 3.9 KA/m 2 ; temp., 90T.
 125

98 C.E. (%)

95
94

Cell Volt (Vat 3KAlm' 90"C)

3.2

3.0
o 5 10
MOL

Figure II. Performance of Aciplex F-4200 in user's finite-gap cell.

Conditions: C.D., 3KA/m2 ; temp., 90'C.

Adoption for KOH production

Aciplex-F permit efficient electrolysis of potassium chloride, as well as that of sodium
chloride, for effective, economical production of potassium hydroxide. The basic perfor-
mance characteristics of the Aciplex F-4200 in this application are shown in Fig. 12.
Potassium hydroxide in concentrations of 30-33 % can be produced with a power consump-
tion of less than 1,600 KWH/T-KOH, with a current density of 3 KA/m 2 • Laboratory-scale
testing indicates the same performance and operation dynamics by the Aciplex-F membranes
may be expected in this application as those which have been widely obtained in NaCI
electrolysis.

KCI
250g/1
98
~ 200g/1 ~ 3.5 E"70
0.
-3
KCI :r: 50

~KCI
~ 96 0
u.i ~250g/1 ~
<394 m / 2 0 0 g/1 ~ 30
u Lt)
...... 250g/1
3.0
92 ~1O 200g/1
25 30 35 40 25 30 35 40 25 30 35 40
KOH (%) KOH (%) KOH (%)

Figure 12. Performance of Aciplex F-4200 in KCI electrolysis.

Conditions: C.D., 3KA/m2 ; temp., 90'C.
 126

INFLUENCE OF BRINE IMPURITIES

Typical brine impurities which tend to degrade the performance of ion exchange membranes
are Mg, Ca, Sr, Ba, AI, I, SO. ions and Si0 2 • Coexistent impurities, such as Ca ion and Si0 2 ,
are known to exert a synergistic degrading effect [6]. The two tend to form certain
complexes which are apt to deposit in the membrane and thus degrade its performance.
Although it is not practical to completely eliminate Si0 2 from the brine by present purifica-
tion technology, the optimization of clarifier pH and co-sedimentation conditions can hold
the Si0 2 content in the brine to less than 4 ppm, sufficiently low to prevent any practical
influence on the performance of the Aciplex-F membranes [7]. We have also found that
interactions between certain combinations of three components, such as Ba, I, and SO. ions,
can seriously affect membrane performance. As indicated by the current efficiency curve in
Fig. 13 and the EPMA of Fig. 14 a-c, in the absence of SO. ion the Ba and I ions tend to
undergo complex formation and deposit in the membrane in the region facing the cathode,
thus lowering current efficiency. If SO. ion is present in the brine in ordinary concentrations,
however, the Ba-I complex is uniformly distributed throughout the rest of the membrane as
well, reducing the effect on current efficiency to negligible levels. In case that SO. concentra-
tion in brine is high level, Na 2 SO. deposits at and near the surface of carboxylic acid layer
over the reinforcement as shown in Fig. 14c, and has a harmful effect on the current efficiency
slowly.

J .-
- - - - - - -fJ{) - - - - - -=-=-0 - - - - - - - - - - - - - -
.a

96
Sa: 0.5 ppm I : 0.6 ppm
--- 0 --- initial
94 -. - after lMOL

o 5 10
S042 - in brine (gil)

Figure 13. Influence of brine impurities (Ba, I, SO.). membrane, Aciplex F-4100,
Conditions: NaOH, 33%; C.D., 4KA/m2; temp., 90'C.
 127

(a)

(b)

(c)

Figure 14 a-c. Distribution of Ba, I (a,b) and S (c) in membrane cross-section, by EPMA.
SO. in brine (gi l) : (a), 0 ; (b), 2.5 ; (c), 10.

In Europe, some brines contain Sr ion, and reportedly may influence membrane
performance. With the new series Aciplex-F membranes, however, no influence has been
found in any cases of operation with brine containing Sr at concentrations as high as 0.5
ppm .
 128

CONTINUING DEVELOPMENT OF THE ACIPLEX-F SERIES

Aciplex F-5000 membranes

Asahi Chemical is now completing development of Aciplex F-SOOO membranes, a new grade
based on the same design concepts as the F-4000 membranes but with the basic development
objective of reducing cell voltage by some 100 mV while maintaining the same high current
efficiency, low NaCl content in product caustic soda, and high mechanical strength. Its
performance characteristics, in comparison with those of the F-4100, are shown in Fig. IS.
The cell voltage is substantially smaller, as shown in Fig. ISa. As indicated in Fig. ISb, the
dependence of current efficiency on caustic soda concentration is substantially reduced with
the F-SOOO, permitting a broader range of product concentrations than previously possible.
As shown in Fig. ISc, the NaCI content in the product caustic soda is at the same low level
as that achieved with the F-4100. Proving trials are now in progress at Asahi Chemical's
Nobeoka Plant, and early availability to membrane users is expected.

a. Volt (Vat 4KA/m', 90'C) b. C.E. (%) 120f c. NaCI/50%-NaOH (ppm)

98
3.4
96 /:-:~~
80
94
3.2
92
40f

L:::==
90
3.0
I 88
o 25
~~~~~~~~

25 30 35 40 25 30 35 40 30 35 40
NaOH (%) NaOH (%) NaOH (%)

Figure IS. Performance of Aciplex F-SOOO (-) and F-4100 (---).

Conditions: NaCl, 3.3SN; C.D., 4KA/m 2 ; temp., 90°C.

Membrane for 50 % strength caustic soda

Asahi Chemical is now engaged in advanced development of a membrane for direct
production of SO % caustic soda by the membrane process, which would eliminate the capital
investment and operating cost of a separate concentration system to achieve the SO % standard
strength, and would be particularly advantageous in Europe, the U.S., and other regions
where the cost of electric power is relatively low. Laboratory-stage development has been
completed for a membrane that exhibits a current efficiency of more than 9S % and a cell
voltage of 3.4 V (4 KA/m 2 , 90°C) at a caustic soda concentration of 4S-47 % as shown in Fig.
16, through development of a modified membrane polymer and a new inorganic coating for
the membrane surface facing the cathode. Further performance impro~ement and advanced-
stage development is scheduled, and is expected to result in an economical, commercially
available membrane in the near future.
 129

98f. C.E. (%)

95/
~ .---------~ ,... ~--------- ..
"'----
93

3.51;OI~~~ ~t ~~~"C.-~__ ~o"''''_.o---~'''--''oo--_O~O_O ~

0 0'--'-0

3.3
r
50 NaCI/50%-NaOH (ppm)

O~"'~'
o 20 40 60
DOL

Figure 16. Performance of test membrane in direct high-strength caustic soda production.
Conditions: NaOH, 45-47%; NaCl, 3.5N; C.D., 4KA/m2 ; temp., 90T.

SUMMARY

The developments described here are part of an ongoing effort at Asahi Chemical, based on
nearly two decades of development, manufacture, and operation of total systems and
components, for improvement and technological advances in membranes and other process
components adapted and advantageous to the operations of existing and new chior-alkali
producers. Based on its longstanding experience, Asahi Chemical will also continue to
achieve further improvements of the ion exchange membrane technology.

REFERENCES

1. Seko, M., Commercial operation of the ion exchange membrane chi or-alkali process,
Paper presented to Amer. Chern. Soc. Centennial Meeting, New York, April 4-9, 1976.
2. Seko, M., The Asahi Chemical membrane chior-alkali process, Paper presented at the
Chlorine Institute Inc., 20th Chlorine Plant Manager Seminar, New Orleans, La., U.S.
A. Feb. 9, 1977.
3. Seko, M., Miyauchi, H., Ohmura, J., Kimoto, K., in Modern Chlor-Alkali Technology,
vol. 2., Chap.6 ed.C., Jackson, Ellis Horwood, Chichester, 1983.
4. Seko, M., Y omiyama. A., Ogawa, S., Ono, H., ibid. Chap. 6.
5. Seko, M., Ogawa, S., Yoshida, M., Shiroki, H., Recent Developments in Electrochemical
Engineering for Application of Ion Exchange Membranes, Paper presented to ISE 34th
Meeting, Erlangen, Germany, Sept. 1983.
6. Keating, J.T., Behling, K.J., in Modern Chlor-Alkali Technology, vol. 4, Chap. 12, ed.
N.M. Prout, J.S. Moorhouse, 1988
7. Ogawa, S., Kanke, T., (to Asahi Chemical Ind, Co., Ltd.) Japanese Patent Publication
59-43556 (Oct.23, 1984), UK Patent 1586952.
 131

NAFION® MEMBRANES FOR THE 1990'S

EVERETT I. BAUCOM
E. I. du Pont de Nemours & Co. U.S.A.
Nafion® Customer Service Laboratory
Fayetteville, N. C. U.S.A. 28302

ABSTRACT
During the 1980s membrane technology for ch10ralkali
production was established as the most economical technology
for new plant installations. Conversions to membranes are
also often justified. Nafion® membranes have contributed
significantly to this technological revolution in
chloralkali, having produced 20,000,000 mT of caustic in
more than 110 chloralkali plants. Du Pont is expanding this
well proven technology to further reduce chloralkali cost
and to serve important emerging needs. Our expectations
include: 1) Power consumption below 2000 kwh/mT. 2)
Membranes tailored for specific applications; e.g.,
operating more efficiently at high current density. 3)
Five year life under demanding conditions. Examples of
developmental products are given.

INTRODUCTION
This paper presents (1) a retrospective look at performance
of Nafion® membranes in the more than 110 plants in which it
is currently operating, (2) a description of how the
well-proven technology of Nafion® 90209 is evolving into a
new generation of products headed by NX-966 and NE-971, and
(3) a prospective look at membranes of the future, including
a view of what can be expected of membrane performance in
the decade of the 90's.
At the 1988 SCI meeting rapid penetration of membrane
technology into the chloralkali industry was described.
During the period 1982 to 1987 membrane capacity increased

Nafion® is Ou Pont's registered trademark for its perfluorinated membranes.

 132

from 2% to more than 12% of worldwide chloralkali

production. During the intervening three years that growth
has continued and now stands at 17%. Approximately 150
plants worldwide now employ membrane technology for
chloralkali production. The reasons for this rapid growth
are well documented and will not be expounded here except to
point out that the performance superiority of membrane
technology over the older chloralka1i technologies continues
to increase.
In 1988, Jochen Behling presented data reporting the long
term plant performance of Nafion® 90209 membrane. Plant
performance was quite respectable with all plants starting
up at 96 - 97% current efficiency and achieving membrane
life of more than two years. With three years additional
experience the story only gets better.

PERFORMANCE OF PLANTS USING NAFION® MEMBRANES

Some plants have now surpassed five years with the initial
set of N-90209 membranes. Current efficiency continues to
be outstanding as illustrated in Figure 1. One plant is
approaching six years with the initial set of membranes.

100

-if: 98 ..
••••
.
•.• p .......-rt../.t(.,.~e.!... \-
....
96
o
*
-........
c
Q)
94

:::J 92
o
90
o 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400
Days on Line
Figure 1. Commercial performance of Nafion® 90209
Current efficiency in that plant remains high at about 95%
and power consumption is just over 2200 kwh/mT. Another
plant, not illustrated here, is approaching six years in
production of KOH with current efficiency still well above
96%. It should be pointed out that the excellent plant
performance documented in this paper speaks well not only of
 133

the membrane but also of the operators and hardware

manufacturers.
Performance at shutdown of the longest running N-90209
membrane to date is illustrated by the asterisk in Figure 1.
This was at the Tofte, Norway, plant. Current efficiency
remained near or above 96% during its more than six years'
service. perhaps more important than any individual plant
data is the fact that in Japan the average N-90209 membrane
has been in service more than three years with current
efficiency still >96%.
One measure of performance is how well the membrane operates
in well-controlled plants such as these. However, Nafion®
membranes can also survive very challenging environments.
One plant in south India using N-90209 has survived over 700
unscheduled shutdowns due to an unreliable power grid.
Performance of the membranes has not been affected. Current
efficiency remains nearly 95% after more than five years.
This is illustrated by the circle in Figure 1.
Performance for Nafion® 954 is equally as impressive
although the membranes generally have not been in operation
quite as long as N-90209. For seven plants with up to four
years service current efficiency remains consistently high
as illustrated in Figure 2. There is very little evidence
of decline in current efficiency even after this long
period. The average N-954 membrane has been in service just
over two years with current efficiency averaging 96.5%.
Power consumption in most plants is less than 2200 kwh/mT.
100

*- 98

---
\
.". ...
- •••• -.::-:'" ::-:.: .....•••"':....-::•.-::':"::....... :-:••~.:O:-- •• - ...
.....-.-._ - -
••••••••• I ••••••••••

:;_-.-=.-.-...;-::..~.='i"-._e::" ~
96 ~
--
-........
C
CD
94

92
!-

I-
~
()

90 I I I I I I I I I I I I I
0 200 400 600 BOO 1000 1200 1400
Days on Line
Figure 2. Commercial performance of Nafion® 954
 134

Nafion- 961 is often selected by end users seeking the

lowest possible voltage and power consumption. The
reinforcement is somewhat less robust than for N-90209 and
N-954. Nevertheless, it does have the capability for long,
reliable performance. Figure 3 presents data from five
plants on two continents. One plant has been operating five
and one-half years with initial membranes. Current
efficiency remains nearly 95%. Performance of these plants
is so similar that it is difficult to distinguish among
them.

--eft.
100

98
>-
0
c:
Q) 96
·u
=
-........
W
cQ):
94

:l 92
()

90
o 200 400 600 800 1000 1200 1400 1600 1800 2000
Days on Line
Figure 3. Commercial performance of Nafion s 961
It is impractical to present data from all of the more than
110 plants presently using Nafion S membranes. However, the
results presented here are representative of plants in which
brine treatment and plant operations are carefully
controlled. These data make it clear that two year life,
which was initially a concern for ion exchange membranes,
has been proven beyond doubt for Nafion- membranes. Three,
four or even more years' service is now commonplace. Gasket
life has become the limiting factor in many operations. The
ability of Nafion- membranes to withstand gasket replacement
contributes to their long average life.

NAFION- DEVELOPMENT STRATEGY

How have we been able to achieve such outstanding
performance? We have developed and perfected membranes with
the basic structure shown in Figure 4.
 135

Sulfonate Polymer-.s:--~ Carboxylate Polymer

Gas Release- -Gas Release

Surface Modification Surface Modification

Reinforcing Fiber---++-

Figure 4. Generic structure of Nafion GD chloralkali membrane

The heart of our product is Du Pont's more than 50 years'
experience in fluoropolymer synthesis technology. This
synthesis capability is supported by technology for key
intermediates and polymer processing. In 1990 Du Pont sales
of polymers exceeded $12 billion, and we invested
substantially in polymer research. Moreover, our
fluoroproducts businesses exceed $1 billion worldwide. This
broad base has enabled us to select the best monomers for
both sulfonic and carboxylic polymers. And we have been
able to produce both types of polymers with the necessary
properties for chloralkali service. Du Pont has more than
30 years' experience in producing perfluoroionomers. This
has enabled us to balance the chemical and physical
properties of these polymers as well as perfect processing
to optimize adhesion of the layers. This adhesion is
critical to the long life of our membranes.
In addition we have developed surface modification for
enhanced gas release useful for some cell designs and a
number of reinforcing fabrics. By independently optimizing
each of these membrane components we have been able to
produce a large number of products designed to meet specific
market needs. Our product design strategy has worked so
well that our basic membrane architecture has remained
intact for 10 years and has become the industry standard.
Nafion GD membranes have been used to produce 20 million tons
of caustic soda. This broad base of experience gives us
confidence that our basic chemical and mechanical structures
are sound and capable of providing long chloralkali service
under ever more challenging conditions. We plan to enhance
our leadership position by continuous improvement of our
existing technology.
 136

The primary guiding principle of our technical development

is to provide products and services with continuously
increasing value to the chloralkali industry. We strive to
help our customers to improve the health of their businesses
through continuously lowering cost. Some ways in which that
can be accomplished are through (1) lower power consumption,
(2) reduced maintenance, (3) minimum downtime, and (4)
increased durability.

RECENT NAFION® PRODUCT DEVELOPMENTS

As illustrated earlier by plant data, Nafion® 90209 is a
highly reliable long-lasting membrane. However, in keeping
with our philosophy of continuous improvement we have
developed an even more rugged and forgiving membrane:
Nafion® NX-966.
Design goals for NX-966 were to (1) produce the most robust
chloralka1i membrane in the industry, surpassing even
N-90209 and providing up to five year life even under the
most severe operating conditions; (2) provide excellent
sealing with simple gasketing in any type of electrolytic
cell; (3) provide lower voltage than N-90209, without loss
of operational flexibility; and (4) build on the wealth of
N-90209 manufacturing technology and chloralkali operating
experience.
NX-966 has considerably greater mechanical strength than any
present product designed for operation at 30-35% caustic.
The tensile and tear properties are more than 50% greater
than the N-90209 series and more than double that of N-961
series. For most applications this greater tensile strength
is not needed. But NX-966 offers an additional margin of
safety. More importantly, the membrane has a much higher
modulus; that is, it is considerably stiffer than most of
our other products. As a result it is easier to handle when
installed and it withstands more severe mechanical upsets
than either the N-90209 or N-961 series.
NX-966 was initially developed for the Niachlor plant at
Niagara Falls, NY (USA), which has 948 3.6 X 1.5 m cells.
plant production is 660 mT/day. Niachlor has successfully
used N-90209 since startup in 1987. Performance has been
excellent, as illustrated by the >96% average current
efficiency for all membranes operating in 1990. However,
Niachlor desired a more robust membrane for improved
operability. While membranes were easily surpassing two
years life, they were not up to expectations based upon
experience in many other plants.
The difference at Niachlor was thought to be due to the
severe operating environment, including the fact that the
cells are the largest in the world. Lifetime of the
membranes was not limited so much by current efficiency
 137

considerations as by Niachlor's strict safety standards. In

determining when membranes are to be removed from service,
Niachlor's standards are much more severe than common
industry practice. NX-966 was developed to meet Niachlor's
need.
In standard 0.5 dm 2 laboratory cells at finite gap NX-966
showed a modest 50 mv improvement vs N-90209, with
comparable current efficiency, with both steel and activated
cathodes. In 0.5 dm 2 cells run in narrow gap configuration
with platinized nickel activated cathode, performance was
intermediate between N-954 and N-961 at both 3 and 4 kA/m 2 •

In a small commercial test cell (20 dm 2 active area)

operated in the Nafion® test facility NX-966 shows
substantially better performance. voltage was >150 mv lower
than N-90209 at 3 kA/m 2 • Conditions are shown in Table 1.

TABLE 1
Performance of Nafion® 966 vs Nafion® 90209 in
commercial test cell

Finite gap, 90°C, exit brine 180/0

320/0 caustic, activated cathodes

CV,v CE,% Wt
--
CD, kA/m2 CI-, ppm
N-90209 3.24 95.4 3.8 3.0 45
NX-966 3.07 95.5 3.4 3.0 34
N-90209 3.42 95.5 4.0 4.0 35
NX-966 3.28 96.0 3.6 4.0 22
Chloride in caustic and water transport are also lower.
Based upon these strong laboratory results, NX-966 was
installed for tests at Niachlor in January 1990.
The advantage seen at Niachlor for NX-966 is of the same
order of magnitude as seen in our 20 dm 2 laboratory cell,
between 100 and 170 mv. The absolute difference depends
upon a number of factors such as level of activation of
cathodes and current density. Niachlor reports that they
see the greatest difference at 4.5 kA/m2 where they commonly
operate with NX-966.
Current efficiency of N-90209 membranes presently in use at
Niachlor averages well above 96%. Current efficiency in
 138

cells operating with NX-966 is the same within the

measurement error. Limited testing of NX-966 began at
Niachlor 18 months ago. Because of its outstanding
performance NX-966 has become the standard membrane at
Niachlor for replacements. Over the past 8 months 1,000 m
have been installed. It is anticipated that within the next
year the rest of the plant will be membraned with NX-966.
Whether NX-966 actually achieves five years service at
Niachlor remains to be seen. However, it is certainly clear
that NX-966 has met all of its initial development goals and
appears to be a very robust membrane in this most severe
test.
NX-966 is also being evaluated commercially in several other
plants with equally impressive results. In two finite gap
plants voltage reduction was 170 mv. These chloralkali
producers intend to install NX-966 on their normal
replacement schedule.
NX-966 has also been tested in the laboratory at current
densities up to 6 kA/m 2 • Performance remained outstanding
during the entire test. Du Pont does not recommend
operations under these extreme conditions. This test is
simply additional evidence of the ruggedness of this
membrane. when electrolyzers are designed which will handle
higher current densities, Nafion® has membranes ready for
evaluation.
In regions where power costs are exceedingly high, membrane
ruggedness is less valued than the lowest possible power
consumption. This section will review recent developments
in low power consumption Nafion® membranes. A new family of
membranes is being developed for use in both finite and
narrow gap cells. Goals in designing this new generation of
low power consumption membranes are (1) to build on N-90209
technology, (2) to provide the same long life as our
existing commercial membranes with no sacrifice in
durability, and (3) lower power consumption achieved
primarily through lower voltage.
Laboratory results show that these developmental membranes
have 2 to 4% lower voltage than commercial membranes such as
N-961. Figure 5 compares N-961 with the developmental
membrane in a commercial electrolyzer. Over a period of
about 9 months voltage for the developmental product at 3 kA
was 75 - 100 mv lower than for N-961. Current efficiency is
also outstanding. Other versions of these low power
consumption membranes have shown up to 98% current
efficiency in laboratory tests.
 139

-
en
~ 0.15

or-
0.20 , . - - - - - - - - - - - - - - - - - - - - ,

0.10
-3.0 kA/m2

~ 0.05
Z 0.00 ~----------------------------------------~
~ -0.05
~ -0.10
~ -0.15
CJ)
C> -0.20
as
0
> ~
-0.25 L_L-...L..-.-Jl..-....L.--'_.J.........L_....L...--L_.......-'-_.&............
-0.30
o 20 40 60 80 100 120 140 160 180 200 220 240 260 280
Days of Operation

Figure 5. Developmental membrane vs Nafion e 961 in narrow

gap test cell
The advantages of the new membrane are even greater at
higher current density. The k-factor for the new membrane
is about 20% lower than N-961. Thus a 100 mv faving at 3 kA
would become a 150 mv saving at about 4.5 kA/m. It is
anticipated that many operators will elect to use these
membranes at higher current density to gain the benefits of
higher productivity. Moreover, most operators depend upon
ohmic heating to maintain thermal balance in their cells.
Higher current density or external steam heating may be
required to maintain thermal balance as the lower voltage
will generate less ohmic heating.
water transport is about 10% higher in these new membranes
than their comparable commercial counterparts. As
previously stated in this paper, water transport of NX-966
is 10% less than N-90209. Obviously, we have the ability to
tailor water transport, within limits, to specific levels.
This is important as water transport affects many operating
parameters such as (1) maximum caustic strength, (2) the
volume of recycled brine and load on the dechlorinator, (3)
the amount of external heating required for the cell, (4)
the operating window for brine depletion, (5) the amount of
water addition needed to control caustic concentration, etc.
 1~

FUTURE EXPECTATIONS
Ch1ora1ka1i producers have much to look forward to! Nafion®
products now under test show power consumption of 2000
kwh/mT. During this decade some of our customers will use
Nafion® membranes to bring power consumption to the range of
1900 kwh/mT. That will be achieved by combining
developments on a number of fronts.
With appropriate cell design, developmental Nafion®
membranes can already operate below 2.8 volts at 3 kA/m2
And, as reported elsewhere in this volume by Yeager and
Gronowski, Nafion® membranes are capable of nearly 100%
current efficiency under ideal operating conditions.
Commercially up to 98% current efficiency should be
achievable. Coupled with Nafion® membranes' unparalleled
durability, new Nafion® membranes will continue to set
performance standards for the 1990's and beyond. Potential
benefits to ch1ora1ka1i producers are enormous.
Although the membrane constitutes a relatively small part of
the total investment in a ch1ora1ka1i plant it is the heart
of the system. Improvements in membrane performance can
yield savings in operating costs and investment much greater
than the initial cost of the membrane itself. For example,
during its expected S-year life 1 m2 of the newest Nafion®
membrane would produce 200 metric tons of caustic. Savings
in operating costs due to extended membrane life, reduced
power consumption, and increased production are estimated to
be up to $1S/metric ton or $3000 per square meter over the
life of the membrane.
Significant advances in other areas are likely as well.
Membranes tailored to specific applications will become more
common. For example, membranes that operate more reliably
in specific types of e1ectro1yzers will be introduced. As
we move into the 1990's producers are becoming more
sophisticated, and the variety of their needs increases to
match a variety of production strategies using widely
differing types of e1ectro1yzers. As previously discussed,
some operators desire the lowest possible power consumption
while others require the greatest possible reliability in
their operations. Still others desire the highest available
current density. The ability to handle high current density
can save substantial investment in hardware and reduce
investment risk. Nafi~n® membranes are operating
commercially at S kA/m an~ have been shown in laboratory
cells to withstand >8 kA/m .
Meeting this wide variety of needs requires tailoring
membranes for specific applications. At Du Pont we expect
to develop membrane products matched to end application
needs and, as necessary, to specific e1ectro1yzer
technology. Knowledge of operational factors is being
expanded, and as our customers gain more operational
experience, five-year lifetime will become commonplace.
 141

Simultaneously, operational flexibility will be increased.

The aim of Nafion® products is to remain the world's leading
supplier of membrane and related technologies to the
chloralkali industry. Within ten years more than one-third
of chloralkali production will be from membrane
installations. Cumulative production of caustic using
Nafion® products will approach 100 million tons. This
vision is not idle speculation but reflects demonstrated
performance of commercial and developmental products in
facilities around the world. Improving performance in
Nafion® products will contribute to acceleration in
replacement of classical technologies.

REFERENCE
Behling, K. J. and Peet, D. L., Modern Chlor-Alkali
Technolo~y, ed. N. M. Prout and J. S. Moorhouse, Published
by Elsevler Applied Science, London, Vol. 4, 1990, pp 63-70.
 143

A . , DIn01ID IB'lB:D I'CR 'l'D ~ (R SCDIOI

Jl'I.IlaX[[B CCDIm' BlTICIDCC IH . . . . . CILtS

G W COWELL, A 0 Ml%R.TIN AND B K REVIIJ..

ICI Chemicals & Polymers Ltd, UK

The energy perfonnance of membrane cells requires the calculation of

the sodium hydroxide current efficiency and measurement of the cell
voltage. Available methods for current efficiency calculation require
either the measurement of the mass of sodium hydroxide produced and the
amount of electricity consuned., or the analysis of the feed and exit
brine and estimation of the brine flow rates. SUch methods are either
cumbersome or subject to significant measurement errors.
A new ICI method, called the ' Sulphate Key' Method, has been
devised which removes these inadequacies. It is based sircply on a
knowledge of the cell chemistry.
The ' Sulphate Key' Method allows accurate estimation of both the
sodium and hydroxide ion fluxes and the total ion flux across the
membrane in relation to the sodium chloride flux in the feed brine.
Measurement of the sulphate ion content of the feed and exit brine is
used to relate or 'key' the other ion species in the cell. This can be
done due to the inert nature of the sulphate ion to the anolyte
conditions which means that sulphate ion in the feed brine passes
through. the cell unchanged.

I Cell current (anps)

F Faraday constant

T'Ij CUrrent efficiency of species j (%)

~aOH Sodium hydroxide production rate (t/hr)

 144
P Sodium hydroxide power consunption (kWh/t)

v Cell voltage (volts)

[ O2 ] Oxygen concentration in dry cell gas (% v/v)

[C12 ] Chlorine concentration in dry cell gas (% v/v)

[OCl] Hypochlorite concentration in exit brine (gpl)
[CI03 ] Chlorate concentration in exit brine (gpl)
[alkali] Alkalinity of feed brine (mN)

cq Feed brine flowrate (l/hr)

OE; Exit brine flowrate (l/hr)

[NaCl]F Salt concentration in feed brine (gpl)

[NaCl]E Salt concentration in exit brine (gpl)

!JC Brine depletion factor

Adjustable constants
Corrected brine depletion factor

e Specific sodium ion flux across membrane

g Specific hydroxide ion flux across membrane
q Total chlorine flux leaving the cell
Gaseous chlorine flux leaving the cell
Total molar flux of feed brine
Total molar flux of exit brine
Molar flux of species j in feed brine
Molar flux of species j in exit brine
Molar flux of species j in cell gas
Molar flux of species j transferred across membrane
Partial molar flux of species j

Mole fraction of species j in feed brine

Mole fraction of species j in exit brine
Mole fraction of species j in cell gas
 145

The 1980' s has seen the firm consolidation of the ion exchange rnerrbrane
cell technology as a robust method for the production of chlorine and
caustic soda . As well as the environmental benefits, the main
attraction of the technology has been the lower energy consumption
performance, compared to the long established mercury and diaphragm
cell technologies, in this, one of the most energy demanding of all the
chemical manufacturing processes .
leI has made a major contribution to the establishment of the
rnerrbrane cell technology since the first commercial introduction of the
leI FM21 Membrane Electrolyser in 1981. Since that time 20 FM21
Cellrooms have been energised, and a further 10 are in the design,
construction or conmissioning phases. These cellrooms represent, in
total, over 20% of the rnerrbrane cellrooms worldwide, excluding Japan.
This is a very significant achievement for the leI FM21 Technology.
The leI 'state-of-the-art' rnerrbrane cell is the FM2000
Electrolyser shown in Fig . 1. This electrolyser has the inherent
flexibility of production output, simple design of construction and
ease of maintenance characteristic of the FM21-SP Electrolysers. It is
available with or without cathode coatings . It can operate with any of
the commercial ion exchange rnerrbranes available from the alternative
rnerrbrane suppliers to give reduced energy consumption of typically less
than 2100 kWh/t NaOH. The largest FM2000 Electrolyser is a 200kA unit
with a production output in excess of 7t/d of caustic soda (100%).

Figure 1. The FM2000 Electrolyser

 146

An inherent part in the selection of membrane cell technology, and the

ongoing assessment of operational perfonnance, is the need to be able
to detenni.ne and evaluate the energy perfonnance of the cell. The
energy perfonnance of an electrochemical cell relates the amount of
product formed in the electrolysis process to the amount of electricity
consumed.
For a ehlor-alkali membrane cell this is expressed in tenns of the
sodium hydroxide power consunption P:

P = ~xV X 103 kWh/t NaOH (1)

aOH

where V is the cell voltage and TlNaOH is the % sodium hydroxide

current efficiency. It is the power consunption, as expressed in eqn
(1), which is the main factor in assessing the perfonnance of membrane
cells.
Inplicit in the accurate measurerrent of power perfonnance
therefore is the ability to measure both the cell voltage, and the
sodium hydroxide current efficiency accurately. While the cell voltage
is readily measured to the required degree of accuracy, to make
absolute and relative assessments of membrane cell performance the
accurate measurerrent of current efficiency is much more demanding.

The need to accurately measure current efficiency has been shown to be

an inherent part of the monitoring and assessment of membrane cell
perfonnance. This leads to the irmediate question as to which methods
can be used to ensure the degree of accuracy is achieved. To date two
basic methods have been used, the so called 'caustic soda collection'
or direct method, and the indirect method, of which there are several
variants.
 147

Dimct Caustic SOda COll.ecl:i.co Mat:bod

Current efficiency, 1'\ can be defined as

1'\= Current usefully enployeci

Total current

In the nenbrane cell for the production of sodium hydroxide the

sodium hydroxide current efficiency, TlNaOHt can therefore be
given by:

_ 67 x WNaOH x 106% (2)

TlNaOH - I

where ~OH is the actual NaOH production in tonnes per hour

and I is the cell current in anps.
Equation 2 is the sinplest practical expression for current
efficiency, and it would awear at first sight the easiest method to
detennine current efficiency, requiring only a knowledge of the rate of
sodium hydroxide production and the measureroont of the cellroan
current. However, it is often quite difficult to carry out in practice
to any degree of accuracy. It requires accurate measureroont of the
current, and is time consuming as it has to be carried out over a
significant period of time (~4 hours) to smooth out fluctuations in
perfonnance. In addition, the volume of sodium hydroxide and its
concentration has to be measured either by collection in accurately
calibrated stock tanks, or by means of direct flow measureroont, which
imnediately brings into question the accuracy of the flow neasuring
device. In large installations this can be particularly onerous.
Finally, the method is not awlicable to individual cells. This is a
significant drawback in that in any working cellroan it is ilrperative
to have a knowledge of the perfonnance of individual cells,
particularly to assess the end of the IISIbrane lifetime and to initiate
meaningful. and cost effective cell refw:bishnent.
Therefore although the method is si1'lple and rigorous in concept
practical difficulties mean it is not a robust method.
 148

MIIDbraDe Cell Aaolyte stoicbiclllatxy

To overcare sare of the difficulties of the direct caustic soda
collection nethod it has becare the nom for operators of membrane cell
technology to develop chemistry-based nethods for the calculation of
current efficiency. These Indirect Mathods have the advantage of
reducing or eliminating the inaccuracies and uncertainties inherent in
the direct collection nethod and are generally quick to use.
All of the indirect chemistry based nethods require a knowledge of the
various reaction processes taking place in the anolyte coopartment,
particularly those related to back migration of hydroxyl ion, and the
stoichiaretry of these reactions.
The relevant stoichiaretric reactions are:

2NaCl --+ Cl2 + 2Na+ + 2e- (3)

NaCI + OH- --+ HOC! + Na+ + 2e- (4)
NaCI + 6OH- --+ NaCl~ + 3H~ + 6e- (5)
4OH- --+ ~ + 2H~ + 4e- (6)
2HCI + 2OH- --+ Cl2 + 2H~ + 2e- (7)
NaCI + NaOH --+ HOC! + 2Na+ + 2e- (8)
2NaCI + Na~ + H~ --+ 2HOCI + ~ + 4Na+ + 4e- (9)

Equations (4-6) give the cell inefficiency reactions due to back

migration of hydroxyl ion through the membrane, while eqns (7-9)
accarroodate the acid/alkali cc:rrponents of the feEid brine.

IDdinct I'loIr/Cua:wIt IIIiJtbod

The indirect detennination of a membrane cell current efficienc:y is
based on the measurement of the size of the inefficiencies and
deducting these fran unity to give the efficiency.
The most basic indirect nethod is the flow/current nethod. This
nethod requires neasurement of the concentration of the various species
in the anolyte coopartment, including the inefficiency species
hypochlorite, chlorate and oxygen. A knowledge of the brine flows to
and fran the cellroan, or individual nerbrane cell, and the current
passing are also required. Equation (10) gives the current efficiency
calculation using the indirect flow/current nethod for a once through
alkaline feed brine system:
 149

(1+0.0268 [alkali] ~ -
I (10)
0.756 ~(0.477([OC1]-0.3)+2[C103]»%
I

where [~] is the oxygen concentration in dry cell gas, [e12] is the
chlorine concentration in dry cell gas, [OC1] is the hypochlorite
concentration in exit brine, [Cl~] is the chlorate concentration in
exit brine, [alkali] is the alkali concentration in the feed brine,
Op is the feed brine flow rate and OE; is the exit brine flow rate.
A recent publication by Tilak, Fitzgerald and Hoover [1] contains
current efficiency equations for a resaturation brine system, making
allowance for sodium chlorate in the feed brine.
Equation (10) is a rigorous treatnent of the sodium hydroxide
current efficiency. However, its weakness is that it contains tenns
related to brine flow rates and current. Accurate neasurercent of these
parameters, particularly the exit brine flow rate, are difficult and
therefore the data provided by the use of such equations may be
considered unreliable. The nethod is, however, applicable to
individual cells and therefore is of more use in a practical working
sense than the direct caustic soda collection method.

IDdizact Briaa DIIpl.eti.al Mathod

Refinenents of the flow/current nethod to accarmodate the inadequacies
associated with the accurate neasurements of flow rates and current
have and are being practised in the industry.
There is a useful tenn, the brine depletion factor OC, or
difference in the sodiwn chloride contents of the feed [NaCl] F and
exit brines [NaCl]E' which can be used in such a refinement of the
flow/current nethod. This tenn is readily obtained from the analysis
of the feed and exit brine strengths. It can be used to provide an
estimate of the ratio between the current and the brine flow rates
based on the mass balances associated with the change in brine
concentration during the electrolysis process. Flows and current do
not, therefore, have to be neasured, thereby offering an inportant
practical simplification.
 150

Using this treatment the tenns for feed brine rate ~ and exit
brine rate OE; in eqn (10) can be replaced by the tenns:

I
(11)
k

(12)

where tJc =
[NaclJ F - [NaclJ E, tJc* = tJc (K2 + K3 tJc) and K1 , K2 , K3
and ~ are adjustable constants.
The term tJc* is introduced to allow for volume changes
accompanying the electrolysis process. These are associated with the
evaporative loss of water from the membrane cell and the electro-
osmotic transfer of water through the membrane. The adjustable
constants Klt K2 , K3 and ~ are therefore directly related to the
specific membrane in use, and the design and operating characteristics
of the particular membrane cell in which the membrane is being
operated.
ICI and the membrane suppliers have used their own derivations of
the brine depletion, or 'Delta C', current efficiency nethods as an
inprovement over the more basic flow/current nethed. Again the
accuracy of the data produced using the 'Delta C' nethod depends
heavily upon the need to adequately assess the correct values for the
adjustable constants. This tends to limit its true and most accurate
applicability to small operating envelopes around the original
experinental data used in the derivation of the constants.

The difficulties and inaccuracies in neasuring sodium hydroxide current

efficiency using the prior direct and indirect nethods have prOItpted
the need for a more robust, reliable and accurate rrethod.
The 'Sulphate Key' Method now developed by the authors in ICI is
just such a rrethod. It makes no reference to the current and brine
flow rates. It also reIOOVeS all enpirical paraneters associated with
water losses fran the current efficiency equation. The practical
accuracy of the result is detennined solely by the care with which the
 151

chemical analyses of the cC>I!pO!lents of the feed and exit brine, and
chlorine cell gas are made. Mass balances or fluxes of components, are
used to generate a new type of current efficiency equation.
The sodium hydroxide current efficiency TlNaOH as defined
in eqn (2) can be redefined as

e x 100% (13)
TlNaOH =
e +g

where e is the specific sodium ion flux across the membrane, and g is
the specific hydroxide ion flux across the membrane. It is the reverse
hydroxide ion flux g which leads to the formation of the impurities
within the anolyte conpartment which can be chemically analysed.
Additional equations for chlorine current efficiencies can also be
defined for completion:

Gross Chlorine Current Efficiency n~

'C12
= ~e
+g x 100% (14)

where q is the total chlorine flux leaving the cell.

Nett Chlorine Current Efficiency n~

. 'C12
= e q+'g x 100% (15)

where q' is the gaseous chlorine flux leaving the cell.

In order to eliminate any reference to the cell current, brine
flow rates and the empirical parameters it is necessary to refer all
the fluxes in eqns (13 - 15) to a cOIllllOn base. It is convenient to use
the feed brine molar flow Mi. Crucial to this reference process is
the identification of an inert ' key' component to link or key the mass
balances together.
The Sulphate Ion is a coomon benign impurity in feed brines and it
also satisfies all the criteria for a 'key' component. It enters in
the feed brine, is unaffected by the electrolysis, is non-volatile,
does not penetrate the membrane significantly and is discharged in the
effluent exit brine.

This means that the molar flux ~ 2 S04 of sulphate ions fed to the
cell is equal to the molar flux ~a2 S04 of sulphate ions leaving the
cell:
(16)
 152

Fran this it can be seen that feed and exit sulphate ion
concentrations ~2S04 and ~2S04 respectively, can be used to generate
the 'Sulphate Key' which relates the total IOOlar feed flow Mi to the
total IOOlar exit flow ~:

(17)

This is the 'SULPHATE KEY' •

Using the stoichiaretry of the manbrane cell fran eqns (3-9) it is
possible to construct several individual cooponent mass balances, to
express the ion fluxes of interest, and thereby allow the calculation of
the required current efficiencies as defined in eqns (13-15). The
derivation used as sumas negligible levels of free chlorine and sulphite
present in the feed brine, and that the exit brine contains negligible
amounts of sodium hydroxide, sodium carbonate and hydrochloric acid.
The equations allow for acid or alkaline feed brine and the tenns should
be used as appropriate.

Sodi1JD loll .1 ame

The sodium ion balance is given by:

~a+ = ~a+ + ~a+ (18)

The sodium ion flux V~a+ across the membrane expressed as a

fraction of the sodium ion entering the cell as sodium chloride yields:

V~a+ = e ~aCl (19)

where e is the fractional brine utilisation:

e= ~a+ - ~a+ (20)

~aCI
Each of these tenns can be expressed as a surrmation of the individual
Na+ fluxes arising in the feed and exit brines respectively:

(21)
 153

or in tenns of concentrations (mole fractions) :

=J (ctacl + ctaOH + 2<ta2~ + ctacl~) (22)

= M' (~Cl + ~aOH + 2~2~ + ~aCl~)

and ~aCl = ~ NaCl (23)

SUbstituting the ' Sulphate Key' eqn (17) and eqns (21-23) into
eqn (20) yields the overall sodium ion balance eqn (24):

i i i i 0 0
CNaCl + CNaOH + CNaCl~ + 2CNa2 ~ - KS04 (C NaCl + CNaCl~)
e= (24)
i
'liacl

JIydraxida IcD 'Sa' .nee

Hydroxide ions enter the anolyte by two routes, back diffusion through
the membrane and introduction in the feed brine. The hydroxide ions
are destroyed. in a number of different ways whose overall effects are:
Destruction of hydrochloric acid:

vlOH- = .}-HCl - v"HCl (25)

Production of hypochlorous acid: There are three possible sources

of hypochlorous acid in the anolyte:
a) by destruction of hydroxide ions fran catholyte
b) by destruction of sodium hydroxide in feed
c) by destruction of sodium carbonate in feed
Hence hydroxide ion flux destroyed. by hypochlorite production is
given by:

v2OH- = ~OCl - ~OCl) - ~aOH - ~aOH) - 2~a2~ - ~a2~) (26)

Production of sodium chlorate:

~H- = 6 ~aCl~ - ~aCl~ ) (27)

Production of oxygen:

V6H- = 4 q' ~ ~aCl E~ /ECl2 (28)

 154

The total hydroxide ion flux V~H- across the membrane is giveIl by:

(29)

Expressing the hydroxide ion flux as a fraction of the feed sodium

flux yields the specific hydroxide ion flux 9

V~_ = 9 ~aCl (30)

~H- + ~H- + v3OH- + V~_ (31)

where 9 = ------;------
~aCl
SUbstituting the 'Sulphate Key' eqn (17) and eqns (25-28) into eqn
(31) and expressing 9 in terms of component concentrations yields:
i ' i i i i
'1icl + 4q CNaClE~ /EC12 - CNaOH- 6CNaC103 - 2CNa2 ~
o 0
+KS04 (C}iOCl + 6CNaCl~)
(32)
g=
i
CNaCl

AtaIIic O1lorina Ral ance

Comparable expressions for the gross and nett specific chlorine
production can be defined by a similar treatrrent to that carried out
above for the specific sodium ion balance eqn (24) and hydroxide ion
balance eqn (32). The resultant equations are:
Gross specific chlorine production q

i i i 000
q = CNaCl + '1icl + CNaCl~ -KS04 (CNaCl + C}iOCl + CNa~)
(33)
i
2 x CNaCl
and gaseous specific chlorine production q'

i i i 000 0
q' =CNaCl
+ CfiCl + CNaCl~ -KS04 (CNaCl + C}iOCl + CNa~ +2CC12 )
(34)
i
2 x CNaCl
 155

, SlJ' fbat8 1'8y' can:.nt Bfficiaacy IlqIJat:.ions

By substitution of the results of the sodium ion balance eqn (24),
hydroxide ion balance eqn (32) and alternate chlorine ion mass
balances (eqns 33 and 34) into the awropriate eqns (13-15) expressions
for the sodium hydroxide and chlorine current efficiencies using the
'SUlphate Key' Method are obtained. The resultant set of equations are
coopletely rigorous, tecbnology and scale independent. They contain no
tems directly requiring the measurement of brine flowrates and
current, as required in the 'indirect' flow/current current efficiency
method, or their estimation, as required in the brine depletion current
efficiency method.
The data required to calculate the ' SUlphate Key' sodium hydroxide
current efficiency is readily available by analysis. It does not
involve extended Il'easurement of the volumes or flowrates of sodium
hydroxide over a period of tiIl'e as needed in the ' direct' caustic
collection method.
Chlorine as well as sodium hydroxide current efficiencies can
readily be obtained with the ' SUlphate Key' Il'ethod using the sarre
measurement data. Again this is a significant benefit over the other
current efficiency Il'ethods.
Finally, the 'Sulphate Key' Il'ethod can be just as readily awlied
to individual cells as well as the total cellroom.

The sinplicity of the 'Sulphate Key' current efficiency measurement is

inherent in the nature of the data required to be Il'eaSUred in the
operating cellroan.
Cooponent analysis of the feed and exit brine streams, together
with the cooposition of the chlorine cell gas, are all that are
required. Concurrent with the developnent of the 'SUlphate Key' Method
ICI has been instrumental in the developnent: of sinple, robust, cost
effective analytical procedures to allow for the accurate measurement
of all the required cooponents in the feed and exit brines. 'Ibis
analytical methodology is built around the chemical sinplicity of
titrimetric procedures, together with the powerful analytical
 156

capability afforded by the availability of modern automated titration

equipnent.
An 'Analytical Package' has been developed by ICI, in
collaboration with CSBP & Fanners, Perth, Australia (an ICI FM21
Cellroom Licensee), which uses the Mettler DL25 Autotitrator. The DL25
Autotitrator controls the automatic analysis of the brine samples for
the required conponents NaCl, NaC103, NaCCI, Na2S04' NaOH, NaiX>3 and
HCl using a 4 titration electrode system. The overall system is shown
in Figure 2. A pen recorder conpletes the system and is used for
direct print out of the conponent data results and the recording of the
titration curves .

Figure 2. The Mettler DL25 Autotitrator System

Chlorine gas analysis is readily and accurately measured using gas

chromatography to provide the chlorine and oxygen content. The
collected data can then be fed into a pre-programned hand held cOllputer
to calculate the current efficiency results .
 157

ICI, and its 9121 Users worldwide, have been using the 'Sulphate Key'
Method since 1987 to assess the performance of the 9121 Electrolysers
operated in their cellroorns. The robustness and reliability of the
procedure have been demonstrated over a range of operating conditions
during this period.
Typical comparative data for the alternative current efficiency
rrethods are given in Table 1.

TABLE 1
Comparison of typical data for alternative current efficiency rrethods
(0.21fn2 cell; Nafion 90209; 85°C)

Current Efficiency %
caustic Collection Brine Depletion Sulphate Key
94.1 94.1 94.8
94.4 94.4 95.1
95.6 95.0 95.6
95.3 95.2 95.8
94.7 95.2 95.8
94.3 95.6 96.2
93.9 95.6 96.2
95.9 95.8 96.4
95.3 95.8 96.5
94.9 95.5 96.1
94.3 95.7 96.2
93.6 95.4 95.9
95.8 95.5 96.1
Mean 94.8 95.3 95.9
S.D. 0.7 0.5 0.5

This data was collected from a pilot cell running over a period of
weeks, this being the only scale at which caustic collection rrethod
data can be obtained for any duration of tire during the operating
period.
The higher current efficiency values recorded for the 'Sulphate
Key' rrethod, over the alternative rrethods, reflects its more robust
nature and the inadequacies and difficulties of accurately collecting
 158

sodium hydroxide, and of the assunptions made in the brine depletion

rrethod in respect of the water balance of the system.
The ' Sulphate Key' Method has wide applicability over the
potential operating range of nanbrane cells in the current efficiency
range 90-97% and the typical sulphate and chlorate specification ranges
allowed by the membrane suppliers.
The small amount of sodium chlorate made per pass through the
membrane cell, operating at high current efficiency, does require the
analysis of chlorate in the feed and exit brines to be carried out
using an accurate analytical procedure. Failure to do so will result
in same loss of accuracy in the current efficiency data recorded.

The ' Sulphate Key' Method for the measurement of current efficiencies
in membrane cells developed by ICI is a more robust and practical
method conpared to the alternative methods available in the industry.
Its value lies in the rigorous mathematical treatment based on the cell
chemistry only. The ability of the method to relate the mass balances
together using the sinple well understood stoichiometry of the system,
and the SUlphate content of the brine, means it is generally applicable
to both total cellrooms and individual cells operating within the
cellroan. It is also independent of the membrane type, or the design
of the membrane cell, and therefore may be applied throughout the
membrane cell industry.

1. Tilak, B.V., Fitzgerald, S.R. and Hoover, C.L. Estimation of

current efficiency in ion-exchange membrane ehlor-alkali cells.
J. of Applied Electrochemistry 1988, 18, 699-704.
 159

ADVANCES IN FLEMION MEMBRANES FOR CHLOR-ALKALI PRODUCTION

YASUO SAJIMA, MAIOTO NAIAO, TETSUJI SJIDI)HlRA*, HARUHISA MIYAKE*

Chemical Engineering Division / * Research Center
Asahi Glass Co.,Ltd.
2-25-14,Kameido,Koutou-ku,TOKYO 136,jAPAN

ABSTRACT

Updated advances of Asahi Glass's membrane cell technology are described.

Design concepts and advantages of the AZEC-F2 electrolyzer, basic properties
and commercial experiences of Flemion 890 series (sulfonate base) membranes,
features and economics of Fx-50 (a membrane for production of 50% caustic
soda) are introduced.

INTRODUCTION

Although less than ten years have passed since the membrane cell technology
was widely adopted in the Chlor-Alkali industry, it has now fully matured
and is recognized as a proven technology, characterized by a pollUtion free
and energy saving process.
In the last five years many efforts have been made to enhance the
operational reliability and, consequently, the following requirements have been
established as common expectations:

1) Higher current density > 3 KA/m2

2) Lower power consumption : < 2300 DC-KWH/t-NaOH
3) Longer membrane life > 2 years

Asahi Glass Co.,Ltd. (AGC) is one of the pioneers and has made many
contributions to this new field since it first synthesized a perfluoro-
carboxylate polymer, and also developed a so-called zero gap electrolysis sys-
tem using hydrophilic membranes coated with inorganic materials. Table 1
summarizes the history of AGC's advances in the membrane cell technology.
The AZEC process, in which AGC does its electrolysis plant engineer-
ing by integration with its membrane technology, was dominant initially in
japan, and has recently been spreading over the world with a high reputation
for excellent performance and reliability. So far AGC has licensed the
AZEC process to 35 clients (I6 in japan, 19 outside of japan) all over the
world, and its cumulative production capacity of caustic soda totals more
than 2.5 million tons/year, as shown in Figure 1.
 160
TABLE I
History of AGC's membrane cell technology

'75 'SO '85 '90

v v v c:::)
Remion Hydrophilic F854, F795, Fx-50 etc.
(Carboxylate-type) Surface F865 (New Development)
Membrane
V V v
Commercial New F890, F892
Production Reilforcement (S-base Membrane)
v v V
Cathode Activated Ra-Ni Catalyst New Catalyst
S. S Co-deposlted CcHIeposited
v V v V
Electrolyzer MH-Type AZEC-M F1 F2
(Metal Frame) (Rubber) (MetaO (MetaQ

Meanwhile, AGC has been moving its development steps forward

towards the next generation by realizing innovative processes, including new
functional membranes and high performance cells.
This paper describes three topics as the latest advances of Flemion
technology.

3000

>- 35Planls
:t::
0 Japan
CO
a.
<3>:-
.....
C:I: 2000
00
~(11
OZ
:I..!.
e D!c
"0"0

Q.
::J
Q) 0
>~ 1000
it:.
"3
E
:I
()

80 85 90

Year

Figure 1. Penetration of Flemion process

 161

AZEC-F2, A REFINED MONO-POLAR ELECTROLYZER

Features of the F2 electrolyzer

The F2 is the state-of-the-art mono- polar electrolyzer of unique design is
based on experience accumulated in the previously ~veloped electrolyzers.
The F2 is designed for high current density (3-4 KA/m ), and ~t is composed
of metal frames having an active electrolysis area of 1.71 m per sheet of
membrane. An outward view of the F2 is shown in Figure 2.

Figure 2. Outward view of F2 electrolyzer

TABLE 2
Features of F2 electrolyzer

Structural Characteristic Advantage

Metal Frame with

Simple Cell Structure and
Side Bus-bar Connection
Easy Maintenance

Plate-type Cathode of
High Conductive Substrate

Natural Circulation with Performance Stability with Uni-

Overhead Electrolyte Holder form Electrolyte. Concentrations

High Performance with

Narrow-gap Electrodes System Sufficient Reliability
 162

The F2 has many advantages, due to its unique design, both in perfor-
mance and reliability. As is shown in Table 2, the adoption of plate type
cathode and metal frame gives a simple structure, which makes it possible to
cut down the manufacturing cost and to reduce maintenance. A narrow gap
electrode system assures both high performance and reliable membrane use.
A large amount of electrolyte circulation due to natural gas lift results in
uniform concentrations of electrolytes overall in the cell, which brings a
stable performance of the membrane for the long term. Details of these
design concepts are described below.

Plate type cathode: This plate type electrode collects current by pass-
ing it inside of the substrate itself. This function eliminates auxiliary cur-
rent conductors. These conductors, such as clad-type lead bars and ribs are
connected to the electrode mesh, and require precise machinery works and
welding procedures. Consequently, the plate type cathode can assist in
providing an inexpensive electrolyzer. The concept of the plate type
electrodes has been already adopted in the AZEC-M electrolyzer, a small size
rubber frame cell. However, for a larger size cell it is difficult to adopt
this idea because of a great increase in ohmic loss due to the poor conduc-
tivity of the substrate.
AGC has solved this problem by adopting a plate type electrode of a
highly conductive material for the cathode substrate, while the anode frame
element adopts a conventional structure with lead bars and ribs. In addition,
the plate type cathode has the advantage of easy replacement and recoating.
The basic structure of the F2 electrolyzer is illustrated in Figure 3

Anode Frame
Membrane

Current in ~ Current out

. Cllthc)de Plate

Cathode Frame

Anode Mesh Anode Frame

Cathode Frame Cathode Current Collector.

Figure 3. Structure of F2 electrolyzer using plate type cathode

 163
3.4

Membrane : F795
32% NaOH, 90C'
3.2
~

I
c
~
3.0

:8 2.8
CD
CI

i 2.6

0 2 3 4 5

Current Density (KAlm')

Figure 4. Voltage characteristics of F2 electrolyzer

Narrow gap electrodes system: Narrow gap is the intermediate gap

between zero gap and finite gap, and it is roughly defined as a gap of 1-2
mm. The narrow gap system results in a reduction of the cell voltage con-
siderably without causing membrane damage due to a hard contact of both
electrodes. Especially in the F2 electrolyzer the narrow gap system is easily
achieved by a slight spacing, because the cathode plate has sufficient flatness
and good flexibility. Figure 4 shows the voltage of the narrow gap system,
and it compares closely to the level of the zero gap system.

Natural gas lift circulation: In order to realize a high and stable

membrane performance for a long period of operation, it is important to
keep uniform electrolyte concentrations overall in the electrolytic area, both
for the anode compartment and the cathode compartment. Uniform
electrolyte concentration is achieved by natural gas lift circulation because it
brings a large amount of flow rate of electrolytes without external pumping
systems. In addition to uniformity of electrolyte concentration, the natural
circulation system has many other advantages.
The advantages of natural circulation are summarized in Figure 5.
Sufficient capacity of an overhead electrolyte tank on each electrolyzer en-
sures that the electrolyte will fill the top of the membrane area when the
power is off. This eliminates the chance of gas mixing of Cl 2 and H2
through a pinhole of the membrane. A chlorine gas pocket at the top por-
tion of the cell, which often causes membrane damage due to salt blister
formation, can be avoided by a large anolyte Circulation rate. These con-
cepts firmly support the safety and reliability of the F2 electrolyzer.
A large anolyte circulation rate also contributes to the uniform dis-
tribution of hydrochloric acid in the anolyte compartment, when acidification
by the addition of hydrochloric acid to the anolyte is required for reducing
oxygen content in chlorine gas. In the F2 electrolyzer a high purity chlorine
gas (0.5% oxygen content) is easily obtained by USing a well designed anode
under reasonable anolyte pH condition, which does not cause membrane
damage. Figure 6 shows the relation of oxygen content versus anolyte pH.
 164

(Qo = 270m'/H)
t
Chlorine Gas
02: <1.0%
1=200KA
HCI

pH 2.5-4
CD Sufficient electrolyte hold-up for
safe operation

® Good mixing of HCI

NaCI_--I-I-?"-
210±5g/l @ Uniformity of electrolytes concs

@ No CI 2 gas pocket
QI=20-40m'/H

pH 1.5-2.0 ®

Figure 5. Advantages of natural circulation of F2 design

F795

....
~
1.6
CE: 95-96%

0'"

--
.5
c
Q)
c
0
u
0.4
0'"
0.2
0
1.0 2.0 3.0 4.0

Anolyte PH

Figure 6. Reduction of oxygen content in chlorine by acidification

 165

Project: Grass root

Electrolyzers: Sixty 200 kA
AZEC-F2 electrolyzers
Capacity: 138,000 MTPY
(100 0/0 NaOH)
Start up: June 1989

figure 7. f2 plant in Asahi Subentra Chemical Co. ,Ltd.

Operating plants
In 1989 the first f2 commercial plant, having a production capacity of
138,000 tons/year, came into operation in Asahi Subentra Chemical Co.
(Indonesia). This is a grass roots plant consisting of 60 electrolyzers, with
an amperage of 200 KA (figure 7). Good operation with an exce~lent per-
formance has been maintained under a current density of 4 KA/m for al-
most 2 years. A certain amount of hydrochloric acid is fed to the anolyte
to reduce the oxygen content in chlorine gas to less than I %. Power con-
sumption of each cell shows sufficiently lower than 2300 DC-KWH/t.
Two other f2 plants in Japan successfully started in the same year.
During 1990, this technology was licensed to Solvay, and two plants located
in Belgium and france will start within a year.

fLEMION 890 SERIES, NEW MEMBERS OF THE FLEMION FAMIL Y

New aspects of the Flemion family
flemion 890 series membranes, new members of the flemion family, are sul-
fonate base membranes which have both good mechanical properties and high
performance. Having new members, the flemion family can expand its
covering range to meet customers' demands, because sulfonate type
membranes cover the field to which carboxylate type membranes are not
freely applied. As is conceptually illustrated in figure 8, the relationship of
both types of membranes is complementary. When we have a chance to
select the membrane for the industrial use we should consider the following
factors and set the priority among them:

1) Performance factor: Power consumption and its stability

2) Product factor Quality of caustic and chlorine
3) Operation factor Operating conditions, including brine specification
4) Cell factor Cell size, gap design, flow design etc.

The existing commercial membranes are fundamentally endowed with the

necessary functions corresponding to the above four factors from the view
point of operation; however, all the membranes have different characteristics
 166

Product Factor
• Caustic Quality

Cell Factor
• Size & Shape
.Gap design
• Flow design

Operation Factor
• Electrolytes Conc.
• Current Density
• Brine Impurity

Figure 8. Flemion family and its covering range

and each membrane has advantages and disadvantages. In order to achieve

high quality operation it is important to understand the differences of the
membranes and to utilize them for membrane selection in accordance with
the minute difference in each plant condition.

Features of F890 and F892

Flemion 890 series membranes are designed so that they may have both high
performance and robustness, that are rarely compatible in the same
membrane. Ion exchange capacity of the constituent polymers, and the coat-
ing which gives hydrophilicity on the surface and the reinforcement, are op-
timized on the basis of accumulated design know-how. In addition to the
excellent durability, both F890 and F892 have good membrane resistances.
Especially in F892, the membrane resistance is equivalent to that of F795,
the existing carboxylate base membrane with the lowest membrane resistance.
The features of F890, series membranes are summarized in Table 3.

TABLE 3
. Features of F890 series membranes

1) High Performance ( 3KAlm')

F-890 F-892

Current Efficiency ("!o) 96-96.5 96-96.5

Ohmic Drop (V) 0.38 0.31

NaC1/35% NaOH (ppm) 15-20 15-25

2) Good Performance Stability

3) Applicability to Wide Range of Cell Design

 167

PI:.
I I

! so i----.t

~
c : 1: Membrane Deterioration
i : due
I
.2 Chlorine Gas pocket; : to San-blistering
;;;
intentionally made : !: :
'"0c
40 -
by placing a porous: :: :
i:ij PTFE sheet :: I :

0 30 FB92 \ i :: :
"
"
;;; :i ::
i! Cathode
:
~.
> Anode
20 Compartment: : Compartment

i ~ I 1::--::,.
E i :. I

E" 200g/l •NaCI:I .: 35%I NaOH

·c 10
Mal-designed Trial Membrane \
, I I. I

~
\
10 SO 100

Lapse of Time (Days)

Figure 9. Mechanical durability of F890 & F892 against salt blistering

Membrane durability: With regard to the durability which firstly

characterizes sulfonate base membranes, it has many aspects in the actual
operating conditions, so that it is difficult to evaluate perfectly. However,
it can be deduced from accelerated tests which simulate typical membrane
deteriorations.
Chlorine gas stagnation causes a lowering of mechanical strength due
to a salt blister. Figure 9 shows the lowering of elongation of the
membranes obtained from the accelerated electrolysis test, in which the
membranes were set to be exposed to the gas phase of chlorine and caustic
solution. Although slight decreases in elongation were observed, both F890
and F892 maintained sufficiently high values after 100 days of duration; on
the contrary, a mal-designed sulfonate base membrane that has a different
constitution in reinforcement from F890 series membrane, showed a remark-
able deterioration.
Another typical deterioration is swelling of the membrane, which
mainly results in a lowering of current efficiency. The swelling of the
membrane is caused by a lower concentration of anolyte locally in the
vicinity of the anode. Figure 10 illustrates the performance durability of
F890 series membranes against lower anolyte concentration, which was
achieved by changing the concentration periodically. Although both F890
and F892 show a certain degree of decrement in current efficiency during
the operation at lower anolyte concentration, it recovered to the normal
level. On the contrary, a mal-designed membrane which was designed for
minimizing membrane resistance showed much lower current efficiency, and
exhibited bad recovery characteristics.

Effect of brine impurity: Thanks to intensive analytical studies, the

effect of brine impurities is understood more clearly. However, its
phenomenon, including synergistic effects, is so complicated that it has not
been clarified completely. From our investigation it is revealed that the sul-
fonate base membrane has different characteristics from the carboxylate base
membrane. The sulfonate base membranes are relatively sensitive to cations
such as Ni, Mg, AI, which result in voltage increment with adsorption to the
functional group, while it is less sensitive to Ca and Sr which result in
lowering of current efficiency due to precipitation inside the membrane as a
hydroxide.
 168

98
I
200g/1 170g/1 NaCI 2009/1

.-.....
V-
,......._.--"'!"!.-
"'-" 1.
F890
i.
,., 96 I-

...-....
"

.r-
CJ
c: l _. .::::a.;.-.-.~-.-
.........

.:!
.~ -.~.""

~ ~
=
W l........ F892

'··7" '.-..
c: •
I!! 94 ~

~ ',
U "............",-
Mal-designed Trial Membrane

~
50
Days on Une

Figure 10. Performance durability of F890 & F892 against swelling

l,.,
.
CJ
c:
98

96
.- _!890(lppm,

'u ~-
= ~892
94
W
c: 92
F892 (1 ppm)
~
::J 90
(10 ppm)
U
I I
0 100 200 300

Days on Une

Figure 11. Durability of F890 & F892 against brine impurity-1

(Effect of iodide)

98~-----------------------------------------,

F890 (6g/l SO,-,

96 ~ .......- . - . - . -......- .-._._._--«"......
/ -..... - - . -..... --.-

94
F892 (6g/l SO,')

92

90

o 200 400 600 800

Days on Une

Figure 12. Durability of F890 & F892 against brine impurity-2

(Effect of sulfate)
 169

Iodide and sulfate are more important brine contaminants for economic
reasons. A solution-mined brine sometimes contains a concentration of iodide
above 0.5 ppm, which has the possibility to cause membrane deterioration;
but, there is no economical method for reducing the concentration. As for
sulfate, the purification cost depends on the concentration of sulfate in the
purified brine. Therefore, durability against both elements is important.
Performance data of F890 and F892 evaluated in the laboratory cells using
higher concentrations of iodide and sulfate in the brine are shown in Figure
11 and Figure 12. Although the operation period is not extremely long, the
data assures considerable durability in actual use for both membranes.

Experience in commercial electrolyzers

Flemion 890 series membranes have been widely used, not only in AGC's
electrolyzers, but also in various other kinds of electrolyzers. Figure 13
shows performance data of F -890 obtained from AZEC electrolyzers. The
longest operation of F -890 exceeds three years, with AZEC-M electrolyzers,
and over this period it has been keeping a good and stable performance.
With regard to experience in the F2 electrolyzers, data has been accumulated
from plant operations. The current efficiency of the plant-C (56 cells) has
been kept in the range of 96-97% during the 18 months since start up.
Regarding commercial experience for F -892, so far both numbers of cells and
duration are not large; however, it has also operated well in various types of
cells, as shown in Figure 14.

99 Plant C (F2 : 56cells)

98
8(F1)

95
A (AZEC-M)
94
93

o 12 24 36

Months on Line
Figure 13. Performance of F890 in commercial electrolyzers

l...
u
c:
98

96 :".'
_. -
..:::::ao<••••_ •• --:-S --=- ..Jl
D - A

.!!! 94
.11
:t:
w
92
c: 32-33% NaOH
~
:::J
90 9O·C
(.)
I
0 6 12 18 24

Months on Line

Figure 14. Performance of F892 in commercial electrolyzers

 170

FX-SO, A MEMBRANE FOR PRODUCTION OF 50% CAUSTIC SODA

Fx-50, which realizes a innovative process to produce 50% caustic soda

directly by membrane cell electrolysis, is a fruit of AGC's technology
development efforts. Fx-50 solves the difficult problems which are inevitable
for the existing membranes in the operation of strong caustic production be-
cause the carboxylate layer of the membrane facing the catholyte does not
work well in the condition of 50% caustic.

Features of Fx-50
The key idea to solve this problem is to place a protective layer on the
cathode side for adjusting the internal concentration of the carboxylate layer,
to the appropriate level, in which the carboxylate polymer works well. In
order to produce 50% caustic soda, another idea was adopted for a base
polymer layer to control the water transport number which determines the
caustic concentration. The concept of Fx-50 membrane is illustrated in
Figure 15. The advantages of Fx-50 are summarized below.

1) Elimination of an investment for a caustic soda evaporator

2) Dispensing of steam consumption for concentration of caustic soda
3) Availability of wide operation range for caustic strength
4) High quality of product caustic with low content of chloride

Chronology of membrane development

As is shown in Table 4, the basic research for Fx-50 started in 1985, when
a researcher discovered unusual data among a huge amount of valueless
results. Through the basic research during '85 to '88 the mechanism of this
unusual phenomenon was anal~zed, and a membrane design was examined by
using laboratory cells (O.ldm). In 1987 the development proceeded to a
pilot cell (20dm 2 ) for studying the scale-up effect. After many trials, ac-
companied with scale-up, a rigid membrane concept induding manufacturing
technology was established, and it enabled the manufacturing of a large
membrane of commercial scale. At the end of 1989, commercial evaluation
was started in our Kashima factory. Through this commercial experience
various operational know-how has been accumulated. In addition to the
evaluation in AGC's factory, further evaluations in customers' AZEC
electrolyzers are planned to begin this summer.

8
3.5N NaCI 50% NaOH

Functional Layer
for Adjusting Concentration

\
Appropriate Concentration
Membrane containing
for Work of Carboxylate Polymer
Carboxylate Polymer Layer

Figure 15. Membrane concept of Fx-50

 171

TABLE 4
Development history and future program of Fx-50

'85 '90

l.abo Cell (0.1dm')

(Basic Design) "1 1: '\
Feed-back for
Improvement

<t
0
'""-
~
Pilot Cell (20dm')
(Durability)
"J
1 Manufacturing
Technofogy

Commercial Cell (1.7m') "'----..t. .

Evaluation
(Actual Operation) Evaluation in Several
in AGC AZEC Customers

l.abo Cell (o,1 dm') 'Z.......,

(Basic Design)

III
0 Pilot Cell (20 dm')
4.,
~ (Durability)
"- l
Commercial Cell (I.7m') v••••••
(Actual Operation) End 01 '91

Meanwhile, after the successful development of the original Fx-50 (Fx-

50A), further research work has been done to reduce power consumption by
an amount of 150 KWH/t-NaOH, which sufficiently competes with the existing
process of 32%-35% caustic production. Recently a new membrane (Fx-50B)
has been successfully developed, and it has been evaluated in pilot
electrolyzers. At the end of this year a commercial scale evaluation using
an AZEC electrolyzer is scheduled to start.

Performance of Fx-50
The electrolytic Ifoperties of Fx-50A and Fx-50B under standard operating
conditions (3KA/m of current density and 210 gIl of anolyte concentration)
are summarized in Table 5. Fx-50B has been improved in performance by
approximately 200 mY of voltage and 0.5-1% of current efficiency, in com-
parison with Fx-50A. As for chloride content in caustic soda the product
caustic obtained from large cells shows less than 20 ppm of NaCI for both
membranes.
TABLE 5
Performance of Fx-50A and Fx-50B

Fx-SOA Fx-SOB
(Origilal Memb.) (Improved Memb.)

Current EffICiency ("!o) 93-94% 94-95%

Electrodes Voltage (V) 3.2S-3.35V 3.1O-3.15V

NaCI/NaOH (ppm) 5-15ppm 5-15ppm

 172

Figure 16. F2 electrolyzer for evaluation of Fx-SO

and an actual size membrane
 173

l 98 ---AZEC-F2 (2ooKA)
~ ---AZEC-M (55KA)
5i 96
'u I Annual Shut-Down
ffi 94 - ..... ....... ~.:t:::... ~
92

90
I I
o 6 12 18 24

Months after Start-Up

Figure 17. Performance of Fx-50A evaluated in AZEC electrolyzers

Fx-50A has been evaluated under commercial operating conditions since

the end of 1989 by use in an F2 electrolyzer, of which the cathode frame is
made of nickel. Thirty eight sheets of Fx-50, having a size of 1.3m by
1.6m, have been installed (Figure 16). This electrolyzer was placed together
with 29 other F2 electrolyzers which produce 32% NaOH production in the
same circuit of 200 KA, and up to now it has been keeping a stable per-
formance with power consumption of 2500 KWH/tNaOH. Fx-50A has also
been evaluated in an AZEC-M type commercial electrolyzer in one of AGC's
factories. The current efficiencies of both electrolyzers are shown in Figure
17.
The evaluation of Fx-50B has continued in two pilot electrolyzers for 5
months. As it is shown in Figure 18, excellent performance has been ob-
tained from both cells. Based on these results, the power consumption of
Fx-50B in AZEC electrolyzers is estimated to be approximately 2350 DC-
KWH/tNaOH.

~
CD
III
3.3 IIIII II I / / U7/ 11 / / / / / /-
~. 3.2 Fx-foA
......--_._} Fx-50B
11:"._.-.-
".....--...~
II) 3.1 •

Jj 3.0
W

l 96
r;
c
II)
'0 } Fx-SOB
m
c
~ 93
Fx-SOA
8
0 50 100 150 200

Days on Line

Figure 18. Performance of Fx-50B evaluated in pilot electrolyzers

 174
Economics of Fx-50
The economics of Fx-50 depends on the relative price for electricity and
steam at the location of each plant being considered. The profit of the use
of Fx-50 is realized by the elimination of the steam required for evaporation
of the caustic soda from 35% to 50% NaOH which amounts to approximately
0.6 ton/tNaOH. The loss is counted by the increase in power consumption of
approximately 300 KWH/tNaOH(Fx-50A), mainly due to voltage increase.
Therefore the higher price of steam relative to electricity results in more
profit to the process.
Plant capacity also influences the economics because the investment
for the evaporator is not proportional to the capacity. The smaller the
plant capacity is, the larger the cost ratio of evaporator to the total plant
cost becomes. Therefore, if Fx-50 is applied to a small plant, the relative
reduction of investment cost is larger than that of a large plant.
In order to argue how the feasibility of Fx-50 varies with conditions
of location, the production cost is calculated by varying cost parameters of
electricity price, steam price and plant capacity. As a premise of the
calculation, the increase in the power consumption accompanied with con-
centration from 35% to 50% is assumed to be the 300 KWH/t, and the
decrease in steam consumption for evaporation is regarded to be 0.6 t-
steam/tNaOH. The evaporator, steam boiler and cooling tower are considered
for the conventional concentration of caustic. Figure 19 shows the calcula-
tion results for Fx-50A, and Figure 20 shows the results for Fx-50B. The
solid line indicates the break-even point for 30 tId of plant capacity, while
the dotted line indicates that for 200 tId. The region defined above the
break-even line gives a profit from the use of Fx-50.

-
--
..- 30T/day
c _.--- 200 T/day
0
......
fh
CI)
20
....r.
r~---------

u
.;:
a. us/~urop-:..../ • ~ ___J~~an
E
10 ,7
-IV
CI)
en ,/
0
0.02 0.04 0.08

Electricity Price ($/KWH)

Figure 19. Break-even economics 35% versus 50% caustic with Fx-50A
 175

30T/day
- -- 200 T/day
20

10

O~~~--~--~--~--~--~~~--~
0.04 0.06 0.08

Electricity Price ($/KWH)

figure 20. Break-even economics 35% versus 50% caustic with fx-50B

Generally, in Japan, the price of electricity is more expensive than it

is in US and Europe; therefore, only a small plant capacity using fx-50A is
feasible in Japan. However, fx-50B can expand a feasible region widely, so
that all of US and Europe are regarded as feasible locations even in the
case of 200 tId production capacity. from this consideration, the feasible
cases are summarized below:

1) Large plants accessible to inexpensive electricity sources, such as

water power and atomic power
2) Conversion from the mercury process without an investment for an
evaporator
3) Small grass roots plants, or small expansion of capacity
4) Severe requirement from users for quality of caustic soda
 177

MERCURY/MEMBRANE CELLS --- WHEN TO CHANGE

A CHLORINE PRODUCER'S CONSIDERATIONS EFFECTING THE TIMING FOR

THIS CHANGE-OVER

MICHAEL R. MARCAN
Consulting Chemical Engineer
Marcan van Gelder Ltd, Givat Downs 33, POBox 7181, Haifa 31071

ABSTRACT

Most Chlor-Alkali producers using mercury type electrolysis

cells are presently confronted with the question if, and when,
to change their operation to membrane type cells.
It is difficult to give a simple answer due to the
complexity of the factors involved and the different situation
at nearly every production facility. Therefore every plant
must evaluate the question according to its own situation and
possible alternatives.
We will try to give some further insight in this complex
question by considering some of the main factors involved.
We will accentuate the existing possibilities for mercury type
electrolysis cells by changing the salt type and quality.

INTRODUCTION
In this paper we want to present some of the alternatives
available to a Chlorine-Alkali producer, operating mercury
type electrolysis cells, who wants either to increase his
plant's capacity and/or, at the same time, to reduce mercury
related environmental problems.
We will limit ourselves to chlorine-alkali production
with mercury- and membrane cells. We do not consider diaphragm
cells a viable and realistic alternative.
This paper will concentrate on
1. The major differences between mercury- and
membrane cells and their economical influences,
without going into all details inherent in a
detailed evaluation,
 178

2. Mercury cells:
- the possibilities to reduce mercury related
environmental problems,
- the built-in, unused investment in most mercury
cells for capacity increase,
3. Attractiveness of a change from mercury cells to
membrane ones.

WHY TO CONSIDER A CHANGE FROM MERCURY- TO MEMBRANE CELLS

The major reasons for a chlorine producer, operating mercury
cells, to consider a different technology, is the fact that
membrane cells eliminate mercury related environmental
problems and save energy.
As first step in the evaluation process between mercury-
and membrane cells we give in table 1 the most obvious
advantages and disadvantages of both processes.

TABLE 1
Advantages and disadvantages of Mercury- and Membrane cells

Advantages Disadvantages

MEMBRANE - Reduced energy use - Higher investment

CELLS - Elimination of Mercury
ecology problems
- More modern technology
- Less maintenance
- Easier operations
- More sensitive to
production upset
conditions
- NaOH needs conc'n
- Need Cor higher
level plant
personnel

MERCURY - Very well proven and - Mercury ecology

CELLS known technology problems
- Rather insensitive to - Higher energy use
production upset - Higher cell
conditions maintenance
- Lower investment at - More shift
high current densities operators
- Capacity increase at most
existing plants easily
realizable by CD increase
- No NaOH conc'n needed

This comparison accentuates that the most important factors to

be considered by a chlorine producer with mercury cells, when
evaluating an investment in membrane cells, are:
- How to cope with mercury related ecology problems,
- Economic appreciation of higher investment against
reduced power consumption.
 179
ECOLOGY PROBLEMS OF MERCURY CELLS
The environmental problems of mercury cells are due to
the use of mercury in the cells. As a result all fluids, such
as brine, caustic soda, hydrogen, solid waste, liquid
effluents, etc., will be contaminated with mercury.
Maintenance and operating personnel must always be aware of
possible exposure to mercury and be protected accordingly.

The extent of the ecological problem is dependent on:

1. Type and quality of the salt,

2. Mechanical condition and maintenance of the cells and
all related equipment,
3. House keeping procedures,
4. Technical level of plant personnel.
Of these factors we consider the first, type and quality of
salt, the most important one. It determines the size and
extent of the mercury ecology problem.
The type and quality of salt strongly influences:

- Frequency of cell openings for cleaning and anode

replacement, (production losses, exposure of plant
personnel to mercury),
- Quantity of solid waste, contaminated with mercury,
- Quantity of mercury containing liquid effluents.

We want to elaborate on this point of salt quality further.

We summarize for two very different types of salt in
table 2 the main quality data, in table 3 the salt quality'S
influence on the brine purification and in table 4 the salt
quality's influence on mercury cell operation.

TABLE 2
Two typical examples of salt quality
Type of salt Solar/Sea Vacuum
Main impurities:
Ca, ppm 300 - 400 10
Mg, ppm 400 1
S04, ppm 1.500 300 - 400
Insolubles, % 5 - 6 not detectable
 180
TABLE 3
Salt quality influence on Brine purification

Brine purification
Brine flow through
Purification, % of total 100 10 - 15

Salt consumption, tit C12 2,0 - 2,1 1,67 - 1,69

Solid waste, kg/t salt 75 - 90 1 - 2

(Mercury contaminated)

Operators per shift for

Brine + waste treatment 2 - 3 0,5 - 1
Chemicals for Brine
treatment, per t C12
33% HCl, kg 110 *) 1 - 2
100 % NaOH, kg 60 **) 1 - 2
Na2C03, kg 11 - 20 0,5
Filter aid, kg 4 - 6 negligible
Remarks:
*) The high use of 33 % HCl represents an approximately
3 % loss of Chlorine capacity if compared with vacuum salt
**) This use of 100 %NaOH represents an approximately
6 % loss of NaOH capacity if compared with vacuum salt

TABLE 4
Salt quality influence on Mercury cell operation
Cellroom
Frequency of cell opening every once per
for cleaning/inspection 2 - 3 months 2 years
or less
Cell operating K-factor 0,086 0,070 - 0,072
(Vm2/kA) (or worse) (or better)
Rectifier power
at 12 kA/m2 CD,
kWh AC/t C12 3530 3330
current efficiency 96 - 96,5 97,5

This example of two different salt qualities clearly

demonstrates that the use of a more suitable salt quality and
type can go a very long way to reduce mercury related ecology
problems.
Depending on the locally available salt at any given
plant all types and variations of different situations are, of
course, possible. But, most likely, all fall within the range
covered by the two examples.
 181

Once the ecology problem is reduced to acceptable limits,

the chlorine producer can concentrate on the actual economic
evaluation of a choice between mercury- or membrane cells, be
it for the expansion or modification of an existing plant or
the erection of a new facility.

THE CHOICE BETWEEN MERCURY- AND MEMBRANE CELLS

We will first consider the case of a new production facility.

We have chosen, arbitrary, the case of a plant with a
capacity of 100 tid chlorine.
In the next table 5 a summary is given of the mercury-
and membrane plant's process units included in the comparison.
Only those plant process units are included, which are
different for the two alternatives considered.

TABLE 5
Plant Units included in the Mercury/Membrane cell comparison

Type of cells Mercury Membrane

Plant Process Units

SALT

BRINE

WASTE LIQUID:
MERCURY
REMOVAL

CELL TYPE MERCURY

NAOH TREATM'T

HYDROGEN
 182

In table 6 the investment is summarized for the various plant

process units. It is followed by a comparison of the electric
power requirements.

TABLE 6
Mercur,v- and Membrane plant process units
Investment estimate (in million 1990 USD) and
Power consumption figures

Type of cells Mercury Membrane

Process Invest't Invest't
steps (MM USD) (MM USD)
SALT DISSOLVING DISSOLVING
and and
BRINE PURIFICATION 7 - 8 PURIFICATION 4 - 5

ULTRA - with
PURIFICATION cells
WASTE MERCURY REMOVAL
FROM EFFLUENTS
and
SOLIDS SEPAR' N 1

CELL TYPE MERCURY MEMBRANE 31 - 32

at 12 kA/m2 15
at 6,5 kA/m2 25

NAOH HG- with NAOH with

TREATM'T REMOVAL cells CONC'N cells

HYDROGEN HG- with

REMOVAL cells
Total plants battery limit
investment estimate 23 35 - 37
34

Electric power consumption

(per ton chlorine)
Rectifier, kWh AC
3,6 - 3,7 kA/m2 2.600
12 kA/m2 3.350 *)
6 - 6,5 kA/m2 3.000
Ancillaries, kWh AC 330 330 125

Steam for NaOH conc'n

(1 t steam 76 kWh) 55
Total kWh AC per 1 t Cl2 3.680 *) 3.330 2.780
Remark: *) For Vacuum salt this figure will be 80 kWh lower
 183

Discussion:
From this comparison it should be clear that the economical
attractiveness of a chlorine membrane plant at its present
investment cost is not too appealing for a chlorine
manufacturer with mercury cells.
This is certainly the case if the chlorine manufacturer
knows how to operate his mercury cells at high current
densities, can obtain a high quality salt at an economical
acceptable price and knows how to cope with the considerably
reduced mercury related environmental problems.
It also might involve the decision by a chlorine producer with
mercury cells to decide on an investment for upgrading the
salt quality prior to committing him to an investment for
membrane cells.
A second conclusion is that the present cost for a
membrane plant is still too high. Future developments and
pricing policies will very probably reduce these.

THE CHOICE BETWEEN MERCURY- AND MEMBRANE CELLS FOR A CHLORINE

MANUFACTURER, OPERATING MERCURY CELLS AT LOW CURRENT DENSITIES

We will now look into the case of a chlorine producer,

operating mercury cells at low current densities, who wants to
increase his capaCity by, for example, 50 to 100 %.
This is a much more complicated situation. A lot depends,
among others, on:

- Present operating current density,

- Original design parameters of the cells,
- Availability of a good quality of salt,
- Existing anode adjustment instrumentation,
- Future capacity reqUirements,
- Local existing and expected ecology requirements,
- Available process- and eqUipment to deal with mercury
related ecology problems.
Based on the locally existing specific situation a proper and
detailed assessment of all the factors involved has to be
made.
But very likely, also in this case, the evaluation of the
route to choose to reach a future minimum chlorine and caustic
soda manufacturing cost, will pOint to the continued operation
of mercury cells.
It might require additional investment to operate at an
increased or at maximum current density, updating of cell- and
anode adjustment instrumentation and the use of a good quality
salt.
The cost of this solution, on condition that mercury related
environmental problems can be sufficiently reduced, will be
considerably lower than the change-over to membrane type
cells.
 184

FINAL REMARK

We are well aware that the above conclusions are in

contrast with the general tendency as heard in the chlorine
industry. But, just this is the reason that we wanted to bring
it to your attention.
We still believe that mercury type electrolysis cells will
remain operative for many more years with gradually reducing
mercury related environmental problems.
However the major technical improvements will, undoubtedly, be
with the membrane electrolysis cells.
The pace, at which the chlorine industry will adjust to the
new developments, specifically the membrane cells, is as yet
concealed in the future.
 185

ISSUES INVOLVED IN MEMBRANE CDlVERSICN OF A CHOOR-ALKALI BUSINESS

RW.CURRY
ICI Chemical and Polymers Ltd.

ABSTRACT

Conversion of a major chlor-alkali business to membrane technology may be

essential to perpetuate the business, but raises questions which are
quite different from the practical issues involved in the conversion of
an individual plant. The conversion programme will reflect legislation
stenuning from environmental concerns over mercury. The scale of
conversion will reflect environmental pressures on tradi tiona!
chloro-derivatives. Conversion will also give rise to other changes since
environmental concerns extend beyond mercury. Improvements may be
required in other areas related to chlor-alkali technology, or just
reflecting the general pressures on the chemical industry. Safety
concerns over chlorine storage and transport may influence the location
of plants and the operating interactions between chlorine producers and
consumers. These various factors may not be easy to reconcile within a
conversion programme and could conflict with the wish to limit capital
cost.
 186

INl'RIDUCTION

'!he title of this paper is "Issues Involved in Membrane Convexsion of a

Chlor-Alkali Business". It prompts questions as to how the conversion of
a business differs from the convexsion of the individual plants within
it. Certainly the convexsion of existing plants from mercury, or perhaps
diaphragm, cells to membrane technology is a fairly 'Well-trodden path.
'!he practical issues have been discussed at length in previous symposia
in this series and elsewhere. Producers with one site may have relatively
straightforward decisions to take over membrane convexsion. However
producers with multiple sites face difficult and complex decisions in the
face of a wide range of environmental and safety issues. These will
manifest theDSel ves as challenges to the business and will become more
severe as time goes on. ICI has gained considerable experience of plant
conversions, based on the FM21 electrolyser, in many parts of the world
The paper will discuss a number of the issues which have emerged as the
company has begun a progranure to convert its own mercury cell assets. It
draws heavily on UK experience but the general principles are believed to
be of wider interest. It will focus initially on the maj or external
factors which will influence the timing and scale of convexsion. It will
then consider the potential for a membrane conversion to initiate other
changes. Finally, it will look at how these factors influence the
development of a conversion programme.

MAJOR EXTERNAL INFLUEOOES ON CHIOR-ALKALI OPERATIONS

Environmental Legislation

The introduction of prescriptive legislation will have a direct bearing

on the chlor-alkali industry. In Europe, the 3m Ministerial Conference
on the North Sea resolved that all mercury cells should be phased out by
the year 2010. Plants which do not give an undertaking by 1996, to
convert before 2000, will be required to meet demanding standards for
mercury emissions to the atmosphere. A separate measure would require all
mercury emissions to be reduced to 30% of 1985 levels by 1995. Taken
together, these measures will bring about maj or conversion from mercury
to membrane cells long before 2010.
 187

Within the UK, the situation could be even nore prescriptive. Recent
envimnmental legislation introduces the concept of BATNEEX: - Best
Available Techniques Not Entailing Excessive Cost. The regulatory
authorities will produce their own view of Best Available Techniques
for each sector of industry. This could specify the technology, plus a
range of other measures, to be used in or:der to achieve the :required
envimnmental performance. A timetable will be given for improvements
to be made to existing plants. All plants, whether new or existing,
will be :required to meet these standams unless the operator can
demonstrate that to do so ~d entail excessive cost. Although much
of the detail of this legislation has yet to be published, there are
indications that the definition of Best Available Techniques for the
chlor-alkali industry will be "non-mercury", with a timetable perhaps
as short as 4 years for this to be achieved. '!he definition may also
be "non-asbestos", but with perhaps a somewhat longer timescale for
convex:sion of diaphragm plants. '!he same legislation also applies to
downstream use:t'S of caustic soda, some of whom are coming under severe
pressure to reduce the mercury content of their own effluent to parts
per billion levels. '!he :regulatory authorities are very open about
using this as a means of exerting pressure on chlor-alkali operatox:s
to eliminate mercury technology.
The cost of wholesale convex:sion will be high and the direct
financial benefits will be low. A:recent European study has concluded
that the investment could be about $900 per tonne of amwal chlorine
capacity, whilst the reduction in operating costs could be limited to
about $25 per tonne of output.

Changes in Chlorine Demand Pattern

At the same time the industry faces the prospect that many traditional
outlets for chlorine will decline or even disappear wi thin the next few
years. It has been predicted that, by the year 2000, the world
consumption of chlorine for pulp and paper bleaching will be only
about one-thh'd of that used in 1980. Usage for water purification
could fall by a similar proportion. Of greater Significance will be the
decline in chlOl.'OCarlxm pl:Oduction J:eSulting fJ:Olll the Montreal Protocol.
Carbon tetrachloride will be most significantly affected since about 95
percent of p%X)duction is used for the manufacture of CFC-ll and CFC-12.
 188
More recently methyl chlorofonn has been subjected to limitations due to
its ozone-depleting potential. In principle it could remain in production
until 2005. However in practice the decline will almost certainly be more
rapid, as political pressure for CFC elimination accelerates and as users
opt for sul:lsti tute products.
The switch from CFCs to HCFCs and to HFCs could impact on the
integration between chlorine production units and downstream use:rs. The
replacements for CFCs contain less chlorine within their molecules and in
general the quantity of HCl discharged. per tonne of fluorocarbon produced
will be higher. With the quantity which can be sold limited both by the
size of the market and by a growing preference for burner-quality acid,
and with possible environmental restrictions on neutralisation and
disposal, produce:rs will need to evaluate their options for dealing with
this additional HCl. Process routes which can use HCl rather than
chlorine will be advantageous. Processes to convert HCl to chlorine have
generally not been considered economically attractive but in future this
perception may change. For example, HCl electrolysis may become more
conunon than hitherto. However with PVC as the only major user of chlorine
which seans likely to remain secure on a global basis, the ability to
consume HCl may depend on the extent to which HCFC or HFC produce:rs are
integrated with vinyl chloride, ethylene dichloride and chlor-alkali. An
oxychlorination unit is likely to remain a very effective HCl sink.
However with limited increase in demand for ethylene dichloride,
increased production from oxychlorination must lead to reduced production
by direct chlorination.
The overall effect may be that individual producers see a reduction
in total chlorine output, at least for a number of years.

These themes could be developed in greater detail but it is clear that

for a producer with multiple sites, decisions over membrane conve:rsion
must be taken in a much broader context. At the very least, the
conversion strategy needs a clear appraisal of the relevant
legislative framework, the changes in chlorine demand pattern and the
sensible location of plants in tEmlll of integration between chlorine
producing and consuming plants. However this will not give a complete
 189

pictul:e. Public expectations and environmental legislation may extend

much further than elimination of mercury and certain chloro-deri vati ves.
A membrane conversion may either initiate, or be seen as an appropriate
occasion to implement, a wide range of other changes. Certainly within
the UK, the regulatory authorities have made it very clear that
elimination of mercury, whilst very welcome, will not prevent all other
aspects of a chlor-alkali operation from coming under close scrutiny.
Features which may have been accepted in the past may not be accepted in
the future. Some of the potential improvements will be specific to
chlor-alkali plants. others will be typical of the improvements being
sought throughout the chemical industry. In addition there may also be
major safety issues being addressed.

Chlor-Alkali Issues

Three examples will be considered from the range of possible issues.

Type of Brine Circuit. Although the majority of plants use some

fOlJll of brine recycle system there remain a number, particularly in
proximity to salt deposits, where once-through brine systerrs are
economically attractive. I t is not clear whether these plants will
come under pressure to adopt recycle. Wi thin UK environmental
legislation there is now the concept of a Best Practicable
Environmental Option. '!be underlying idea is that where a process will
involve the discharge of sulJstances into lOOre than one environmental
medium, it should be designed so as to minimise pollution to the
environment taken as a whole. '!he way in which the authorities will
interpret this remains uncertain since it raises many difficult
questions. Is it better to discharge a saline effluent to a tidal
estuary than to discharge carlJon dioxide, probably plus SOK and IDx,
to the atIooephere in order to generate steam to make white salt
available for resaturation? Plants close to salt deposits may have
options regarding possible brine recycle systeue but which is the lOOSt
environmentally acceptable? Is it a conventional system based on solid
salt, or is it preferable to reconcentrate the depleted brine leaving
the cellroom using an evaporation un! t and mix with new brine obtained
by solution mining? Al ternatively, should the depleted brine be
returned to the salt boreholes and be resaturated underground?
 190

Analysis of these options in economic or technical tenns is fairly

straightfozward. Analysis in environmental terms is more difficult.
Sodium Chlorate. This can be considered as a new environmental
issue introduced by membrane technology since it is fonned to a
significantly greater extent than in mercury cells. Chlorate
destruction units have been included in some membrane plants in the
context of brine resaturation system;. Whilst the available evidence
suggests chlorate is not particularly toxic to fish, the concentration
in the purge from a resaturation system could be high enough to
present problem;, although the discharge can be avoided by evaporating
the purge to dryness. Chlorate is significantly more toxic to species
lower down the food chain These could be adversely affected at the
concentrations present in the discharge from a waste brine system. It
is likely that chlorate destruction will be required for some plant
locations. ICI has initiated further investigations into toxicity and
al ternati ve treatment methods.
Bromine Compounds. Depending on the source of salt, significant
quantities of sodium bromide may be present and give rise to bromine or
bromine chloride in the chlorine product and to sodium bromide and sodium
bromate in the depleted brine. For a variety of reasons there is
increasing demand for chlorine with very low levels of bromine
contamination Safety considerations dictate that this should be
achieved wi. thout the distillation of liquid chlorine, which has been
the traditional method of purification other methods of debromination
have been proposed and ICI is continuing development work in this area.
However all the potential methods give rise eventually to a saline
effluent containing bromine compounds. The acceptability of such
discharges remains to be established, certainly within the UK.

Chemioal IndustJ::y Issues

Whatever specific issues it may face, the chlor-alkali industry remains

part of the chemical industry as a whole, and changes are taking place at
this level. Again, many examples could be considered, but discussion will
be confined to two.
 191

Refrigerants. It is COllllOOIl practice in the UK for chlorine to be

liquefied at low pressure, say about 2.5 bara, usinq a CFC zefrigerant.
The impact of the Montzeal Protocol on CFC availability will requize a
zeview of liquefaction system!3 and raises many questions. Will an HFC
have the same properties as the CFC it replaces? can it be used within an
existinq zefrigeration system? Will the HFC be available on the requiI:ed
timescale or will an HCFC be requiI:ed as an intennediate solution? Moze
traditional zefrigerants such as antIIOIlia or carbon dioxide may be
consideI:ed again, despite the safety considerations which led to their
decline and their association with global wann:Lnq. Finally liquefaction
at high pressure usinq water may have to be consideI:ed, despite the
safety arguments against such practice. In this issue theze is the
potential for an envimnmental improvement to conflict with safety
considerations and it is unclear how the authorities in the UK will
approach this.
General Effluent Contaimnent. The need to avoid accidental
discharge of effluents leads to a ranqe of possible p.rotective measures.
Should magnetically-driven pumps be used in pzeference to pumps with
conventional glands or mechanical seals? Should all effluents be tzeated
on-plant rather than in a central facility? Central tzeatment may have
the benefits of economy of scale and the potential for neutralisation or
treatment of effluent from one plant by that from another. However it may
be unable to handle all the combinations of effluent which could arise
due to plant upsets or shut-downs. On-plant treatment may be moze
expensive to build and operate. However it does focus moze clearly the
possibilities for zecycle rather than tzeatment. It may also promote
development of tzeatment technologies which avoid reagents which may be
harmful in them!3elves. A further measure would be the use of alx>ve-gJ:OUIKi
pumped effluent transfer system!3, constructed from modern
corrosion-resistant materials, rather than traditional earthenware
underground gravity drains. '!he objective is the avoidance of soil, and
hence groundwater contamination, and ensurinq pipework is clearly visible
and amenable to routine inspection.
 192
Safety Issues

It is right to also recognise concerns over the safety of the chemical

indushy. I believe society will continue to seek reductions in the risk
they perceive to be associated with our activities. Although the safety
recom of the chlor-alkali indushy is undoubtedly good, there:remain
concerns over the size of chlorine inventories and. over the tonnages of
chlorine noved by mad and. rail. In some countries there is interest in
enclosing stock tanks and. tanker loading/off-loading points in leak-pmof
structures which vent to an emergency absorption plant. Within ICl we
have certainly ~een storage inventories reduce over the yecu:s and. liquid
chlorine handling systema have been sillplified to reduce the scope for
operator error. Our plans for further development of our sites are based
on zero movement of liquid chlorine between them.
A membrane cOnveISion is likely to be a high profile issue,
certainly in the OK where legislation :requires that the process of
vetting the proposed development by the regulatory bodies takes place
in the public arena. It may well initiate d.enIaOOs for other
iII'!Provements. If these focus on chlorine inventories or handling
systema, they may involve changes in the way a production site
operates. Reduced inventories for exaIIple would bring a much closer
coupling of chlorine producer and consumer, giving less flexibility
for independent operating rates.
In recent yecu:s increasing use has been made of Quanti tati ve Risk
Assessment to examine the benefits of potential safety improvements. QRA
is not a precise science. It:requires many assumptions to be made, each
of which may be subjective and. open to challenge. It must also be said
that an operation does rot become safe just because a QRA calculation
p.rod.uces a result which meets a pre-set criterion. Safety essentially
derives from the manner in which a plant has been designed and. built, and.
ultimately how it is operated and. maintained. However, if QRA is used in
a comparative manner, with consistent assumptions, it can indicate the
benefits of changes to plants or to rore broad-scale operations.
Within ICl we have used QRA to analyse changes at a number of our
sites. At one site, for historical reasons, virtually all the chlorine
p.rod.uced was used for ethylene dichloride production at a vinyl
chloride plant. 'lb supply a second consumer, liquid chlorine was
imported from another site about lOOlan away. Inventories of liquid
 193
chlorine wexe maintained at both the pnXluction plant and the liquid
consumer. QRA showed that off-site risk could be substantially reduced by
construction of a liquid chlorine pipeline between these two plants and
eliminating the inventory at the consumer. An added benefit would be a
reduction of about 20% in the chlorine movements wi thin UK. '!bese safety
improvements wexe an important part of the justification of the scheme.
It was seen as compatible with future membrane conversion on the site and
came into operation about two years ago.
At another ICI installation, large scale chlorine production is
concentrated in one part of the site. Chlorine is distributed, mainly in
liquid fcn:m, to a range of COIISumeJ:S some of whom are 2km away. The
chlorine distribution network involves over 5km of pipework and
includes a very large central storage inventory. In considering a
membrane conversion of this site, a number of options wexe identified,
instead of simply pez:petuating the present configuration. QRA showed
that risk contours could be reduced by about 25% by substantial
reduction in chlorine inventory. The contour reduction would be about
50% i f chlorine production units were close to each consumer, i f
liquid chlorine inventories were eliminated and direct cell gas
transfer was introduced. Such furdamental reorganisation of the site
raised major operability questions. It would require membrane cellroom
capacity to be based mre on instantaneous than on average levels of
chlorine demand In addition, a plant which currently uses chlorine as
revaporised liquid may not be able to accept the impurities present in
cell gas without major IOOdification. '!he cost of all the alternative
schemes was higher than simply converting the existing cellroons. In
rost cases the premium was 30-50%. However in the option with the
greatest improvement in safety, the premium was about 100%. Analysis
of this sort provides a basis on which the cost-effectiveness of
safety improvements can be examined and will undoubtedly figure in
discussions with the regulatory authorities over the development of
the site.

Again, all these themes could be developed much further. However, my

basic point is that a membrane conversion may well require an operator to
think about a much wider range of issues. He must therefore make
provision for this within the business appraisal of the conversion and
the resources required to implement it.
 194

From what has been said above the conversion cost for a multi -site
business will be high. '!he expenditure may take place within a period of
only a few yean! and existing plants may be converted long before they
have become uneconomic. '!he business therefore must take a view of all
its plants together, rather than each one in isolation.

Chlorine Demand

In view of the points made earlier, an overall review should begin with
the chlorine consUlllEU.'S on which the business depends. '!he present
portfolio is an inadequate guide. It will look very different in ten
yean! time. Predicting the future is notoriously difficult but the
business needs a clear view of each site. Will the chlorine demand
decline or grcNI? If the decline is dramatic, will the remaining
chlor-alkali system remain viable? Would it be better to consolidate it
with another site, or in an extreme case to exit that particular segment
of the business altogether?
'!he case for consolidation may be strengthened if major expenditure
on safety and environmental issues, other than the chlor-alkali
technology, is required. Each site will represent a potential increment
of expenditure. Other multiple-site businesses have recognised that it
may be better to have fewer sites to improve, even if that results in
higher product distribution costs. Similar considerations could well
apply wi thin chlor-alkali businesses.

The Timing of Convel:sion

Turning to the actual timetable and sequence of conve:rsion, a number of

potentially conflicting facto:rs can be identified. A phased programme, in
which the conve:rsion of the plant with the wo:rst environmental
performance takes place fi:rst, with the remainder following in an orderly
sequence, seems attractive since it makes the largest environmental
improvement fi:rst whilst the investment takes place over a period of
time. Narrow financial considerations may suggest that conve:rsion should
be delayed, or at least extended, for as long as possible. However such a
policy may conflict with environmental legislation. The Montreal Protocol
 195
demonstrates the scope for specific dates for envirorunental improvements
not only to :be legislated but to advance as time goes by. As yet, there
may :be few examples of this other than in relation to CFCs, but there
seems no obvious reason to assume that the European target dates for
mercury elimination will not advance in a similar way. Regulatory
authorities may not recognise the cOl1Ullercial arguments for phased
compliance with legislation. They may see anything other than concurrent
conversions at each site as undue lenience towards industry. It therefore
seems prudent, to say the least, for multi-site operators to :begin their
conversion sooner than may :be strictly required by their national
legislation. This approach enables them to retain a high degree of
control over their progranune, rather than :being constrained to react to
external events and with a timetable which is too short for all the
issues to :be properly addressed.

Containing C&pi tal Coats

With the direct :benefits from the expenditure :being so low, means of
limiting the overall capital expenditure will :be a maj or priority.
Re-use of equipment. In many cases the existing cellroom buildings
and rectifiers will :be re-usable. However for this to :be practical,
conversion must take place when chlorine demand has fallen to a level
which permits a particular cellroom to :be wholly, or partly, shut down.
If this conflicts with the environmental pressures, conversion may
involve a completely new cellroom or conversion of the existing unit in
small stages, with all the complexity and cost of protracted engineering
construction wi thin an operating plant. The principal of re-use can
hopefully :be extended to the brine purification and chlorine handling
systems, although modifications will probably :be required. The age and
condition of this equipment must clearly :be coapatible with a new
membrane system. One particular aspect of this is the question of mercury
contamination. This must :be removed from any systems from which it could
contaminate the new electrolysers. Another issue is the extent to which
products, particularly caustic soda and hydrogen, will continue to :be
contaminated through the retention of existing facilities.
Repeatable designs. In principle there could :be savings in design
costs resulting from a lOOdular plant ie a staIX!ax:d design which could
simply :be repeated on different sites. Sites with large chlorine output
 196

would have several modules. Smaller sites may have one or two. Within
ICI, whexe theJ:e is a very l~ difference between the smallest and the
largest sites, we have really concluded that economy of scale in a large
unit outweighs the benefits of x:eproducibility. In addition theJ:e az:e
major differences in the equipment which can be J:e-used at each site. We
az:e theJ:efOJ:e thinking lOOJ:e in tEmlV!! of generic designs for the cOJ:e
features which will be J:eqUi.J:ed at all sites so that, having thought a
problem through at one site, we take the same approach at another even if
the equipment is of a diffeJ:ent size.

Chlorine Plant capacity

Pel:haps the II'OSt significant contribution to cost containment lies in

minimising the installed capacity. However this raises difficult
questions over the operating patterns of the chlorine producer and
consumexs. '!he minimum cost position would pmbably arise if the
chlorine output equals the average consumer demand. This presupposes
that it is possible to buffer the variations between the diffeJ:ent
plants. Traditionally this has meant a large liquid chlorine
inventory. If, as has been discussed earlier, safety considerations
will lead to J:educed inventories and, as is quite likely, theJ:e az:e
p.robleus in changing the basic operating patterns of the consumexs,
chlorine plant capacity will be higher than the average. In the
extreme case it may have to J:eflect peak instantaneous demand.
AnalysiS of ICI operations shows that on a small site, with a single
liquid chlorine consumer and storage inventory of less than 10 hours
production. a chlorine plant could J:equiJ:e as much as 20% capacity above
the average rate. '!he situation is improved. on a larger site wheJ:e
several consumexs az:e being supplied in COIIIOOIl, particularly i f one of
them can act as a swing consumer ie can vary its load over a wide range
at short notice. In practice this is likely to be a direct chlorination
unit. This may be linked to a vinyl chloride plant which will itself
depend on sul:stantial ethylene dichloride stocks to enable it to operate
steadily. However existing J:'eactOJ:S will have finite capacity and may be
incapahl.e of al:Jsorbing all the chlorine which is available when other
plants az:e disrupted. si~taneously. Some over-capacity may be inevitable
with chlorine production having to fluctuate, to same degree, in J:eSponse
to changes in consumer plant operation.
 197
Plant capacity may also need to be considel:ed on the basis of the
structure of electricity tariffs. In the UK electricity prices change at
half-hourly intervals. Depending on his contractual arrangements, a
ehlor-alkali pJXXiucer may be subj ect to these variations or may have a
composite tariff comprising, typically, 5 or 6 different price bands
within a 24 hour period. '!he price in the most expensive band can be
twice as high as in the cheapest band, or even more. There could be a
financial argument for addi tiona! chlorine capacity to exploit this by
raising chlorine output when electricity is cheap and l:educing when it
is expensive. Such an operating strategy ~d conflict with pressure
to l:educe inventories since consumers rely on liquid chlorine stock to
operate steadily despite a fluctuating chlorine supply. However this
type of tariff is well established in the UK and, in the context of
the return to private owneJ:Ship of the electricity supply industry,
has every sign of continuing.
A chlor-alkali producer, wiShing to minimise the capital expenditure
necessary to satisfy enviromnental considerations, may find this is in
conflict with the thrust of safety pressures and of electricity prices.
We have the prospect of three different strands of government policy with
major potential impact on the industry which, regrettably, have every
sign of leading in different directions.

I began by raising the question as to how the conversion of a business to

membrane technology diffel:ed from the conversion of the individual plants
within it. My principal objective has been to establish the potential for
a membrane conversion to raise many other issues and to be the focal
point for a wide range of other changes. Many of these will stem from
public perception of industry, and the influence this has on legislation.
'!he elimination of mercury is certainly not the only issue. A large
IlUlIIber of other environmental and safety issues will be involved and need
to be thought through in the context of the changing ehlorine
supply-demand balance within the business. My discussion has been
admittedly selective. 'lhere are many other significant issues which could
have been included such as the impact of PVC recycling on chlorine
demand, or the recycle of salt from waste incineration plants to
 198
chlor-alkali processes, or the various technical p:roblems currently
associated with membrane technology. However I hope I have said enough to
make it clear that there are major issues which need to be addressed at
the level of the business rather than the plant.
It will fall to individual businesses to develop their own view on
many of these issues. There will be different emphases in different
situations. There is no single strategy which can be presented as
univel:Sally correct. However strategy is IlIClSt certainly needed. OUr
existing plants, whether they use mercury or diaphragm cells,
represent a technology plateau. Although individual changes and
improvements have been made over the yeal:B, the fuOOamental stability
of the technology has provided a firm production base on which our
businesses stand. The changes which will take place over the next ten
yeal:B or so should ideally move the industry to a new plateau, which
will provide a similarly firm production base. It is unlikely that
this can be achieved unless all the relevant issues are considered.
There will be scope for decisions to be made as to whether all issues
will be tackled sinrul taneously or some left until a future date;
whether changes will be made at the last possible date permitted by
the relevant legislation, or whether a more proactive policy will be
followed. However the convel:Sions of individual plants should take
place as specific steps towards an overall business objective.
It is common today to talk about industry having a licence from
society to operate. This is certainly so in the case of the chlor-alkali
industry. The convel:Sion strategy nrust extend far beyond the replacement
of mercury with membrane if the industry is to continue to enjoy such a
licence.
 199

PRODUCTION OF 70% CAUSTIC SODA DlRECI'LY FROM

DECOMPOSER, AN EFFECTIVE WAY TO SAVE ENERGY

A.J.ACIOU
Salgema Industrias Quimicas SA, Brazil
and
E. F. POWELL, F. C. VIANA
Cia. Quimica do Reconcavo - CQR, Brazil

ABSTRACT

70% caustic soda directly from the decomposer has been successfully producing in a
Mercury cell. An important energy saving has been achieved since the conventional
process to evaporate caustic soda from 50% to 70% has demanded 0.7 - 0.9 ton of
steam per each ton of caustic soda (100%), which is equivalent to a saving of 280 -400 KWh.
Several plant tests were carried out either testing DE NORA or UHDE cells. Periods
up to 60 days operating without interruption have been performed in a vertical
decomposer, in which an activated graphite with Fe (0.3%) and Mo (0.1%) has been
used.

INTRODUCTION

Cia. Qufmica do Reconcavo - CQR, a subsidiary of Salgema Holding and located in the
Petrochemical Complex in Cama~ari, Bahia, Brazil, has been successfully producing
70% caustic soda directly from the decomposer in a Mercury cell since 1984. A
remarkable amount of flaked caustic soda has been produced and commercialized
leading to an important energy saving. The plant has operated a circuit of 38 DE NORA 14H3
cells, with current density of 10.4 KNm2 . Only ten cells in the mentioned circuit have
been able to produce 70 % caustic soda, whose capacity amounts to 15,000 tJ year.
Besides being commercialized as flakes, 70% caustic soda can also be concentrated to
produce 99% anhydrous caustic soda.
 200

PROCESSENERGYSA~NG

Conventionally the Mercury cell process has produced 50% caustic soda, while
Diaphragm and Membrane cells processes have produced 11% and 35% caustic soda
respectively. Differently from the other ones, the Mercury cell process has presented a
peculiar characteristic. The concentration of caustic soda, which has been produced
through this process, neither has had influence in the current efficiency nor in the
energy efficiency. The direct 70% caustic soda production from the decomposer has
demanded no extra energy consumption when compared to the process to produce 50%
caustic soda. Such fact is easily understood because the product - sodium amalgam,
Na(Hg) - which is obtained in the electrolyzer, has energetics level higher than those
ones of 70% and 50% caustic soda. Thus the amalgam Na(Hg) decomposition reaction,
which takes place in the decomposer, is an exothermic reaction and it is shown in
equation 2. The reaction heat can be calculated through the heats of formation of the
compounds, as shown in table 1.

GWBAL REACTION IN THE ELECTROLYZER

NaCI + (Hg) -+ 1/2 Clz + Na (Hg) + 77,940 Cal (1)

GWBAL REACTION IN THE DECOMPOSER

Na (Hg) + H20 -+ NaOH + 1/2 H2 + (Hg) - 18,730 Cal (2)

TABLEl
Heats of Formation

Compounds Cal/mol

Na(Hg) -19,900 [3]

H2O -68,370 [3]
NaCI -97,840 [3]
NaOH(loo%) -102,000 [7]
NaOH (70%) -104,000
NaOH(50%) -107,000 [3]
 201

(Cal/mol)

-19,900 _~C!QIR -

0 0 0 0 0 0
<t
a> ,...r<l <t
a> ,...r<l <t
a> ,...r<l
t.:"
,... t.:" .n ,...
,...
-
r<l ,... t:D
+ I + I + I
NoCI
- 97, 840
NoOH( 100 %)
-102,000
No OH (70 %)
-104,000
NoOH ( 50%)
-107,000

Fig.l. A plotting showing the energy variation for each compound.

It is illustrated in fig. 1 the energy variations to obtain products as Na(Hg), NaOH (50%),
NaOH (70%) and NaOH (100%), according to equations 1 and 2. The mentioned
peculiarity of the Mercury cell process has allowed the advantage of achieving a more
concentrated caustic soda, either being an intermediate product to produce anhydrous
caustic soda (99%) or being a final product (70%) to be commercialized as flakes,
without additional energy consumption. The caustic soda concentration limit has been
73%, above that there is no temperature able to keep the caustic soda fluidity. The
conventional process to evaporate caustic soda from 50% to 70% has demanded 0.7 to
0.9 ton of steam per each ton of caustic soda (100%), which is equivalent to 280 to
400 KWh . It has been the saving achieved per each ton of caustic soda produced in
regard to the normal evaporation process.

EXPERIENCE ON 70% CAUSTIC SODA PRODUCTION

General Considerations

It has been reported in the state of art [1], [2], [4], [5] the possibility of producing 73%
caustic soda directly from the decomposer. Nevertheless most of the authors have
omitted the details regarding to the production process. Some authors have mentioned
the necessity of a special design for the decomposer as well as different operational
characteristics referring to the production of 50% caustic soda.

At first glance, two adverse features were identified to achieve a safe and continuous
70% caustic soda operation. The first one regards to the amalgam decomposition in the
decomposer, and the second one refers to the lower temperature to be established in
virtue of a lower heat generation, due to a lower caustic soda dilution.
 202

• On the first case, the rate of amalgam decomposition, which is determined by the
electromotive force, E, eq.3, decreases for high caustic soda concentrations into the
decomposer. The fig.2 shows the variation of the electromotive force as a function of
caustic soda concentration.

E = Eo + RTln [Na(Hg)] [H20]

(3)
F [NaOH]
1.0

0.9

>
u:
LLi 0.8

0.7

0.6 (0 30 50 70
NaOH %

Fig.2 Electromotive force versus caustic soda concentration for

Temperature = SO" e and 0.3% Na (Hg). [data from ref.1]

In order to surmount such difficulty, it has been fundamental to alter the kinetics of
amalgam decomposition reaction by using a catalytic agent to promote higher velocity
to this reaction. Such changes can be achieved by using techniques already known,
which aim at an overvoltage reduction of hydrogen liberation into the graphite cathode
of the decomposer. In fact, the mentioned techniques have meant the graphite
impregnation with metals or metal salts, which have the property of reducing the
overvoltage to liberate hydrogen. Deeper discussions on amalgam decomposition
kinetics are indicated in references [S] to [13] .

• On the second case, one can conclude that in a 70% caustic soda process, the
temperature has been lODe inferior than that one of the 50% caustic soda process,
when keeping a same variation of ~e Na(Hg) for both processes. Either the process
heat balance or the practicing have indicated such difference at the temperature,
since the liberation of dilution heat is lower in the 70% caustic soda process.

As follows, it is described our experience to produce 70% caustic soda directly from
conventional vertical decomposers, originating of chlor-alkali technology traditional
 203

suppliers, DE NORA and UHDE. The parameters, such as, amalgam concentration
and decomposer temperature were evaluated.

Plant Tests Procedures

The first tests started in another plant in 1982. UHDE 130/11OG cells were used, with a
decomposer consisting of 270 Kg of activated graphite with iron, to 70% caustic soda
operation. The cell operated with a current density of 10KNm2 and specific mercury
flow at about 600 Kgrnol/h.m2 in the decomposer. Such experiment was not very
successful and was repeated later with a DE NORA 14H3 electrolyzer and a
decomposer of different dimensions. Activated graphite with iron was also used. The
operational conditions were 10,4 KNm2 and specific mercury flow at about
430 Kgmol/h.m2 (Table 2). During the plant tests (as shown in fig.3), a gradual increase
of amalgam concentration was observed in the inlet and outlet cell, as an effect of the
increase of caustic soda concentration, which indicated a reduction of amalgam
concentration when caustic soda content was reduced in the decomposer. Although a
simultaneous increase of amalgam concentration was observed in the inlet and outlet
cell, the dC Na(Hg) had kept almost constant. Such behaviour demonstrated an
insufficient graphite activation to promote a complete amalgam decomposition in a
more concentrated caustic soda solution. Therefore, the plant tests to concentrate
caustic soda were characterized by a simultaneous increase of amalgam concentration
in the inlet and outlet cell up to reach inadmissible levels. As a consequent effect, a
hydrogen evolution in the electrolyzer was observed, requiring the caustic soda
deconcentration.

TABLE 2
Decomposer and Graphite Data
DE NORA 14H3 UHDE 130/1100
DECOMPOSER
• Type Vertical Vertical
• Dimension(mm) 0760 x 800 0850 x 600
• Graphite Weight(Kg) 360 270
• Specific Flow (Kgrnol/h.m2) 430 600
GRAPHITE
• Type SIGRI-EH-X SIGRI-UCAR
• Size(mm) 20-30 15-25
• Fe Content(ppm) 3,000 6,000
• V Content(ppm) 20 20
• Mo Content(ppm) 1,200 1,000
 204

74.00

68.00

0~
J:
0 62.00
0
z

56.00

50.00

0.80

0.60

0~
-;;.
J:
0.40
0
z

0.20

0.00
20 40 60 80 100
HOURS ON LINE
-No(Hg)in +No(Hg)out
Fig.3. Decomposer performance of DE NORA 14H3 cell using
an activated graphite with 0.3% Fe.
Another plant test was carried out with a UDHE cell, at this time by using a previously
activated graphite with Molybdate of Sodium. The Molybdenum residual content in
the graphite was 0.1 %. This graphite also had an iron content of 6,000 ppm. Figure 4
shows the operational performance of UHDE decomposer during a period of 213
hours. A gradual increase of amalgam concentration in the inlet and the outlet cell was
also observed, although the amalgam concentration had kept almost constant in the
inlet cell. The conclusions can be demonstrated as follows:
• the graphite activation capacity has been considered good, therefore being able to
reduce the high amalgam concentration to tolerable levels.
• the variation of amalgam concentration AC Na(Hg), has gradually increased,
indicating a Hg flow reduction. Such fact can be explained as an effect of a lower
amalgam flow into the electrolyzer. During a plant routine operation, this condition
can be interrupted by action of the operator.
• An increase of temperature in the decomposer has also been observed, as an effect of
a lower Hg flow (higher AC Na(Hg». The relationship between the temperature of
decomposer and increase of ACNa(Hg) is illustrated in fig.5.
 205

O.B

0.6

0~

a.
:I:
0.4

0
z
0.2

0.0 +n-rnmmTTTTTTTTTrrnr-i-n"TTT"TTTTTTTTTTTT"TTTrrn"TTT"TTT""T"TT"l
53 93 136
HOURS ON LINE
-Na(Hg)in + Na(Hg)out ONa(Hg)diff
Fig. 4. Performance of the UHDE decomposer using an activated
graphite with Fe (0.6%) and Mo (0.1 %).
130

124
u
0

IIJ II B
a:
=>
I-
«
a: 112
IIJ
a.
:;:
IIJ
I-
106

100
0.40

0.30

0~

~ 0.20

'"
:I:
0
z 0.10

0.00
53 93 213
HOURS ON LINE

Fig.5. The temperature variation of the UHDE decomposer as

a function of the variation of amalgam concentration.
 206

CONCLUSIONS

• Plant Routine Operation

The knowledge acquired during plant routine operation to produce 70% caustic soda
in vertical decomposer has demonstrated that such process has been more critical and
has requested additional cares either to the cell renewal or during the operational
procedures. The decomposer has shown evidence of a shorter cell life time than that
one showed to produce 50% caustic soda, however, it can require an activation in a
period of 6 months. Although the cell life has had a tendency to be shorter, periods up
to 60 days operating without interruption can be presented, as it is illustrated in fig.6.
On the other hand, the temperature of the decomposer has shown a tendency to be
lower than that one of 50% caustic soda operation, for a same ~C Na(Hg) in both
processes. Nevertheless this temperature level has not compromised the operation
safety (risks of caustic soda crystallization). As the ~C Na(Hg) in the 70% caustic soda
process has had a tendency to be higher than that one in the 50% caustic soda process,
the temperature of the decomposer for both processes has been very close. Therefore
there is no necessity of additional heat in the decomposer. A good operation has
requested a well activated graphite. Our experience has been using the doubly activated
graphite with Fe (0.3%) and Mo (0.1 %), which has seemed to supply a synergistic effect
in the amalgam decomposition. The decomposer basket must be well compacted and
pressed in order to avoid a premature abrasion of the graphite and consequently the
loss of its activity. It has also been important to have a cell bottom in good conditions.
The quality of brine has been fundamental, mainly regarding to iron and calcium
contents, because a higher tendency to develop butter in the electrolyzer has been
observed.The butter development is followed by a mercury flow reduction which has
led to an increase of sodium content in the amalgam. The efficient procedures to
reduce the levels of sodium content in the amalgam and restore the good mercury flow
conditions have been either a water injection in the amalgam stream of the inlet and
outlet cell or the cleaning of the end boxes. Such procedures have been effective when
the activity of graphite has been preserved. It has been also useful to inject molybdate
of sodium solution (200 ml-30% sol.) in the water process stream in order to reduce the
amalgam levels and extend the life of the cell.
 207

0.8.-------------------------------------,

0.6

:.e
°.,. 0.4
::J:

z'"

0.2

10 20 30 40 50
ONo(Hg)out DAYS ON LINE + No (Hg) in
Fig.6. Performance of the DE NORA 14H3 cell using activated
graphite with Fe (0.3%) and Mo (0.1 %) during a normal
operation.

• Plant Modifications

Modifications were introduced at the plant aiming at to produce 70% caustic soda in a
separated circuit. They refer to a 70% caustic soda collector header with a tank,
pumping and soda filtration systems. The pipe lines, tank and filter must be heated by
steam-traces in order to avoid the crystallization of caustic soda.

I-DECOMPOSER
2· HYDROGEN HEAT EXCHANGER
3·MERCURY PUMP
4· 50°/' CAUSTIC HEADER
5·70 ~ CAUSTIC HEADER
6·70dJc, CAUSTIC TANK
7-70% CAUSTIC PUMP
8-CAUSTIC FILTER
9-70% CAUSTIC FLAKE

Fig 7. Flow diagram of the 70% caustic soda process.

 208

REFERENCES

1. Sconce, J. S. - Chlorine: Its Manufacture, Properties and Uses. Reinhold, N. Y., 1962.

2. Hine, Fumio, Electrode Process and Electrochemical Engineering, Plenum Press, N.Y.,
1985.

3. Gallone, Patrizio, Principi Dei Process Electtrochimici, Tamburini Editore, Milano,

1970.

4. Gallone, Patrizio, Trattato Di Ingeneria Electtrochimica, Tamburini Editore, Milano,

1973.

5. Ullaman's, Encyclopedia of Industrial Chemistry, Vol. A 6

6. Hardie, D. W. F., BSC, Ph.D, Electrolytic Manufacture of Chemicals from Salt, 1975
Edition, The Chlorine Institute, Inc.

7. Perry, H. & Chilton H., Chemical Engineers' Hand Book, Mc Graw Hill, 5th Edition

8. Hostomsky, J. & Roosar, I. & Cezner, V., Thermodynamic Relations for Amalgam
Decomposers, Collection Czechoslov. Chem. Commum. [VoI.40], 1975.

9. Rajasekaran, S .& Roosar, I. & Cemer, V., Determination of Radial Distribution

Coefficient of Amalgam for Vertical Tower Decomposer, Collection Czechoslov. Chem.
Commum / Vol. 38, 1973.

10. Roosar, I. & Rajasekaram, S .& Cemer, V., Theoretical Relations for
Decomposition Kinetics of Sodium Amalgam in Tower Decomposer, 1. Electrochem.
Soc., Vo1.121. number 3, pg 336, March 1974.

11. Rajasekaran, S. & Roosar, I. & Cezner, V., Measurement of Amalgam

Decomposition Rate in Tower Decomposer, 1. Electrochem. Soc., Vol. 121, number 3,
pg.340,March,1974.

12. Roosar, I. & Cemer, V. & Krajca, M. & Kolarik, K., Comparison of Different Sorts
of Graphite Bed for Decomposition of Amalgam in Tower Decomposer, 1.
Electrochemi. Soc., Vol. 121, number 3, pg. 343, March, 1974.

13. Butrin, G. M. & Demin, K. A & Kocinskii, V. P. & Tcheviruk, V. P. & Koneja, N.
X., Effect of Porous Structure of Graphite on the Effective Sodium Amalgams
Decomposition, - Grajita, Part 10, pg. 169 - 175, 1975.
 209

POLYRAMIX- DIAPHRAGM

A COMMEROAL REALm

THOMAS F. FLORKIEWICZ
Vice President, Technology and
Diaphragm Cell Business

and

L. CALVERT CURLIN
Business Manager - Diaphragm
and Process Technology

OxyTech Systems, Inc.

100 Seventh Avenue
Chardon, Ohio 44024-1000, USA

ABSTRACI
Ever since OxyTech first publicly announced the development of the Polyramix'"
diaphragm, or PMX diaphragm, at the 31st Plant Manager's Seminar at the
Chlorine Institute Meeting on March 9,1988, the Polyramix diaphragm has gained
wide acceptance. It's acceptance is the result of two major driving forces -
environmental and economic. These two forces have directly affected the
development and commercialization of the Polyramix technology. This paper will
review these driving forces and review how the marketplace has developed since
that first public announcement. The progression of Polyramix technology from
demonstration cells, to commercial blocks, to full plant conversions will be
discussed. Lastly, the paper will examine the continuous improvements underway
and their effects on the commercialization of Polyramix diaphragms.
 210

INTRQDUCIIQN

At the 1988 London Symposium, OxyTech presented a paper on Polyramix

diaphragms. The paper concentrated on introducing the Polyramix diaphragm to
the chlor-alkali industry. In the intervening 3 years, it has grown from an R&D
project into a commercial reality. The purpose of this paper is to review the
commercial progress of Polyramix diaphragms in light of the environmental and
economic driving forces and to take a look at future areas of commercial
improvements.

As a matter of brief review, a Polyramix diaphragm is a non-asbestos replacement

for asbestos or polymer modified asbestos diaphragms. It is a composite fiber
made up of a Teflont backbone with metal oxide particles impacted into the fiber
during the manufacturing process. Since it has a branched chain structure of
varying length, it is more aptly defined as a fibrid It retains many of the porosity
and flow characteristics of asbestos and it can be vacuum deposited similar to
asbestos based diaphragms.[1]

DRMNG FORCES FOR COMMERCIAL ACCEPTANCE

The Environmental Factor

It is public record that the United States Environmental Protection Agency (EPA)
has released a regulatory ruling which bans approximately 95% of the previous
applications of asbestos by 1994. Although the chlor-alkali industry has received
an exemption from the ban, the EPA has made the following statement in the
preamble of the regulation:

"... users of asbestos diaphragms use non-asbestos diaphragm cells

in facilities that will accept them and in the design of new
facilities."[2]

Also, The EPA, under the New Clean Air Act, must amend regulations on a
number of compounds including asbestos. Until the revisions are published, the
National Emission Standards for Hazardous Air Pollutants (NESHAP) for
asbestos will remain in effect. NESHAP mainly regulates the handling and
disposal of asbestos. In addition, the USA Occupational Safety and Health
Agency (OSHA) has established a standard covering air borne asbestos fibers of
0.2 fibers/cc, however, it is rumored that OSHA is considering a reduction in the
standard to 0.1 fibers/cc.

lTeflon e is a registered trademark of E. I. DuPont de Nemours and Company

for fluorocarbon resins.
 211

New, tighter standards not only apply to the United States, but to Europe as well.
These tighter asbestos regulations in the United States and Europe are significant
because diaphragm cell capacity in Europe and the United States represents
approximately 40% of the total world ehlor-alkali capacity.

Environmentally, Polyramix fibrids are physically different than asbestos fibers.

Table 1 pictorially shows the size difference between Polyramix fibrids and
asbestos fibers. Polyramix fibrids are much longer and coarser than asbestos and
its diameter is several factors larger than asbestos. Combined with its greater
density due to the impacted metal oxide particles, Polyramix fibrids are a heavy
material which is very difficult to suspend in air.

Table 1
CARCINOGENIC POTENCY OF FIBERS
AS A FUNCfION OF DIAMETER AND LENGTH
Peak Chrysotile Polyramix
Carcinogenic Asbestos Fibrids

Diameter
•
0.0625 to 1JIm
•
0.1 to 3J1m 10 to 100Jlm

Length «:>
15 JIm 0.1 to 60Jlm 1000 to 7000 JIm
Source: Figure 4.5 Pott (1980)

OxyTech has sampled the air quality at both the Polyramix manufacturing facility
located in Fairport Harbor, Ohio and the Polyramix depositing facility located at
Occidental Chemical's Battleground, Texas Plant. The sampling procedures and
analyses were completed by a commercial AIHA certified laboratory and NIOSH
(National Institute for Occupational Safety and Health) methods were employed
for nuisance dust and for asbestos fibers.

The results of the sampling are presented in Table 2. In both the manufacturing
facility and the depositing facility, the levels of nuisance dust and asbestos fibers
were below the OSHA permissible exposure limit (PEL). Thus, the workplace
was found to be well within compliance with OSHA standards.
 212

Table 2

RESULTS OF AIR. QUALI1Y SAMPLING AT POLYRAMIX

MANUFACl'URING AND DEPOSITING FACll.ITIES
Actual OSHA PEL
Location Sample Results Limits

Manufacturing Nuisance Dust,(1) <2 5

Facility Mg/M3

Total Fibers,(2) 0.01 0.2(3)

Fibers/cc

Depositing Nuisance Dust,(1) 0.2 5

Facility Mg/M 3

Total Fibers,(2) 0.01 0.2(3)

Fibers/cc

(1) NIOSH #0600 Method for Nuisance Dust

(2) NIOSH #7400 Equivalent Method for Asbestos Fibers
(3) OSHA Limit for Asbestos Fibers

To better evaluate the health risks of using Polyramix fibrids, OxyTech contracted
with the environmental risk management firm of RiskFocus.2 RiskFocus
attempted to verify the occupational health risks of air borne Polyramix fibrids,
but the density of Polyramix fibrids made it impossible to maintain an adequate
airborne concentration for conducting inhalation toxicity experiments. An attempt
was made to administer Polyramix fibrids via intratracheal instillation, however, it
was again technically impossible to conduct the procedure. RiskFocus concluded
that even if Polyramix fibrids were of a size which could be inhaled, which it is
not, the toxicity of its individual components is sufficiently low that no affects
would be observed.

Based on these facts, OxyTech has applied to the EPA under the Toxic
Substances Control Act (ToSCA) to have Polyramix fibrids/diaphragms approved
as an "Article". On March 27,1991 the EPA notified OxyTech that Polyramix
fibrids/diaphragms have been listed as an "Article". Approval as an "Article"
defines Polyramix fibrids/diaphragms as:

2 RiskFocus is the health sciences and regulatory affairs division of Versar,

Inc., who provides consultant services in toxicology, risk assessment, and risk
management.
 213

"... a manufactured item (1) which is formed to a specific shape or

design during manufacture (2) which has end use function(s)
dependent in whole or in part upon its shape or design during end
use, and (3) which has either no change of chemical composition
during its end use or only those changes of composition which have
no commercial purpose separate from that of the article ..."

As an "Article", Polyramix fibrids/diaphragms are not subject to further toxicology

testing, are approved for manufacture by the EPA, and are not considered a
health hazard

The environmental driving force is even greater when one considers the reduced
waste handling of Polyramix diaphragms versus asbestos diaphragms. With a
Polyramix diaphragm life expectancy of 3 years versus 9 - 15 months for polymer
modified asbestos diaphragms, the volume of wastes generated on diaphragm
renewal is substantially less, and the Polyramix waste is non-hazardous. In fact,
the chemical industry is now actively seeking to reduce and minimize solid wastes
through cooperative programs with government and the public to jointly set
regulations. Voluntary industry programs such as Responsible Care3 drive users
to reduce solid wastes.

Finally, the potential liability issues and product stewardship must always be
considered when evaluating alternative technologies. It is difficult to assign values
to it, but it represents a subjective issue which must always be considered,
especially in today's environmentally conscious society.

The Economic Factor

Economics are always the most powerful commercial driving force. In the case of
Polyramix diaphragms, the economical driving force is presently secondary to the
environmental driving force. Nevertheless, it is extremely important; progress
achieved in the last three years has been significant.

Since the cost of electricity represents approximately 50% of the manufacturing

cost for an ECU, it is the most significant economic factor. If 100 mv of voltage
can be saved over regular polymer modified asbestos diaphragms, the chlorine
producer will achieve approximately a $2.00/Ton savings at power costs of 30
mils. Power savings of this magnitude are being achieved in Polyramix cells in
operation throughout the industry. Depending on the weight of the Polyramix
diaphragm, which influences the voltage savings, some customers are realizing a
break-even investment on the Polyramix diaphragm of 1 - 2 years. It is significant

3 Responsible Care is a voluntary group of companies of the Chemical

Manufacturer's Association committed to support a continuing effort to improve
the industry's responsible management of chemicals.
 214

to note that the longest life Polyramix diaphragm has now achieved over 1,600
days on line, and another nine Polyramix diaphragms have exceeded OxyTech's
target life of 1,000 days.

Environmental factors can also be translated into economic factors. One such
factor is waste disposal. The review of asbestos handling costs at chlor-alkali
facilities yields a cost of $0.25 per ton of chlorine. As public opinion forces
stricter standards and solid waste disposal sites are closed, the cost of waste
disposal will continue to increase. There is today a wide difference in dealing
with a hazardous waste versus non-hazardous, non-asbestos waste. This increase
will certainly favor non-asbestos diaphragms. However, the present cost of
disposing of asbestos waste has not increased to the point where it alone can
economically justify the switch to Polyramix diaphragms.

Every diaphragm cell producer must ask himself the question, "Should I switch to
membrane cells?" This frequently asked question results in an economic
comparison of converting to membrane cells versus investing in new diaphragm
cathodes and utilizing Polyramix diaphragms. The use of membrane cells could
entail either retrofit of the diaphragm cells with membrane ''bags'' or complete
conversion to membrane cells. In a conversion to membrane cells, salt can be
supplied to the membrane cell by returning depleted brine back to the brine well
or by evaporating the brine feed to a salt slurry. Also, a recirculating brine
system is required. Besides revising the layout of the cellroom, the existing
diaphragm cell caustic soda evaporator must be revised and simplified to accept
essentially high-strength, salt-free caustic soda.[3] Thus, the membrane cell
alternative will require an extensive capital investment.

The continued use of diaphragm cells entails both the conversion to Polyramix
diaphragms plus the replacement of the existing diaphragm cell cathodes when
they have reached the end of their life. At a minimum, the inner assembly
portion of the cathode (the cathode tubes or fingers) should be replaced. Thus,
the alternative of continued diaphragm cell operation with Polyramix diaphragms
results in low capital investment.

A comparison of the manufacturing cost of a membrane conversion versus

continued diaphragm cell operation with Polyramix diaphragms is dependent on
steam costs. Figure 1 depicts the economic tradeoff of the comparison. Referring
to Figure 1, a respectable 20% incremental return on capital investment can only
be achieved at high steam costs. Even if the membrane cell caustic soda can be
sold for a $10/MT premium in the market place, and we choose the lowest
estimated capital investment for the conversion, the switch to membrane cells is
only economical at steam costs above $2O/MT. In the United States, 60% of the
diaphragm plants operate with co-generated electric power and steam. In
Western Europe, diaphragm producers also heavily rely on co-generation facilities.
 215

DIAPHRAGM TO MEMBRANE CONVERSION ECONOMICS

AS A FUNCTION OF STEAM COSTS
50~--~----~----~------~r-~

• 730 MTPD NaOH

Steam 30 j----t-----"7"f-----"Wfo"c---t-----; • NaOH Sold

Costs, at $101MT Premium
$/MT
• Equivalent Cell
Power Consumption

Incremental Return on Investment, % (BFIT)

Since most diaphragm chlor-alkali facilities experience relatively low cost steam, it
is extremely difficult to economically justify conversion to membrane cells.

MARKET DEVEWPMENI
Demonstration Pro~ams

Early in the commercialization of Polyramix diaphragms, OxyTech realized that

no chlor-alkali plant would convert without successful demonstration of Polyramix
diaphragms in their own plants. Based on this industry philosophy, OxyTech
developed a program to allow customers to evaluate commercial size Polyramix
cells in their own plants.

Approximately 25 diaphragm cell plants in the USA and Europe have elected to
evaluate from 1 to 5 Polyramix cells. These 25 diaphragm cell plants represent
approximately 70% of the diaphragm plants in the USA and Western Europe.
There are now more than 140 diaphragm cells operating with Polyramix
diaphragms. The types of diaphragm cells include the OxyTech MDC-20, MDC-
29, MOC-55, H-2A. H-4, HC-3BT, HC-4B, and others. OxyTech continues to
actively pursue the testing of Polyramix diaphragms in the remaining diaphragm
cell plants. This phase of development began at the last Symposium. It is based
on OxyTech depositing the Polyramix diaphragm on the customer's cathode and
 216

shipping the cathode to the customer's plant for installation. Such a program
saves the customer the cost of installing the capital equipment required to deposit
Polyramix diaphragms at his plant. The deposition of all of these demonstration
cells has taken place at Occidental Chemical's Battleground, Texas facility. This
program will continue until every major diaphragm cell producer has had the
opportunity to commercially evaluate Polyramix diaphragms.

Commercial Blocks

OxyTech is now entering a second phase of commercialization which we call

"Commercial Blocks" of Polyramix diaphragms. The market strategy is based on
the customer depositing between 10 to 30 Polyramix diaphragms at his own site
and utilizing most of the equipment which exists for depositing polymer modified
asbestos diaphragms. Figure 2 presents a flow diagram of a typical installation.

Fi~2

FLOW DIAGRAM OF COMMERCIAL BLOCK

DEPOSmNG SYSTEMS

PMX
Fiber

Preparation Vacuum
Module Source

Thickening Existing or
Agent Modify

New or
Drying
Existing Oven '--_ _ _--' ~ Diaphragm
PMX

OxyTech's strategy is to allow the customer to deposit a large block of Polyramix

diaphragms without sacrificing the ability to switch back to polymer modified
asbestos diaphragms. In this approach, OxyTech has developed a modular design
for the tankage and mixing equipment required to prepare Polyramix diaphragms.
The module can be purchased or leased from OxyTech.
 217

The customer can either purchase a new depositing tank or install a corrosion
resistant liner in his existing depositing tank. A liner is required because iron
contamination destroys the effectiveness of the thickening agent required to
suspend the Polyramix fibrids in the depositing tank. For a vacuum source, the
existing vacuum tank and vacuum pump may be utilized. The fusion temperature
of a Polyramix diaphragm is similar to the temperature used for fusing OxyTech's
SM-l, SM-2 or SM-3 diaphragm formulations. The temperature utilized for a
HAPP diaphragm is too low and the oven must be modified to increase the
temperature.

A Actiye Projects

Following the market strategy laid out above, OxyTech has negotiated
several contracts based on installation of 10 to 30 cells. The justification
for the projects ranges from strong environmental reasons to strong
economic reasons. For confidentiality reasons, OxyTech can discuss the
scope of some of the projects, but not the cost or economics.

1. Taft-Convent 20/20 Project

OxyTech, together with Occidental Chemical, have created a second

Polyramix depositing site at the Occidental Chemical Plant at Taft,
Louisiana. The purpose is to deposit Polyramix diaphragms on 20
H-4 cells for the Taft Plant and 20 MOC-55 cells for the Occidental
Chemical Plant at Convent, Louisiana. This project will give
Occidental Chemical a large demonstration block of Polyramix
diaphragms in large diaphragm cells. It will also allow OxyTech to
open a second facility capable of depositing Polyramix diaphragms.

The project is based on modular design of the required Polyramix

preparation equipment, a new, lined depositing tank, modification of
the HAPP curing oven, and the use of a vacuum truck.

2. Vulcan Chemicals - Geismar, Louisiana

Vulcan is proceeding with a commercial block of 25 Polyramix

diaphragms on MOC-55 cathodes. OxyTech has leased the
Polyramix preparation module to Vulcan. The existing depositing
tank has been lined and the existing SM-2 diaphragm curing oven
can be used to bake the Polyramix diaphragms. As a source of
vacuum, Vulcan shall employ their existing vacuum system. The
project is in the startup phase and Vulcan will begin commercial
deposits at any time.
 218

3. BASE - Germany

Driven by some very stringent German environmental regulations,

BASF wishes to evaluate Polyramix diaphragms on a commercial
basis. Their plan is to install up to 30 Polyramix diaphragms on
their MOe-55 cathodes. The design is based on utilization of the
existing depositing system. OxyTech has leased the Polyramix
preparation module, and like the Vulcan system, the project is at
the stage of startup.

B. Full Conversions

The next phase after commercial blocks is the complete plant conversion.
Full conversion would normally take place after successful operation of a
commercial block of Polyramix cells. Because of favorable economics
andlor environmental factors, two customers have proceeded directly to a
full conversion.

1. General Electric

General Electric, at both the Mt. Vernon, Indiana and Burkville,

Alabama Plants, have no diaphragm depositing facilities. General
Electric has a contract with OxyTech to have HAPP diaphragms
installed on their cathodes at Occidental Chemical's Taft Plant.
Thus, it was only a matter of shifting the diaphragm depositing
service from the HAPP diaphragm at Taft to the Polyramix
diaphragm at the Occidental Chemical Battleground, Texas Plant.
OxyTech has converted approximately 80% of the Mt. Vernon Plant.
The Burkville conversion is also underway.

2. HllIs - Germany

As a result of several tests with Polyramix diaphragms and following

the internal HllIs decision to stop the use of asbestos, HllIs has
elected to convert to the Polyramix diaphragm. Like others, HUIs
will purchase the Polyramix preparation module and also convert
their existing depositing equipment.

HllIs has just begun their program, and as with others, they are
receiving the technical support of OxyTech personnel as they
convert to Polyramix diaphragms.

As with the first full scale commercial application of any technology, there
are improvements which are learned, and which help in the further
development of the technology. By commercially depositing General
Electric's H-2A cells at the Occidental Chemical Battleground, Texas
Facility, and depositing test cells for others, OxyTech has been able to
 219

improve the commercial viability of the technology. Since the Polyramix

diaphragm is a combination of only Teflon and metal oxide, it does not
contain the magnesium hydroxides and silicates which are found in
asbestos. It is surmised that the hydroxides and silicate compounds help
retard the corrosive effects of anolyte flowing into the catholyte during
shutdown. For this reason, OxyTech recommends that any user of
Polyramix diaphragms should have available the means to add alkaline
brine and sulfite solution to the cells immediately on power failure to
neutralize the harmful effects of hypochlorite at the cathode. Such a
procedure not only protects the Polyramix diaphragm, but it will also guard
against early cathode screen plate corrosion, thus extending the cathode
life. Also, OxyTech has instituted procedures during the surfactant wetting
cycle, baking cycle, and cell assembly to aid in retarding the corrosion of
the cathode.

Suffice it to say that OxyTech continues to learn more each day about
operating Polyramix diaphragms. As more Polyramix diaphragms are used
in the industry, further refinements and improvements will be forthcoming.

FImJREWORK

No one can rest on what has gone before, and Polyramix technology is no
different. To insure that Polyramix diaphragms become a true market success,
OxyTech is addressing the following areas:

Continued Operational Improvements

Oosing the Environmental Loop
Long Life Diaphragm Cell

Continued Operational Improvements

As more and more Polyramix diaphragms are applied, the knowledge gained by
operator training and use will lead to further improvements. Moving a product
from the R&D stage to commercialization results in the product being taken out
of the hands of the researcher and into the hands of the operator. Although new
problems arise, it is amazing how plant operators can adapt and attack problems
from a more practical viewpoint. This approach can result in improvements in
diaphragm quality, life, and performance. OxyTech sees such improvements
occurring, and indeed looks forward to gaining additional knowledge from plant
operator experience.

Also, it must be recognized that the application of a Polyramix diaphragm is a

more expensive proposition than a polymer modified asbestos diaphragm.
Therefore, the plant managers rightfully want and expect a longer lasting
 220

diaphragm. OxyTech continues to work to this end, but it must be recognized by

the customer that a new and different plant operating philosophy toward
Polyramix diaphragms may need to be developed. The use of a more costly
diaphragm means greater operator attention to brine quality, outages and upsets.
Stricter monitoring and control of any diaphragm will result in longer life. Since a
Polyramix diaphragm is a factor of 7 to 10 times more expensive than a polymer
modified asbestos diaphragm, closer monitoring and control is a necessity, and the
plant managers and operators must be aware of it. The diaphragm cell plant
operator and OxyTech must work together to revise their operating philosophies.
As an aid, OxyTech has developed operating procedures to teach and allow the
diaphragm cell operators to assimilate new operating philosophies geared to the
Polyramix diaphragm.

OosinK the Environmental Loop

OxyTech envisions the day when the only waste emissions from the plant using a
Polyramix diaphragm, is the Polyramix diaphragm itself. OxyTech is now working
on defining the steps necessary to recycle all filtrate back to the brine treatment
system, and to return any free zirconia or metal oxides to OxyTech for recycle
into new Polyramix material. As a long tenn goal, OxyTech foresees a need to
study the eventual recovery of used Polyramix diaphragms to completely close the
environmental loop. This goal is indeed long tenn, but it is the operating
philosophy of the future.

LonK Life piaphriliDl Cell

The use of a long life diaphragm such as a Polyramix diaphragm may not be
justified if the failure of the other components of the diaphragm cell result in
removal of the cell before the end of the Polyramix diaphragm's useful life.
Therefore, OxyTech continues its search for improvements in diaphragm cell
components. Test work on TIBAC base covers to replace rubber base covers
have resulted in an extended base cover life of many times that of the
conventional rubber cover. Although marginally economical versus rubber, they
do give the customer the ability to match the base cover life with the Polyramix
diaphragm.

OxyTech is testing a cell head material using a new resin called Telene' to
extend the life of cell heads without relining. To date, Telene cell heads are
operating in commercial plants with up to 12 months on line. Preliminary results

4 TIBAC" is a trademark of OxyTech Systems, Inc. for a titanium alloy base

cover used for diaphragm cells.

, Telene e is a registered trademark of B. F. Goodrich for diC)'clopentadiene

resin.
 221

are very encouraging. Testing has also commenced on an inflatable rubber base
and cell head gasket. Such an approach would enable the user to re-inflate the
gasket to the correct air pressure to seal the cell as the rubber ages due to
corrosion and compression set. In addition, OxyTech has developed a new cell
head hold down assembly which will be safer and less expensive than the standard
designs utilized on the typical diaphragm cells.

All of this work is directed to extending the life of all diaphragm cell components
so that together with the use of a Polyramix diaphragm, the chlorine plant
operator has the opportunity to achieve a cell life which is comparable to or
greater than that achieved by membrane cells.

CONCLUSION

OxyTech is well aware of the value of a non-asbestos separator for diaphragm

cells both from an environmental and economic standpoint. Environmentally,
there is a strong driving force from a health standpoint and waste disposal.
Economically, OxyTech continues to seek improvements in voltage and life which
will make the economic driving force even stronger. The environmental and
economical driving forces have directed OxyTech into a market development
strategy based on demonstration cells, commercial cell blocks, and finally
complete plant conversions. To aid in the complete conversions, OxyTech
continues work not only on a long life Polyramix diaphragm, but improvements in
diaphragm cell components which will lead to the ultimate goal of a diaphragm
cell operating for 3 years plus without replacement. Great progress has been
made in the market development of Polyramix technology. There is still a lot of
work to do, but OxyTech is confident that it can satisfy the industry's needs and
expectations of a non-asbestos diaphragm separator with the POLYRAMIX
diaphragm!

1. Curlin, L. C., and Matousek, R C., Polyramix"', a Depositable

Replacement for Asbestos Diaphragms, 1988 London Symposium, 1 - 3
June, 1988.

2. Elkins, C. L., Director, Office of Toxic Substances, U.S. EPA, letter to

Chlorine Institute Insider Newsletter.

3. Esayian, M. and Austin, J .H., Membrane Technology for Existing Chlor-

Alkali Plants, 27th Chlorine Institute Plant Operations Seminar
Proceedings, February, 1984
 223

CHLORINE VAPOR SUPPRESSION TESTS

D.O.E. NEVADA TEST SITE JUNE 1990

J. R. Thomerson, D. E. Billings
The Dow Chemical Company, Freeport, Texas, 77541, U.S.A.

ABSTRACT

This paper provides information on Chlorine Mitigation Tests, conducted at the

Department of Energy, Nevada Test Site in June 1990, by Dow Chemical USA.
Typical audiences include Producers and Distributors of Chlorine, and Emergency
Response Personnel. A twelve minute video has been made to assist in emergency
response training. Copies are available from The Chlorine Institute, Washington DC.

THE STATEMENTS ARE DIRECTED AT THE SPECIFIC FIELD TESTS CONDUCTED

AND DESCRIBED BELOW, AND MAY NOT APPLY TO OTHER CONDITIONS.

INTRODUCTION

One of the components of any emergency response plan, is the mitigation of the
release to minimize the harmful effects on people and the environment. Most
mitigation techniques are aimed at leak repair, or spill containment at storage
facilities, with little field test data available on vapor suppression techniques. In June
1988, Chubb National Foam and Dow Chemical U.S.A. conducted some preliminary
field tests using foams on liquid chlorine pools, with positive results. In 1989, Dow
started planning this set of field tests which were conducted in June 1990. The
purpose of these tests were to provide further data on the effectiveness of aqueous
foams and water sprays on suppression of chlorine vapors.
 224
The use of the Department of Energy Spill Test Facility in Mercury, Nevada,
allowed the tests to be conducted safely and without endangering the public or
the environment. The test facility was built in 1986 for $79 million, and is ideally suited
for tests due to its remote location and consistent winds.

TEST PROGRAM

Chlorine was released at rates up to 150 Ibs per minute, with fifty-five chlorine
sensors used for dispersion analysis. Tests ran for five days and included downwind
water sprays, application of foams and neutralization of a liquid chlorine pool.

The equipment layout included an insulated 50 square foot pan, weigh cells on
the pan and chlorine containers, temperature sensors in the pan and immediately
downwind. Fixed water spray headers were set at ground level and 20 foot elevation
downwind of the chlorine release pan. The water headers were forty feet long with
nozzles spaced 1.5 feet apart. The water headers delivered 325 gpm for each header
at a water pressure of 100 PSI. Fifty-five chlorine sensors were mounted on
seventeen towers at heights of 5, 15 and 25 feet, with several extra at a one foot
elevation. The towers were arranged in four rows, with five towers in each of the first
three rows and two towers in the last row. The first three rows were located 250, 500
and 750 feet downwind of the release pan and the last two towers were located 0.5
miles downwind. Within each row the towers were spaced 150 feet apart. Five local
weather monitoring stations were used to measure wind speed and direction. Data
was collected every 10 seconds for all instrumentation, resulting in over 500,000 data
points for the tests.

Six tests were conducted as listed in Table 1, evaluating different water spray
configurations, aqueous foams and neutralizing agents.

TABLE 1
Description of the tests conducted
CL2
RELEASE
TEST RATE TESTS CONDUCTED
LB/MIN
1 150 Water Headers, portable monitors
2 5 Water Headers, 3M AFFF Foam , Soda Ash Neutralize
3 5 Water Headers, Chubb VaporShield AC Foam, Soda Ash "
4 5 Water Headers, portable monitors, Water Mist, 50% NAOH"
5 5 Water Headers, Chubb VaporShield AC Foam, 1OO%NAOH"
6 100 Water Headers
 225

In test 1 and 6, the chlorine was released at up to 150 Ibslmin from three chlorine
one ton containers. The liquid chlorine was routed to a header and screen, which were
located above the pan and vaporized most of the liquid chlorine. Water was placed
in the pan to vaporize the remainder of the liquid chlorine. In order to improve the
visibility of the chlorine, a small amount of ammonia gas was intermittently released
upstream of the pan, producing a white cloud. Once the chlorine sensors stabilized,
the water spray headers were activated. Combinations of top and bottom water
spray headers were tested, along with up and down nozzle orientation on the top
water header. With the 20 mile per hour winds common at the Nevada Test Facility,
the water stayed airborne for approximately 250 feet. In several tests, two portable
firewater monitors were set up on wide fog downstream of the pan. The capacity of
each portable firewater monitor was 350 gpm of water.

Tests 2,3 and 4 were all conducted by establishing several inches of liquid chlorine
in the pan. Approximately half of the chlorine was vaporized while establishing the
chlorine pool. The temperature in the liquid chlorine pool stabilized at -60' F, well
below the boiling point of -29' F. This was due to the well-insulated pan and
subcooling by the wind vaporizing the chlorine. Free evaporation rate of the chlorine
liquid pool was approximately five Ibs/min. The ambient relative humidity was 4%
during the tests which resulted in minimal hydrate formation in the chlorine pool.
Various water spray header tests were conducted during these tests also. With a
liquid chlorine pool, the water spray must be directed downwind of the pool, to
prevent the water from contacting the liquid chlorine and increasing the vaporization
rate.

RESULTS AND DISCUSSION

In Table 2 the percentage reduction in downwind chlorine readings is shown for each
of the water spray configurations, for Test 2.
TABLE 2
Test 2, Water Spray Headers

WATER MINUTES CL2 f'\LL TWRS TWR3 % WIND WIND

SPRAY IN LBI AVG AVG REDUCT SPEED DIR.
CONFIG. STEP MIN PPM PPM -ION MIS DEGREES
NONE 5.3 5.4 1.0 3.0 BASE 8.8 224
BOTH 3.8 7.6 0.5 1.4 65.0 9 .3 227
GROUND 3.3 4.2 0.4 1.0 56.9 8 .8 240
20' UP 3.3 6 .9 0.4 1.4 60.6 9 .5 232
NONE 4.3 4.6 0.8 2.6 - 0.6 8.7 225

Percentage reduction based on Tower 3 chlorine readings, corrected for release

rate and wind speed. Tower 3 was located 250 feet directly downwind of the
release pan, with chlorine sensors mounted at the 1, 5, 15 and 25 foot elevations.
 226

Figure 1 depicts another representation of the downwind concentration

reduction in Test 2 with water on both spray headers. The average of the four
chlorine sensors located on tower 3 are plotted with, and without downwind water
sprays. When the water spray headers were activated, the average indication of the
four chlorine sensors on tower 3 decreased below the previous mean.

FIGURE1
Test 2, Tower 3 Average chlorine readings
Before and after water spray activation

lOr-------------------------------------------------------~
~N~O~W~A~T~E~R~S=P~RA~Y_______UCL

BOTH WATER SPRAYS ON

_ _ PPMCL2

Data was taken every 10 seconds. Tower 3 was located 250 feet directly downwind
of the release pan, with chlorine sensors mounted at the 1, 5, 15 and 25 foot
elevations.
 227

A summary of the average reduction in downwind concentrations for each test, is

shown in Figure 2. The percentage reduction ranged from no reduction in test 4, to
63% in test 3, with an overall average of 31 %. The variability is predominantly
due to the wind variation. Five weather stations were located in the immediate test
area. Typically the wind direction was +/- 23 degrees and speed was +/- 3.3
meters/second. With the concentration profile across a chlorine cloud, small
changes in wind direction can greatly change the chlorine concentration at a tower.
The percent reduction, on average was similar for the low chlorine release rates, tests
2 to 5, as it was for the higher release rates, tests 1 and 6. There is minimal solubility
of chlorine in water and the water sprays work by increasing dilution air by
momentum transfer and do minimal scrubbing. The variability was higher in the low
release rate tests than in the higher release rate tests. This may be due to using
data from only the four chlorine sensors on tower 3, at low release rates and ten
sensors on tower 2, 3 and 4, at the higher chlorine release rates. At the lower release
rates of test 2, 3 and 4, the chlorine cloud was smaller, and only the chlorine sensors
on tower 3 indicated high enough chlorine concentrations to show the effect of water
sprays.

FIGURE2
Percentage reduction in downwind chlorine concentrations
Water spray downwind of the chlorine release
Summary by test
 228

Table 3 summarizes the same test data as Figure 2, but sorts the test data by
water spray configuration. The portable firewater monitors were proved less effective
than water spray headers in these tests.

TABLE 3
Percentage reduction in downwind chlorine concentrations
Water spray downwind of the chlorine release
Summary by water spray configuration

WATER SPRAY ORIENTATION

TEST 20' HDR 20' HDR GROUND PORTABLE GROUND GROUND AVERAGE
# DOWN UP HDR MONITORS & 20' ON &20' UP

1 55 26 33 17 24 26 30
2 61 57 65 61
3 79 43 67 63
4 7 - 3 -1 8 -5
5 12 12
6 29 28

AVG 47 33 44 7 24 40 31

The water sprays also affected the elevation of the chlorine cloud as shown in
Table 4. The chlorine concentration at the five foot elevation increased with the water
spray activated, and the chlorine concentration at the 20 foot elevation decreased.

TABLE 4
Test 1. Effect of Water Spray on Cloud Elevation
Average chlorine sensor ppm reading

CHLORINE DOWNWIND DISTANCE

SENSOR 250 SOO 750
ELEVATION FEET FEET FEET
NO WATER SPRAY
5 FOOT 12.0 6.1 2.2
15 FOOT 6.6 5.5 4.1
25 FOOT 3.2 3.7 1.5
GROUND WATER SPRAY ON
5 FOOT 20.0 7.3 7.3
15 FOOT 2.4 4.3 7.8
25 FOOT 0.3 1.6 2.7
 229

For three of the tests, foam was applied to the liquid chlorine pool after the water
spray tests were completed. Two foams were tested; 3M AFFF/ATC, and Chubb
National Foam VaporShield-AC. The foam was applied with a 60 gpm, 50 to 1
mid expansion nozzle. The foam was rolled onto the chlorine pool to prevent
turbulence. Chimneys of chlorine breaking through the foam could be seen. The
foam provides an insulation blanket from the wind, and helps form a hydrate on the
chlorine surface. After approximately th irty minutes the hydrate started to break
down necessitating reapplication of the foam. The average reduction in chlorine
vaporization rate for the three foam tests was 38% and is shown in Table 5. The
release rate was calculated using the release pan weigh cells, so wind variability was
not a factor.

TABLE 5
Foam suppression of chlorine released form a pool

% REDUCTION
DESCRIPTION TEST # IN RELEASE RATE

3M AFFF 2 37
CHUBB VaporShield-AC 3 21
CHUBB VaporShield-AC 4 55
OVERALL 38

A garden sprayer was tested as another means to hydrate the chlorine pool. The
mist reduced the vaporization rate but was much slower to apply than foam and
required personnel to work near the chlorine pool. A fire nozzle set on a fog spray
was also tested, but resulted in too much water contacting the liquid ch lorine pool
which increased the chlorine vaporization rate. The reduction in free evaporation for
the mist and fog are shown in Table 6.

TABLE 6
Test 4, Water Mist I Fog Effectiveness

WATER MINUTES CL2 lWR3 % WIND WIND

SPRAY IN LB AVG REDUCT SPEED DIR.
CONFIGURATION STEP MIN PPM -ION M/S
FREE EVAP 4.3 5.5 1.3 BASE 7.1 218
WATER MIST 8.7 3.3 0.5 40 6.1 206
WATER FOG 24.7 5.9 1.3 - 7 8.3 214

Percentage reduction was based on the vaporization rate from the chlorine pool.
 230

After the foam tests had been conducted and a layer of hydrate had formed on the
chlorine pool, several neutralization agents were tested. The neutralization agents
were intended to reduce both the total quantity of chlorine released and the duration
of the release. Anhydrous caustic was tested, and deemed unsuitable due to the
violent reaction and significant increase in the chlorine vaporization rate. The
addition of dry powder soda ash was also tested. The soda ash reaction with
chlorine is endothermic and the addition of a small amount of water was necessary to
initiate the reaction. Carbon dioxide is evolved in the reaction, which improved
mixing.

NA2C03 + Cl2 = > NAOCL + NACL + C02

The chlorine vaporization rate did increase during neutralization, compared to the
hydrated chlorine pool. Water addition to start the reaction must be minimized.
Figure 3 plots the relative chlorine release rate for the initial filling of the pan, foam
application and soda ash neutralization.

FIGURE3
Test 3, Soda Ash Neutralization
50

42.3

<IOf-

0
Ul
~
..J
Ul
co:: 30-
Ul
Z
C2
0 21.3
..J
:t
U 20 -
z
::E
iii
..J

10 f-
7.5
4.6 5.4
4.3

FILLING FREE AFTER SODA AFTER SECOND

PAN POOL FOAM ASH WATER SODA
EVAP. ADD'N ADD'N ASH
 231

CONCLUSIONS

These field tests provided data on several techniques which could be used to reduce
the severity of accidental chlorine releases.

In these tests the water sprayed downwind of the chlorine releases reduced the
average indication of the downwind chlorine sensors. However, the water spray
headers used in these tests also lowered the height of the chlorine cloud, which
resulted in higher chlorine concentrations at the five foot level, within 750 feet of the
release. To prevent water from contacting a liquid chlorine pool, care must be taken
due to varying wind direction, or where the water might run back into the chlorine
pool. Water sprays contacting the chlorine cloud result in pH 2 water effluent on the
ground which must be handled.

The two foams tested reduced the chlorine vaporization from the pool by
hydrating the surface. Foams must be applied with the correct expansion ratio, and
are an effective means to reduce vaporization caused by wind or solar effects.

Neutralization with Soda Ash will reduce the length and total quantity of the
chlorine release, however the downwind chlorine concentrations will increase during
the neutralization.

REFERENCES

1. Davis, D.S., DeWolf, G.B., Ferland, KA, Harper, D.L., Keeney, R.C., Quass, J.D.,
Accidental Releases of Air Toxics, Prevention, Control and Mitigation, Pollution
Technology Review No. 170, Noyes Data Corp. 1989.

2. Harris, C., Mitigation of Accidental Chlorine Releases, Paper presented at the

30th Plant Operations Seminar of the Chlorine Institute, Washington D.C., 870325.
 233

CHLORINE SAFETY

EURO CHLOR Working Group on Production, Storage and

Transport safety (GEST)
EURO CHLOR Secretariat
Avenue E. Van Nieuwenhuyse 4, Box 2, 1160 Brussels, Belgium

This lecture was presented by Mr. J.A. Walkier, AKZO,

The Netherlands on behalf of EURO CHLOR.

ABSTRACT

EURO CHLOR is a grouping of the chlorine producers in Western

Europe.
EURO CHLOR has made, by summating the experience of all the West
European Chlorine producers, more than 40 Technical
Recommendations in the area of chlorine production, storage,
transport, loading, unloading and handling.

Chlorine producers outside Western Europe as well as industrial

consumers of chlorine and engineering and equipment supply
companies world-wide can have access to the knowledge and
experience by becoming a Technical Correspondent of EURO CHLOR.
Special attention is given to the restriction in the use of
Titanium as a construction material for wet chlorine.
At temperatures below 15° C it is not safe to use Titanium even
if the chlorine is saturated with water.

INTRODUCTION

EURO CHLOR is a grouping of the chlorine producers in Western

Europe. It is integrated within CEFIC, the European Chemical
Industry Council.

Since 1953 exchanges of safety experience have been on the

agenda of the technical meetings of EURO CHLOR.
 234

In 1972 a specific working group called GEST started to prepare

guidelines in the area of chlorine production, storage,
transport, loading, unloading and handling. These guidelines
are now called EURO CHLOR Technical Recommendations.

Summating the experience of all the European chlorine producers

is the main intention of the group and by so doing EURO CHLOR
makes a significant contribution to enhanced safety.

Safety in the manufacture and handling of toxic and potential

corrosive products such as chlorine depends on several factors
e.g.
- The design of the plant should be made on the very
specific characteristics of chlorine and based on the
well established operational experience with chlorine.

- Strict specifications for equipment

Safety in operation of the plant and handling of

chlorine.
This implies that given guidelines and procedures are
strictly followed and a safety consciousness among
personnel is required.

It is obvious that proper guidelines need the continuous input

from analysis of all incidents with chlorine.

The study of each incident with chlorine shows that even the
smallest detail in auxiliary equipment is important and that
safe handling of chlorine needs great care and expertise.
Against this background it is not surprising that EURO CHLOR
created in 1972 the already mentioned GEST group.
At each meeting of this Safety Working Group incidents that have
occurred since the last meeting are discussed for their causes
and if necessary findings are incorporated in the existing EURO
CHLOR Technical Recommendations or new ones are made.

EURO CHLOR TECHNICAL RECOMMENDATIONS

Since 1972, more that 40 Technical Recommendations have been

published on a great number of topics by EURO CHLOR :
- Chlorine storage, under pressure, without pressure
Liquid chlorine transfer, pumps, compressors.
Chlorine vaporizers.
Loading and unloading stations.
Transport of chlorine by long distance pipeline.
Bulk chlorine transport and loading and unloading.
Chlorine absorption systems.
Nitrogen trichloride problems.
Chlorine valves.
Chlorine isocontainers, tank wagons, tank cars.
Chlorine dispersion.
Construction materials.
Chlorine pipework.
 235

- Risk assessment studies.

- First Aid equipment. Emergency response.
- Operation (commissioning, maintenance, handling, analysis
chlorine monitoring).

EURO CHLOR recently organised a Safety Seminar for chlorine

producers, consumers and engineering and equipment supply
companies worldwide. The Seminar held during November 1990 was
attended by 275 participants.

It is now possible for chlorine producers outside western Europe

as well as industrial consumers of chlorine and engineering and
equipment supply companies worldwide to establish a permanent
relationship with EURO CHLOR by becoming Technical
Correspondents. This membership enables them to have access to
the knowledge and experience gained by the European chlorine
manufacturers.

Investigations show that many accidents would not have happened

if the EURO CHLOR Technical Recommendations had been applied.
This implies the need to make these recommendations better known
and was a basic consideration for the creation of the Technical
Correspondent membership and the regular organisation of
Technical Seminars.

LEARNING FROM PAST EXPERIENCE

We would like to illustrate these efforts with some examples

Chlorine Transport in Bulk

Despite the fact that there have been several road and rail
accidents wi thin the last 40 years, not a single fatality
resul ted. In fact there was not even any puncture of the
container. An important contribution to this excellent
performance is due to the adoption of the EURO CHLOR standards
which in many respects exceed the national and international
transport regulations.

Illustrations of these more stringent requirements are :

- the requirements for minimum wall thickness and low
temperature tensile strength and for the mechanical
properties of the construction steel
- the double closure valve on railway cars developed by
EURO CHLOR

Drums and Cylinders

Drums and cylinders are normally designed to withstand transport

accidents. Again, in the same 45 years period of time, there
was only one fatal accident in Spain (Malaga in 1975) where a
one ton cylinder was damaged during a shipping operation. The
leak was caused by the fracture of a plug on the drum. The
presence of this plug is not in accordance with the EURO CHLOR
Recommendation on drums.
 236

Pipework, Valves and Materials of Construction

EURO CHLOR has produced a specification code of chlorine

pipework (GEST 79/81). If followed this code will give trouble-
free chlorine service. However, maintenance procedures,
especially disconnection of undrained and non-vented pipes are
a frequent cause of accidents.
Unintended back flow is another frequent cause leading to severe
corrosion (back flow of water) or explosions (back flow of
organics) .

EURO CHLOR has established a very strict specification for

liquid chlorine valves (GEST 86/140) to ensure better safety.
Titanium

It is well known that titanium is not resistant to dry chlorine.

The minimum humidity needed is incorporated in GEST
recommendation 79/82. However, at every meeting of the GEST
working Group, incidents with burning of titanium by chlorine
are reported.
For that reason we would like to emphasise strongly that
everybody should be aware of the limi tations of the use of
titanium and some examples are given to illustrate it.
Below 15° C it is not safe to use titanium even if chlorine is
saturated with water as is demonstrated in the appendix.

In tests done by AKZO, titanium wires covered by chlorine

hydrate started to burn in this wet chlorine atmosphere at
temperatures below 15° C by simply stretching the titanium wire.
All these data are based on atmospheric pressure, what the
effect is of a higher chlorine pressure in the safe temperature
limit is still under investigation.

Another example of the limitation of the use of titanium

concerns a fire in a titanium butterfly valve with chlorine
saturated with water at 15° C and 1,3 bar. Chlorine became too
dry at the back side of the valve because of a pressure drop of
0,3 bar. Spraying sufficient water in the pipe is one of the
solutions.

Be also aware that if there is a possibility of the temperature

falling below 15° C such as during a shutdown in the winter,
then titanium by itself is not suitable for wet chlorine.
Additional precautions such as steam injection or heat tracing
will be required.

Unloading
EURO CHLOR Recommendation GEST (78/73) on the design of an
unloading station calls for a liquid trap equipped with a level
or temperature alarm, to detect a liquid flow and prevent liquid
chlorine flooding the absorption system.
 237

Gaskets

New areas for study arise all the time. An example for this is
the likely future need for a replacement of compressed asbestos
fibre gaskets. Several alternative materials have been tested
but additional work and time will be necessary to prove
acceptable alternatives.

RISK ASSESSMENT

In line with the implementation of the Directive EEC 82/501 on

major risks ("Seveso"), EURO CHLOR has developed guidelines for
conducting hazard summary studies in typical sections of the
chlorine plants.

Due to a lack of knowledge on the toxicological effects of

chlorine for short time exposures, EURO CHLOR sponsored a test
programme with TNO (Netherlands organization for applied
scientific research). The results have added substantially to
the data base required for production of risk assessment
criteria.

CONCLUSION

Any responsible manufacturer or user of hazardous substances

such as chlorine must be able to satisfy himself, his workforce
and his regulatory authorities that his process is safeguarded
against major loss of containment.

To do this, the manufacturer needs to demonstrate that he has

identified all foreseeable hazards and is aware of their causes.
He must be able to show that the plant has been designed and
maintained using procedures which give very high certainty that
such hazards will not arise.

By summating the experience of all the European Chlorine

Producers and incorporating this experience in more than 40
Technical Recommendations, EURO CHLOR has made a significant
contribution to help all people concerned with chlorine handling
and safety to achieve these objectives.
 238

., 1.5 - 0 Ref: A:B - Timet (USA)

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 239

DESIGN AND OPERATION OF EMERGENCY CHLORINE ABSORPTION SYSTEMS

THOMAS F. O'BRIEN
Catalytic Division
United Engineers and Constructors Inc.
Philadelphia, USA.
and IAN F. WHITE
Badger Catalytic Ltd.
New Malden, Surrey, UK.

ABSTRACT

It is inevitable that during its production and processing, there will be

occasions when chlorine is released from its containing equipment. The
established method of dealing with this released gas is by neutralization
with a caustic 1iquor; most often sodium hydroxide. In this chapter
aspects of the design and operation of the systems used to accomplish this
neutralization are discussed.
The need for care in design and operation is brought out by reference
to statistics which show that a significant proportion of chlorine releases
to the atmosphere involve overloading emergency scrubbers.
Considered in greatest detail, as it represents the majority of
neutralization systems in service world wide, is a single stage scrubbing
device using a discrete batch of circulating aqueous sodium hydroxide. The
protected process is assumed throughout to be a chlorine production plant
or other continuous process utilizing the gas.

INTRODUCTION

In the industrial production of chlorine, it is essential that the operator

prevent the release of dangerous quantities of gas to the atmosphere. What
would otherwise be routine emissions from the process are captured and
converted to useful products or simply destroyed by alkaline
neutralization. Various systems are used to allow routine maintenance to
be done safely, and today there is growing interest in the design of
 240

containment and leak mitigation systems for liquid chlorine storage areas.
The designer and operator must also consider the possibility of accidental
release from the process in an emergency. The usual approach is to provide
seals at appropriate locations in the chlorine processing train and to pipe
any releases from them to an absorber. The absorber can take any of a
number of forms and may also have other functions. In this chapter, we
consider it solely as an emergency device. We shall see that development
of a proper system (where "system" includes the operator) involves much
more than the design of a mass-transfer device.

The simplest system, is based on a single scrubbing device through

which a discrete batch of alkaline material (assumed here to be sodium
hydroxide solution) is circulated. More complex arrangements may sometimes
be found more economical, convenient, or reliable, but this minimum system
can be considered the baseline. It is, in fact, the one most often found
in practice and is exemplified by that described by Patel and Scarfe [1].
Any additions or elaborations must be justified by the improved results
which they may offer. First, we shall consider the characteristics of the
single-stage design.
,STARTS
TO ATMOSPHERE I SPARE r ___ .,

A
~ PUMP II _t>Iol ::l--_-1I><1-__. C.W.
r
I I RETURN
I I
@
L_: $
I I
.Jt-T-:;n..--~<l-_C. w.
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I
,
, \ 1\

HIGH TO WASTE
LIQUOR HOLD
.----~---._~-~--TANK

r-----------
I
--, I
EMERGENCY ~ /'IK) .J..EMERGENCY
POWE~ I ~ r®POWER
L.!_.J 1/ 1/ L.L_~

Figure 1. Emergency vent scrubber - Flow scheme

 241

A typical example of a scrubbing system is shown in Fig. 1. Here, the

caustic soda solution is circulated around a packed-bed scrubber. Chlorine
vents and releases are piped to the column below the packing. Chlorine,
from sources under pressure, is introduced below the surface of the liquid
in the sump of the column. That sump serves as the storage chamber for the
liquid. The drawing also shows some of the instruments provided to enhance
safety.

With such a system, however, instrumentation alone will not suffice.

Administrative controls are necessary, and plant operators must remain
constantly aware of the state of their system. One can easily hypothesise
many causes of failure if this is not done.

For example, since there is a finite batch of caustic liquor, only

a limited quantity of chlorine can be destroyed. One of the designer's
tasks is to fix the size of this batch. The operator of the plant then has
the problem of maintaining an adequate supply to the scrubber at all times.
This means that the rate of delivery of caustic soda must always be
adequate; either a low flow rate or a low solution concentration can allow
chlorine to break through.

Low flow can result from pump problems or failures in the delivery
system. A pump may fail electrically or mechanically. Flow to the
scrubber can be reduced by improper operation of valves (including opening
the valve intended for removal of waste liquor) or by failure of the
packing. If a spray system were used instead of a packed bed, the failure
analogous to the last named would be plugging of or damage to some of the
spraying devices.

Low caustic concentrations can result from errors in preparation of

solution or from reduction by exposure to chlorine.

The latter could in the limit be avoided by continuous, once-through

supply of caustic soda. This would in most cases create another problem by
generating large volumes of waste [2]. This also can be intolerable. We
must therefore be able to design and operate systems which meet the
constraints on both sides.
 242

We can also list events which lead to an unusually high demand.

These, like the listed causes of an inadequate caustic supply, act
independently. Anyone event then can lead to a failure of the system.
In the construction of a fault tree in hazard analysis, these events would
propagate through "OR gates".

This is the reason for the particular importance of administrative

controls to the successful operation of a scrubber such as that of Fig.l.
In some of our analyses, thirty or more events are linked to the top of a
fault tree solely through OR gates. Given a release of chlorine from the
process, anyone of these events could therefore cause a breakthrough and
allow chlorine to escape to the atmosphere.

This aspect must be partly responsible for the large number of

releases from scrubber systems. A recent ten-year survey by The Chlorine
Institute, for example, showed that 21% of the releases reported by North
American producers were from emergency scrubbers [3]. An earlier study by
EuroChlor [4] showed that 14% of the "incidents" reported in the
manufacture, distribution, and handling of chlorine involved the
overloading of emergency scrubbers.

BASICS

Chemistry
The essential reaction is the destruction of chlorine, with formation of
hypochlorite:

C1 2 + 2 NaOH ---> NaCl + NaOCl + H20 (1)

With proper control, this can be practised commercially at high

efficiency to produce bleach solutions. The basic problem is the
instability of sodium hypochlorite and the need to remove the exothermic
heat of reaction (1463 kJ/kg of chlorine gas).

In emergency operation, the required control may be absent, allowing

other reactions to become important. One of these is disproportionation
 243

of hypochlorite to chloride and chlorate:

3 NaOCl ---> 2 NaCl + NaC10 3 (2)

Another is the decomposition of sodium hypochlorite, which is

favoured by high temperature and by the presence of certain metal ions:

NaOCl ---> NaCl + ~ 02 (3)

For comparison with reaction (1), the complete reactions for the latter two
cases can be written:

3 C1 2 + 6 NaOH ---> 5 NaCl + NaC10 3 + 3 H20 (4)

and
(5)

Heats of reaction (at infinite dilution) become 2002 and 2272 kJ/kg,
respectively.

Mass transfer
This process presents a complex and interesting problem in mass transfer.
Space does not permit a thorough description. Several points should be
made here, however, which we have found to be important in our development
of our design techniques.

1) Liquid-phase mass-transfer coefficients are influenced by

reaction of an absorbate. One of the first studies which
dealt with this phenomenon was the work of Vivian and Whitney
on the absorption of chlorine in water [5]. They explained
apparent inconsistencies in data by recognising that the
equilibrium partial pressure of chlorine is determined by the
liquid-phase concentration of molecular chlorine - not by the
total amount of chlorine dissolved. Development of the theory
of gas-l iquid reactions has now shown that in the case of
rapid consecutive reactions there may be either one or two
reaction planes established in the liquid film. In our case,
the two reactions can be taken to be:
 244

(6)
and
HOCl + OW <--> ocr + H20 (7)

The work of Hikita et al. [6] showed that, with reaction (6)
even more favourable than reaction (7), there will be two
planes of reaction. The mathematics of the system are
affected by this conclusion, and predicted mass-transfer
coefficients are somewhat different from those given by a
single-plane model.

2) In a liquid-film controlled absorption process, the above

considerations are important. Absorption of chlorine from
concentrated gases is unquestionably such a process. With
weak gases, however, the gas film may become controlling.
Makhneva and Gertsen [7] have shown this to occur and have
suggested a criterion to use to identify the regime. Weak
gases are found in some scrubbing applications (e.g., tail gas
destruction), and at the top of a very efficient strong-gas
scrubber.

3) Temperature effects are very important. These are discussed

separately in the next section.

Effects of temperature
Because of the heats of reaction and of condensation of water, the
temperature of the caustic soda solution will increase as it passes through
a scrubber. In those systems without coolers, the temperature will
continue to increase until the flow of chlorine is cut off or the caustic
is consumed. Higher temperatures wi 11 have severa 1 effects on the process:

1. the physical solubility of the chlorine will be lower,

reducing the driving force for diffusion.
2. the vapour pressure of any given solution will be higher,
increasing the concentration of water in the gas phase.
3. in the limit, the probability of boiling or of sudden
decomposition of hypochlorite will be increased.
 245

The first effect is illustrated by Fig. 2. The curve is the result

of our calculations. The one point highlighted is that given by Hikita et
aT. [6]. Agreement is excellent. The second effect reduces the partial
pressure of chlorine and again may impede mass transfer. This was pointed
out by Updike [8], who showed calculated examples of the mole fraction of
chlorine along the length of a column. When the temperature remains low,
the chlorine concentration actually increases as the gas rises. This is
due to the condensation of water and can be very useful in preventing the
onset of gas-phase control .

.........
....
Q) 80
Q)
..c
a.. 70

-
<II
0
E 60
c
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~ 50

" <II
0
E
40

30
C')
E
'-" 20
~
:.0 10
:::l
0
(/) 0
20 40 60 80
Temperature ("C)

Figure 2. Solubility of chlorine in water

In a typical design the temperature of the caustic can rise by about

30 deg.C as it passes through the scrubber. If the design event is a
twenty-minute release of cell gas, the batch of caustic will be turned over
nearly three times. The indicated 90 deg.C rise is clearly excessive. It
will be prevented by a change in the process. First, the condensation of
water will stop. Finally, the solution actually will come to a boil, or
the efficiency of absorption of chlorine will drop off. The high
temperature coincides with a low concentration of sodium hydroxide in the
solution. The latter also leads to a deterioration in mass-transfer
 246

capabil ity, because the enhancement of the mass-transfer coefficient by the

reaction is smaller.

While it is possible to install and operate a scrubber without

cooling, many units will have an exchanger on the caustic recirculating
line. Fig. 1 is an example. Other techniques also are used. For example,
an auxiliary supply of solution, besides offering a safety margin, can help
to absorb some of the heat of reaction. In any event, the heat effects and
the possibility of developing excessive temperatures are two more issues
which must be faced by the designer.

Best practice may be to maintain a temperature low enough to

discourage the side reactions discussed earlier. EuroChlor [9] recommends
a maximum of 55°C. While The Chlorine Institute makes no official
recommendation, participants in one of its symposia [1] named the same
temperature as a desirable limit.

Effects of gas composition

Other components in the gas will influence the composition of the scrubbing
liquor and of the final vent. Carbon dioxide will be absorbed while
hydrogen and the components of air will not. The calculations and plots
found in later sections of this chapter apparently do not recognise the
presence of carbon dioxide. It is easily accommodated in final design.
In the generalised approach we present here, it can simply be equated, mole
for mole, with chlorine.

If a unit is used to scrub ventilation air or a gas with a high

carbon dioxide concentrat ion, the 1iquor wi 11 eventually conta in high
concentrations of carbonate. To avoid precipitation, the starting liquor
then must be more dilute. The recommended strength for pure caustic of
about 20% sodium hydroxide would be reduced to something with a higher
freezing point. Normal diaphragm-cell liquor would also require dilution.

When used to scrub air, cont i nuous exposure of the 1i quor can
seriously deplete its capacity for chlorine. A system based on diversion
of air to the scrubber only when chlorine is detected is worth
 247

consideration. The alternative is a more elaborate design or extra

precautions against depletion of the caustic.

Concentrations of hydrogen and oxygen in the gas will increase in the

scrubber. In many cases, the effluent gas can be in the explosive range.
The designer must also consider this problem and will often choose to add
a diluent gas to the scrubber.

EQUIPMENT AND SYSTEMS

Mass-transfer devices
Any of the common mass-transfer devices might be considered for the
absorption of chlorine. In addition, high-pressure gases often are simply
sparged into a pool of caustic solution (usually in a vertical tank). The
two types most frequently found in producers' plants are packed beds and
sprays. These are treated briefly below.

Packed Beds: The diameter of a column must be great enough to allow

the gas to pass through without excessive pressure loss. In a packed bed,
the gas flow rate interacts with the liquid flow rate and the type and size
of packing.

The familiar correlating plot is redrawn for a typical cell gas and
20% caustic soda solution in Fig. 3.

In an emergency scrubber exposed to a release of cell gas, there will

be sudden huge changes along the column in gas flow and in the slope of the
gas pressure profile. There are accompanying changes in liquid holdup.
In the absence of a flow of gas, this holdup is determined by the rate of
liquid circulation and the characteristics of the packing. When the gas
flow begins, the steady state is upset. The system will adjust, and the
effects will be most pronounced at the bottom of the column.

A conservative practice is to design the column to operate below or

in the lower range of the loading zone. The loading zone is that region
of operation in which liquid begins to accumulate on the packing and its
 248

holdup to increase. This reduces the area available for flow of gas and
so increases its pressure drop. Below this zone or at its lower limit, the
sudden introduction of a large flow of gas will have relatively little
effect on the dynamics of liquid flow, and the transient will be less
pronounced. At higher velocities, with greater changes and more severe
transients, there would be a greater risk of instability.

3.5

2.5
,......
a.
u...
.e" 2
'-J
0)
0
1.5

o 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2

log(L/G)

Figure 3. Correlation of packed chlorine scrubber flooding points.

Design points for some of the systems with which we have worked are
marked on Fig. 3. EuroChlor [9] recommends a gas velocity equal to about
60% of flooding. Such a line is also superimposed on the plot.

Spray Systems: Spray columns are often used as alternatives to

packed beds. They can have the advantage of a low pressure drop when cells
are operated at pressures near or below atmospheric. The protective seals
then are often set at a few millibars. The remote possibility of equipment
pluggage does not exist, as it does with a packed bed. Even when a
demisting pad is added, development of unsafe pressures can be avoided.
 249

Packed-bed systems often make use of an exhaust blower. This helps

to offset the pressure drop inherent in the bed, but it also adds another
mechanical component to the system and another failure event to the fault
tree. This is not necessary in a spray system (and perhaps not when
membrane cells are used).

Spray columns on the other hand present a few new problems. While
their mass-transfer capacity can be increased up to a point by producing
finer sprays, there are still deficiencies. A finer spray requires the
input of more energy and increases the probability of entrainment from the
column. The action of a spray always produces backmixing and reduces the
countercurrent nature of the process. While a spray column may have the
capacity for absorption of large quantities of chlorine, a problem can
remain with the residual concentration in the scrubbed gas. Because of the
backmixing, an increase in the volume of a spray chamber does not
necessarily give an equivalent increase in mass-transfer efficiency.
Typical illustrations given by Sherwood and Pigford [10] suggest that
extending the length of a column by the ratio L increases the number of
gas-phase transfer units only by LO. 4 _Lo. 5 • Columns with a practical depth
of packing gave 1.5 to 3 or more times as many transfer units as spray
columns of equal volume.

Without special precautions, then, we can expect more escape of small

quantities of chlorine from a spray column than from a long packed bed.

This consideration should not be allowed to outweigh the advantages

of sprays when they are otherwise the proper choice. One should keep in
mind the fundamental purpose of an emergency scrubber, which is to provide
a highly reliable means of prevention of objectionable releases of
chlorine. While each reduction in effluent concentration is welcome, even
with a system in very infrequent use, the ultimate reliability should not
be compromised for this lesser goal.

Other System Requirements

Space does not permit full development of the details of scrubber design.
As mentioned above, it is equally important that the rest of the system be
properly designed. When we consider an installation which continuously
 250

recycles a fixed batch of scrubbing liquor around an absorber, the size of

the batch and the rate of circulation become of paramount importance.
Usually, a major criterion is the ability of the scrubber to cope with a
release of the full process flow of chlorine for a given period of time.
This fixes the amount of sodium hydroxide which must be available for
reaction. Given the concentrations of sodium hydroxide in the starting
solution and in that defined as "exhausted" solution, we can size the batch
and the circulating system. While a final design must deal with the
specifics of the plant under consideration, it is useful also to have a
generalized method. This gives the designer an intuitive feel for his
task, allows rapid preliminary estimates, and assures some consistency
among projects.

For rapid estimation, we have used the curves shown in Figs. 4 and
5. Consider a plant producing P tonnes a day of chlorine in which a
scrubber is to be made ~apable of absorbing a release of cell gas for T
minutes. A typical cell gas composition is assumed, with all its water
condensing in the scrubber.

1.5
1.4
1.3
:;:: 80
:::J
:r 70
o
o
z 60

0.9 ~ 50
E
0.8 x 40
o
~

o 246 8 o 2 468
Final NoOH Concentration (Wt.%) Final NoOH Concentration (Wt %)

Figure 4. Figure 5.
Caustic batch sizing parameters. Caustic utilization efficiency
 251

The amount of chlorine to be absorbed is PT/1.44 (kg). The

corresponding quantity of sodium hydroxide required in a batch is:

x = PT.f(C) (8)
where
(9)

Values of this function in which the starting weight fraction of

sodium hydroxide is C1 and the final value C2 are shown in Fig. 4.

In order to be able to absorb the last traces of chlorine even at the

end of an incident, one must ensure that the rate of circulation of caustic
soda is adequate. This means that, at the design flow rate of chlorine,
the instantaneous rate of supply to the top of the column must be at least
stoichiometrically equivalent even at the minimum concentration C2 • The
required rate, in kg/h of solution, is about 47 P/C 2• A small safety
factor makes the constant 50. With C2 = 0.05 in such a case, the minimum
circulation rate in te/h of solution is equal to the rate of production of
chlorine in te/day. This is easily remembered and easily converted to
other values of C2 •

When a spent batch of caustic liquor is removed from a scrubber, the

unconverted portion is often wasted. While this may be a secondary
consideration in operation of a safety system, the designer should consider
the environmental impact and make some provision to reduce the amount of
effluent generated. The maximum amount of sodium hydroxide which can be
consumed in a given batch is equivalent to the design loading of chlorine,
PT/1.44 (plus any safety factor). The amount to be charged is given by Eq.
(8). The maximum fractional utilization of sodium hydroxide is the ratio
of these two quantities:

U = 0.7836/f(C) (10)

The achievable efficiency in caustic soda use is therefore fixed by

the starting and ending concentrations of the scrubbing solution. For a
plant of a given capacity, the minimum circulation rate is fixed by C2
only. The batch size also depends on the duration of chlorine release
 252

which is to be designed for. We can now summarize the relationships

between dependent and independent variables:

Depends on
Variable Plant Length of Initial Final
Size Release Cone. Cone.
Batch She X X X X
Circulation Rate X X
Caustic Utilization X X

Of these, only the size of the batch depends on the length of the
release. One might therefore consider simply increasing the size of the
caustic batch in order to be able to cope with a more substantial release
of chlorine. At this point, however, another decision is required. While
a caustic charge may last for, say, fifteen minutes, one must also decide
what to do after a five-minute release. Is the remaining ten-minute
capacity sufficient, or should the batch be replaced after having consumed
only a small fraction of the caustic soda? This is a matter of operating
pol icy.

If the caustic batch were indeed made larger (say, thirty minutes
instead of fifteen), the disposal problem might be aggravated. After the
hypothetical five-minute release, the safety margin again may be deemed too
small or at least no longer to provide the intended improvement. Caustic
utilization would be very low, and nothing would have been accomplished
with the larger batch. If the batch size is increased with the intent of
allowing a minor release without dropping below the minimum acceptable
caustic inventory, however, that small release can be accepted without
violating the minimum or disposing of the batch prematurely.

We might then consider two criteria for design and operation:

1. a mi nimum inventory of caust i c soda wh i ch wou 1d call for

replacement of the liquor
2. provision of some multiple of this minimum amount in order to
improve the utilization of sodium hydroxiae.
 253

The maximum achievable utilization as given by Eq. (10) is not

affected. What does change is the degree of approach to this ideal. If
we were to supply twice the minimum amount of caustic soda, we would be
sure to achieve at least 50% of the maximum efficiency. This would be at
the expense of larger storage volumes.

AUGMENTED SYSTEMS

Improved results may be possible with more complex systems. These will be
more expensive, and the designer must take care that added complexity does
not reduce reliability.

The simplest way conceptually to overcome any perceived deficiencies

of a single-stage design is to add a second column. Fig. 6 is a sketch of
a possible arrangement. Here, the caustic would cascade through the two
scrubbing stages. The existence of the second column would add some
security, and the cascaded arrangement would allow better caustic
utilization.

VENT GAS

WASTE L10UOR FRESH NoOH

,-----d
•

Figure 6. Two column vent scrubber

Fig. 7 keeps the two-stage arrangement within a single shell.

 254

While the upper section could be the same in design as the lower section,
the sketch suggests a tray column mounted above a packed bed. This could
allow a lower inventory and flow rate of caustic in the second stage.
Operation would be somewhat cheaper and simpler, but the security
associated with a greater inventory of caustic would be lacking.

VENT VENT
GAS FRESH GAS
NaOH
FRESH
WASTE WASTE NaOH
LIOUOR LIOUOR

Figure 7. Figure 8.
Two-stage scrubbing column Scrubber with auxiliary caustic supply

Fig. 8 is not a true two-stage operation. An extra supply of caustic

is available, here by way of a head tank. This provides the extra supply
without the need for continuous pumping, but there are more controls and
an uncertain mass-transfer situation when the caustic is released.

Finally, Fig. 9 shows an emergency scrubber in parallel with a bleach

production operation. All the design considerations which pertain to a
single-stage scrubber hold here. Mass-transfer capacity must be adequate
in each column, and excessive temperatures must be avoided.
 255

VENT GAS

U
FRESH
NoOH I SPENT
LIOU R
FRESH NoOH (PRODUCT)

Figure 9. Combined emergency vent scrubber/hypochlorite production.

REFERENCES

1. Patel, H.M. and Scarfe, T.S., Safety aspects of Niachlor membrane

cell plant. Proceedings, 31st Chlorine Plant Operations Seminar, New
Orleans, March 1988.

2. The Chlorine Institute, Minutes, 2nd Chlorine Plant Operations

Workshop, Washington, March 1987.

3. Chlorine Institute Pamphlet 86, Recommendations to Chlor-Alkali

Manufacturing Facilities for the Prevention of Chlorine Releases,
edition 1, October 1990.

4. Papp, R., Chlorine safety and handling in the European situation.

In Modern Chlor-Alkali Technology vo1.2, ed.C. Jackson, Ellis
Horwood Limited, Chichester, 1983, pp. 376-85.
 256

5. Vivian, J.E. and Whitney, R.P., Absorption of chlorine in water.

Chern. Eng. Progr., 1947, 43, 691.

6. Hikita, H., Asai, S., and Takatsuka, T., Absorption of chlorine.

Chern. Eng. J., 1973, ,2, 77.

7. Makhneva, T.A. and Gertsen, P.P., Absorption of chlorine at low

concentrations from gases by alkaline absorbents. Zh. Prik. Khim.,
1970, 43, No.4, 766.

8. Updike, L.J., Emergency vent scrubbers - design considerations.

5th Chlorine Plant Operations Workshop, Houston, March 1990.

9. EuroChlor pamphlet, GEST 76/52, Eguipment for the Treatment of

Gaseous Effluents containing Chlorine, 9th Edition, October 1986.

10. Sherwood, T.K. and Pigford, R.L. Absorption and Extraction. McGraw-
Hill Book Co., New York, 1952, pp 273-4.
 257

lURGI's EXPERIENCE WITH STEEL AND RANEY-NICKEL AS CATHODE MATERIAL

R.DWORAK, K.lOHRBERG, R.MOLLER

Lurgi ChemieoMetallurgieoIndustriebau GmbH
Lurgi Allee 5 0-6000 Frankfurt 11
0

Chlorine Chemistry Section

ABSTRACT
In the early days of the membrane cell technology steel was often used as
material for the cathodes as well as for the cathode frames. However it
turned out soon that corrosion of the steel in the membrane cell becomes a
severe problem. The mechanism of this corrosion has been investigated and
as a result it will be shown what the measures are to prevent/reduce the
corrosion.
The alternative to steel is a Raney-Nickel coated cathode with a nickel
frame. The chemical resistance of nickel in caustic is very well known.
Some longtime experience from operating plants equipped with nickel
cathodes is presented here.

INTRODUCTION
For more than twenty years Lurgi has been engaged in chlor-alkali
technology. Originally, it started with the mercury cell process, which
was superseded by the diaphragm cell technology because of pollution
problems. During the past decade the membrane cell took the lead due to
its steadily increasing economical advantages and improvement of
operation.

The Lurgi membrane electrolyzer actually is an assembly of individual

membrane cells comparable to a filter press. Bulk heads and tie-rods
compress a sequence of anodes, cathodes and membranes together.
 258

~o
VERTICAL
ANODES MESH

BRINE

Figure 1. The monopolar lurgi membrane electrolyzer

The following considerations were made when sizing the cell. As is shown
in figure 1 our electrolyzer is a monopolar one. Current is entering the
electrode from one side and distributed from there over the whole active
area. Together with the prerequisite to build a compact electrolyzer for
substitution of existing technology we were not allowed to apply internal
copper bars for even current distribution. Otherwise the siz~ of the
individual frames would be enlarged to too great an extent. So we had to
use the electrodes as such as conductors.

The basic materials used today for cathodes in membrane cells are mainly
carbon steel, stainless steel and nickel. A comparison of the specific
resistance of these materials shows easily that only carbon steel and
nickel would be suitable to fulfil the desired requirements. Of course,
 259

TABLE 1
Specific resistance of different materials

Material Spec.Resistance pOocm

Carbon steel 10
Stainless steel 72
Hastelloy-C 139
Nickel 10
Titanium 80

stainless steel as such is suitable for the process and is often used in
bipolar cells. In monopolar cells however, the low conductivity requires
an internal current distribution system. For this reason it was not
considered as cathode material in the Lurgi membrane cell.

Due to the higher conductivity of carbon steel and nickel the titanium
anode became the limiting factor for the cell width. We found the optimum
cell width to be 660 mm considering the required amount of titanium and
the respective voltage drop in the structure.

THEORY
Due to its low price and its sufficient activity carbon steel is used
successfully in diaphragm cells and is often used - or better has been
often used - as cathode material in membrane cells. The frame will be made
also out of steel in order to avoid local elements. Because of the
different potential of the active cathode and the remote frame structure,
different equilibrium concentrations of iron ions are established. As a
consequence there is a slow but steady transportation of iron from the
remote structure to the cathode. This process is so slow that the normal
lifetime of the cathode frame of more than six years is not affected. But
often operator~ have observed severe corrosion leading to a drastically
reduced lifetime.

The theoretical potential pH-diagrams [1] according to Pourbaix are an

efficient means to collect and represent thermodynamic data for corroding
systems. They are therefore a natural starting-point for theoretical
 260

considerations of corrosion processes. They have certain inherent

limitations, however, which should always be born in mind. These include
the following:

The Pourbaix diagram presupposes equilibria between the metal and its
ions and between the ions in the solution and corrosion products
containing these ions. In practical corrosion cases, conditions may
be far from equilibrium, however.

The term passivity in the Pourbaix diagram is applied to the field of

existence for oxides, hydroxides or other barely soluble substances,
irrespective of their protective properties.

The pH-value, referred to in the diagram is the one prevailing at the

surface of the metal considered. This often varies from point to
point and is usually lower at anode surfaces and higher at cathode
surfaces than the (measured) value in the bulk of the corrosive
solution.

The Pourbaix diagram gives no information on the corrosion rate,

since the diagram is based on thermodynamic and not on kinetic data.

So the theoretical potential-pH diagram must be supplemented by

experimental and experience data.

CORROSION OF STEEL FRAMES

The Pourbaix diagram of iron (see figure 2.) shows two areas, where we
know that carbon steel can be used successfully. The region of passivity
reflects the condition prevailing for example in caustic storage tanks and
the region of immunity represents the situation under cathodic protection.
Both areas are separated by a gap where iron is unstable. Corrosion will
occur.

Since the cathode itself is operated in a potential range where it is

cathodically protected all other parts of the steel structure which are in
direct contact with the caustic must also be protected. This means that in
technical plants the potential must not exceed the equilibrium potential
 261

1.5.

--- -- __~:,~o
--
1.0

Pass; vily
Fe2 0J
........
........ ----
-0.5

-1.0' Immunity
Fe

-1,5 L_~~,........,"'--'c-!--,:--r--r--r--r-=-:-=-"'7.:""""'.
pH -2 --I a I 2 J , 5 6 7 8 9 10 /I 12 ,rii 15

Figure 2. Potential - pH diagram for iron

related to the dissolved iron. In practice this iron concentration will be

established by the peripheral equipment of the plant. For example, if the
iron concentration is 5 ppm, the potential of any point of the cathode
frame should be about 250 mV below the hydrogen electrode potential in the
same solution. The cathodic overvoltage at 3 kA/m2 is about 350 mV and
consequently the voltage difference between the cathode and the steel
structure of the frame must be less than 100 mY. Under such conditions we
can expect that no corrosion will occur [2].

In general, the frame is sufficiently protected, if the distance to the

active cathode is less than 20 cm. In case hydrogen accumulation will
reduce the effective conductivity of the catholyte this figure must be
reduced. The situation will become even worse if there is a gas buffer
formed in the upper part of the cell due to an improper design of the
discharge pipe.

In various cathode frame designs corrosion damage to the upper horizontal

frame beam has been observed. Preferred areas are the edges because of
 262

the extended distance to the cathodes and the threads of the discharge
nozzles because of the reduced cross section. There are no doubts, that
any hydrogen holdup outside the active electrode gap will cause corrosion.
Sometimes, the gas zone can be traced back by the corrosion pattern.

A special problem will occur, if a hollow frame structure is used for

internal circulation of the catholyte. The catholyte will be degasified in
the upper part of the cell, will be circulated via the vertical beams back
into the lower part of the cell and enter the cathode compartment again
with the feed caustic.

It can be assumed that the surfaces inside the vertical beams are not
affected by the current passing the cathode. Like a caustic storage tank
the iron surface will form a stable passive layer. But on the other hand,
the cathodes themselves are cathodically polarized. Consequently, there
must be a zone between both regions where the steel is forced into the
range of active iron dissolution. This built-in corrosion mechanism will
destroy the frame structure.

CORROSION OF STEEL FRAMES

As mentioned before steel cathodes can heavily corrode if some parameters
are not carefully considered. Such experiences have been made also by us.
NoOH/H2 NoOH-FEED
DISCHARGE
t ~

\
\j
Figure 3. Design principle of an unfavourable cathode frame (left) and
the experienced corrosion pattern expressed as reduced wall
thickness of the frame (right).
 263

When introducing our louvered cathode design originally the cathode frame
design looked as shown in figure 3. Severe corrosion was detected all
around the frame, inside and outside and as well the inlet and outlet
tubes showed heavy corrosion. From the above said theoretical background
it is clear what has happened.

But as a rule an exception can always be found. The same design working in
another cellroom did not show significant corrosion within two years. This
is not in contradiction to the theory. If we look to the operating
parameters the second cellroom was operated at lower temperatures - 15 to
20 ·C lower - and the caustic concentration produced was in the range of
10 %. This indicates what was said before: The Pourbaix diagram has some
side conditions which can not be neglected.

Based on the negative experience with steel cathodes a modified design was
developed which fits with todays dimensions of the Lurgi membrane
electrolyzer. However, after one year of operation it was detected that
corrosion did occur at the outlet nozzle (see figure 4a.) of the frame

CATHODE FRAME
MATERIALtSTEEL

a b

Figure 4. Corrosion pattern of different cathode frame designs

which ended up in leakages through the weld. The frame itself did not show
a corrosion attack. A slight loss of material at the upper horizontal beam
of less than 2/10 mm can be assumed as normal. It was clear that the
outlet nozzle was the most critical area of the frame.
 264

There is a two phase flow, therefore a reduced conductivity of the caustic

solution and a reduced cross section in the nozzle resulting in a reduced
cathodic polarization. From the corrosion pattern we thought that the
frame itself was protected sufficiently and only the nozzle has been
attacked. Therefore a trial was made with a modified design. The nozzle
material was changed to nickel and then fixed to the frame electrically
isolated in order to avoid a local element. The result was even worse.

Now the frame itself was attacked and corroded as shown in figure 4b. Just
by mistake a few nickel tubes were also welded directly to the frame and
the corrosion pattern was the same as in the isolated design. The
assumption that the steel frame was sufficiently cathodically protected
seemed to be not true anymore. To get a better understanding of the
situation prevailing at the outlet nozzle, a computer simulation was made
in order to define the area of cathodic protection. The result can be
expressed as follows [2]:
Under all circumstances we can observe only a very small area with a high
electrical field, but the main area which we wanted to protect
cathodically is more or less not influenced. If we convert the electrical
field into current densities, we can see a "hot spot"- a place of high
current density - but the major part of the nozzle surface is almost not
working. Considering this and the theoretical background we came to the
conclusion, it would be impossible to avoid corrosion in the area of the
outlet nozzle. So the only solution will be to design the outlet nozzle as
a sacrificing piece, which is inexpensive and easy to exchange during
maintenance. By doing so the frame is sufficiently protected and the
outlet nozzle does not represent major costs of maintenance. But of
course, we have to come back to the situation of the first design. Our
explanation today why in the first design the corrosion was limited just
to the nozzle is the following: During welding the introduced heat has
changed the behavior of the small nozzle in such a way, that it was the
preferred area for corrosion. Consequently the final design must be also a
welded piece directly fixed to the frame.
 265

CORROSION OF ACTIVATED STEEL STRUCTURES

The corrosion of activated steel cathodes is similar to the corrosion of

steel frames. In principle, the same argument is valid: The lowering of
the hydrogen overvoltage - means the raising of the cathode potential- by
some 250 - 300 mV is equivalent to the increase of the equilibrium
concentration of the dissolved iron ions [2].

According to our experience at a current density of 3 kA/m2 and an

overvoltage of 70 mV the coating will flake off the structure because the
iron will be dissolved at the phase boundary. Meanwhile, all suppliers of
cathode activations have made their experiences in this field, the number
of new patent applications dealing with such electrodes dropped to almost
zero. Cathode activations are offered today only with nickel structures or
nickel plated steel structures. The risk of the latter structures is
clear: Any single scratch may expose the iron to the caustic with the
consequence of corrosion.

DEACTIVATION OF ACTIVATED NICKEL CATHODES

Activated anodes are commonly used in chlorine caustic business. But
activated cathodes can only be used in membrane cells. Diaphragm cells
d~pend on mild steel which cannot be activated as outlined before.

Several coatings were developed for membrane cells, which baSically may be
divided in three groups:

Metallic noble metal activations

Noble metal oxide activations
Raney- metal activations

The most active coatings are still based on Raney alloys, mostly Raney-Ni
is used. At 3 kA/m2 the overvoltage of industrially produced coatings is
70 - 90 mV, special coatings may reduce the overvoltage to 50 mY. The main
advantage of Ra-Ni is that it will not corrode, but the deactivation is
caused by a recrystallisation process, which will take years. Eventually
an extremely rough Ni-surface will be formed, the overvoltage of which is
still about 200 mY below a non-activated Ni-cathode.
 266

The Ra-Ni will exhibit a constant cathode potential for about two years,
then the recrystallization process will cause an increase of the
potential, which finally reaches the potential of an extremely rough
Ni-surface, which is stable.

In practice we found out that besides the recrystallization another

process is influencing the activity of the Ra-nickel coating. Whenever a
cell had to be opened due to maintenance we observed an increase of
voltage after reassembling of about 50 mY. Part of the increased voltage
is recovered after a certain time of operation, but the irreversible loss
in voltage will be still around 30 mY. We assume that right after the
shut-down of the cell and the exposure of the highly active hot cathodes
to the atmosphere the Ra-nickel is forming nickel hydroxide in the
presence of concentrated caustic and air. This Ni(OH)2 is blocking the
pores of the Ra-Ni and lowering its activity. Part of it is reduced
later on during operation but not completely. So it is an important factor
for maintenance that the inventory of the catholyte compartment is first
displaced by demineralized water in order to lower temperature and caustic
concentration before the cell is drained and disassembled. Any further
handling of the activated cathodes is then not critical.

CONCLUSIONS

The main part of this presentation has been reserved for Lurgi's
experience with carbon steel used as cathode material in membrane cells.
The reason is that in our opinion steel cathodes are still a good
alternative for Ra-Ni activated cathodes, wherever prices for electrical
energy will result in an economical advantage over more expensive other
types of cathodes. For the present design of our steel cathodes lifetimes
are expected up to ten years.

ACKNOWLEDGEMENT

The author wish to thank his colleagues from the chlorine department for
their valuable help in providing data for the presentation.
 267

REFERENCES

[1] Wranglen,G., An introduction to corrosion and protection of metals.

Institut for Metallskydd 1972, Fack 10041, Stockholm 26

[2] Kohl,P. and lohrberg,K., Material problems in the three versions of

chloralkali electrolysis. Journal of Applied Electrochemistry, 1989,
19, 589-595
 269

IMPROVEMENT OF ELECTRODE PERFORMANCE RESULTING FROM COMBINED

OPTIMIZATION OF COATING COMPOSITION AND STRUCTURAL DESIGN

CARLO TRAINI, GIOVANNI MENEGHINI

De Nora Permelec S.p.A.
Via Bistolfi, 35
20134 Milan, Italy

INTRODUCTION

The design of an electrode to accomplish a specific electrochemical

process requires consideration of the following two primary factors:

1. The chemical and physical properties of the catalytic coating

2. The structural configuration

The specifications for the coating can be optimised so as to maximize

the desired reaction and to minimize side reactions through laboratory
studies carried on by means of small scale cells where the experimental
conditions can be accurately controlled. The type of coating selected
must maintain its original high performance characteristics over a long
period of time so as to provide continued economical operation under
normal conditions.
In commercializing coatings found to exhibit excellent performance
under laboratory conditions one is confronted with problems attendant to
SCALE-UP. These can only be studied in the laboratory with great
uncertainty, if at all. In industrial large scale cells the operating
electrolytic conditions can vary widely from place to place within the
cell. For example, bulk concentrations can be different from those found
in the vicinity of the electrodes, or the current density may not be
uniform over all of the active electrode area. As a consequence, a
coating composition chosen for commercialization on the basis of
laboratory evaluation may be found unsuitable for industrial application.
The logical outcome from such scale-up failures is (1) to move toward more
costly coatings or (2) to accept the economic penalty that accompanies
operating with electrodes having a shorter life than planned.
An alternative approach focusing on electrode design (configuration),
has been followed by DE NORA PERMELEC S.p.A. (DNP ) based upon more than
20 years of experience in the study and production of industrial
electrodes and cells for the electrochemical industry. The real core of
such approach is represented by the continued attention given to the
design configuration of industrial electrodes with the objective of
guaranteeing that the operating conditions within a commercial cell
reflect as closely as possible those used in the laboratory for optimizing
the type of coating chosen.
 270

A few examples illustrate some practical industrial applications,

".o/here elec trode configuration is all .important.

CHLOR-ALKALI AMALGAM CELLS

The first generation commercial anodes were based on a rod type structure,
where the electrocatalytic coating is applied to an array of parallel
wires. Their average industrial performance is represented by band B in
fig. 1 where the life time, measured in terms of tons of produced
chlorine and the current density in terms of Kilo Amperes per square meter
of projected area are given on the vertical and horizontal axes
respectively.

TDfI Clz 1m'

NOD IINOoES
100
--~
600

400
ROO IINOoES

tOO " " " \ IN 1!WI'TRlAl CEll.!

O+--r---.~'---~--~~~--
5 to 15 20 25 JO
KII/m t

Figure 1. Coating life - Tons of Chlorine produced per square metre of

electrode surface versus current density (KA/m2)

It goes without saying that such a performance was rather

disappointing in view of the data collected from small size laboratory
cells which totalized substantially longer operating times as is shown by
curve A in the same fig. 1.
This data suggested that the coating "per se" had a potential yet to
be exploited.
A careful analysis of worn-out commercial anodes as well as the
inspection of the geometry and hydrodynamics of the industrial cells
demonstrated that the poor performance of the coating, especially at high
current densities, was due mainly to uneven supply of brine to the active
surface of the anode which fact, in turn, was associated with the size of
the cell, the current density and the anode to cathode distance as well.
Uneven supply of brine leads to strong brine depletion, which brings
about a chemical deterioration of the coating and its loss in a short
period of time.
The gap between actual and potential performance was overcome when
the RUNNER (R) type anode was first installed (fig. 2).
 271

Figure 2. RUNNER anode

The structure of such an anode consists of an array of parallel bars

having triangular cross section in place of the former array of wires
(fig. 3).

Figure 3. RUNNER anode - structure detail

Titanium Hydrodynamic Means (THM) in fig. 4 are positioned on the

upper surface of the array crosswise with respect to both the length of
the bars and the bulk flow of the brine.

Figure 4. RUNNER anode - brine circulation mode

 272

The THM define spaces of electrolyte having different populations of

chlorine bubbles. The resulting density difference generates strong
recirculation flows which essentially eliminates overdepletion of brine
even in the most critical and less accessible areas created by the
anode-to cathode spatial relationship.
In addition the sloped shape of THM forces the chlorine bubbles to
collide together so that gas disengagement is accelerated and no gas is
entrained in the downflow of brine moving toward the anode to cathode gap.
The performance of the RUNNER (R) anode is shown in fig.S band C,
where the data relating to lab cells, fitted with rod type anodes, is also
collected. It shows quite clearly that the RUNNER (R) anode behaviour
approaches closely that of the lab cells and in some cases its industrial
performance is even better than expected. This is demonstrated by a total
production of 910 tons of chlorine/m2 of anode obtained at 13.9 KA/m2 in
an industrial plant.

ROll IINOllES
8fJO ,~ IN L1I8. CELLS
' - ( --;UNNEN
"'" TYPE IINOO[S
6IJ0 IN INllUSTNllIL CELLS

400
HOll IINOlJES

2D0
~IN INDUS"''' e£us

O+--.---.--~---.---.---.--~
5 fO 15 20 25 JO
KII/m 2

Figure 5. Coating life - Tons of chlorine produced per square meter of

electrode surface versus current density (KA/m2)

It is to be pointed out that the unique hydrodynamics of the RUNNER

(R) anode allows for a reduction of the interelectrode gap, without any
loss of current efficiency. The reduced gap leads, in turn, to reduced
cell voltage and lower energy consumption.
Fig. & shows a set of data covering current efficiency and energy
consumption as function of cell voltage and Kf derived from an industrial
plant operating at 13.1 KA/m2, where:

Kf = v - 3,15
KA/m2
 273

~% KWh/Tet,
99 3500

98
J400
97

96 JJ80
WORKING (Q/fUITIONS
95 KI/:2()(J (IJKIII",t)
Tln/()Vt'1Ot/S5'C
JZI/6
HaCf i~/IMU"I/tIm,/t
94
CELL SlAf'FIICE: 15.J 11ft
CELL TYI'E,lIN UNt
9J J/I8
J.8oo J.1JO 4861 4.198 4J28 4.456 4.581 V
0.85 0.06 0.01 0.08 0.8! D.IO 0.11 Kf

Figure 6. Current efficiency and power consumption versus cell voltage

and Kf at 13 KA/m2

CHLOR-ALKALI DIAPHRAGM CELLS

The first generation metal anodes for diaphragm cells were referred
to as "box type" anodes and which as long ago as 1970 replaced graphite
anodes. Their configuration kept the external rectangular shape unchanged,
but being manufactured with expanded mesh the internal space was void
which allowed for some disengagement of the chlorine bubbles from the
confines of the anode-to-diaphragm gap (fig. 7A).

"-0
BOX TYI'E 1I110JlE
EXI'IINOA8iE TYI'E AllON

Figure 7. Titanium diaphragm cell anodes

 274

The second generation anodes, known as "expandable type" anodes (fig.

7B) were designed to provide diaphragm cells with a reduced distance
between the anode surface and the diaphragm (2-3 mm).
This resulted in a remarkable reduction in the cell voltage, but also
in a noticeable increase in the oxygen content in chlorine, most probably
linked to the substantial backmigration of caustic through the diaphragm
reaching the nearby anode surface.
At the present time a new anode system is under industrial testing.
This system comprises expandable anodes and baffles (Titanium Hydrodynamic
Means) positioned on the top edges of the anodes (fig. 8)

Figure 8. Titanium Hydrodynamic Means (THM) in diaphragm cell - Brine

recirculation mode

The system is directed both to facilitate better gas disengagement

from the anode-to-diaphragm gap into the internal space and to create a
net substantial downward flow of degassed brine to be in1ected along the
bottom rim of the anodes.
The expected results should include:
- reduced energy consumption
- reduced oxygen in chlorine
- increased diaphragm life.
 275

CHLOR-ALKALI MEMBRANE CELLS

As is well known, the content of oxygen negatively influences the quality

of produced chlorine. The oxygen, in membrane cell gas, is expected to be
higher due to the fact the cells operate with relatively high pH levels in
the anolyte which ranges between 3,5 and 4,5, provided that hydrochloric
acid is not added to the anolyte.
As a consequence an amalgam cell grade chlorine is likely to be
obtained in membrane cells only if highly selective coatings (Low Oxygen
Coating, LOC) are applied to the anode structure.
Fig. 9 shows the behaviour of the DNP LOC in terms of oxygen content
in the chlorine as a function of the bulk pH of the anolyte compared to
that typical of standard coating currently installed in amalgam cells.

02 .. VOL.
1.6,.------------------------,

1.4

1.2

1.0

0.8
Standard Coating
0.6
0.4 "-
Low Oxygen CoaUng (LOCI
0.2
0.0 L-_~ _ _.L.-_-..L_ __'___ __'__ _....L.._ ____''___...J

t.6 2.0 2.6 3.0 3.6 4.0 4.5 6.0 6.6

ANOLYTE PH
Anolyte concentraUon 2tO-216 gIl
CD . • 3 KAlM2 T • 90 C Anode/membrane 20 mm

Figure 9. Coating Test Cell - Oxygen Versus pH

It is important to point out that such data were obtained in the

so-called Coating Test Cell (CTC), the exploded section of which is given
in fig. 10.

(1) Solution outlet;

(2) solution inlet;
(3) drain; (4) cathode;
(5) top lid; (6) ion
exchange membrane; (7)
membrane holder; (8)
sight glass; (9) anode;
(10) back lid; (11)
thermosensor; (12)
thermometer; (13)heater

Figure 10. Exploded section of the Coating Test Cell (CTC)

 276

This test cell has been described by Nishiki and others of Permelec
Electrode, Japan in Journal of Applied Electrochemistry 19 (1989) 90-94.
The CTC is a membrane cell where the anode sample is held
approximately 20 mm away from the membrane. This assembly allows the
evaluation of the anode behaviour as a function of the temperature, pH and
concentration of the bulk anolyte, without any influence due to any
particular design aspect of the cell.
Temperature, pH and concentration of the anolyte are kept under
control as is shown in fig. 11.

(b) (a) Rectifier; (b) H2; (c)

C12+02; (d) Gaschromatrograph;
(e) Heaters; (f) Anolyte
sampling for pH control; (g)
Demi water tank; (h) Saturated
brine tank NaCl 300 gpl; (i)
5% HCl tank; (1) Catholyte
outlet; (m) Anolyte outlet.

(l) (m)

Figure 11. Coating Test Cell (CTC) - Simplified flow diagram

Fig. 9 demonstrates that LOC has the potential for producing high
quality chlorine, having an oxygen content running between 0.3 and 0.9\.
This is well below the threshold limit of 1,5% commonly accepted by
downstream user plants.
The standard coating, on the contrary, is completely unsuitable for
membrane operations, as the oxygen content in chlorine is expected to soar
well above the above mentioned limit of 1,5%.
In fig. 12 the LOC behaviour in the CTC cell is compared with that
which characterizes the same coating applied to single mesh, flattened
structure installed in an anodic zero gap arrangement with the membrane
both in a lab cell and in an industrial electrolyser.

2.0;:.O.::.2~":...Y:..:O:..:L::..._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _--,

1.a Induetrl.. Cell

- .. -_ .. -- I

1.a
1.4
81l1li1. MHII
""
"
II
II
1.2
1.0
"
10

o.a Lab. Cell "

o.a 81l1li1. M.... ~oetlllll Tnt Cell
" "
0.4
0.2
:'
"
0.0 L-~__'__'___'____'__'___'___I._'___L....I1_L_'--__'____I "
0.0 0.1 to 1.1 2.0 2.1 3.0 3.1 4.0 ..I 1.0 I.. 1.0 a.. 7.0
ANOLYTE PH
NIICI21I on LOC coatlllll
ONE M88 THROUGH
C.D.o aKA/III2 TotO C

Figure 12. Comparison between Laboratory results and industrial cell

Single Mesh Anode
 277

Such arrangement is due to the fact that in industrial cells a

positive pressure differential is kept between the cathodic and anodic
compartments so as to press the membrane against the surface of the anode.
The mesh is flattened to avoid sharp edges from damaging the delicate
membrane.
The values of pH reported are those taken at the brine outlet. At a
pH of 4 the industrial cell produces chlorine containing around 2\ of
oxygen. In the CTC the same level of oxygen would be obtained at a pH of
around 5,2.
The higher oxygen content in chlorine produced with single mesh
anodes demonstrates that the local recirculation of the anolyte, for
removal of the backmigrated alkalinity and replenishing of the brine in
the "windows" of the mesh, especially in the barely accessible edges
confined between mesh and membrane, is not satisfactory and must be
improved.
This poor recirculation rate of the brine is probably caused by the
flattening of the mesh, which hinders the development of locally separated
flows of brine characterized by different populations of chlorine bubbles
(local gas-lift recirculation).
It should be also pointed out that an insufficient local flow of
brine to the mesh anode may cause the oxygen content in chlorine to
further increase as a consequence of the decreased chloride concentration;
the relationship between oxygen content and brine concentration is given
in fig. 13. The data shows that the oxygen content is particularly
responsive to chlorides when the anolyte concentration is kept below 200
gpl.

1.0

0.8

0.8

0.4

0.2
~~==============
pH2

0.0 ' - _ - ' - _ - L _ - - - ' ' - _ . L - _ - ' - _ - ' - _ . _ - ' - - _ - ' - _ - - '
~ ~ * ~ ~ m ~ ~ ~ ~
ANOLYTE CONCENTRATION « NaCI 1111 )
LOC coallnll
T • to C - C.D. 3 KA/m2 Anode/membrane 20 mm

Figure 13. Coating Test Cell - 02 versus anolyte concentration

A solution to the above mentioned problems is represented by the DNP

DUPLEX ANODE, the structure of which comprises a coarse expanded
unflattened mesh and a fine expanded, fully flattened screen (fig. 14).
 278
The DUPLEX ANODE structure divides the dual and conflicting role of
supporting the membrane (which requires a flattened mesh) and of providing
a substantial recirculation of the anolyte (which requires an unflattened
mesh): each function is assigned to a separated component. The DUPLEX
ANODE configuration allows a notable replacement of the electrolyte in
the vicinity of the membrane, which favours an improved control of the pH
and of the concentration of chlorides in contact with the electrode
surface.

Figure 14. DUPLEX ANODE

Fig. 15 represents the behaviour of LOC both applied to an

industrial DUPLEX ANODE and in the CTC, whereas fig. 16 summarizes all
data of fig. 9, 12 and 15 to allow for an easier comparison.

2.0;:.O=.2...::,.:....Y:....OL:.:::.._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _---,

1.1
1.11
1.4
1.2 'nduat,," oell OUplex Anode - -
1.0
0.8
0.8 Coat'ng Teat CeI'
0.4
0.2
0.0 L---'-_'---'----''---'----'_-'----'_-'--'L....o._...L..---'-_..!.-.-'
0.0 0.1 1.0 1.1 2.0 2.1 3.0 3.1 4.0 4.1 1.0 1.1 8.0 8.1 7.0
ANOLYTE PH
NaCI211 gn LOC coating
coo.' 3 KAlm2 - T • 10 C HIGH RECIRCULATION RATE

Figure 15. DUPLEX ANODE Comparison between Coating Test Cell and
industrial cell
 279
The DUPLEX ANODE is also expected to be capable of producing a more
uniform distribution of current across the membrane.
A possible method to demonstrate the degree of local homogeneity of
the current density consists in analysing the distribution of some
impurities which concentrate in certain areas of the membrane according to
the strength of the electric field (e.g. calcium, magnesium, sulphates):
in other words the map of the impurities precipitated inside the membrane
is the image of the distribution of the current density (J.T. Keating, Du
Pont, Electrochemical Society Meeting, Honolulu, Hawaii, October 1987).
DNP is currently mapping the impurities in used membranes coming from
industrial plants: the data collected to now seem to support the above
idea and demonstrate the superior ability of the DUPLEX ANODE to
distribute current density across the membrane.
2.0;O~2~~~V~0=L.______________________________________,

1.8
Industrial Cell
1.6
Duple" Anode
1.4
1.2
1.0 r
0.8 r- Lab cell

~:: f Singl~ Meah An~

0.0 L--........__"---"-__-'-____..J.-_ _ _ _ --'-----''--~ _ _____'_

0.0 0.6 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.6 5.0 5.5 6.0 8.5 7.0
ANOLYTE PH
NaCI 215 gpl LOC coating
C.D.• 3 KA/m2 - T • 90 C

Figure 16. Summary - Comparison between lab results and industrial cells

ELECTROGALVANIZING

The preceding presentation can be summarised in just one sentence. The

best performance of catalytic electrodes is obtained from a close
cooperation between the coating and the supporting structure.
The same concept has also been proven to be valid in quite a
different field of the electrochemical industry, that is in the high speed
electrogalvanizing of steel (EGL), where the metal anodes are operated at
current densities of 10 to 15 KA/m2 in acidic, sulphate-bearing
electrolytes under oxygen discharge.
Under such conditions any electrocatalytic coating applied to
conventional titanium structures would exhibit too short a life
thus considerably reducing industrial interest.
The basis for a new design has been provided by the relationship
between life of the coating and current density. Such relationship is
logarithmic in nature, so that, for instance, the useful life is more than
doubled when the current density is reduced to 50\.
The new structure which has been developed by DNP for EGL
applications comprises a plurality of parallel, interconnected, thin,
 280
coated titanium layers having different degrees of expansion called PLURAL
ANODE (fig. 17).
Size of the mesh and open area ratio are chosen for each layer in
such a way that the total current distributes homogeneously among the
various layers and the current density does not exceed the value
corresponding to the minimum desired lifetime of the anode.
Such an anode can operate at a relatively low current density for
each electrode layer with the consequence of rather long and profitable
lifetimes, even if the total current load per m2 of projected area is
high.

Figure 17. PLURAL ANODE

 281

HYDROGEN EVOLUTION ON OXIDE ELECTRODES

SERGIO TRASATTI
Department of Phy~ical Chemi~try and Electrochemi~try
Univer~ity of Nilan, Via Venezian 21, 20133 Nilan, Italy

Hz evolution on RuOz, IrOz and C030" prepared by thermal decomposition of

suitable precursors at temperatures between 300 and 500·C has been studied
in alkaline solution (1 mol dm-3 NaOH) by means of quasistationary
potentiostatic curves and reaction order determination. The electrodes have
been characterized by vol tanmetric curves before and after each set of
experiments to monitor their surface state. The variation of the
voltanmetric charge with use, and hysteresis phenomena in recording
polarization curves are explained in terms of wetting of the oxide surface
promoted by hydrogen discharge. The same kinetic parameters are observed
for RuOz and IrOz. A Tafel slope close to 40 mV and a fractional reaction
order of -0.5 with respect to OH- are explained with a mechanism involving
a step of reduction of the active sites, a pH dependence of the potential
at the reacting plane and a pH dependent surface concentration of OH-. The
mechanism is different for C030" , which exhibits an appreciably higher
overpotential. In the case of RuOz and IrOz electrodes there is no evidence
that oxide surfaces are reduced down to metal.

INTRODUCTION

In the continuous search for new materials and for new

applications of technologically established materials, recent
patents have claimed good performances for oxide electrodes in
the ca thodi c evo I ut i on of hydrogen [1-5]. It appears tha t the
most interesting feature is not the electrocatalytic activ-
ity itself but rather the resistance to deactivation due to the
deposition of metallic impurities in technical solutions [S,7].
As often happens, applications have anticipated
fundamental understanding. There are in fact only very few
papers in the open literature dealing with kinetic aspects of
 282

hydrogen evolution at oxIdes. Actually, the first work was

carried out in this laboratory [8] long ago before any
practical appl ication was envisaged. In that study, some Tafel
lines for Ha liberation at RuOa electrodes were reported but
complete mechanistic and stability investigations were not
performed. Recent I y, RuOa has been compared to Pt and Ru for
its ability to remain active for Ha evolution even in the
presence of metallic impurities [9], A comparative study of
RuOa, electroless Ni and electroless Ni-coated RuOa cathodes
has been carried out by Jaccaud et a\. [10] on electrodes
prepared according to the ATOCHEM patent [5]. Finally, hydrogen
evolution on RuOa layers has been investigated [11] to
elucidate the rol e of colloidal RuOa as a cata I yst in the
photochemical reduction of water, a I though no definite
mechanism has been proposed.
The most intriguing aspect of oxides is that they are in
principle thermodynamically unstable in the hydrogen adsorption
region [12] and are not expected to be good candidates for
cathodes. Fundamental research should find an answer to such a
crucial question. A prerequisite is that the details of the
kinetic mechanism and of the surface response should be known.
A systematic study of hydrogen evolution on oxide cathodes
has been carri ed out in thi s I aboratory for about four years.
The mechanism of the reaction on RuOa and IrOa in acid solution
has already been discussed [13,14]. This work reports a
preliminary comparative analysis of the kinetic parameters in
alkaline solution for RuOa, IrOa and C0304.

EXPERIMENTAL

Electrodes
Electrodes of RuOa, IrOa and C0304 were prepared by depositing
a layer of the given oxide on both sides of 10xI0xO.2 mm Ti
plates. The precursors were hydrated RuCl3, IrCI3 and Co(N03)a,
respectively. They were dissolved in a suitable solvent and
spread onto the support by a brush. The plates were then fired
for a few minutes at the selected temperature in an oxygen
 283

stream. The operation was repeated until the desired amount of

catalyst was loaded (a few mg em-a). Samples were finally
annealed for h at the same temperature. Calcination was
carried out at the following temperatures: 300, 330, 360, 400,
450 and 500·C.

Solutions
1 mol dm- 3 NaOH solutions were used throughout except for the
determination of the reaction order for which solutions at
mol dm- 3 constant ionic strength were made by adding the
necessary amount of NaClO" to NaOH solutions in the range 0.1
to 1 mol dm- 3 •

Experimental Procedure
The surface state of the electrodes was characterized [15] by
means of voltammetric curves at 20 mV s-1 within a suitable
potential range prior to Oa evolution. Vol tammetric charges
(q") were recorded for the fresh electrodes, and again after
each set of experiments to monitor the surface state.
Potentiostatic experiments were performed by first
conditioning the electrode at 0 V(SCE) then moving down by 50
mV steps to -0.2 V, and further to more negative values by 10
mV steps. Current was read after 3 min at each potential.
The reaction order was determined by measuring the current
at a single constant potential for several pH's after a
suitable potential sequence.

RESULTS AND DISCUSSION

Voltammetric Curves
Voltammetric curves were recorded to monitor changes in surface
state. In order to elucidate the effect of the cathodic
treatment, voltammetric curve a were also recorded by
periodically enlarging the cathodic limit. Fig. shows the
case of a RuOz electrode. It is clearly seen that the
modifications introduced by the cathodic potential are totally
removed during the anodic scan. This indicates that if surface
 284

Fisun 1. Typical voltammetric curve of a RuOa electrode with variable cathodic

potential limit.

reduction takes place, it is reversible. An intriguing

observation is that after prolonged Ha evolution the
voltammetric charge is larger than for fresh electrodes,
although the shape of the curve remains qualitatively exactly
the same [16]. Larger values of ~ are observed systematically
for fresh electrodes, as Fig. 2 shows. It is thought that the
aveileble oxide surface is not totally wat on fresh electrodes.

250
/
/

. ..
/
/
/
/

. .y/..
/.

.....
.. / ................ .6
i" ....
t

...
... / .6

..
/
50 /
/
/
/
50

Fiau" 2. (.trJ Voltammetric charse before (1) and after (f) hydrosen evolution
experiments for frah RuOa electroda. (A) The ..me plot for the ..... electrode.
after about ona YMr.
 285
Wetting is presumably promoted by strong hydrogen discharge.
Once out of the solution. electrodes tend to be slowly dewetted
again [ 131. Thus. the actually active surface does not
necessarily coincide with the available active surface which
may be partly excluded from the electrochemical reaction.
However. as Fig. 2 also shows. "aged" electrodes do not change
their active surface area any more even after prolonged
cathodic load.
The behaviour of C030. is different. This oxide shows
anodic peaks whose height increases with the cathodic potential
1 imit (Fig. 3>' Therefore. C030. is more drastically modified
than IrOa and RuOa. although it can also recover the original
qualitative behaviour after an anodic potential scan or
prolonged permanence in the air. Such a reversibility of the
cathodic-anodic behaviour suggests that the surface is reduced
but without destruction of the oxide lattice. Tentatively.
dur ing mi 1 d Ha di scharge. a tomi c hydrogen is present on the
surface as (OM)-H sites which are reoxidized to (OM)-OH by
water molecules as the electrode is released from the cathodic
potential.

Figure 3. Typical voltl!lmmetric curve of • C030. electrode with variable cathodic

potenUal limit.

"Up" and "down" Tafel line. on fresh RuOa and IrOa electrodes
showed appreciable hysteresis which decreased with the number
 286

of runs [141. The hysteresis disappeared for IrOa after three

to four runs, but it persisted somewhat for RuOa. The form is
also different. The shape of the hysteresis suggests that the
active surface increases under strong hydrogen evolution. This
fact corroborates the idea that wetting is promoted by cathodic
hydrogen discharge. The non-wettabi I i ty of part of the
"internal" surface [17] of the fresh oxides is not surprising
in view of their thermal preparation.
In the case of RuOa electrodes in particular, the Tafel
line shows a much lower slope when recorded backwards. This may
be related to some effects of the backward reaction which can
take place in the pores oversaturated with the evolved Ha gas.
The smaller effect with IrOa is probably related to the lower
activity of this material and therefore to the higher
overpotential [14].
Figure 4 compares the behaviour of IrOa, RuOa and C030•.
While the first two oxides exhibit a qualitatively similar
pattern, the behaviour of C030. is dramatically different. In
particular, while Ha evolution commences at about -1.05 V(SCE)
with RuOa and IrOa, it begins only at -1.25 V(SCE) with C030.,
being preceded by a slow reaction whose Tafel slope is of the
order of 180 mY. This reaction is assumed to involve hydrogen
penetration into the oxide structure.
The analysis of the hysteresis-free kinetic data show that
in the case of RuOa and C030. they consist of a single Tafel
I ine up to about 0.1 A cm- a, the I imi t of the current range
explored. Since for RuOa electrodes the Tafel slope depends on
the direction of potential scan, only the data for the first
forward potential scan have been taken into consideration for
the mechanistic analysis. Under similar circumstances, any
deviation from linearity can be totally accounted for in terms
of uncompensated ohmic drop. In the case of IrOa electrodes the
data can only be interpreted in terms of two Tafel I ines of
different slopes.
The Tafel slope was found to scatter within narrow limits
as the calcination temperature was changed, despite the effect
of the linearization of the data in the presence of substantial
ohmic drop (Fig. 5). In particular, the Tafel slope is close to
 287

-0.9

. ..
-1.0

>
.
-.....---~.-------
'l-1.1
.
---.~
$ ~-"~
IJJ -1.2
. 2• . . .""."0.
~
-1.3
--------.----.--- ... ..
. -..
.....
3 .~"'''' ...

.
-1.4
~

-4 -3 -1

Figure 4. Typical quasi-stationary potentiostatic curves for hydrogen evolution

on (1) RuOa. (2) IrOa. and (3) C030.. Theoretical Tafel slopes have been drawn
through the points: (1) 40 mY; (2) 40 and 120 mY; (3) 60 mY.

---.. --.--.---

___ e ___ e ____________ _

50
! t
40 ---1--1--:---&---6--- ... - _ - -

30
300 400 500
ttc

Figure 5. Tafel slope for hydrogen evolution as a function of the calcination

temperature: (I) RuOa. (.) IrOa. (e) C030 ••

40 mV with RuOa. and with IrOa in the low overpotential range.

while it is close to 60 mV with C030•• In the case of lrOa. in
the high overpotential region. the Tafel line is of the order
of 120 mY.

Order of Reaction
Figure 6 shows typical dependences of log j at constant
potential as a function of the OH- concentration. The potential
was chosen so as to I ie on the I inear section of the Tafel
lines as the pH is changed. Despite unavoidable scatters. the
 288

.~

13.0 13.5 14.0

pH

Figure 6. Typical reaction order determination for hydrogen evolution at

constant potential: (1) RuOa, (2) IrOa, (3) C0304.

reaction order is clearly integer (-1) with C0304, while it is

fractional (ca. -0.5) with RuOa and IrOa <in the low
overpotential region). The negative order of reaction means
that the reaction rate is depressed as the alkali concentration
is increased. Fractional reaction orders (but close to -1.5)
have been observed with RuOa and IrOa in acid solution [13,14J.

Reliction Mechanism
The classical mechanisms for hydrogen evolution have to be
modified to be able to reproduce the kinetic features observed
here. In particular, the mechanism predicting 40 mV for the
Tafel slope in alkaline solutions:

HaO + e ~ Had + OH- (III)

Had + HaO + e ~ Ha+ OH- <1b)

with step (lb) being rate determining, requires an order of

reaction. with respect to OH-, equal to -1, which has not been
observed here. Taking into IIccount the different behaviour of
 289

with respect to RU02 and Ir02, the following

"generalized" mechanism is proposed:

M-OH + H20 + e * M-OH2- + OH- (2a)

M-OH2 - ... M-OH2 (2b)
M-OH2 + e ... M-H + OH- rds (2c)
M-H + H20 ... M-OH + H2 (2d)

where M-OH is an active site on the oxide surface. Step (2b)

involves the "chemical" rearrangement of the unstable
intermediate M-OH2-. Step (2c) corresponds to the reduction of
a surface active site, and is assumed to be the rate
determining step wi th RU02 and I r02 electrodes, whereas step
(2b) is the rate determining step with C030". Step (2d) is a
chemical reaction whose occurrence is supported by the results
of the experiments with bubbling H2 gas at open circuit. Step
(2d) is fast but irreversible so that if the electrode
potential is released, surface sites are rapidly reoxidized.
Conversely, it can be stated that H atoms on active sites are
reactive enough as to reduce water, ie, they are not firmly
stabilized by chemisorption. This supports the view that such H
atoms differ from those present on the surface of a metal.
Mechanism (2) predicts a reaction order of -1 for all
electrodes. The observed fractional reaction order with RU02
and Ir02 is explained on the basis of the known acid-base
behaviour of oxide surfaces [18]. During the reaction order
determination, the solution pH is systematically varied.
Therefore, the electric potential at the reacting site also
changes systematically according to:

<II- - -(RTIF)pH == -(RT/F)ln[OH-] ( 3)

as a consequence of the surface equilibrium:

0-
+ OH- * MI + H20 (4)
'H
The kinetic equation, for step (2c) being rate determining, is
 290

to be corrected for the ~e effect:

j - [OH-]-lexp[-(l+ac)(E+<II e )FIRT] (5 )

If eqn.(3) is introduced into eqn.(4) the result is:

j - [OH- ]-« exp[-( l+ac )EFIRT] (6)

where ac is the cathodic transfer coefficient. Equation (6)

shows that a fractional reaction order of -0.5 should be
observed if the local electric potential at the reacting site
is influenced by the pH. Coincidence with the experimental
value is thus obtained. Therefore, the fractional reaction
order is in fact an effect of the electrode charging mechanism
[19], ie, a double layer effect which cannot be avoided even at
constant ionic strength.
In the case of C030. electrodes, step (2b) is assumed to
be the r.d.s. Therefore:

j - [OH2 e ] (7)

If the step (2a) is in quasi-equilibrium:

[OH2 e ] [OH-]-I exp{-FE/RT} (8 )

From eqns.(7) and (8):

j - [OH- ]-1 exp{-EF/RT} (9 )

which reproduces the observed kinetic data.

With Ir02 electrodes, in the high overpotential range, the
observed Tafel slope of 120 mV suggests that the primary
discharge, step (2a), is rate determining. Under similar
circumstances:

( 10)

whi~h, with @qn.(3) gives:

 291

j - [OH- lIKe exp (-occ EF IRT) ( 11>

Eqn.(ll) predicts a reaction order of 0.5. However, the

experimental value is not available.

Geometric effects
Since the charge q'I is proportional to the active surface area,
a plot of current at constant E against q'I should provide a
mean to separate geometric from electronic factors [201. A
typical plot is shown in Fig. 7 for Ir02 and RuOz. The linear
dependence indicates that hydrogen evolution does not give rise
to pore exc I usion; otherwi se. the s lope wou I d be higher than
one and increasing with q'I [211. At the same time. no extra
electrocatalytic effects are introduced as the surface area is

./
,/
,/0

,/
/0
,/0
"
0'/ 0

-.
/. 0

~/
,/
,/
Q3 1.8 2D 2.8

Figure 7. Plot of current for hydrogen evolution lit constant potential against
the voltammetric charge of RuOz electrodes. (--) Unit slope.

.
/
00
• • • tI'
'" '"
?'''
o ,,/ ~.

'" '"
'" '"
-Q2

1.7 1.9 2.1 2.3 2.5 2.7

log (q;/mCcm-2 )

Pisure I. Plot of current for hydrosen evolution at constant potential asainst

the (final) voltammetric charse of CO,O, electrode.. ( - ) Unit slope.
 292

increased; otherwise, a slope lower than one decreasing with ~

should be observed [22]. In the case of C0304 the plot shown in
Fig. 8 suggests that j and q- do not depend on the same
factors. This behaviour is likely to indicate> that q- is no
longer a purely surface parameter with C0304. The reason is
thought to be the bulk penetration of hydrogen during heavy
cathodic load.

CONCLUSIONS

(a) I r02 and RU02 are good electrocatalysts for hydrogen

evolution. However, these oxide electrodes do not take the
equilibrium potential in the presence of bubbling H2. The
presumable reason is that the "reduced" sites necessary for the
establishment of the equilibrium can only be formed
electrochemically and not by H2 dissociation.
(b) The formation of "reduced" sites promotes the wetting
of the electrode surface. This results in an apparent increase
in activity at the beginning of hydrogen evolution.
(c) The electrocatalytic activity for Ha evolution varies
in the order RU02 ~ Ir02 » C0304. The reaction on the spinel is
preceded by the reduction of the electrocatalyst. The Tafel
slope is 40 mV for Ru02 and Ir02 and 60 mV for C0304. A second
Tafel line of higher slope is observed with Ir02 in the current
density range> 10 rnA cm- a .
(d) RU02 and Ir02 do not appear to be reduced during
cathodic polarization. There is evidence that the reaction
involves only the very surface of the oxide while the lattice
is never modified. Reasons for that are mainly to be sought in
the metallic conductivity of these oxides and in the inherently
difficult reducibility of these transition metal ions to metal.
(e) C0304 is not stable under heavy cathodic load. The
reason may be sought in its intrinsic semiconducting
properties. The penetration of the electric field into the bulk
can assist the migration of protons. The independence of the
final values of q- on the calcination temperature indicates
that q- is no longer simply a surface parameter.
 293

(f) Hydrogen evolution on oxides differs by different

reaction orders from the classical mechanisms predicting the
same Tafel slopes. This is due to the involvement of the active
site reduction as one of the steps in the mechanism. A
fractional reaction order is observed which can be explained in
terms of the known acid-base response of an oxide surface to pH
[101. This provides further support to the view that the
surface is never "like that of the metal" even during strong
hydrogen evolution. It also explains the dramatically different
adsorption properties between Ru and RuOz in respect to
metallic impurities present in solution [51.
(g) The calcination temperature does not influence either
the mechanism or the electrocatalytic activity. Any variation
of apparent activi ty is thus to be attributed to changes in
active surface area.

Acknowledgements
This work was supported by the National Research Council.

REFERENCES

1. Cairns, J.F, Denton D.A. and Izard, P.A., Cathode for use in
electrolytic cell. Eur. P.t. AppJ., 1984, EP 129 374; Chem. Ab.tr.,
1985, 102, 102442.

2. Nidola, A., Cathode for aqueous electrolysis. PeT Int. Appl., 1986, we
86 03 790; Cham. Ab.tr., 1986, lOS, 122974.

3. Debrodt, H., Electrode for use in electrochemical processes. Eur. P.t.

Appl., 1984, EP 129 088; Cham. Ab.tr., 1984, 102, 122040.

4. Nicolas, E., Cathode for the electrolytic production of hydrogen. Eur.

P.t. Appl., 1981, 23 368; Cham. Abstr., 1981, 94, 199838.

5. Clerc-Renaud, J., Leroux, F. and Ravier, D., Cathode and its

manufacturing for electrolysis of .ater and alkali metal halides. Eur.
P.t. Appl., 1987, EP 240 413; Cham. Abstr., 1988, 108. 45864.

6. Nidola, A. and Schira, R., Poisonins mechanisms and structural

analyses on metal I ic contaminated cathode catalysts in chlor-alkal i
membrane cell technolosy. J. Electrocham. Soc., 1986, 133. 1653-6.

7. Nidola, A., Ceramic electrocatalysts in the field of chlor-alkali

membrane cell technoiosy. In Hi6h Tech Ceramics, ed. P. Vincenzini,
Elsevier. Am.terdam. 1987, p. 2191-202.
 294

8. Galizzioli, D., Tantardini, F. and Trasatti, S., Ruthenium dioxide: a

new electrode material. II. Non-stoichiometry and energetics of
electrode reactions in acid solutions. J. Appl. Electrochem., 1975, 5,
203.

9. Kotz, E.R. and Stucki, S., Ruthenium dioxide as a hydrogen-evolving

cathode. J. Appl. Electrochem., 1987, 17, 1190-1197.

10. Jaccaud, M., Leroux, F. and Millet, J.C., New chlor-alkali activated
cathodes. Hater. Chem. Phys., 1989, 22, 105-19.

11. Kleijn, M. and Van Leeuwen, H.P., Voltammetric characteristics of the

RuOa film electrode in relation to the catalytic properties of RuOa
for the photochemical production of hydrogen. J. Electroanal. Chem.,
1988, 247, 253-263.

12. Trasatti, S. and Lodi, G., Properties of conductive transition metal

oxides with ruti Ie-type structure. In Electrode!J of Conductive
Hetallic Oxides, ed. S. Trasatti, Part A, Elsevier, Amsterdam, 1980,
p. 301-58.

13. Boodts, J.C.F. and Trasatti, S., Hydrogen evolution on iridium oxide
cathodes. J. Appl. Electrochem., 1989, 19, 255-62.

14. Boodts, J.C.F., Fregonara, G. and Trasatti, S., Hydrogen evolution on

oxide cathodes. In Performance of Electrode!J for Inau!Jtrial
Electrochemical Rellctor!J, eds. F. Hine, B.V. Tilak, J.M. Fenton and
J.D. Lisius, The Electrochemical Society, Pennington, NJ, 1989, p.
135-45.

15. Ardizzone, S., Carugati, A.and Trasatti, S., Properties of thermally

prepared IrOa electrodes. J. Electroanal. Chem., 1981, 126, 287-92.

16. Ardizzone, S., Fregonara, G. and Trasatti, S., Influence of hydrogen

evolution on the voltammetric charge of RuOa electrodes. J.
Electroanal. Chem., 1989, 266, 191-5.

17. Ardizzone, S., Fregonara, G. and Trasatti, S., "Inner" and "outer"
active surface of RuOa electrodes. Electrochim. Acta, 1990, 35, 263-7.

18. Daghetti, A., Lodi, G. and Trasatti, S., Interfacial properties of

oxides used as anodes in the electrochemical technology. Hater. Chem.
Phys., 1983, 8, 1-90.

19. Angel inetta, C., Falciola, M. and Trasatti, S., Heterogeneous acid-
base equilibria and reaction order of oxygen evolution on oxide
electrodes. J. Electroanal. Chem., 1986, 205, 347-53.

20. Trasatti, S., Oxide/aqueous solution interfaces. Interplay of surface

chemistry and electrocatalysis. Hater. Chem. Phys., 1987, 16 157-74.

21. Boggio, R., Carugati, A., Lodi, G. and Trasatti, S., Mechanistic study
of Cia evolution at Ti-supported Co30, anodes. J. Appl. Electrochem.,
1985, 15, 335-49.

22. Tresetti, S., Electrocatalysis in the anodic evolution of oxygen and

chlorine. Electrochim. Acta, 1984, 29, 1503-12.
 295

IMPURITY EFFECTS IN CHLORATE PLANTS

Johan WanngArd
Eka Nobel, Electrochemicals Division,
Box 13000, S-850 13 Sundsvall, Sweden

ABSTRACT

Minimum energy consumption and overall highest performance of

chlorate plants are demands which motivate increasing investments
in systems to control the electrolyte purity. Generally, no
electrolyte bleed is possible for environmental reasons and
shipments of chlorate electrolyte are decreasing significantly.
A specific problem in chlorate technology is ,therefore, that
several impurities that are fed to the process with the raw
materials accumulate in the electrolyte and on the electrode
surfaces.

This paper considers a classification of impurities and their

effects on the electrode performance, solubility of NaCl and
catalytic decomposition of hypochlorite. Systems for brine and
electrolyte treatment are also discussed for some important
impurities.

INTRODUCTION

The use of chlorine in pulp bleaching has for environmental

reasons decreased dramatically during the 1980's. It has mainly
been replaced by oxygen, hydrogen peroxide and chlorine dioxide.
This fact explains the strong expansion of Eka Nobel being the
world leading chlorate producer and one of the dominating
peroxide producers of today.

Some important trends in the future development of the chlorate

technology are:

1/ Minimization of energy consumption, utilization of hydrogen

and low grade waste heat and possibly also utilization of
variable energy tariffs.
2/ Environmental aspects demand closed plants with ever
reducing possibilities of electrolyte solution shipments,
process bleeds and other other effluents to sewer and
atmosphere.
3/ Sophisticated electrode and construction materials which
 296

require highest possible utilization and systems to avoid

corrosion, deactivation and other kinds of degradation.
4/ On-site generation of chlorine dioxide in highly closed,
integrated CI02-NaCI03 plants.
A common requirement is the increased significance of careful
control of the electrolyte purity. However, little knowledge
exists on quantitative impurity effects with relevance to modern
chlorate technology. This paper considers a brief discussion of
impurities with respect to qualitative and quantitative effects,
critical levels and purification systems.

BRIEF PROCESS DESCRIPTION

A simplified flow sheet demonstrating the most important parts of
a modern chlorate plant is shown in figure 1.

Reactor-
Hz gas HzO

NaOH

Hel

Air

Figure 1: Block sheet for a chlorate plant

1 Water purification 8 Thickener
2 Sodium chloride purification 9 Wash filter or centrifuge
3 Sodium chloride dissolver 10 Dryer
4 Electrolyzers 11 Dust scrubber
5 Scrubbers 12 Condenser
6 Reactor 13 Electrolyte cooler
7 Crystallizer

The global mass balance is

NaCI + 3~O -~ NaCI03 + 3~ (R1)
 297

Water is purified (generally deionized) and fed to a sodium

chloride purification system. The chloride is fed to the
electrolyte as a high grade brine or salt slurry. Chloride rich
electrolyte containing appr 600 gil NaCI03 and 120 gil NaCl is pH
adjusted with HCl and fed to the electrolysis which generally
works around 70°C, pH 7. A low concentration of sodium
dichromate in the range 2-6 gil is used to improve the current
efficiency (1). The cell and reactor gases are washed with
caustic in a scrubber system and the caustic excess in the
scrubber liquid is used to alkalize the crystallizer or filter
feeds. Modern plants are equipped with electrolyte scrubbers
utilizing the alkalinity in the crystallizer effluent (15).
The major fraction of the electrolyte is recirculated to the
cells after cooling and only a small fraction is used in the
crystallization loop. Modern chlorate plants are generally
equipped with flash crystallizers operating at temperatures
between 20 and 40°C achieved with powerful vacuum systems. Feed
of additional heat provides possibilities to control the water
balance. The chlorate crystals are separated from the mother
liquid and washed to reduce the chloride and dichromate
concentrations before the crystals are sent to the dryer.
The crystallizer condensate can be reused in the process using
indirect condensers. Condensate can only be sent to sewer if
contamination of electrolyte drops and chlorine vapors are
eliminated. Dust scrubbing to reduce the chlorate contents in the
effluent gas from the dryer to a few mg/Nm3 is generally
necessary for safety and environmental reasons. Treatment of
sludge from brine and electrolyte filters with reduction of
chlorate and chromium is required before disposal. Rejects from
ion exchangers must also be processed before discharge.

THE ELECTRODE GAP

The electrolysis is generally made using DSA anode and steel

cathode with the main reactions
2cr --~ Cl z + 2e- (R2)
2HzO + 2e- -~ Hz + 20H- (R3)
A quick hydrolysis of the chlorine follows close to or even on
the anode surface forming hypochlorous acid in a first step,
hypochlorite in a subsequent dissociation step and clorate by
disproportionation
CI Z + HzO --~ HCIO + H+ + Cl- (R4)
HCIO .--~ CIO- + H+ (Rs)
2HCIO + ClO- --~ CIO-3 + 2H+ + 2 cr (R6)
The electrode gap is typically around 3 mm and with current
densities in the range 2-3 kA/mz. Under these conditions the
following voltage components can be distinguished :
 298

Anode potential 1.4

iR drop in electrolyte 0.2
due to bubble effects 0.1-0.15
in the cathode diaphragm 0.15-0.3
cathode potential 1.0
Total voltage (excl hardware) 2.85-3.3
The anode works close to the reversible potential with an
overvoltage of about 50 mV. A NaCl concentration above 110 gil is
sufficient to supply chloride to the anodic chlorine formation.
It should be pointed out that the mass transfer is very efficient
in a chlorate electrolyzer due to the gas lift which gives
velocities from 0.2 up to 0.8 mls in the electrode gap depending
on the electrode distance and the gas lift design.
Approximately 0.5 V of the cathode potential is concentration
polarization. Hydroxide generated on the cathode forms a
diffusion layer next to the cathode with a hydroxide
concentration in the order of 0.5 mole/l. A rough estimation
shows that the effect of a 0.1 mm layer of corrosion products may
increase the hydroxide concentration in the order of 0.5-1 molell
which may cost 20-30 mV.

It is more complicated to determine the anode pH due to the

buffering effects of dichromate and hypochlorite and since good
physical data for the rates of chlorine hydrolysis, buffer
reactions and proton diffusion are not available. The atmosphere
of saturated chlorine indicates that it may be well below 2.

CLASSIFICATION OF IMPURITIES
Pure chlorate electrolyte consists of NaCl, NaCI03 and Na 2Cr20 7
with small amounts of hypochlorite and hypochlorous acid as
principal intermediates in the chlorate formation.
Oxygen and perchlorate formation
2~0 --~ O2 + 4H+ + 4e- Eo = 1.23 V, 25 °c (R7)
ClO-3 + ~O --~ CIO-4 + 2H+ + 2e- Eo = 1.19 V, 25 °c (R8)
are the two most important anodic parasite reactions and the
standard potentials are lower than that for chlorine ~ormation

Eo = 1.35 V, 25 °c (R9)

The chlorine selectivity must therefore be promoted by efficient

chloride supply and by avoiding deactivation (poisoning, blockage
or bad adherance). This means that the presence of lead,
manganese, tin, fluoride, aluminum, silicon and BaS04 must be
minimized.
Other current efficiency losses occur due to decomposition of
hypochlorite and hypochlorous acid to chloride and oxygen . These
reactions are well known in the chlor-alkali industry but
 299

practically nothing has been reported applicable to conditions in

a modern chlorate plant. A screening study has shown that Co, Ni,
Cu and Ir are efficient decomposition catalysts accelerating the
ever progressive reaction
2HClO --~ 02 + 2H+ + 2Cr (R10)
It is also known (3) that iron particles which are ever present
as corrosion products may serve as carriers for Co and Ni oxides
which increases their individual activities significantly.
There is also a group of relatively inert impurities which, due
to their high solubilities, are difficult to separate once they
appear in the electrolyte. To this group belong in particular
sulphate and perchlorate which may affect the NaCl dissolving,
crystallization, water balance and the cathode performance due to
their effects on the solubilities of both sodium chloride and
sodium chlorate.
Several well known cathode poisons such as mercury, cadmium, zinc
and lead are known to lower the exchange current density several
orders of magnitude. The alkaline earth metals which form
resistive hydroxide deposits on the cathodes is another group of
important impurities. Corrosion products may be built into the
cathode diaphragm. This increases the voltage and may also under
certain conditions cause decreased current efficiency by an
electrochemical redox cycle with hypochlorite as oxidant. Silicon
and iron form a very stable complex Fe2Si04 which deposits on the
anode. Addition of Fe(2+) can therefore be used for efficient
reduction of silicon down below 1 mgll (14).

EQUILIBRIUM ABO SOLUBILITY DATA

As already mentioned, chlorate electrolyte generally contains 600
gil NaC103 • In addition, good anode performance requires around
120 gil NaCl in the electrolyte. Figure 2 shows that 20 gil N~S04
and 40 gil NaCI04 lower the NaCl solubility from 135 to 120 gil
and the marginal to cathodic chloride deposition decreases from
15 to 0 gil NaCl. The solubility limit is also easily exceeded by
too high concentrations of NaCI03 and NaOH on the cathode.
Most metals of importance except alkali and alkaline earth metals
have much higher standard potentials than the cathode potential
and may therefore be deposited on the cathode as metals. Mn02
(1.23 V) and Pb02 (1.46 V) for Pb(2+) activities above 0.3 mgll
may precipitate on the anode assuming a local pH of 2 and an
anode potential of 1.4 volts.
It is also well known that most metals can be deposited on the
cathodes as hydroxides and some as carbonates. The solubility
product is generally 10 to 100 times higher in chlorate
electrolyte than in water which depends on the high ion strength
with association effects and complex formation. This is for
instance exemplified by copper(2+). More than 80 , forms
 300

chloride complexes in 6 M NaCI04 and 2 M NaCl (2). Table 1

illustrates media effects on calcium carbonate solubilities:.
TABLE 1

pKs for CaC03 in various media

Water 7.8-8.3
Brine (300 g NaC1/l) 5.9-6.4
Chlorate electrolyte 7.2-7.4

The solubility product of CaC03 is consequently two orders of

magnitude higher in brine (4) than in water and that the
corresponding value in chlorate electrolyte lies between these
extreme values. Proton and hydroxide activity coefficients are on
the other hand in the range 10 or higher.

250 r----r--r----r--r--"""T'""----,

200 I___+-+-~f__-+-_t______f

S;150~~~+--f---+--t------f
t..,)
as
:z:;
~1001___+~~~~~-_t______f

50

o
400 500 600 700 800 900 1000
g NaCI0 3 /1

Figure 2: Solubility limits for NaCl and NaCl03 in the pure

system (full line) and with 20 gil N~S04 and 40 gil NaCI04
(broken line).

ASPECTS OR JlASS BALARCES .AID) PURIF:ICAT:IOR CORCEPTS

The best way to analyse the imp~rity concentrations in a plant is

to work with mass balances with respect to the electrolyte system
 301

which in it's general form is written for component i:

F(i) + P(i) = V dc(i)/dt + A dm(i)/dt + E(i) (E1)
where F(i) is the feed rate in raw materials
P(i) rate of generation
V total electrolyte volume
c(i) concentration
t time
A electrode area
m(i) mass deposited on the electrodes
E(i) rate of effluents (product, bleed, sludge,
etc)
The applicablity of eq E1 and some alternative purification
systems will now be discussed for some common impurities.
Sulphate:
Raw water and sodium chloride are the most important sulphate
sources. The salt may contain between 10 and 5000 ppm of sulphate
depending on whether it is a high grade vacuum salt or rock salt.
An anion exchanger for the process water is therefore often
insufficient. A maximum level of 15 gil Na 2S04 is recommended to
avoid precipitation in the electrode gaps. Sulphate is trapped in
the chlorate during the crystallization and concentrations around
50 ppm may be obtained in the product.
This means that about double the concentration, in the present
example 100 ppm, can be tolerated in the NaCl feed. However, the
sulphate concentration in the product depends on several factors
as for instance crystallizer temperature and particle size and is
difficult to predict. Plants with electrolyte solution shipments
have generally no problem keeping the concentration far below 10
gil. A common problem in many other plants with insufficient salt
purity is that the sulphate level increases a few gil each year.
A number of measures may be taken to rectify this and are
discussed below.
It is important to distinguish between processes for salt and
electrolyte purification. The following methods may be used for
brine purification:
- rapid dissolving of rock salt separates up to 50% of the
sulphate
- salt evaporation separates the salt crystals from the sulphate
which is concentrated in the mother liquid (6). The latter
concentration can be controlled with a Glauber system
producing Na2S04 .10Hz0(s), a conventional Ca precipitation
producing glauberite Na2Ca(S04)2(s) or, if a good recipient
exists, with a slight bleed of mother liquid.
- barium precipitation is efficient but risky. This is a method
that requires high performance filtration and check systems
to ensure that no BaS04 crystallites enter the electrolyzers
and pOison the anode.
 302

Generally speaking, a good salt evaporation system is recommended

which may be efficient for separation of other impurities as
well.

Sulphate may be recovered from chlorate electrolyte by

- hot evaporation gives a NaCI+Na2S04 precipitate (see fig 3).
- precipitation with barium (not recommended) or calcium (6).
The precipitation product using calcium chloride is
glauberite which is formed when the calcium concentration
exceeds 200 mg/l. Therefore, a carefully controlled
treatment with soda ash and caustic is necessary in a second
stage. Coprecipitation of chromate must be minimized by
careful pH control and slow precipitation to accomplish
sludge disposal.
- cooling crystallization leading to coprecipitation in the
product (7). This may lead to small crystals which are
difficult to purify from chromate and chloride and may be
unacceptable to the customers.

200 ~---+-+---+--+--f---I

~150
~
~100~~~~~~.-+-~---I
D
50
\ \
\ \
o
400 500 600 700 800 900 1000
g NaCI0 3 /1
Figure 3: Selective precipitation of NaCI and Na2S04 by hot
evaporation. A-B: Concentration, B-C: Precipitation of NaCI,
C-D: precipitation of NaCI + NazS04' D-E: optional crystallization
of NaCI03 .

Perchlorate:
No perchlorate is added to the process but small quantities are
formed due to poor anode selectivity (reaction R8) and slow
disproportionation of hypochlorite and chlorate. Regular checks
 303

of the anode performance must be made (oxygen formation and anode

potential) to sort out those electrodes that are responsible for
the perchlorate formation. If no measures are taken and no
electrolyte shipments are possible an annual concentration
increase of 10 g NaCI04/1 may result which in turn may lead to
salt deposition on the electrodes.
The solubility of NaCI04 is around 1000 gIl and the only
realistic possibility is to precipitate it with KCl as KCI04
(8). using this method it is possible to keep the concentration
at 40 gIl NaCI04 • This limitation depends on the coprecipitation
of KCI03 that sets in at lower perchlorate concentrations. As
already shown in figure 2, this is sometimes too high to be
acceptable and the remaining possibility is to evaporate the
electrolyte, separate the chlorate precipitate and finally carry
out the KCI04 precipitation (8).

Figure 4 shows how the perchlorate concentration in the plant can

be controlled using this process. The preconcentration ratio is
the ratio between the liquid volumes before and after
evaporation.

40

30
1l ____ : 10'C
~
.::::::.. : 25'C
en
~
o
20
~
~

10

10 20 30 40 50 60 70
g NaCI0 4 /1 in electrolyte feed
Figure 4: Maximum selective recovery of KCI04 from sodium
chlorate electrolyte by precipitation with KCl for various
preconcentration ratios (1,2 & 4) and temperatures.

Calcium:

Calcium is one the most important impurities which severely

deteriorates the cathode performance, Modern chlorate plants are
 304

therefore generally equipped with ion exchange for alkaline earth

metals to reduce the concentration to 50 ppb or lower in the
brine. This would result in an annual feed of 4.4 kg in a plant
with a capacity of 50000 tonnes/year. Solutions recovered from
concrete trenches and floors may contain 200 mg/l Ca and may be
the dominating Ca source unless good systems for electrolyte
handling exist and suitable materials are chosen for floors and
trenches. It should be pointed out that the Ca concentration used
in the other raw materials (HCI, BaOH, soda ash, filter aid,
Ba2Cr20 7 ) frequently can be the dominating Ca sources. A
consumption of 60 kg 33 % HCI and 40 kg 50 % BaOH/tonne
containing 2 ppm contributes with another 10 kg/year.
The chlorate product contains generally very low Ca
concentrations and can therefore never provide a sufficient
bleed.
Soda ash precipitation in the electrolyte is therefore necessary
to minimize the accumulation on the electrodes. In practise, it
is difficult to come below 1 mg/l in the filtrate effluent. This
Ca level in the system leads to rates of Ca deposition in the
order of 1-5 g/m2/month which generally corresponds to voltage
increases about 10 to 50 mV/month. The precipitation depends
strongly on the alkalinity on the cathode surface which, in turn,
depends on the thickness of the diaphragm (1). It is therefore
obvious that cathodic precipitation processes may be self
maintaining. In practise, 1 mg/l is a tolerable level but good
cathode performance can never be guaranteed if strong effects of
corrosion products or other cathodic deposits exist.
A brine settler system fed with caustic and soda ash is necessary
for pretreatment of rock salt which may contain several thousands
of ppm Ca and produces a brine containing about 5 mg/l Ca. This
stream is treated in a cation exchanger. Salt evaporation may be
used to reduce the calcium concentration at least one order of
magnitude. However, an equally important function of a salt
evaporator is to separate silicon, fluoride, heavy metals and
sulphate.
The cathode deposit dissolves generally within a few hours after
shut down due to the acidification according to reaction R6. The
only possibility to separate such deposits is to install a
filtration system which is fed with cell liquid during shut
downs. Such a system is also valuable to protect the anodes from
high impurity levels that otherwise would exist at start up.

Hypochlorite decomposers:
Previous work on decomposition of hypochlorite (3),(9)-(11) have
not considered conditions of direct relevance to modern chlorate
manufacture. Therefore, it is necessary to continue these studies
to
1/ determine how much of the oxygen is formed on the anode and
how much is generated in the electrolyte and thereby also be
able to judge the anode performance
 305

2/ find criteria for sufficient electrolyte purity

3/ set criteria for sufficient analysis methods
4/ find optimum current concentration as discussed below

Some simple studies with one element at a time have shown that
the following effects are obtained in electrolysis at 70°C:

TABLE 2

Increased oxygen concentration and detection limits for the

most important hypochlorite decomposition catalysts.

Addition Effect 0.1 % 02 Appr detection limit

mg/l incr % °2 mg/l AAS AAS-GO ICP ICP-MS

Ni 1.0 2.0 0.05 1.0 0.02 0.1 0.2

Cu 1.0 0.7 0.14 0.2 0.005 0.02 0.02
Co 0.1 1.0 0.01 2.0 0.01 0.06 0.01
Ir 0.1 1.6 0.006 100 0.2 0.3 0.02

Detection limit: 6 SO in chlorate electrolyte. (Platinum,

ruthenium and iron show no effects at all.) A correct judgement
of the anode performance does therefore require considerably
better sensitivity than that which can be obtained with AAS and
ICP. ICP-MS is sufficient for Co and Cu but Ni and Ir requires
lower detection limits.

Alkaline filtration steps in the brine and electrolyte systems

and salt evaporation help keep the electrolyte concentration and
electrode contamination low. Table 2 shows that construction and
electrode materials containing the above elements should be
avoided unless long term testing proves that the dissolution
rates are negligible with respect to the above data.

The major current efficiency losses stem from anodic hypochlorite

oxidation and chemical hypochlorite decomposition. It has
previously been reported (12) that the oxygen concentration is
proportional to the hypochlorite concentration which ,in turn, is
proportional to the cubic root of current concentration I/V (13).
If kd and ka quantify the rates of hypochlorite decomposition and
anodic oxygen formation and it is assumed that these two
processes are first order with respect to hypochlorite we may
write

(E2)

It is easily shown that the minimum oxygen concentration and

current efficiency loss is obtained for I/V 2kd/ka.
Consequently, a pure system with low decomposition rate can be
equipped with large electrolyte volume while a contaminated
system should have a much smaller volume.
 306

REPERENCES
1. Lindbergh G.," The Effect of Chromate Addition on Chlorate
Cathodes" , Royal Institute of Technology, Stockholm ,Thesis
1990
2. Iuliano M. et aI, Ann de Chim 79, 439 (1989)
3. Gokhale S.D. and Frank L.L. in "Waste Water Treatment &
Utilization", Vol 2, Pergamon Press 1982, (ed Murray
Moo-Young et all
4. McKetta and Cunningham, "Encyclopedia of Chem Proc and
Design", Marcel Dekker 1978.
5. Welander B., Pat nbr US-4,888,099 (Eka Nobel)
6. Maloney B.A. and Carbaugh J.E., Pat nbr US-4,636,376 (PPG
Industries)
7. Burkell J.E. and Warren I.E., Pat nbr US-4,702,805 (Chemetics
International Co Ltd)
8. WanngArd J., Pat nbr SE-463 626 (Eka Nobel)
9. Lister M.W., Can J Chem 30, 879 (1952)
10. Lister M.W., Can J Chem 33, 479 (1955)
11. Lister M.W., Can J Chem 34, 465 (1956)
12. WanngArd J., Poster presented at the joint meeting of Dechema
and the Society of Chemical Industry, " Electrochemical Cell
Design and Optimization Procedures", Bad Soden, 24-26
September 1990
13. Viswanathan K. and Tilak B.V., J Electrochem Soc 131, 1551
(1984)
14. HAkansson B., Pat nbr US-4,946,565 (Eka Nobel)
15. Bolduc G. and WanngArd J., Pat nbr US-4,795,53516 (Eka
Nobel)
 307

CAUSTlC EVAPORATOR CORROSION: CAUSES AND REMEDY

Tilak V. Bommaraju and Paul J. Orosz

Occidental Chemical Corporation
PO Box 344
Niagara Falls, New York 14302, USA

ABSTRACT

Historically, sodium chlorate, produced by way of inefficiencies within a chlor-alkali cell, has
been considered to be primarily responsible for the first effect caustic evaporator failures.
Based on laboratory studies and in-plant surveys of failures and repairs it is shown that
sodium chlorate is not the primary cause of equipment failures. Failures are clearly
identified as localized - frequently related to areas of high velocity - and not generalized in
character. The present investigations suggest that the corrosion of nickel in alkaline media
proceeds following the reaction scheme:

Laboratory and plant data are presented demonstrating the suppression of the
corrosion rate of nickel in 50% caustic solutions with the addition of sodium borohydride to
the first effect evaporator.

INTRODUCTlON

Fifty percent NaOH is generally produced by concentrating the 12% NaOH + 15% NaCI from
diaphragm-type chlor-alkali cells in triple or quadruple evaporator systems or the 33% NaOH
from ion-exchange membrane chlor-alkali cells in a single effect evaporator system (1). The
most commonly employed material of construction for the first effect of caustic evaporation
systems in chlor-alkali operations is nickel (2,3). While it is an excellent material of
construction in view of its stability in alkaline media, it is prone to increased general
corrosion at high temperatures and under the highly turbulent conditions prevailing in the
 308

evaporators. This results in 50% NaOH containing nickel in measurable amounts (Le., ppm
levels) which is undesirable for certain end uses.
Corrosion is also responsible for the premature failure of some evaporator systems
resulting in extensive repairs and production losses due to down time. Several reasons
have been attributed to these failures, including: presence of sodium chlorate in the cell
liquor, poor welds, turbulent erosion, materials of construction (e.g., Ni-Clad), higher
temperature of operation, presence of sodium hypochlorite, solids, or oxygen, poor
operation, under design, and over capacity (4 to 6). Of these, sodium chlorates in the cell
liquor, produced by way of inefficiencies in a chlor-alkali cell, were suspected to be primarily
responsible for the corrosion of the nickel evaporator systems.
The purpose of this communication is to address the causes for the failure of the
evaporators with prime emphasis on the role of chlorate as related to the corrosion of nickel
in caustic solutions and develop remedial measures via the addition of 'corrosion inhibitors'
to suppress the corrosion rate of nickel.

EXPERIMENTAL

All the tests were performed at 158°C unless otherwise stated using synthetic and first effect
(IE) liquors. Corrosion rates under dynamic conditions were evaluated from the metal pick
up by the medium over a defined period of time.
Dynamic corrosion tests were performed using rotating cylinder electrodes (RCE) to
simulate the turbulent conditions to which the metal is exposed in the evaporators. It may
be noted that the degree of turbulence around a RCE is related (7) to that through a tube
in terms of Reynolds number as:
log Retube = 0.670 + 0.833 log Re cyl
where Reynolds number is defined as velocity (linear or peripheral) times the diameter
divided by the kinematic viscosity. It is worthwhile mentioning at this stage that the
corrosion data generated using RCE is not totally reflective of the corrosion rates observed
in the plant since not only the velocities are different in various regions in the evaporator but
also the nature of the metal which is structurally and compositionally different from bulk
nickel because of extensive welding required in building the evaporators. Nevertheless, RCE
studies do permit evaluation of the corrosion rates under turbulent conditions. Other
advantages of these studies include usage of relatively small volumes, control of velocity,
 309

and maintenance of temperature during the duration of the tests.

Initially, a pure nickel electrode (diameter: 1.6 cm) rotating in the range of 5500 to
9500 rpm (which corresponds to a flow velocity of 4 to S ft/sec through a 3' tube or
Reynolds No. of 1 to 2 x 105) was used. It is interesting to note that whereas the flow
velocity through IE tubes is ~6 ft/sec, the velocity in duct regions varies between 7 to 20
ft/sec, near the impeller as high as 60 ft/sec, and the vapor body region being in a near-
stagnant domain. Solutions used in this investigation are given below:
1) SOO gpl NaOH
2) SOO gpl NaOH + ~ 120 g solid NaCI
3) SOO gpl NaOH + 2.5 gpl NaCI03
4) SOO gpl NaOH + 2.5 gpl NaCI03 + ~ 120 g solid NaCI
5) First Effect Liquor (710 gpl NaOH + 2.2 gpl NaCI03 + 163 NaCI + 19.3 g
Na2 S0 4 , mostly in solid form)
During each experiment, about 400 ml of a given solution was placed in a teflon
container and heated to the desired temperature before the electrode was introduced. In
the 15SoC runs, the electrode was introduced when the solution started boiling (14S-156°C)
and then brought to 15SoC as water was driven off. Attached to the teflon container was a
nitrogen purge and a condenser. Each experiment was run for a total of six hours. After
each run the final solution was cooled and diluted to the original level (400 ml). A sample
of this was then taken and analyzed for Ni. From the nickel content in the solution, the
nickel loss of the electrode was calculated in g/m 2 hr.
Experiments were also performed using the nickel electrode and first effect liquor at
110°C, 140°C, and 15SoC (corresponding to 2nd effect quad, 1st effect triple, and 1st effect
quad, respectively) and at a flow rate equivalent to 6 ft/sec.

RESULTS AND DISCUSSION

A) Corrosion of Ni and Ni Welds Under Dynamic Conditions

The experimental data obtained with nickel electrodes under dynamic conditions are
illustrated in Figure 1. These results show that the corrosion rate of nickel is a linear
function of velOCity. The corrosion rate of nickel at Reynolds number of >2 x 105
corresponds to 2 ppm in Ni in 50% NaOH. The linear dependence of the corrosion rate of
nickel can be antiCipated if the product of nickel corrosion i.e., HNi02 · which is in equi-
 310

1:
0.4
N
E
!Ii
E 0.3
E?
Ql
"@
a:
c 0.2
a
'w
e
0 0.1
()

2 4 6 8 10
Flow Velocity
(fUsee)
Re tube X 10-5 = 0.5 1.0 1.5 2.0

Figure 1. Corrosion rate of Ni in 800 g/I NaOH at 158°C.

.:NaOH; o:NaOH + CIO a'; A:NaOH + solids; A NaOH + CIO a- + solids;
~:synthetic IE liquor + 02; x:plant IE liquor

librium with nickel is continuously swept away from the metal/solution interface resulting in
greater rate of dissolution to maintain the equilibrium constant of Ni .. HNi02 reaction at a
given value imposed by the thermodynamics (8) and kinetics of the reaction. Thus, the
nickel dissolution reaction in alkaline media may be envisaged as:
(1 )
Since the corrosion rate is a linear function of velocity, one should expect high
corrosion rates and hence, high frequency of failure of components in regions where flow
velocity is high (i.e., near impellers) in contrast to static regions, such as, vapor body where
the corrosion rate should be minimal. These conclusions are consistent with observations
in first effect bodieo in triple or quadruple evaporator systems.
Results in Figure 1 also suggest that the presence of chlorates and 02 has no
significant effect on the corrosion rate of nickel. These observations indicate the
contribution of the cathodic reactions involving CIO a- and 02 (Eq. (2) and (3» to the con-
 311

jugate anodic reaction Le., (Eq (4» is negligible due to either thermodynamic or kinetic
factors.
C103- + 3H 20 + 6e • cr + 60H- (2)
02 + 2H20 + 4e - - - . . 40H- (3)
(4)
The absence of any effect from 02 is probably a consequence of poor solubility of
02 at the high temperatures prevailing in the first-effect evaporators, whereas the negligible
influence of chlorate on the corrosion rate of Ni is a result of the slow kinetics of the cathode
reduction of chlorate on nickel substrates (9). The later is substantiated by the chlorate
material balance calculations which showed no chlorate losses around the first effect
evaporator. Data are available (10) demonstrating that sodium chlorate does not decompose
to any great extent until a temperature of at least 250°C is attained. This rules out the
suggestion that 02 formed by the thermal decomposition of NaCI03 is responsible for the
nickel corrosion.

0.6
Other Ni Welds
(see table 1)

-;:-
.c
0.4
C\I

--EE
CIl

El
Q)
1ii
a:
c 0.2
0
·00
....0
0
0

0
0 2 4 6 8 10
Flow Velocity
(ft/sec)
0. 5 1.0 1.5 2.0
Retubex 1 = 0.5

Figure 2. Corrosion rate of Ni-200 and Ni welds in SOO g/I NaOH at 15SoC.
Symbols are the same as in Figure 1.
 312

Table 1. Corrosion Rate of Nickel Welds at Rlltube = 1.5 x 105

Weld Temp rC) Corrosion Rate

(gms/m2 .hr)

Heliarc- 158 0.48

Heliarcb 158 0.52
Rod (stick)- 158 0.42
Diversified- Heliarc 158 0.56
Heliarc- 140 0.18-0.27

a: First effect liquor from the plant; b: synthetic first effect liquor without chlorate

Since the evaporators are constructed by welding nickel sheets, the weld region
constituting ~5 to 10% of the total area, the influence of flow velocity on nickel welds was
examined. Corrosion rates were determined using nickel RCE on which rod and heliarc weld
beads were drawn around the perimeter. Results obtained with these welds, presented in
Figure 2 (See also Table 1), exhibit significant degradation effects, the corrosion rate on
welds being 2 to 3 times higher than on pure nickel. It may be pointed out that the 'weld
corrosion' rates shown in Figure 2 were calculated taking into account the entire surface.
However, if the weld area above is considered, the weld corrosion rates will be 20 to 30
times (i.e., 20 to 30 g/m2 .hr) more than the values shown in Figure 1 with pure nickel. As
with the pure nickel, weld corrosion rates are also dependent on velocity. These results with
welds are not surprising since the welds and the weld areas surrounding it are generally
mechanically (grain boundaries, stress, hardness, etc.) and compositionally different from
the bulk metal with the result that the 'weld zones' are more prone to corrosion than a 'pure'
surface.

B. Influence of Temperature on Corrosion Rate of Nickel

In addition to velocity, temperature also has a pronounced influence on the corrosion rate
of pure nickel and nickel welds (See Figure 3). Visual observations show a dark film at 100°
to 140°C and a clearly metallic character at 158°C substantiating the corrosion data at
 313

0.6 . . . - - - - - - - - - - - - - - - -....

E 0.4
en
E
~
Q)
iii
a:
c
o
·iii 0.2
e
o
o

o~--~----~--~----~--------~--~
100 120 140 160
Temperature (0C)
Figure 3. Effect of temperature on the corrosion rate of Nickel-200 and Ni welds at
Retube = 1.5 x 105 in 800 gIl NaOH solutions.

elevated temperatures. Thus, welds and weld areas corrode faster than pure nickel at all
temperature and velocities.
It is pertinent at this stage to note that the liquor entering the first effect has zero
ppm nickel whereas the exiting NaOH contains 2 ppm Ni. These values correspond to a
corrosion rate of 0.33 g/m 2 .hr at Plant A and 0.2 gm/m 2 .hr at Plant B. Based on these
figures, the life of these systems should be 40 and 60 years at plant A and B respectively
where as failures were observed within 5 years. These results suggest that while general
corrosion of nickel occurs, it is not the failure mechanism of the evaporators. An
examination of the operating and the maintenance history of quadruple effect systems at
three operating plants and triple effect systems at four operating plants (See Figure 4)
showed that the failure areas observed at various plants are primarily high velocity zones
 314

Figure 4. Failure zones (shaded areas) in first effect evaporators at various chlor-alkali
manufacturing operations marked A to E.

(e.g., distributors, valves, pumps, impellers) and weld regions in accordance with the
observations based in laboratory studies. Thus, the results observed so far strongly suggest
that failures are promoted by increasing temperature of operation, increased liquor velocity,
welds and weld zones, and are not due to chlorate. Furthermore, failures are a
consequence of localized corrosion and not because of general corrosion.

C. Influence of Solids on the Corrosion Rate of Nickel

Corrosion rate measurements with nickel RCEs have shown that the presence of solids has
no influence on the corrosion rate beyond the corrosion rate expected in SOO gpl NaOH at
15SoC (See Figures 1 and 2). These results may be compared with the nickel pickup values
of ~ 1.0 ppm in the first effect of a triple effect evaporator system with diaphragm cell liquors
to the ~ 0.75 ppm nickel pickup in a single effect evaporator system using membrane cell
liquors, both effects operating at ~ 140°C.
 315

D. Mechanism of Corrosion of Nickel

Based on the above results, it appears that the corrosion of nickel proceeds following the
overall reaction (1) and not via reactions involving 02 or CI0 3". If indeed, the corrosion
process follows Eq (1), then it should be possible to suppress the forward rate of reaction
(1) by providing H2 to the system either directly or by adding compounds such as N2H4 or
NaBH 4, which would decompose at the temperatures in the first effect to form H2 (11).
Corrosion rates measured with presence of H2, N2H4, and NaBH4 indeed show dramatic
lowering of the nickel content in caustic (See Table 2).

Table 2. Corrosion Rate of Nickel in 50% NaOH at 160°C

(Rawbe = 2 x 105)

Corrosion Rate (gmlm2.hr)

Additive
Without Additive With Additive

H2 Gas (Constant Rate) 0.2 to 0.3 0.08

N2H4 (20-100 ppm) 0.2 to 0.3 0.02
NaBH4 (5-50 ppm) 0.2 to 0.3 0.01 - 0.03

The electrode surface following the tests with NaBH4 was found to be blackish in
color. Analysis of the surface by ESCA (See Figures 5 and 6) showed the surface
to analyze not nickel boride or nickel-boron compound (since there is no peak
corresponding to it at a binding energy of 187 ev) but hydrated nickel oxide (note
the peak at a binding energy of 855.6 ev) which is very tenacious and abrasion resistant.
It is possible that the hydrated nickel oxide formed by interaction of HNi02" with H20
resulting in the formation of NiO.H20 + OH" is getting crystallized at the surface in a manner
that is compact and adherent, thereby providing protection from general corrosion and
erosion-type corrosion as will be shown later.
 316

.. Region Where Boron is Found

200 195 190 185 180

Binding Energy (eV)
Figure 5. ESCA spectra of Ni treated with and without NaBH4 •

Ni 2p 1/2 Ni 2p 3/2
NiO + NiO· H 20 x
oC\I
\
:::c

o
Z~"'"
o
Z

900 885 870 855 840

Binding Energy (eV)

Figure 6. ESCA spectrum of Ni treated with NaBH4 •

 317

E. Commercialization of NaBH 4 for Reducing the Corrosion Rate of Nickel

Several tests were run in various commercial chlor-alkali operations by feeding NaBH 4 to the
first effect (See Figure 7) and monitoring the nickel pick-up in caustic. As shown in Figures
8 and 9, the nickel in caustic is dramatically lowered from an initial level of '" 1.6 ppm to
<0.4 ppm as the concentration of NaBH4 is increased.
The lowered corrosion rate of nickel is clearly reflected in the reduced nickel tube
wear rate as presented in Figure 10.
Thus, NaBH4 addition not only lowers the corrosion rate of nickel equipment but also
improves the product quality of caustic. It should also be noted that the chlorate level in
the 50% caustic is unaltered from what is fed in the first effect, thereby reaffirming the
corrosion mechanism of nickel in caustic media to be as described by equation (1). The
oxide film formed during NaBH4 addition is very hard and hence, the erosion-effects resulting
in high Ni pickups normally found with diaphragm cell liquors, are negligible.
Since the nickel pickup in 50% NaOH is lowered from '" 1.6 ppm to '" 0.5 ppm, with
NaBH4 additions, it is reasonable to project a three-fold increase of the life of the nickel
steam chest tubes. The cost of replacing these tubes every five years is about $1 million
while the cost of NaBH4 (as 12% solution), at $2/lb, is "'$300,000 over that five year period
for a 1000 tons/day IE caustic evaporator. Thus, NaBH4 addition to the nickel evaporators
not only lowers the downtime and replacement costs associated with tube replacement but
also provides superior product quality and reduced sludge disposal costs since the amount
of sludge generated with NaBH 4 addition is small.
U.S. Patent 4,585,579 describes the use of NaBH 4 for the suppression of the
corrosion of nickel evaporators (11). The process of adding sodium borohydride is patented
and licensed by OxyTech Systems, Inc. through Morton International.

CONCLUSIONS

The present studies with rotating nickel cylinder electrodes in 50% caustic solutions at 150-
160°C have shown that nickel corrosion is a linear function of velocity and that chlorate has
no significant effect on the nickel corrosion rate. Based on these studies, the mechanism
of nickel corrosion in alkaline media is proposed as:
Ni+ H20 + OH- • • HNi02- + H2
HNi02- + H20 . • NiO.H20 + OH-
 318

Vapor
Body

Figure 7. Feed system for NaBH 4 addition to the first effect evaporator.

1.5

E
0..
8 1.0
c
0
.~

'E
Q)
u
c
0
0
Qi 0.5
.::.:
u
Z

o~--~--~--~----~--~--~--------~
o 0.5 1.0 1.5 2.0
Sodium Borohydride Rate (#/Hr.)

Figure 8. Variation of Ni content in 50% NaOH with the addition rate of NaBH 4 .
 319

2.5

2.0
J:
0
C\l
z 1.5
~
0
0
l!)

.~
Z 1.0
E
a.
a.
0.5

0
0 2 4 6 8 10 12 14
ppm NaBH4 Added to Caustic

Figure 9. Dependence of Ni content in 50% NaOH with the concentration of NaBH4 .

100

90

80
Cl
c:
·c
.n; 70
E Start of NaBH 4
Ql
II: 60 ,--- Addition
(ij
~ 50
o
Q)
.c
:>
t- 40
"0
~
0
30

20

10 Failure Based on
Previous Heater ~
0
'90
Year

Figure 10. Variation of tube wall thickness with NaBH4 additions to the first effect
evaporator.
 320

By providing H2 via the addition of NaBH4 , it was shown by laboratory and plant
studies that the corrosion of nickel can be suppressed effectively and with ease, without
however, any change in the sodium chlorate level in 50% caustic solution. The generalized
and localized corrosion of nickel has been shown to be reduced by the abrasion resistant
nickel oxide films formed during NaBH4 additions.

REFERENCES

1. L.C. Curlin, T.V. Bommaraju, and C. B. Hansson, 'Alkali and Chlorine Products',
Encyclopedia of Chemical Technology, John Wiley & Sons, NY (1991).

2. INCO Corrosion Engineering Bulletin, CEB-2, Corrosion Resistance of Nickel and

Nickel Containing Alloys in Caustic Soda and Other Alkalies (1973).

3. M. Okubo and K. Tokunaga, Kagaku Kogaku, 40, 577 (1976).

4. T. Ohashi and H. Kajiyama, 'Summary of Lectures of Soda Industry Discussion

Society', Japan, p.45 (1977).

5. B.M. Barkel, Corrosion/79, paper #13, Atlanta, GA, March, 1979.

6. M. Yasuda, F. Takeya, and F. Hine, CorrOSion - NACE, 39, 399 (1983).

7. G. Wrangler, J. Berendson, and G. Karlsberg, Levich Symposium, London (1979).

8. R.L. Cowan and R.W. Staehle, J.Electrochem. Soc., ill, 557 (1971).
9. B.V. Tilak, K. Tari, and C.L. Hoover, J. Electrochem. Soc., 135, 1386 (1988).

10. M.B. Brodbeck, unpublished results (1953).

11. U.S. Patent 4,585,579 (April 29, 1986), T.V. Bommaraju, W.V. Hauck, and V.J. Lloyd
(OxyTech Systems Inc, Chardon, Ohio).
 321

INDEX OF CONTRIBUTORS

Abbott, P.E.J., 23 Meneghini, G., 269

Acioli, AJ., 199 Miyake, H., 59, 159
Alford, RE., 43 MUller, R, 257

Baucom, E.I., 131 Nakao, M., 159

Billings, D.E., 223
Bommaraju, T.V., 307 O'Brien, T.F., 239
Borrione, P., 93 Ohta, T., 117
Orosz, PJ., 307
Carlin, M., 23 Ottaviani, A., 93
Cowell, G.W., 143
Curlin, L.C., 209 Perham, D.A., 13
Curry, RW., 185 Powell, E.F., 199

Dworak, R., 257 Revill, B.K., 143

Fakley, M.E., 23 Sajima, Y., 159

Florkiewicz, T.F., 209 Schneiders, K., 105
Friedfeld, B.A., 1 Shields, J.P., 35
Shimohira, T., 159
Gronowski, A.A., 81 Shiroki, H., 117

Hancock, F.E., 23 Thomerson, J.R., 223

Hiyoshi, T., 117 Traini, C., 269
Trasatti, S., 281
Keating, J.T., 69
King, F., 23 Viana, F.e., 199

Lohrberg, K., 257 Walkier, lA., 233

Liike, B., 105 Wanngard, J., 295
White, I.F., 239
Marean, M.R, 177
Martin, A.D., 143 Yeager, H.L., 81
 323
SUBJECT INDEX
Acetone, 9
Acip1ex-F membrane, 117-129
Activated carbon, 26
Absorbable Organic Halides,
AOX, 13-14, 47
Aluminium
As membrane impurity,
71, 126, 167
Deactivator in chlorate
electrolyte, 298
Ammonia, 43, 49, 52-54, 191
Ammonium perchlorate, 44
Anodes
Diaphragm cells, 273-274
Duplex, 277-279
Membrane cells, 275-279
Mercury cells, 270-273
Runner, 270-271
Ano1yte composition, 155-156
Ano1yte stoichiometry, in membrane
cells, 148
Asbestos, environmental pressures,
210-214
AZEC-F2 e1ectro1yzer, 159, 161-165
Barium, as membrane impurity,
72, 126-127
Barium chromate, 49
Barium sulphate, deactivator in
chlorate electrolyte, 298, 301
BAT; 187
BATNEEC, 187
Bipolar membrane cell configuration,
108
BPEO, 189
Brine
Acidification, 77-78
Discharges to effluent, 189
High f10wrate recirculation,
94-99
Impurities, effect on membranes,
71, 126-127, 167-169
Once through system, 189
Bromine, levels in liquid chlorine,
190
Cadmium, cathode poison in chlorate
cells, 299
Calcium
As membrane impurity,
71-72, 126, 167
Impurity in chlorate
electrolyte, 303-304
Calcium carbonate, sOlubility in
brine and water, 300
Carbon tetrachloride, 187
Carcinogenicity of fibres, 211
Cathodes, in membrane e1ectro1yzers
Corrosion of steel in cathodes,
260-265
Deactivation of nickel cathodes,
265-266
E1ectro1ess nickel, 282
Nickel as cathode material,
113-114
Plate-type, 162
Specific resistance of materials,
259
Steel as cathode material,
257, 265
Catho1yte recirculation in membrane
cells, 94-99
Caustic Soda
Anhydrous, in chlorine vapour
suppression, 230
Determination of current
efficiency in membrane
cells, 143-158
Evaporator corrosion, 321-334
Forecast demand, 11
Historical demand, 4-5
Production from soda ash, 2, 12
Production from sodium sulphate,
6
Production of 50% in membrane
cells, 128-129
Production of 70% in mercury
cells, 199-207
Substitution with soda ash, 12
Usage in pulp and paper industry,
6-7
CEFIC, 233
CFCs, 1, 5, 8-10, 37, 187-188
 324
Chlorinated caustic effluent, 23-34
Chlorination of drinking water, 24
Chlorine
Absorption in scrubbing towers,
24, 239-256
Bleach, environmental concerns,
35-41
Chlorine/caustic soda balance,
2, 11-12, 14
Discharges into aqueous effluent,
25
Drums and cylinders, 235
Effect of gas composition on
absorption, 246-247
Environmental issues, effect on
demand, 2
Forecast demand, 9-10, 187-188
Gaskets, 237
Historical consumption, 2-3
Liquefaction options, 191
Liquid inventories, 192-193
Mass transfer effects in
absorption, 243-244,
247-249
Offloading, 236
Pipework, valves, materials of
construction, 236
Plant capacity considerations,
196-197
Pulp bleaching, 6-7, 13-21,
187, 295
Solubility in water, 245
Temperature effects in
absorption, 244-246
Titanium, limitations of use,
236, 238
Transport in bulk, 192, 235
Vapour suppression tests,
223-231
Water treatment, 1, 5, 8, 24
Chlorine dioxide, 1, 6, 13-21,
43-44, 47, 295-296
Chlorine Institute, 242
Chloroform, 6
Chromium hydroxide, 49
Chromium oxide, 55
Cobalt oxide, electrode coating,
282, 285-293
Cobalt salts, for hypochlorite
destruction, 27-28
COD, 26
Current efficiency measurement
Caustic soda collection
method, 147
Comparison of methods, 157-158
Indirect brine depletion
method, 149-150
Indirect flow/current
method, 148-149
'Sulphate Key' method, 150-155
Cyclochrome Process, 43-58
Decomposers, operating data, 203
Diaphragm cells
Anodes, 273-274
Carbon steel as cathode
material, 259
Conversion to membrane cells,
214-215
Polyramix diaphragms, 209-221
Dichloroethane, 99
Dioxins, 5, 13, 37, 47
Disinfection with chlorine,
1, 5, 24
Duplex, membrane cell anode,
277-279
Dysentery, 36
ECU, 2, 13, 15, 20, 213
Effluent containment, 191
Electrodes
Cobalt oxide, 282, 285-293
Hydrogen evolution on, 281-293
Iridium oxide, 282, 285-293
Ruthenium oxide, 282-293
Electrogalvanizing, 279-280
Electrolyzers, membrane
Acid addition to reduce anodic
by products, 99-100, 163-164
Advantages/disadvantages of
membrane electrolyzers, 178
Anodes for membrane
electrolyzers, 275-279
Anolyte stoichiometry, 148
AZEC-F2, 159, 161-165
Bipolar arrangement, 108
Computer simulation of, 103-104
 325
Electrolyzers, membrane - contd
Configuration in cellroom,
107-110
Corrosion of steel in cathodes,
260-265
Current efficiency measurement,
143-158
Deactivation of nickel cathodes,
265-266
Economic operation of, 105-116
Electrical insulation, 112-113
Energy performance, 146
Explosions in, 114
FM2000, 145
FM21, 158
Hoechst-Uhde type, 107-116
Instrumentation and interlocks,
108-110
Liquid hold-up gas disengagers,
101-103
Lurgi, 257-258, 263
Materials of construction,
113-114, 258-259
Narrow gap, 163
Natural gas lift recirculation,
94-99, 163
Operating problems, 114-116
Safe operation of, 105-116
Shutdown, 101-102
Single element design, 110-112
Start-up, 102-104, 114
Steel as cathode material,
257, 265
Emergency absorption of chlorine,
239-256
Environmental legislation, 186-187,
194-195
Environmental Protection Agency,
EPA, 210
Ethylene dichloride, 188
EUROCHLOR, 233-235, 242
F1emion membranes, 59-68, 159-175
Fluorine, deactivator in chlorate
electrolyte, 298
FM21 electrolyzer, 158
Foam, for chlorine vapour
suppression, 229-230
Food poisoning, 38-41
Formaldehyde, 48
Furans, 13
Gastro-enteritis, 36
GEST, 234
Glauberite, 301-302
Graphite, for decomposers, 203
Hardwood pulp mills, 15-16, 18, 20
HCFCs, 188
HFCs, 188
Hoechst-Uhde electrolyzer, 107-116
, Hydecat' process, 23-34
Hydrazine, 49, 52, 329
Hydrochloric acid
Acidification of anolyte, 99-100
Chlorine dioxide production,
6, 15-21, 47-48
Electrolysis, 188
Hydrogen
Atomic, 285
Evolution on oxide electrodes,
281-293
In suppression of nickel
corrosion in evaporators,
329-334
Reaction mechanism for evolution
at electrodes, 288-291
Hydrogen peroxide, 1, 6, 26, 295
Hydrogen sulphide, in chromate
removal from chlorate liquors, 49
Hydroxylamine, in chromate removal
from chlorate liquors, 49, 52
Hypochlorous acid, 5-6, 25, 27, 99,
153, 297
Iodides, as membrane impurity
71, 126-127, 168-169
Ion exchange, chromate removal by,
49
Incineration, 31
Iridium oxide, electrode coating,
282, 285-293
Iron, Pourbaix diagram, 259-261
 326
Kraft pulp manufacture
Bleaching, 1, 5-6
Chemical requirements, 15
Chemical unit costs, 17
Chlorate reduction, 17
Chlorine-related green issues, 5
Economic considerations, 15-21
Environmental pressures on
organic discharges, 13-22
Methanol based processes, 20
On-site chlorate production, 21
Total HC1 and integrated
processes, 20
Lead, deactivator in chlorate
electrolyte, 298
Load shedding, 76
Lurgi e1ectro1yzer, 257-258, 263
Magnesium, as membrane impurity,
71-72, 126, 167
Manganese, deactivator in chlorate
electrolyte, 298
Membranes
Absorption of nickel, 71
Achievable caustic soda
concentration, 67
Acip1ex-F series, 117-129
Ano1yte concentration, 75-76
As a polymeric salt, 71
Brine acidification, effect of,
77-78
Brine impurities, 71, 126-127,
167-169
Catho1yte concentrations, 75-76
Cell start-up, effect of, 76-77,
120-121
Characterization of polymers,
61-63
Conductivity, 65-66
Current density, 72-73, 140
Current efficiency, 65, 70, 84-89
138, 143-158
Electrical conductivity, 65
Energy consumption, 67
Membranes - contd.
50% caustic soda production,
67, 128-129, 170-175
F1em1on, 59-68, 159-175
Ion diffusion, 65-66
Life, 134
Load shedding, effect of, 76
Mass transport in, 71, 139
Mechanical strength, 63, 67, 136,
167
Nafion, 69-80, 82, 131-141
Operating conditions, 72-80
Perf1uorinated membranes, 59-67
Performance data in plants,
122-123, 132-134, 136-139,
169-170
Permse1ectivity, 60, 63-64, 81-9J
Potassium hydroxide production,
125
Preparation of perf1uoro-
carboxylated polymers, 60-61
Proton tunnelling, 82, 90-91
Punctures, 69, 115
Reinforcement, 86-87, 118
Solution mixing, 82, 85-86
Stability and reproductibi1ity,
120-122
Structure, 67, 69-71, 118, 135
Temperature, effect of, 73
Zero-gap, 82, 87-88, 123-124" IS!
Membrane cells (see B1ectro1yzers)
Advantages/disadvantages, 178
Conversion issues, 185-198,
214-215
Investment costs, 102
Power consumption, 102
Mercury, cathode poison in chlorate
cells, 299
Mercury cells
Advantages/disadvantages, 178
Anodes, 270-273
De-Nora type, 199, 203
Displacement in Japan, 59
Bconomics of change to membrane
cells, 177-184, 195-196
Effect of salt quality, 179-181
Environmental pressures on,
185-187
Factors in conversion to membran'
cells, 185-198
 327
Mercury cells - contd.
Investment cost, 182
Power consumption, 182
Production of 70% caustic soda,
199-208
Uhde type, 203-205
Methanol in chlorine dioxide
production, 15-21, 48
Methyl ethyl ketone, 9
Montreal Protocol, 8, 187, 191,
194
Nafion, membranes, 69-80
National Emission Standards for
Hazardous Air Pollutants
(NESHAP), 210
Natural gas lift recirculation,
in membrane cells, 94-99, 163
Nickel
Cathode material in membrane
electrolyzers, 265-266
Corrosion in caustic
evaporators, 321-334
Hypochlorite destruction, 27, 29
Membrane impurity, 167
North Sea Conference, 186
occupational Safety and Health
Agency (OSHA), 210
Oxygen
Bleaching agent, 1
Deliqnification, 5, 8
Levels in membrane cell chlorine,
99, 119, 163-165, 276-277
Pulp bleaching, 6, 295
Ozone
Depletion, 1, 8
Drinking water disinfection, 1, 8
Polyramix diaphragms, 209-221
Economic factors, 212-215
Environmental concerns, 210-213
Long-life cell, 220-221
on-site deposition, 216-217
Potassium hydroxide, production in
membrane cells, 125
Potassium perchlorate, 303
Power tariffs, 197
pulp bleaching, 5-8, 43, 187, 295
PVC, 2, 188
Quantitative Risk Assessment,
192-193, 237
Raney alloys, 265-266
Refrigerants, 191
Responsible Care, 213
Ruthenium oxide, eletrode coating,
282-293
Salt (see Sodium chloride)
Seveso Directive, 237
Silica
Deactivator in chlorate
electrolyte, 298
Membrane impurity, 7, 126
Sodium bisulphate, in hypochlorite
destruction, 26-27
Sodium borohydride, 329-334
Sodium carbonate, for chlorine
vapour suppression, 230
Sodium chlorate
Caustic evaporator corrosion,
321-325
Chromate removal, 49
Deactivation of cell electrodes,
298
Dichromate recovery during
manufacture, 43-57
Electrode gap, 297-298
HerbiCide, 44
Impurity effects in plants,
295-306
Space programme fuel production,
44 .
Toxicity to environment, 190
 328
Sodium chloride
Calcium content of salt, 303-304
Effect of quality on mercury
cell performance, 179-181
In chlorate electrolyte, 298
Reduction of sodium chlorate, 48
Sulphate content of salt,
301-302
Sodium dichromate
In chlorate electrolyte, 298
Recovery in chlorate
manufacture, 43-48
Sodium hypochlorite
Destruction, 23-34, 53, 304-305
Destruction by chemical
addition, 26-27
Destruction by heavy metal
catalysis, 26-28
Dichromate recovery in chlorate
manufacture, 43, 52
Effect on aquatic life, 24-25
Light-catalysed decomposition,
25
Thermal disproportionation, 25
Sodium molybdate, for graphite
activation, 204-206
Sodium perchlorate, 302-303
Sodium sulphate, 6, 48, 301-302
Sodium sulphide, in hypochlorite
destruction, 26-27
Sodium thiosulphate, in hypochlorite
destruction, 26
Softwood pulp mills, 15-16. 18, 20
Specific resistance, of cathode
materials, 259
Steel, as cathode material in
membrane cells, 257-265
Strontium
Deactivator in chlorate
electrolyte, 298
Membrane impurity, 126-127, 167
Sulphate, ions as membrane
impurity, 126-127, 168-169
'Sulphate Key' determination of
current efficiency in
membrane cells, 143-158
Sulphur, precipitated in
chromate removal, 49
Sulphur dioxide, in
hypochorite destruction, 26-27
Sulphuric acid
Chlorate reduction, 17, 48
Chlorine drying, 26
Surface cleaning, 8
SVP-MeoH process for chlorine
dioxide, 15, 18-20
SVP sulphuric acid process for
chlorine dioxide, 15, 17-20
Tafel lines, 285-287
Teflon, in Polyramix diaphragms,
210-219
Tetrafluoroethylene, 60-61
Tin, deactivator in chlorate
electrolyte, 298
Titanium, limitations in chlorine
use, 236, 238
Titanium dioxide, applicability of
hypochlorite destruction, 23
Titanium Hydrodynamic Means, THM,
271, 274
Total Organically-bound Chlorine,
TOCl, 13, 24
1, 1, 1, trichloroethane, 8, 187
Trihalomethanes, formation in
drinking water disinfection, 1
Trona, 2
VCM, 9, 23, 188
Volatile organic compounds, removal
from hypochlorite streams,
23, 31, 37
Water treatment, 8, 24, 187
Water sprays, for chlorine vapour
suppression, 224-228
Zinc, cathode pOison in chlorate
cells, 299
Zirconia, from diaphragms, 220