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iLORINE BICENTENNIAL SYMPOSIUM

da<^ Krt Mt ^ <* , 14 7*/.

Edited by

Thomas C. Jeffery Peter A. Danna

PPG Industries, Incorporated Marstolin Systems
Lake Charles, Louisiana Hamilton, Bermuda

H. Stuart Holden
Electrode Corporation
Chardon, Ohio

This symposium was cosponsored by

The Chlorine Institute, 342 Madison Avenue, New York, New York 10017

INDUSTRIAL ELECTROLYTIC DIVISION

THE ELECTROCHEMICAL SOCIETY, INC., Post Office Box 2071, Princeton, New Jersey 08540
Otwnktry Library
IP
345
.t5

1974

Copyright 1974
by
The Electrochemical Society, Incorporated

Papers contained herein may not be

reprinted and may not be digested by pub
lications other than those of The Electrochemical
Society in excess of I /6 of the material presented.

Library of Congress Catalog Card Number: 74-78467

Printed in the United States of America
 PREFACE

To commemorate the 200th anniversary of Carl Wilhelm

Scheele's discovery of chlorine, the Chlorine Bicenten
nial Symposium sponsored by the Industrial Electrolytic
Division of The Electrochemical Society and cosponsored
by The Chlorine Institute was held during the Society's
Meeting in San Francisco, May 12-17, 1974.
In the United States alone the sales volume of chlo
rine and caustic exceeds one billion dollars annually.
This is but a portion of the worldwide output, and inter
national interest in chlorine technology remains high
with 13 of 36 papers given by authors who reside outside
the United States, and all major industrial nations of
the world were in attendence.
Papers were solicited from the broad spectrum of
chlorine production, including:
GENERAL AND ECONOMIC TRENDS - HISTORICAL
AND FUTURE
SOLUTION MINING, ROCK SALT, BRINE TREATMENT
CELL DESIGN, DIAPHRAGM, MERCURY
ANODES
CELL ROOM AND PLANT LAYOUT
PLANT GENERAL - COMPRESSION, LIQUEFACTION
SAFETY HYGIENE, ENVIRONMENTAL
In the recent past, chlor-alkali production in the
U.S. has grown at a steady 6-8% per year, now standing
at about 10.5 MM tons of chlorine per year. Fortunately,
capacity and production figures for the industry have
been essentially the same for the past few years as all
producers were operating near 100% output. The timely
nature of this Symposium for discussion of new technology
is evidenced by the fact that expansions underway in the
U.S. will boost capacity by 15-17% by 1975.

iii
Symposium Co-Chairmen
Industrial North America
Thomas C. Jeffery*
PPG Industries, Inc.
P.O. Box 1000
Lake Charles, Louisiana 70601
Industrial Overseas
H. Stuart Holden*
Electrode Corpora; tion
P.O. Box 229
Chardon, Ohio 44024
Academic Worldwide
Peter A. Danna*
Marstolin Electrolytic Systems, N.V.
Colony Building, Suite 204
Trott Road
Hamilton, Bermuda
Assisted by:
Howard A. Sommers
710 Berwyn-Baptist Road
Devon, Pa. 19333
William C. Gardiner
2278 Shoshoni Lane
Stratford, Conn. 04697
Ernest G. Enck of The Electrochemical Society and Robert
L. Mitchell, Jr. of The Chlorine Institute and their
respective staffs provided invaluable assistance in the
organization and production of the Symposium.
Special thanks are due the authors of each paper who put
forth the effort to the benefit of the many who attended,
and to the management of their respective companies whose
approval made this participation possible.

* Session Chairman

September 1974

iv
 TABLE OF CONTENTS

PREFACE iii
^•^JTHE CHLORINE INDUSTRY - PAST, PRESENT AND FUTURE
H. W. Schultze 1

CHLORINE - GLIMPSES FROM ITS HISTORY

I. Eidem and L. Lundevall 20

CASTNER, A PIONEER INVENTOR IN ALKALI -CHLORINE

W. C. Gardiner . 35

TRENDS OF DEVELOPMENT OF CHLORINE INDUSTRY IN

DEVELOPING COUNTRIES
R. K. Gupta 44

DISPOSAL OF BRINE TREATING SOLIDS BY RECYCLING TO

A BRINE WELL
T. F. LaGess 60

TECHNIQUES IN THE DEVELOPMENT OF SALT CAVERNS

FOR MULTIPLE USE
M. Slezak 63

APPLICATION OF TURBULENCE IN SOLUTION MINING

C. W. Querio 74

TRACE METALS IN SALT SOURCES TO ELECTROLYTIC

INDUSTRY
C. E. MacKinnon and R. C. Morris 86

BRINE PREPARATION FOR CHLORINE PRODUCTION

S. Pribicevic 97

INFLUENCE OF STRONTIUM ON MERCURY BUTTER

FORMATION
J. P. Guptill and C. J. Kaminski Ill

v
 A CASE STUDY OF MERCURY LOSSES IN A MERCURY
CELL PLANT
R. E. Ross 120

MERCURY RECOVERY FROM CHLOR-ALKALI PROCESS

STREAMS
R. A. Perry 131

\\ CHLORINE PRODUCTION - ECOLOGICAL AND ECONOMIC

ASPECTS
S. Payer and B. Strasser 133

AUTOMATION OF MERCURY CELL ANODE ADJUSTMENT

R. W. Ralston 145

\. CHLORINE CELLS OF THE FUTURE

V. de Nora 147

CLAD METAL ANODES

R. Baboian 158

MORPHOLOGY OF DIMENSIONALLY STABLE ANODES

K. J. O'Leary and T. J. Navin 174

FUTURE TRENDS IN CHLORINE CELLS

J. E. Currey, A. T. Emery, and C. S. McLarty... 187

BIPOLAR CHLORINE CELL DEVELOPMENT

P. J. Kienholz 198

THE DEVELOPMENT OF HOOKER'S H-2A AND H-4 CELLS

M. P. Grotheer and C. J. Harke 209

ADVANCE TECHNOLOGY IN CHLORINE PRODUCTION

V. H. Thomas and K. J. O'Leary 218

NEW CHLORINE PURIFICATION PROCESS

R. Alessandrello, R. Bosio, and M. Ghezzi 231

vi
 CELL ROOM SAFETY
A. T. Emery and J. E. Currey 235

V THE QUANTITATIVE ASSESSMENT OF CHLORINE EMISSION

HAZARDS
A. N. A. Dicken 244

CHLORINE RECOVERY BY HYDROCHLORIC ACID

ELECTROLYSIS
S. Payer and W. Strewe 257

AN OPERATING CHLORINE DESTRUCTION SYSTEM

J. E. O'Connell and A. J. Pecquet 267

. RECOVERY OF CHLORINE FROM WASTE GAS - PILOT

EXPERIEMNT
F. Hine, M. Yasuda, and M. Higuchi 278

THE USE OF COMPUTER MODELING IN DEVELOPING

CHLOR-ALKALI PLANT DESIGNS
E. L. Sokol and C. S. McLarty 285

SIMULATION OF A SALT CRYSTALLIZER DURING PERIODS

OF POSITIVE AND NEGATIVE EVAPORATION
I. R. Williams 299

THE EFFECTS OF OXYGEN CONTAINING ANIONS ON

CHLORINE ANODE EFFICIENCY
E. H. Cook and M. P. Grotheer 324

ENERGY CONSIDERATIONS IN HYDROGEN COLLECTION

L. W. Condra, Jr 332

PRESENT AND FUTURE CONCEPTS OF CHLORINE

CONTROL SYSTEMS FOR DISINFECTION OF POTABLE
WATER AND WASTEWATER
G. C. White 342

vii
REDOX CONTROL OF SULFHYDRATE ADDITION FOR MERCURY
SULFIDE FORMATION
L. K. Norton 360

MODERN CENTRIFUGAL COMPRESSORS FOR CHLORINE

SERVICE
R. M. Salzmann 368

ELECTROLYSIS OF AQUEOUS SODIUM CHLORIDE

SOLUTIONS WITH A MERCURY CATHODE AT
20-30 KA/m2
I. T. Rodeanu 384

DEPOLARIZATION AND INHIBITION OF AMALGAM

DECOMPOSITION AND DESIGN APPROACH TO
MERCURY CELL DECOMPOSERS
M. M. JakSic, I. M. Csonka, and
R. T. Atanasoski 399

INDEX 403

viii
 THE CHLORINE INDUSTRY - PAST, PRESENT AND FUTURE
H. W. Schultze
Allied Chemical Corporation, Morristown, New Jersey 07960

ABSTRACT
A survey of the growth of the chlorine indus
try, its current status and its future is
presented. Those events which had or will have
far-reaching technical and socio-economic impact
are emphasized. The discussion covers scien
tific and technological developments which have
changed methods of manufacture, distribution and
use. Factors external to the chlorine industry
which influence it are also considered. Among
these are changes in the market place, develop
ments in other industries, availability of
energy and preservation of environmental quality.

Introduction
The discovery of chlorine two hundred years ago by
the Swedish chemist, Carl Wilhelm Scheele (1), was destined
to exert a profound influence upon future generations.
Chlorine would grow to become one of the most versatile
commodities, finding its way into hundreds of applications
and products beneficial to the health, comfort and enjoy
ment of people throughout the world.
This paper traces the growth of chlorine over the
years to its present status as a product with an annual
worldwide market value of over a billion dollars. Included
is a discussion of the early scientific advances that
started chlorine on its way toward the position of great
importance it occupies in everyday life. More recent
advances in technology, product distribution and end use
patterns which have supported a growth rate of 7 to 8% per
year during the post World War IJ. period are discussed
along with projections for the future.

History
The first commercial use for chlorine was in the
bleaching of textiles. Chemical bleaching with chlorine
quickly gained importance in Great Britain and in 1798
Charles Tennant produced bleach by absorbing chlorine in
\

1
milk of lime. Shortly after this he produced bleaching
powder by passing chlorine over hydrated lime, a product
that was to become the most widely used form for supplying
chlorine for more than 100 years (2,3).
The development of chemical bleaching with chlo
rine, and the invention of calcium hypochlorite bleaching
powder as a practical form for transporting chlorine to
the consumer, may seem of small significance today. How
ever, viewed in the context of the early nineteenth
century, these developments were of great importance. One
must remember that Great Britain and Europe were in the
throes of the industrial revolution with an expanding
population and a corresponding increasing demand for
textiles. The invention of the power loom provided the
needed capacity to weave textiles but the ancient method
of bleaching, called crofting, by spreading cloth in open
fields for months at a time, continued to be used. This
process became increasingly more costly in the face of
soaring land values. The development of chlorine bleach
ing shortened the process from months to a few days and
freed vast acreages for more productive use (4) .
During this period, the method used to manufacture
chlorine was much the same as that discovered by Scheele
employing the reaction of hydrochloric acid with manganese
dioxide (1) .

„ , 100-110°C ^ ,
Mn02 + 4HC1 > MnCl2 + Cl2 + 2H20

In later refinements the manganese was recycled and it

became known as the Weldon process (5) . The Deacon
process which produced chlorine by the direct catalytic
oxidation of hydrogen chloride with air came into use in
the 1860's (2) .

450-460°C
4HC1 + 02 (Air) > 2C12 + 2H20
, CuCl2

Hydrogen chloride used in both processes was available as

a waste by-product from the manufacture of soda ash by the
LeBlanc process (6,7).

H2S04 + 2NaCl > Na2S04 + 2HC1

Na2S04 + CaC03 + 2c '» Na2C03 + CaS + 2C02

Disposal of LeBlanc process hydrogen chloride had created
serious environmental problems. Utilization of the HCl to
produce chlorine, not only provided a useful product, but
also eliminated water and air pollution problems previously
associated with the disposal of the HCl.
Scientists quickly recognized the reactivity of
chlorine and its potential in the manufacture of many
inorganic and organic derivatives. However, certain
problems had to be solved before chlorine could attain its
full potential. These problems included a means of coping
with its corrosiveness , a way of supplying it to customers
as a pure material in concentrated form and a process for
producing it from a low cost and widely available raw
material. Scientific progress and technological develop
ment were to culminate in solutions to these problems
within a brief span of years.
The discovery by Knietsch that dry chlorine did
not attack steel was very significant. Solving the
material of construction problem permitted the first
commercial production and distribution of dry liquid chlo
rine by Badische Anilin-und-Soda Fabrik (BASF) of Germany
in 1888 (8,9). The process, which employed sulfuric acid
for drying, followed by compression and finally condensa
tion by cooling, was much the same as is practiced today.
After solving the corrosion problem and developing
a means for producing liquid chlorine, one need remained.
That was a need for a process for the manufacture of chlo
rine that did not depend on by-product HCl from the
LeBlanc process. This need became increasingly more
important when the more economic Solvay soda ash process
started to replace the LeBlanc process during the latter
half of the nineteenth century. Electrochemistry was
destined to provide the solution. By 1833, Faraday had
formulated the laws that governed the electrolysis of
aqueous salt solutions and in 1851 an English patent was
issued for the electrolytic production of chlorine from
brine (10) . Development of dynamos provided an inex
pensive source of power and in 1890 the first electrolytic
chlorine plant began operation at Griesheim, Germany.
This was followed closely by the construction of electro
lytic chlorine plants in the United States and Great
Britain and within a decade numerous plants were in oper
ation (2,10). Today more than 96% of all chlorine is
produced by the electrolysis of brine (11).

3
 End Uses of Chlorine
As mentioned earlier the use of bleaching powder
by the textile industry greatly improved the efficiency of
textile finishing (4). The pulp and paper industry also
began using bleaching powder shortly after bleaching powder
was introduced (12). Available facts show that virtually
all of the chlorine manufactured during the nineteenth
century was consumed by these two industries. They
remained the leading consumers until overtaken by uses for
chemical synthesis in the 1930' s (13).
Sanitation was the next important end use to
develop. While the quantities consumed were not large,
the benefits to society were very significant. The popu
lation growth in the eighteenth and nineteenth centuries,
and the accompanying increase in the discharge of sewage,
placed an overwhelming burden on natural processes which
reduce the pathogenic bacteria content of receiving waters
to an acceptable level for subsequent use as drinking
water. A chemical agent or process was needed to disin
fect sewage and render contaminated water potable.
Chlorine was recognized as a sanitizing agent early in the
nineteenth century (12) , probably because it destroyed
fpul odors , which were believed to be an agent in the
transfer of disease. With the discovery that bacteria
were responsible for the transmission of certain diseases,
interest in means of destroying bacteria developed, and in
the 1890' s several investigators studied the chlorination
of both sewage and potable water (12). By 1912, chlorine
had become widely used for these purposes (14) . There was
an immediate reduction of the incidence of such water-
borne diseases as typhoid (15) and an overall improvement
in public health was observed (16) . One of many examples
that may be cited is the experience of Montreal, Canada.
There were 549 cases of "winter typhoid" reported for the
months of October through December, 1909. After chlorin
ation of drinking water was begun in 1910, only 170 cases
were reported during the same months (17). This was
considered a very substantial reduction and generally
speaking when typhoid cases occurred in areas where drink
ing water was treated with chlorine, they were traceable
to other sources (8) .
Commercial applications of chlorine considered up
to this point involved utilization of aqueous solutions of
elemental chlorine or bleach. Very early in the history
of chlorine, an entirely different thrust began to develop
as the first chlorinated organic compounds were prepared.
Chlorine eventually played a very important role in the

4
organic chemicals industry. Progress in synthetic organic
chemistry in the nineteenth century led to preparation of
substitutes for natural products as well as the preparation
of entirely new and useful compounds : both intermediates
and final products. Chlorine, because of its reactivity,
interesting properties and low price, was incorporated in
many of these, including solvents, pharmaceuticals and
dyes (12,18,19). In 1795, a material later identified
as dichloroethane was produced. In 1831, chloroform was
synthesized. By 1848, the anesthetic properties of chloro
form were recognized and its proven utility during the
United States Civil War made it an acceptable part of
surgical practice (18,19).
Many inorganic derivatives of chlorine also became
important during the latter part of the nineteenth century
and the early part of the twentieth century. These
included the chlorides of aluminum, sulfur, tin and
phosphorus as well as many others. High purity hydrogen
chloride or hydrochloric acid became available as a
by-product of chlorinated organics (19-23) .
Historical data and near term future projections
for the end use pattern in the United States are presented
in Table I (13,25,26). These data, while not detailed,
serve to illustrate the profound changes which have taken
place in the chlorine consuming industries during the past
50 years. Most striking is the growth of chlorine con
sumption in the manufacture of organic chemicals. Most of
the 3% listed under miscellaneous for the year 1926 was
probably consumed in this manner. By 1970, 70% of the
total was consumed in the manufacture of organic chemicals.
While the quantities of chlorine used in the pulp and
paper industry and in water treatment increased, these
end uses assumed less significant positions in the ranking.
Textile bleaching, which stimulated the early growth of
the chlorine industry, declined to such an extent that the
quantity consumed was not large enough for separate list
ing in 1970. The initial decline in use for textile
bleaching was due to the development of more efficient
textile Bleaching processes. The substitution of hydrogen
peroxide as a bleaching agent for cotton and the develop
ment of synthetic fibers contributed to the further
decline in later years.

5
 Table I
CHANGING CHLORINE DEMAND BY END USE — UNITED STATES
Thousands of Net Tons (M-NT)

Pro j ected
1926 1939 1970 1975
M-NT % M-NT % M-NT % M-NT %
Organic Chem. - - 6,928 70 8,434 70
1348 60 962 10 1,152 10
Inorganic Chem.
Pulp & Paper 126 65 122 21 1,133 12 1,416 12
Water Treatment 19 10 35 6 377 4 527 4
Textiles 44 22 29 5 - - - -
Miscellaneous 6 3 46 8 364 4 471 4
Total 195 100 580 100 9,764 100 12 , 000 100

The relative ranking of chlorine consumption by

end use is expected to remain the same in the near term
future although some changes are likely in the share con
sumed by each. Because the organic chemicals industry is
the largest consumer, with the greatest growth potential,
it will have the most pronounced effect on the overall
growth of the chlorine industry. Leading the way will be
vinyl chloride monomer with a projected average growth of
10% per year for the short term future. Also strongly
influencing growth in this area will be the manufacture of
chloromethanes and the propylene chlorohydrin intermediate
for the production of propylene oxide, both of which are
projected to increase at rates of about 7 to 8% per year.
On the other hand, this high growth rate for chlorinated
organic s may be moderated by a shortage of organic feed
stocks and environmental concern associated with the
manufacture, use and disposal of some chlorinated hydro
carbons. Inorganic chemicals are expected to maintain
their position as third in the list of end users. However,
there are some developments that may alter this in the
future beyond 1975. Expanded production of titanium
dioxide by the chloride route offers growth potential. On
the other hand, commercial success of oxygen bleaching in
the paper industry could reduce the growth in the con
sumption of chlorine by that industry and result in a
decline in the importance of this market. The net effect
of these two changes may move inorganic chemicals up to

6
second place in the table. Water treatment, which now
utilizes only a small portion of the chlorine manufactured,
is expected to show increased growth in chlorine con
sumption for wastewater chlorination to meet environmental
needs .
As the result of the proliferation of end uses,
the demand for chlorine in the United States has nearly
doubled every ten years over the past two decades (11) •
As can be seen in Fig. 1, it is expected that this trend
will continue through the next 10 years with a growth rate
in the order of 6% per year. Worldwide demand is expected
to increase at a greater rate, about 7 to 8% per year, due
to more rapid growth of the use of organic chemicals,
primarily plastics, outside the United States (25,26,27).
Consideration of the projected growth figures
raises the question as to whether a similar increase in
demand can be expected for caustic soda and other
co-products from chlorine production. The combined growth
in demand for caustic soda, caustic potash, metallic
sodium, potassium nitrate, magnesium and other co-products
is not expected to keep up with chlorine, but other factors
will be in force to maintain the balance. Even greater
efforts will therefore be made to recover the chlorine
value from by-product hydrogen chloride by techniques such
as direct electrolysis, oxidation, and oxyhydrochlorin-
ation. Non-electrolytic routes for producing chlorine
from metallic chlorides will be re-examined. However, in
spite of these several alternatives, the production of
chlorine by the electrolysis of sodium chloride brine will
continue to predominate and surplus caustic will find its
way into markets normally served by soda ash, the other
major source of sodium oxide. Alkali consumers who can
substitute caustic soda for soda ash will do so, and soda
ash production will be adjusted to balance total sodium
oxide supply and demand.

Distribution
The widespread development of end uses for chlo
rine could not have occurred without efficient means for
its distribution from the manufacturer to the consumer.
Over the years , the changing end use pattern and growing
consumption made new demands on the manufacturer and as ,a
result more sophisticated methods of transporting greater
quantities of chlorine were developed.
As mentioned earlier, the first shipments of

7
significant quantities of chlorine were as calcium hypo
chlorite bleaching powder. This method of shipment, which
prevailed from about 1800 through the early twentieth
century, suffered from a number of drawbacks. The avail
able chlorine per unit weight of material shipped was
relatively low, losses resulted from decomposition in
storage and the chlorine was not in a form readily avail
able for many organic chlorinations . Therefore, when
liquid chlorine became available, shipment and use as such
was favored because of its high assay and unlimited storage
life.
The first containers used to ship liquid chlorine
in Germany were cylinders containing 100 pounds. By 1908,
small railroad tank cars of about 5 ton capacity had come
into use. In the United States at that time, comparatively
little liquid chlorine was being shipped, and that was in
100 pound cylinders. In order to promote the sale of
liquid chlorine and to improve the efficiency of transpor
tation, the 1 ton container was introduced and special
"multiple unit" flat bed railroad cars were designed to
carry 12 to 15 of these containers secured to the car in
cradles. Railroad cars with 15 ton capacity tanks were
introduced in 1910. However, in 1914, the Bureau of
Explosives decreed that for safety reasons cylinders with
contents no greater than 150 pounds could be used.
World War I created a need for liquid chlorine and caused
the decree to be rescinded. Liquid chlorine was again
shipped in the larger containers. The experience gained
during the War demonstrated that the larger containers
could be shipped safely, if appropriate care was taken,
and by 1921 liquid chlorine was available in various size
cylinders up to 150 pounds, in 1 ton containers mounted on
"multiple unit" railroad cars , and in 15 ton railroad tank
cars (28,29). By 1931, 30 ton capacity railroad tank cars
had come into use (30) .
The modes of distribution have continued to evolve
with the dual aim of supplying customers product in effi
cient quantities at low cost, while providing for the
safety of the general public and those involved in trans
porting and using it. Today, in the U.S., chlorine is
available in individual cylinders up to 150 pound capacity,
in 1 ton containers, in "multiple unit" railroad tank cars
of 15 ton total capacity, and in railroad tank cars of 16,
30, 55, 85 and 90 ton capacity. Chlorine in both liquid
and gaseous form is frequently transferred by pipelines
from producers to nearby consumers. Transportation of
liquid chlorine in barges with capacities up to 1,200 tons
is also practiced and some short hauls are made by tank

8
 trucks of 16 ton capacity. All of the cars, containers,
valves and safety devices used in the transportation of
chlorine are built to very rigid specifications, developed
cooperatively by government agencies and the chlorine
producers through their trade organization. The Chlorine
Institute.

Technology and Manufacturing Facilities

To this point, the early history of chlorine has
been traced from its discovery, through its early commer
cial use. Developments in chlorine distribution techniques
have been discussed and, of major importance, the changing
and growing end uses of chlorine have been described.
Accompanying these changes, many significant advancements
have been made in equipment and process technology.
Materials of construction have vastly improved and
such materials as plastics, titanium, and specially formu
lated hard rubber for lining steel are now used to effec
tively combat the highly corrosive nature of wet chlorine
and chlorinated brine.
Important advances have been made in equipment for
converting alternating current to direct current for use
in cells. Motor generator sets, mercury arc and mechanical
— rectifiers have been largely replaced by highly efficient
semiconductor rectifiers which operate at efficiencies in
the order of 97% as compared with the efficiencies of about
90% experienced with mercury arc rectifiers at lower cell
circuit voltages 25 years ago.
! Centrifugal chlorine compressors are now available
—^ith unit capacities in excess of 600 tons of chlorine per
day and with the capability of operating at 10 atmospheres
discharge pressure. These units have superseded the lower
capacity non-lubricated reciprocating compressors and the
earlier sulfuric acid-sealed rotary compressors which had
capacities in the order of 30 to 50 tons per day and
typical discharge pressures of 3 to 4 atmospheres.
/) The greatest advances, specific to the chlorine
/industry, have been in cell design (31-40) . Cell technol
ogy has developed rapidly in support of the growth of
chlorine demand. Fig. 2 illustrates that the rough rule
I of thumb of capacity doubling every ten years applying to
| chlorine growth rate can also be applied to individual
chlorine cell capacity. This figure covers a span
ranging from diaphragm cells such as Allen-Moore and

9
Billiter-Siemens cells, common in the 1920' s, with ratings
of 1,300 to 3,000 amperes, respectively, up to the present
time when 150,000 ampere diaphragm cells are being offered
commercially. Table II lists characteristics of just a
few of the commercial diaphragm cells to illustrate some
of the changes which have occurred over the years.

Table II
EXAMPLES OF CHANGES IN DIAPHRAGM CELL CHARACTERISTICS

Allen- Hooker Hooker Hooker Diamond

Cell Type Moore S S-3B S-4 DS-85

Year 1920 1938 1952 1965 1974

Anode Material G* G* G* G* CM**
Operating Kilo-
amperes 1.3 6 27 55 150

Cathode Current- 0.4 0.6 1.3 1.3 2.7

Density, KA/m2
Voltage/Cell 3.6 3.3 3.9 4.0 4.2
Ton Cl2/Cell-day 0.04 0.20 0.90 1.83 5.05

*G = Graphite
**CM = Coated Metal

Likewise, mercury cell unit capacities have increased at

about the same rate as diaphragm cells. Starting in about
1920 with a cell such as the Solvay mercury cell rated at
4,000 amperes, mercury cell ratings have increased to the
300,000 amperes and higher levels. Table III shows
characteristics of a few typical mercury cells to point
out some of the changes that have occurred in cell design
over the past 50 years.

10
 Table III
EXAMPLES OF CHANGES IN MERCURY CELL CHARACTERISTICS

Kellner- 01 in Solvay 01 in DeNora

Cell Type Solvay E-8 V-100 E-11 27M2

Year 1920 1951 1956 1961 1971

Anode Material G* G* G* G* CM**
Hg Inventory, 1,500 3,100 4,600 4,900 7,500
lbs/cell
Operating Kilo- 4 30 96 125 300
amperes
Cathode Current- 0.6 4.8 5.3 8.3 ~10
Density, KA/m2
Voltage/Cell <5 4*. 5 4.4 4.8 ~4.2
Ton Cl2/Cell-day 0.13 1.0 3.2 4.2 10.0

*G = Graphite
**CM = Coated Metal

Due to the pressures that have arisen from concern

for the environment, no new mercury cell plants are being
built at the present time in North America or Japan and
some existing mercury cell installations, principally in
Japan, are being phased out of operation. Because of the
reduced demand for mercury cells, the amount of mercury
cell developmental work is expected to decrease, particu
larly in comparison with the efforts expended in the
1950' s and 1960's.
Attention instead will be concentrated on develop
ment of improved diaphragm cells taking advantage of new
developments in membrane technology and anode materials .
More effort will likely go into reducing the operating
costs of diaphragm cells by developing improved diaphragms
with longer life and improved mechanical and electrical
designs to take full advantage of economies made possible
through the invention of metal anodes.

11
 In light of the energy situation, design of dia
phragm cells to operate at higher current densities will
require critical review since such operation consumes more
energy per unit of production. Greater emphasis may be
placed on lower voltage operation as power shortages and
escalating power costs erode away capital related benefits
associated with high current density cells. This does not
imply, however, that cells will not be developed with
greater unit capacities due to larger physical size.
Improvements in technology, primarily the use of
metal anodes, have improved diaphragm cell operating costs
in recent years, but diaphragm technology has not kept pace
with the advances in anodes. Thus it is highly likely that
more efforts will be concentrated on this facet of cell
technology. One particular type of diaphragm which is
expected to be thoroughly investigated and which may create
a whole new generation of chlorine cells is the permselec-
tive membrane. Investigators believe that such a diaphragm
would have better physical characteristics than the classic
asbestos diaphragm, and produce cell liquor with substan
tially lower sodium chloride content and higher caustic
soda strength.
With the rapid growth rate in chlorine demand,
larger increments of new capacity have been required each
year and this has supported a steady increase in the size
of new facilities that have been built. In 1950, the 6%
growth in U.S. demand could have been satisfied by the
construction of three new plants with an average capacity
of about 120 tons per day. In 1970, a 6% change divided
among three locations would have averaged nearly 540 tons
per day. It is this ever-increasing absolute demand
coupled with continually improving technology, that has
permitted construction of larger-and-larger chlorine
plants .
Large production facilities, using new technology,
can be constructed at a significantly lower capital invest
ment per unit of capacity than small production facilities.
Fig. 3 has been developed to illustrate the change in
capital investment required per daily ton of chlorine
capacity over the past 40 years as a result of increased
plant size and improved technology. For the purpose of
comparison, costs for the older plants have been adjusted
to a common 1973 dollar base. This figure illustrates
that the relatively small 100 tons per day plant, consid
ered competitive only 25 years ago, if built today using
equipment and technology of the type available 25 years
ago, would require nearly twice the capital investment per

12
unit of capacity that the large plants built in the late-
1960' s and early-1970's required.
Excluding the special cases where unique local
situations may support relatively small chlorine plants,
even new large plants with 500 tons per day capacity are at
a disadvantage when compared with plants now being con
structed which are typically 1,000 tons per day or greater.
Fig. 3 shows that the relative battery limits capital
requirements are $40 , 000/daily ton for the 500 tons per day
plant versus $29 , 000/daily ton for the 1,000 tons per day
plant. (Again for ready comparison, these costs have been
developed on a 1973 base.)
In looking at costs, items which could add signi
ficantly to plant capital investment as well as operating
costs will be the tightening safety, health and environ
mental regulations, particularly if the EPA's proposed zero
discharge of process wastewaters guideline (41) is promul
gated. These controls have necessitated and will continue
to require changes in design and operating practices for
existing and new plants.
Chlorine plants differ greatly in size, design,
and operating features. These differences have very
significant affects on achievable effluent or emission
levels and the expenditures required to reach them. Costs
per unit of production for compliance with the new environ
mental regulations in existing older plants may be high in
comparison with the newer plants (42).
Because of the aforementioned wide diversity among
chlorine plants, projection of typical environmental
control-related costs is not readily accomplished.
But as an illustration, Table IV has been prepared
for two particular types of chlorine plants. This example
compares the capital and operating costs to reach zero
discharge of process wastewaters for an older diaphragm
cell plant of the type constructed in the late-1950's with
a capacity of 250 tons per day with a new 1,000 tons per
day plant. Both plants have been assumed to be in the
same geographical location, and have the same sources of
raw materials, water, power and other productive materials.
The availability of land to use for solids disposal has
also been assumed to be equivalent.

13
 Table IV
REQUIREMENTS TO MEET "ZERO DISCHARGE"
EFFLUENT GUIDELINES
DIAPHRAGM CELL PLANT, GULF COAST AREA

Plant Existing New

Capacity, ECU*/day 250 1,000

Total Fixed Capital 0.9 — 1.0 0.9 — 2.5
Added ($MM)
Added Manufacturing 5.30 — 7.40 2.00 — 2.50
Cost, $/ECU

*ECU = Electrolytic Cell Unit = 1.0 T chlorine plus

1.1 T caustic soda.

The numbers listed in Table IV are for specific

situations and will vary widely from location to location.
They are intended only to show that costs for compliance
with environmental regulations will be significant and
place some locations at an economic disadvantage with
respect to others.
Another illustration of the differential in demands
placed upon existing mercury cell plants in meeting mercury
emission and effluent regulations is shown in Table V
(42). The plant in Case 1 is operating older cells at
lower current densities than the plant in Case 2. The
Case 1 plant has many more cells, more potential points
for mercury loss and a far greater mercury inventory than
does the Case 2 plant. These examples serve to point out
some of the problems that the chlorine industry is facing
in attempting to comply with existing or pending environ
mental regulations while still protecting stockholders'
equity in existing facilities.

14
 Table V
COMPARISON OF TWO MERCURY CELL PLANTS

Case 1 Case 2

Plant Capacity (tons Cl2/day) 300 150

Cell Type Olin E-8 DeNora 24 H-5
Number of Cells 258 18
Total Mercury Inventory (lbs) 672,000 144,000

Creativity, innovation and application of sound

engineering principles will be required to comply with
tightening environmental controls and Occupational Safety
and Health Act regulations without excessive costs which
must be passed on by producers to ultimate consumers.
Government also has a responsibility which must be faced
squarely by our elected officials in Washington and local
municipalities. They must develop in-depth facts on
legislation while it is in committee so that when it comes
up for vote they have an understanding of the real environ
mental needs and the cost to benefit relationships of the
regulations imposed under the pending legislation.

Energy
The chlorine industry has a potentially bright
future but with many challenges to be faced. Some of
these have been discussed earlier, but one in particular
warrants further comment that is the energy situation.
Careful planning is needed to assure the future
availability of feedstocks for the largest chlorine end
use in chlorinated organic products, as well as energy for
the production of chlorine. The energy picture is some
what confused at this time and firm projections on sup
plies cannot be made. One thing is certain and that is
that ample energy and feedstocks must be obtained if the
chlorine industry is to continue to grow. A whole paper
could easily be written on this subject alone. It
suffices to say here that there are a number of things the
industry is doing to get the most out of available energy
supplies over the short term, and that given the

15
opportunity, scientific ingenuity will prevail and provide
appropriate long term solutions .

Conclusion
Chlorine has grown from a laboratory curiosity to
become one of the World's largest chemical commodities in
the relatively short span of 200 years. In the even
shorter period of time, since the first commercial chlorine
was produced in the United States at Rumford, Maine in 1893
(43), U.S. chlorine production has increased to more than
10 million tons per year, making it the Nation's sixth
largest chemical commodity. Advances in manufacturing
technology and distribution procedures have made it avail
able at relatively low cost for uses in hundreds of prod
ucts that contribute to the health, comfort and enjoyment
of people throughout the world.
Such rapid growth of an industry might have taken
place without proper regard for socio-envlronmental impact,
but this has not been so in the case of the chlorine indus
try. It has been a leader in employee health protection
and development of safe practices for producing, trans
porting and using its products. It has also been a leader
in the environmental area as demonstrated by its recent
very rapid and effective response to control of heavy metal
discharges. Since its founding 50 years ago, The Chlorine
Institute has been an effective focal point for cooperative
industry actions in achieving its common goal of being a
leader in the acceptance and fulfillment of responsi
bilities to society.
Looking back over the past 200 years, one cannot
help but be impressed by the technological progress made
in the production of chlorine and chlorinated products.
Much of this progress was made during a period when the
level of scientific knowledge was minute compared with
today's position of technological wealth. While some pro
jections have been made in this paper for relatively near
term technical improvements , there no doubt will be many
more that are beyond our present imagination. However,
based on past performance, one may expect the chlorine
industry to face the challenges of the future and continue
to meet the needs of society in a rapid and responsible
fashion.

16
 Fig. 1. Growth of Fig. 2. cell Capacity
Chlorine Demand

i120 A - 50 TPD
B - 100 TPD
C - 500 TPD
i 100 ^A D - 1,000 TPD

•80
—B
i60

• 40
—D
20
1940 1960 1980
YEAR
Fig. 3. Battery Limit Capital
Constant 1973 Dollars

17
 Acknowledgments
The author acknowledges with appreciation contri
butions made by the following individuals — E. F. Booth,
J. P. Guptill, A. S. Robertson and A. L. Wadsworth, 3rd —
all of Allied Chemical Corporation, Syracuse, New York.

REFERENCES
1. The Early History of Chlorine, Alembic Club Reprints
No. 13, Edinburgh (1905).
2. L. Mond, J. Soc. Chem. Ind. , 15, 713 (1896).
3. P. S. Brallier, Chem. Met. Eng., 30 (13), 508 (1924).
4. H. Ashworth, Chem. News, 4 (95), 169 (1861).
5. W. Weldon, Chem. News, 20 (510), 109 (1869).
6. M. Gossage, Chem. News, 4 (95), 172 (1861).
7. F. Hurter, J. Soc. Chem. Ind., 2, 103 (1883).
8. G. Ornstein, Trans. Amer. Electrochemical Soc., 29, 529
(1916) .
9. J. L. K. Snyder and H. P. Wells, Trans. Amer. Inst.
Chem. Eng., 14, 145 (1921-1922).
10. R. T. Baldwin, J. Chem. Ed., 4 (3), 313 (1927).
11. North American Chlor-Alkali Industry Plants and Pro
duction Data Book, Chlorine Information Pamphlet
No. 10, The Chlorine Institute, Inc. (January 1973).
12. R. T. Baldwin, J. Chem. Ed., 4 (4), 454 (1927).
13. Anon., Chem. Met. Eng., 47, 75 (1940).
14. J. Race, The Can. Eng., 53, 255 (1912).
15. J. Race, Chlorination of Water, John Wiley, New York
(1918) .
16. A. H. Hooker, Chloride of Lime in Water Purification,
p. 13, John Wiley, New York (1913).
17. J. 0. Meadows, Eng. News, 65, 80 (1911).
18. J. T. Conroy, Trans. Amer. Electrochem. Soc, 49, 209
(1926) .
19. V. R. Kokatura, Chem. Met. Eng., 19, 667 (1918).
20. P. S. Brallier, Chem. Met. Eng., 58 (19), 846 (1923).
21. R. G. MacDonald, Chem. Warfare, 9~J8) , 2 (1923).
22. H. R. Feeny, J. Soc. Dye colour., 45 (10), 283 (1929).
23. Anon., Can. Chem. Met., 14, 108 (1930).
24. D. A. Pritchard, Trans. Amer. Electrochem. Soc, 49,
29 (1926) .
25. Source: Allied Chemical (1973).
26. H. F. Mark, J. J. McKetta and D. F. Othmer, Kirk-Othmer
Encyclopedia of Chemical Technology, 2nd ed. , Vol. 1,
p. 676 (1963).
27. A. Theurer, Growing Chlorine Consumption in Chemical
Industry, Chlorine Institute Pamphlet No. Rll, The
Chlorine Institute, Inc., New York (1969).

18
28. M. Mauran, Trans. Amer. Inst. Chem. Eng., 14, 167
(1921-1922) .
29. J. L. K. Snyder and H. P. Wells, Trans. Amer. Inst.
Chem. Eng., 14, 145 (1921-1922).
30. W. L. Savell, Comp. Gas. Mfgrs. Assoc. Proc . , 19, 28
(1931) .
31. R. Taussig, Trans. Farad. Soc . , 5, 258 (1910).
32. J. B. C. Kershaw, Chem. Trade J. Chem. Eng., 463, 491,
521 (April 10, 1920) .
33. A. J. Allmand and H. J. T. Ellingham, The Principles of
Applied Electrochemistry, p. 392, Edward Arnold,
London (1931) .
34. K. E. Stuart, T. L. B. Lyster and R. L. Murray, Chem.
Met. Eng., 45, 354 (1938).
35. W. C. Gardiner, Chem. Eng., 54, 108 (November 1947).
36. W. H. Shearon, C. Chrencik and C. L. Dickinson, Ind.
Eng. Chem. , 40 (11) , 2002 (1948) .
37. H. A. Sommers, Chem. Eng. Prog., 53 (9), 409 (1957).
38. H. A. Sommers, Chem. Eng. Prog., 61 (3), 94 (1965).
39. Source: Diamond Shamrock Corporation (1973).
40. Anon., Chem. Eng. News, 47 (12), 13 (1969).
41. Environmental Protection Agency, Fed. Reg., 38 (196),
28184 (October 11, 1973).
42. E. F. Booth, Pollution Abatement — Chlor-Alkali Indus
try, Presentation to the Environmental Protection
Agency, Washington, D.C., November 16, 1972.
43. Chlorine Institute, Inc. Booklet, Exceeding All Expec
tations — A Short History of Chlorine.

19
 CHLORINE - GLIMPSES FROM ITS HISTORY
I. Eidem and L. Lundevall
KemaNord AB, Stockholm, Sweden

Abstract
The discovery of chlorine in 1771 or 1772, not 1774
as is generally accepted, is described and the life
of the discoverer, Carl Wilhelm Scheele, is treated.
The rapid research in chlorine chemistry shortly
after the discovery and the subsequent, slower in
dustrial development are sketched, and two tables
with historical dates are given. Scheele's labora
tory notes and correspondence are important tools
in this study of the history of chemistry.

"On 1/2 uns1) finely ground Brownstone /an ore, consist

ing mainly of manganese dioxide/2) was poured 1 uns pure
Spiritus salis /hydrochloric acid/. After this mixture had
been standing in the cold for 1 hour, the acid had assumed
a dark brown colour. One part of this solution was poured
into a glass, which was placed over the fire. The solution
gave off an odour like warm aqua regia, and after 1/4 hour's
duration, she was as clear and colourless as water, and the

"In order to
investigate this
new matter
clearly, I took
a retort, /Fig.l/
in which there
Fig.l. Gas
collecting in an
ox-bladder - a
common object in
a pharmacy 200
years ago. From
Scheele's book
on Air and Fire,
written 1775.

1) 1 uns is a weight unit, in a pharmacy equal to 29.60 g.

2) The texts within // brackets are our comments.

20
was a mixture of brownstone and Acidum salis /hydrochloric
acid/. Over the neck I bound an air-free bladder /an ox-
bladder/, and put the retort in hot sand. By the effer
vescence in the retort the bladder was expanded. When the
acid no longer was fizzing, I loosened the bladder and
found that this air /gas/ had coloured the bladder yellow
as would spirit of nitre /nitric acid/. No trace of ASr
fixus /carbon dioxide/ was to be found, but a rather per
ceptible, pungent smell, which was highly irritating to the
lungs. She resembled the smell of warm Aqua regia."
"This acid of salt, deprived -of phlogiston /here hydro
gen/3] as if from one of its ingredients, combines to a
rather small quantity with water, and gives to water a
slightly sour taste, but as soon as she touches combustible
materia, she becomes genuine acid of salt again. All
vegetable flowers, red, blue
and yellow, became white in a KONGL
short time; the same occurred VETENSKAPS
to green plants."
These descriptions are ACADEMIENS
extracts from a long report HANDLINGAR
in Swedish: "On Brownstone or F6rAr 1774.
Magnesia and its properties". Vol. XXXV.
It was written by the Swedish
pharmacist Carl Wilhelm
Scheele and published in two
issues of the Transactions
of the Royal Swedish Academy
of Sciences vol. 35, 1771.
The discovery of chlorine
appears in the number for
April to June (1, p. 93-94,
105-110) issued in June or
July. That report is evi
dently well known, as text
books on chemistry general Upligdf piSTOCKHOLM
StLvilfca ~
ly give the year 177^ for
the discovery of chlorine.
Fig. 2. Facsimile of the
That report is probably title-page of the Transac
the main reason why we are tions of the R. Acad, of
celebrating the 200 years' Sciences in which the long
anniversary of the discovery brownstone report by Scheele
of chlorine, now, in 197** • was printed.

3) In the phlogiston theory a hypothetical element,

present in reducing agents, such as coal.

21
It is a good reason, but we do it a few years too late.
It is quite clear that Scheele did not discover the
chlorine in 1774 • The first proof is that he sent his re
port for publication, half a year earlier to the chairman
of the Academy of Sciences, professor Torbern Bergman of
Uppsala University (2, p.4). In a letter dated November
7th, 1773 to J.G. Gahn Torbern Bergman writes that he has
finally received Scheele's report on Magnesia Nigra, a
little book . . .

Earlier presentations PHYSISK

BESRRIFNING
The report was first 6FVER
public by oral presentation
to the scientists of Sweden JORD-KLOTET,
on the 14th of January, 1774 PA
at the meeting of the Academy COSMOfjRAPHlSKA SAUSgJFETS
of Sciences (3). Further, the VAGNM
Transactions of the Academy forfattad,
of Sciences is not the ear af
liest publication. ' As C.W. Torbern Bergman,
Oseen has shown (2, p. 7) Pmortnon
ieEiaauM uri C—iw
oc« laaMM ra KdMU Aeunan
•r Haw, i Uru-
professor Bergman has includ Acm»hw NhniWm-Ouar;
Ce«tatoaeM, tnum
Kow«. V•-M
ed the discovery in his book:
Physical description of the
Earth, written on behalf of SENARE BANDET.
the Cosmographical Society,
2nd edition (4, p. 296). 5)
nun wi fUlmi
In translation Bergman UPS A LA,
writes: "Concerning the acid Tiratt hoi JOH. EDMAN, KoNsu Acad.
of salt we now know with Bokh, At 1774.
full certainty about the
presence of phlogiston, for
it can now really be dephlo-
gistonized with brownstone,
which stronger attracts the Pig. 3. Facsimile from pro
combustible materia. This fessor Bergman's book:
acid is then transformed to "Physical description of the
a compressible, reddish Earth, 2nd ed . , 1774. (The
vapour, which scarcely com first printed source where
bines with water, and which chlorine is described.)

41 The earliest publication date of the number for the

second quarter of the year has been searched for by the
library of the Academy and others, but was not found. Later
lists were found. If common publication rules were followed,
July 1774 is most probable, but June is possible.

22
makes Lacmus and other vegetable colours white" etc. He
adds in a footnote: "This remarkable discovery by Mr.
Scheele will be published as soon as possible in the Trans
actions of the R. Acad, of Sci."

Scheele^s Literary Remains

In the manuscripts depart
ment of the Library of the
Academy of Sciences about
half a meter of shelf space
is taken up by manuscripts,
letters and other documents
from or about Carl Wilhelm
Scheele. Different parts of
the almost unreadable labo
ratory notes - in the old
German style, in German and
full of old chemical sym
bols - have been deciphered
and issued by A.E. Norden-
skiold (5), C.W. Oseen (6; 7)
and Uno Boklund (8).
Scheele wrote several
letters to his friend Johan
Gottlieb Gahn, a mining
chemist. In a letter of the
2nd December, 1771 Scheele
promises to give an account
on his Investigations of
magnesia nigra, nota bene,
before the end of the year. Pig. 4. One of Scheele's
This promise is held later handwritten notes . See text
but the original letter is on chlorine from^ about one
not available. Gahn has left third from the bottom: "wird
among his papers a copy made Uber ..."

5) This book was public before July 1st, 1774 probably in

the beginning of the year. According to the University lib
rary of Uppsala, it stands at the top of a printed list of
deliveries for the first half of the year 177 4 from the
printer, Joh. Edman. (Such deliveries are compulsory in
Sweden since 1661). Since alphabetical order is not used,
and furthermore since part one of the work stands as fifth
item on the printed list for the second half of 1773, it
seems correct to assume that the lists are chronological.
Conclusions: The first public evidence on chlorine gas came
in the early part of 1774, not in the second quarter.

23
by himself from a paper of Scheele's on magnesia nigra. The
copy is dated 28th March, 1773. (5, p. 74-76) . It contains
a full description of the discovery of chlorine.
The "oldest" notation by Scheele's hand on the chlorine
discovery is found in handscript No. 44, p. 9 (7, p. 93-94 )
and (6, p. 113) . (See fig. 4)
About one third from the bottom we can find: "Wird Uber
pulverisierten braunstein spiritus salis 2 partes de-
stilliert so gehet in Anfang ein sehr volatilischer spiri
tus, welcher mit gelinder hitze in der recipiente kochet."
(If over pulverized brownstone 2 parts of acid of salt is
distilled, there is given off at the beginning a very vola
tile vapour, which boils in the recipient with moderate
heat.) Later in the same handscript Scheele explains how he
treated the mineral with common salt + sulfuric acid and
found a gas, which could bleach litmus and flowers white.
The dating of that document is given by C.W. Oseen to
be 1769 or 1770. (7, p. 167) His dating is criticized by
Johan Nordstr6m (9, p. 272, and we have found 1771 (or 1772)
during Scheele's Uppsala period more likely than before
1771 or after 1772. 6i

6) Professor Oseen tries to prove that the experiments on

Magnesia Nigra started before August 1770, when Scheele
for the first time met Torbern Bergman, though the latter
says himself that he asked Scheele to start the brownstone
investigation (1, p. 194; 5, XVIII). But Oseen makes the
fatal mistake of taking magnesia (talcum earth) for magne
sia nigra (brownstone). Further, it seems doubtful that
Scheele could carry out his discovery before he came to
Uppsala in Aug. 1770, as Scheele had difficulties to make
his experiments in the pharmacy in Stockholm. In Uppsala,
however, he got permission to work one day a week with his
own experiments. As Oseen has shown, Bergman delayed the
brownstone investigations with new questions when Scheele
thought he had finished the investigation. The discovery
of chlorine Belongs to his independent work in the early
time of the period, autumn 1770 - spring 1773- Our conclu
sions are therefore that chlorine was discovered in 1771
(or less probably in 1772). Professor Bergman also suggest
ed that Scheele should study the mineral "flusspat (in
Swedish) now called fluorspar (in English), what he men
tions in a letter to Macquer (10, XXXIII). The fluorspar
experiments, which led to the discovery of a new mineral
acid, hydrofluoric acid, were made in 1770 and published
(contd)

24
 0 cfu/injjenerc . Common salt, NaCl
Acid; c. cone., d. diluted
+«r. (Lidum minerals. Mineral acid
Ut'tt/um Viiricli . Sulfuric acid
+dta concentra/um; i/. diluium . " " c. cone., d. diluted
+0 Cttdum tlUri Nitric acid; nitric oxides
V <7^f.*fjoriu ' " " concentrated
+ @ GadurnJatiji *&fr*fJ*pU*$liu*l"* Hydrochloric acid; chlorine
Uifua Re/jit. Aqua regia, HC1 + HNO,
dcidumfincri/ mmeralii . Hydrofluoric acid
*f° Ucufum ar/fnici . Arsenic acid

Pig. 5. Examples of chemical symbols

and Latin names used by Scheele.
Some examples of the chemical names in Latin which are
still used in today's pharmacies to some extent, and sym
bols for elements and ' compounds , in Scheele 's time are shown
in fig. 5. This is taken from a book from 1775, also issued
by Torbern Bergman (11, last page), but its origin are lec
tures held 1749 to 1751.

Milestones
The above is a rather lengthy description of the disco
very of chlorine. To dig deep in letters etc. after Scheele
is difficult for a Swede, but a summary of the continuation
will be given. The 'Transactions 'containing Scheele's report
was translated and available in German 1778, in French 1785
and in English 1786 (1). But the leading chemists got the
information of the new gas earlier by letters from Bergman
etc. The French chemist Antoine Lavoisier founded a new
theory on the combustion and the important role of oxygen -
contrary to the phlogiston theory. He gave the name oxygen
from the greek word for sour, oxys. In the 1780's his
disciple Claude Louis Berthollet' studied chlorine and called
it oxymuriatic acid (in translation) because he thought that
the gas was a compound of muriatic acid and oxygen. About
1809 J.L. Gay-Lussac and L.J. Thenard tried to find the
oxygen in oxymuriatic acid by passing the oxymuriatic gas
over glowing carbon, but no reaction occurred. They proposed
it could be an element but concluded that the gas contained
oxygen. The British chemist Sir Humphry Davy made many expe
riments with the gas and gave the explanation of the "oxy-
6) contd. in 1771. The year 1770 is therefore less like
ly for the brownstone investigations .

25
1781 HAGEMAN: Sulfur chloride (16)
1785 Claude Louis BERTHOLLET, prof, in Paris: (13)
Hypochlorites; chlorine water and hypochlorites (14)
for textile bleaching (Eau de Javel) (15)
1787 Professor BERTHOLLET: Chlorates (13)
1789 Charles TENNANT, England: A method to absorb
chlorine gas in milk of lime. No patent granted
1790 C. TENNANT: A method to make dry bleaching powder (15)
by absorbing chlorine in dry hydrate of lime
1809 Joseph Louis GAY-LUSSAC, prof, in Paris, and Louis (12)
Jacques THENARD thinks the gas might be an element(13)
1810 Sir Humphry DAVY, prof, in London, demonstrates (13)
that chlorine is an element and names the gas
1811 Bernard COURTOIS, a French pharmacist: Iodine (12)
This supports the existence of elementary chlorine(13)
1812 (or 1813) Pierre Louis DULONG , director of Ecole (15)
polytechnique : Nitrogen trichloride (16)
1813-1815 DAVY investigates chlorine oxides
1815 Chlorine oxide or hypochlorous acid (16)
1815 Count Friedrich von STADION, Vienna: Also
hypochlorous acid (16)
1816 F. von STADION: Potassium perchlorate (16)
1820 The French chemist LARBARRAQUE prepares sodium (15)
hypochlorite by saturating soda lye with CI gas
1831 Michael FARADAY, prof, in London: Two chlorides (13)
of carbon
1823 M. FARADAY succeeds in liquefying chlorine (13)
1834 Antoine Jerome BALARD, prof, at Sorbonne: (131
Chlorine monoxide
1884 K. OLSZEWSKI: Solid chlorine at -102°C (16:

Fig. 6. Discoveries in chlorine chemistry after Scheele

26
1789 Scheele's method, brownstone and sodiumchlorid + sul
furic acid, is used by BERTHOLLET in his factory at
Quai de Javelle, Paris, to make bleaching solutions
containing hypochlorites.
I8b6 First electrolysis of HC1 is probably made by BELLONI .
I838 MAUGHAM recovers exhaust HC1 and brings it in reaction
with MnOj, Scheele's first method.
1851 WATT, Br. P. 13755, describes an apparatus for elec
trolysis of molten NaCl.
1855 DUNLOP is granted a patent on reuse of Mn waste by
precipitation of MnCO, with chalk and oxidation by
air . 5
1866 WELDON process. MnCl- + lime flows through a tower
against an air stream. Excess of CaCl? necessary for
good regeneration of Mn compounds to reaction with
HC1.
1871 WELDON uses magnesit, MgCO, , for precipitation.
MgMnO^ is the oxidating agent.
1868 DEACON & HURTER conduct a gas mixture of HC1 and air
over
lyst. a heated surface with CuSO,.,
4 later CuCl9,
,L cata
1885 Electrolysis of NaCl. Diaphragm from cement and NaCl.
1890 First CI plant in Griesheim, Germany, in operation.
Vertical diaphragm and non-flowing electrolyte.
1897 HARGREAVES and BIRD, Br. P. 21178 etc. introduce the
horisontal diaphragm and the flowing electrolyte.
1892 Mercury cells are invented by H.Y. CASTNER, USA, and
C. KELLNER, Austria, almost simultaneously.
1957 First patent on Ti anodes with noble metal or noble
metal oxide coating, Neth. P. 216 199, DE BEER.
First type for commercial operation patd. 1965.
1969 First CI plant with DSA, dimensional stable anodes,
on streamy with the capacity 600 tons of CI a day.
It belongs to PPG.
1874 Production of liquid chlorine by pressure increase
is described. Hydrate of chlorine is used.
1919 Production of liq. CI by cooling the pressurized gas
and pressure release in a continous plant.

Fig. 7- The industrial development, mainly in the 19th

century .

27
muriatic acid". He said that it is an element, not a com
pound, and that marine acid (Acid of salt) is a compound of
only hydrogen and chlorine, as he called the new gas from
the greek word for green, chloros. The formal explanation
came in a speech to the Royal Society on the 15th November
1810. (15) Partington gives the date to be the 12th of July.
(16, 185-188)
The further research and development of chlorine che
mistry is summarized in a chronological table, fig. 6.
The industrial develocment is sketched in a similar table
fig. 7.

The life of Carl Wilhelm Scheele (17) (18)

As expected in the symposium invitation, special atten
tion will be devoted to Scheele.
Carl Wilhelm Scheele was born the 9th of December 1742
at Stralsund, then Swedish, at the Baltic coast of Northern
Germany. He came from a German family, and his language was
German, but he lived most years of his life in main Sweden.
He learnt Latin, French and natural science at the local
grammar school. An apothecary, a friend of his father's,
taught him to read recipes and to write the old chemical
symbols. At the age of fourteen the young Wilhelm, as he
was called at home, came as an apprentice to a pharmacy in
Gothenburg, where he replaced his eldest, deceased brother.
His master, the apothecary Bauch was a friend of the family,
and he gave him permission to make chemical experiments.

Pig. 8. Uppsala
New Market
Place with the
Town Hall and
1 1II (right) the
■ ■■■ corner of the
—pharmacy
1 1ITT
"Upp-
lands Vapen".

28
 Pig. 9.
Uppsala
APOTEKET LEJONET, UPPSALA L°kk's pharma-
STORA TORGET N° cy

Lokk's Pharmacy
Uppsala ~i8oo

Fig. 10.
Uppsala, the
pharmacy "Upp
Outer courtyard lands Vapen",
built for the
apothecary C.L.
Lokk . Ground
plan of the
buildings about
the year of
1800.

1 i

1
B'BeJroom
k* Kitchen

29
In 1765, when he had passed his apprentice time and more,
he moved to a pharmacy in Malmo where he stayed for three
years. He could continue his experiments there and could
also study many chemical books, some of which he bought
with money saved from his little salary. He tried to repeat
the experiments he was reading about, but often he found
errors, so he became suspicious of all written sources. He
had to check everything. He made his experiments after the
daily work, often late, only guided by his searching for
the truth. After two years' work in a pharmacy in Stockholm
1768-1770, where he had only a small place for experiments,
in a window-display, Scheele came as a laboratory-worker
to the pharmacy "Upplands Vapen" at Uppsala. Some pic
tures show how the pharmacy buildings looked 200 years ago.
The pharmacy was built at the New Market Place near the
Town Hall, in 1767. It consisted of the main building at
the corner and two courtyards surrounded by rooms and work
shops for different purposes.
In one of these many rooms
Scheele had his dwelling.
In the laboratory at the
outer yard Scheele had pre
mises to work with his own ex
periments one day every week.
(19) Fig. 11 shows where
chlorine was first discovered.
We cannot come closer to that
"famous event". The pharmacy
buildings were demolished in
1959.
In Uppsala the famous la
boratory-worker was introduced
to the professor of chemistry
at the University of Uppsala,
and to the learned world.
Professor Bergman became a
respected friend of Scheele's,
and Bergman found in Scheele
a very clever experimentator
and also a deep friend.
Scheele was invited to make
chemical demonstrations to
Pig. 11. Lokk's pharmacy, prominent guests etc. in the
Uppsala. Behind the windows University building "Laborato-
on the ground floor: rium Chemicum". In 1775
The pharmacy laboratory Scheele moved in order to be
where chlorine was dis- "his own master" to a small
covered. town west of Uppsala, to

30
 Fig. 12. Koping,
Scheele's phar
macy and home at
the Market Place
built for him
1783-1784 (20).
Drawing by
W. Meyer in Nor-
denskiold's book
(5, XXIV) .

KSping. He was employed as a master for the local pharmacy,

owned by the young widow of the former pharmacist. He had
no money but was accepted as he was supposed to marry the
widow. After much trouble - which is too long to describe
here - he could take over the pharmacy, on the condition
that he should provide for the widow and her baby son and
take the responsibility of the pharmacy debts. He was eco
nomical and diligent and could pay the debts and in 1781
buy a large house at the Big Market Place. During 1783-84
Scheele built his new pharmacy house, as seen on fig. 12.
This wooden house was replaced by a brick building for the
pharmacy after 1889. (20) .
In 1775 Carl Wilhelm Scheele was elected a member of
the Royal Swedish Academy of Sciences, while he still was
a laboratory-worker, an entirely unique election. His title
in the official papers was "pharmaciae studiosis". He
visited the Academy only once, in October 1777, when he
took his seat. Shortly afterwards he was approved as a
pharmacist by Collegium Medicum in Stockholm. The examina
tion was most formal and all the examiners paid homage to
him and gave him the highest marks etc . , since his ability
and chemical knowledge were already well-known to all.
Scheele was also a member of five foreign scientific so
cieties, among them Academie Royale Franchise de Medecine
in Paris.
Scheele's list of discoveries is very long, too long to
be included here. Shortly: he discovered or described the
existence of oxygen, nitrogen, chlorine, barium, manganese,
fluorine, molybdenum and tungsten, and -many organic acids.

31
Manganese metal was prepared after his instructions - as
he had no furnace with sufficiently high temperature - by
the Swedish mining chemist Johan Gottlieb Gahn. Molybdenum
metal was prepared for the first time, according to
Scheele's instructions, by Peter Jacob Hjelm.
Carl Wilhelm Scheele died the 21st of May 1786 at the
age of only 43 1/2 years at KSping, where he was buried.
Three days before his death he married the widow, Margareta
Pohl , and in his last will he gave her back the pharmacy.
Many medals and also two statues pay homage to him but no
picture from his life time is known. The only one, which is
said to show his likeness, is the medal struck in 1789 by
the Royal Swedish Academy of Sciences. This portrait and
that of Humphry Davy are shown on the last pictures No. 13
and 14.

Pig. 13. Carl Wilhelm Scheele Pig. 14. Humphry Davy

1742 - 1786 1778 - 1829

Acknowledgements : For valuable help our best thanks are

expressed to Docent Uno Boklund, Stockholm, to Dr. Wilhelm
Odelberg and others at the Library of the Academy of
Sciences, to the Library of the Uppsala University, to BZ
Potoservice, Stockholm, and to Dr. Nils Sundquist and Dr.
Ola Ehn, Uppsala, Mr. Oscar Bjornanger and the photograph
Jannerman (for the portraits), Koping. Mr. Michael Hatcher,
KemaNord, has checked the language.

32

\
 Literature
(1) Scheele, Carl Wilhelm: Om Bruns-sten eller Magnesia, och dess
Egenskaper. (On Brownstone or Magnesia, and its Properties)
Kongl. Vetenskapsacademiens Handl. 3S(1774):2, p. 89-116, :3, p.
177-194; J94-196 (Comments by T. Bergman) (In Swedish)
Der K. Schwedischen Akaderaie der Wissenschaften, Abhandlungen
Vol. 36(1778), p. 95-120, 183-198. (In German)
Mémoires de Chymie... tirées des Mémoires de 1'Académie Royale
des Sciences de Stockholm, traduites de Suédois et de 1'Allemand.
Dijon i, p. 39-115, 1785 (In French)
Beddoes, Thomas: The Chemical Essays of Charles -Wilhelm Scheele.
Translated from the Transactions of the Academy of Sciences at
Stockholm. With Additions and with a Sketch of the Life of Karl
Wilhelm Scheele by John Geddes M'Intosh. (In English)
London 1786. (Re-issued London 1901)
(2) Oseen, C.W. : Torbern Bergman och Carl Wilhelm Scheele. (In
Swedish) (Torbern Bergman and Carl Wilhelm Scheele)
Stockholm 1940, 29 p.
= Levnadsteckningar över K. Svenska Vetenskapsakademiens leda
möter. 113
(= Memorials on members of the R. Swed. Acad. Sci. No. 113)
(3) Sjöstén, Carl Gustaf: Åminnelse-Tal hållit för Kongl. Veten
skaps Academien öfver dess framledne Ledamot Herr Carl Wilhelm
Scheele, den 14 Oct. 1799. (In Swedish) (Oration held for the
Royal Academy of Sciences in memory of its deceased member Mr.
Carl Wilhelm Scheele, the 14th Oct., 1799)
Stockholm 1801, 84 p.
(4) Bergman, Torbern: Physisk beskrifning öfver jord-klotet, på
Cosmographiska Sallskapets vagnar författad. Senare bandet.
Andra Uplagan, tilökt och förbattrad. (In Swedish) (Physical
description of the Earth, written on behalf of the Cosmographi-
cal Society. Vol. II. 2nd ed. , enlarged and improved.)
Upsala, 1774
= Werlds Beskrifning, Sednare Bandet. (World descript ion.Vol. II)
(5) Nordenskiöld, Adolf Erik: Carl Wilhelm Scheele. Efterlemnade
bref och anteckningar. (In Swedish) (Letters and notes)
Stockholm, 1892, 490 + 10 p.
(6) Carl Wilhelm Scheele. Manuskript 1756-1777. Ordnade av C.W. Oseen.
Ljustryck. (In German) (Manuscripts 1756-1777. Arranged by
C.W. Oseen. Photoprints.)
K. Svenska vetenskapsakademien, Stockholm 1942. 182 p.
(7) Carl Wilhelm Scheele. Manuskript 1756-1777. Tolkning av C.W. Oseen
(In German) (Decipherment and comments by C.W. Oseen
K. Svenska Vetenskapsakademien, Stockholm 1942. 173 p.

33
 (8) Boklund, Uno: Carl Wilhelm Scheele. His work and life. I/II.
The Brown Book. (In English)
Stockholm 1968, 499 p.
/This book is an enlarged and revised translation of the authors
dissertation in Swedish, 1961/
(9) NordstrBm, Johan: En edition av Scheeles efterlamnade manuskript.
(In Swedish) (An edition of Scheele's handwritten remains)
Lychnos 1948, p. 254-277
(10) Carlid, Göte & NordstrBm, Johan (editors): Torbern Bergman's
foreign correspondence. Vol. 1.
Stockholm 1965, 466 p.
= Lychnos-biblioteket vol. 23, No. 1)
(11) Bergman, Torbern: H.T. Scheffers Chemiske fOrelasningar. . .andra
tillBkta uplagan. (In Swedish) (Chemical lectures ... 2nd enl.ed.)
Stockholm 1796, 509 + 18 p. (First ed. 1775)/First manuscr.1749/
(12) Weeks, Mary Elvira: The discovery of the elements. Collected Re
prints of a series ... in the Journal of Chemical Education.
Second Edition Revised.
Easton, Pa, 1934
(13) Partington, J.R. : A short history of chemistry. Third edition.
London, 1957 and New York (Harper Torchbooks) 1960, 415 p.
(14) Salmon, P & Magne, M: Le chlore. (In French)
Institut National de Securite pour la Prevention des Accidents
du Travail et des Maladies Professionelles , Paris 1960, 312 p.
Chapitre I, apercu historique, p. 15-23.
(15) Chlorine bleach solutions.
Solvay Technical and Engineering Service, Bull, No. 14, 2nd Ed.
1957
(16) Gmelins Handbuch der anorganischen Chemie. (In German) 8. vb"llig
neu gearbeitete Auflage Chlor, System-Nummer 6
Berlin 1927
(17) Fredga, Arne: Carl Wilhelm Scheele. Minnesteckning ...(In Swed.)
Stockholm, 1943, 23 p. (Oration held Dec. 11, 1942)
= Levnadsteckningar Over K. Svenska Vetenskapsakademiens leda-
möter. 119 (Memorials on Members of the R. Swed. Acad. Sci. 119)
(18) Sveriges Apotekarhistoria - fran Konung Gustaf Its till narva-
rande tid. (In Swedish) (Sweden's pharmacist history - from King
Gustaf I's time to the present.) Vol. Ill, p. 1538-1551
Stockholm, 1923-1925
(19) Uno Boklund, Stockholm. Private communication.
(20) Oskar BjörnHnger, KBping. Private communication and from his
book on the Town of KBping (in preparation)
 CASTNER, A PIONEER INVENTOR IN ALKALI -CHLORINE

William C. Gardiner, Consultant

227B Shoshoni Lane, Stratford, Connecticut 0649 7

H. Y. Castner, inventor of the first industrial mercury

cell process for alkali -chlorine, was born in Brooklyn,
N.Y., September 11, 1858; entered Columbia University
1875; operated analytical laboratory 1879-85 in New York.
Went to England in 1886 to exploit new chemical process
for sodium and invented alkali peroxide, alkali cyanide,
electrolytic sodium processes, rocking mercury alkali -
chlorine cell and graphitized carbon anodes. He was
Managing Director, The Aluminium Company Ltd. , and
Castner -Kellner Alkali Company. He wintered in
Florida after 1898 due to tuberculosis. Died 1899.

"The inventor is like a poet, he is born and not made"-.

Professor Charles F. Chandler, Columbia University.
"Genius is one percent inspiration, ninety -nine percent
perspiration"- Thomas A. Edison. (2)
For many years I worked on Castner 's rocking cells at Mathie-
son Alkali Works, Inc. , now Olin Corporation in Niagara Falls,
New York. Next door in the Niagara Electrochemical Company (now
Electrochemicals Division of E.I. Du Pont de Nemours Co.) three
other processes of Castner made sodium, sodium peroxide and
sodium cyanide. There was still a special transformer at Mathie-
son that had been used to make anodes for the Castner cells by
graphitizing carbon shapes made by National Carbon Company
according to a Castner patent. Sodium peroxide and graphitized
carbon are probably the only products still made by Castner 's pro
cess and the latter is challenged by metal anodes, at least for a
chlorine anode.

It seems appropirate at this bicentennial of Scheele's discovery

of chlorine to also pay homage to the inventor of the first success
ful industrial mercury cell process for chlorine and alkali.

A bronze tablet to the memory of Hamilton Young Castner (1), (3)

was unveiled in Havemeyer Hall, Columbia University, on December
16, 1902, with addresses by Professor Charles F. Chandler, Dr.
M. Benjamin, and Dr. J. W. Richards, President of the American

35
Electrochemical Society. Castner's chemical inventions were listed
on the tablet as follows:

1886 -
Chemical Process for Sodium
1890 -
Electrolytic Process for Sodium
1891 -
Manufacture of Alkaline Peroxide
1892 -
Electrolytic Process for Soda and Chlorine
1893 -
Electrolytic Apparatus
1894 -
Electrolytic Apparatus and Apparatus for Soda and
Chlorine
1894 - Process for Cyanides
1896 - Graphitized Anodes for Electrolysis

Hamilton Young Castner was born in Brooklyn, N. Y. , on 11th

September, 1858. He studied in Brooklyn schools and then prepared
at Brooklyn Polytechnic Institute for the School of Mines of Columbia
University. He entered as a regular student in the course of analyti
cal and applied chemistry in September 18 75. After his first year,
he deviated from the prescribed course and devoted his attention to
those branches of chemistry which he believed would be the greatest
value to him - an early expression of the independence of thought and
action so characteristic of him in later years.

During the first year, Castner pulled bow on the first freshman
crew that Columbia ever sent to an intercollegiate regatta. He
served as coxwain to the four-oared crew that won the Harlem re
gatta in June, 1877, and was also coxwain to the eight that lost to
Harvard at Springfield a few days later. He was a member of Psi
Upsilon Fraternity and the Junior Society in the School of Mines.
In the spring of 1878 after the term was over, Castner sampled
and analyzed water from all the wells still in existence in New York.
As a result, the Board of Health, of which Professor Chandler was
then President, soon ordered all wells used as a source of drinking
water to be closed up.

Soon after this, in 1879, Castner started to practice as an analy

tical and consulting chemist on Pine Street, New York, doing much
work in connection with fertilizers. This venture proved so success
ful that he took his elder brother, E. B. Castner, into partnership
with him, and moved into larger quarters on West 20th Street. This
consulting practice brought him many clients with operating diffi
culties in chemical processes. His success in solving their pro
blems led him to devote more and more attention to the design and

36

-
improvement of chemical plants. He sold his analysis business to
three Columbia graduates. Thus, he started a business at 21, made
a success of it and sold it when he was 27, no small achievement.

He patented a process for manufacturing animal charcoal for

sugar refining but the charcoal producers were not interested.

His first success was the invention of a process for producing

sodium (5) by the reduction of caustic soda with a mixture of carbon
and iron having about the same specific gravity as molten caustic
soda. Castner described his process on October 12, 1886, at a
meeting of the Franklin Institute and attracted world-wide attention.
He was later awarded the Institute's coveted gold medal. However,
he failed to obtain support of American industrialists, so he went
to London, England. There he set up a small factory in the Lambeth
area, near Waterloo Bridge, turning out 120 pounds of sodium per
day to demonstrate his process. He interested the Webster Crown
Metal Company which used sodium to prepare small quantities of
aluminum by reduction of aluminum chloride. This metal had been
produced for 30 years by the Deville process but due to the high cost
of sodium, the aluminum still cost about $10 per pound. Castner's
improved sodium process promised to cut the cost of aluminum to
$1 per pound. The Aluminium Company, Limited, was formed
with Castner as Managing Director. A plant was built at Oldbury
near Birmingham, in 1888 to produce 500 pounds of aluminum per
day.

The Sodium and Aluminum Processes (6)

In 1851, St. Clair Deville made aluminum by reducing aluminum
chloride with sodium. Sodium was made by reducing fused caustic
soda with charcoal at 1000° C. The reaction was very slow because
the charcoal floated on top of the melt. Castner's improvement was
to use an iron carbide or equivalent made from pitch and finely di
vided iron. Powdered "iron carbide" and ground caustic soda were
mixed and heated. The "iron carbide" had about the same density
as the caustic soda and acted as a very efficient reducing agent at a
relatively low temperature.

Instead of aluminum chloride, Castner used a double salt made

from a mixture of alumina, salt, and charcoal treated with chlorine
gas having less than 0. 1 percent iron. The double salt was ground
with about half its weight of cryolite and then mixed with thin slices
of sodium in a revolving drum. The charge was introduced into a

37
reverbatory furnace having a hearth about 6 feet square. When the
reaction was complete after about two hours, the aluminum was cast
into 60 -pound ingots. Each charge yielded 115 to 120 pounds of
aluminum, 99.2 percent pure. For the first time since its discovery
by Woehler in 1827, aluminum was supplied at a price at which it
could be used for practical purposes.

The Aluminium Company prospered for about two years when the
Hall-Heroult electrolytic process became commercial and the price
dropped to about $0.15 per pound. Castner's process could not
compete and electricity was too expensive at Oldbury to consider
licensing the electrolytic process. Castner salvaged the finances of
the Aluminium Company with spectacular success by developing
sodium peroxide, sodium cyanide (7), electrolytic sodium (8), and
electrolytic caustic soda and chlorine by the mercury cell process(9).

Sodium Peroxide
Sodium peroxide was made by burning sodium in a current of air
on aluminum trays. Unfortunately, the plant was destroyed by an
explosion - a Thermite reaction between aluminum and sodium pero
xide. Castner learned that sodium could be burnt satisfactorily in
aluminum trays if the reaction temperature was kept under control.
The product found a ready market for bleaching woolens and straw
hats, which were then very fashionable .

Sodium Cyanide (7)

Sodium cyanide was made by reacting sodium, charcoal and
ammonia. Cyanide was in great demand all over the world for gold
mining, pharmaceuticals and electroplating.

Electrolytic Sodium (3), (8)

The demand for sodium became so great that Castner looked for
a better process. Sir Humphrey Davy had isolated sodium in 1807
by electrolysis of molten caustic soda. In 1890, Castner developed
Davy's idea on an industrial scale. This was a commercial process
until the last plant was shut down in England in 1952 (4). In the
United States, the electrolysis of fused caustic soda at Niagara Falls
lasted until about 1925 when Castner cells were replaced by Downs
cells using fused NaCl-CaCl2 electrolyte to make sodium and chlorine.
Caustic soda was melted in an iron pot, through the bottom of which
passed a cylindrical iron cathode, held in place by a solidified mass

38
of caustic soda. The anode was a nickel cylinder separated from
the cathode by an insulated gauze diaphragm. Each cell was about
two feet deep and one foot in diameter. As electrolysis proceeded,
molten sodium rose from the cathode into a small metal receptacle,
from which it was ladled about every half hour. The purest caustic
soda available at the time gave trouble in the cells due to silica de
positing on the cathodes. The head of the cathode was made detach
able so that it could be replaced when dirty. This was far from satis
factory, so Castner looked for a way to make pure caustic soda. His
ultimate solution was the famous rocking mercury cell for the elect
rolysis of brine to make caustic soda and chlorine.

The Castner Rocking Cell for Caustic Soda and Chlorine

Many attempts had been made to electrolyze a solution of sodium
chloride in water (brine) but the products at the electrodes combine
to make hypochlorites, chlorates, etc. The problem was to keep
the products isolated after formation at the electrode.

The mercury cathode had been suggested by a Belgian chemist,

A. L. NoIf , in 1883 and unsuccessful experiments had been made by
LeSueur in 1889 (but he soon thereafter developed a successful dia
phragm cell) .

Castner 's mercury cell (3), (9) was in principle very simple. It
was a rectangular slate box divided into three compartments by slate
partitions reaching almost to the bottom. The cell contained enough
mercury to seal off each of the three compartments. One side of the
cell rested on a rotating cam, and the resulting rocking motion
slowly circulated the mercury. The two outer compartments were
supplied with brine and fitted with carbon anodes. The middle com
partment contained caustic soda solution and an iron cathode short-
circuited to the mercury. Electrolysis discharged chlorine gas at
the anodes and Na-ions at the mercury in the two outer compart
ments, forming sodium amalgam. Circulation of the amalgam
brought it into the center compartment where water reacted with the
sodium to form caustic soda and hydrogen. The device of rocking
the cell was adopted after Castner ran into difficulties with ram
pumps working in the stationary cast-iron base of an experimental
cell.

The chlorine was a valuable by-product for making bleaching

powder, of which 150, 000 tons per year was then being made in
Great Britain for bleaching textiles and paper.

39
 A battery of cells was erected in Oldbury in August 1894 and its
performance came up to expectations. Current efficiency was 88-90
percent and 20 percent caustic soda was produced. This had very
high purity. A similar pilot plant was built at Saltville, Virginia as
will be described later.

Corrosion of the carbon anodes was a problem but Castner dis

covered (10) that their life could be lengthened considerably by first
heating them in an electric furnace to a white heat, thus converting
them to graphite.

Castner proceeded to patent his mercury cell in many countries

with success except in Germany. There he found that he could get
only a provisional patent because Carl Kellner had already filed a
patent for an apparently similar process (11). Carl Kellner (3) was
an Austrian, born in Vienna in 1850. Like Castner, he first set up as
a consulting chemical engineer in Vienna. Like Castner, he recog
nized the possibilities of using a mercury cathode for obtaining pure
caustic soda by electrolyzing brine. He sold his patent rights to
Solvay and Company of Brussels. Rather than engage in litigation,
Castner sought out Kellner and negotiated an agreement for the ex
change of their patents and processes.

Castner -Kellner Alkali Company (3)

The Aluminium Company had ceased to make aluminum and Old -
bury was an unsuitable location for an alkali -chlorine plant because
of lack of salt and cheap electricity. The Aluminium Company was
liquidated and the Castner -Kellner Company was formed with both
Castner and Kellner serving as Directors. Kellner was more in
terested in the pulp industry and visited the plant only four times,
although he corresponded regularly with Castner. He died in Vienna
on June 7, 1925.
A suitable site was found in the Cheshire salt area, Weston Point
at the confluence of rivers Mersey and Weaver and adjacent to the
Manchester Ship Canal and the Weaver Canal. The Weston Point
Works was planned for 4000 h.p. to be built in 4 sections. Each
section had a cellroom with 5 circuits of 54 cells each, 270 cells
total. The power plant had direct current generators. Chlorine
went to the bleaching powder chambers. Unfortunately, the floors
of the chambers were covered with tiles set in molten sulfur so that
they had to be rebuilt. The caustic finishing plant evaporated the
20% cell liquor in open pans heated by flue gases from the finishing

40
pots. These pans had to be replaced with double -effect evaporators
because the settings were unsatisfactory and corrosion was excessive.

The first section started operation early in March 1897, and con
struction of the second section was underway. The caustic soda was
99. 32% NaOH, better than ever had been known before in the trade.
There was actually trouble in selling this pure material because the
trade was accustomed to 90% material.

A "long cell" was developed by the Chief Chemist, Harry Baker,

in 1902, and it was used to replace the rocking cells as fast as
possible. It was much larger and circulated the mercury with an
Archimedes screw.
The Aluminium Company entered into an agreement with the
Mathieson Alkali Works, Inc., on December 1, 1894 for operating
Castner's process in the United States. A pilot plant consisting of
54 cells was built at Saltville, Virginia in 1895 and by March 1896
had proved completely successful. A team from the Aluminium
Company assisted in the construction and operation of this pilot. plant.
Castner visited Saltville on December 9 th to 11 th when the cells
were operating at 415 amperes, making 17% NaOH at 87% current
efficiency. The electrical equipment was inadequate to provide the
rated 550 amperes.

The Mathieson Alkali Works, Inc., proceeded to build their

alkali -chlorine plant at Niagara Falls, N.Y., on property adjoining
the sodium plant of the Niagara Electrochemical Company so that
drums of caustic soda could be rolled from one plant to the other.
Hydro-electric power and salt were both available . No. 1 cellroom,
with 10 circuits of 54 cells each, was started on Thanksgiving Day,
1897, eight months later than the Castner -Kellner plant in Great
Britain. Cellrooms No. 2 and No. 3 of the same capacity were
started in 1901. According to Professor Chandler, this was the
first time that bleaching powder was made cheap enough in the
United States to compete with European sources. A chlorine lique
faction system was developed in 1909. The hydrogen was wasted
until an ammonia plant was built in 1926. Contrary to Castner -
Kellner, the Mathieson Alkali Works, Inc., kept improving the
Castner rocking cells so that it was not economical to replace them
until I960. They were finally shut down on February 21, 1961. At
that time they were operating at 1800 amperes, a 300 percent in
crease over their design current in 1897.

41
 Castner, The Man
Those who knew Castner spoke of him as a rather quiet and un
assuming man. As a chemist, he was a fine experimentalist and a
direct thinker. He worked late several nights a week and the speed
with which experimental work proceeded to a successful process was
remarkable. Due to his enthusiasm for his work, he maintained a
bedroom under the laboratory at Oldbury and had a cottage near the
plant gate at Weston Point. By this time, he relied on his technical
assistants for practical work. He was never seen at Weston Point in
clothes other than a black morning -coat and striped trousers, always
looking immaculate. He was a great cigar smoker and imported a
special brand, each cigar encased in a separate test-tube.

Unhappily, symptoms of tuberculosis appeared in 1889 and he was

obliged to spend the winters in Florida. However, he received
weekly reports from his assistants and was able to give much useful
advice. In the six months of each year which he spent in England,
he was able, assisted by his enthusiastic staff, to accomplish more
than many men achieve in a year.

Castner died at Saranac Lake, New York, on October 11, 1899,

a month after his forty-first birthday. He had no children but was
survived by his wife. He certainly left a rich legacy to industrial
chemistry.

42
 REFERENCES

1. Charles F. Chandler, M. Benjamin and J. W. Richards, "The

School of Mines Quarterly", Columbia University, XXV. ,
January 1904, No. 2.

2. "Hamilton Young Castner", Industrial Chemist (England)

September 1958.

3. "Castner -Kellner Alkali Company, Fifty Years of Progress,

1895-1945", ICI, London, England.

4. C. A. Hampel, Editor, "The Encyclopedia of Electro

chemistry" Reinhold Publishing Company, 1964, page 154.
5. H. Y. Castner, "Manufacture of Sodium", United States
Patent No, 342,897 (1886).

6. M. Schofield, "Some Highlights in Aluminium History" The

Industrial Chemist (England), June 1957, page 294.

7. H. Y. Castner, "Sodium Cyanide", British Patents Nos .

12, 218 and 12, 219 (1894).

8. H. Y. Castner, "Electrolytic Sodium", United States Patent

No. 452, 030 (1891).

9. H. Y. Castner, "Electrolytic Apparatus", United States

Patent No. 518, 135 (1894).

10. H. Y. Castner, "Graphitized Anodes", United States Patent

No. 572, 472 (1896).

11. C. Kellner, Deutsches Reichs Patent 88,230 (1890).

43
 TRENDS OF DEVELOPMENT OF CHLORINE INDUSTRY
IN DEVELOPING COUNTRIES
Rajeshwar Kumar Gupta
Projects Division, DCM Chemical Works
New Delhi, 110015 India

ABSTRACT
Essential features of development of Chlorine
Industry in developing countries are discussed. From the
existing small capacity plants, mostly captive for Caustic
Soda, with Chlorine an unavoidable by-product, with know-
how and plants mostly imported, and choice between
diaphragm and mercury cells and the cell amperage ratings
dependent on super-salesmanship of suppliers and not on
economics or pollution considerations, the industry is
likely to move to somewhat bigger capacities, with decisions
based on economics, improved Chlorine-utilisation and
preference for diaphragm cells. The likely effect of the
oil crisis on the development of the industry is also
discussed.
INTRODUCTION
Though we are presently celebrating the 200th anniversary of
Carl Wilhftlm Scheele's discovery of Chlorine, I need hardly remind
that even until the beginning of the 20th century Chlorine was not a
commercial tonnage product and Caustic Soda was made by causticising
soda ash with milk of lime. Even in U.S.A., the largest producer and
consumer of Chlorine with over 30,000 tons per day capacity, the
Chlorine capacity in 1920 was only 600 tons per day, and it was con
sidered the almost superfluous by-product of salt electrolysis. The
transition from chemical caustic to electrolytic caustic and the
phenomenal growth rate for chlorine, until recently as much as 8%
(more than double the growth rate of Caustic Soda), was as a result
of development of new uses of Chlorine, large tonnages going into
petrochemicals and especially the plastic industry. The World
Chlorine capacity which was around 20 million tons in 1970 is expected
to rise to 45 million tons in 1980, on account of the phenomenal
growth of the plastics industry, unless the recent oil crisis acts as
a severe deterrant to the growth of the petroleum-based manufacture
of plastics, and as a result slowing the anticipated growth of the
Chlorine capacity. Because of the new large captive uses for
Chlorine, the Chlorine plants have been getting larger and larger.
Fifteen years ago a 200 TPD plant was considered large. But today,
almost peralleling the capacities in ammonia plants, in the developed
countries Chlorine plants of 600-700 TPD are quite commonplace.
Capacities of 1000 to 1500 TPD in single stre*am are not unusual.
The picture is quite different in the developing countries.
Hany of these countries, which though have moved into the industrial

44
age, have yet to step into the Chlorine age. Even in some of the
relatively developed developing countries where Chlorine is produced
in tonnage quantities, the scales of production, the sizes of indivi
dual plants, and Chlorine being almost a superfluous by-product in
the manufacture of Caustic Soda, the need for Chlorine utilisation
acting as a big restraint on the Caustic Soda industry growth, are
important factors, making this industry in these countries almost 20-
50 years behind some of the developed countries. In many of these
countries the total capacity is less than the figure of 600 TPD in USA
in 1920, and individual plant capacities all the way from 5 to 50 TPD
are quite common. Capacities above 100 and at least above 200 1PD
are quite unusual and rare, Caustic Soda is still the main product in
most of the plants and Chlorine an unwanted by-product, though in
most plants Chlorine utilisation and the realization from Chlorine
now determines the viability of merchant plants.
This paper attempts to outline the essential features of the
development of the Chlorine industry in the developing countries, the
present capacities/production levels, the e*pected trends of develop
ment, and the likely effect of the current oil crisis on this
development. Jndia, being still essentially a developing country,
and presenting all the features of the development of the industry in
the developing countries, is used as a model.
DEFINITION OF DEVELOPING COUNTRY
Though the term "Developing Country" is fairly well understood
in the political and economic sense, and by and large, the same
definition applies for defining the battery limits of this paper
also, specifically with regard to the Chlorine industry the following
are essential features of most of the developing countries covered
by the paperi
- Total chlorine capacity is relatively small and less than
500,000 tons per year.
- Individual plant capacities are relatively small and less than
100,000 tons per year (in most cases less than 50,000 tons
per year).
- Except in small captive plants, Chlorine is still considered
as by-product of Caustic Soda manufacture and ways have to be
found for its disposal with economic utilization to the extent
possible.
Most of the countries of Africa, Middle East, Asia, and Latin
America, with a very few exceptions, are covered by this definition.
It covers a large part of the World land area and population. Though
strictly speaking, India is a border line case for inclusion in the
above definition of "Developing Countries", since the installed
capacity in India stood at 533,816 tonnes per annum of Caustic Soda
(corresponding to 445,000 tonnes per annum of Chlorine), and the
actual production in 1973 being 411,500 tonnes (corresponding to

45
357,000 tonnes of Chlorine), it is taken as a model for the trends of
development of the industry in the developing countries, because the
development of the industry here is typical of the development in most
developing countries. Conversely many of the developed countries,
being small in size, may meet the above criteria, but these are not
considered here.
Since in most of the developing countries, Chlorine is only a
by-product of Caustic Soda manufacture, the industry is largely
'referred to as Caustic Soda industry and the capacities specified in
terms of Caustic Soda (lOO#NaOH basis).
EXISTING CAPACITIES/PRODUCTIONS AND PROJECTS IN PLANNING
Very reliable and up-to-date data on capacities and production
figures for the developing countries are not readily available, it
often being clubbed together under "Other Countries" in most published
data. Table I gives the capacities and production data for the latest
years available for some of developing countries.
Exact data on individual plants in the various developing
countries are not available. However, the data on the 32 plants in
India with a very large variation in capacities and technology are
quite representative of the state of the industry in most of the
developing countries. Table II gives the capacities and actual
production in 1973 along with future plans of expansion, and some
particulars about technologies and Chlorine utilization, for the
different plants in India, which will show that the existing capacities
for individual units range all the way from 2 tonnes/day to 164 tonnes
per day(l003j NaOH basis), covering most of the available technologies.
Table III gives some of the proposed new projects( already approved
by the Government upto 1973) likely to materialise before the end of
the decade, which gives an idea of the trend of future development of
the industry in the country for the rest of the decade.
Table IV gives some particulars of Caustic Soda/Chlorine
projects in concrete shape of planning in some of the Developing
Countries for which data could be available(excluding India, for
which detailed data are given in Table III). This by no means is a
complete listing of all the projects in all the developing Countries?
Neither complete data are available for such a complete listing, nor
is it necessary for the scope of this paper, as long as the available
data enables a study of the special characteristics, if any, of the
industry in these countries, and to predict the trends of development.
CHLORINE UTILISATION
One of the most important aspects of the development of the
Caustic Soda/Chlorine industry in any country is the extent and mode
of the Chlorine utilisation. In most of the Developing Countries,
except in the case of a few captive plants, Chlorine is still an
unavoidable by-product of Caustic Soda manufacture and means for its
gainful utilisation have to be found to make Caustic Soda production

46
an economic proposition. The Chlorine which cannot be gainfully uti
lized is neutralized and drained in the form of HC1 , or to some small
extent even vented with tall chimenys. As is seen from Table II, for
the different plants in India, which represent a cross-section of the
industry in the developing countries, the extent of Chlorine utilisa
tion varies all the way from 40% to 100%, the average for the entire
industry in the country being around 70-80*.
In the Developed Countries like USA, West Germany, Japan, etc.
the chief uses of Chlorine in the early stages of the development of
the industry were pulp and paper, bleaching powder, hypochlorites,
metallic chlorides etc. and the major use now being in the organic
chemicals and plastics industry. In the Developing Countries, however,
pulp and paper, bleaching powder, hypochlorites, metallic chlorides,
and direct use for water Chi ori nation, still constitute major
consumers of Chlorine. The use of Chlorine in organlcs and particu
larly plastics is picking up, though slowly.
Table V gives the use pattern of Chlorine utilization in India
in 1972-74 and the likely pattern by 1979-60, and a comparison with
the use pattern in USA in 1966. With the increase in tonnage of
Chlorine production, higher and higher proportions have to be used in
the organics, especially in plastics. Whereas the current use of
Chlorine in organics is only about 44% it is expected to rise to
about 50* by 1979-60, which would still be short of the 57-58* in USA
in 1966. (Ref 7). The percentage use of Chlorine in organics for
Japan for 1968 is 78* and for West Germany for 1966 is reported as
81.8*. In many of the present and projected units in the Developing
Countries, the use of Chlorine will still be only for pulp and paper
and other bleaching uses and very little for organics.
ESSENTIAL FEATURES OF DEVELOPMENT OF CHLORINE INDUSTRY
IN DEVELOPING COUNTRIES
As would be seen from the data reported in Tables I to V, and
from other facts about the development of the Chlorine Industry in
many of the Developing Countries, following are some of the essential
features of development of the industry in these countriesi-
- Caustic Soda is normally the main product and Chlorine is an
unavoidable by-product, which sometimes has to be destroyed and
drained to some extent. The exception is only where the plants
are for captive use in a pulp/paper or some other Chlorine
consuming industry.
- Plants are of rather small capacities, ranging mostly between
10 and 100 tonnes/day of NaOH. Even some of the newer plants
in relatively developed countries of the Developing ones are of
capacities ranging between 10 and 50 tonnes per day. The
largest single unit capacities even in such countries are
rarely above 100 tonnes/day. The exceptions are few and far
between. In some of these countries, e.g., Argentina and

47
 Brazil in Latin America and Iran in Asia, fairly large plants
of around 300-700 tonnes/day capacity are being set up by comp
anies well established in the field in the Developed Countries
like USA, Japan, etc., as part of large petrochemical complexes.
This, it appears, is on account of the availability of oil and
oil-based feedstocks for Chlorine based petrochemicals in these
countries.
- Plants are mostly for captive use of Caustic Soda rather than
of Chlorine, like plants set up along with rayon plants. Also
there are several plants with pulp and paper plants, where
Chlorine is also captively used. Most such plants are of
rather small capacities.
- Choice between diaphragm and mercury cells and the amperage
rating of the cells is detided not based on economic or
pollution considerations, but largely on ad-hoc decisions, sales
pitch of plant suppliers and general trends especially to "keep
up with the Jones". Though, the requirement of Caustic Soda is
mostly for pulp, paper, aluminium, soap and textile industries,
and only rarely for rayon manufacture, there is an unexplained
preference for mercury cells and high purity caustic, without
regard to end-use requirement and economics of production.
- Supply of know-how and plant and equipment is mostly from the
Continent and Japan for mercury cells and from USA for
diaphragm cells, largely on turn-key basis. However, lately
there is emphasis on indigenous fabrication in most of these
countries, but such indigenously manufactured equipment
represents only a small fraction of the capital investment.
- There is a perennial shortage of electric power, with the
result that even existing capacity is often under-utilised.
Power interruptions and flucteations are quite common. The
power tariffs, even the preferential ones for this industry
being power intensive, are quite high, mostly above one US cent
and often as much as two US cents per K.VI.K.
- Chlorine utilisation is normally poor and large quantities are
neutralised and drained. Some of the newer larger plants
forming part of petrochemical complexes may be exception to
this.
- There is very little attention to pollution hazards from
mercury cell plants.
EFFECTS OF OIL CRISIS
The current oil crisis should have a marked effect on the
development of the Chlorine industry. Since the industry is a power
intensive one, it would find more encouraging climate in countries
where power generation is hydro-or coal-based or even atomic, except
in case of oil producing countries. Uptil now the industry is
almost non-existant in many of the oil producing developing countries

48
of West and South East Asia. However, in view of the continuing pro
blems with availability of Oil and pressure on its prices, coupled
with a realisation in these countries that the oil should be used as
a feedstock for petrochemicals in their own countries thus helping
in their development, rather than feeding the energy requirements of
the developed countries, there is good likelihood of petrochemical
complexes, with the accompanied fairly large electrochemical plants,
mostly by or in collaboration with the established companies of the
developed countries, coming up in these countries. Recent develop
ments in Argentina and Brazil in Latin America and in Iran in Asia
are indications of this trend. This trend is also likely to be
followed in countries like Kuwait and Saudi Arabia in West Asia, in
Malaysia and Indonesia in South East Asia and in Nigeria in Africa.
LOGICAL CHOICE OF TECHNOLOGY
With the rapid increase of capital costs and unit cost of raw
materials and utilities, the newer plants, even in the developing
countries, will have to take into account economic considerations for
deciding the technology, unlike it has been uptil now. Also, with
the World-wide scare about pollution and the care for ecology,
pollution considerations will also become quite important, though not
to the extent in some of the Developed Countries. In addition, since
mercury would need to be imported perpetually in most of these
countries, and on account of the foreign exchange shortages persis
ting in most of them, there should be a gradual trend away from the
mercury cells and towards the diaphragm cells. The serious power
shortages and high cost of power in most of these countries, with the
comparatively lower power requirement of the diaphragm cells, also
should set the trend towards diaphragm cells. This should also
favour the use of metallic anodes. However, to make this more
encouraging, the lease charges would need to be more attractive, and
the recoating facilities made more geographically spread.
Since a bulk of the individual plant capacities are likely to
be relatively small, in very few cases exceeding 100 tonnes/day, the
use of very high cell amperages, especially in the case of mercury
cells, will result in the total circuit voltage being low, resulting
in lower, and therefore, uneconomic rectifier efficiencies, which
fall off sharply below circuit voltages of 100 volts. Gupta & Mehta
(Ref. 3) discflss in detail the various factors involved in the
choice of the maximum economic amperage ratings of mercury and
diaphragm cells for the different capacities between 15 and 200
tonnes per day and conclude that irrespective of the choice of the
type of cell, in view of the capacities of individual units required,
it is not worthwhile going in for amperage ratings above 100 KA and
preferably 50 KA for mercury cells and 30-40 KA for diaphragm cells.
FUTURE EXPECTED TRENDS OF DEVELOPMENT
Considering the socio-economic changes taking place in the
developing countries, with the resultant urge for industrialization,

49
the Caustic Soda/Chlorine industry is bound to grow in the Developing
Countries, the rate of growth being likely to be higher than in the
Developed countries. Following are likely to be the important trends
of the development of the industryi
-The individual unit capacities would become slightly higher, but
still would be around 20-100 Tonnes/day, with bulk of the newer
units being around 50 or 100 Tonnes/day. A very few large units,
possibly around 200-500 Tonnes/day capacity, may come up as part
of petrochemical complexes in oil producing countries.
-With increasing capital costs, and difficulties of foreign excha
nge and credit, economics will become more important and therefcie,
especially due to high cost of power, there would be preference
for medium amperage cells and towards diaphragm cells, away from
mercury cells.
-Though pollution is not such an important factor in many of the
developing countries as in the developed countries, the general
pollution scare will move the choice away from mercury cells and
towards diaphragm cells.
-Foreign exchange difficulties would dictate more indigenous
designing, detailed engineering and fabrication. There would be
development of technology in some of the relatively developed
Developing Countries and most of these countries would wish to
develop and utilize indigenous engineering and fabrication
facilities.
-The Chlorine utilization may improve quantitatively. However,
largely Chlorine would 3till be used for water chlorination and
for bleaching. In some of the countries where petroleum feed
stocks are available and investment climate is good, Chlorine-
based petrochemical plants may come up, in many cases set up by
or in collaboration with some of the established companies from
the Developed countries.
-Though use of metal anodes should offer excellent advantage in
power saving, their use may not be very wide-spread, due to heavy
recurring foreign exchange expenditure on royalties.
CONCLUSIONS
The paper reviews the state of the Chlorine Industry in many of
the Developing Countries, using India as a model. The new projects
coming up in these countries, essential features of the development,
the logical choice of technology and the trends of future development
are discussed. This, it is hoped, would be of use to interested
Process Licensors, Plant Suppliers and Engineering companies , and also to
other companies considering investment in the Chlorine industry in the
developing countries, and to the financial institutions offering
finance/long term loans for such projects.

50
 REFERENCES
1. Alkali Manufacturers Association of India - different publications
and circulars.
2. Amercian Airmail & Peruvian Times, June 29,1973.
3. Chemical Age of India, June 1972.
4. Chemische Industrie International 1973.
5. Chlorine Institute Pamphlet No. 10,January 1974.
6. Search, 1970,71,72,73.
7. Theurer, A., Chemische Industrie. 1/1969.

51
 TAHIK-y
EXISTIMG CAPACITIES AND PRODUCTIONS IM DEVELOPING CPffi^Hi
Capacity,Th. Production, Th. No. of
Country Tonnes NaOH/Year Tonne 3 NaOH/Year Plants.
ETfTVfl

Burma 1973 7 - NA 1
India 1973 534 1973 412 32
Indonesia 1971 6 1971 6 1
Iran(b) NA NA 1967 3 NA
Israel(b) NA NA 1967 11 NA
Kuwait 1971 5 - NA 1
Pakistan(b) NA NA 1967 5 NA
Phillipines(b) NA NA 1967 4 NA
Sri Lanka(C8ylon) 1972 2 1967(b) 1 1
Taiwan(d) NA NA 1971 134.5 NA
Turkey(b) NA NA 1967 10 NA
Vietnam,Rep.of(b) NA NA 1967 2 NA
Africa
Algeiia(b) NA NA 1967 3 NA
South Africa, NA NA 1967 50 NA
Rep. of (b)
United Arab NA NA 1967 17 NA
Republic (b)
Uttl America
Argentina(b) NA NA 1967 50 NA
Brazil(e) NA NA 1968 135 NA
Chile(c) 1970 19 1967 18 2
Golombia(b) NA NA 1967 40 NA
Cuba(g) NA NA NA NA 1
Mexico(e) NA NA 1970 155 6 (g)
Peru(f) NA NA 1973 38 2
Venezuela(b) NA NA 1967 10 NA
NA denotes data not available.
(a) The latest year for which data available.
(b) The latest production figure available for Chlorine production
for 1967 from Theurer's Article of 1969.
(c) Search Sept. 1970. (d) Chemische Industrie International, 1973.
(e) Chem. Age of India, June 1972. (f) American Airmail & Peruvian
Times, 1973. (g) Chlorine Institute Pamphlet No.lO^January 1974.
Rest of the data are from personal contacts.

52
 TABLE II
Fariculara of Existing Plants and their Expansion Plans In India
- Trac rine Utilization
- o Yeae B <
>i c <H • er
o
+i cO *"
•H o to 'p oat; 1 13■
•H § 6-1 S to to > to c c •H WQ, ft|
n £X T3 t- OJ <BC •H ! * a3 -Ho 'P rH
H C o s io 2;? 13V to -fJ r-1 +Jt0
•H
o § a rH tDW. 4?
CD y
u a!! 9 - c
1 8. a$
o o O
•H C-^
'p -H i-l 0) TJ3O ^
s •H(0 •—
v-i W
I -s §*
g ^ Peodi—( Tho.im (1009
vr R w iJ |£ & TJ O P a!
+=P. 4-1O 1]
ti C O rHo CO <M
1 | X ® |SEa 1
|S
8 4 O -H rH
1 2 3 4 5 6 '7 8 ? 10 11
-Andhra Sugars 33 8.5 <er GDR 20 13.2 76 1.5 80-95 Chloro-
Limited. Japan aalphonic
ese . Acid
-Alkali & Chem. 8.8 7.4 Dia Gibbs 1.5 - 57-50 93-100 BHC
Corpn.
-Atul Products 6.4 6.1 iler Jhde 40 21 76 55-60 90-99 Drugs &
Limited. Dyes inte
rmediates
-Ballarpur 6.6 3 Dia Stuart 30 - - NA NA Pulp/
Paper Mills Paper
(Shri Ciopal)
-Calico Mills, 2.9 2.6 Dia Hook- 10 1.04 76 NA NA Bleach
Ahaedabad. ker-5 Liquor
-Calcio Mills, 29 27 Mer Krebs 30& 33 76 41 84-87 PVC
Bombay. BASF 50
-Century 16.5 19.9 Mer Krebs 50 - - 1-1.5 97-100 None
Chemicals
-D. CM. Chen. 17.2 16.8 Dia - Vbroe 1.2 SBP, Act
Works. SR-40 40 33 76 35-40 90-100 ivated
Earth.
-Dharangadhra 49. E 33.1 Mer Krebs 50 10.5 74 55-60 75-85 PVC,
Chem. BASF Enric
hed 11-
menite
-Durgapur 10.05 2.5 Mer Krebs 50 5.1 77 NA NA Interm
Chem. BASF ediates
-Gwalior 33 37.3 Her DeNora 150 - - 1 40 None
Rayons
-Hindustan 3.1 3.2 Mer Jrebs 20 2.75 75 NA NA None
Heavy Chem. BASF

53
 1 2 3 4 5 6 7 8 9 10 11
-HukumChand 20.5 16.4 Mer Osaka- 65 2.16 74 1 70-75 None
Jute Mills Soda 14.0 77
-Jayshree 16.5 17.2 Mer Krebs- 50 25.5 77 1 70-97 None
Chem. BASF
^J.K.Chem. 2.3 2.1 Mer Krebs- 15 - - NA NA NA
BASF
-Kanoria 53 20.3 Mer Krebs- 50 53 77 30-35 70-77 SBP
Chem. BASF
-Mettur Chem. 26.4 15.9 Mer Krebs 50 ) 16.5 76 20-2E 75-85 Chloro-
19.8 7.3 Dia Hpoker- 10) methanes
S SBP
-Mysore Paper 0.6 0.2 Dla Krebs 1 - - NA NA Pulp/
Mills. Paper
-National Ray 31.4 52.3 MerDe- 45 33 76 4-5 75-90 None
on Corpn. Nora
-Repa Mills 4.05 3 Mer Krebs- 40 1.9 77 NA NA Pulp/
BASF Paper
-Orient Paper 3.2 2.1 Mer -do- 12 - - NA NA -do-
Mills.
-Rohtas Ind. 4.5 4 Mer -do- 24 2.4 76 NA NA -do-
1.7 1.5 Dia Allen- 1.5
Moore
-Saurashxra 23.3 23 Chem - - - - - - -
Chem.*
-Sirpur Paper 7.2 5.5 Dia Allen- 1.5 - - NA NA Pulp/
Mills Moore Paper
-Shriram 22.4 16.8 Mer Shin- . 70 10.6 74 50-60 68-85 PVC
Chem. Ind. Etsu 53 76
-Standard 54.5 42.7 Mer DeNora '325 53 76 1-3 94-98 None
Mills Co. Uhde 180
-Tata Chem. 7 5.7 Dia Hooker- 10 NA NA BHC, Va
rious
Chlorides
-Travanoore 33 24.2 Mer Krebs/ 18/ 33 76 2 40- None
Cochin Chem. Uhde 30/ 75
60/
LS0/
*No Chlorine produced being a caustic! zation process plant.
Source: Various publications and circulars of Alkali Manufacturers
Association of India( Chlorine Utilization data from Oct. 72
to June 73).

54
 TABLE-IIJ
J?j?jaaed,Hw Pwlecta for Caustic Soda/chior,i,n,a An .la<&A

I
I ia =6 < n
"8 2 •h1 ce
Namer\i H ea1 aX O a o c *> na.
=>
Part0 •H
+1>- \z
>. n xatia,
m +i tn (h +1
e C0) co
«<v o o tJS
(ne. e2
2.S8
e o 8M 1e • o rt
OH >• +1o
0)
0. H f
'5 oS
1 z --3 4 5 6 7
-Ashok Paper Mill s 7.7 1977 Mer Uhde 100 Pulp^aper
(Assam)
-Ballarpur Paper 6.6 1974 Ola Stuart 30 Pulp/Paper
Mills(Maharashtra) 1976 Dia Stuart Pulp/Paper
3.3 30
-do- (Mysore) 33.0 1975 Mer Krebs 100 Pulp/Paper & Sale
16.5 1977 Mer Krebs 100 -do-
-Baroda Rayons(Guj.) 33.0 Unce Mer ND ND ND
rtain
-Basudeo Kanoria 33.0 -do- NO ND ND ND
(Raj as than)
-Binod K.Kafloria 33.0 -do- ND NO ND ND
(Mysore)
-D.P .Goenka(Goa) 33.0 -do- ND NO ND ND
-Deccan Sales Corpn. 33.0 -do- NO ND ND ND
(Maharashtra)
-development Corpn. of 33.0 -do- NO ND ND ND
K tn k a n(Ma ha ras htra )
-F.A.C.T. (Kerala) 33.0 -do- ND ND ND ND
-Gujarat Alkalies 37.4 1976 Mer Uhde 140 Sale
Ltd. (Gujarat)
-Haryana State Ind. 33.0 Unce ND ND ND ND
Dev. Corpn. (Haryana) rtain
-Hindustan Dev. 16.5 -db- ND ND ND ND
Corpn . ( Ma h a ra shtra )
-Hindustan Insecti 16.5 -do- ND ND ND Captive for DDT.
cides (New Delhi)

55
 1 2 3 4 5 6 7
-Hindustan Insecti- 16.5 Uncer ND ND ND Captive for DDT &
cides(Kerala) tain BHC
-Hindustan Organic 33.0 -do- ND ND ND Mostly Captive for
Chem.( Maharashtra ) Intermediates
-Krishna Kishor Kar 33.0 -do- ND ND ND ND
(W. Bengal)
-Kothari & Sons 33.0 -do- l*r Uhde 125 Sale
(Tamil Nadu)
-M.P. Alkalies & 33.0 1976 Oia SR-40 40 SBP, Chloro sulfonic
Chem.(M.P.) Acid, PVC & Sale
-Orissa State Ind. 33.0 Uncer ND ND ND ND
Dev.Corpn.(Orlssa) tain
-Punjab State Ind. 33.0 -do- ND ND ND ND
Dev. Corpn. (Punjab)
-R.K. Raman(Tamil 33.0 -do- ND ND ND ND
Nadu)
-Raj as than State Ind. 16.3 -do- ND ND ND ND
& Mineral Dev.
3orpn.(Raj as than)
-Titaghur Paper 1.65 1974 ND ND ND Pulp/Paper
Mills(Orissa)
-U.P. State Ind. 33.0 U ncer- ND ND ND ND
Dev.Corpn.(U.P.) tain

ND indicates Not Decided.

-Only projects approved by the Government upto end 1973 are
included. Several more projects have since been approved or are
under consideration. However, out of the projects whose date of
materialization is indicated as uncertain, there is likely to be
heavy mortality and even those which are implemented may take upto
1980 to implement. On the other hand, some of the projects
cleared subsequently by the Government may come up in 2-3 years.

56
 Tim TY
CAUSTIC SODA/CHLOMNE PROJECTS IN DfiifflLOPIKti
COUNTRIES B CONCRETE SHAPE OF Pl.ANWTWti
V ' —E
'p y■ ippli* Com- .on0eae
;ted 3
ao IS
° 1" V CO 1
•HN
1 I i o it i—I
is .3 m O of
ifc Q s IS
I 2 6 4 i b •T—" i ~8
ilia
Iraq Iraqi Govt. Basra 56,900 Ton NA NA 76/ PVC
ne s/yr CI;, 77
Iran national Sniraz 60,000 Ton NA NA 73 Petro-
Petrochem- ne s/yr NaOH Chem.
Co.
-do- Iran Nipper Bandar 300, OOOTbn- NA NA 76/ For Chem.
Chem.Co. Shahpur nes/yr NeOH 77 Complex.
Israel Electro- Aore 14,000 Ton NA NA 74 NA
Chem.Ind. ne s/yr to
(Frutarom) 28,000 Ton
ne s/yr ci2 i
Kuwait fear Su Exp. 5000 Mer Krebs HC1 for
prayah Tonne s/Yr Zori- oil drill
Puner to 12000 ch. ing.
3tn. Tonnes/yr
Cl2
-do- Kuwaiti £xp.4.8Ton- NA NA 74 NA
Chem.fc Fer nes/day to
tilizer Co. 32 tonnes/
day Cl2
Pakistan Fauji Foun Hear 13,520 Ton- NA De- 74 PVC
dation Karachi nes/yr Clg Nora
Saudi Aramco/ DanunaM 12.25 Ton ND ND U HC1 for
Arabia Triad nes/day oil drill
NaOH ing
Sri Lanka Paranthan Exp. 5 Ton Low NA 75 NA
(Ceylon) Chem.Corpn. nes/day to Amp.
11 tonnes/ Dia
Africa day NaOH
Algeria SONIC Mostag- 12000 Ton- ND ND Pulp/
aneara nes/yr Clg Paper

57
 7
Misr Chen. At Mex p.00,000 1bn-)RA 7F Sod.hypo-
Ind. Go. Near Ale- ties,i/yr of chlorite
xandria feod. hypo
chlorite
ID ID koOOOTomies/NA Kl HA
tr.NaOH
Panafrlcan BrodrV 14 tonnes/ HA HA ! Pulp/
Paper Mils cksfall day Clg Paper
Klip Fonte- POOO Ton- KA Olin 74/ Cal.hypo
in Organic be s/yr Gfe of T6 chlorite
Product s(K0J7 USA ' Chlorin-
I ated Para-
, finaSJenv
3c Chloride
-do- Kerapton 9,900 Ton HA Uhde TV ! NA
Park ne s/yr CI2 75

Petroque Q4- Bahia ©0,000 Tbn- NA HA 75/ Petro-

mico Bahia Blanca bes/yr Qjj 76 Chem.
Blanca(with Complex.
DOW Chem.of
USA)
Salgema Ihds Maccio 220000Ton- Dia Hook HA Petro-
Quimica.SA. [nes/yr Clg Hsok- er Chem.
(with DaPont erB-2Cheni,
of USA) Cell Corpn|
with
metal
anodes
Oran zio Db- Sao KA NA I NA HA NA
Nora of Italy Paulo
Companhia Recife 15000 "ton HA Uhde 73/ HA
Agro Ind. ne s/yr ag 74
Guanos Fer- lSOOOTbn-
tilizants de nes/yr Clg Merc| Krebs. 71 HA
Mexico
Induperu Pomalca 45 Tonnes/ HD HD Pulp/
day NaOH Paper
Instituto-^n^- El T»H 40000Ton- HA Uhde/ 74/ Petro-
lazo/ nes/yr Clg
.roqu'Sniiea Miran Nora 75 Chem.
U denotes Uncertain
NA denotes Data Not Arailable
ND denotes Not yet Decided.

58
 TABLE V
USE PATTERN OF CHLORIHE IK INDIA

1 Percentage of total Comparable utili

ITEMS Chlorine used sation In USA In
1972-74 Expected 1966
1979-80
Pulp/Paper 30.20 ) 17.00
) )
Textile 6.10 )
) 40 | 15
Water Treatment/ 6.40 )
Sanitation ) )
) )
Direct use as HCL 2.00 ) )
Zinc Chloride 0.04
Ammonium Chloride 4.56
Other Chlorides 0.08 10 12
Rare Earth Chlorides 0.06
Bleaching Powder/Earth 6.18
Fertilizers -
Insecticides 18.00 15 10
Chlorinated Rubber etc. 0.14 5 5
Dyestuffs, drugs
intermediates 2.14
Plastic Raw Materials 19.00 25 28
Organic Solvents/
Chemicals 5.10 5 IS

Sources: - Indian Data Chemical Age of India, June 1972

US Data Theurerte 1969 paper.

59
 DISPOSAL OF BRINE TREATING SOLIDS BY RECYCLING TO A BRINE WELL
T. F. LaGess
Texas Division, Dow Chemical U.S.A., Freeport, Texas 77541

ABSTRACT
Calcium carbonate sludge from treating brine for chlorine
production in diaphragm cells is recycled to a brine well.
The calcium which left the well as a sulfate dissolved in
brine is returned as a carbonate slurry in mining water.
The solids from treating brine from many wells can be
returned to a single well. The inert solids accumulate at
the bottom of the well while mining proceeds and clear
brine of good quality is produced. This method of operation
protects the environment, and the same well can be used for
many years.

Raw sodium chloride brine produced by solution mining contains

calcium sulfate as a dissolved impurity. Brines used for chlorine
production often contain 1000 parts per million calcium, or more.
In addition, most brines contain some magnesium. If both these
ions are not removed before the brine is electrolyzed in a
diaphragm cell, they will precipitate as hydroxides on reaching
the alkaline zone and will plug the diaphragm.
Calcium and magnesium are usually removed from brine by treating
with solutions of sodium carbonate and sodium hydroxide. After
the addition of the proper amount of sodium carbonate and adjustment
of the pH of the solution with sodium hydroxide, a precipitate of
finely divided calcium carbonate, along with a little magnesium
hydroxide, results. This precipitate can be separated in a con
tinuous clarifier. A convenient underflow composition at which
to operate is 5 - 10% solids by weight.
At a major chlorine production facility, many tons of brine
treating solids will be produced daily. Producers who can find
in-plant or across-the-fence uses for this slurry of calcium
carbonate in brine are fortunate. If it is desired to recover
calcium carbonate for use as such, it must be filtered and washed
free from brine. The cost of working up the solids for use as
calcium carbonate can sometimes only be justified as a waste control
expense. At some locations the solids may be put into landfill

60
after being dewatered. The cost of this procedure will be high, and
new landfill sites will have to be made available as needed.
A brine well in a salt dome is the ideal location for disposal of
the solids from brine treating. The boundaries of the well are
definite. There is no communication below ground with anything else,
with the possible exception of another brine well which will also
have definite boundaries. The calcium which originally came from the
well as a sulfate is returned as a carbonate. Once the solids are
returned to the well, they settle to the bottom and remain there.
They have been permanently removed from the outside environment.
Since there is already at the bottom of a typical brine well a mass
of anhydrite debris accumulated from mining, the addition of inert
calcium carbonate results in a compatible and stable mixture.
By diluting the brine clarifier underflow with water, mining can
be continued in the well to which the solids are recycled. If the
dilution water contains dissolved calcium, calcium will precipitate.
Thus, if the diluted underflow is immediately put into a pipeline,
scaling will probably occur. However, if dilution is done in a tank
with a few minutes retention time, the calcium precipitation from
the water will be completed and there will be no significant scaling
of the pipeline.
Another reason for diluting the underflow slurry is to reduce the
concentration of solids in the pipeline. It has been found in
practice that a slurry containing a maximum of about 1.8% solids by
weight can be successfully pumped through nearly five miles of
pipeline. As a result of low liquid velocity and of occasional
interruptions in pumping, it is sometimes necessary to clean out
this pipeline with a flexible "pig."
Investigation of the settling characteristics of slurry samples
from brine treating clarifier underflows showed that on standing,
they could be further separated into clears and thickened pulp.
The thickened pulp samples, after sixteen hours of settling, varied
in solids content from 600 grams per liter to 1000 grams per liter
with an average value of 800 grams per liter. It was also found
that the pulp would further compact on standing for several days.
This value of 800 grams solids per liter, converted to 49.94 pounds
solids per cubic foot appears to be a conservative value for
estimating volume occupied in the well.
When one considers the ratio of salt to calcium and magnesium for
any given mining situation, it becomes apparent that a single well
may be used indefinitely for the disposal of solids accumulated from
the output of many other wells. This is true even when allowance is
made for the volume penalty with rock salt at approximately 135 pounds/
cubic foot and the sludge at only 49.9 pounds/cubic foot. For example.

61
with wells producing brine containing 2000 parts per million calcium
and 60 ppm magnesium, neglecting anhydrite and other inclusions in
the salt, one can calculate that a single well for solids recycle
would take care of the solids from treating brine from 72 other
wells, each producing at the same rate as the recycle well. In
practice, one solids-recycling well could certainly be used to
handle solids from 15 to 20 other producing wells.
In the first actual trial of mining with fluid carrying sludge,
top injection was tried with brine being withdrawn from near the
bottom of the well. This soon resulted in the return of some solids
in the product brine. The operation was then changed to bottom
injection. Using this technique, with brine being withdrawn from
near the top of the well, operation has now continued for more than
a year with solids entering the well and settling to the bottom.
All of the brine produced has been free of entrained solids and of
good quality.
The recycling of brine treating solids to a brine well has been
demonstrated to be a superior method of protecting the environment.
Operating experience indicates that the well can be continued in
this service for decades.

62
 TECHNIQUES IN THE DEVELOPMENT OF
SALT CAVERNS FOR MULTIPLE USE
Michael Slezak
Allied Chemical Corporation, Syracuse, New York 13209

ABSTRACT
Abundance of salt, the basic raw material in
the production of chlorine, had made it unneces
sary for salt producers to exercise careful
planning in the design, installation and oper
ation of their salt wells. New State and Federal
regulations are being enacted to control solution
mining that require planning by the industry.
Beyond the need to comply with the law,
there are economic advantages to be realized in
the planned development of salt well cavities
brought about by an increasing demand for use of
the cavities to store petroleum and other prod
ucts. These uses require stable caverns of
particular size and shape.
Allied Chemical corporation employs two
basic methods for the planned development of
brine caverns. A single well method is used in
thick, salt dome type deposits, and a method
utilizing two or more interconnected wells is
used in thin layered deposits.
The techniques and advantages of both
methods are discussed.

Introduction
Sodium chloride, commonly known as salt, is the
basic raw material utilized in the production of chlorine.
Nearly forty percent, or 18 million of the 45 million tons
of salt produced during 1972, was produced for the chlo
rine industry utilizing brine wells (1) .
As recently as the mid-19501 s, the industry pro
duced brine, almost exclusively, by the conventional
method of brine well operation shown in Fig. 1. The
practice was to drill to the top of the salt deposit and
cement in a well casing, usually 6 inches in diameter. A
hole was then drilled through the salt layer and a 3-inch

63
diameter tube was installed extending from the top of the
well to the bottom of the salt deposit. Water was pumped
through the annular space to the top of the salt deposit
where it preferentially dissolved the exposed salt. The
brine that was formed gravitated toward the bottom of the
salt cavity as it grew in density, and finally exited
through the center tube to the surface.
The ability of water to dissolve salt more
rapidly than partially saturated brine, influences cavity
growth to form a "Morning Glory" type cavern that is wide
at the top, where water enters, and narrow at the base,
where the brine exits.
Eventually, the span atop the salt cavern grows
to such dimensions that it can no longer support itself
and thereby collapses, breaking the well casing and tubing
off. The rubble funnels into the narrow base of the
cavern and destroys the well as a brine producer (Fig. 2).
Some effort may be expended to repair the well,
but generally, the repair is found to be too expensive.
The well is abandoned and a new well drilled because that
is the easier solution, especially for companies that have
ample brine field property.
Not much planning went into the design of brine
wells nor was much creative thought given to new operating
techniques as salt is abundant and one of the less
expensive commodities to produce. However, legislation
passed and pending to regulate solution mining of salt in
the various salt-producing states will require the salt
producers to devote more time and effort to the design and
planning of future well installations in order to protect
the land surface from settlement and to prevent pollution
of streams and ground water. Eventually, all brine well
operations will be regulated by either State laws or by
Federal laws administered by the Environmental Protection
Agency.
Beyond the need to comply with the law, there
are economic advantages to be realized in the planned
development of a salt cavity. Besides lower operating
costs and greater salt recovery per well, there is an
increasing demand for mature salt caverns for the storage
of products such as petroleum and for use in waste dis
posal. Among other exotic uses advanced is the storage of
compressed air at high pressure by electric power gener
ating stations during "off-peak" demand periods. At
"high-peak" demand, the compressed air would be used as a

64
source of power to drive gas turbines (2) . These uses
require stable underground caverns of a particular size
and shape which normally take years to develop. It is to
the interest of every brine field operator to plan his
brine well development with this end in mind.
Allied Chemical Corporation has operated brine
fields over the past 80 years in New York State, Michigan,
Louisiana, West Virginia, Canada and Mexico. Allied
Chemical employs two basic methods for the planned develop
ment of brine caverns and many variations of the two
methods, depending on specific circumstances. One method,
employing a single well, is used in thick salt deposits as
found in the salt domes of Louisiana. The second method,
using two or more interconnected wells, is practiced in
relatively thin layered salt deposits of under 500-foot
thickness such as found in the Silurian salts of the
northeast United States. In both cases, the mining
progresses from the bottom of the well upwards.

Single Well Method

The single well method employed by Allied
Chemical in salt dome type deposits, covered in U.S.
Patent No. 3,632,171, is illustrated in Fig. 3. In this
particular example, an 18-inch casing is cemented in place
at approximately 500 feet below the top of the salt or at
about the 1,200-foot depth. The well is then drilled down
to a total depth of 4,450 feet. A 13-inch casing is
suspended from the well head to the 4,350-foot depth
through which is hung an 8-inch casing to approximately
the 4, 400- foot depth. With the well standing full of
fluid, a calculated volume of oil is injected into the
annulus between the 18-inch and 13-inch casings to fill
the annulus to the bottom of the 13-inch casing. The oil
will establish the upward limit of the initial mining cut
by protecting the salt above this level from the dis
solving action of the water. Dissolving is begun by first
pumping water down the 8-inch casing at a slow rate and
discharging through the annular space between the 8- and
13-inch casings. Over one day's operation, the flow is
increased to a rate in the order of 600 gpm. Operation in
this manner, with water flowing down the center and brine
out the annulus, is referred to as "reverse flow" and its
purpose is two-fold. First, it positively establishes the
level of the oil pad at the bottom of the 13-inch casing
since any excess oil will return to the surface up the
annulus with the exiting brine. Secondly, by injecting
water at a 600 gpm rate down the center 8-inch casing, the

65
flow impinging on the bottom of the well rapidly forms a
pocket into which sands may accumulate during the very
early stages of development when the cavity is in need of
some working room.
After about one week's operation, the well is
put in " forward flow" by pumping water down the annular
space between the 13- and 8-inch casings with brine flowing
out the center 8-inch casing. As soon as the pressures in
the columns stabilize, flow is stopped and the well is
"locked-in" by closing all of the valves. The oil, water
and brine pressures are obtained at the well head. By
treating the well as a huge manometer with fluids of
different specific gravities occupying each column, the
oil pad level can be calculated to confirm its existence
at the bottom of the 13-inch casing.
A high rate of flow is maintained at about
600 gpm. This has the dual advantage of rapidly exca
vating the cavity and also, because of the high velocity,
keeping the sands swept out of the bottom of the develop
ing cavity. To dispose of the sands and the weak brine
produced by the developing well, it is Allied Chemical's
practice to run one of the mature brine wells in series
with the developing well as shown on Fig. 4. The weak
brine is run down the tube of the mature well allowing the
sands to drop out in the vast cavern. The weak brine is
saturated in the mature brine well cavity and returns up
the annulus as production brine.
At a rate of 600 gpm, the brine from the
developing well can be expected to reach 90% saturation
after about 3 months' operation, which calculates out to
be approximately 15,000 cubic feet of salt removed per
day. A period of approximately 1 year will be required
for the "initial cut" to develop a diameter of 300 feet.
At this point, a Sonar Survey is obtained to confirm the
calculated volume and to establish more precisely the
shape of the cavern.
If the cavern is at its desired diameter, the
next step is to bleed off oil until, by calculation, the
oil pressure drop is sufficient to raise the level of the
oil pad in the well by 50 feet (Fig. 5). Depending on the
specific gravity of the oil and brine columns, a 5 psi
drop in oil pressure generally is sufficient to allow the
oil level to retreat to a 50-foot higher elevation. Oper
ation of the well is resumed. Now with the salt forming
the roof of the "initial cut" exposed for dissolving, the
well should produce saturated brine directly for

66
production use. As the cavern grows larger, capacity of
the well to produce saturated brine should increase to a
rate of 800 to 1,000 gpm. By keeping records of the
volumes extracted and by taking an occasional Sonar Survey
to verify cavity growth, the development of the cavity can
be directed in successive upward steps until some years
later, it has reached its final design shape.
It has been Allied Chemical's policy to install
the largest casings practical in a well of this type,
hence, the production casings of 13- and 8-inch size.
These sizes are considerably larger than those found in
most brine wells but there are several advantages worth
noting. First, as wells mature, they become capable of
producing large volumes of brine if the piping is capable
of delivering it without excessive pressure drop. The
surface piping size can be increased but little can be
done toward increasing the well casing sizes once the well
is installed. The 13- and 8-inch casings will permit
flows of up to 1,000 gpm without excessive pressure drops.
Secondly, high capacity wells reduce the need for oper
ation of a large number of wells, hence reduced mainte
nance costs. Obviously, it is more economical to operate
three 1,000 gpm brine wells than ten 300 gpm wells.
Thirdly, operations of a well at high rates hastens the
day when the cavern can be put to uses other than pro
ducing brine. In a 300-foot diameter well as shown in
Fig. 5, the well has a potential of producing approxi
mately 14 million tons of salt from its 3,000-foot final
cavity height. At a 1,000 gpm rate, over 20 years will be
required to bring this cavity to its final design shape.
At lower production rates, the well casings could deteri
orate and fail before the cavern has reached the desired
stage of development.
Caverns can be used for storage while they are
still producing brine. As soon as some size has been
developed, say 20 million cubic feet or more, consider
ation may be given to simultaneous use of the cavern for
storage of petroleum or other products as well as for
producing brine. This requires replacement of the crude
oil blanket by the product to be stored. During periods
of storage, the salt roof would be protected and dis
solving of the salt to make brine would take place along
the sides of the cavern, enlarging the cavern diameter.
This possibility is taken into account in Allied
Chemical's well spacing plan and provision is made to
allow the cavity diameter to grow to as much as 500 feet.
Needless to say, increasing the diameter from 300 feet up

67

v.
to 500 feet adds tremendously to the total tons of salt
recoverable from the well and the size of the storage
space ultimately produced. In summary, the advantages of
Allied Chemical 1 s single well scheme in thick salt
deposits are:
1. Controlled growth of a cavern of the proper
design, shape and size for use as valuable storage space
for petroleum and other materials.
2. Greater salt recovery per well.
3. Reduces the need for frequent adjustments
of the well casings.
4. Provides high volume of high density brine.
5. Permits removal of insoluble sands from the
development well at the high flow rates.
6. Develops a reservoir at the bottom of the
well during the "initial cut" into which sands may
accumulate as mining progresses upward.

The Air Pad Method

In relatively thin layered salt deposits, of say
less than 500 feet, Allied Chemical uses the air pad
method (3) whereby two or more wells are joined together
by undercutting near the base of the salt layer. In this
technique, two or more wells are installed in a manner
similar to that shown on Fig. 6. Air is mixed with water
and carried down the annulus to the salt cavity. Once in
the cavity, the air separates from the liquid forming an
air pad above the liquid level protecting the salt roof
from dissolving. Limitation of upward growth by the air
pad forces dissolving to take place in a lateral direction
at the periphery developing a cavity in the shape of a
huge inverted cone. A slight excess of air is supplied to
the well to assure that the development level is main
tained at the selected elevation. The excess air returns
up the center tube with the discharge brine expanding as
it rises providing an air lift to bring the brine to the
surface.
Care must be taken to establish the development
levels for the wells at the same elevations so that the
period of time required to connect the wells is not pro
longed by overlapping of the developing cavities. The

68
development level is determined by the elevation at which
the bottom of the "bell" is placed. After about one year
of development, the cavities of adjoining wells should
grow sufficiently in diameter for the two cavities to
connect .
When the connection is accomplished, the develop
ment assembly is removed from the wells and a production
liner is installed (Fig. 7). Air is introduced down the
annulus of both wells, while in a "no-flow" condition,
until a show of air is evident in the center tube of each
well. This establishes the air pad at the level of the
air outlet holes which were drilled into the production
liner previous to installation. The air pressure required
to establish the pad to the depth of the air outlet holes
is recorded and used as a reference point for subsequent
setting of higher mining levels during the producing life
of the well. Using the reference pressure as a base, a
5 psi drop in the air column will shorten the column or
raise the dissolving level approximately 10 feet.
The wells are then operated by injecting water
down one well into the joined cavities where it dissolves
salt along the sides and roof of the cavern becoming
saturated enroute, dropping out the insolubles to the
bottom of the cavern and eventually exiting at the
companion well.
When, by volumetric measurement or by a periodic
Sonar Survey, it is found that the cavity growth has
proceeded to its planned dimensions, the direction of flow
can be reversed and the air pad raised to a higher ele
vation to permit uniform mining of the product upward
step-by-step until the final cavity height is achieved
(Fig. 8) . It is advisable to allow a thin salt roof to
remain atop the final cavity to provide protection against
roof collapse.
The advantages of Allied Chemical's air padding
technique in layered salt deposits are:
1. Dissolving of the salt layer from the
bottom upwards allows the debris and insolubles to settle
and remain on the bottom of the cavern.
2. Provides greater salt recovery per well.
3. Provides a high-density brine because of
the large roof area made available for solution of salt.

69
 4. Provides a valuable storage cavern after
salt production is terminated.

Conclusion
Allied Chemical has used the techniques described
above in their brine field operations- At their Choctaw
Salt Dome in Louisiana, Allied Chemical has converted six
brine wells to the storage of petroleum products , thus
realizing additional benefits from mature brine cavities.
The chlorine industry, in operating its brine
fields , should be aware that it is in a unique position to
develop valuable space for underground storage in salt
caverns. In today's world of environmental concern, under
ground storage caverns cannot be developed unless the
material removed during their formation is consumed above
ground for a useful purpose rather than disposal in a
manner that creates pollution. The industry's position to
use the salt provides it with an opportunity to derive
additional revenues from the operation or sale of under
ground storage caverns.
In summary, there are benefits to be derived in
planning the growth and development of brine wells,
especially with today's high cost of well installation and
potential use for the resulting cavities. These high
costs can be offset by planning to utilize the brine well
to the utmost — first, in producing an ample quantity of
high-quality brine at lower cost, and secondly, for long-
range use in the storage of petroleum products.

70
 /^ZZS—> Brine

Shale
&
Limestone

Fig. 1. Conventional Fig. 2. Conventional

Brine Well Brine Well-Broken Down
^*J-> Brine
water
water -> Cjj Oil^^
«^ Oil ///VW

Overburden^
z z z ^
laprocK
Salt
1200' Bottom
Oil_ 18" Casing
Column

Oil Pad\

^ ^" ^4450' Well

Depth
Fig. 3. Salt Dome Fig. 4. Weak Brine and Sand
Brine Well Disposal Method

71
 water
Pressure <? d
Gauge ^
Overburden^
44caprock^
700' TopJ"
of Salt
Oil
Column
50'
Mining^
\ Levels ^

3450* Depth
Fig. 5. Salt Dome Brine Fig. 6. Air Pad Method
Well Growth
Water;
Pressure Brine Brine ^T<-Water
^ Gauge

> > i i ft
Limestone^
&
Shale

1st Step
Mining
Level

Air Pad
j^Air
$10' \\ ^Holes

Fig. 8. Final Two-Well

Fig. 7. Two-Well Air Cavity Outline
Pad Method

72
 REFERENCES
1. Minerals Yearbook, 1972.
2. W. J. Lang, Underground Energy Storage for Electrical
Power Generation, 4th Salt Symposium, Houston, Texas
(Strata Power Co., Libertyville, Illinois).
3. U.S. Patent No. 1,923,896, Mining Soluble Salt, by
E. N. Trump, August 22, 1933.
U.S. Patent No. 1,960,932, Method of Mining, by L. S.
Tracy, May 29, 1934.
U.S. Patent No. 2,009,534, System for Mining a Soluble,
by E. N. Trump, July 30, 1935.
U.S. Patent No. 2,009,535, Method and Means for Mining
a Soluble, by E. N. Trump, July 30, 1935.

73
 APPLICATION OF TURBULENCE IN SOLUTION MINING
C. W. Querio
Texas Brine Corporation
2000 West Loop South
Houston, Texas 77027
Abstract
The effects of laminar and turbulent flows on salt
solutioning rates have been established in labora
tory tests. The authors present a brief discussion
of the mechanism and solution rate curves based on
these laboratory tests. Typical modes of brine well
operation in the field are presented and discussed.
The paper covers the planning and construction of
several brine wells designed to perform at turbulent
rates of flow. The results of these operations are
presented. The importance of applying this technique
in specific operations is discussed along with the
limitations of turbulent flow potential in solution
mining.
Many chlorine-caustic plants receive their basic raw material,
sodium chloride, in solution form via pipelines at their fence line.
This solution, brine, is water containing 24% to 26% (by weight) sodium
chloride. For most of these plants, the brine was produced by solution
mining a rock salt deposit that is usually thousands of feet below the
ground surface.
Solution mining is a method where fresh water is pumped down to the
rock salt (usually 96% + pure NaCl) zone through a pipe; the salt is
dissolved by the water forming a brine solution which is forced to the
surface through another pipe. Some of the typical modes of brine well
operations are shown in Figure No. 1.

Top Injection System

A single tubing string is run in the well bore below the top of the
salt deposit. Water Is pumped down the main casing, in the annular
area, to the top of the salt bed which is exposed in the well bore.
Brine is produced from the lower portion of the well and returns to the
surface through the inner tubing string.
A very high percent, perhaps 85-90%, of the solutioning takes place
in the upper few feet of the salt zone. This type of production
usually results in a morning glory shaped cavern. The roof rock becomes
unstable before any large quantities of salt are removed from the well.

74
The resulting rock falls shear off tubing requiring workover and re-
tubing. Maintenance costs per ton of salt removed are usually high
with this mode of operation.

Bottom Injection
The construction within the salt zone is usually the same as with
top injection. However, in this procedure the water is pumped down the
inner tubing string and brine is retrieved through the annular area of
the casing which is set near the upper salt surface.
Bottom injection can produce a more cylindrical cavern shape but
the production rate of saturated brine per well is considerably re
duced. The cylindrical shape results in greater cavern stability per
ton of salt removed.

Air or Oil Pad

This system requires that an extra concentric string of casing be
installed in the well. This casing is used to introduce air, oil or
LPG which is maintained at a desired level in the salt zone. The pad
material is used to retard or control the upward solutioning of the
salt.
Padding is used to control the shape and roof stability of a
cavern.

Variable Annular Injection

This procedure is used to develop greater mixing in the salt cavern
by changing the flow patterns so that some bulk mixing occurs.
Water can be introduced at varying points in the cavern depending
on casing setting. The water will rise in the cavern but will achieve
some saturation well below the salt roof. This method can reduce the
morning glory effect as noted in the straight top injection system.
Production rates are higher than bottom injection systems and cavern
stability is improved over-straight top injection.

Coalescence
In this method, brine well caverns are located (spaced) and
operated so that they will interconnect as solutioning and development
take place. Final connection can result in high rate production be
tween the wells.

75
 The dip of the salt structure is taken advantage of in laying out
such a system. When used in layered or bedded salt the connection is
planned to take place in the lower salt zones.

Hydraulic Fracturing
A fluid, water or brine, is pumped into the injection well until
the hydraulic pressure is great enough to fracture the formation.
After fracture occurs pumping is continued to extend the fracture
through the formation, and hopefully, intersect the target well at some
distance away. There are many factors which come into play during
fracture attempts and makes successful connections somewhat unpredict
able.
However, when connections are successful this procedure can result
in immediate high rate production of saturated brine without long
development time requirements. Some aspects of hydraulic fracturing
will be discussed in the oral presentation.
In the early days of brine well operation, not too much attention
was given to the mechanism of solutioning. Brine was being produced
to meet the needs and with fair economics. However, as the method
increased in application and as higher and higher demands were
required to meet increased chlor-alkali plant sizes a number of factors
became increasingly important to continued economic use of the method.
A list of these factors would include:
1) Down hole maintenance and methods of operation.
2) Maximum use of salt reserves.
3) Productivity per well.
4) Extraction or percent recovery per well.
5) Surface subsidence.
6) Protecting the rights of others (2 & 5) .
To fully evaluate the ways of improving items on the above list
required a better understanding of what was really taking place during
the dissolutioning process. One of the first and simplest attempts
taken in laboratory tests was to establish the rate of dissolutioning
for salt per square foot of salt surface exposed. Graph No. 1 is a
plot of this data. The solid curve was developed using a series of
salt cores with impurities varying from VA-h% and under quiescent
conditions. This curve points out that as the salinity of a solution
increases, the dissolution rate of salt decreases. One data point has
been shown on the figures to indicate the greatly increased rate of
dissolutioning when a salt sample received only minimum agitation.
Present studies* being made at the University of Texas under
sponsorship of the Solution Mining Research Institute indicates that
turbulent flow conditions can increase the rate of dissolutioning 4 to
4.5 times that achieved under laminar flow conditions. Graphs 2, 3,
and 4 are plots of data obtained in these studies. These graphs also

76
show that laminar flow produces higher dissolutioning rates than
quiescent conditions which primarily depend on convection and density
flow patterns.
Model studies conducted at the University of Texas have greatly
increased our understanding of the mechanism of solutioning. Durie &
Jessen in 19642 and 19663 performed some of the basic studies. In
these experiments, they derived boundry layer thickness, parallel
velocity components and the mass transfer rates from vertical flat
solid salt surfaces. McCue^ also has applied boundry layer theory to
mass transfer problems in which he assumed equal boundry layer thick
ness for both velocity and concentration distributions.
Further studies''' have been conducted to investigate the effects of
the following:
1) Non-vertical surfaces.
2) Roof Surfaces.
3) Concentration gradients.
4) Impurities in salt (particularly insolubles) .
5) Relationship of height to overall removal.
6) Mixing effects in the cavern.
7) Methods of fluid injection.
a) Top, b) Bottom, c) Mid-point, and varying positions.
8) Roof padding.
9) Single well operations.
10) Gallery well operations (including hydraulic fracture
connections) .
The ultimate aim of these studies is to develop computer programs
which will give satisfactory results in calculating the shape and
volume of cavity development with time. Work is being undertaken to
incorporate the changes in turbulent rates of removal with concentra
tion of brine into the computer programs.
Field technology has also grown. Today Sonar surveys can be taken
of the cavities (at least in dome salts) and can be compared to the
computer simulation results. We anticipate a working computer model
and program by mid-1974.
In 1968, Texas Brine Corporation began the development of a new
brine field in Texas. Prior field development had all required a
lengthy period of well operation at less than saturated brine concen
tration. This undersaturated brine had to be disposed of, recycled
for saturation or the plant took the brine and operated at less than
hoped for efficiencies. For this new operation it was desirable to
produce saturated brine initially and at a rate equivalent to plant
needs. Wells were designed for high flow rates and to have approxi
mately 2,000 feet of vertical salt face exposed for solutioning.
Figure No. 2 is a schematic of a typical well completion at this
location. Approximately 230 feet of 30-inch casing is set to shut off

77
near surface ground water and loosely compacted sediments. This casing
is cemented to the surface. 2080 feet of 18-inch casing is set into
the caprock above the salt and cemented to the surface. This string
shuts out any deep water zones (which are often corrosive) , zones of
porosity or loss of circulation and provides structural support for
final access casing to the salt zone. The next casing, a string of
13-3/8-inch, is set at approximately 3455 feet and cemented to the
surface. This casing is set approximately 1000 feet below the top of
the; salt zone and provides final access to the salt, structural support
for all hanging strings, seals off all waters from above and ensures a
pressure tight system as salt cavern is developed. The well was
drilled to a total depth of 6620 feet with a 16-1/4-inch bit. The
production strings, 4410 feet of 10-3/4-inch and 6040 feet of 7-inch
were then run in and suspended from the well head assembly. This well
was first placed in operation in 1969. Initial production rate was set
at 450 GPM. Water was pumped down the 7-inch tubing with brine being
produced through the 10-3/4-inch hanging casing. An oil pad was
pumped down the 13-3/8-inch casing to the bottom of the 10-3/4-inch.
This flow pattern creates a more cylindrical cavern shape resulting in
greater roof and wall stability. Vertical roof dissolutioning is con
trolled by pad placement. As a result, these wells are relatively free
of maintenance problems caused by large salt or rock falls from the
roof or spalling from the wells. Saturated brine was produced after
two volumes of the bore hole and pipe system were displaced. Product
ion continued at this rate without salinity decline. Operation at
this rate was producing salt at 810 tons per day. This is equivalent
to 67,500 pounds per hour. The original bore hole had a surface area
of approximately 10,647 square feet. The average dissolutioning rate
was 6.44 pounds per square foot.
Referring back to Graph No. 1, it is apparent that the dissolution
ing rate occuring in this well was greater than would be expected from
quiescent solutioning laminar or turbulent flow. The high rate inject
ion created both turbulent bulk flow conditions and active mixing in
the small bore hole cavern. The salt surface was rough and this
created further eddies at the fluid salt interface causing more rapid
solutioning than would have been induced by the normal turbulence with
in the boundry layer.
Assuming a rate of solution equivalent to one pound per hour per
square foot, the production of 60,000 pounds per hour would require
60,000 square feet of salt surface. An area of this size would be
reached when the cavern diameter had developed out to approximately
9.5 feet. This well has been primarily limited in production by the
hydraulic losses and velocities in the system. Sonars taken after
lengthy production show that we were able to develop a nearly cylin
drical shape. As greater surface area became available, the cavern
did begin to enlarge in the bottom sections. Figure No. 3 is a
schematic of a well completed in late 1973 at Texas Brine Corporation's
Pierce Junction Plant in Houston, Texas.

78
 This well was placed in operation on January 21, 1974. This well
operates with bottom injection of fresh water, which is our normal
method of operation. Graph No. 5 is a plot of the production rate in
gallons per minute with corresponding salinity expressed in degrees
salometer. Initial production was 600 to 650 GPM of saturated brine or
approximately 1125 tons of NaCl per day. The surface area available in
the original bore hole was approximately 10,880 square feet. The
dissolutioning rate was equivalent to 9.0 pounds per square foot per
hour. This is at least four times what would be expected under laminar
flow conditions.
On February 11, after twenty-one days of operation the production
rate was dropped to 450 GPM (a reduction of almost 30%), and the salin
ity of the produced brine dropped slightly. After several days the
saturation again approached saturation. This well has produced
saturated brine at a rate of 720 GPM, another indication that turbu
lence created in the bore hole (or small cavern) can result in high
dissolutioning rates.
Graph No. 6 is a plot of the solubility of NaCl versus temperature.
Temperature can have a measurable effect on the dissolutioning rate and
total salt that will go into solution. Rock salt is solution mined in
many places around the world and at depths varying from only hundreds
of feet down to many thousands. Earth temperature nominally increases
at approximately 1°F per hundred feet of depth. Texas Brine Corpora
tion is operating brine wells which vary in depth from 1400 feet to
6500 feet. The shallow wells have salt temperatures at 64 °F and the
hottest 6500 foot well has a bottom hole temperature of 170°F. This is
a considerable span. At 170°F, 27.4% by weight of sodium chloride can
be held in solution compared to 26.4% at a temperature of 64 °F.
The well described in Figure No. 2 has a bottom hole temperature
of 170°F. The well shown in Figure No. 3 has a temperature of 165°F.
The relatively high temperature in these wells increases their capa
bilities of producing saturated brine at rates higher than those of
shallower wells.
Turbulent flow and a long salt face surface were used to place
these brine wells into immediate high rate production. Turbulent flow
conditions can materially cut down the required development time for
brine wells even when the vertical salt surface is limited. However,
where salt surface is limited, the produced brine will, of course, be
undersaturated. High rate development at undersaturation can rapidly
develop salt surface for solutioning. The effluent brine would have
to be handled in some manner until sufficient capacity is available to
meet plant needs on a saturated basis. The final solutioning surface
required would be available in less time than it would be by producing
only saturated (or near saturated) brine. The cavern thus created
would also be a more stable structure. Once the necessary surface is
available, production rates could be lowered and a near saturated brine

79
produced .
When there is unlimited depth of salt, high rate wells capable of
producing 1000 GPM of saturated brine, are certainly feasible. Total
depth, however, can present problems in several ways: 1) Higher temper
atures found at greater depths help to produce supersaturation. This
can result in salting out in well casings as the fluid moves up hole
and temperatures drop; 2) Rock salt we know will flow beyond certain
depths and can cause significant closure in bore holes and salt caverns.
This closure can create major maintenance and operational problems.
The design, construction, and operation of high rate brine wells
which take full advantage of turbulent flow in early development stages
is practical. Ultimate success depends on a thorough evaluation of the
salt structure, the application of known and proven technology in
construction, with production and control procedures that assure
minimum down hole problems .

References
1. Progress Reports, Solution Mining Research Institute Project,
Contract No. 30852-2, and Contract No. 30852-3, University of Texas,
Reports from December, 1970 to December, 1973.
2. R. W. Durie and F. W. Jessen, "Mechanism of the Dissolutioning of
Salt in the Formation of Underground Salt Cavities", pages 183-190,
Society of Petroleum Engineers Journal, AIME, June, 1964.
3. R. W. Durie and F. W. Jessen, "Laminar Boundary Layer in the Free
Convection Dissolution of Salt", pages 326-335, Second Symposium on
Salt, Volume 2, Northern Ohio Geological Society, 1966.
t\. A. P. McCue, FMC Corporation, New York, New York, Personal Communi
cation to Dr. F. W. Jessen, May, 1972.

80
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 GRAPH - I GRAPH- 2
DISSOLUTION OF SALT SAMPLES
EFFECT OF WATER SALINITY ON INITIAL
RATE OF SOLUTION OF ROCK SALT AND AVERAGE RATES OF SALT REMOVAL
FOR TURBULENT FLOW.
VS. (U. OF TEXAS STUDY)
SALT CONCENTRATION
LEGEND
A INITIAL RATES
o AVERAGE RATES

o MINIMUM AGITATION

SALT SOLUTION CONCENTRATION SALT SOLUTION CONCENTRATION

WEIGHT % WEIGHT %

GRAPH- 3 GRAPH- 4
DISSOLUTION OF SALT SAMPLES DISSOLUTION OF SALT SAMPLES
EFFECT OF WATER SALINITY ON EFFECT OF WATER SALINITY ON
INITIAL
FOR RATES
LAMINAR OF SALT
AND REMOVAL
TURBULENT FLOW AVERAGE RATESANDOF TURBULENT
SALT REMOVAL
FOR LAMINAR FLOW
(U. OF TEXAS STUDY) (U.OF TEXAS STUDY)
LEGEND LEGEND
& LAMINAR
> LAMINAR
DURIE (6)FLOW- DURIE (6)FLOW —
o TURBULENT FLOW o TURBULENT FLOW

SALT SOLUTION CONCENTRATION SALT SOLUTION CONCENTRATION

WEIGHT % WEIGHT %

83
84
 Table No. 1
Metric & English Conversion
For Graphs 1-2-3-4
Lb/ft2/hr. cc/cm /sec.
1.00 .06 x 10"3
2.00 .13 x 10"3
3.00 .19 x 10-3
4.00 .24 x 10-3
5.00 .31 x 10-3
6.00 .38 x 10~3
7.00 .44 x 10-3
3.19 .20 x lO-3
6.38 .40 x 10"3
9.57 .60 x 10-3
12.76 .80 x 10-3
15.94 1.00 x 10"3
19.13 1.20 x 10-3
22.32 1.40 x 10 3

Salt Solution Cone.

By Weight - Percent Moles/Liter
5 0.90
10 1.83
15 2.85
20 3.93
25 5.09
30 6.34

85
 TRACE METALS IN SALT SOURCES TO ELECTROLYTIC INDUSTRY
Charles E. MacKinnon and Roger C. Morris
United Salt Corporation, Houston, Texas 77027
Texas Brine Corporation, Houston, Texas 77027
ABSTRACT
Atomic absorption techniques have been used to study the
trace metal content of various salt and brine sources used in
the United Sates for the production of chlorine. Solar salt
from San Francisco, Baja California, and Bonaire (NA), rock
salt from New York, Ohio, Michigan, Louisiana, and Texas, and
brine from New York, Michigan, Louisiana and Texas were tested
for sixteen trace metals selected as being of primary interest
to chlorine producers. Several salt dissolving conditions
were used.
Principal sources of bedded rock salt for the commercial prepara
tion of chlorine and caustic occur in 28 of the United States and in
the Province of Ontario. Solar salt from the San Francisco Bay area,
from Black Warrior Lagoon (Baja California), from Bonaire (Netherlands
Antilles) or other sources is also used where economic advantages pre
vail. Cell grade brine is obtained from raw brine from surface dis-
solvers or from underground by brine well operation.
Trace metals may be introduced into the brine from the salt, from
erosion or corrosion of metal processing equipment, from graphite or
other anode material, or from extraneous contamination from the in
dustrial environment. Though relatively insoluble, these metals may
survive the brine purification process at parts per million or billion
levels, sufficient to affect the electrolytic process.
One of the most undesirable effects of trace metals in the elec
trolyte occurs in mercury cell operation, where minute concentrations
of chromium, vanadium, titanium or molybdenum cause evolution of hy
drogen at the mercury cathode instead of in the decomposer, leading to
the possibility of explosive concentrations of hydrogen in the chlor
ine system. Similar effects may occur with other trace metals, though
to a lesser degree.
The most predominant impurity in salt is calcium sulfate, present
in rock salt as the mineral anhydrite (CaSO^) and in solar salt as an
hydrite, gypsum (CaSO^ i 12 H2O), or as dissolved CaSO^ in the brine
occluded within the crystal. Rock salt may also be contaminated with
other minerals relatively insoluble in water or brine, but sufficient
ly soluble in neutral or acidic aqueous solvents to significantly af
fect the brine for industrial electrolysis.

86
 Thus, this paper serves three purposes:
(1) to compare the trace metal content of brines prepared from a
variety of industrial salt sources
(2) to compare the effects of solvent acidity and alkalinity on
the solubility of the trace metals, and
(3) to demonstrate an analytical technique which can be perform
ed on standard atomic absorption equipment without resorting
to the more sophisticated accessories currently being devel
oped for ultra micro analyses.
EXPERIMENTAL
Instrumental
All analyses were performed on a Perkin-Elmer Model 403 double
beam atomic beam spectrophotometer equipped with a strip chart record
er and deuterium arc background corrector. A titanium nitrous oxide
(5 cm) burner head was used in all determinations. Air-acetylene was
used except where noted in Table V. Single element, hollow cathode
tubes were used in accordance with the manufacturer's recommendations.
Reagents and Equipment
All reagents used, with the exception of lanthanum chloride, were
ACS Reagent Grade chemicals. Water was commercially available bottled
water, which was passed through a deionizing column; it was then neu
tralized with 1.0 N sodium carbonate. All glassware and plastic ware
were washed and rinsed in a succession of: tap water, 1:1 nitric a-
cid, distilled water, and acetone.
Solutions and Standards
Working standards were made up by dilution of commercially avail
able 1000 ug/ml standards. To minimize the effort required in the
preparation of operating standards, the sixteen metals were divided
into three groups, and mixed standards of each of the groups of metals
were prepared. All standard solutions were diluted with a solution
containing 1% (v/v) nitric acid and 0.1% (w/v) lanthanum. For those
analyses in which aqueous solutions were aspirated into the spectro
photometer flame, the salt content of the samples was matched in the
standards by the addition of appropriate volumes of 10% (w/v) reagent
salt solution. Daily preparation of standards was not necessary since
the standards were stable over a period of several weeks when made up
in acid solution and stored in polyethylene bottles. Extractions for
those analyses in which aspiration of an organic extract was necess
ary, were carried out by pH adjustment, followed by chelation and ex
traction. The pH of the already somewhat acidic salt and brine sam
ples was adjusted with 1.0 N hydrochloric acid or 1.0 N sodium hydrox

87
ide and, following the addition of APDC, of pH 3.6 (Clark & Lubs) buf
fer. Chelation was obtained with a 5% (w/v) aqueous solution of ammo
nium pyrrolidine dithiocarbamate, which was filtered upon dissolution,
stored in an amber polyethylene bottle under refrigeration and ex
tracted before use with MIBK. (The APDC solution is sufficiently sta
ble under these conditions to be used for a period of at least a week,
but normal practice was to make up only so much as would be used in
one or two days.) The MIBK used was extracted with 1% hydrochloric
acid and washed with deionized water. Analyses of extracted samples
were run the day of extraction, due to the metal chelates in MIBK.
Salt Sample Preparations
To determine the effect of the pH on the recoveries of the six
teen metals from the brines made up from rock and solar salt samples,
salt samples were dissolved at three different pH values: acidic,
neutral, and basic. Neutral water (pH 7.0+ 0.1) was obtained from the
somewhat acidic deionized water by neutralization with 0.1N sodium
carbonate; basic water by the addition of 0.05 eq/1* excess of sodium
carbonate; and acidic water by reacidif ication of neutral water with
0.05 eq/1* of hydrochloric acid.
Procedure
A 250 gram sample of the salt was dissolved in 750 ml deionized
water, stirred with a magnetic stirrer for 60 minutes and filtered
through a 0.45 urn membrane filter. The filtrate was acidified with 5
drops of concentrated hydrochloric acid and diluted to 1 liter with
deionized water.
A 200 ml aliquot was then adjusted to pH 2-2.5 with 1.0 N HC1 or
NaOH. Two (2) ml of 5% APDC solution was added and the pH adjusted to
3.6 + 0.1 with 1.0 N HC1 or NaOH and 5 ml of 3.6 pH buffer added.
The chelated sample was transferred to a 250 ml separatory fun
nel, 10 ml MIBK added and the mixture shaken vigoroesly for 60 sec
onds. Separation of the phases took place in three minutes after
which the lower aqueous phase was discarded and the organic phase
transferred to a 25 ml volumetric flask and brought to volume with
MIBK.
If necessary, a second dilution of the sample was made by taking
a 5 ml aliquot of the organic extract and diluting it to 25 ml with
MIBK.
For analysis for potassium and the alkaline earth metals, the 250
gpl brine solution is diluted as required to bring the metal concen
tration within the operating range of the aa unit.
*Equivalent to an assumed 2% CaS04 in the salt

88
 Commercial brine samples were filtered, the pH adjusted, and pro
cessed as described above.
RESULTS AND DISCUSSION
1. Analytical results are shown for brine samples in Table I,
for solar salt samples in Table II, for coarse screened rock salt sam
ples in Table II, and for fine screened rock salt samples in Table IV.
2. In Tables I - IV, the sensitivity of the test method (not the
absolute sensitivity of the instrument) is shown in parentheses after
each element. A designation of ND means none detected at the indica
ted limits of sensitivity.
3. With the single exception of calcium, the trace metals showed
essentially the same solubility in alkaline solvent as in neutral sol
vent; therefore, only the value for neutral solvent is reported.
4. As expected, the trace metals showed greater solubility in
acid solvent. This was particularly true of iron, for which the solu
bility increased by an order of magnitude.
5. Fine screenings of rock salt generally contain higher trace
metal concentration than coarser crystals of salt from the same source,
as indicated by a comparison of Tables III and IV.
6. Interference from the salt matrix, and absorbances at or be
low the level of sensitivity prevented reliable interpretation of re
sults for lead.
7. No attempt was made to assure statistical validity to the
samples. The samples were submitted by the respective companies as
being typical of industrial grade salt used by chloralkali producers.
Thus, these analytical results should be interpreted only as being in
dicative of the quality of particular source.
The authors acknowledge, with thanks, the following sources of
salt and brine samples:
Hooker Electrochemical Division
Montague, Michigan
Baja California, Mexico
International Salt Company, Clarks Summit, Pa.
Avery Island, Louisiana
Bonaire, Nether land Antilles
Cleveland, Ohio
Detroit, Michigan
Retsof, New York

89
 Leslie Salt Company. San Francisco, California
San Francisco, California
Morton Salt Company, Chicago, Illinois
Grand Saline, Texas
Sifto Salt Company, Montreal, P. Q.
Goderich, Ontario
Texas Brine Corporation, Houston, Texas
Dale, New York
Grand Bayou, Louisiana
Houston, Texas
United Salt Corporation, Houston, Texas
Hockley, Texas
REFERENCES
1. "Analytical Methods for Atomic Absorption Spectrophotometry",
Perkin-Elmer Corp., Norwalk, Connecticut, (1973) .
2. Slavin, "Atomic Absorption Spectroscopy", Interscience Publishers,
Division of J. Wiley & Sons, New York, (1968).
3. Morrison and Freiser, "Solvent Extraction in Analytical Chemistry",
J. Wiley & Sons, New York, (1957).
4. Stary, "The Solvent Extraction of Metal Chelates", Pergamon Press,
(1964) (ed. H. Irving).
5. J. Nix and T. Goodwin, "Atomic Absorption Newsletter, 9-, 119,
(1970)
6. S. Sprague and W. Slavin, "Atomic Absorption Newsletter, No. 20,
May, (1964).
7. A. Bloomberg and K. Ladenburg, Jr., Electrochem. Soc, 106, 54,
(1969) .

90
 FIGURE I

25 0 g SALT 500ml BRINE

I
DISSOLVE

FILTER
DILUTE TO I LITER

ORGANIC AQUEOUS

Cu.Pb.Zn.Co.Cr.Mn.Mo.Ni.Fe.Ti.V K,Mg,Ca,Sr,Ba

I
CHELATE DILUTE
with
1 TO 5
APCD

1
EXTRACT DILUTE
with
MIBK 1 TO 10

\
DILUTE DILUTE
TO
VOLUME 1 TO 10

ATOMIC ABSORPTION SPECTROSCOPY

91
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96
 BRINE PREPARATION FOR CHLORINE PRODUCTION
Svetozar Pribicevid
Salt-Chemical Company SODA-SO
Tuzla, Yugoslavia

A considerable number of electrolyses has availa

ble brine instead of solid salt. This is. obtained using
the natural salt waters through the underground solution
or surface solution of solid salt if its composition is
not suitable. On the brine preparation has been already
much said, but the author considers the problem which has
been solved for the requirements of electrolysis of loo
tons/day of chlorine in Tuzla to be interesting enough
for the presentation.lt is the question about unfavourable
brine having the following composition: Ca-ion o-l.o gr./
/litre, Iig-ion o-o.2 gr/litre ,HCOa-ion o-J.o gr. /litre,
SO^-ion o-2o.o gr. /litre, H^S o-o?o7 grs/litre and heavy
metals (Cr,Va,etc.) up to 25 ppm.
If the salt loss in the electrolysis is to be
made up for by the brine, there are available two flow
sheets (illustrated in Fig. 1) .According to the scheme a.
the brine is introduced into the purification installation
together with the brine which is circulated in the elec
trolysis, purified, evaporated and again subjected to the
electrolysis. According to scheme b. the brine is purified
separately, evaporated to the salt crystallization, the salt
is then washed and introduced into the electrolysis proce
ss over the solvent of salt. Here the salt plant can be
treated as a plant separated from the electrolysis.
The basic diasadvantage of scheme a. lies in
that, that all the impurities from the brine must be intro
duced into electrolysis and then removed from the process,
only that at that time they are contaminated by mercury.
The basic disadvantage of scheme b.i represents the HaCl
crystallization in salt plant which is considerably more
complicated than the densif ication itself in scheme a..
The choice of the installation type is the matter of
feasibility study in every concrete case. In case of sul
phate presence in the brine, the sulphate becomes the de
terminative factor in the selection, therefore we are going
to present only this procedure.
Because of extremely high costs resulting from
the use of BaClp for sulphate removal, we have developed a
method for sulgHate removal by means of calcium chloride
from the soda factory waste waters. /I, 2/
When CaClo is used as reagent for sulphate re
moval, the sulphate Is removed in the form of calcium sul
phate which will be by the time when we define it more

97
precisely, considered as gypsum. It is very soluble in the
brine, its solubility being subject to regulation, so that
it offers plenty of possibilities for the way of running
of technological process. The basic data which are being
considered are the quantities of sulphate ion that are
passing through the reactor in the form of dissolved
gypsum for the removal of which the additional soda is
used, while the liberated sulphate-ion consumes CaCl2
again. Therefore, we are going to use the data on CaClp
consumption in order to compare the schema.
In the Fig. 2 the balance schema of the plant
showed in Pig. l.a. is illustrated. The CaClo consumption,
expressed by volume value of the solution Vc which conta
ins Cc gr. /litre of calcium chloride, is given by the
expression:
Vc = a„ t }<"(i n= A.156(V+Vo)+1.156Vo.Co-2.775(VoM+
oc-l.l-'b 0r +VM3)/

The value of V is defined by the conditions of. running of

electrolysis or by the difference of NaCl concentrations
after the plant III and the plant IV. , and by the electro
lysis capacity. The value Cc is independently variable.
The values for the range Cr are being taken from the
manual taking into account the oversaturations . One po
ssible type of data source is given in Pig. 3. The value
C is independently variable and ranges usually from o-9
kgs./m3. The value M is independently variable, and the
value from Mi to M3 can be influeneced upon. Prom this
it; is easily possible to establish the influence of indi
vidual values if for the adaption of a number of values
the considered value is varied.
The process can be run in two basic ways. The
addition of CaCl2 is smaller than the sum of sulphates
in I or it is greater. Usually it is more favourable that
there is excess sulphate in I. For the brine which was
here available: NaCl-3oo kgs./nK, Ca-o.o5 kgs./m5,
Mg-o.o5 kgs./m3 SO4.-20 kgs./m3 the basic relations can
be established, (production of 1 ton/hour of chlorine, the
salt utilisation in electrolysis amounts to 4o kgs./m*,
the salt consumption ig 1.7 tons per ton of chlorine).
The most favourable conditions are :,Cc~max. (accepted 45o
kgs./m*), C-max. (accepted lo kgs./nr), M,-max. (accepted
solution saturated by CaSCty.). Then it is2
Vc - o.l23 Gr + 0.289 - o.262 M3
Prom the conditions C.V = Vp.(Cr+Cv), it is obtained that

98
 BRINE SLUDGE
KONDENZAT OnCfr It
SLUDGE,
7/
777
Cr*Cv
SLUDGE
IV 111 jon^
BRINE KONDENZAT C'Cr*Cv
0
n 1.11 BRINE PURIFICATION
III EVAPORATION
IV ELEKTROLYSIS
in ] C 7Y
Pig. 2. Basic schema of brine
8 treatment a ccording
7 Sff/Wf PURIFICATION to the method A.
II EVOPORATION -Cr-sulphate ion in
ID ELEKTROLYSIS kgs./m?, which origi
1Y SALT USSOLVER nates from dissolved
Fig. 1. Basic schema for the ori- gypsum ;Cv-sulphate ion
ne introduction intu ele- which originates from
ctrolysis process. Ea2b0zj., given in kgs/m*;
H-Ca-ion concentration,
given in Lgs./m3;CaCl2/
/Ca=2 .-775 ; CaCl?/SO^=
=1.156 other signs are
clear.

10 20 X Na2S0i g/l

J Fig. 5. Solubility of GaSO^ in

r y solution 5oo gpl Had,
V containing iia2S0/(.
(CaCl2) (Heated 5 hours)
4'
so to 20
Ca

99
Cr+Cv-o.87 C or 8.7 kgs./nr5. ,
From the Fig. 3 it is obtained that Cr=3 kgs./m''
for t«5o C, and the calcium quantity of 1.2 kgs./m3 and
after the reduction in II by 13# - l.o4 kgs./m3, respec
tively, based on this M3 amounts to 1.2 kgs./m3. This
results in CaCl2 consumption of 173 kgs./ton of chlorine.
The minimum value for C is 5^8 kgs./m3. The GaCl2 utili
sation is 85;o. For such a good CaCl2 utilisation it is
necessary to rim the electrolysis process at the satura
tion of the solution with UaSO^. If Ca-ion is removed
from the solution (Mj=0) , the CaClg utilisation decreases
with C=lo down to <V^p. If the scheme l.b. is used, the
observating of CaCl2 influence can be reduced to salt
plant. The basic conception of salt plant is given in
Fig. 4.
Starting from the balance condition of the
system Na2S0/).-NaGl-H20, accepting the temperature at the
outlet from the installation II of - 5o C, it is possible
to extract from the mentioned brine about 65$ of salt
before the .NaoSO^ crystallization has started, i'herefore
is the value conditioned by independent factors. CaClo
is introduced xnto installation III at which occasion
gypsum is being separated. The additional CaClp quantity
is such that Cv amounts to zero or is greater than zero.
We have established that it is considerably more favoura
ble that-Cv is greater than zero, therefore only this
case is presented here.
It is convenient to observe the process through
a certain coefficient n. The value of coefficient n and
the dependence of the quantity of consumed CaCl2 and
Na2CCi3 per m* of raw brine on n is given by the expression:
n = i1 " V0TS0
Y.Cr

Na200, =2 . 65 . M-l . 424 . Vo . ( HCO^ ) +1 . lo3 C 1-n) . V0C0 kgs . /m5

CaCl2 = 1.156 (2-n) V0C0 kgs./m5
As it is n ■ f(V), the simplest way to determine n is to
determine V. The calculation is based on the fact that all
the sulphates, both from the raw brine and from the
stream V are converted into Na2S04 under the effect of
KaOH and Na2C!03 in the installation I. The stream V
represents practically the solution NaCl-Na2S0z|.-H20 with
some COj-ion which has certain influence on the balance.
The influence of COj-ion will be observed later as the
correction factor of derived result. Consequently, it is
V i= Vl + Vc.

100
 Since it is VL.CL=Vo.Oo+V(Cr+Cv) , and Vc.Cc =
= 1.156(Vb.0o+V.Cr) , the following expression for V is
obtained :
Vo.Uo (1.156CL+Cc)
V = CL.Cc - Cc.Cr - Cc.Cv - 1.156 CL.Cr

The type of diagram of dependence of V on Ct and Cv is

shown in Pig. 5. This diagram is made for the data: Cc-17o
kgs./m3, Co-6.67 kgs./m3, t-lo8 . It is evident that
value for V increases slowly in order to increase quickly
at high requirements for Cv, which is quite logic. On the
same diagram^is plotted alsovthe line for V, made for,
Uo-2o kgs./m-', Cc-450 kgs./m?, t-85°C, CL-33,5 kgs./m2.
In the Pig. 6 is shown the change of the value for n in
both cases, which are illustrated in Pig. 5»
According to Fig. 6, the maximum use of CaClp
exists when Cv-15-2o kgs./m . Since the capacity of the
installation increases linearly with the value V, the
working conditions are selected according the minimum
value V which still makes possible the use of CaClp. The
process can be run with UaCl2 utilisation of 93-95* >
which is for about lo# better than is CaClp utilisation
in the procedure according scheme a. (Pig. I.)
The disadvantage of this procedure is in the
fact that soda is to be consumed for the removal of
calcium which comes with the stream V. In case of the
brine being considered, considerably greater quantity of
soda than is necessary is produced by the neutralization
of present bicarbonate. This soda is in both cases remo
ved under the effect of CaClp which does not influence
the comparation procedure.
The similarity of the coefficients from both
schema is only apparent. The calculation is done with
the values which are valid for those solutions that are
balanced under industrial conditions. However, this
balancing is problematic and takes a lot of time, in order
to eliminate the oversaturation of the solutions after
the precipitation of gypsum, it is necessary to treat
according scheme a. V + Vo of solution or about 5o m3/ton
of chlorine, and according the scheme b. approximately
V ■ o.33»^o. The maximum volume which could be expected
with the water being observed is 6.6 m*/ton of chlorine.
It is clear that it is easier to design different reac
tors, as those with fluidized bed of gypsum crystals
which forcibly eliminate the oversaturation. The Pig. 7
indicates another problem which is also in connection
with the supersaturation of gypsum in the solution. In

101
 V
1 i
NaCI 1
0-
NaOH KONDENZAT 1
0 -0 1
J
t/ 11
1
1
1 —ii 1
CaCI2 It 1
Vt
Cc d //a w•!
S1 i ~**\
I BRINE PURIFICATION 'i 1
II EVAPORATION dj c i, di
IE S0i - REMOVE A i
\
Fig. 4. Block diagram of 1
salt plan insta- I
lation.
VL-raother liquor 10 20 30 tO C*
with wich sulpha SOi kg/m3
te ion leaves eva
poration units;
CL-sulphate con 100
centration in mot
her liguor in \t
kgs . /m3 .
r/- *—l
. 1
\ !i ii
NON-FIUERED i 1
SO ; mi
&2 ! N?j
Hi .it-
■ «
<oj i 4
WITHOUT PRESENCE 0FMgl0H)2

10 20iO Cv30
160 200' S(fc kg/m3
t; min
6. Change of Vend n
Pig.7.I'ig(OH)2 influence on with change of Uv
oversaturation of CaoOzj. when and Gjj.
precipitating together :Mg(H)2 -Without marks :Ce-
-0.5+1.0 gr./litre ;CaC03-2.5 lo7 kgs./m3;Co-6,67
gr. /litre ;CaSOz,-25 gr./litre; kgs./m3;6-lo80C;
Cv-lo gr./litre ;t-9o°C. -Cc-45o kgs./m3,Co-
I.Konf iltered solution(clear) 2o kgs,/m5;CL-35,5
II. Dotted field efter foltering kgs./m3,t-850o.
III. All same only in absence of
Hg(GH)2

102
the installation according scheme a. magnesium is aslo
present besides gypsum, which stabilizes the supersatura
ted solutions so that it is very difficult to balance them.
Finally, the comparative calculation indicates
that it is necessary to provide two reactors with dia. of
12 m for the purification of the brine according the
scheme a. for the development of the process in the insta
llation II, and one reactor with dia. of 12 m for the
development of process in the installation I. In case of
brine purification according the scheme b. one reactor
with dia. of 6.5 m is necessary for the development of
the process in the installation I, and one reactor with
dia. of 5 for the development of the process in the in
stallation III. If we add to the above said, that accor
ding scheme b. CaCl2 is better utilized, that separated
precipitates do not contain the mercury, that electrolysis
takes place in absence of Oa-and Mg-ions, that the heavy
metals from the brine are not introduced into electrolysis
system, the procedure according the scheme b. is selected.
The scheme shown in Pig. 4 was adopted. The raw
brine is made free of heavy metals, H2S, bicarbonate,
Ca-and Mg-ions in the installation I. Pure brine is
evaporated in the installation II until the sulphate ion
content reaches 53.5 gr. /litre (5o gr. of Na2304per litre).
The mother liquor of this composition is carried into the
installation III where sulphates and accumulated Coj-ion
which originates from neutralized bicarbonates and excess
OOj-ion added into the installation I, are removed by
means of CaCl2 (Observed water has high concentration of
HCOj-ion therefore soda is not added). The precipitation
of gypsum is done in excess SO/j.-ion of 15 kgs./m*.
In Fig. 8 is shown central reactor of the
installation I /3/. It originates from a number of solu
tions of Soviet authors /4,5/. The reactor is constructed
of steel and coated with epoxy resin. Its height is 14
meters, and dia. i3 9/6.5 m. Operating temperature is 55
so that the waste condensates could be used for brine
preheating. The brine enters at point A where the tangen
tial movement is calmed down and air bubbles are removed.
In zone 3 the brine is made free of gases, and in zone 6
it is mixed with reagents. The reagents are added at point
8, and the gases are discharged at 4 and 5« The mixture of
reagents and the brine is introduced over 9 and the ejec
tor lo into mixing zone 1 and calmed down by means of
eight radially located ribbons 11, it enters the zone of
contact bed II. The space to the level U III is previo
usly filled with the formed precipitate through which

103
flows upwardly the brine causing the flocculation of the
material and the crystallization of CaCO*. i'he precipi
tate is separated over 16-18 and is passing into lower
section which serves as classical clarifier. The^densi-
fied solution with loo kgs. of precipitate per nr is
discharged at 24, and clear solution passes through 19
and joins the clear solution. Above the level U III is
the stabilization zone where the solution is clarified,
in general of the precipitate carried by air bubbles
which penetrate into reactor, i'he brine water discharge
from the reactor is done over the screens 15, through
which flows the brine at the rate of 1 m/sec. This rate
prevents the transfer of horizontal movement component
and thermic flows into the section below the screen,
consequently the reactor is not covered, and the system
of the brine collection into the duct 14 is simple.
Through the system 21-23 a part of brine is taken out
and the recirculation Vr is formed. The reactor operates
under the conditions V ■ constant which permits the
varying of the capacity from 0 to the designed values.
The reactor has been in operation already for 4 years
at the capacity Vc of loo - 12oo m^/h. Wo scale formation
has been noticed, and the precipitated slurry has been
removed once a year, maximum twice a year. The average
Ca-ion concentration in the brine taken from the point
UI-UVT is shown in ^ig.9» The precipitate content in the
zone II is 2o kgs./m3, in the zone III - lo kgs./m?, in
the zone IV - loo kgs»/m3, and the overflow of fully
clear brine through 19 amounts to 2o^ of the general ca
pacity. The pure brine is free of magnesium, and the
heavy metals content has not been proved by the test for
the control of salt for intravenous solutions.
The reactor of this type cannot be replaced in
the case when in the brines small quantity of impurities
exists, or when there are colloidal solutions or heavy
metals in them. In such cases it is not possible to form
normal flocculent substances and to organize continuous
purification withou extraordinary great reactors, however,
in case of application of reactors with contact bed it is
practically no difference what impurities content exists
in the brine, and it is only with very great concentra
tions that the advantage of these reactors as compared
with clarifiers vanishes, respectively. An example of the
effects provoked by the present precipitate is given in
Pig. lo. It is clear that there is no period of the in
duction of the precipitate , consequently the need for
special reactor besides the clarifier disappears, as well
as the need for constant reduction of calcium concentra-

104
105
tion. 'x'he precipitation rate decreases with the increase
of precipitate concentration, so that the operationg
conditions have to be selected in each concrete case. The
calcium content is the determinative factor in the brine
purification for the salt plants, while can be in the
purif ication of the brines in the electrolysis circle
where the impurities content extremely small, the deter- **•
minative factor the ability of these reactors to filter
the brine and retain the impurities.
The main reactor of the installation III (Fig.
4) is the reactor for the removal of sulphate ion. The
basic problem lies in the extraordinary ability of the
gypsum to form supersaturated solutions. The gypsum
crystallizes at the saturations greater than 1.4. accor
ding vOLMER, forming spontaneously crystal nucleus there
fore in this period it is not possible to regulate the
crystallization. At the supersaturations below 1.4, the
gypsum crystallizes according the dislocation system and
consequently the regulation is possible. The regulation
is performed by adding crystals of gypsum into the solu
tion from which the gypsum is being crystallized. It is
clear that in case of the brine purification the gypsum
solubility amounts to about 6 kgs./m*, therefore only
2-3 kgs. per xaP can be crystallized. The balance of about
5o kgs./m* is crystallized by spontaneous formation of
crystal nucleus, which represents the danger for the
elements of reactor which offer the opportunity to the
gypsum to initiate the crystals on their surfaces, and
what is actually done in such a way which makes this
method very often unacceptable. To the crystallization
are specially subjected steel, Al, nickel, Honel, etc.,
while Ti, Cr-Ni steel, Hastelloy and different plastics
are less subjected. The solution must be sought for in
the design of the reactor in accordance with Fig. 11.
The solution of sulphate and CaCl2 is introduced at B and
P over plastic, elastic, vibrating pipes. They direct the
solutions in such a way that the reaction and the crystal
lization according VOLMKH take place in the centre of
reactor, remoted from the walls. The reactor is packed
with the crystals of gypsum which protect the walls
against the crustallization of residual gypsum which
crystallizes considerably slowlier.
Heavy metals are freequent companions of the
brines, 'x'hey originate fi>em the salt waste, from the
corrosion of construction materials, from auxiliary raw
material, etc. :±'he removal of heavy metals from the brine
and the removal of mercury from waste waters will be

106
illustrated in the following example. In the process
which has been realized, three such systems have been
developed} one for the purification of CaCl2 of chromate
coming from the lime, the second for the purification of
the brine of H2t1 and of heavy metals, and one system for
the purification of waste waters of mercury, chromate,
hypochlorite, etc. i'he processes are based on known and
used equations, only that the effects in the reactors
with contact bed are considerably better. The basic
problem with heavy metals is the formation of coEpidal
solutions, of complex compounds and of compounds which
are well soluble.
In Fig. 12 is shown the reactor for the removal
of mercury and chromate from waste water. The solution
is fed into conical mixing reactor where it is acidified
to pH 4. Here tta2S is added to the solution. The chroma-
tes are reduced to Cr3+, and the mercury produces collo
idal slurry HgS. Through the activity of hypochlorite
some elementary sulphur is extracted which binds elemen
tary dispersed mercury. The low pH prevents the formation
of complex mercury sulphide, the ^formation of which
practically degrades this method. The next step is the
addition of ferrous (ferric) sulphate which does not
precipitate yet in acid surroundings, in a quantity which
is slightly greater then the quantity of additional
sulphide (2o# more). In the reactor NaOH is added to the
solution and pH increased to lo. The chrome is precipi
tated in the form of colloidal Cr5+-hydroxide, while the
iron ions block sulphide ions and prevent them to produce
complex sulphides with the mercury. Excess iron is preci
pitated as hydroxide. All above said is in accordance
with the basic thermodynamical values, but the kinetics
of the process is such that in microelements of the
system the compounds are formed for which no conditions
exist if the average conditions in the system are consi
dered. Thus the complex mercury sulphide is produced too,
the solution of chrome hydroxide in KaOH occurs, etc. The
experiments show that in unsuitably designed processes
from the engineering point of view 1-2 ppm of mercury
or chrome can easily penetrate v^iich is some hundred
times more than the permitted concentrations /6/.
The solution to the problem is the formation
of filter through which the solution is filtered , while
the necessary ion exchange or other reactions are going
to be performed between the filter particles and the
solution. This has been done in the illustrated reactor,
rhe basis for the formation of active particle is

107
 CaCOj, and the active material is Hg(0II)2 and FeCCH)-*,
while the binding material is Iig(OH)p and polyacryla-"^
mide /7»8/. The essential thing is the formation of
maximum dense bed. , with the greatest surface area in the
volume unit. This can be achieved by maintaining the
ratio Ca/Mg as in Fig. 13. a. The temperature increase is
favourable for the densification of the bed (Fig. 13. b.).
The addition of polyacrylamide considerably increases the
density of the bed (Fig. 13. c). Around GaCOj particles,
Mg(CH)? is trapped which binds individual particles into
flocculent substances. llig(0H)2 binds the particles of
iron hydroxide, while polyacrylamide stronger binds the
flocculent substances. In this way the active bed is
formed which fills the reactor to the height of overflow
pipe. The reaction scheme between the solution and the
active bed is shown in Fig. 14.
I. The dissolved GaCoj crystallizes on CaCo,
crystals. 5
II. Sulphide ion binds itself to Fe(OH)p partic
le by the reaction Fe(0H)2+S2~=FeS+2 OH".
III. Colloidal particle is apsorbed on mg(OH)p.
IV. Complex ion of mercury sulphide is destroyed
by the equation (HgS)2-+Fe(0H)2=FeS+HgS+20H~.
V. Hg(OH)2 absorbes OH-ions from the solution
and decreases pH which causes the destroying
of CrOp which is as Cr(OH)x absorbed in
Mg(OH)|.
The laboratory and industrial tests which have
been done, show that the filtration is complete. In the
mentioned test there is no heavy metals, and the test for
mercury with dithizon is negative.

108
02 Oi 08 10 0 20 X 10 50 10 BO
Cd* g/l rc mg/1
a b
Fig. 13. Some of the properties of floccule Mg(0H)2
+CaC03 from the brine :3oo gr. /litre NaCl;
Ca-0.8 gr. /litre ;Mg-0.2 gr. /litre
a. The influence of ratio Ca/Mg; b. Influence
of temperature; c. Addition of polyacryla-
mide without mixing CI) and with mixing(2).

at s^T- [hssJ 10j Cr02-

i//• — . tv—»- 1 v -
— HON FILTERED —
Fig.l4.Proces in con
tact bed.
1. CaCC'5 crystals;
2. KgC^n)2;3-I,,e(OH^
particle ;4. Binding
over polyacrylami-
de ;5. Colloidal
particle.
Pig. 12. Reactor with con-
tact bed for the
removal of Hg2+ i
Cr02"4.
- I...V and UI..UV,as in Pig. 8. - A. -Waste water;
3 . -HC1 ; C . -Ha2& ; D.-^eSCvj.; S.-IIaOH; F.-Polyacrulami-
de; G.-Air bubbles; H.-Pure water; I.-Sluryy

109
SUMMARY:
The procedure of the use of brine containing
sulphates in electrolysis in order to obtain chlorine is
presented. It has been established that the waste CaClp
from the production of soda can be used as agent for the
precipitation of SO^-ion. The preferred way is to extract
NaCl by means of crystallization from the brine and to
feed it into electrolysis. The technics of reactors with
contact bed providing: more efficient gypsum crystalli
zation, higher purity of the brine, removal of colloidal
slurries of heavy metals, etc., has been broadly used.
The conditions for the removal of individual materials,
such as: Ca-ion, Mg-ion, H2S, heavy metals, mercury, and
the like have been defined. The processes have been tested
in industrial-scale installation and good results have
been obtained.
LITERATURE
1. S.PRIBI6EVI6 at all: "Hemijska industrija" ,
Beograd, ll,5o3 U97o)i 2,63 (1?71>* 4,153 (197D ; 5,2ol
(197D; 1,25 (1973). 2. S.PRIBICEVIG: "Optimalna tehno-
loska sema za dobijanje NaCl iz slanih voda sulfatnog
tipa", Institut - Tuzla, 1964. 3. S.PRIBICEVTC. at all:
"Materijali I. Kongresa hemijskog in^enjerstva" , Beograd,
3o7 and 311 (197o). 4. FURMAN A.A at all: "Prigotovlje-
nije i ocistka rassola" , Nauka, Moskva, 1968. 5. aURGAJEV
E.P. : "Metodiceskie ukazanija po konstruirovani ju osvet-
liteljej s vzvesenim slojem" , Vodokanalprojekt, Moskva,
1952.. 6. uOVAK B. : Nota FSL, Lukavac, i960. 7. S. PRIBI-
6EVI6: Chim.Soc.etim. , Beograd, 35.369 (197o)^ 35,363
(197o); 35,517 (197o). 8. S.PRIBI6EVIC: Disertacija,
^eograd, 197o.

110
 INFLUENCE OF STRONTIUM ON MERCURY BUTTER FORMATION
J. P. Guptill and C. J. Kaminski
Allied Chemical Corporation, Syracuse, New York 13209

ABSTRACT
Mercury butter, or thick amalgam as it is also
called, is a semisolid material formed in the
electro lyzer section of mercury cells. It
consists primarily of mercury. The other
principal components are finely divided particles
of iron, graphite, where graphite anodes are
used, and sometimes nickel. The formation and
stability of mercury butter is generally
attributed to the iron and nickel. It has now
been found that strontium present in the cell
feed brine at concentrations on the order of
1 mg/kg can also contribute to mercury butter
formation. This has been verified by the com
parison of the mercury butter formation rates for
two mercury cell plants and the addition of
strontium to the feed brine of a test cell at the
plant experiencing the lower mercury butter
formation rate. By reducing the strontium
content of cell feed brine from 1 to 0.1 mg/kg,
the mercury butter formation rate should be
reduced to about one-third of the rate observed
at 1 mg/kg strontium. Two methods of accomplish
ing this have been found. Strontium may be
removed from the cell feed brine with the Dowex
A-l chelating ion-exchange resin or may be
prevented from entering the feed brine by the
addition of caustic soda to the brine evaporators
used to produce crystalline salt for resaturation
of the feed brine.

Mercury butter, or thick amalgam as it is also

known, is a semisolid material formed in the electrolyzer
section of mercury cells. Table I shows the typical
composition that one might expect:

111
 Table I
Typical Composition of Mercury Butter
Concentration
Component (%)
Hg 95
Fe 0.5—2
Graphite 1—3
(Ni) (0.1—0.2)
Ca, Mg, Sr, Al,
Ni, Cr, V, Ti, Traces up to
Pb, Co, Mo, Zn, 500 mg/kg
Ba, Sn, As, Cu,
Mn
The mercury content is about 95%, the iron content
is 0.5 to 2% and the graphite content 1 to 3% where
graphite anodes are used. Nickel may also be present in
appreciable quantities where nickel is a significant
impurity in cell feed brine. These major impurities are
present as finely divided particles. The remaining
impurities are considered of minor importance and will
vary considerably depending on the impurity content of the
feed brine and the types of impurities present.
The formation of mercury butter is undesirable for
several reasons. Because of its stability and consistency
it may deposit within the cell, hampering the free flow of
mercury and decreasing operating efficiency. This can
also contribute to the formation of hydrogen within the
electrolyzer which decreases the amount of chlorine that
can be safely recovered from the cell gas. In the most
severe cases, deposits can cause electrical short circuit
ing of the cell which in turn causes excessive wear of
graphite anodes and can destroy the coating and damage the
structure of metal anodes.
Because of the problems created by mercury butter
formation, the butter must be removed periodically and the
mercury recovered by washing and/or distillation. Apart
from the economic penalty incurred due to mercury losses
and manpower consumed in the operation, hygiene and
pollution problems are also created. The opportunity for
worker exposure and airborne emissions may be increased,
and an additional burden may be added to effluent purifi
cation systems.

112

-
 The fundamental cause of mercury butter formation
is not well understood. The best explanation has been put
forth by DeNora^D. It was once thought that the alkaline
earth metals, particularly calcium and magnesium contained
in the cell feed brine were responsible. However, modern
brine treatment systems are capable of reducing calcium to
less than 10 ppm and magnesium to less than 1 ppm. At
these concentrations they have only a minor effect if any.
Today iron and, in some instances, nickel are regarded as
the main contributors to butter formation.
The stability of mercury butter is explained by
the interaction of two factors &) . The first is the
extremely fine dispersion of iron particles which may have
diameters on the order of 1 fim. Secondly, while pure
mercury will not wet iron, sodium amalgam, even with a
small amount of sodium in it, wets iron very well. Follow
ing Gibb's rule (2) , the surface active agent, sodium,
concentrates at the interface between the iron particles
and the amalgam, minimizing the energy of the system and
producing a heterogeneous system more stable than an
amalgam containing only sodium and mercury.
One of Allied Chemical's mercury cell plants has
historically experienced a higher rate of mercury butter
formation than another similar plant. For convenience in
the later discussion, the plant with the higher butter
formation rate is designated plant A and the plant with
the lower rate is designated plant B. The respective
rates of mercury butter formation are presented in
Table II:
Table II
Mercury Butter Formation Rate

Plant (lb. /NT Cl2)

A 2.33
B 0.74

Plant A has a butter formation of 2.33 lb. /NT Cl2

(pounds per net ton of chlorine produced) and the rate at
plant B is 0.74 lb. /NT Cl2 . Thus, plant A is producing
butter at a rate three times that of plant B.

113
 As a first step towards identifying the reason for
this large difference in formation rates, an emission
spectrographic analyses of butter formed at the two plants
were obtained and are shown in Table III.
Table III
Metallic Impurities in Mercury Butter
Expressed in mg/kg

Plant A B
Metal
Fe 5000 7000
Ni 80 1500
Sr 400 <100
Ca <50 <50
Mg <10 <50
Al <30 <50
Cu 100 25
Mn <10 30
Cr <15 35
V <15 75
Ti <20 <20
Pb 20 <40
Co <10 7
MO <10 20
Zn <30 700

While only two examples of analyses might not

indicate this, our experience with many analyses leads us
to the conclusion that the butter formed at plant A is
about the same as plant B. Iron is present in the same
order of magnitude; being 5,000 and 7,000 mg/kg
respectively. Nickel is higher at 1500 mg/kg in the
plant B butter. Only in the contents of strontium, at
400 mg/kg, and copper, at 100 mg/kg, is plant A worse off
than plant B. High concentrations of copper had been
observed in mercury butter before and this did not appear
to be a cause for concern. However, the high concen
tration of strontium did appear to be quite unusual at
400 mg/kg in the butter formed at plant A and could only
have come from the feed brine. Table IV shows analyses of
feed brine from the two plants.

114
 Table IV
Metallic Impurities in Feed Brine
Expressed in mg/kg

Plant A B
Metal
Fe 0.1 <0.1
Ni 0.01 0.03
Sr 1.2 <0.1 ND*
Ca 4.3 4.2
Mg 0.6 0.3
Al 0.5 0.4
Cu 0.01 0.02
Mn 0.0005 0.002
Cr 0.002 0.002
V 0.004 0.008
Ti 0.005 0.002
Pb 0.009 0.04
Co <0.0008 ND* <0.001 ND*
MO 0.0003 0.003
Zr <0.008 ND* <0.01 ND*
Zn 0.03 0.2
Ag 0.0004 0.001
i*Not Detectable
While the strontium content of the feed brine of
plant A is only 1.2 mg/kg, at plant B the strontium
content is less than 0.1 mg/kg and is not detectable.
The literature contains no specific reference to
strontium as a cause of mercury butter formation, nor had
we any practical experience that would indicate that it
is. However, because of the apparent correlation between
the butter formation rate and the respective concen
trations of strontium in the butter and feed brine, it was
decided to determine if strontium was indeed a causative
agent in the formation of mercury butter. To do this,
strontium chloride was introduced into the feed brine of a
cell at plant B which was experiencing the lower mercury
butter formation rate. The strontium chloride solution
was fed at a rate sufficient to establish a strontium
content in the feed brine of 1.0 to 1.5 mg/kg.
The mercury butter formation rate in the test cell
began to increase immediately after the test began; form
ing essentially at a rate proportional to the strontium

115
content of the feed brine. In Figure 1 the amount of
butter removed from the cell over or under pre-test
averages is plotted versus days before, during and after
the test. The test began on day 0 and was terminated on
day 9. The circles tied together with dotted lines
indicate the amount of butter removed from the test cell.
The other data plotted in Figure 1 are the amounts of
mercury removed from the other cells in the circuit. These
points are indicated by the squares tied together by solid
lines . The increase in the mercury butter formation rate
in these other cells is explained by the increase in the
strontium content of the feed brine circuit for the entire
plant. This occurred because the spent brine from the test
cell was discharged, along with spent brine from all the
other cells, into a common header. After resaturation with
pure crystalline salt, this brine was recirculated to all
of the cells and the strontium content eventually averaged
0.5 mg/kg in the feed brine.
Further describing the data presented in Figure 1,
the normal practice in plant B is to remove mercury butter
from each cell at 3 to 4 day intervals. The average
amount of butter removed from the test cell was computed
from data obtained during a one and one-half month period
preceding the test. The average for the test cell was
7 lb. butter/removal (pounds of mercury butter per
removal) on each instance when it was removed. The
influence of strontium on the formation of mercury butter
is quite evident. During the course of the test, mercury
butter was removed from the test cell on three occasions
as shown in Figure 1, 46 lbs. on day 2, 28 on day 5, and
35 on day 8. Thus, 109 lbs. were removed during the test
while 21 lbs. would have been expected under normal
operating conditions. Similarly, after the strontium
inventory in the brine circuit was established, 1733 pounds
of butter were removed from the other cells while
1022 pounds would have been expected.
The data in Table V represent a summary of the
work on the influence of strontium on mercury butter
formation:

116
 Table V
The Influence of the Strontium Content of
Feed Brine on the Rate of Mercury Butter Formation

Plant Circumstance Sr Butter

(mqAg) (lb /NT CI,)
B Normal operation <0.1 ND* 0.74
Cells other than
B the test cell 0.5 1.17
during test
A Normal operation 1 2.33
Test cell during
B test 1.5 2.96

*Not Detected
The data presented indicate an obvious relationship
between the strontium content of mercury cell feed brine
and the rate of mercury butter formation. When plotted,
the data show that the rate of mercury butter formation is
a linear function of the strontium content of feed brine.
This is shown in Figure 2.
It has been demonstrated that strontium con
tributed to the mercury butter formation rate in mercury
cells and, under the conditions and within the ranges
studied, that the rate is directly proportional to the
strontium content of the feed brine.
The cause of the excessive mercury butter
formation rate at plant A has been identified but the
solution to the problem remains.
Plant A with the high mercury butter formation
rate has a standard carbonate— caustic brine purification
system. Salt is crystallized by evaporation from the
purified brine for resaturation of the brine fed to the
cells. Referring to Table IV which shows that the
strontium content of the cell feed brine only amounts to
about 1.0 mg/kg, it is apparent that strontium removal
must be accomplished by methods other than those commonly
practiced in the purification of brine.

117
 Two effective methods for reducing the strontium
content of feed brine have been developed. These methods
are now under review to determine if they can be
economically applied.
The first is the removal of strontium from brine
by the Dowex A-l chelating ion-exchange resin. With this
resin it is possible to reduce the strontium content to
0.1 mg/kg. By reducing the strontium content of feed
brine from 1 to 0.1 mg/kg, the mercury butter formation
rate should be reduced to about one-third of the rate
observed at 1 mg/kg strontium.
The second method consists of adding caustic soda
to the brine evaporators. This can reduce the strontium
content of the crystallized salt to about 0.5 mg/kg. The
result will be an operating steady state of 0.1 mg/kg
strontium in the resaturated brine fed to the cells and
will have an effect comparable to that of the ion-
exchange treatment.
In conclusion, the cause of the high mercury butter
formation at plant A has been identified. Under the
prevailing operating conditions, and within the ranges
studied, it has been found that strontium contained in the
feed brine is the cause and that the rate of formation is
directly proportional to the strontium concentration.
Two methods have been found which will reduce the
operational steady state concentration of strontium in the
feed brine from about 1 to 0.1 mg/kg, thereby reducing the
butter formation rate to about one-third of the former
value. The first is to treat the brine with the Dowex A-l
chelating ion-exchange resin and the other consists of
adding caustic soda to the brine evaporators. These
methods are undergoing continuing review and evaluation.

118
 Acknowledgement s
The authors wish to express their appreciation for
the guidance provided by A. S. Robertson, under whose
direction the work was carried out, and for the assistance
and cooperation of the management and staff at the two
plants involved in this study.
REFERENCES
1. 0. DeNora, Chemie Inq. Tech., 43(4), 182 (1971).
2. A. J. Rutgers, Physical Chemistry, p. 229, Interscience,
New York (1954T.

—r
' 1 i
.; l<l\1
'+20 _
u
+J0 1
' M
n T Tfi"
'p +10 1 ThQ *
a
n 10 njill
W
&
3 V
Ou
v 6 OTest Cell
S -10
□Other Cells
1 1 1
1 1 1 1
0
+8 +16 1.0 276 3^
Day Mercury Butter
(lb. /NT Cl2)
Pig. 1. Mercury butter Fig. 2. Mercury butter
removed over or under formation as a function
pre-test average. of Sr in feed brine.

119
 A CASE STUDY OF MERCURY LOSSES
IN A MERCURY CELL PLANT
R. E. Ross
FMC of Canada Limited
Industrial Chemical Division
Box 860
Squamish, B.C., Canada VON 3GO

Abstract
ATase study of mercury losses 1n a mercury cell plant
describes the circumstances surrounding discovery in 1970
of unacceptable high mercury levels in effluent entering
the waters of Howe Sound from the FMC of Canada Limited
chlor-alkali plant at Squamish, B.C. Backgrounded against
recent scientific recognition of inorganic mercury's
potential hazards, the study details the technological
difficulties overcome by the company in reducing mercury
losses to an acceptable level. It also touches on the
effect of this highly-sensitive environmental problem on
the company's public and- governmental relationships.

120
Historical Background
The mercury cell has been an experimental and commercial method
of producing chlorine from salt brine since about 1888.
Chlorine itself was first produced as pure chlorine by Swedish
apothecary Carl Wilhelm Scheel in 1774, his discovery resulting from
an investigation of a mineral called brownstone or magnesia. During
this investigation of a solid material, he obtained one of the most
non-metallic and important substances known to man.
During the subsequent 75 years many famous names in chemistry
became associated with chlorine, among them Antoine Lavoisier,
Humphrey Davy, Count Berthollet, Patrick Copeland, and Michael
Faraday.
The first man to come up with a practical way of producing
chlorine in an electrolytic diaphragm cell was Charles Watt of
Kensington, England, in 1851. The first practical cell in the United
States was the work of a Canadian, Ernest A. LeSuer, although the
first patent was issued to a Belgian. Development of the electro
lytic cell was delayed for several years after Watt's success until
more efficient electrical generators were developed.
In a diaphragm cell, the electrolytic reaction products are kept
apart by an asbestos diaphragm. When an electric current 1s applied
to a salt solution within the cell, chlorine Is generated at the
positively charged anode on one side of the diaphragm. The negatively
charged cathode on the other side of the barrier attracts dissolved
sodium ions, producing caustic soda and hydrogen gas.
In a mercury cell, two layers of liquid flow by gravity from one
end of the cell to the other. The lower layer is liquid mercury and
is used as a cathode. Above this is a layer of salt brine in which
are located graphite anodes. During electrolysis, chlorine is re
leased at the anodes, while sodium ions are drawn to the mercury
cathode, where they combine with mercury to form an amalgam. This
amalgam is removed from the cell and reacted with water to make
caustic soda, hydrogen and mercury. The mercury is then recirculated
through the cell .
About 70% of the chlorine production in the United States and
Canada utilizes diaphragm cells. However, since 1968 the ratio of
diaphragm and mercury cells in new plant construction has been
approximately 1-to-l.

FMC's Sguamish Plant

The FMC of Canada Limited plant at Squamish, B.C., started
operations on Christmas Day, 1965. This was FMC's first mercury
cell plant and departed from standard practice by utilizing high

121
pressure rotary chlorine compressor operation for gas handling. The
mercury cell chosen for this plant was the DeNora cell, certainly one
of the top mercury cells in the world. Another unique feature of this
installation was the planned "open air" cell room. This type of
construction 1s practical provided the climate 1s no more severe than
at the British Columbia location.
Steady plant operation was achieved at a rated capacity of 162
co-tons of chlorine and caustic soda (co-tons are equal to tons of
chlorine) and a levelling of mercury consumption at below 0.5 pounds
per ton of chlorine produced. This was in line with average DeNora
mercury cell plants throughout the world. FMC was aware of specific
other plants which operated below this figure, and continued to take
steps to decrease plant consumption. Specific equipment to reduce
this consumption at one point in the hydrogen handling process was
scheduled for installation by mid-1970.
Mercury consumption is synonymous with mercury losses; the use of
mercury in the cells is a designed recycle process. Furthermore, to
date FMC is unaware of any mercury cell chlorine producer that has
completely closed a mercury balance.
A primary objective of plant management from the time a mercury
cell plant became a probability was to ensure healthy working condi
tions for plant employees. Plant procedures include pre-employment
physical examinations, the use of approved safety equipment, frequent
changes of clothing, attention to personal hygiene, and routine
urinalyses. These efforts have resulted in excellent control of
mercury urine levels which have been consistently below Workmen's
Compensation Board standards.
The Squamish plant operates under a permit issued by the
Pollution Control Branch of the Province of British Columbia, which
sets regulations and standards for the discharge of liquid effluent
into a body of water supporting several natural varieties of fish and
animal life.
TABLE 1
The 1965 permit restriction The permit amendment restrictions in
covered: 1970 covered in addition:
1. Quantity of effluent. 1. Total sulfide.
2. Suspended sol Ids in effluent. 2. Hydrogen peroxide.
3. Chlorine in effluent. 3. Mercury.
4. pH of effluent.
5. Construction approval of
sedimentation lagoon.
6. Provision for a second lagoon.
7. Records of process and
monitoring for inspection.
When these restrictions were detailed in the plant's permit in

122
1965 no mention was made of mercury because at that time this material
was known to be of an inorganic form in the plant. It was extremely
insoluble and because of Its high density was assumed to be completely
contained within the lagoon. In 1972 the Pollution Control Branch
also requested a quarterly bio-assay test to determine the 96 hour TLM
for effluent receiving water mixtures.

Organic Mercury
The human response to alkyl mercury exposure has been documented
over the past 100 years. In 1865, two young chemists died from
inhaling the vapours while preparing diethyl mercury. The most recen
tly publicied incidents of mercury poisoning have involved organic
mercury and have not been associated in any way with chlor-alkall
plants. The highly publicized deaths from Minamata disease in Japan
and several instances of human consumption of grain treated for seed
purposes were all due to ingestion of methyl and other alkylmercury
compounds, either directly or through the food chain. The Huckerby
family In New Mexico ate pork which they had raised on treated seed,
and the results were catastrophic. The apparent reason for this is
that the organic mercury compounds are absorbed to the extent of
50-80% of the available mercury while inorganic compounds are absorbed
to the extent of only 2%.
In the early 1960's, research by Swedish scientists on wild birds
demonstrated that they were victims of methylmercuric poisoning traced
to consumption of alkyl mercury-treated seed grain. In 1967, it was
reported that unidentified micro-organisms can methylate inorganic
mercury to organic mercury. This transformation was found to be a
natural phenomenon with both anaerobic and aerobic systems, although
the process is more efficient in the latter. The discovery of this
transformation started investigation to determine mercury levels in
human foods, how mercury Is deposited in foods and the sources of this
contamination. In logical sequence, this resulted in evaluating every
facet of mercury consumption, which obviously included mercury chlor-
alkall plants.
Since the whole concept was a new area of research investigation
there were few basic data and new analytical methods had to be
developed. Previously obtained results required further verification,
limits of accuracy of results had to be established and, most Impor
tant, sampling techniques had to be developed to provide significant
information for later correlations.
Despite the scope of the Minamata disaster in Japan between 1953
and 1960, most investigators failed to acknowledge that the mercury
deposited in Minamata Bay was organic. This was a totally different
problem from the one encountered at Squamish.

123
Sources of Mercury
Mercury Is distributed throughout the environment, and the usual
sources in an industrial country and agricultural country such as
Canada are:
TABLE II
1. Chlor-alkali plants.
2. Industrial processes using mercurial catalysts.
3. SUmicides used primarily in the pulp and paper industry.
4. Seed treatment.
5. Burning of fossil fuels.
6. Natural occurrence from geological formations.
7. Miscellaneous sources - usually disposal sources.
Naturally, each of these sources must be evaluated for a possible
return to the environment, and to the potential uptake into the human
food chain. Since fish is a major source of human food and comparable
data are available from Sweden, this natural resource was felt to be
an excellent measure of the extent of mercury contamination in an area.
A graduate student at the University of Western Ontario, Normal
Fimreite, analyzed fish from Lake St. Clair and determined mercury
levels well above the 0.5 ppm considered safe in Canada (compared to
the 1.0 ppm in Sweden). These results prompted an investigation by the
Department of Fisheries throughout Canada, with the result that fish
in many areas were found to contain levels above 0.5 ppm. This
obviously required urgent remedy.
Of course the coincidence of recent and widespread construction
of mercury cell chlor-alkali plants across Canada brought these major
users of mercury under immediate suspicion. Virtually ignored was the
fact that mercury compounds are used as wood preservatives, paint
ingredients, slimicides in pulp mills, seed treatments, fillings for
teeth and even medicine for serious diseases.

Specific Actions at FMC's Squamish Plant

On April 11, 1970, the Department of Fisheries personnel sampled
the overflow from the plant sedimentation pond and found a mercury
level of 1.2 parts per million prior to its entering the waters of
Howe Sound. This value did not seem extremely high at the time, but
when considered against the fact that the plant effluent has averaged
just 2.5 parts per billion for the past two years, this was a very
high reading indeed.
On April 22, 1970, the Department of Fisheries announced closure
of all sports fishing at the upper end of Howe Sound, prompting a
deluge of inquiries from news media representatives.
The Department of Fisheries started sampling resident fish from
upper Howe Sound 1n the area just off the point of plant effluent

124
discharge for a distance of one mile during the period of April 21-25.
The fish flesh sampled was the dorsal muscle mass for fish and leg meat
for crabs. The results were listed Into five categories in the
following table:
TABLE III
Categories Mercury Concentration No. Samples
Crustaceans 2.91 PPM 4
Bottom- feeding fish 1.51 6
Salmon & trout 0.05 2
Herring & anchovies 0.31 4
Dogfish 1.13 2
These results were well above the safe food limit established by
Canada of 0.5 PPM for three of the five categories and definitely were
limited to resident bottom feeders in the sampled area. There were
many questions concerning the results - were the analyses accurate;
were the samples representative; was the choice of categories signif
icant; and was the closure necessary? Actually, subsequent results
have shown the crustaceans to be the most representative of the
presence of mercury in the Sound and FMC's biological consultants have
recommended that they be used as the indicator species. Samples taken
in the two years following the 1970 fishing closure include over 200
separate analyses and show that crustacean readings have decreased from
an approximate 3 PPM level to an approximate 1 PPM.
There are numerous factors which can influence these results, but
the most apparent factor seems to have been a reduction in material
losses from the plant. The incidence of dredging in this same area for
the deep sea port and clearing adjacent log booming areas of debris has
not been evaluated as a factor In ultimate decontamination of the area
being sampled. Since the April 1970 closure, salmon, trout and herring
have been removed from the restricted list. Crustaceans and resident
bottom- feeding fish are still restricted, although this could be
removed by the end of 1974.
The Minister of Fisheries and his staff visited the plant with
representatives of the Provincial Pollution Control Branch on
April 25, 1970, to observe actual plant conditions and determine FMC's
plans for correcting what was considered a very serious situation.
Obviously, FMC could not know the steps required to correct the prob
lem, since technology was not readily available and the regulatory
agencies would discuss only zero mercury losses at that time. However,
company officials did propose several possibilities for immediate
action, with ultimate mercury loss limits to be defined at a later date.
The cease-and-desist aspect of mercury pollution was in the hands
of the Provincial Government under the regulations of the Pollution
Control Act of 1967. Moving swiftly, the Provincial Government
requested a short-term plan for curbing effluent mercury losses, as
well as long-term plans. These were presented to the Branch on

125
May 11, 1970.
The short-term plan was directed specifically at effluent mercury
losses which were reduced from 20.0 pounds per day to 2.95 pounds per
day by June 1 , 1970.
The long-term plan considered liquid effluent losses, air emission
losses, and solids disposal losses as a whole, to counter the possi
bility of shifting from one point of loss to another without providing
overall improvement. A schedule was set up requiring a reduction of
effluent losses from the June 1 level to 0.45 pounds per day by
January 1, 1971. This was achieved, and the loss level was subsequen
tly decreased to 0.15 pounds per day by February, 1972. Overall losses
including air, effluent and solids, plus product losses, have been
reduced to 3.5 pounds per day or 0.02 pounds per ton of chlorine pro
duced. Additional steps will be required to meet the 2.98 pounds per
day Level A proposed by the Pollution Control Branch, stemming from a
public inquiry in May, 1972.
Cost to the company to date has been approximately $700,000 for
mercury recovery control and $300,000 for chlorine recovery equipment
for air emissions and effluent control. This total program was con
ceived, engineered, constructed and in operation within a period of
ten months.

Mercury Pollution Control

The government's request that FMC provide plans within two weeks
was almost impossible to meet. It should be remembered that technology
to do these tasks was not a shelf item in the industry. A thorough
knowledge of the plant process was essential, plus a return to the
basic chemistry books to see what possibilities existed. Solubility
of elemental mercury in various solutions, vapour pressure of mercury,
vapour pressure of mercury covered with water, insoluble mercury
precipitates were all problems that had to be evaluated. Then too,
key words such as recycle were being used by the regulatory agencies
and the media.
A careful review of the actual process showed potential points of
loss from vapours, solutions and solids. Flows of cooling water streams
were examined to determine volumes and contamination, and many basic
process streams were analyzed to determine normal levels of contam
inants. Levels of production were evaluated, steady operation versus
unsteady operation, etc. Obviously, if contaminated cooling waters
could be recycled, this could protect the environment; and where these
could not be recycled, treatment was required.
The proposed long-range solution was to recycle headbox wash
waters, recycle tailbox wash waters, cool gaseous exhaust streams to
lowest ambient levels, recover mercury values from precipitated salt

126
impurities, and treat effluent process streams for mercury recovery.
One basic problem with the whole plan was that it required a
denial of approved engineering techniques at every university through
out the world. It required going directly from the laboratory to plant
operations without benefit of bench scale or. pilot plant information.
However, the plan as developed was broken down into three segments:
TABLE IV
1. Maximize recycling.
2. Treat waste streams for mercury removal.
3. Mercury recovery.

(1) Maximize recycling

Endbox cooling waters were separted and individual cooling systems
installed to provide optimum process control and product quality. When
a limit determined by experience was reached, the recycle stream con
centration was maintained by bleeding off an adequate volume to balance
the incoming impurities. Individual hydrogen coolers were installed on
each cell decomposer to recover maximum mercury from the stream at that
point, to eliminate later handling of recovered mercury. A separate
cooling system was required for the individual hydrogen coolers because
the normal plant cooling water, sea water, requires sophisticated
construction materials.
The mercury cell inventory procedure required further refinements
to improve this recycle stream. Physical weighing every two months was
considered better than several available tracer techniques. This step
required careful co-ordination of all cell operating procedures and
maintenance techniques used in cell operations.

(2) Treat waste streams for mercury removal

Heat exchangers and Brinks mist eliminators were installed on
gaseous discharges from specific points. In addition, ventilation air
concentrations were reduced to low levels by improved housekeeping,
eliminating vapour contaminated points around process equipment, and
policing all operating procedures.

(3) Mercury recovery

The recovery segment of the plan was the portion that has been
patented under U. S. No. 3,691,037 with applications in Canada and
several other countries throughout the world. The invention recovers
mercury values from precipitates obtained during purification of the
brine feed to the electrolytic cells, as well as from precipitates
obtained by treating effluent streams with sodium sulfide to precipi
tate mercuric sulfide from these streams.
The invention utilizes common chemical process equipment including

127
tanks, pumps, instruments, hoists, mixers, and a rotary vacuum filter
integrated into the normal equipment in a chlor-alkali plant. The
recovery efficiencies obtained from both the effluent stream and brine
sludge treatment stream average well above 99 percent of mercury
values. The advantages of using a solution method of mercury recovery
were obvious when compared to the best-known volatilization methods.
The mercury recovery process as developed is an integrated mercury
control system that includes liquid effluents and solids disposal, and
returns recovered mercury to the brine system, where it is ultimately
recovered in the electrolytic cells themselves. In other words, it
has been recycled.
The cell room basement drains to a network of lined sewer trenches,
which conduct all spills to a single concrete tank equipped with a
cascade of trays to collect any major mercury spills. This concrete
tank provides a retention time ranging from 2 to 10 hours for the
reaction of sodium sulfide and mercury present in the cell room sewer
waters. The resulting slurry is then pumped to a holding tank pro
viding approximately three days storage capacity. From the holding
tank, the slurry is pumped to a rotary vacuum pre-coat filter where
the filter cake is recovered for later mercury treatment. The fil
trate from the filter is discarded to the sewer which is monitored
for mercury at the plant outfall, and results in effluent mercury
losses averaging 0.14 pounds per day.
The filter cake from the effluent treatment is then mixed in a
treatment tank with the brine treatment clarifier underflow and
reacted with sodium hypochlorite to solubilize the mercury present in
the resultant slurry. This mixture is then filtered through the
rotary vacuum pre-coat filter where the filtrate is returned to the
brine loop and the filter cake is prepared for land disposal. The
preparation consists of mixing with an equal weight of sand, moving
it to a landfill site which is sealed against leaching by normal
rainfall. Filter cake losses have been averaging 0.07 pounds of
mercury per day.
The recovery process is quite flexible in that all backlog mer
cury sludges accumulated between April, 1970 and February, 1971 have
been treated and the mercury involved has been recovered in the cells.

Other In fl uences
This case study involves much more than the solution of a
chemical engineering problem. A chemical engineering problem can be
handled within the corporate environment, and it depends upon the
technical skills available, and the managerial talent in planning and
budgeting, and in organization and control. Normally, seeking solu
tion to such a problem may place a professional life on the line, and
it leaves no room for error. But, in case of plant mercury loss at

128
Squamish, the political and public relations factors could well have
scuttled a perfectly valid technological solution.
The public relations problems alone were disturbing. At a time
when all attention should have been devoted to the technological
problems, considerable time and effort were directed to informing and
reassuring the public through the news media. It was important both
in the short and long term to refute erroneous information, assuring
the press and public of FMC's grasp of the situation, and countering
prejudices from pressure groups. Perhaps most difficult was having
to acknowledge that FMC was charting a new and previously uncharted
course. Environmental groups were very active, citing the FMC situ
ation as further proof of industry's careless treatment of the environ
ment. Understandably, in the Squamish region, just about everybody -
singly and in groups - pressed for some real and lasting reassurance
that there was no personal danger.
While engineers and industry devote a major portion of their
time to communication, most of this effort 1s directed toward
engineers, scientists and businessmen. Communication with the general
public is a field for which engineers as a group have shown little
aptitude. An engineer's very familiarity with technical matters
creates severe problems when he tries to explain them to non-technical
people. Experience with the mercury loss problem at Squamish has
convinced FMC management of the importance of expending time and
effort to simplify basic operations, normal problems, and the solutions
for public consumption. It 1s not easy. It requires patience. But
it can help create an environment of public confidence that can be of
inestimable value in countering the latent public hostility and fear
with which the chemical industry lives. The average person's under
standing of what happens in a chemical plant 1s akin to the super
stition and mistrust that was held for the alchemists who were trying
to convert lead into gold in medieval times.

Conclusions
(T) Tn the 200 years since the discovery of chlorine, its overall
importance as an industrial chemical still requires new technology
for its production.
(2) The two basic commercial processes for producing chlorine
are in a continuous state of change, which leads to new and numerous
improved methods of production.
(3) The chemistry involved in standard production processes
must be reviewed and researched to provide optimum material
efficiencies.
(4) The impact of environmental problems should be thoroughly
investigated prior to choosing a plant location, and close control

129
should be maintained continuously over this specific aspect of a
plant's operation.
(5) The solutions to major plant problems at Squamish were
obtained fortuitously at the plant level in a minimum period of time.
(6) Public relations and political contacts provide a total new
area of communication responsibility for the engineer in management.

130
 MERCURY RECOVERY FROM CHLOR-ALKAU PROCESS STREAMS
Richard A. Perry
Georgia-Pacific Corporation
Bell ingham, Washington 98225

Under an EPA Grant, Georgia-Pacific Corporation has undertaken

a project to design, construct and operate a plant to recover mercury
from a mercury-cell Chlor-Alkali Plant's solid and liquid wastes.
Following a literature survey, a one-year research project was begun
to test in lab and pilot scale nearly all known methods of mercury
separation from liquids and solids. Following the lab results a full
sized plant would be built.
Laboratory investigations were conducted with graphite anode
brine sludge using the following processes: ()) hypochlorite and
chlorine oxidation; (2) electrolytic oxidation with brine; (3) roast
ing, and (4) acid digestion followed by roasting. The minimum Hg
levels achieved with each technique in our brine sludge were respect
ively: (l) A2 ppm; (2) 100 ppm; (3) 0.1 ppm, and (k) 0.02 ppm.
Hypochlorite oxidation was also tried with metal anode sludge with
a lower Hg result of 9 ppm. As indicated, the only processes demon
strated in the lab to achieve a final Hg level below 5 ppm involved
roasting.
From the lab tests, the roasting method was selected for further
study on the pilot scale. Batch tests and continuous runs were made
in two types of furnaces, with the multiple hearth furnace producing
lower Hg sludge than the indirectly fired rotary calciner. Tests
were conducted on a 30" diameter, 6 hearth furnace, with 600 lbs. of
sludge. Similar Hg levels observed inlbatch lab tests were found in
the large pilot tests.

The proposed mercury recovery system for sol id wastes incor

porates sludge collection and concentration through a thickener
followed by filtration to 50% solids in a rotary vacuum filter.
This dewatered brine sludge, plus other mercury-containing solids,
is fed into the multiple hearth furnace. The Hg is collected In a
series of water cooled condensers and demisters on the vapor outlet
from the furnace. Our system was designed to handle 7,000 lbs. per
day of dry sludge and other solids.
The water treating portion of the project involved testing
many of the proposed methods of removing dissolved or suspended Hg
from water effluents. The various methods proposed include:
oxidation, reduction, precipitation, absorption, and others. Of the

131
methods tried, the precipitation with sodium sulfide was selected
due to its simplicity and effectiveness. Sulfide treatment reduces
the mercury concentration in our Chlor-Alkali Plant wastes from 1
to 20 ppm down to 7-k0 ppb. From lab and pilot studies it requires
less than two minutes for the sulfide to react with the Hg present.
The process selected requires pH adjustment to the range of 5"9
followed by sulfide addition, diatomaceous earth addition and
immediate filtration on a pressure filter. Sulfide addition can be
governed by ratio control to waste water feed rate or redox control
for excess sulfide.
It appears from the lab and plant tests that pH levels above
10 or below 2 result in excessive mercury loss through the pressure
filter. Continuous body feed is necessary, at first, to keep the
filter from blinding.
The plant construction was begun in May, 1973 and completed in
January, 197A at a cost of $280,000 for the sludge system and
$110,000 for the water treatment system. Detailed data from the
plant start-up is not available at present, but indications are that
the water treatment portion of the project is operating as expected,
with some modifications during start-up.
A more detailed discussion of the operating data and results
is expected for the paper presentation in May, \97k after four
months of plant operation.

132
 CHLORINE PRODUCTION
ECOLOGICAL AND ECONOMICAL ASPECTS
Stefan Payer and Bernd Strasser
Friedrich Uhde GmbH, Dortmund, Germany

Economic and Ecological Aspects of Today's Chlorine and Alkali Production

According to the classic teaching of Industrial Management, two factors

are decisive when planning the realization of an industrial project under
economic aspects.

1. the market situation

= adapting the plant to the market requirements as regards plant

size, product qualities, location, etc.

2. the cost situation

= determining the capital expenditure and operating cost in relation

to the process technology, the price of raw materials and utilities,
plant size, location, etc.

As a result of industrialization, the industries must give ever more

consideration to the environment. The two factors mentioned are no
longer sufficient for project planning. Two further factors have crystallized,
both of which give consideration to ecological aspects:

3. the environmental conditions

= protecting the place of work and the environment against aggravating

influences (dirt, noise, hazardous substances, etc. )

4. the raw materials and utilities situation

= reducing the consumption of raw materials, power and utilities

by better process technology, recycling, waste heat recovery etc.

These two additional ecological factors may well make the decision to
realize a new industrial project considerably more difficult, particularly
because the various factors cannot be covered by conventional methods
alone.

133
This paper is intended as an attempt to illustrate the situation using
chlorine/alkali industries as an example.
For the production of chlorine and alkaline products, two perfected and
commercially proven processes are available:

the mercury electrolysis process and

the diaphragm electrolysis process.

A further development of the diaphragm process using ion exchange

membranes, here called "membrane process", appears to be promising
and should be part of the following comparison.

1. The market situation

.-The typical daily chlorine capacity of new plants is between

500 and 1, 500 tons. Both marketing and transport facilities
today are such that these capacities are perfectly feasible;
in this respect, the USA heads the list while Europe ranks
behind. Because of the further processing requirements, the
market normally demands that the chlorine be as pure as possible,
that the hydrogen contain no mercury and, for transport and
distribution reasons, that the concentration of caustic soda
solution be around 50%.

The presence of hydrogen and oxygen in the chlorine will affect

organic chlorination and other processes. The specification for
caustic soda solution is frequently Rayon grade, particularly
in Europe, where the reason is frequently a certain prejudice
on the part of the consumers.
Fig. 1 illustrates the product qualities that can be obtained
with the three processes mentioned. Purest chlorine and
caustic is obtained in the mercury process. One can expect
a reasonable improvement regarding the salt content of caustic by
using the membrane process. Even diaphragm caustic contains
small amounts of mercury.

2. The cost situation

In performing cost studies, the major factors affecting the

selection of the optimum process technology and, consequently,
the capital expenditure are plant size, location, and the cost
of power, utilities and raw materials.

134
The plant size is dictated by the market independently of
the technology.

The location, on the other hand, is particularly affected by

the cost of power, utilities and raw materials as well as
transport, etc.

Because of the advantages of "well mining", a diaphragm plant

should be located in the vicinity of a salt pit. The combined
steam/electric power requirements must be considered, and
this also applies to membrane technology. As regards salt
quality and salt cost, the location of mercury electrolysis
plants is immaterial. The major factor for selecting the location
of this technology is low power cost.

Fig. 2 illustrates the production cost for a plant with 500 tons
daily chlorine capacity (European conditions, i. e. European
investment cost, high energy cost etc. at an exchange rate
of 1$ = DM 2. 50).

For the mercury electrolysis plant, investment cost includes

a technological mercury emission of approx. 4 grams per ton
Cl2- Because of the high state of development of the mercury
technology, it is not expected that the total production cost
can be improved very much, even though the mercury emission
should be reduced to virtually zero.

For the diaphragm electrolysis plants, the two extremes are

shown, that means "well mining" without caustic purification
and the use of rock salt with caustic purification.

Moreover, "Future" costs are shown, too, because major techno

logical improvements are already available or expected in the
near future, especially by the use of new types of diaphragms.
The membrane electrolysis plant data were taken from literature,
laboratory test results or by making assumptions. Some form of
basis is thus obtained for comparison to show what characteristics
such a process has to achieve when competing with existing processes.

Fig. 2 indicates lowest production cost for today's and "future"

diaphragm process without caustic purification. Production cost
of "future" membrane process could be very attractive if 20%
caustic concentration can be achieved.

135
3. Environmental Conditions

The attempts currently being made the world over to improve

environmental conditions have resulted in the public, and
especially the politicians, taking a great interest in alkaline
chloride electrolysis processes.

Because of the toxic effect of mercury, the emission problems

of a mercury electrolysis plant are considerably more serious
than in the case of diaphragm plants. A major effort was there
fore made in the past to reduce the mercury emission drastically.
The results are broadly summarized in Fig. 3.

The various measures for eliminating mercury from products and

effluents are necessarily coupled with additional capital
expenditure and operating cost. However, in the last 10 years
major technological improvements of the mercury electrolysis
process were introduced. As a result, the overall economics
could be improved during this period in spite of the environmental
pollution control requirements becoming more stringent.

From the technological point of view, a further reduction of the

mercury emission could be possible.

This primarily entails the reduction of the mercury content

in cell-room air. To achieve this, the cell contamination must
be reduced, thus prolonging the periods between opening the
cells for cleaning purposes, which will automatically reduce the
mercury content in the air.

The immediate future will show whether such costly development

work for the mercury process is economically justified in the light
of the improvements expected for the other technologies.

Compared with the mercury problem, the emission of the other

substances from alkaline chloride electrolysis plants is of
secondary importance. The diaphragm process has a certain
emission of NaCl with the alkaline liquor. This is where major
improvements may be expected from the membrane process.
A major ecological problem, on the other hand, is the heat
emitted by electrolysis processes.

Regarding the conditions at the place of work, no major advantages

or disadvantages are offered by the processes being compared.

136
The maintenance effort required for mercury cells is comparable
to the diaphragm handling and the maintenance of the evaporation
units in both the diaphragm and membrane processes.

This means that all efforts will have to concentrate on prolonging

the service life of all electrolysis cells and improving the
evaporation units.
Raw materials and utilities

Raw materials
The raw materials - salt and water - required for the electrolysis
processes, are available in virtually unlimited quantities.

Consequently, problems will not be posed in future by the

raw material availability, but rather in the selection and
transport of the various forms of raw material, such as
rock salt, sea salt, evaporated salt and natural brine.

From this point of view, the diaphragm process is more flexible

than the mercury process since in the former all kinds of raw
material can be utilized without major changes in the technology
and with roughly the same economy.

In the mercury process, however, evaporated salt is preferred

for ecological reasons while economical reasons may dictate
solid salt.

Utilities (energy)

The production of chlorine requires a large amount of energy in

the form of electric power.
Electricity is, today, still predominantly produced by thermal
energy conversion using fossil or nuclear fuels. The Clausius-
Rankine Process is well known in this connection and has been
technically perfected in the course of the last 100 years.
Nevertheless, the degree of energy conversion obtained is still
only about 40% of the primary energy.

An ecological analysis of the energy balance of an electrolysis

plant leads to the conclusion that most of the energy is lost in
the form of heat outside the plant, and that is the one main reason
why the theoretical minimum power consumption of about 1, 700
kWh per ton Cl2 cannot be achieved.

137
From the other point of view, the energy losses in the alkaline
chloride electrolysis plant itself are also quite considerable.

This can best be illustrated by the optimum cell voltages applied

*to plant operation: about 3.8 V for the diaphragm and about
4. 4 V for the mercury process.
On the basis of the theoretical minimum voltage of 2. 3 V, the power
efficiency of an electrolysis plant is therefore only about 50 - 55%.

The two main reasons for the high losses are irreversible
processes that take place on the electrode surfaces and the
ohmic resistance of the electrolyte and of the current conductors.

Major improvements with savings of 0. 5 to 0. 6 V could be

achieved in the mercury process if one could succeed in utilizing
the energy released in amalgam decomposition electro-chemically.
This would justify major additional capital investments,
especially under the aspect of increasing power prices.

In the case of the diaphragm and the membrane processes, the

reduction of the steam consumption is likewise important.
To do this, attempts should be made to utlize as much waste
heat as possible and by aiming at a high cell liquor concentration.
This would appear to be particularly feasible in the membrane
process.

Fig. 4 illustrates the relative energy consumption for the process

alternatives mentioned. It is worth noting that, although the
electric power consumption of the diaphragm and membrane
processes is considerably better (see line 3), the total energy
consumption is lowest for the mercury process (line 7).

However, in spite of that and because of the influence of the DC

power conversion rate, the overall energy consumption including
the losses in a thermal power station (with an efficiency of about
40%), is about the same for all improved processes (line 9). The
last two lines of Fig. 4 illustrate the influence of the energy yield
obtained in the power station. For this purpose, the efficiency
assumed was not 40% but 90%, such as might be achieved in a
hydro-electric power station. In this case the mercury process
would again head an ecological comparison with a total energy
utilisation efficiency of more than 44% (line 13) or, if in addition
the energy released in the decomposition of amalgam is utilized,
even 54% (line 15).

138
To sum up the description of the 4 major factors of production
planning, fig. 5 shows the qualitative comparison of the technology
of caustic-chlorine production in a 500 tpd plant under economic
and ecological aspects.

The mercury process still offers the most favourable product

qualities, whereas with the diaphragm process one can achieve
lowest production cost. Therefore, from the economical point of
view, the diaphragm process shows a very sound basis, particularly
as the market for salt-bearing caustic should be broad enough.

Regarding ecology, the diaphragm process appears to be quite

neutral, whereas the mercury process has the burden of Hg pollution,
although with an objective approach, this drawback has meanwhile
been technologically reduced to negligible limits.

The total energy consumption must and can be further improved for
the diaphragm process, whereas the mercury process is already
highly developed.

The membrane process, when perfected, is likely to produce

well-balanced results from both the economic and ecological point
of view.

One can hope that this process will find applications especially
in North America, if an additional demand for high quality caustic
is given. In Europe, the big producers should now be ready to
use the economically improved diaphragm technology, at least
to the extent by which internal consumption of diaphragm caustic
will allow, especially in combination with the existing mercury
plants.

139
 PRODUCT COMPOSITION

technology mercury diaphragm membrane

without /with
1974 caustic 1974/future
purifica

1 chlorine gas, dry

ci2 99-99.4 97 - 97.5 97 - 97.5 vol%

o2 0. 1 1 - 2 1 - 2 ii

H2 0. 1-0. 4 0.1 - 0.4 0. 1 - 0.4 ii

C02 0.2-0. 5 0. 2 0. 2 ii

N2 0.2 0.2 0.2 ii

2 caustic
NaOH 50 50 50 50 50 Weight%

NaCl 30 10000 1000 3000 500 ppm

Na2C02 200 1200 1200 1.200 1200 ii

NaC102 1 800 5 800 800 ii

Na2S04 10 100 100 100 100 ii

Hg 0. 1 0.002 0.002 0.002 0. 002 ii

3 hydrogen gas, dry

H2 99.9 99.8 - 99.9 99.8 - 99.9 Vol %

Hg 0. 01 - - weight
ppm

Figure 1

140
 f.teee 0 n 7. 0 00 07
7 10% 0
membea7 eaestie 0 06 z
tCl1/da0
plant
n1
size: 8 11n 113
1070 0
6 0 0 n7
0% 0 0 16 0

epeei
aestie fet.e 116 10
0 n1 0 0
n with
Salt fieation 0 n 0 0 0
1070 0 0 101 11,
0 0m 0 n 16 n6 0
0 0
bei7,
witho.t ep.eif
ph
dia
0 a.stie 16 01 01 1
fet.ee 7 11
0 0
0 1 0 0 0 Fig.re
1
P($/tCl2>
0eeost
odm.eptai0oinson ieation
1070 17
, 01 00 07
0 0
1 0 0 11 0

m0e e0 0 , 01 116 117

1070 0
1 n - 1
0 n

etotal
oeostmpaeable
ehemieals seb
[,$/t
NaCl total total
s.b
[salt
lbei7
7$/tNaCl],
wat0en0g0;e. [1,1
d. ]
kwh
eet.e ent 1%
e0=l
(%
eompa0ison
maeawt0ials
[7
$/t]
steam maintenane eapital
eost
te helog0-

wat0

I. 1. 0. 7. n. 6.
 REDUCTION OF MERCURY EMISSION

technology Hg-emiasion

obsolete 500-30 g/t Cl2

improved 30-10.

modern 10-3

future 3-0

Figure 3

142
 Energy consumption

No 1 2 3 6 1 7
technology- mercury diaphragm membrane
date 1974 1974 future 1974 future

1 opt. cell voltage V 4.4 3.8 3.5 4. 1 3. 8

2 current efficiency % 96 96 96 95 96
3 d. c. power consumption 3450 3000 2750 3250 3000
kwh/tCl2
4 conversion rate (crt) % 49. 1 56.8 61.7 52. 1 56.8
(theoretical basis 1700
kwh/tCl2)
5 opt. steam consumption
t/tci2 - 3. 0 2.5 4. 0 1.5
6 transferred from 5. into
kwh/tCl2 - 2100 1750 2800 1100
(conversion rate 100%)

total energy consumption

7 electrolysis kwh/tCl2 3450 5100 4500 6050 4100
8 conversion rate (crt) % 49. 1 33.4 37. 8 28. 1 41. 2

9 electrolysis + power -
kwh/tCl2
station (c. r. t. 40%) 8650 9600 8650 11000 8650
10 conversion rate (total)% 19. 7 17. 7 19. 7 15.5 19.7

11 comparison % 100 90 100 80 100 1

12 elektrolysis + power -
station (c. r. 90%) kwh/
tci2 3850 5450 4800 6400 4400
13 conversion rate (total) % 44.2 31. 2 35. 4 26. 5 38. 6
14 utilising amalgam
decomposition kwh/
tci2 3150 - - - -
15 conversion rate (total)% 54. 0

Figure 4

143
QCOF
U0HE
0OEMLCPIH0NROI0LSOVGNEY f.te e
7
0 +
E0ND
C0OSNLPOMEGIC0SL. jea7 10% tie3 + + +
CPUNDER
OF0HROLUDSURC0INCOEN
mem' ea. 1070 0 0 -
6 10% + -
feteee
peei-
le
n 0 0 - 0 -
/ith
>n
salt,v caest fieati
0agm 1070
7 0 0 - 0 -
ph withoet p.eif-
dia : f.t.0e
0 0 1
+ Figere
0
0 +
ea.stic ieatior
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 AUTOMATION OF MERCURY CELL ANODE ADJUSTMENT
R. W. Ralston
01 in Corporation
Charleston, Tennessee 37310
This presentation covers the development of a system for the
automatic adjustment of anodes in the Olin E-510 and E-812 mercury
cells .
The following areas will be covered:
A. A Description of Olin Cells.
B. The History of the Development.
C. System Features.
D. Anode Adjustment Techniques.
A. Description of Olin Mercury Cells
Olin now operates three types of mercury cells. These are:
1. The E-8 cell, which is an older and smaller cell (6.6 meter).
2. The E-510 cell (15 sq. meters). Anode size is about 9" wide
x 4' long. Anodes are grouped across the cell for a 45" x
4' area. There are 10 groups in the cell. Each group is
supported from four points that are raised and lowered as a
group by a chain drive system.
3. The E-812 cell (28.8 sq. meters). This cell is similar to
the E-510. The same anodes are used and are grouped 8 per
group across the cell with 12 groups in the cell. All anodes
in a group are moved together.
The automatic anode adjustment system is fully operational in
E-510 and E-812 cell rooms.
B. History of the Development
The development of an automatic anode adjustment system started
about eight years ago with the installation of drive motors on one
E-510 cell. A remote adjustment station with indicating meters for
current in bus bar was added. A detector for high current was
developed (reed switch type) and connected to automatically raise
anodes in case of high current.
This type system was installed on one cell and test work using
a mini-computer to automate adjustment was started. Feasibility
was proven on two cells, and about three years ago an automatic
adjustment system was installed in one cell room.
Three cell rooms have now been automated using this system with
a resulting voltage reduction of .4 to .6 volts per cell.

145
c. System Features
The major system features are:
1. Automatic anode adjustment with a back-up system for remote
manual adjustment.
2. An independent system to automatically detect high current
and raise anodes.
3. Control room console with meters that can be switched to
display current and voltage readings anywhere in the cell
room.
D. Anode Adjustment Techniques
Anode adjustment is based on both current to anodes and voltage
coefficient .
Current to the cell is set by rectifiers that supply all cells
with equal current. In one cell, current can be shifted to or from
any group of anodes by raising or lowering it individually.
The computer performs several functions. Priorities are:
(1) a program that scans all cells about once per minute and raises
anodes if any current exceeds a certain fraction of the total;
(2) a thorough check of each cell once per hour and adjustment if
required; (3) type out of information as requested by operators.
No single criteria has satisfactorily shown anode position.
When an anode is lowered, several tests are used to determine if the
anode is too low. One factor is the following.
The current to an anode group is sensitive to approach to the
mercury because brine resistance is directly related to the anode-
cathode gap. By adjusting a small fraction of a cell, the total
voltage tends to be constant and as the gap for the adjusted anodes
approaches zero, the current increases rapidly. The attached plot
shows the expected change in current as the gap approaches zero.
From this, it can be seen that if the anode is moved toward the
cathode at a constant rate, the current increase will accelerate and
this acceleration will signal the approach of zero gap.
This technique and several others are used to position anodes
and to insure that anodes are not damaged by short circuiting or
incipient short circuiting. These will be discussed at the meeting.

146
 Chlorine Cells of the Future

Vittorio de Nora
Milano - Italy

Summary

Half a century of developments in chlorine cells have pushed

chlorine production by some hundred folds. The next fifty years
will bring new cell technology. Chlorine cells of the future will
be substantially different from present design. An imaginative
review on a basis of today's knowledge anticipates expected
improvements, possible achievements, and hopeful break
throughs.
New materials of construction will be used for mercury and
diaphragm cells. Dimensionally stable anodes will facilitate
construction of cells having higher capacities and operating
at higher current densities.
Mercury cells will take advantage particularly of new decomposer
design and possible bipolar arrangement.
The greatest advance in diaphragm cells will come with impro
vements in the diaphragm and with the use of permionic mem
branes which will permit production of caustic of higher concen
tration and free of chloride.

147
Chlorine Production in the World

World production of chlorine will total almost 24 million

tons in 1974. If production continues to increase about 7% a
year, as it has in recent years, the output of chlorine should
reach about 35 million tons a year by 1980, corresponding to
100 thousand tons per day. If this trend then continues, as it
seems likely to do at the very least, production will double
to 70 million tons by 1990 and double again to 140 million tons
by the year 2000.
Plants in North America make about half of the chlorine
produced worldwide today, while those elsewhere account for
the balance.
Until roughly the middle of this century, manufacturers
in the U.S. used diaphragm cells mostly, while those in
Europe and Japan used mercury cells. The reason for using
two different processes was due to the fact that Americans
had available sodium chloride from brine wells and low cost
steam, conditions that favour diaphragm cells particularly for
large plants. Mercury cells, on the other side require little
steam, use solid salt as raw material, and produce pure and
concentrated caustic. Demand for pure caustic plus the lower
cost to manufacture chlorine with mercury cells have favoured
the growing use of mercury cells by manufacturers even in the
U.S. Today as a result, about one third of the chlorine made
in the U.S. comes from mercury cells, while in Europe more
than two thirds come from mercury cells. The disparity is
even greater in Japan, where mercury cells have accounted
for some 95% of capacity, at least up to very recent times.
It might be interesting to examine what factors will
affect the future of the chlorine industry and what technical
improvements are likely to be made in the next several years.
Pollution Problems
Prospective chlorine manufacturers today have to make
their choice of process not only on the basis of plant cost
and, in the last analysis, of manufacturing costs, but have

148
to face a complication due to pollution of the environment.
In a number of countries authorities and manufacturers have
become much more conscious of and in many cases concerned
about pollution and possible threats of pollution from industrial
activities. Mercury may be a severe health hazard if it is
not used properly and controlled well. All of the evidence has
not been collected about the exact role of the mercury cell
process in putting mercury into the environment or about what
are the hazards of the mercury in question and how they can
be controlled. Nevertheless, concern has arisen about possible
excessive contamination of the environment, and stricter
control regulations have been imposed.
In the United States, for example, operators of mercury
cell plants have cut mercury losses by 95% or more and no
plant should emit more than 5 pounds of mercury to the air
per day to meet a regulation of the U.S. Environmental
Protection Agency. The Japanese, meantime, have reacted
even more drastically and, because of possible hazards from
mercury, the Japanese government is forcing manufacturers
to shift rapidly to diaphragm cells and to have at least 65%
of the industry based on diaphragm cells by the end of 1975.
Prospects for the mercury cell process thus on the
surface may appear somewhat gloomy, but the mercury cell
process is by no means destined to disappear. In fact, it is
now possible to reduce mercury losses to a few hundred grams
a day even from large plants and the mercury process might
have replaced even larger amounts of the total production of
chlorine in the world. Manufacturers in some countries have
continued to expand mercury cell capacity, and mercury cell
plants should continue to provide a good part of total chlorine
production. In addition, perhaps government agencies,
industrial organizations, and concerned citizens will come to
understand that hazards of the mercury cell process are no
greater than those of the diaphragm cell process, from which
asbestos from the diaphragms may similarly threaten to-day
the operators. Thus, choice between the two processes may
not be affected by ecological concerns as much as might at
first be expected.

149
Recent Trends in Cell Design
As short a time as 30 years ago, in the mid forties,
the typical chlorine cell, whether mercury or diaphragm,
operated at only a few thousand amperes and produced a few
hundred pounds of chlorine a day. As a result, plants needed
hundreds of cells to reach a daily capacity of only 100 tons
of chlorine. The tremendous increases for chlorine demanded
by such industries as pulp and paper, fibers, textiles,
agriculture products, plastics resins, solvents and the many
others have stimulated the chlor-alkali industry to double
production every ten years. To meet the growing demand,
manufacturers have turned increasingly to plants with larger
and larger capacities, changing from plants making less than
100 tons a day to ones making hundreds of tons of chlorine
a day. In fact, some plants today have capacities of more
than 1,000 tons of chlorine a day.
Such large plants have been made practical only by
designing and building cells that operate with much larger
currents. Whereas diaphragm cells once operated with a few
thousand amps, for example, they now operate with more than
100,000 amps. Mercury cells, meantime, now operate' with
currents three to four times those of diaphragm cells, and
one plant built by Oronzio de Nora in Japan has cells with
capacities of half a million amps.
Building both diaphragm and mercury cells with such
large capacities has been made possible in turn by the
invention of silicon rectifiers and dimensionally stable anodes.
The introduction of D.S.A.(R) has been the greatest single
contribution to the development of modern chlorine cells.
These anodes consist of a titanium substrate with a conductive
coating containing oxides of ruthenium or other platinum group
metals. Their geometrical configuration permits cells to be
operated at the higher current densities called for by the
very large amperages yet keep overall cell size and cell
voltage at a minimum.
Also important to the development of mercury cells has
been the development of the vertical decomposer. With all

150
these advances, mercury cells can be considered as highly
perfected, but it is to be expected that they would be improved
even further.
Mercury cells operating at currents exceeding 500, 000
amps can be combined in circuits of 100 units and still
maintain cell room voltage well below the 500 volts which is
the accepted voltage for safe operations. Moreover, such large
cells are connected to their circuit in such a way that individual
ones may be disconnected without interrupting production in
the circuit as a whole. Individual cells may then undergo
maintenance for cleaning, making small repairs and eventually
replacing the dimensionally stable anodes when their coatings
become less active.
Also diaphragm cells have been developed to a high
degree. Plants using both monopolar and bipolar cells are
under construction. Of course, any producer wanting large
capacities must use more than one circuit if he is to keep
the voltage of each below the safe level of 500 volts.
Again, dimensionally stable anodes have played the greatest
role in diaphragm cell improvements, and producers can
expect their better cells to operate smoothly at the high
amperages utilizing brine feed of high impurity.
The choice of the cell for future plants will be made on the
basis of changes and improvements to be expected in the cell
of the future.
Prospective Improvements in the Mercury Cell Process
It does not appear likely that manufacturers will build
mercury cells with capacities much greater than the largest
used today. There is no great problem however in designing
cells to operate at one million or more amps, but such cells
could be built only by increasing cell dimensions.
Otherwise current densities should be higher than the
12,000 to 15,000 amps per square meter used today, and
higher current densities are neither technically nor
economically advantageous. Voltage drop across the cell would
be too high, even with diamensionally stable anodes, which

151
while operating at practically theoretical voltage would not
avoid the bubble effect. With electricity becoming increasingly
expensive, one cannot expect to operate cells economically
at current densities much higher than those used today.
Improvements can be expected in the design of the
decomposer. Up to the present, graphite has served as the
catalyst to decompose the amalgam. New types of graphite or
treated graphite have now been used to increase the reactivity
or to reduce the overvoltage required for hydrogen evolution.
Such changes have allowed engineers to design smaller
decomposers and also to reduce the mercury inventory.
In addition, these changes have allowed caustic to be made at
concentration above the standard 50%. Other materials having
even lower overvoltages for hydrogen are likely to be found
for use as catalytic packing or electrodes for decomposers.
If they are, the result could be even smaller decomposers
producing caustic at still higher concentrations. Though several
attempts have been made to recover the energy of amalgam
decomposition, it seems unlikely that such saving process
will be feasible in the near future.
One may expect mercury cells to have longer operating
life, reduced maintenance requirements and to cost less
because of new materials of construction. Such new materials
will allow cells to operate at slightly higher temperatures
and thus reduce the voltage drop in the electrolyte.
Developing bipolar cells is another approach to
improving the mercury cell process, since many bus bars
connecting the cells would be eliminated and the total voltage
drop of the cell circuit will be lower.
Prospective Improvements in the Diaphragm Cell Process
Progress in improving diaphragm cells slowed almost
to a standstill in the decades following the 1940's. In the past
few years, however, improving diaphragm cells has once
again become appealing, stimulated as the industry has been
by fears associated with using mercury. Recently diaphragm
cells have been built to operate with significantly higher

152
currents and greater capacities. Substantial progress along
these and other lines can still be made, however. Cells to
operate at half a million and more amps have been designed
and their construction would present no insurmountable
problems. Such large cells would permit a plant to be built
having only one circuit for a daily capacity of 2 , 000 tons or
more.
While monopolar diaphragm cells will continue to be
built, bipolar ones will offer greater attractions. They are
compact, have a lower total voltage drop, operate longer
between down times for maintenance and diaphragm replacement,
and each electrolyzer can have capacities of more than 50 tons
of chlorine.
Bipolar cells of the future will be either horizontal or
vertical. Their main characteristics are the same, although
each has certain advantages and disadvantages. As with the
mercury cell, both types will be improved by using materials
less subject to corrosion and wear. Titanium linings instead
of rubber linings for example, will be used, reducing cell
maintenance to a minimum. Other materials replacing resinous
products for protective coatings and sealants will reduce levels
of undesirable impurities in the products. Cells that make
chlorine containing less hydrogen and oxygen will also result
from changes in materials of construction and cell design.
The greatest advance in diaphragm cells, however, will
come with improvements in the diaphragms, so that they will
last longer, have a lower voltage drop, control brine flow
better, and allow cells to be fabricated at less expense.
Such diaphragms will permit cells to operate at higher current
densities and also produce caustic that is more concentrated
and purer. Likely materials are synthetic fibers and porous
plastics, both of which should permit diaphragms to be
thinner. With thinner diaphragms, cathodes and anodes may
be placed nearer to each other, which in turn decreases the
voltage drop through the electrolyte.
Permionic membranes might also be developed that
have suitable low voltage drops and long enough life.

153
Such membranes should produce caustic free of chlorine and
methods will be found to produce caustic concentrated enough
to be used directly, thus eliminating the need for evaporation.
Such membranes and methods, if perfected, would certainly
be a major advance, particularly if they will not require higher
voltage drops and will not operate at lower current efficiencies.
Cells with membranes could be a great advantage, in any case
for plants with smaller capacities, where the cost to build
and operate evaporation and purification equipment contributes
too much to overall costs.
Anode shape rather than anode material will be improved,
because the overvoltage of the dimensionally stable anodes
used today is already negligeable. The new geometrical shapes
for anodes, will result in their having lower voltage drops
than at present. As for cathodes, the standard steel mesh
used for so many years in diaphragm cells may be made not
only of different material, but cathodes may be fabricated in
different shapes as well. Such changes in material and shape
may reduce the electrode potential at the cathode and thus
contribute to savings in total power used. Materials that have
a lower overvoltage for the hydrogen evolution have already
been developed, and others may be developed that would permit
to optimize total voltage drop across the cell. Doing so would
then make it possible to use higher current densities.
Thus, cells operating at current densities up to maybe
10, 000 amps per square meter but at voltages that are
economically acceptable are surely likely. Prospects may not
be too great, however, for using the higher current densities
possible with mercury cells.
Diaphragm cells operating with anolytes having higher
concentrationswill be used. So will cells having an empty
cathode space, which will reduce the back migration of
hydroxide ions and produce caustic with a lower concentration
of chlorate.
In diaphragm cells today, brine flows from the anode
compartment to the cathode compartment, and the caustic
always contains some chlorate. A possible advance in the

154
future could be to design cells in which brine from a central
compartment splits and flows through two diaphragms, one
of which faces the cathode and the other the anode. Using this
scheme, brine in the central compartment could be much
more concentrated than today's average concentration in anode
compartments. The voltage drop between the electrodes would
thus be lower than at present because of the higher
conductivity of concentrated brine.
Using two diaphragms would also permit to separate
their functions. One could be permionic and permit chloride-
free caustic to be made in the cathode compartment, while
the other would need only to resist brine and chlorine.
By separating functions in this way, it would become possible
to choose among materials that do not have to resist caustic
and chlorine at the same time, as is the case today.
Naturally, such cell will be complicated, but that complication
should be offset by the advantages eventually realized.
Product Quality and Products of the Future
Much, could be said, of course, about improvements
in product quality, and only a few general points have been
touched. Clearly many improvements have been made and
more are to come. Before concluding, however, there is one
product change in the offing that has much merit. It is often
sufficient when using chlorine to have active chlorine
available in the form of hypochlorite solutions. Therefore it
is possible that many uses for chlorine in the future will
be satisfied by operating cells that directly produce
hypochlorite, which may then be substituted for chlorine in
many industrial applications.
Overall Outlook for the Future
Speaking of the cell of the future is like designing the
cell of the future, and designing the cell of the future is like
having the cell of the future today. This forecast is only a
presentation of the ideas of today and lacks of all inventions
and ideas of tomorrow. Chlor-alkali technology will then

155
advance in steps, each of which will be contributed by hundreds
of scientists, engineers and operators.
Table 1 gives a summary of the possible advances which
might be included in the cell of the future.
Regardless of the details of our as yet unrealized
advances, the chlorine industry clearly has a bright future.
Two hundred years have passed since Karl Scheele in Sweden
made the first few grams of what he called "dephlogisticated
marine acid air" and he and his contemporaries noted its
color and odor and were intrigued by its possible uses.
No one would have predicted then, or even a hundred years
later, how much the industrial world would come to depend
on chlorine for paper, plastics, solvent, dyestuffs, insecticides
and textiles; for sanitation and in households. Nor would anyone
in 1774 or even 1874 have predicted the thousands of other
products that depend completely on chlorine for their existence.
Chlorine has become so prominent obviously of its
widespread utility in so many applications. No one can guess
what place it will have in industry and in our daily lives two
hundred years from now, or even 100 years from now.
However, it does appear clear that chlorine demand will
continue to increase. How rapidly none of us knows for certain.
Whether manufacturers will be using then cells
resembling the ones we have today or whether they will use
at all cells, nobody can guess. It is certain, however, that
no other element will be produced in such large amounts and
that no other element will have contributed more than chlorine
will have to human well-being, whether by eliminating disease
or by making it possible to have new and useful products.

156
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 CLAD METAL ANODES

Robert Baboian
Texas Instruments Incorporated
Attleboro, Massachusetts 02703

ABSTRACT

Recent advancements in the technology of metal

cladding have allowed the development of new material
systems for industrial anode applications. Electro
chemical techniques were used to investigate the
behavior of anodes under conditions simulating
industrial electrolytic processes. Included in this
investigation are coatings of the platinum group metals
and their alloys. The overpotential characteristics
and the stability of the anode materials was evaluated.

INTRODUCTION

Clad metals are metallurgical materials systems

that are a part of a large group of materials termed
composites. They are categorized as bonded metal-metal
laminar composite systems which can be fabricated by
several processes. They are also referred to as
sandwich metals, metal laminates, and multimetals, and
can be provided in strip, tube, rod, and wire forms.
By combining two or more metals into a single clad
material system, the following advantages can be realized:
(1) properties not found in the individual metals;
(2) lower cost; (3) easier fabrication; and (4) better
performance. The behavior and properties of the clad
metals depend on the form and structural arrangement of
the constituents, the materials of which the constituents
are composed, and the interaction between the constitunts.
The basic purpose of clad material systems is to
make the most efficient use of the engineering metals
that are available. This includes selecting the metal
combination and putting them together is such a way as

158
to achieve maximum efficiency. In order to do this,
we must not only know the behavior of the individual
metals, but we must also know how the metals effect one
another in the laminar structure.
An important application for clad metals is their
use as electrolysis anodes. For example, platinum clad
tantalum anodes (Figure 1) have been used in the
electroplating industry for over ten years. Some
installations have reported excellent performance with
these anodes used almost continuously over this time
period (1, 2) .
In Figure 1, the photomicrograph of a cross
section of a roll bonded anode shows the integrity of
the Pt/Ta bond and the uniformity of the platinum
cladding . In recent years , clad metal anodes having
platinum coatings as thin as 40y inch thickness and on
columbium substrates have been available. Photo
micrographs of cross sections of these materials are
shown in Figure 2 .
The most important property requirements of anode
materials are listed in Table I. An efficient, highly
active, stable coating on an inert, highly conductive
substrate is required. These properties must be
maintained while other factors such as cost, strength,
and fabricability are considered.
Development of new electrode materials for
industrial electrolytic applications, therefore, involves
investigations of electroactive materials and metal
substrates .

EXPERIMENTAL

Clad materials used in this investigation were

prepared by Texas Instruments Incorporated solid phase
roll bonding processes. Powder metal compacts were
prepared by compacting the appropriate mixture and
sintering at the temperature required to form the alloy.
Alloy formation was determined by X-ray analysis.

159
 Solutions were prepared by dissolving the appropriate
quantity of reagent grade NaCl in distilled water.
Polarization curves were measured using the potentio-
dynamic method (continuous potential scan and current
recording) (3-6) . The reference electrode was a
saturated calomel electrode (SCE) , and a luggin probe
was used to minimize solution resistance effects.
Disc-shaped specimens for the polarization measure
ments were prepared by ultrasonic cleaning in detergent
solution and rinsing in distilled water. The specimen
was mounted in the type holder described previously (7)
which exposes only Teflon and 1 cm of specimen surface
to the electrolyte. Anode materials were conditioned by
electrolysis in 300 g/1 NaCl solution for one week prior
to potentiodynamic polarization.
Performance of various anode materials was evaluated
over a period of over two months by electrolysis in
300 g/1 NaCl solution. The test cell consisted of ten
compartments (1.5" x 8" x 10") through which electrolyte
from a common 50 liter reservoir was circulated. Fresh
electrolyte was prepared as described above every five
days. The compartments were isolated from one another
so that anode materials were connected in series to a 50
volt D.C. power supply.

RESULTS AND DISCUSSION

Metal Substrates
The most frequently used substrates for anode
coatings are titanium, columbium, and tantalum. These
metals form protective passive films under anodic
polarization in chloride containing solutions. However,
above some critical potential, these films will break
down leading to a highly localized form of corrosion.
This behavior is demonstrated by the polarization
curve for titanium in 1 M NaCl in Figure 3 . The
corrosion current remains extremely low and unchanged
up to 6.0 volts vs. the SCE during anodic potentio
dynamic polarization (solid lines) in either air or argon
saturated electrolyte. However, above 6.0 volts vs. the
SCE, the current increases rapidly, and localized

160
corrosion of the titanium specimen is observed (due to
breakdown of the passive film on the titanium surface) •
This potential is referred to as the critical
breakdown potential (Ec) .
On reversing the scan direction back to less positive
potentials, (dashed lines) repassivation does not occur
at Ec . It occurs at the much lower potential of about
2.0 volts vs. the SCE. Thus, although pit initiation
on titanium occurs only when the potential is above
6.0 volts vs. the SCE, corrosion of existing pits and
crevice corrosion can occur at potentials below 6.0
volts and above 2.0 volts vs. the SCE. However, below
this potential (2.0 volts), titanium should be immune
from localized corrosion. This potential is usually
referred to as the critical protection potential (Ep)
for stainless steels (8-10) .
The critical potentials for titanium, columbium
and tantalum measured in 5% NaCl solution are listed
in Table II. These potentials are sensitive to the
metal properties such as composition and metallurgical
structure. Thus, polarization measurements can be used
to rapidly check the stability of substrate materials.
It is important to note that the critical break
down potentials (Ec) and critical protection potentials
(E-) for tantalum and columbium are extremely high in
NaCl solution. The excellent resistance to localized
corrosion of these metals under anodic polarization in
chloride solutions can be explained by their high critical
potentials.
Although the stability of titanium, columbium, and
tantalum as anode substrates is relatively high, other
properties such as electrical resistivity are relatively
poor. For example, the resistivity of titanium is over
4 times that of steel and about 25 times that of copper.
The resistivity of columbium and tantalun is 7 times
that of copper. Thus, combination of these metals in
the clad configuration can provide a material system
which more fully satisfies the requirements for anode
substrates. An example of such a material system is
shown in Figure 4 . The photographs of cross sections
of titanium clad copper show the sequence of edge
welding to cover the electrically conductive copper base.
Anode substrate panels are fabricated by continuous
edge welding.

161
 Electroactive Metal Coatings
Performance of electroactive metal coatings
involving the anodic evolution of chlorine is affected
by the halogen overvoltage, surface structure, and
stability. Platinum has been used widely because of its
excellent properties; however, it is mainly used as a
coating on other substrates because of its high cost.
It has been recognized that surface oxidation occurs
on platinum under anodic polarization in aqueous chloride
solution. The presence of oxide films on platinum was
confirmed by several investigators (11-14). Dissolution
of this oxide film on platinum in chloride solutions
has also been investigated extensively (11, 14, 15).
This film dissolution appears to be the likely mechanism
of platinum loss during brine electrolysis. Factors
effecting the rate of platinum dissolution include
solution composition, temperature, agitation, and
electrochemical parameters such as potential and super
imposed alternating current.
Platinum consumption during electrolysis of sodium
chloride solution has been measured previously (16-19) .
But, because of the large number of factors affecting
this dissolution, it is difficult to produce reproducible
quantitative rate data.
Figure 5 is a log-log plot of current density vs.
projected anode life of the platinum coating (40y inch)
on platinum clad columbium in 300 g/1 NaCl. The data
plotted for three time periods are linear and fairly
consistent and show a strong dependence of current
density (and therefore potential) on the projected life
of the platinum coating.
The nature of the platinum surface can also effect
the stability during electrolysis. For example,
degradation of electroplated platinum coatings is more
rapid than platinum clad coatings (2) . The porous
nonuniform electroplated platinum coatings degradate
due to spalling as well as dissolution (18).

162

■
 Roll bonded clad platinum surfaces also have a
slower dissolution rate than solid platinum strip (as
purchased) . This effect is shown in Figure 6 where
platinum thickness loss is plotted vs. electrolysis
time for platinum clad columbium and solid platinum
materials. This behavior is not clearly understood;
however, it may be due to differences in the metallurgical
structure of each material .
Addition of alloying elements such as iridium will
effect the stability of platinum. For example, the rate
of dissolution of 90 Pt 10 Ir alloy is slower than that
of pure platinum as shown in Figure 7 . Thus , development
of more stable metal anode coatings by alloying can be
accomplished.
Halogen overvoltage is an important consideration
in electrolysis because of its direct effect on power
consumption. Thus, a more active surface is desired for
chlorine production to realize power savings which can
be obtained through the lowering of cell voltage.
The effect of platinum surface structure on halogen
overvoltage is shown in Table III (20) . More pronounced
differences are observed between platinum and graphite
where the overvoltage for chlorine evolution on graphite
is higher by 200 mv.
In order to reduce the halogen overvoltage on
platinum, alloying constituents were considered. Iridium
and ruthenium were chosen for this purpose after
observing the potent iodynamic polarization curves in
Figure 8. The curves for the platinum group metals
(excluding osmium which could not be fabricated for the
measurements, and palladium which dissolved rapidly
during the measurements) show that iridium and
ruthenium have low overvoltage characteristics in
300 g/1 NaCl.
The potentiodynamic polarization curves for
platinum with iridium and ruthenium additions in
Figures 9 and 10 show that the overvoltage on platinum
can be lowered considerably by alloying with these
constituents. At the higher current densities, an
overvoltage reduction of about 0 . 5 volt is observed
with the 50% alloys.

163
 CONCLUSIONS

Stability of platinum during chlorine electrolysis

can be improved by several factors including roll bonding
and alloying. In addition, the halogen overvoltage can
be reduced considerably by alloying. Combinations of
this technology with the use of clad metal substrates
will provide an anode material system which more fully
meets the rigorous requirements for electrolysis anodes.

ACKNOWLEDGMENTS
The author wishes to thank Gardner Haynes, John
Delang, and Teuvo Santala for their assistance in this
work.

REFERENCES

1. Baboian, R. and Rubin, E.J., Paper Presented at the

139th National Meeting of the Electrochemical
Society, Paper No. 167, May 11, 1971.
2. Skomoroski, R.M. , Baboian, R. , Zobbi, R.G., and
Camp, E.K., Plating, 60, 1115, 1973.
3. Greene, N.D., "Experimental Electrode Kinetics,"
Rensselaer Polytechnic Institute, Troy, N.Y. , 1965.
4. Littlewood, R. , Corrosion Science, CRRSA, Vol. 3,
1963, p. 99.
5. France, W.D. and Lietz , R.W. , Corrosion, SBIIA,
Vol. 24, 196 , p. 298.
6. Baboian, R. , "Corrosion Resistant, High Strength
Clad Metal System for Hydraulic Brake Line Tubing,"
Paper 720290 presented at SAE Automotive Engineering
Congress Detroit, January, 1972.
7. Myers, J.R., Gruewler, F.G., and Smulczenski, L.A. ,
Corrosion, SBIIA, Vol. 24, 1968, p. 352.

l-64
 8. Pourbaix, M. , ; Klimzack-Mathieiu, L. ; Mertens, C;
Meunier, J.; Vanleugenhaghe , C; DeNuncky, L. ;
Lavreys, J.; Neelemans, L. ; and Warzee, M. ;
Corrosion Science, CRRSA, Vol. 3, 1963, p. 239.
9. Pourbaix, M. , Corrosion, Vol. 26, 1970, p. 431.
10. Baboian, R. , "Investigations of Galvanically Induced
Localized Corrosion," Localized Corrosion - Cause of
Metal Failure, ASTM STP 516, American Society for
Testing and Materials, 1972, pp. 145-163.
11. Anson, F.C., amd Lingane, J.J., J . Am . Chem . Soc . ,
Vol. 79, 1957, p. 4901.
12. Laitinen, H.A., Anal . Chem . , Vol. 33, 1961, p. 1458.
13. Latimer, W.L., "Oxidation Potentials," Prentice
Hall, N.Y., 1952, p. 41
14. Laitinen, H.A., and Enke, C.G., J. Electrochem. Soc,
Vol. 107, 1960, p. 773.
15. Brieter, M.W., and Weininger, J.L., J. Electrochem.
Soc. , Vol. 109, 1962, p. 1135.
16. Mantell, C.L., "Electrochemical Engineering,"
McGraw Hill, N.Y., 1960, p. 333 and 349.
17. Juchniewicz, R. , Platinum Metals Rev., Vol. 6,
1962, p. 100.
18. Antler, M. and Butler, C.A., Electrochem. Tech.,
Vol. 5, 1967, p. 126.
19. Marshall, C. and Millington, J. P., J . Appl . Chem . ,
Vol. 19, 1969, p. 298.
20. Knobel, M., Caplan, P., and Eiseman, M. , Trans.
Am. Electrochem. Soc, Vol 43, 1923, p. 64";

165
 TABLE I

Anode Requirements
Electroactive Surface
Stability
Strength
Electrical Conductivity

TABLE II

Critical Potentials (Volts vs. SCE) of

Anode Substrate Metals in 5% NaCl

Metal fc
Titanium (low grade) 6 2
Titanium (pure) 12 6
Columbium > 120 > 120
Tantalum > 120 > 120

TABLE III

9
Chlorine Overvoltages at 100 ma/cm

Anode Overvoltage (volts)

Smooth Platinum 0.05
Platinum black 0.03
Graphite 0.25

166
 PLATINUM CLAD TANTALUM ANODE

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VtVroViYtVroYtVrW
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iYiYiYiYiYhVoYoYiYitYtYm
iYiYt iYiYmnYiYiYtiYtYnViY

WmVAYtYmYtYiYtYiYlVtYiY

EXPANDED

PHOTOMICROGRAPH OF CROSS SECTION

(500X)

•• IT —i > ' i
' $

PLATINUM CLAD LAYER 0.2 MIL

FIGURE 1
PHOTOGRAPHS OF PLATINUM CLAD TANTALUM ANODE MATERIAL

167
 2S0 /* INCHES Pt

40 fl INCHES Pt
FIGURE 2
PHOTOMICROGRAPHS OF CROSS SECTIONS (500x) OF
PLATINUM CLAD COLUMBIUM ANODE MATERIAL

168
 7.0

6.0 \-
7

5.0 h
id I
6 .ARGON

• 4.0 AIR
> \

O
> 3.0

5 2.0|
Q.

1.0 h
ARGON
AIR

Ull| I I I IIH| I lllllll| 1 ' "ini| i i mill

10"* 10v 10* 102 103 104 105
CURRENT DENSITY (/ia/cm2 )
FIGURE 3
POTENTIODYNAMIC POLARIZATION OF TITANIUM
IN 1 M NaCl AT 30 C

169
 INITIAL

RECESSED EDGE

WELDED EDGE
FIGURE 4
PHOTOGRAPHS OF CROSS SECTIONS (3 Ox) SHOWING SEQUENCE
OF EDGE WELDING ON Ti/Cu/Ti CLAD ANODE MATERIAL

170
 20S

S 100
I BO
u 60
° SO
5 40
■
« 30

-i
5060 SO 100 200 300 500 7C
ANODE LIFE (DAYS)
FIGURE 5
LOG-LOG PLOT OF CURRENT DENSITY VS. PROJECTED ANODE
LIFE OF 4 0 M INCH PLATINUM CLAD COLUMBIUM (SOLID)
IN 300 G/L NaCl, 30 C

TIME (DAYS)
FIGURE 6
PLATINUM THICKNESS LOSS OF ANODE MATERIALS VS.
TIME OF ELECTROLYSIS (100 AMPS/FT. ) IN
300 G/L NaCl, 30°C

171
m
hi

m
e

hi
Z
X
o

20 30 40 80
TIME (DAYS)
FIGURE 7
THICKNESS LOSS OF ANODE MATERIALS VS.
TIME OF ELECTROLYSIS (100 AMPS/FT.2)
IN 300 G/L NaCl, 30 C

FIGURE 8
POTENTIODYNAMIC POLARIZATION OF SINTERED POWDER
METAL COMPACTS IN 300 G/L NaCl, 30 C
- PLATINUM GROUP METALS

172
 -1 1 n—i i 1 1

2.0
u
in
- 1*

e
> 1.6
<
1.4 h

1.01 L.
10' 10"
CURRENT DENSITY (/Ji/cm*)
FIGURE 9
POTENTIODYNAMIC POLARIZATION OF SINTERED POWDER
METAL COMPACTS IN 300 G/L NaCl , 30°C,
- PLATINUM IRIDIUM ALLOYS

FIGURE 10
POTENTIODYNAMIC POLARIZATION OF SINTERED POWDER
METAL COMPACTS IN 300 G/L NaCl, 30 C
- PLATINUM RUTHENIUM ALLOYS

173
 MORPHOLOGY OF DI ME NS I ONALLY STABLE ANODES
K. J. O'Leary and T. J. Navin
Diamond Shamrock Corporation
P. 0. Box 348, Painesville, Ohio 44077

The electrochemical properties of dimen-

sionally stable anodes (DSA) have been reported
on in a number of recent studies. However, the
solid and morphological properties of these
unusual conducting oxides have been generally
overlooked. This study undertakes to determine
the properties of these conducting oxides as they
are dictated by various composition variables and
preparation consi di ti ons . X-ray data indicate
that firing temperature determines whether the
films exist as amorphous oxides or fully crys
tallized solid solutions. The physical proper
ties of the thin films, surface area, crystal
size, crystal structure, growth rate of crystal-
Unity, electrical conductivity, are correlated
with composition and methods of preparation.

Introduction. Electrodes which retain their dimen

sional stability have been utilized in laboratory and pilot
studies for many years.1 However, their costs, operational
life, and availability limited their industrial use. The
introduction of the DSA© electrodes has been a significant
exception principally in the production of chlorine.2
Today, chlorine produced via DSA anodes under contract
accounts for approximately 50% of all U. S. chlorine and is
divided about evenly between mercury and diaphragm cells. *
The present economic and environmental climate both in the
U . S. and the world are se^n as driving forces for further
conversion to such electrodes.
Commercial DSAs were first introduced in the U. S.,
after extensive testing by Electrode Corporation, in 1968.
Electrode Corporation, then a joint development of Diamond
Shamrock-Oronzi o DeNora, Italy, is now a wholly owned sub
sidiary of Diamond Shamrock.
Henri Beer's original innovative work with these
precious metal conducting anodes should be considered the
foundation of today's DSA technology. His later work in
refining these properties in the form of solid solutions of
® Registered trademark of Electronor Corporation.

174
precious metal and valve metal oxide has resulted in the
development of today's commercial anodes.1*
Since these anodes have had a major impact on the
chlor-alkali industry, they have generated a great deal of
discussion in the open literature. However, the majority
of this literature deals with their operational and eco
nomic benefits,5'6 and only superficially deals with scien
tific properties. There are, however, a few scientific
reviews of the electrochemical properties of both the
single precious metal oxides and mixtures of precious metal
oxides with valve metals.7'8'9
One of the most recent studies is that of Kuhn and
Mortimer10'11 who discuss the kinetics and electrochemical
properties of chlorine evolution on precious metal oxide
films and solid solutions of precious and valve metal
oxides on titanium substrat es. The solid state and morpho—
logical properties of the Ru02 films were studied by
Pizzini et al.12 However, very little attention has been
given to these solid state and morphological properties of
mixtures of precious and valve metal oxides. While the
actual composition of commercial DSA anodes remains proprie
tary, it is instructive to investigate one potential com
bination that is suggested in U. S. Patent 3,632,498.
The crystal structures and unit cell dimensions of the
dioxides of ruthenium and titanium are shown in Table 1.
The high temperature form of Ti02 exists as the well-
known rutile crystal. The low temperature form of Ti02
(anatase) is converted to rutile above 800-1000°C. As will
be shown, the rutile form appears to be one of the keys to
the useful properties of DSA.
The patent and scientific literature refer to these
oxides as mixed crystals or a mixture of crystals. This
can cause confusion, so we will use the term solid solution,
a terminology well-defined in solid state physics. A series
of rules has been formulated by Hume Rothery to define a
potential solid solution (Table 2) .
The theory predicts the formation of solid solutions
of the type Ti1-xRux02< where x varies from 1 to 0.

Experimental . To determine the effect of fixing

temperatures on the resultant crystal habit, crystal size,
and morphology, three coats of two to one molar ratio solu
tion of titanium and ruthenium were prepared by dissolving
RUCI3 and Ti(OCitHg)i4 in butanol. This solution was then

175
painted onto the flat titanium sheets and air dried. After
drying, these sheets were then heated for seven minutes to
the final firing temperature. The development of the crys
tal structure of these oxide films was followed by x-ray
diffraction. By monitoring these diffraction patterns, it
is possible to determine when and if the solid solutions
are formed (Figure 1) . The x-ray pattern remains feature
less until we reach 400°C, that is, no discrete diffraction
is observed above the background. Thus, the composition of
the surface solids formed at these temperatures does not
possess a long range three dimensional order. At 400°C, we
begin to see the development of discrete diffraction peaks.
This is most apparent by observing the d(iig) diffraction
line, the most intense and inter ference- free rutile line.
The oxide film begins to crystallize as we increase
the firing temperature until at "WOCC all of the surface
oxides have crystallized. While the shape of the diffraction
peak remains uniform and sharpens and intensifies, at 600°C,
the peak begins to develop a slight shoulder on the high 26
side, indicating that a ruthenium-rich crystal and a titan
ium-rich crystal are being formed. Heating to higher tem
peratures, ^800-900°C, further separates the maxima into
clearly discernible peaks. It is not surprising that this
occurs since the process can be considered to be as follows:
True Solution of RUCI31 Ti(0Bu)i4
l Air Dried
Glassy Gel
I 300-650°C Volatilization
{ of Solvent and Oxidation
Glassy-Crystalline S olids -Nonequi lib ri um Rutile Solid
I Above 650°C
Equilibrium Rutile Structure
The formation of the glassy solids occurs under highly
nonequilibrium conditions by the rapid evaporation of the
volatile solvent. It is hypothesized that the metal atoms
take up random positions in a highly disordered oxide
latti ce .
At the higher temperature, there is sufficient energy
available to allow restricted lattice motion and emergence
of cry s t al li ni ty .

176
 The role of the underlying titanium metal should not
be overlooked. The surface layer of rutile TiO2 normally
forme1, on oxidizing titanium metal13 acts to seed the ini
tial growth to the correct rutile crystalline form, which
can then act to catalyze subsequent layers.
The interfacial layer between the titanium metal and
the rutile oxides, Tii-xRuxCi2» allows a gradual transition
of the form TiOx, where x varies from 0 to 2. These oxide
layers, where x lies below 1, do not contribute to any
electrical resistance loss since TiO is well-known as a
metallic conductor. Above 1, they may contribute to in
creased resistance until the dioxide is reached.
Calculation of the necessary lattice expansion of the
titanium crystal to accommodate the rutile structure would
indicate a potential for large lattice stress. If the
transition were to occur over a sharp boundary area, a
large disruptive force on the adhesion crystals to the sur
face does result.13 Thus, the controlling of the firing
temperature is critical to assure excellent adhesion nec
essary for coating performance.
As mentioned previously, the x-ray patterns remain
featureless until a 400°C firing temperature is reached.
Then, a broad, weak peak appears with a maximum intensity
at 3.22 A. By integrating the area under the d(iiojline,
an estimate of the percent crys tal li ni ty can be obtained
utilizing the following formula.
.% Crystallinity
„ - -i -i ' Area Sample
= Area * —Crystalline
—— - ;—r
(100% Sample)
The 100% crystalline sample was obtained by heating a
sample to the higher temperatures until no increase in
area was observed on further heating. The area of the 100%
standard correlated well with the areas of large crystals
of pure rutile TiO2 and Ru02- As we can see from Figure 2,
there is an increase in crystallinity with increase in
temperature. Thus, a two-phase system exists between 300°
and 700°C. These temperature regions may be changed in
either direction by adjusting the firing time.
The x-ray diffraction data also allows us to estimate
the crystalline size by the use of line broadening. Uti
lizing the Scherrer formula,
KX where D = mean dimension
Si cos9 K = constant .9
X = wavelength

177
 (3 i = corrected half-line width1
9 = diffraction angle
The results are shown in Table 3.
Thus, as the firing temperature is increased, we have
an increase in both cry s t al li ni ty and crystalline size.

Morphology . Scanning electron micrographs of DSA

anodes treated at several temperatures display a micro-
cracked surface composed of discrete islands of material.
Examination of Figures 5 through 9B reveals how the surface
morphology develops and makes it evident that the mud
cracked configuration is established at room temperature.
As the coating dries at room temperature, the solvent evap
oration gives rise to a gel of essentially unreacted RUCI3
and Ti ( OCi,Hg ) it • Experiments with various drying times and
temperatures below 200°C indicate that the number and width
of the cracks can be varied within certain limits, but the
gel formation of RUCI3 and TifOC^HgJi, almost precludes the
elimination of the mud cracked surface configuration. The
mud cracks are formed by the volume contraction of the gel
which accompanies solvent evaporation. Increasing the
temperature of the dried film drives off progressively more
of the solvent that is contained in the gel with a conse
quent widening of the cracks. This sequence can be follow
ed in 5B and 6B . Increasing the temperature to 400°C
establishes the final surface morphology of the coating
which is stable, at the very least, to 700°C.
Close study of the figures indicate that, at tempera
tures greater than 200°C, the depth and width of the cracks
is roughly one-third the diameter of the islands. Based on
measurements of the island diameter, the crack depths, and
crack widths, the macroscopic surface area is about twice
the apparent geometrical area. Measurements of the atomic
surface area by BET nitrogen adsorption indicate a value of
180-230 times the apparent geometrical area. This is in
good agreement with the 230X measurement of Kuhn and
Mortimer1 1 and places the anode in the category of many of
today's industrial catalysts with respect to atomic surface
area .
The surface area must be a major contributor to the
low chlorine discharge potential of the DSA anodes. The
atomic surface area provides a large number of catalytic
sites for electron transfer while the macroscopic surface
area allows adequate gas evolution with a minimum of con
centration polarization.

178
 In general, the stability of the coating has been good
over long periods of time despite the fragile appearance of
the mud cracked surface. Anodes evolving chlorine at cur
rent densities of one ampere per square inch for a period
of one year show little detectable change. The character
of coating erosion by chlorine is such that there is little
or no smoothing of the coating and consequently no change
in the chlorine discharge potential.
In Figures 5 through 9, at the low magnification, it
is apparent that the coating conforms to the configuration
of the substrate. This is especially evident in Figures 5
and 6. It can be inferred that the character of the sub
strate surface might have an effect on the coating morphol
ogy and, hence, its performance.

Electrical Properties. The measurement of the electri

cal conduction of these surfaces is seriously handicapped
by short circuits to the titanium substrate and the inter-
grain boundaries of the crystals. However, some general
idea of the electrical conduction of these systems can be
gleaned from the following experiment. A thin ^1000 A
thick titanium layer was vacuum deposited on a quartz sub
strate. A thin coating was then painted on the titanium
surface and air dried. The plate was then heated to 500°C
for 5 hours in air to assure complete oxidation of both the
surface films and the underlining sheet. Figure 3 shows
the results for AC, resistance measurements, and comparison
to the "metallic" conducting RuC^1** and insulating Ti02-*5
As can be seen on the graph, these coatings have a
resistance intermediate between insulator and a metallic
conductor and so can be considered a semiconductor.
These electrical measurements have been made on highly
crystalline solid and care must be taken in too liberal an
extrapolation of this data since many of the coatings pre
pared at lower temperatures are, in fact, a two-phase
crystalline -amorphous compos iti on.
The half cell potential under chlorine evolution does
not vary greatly as a function of preparation temperature
(see Figure 4) . It is apparent from this figure that the
amorphous region below 300°C is conductive, and there is no
abrupt change in going from amorphous to crystalline region.
These findings are not in agreement with those of
Kalinovskii et al.8, who found a significant potential
increase when butyl titanate was added to RUCI3. A pos
sible explanation lies in the different methods of prepara-
ti on .

179
Discussion and Conclusions
1. The oxides of titanium and ruthenium form predicted
rutile solid solutions. While it is apparent that the
metallic conductor RuO2 contributes to the conductivity
it is the titanium which contributes to the chemical
stability and a significant reduction in cost.
2. Below 300°C, these films are glassy solids. Between
300° and 650°C, they are two-phase systems, and above
700°C, they become fully crystalline.
3. The crystal size remains extremely small/ ranging from
100-500 A, at firing temperatures between 300° and 700°
These crystalline regions are expected to act as rein
forcing points within a glassy matrix, thus strengthen
ing the overall film.
4. Scanning electron microscope studies clearly show high
surface roughness.
5. BET measurements indicate high surface areas between
180-230 cm2 per cm.
6. Electrical conductivity of fully crystalline solid solu
tions falls between the insulator TiO2 and the metallic
conductor Ru02 •
7. Voltage measurements indicate that despite the rather
poor electrical conductivity of these thin films, the
very high surface area overcomes the resistance prob
lems and greatly enhances the electrochemical activity.
It is, therefore, not surprising that these anodes are
preferred in high current density operation (4 to 10
ASI) required for mercury cell anodes. Since even at
high current feed rates, the actual surface current
density remains very low. When this is coupled with
the good absorption rates for chloride ion and the ex
cellent desorption for chlorine gas molecules, we can
understand why the chlorine industry has so readily
accepted the DSA anodes.

References
1. Hampel, C. A., "The Encyclopedia of Electrochemistry,"
Reinhold Publishing Corp., New York ( 1964) .
2. Emery, A. T., Parker, J., J. Electrochem. Soc . , 120,
321C ( 1973) .

180
 3. Private communication Electrode Corp.
4. Beer, H., South Africa 66/2667.
5. Anon., I nf ormat i ons -Chimi e No. 68, 67 (1969) .
6. Horacek, J. R., and Puschaver, S., Chem. Ing. Progr.,
67, ( 3) , 71 ( 1971) .
7. Faita, G., Fiori, G., J. Appl. Electrochem . , 2, 31
(1971) .
8. Kalinovskii, E. A., Bondar, R. U., Meshkova, N. N.,
Elektrokhimiya , 8, 1468 ( 1972).
9. Erenburg, R. G., Krishtalik, L. I., Bystrov, V. I.,
Elektrokhimiya, 8, 1740 (1972).
10. Kuhn, A. T., Mortimer, C. J., J. Appl. Electrochem.,
2, 283 ( 1972) .
11. Kuhn, A. T., Mortimer, C. J., J. Electrochem. Soc . ,
120, 231 ( 1973) .
12. Pizzini, S., Buzzanca, G., Mari, C., Rossi, L.,
Torchio, S., Mat. Res. Bull., 7, 449 (1972).
13. Hurlen, T., J. Inst. Metals, 89, 128 (1960) .
14. Rogers, D. B., Shannon, R. D., Sleight, A. W.,
Gillson, J. L., Inorg. Chem., 8, 841 (1969).
15. Cronemeyer, D. C., Phys . Rev., 87, 876 ( 1952) .
16. Klug, H. P., Alexander, L. E., "X-Ray Diffraction
Procedures for P oly c ry s t al li ne and Amorphous
Materials," John Wiley and Sons, Inc., New York (1954) .

181
 •T0.«l I
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 0Fig. 5. 0Fig. 5B.
25 C, 1000X 25 C, 3000X

184
 Fig. 7. Fig. 7B.
400°C, 1000X 400°C, 3000X

185
 Fig. 9. Fig. 9B.
700°C, 1000X 7O0°C, 3000X

186
 FUTURE TRENDS IN CHLORINE CELLS
John E. Currey
Alvi.il T. Emery
Colin S. McLarty

Chlor-Alkali Systems
Hooker Chemicals & Plastics Corp.
PO Box 344
Niagara Falls, New York 14302

ABSTRACT
Future trends in chlor-alkali cell design, construction and method
of operation, are explored. Near term trends of 1 to 5 years are
based on past evolutionary developments, "educated guesses" and
present explorations. Longer range developments of 4 to 25 years
may be influenced also by break-throughs in unrelated fields.
Various economic, social and environmental pressures, which will
influence the directions and rate of development, are discussed
along with their possible impact on the developments.

187
The purpose of this paper is to arrive at a prediction of what future
commercial chlor-alkali cells may be like in the period of 1976-1986.
The method of arriving at these predictions is by extrapolation of
past trends, intuitive approaches, and by technological forecasting.
Papers predicting the future are common to many technical symposia.
The chlor-alkali field is no exception. The most recent report on
this subject was a comprehensive paper given about nine months ago at
an AlChe meeting by P. J. Kienholz.
I am in general agreement with Mr. Kienholz' s comments with one major
qualification. He indicated commercialization of membrane cells with
in four to seven years.
The real message of this paper is that "Ion Exchange Membrane" cells
are here nowl There are at least two commercial-sized plants actively
being engineered; construction and startup of these plants will follow
as fast as the manpower and material and equipment procurement will
allow. Furthermore, we predict that membrane cells will become one
of the predominant cell types within a very short period.
A second purpose of this paper is to try to predict other cell
developments; which have not been generally recognized as possible or
probable. Quite frankly, this turned out to be more difficult than
I had originally anticipated.
The problem here is the "surprise factor" due to breakthroughs in
other fields impacting on chlor-alkali technology.
For example, the development of a low-cost metal super- conductor
could mean the complete redesign of all cell equipment and their
electricals. Or, think what a chemically inert, conductive plastic
could do to the design of anodes and cathodes. Note that other
industries have far greater incentive to develop these specific items
than the chlor-alkali industry. If they are developed, it will
probably be based upon a number of scientific breakthroughs achieved
at one of the larger scientific laboratories.
An examination of the way we have arrived at our present day state-
of-the-art in chlor-alkali cells gives some clues as to the way
future developments will take place.
First, it is necessary to recognize that electrolytic cell technology
is dynamic, that is, constantly changing with time. It is an evolu
tionary process catalyzed and given sporadic forward thrusts by
certain events, usually described as "breakthroughs".
In times past parts of chlor-alkali technology were virtually static.
The changes being made in the 1940' s, 1950' s and early 1960's to

188
industrial diaphragm cells involved few new concepts or new basic
principles; but only refinements in techniques or relatively simple,
modest engineering scale-ups.
Today our chlor-alkali industry is described by those involved as
being in a state of rapid change and far-reaching new developments.
This is certainly true if you compare the developments on the drawing
boards, and in the pilot plants today with the 30 year period from
1935 to 1965. A stagnant technology tends to remain dormant due to
the fact that industries become comfortable with a given technology.
Personnel become suspicious of new things. They convince themselves
that everything worthwhile has been thought of and already tried.
This, in turn, is reflected in the attitude that the area is not a
fruitful one for research or development. Research and development
budgets are cut back. No effort is made to innovate and the technology
remains unchanging.
On the other hand, a few initial changes result in more changes,
which, in turn, catalyze further changes. Thus we end up with a chain
reaction. As you know, there are many changes, developments,
innovations now taking place as a consequence of overall changes in
our society which impact heavily on electrochemical technology, for
example:
Safety awareness A) by the public
B) management
C) union
D) government - OSHA, EPA
Pollution awareness (ditto)
Increase in the cost of or non-availability of energy
Shortages of skilled labor
Of course, the new technological developments and the rapid technical
changes are forcing even more innovations. Thus, there is a snow
balling effect. A good example of a far-reaching technical innovation
is, of course, the coated metal anode.
Another aspect of such a hyperactive period is that research and
development budgets, manning, and programs blossom in those companies
committed to be leaders in the technology.
What are our goals? - Let's list them:
1. Economical capital investment, operating and maintenance costs.
2. Safe, healthful plants.
3. Non-polluting operations.
4. Pure products.

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 5. Minimum power consumption per unit of product.
6. Ease of operation.
7. Simple processes and hardware.
8. Versatility.
9. Compactness.
10. Non-sensitivity to feed impurities.
11. Readily available materials of construction.
I will take each of the various cell types and comment on their latest
developments, as I know them, and suggest the trends of the future.
I have no comments on the fused salt, i.e., Downs cells, or the HC1
electrolysis cells, other than that I believe it is technically
possible to improve these systems. It would appear that this
technology is fairly dormant; and it is difficult to see any big
incentive for upgrading this technology.
Note: In this talk I use the term "diaphragm" to mean any percolating
barrier between anolyte and catholyte. I also use the word "membrane"
to mean a non-percolating ion exchange membrane.

MERCURY CELLS
The recent history of mercury cells and their pollution problems are
familiar to everyone involved with chlor-alkali technology: the
actions and legislation by the U.S. and Canadian governments,
industries' fast response to lowering mercury effluent levels, the
shutting down of some mercury cell plants, etc.
The Japanese government has, by edict, forced the Japanese chlor-
alkali industry to take those actions necessary to insure that a
major portion of the industry is producing chlorine in diaphragm- type
cells by the end of 1975.
European companies, in response to the news media, have become much
more sensitive to mercury pollution problems. It appears probable
that many or perhaps even a majority of the new European chlor-
alkali plants will use diaphragm or membrane cells. From our point
of view, we believe the use of mercury cells will slowly decrease.
The first round of new plants will use the standard or improved dia
phragm technology.
Long term the basic reason that the use of mercury cells will decline
is that there is now an option in the form of "membrane" cells which
produce economic results similar to a mercury cell without the risks
resulting from the handling and use of mercury.

190
Mercury cell technology Is highly developed. The cells are large,
i.e., up to 500 KA, operating at high current densities - 15KA/m2.
Group anode adjustment, manual or computer-controlled, and automatic
"short" detection and elimination, are standard for the latest models
of mercury cells. Thus further improvements that will have any
significant impact will be difficult to achieve and are probably
unlikely. Thus it appears now that mercury cell technology will
remain fairly static, at least for the short term.
While attitudes, regulations and economics concerning mercury
pollution are in a state of change, companies will be hesitant to
proceed with the new mercury cell plants. However a point will be
reached where the environmental impact, the acceptable effluent levels,
the economics, etc., will become precisely defined and more or less
fixed, and at that point the question of the mercury cells versus
other types of cells will be resolved primarily by the competitive
economics.

DIAPHRAGM CELLS - Engineering Trends

During the past two years, diaphragm cells have been redesigned to
larger capacities to gain the economies of scale for the large 1000-
1500 TPD plants which are becoming more commonplace in the industry.
The Glanor cell, Diamond's DS-85 and Hooker's H-4 cell, are examples
of cells specifically designed for the large merchant plant.
The first circuit of these larger cells to go on stream will be the
400 TPD H-4 cell circuit at Hooker's Niagara Falls plant. This plant
is scheduled to be in operation in June 1974.
Although there is a strong economic incentive for the development of
these high capacity cells, other factors such as safety, pollution
control, and improved environment have offered equal or even more
compelling incentives.
The emphasis on safety and OSHA regulations have resulted in a re
examination of designs and of operating procedures. Electrical
safety in cell rooms has been the subject of much discussion in the
Chlorine Institute, the Standards Committee of the IEEE, and within
the chlor-alkali producing companies. Cells with 150KA ratings make
possible the production of 500 TPD of chlorine in a single electric
circuit, while maintaining the circuit voltage under 400 volts. We
believe a circuit in the 400-500 volt range is considerably safer
than the 600-800 volt circuits which are typical of older cell rooms
using mercury arc rectifiers.

191
In keeping with this philosophy the three 400 TPD circuits of H-4
cells being installed this year at Hooker will operate at circuit
voltages between 300 and 350 volts.
The continued emphasis on electrical safety will result in continued
pressure to lower circuit voltages. Circuit voltages of 200 to 300
volts could very well become mandatory for new circuits at some point
in the not too distant future. This, in turn, will continue the trend
to even higher amperage monopolar cells in the range of 200 to
500 KA. Increased cell size has further advantages of space savings
and of improved environment for the operators and renewal personnel.
Larger cells must have wider aisles in order to remove and replace
cells during renewal. These wide aisles eliminate the possibility of
a man touching two rows of cells at one time, and thus eliminate
being exposed to a severe electrical shock. Wider aisles also give
workmen more maneuvering space, decreasing the possibility of
mechanical accidents.
The large cells and wide aisles make possible more acceptable
temperatures and humidities, thus improving the working conditions.
A further point is that, because of their size, these cells are virtu
ally unaffected by exposure to cold ambient temperatures or to rain.
This opens up the possibility for outdoor cell installations.
A last point is that with these large cells, it is possible to
justify monitoring equipment on each cell. This can, in turn, reduce
labor and increase the safety of the operation.
Thus, we see clearly that, because of these factors, the trend to
develop new larger monopolar cells during the next three to five
year period will continue.

DIAPHRAGM CELLS - Technical Trends

Diaphragm cells, that is cells with a percolating diaphragm, are in
a state of rapid development and change.
The escalating energy costs have re-emphasized the necessity of
lowering the power consumption per ton of product. The chlor-alkali
industry has reacted by accelerating the adoption of a number of
power-saving developments, which have been around conceptually for a
long time.
The tried-and-true true traditional diaphragm of deposited asbestos
is being replaced by a number of attractive alternatives.

192
The first development which may reach commercial use is the substi
tution of a thin modified or stabilized asbestos diaphragm for the
conventional 1/8" thick deposited pad. The key to these modified
asbestos diaphragms is that the asbestos fibres are held in place by
the cementing action of an inert plastic. There are a number of ways
by which this can be accomplished.
It seems that this may be only a short term solution due to the
changing cost and availability of asbestos. In addition asbestos
fiber in-plant handling, use, and disposal will become more difficult
because of the increasing awareness of a possible health hazard. To
illustrate this trend, GAF, which in the past has been the major
asbestos supplier to the chlor-alkali industry, has notified its
asbestos customers that GAF will not supply asbestos for diaphragms
beyond mid- 1975.
Thin, stable, fluorocarbon percolating membranes appear to be a better
method of obtaining the voltage savings so eagerly sought. The
development of these membranes has not been easily achieved. Finding
the right combination of chemically stable film, film thickness,
reinforcement, porosity and pore size, has been difficult. We expect
to see commercial plants installing this material in large quantities
in one or two years. Voltage reductions of 0.2 to 0.3 volts are
achieved at current efficiencies comparable to those obtained with
the standard asbestos diaphragms,
A reproducible, uniform microporous membrane, or a stabilized
asbestos diaphragm such as described, also makes possible one further
major voltage reducing step. That is, the electrolyte gap can be
reduced. This provides the possibility for another 0.2 volt savings
over the older diaphragm technology.
The extension of diaphragm life between renewals is an added bonus.
The last achievable power-saving step is a reduction of the hydrogen
overvoltage at the cathode. Savings of the order of 0.2 to 0.3 volts
are achievable by replacing the standard mild steel active surface
with a material utilizing voltage- lower ing concepts similar to those
used in the metal anodes.
Adding up all of the above savings in voltage points toward a 0.6 to
0.8 volt savings using fairly well-known technology. This will
bring the voltage of a cell to the level of 3.0 to 3.1 volts.
Although there are additional costs associated with these new
developments, these costs appear to be far outweighed by the savings
in power. The incentives are so strong that we expect to see
commercial plants using this new technology within one or two years.

193
Of course, these developments may be most advantageously used in
redesigned cell systems operating at higher current density, thereby
reducing the capital investment.
Thus I suggest that current densities of 2 to 5 ASI will become
commonplace in spite of higher power costs.

MEMBRANE CELLS
Electrolytic cells using ion exchange membranes are a relatively old
concept first explored in the late 1940's for use in electrolyzing
brine. A member of our company tried depositing asbestos diaphragms
containing ion exchange particles in 1946. The concept of utilizing
ion-exchange membranes for electrodialysis , and the separation of salt
from brackish waters to make fresh water, was explored, developed,
and commercialized in the 1940's and 1950' s. This led to the work
which has as its goal, electrolyzing sodium chloride brines to produce
caustic and chlorine, utilizing an ion-exchange membrane. During the
early 1950' s, Hooker Chemical Company, as well as a number of other
chlor-alkali producers, did a considerable amount of research work
on cell systems using the ion-exchange membranes then available.
These development programs evolved the hardware which could operate
successfully under chlor-alkali cell conditions. Very quickly it
became obvious that the key to making this system work was an adequate
ion-exchange membrane which would give low voltages, high current
efficiencies, and have mechanical properties which stand up satis
factorily to this severely corrosive environment.
A number of companies tackled the problem of developing a satis
factory membrane which could be used in a number of electrochemical
systems as well as in the chlor-alkali area. After a number of years
of frustration and the expenditure of sizeable sums of research
dollars, virtually all of the companies dropped these research
projects, and the idea of developing an ion-exchange membrane cell
lay dormant during the early 1960's.
The commercial development of the titanium-based anodes with their
obvious dimensional stability and longevity tended to highlight the
remaining major weakness in diaphragm chlor-alkali cells - the
material of the diaphragms. Recognition of this fact forced the re-
establishment of research programs to seek more suitable permanent
diaphragm materials.
In the meantime, progress was being made continually in the area of
fluorocarbon chemistry.

194
In the early 1960's, an exploratory organic chemistry group at duPont,
working specifically on fluorocarbon polymers in an effort to expand
into new businesses based on Teflon'^' chemistry, discovered a new
ion exchange polymer. A review of its properties indicated a plastic
material markedly different from the other Teflon^' materials. An
effort was made to find someone who could use a material with these
unique properties. The first people duPont approached were the fuel
cell people at General Electric, because they already had a related
membrane being used in a satellite program. This GE membrane did not
have adequate chemical stability. The duPont membrane was tried and
found to work satisfactorily in the GE fuel cell. Subsequently this
fuel cell was used in a number of satellite programs.
DuPont researchers became aware of the potential value of this
membrane in chlor-alkali cells, and have been working diligently
since 1971 to tailor-make membranes suitable for use in chlor-alkali
cells.
It appears that duPont is leading the field in membrane developments.

FACTORS AFFECTING ACCEPTANCE OF MEMBRANE CELLS BY INDUSTRY

I will try to assess whether membrane cells will be readily accepted
by industry, and whether the membrane cell will replace the diaphragm
and mercury type cells. It is important to understand that the
characteristics, results, products, costs, etc., are very much
dependent upon the specific design and the materials available. For
example, a poor membrane can result in high voltage, low current
efficiency, high salt in caustic, high hydrogen in chlorine, high
corrosion rates and early failure, etc. Obviously a cell with such
a membrane would be unacceptable from a performance and cost point
of view.
I assume that membrane cells developed by other companies will be of
comparable size and quality. Therefore, the discussion and arguments
can be set forth in a general way without going into specific
details on membranes, cell size, performance, operating factors, etc.
PRODUCTS
Caustic
Caustic purity from the membrane cell is far superior to that from a
normal diaphragm cell. It approaches the purity of caustic from a
mercury cell. The salt content is of the order of 0.27.. The heavy
metal content is also very low. There is no chlorate in the caustic.
This grade of caustic is certainly adequate for, and will be accepted

195
by, the rayon manufacturers. This will be the most important single
factor favoring membrane cell acceptance in Europe and Japan.
Chlorine
Chlorine quality is also superior, primarily because there is no
hydrogen contamination. Elimination of hydrogen in the chlorine
will mean a safer plant and will reduce the cost and complexity of
a liquefaction system.
Hydrogen
The hydrogen quality is equivalent to that from a regular diaphragm
cell.

PLANT INVESTMENT AND DESIGN FACTORS

At this stage of development, as evidenced by the costs for Hooker's
MX cell process, the membrane cell plant investment is for many
situations equivalent to or less than a standard diaphragm cell
plant. The ability to accept some dilute caustic in a nearby process
can drastically reduce the investment in caustic equipment.
The cell sizes available (Hooker's MX cell) are adequate for plants
ranging from 5 to 300 tons per day of chlorine. No doubt in the
next few years, larger capacity cells will be forthcoming. This
will improve the economics for larger plants.
The Hooker membrane (MX) cell is more versatile than the standard
diaphragm cell. Operation is possible at low (0.5 asi) or high
(2.0 asi) current density. This means there is a wider operating
range which can be used in optimizing the capital costs versus the
operating costs. Another factor affecting optimizing capital costs
is that the MX cell can be operated in a bipolar mode, that is with
individual cells in series or the cells can be paralleled. Thus,
there is an almost unlimited range of amperage and voltage
combinations for any specific plant. This will be an attractive
plus factor, for example, when converting a plant from older cells to
membrane cells.
One other important advantage which will favor selection of membrane
cells for small plants is that the total plant design is simpler to
construct and operate. The reliability of the MX cell will favor
outdoor construction since less operating or renewal attention will
be necessary.
Where does the development of membrane cells stand? Quite frankly,
we do not know where Diamond, PPG, Ionics or others stand. However
we believe their technology is also well advanced.

196
We, at Hooker, have over the past three years, worked through
laboratory to pilot plant to commercial prototype programs.
Work is now in progress on a 40 TPD chlorine plant to be installed
at a pulp mill. These new cells will replace existing mercury cells.
We expect shortly, to release an announcement to the press giving
details of this development.
Secondly, the engineering on a 250 TPD membrane cell plant, owned by
Hooker, is well on the way to completion.
These two plants were chosen to demonstrate this technology for a
small capitve installation, and for a reasonably sized merchant plant.
The commissioning of this first commercial membrane plant will usher
in a new era in chlor-alkali technology. After obtaining additional
operating experience in a commercial plant, we expect to make this
technology available to other chlorine producers. Such an offering
of the cell will probably come in 1975.
We believe the membrane cell is the cell of the future as well as
the present.

197
 BIPOLAR CHLORINE CELL DEVELOPMENT
P. J. Kienholz
PPG Industries, Inc.
One Gateway Center
Pittsburgh, Pennsylvania 15222
This paper presents the history of the development of
the PPG-De Nora
electrolyzer. Some of the problems considered during the
initial stages of development, and their solutions, will be
discussed. A review will be made of the basic characteris
tics of the commercial design. The advantages which result
from the bipolar, electrolyzer principle of design will be
pointed out and discussed.

The diaphragm cell has for many years served as the mainstay for
chlorine-caustic soda production in the United States. Development
of the synthetic graphite anode and later, the method for vacuum
deposition of asbestos fibers on a wire mesh cathode was to impact on
chlorine cell design for many years. The Hooker Type S monopolar cell
and its many off-spring, including the Diamond- Shamrock and Columbia
designs, all utilizing deposited diaphragms account, for a large
percentage of the chlor-alkali capacity in the United States. A
second major design variation, the Dow bipolar electrolyzer is also:
utilized on a large scale throughout the world. Diaphragm cells will
soon be a major factor in chlorine production in Japan.
PPG Industries has for many years operated electrolytic chlorine
diaphragm cells of various types. Many Hooker cells are utilized,
together with PPG's adaptation of this basic design, the Columbia
cell, in various PPG manufacturing locations. In common with others
in the industry, PPG for many years had also been engaged in the
development of improved diaphragm cells, through an active research
and development program.
Why then, the necessity for a new design concept, which would
represent a major departure from the then existing designs?
First, there is the continuing need to improve on any technology
to combat the effects of inflation and rising standards with respect
to the worker environment. Or more simply, to maintain the best
overall competitive position relative to other companies in the
field.

GLANOR^ ' is a registered trademark of Oronzio De Nora Impianti

Elettrochimici, S.p.A.

198
 Second, the ability to adapt existing designs to properly exploit
new technologies becomes more limited, the longer the basic design is
utilized. This point was to become more apparent several years later
with the advent of commercially practical metal anodes.
Thirdly, there was the desire to broaden the options available
with respect to what cell technology could be installed in operating
facilities planned for the future. The availability of a proven,
bipolar electrolyzer would provide an additional technology to choose
from.
In contrast to the past, chlorine plant designers now have an
interestingly wider selection of chlorine cell technologies available
to them, because of the entrance of the PPG-De Nora GLANOR electro
lyzer into the market place.

PPG-De Nora Development Program - What then can be said regard

ing the PPG-De Nora cell development program? In the 1950' s, partly
as a result of our analysis of the benefits of the bipolar configur
ation, PPG organized a cell development group which was given the
assignment to design an electrolyzer to produce chlorine and caustic
soda.
After numerous design concepts employing graphite anodes were
tested in the pilot plant, a 30 KA, 15 cell electrolyzer system was
placed in a commercial circuit and operated for over seven years.
During this time many problems in design and materials of construc
tion were encountered and overcome.
The advent in the late 1960's of the commercially practical
metal anode caused the PPG engineers to look again to the future.
The many advantages of the bipolar concept could be enhanced with the
use of metal anodes. So the decision was made to utilize the back
ground in existing bipolar technology in the development of an
electrolyzer designed to take full advantage of the opportunities
offered a cell designer by metal anodes.
At that time PPG joined forces with Oronzio De Nora Impianti
Elettrochimici , S.p.A. of Milan, Italy. The De Nora name is well-
known throughout the world for its excellence in chlorine mercury
cell design and fabrication. More than 130 chlorine plants with a
total capacity of more than five million tons per year, correspond
ing to about one-quarter of the world production, have been built
by Oronzio De Nora, utilizing De Nora mercury cells, ranging in capac
ity from 36,000 amps up to 450,000 amps.
As a result of this cooperation, designs for bipolar electroly-
zers ranging in capacity from 30 KA to 80 KA, equipped with metal

199
 anodes, embodying contributions from both PPG and De Nora, were built
and installed in commercial circuits at various PPG Industries facil
ities. Over ten years of operation of the various bipolar designs
has proven out the design concepts and operating characteristics of
the PPG-De Nora GLANOR electrolyzers. This makes PPG the only major
chlorine producer with extensive expertise in both monopolar and
bipolar chlorine cell technology.
During the development period many new areas of study were pur
sued, due to the necessity of picking the proper materials of con
struction and methods of assembly and current transfer, that would
meet the goals of the cell development group. Some of the disci
plines that were called upon in varying degrees were electrochemical
specialists; chemical, electrical, mechanical and civil engineers;
operations representatives; chemists; corrosion specialists; hy
draulics experts; and rubber compounding specialists. The use on a
spot basis of outside consultants and university research people was
beneficial.
The proper support for such an extensive development program
requires well defined goals, strong management commitment and ade
quate financial funding.

Goals- Advantages of Bipolar Configuration - What were the goals

that the cell development group had in mind in those early days?
They included an electrolyzer with a potentially long operating cycle,
designed to take full advantage of metal anodes such as the DSA^ ';
more efficient use of power; compact design; superior operating
characteristics; minimum maintenance; reduced operator attention;
high production to floor area ratio; improved electrolysis area
housekeeping, ventilation and operator comfort; minimum leakage;
uniformity of operation; reduced exposure to the safety hazards at
cell cutout and other electrically "hot" work, (improved overall
safety); reduced investment; simplified electrolysis room layout;
and easier cell assembly, less dependent upon the worker quality with
respect to anode-cathode alignment and other factors of cell renewal
such as the need to eliminate the possibility of damage to the dia
phragm during assembly.
This is a listing of only the broad goals. Each item mentioned
entails the consideration of numerous factors that during the de
velopment years were considered, evaluated, optimized and finally
agreed upon. All this was done in a climate of rapid technological
. change wherein programs had to be, and still must be, continually
evaluated and revised to meet the requirements of constantly shift
ing goals.

DSA (R) is a registered trademark of Electronor Corporation.

200
 Results - The first commercial result of the efforts of the PPG-
De Nora development program is the GLANOR electrolyzer , more speci
fically designated the GLANOR Vertical Type 1144 Electrolyzer. Here
after we will refer to the unit as the GLANOR for the sake of brevity.
The GLANOR usually consists of ten bipolar elements positively
clamped together between two end electrode elements with tie rods,
resulting in an electrolyzer module of eleven cells. A lower or
higher number of cells can be assembled in one electrolyzer, but
eleven seems to be a very practical number for a wide variety of
plant capacities. (Figure 1)
The current is carried into the electrolyzer by means of the
anodic and cathodic end elements. In the bipolar design current
flows from cell to cell within the electrolyzer, through numerous
very short internal connections. Externally, copper connections are
used between electrolyzers.
The reduction in the number of external copper bus bar connec
tions required between operating electrolyzers in a circuit of the
bipolar design; the geometry of the GLANOR electrode configuration
with respect to the short intercell current path; and the essentially
straight through current travel are the three factors mainly respon
sible for the lower voltage drop and thus the lower power consumption
exhibited by the GLANOR design, as compared to the traditional mono
polar designs, when operating at the same current density and
equipped with same diaphragm systems.
The GLANOR is equipped with dimensionally stable metal anodes.
The cathodes are constructed of the standard steel wire mesh. While
traditional asbestos diaphragms are utilized presently, it appears
that new diaphragm technology now being developed by PPG and others
will be available in the near future, allowing for further improve
ments in power consumption, diaphragm life and renewal cycle time.
To digress briefly, we believe that one of the very interesting
features of the cathode design is the fact that the cathode fingers
extend out from the backplate allowing for much easier inspection of
the screen surface than is possible with the monopolar designs.
(Figure 2) This feature also makes the GLANOR design one of high
interest when discussing the type of cell that can best utilize
forthcoming pre-formed ion exchange membranes.
The anolyte compartment is connected to an independent brine
feed tank by means of flanged connections. Chlorine gas leaves
each cell from the top, (Figure 2) through the brine feed tank and
thence to the cell room collection system. Hydrogen gas leaves from
the top of the cathodic compartment of each cell while the cell
liquor is discharged via a traditional "perc" pipe system.

201
 The individual bipolar elements, held together by external tie
rods, comprise a tight, essentially leakproof unit resulting in
improved cell room working conditions, housekeeping and maintenance.
Each electrolyzer is equipped with a level alarm that monitors
the level of all the cells in the unit, relieving the operator of one
very tedious duty of frequently checking cell levels. By monitoring
only each electrolyzer, it is a simple matter to supply instrumenta
tion for a circuit, of say, from 14 to 20 electrolyzers as opposed to
the greater cost and complexity of supplying the instrumentation re
quired for the anywhere from 100 to 200 individual cells that would
be required in a modern day monopolar circuit.
The basic unit of the GLANOR electrolyzer is the bipolar
electrode. It consists of a steel plate to which the anode fingers
are connected on one side and the cathode fingers on the other side.
The bipolar electrode is set into a bipolar element (Figure 3)
which consists of a channel frame surrounding the anodes, appropriate
ly lined for protection against corrosion in the anolyte environment.
The electrical connection between the cathodic and anodic sec
tions is made with a special, newly developed technique that provides
for a very low voltage drop and low fabrication cost for this very
important part of the bipolar electrode.
The gasket that is used to seal the individual bipolar units is
made of a special elastomer that was developed and tested over a
several year period. It has met all the demands put on it, with
excellent results.
We now have a unit that has essentially no elements that are
subject to deterioration due to the conditions normally encountered
with chlorine cell operation.
It may be of interest to discuss a little more specifically
some of the more important considerations and problems encountered
and resolved in the development of the GLANOR.
First, the electrode configuration was optimized so as to obtain
the lowest possible voltage drop characteristics consistent with the
limitations of investment and operating requirements. This entailed
an analysis of the relationship of the height and current path length
of the electrodes to the optimum intercell connection system required
to carry the current from the cathode to anode.
A balance also was struck with respect to the height of the
electrodes, the range of operating current densities to be encount
ered and the anode-cathode gap so as to meet the goals with respect
to diaphragm life.

202
 Another objective of the GLANOR development program was that of
easy maintenance during the renewal cycles. That is, the design
criteria had to consider the practical aspects of diaphragm depositing,
assembly, dis-assembly , cathode washing and inspection of electrodes.
Thus, consideration was given to points that eventually would
allow for electrolyzer assembly with only the most remote chance for
damage to the diaphragm. The traditional method of cell assembly
leaves much of the success of assembly and anode-cathode alignment up
to the cell repair crew. In managing the GLANOR on turnaround, it is
difficult to mis-align the electrodes or to damage the diaphragms on
assembly. This is because of features built into the unit in conjunc
tion with the use of simple assembly fixtures. Obviously, this is an
important consideration for an electrolyzer design, but leads to the
by-product quality of very uniform current distribution and electroly
sis throughout the unit, because of good control of alignment.
Thus, not only did the GLANOR result from the development program,
but a completely new system of cell renewal.

Operating Characteristics - As mentioned previously, units rang

ing from 5 to 80 KA and from one to eleven cells have been in opera
tion for several years now. It may be of interest to review some of
the basic operating characterisitics of the GLANOR. This, of course,
is one of the better measures of the success of the electrolyzer
development program.
First, some general statements can be made. The GLANORs have
generally demonstrated a minimum diaphragm life of about one year
with every expectation that the range in diaphragm life will be from
12-18 months, or longer.
The electrolyzer also seems to demonstrate the ability to take
operating interruptions easily and with essentially no discernible
deterioration in performance. This is of major interest to us.
However, we still feel that the best operating attitude with respect
to diaphragm cells is to maintain a steady, full-rated load on the
units as much of the time as possible.
Let's take a brief look at the results, as listed in Table II,
of a run still underway, after considerably more than one year.
This is for an eleven cell GLANOR operating at 72 KA.
Table II
GLANOR V Type 1144 Electro!
Typical Operating Data'
Load, KA 72-73
Cell Voltage, average 3.55 + 0.1

203
 Current Efficiency, 7. 95.5-97.87.
Power Consumption, DC KWH/TCI2 2,535 + 50
7. CI2 in Cell Gas, by volume 97.5-997.
7. H2 in Cell Gas, by volume 0.02-0.15
7. O7 in Cell Gas, by volume 0.8-2.0
GPL NaOH - Cell Liquor 130-140
7. NaC103, A.B. - Cell Liquor 0.03-0.12
Production: STPD
Chlorine 26.7
NaOH (1007. Basis) 29.8
(1) Brine Feed; 320-325 gpl NaCl, 160-165° F with a
pH range of 10.5-11.0.* Standard asbestos diaphragm
system.

* The use of acid in the feed brine will further im

prove current efficencies. However, this should be
evaluated specifically for each plant situation.
I believe the results speak for themselves as to how well the
PPG-De Nora development effort succeeded in meeting its initial goals.
Shown in Table III are some of the physical characteristics of
the GLANOR electrolyzer .
Table III
Dimensions and Weight of the GLANOR V Type 1144
(Approximate)
Length Ft. 17
Width Ft. 11
Height, overall Ft. 12
Weight, empty Lbs. 85,000
Weight, in operation Lbs. 150,000

Installation - It is not sufficient in itself to develop a unit

that operates in the fashion depicted here. The unit must fit into a
sound layout and allow for routine operation and maintenance with a
minimum of care and concern on the part of the operator. The invest
ment cost must be competitive and the technology should be capable of
utilizing new developments, in the future, as a hedge for the opera
tor against obsolescence.
The electrolyzer allows for a very simple, and safe electrolysis
area configuration. The number of electrolyzers that can be in
stalled in one circuit varies, with the general range being between
eight (8) and twenty (20) electrolyzers.

204
 Taking into consideration the concerns of circuit voltage, a
fourteen (14) electrolyzer circuit offers some interesting possibili
ties. Refer to Figure 4 for a typical GLANOR electrolyzer circuit
layout. You will note the absence of aisle ways in mid-circuit, as
well as the fact that the circuit is made up of only two rows of
units. This, of course, reduces the amount of bus copper required
traditionally at the mid-point of the monopolar circuits, and also at
the crossover points. Note that there are only twelve sets of inter-
electrolyzer bus copper. Thus, it is apparent that renewal work is
greatly simplified with the bipolar electrolyzer layout, especially
in those more hazardous jobs of cutout and hot work because of the
relatively small number of units that must be electrically bypassed
compared to that required for the monopolar designs.
Another interesting point is the floor space required. A
circuit of 14 electrolyzers , operating at 80 KA, will produce approx
imately 415 tons of chlorine per day. Excluding the rectifier-
transformer area, you will notice that the length of the circuit is
only about 160'. This compared to traditional monopolar circuit runs
of 250-300 feet. The floor area required for the GLANOR circuit is
about 160' x 80' .
Thus, we have a floor area to capacity ratio of 12,800 square
feet to 415 tons per day or 12,800 sq. ft. "= 31 sq. ft. required.
415 TPD Capacity
The GLANOR can be installed in an elevated position to allow for
the use of certain types of transportation equipment to convey the
electrolyzer back to the repair area for renewal work. The circuit
can be an outdoor installation, especially suitable for the electro
lyzer where you have so few units to replace. These factors allow
for vastly improved ventilation in the electrolysis area and result
ant improved operator comfort. We believe the outdoor installation
will be considered more and more in future diaphragm cell installa
tions .

Renewal - Let's take a look at some of the features of the

GLANOR that are pertinent to the area of diaphragm renewal activities.
Here I think it will be easier to list some of the features that we
feel are advantages that are obtained with the GLANOR, with respect
to renewal work.
1. The frequency of cutout activity, and thus the exposure to the
attendant hazards of this type of work is reduced by a factor of
from 6 to 11 times that of the monopolar designs. That is, even
in comparison with the new larger monopolar cells available, the
number of "cuts" required is reduced considerably. Compare a
circuit of say, 80 of the larger monopolar cells with the GLANOR
layout, and assume a one year diaphragm life. With the monopolar

205
 designs, a minimum of 80 cuts per year would be required. With the
GLANOR a minimum of 14 cuts are required. This ratio is even
greater in those plants where the smaller monopolar cells are in
stalled. For example, in a circuit of 160 cells, the ratio would
be 160 cuts/year as compared to 14 per year for GLANOR.
2. At all times during the cell renewal activities the GLANOR element
is in the operating position. No longer is it necessary to turn
the cathodes over for one part of the work and stand them upright
for another. This allows for greatly simplified material handling
as well as reducing the opportunity for damage to a new diaphragm
due to an excessive number of handling operations.
3. All cell renewal activity is done in the repair area. Only the
absolute minimum of work is required in the operating location,
for increased operator safety.
4. The incorporation of design features that allow for the use of
simple assembly jigs and fixtures has almost eliminated the pro
blem of scraped diaphragms, that were so common during the place
ment of the cathode on the anode in the monopolar cell assembly.
Easily reproducible anode-cathode alignment is achieved with
minimum reliance on the judgment factors on the part of the cell
renewal crew.
5. The cathode fingers, as mentioned previously are shorter, and all
exposed to view for ease of inspection prior to and after dia
phragm depositing. (Figure 2)
6. The cathode design has allowed the designers to build an automatic
cathode washer which can eliminate the job of manually washing
cathodes. Superior results are achieved with only a fraction of
the manpower required.
7. Traditional diaphragm depositing techniques can be utilized.
8. Portable cutout switches can be utilized in an electrolyzer cir
cuit in much the same way as cutout switches have been historical
ly used.
9. There is a minimum amount of bus copper that must be connected-
disconnected during the cutout procedure. It is not necessary to
remove the bus copper completely while out in the circuit. A
simple job of removing only one set of the bolted connections
from each piece of bus copper allows the operator to remove the
electrolyzer from the circuit, and remove and clean up the copper
either in the cell repair area or out in the circuit where now
there is more than sufficient room to work on the copper in
safety.

206
10. The electrolyzers can be spaced from 3'-5' apart with insignificant
copper cost considerations, but with a large improvement in the
room available to the cutout man for doing what little work is re
quired in disconnecting and hooking up the bus copper.
11. A transporter system allows for easy transfer of the electrolyzer
from its circuit position to cell repair and back.
These are just a few of the features that relate to the renewal
and cutout activities that I felt would be of interest to you.
I think one can agree, basis the foregoing review, that for the
most part, the total goals of the development program have been met.
Of course, now the challenge facing the project is to continue with
the development of new technologies that can be incorporated and
adapted to the GLANOR to the benefit of those utilizing this technology
for producing chlorine.
Some of the new developments are well known to most people and
have been elucidated previously in several articles. Certainly the
improvements that are forthcoming in the area of diaphragm and membrane
technology will have an important affect on the economics of manu
facture of chlorine. I will not go into the specifics as it is out
side the scope of this article.
The trend to larger diaphragm cells has been accepted and is
logical in many cases. A unit such as the GLANOR, capable of produc
ing almost 30 tons per day of chlorine per electrolyzer, is considered
by many as being in the forefront with respect to capacity in today's
emerging diaphragm technology.

Commercial Activities - An important and visible way of evaluat

ing the overall competitiveness of this new GLANOR electrolyzer
technology is to review the acceptance by the marketplace of the
GLANOR. We first approached the market with the GLANOR in the summer
of 1972. The results have been impressive.
At present, plants are being, or have been designed in the United
States and Japan that range in capacity from 200 to 1,500 TPD capacity.
A total of about 3,125 tons of GLANOR capacity has been contracted for
in six plants in these two countries.
By 1975 it is anticipated that the total capacity of projects
involving the use of the GLANOR technology, exclusive of PPG's own
plans, could exceed 1,750,000 TPY chlorine.
As plant installations are completed and people have an opportun
ity to evaluate firsthand the end results, we are convinced that the
bipolar design concept employing metal anodes, as first presented to
the trade in the GLANOR, will become an increasingly important factor
in the manufacture of chlorine throughout the world.

207
Fig. 1 - Glanor V Type 1144 Fig. 2 - Isometric Cutaway
Electrolyzer of Glanor
BI-POLAR ELEMENT

NOZZLE
CATHODES

TYPICAL OLAWO«' CKCWT ARRANGEMENT

ANODES

Fig. 3 - Glanor Bipolar Element Fig. 4 - Typical Glanor Circuit

Layout

208
 THE DEVELOPMENT OF HOOKER'S
H-2A AND H-4 CELLS
M. P. Grotheer and C. J. Harke
Hooker Chemicals & Plastics Corp.
P. 0. Box 344
Niagara Falls, New York 14302

Hooker's new diaphragm cells have improved operating

economics and improved environmental and safety features.
New design features include perforated plate cathodes,
copper conductors built inside the cathode tubes, metal
anodes, plastic tops and the elimination of previously
used lead and mastic in the anode system. These new
cells are modifications and scale-ups of our previous
C-60 cells. An analysis of cell voltage and heat and
material balances are discussed.
Hooker has developed two large diaphragm chlor-alkali cells with
improved investment and operating economics as well as improved envi
ronmental and safety features. The development of these cells has
been a natural continuation of diaphragm cell developments that have
extended over a period of seventy years. This paper will describe
some of the development efforts and accomplishments of the last five
years.
In 1969 Hooker was operating diaphragm cells of all the types
shown in Table 1.
Table 1
Hooker Cells in Operation in 1969
Type of Cell S-l S-3 S-4 C-60
Rated Capacity, KA 10 30 55 55
Maximum Capacity, KA 15 36 60 60
Tons/Day of Production 1100 4700 2970 370
The tons per day of production shown in Table 1 were the approximate
world-wide totals. The well-known S Type Hooker cells had been
licensed extensively to chlor-alkali producers. The C-60 cell was
Hooker's last diaphragm cell designed for graphite anodes. It had
been developed for commercial use in Hooker's own plant expansions
and went into service in 1967 in our North Vancouver, B.C. and Taft,
Louisiana plants.

209
 Both the C-60 and the S-4 cells are rated at 55 KA. The major
differences are:
1. Cathode finger design
2. Cell orientation in the circuit
3. Current conductor arrangement
The S-4 cell cathode and all the S Type cell cathodes that
preceded it have an open anolyte circulation area in the center of
the cathode. That is the fingers do not extend all the way across the
cathode. (See Figure 1) This design developed from a cell that had
anodes and cathodes protruding from opposite sides. The S-4 anodes
and cathodes are perpendicular to the rows of cells in a circuit.
Copper extends from the cathode connection around to the two adjacent
sides to conduct current into the fingers on either side. The copper
on the sides is tapered to minimize the use of copper. The required
cross sectional area for current conduction decreases as the current
enters the cathode fingers, thus the copper conductor is tapered.
The C-60 cell cathode, Figure 2, has fingers that extend all the
way across the cathode. Hooker had built a few cells with this type
of cathode in the early and mid-1940's and had patents^) > \3; covering
the concept of straight across cathodes. Results with a few cells
indicated that the current efficiency was slightly lower than for cells
with the open circulation channel. The anodes and cathodes are
parallel to the rows of cells in a circuit. There is copper on the
cathode connection side and current conductors on the. inside of the
cathode, but no copper on the outside of the three other sides of the
cathode shell. Copper conductor is used most efficiently inside the
cathode tubes such that the current path is short. The C-60 cell
design enabled us to conduct the current more directly thus saving on
materials costs. The bimetalic couple of steel and copper inside the
cathode has proven to be very satisfactory. During operation the
system is so overwhelmingly cathodic that no corrosion occurs. When
shut down the corrosion rate of the steel adjacent to the copper is
negligible. Cathodes of this type have been in service since 1968.
The interior of one of these cathodes was recently inspected and
found to be in excellent condition.
Although the C-60 cell was economical to build, capital costs
were lower than for the S-4 cell, its performance particularly with
new graphite was somewhat less satisfying than the S-4 cell perfor
mance. Current efficiencies were slightly lower, but this was
partially offset by lower cell voltages. This confirmed earlier
results with cathodes of this type. The reason for this was believed
to be the small volume of anolyte between anodes and diaphragms and
poor circulation as a result of new graphite nearly filling the
spaces between cathode tubes.

210
 Hooker installed metal anodes in several of the various commercial
diaphragm cells in 1969 and 1970. It was hypothesized that the C-60
configuration with metal anodes would be satisfactory because of the
greater anolyte space inside the metal anodes. Our early test work
with metal anodes in C-60 cells proved them to be entirely satis
factory and in some respects, better than other configurations. It
was found that replacement of the high volume graphite with low volume
metal anodes, increased the volume of anolyte in the cell and improved
the circulation and operating characteristics of the cell.
Greater amounts of copper were designed into all the current
conducting members of the C-60, a metal anode base system was developed
and the new cell rated at 80 KA was designated the H-2A. The H-4 cell
rated at 150 KA is a scale-up of the H-2A cell. The H-2A cell has 42
metal anodes in 2 rows while the H-4 cell has 75 metal anodes of the
same size in 3 rows.
The trend in cell development had been toward larger cells that
required less floor space per unit of production. The H-2A and H-4
cells would have required considerably less space per unit of
production if we had not provided more space between cells and rows of
cells. By providing more space around cells the working environment
has been improved. Ventilation is better and overall conditions are
safer.
The redesign and scale-up of these cells for the utilization of
metal anodes involved several changes. An anode base (Figure 3) for
metal anodes equipped with cathode to anode alignment and locking
devices and hold-down clamps to assure a leak-free seal between the
base and cathode was designed.
The new anode base and metal anodes completely eliminated the use
of lead and mastic in the anode structures. This eliminated the
hazard of lead vapors around lead melting pots and the smoke problem
associated with recovering the old lead slabs that always had some of
the asphalt or bitumenous mastic left on them. The anode assembly
and renewal work is now preferably done in a clean atmosphere with a
minimum of equipment. The building area required is only a fraction
of that required previously with graphite anodes.
The cathodes (Figure 4) have alignment and clamping fixtures to
compliment those on the anode base. A hydrogen seal on the cathode
prevents excessive hydrogen back pressure and dangerous hydrogen-
chlorine mixing through the diaphragm. The cathode surface was made
of perforated plate instead of the previously used woven wire mesh.
Perforated plate is less expensive and electrical continuity is much
better.
The cell tops or covers (Figure 5) are of fiber reinforced
plastic construction. They are held in place by spring- loaded turn

211
buckles to form leak-free seals between the top and the cathode. The
light-weight plastic tops have made hold-down clamps necessary at both
the cathode-base and cathode-top seals.
All the intercell connectors (Figure 6) on a cell are removed
with the cell shorted out of the circuit. This plus greater spaces
between cells has improved the working environment and safety of the
cell renewal operation.
The relationships between cell voltages and current loads for
the H-2A and H-4 cells are shown on Figure 7. The current densities
are 1.5 amps per square inch at 150 KA and 84 KA for the H-4 and H-2A
cells respectively. An analysis of the H-4 cell voltage indicates
that the structural components of the cell have been designed to
minimize the cell voltage. Table 2 shows an analysis of the H-4 cell
voltage at 150 KA.
Table 2
Analysis of H-4 Cell Voltage at 150 KA
Decomposition - anode 1.32
- cathode 0.93
Overvoltage - anode 0.03
- cathode 0.30
Brine Gap (with 107. gal vol) 0.49* 0.35+
Hardware - anode & contact to base 0.11
- base 0.06
- cathode 0.09
Asbestos diaphragm 0.46** 0.60++
Cell Voltage 3.79
*Brine gap from anode to cathode
**Due to presence of asbestos diaphragm
+Brine gap from anode to face of diaphragm
++Due to diaphragm and gap occupied by the diaphragm
The decomposition potentials were calculated from standard
electrode potentials making corrections for temperatures and concen
trations. The overvoltages were obtained by measuring electrode
potentials at this current density using Luggin capillaries and sub
tracting the decompositions potentials. Voltage losses in the brine
gap and asbestos diaphragm were measured by placing Luggins'
capillaries in the appropriate locations. However, the outer face of
the diaphragm is rather irregular and it is difficult to place the
capillary on this soft poorly defined surface. Voltage losses were
calculated for the brine gap from anode to cathode and for the
presence of the asbestos diaphragm. The equation for calculating
the effect of gas evolution on ohmic resistance developed by Tobias*'
was used to calculate the voltage loss in the electrolyte gap.

212
 The total voltage due to the brine gap and the diaphragm is about
0.95 volts. Considerable effort is presently directed toward de
creasing this power loss. Recent results with new diaphragm materials
and smaller gaps have shown that cell voltages at 1.5 amps per square
inch can be decreased by about 0.4 volts.
The current efficiency of H-2A and H-4 cells varies with current
density and the concentration of caustic produced. Figure 8 shows
the relationship between current efficiency and caustic concentration
for the H-4 cell at 150 KA.
A computer program for H-2A and H-4 cell material balances has
been developed. The program is a direct simulation of the diaphragm
cell process in that the inputs are process inputs of brine feed
concentrations (g/1) and amount of acid additions, current load (KA),
and caustic concentration to be produced (g/1). The relationships
between current load and cell voltage shown in Figure 7 and current
efficiency and caustic concentration in Figure 8 are used in the
program. The computer program calculates internal flows, concen
trations in the cell, cell temperatures and product stream quantities
and compositions. A typical material balance printout is shown in
Table 3.
Table 3
Typical Material Balance
*Cell Load 150.00 KA
Cell Voltage 3.788 volts
Current Efficiency 96.537.
*Brine Feed Concentration 315.00 gpl at 65°C
*Caustic Concentration 140.00 gpl
*Acid Addition 20 lb/T Cl2
S/C Ratio 1.3405
Anolyte Concentration 266.10 gpl
Anolyte Temperature 94.19°C
Catholyte Temperature 100.19°C
Units in LB/MIN unless specified
Brine Feed Salt 22.0228 26.20 PCT
Water 62.0571
Total 84.0799 8.5690 GPM
Acid Feed HC1 0.0704
H20 0.3000
Total 0.3704

213
 CI2 Gas Cl2 7.0373
02 0.0474
H20 3.5275
H2O 0.5013 LB/LB Cl2
H2 Gas H2 0.2073
H2O 4.6404
H20 22.3851 LB/LB H2
Caustic NaOH 7.8614 11.3950
NaCl 10.5380 15.2746
H20 50.5908
Total 68.9903
*Input Information
The addition of acid beyond neutralization is not necessary but
chlorine production efficiencies are improved by the addition of
hydrochloric acid to the feed brine. Economically this is not
advisable unless hydrochloric acid is available at very low cost.
The product compositions are shown in pound/minute unless specified
in other units.
Large production capacity can be achieved with relatively small
numbers of these large cells. A single circuit of 100 H-4 cells will
produce about 500 short tons of chlorine per day. Table 4 shows the
number of cells, number of circuits and circuit voltages associated
with a 500 ST/D Cl2/NaOH plant using various cells.
Table 4
Cells Required for 500 Short Tons Per Day of CI2 Production
Cell Rated KA No. of Cells No. of Circuits Approx. Cir. Volt?
H-4 150 100 5 1 386
H-2A 80 188 2 360
S-4B 55 272 2 546
Circuit voltages may therefore be lower providing greater cellroom
safety. Fewer cell units to construct and maintain result in
lower engineering and construction costs, lower operating and renewal
costs and lower maintenance costs.
The external surface area to volume ratio for the large cells
is relatively low. Table 5 shows the approximate surface area,
volume and surface to volume ratios for several cells.

214
 Table 5
Approximate Surface to Volume Ratios for Several Hooker Cells
Cell Surface Area Volume Ratio
S-l 60.55 sq ft 35.34 cu ft 1.713
S-3 118.9 91.9 1.294
S-4 163.0 147.9 1.102
H-2A 164.6 147.6 1.115
H-4 253.9 276.4 0.918
The large cells are not easily or readily influenced by ambient
conditions. H-4 cells are well suited for outdoor installations in
mild climates. "*
The development of diaphragm cells had been a rather slow
evolutionary development until about 1969. The advent of metal
anodes has caused a revolution in diaphragm cell development over the
past 5 years. Improved diaphragms and permionic membranes will
probably maintain a rapid pace in cell development for the next
several years.

Literature Cited
(1) J. E. Currey, "Current Conducting Members for Electrolytic
Cell", U. S. Patent 3,432,422 (March 11, 1969).
(2) J. A. Flynn, et. al., "Electrolytic Alkali Chlorine Cell",
U. S. Patent 2,330,415 (September 28, 1943).
(3) D. R. Means, "Electrolytic Cell", U. S. Patent 2,368,861
(February 6, 1945).
(4) C. W. Tobias, "Effect of Gas Evolution on Current Distribution
and Ohmic Resistance in Electrolyzers", J. Electrochem. Soc,
106, 833-838 (1959).

215
 FIGURE I FIGURE 2
S-4 CATHODE C-60 CATHODE

216
 FIGURE 5 FIGURE 6
H-4 CELL TOP H-4 INTERCELL
CONNECTORS

FIGURE 7 FIGURE 8

H-4 CELL CURRENT EFFICIENCY

. VOLTAGE VS CURRENT LOAD VS CAUSTIC CONCENTRATION
H-2A AND H-4 CELLS

40 60 80 100 12
CURRENT LOAD- KILOAMPERES lao is5 i3o iso i60 iW
CAUSTIC CONCENTRATION-GPL NaOH

217
 ADVANCED TECHNOLOGY IN CHLORINE PRODUCTION
V. H. Thomas and K. J. O'Leary
Electrode Corporation
P. O. Box 229, Chardon, Ohio 44024
and
Diamond Shamrock Corporation
P. 0. Box 348, Painesville, Ohio 44077

Recent developments have reawakened interest

in diaphragm cell technology. Several manufacturers
have already profitably substituted d imensi onal ly
stable anodes as replacement parts in commercial
diaphragm cells. A new concept has recently been
introduced by Diamond Shamrock wherein the dimen
sional stability and superior operating charac
teristics of the DSAs have been optimized. This
concept is based on an anode with self-adjusting
gap which controls anode- cathode spacing to allow
optimum performance levels. At present, the major
operational weaknesses in diaphragm cells lie
within the diaphragm-cathode area itself. These
deposited asbestos diaphragms are subject to a
number of operational disadvantages. A new concept
in a c at hode -d iaphr agm separator will be intro
duced and its ramifications to cell operation and
power saving alone and in combination with a self-
adjusting anode will be discussed. Other new
innovations will be discussed.

In tr oduc t i on . The production of chlorine-caustic via

diaphragm cells in the U. S. dates back to the early 1890s.
In the ensuing years, diaphragm plants proliferated until,
by 1930, they completely dominated the chlor-alkali
industry. The diaphragm cell process is still dominant
in the U. S. today, while elsewhere in the world the mer
cury cell has assumed supremacy. The mercury cell share
of the U. S. market rose from 4% in 1945 to a maximum of
over 30% in 1970-71, but has since lost ground, dropping to
24% today. This will further decrease when the new dia
phragm plants under construction come on line.
This swing back to diaphragm cell production and away
from mercury cells results principally from environmental
concerns.1 Several mercury plants in the States have shut
down and others are converting to diaphragm cells.

218
 Japan has taken a firm environmental stand and requires
75% of its mercury cell production be converted to diaphragm
cells by 1975. Environmental concerns are now reaching
Europe and it is expected that any new plants there will
most likely use the diaphragm cell.
In addition to these environmental cons iderations , all
U. S. chlorine manufacturers are making significant efforts
to improve their plant safety. This includes better cell
maintenancef improved worker areas, conditions and equipment
Examples of such improvement are the elimination of lead and
asphalt by replacement with new dimensionally stable anodes
and cell bases, nonslip floors, guard rails, and removal of
projections. We predict that this trend will continue,
particularly if the current legislation of the Department
of Labor under the Occupational Safety and Health Admin
istration (OSHA) is strictly enforced and further strength
ened by additional legislation.
This renewed interest is diaphragm cell technology,
both at home and abroad, has induced a number of U. S. com
panies to expand their cell licensing activities. It has
also accelerated research efforts to incorporate the most
advanced technology into their diaphragm cells. These ad
vances are keynoted by use of dimensionally stable anodes
in diaphragm cells. A comparison of graphite and DSA**
anodes and their effects on performance is shown in Table I.
The availability of these electrodes with their super
ior properties has led a number of cell manufacturers to
profitably redesign their diaphragm cells around DSA using
steel, plastic, and titanium, thus eliminating the older
construction materials of concrete, lead, graphite, and
mas t i cs .
Table II shows some of the manufacturers who have now
converted their cell designs to dimensionally stable anodes.
Diamond Shamrock Corporation has been experimenting
with DSA electrodes in its diaphragm cells since 1966.
Shown in Figure 1 is a set of anodes before installa
tion in a DS-85 cell. Figure 2 shows the comparative
voltage for cells containing DSA and graphite anodes.
The performance of two types of Diamond Shamrock cells
is shown in Table III. In addition to the replacement of
graphite with DSA anodes, the overall system was optimized

egistered trademark of Electronor Corporation.

219
by introducing an improved current distribution system, an
assured parallel anode orientation, and specifically design
ed base assembly (both patented concepts).
These cells can now produce 360% more chlorine at 2.5%
less power per ton on one-half of the original floor space.
Diamond Expandable Anodes. Diamond Shamrock introduced
a new concept in anode des ign 3 in 1972. A schematic drawing
is shown in Figure 3. This highly innovative design allows
a great deal of flexibility. A list of its advantages is
shown in Table IV.
Pi aphr aqms i The remaining major area for savings in
the diaphragm cell is the diaphragm itself. Most percolat
ing commercial chlorine-caustic cells utilize diaphragms
made from a specific asbestos called chrysotile. Chrysotile
fibers are some of the finest materials discovered in nature
ranging in their ultimate fiber diameter from 200 to 500 k.
Normally, these mined filaments are grouped into bun
dles, which range in size from 400 y to .2 \i with the major
ity in the range of 40-4 y. This can be seen clearly by
observing the scanning electron photomicrographs of a de
posited asbestos diaphragm (Figures 4, 5, 6). Diaphragms
were prepared from a standard vacuum deposited solution.
There appears to be a wide variation in the average bundle
sizes and distribution over the face of the cathode sheets.
While many manufacturers specify certain long and short
fiber ratios, these scanning photos clearly demonstrate
there is also a wide distribution in fiber length.
The asbestos bundles break up into smaller units under
operational conditions of the diaphragm cell. This degra
dation is generally demonstrated by swelling which normally
occurs after a few days. A photo of the swelling in a
laboratory cell is shown in Figure 7. As can be seen, the
asbestos has completely filled the anode-cathode gap. An
example of this phenomena is shown in Figure 8 for a DS-45
cell removed ^fter 180 days. Again, the diaphragm has ex
panded to almost fill the gap.
Since asbestos is known to have ion exchange proper
ties and a charged surface, the swollen asbestos acts as an
efficient filter, absorbing, for example, any eroded car
bon when graphite anodes are used, cement from the old
concrete heads, and particulate matter in the brine. After
years of commercial testing, Diamond Shamrock has incor
porated into its new cells the light-weight noncorrosive
polyester cell heads which have replaced the older heavy

220
concrete head. The swelling and clogging of the diaphragm
acts to increase the voltage and decrease the hydr odynamic
flow through the diaphragm, thereby increasing power con
sumption and shortening diaphragm life.
With high quality brine, asbestos diaphragms were pro
jected to last up to two years, when used with DSA anodes.
The rationale for this expected longer life was that when
the degradation of the carbon anodes, which contributed to
diaphragm pluggage, was removed, there would be sufficient
economic incentive to improve feed brine quality. In
actual practice, we have found the diaphragm life to be
much shorter, approximately 200 to 250 days. Observation
of cell operation indicates that towards the end of the
life, these cells become what is referred to as fast run
ners, that is, the percolation rate through the diaphragm
is higher than optimum. It is theorized that the swollen
asbestos fibers are eroded from the surface until the dia
phragm becomes thinned to allow the high permeability.
This problem is particularly evident if the gap has been
minimized or the cell operated at high current densities.
Both patent and technical literature note that many
attempts have been made to modify asbestos diaphragms; the
majority of these involved polymer addition. However, none
were successful due principally to the inherent short life
of the diaphragm in operation and the lack of stability of
the polymer materials themselves.
Diamond Shamrock has recently developed and is cur
rently optimizing a new type of cathode-diaphragm (patent
pending) in which the asbestos diaphragm is modified to
preserve the excellent qualities of the asbestos diaphragm
and reduce their troublesome properties. This new cathode-
diaphragm's advantages are given in Table V.
Figure 9 shows the relative performance of this new
type of modified diaphragm in a MDC series cell. When
this new diaphragm is combined with expandable anodes, it
allows an additional voltage saving, as shown in Figure 9.
Needless to say, in these days of rapidly escalating power
costs, every millivolt saved has economic significance.
Membrane Cells. Many chlor-alkali research centers
are experiencing a flurry of activity today on a special
type of diaphragm cell, a membrane cell. A membrane cell
is a relatively old concept that should allow the produc
tion of high purity, high strength caustic directly from
the cell. Experiments in late fifties with ion exchange
membranes demonstrated this concept to be technically

221
feasible. ' However, the short membrane lifetimes com
bined with poor current efficiencies due to the high
hydroxy 1 ion b ackmigr a tio n and difficulties with the carbon
anodes made this process uneconomic. Today, this renewed
interest in membrane cells has been brought about by two
developments the DSAs and DuPont's NAF ION® membrane . While
these developments are still in the research and develop
ment stages, there is little doubt that we shall see some
special application of this technology in the next few
years .
Plant Construction. Open air cell rooms have been an
accomplished fact for many years. Many new diaphragm
plants in certain geographical sections are favorably con
sidering this alternative in construction. The advantages
of cost, ease of maintenance in cell repair and cell room
modification have outweighed the disadvantages of certain
climatic conditions on cell operation. For those who still
prefer the more traditional enclosed cell room, the trend
appears to be an elongated building, with the open sides in
the warmer climates for improved air circulation. The
roofs are highly pitched with a central ridge vent to as
sist in upward outflow of internal heat.
Materials of Construction. New materials of construc
tion are being incorporated in all new plants. Plastics
are playing a more important role, particularly in pipe and
pipe linings. Metals such as titanium and nickel are also
finding increased usage. Despite their higher cost, their
superior properties and long life make them cost effective.
The high price of copper has compelled many design engineers
to seek alternate replacement conductors. Aluminum remains
one of the principle contenders, but opinions vary widely
on its use in cell rooms. Some older concepts, such as
metallic sodium filled steel pipes, are again being con
sidered as bus bar systems.
Plant and Quality Control. With power costs skyrocket
ing, most engineering departments are carefully scrutiniz
ing and incorporating any new energy conserving equipment
into their plants. The increasing popularity of a thy-
resistor controlled AC/DC conversion system is one example.
A thyrisistor is an electronic device which replaces the
tap changer as a continuous control over the full rectifier
operation range and allowing precise control over load and
demand. This is particularly true when used in conjunction
with a computerized KWD or KWA demand production equipment.
Many new plants are adopting air cooled rectifiers, thus
reducing capital cost. It should be mentioned that this
Sfeegister ed trademark of E. I. du Pont de Nemours & Co., Inc.

222
modification may create space problems if large capacity
rectifiers are used.
Another innovation which was recently incorporated in
to our new Battleground diaphragm project is a vacuum bot
tle tap changer, which increases the number of tap changes
before replacement from 250,000 to 1,000,000.
The trends toward high current diaphragm cells re
quires larger shorting switches, in replacing cells. Dia
mond Shamrock Corporation has developed a compact water
cooled switch with capabilities of upwards of 130,000 amps.
The switch incorporates pneumatic operators and interlocks,
temperature sensors and alarms, cabinet is air purged to
reduce corrosion.
An interesting development on plant equipment is the
entry of Japanese rectifiers into the U. S. market. Their
position has been strengthened by the reduction in the num
ber of O. S. manufacturers.
The performance of diaphragm cells is normally moni
tored by the analysis of cell liquor, anolyte brine and the
gas analysis. Since the number of diaphragm cells in most
plants is quite large, this places a severe burden on the
plant lab capabilities. With rising power costs, the need
to optimize cell performance is essential. To accomplish
this, there is a trend toward more sophisticated automated
analytical equipment. Gas chromatograph analysis for cell
gas, atomic absorption spectrometer for metals, and auto
mated colorimetric equipment, such as the Technicon Auto-
analyzer for anions, have greatly aided in the speed,
accuracy, and precision of these analyses. We would ex
pect to see increased use of these tools in the future.
Certainly the present cells are not the ultimate in
improvement of cell design and cell operation. A number of
areas for future improvement are shown in Table VI.
Acknowledgment . The authors would like to express
their gratitude to Mr. T. A. Liederbach and Mr. J. Parker
for their invaluable assistance in preparing this paper.

Ref er enc es .
1. Chem. Eng. News, 48, 36 (June 22, 1970).
2. Chem. Week, 113, 31 (Aug. 1, 1973).

223
3. Diamond Shamrock Corp., 0. S. Patent 3,674,676 (July 4,
1974) .
4. Ionics, Inc., U. S. Patent 3,124,520 (Mar. 10, 1964).
5. Diamond Shamrock Corp., U. S. Patent 3,017,338 (Jan. 16,
1962) .

224
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FIG. 4. Scanning Electron Micrograph of an Asbestos
Deposited Diaphragm
(Small cubes are dried NaC 1 , Na2CO3 from
depositing solution.)

FIG. 5. Scanning Electron Micrograph of an Asbestos

Deposited Diaphragm

228
FIG. 6. Scanning Electron Micrograph of an
Asbestos Deposited Diaphragm

FIG. 7. Operating Laboratory Cell, with Swollen

Asbestos Diaphragm.
(A) Anode (B) Swollen Asbestos
Filling 1/2 in. gap. (Bubbles on right
are chlorine gas being evolved [photo
rotated 90°])

229
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 NEW CHLORINE PURIFICATION PROCESS

Rosario Alessandrello
Riccardo Bosio
Mario Ghezzi
Tecnimont Via Traiano, n. 7 - 20100 Milano
Montedison Via dell'Elettricita, n. 41 - 30175 Porto Marghera-Venezia
Montedison Largo Donegani, n. 1 - 20100 Milano

Modern technologies using chlorine often require high

purity chlorine with a minimum inert gas content. The new
chlorine generating system installed and operating at Porto
Marghera, Italy, utilizes technology capable of supplying
chlorine with a purity of 99-9$ and an inert content of
about 1,000 ppm.

This level of purification is based on an integrated

condensation - evaporation process, the heat for the evapor
ation of the liquified chlorine is obtained from the conden
sation of the gaseous chlorine from the electrolytic plant.

A fully automatic control system has been developed

so that all necessary instructions can be followed. The
maximum plant capacity is 150, 000 Tons per Year of chlorine
of this high quality.

The total plant is integrated and incorporates all

the latest technologies to meet ecological needs at the lowest
cost. The plant investment costs are similar to those for a
normal Freon liquifying and steam evaporation plant but
considerable savings in operating costs are obtained.

1. Old process

The conventional chlorine purification process is based on chlorine

231
 liquefaction at the expense of frigories supplied by a Freon
refrigeration unit and on the subsequent evaporation at the expense
of calories supplied by heat. Therefore it consists of a Freon
liquefying plant and of a liquid chlorine pump to feed the
evaporator (Fig. l) .

2. New process

A new process developed by Montedison at the Porto Marghera plant,

Italy, offers the possibility to liquefy chlorine partially using
the Freon plant's frigories and partially using the frigories
supplied by the chlorine evaporation. Thus, under operating
conditions, the Freon refrigeration circuit supplies only frigories
corresponding to the process losses.

The particular situation at Porto Marghera required the addition

of a compressor for chlorine gas as the user plants were located
at a considerable distance from the purification plant (Fig. 2).

3. Comparison between both process

The investement costs for both plants are somewhat equivalent as

the higher cost of the old process equipment (liquid chlorine pump,
chlorine evaporator and Freon refrigeration plant with higher
capacity) is somewhat equivalent to the chlorine gas compressor
cost for the new process.

The new process cost would be lower in a plant where the evaporated
chlorine does not require any compression.

Comparison between utilities consumptions of both plant referred

to a 50,000 Tons per Year purified chlorine plant is as follows :

old process new process

Power consumption kWh/t chlorine 44 8
Vapour Kg/t chlorine 127
Cooling water m^/t chlorine 16 4

232
4. Purification plant control

The Porto Marghera plant control system has been carried out to
assure the following conditions (Fig. 3)

- constant pressure at the compressors inlet from cells

- liquefaction capacity : at 90$ or higher values
- chlorine condensation in the Freon condensor limited to the
quantity strictly required for the process

5. Chlorine quality

The evaporated chlorine quality is as follows :

chlorine 99.9 w/w

oxygen 150 ppm w/w
H20 10 ppffl w/w
N2 400 ppm w/w
C02 450 ppm w/w

233
 USE
VAPOR

1 CHLORINE COMPRESSOR
1 LIQUIFIER
3 RECEIVER
CIS. 1 OLD PROCESS
4 EVAPORATOR
5 CHLORINE PUMP

VAPOR VAPOR

USE

c J
1 CHLORINE COMPRESSOR
2 LIQUIFIER
9 RECEIVER
FIG. 2 NEW PROCESS A EVAPORATOR
5. COMPRESSOR

234
 CELL ROOM SAFETY
A. T. Emery and J. E. Currey
Hooker Chemicals and Plastics Corporation
Niagara Ealls, New York 14302
While the chlorine industry has had a good safety record relative
to industry as a whole, the record is still not as satisfactory as it
can be. Serious injuries occur more frequently than the industry can
tolerate. We, and others, are making a determined effort to improve
this situation in a number of ways. Cell safety is currently the
subject that is of great concern to our plants and all producers of
chlorine which use electrolytic diaphragm cells. This concern for
safety and the need for compliance with new regulations is having
important implications on cell design, cell operation and cell renewal.
I would like to describe some recent activities of our company and
others in the design of safer diaphragm cell systems.
There are many aspects of chlorine plant safety which might be
covered in this type of presentation. Many of the problems relating
to hazards in the overall plant have been discussed previously. The
contents of this report will concern only the electrolytic cell area.
During this presentation I would like to comment on our philosophy
regarding cell room safety; to present our analysis of the hazardous
areas and their injury potential; finally, I would like to describe
what we are doing or plan to do to remove or minimize these hazards.
There are several incentives for improving cell safety, viz:
humanitarian concern, better community relations, better employee
morale, better operating efficiencies, and fewer injury-related law
suits. Overlaying all of these are the regulations contained in the
Occupational Safety and Health Act dated December 29, 1970.
There has been much concern over cell room safety by the chlorine
industry and particularly by the Chlorine Institute over the past few
years. Most of you who are associated with major chlorine producing
companies know of the work the Chlorine Institute is doing in these
areas.
There are unquestionably many more improvements that can be made
and that will be suggested. The more important of these and which
will have the greatest impact on reducing hazards will be discussed.
Development of an effective cell safety program has several
aspects. First, a basic philosophy must be stated based on positive
management attitudes and a solid management commitment. More than
lip service is required. The dollar expenditures will be high and it
will be easy to find reasons for not implementing expensive modifica
tions. Secondly, the types of hazards and their injury potential must
be identified. Thirdly, programs must be implemented in the design,
operations, maintenance, and training areas to remove or reduce the

235
injury potential in each hazard area.
Obviously, desirable changes are fairly easy to make in those
installations now going in, but it will be much more difficult to bring
existing cell rooms into better compliance.
In developing an appropriate safety philosophy, we think that the
following concepts are basic:
1. The total safety system must be reliable and effective regardless of
the education and training of the exposed personnel. Many of the
cell room workers having the highest degree of exposure to hazards
have the least amount of training and experience.
2. The design parameters, control systems, operating procedures, and
renewal procedures must be explicitly defined. Employees must be
trained to understand the normal operating routines and to react
correctly in emergency situations.
Power outages, spills, high hydrogen cells, low level cells, etc.
are representative of the operating problems which must be
recognized and corrected before more serious emergencies develop
with their higher probability of personnel injuries.
3. Two levels of safeguards should be provided to approach zero
accident potential in the hazard areas. The first level relates
to the use of proper personnel protective clothing and equipment.
The second to safe mechanical and electrical design of cells, piping,
busbars, mechanical equipment and surrounding structures.
4. Protective systems must be frequently monitored to insure maintenance
of proper safety, that is protective clothing, control devices,
electrical insulation, alarms, etc.
Inspection and maintenance of major cell components and renewal
equipment must be scheduled on a regular basis.
5. Management must recognize that safety will cost investment and
operating dollars.
The types of modifications which we have proposed and are being
incorporated into our newest plants have increased the cost by
10-207. for the electrolytic area (not including rectifier) depending
on the extent of the modifications and the number of cells involved.
This includes such basic changes as longer and wider cell buildings,
more intercell copper, larger cranes, trenching of floor piping,
elimination of packed joints on cell branch piping, more cell copper
at lower current densities, additional copper terminals for easier
and safer jumper switch installation, bus and steel insulation, etc.

236
 However, it is also important to recognize that several improvements
intended to minimize cell room hazards have also produced positive
operating improvements or savings as well, for example, improved caustic
accountability, lower intercell voltage drop, lower risk of dry cells
and damage to electrodes, better productivity of personnel.
Hazards in the cell room can be broadly categorized as:
1. Electrical hazards.
2. Mechanical hazards such as trips, falls, etc.
3. Chemical hazards such as chlorine fumes, caustic burns.
4. Thermal hazards such as hot surfaces, hot fluids.
5. Fire/Explosion.
6. Comfort, such as excessive cell room temperatures.
Chart 1 illustrates the major contributors in each category of
hazards, typical exposure frequencies, injury potential and some of
the ways in which the hazards can be eliminated or minimized.
Most of these hazards are in one way or another covered by OSHA,
NIOSH, EPA or other regulatory bodies on both the federal or state
level. Obviously, if we can identify a hazardous situation it is
important that something be done to rectify it.
To minimize the injuries associated with these hazard areas, we
have taken the following steps in our newest plants. We are also
making similar recommendations to those plants installing our cell
equipment.
1. Design of a cell room to reduce personnel exposure, for example,
monitoring devices on cells, fewer numbers of cells in each
circuit, longer periods between renewals.
We think for example that the shock hazard severity increases
markedly in circuits above 400 volts. We have taken the position
for our own plants that cell size and number of cells should be
selected to insure that circuit voltages do not exceed 400 volts.
All grounded metal is either insulated in the working zone or is
over 42" away from the closest energized bus. All back aisle
pipe supports which cannot be moved are insulated in the work
area.
Minimizing certain high exposure but routine operations such as
remote voltage and temperature monitoring of each cell.
Obviously, the use of metal anodes has extended the time between
cell renewals thereby reducing the exposure frequency.
2. Design of cell hardware and auxiliary equipment to reduce injury
potential. For example, more thermal and electrical insulation,

237
 greater spacing between adjacent cells, greater front and back
aisle widths, elimination of cell drips and leaks. For example,
we have increased the intercell spacing to 18' 1 clearance and
back aisles are now over 6 feet. An improved gasket system has
been designed for both the top and bottom flange areas of the
cells. Various clamps and hold down devices are used to improve
the seal quality. Mats or blankets for thermal and electrical
insulation in the area of cell renewal will be used to protect
personnel. These will be used on exposed bus, cell surfaces,
and surrounding floor.
3. More attention to the selection and training of personnel
associated with the operation and renewal of electrolytic cells.
We have found that a great many of the injuries in the cell area
are directly attributable to inexperience and lack of knowledge
of the cell systems. This is particularly noticeable in new
installations in areas where the work force does not have
chemical plant experience.
The ranking of the job categories in a chlor-alkali facility by
hazard potential could be:
a. Cell Renewal
b. Cell Tender
c. Chlorine Operator/Caustic Operator
d. Brine Operator
Unfortunately, in many plants the most inexperienced personnel
are assigned the highest risk job.
We have adopted the concept of using a start-up team to train and
break-in inexperienced employees in the various job functions.
Normally these teams begin formal classroom and plant training 2-3
months before start-up. They are present in every key area on every
every shift during start-up and for several weeks after. The team
consists of a core of experienced technical and operating personnel
on permanent assignment, augmented as necessary with additional
personnel from other of our chlor-alkali plants.
4. Alerting personnel to hazardous areas by posting of signs and
controlling access to these areas.
Controlled access to the cell and rectifier areas by fences, one
way doors, posting of appropriate signs, etc. Some plants have
decided to treat the electrolytic area the same way they would
treat a high voltage transformer yard.
5. The design of renewal equipment to reduce the hazards associated
with the renewal of cells, for example, the use of non-magnetic
tools, more accessible jumper switch hook-ups, lighter manual
lifting loads, use of power tools, removal and replacement of
cells as completely assembled units.

238
 We are working on the development of non-magnetic impact wrenches
for removing and installing intercell copper. We have begun using
non-magnetic stainless nuts and bolts for making intercell
connections. Non-magnetic hand tools and slings have been in use
for several years.
On the newest cell designs, the anode and cathode units are
furnished with back aisle lugs so that the by-pass switch can be
easily installed without pre-disconnecting intercell copper pieces
and without requiring personnel to work in the very confined areas
between closely coupled cells.
Tools and cell parts that must be lifted by hand will weigh less
than SO pounds.
Most new installations have adopted the concept of removing a cell
completely assembled instead of breaking it down on the cell line.
The exposure time in the cell room is reduced as well as hazards from
the hot caustic and anolyte.
6. Installation of improved natural and/or forced ventilation to insure
better levels of comfort for renewal personnel working on the cell
lines. A number of schemes have been proposed or are in use
includ ing:
a. Side wall fans blowing outside air across the cell room.
b. Half walls with roof monitors /natural ventilation.
c. Out-of-doors installation of cells.
d. 2nd floor installation to improve natural ventilation.
e. Center plenum trench with slot openings to provide ventilation
and air movement on back aisles.
Although definitive criteria for heat stress are still being
considered, it is expected that regulations now being drafted will
be enacted within two years. In all probability these will state
the length of time an individual can remain in the cell room area
under various ambient conditions. We can anticipate that improve
ments in cell room ventilation will be required.
High summertime temperatures in the cell rooms in the Gulf Area
are a particularly difficult problem. In this area the only
reasonable solution may be outdoor installation.
7. Elimination of tripping hazards by installing ground level pipes
in trenches, design of branch connections to eliminate routine
work above the cell tops or to provide safe ladders and safe
portable platforms when work above the cell tops is required.
One of the most difficult problems to resolve is the question of
servicing cell connections above the cell.

239
8. Establishment of a safety committee specifically chartered to
review and approve cell room designs and operating procedures.
The cross-section of the group contains professionals associated
with development, production, business, engineering, and
corporate safety.
This committee meets on a regular basis or as needed to resolve
questionable areas.

A series of slides was presented to illustrate some of these

changes as incorporated in our new plant at Niagara Falls, New York.
Most of the cell room features discussed here will be included with
the new chlorine cell plants presently under construction. Older
plants with larger numbers of closely spaced small cells will find it
more difficult and expensive to bring the cell room area up to desired
standards of safety. However, many of these existing plants recognizing
the potential impact of OSHA on their operations, have already set up
extensive safety programs and are proceeding with their implementation.
A few chlorine producing plants have already had OSHA inspections.
Certainly there will be many more in the months and years ahead. Most
plants have programs under way to remove obvious hazards.
In reviewing the OSHA regulations and inspections already held,
areas that may be closely scrutinized include the following:
1. Isolation of cell area - controlled access - signs.
2. Suitable training of personnel.
3. Protection of exposed bus in working areas.
4. Better access to cells in operating, renewal.
5. Suitable protective clothing.
6. Removal of mechanical hazards - lifting, ladders, cell tops.
7. Reduction in chemical hazards, due to spills, cell disassembly,
etc.

240
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Re ferences
1. Electrical Safety Standard for Electrolytic Cell Line Working
Zones, Ninth Draft, January 1974, Institute of Electrical and
Electronics Engineers, Inc.
2. Proceedings - Plant Managers' Seminar - 16th Meeting of
Chlorine Plant Managers - The Chlorine Institute -
February 7, 1973, Hyatt Regency, Houston, Texas.
Chlorine Plant Accident Survey Summary and Conclusions
(given by A. S. M. Wood, Plant Manager, Stauffer Chemical
Company, Axis, Alabama)
3. Proceedings - Plant Managers' Seminar - 12th Meeting of
Chlorine Plant Managers - The Chlorine Institute -
February 5, 1969, Hotel Plaza, New York City.
Electrical Hazards Involved in the Operation and Repair of
Diaphragm Cells
(given by Jack Schmidt, Area Superintendent, Chlorine, NaOH,
Steam and Power Units, Inorganic Chemicals Division, FMC
Corporation, South Charleston)

Electrical Safety in Mercury Cell Rooms

(given by W. L. Kaiser, Technical Manager, Electrochemical
Operations, Inorganic Chemicals Division, Wyandotte Chemicals
Corporation, Wyandotte)
4. Occupational Exposure to Hot Environments, U.S. Department of
Health, Education, and Welfare, 1972.

243
 THE QUANTITATIVE ASSESSMENT OF
CHLORINE EMISSION HAZARDS
ANA Dicken,
ICI Limited, Mond Division, Runcorn,
Cheshire , England

The paper will start from the premise that all

human activity is fraught with hazard. The duty
of industrial management, as a responsible part
of society, is not to eliminate hazard, because
this is impossible, but to reduce hazard to a
socially acceptable level. It will develop the
argument that this may best be achieved by
quantitative methods and will indicate how
these may be applied to chlorine and how reduced
hazards can be achieved.

INTRODUCTION
Chlorine is a highly toxic element which is produced
in vast quantities all over the world. This apparently
undesirable practice continues because elemental chlorine
makes possible the manufacture of a host of chemical
products which are highly valued by our society. As well
as allowing the production of the plastics and solvents
which are an essential part of our daily lives , chlorine
itself saves life. For many years it has been of
inestimable value to mankind in the treatment of drinking
water and in the manufacture of powerful agents to combat
disease.
Nevertheless, the manufacture of chlorine is not
undertaken lightly, and much effort has and is being put
towards achieving a very high degree of safety in the
production and handling of liquid and gaseous chlorine.
Despite all these efforts the operation of a chlorine
plant can never be absolutely safe. Like most other
human activities, there is an associated risk. It may be
likened, for example, to the operation of air transport
or to the inhabitation of an earthquake zone, where a
risk which is small and understood is judged to be
acceptable. One of our fundamental responsibilities in
operating chemical plant is to control the risks
associated with our activities at a socially acceptable
level .

244
DEVELOPMENT OF A NEW APPROACH
Several years ago, at the start of the study which
led to the production of this paper, we asked ourselves
this question. What is a socially acceptable level for
the risk to the public associated with the escape of a
toxic gas. We operate in a society where we value
industrial growth at the same time as social improvement.
We must therefore develop a philosophy of operation where
increases in scale and complexity of operation are more
than matched by improvements in safety and in the pro
tection of our environment. Therefore in 1970, the Chlor-
Alkali Group of the Mond Division of Imperial Chemical
Industries Limited set up a Working Party to consider
this question.
It was immediately recognised that statements such
as "shall never be allowed to happen" or "escapes shall
be absolutely eliminated" are in fact meaningless:
absolute safety and zero risk are in fact unattainable
ideals. The principle of controlling the risks associated
with chlorine production at a socially acceptable level
was accepted.
From this starting point a plan was formulated to
take a new look at the safety of our chlorine production
plants . The approach was a serious quantitative re
examination of the risk of chlorine emission hazards.
The requirements of the team which was commissioned to
carry out this study were as follows :-
to establish socially acceptable risks
associated with chlorine emissions, for use
as criteria against which to judge plant
operation
to study all the company's chlorine pro
duction and handling plant and to identify
areas where unacceptable escapes could take
place
to propose and to cost practicable solutions
which, when implemented, would meet the
criteria of acceptability.
The study now being clearly defined, staff were
selected to carry out the examination. Care was taken
to ensure that these people were competent to carry out
such a study by virtue of technical understanding, level

245
of seniority and independence from line management. The
last requirement was and still is seen as a fundamental
principle of studies of this sort.
THE CRITERIA OF ACCEPTABILITY
This is a management responsibility, and quantita
tive criteria were established at the outset. The risks
to the public resulting from a chlorine emission were
seen to fall into three categories. These were defined,
and acceptable frequencies were suggested for each.
Firstly, there is a chance that a chlorine emission
may be smelled and thereby cause a nuisance to the public
outside the plant. Although highly undesirable, such an
event is unlikely to cause any harm, and will therefore
be socially acceptable relatively frequently. A fre
quency of once per year was suggested. Secondly a more
severe escape could cause some degree of distress to
people, or damage to vegetation which would cause a
nuisance and which could lead to claim for compensation.
It was considered that this would not be acceptable more
often than about once per decade. Thirdly, a major
emission of chlorine could lead to personal injury or
risk to life outside the plant. In our daily lives we
accept some surprisingly high risks of personal accident
(see Table 1). For example in travelling by air or in
commuting by car, we accept risks which are tens or
hundreds of times greater than those associated with
staying at home. At the other extreme we rarely stop to
think of the risk of being hit by a meteorite or struck
by lightning. The risk of serious injury to the public
arising from our chlorine production activities must
clearly be pitched nearer to the latter than to the
former situations. Here each case will need special
investigation relative to the risk involved.
These three categories of risk were identified in
order of increasing severity as Category I, II and III.
Category 0 was defined as no nuisance to the public. Next,
by collecting published and private data on the toxicity
of chlorine gas, a diagram was produced defining the
effects of exposure to chlorine (Figure 1). The three
hazard categories were then defined more precisely in
terms of their effect, by indicating the range of
chlorine concentrations and exposure times covered by
each. This definition of the three hazard categories is
shown on Figure 2.

246
THE INVESTIGATION OF EACH PLANT
Thus three categories of chlorine emission hazard
were fully defined in relation to their effect on the
public, their minimum socially acceptable frequencies and
their quantitative definition in terms of concentration
and duration.
The application of these standards of control of
emissions requires that the probability of chlorine
escapes from each plant be assessed quantitatively against
these standards. A technique for doing this has been
developed over the last three years.
A team of two men carry out the study at each plant.
Typically they include a Chemical Engineer or Industrial
Chemist with an Instrument or Reliability Engineer: they
work indepedent of design and production groups, but
obviously need their full co-operation and assistance.
Their study has four distinct phases :-
a) All possible sources and causes of emission of
chlorine from the plant are identified.
b) All of these potential escape situations are
quantified, using their estimated frequencies
and effects, to calculate the frequency with
which a hazard to the public could result .
c) these predicted frequencies are compared with
the acceptable target frequencies of Category I,
II and III hazards.
d) The situations which lead to the highest risks
are then picked out , and recommendations are
made to reduce or to eliminate them. This con
tinues until the total plant frequency becomes
acceptable .
This technique has been applied in turn to each
chlorine production, treatment, distribution and user
plant. The nature of the study is such that reasonably
small self contained production areas must be scrutinised
individually. A Works is therefore initially divided in
this way. For example each cellroom, each chlorine
liquefaction plant and each hypochlorite plant is treated
as a separate study.

247
 This introduces the problem of how to allocate the
total acceptable hazard frequency for the site between the
individual production areas. It is generally necessary to
do this arbitrarily, taking into account the historical
record, size and difficulties of each unit. Each unit is
thus allocated its own set of acceptable chlorine emission
frequencies.
IDENTIFICATION OF POTENTIAL CHLORINE ESCAPES
This is the first stage of the detailed study of each
production unit. A thorough understanding of the process
is necessary. With the help of the plant manager and
process supervisors, the team study historical records of
chlorine escapes and near misses. They examine process
descriptions, design bases, line diagrams and operating
procedures - unofficial as well as official. All possible
ways in which chlorine escapes could occur are identified
and noted.
A systematic study of each line on the line diagram
and each operational procedure is made: all possible
deviation and errors are considered, and events or
combinations leading to a chlorine release are recorded.
Sometimes a hazard tree diagram is necessary because of
the complexity of the logic.
Eor each possible situation, the quantity of chlorine
emitted and likely duration of the escape are estimated.
QUANTIFICATION OF RESULTING HAZARDS
The next stage of the analysis is to estimate the
frequency and magnitude of each potential chlorine escape.
This is done by combining the frequencies, probabilities,
and the relative durations of all of the events which
lead up to that incident.
At this stage a computer program is used to calculate
the probability of each of these escapes causing a hazard
of Category 0, I, II or III at the. Works boundary.
It is these two steps - the full quantitative
description of each chlorine escape, and the prediction
of its effect in terms of the hazard categories - which
are the key to the success of this approach. Together they
cross the barrier which hitherto existed between knowing
of the possibility of escapes of chlorine, and being able
to predict their probability and relative effects outside
the Works .

248
 The computer program has been under continual
development over the three years since the start of these
studies, and has now reached a considerable degree of
sophistication. It basically calculates the concentration
of chlorine at the Works boundary for each of the potent
ial chlorine escapes. It is necessary to do this for all
the possible combinations of wind direction, wind speed and
degree of atmospheric turbulence, or lapse rate.
Allowance is made for the effects of buildings and
hills, and for the effects of a dispersed or elevated
source of emission of chlorine. The gas dispersion methods
which have been used are based on the work of Pasquill (2)
and Sutton (3) and more recent contributions to these
techniques (4) (5). At the end of its calculations the
computer produces the probability of a Category I , II and
III hazard arising as a result of each of the chlorine
releases .
COMPARISON OF ESTIMATED AND ACCEPTABLE FREQUENCIES
The total hazard frequencies for each plant area are
then compared with the allowed frequency of hazard for that
area, as allocated from the total for the Works. It is the
responsibility of the team to assess where possible changes
would have the most effect in reducing the frequency of
hazard. These changes are not only in equipment - like
providing alternative power supplies, spare pumps, or
duplicated controllers - but also in operating procedures,
such as precise definition of the conditions requiring
load reduction or shut down, and inspection or testing
frequencies.
DISCUSSION OF THE TECHNIQUE OF HAZARD QUANTIFICATION
This quantitative approach does not produce a
precise answer, since the results can only be as good as
the data used in the analysis. However, it allows the
relative magnitude of the hazards to be displayed, so
that action may be taken to improve the safety of the plant
relative to the quantitative guidelines established at the
outset .
There are several important aspects of the procedure
for the study of each plant, which deserve further
explanation .

249
 The first problem is getting failure rate data. This
is needed to estimate the frequency of occurrence of each
event. Sound data on equipment failure rates are slowly
being accumulated. For example, data on the failure rate of
joints or tripping of fans are available from records. Data
have been collected from published and commercially
available data (6) and by bracketting techniques using
plant experience.
We also use and contribute to the reliability data
bank of the United Kingdom Atomic Energy Authority's
Systems Reliability Service, where similar data and
techniques are in use in the assessment of the safety of
nuclear power installations.
Where operator intervention is concerned data is
limited, and it is necessary to assess the complexity of
the operation involved and whether the operator is under
stress. The prediction of human error rate is particularly
difficult. Although the subject of much study (7) its
estimation in quantitative terms is always difficult and
probably imprecise.
A further aspect of the analysis which is bound to be
imprecise is the estimation of the duration of the escapes
and the rate of release. This was done by a combination of
operating experience and prediction. Durations are generally
based on operator response times and valve or machine
operation times.
The prediction of downwind concentrations of chlorine
arising from each release is probably at least as accurate
as the data used to define the release: an accuracy of
^50% is likely in this part of the calculation.
CHECKS ON VALIDITY OF THE ASSESSMENT PROCEDURE
The real check on the results of the study is the
final comparison between the predicted frequency of gas
release, and the observed frequency of hazards occurring
outside the plant.
Fortunately chlorine hazards to the public have very
rarely occurred in the history of UK chlorine production,
and the evidence is not statistically significant . However ,
based on the total number of recorded chlorine escapes of
all kinds , the predicted frequency has normally been
between 100 and 200% of the observed frequency. We accept
this as a reasonable agreement.

250
 In fact we believe that our prediction of frequency
of incident is about right , but that we have a built in
safety factor in the calculation of the effects on the
public .
One distinct study was submitted to an independent
hazard assessment organisation. Their criticisms helped to
improve our techniques, and confirmed our confidence in the
validity of the methods used.
EFFECT OF THE STUDY ON OPERATIONS
Studies of this type have been applied to almost all
of ICI's chlorine plant in the UK. The conclusions of these
studies embrace many hundreds of distinct recommendations.
However, several principles have emerged, and the studies
have had several effects which were not anticipated at the
start .
For example, the hypochlorite towers which absorb
emergency vents, intermittent vents and continuous weak
chlorine purge streams were generally found to be lacking
in reliability, and historically have contributed to many
of our chlorine incidents (Table 2). In general we now /
have two towers in series where the quantity of chlorine to
be absorbed is significant and the integrity of the caustic
soda supply has been improved. The principal means of pro
tection at our larger Works is to provide the facility to
vent total chlorine production from cells or compressors to
an emergency type tower (Figure 3) which is now a high
integrity system. Most of these chlorine pressure relief
systems now have duplicated control systems and relief
valves. Procedures to avoid dangerous levels of hydrogen
and NCl^ in chlorine have been improved. Inspection of
mains for external corrosion has been increased, and
sources of physical or fire damage to large mains reduced.
Some older chlorine mains, relief systems and chlorine
vaporisers have been declared obsolete. Critical control
loops have been simplified in order to improve reliability
and they have been specially identified and made subject
to strict and regular test procedures.
Safer methods of operation and maintenance have been
suggested in several studies, and in many cases new written
procedures have been laid down for operation of the plant,
and routine testing schedules established for standby
equipment and protective devices. The integrity of vital
services such as instrument air and electric power are being
improved.

251
 It has been noticeable that the act of carrying out
this study, with the involvement of everyone from Works
Management down to Junior Supervisor level did in itself
lead to an improvement in standards of chlorine safety.
Attitudes of people were changed, so that actions which
could lead to chlorine release are now regarded more
seriously. Management is more willing to limit production
if protective systems are not available, and operators are
more prepared to push the trip button if in doubt, without
risk of recriminations later after false alarms.
CONCLUSIONS
The quantification of risk associated with escapes
of chlorine gas has proved feasible and of sufficient
accuracy to be of value. The conclusions of the study have
largely been implemented, and there has already been a
reduction by about 40% in the number of recorded incidents
involving the release of chlorine gas to atmosphere in the
areas reviewed.
In addition to implementing the recommendations of
the study there has been an increased awareness of the risk
by the operators at all levels , which in itself con
tributes to safety.
At our largest Works in Runcorn, over £1,000,000 was
spent in three separate expenditure proposals towards
achieving the target levels of risk.
The quantitative chlorine emissions study occupied
about 1 man year per £10m of plant, and the average study
lasted about a month for a plant section. It is now seen as
a continuing requirement to monitor the standards which we
have set at each of our Works on about a two year frequency.
At the larger sites, this has justified a permanent post
as Works Hazard and Operability Manager.
On the credit side of the cost sheet, the study has
reduced the frequency of chlorine escapes , has contributed
to the availability of the chlorine plant, and has reduced
the risk that our operations will be jeopardised as a result
of a serious incident. However, the main justification of
the study is that we believe we have reduced the risk of
damage to people and property both inside and outside the
plant. The cost of achieving the improved standards may be
regarded as an insurance policy against this risk.

252
ACKNOWLEDGEMENT
Thanks are due to many colleagues who have con
tributed to these studies, and to S B Gibson, J T Illidge
and B G Ritter for their help with the preparation of
the paper.

REFERENCES

1 H G Lawley, Operability Studies and Hazard Analysis,

AIChE Symposium "Loss Prevention in the Chemical
Industry" 11-15 Nov 73, Philadelphia, Pa.

2 Pasquill F, "The Estimation of the Dispersion of

Windborne Material", The Meteorological Magazine,
Vol 90, Feb 1961, pp 33-49.

3 Sutton O G, "Micrometeorology" McGraw-Hill 1953

pp 134-136 pp 277-288.

4 Bryant Pamela M, "Mwthods of Estimation of the

Dispersion of Windborne Material and Data to Assist
in their Application", Report ASHB (RP) R42 ,
HMSO, 1964.

5 Turner D B, "Work Book of Atmospheric Dispersion

Estimates" Publication No AP-26, Office of Technical
Information and Publications, Office of Air Programs,
Environmental Protection Agency, Research Triangle
Park, North Carolina 27711, USA. 1970.

6 Anyakora S N, Engel GFM and Lees FP, "Some data on

the Reliability of Instruments in the Chemical Plant
Environment" The Chemical Engineer, Nov 1971,
pp 396-402.

7 Rigby L V, "The Nature of Human Error"

Chem Tech., Dec 71, pp 712-718.

253
 TABLE 1 (a)
TYPICAL FATAL ACCIDENT FREQUENCY RATES
Q
(Frequency per 10 exposed hours)

Industrial (UK) Domestic (UK)

Horse Racing Jockeys 50,000 Rock Climbing 4,000
Air Crew 250 Canoeing 1,000
Construction Workers 67 Travel by Motor
Railway Shunting 45 Cycles 660
Coal Mining 40 Travel by Air 240
Fishing 35 Travel by Bicycle 96
British Industry 4 Travel by Car 57
Chemical Industry (UK) 3.5 Travel by Train 5
Staying at Home 1

TABLE 1 (t>)
TYPICAL RANGE OF FATAL ACCIDENT RISKS TO THE
GENERAL PUBLIC
Fatal Risk per Person per Year

Cause Fatal Risk/Person/Year

Run over by road vehicle UK 6000 X 10 -7
Travel by Car (1 hour/day) 2000 X 10'-7
-7
Run over by road vehicle (USA) 500 X 10 -7
Travel by train (1 hour/day) 200 X 10'-7
Use of contraceptive pill 200 X 10 -7
Transport of hazardous material (USA) 1.0 X 10 -7
Lightning strike (UK) 1.0 X 10 -7
Falling Aircraft (USA) 0.8 X 10 -7
Explosion of pressure vessel 0.5 X 10
Accidental release from atomic
Power Station ->(USA )
at 56 miles radius ~0.001 x 10 -77
neighbouring town ~0.01 X 10 7
at 1 km radius 1.0 X 10 7
Flooding in Holland 0.08 X 10
Meteorite impact 0.0006 X 10 7
Cosmic Radiation from Supernova 0.0001 X 10 -7

254
 TABLE 2
SURVEY OF TOTAL RECORDED CHLORINE ESCAPES 1966-1970
CASTNER-KELLNER WORKS, RUNCORN, ENGLAND.

Source of Escape Primary Cause

Chlorine Cellroom 15% Unknown/Not Recorded 25%
Dechlorination of Brine 13% Instrument/Control
Hypochlorite Tower 12% Failure 17%
Tail Gas Treatment Plant 11% Human Error 12%
Drains 10% Machine Failure 995
Chlorinated Organics Plants 795 Leaks 895
Chlorine Filling/Loading 6% Maintenance/Start-up 6%
Cell Gas Treatment Plant 695 Service Failure 595
Others 20% Miscellaneous 18%

100% 100%

255
256
 CHLORINE RECOVERY BY HYDROCHLORIC ACID ELECTROLYSIS
Stefan Payer and Wolfgang Strewe
Friedrich Uhde GmbH, Dortmund, Germany
A major portion of all chlorine produced is utilized in
chlorination processes from which a portion of the feed
chlorine is released in the form of hydrogen chloride.
The most important processes from which HC1 is obtained as
a by-product are discussed.
For the recovery of chlorine out of hydrochloric acid two
processes may be considered: the modified Deacon-process
and the electrochemical decomposition.
After discussion of the theory of the hydrochloric acid
electrolysis, the design of the cell and the auxiliary
units will be described. With a report of the experiences
of 10 years of operation, the paper closes.
"~—Ihe electrolysis of alkaline chlorides still is the most
-—eommon method employed for the production of chlorine. As
a result, the quantity of caustic alkalies, mainly sodium
hydroxide, has necessarily risen also. Now, the demand for
this product has not risen to the extent as for chlorine
and, consequently, there appears to be a definite need to
produce chlorine without obtaining caustic alkali as co-
product. On the other hand, a major portion of the chlo
rine produced is utilized in chlorination processes in
which a portion of the feed chlorine is recovered in the
form of hydrogen chloride.
The more important processes in which HC1 is obtained as
by-product are shown on figure 1. The first reaction is a
substitution. In addition, KC1 is obtained during halogen
replacement , that is in the production of organic fluo
rine compounds according to reaction 2 . The same appears
in reaction 3 for the production of silicons. But also in
the production of isocyanates used as starting materials
for polyurethanes , the chlorine introduced into the re
action in the form of phosgene is recovered as gaseous HC1.
Consequently, the amount of hydrochloric acid available for
marketing is constantly increasing with rising chlorine
production; the same applies to caustic soda.
Although the introduction of new processes, such as oxy-
chlorination in the production of ethylene dichloride as
starting product for vinyl chloride, or the use of hydro
chloric acid in the metallurgical industries instead of
sulphuric acid for pickling purposes, or its use for
phosphate rock digestion, did alleviate this situation to
a certain degree, it does not constitute a universal so
lution to the problem of excess hydrochloric acidi
Neutralizing the hydrochloric acid with caustic soda or

257
limestone isn't the final answer either, since the inorga
nic salts so obtained cannot be discharged into our rivers
or lakes . In other words , the recovery of chlorine from
hydrochloric acid seems to be a must.
Several processes are available today for this purpose:
1. The direct oxidation of hydrogen chloride with oxygen
or other oxidizers according to equation 5 shown on
figure 2 . This includes the Deacon process (1868) and
its numerous varieties, such as the Kellog process.
All these processes are accompanied by corrosion pheno
mena and produce a more or less diluted chlorine gas.
2. Electrolytic chlorine production from hydrochloric acid;
four processes are known, three of which are based on
indirect electrolysis via metal salt solutions:
a) -Direct electrolysis of aqueous hydrochloric acid to
Cl2 and H2 (equation 6);
b) Westvaco process: electrolysis of a cupric chloride
solution and oxidation of the monovalent copper
formed with hydrochloric acid and oxygen (equation 7)
c) Electrolysis of a mercuric chloride solution on a
mercury cathode and subsequent dissolution of the
mercury in hydrochloric acid while adding oxygen to
obtain mercuric chloride (equation 8);
d) Schroeder process: electrolysis of a nickel chloride
solution with subsequent dissolution of the metallic
nickel obtained in 30 % hydrochloric acid accompa
nied by the formation of hydrogen (equation 9).
Of these four electrochemical processes , only the direct
electrolysis has been widely adopted and has been used on
a commercial scale since 1964, despite the fact that the
decomposition potential is considerably higher than in the
case of indirect processes. The reason why producers have
preferred the indirect electrolysis process is probably
because the other three processes each consist of two in
dependent stages working at different rates and efficien
cies, thus being more costly, for instance because larger
reaction vessels are required. Moreover, the high current
densities that are possible in direct electrolysis can
not be achieved in the indirect processes.
The decisive factors in selecting a direct oxidation
process or one of the electrolysis processes for recover
ing chlorine from hydrogen chloride are profitability and
reliability .
In the electrolytic decomposition of aqueous hydrochloric
acid it is essential to realize efficiently, that is at

258
minimum power requirements, the two reactions, namely 2 CI
= CI2 + 2 e at the anode (equation 10) and 2 H + 2 e = H2
at the cathode (equation 11). The theoretical minimum
electrolysis voltage between the two electrodes is the
potential of the chlorine-hydrogen cell of about 1.36 volts.
In practise, this voltage will increase in line with the
polarization at the two electrodes at the commonly used
current densities. To this voltage at the electrodes one
must add the voltage drop in the electrolyte which will
depend on the cell construction and the operating con
ditions selected. The voltage will further be influenced
by factors such as the diaphragm permeability and the
specific conductivity of the hydrochloric acid.
Fig. 3 shows how the cell voltage depends on the hydro
chloric acid concentration. As you can see from the graph,
the cell voltage rises sharply for hydrochloric acid
concentrations under 20 %, because of the decrease in
conductivity. The optimum concentration of hydrochloric
acid for best conductivity is between 20 and 22 % at a
temperature of 75°C; at concentrations above 22 % the
conductivity will again decrease. Contrary to what might
be expected, and as can be seen from the figure, for hydro
chloric acid concentrations above 22 % the cell voltage is
largely independent of the concentration. The reason for
this apparent anomaly is the fact that, with rising ion
concentration in the electrolyte and aided by the violent
agitation caused by the gas bubbles, the concentration
polarization will decrease and this will largely compen
sate the voltage loss caused by conductivity.
Hydrochloric acid at any concentration above 20 % can
therefore be used for the electrolysis process. In con
sideration of the rising vapour tension of HC1, the
hydrochloric acid concentration is normally kept below
26 %.
It goes without saying that the temperature will also
affect the cell voltage. This is very marked at tempera
tures between 40 and 50°C , but is less noticeably at
higher temperatures . Although the voltage can be improved
at temperatures higher than 80°C , this value should nor
mally not be exceeded so as not to impair the durability
of the materials of construction used.
It is well known that the deposition potential of hydrogen
on graphite is relatively high. This may be effectively
reduced by admixing depolarizing additives to the electro
lyte. At a current density of 4 kA/m2 , voltage gains of up
to 300 mV can be recorded when employing this method.
Taking a brief look at the history of HC1 electrolysis,

259
it was in 1939 to 1942 that 1.6. Farbenindustrie , as it was
known then, began to develop hydrochloric acid electroly
sis in its central German works at Bitterfeld and to des-
pose of excess HC1 in this manner. Having then used this
process on a commercial scale at Wolfen from 1942 to 1944,
a pause set in because of World War II.
The first experimental cell had all the characteristics of
today's cells. It was, in fact, the first bipolar cell to
be used in the chlorine industry. Water electrolysis fur
nished the concept because of its similarity to HCl-elec-
trolysis: two gases are formed, which must not mix, where
as the anolyte and catholyte may be mixed.
The problem was taken up again by a number of people in the
fifties. In Germany, Farbwerke Hoechst AG and Friedrich
Uhde GmbH continued to develop the Bitterfeld cell. Where
as Hoechst soon discarded the idea of an anode consisting
of loose material, this was kept up elsewhere and even the
cathode space was filled with lumpy graphite in order to
obtain identical flow conditions in both electrode spaces.
This type of cell is now completely obsolete.
The Hoechst-Uhde electrolyzer consists of 30 to 45 single
elements working at current densities from 4 to 5 kA/m*.
The electrolyzers are of simple and rugged construction.
The cell itself basically consists of a frame of phenol
formaldehyde or cresol formaldehyde based plastics, con
taining ducts for the products and for the feed and
effluent hydrochloric acid. Cemented into the frame is the
bipolar graphite plate which has slots on both sides for
the purpose of withdrawing the gaseous products obtained.
Figure 4 illustrates an electrolysis cell;figure 5 shows
a cross-sectional view. The gases rise along the vertical
electrodes and are distributed at the upper edge of the
graphite plate through a system of ducts into the dis
charge openings , the chlorine being directed together
with the anolyte to one end and the hydrogen with the
catholyte to the other end. The diaphragm is fixed to the
sides of the frame. The electrolyzer is closed at each end
by a steel plate with rubber-lined inside surface. The end
plates and cell frames are held together by 8 spring-loaded
tie-rods in a manner similar to a pressure filter. Elec
tric power is fed to the graphite plates mounted in the
end plates through graphite nipples with stuffing boxes.
The electrodes of the Hoechst-Uhde electrolyzer have an
effective surface of 2.5 m2 and can withstand a current
load of up to 12 000 Amps. The diaphragm consists of a
PVC fabric specially developed for this purpose and serves
to separate the electrode chambers and, consequently, to
prevent the two products from mixing. The electrolyzers

260
are supported by steel frames which, in turn, rest on ce
ramic insulators .
An electrolyzer with 30 elements is about 3.5m long,
2.2 m wide, 2.2 m high, and requires a floor space of 4
by 4.8 m.
The process flowsheet of a hydrochloric acid electrolysis
plant is shown on fig. 6. The hydrochloric acid is pumped
through 2 cycles separated by diaphragms. Each cycle
consists of an elevated tank, a collecting tank, the
circulating pumps, heat exchangers, and the filter unit.
In full-load operation, the heat exchangers serve for
dissipating heat generated in the cell and, during start-up
and in medium-load operation, for preheating the acid.
The purpose of the filters is to remove abrasion particles
and precipitated substances from the acid cycles.
A part stream of the 20 % hydrochloric acid from the
catholyte cycle is sent to the absorption unit, enriched
with hydrogen chloride from organic chlorination processes
to about 30 % concentration, and returned to the two
cycles as required.
The gaesous chlorine and the hydrogen are obtained at a
temperature of between 7 5 and 80°C and are saturated with
water vapour and hydrogen chloride in accordance with the
vapour tension over 20 % hydrochloric acid.
Both hydrogen and chlorine are cooled. The 8-12 % hydro
chloric acid obtained in these process steps is returned
into the anolyte or catholyte cycle, respectively.
After cooling, the chlorine can be further treated as it
would be in alkaline chloride electrolysis plants. Hydro
gen chloride and chlorine are removed from the cooled and
scrubbed hydrogen with the aid of caustic soda solution
after which the hydrogen can be further processed depen
ding on the requirements. The composition of the gases
produced is illustrated on fig. 7. The product chlorine
and hydrogen obtained in hydrochloric acid electrolysis
are of extraordinarily high purity.
When using new diaphragms, the chlorine content of the
gaseous chlorine produced is over 99.9 % by volume, the
hydrogen content being less than 0.1 % . As the diaphragms
become more permeable in the course of tine, the chlorine
quality will deteriorate. To achieve an average chlorine ,
gas quality of over 99.5 % CI2, the electrolyzers are
fitted with new diaphragms every two to three years .
After neutralization (MaOH-scrubbing) , the product hydro
gen will contain over 99.9 % by vol. H2 and only 10-20
ppm oxygen, and can thus be used for hydrogenation pur
poses, for example for hydrogenating dinitrotoluene

261
to toluyelene diamine.
Fig. 8 shows an overall view of the plant. The cell room
in the center accommodates 12 electrolyzers , 10 of which
have 30 and the other two 45 elements. The equipment for
the acid cycles is arranged on the left, the rectifier
unit is on the right. As you can see from the picture, the
whole plant is of the open-air type. The cell room is
roofed, but is open at the sides.
The major portion of gaseous HC1 obtained in the chemical
industries originates from organic chlorination processes.
As a result, the gas is polluted to a greater or lesser
degree with organic substances. These organic substances
have two kinds of effect:
- They adversely affect the product quality;
- They may impair the electrolysis process by
clogging the diaphragms and by forming deposits
on the electrodes.
In the electrolysis of hydrochloric acid originating from
the methane chlorination process, it was found that the
electrolysis process will not be influenced, as long as the
chlorine derivatives of methane are truly dissolved in the
hydrochloric acid, as opposed to being present in the form
of a second liquid phase, since otherwise the diaphragms
would soon be affected. When using unpurified acids con
taining chlorine derivatives of methane, the compounds
dissolved in the catholyte will appear in the hydrogen. The
chlorine, on the other hand, will only contain carbon tetra
-chloride, since all the other chlorine derivatives of
.methane are oxidized at the anode to carbon tetrachloride.
In an attempt to electrolyze a hydrochloric acid contain
ing benzene, chlorobenzenes , phenol or chlorophenols , it
will be found that the cell resistance rises sharply in a
very short space of time. This is caused by deposits on
the anodes and diaphragms, consisting of hexa- and penta-
chlorobenzene , tetra- and pentachlorophenol and hexachloro-
cyclohexane. This causes the diaphragm resistance to
increase. The growth of crystals of these compounds in the
graphite lattice may destroy the electrodes, thus enlaiging
the electrode gap.
By taking appropriate measures , such as by employing a
suitable adiabatic absorption process followed by ad
sorption by activated carbon, it is possible to produce
hydrochloric acid that can be used in electrolyzers with
out the afore-mentioned difficulties. The treatment selec
ted depends on the origin of the hydrogen chloride. It can
be said that, for all practical purposes, any hydrogen
chloride can be processed to electrolyzable hydrochloric

262
acid. It is even possible to use hydrogen chloride that is
polluted by hydrogen fluoride and chlorinated fluorhydro-
carbons obtained in the production of fluorine-bearing re
frigerants.
As regards inorganic impurities, it is ions with multiva
lent character that will adversely influence the current
efficiency. Other ions, such as • sulphates , may destroy the
anodes. Generally, however, the permissible content of in
organic compounds is larger than that of organic and, in
particular, aromatic- and cyclic compounds. Thus, 40-50 g
SO4/I can, for instance, be tolerated, whereas the upper
limit for orthodichlorobenzene is 5 ppm.
The most successful designer of hydrochloric acid electro
lysis plants was Friedrich Uhde GmbH who was able to gain
sufficient valuable experience in the two plants con
structed in 1964, namely:
1. for Farbwerke Hoechst AG of 120 tons daily
chlorine capacity;
and 2. for Farbenfabriken Bayer AG, Leverkusen, of
90 tons daily chlorine capacity.
As a result, Uhde secured contracts in the early seventies
for 4 further plants with an aggregate capacity of 5 20
tons per day. All four plants are coupled with isocyanate
plants. It is worth noting that 3 of these plants are not
combined with an alkaline chloride electrolysis plant,
which meant that special care had to be taken to ensure
that the isocyanate and hydrochloric acid electrolysis
plants were taylored to each other needs . Two of these
plants were equipped with so-called chlorine recovery
facilities, in which the chlorine is almost completely
recovered from the bleaching-liquor obtained when the
plant is started up or shut down and in the hydrogen
scrubbing unit (98 % yield).
The overall annual chlorine output of the 7 plants de
signed and constructed by Uhde is 300,000 short tons.
Three further plants are on the drawing board. When the
latter are on stream, the aggregate chlorine output of
these hydrochloric acid electrolysis plants will be
4 25,000 short tons per year.

263
 R-H.Cl, R-CL*Ha (1]
2HCI.'*0l a,.^
jUP, fclricolfttrgy,^ h,
2Cuq*kclnco1 ""W,2Cua . ci,
H- C1.HF R . F. Hg- (21
2CuCI.2HCI.Kk—- 2CoCl^rtf
HgCl, 1>ctriccl tnwfljr, ^ , Clf
Production of silicons
4R-CU 2 Si 2R3Si Cl^ HQ.2HC1 . 'AO, HbCI,» HJ)
2 RjSiC!,. H.0 ^S-O-Si
S-O-S^ . 2HCI 131
Ni *2HCt
Anodic r»0d'on

COCIj.R-NH, - R-NCQ. 2HCI Cathodic eaction

2 H* . 2$ . H,
R» acyclic -or aromalic hydro carbons

265
Process Flow Diagram Fig. 6

Clz * 99.45% IV/V] H2 89.914

CO, 00.05% IV/V )
Hi -= 00.50% IV/V ]

Si ?

266
 AN OPERATING CHLORINE DESTRUCTION SYSTEM
Joseph E. O'Connell
Ashton J. Pecquet
Kaiser Aluminum and Chemical Corp.
300 Lakeside Dr.
Oakland, California 94643
Kaiser Aluminum and Chemical Corp.
P. 0. Box 337
Gramercy, Louisiana 70052

A system to destroy chlorine during plant upsets was de

signed and installed at the Kaiser plant in Gramercy,
Louisiana. Two separate units were required to handle
both the small steady flow of tail gas as well as the
entire cell production should the compressors fail.
When construction was complete the system was tested by
shutting down the compressors while the cell room was
still operating. Continuous gas sampling of the scrubber
indicated the efficiency was greater than 99%.

INTRODUCTION
In the electrolytic manufacture of chlorine, the gas is produced
in a number of small cells at slightly below atmospheric pressure.
Gas leaving the cells is collected in large headers; cleaned up by
removing solids, water, and organics as required; compressed; and
liquefied. In some instances, where gaseous chlorine can be used
directly in further processing operations, compression and liquefac
tion are not required.
Since chlorine is a noxious gas, great care must be taken to
confine it during any manufacturing operation. At points where
chlorine is likely to escape, gas destruction units are usually in
stalled to convert the gas to an inorganic chloride salt. In normal
chlorine plant operation there are generally two places where the
gas must be destroyed as shown in Figure 1. One is the tail gas re
maining after compression and liquefaction of the main stream. The
other, cell gas, occurs where there is a failure in the downstream
equipment and the entire output of the plant must be destroyed until
the cells can be shut down.

267
 The two gas loads have quite different characteristics. The tail
gas contains about 85% air, 127. CO2 and 37. CI2. It is a steady flow
at high pressure. Cell gas on the other hand is about 707. water vapor,
267. Chlorine, and 47. CO2 and air. It is available only infrequently
at a very high flow and low pressure. The requirements for a system
to handle the chlorine flow during compressor failure depend on two
factors; first on how rapidly the cell rooms can be shut down and
second on how effectively the one way check valves operate at the
compressor discharge to avoid back flow of chlorine from liquefaction
through the compressor.
Some plants either purchase power or use only a small percentage
of the total power from a generating facility. These plants usually
shut off the entire power supply to the chlorine producing cells
immediately whenever plant equipment malfunctions. Therefore, the
cell gas chlorine destruction equipment requirements can be quite
small.
Other plants, such as the Gramercy, Louisiana plant of Kaiser
Chemicals, a division of Kaiser Aluminum & Chemical Corporation, con
sume a large portion of the power from the on-site generating facili
ties. As a consequence, it is not possible to shut off the power
supply to all chlorine producing cells instantly without serious risk
to power generating equipment. These plants require a programmed
power shut off usually necessitating two to five minutes for an order
ly shutdown. During this time, the chlorine produced must be routed
to a chlorine scrubber where it is reacted with caustic or lime. The
capacity of the scrubber must be large enough to handle the entire
chlorine production load for a few minutes.
The two streams have widely different characteristics in terms
of flow, concentrations of chlorine, frequency, heat generation, mass
transfer, and chemistry. By taking these factors into account, a
scrubbing system has been developed which offers maximum protection
for emergency gas releases and maximum utilization of alkali for the
continual removal of chlorine from the dilute tail gas stream. The
system described below has been designed, installed and tested under
plant operating conditions.

OPERATING HISTORY
The original system at Kaiser consisted of a spray scrubber, two
tanks, and a pump as shown in Figure 2. Caustic solution (12% NaOH
initially) was circulated through the sprays in the scrubber column
to react with any cell gas vented to the scrubber in an emergency.
There was enough caustic present to destroy all the chlorine produced
in the cell room for five minutes. Tail gas from liquefaction was
sparged into the other tank which was not circulated. When the

268
caustic in the sparge tank reached 1%, the tail gas was routed to the
circulating tank while the spent solution was discharged and the tank
refilled with 12% caustic solution. The fresh tank was then put on
circulation.
Careful examination of the scrubber system as designed revealed
there were some conditions under which adequate performance might not
be obtained. The recirculation rate of caustic solution through the
scrubber was designed so that the caustic concentration would be re
duced from 12% to 2% by reaction with chlorine. As absorption pro
ceeds, the average caustic concentration in the recirculation tank
drops which could cause two problems. First the reduced concentration
would cause a reduction in total absorption capacity for a given
amount of solution circulated. Second, at low concentrations there
is some indication that mass transfer is substantially reduced.
Furthermore, when the tail gas was diverted into the circulating tank
the caustic needed for an emergency shut down was being depleted.
Unless the operators quickly refilled the spent tank with fresh solu
tion and put it back on circulation, the spray tower could be opera
ting with caustic that was too dilute to be effective.
Clearly a chlorine destruction system is required that would be
effective under all conditions. Before embarking on the design of
such a unit we discussed the problem areas with other chlorine pro
ducers. Each plant operates under a different set of conditions and
the destruction systems were a little different for each one. The
following general observations were made:
1. ) Only a simple sparged system is required for tail gas.
Caustic (NaOH) or lime can be used to absorb the chlorine.
Many plants use absorption and stripping with carbon
tetrachloride which has the added advantage of recovering
the chlorine.
2. ) Operations where chlorine is used as a gas, for chlorina-
tion, transfer the tail gas disposal problem down stream
and have no tail gas absorber in the chlorine plant.
3. ) Emergency cell room shut downs can be shortened drastically
when the chlorine operation uses a small fraction of the
total power generated. The cell power can be shut off
instantly without upsetting the generators.
4. ) Back flow of chlorine through the compressor must be stopped
to avoid overloading the destruction system. One producer
does this effectively with parallel automatic valves on the
compressor discharge which are stroked once per week to
assure operability.

269
 5.) After plant tests, one producer found it necessary to beef
up the CI2 destruction unit for cell gas by increasing the
spray tower height and adding a once through caustic system.
The protection time went from one minute to ten minutes.

DESIGN CRITERIA
Any system to be used at Kaiser has to be able to handle both the
tail gas stream, which is mostly inert gases (85 to 90%) but contains
some CI2 and CO2, and the cell gas stream, which is practically all
chlorine saturated with water vapor.
In the tail gas absorber, it is important that the NaOH be util
ized effectively, since this is a direct usage of caustic product
amounting to a few percent of production. For a given final concen
tration the utilization of NaOH can be improved by increasing the
initial NaOH concentrations. However, the NaOH concentration should
be chosen so that solid sodium carbonate (Na2C03) will not form and
clog up the scrubber or piping. Plant experience has shown that if
the initial caustic strength is much above 12.5 %, solids will pre
cipitate in the tail gas absorber before the caustic is depleted.
Cell gas absorber design must be concerned with both mass and
heat transfer to minimize the size required. However, caustic utili
zation is not very important because the system is seldom used.
Mass transfer rates as determined by Vivian (1) for the chlorine
caustic system, are gas film controlling for caustic concentrations
above 2 normal (about 8 wt %) , with no appreciable increase for
higher concentrations. For caustic concentrations below 2 normal,
however, the mass transfer rates become limited by the liquid film
resistance and are liquid film controlled at low caustic strength.
See Figure 3.
The data show that if the caustic concentration is kept above
10% (about 2.5 normal) the absorption capacity coefficient is
32 lb. mols per hour-cubic foot. Whereas, if the concentration is
reduced to 17„ (about 0.25 normal) this coefficient is only 10 lb. mols
per hour-cubic foot. Although Vivian's work was done on packed or
wetted wall towers, the behavior of the mass transfer coefficient
with caustic concentration is believed to show the same general trend
in spray towers. (2)
A spray tower was suggested because of the low pressure drop
required, the high cost effectiveness offered, and the large decrease
in gas volume observed across the unit. To maintain a high mass trans
fer coefficient through the scrubber, a high inlet NaOH concentration
whould be used so the exit concentration is always above 10%.

270

v
 Heat is evolved when cell gases are absorbed in the circulating
caustic stream. Cell gas is saturated with water at about 200°F, so
both the heat of reaction for chlorine with caustic and the latent
heat for water must be taken into account. For a production rate of
560 TPD of chlorine the heat load would be:
Load Million BTU/Hour
1. Condensation of Water in Scrubber 34.5
2. Heat of Reaction 31.5
3. Sensible Heat of Gases 0.5
TOTAL 66.5

As discussed previously mass transfer considerations indicate

the caustic concentration leaving the scrubber should be 107. minimum.
If the scrubber outlet temperature for the liquid is fixed at 185°F
to avoid boiling, a heat balance suggests an inlet concentration of
about 20%. Inlet concentrations greater than 207o could be used but
if the liquid rates are reduced to achieve 107» on the exit the scrub
ber would overheat.

FINAL DESIGN
Three improvements were made in the new system (as shown in
Figure 4) .
1. ) An automatic sequential cell room trip system was installed.
2. ) Reliable shut off valves were added to the compressor
discharge.
3. ) The two destruction systems were separated.
Fast orderly shut down of the cell rooms is provided by controls
which automatically shut off the power to the cells. One-third of
the cells are shut down immediately; another third is shut off after
one minute; and the remaining power is off 120 seconds after acti
vating the shut down controls.
Two valves were installed in parallel in the compressor discharge
piping. One valve can be stroked while the other is in service. The
valves are instrumented to close automatically should the compressor
trip out for any reason.
A major improvement in reliability was made by separating the
cell gas and the tail gas destruction systems. The tail gas absorber

271
operates on 127„ caustic to provide good caustic utilization and avoid
carbonate precipitation. Referring again to Figure 4, the tail gas
consists of two tanks and associated sparge tubes. One tank is in
use while the other is being emptied, filled and placed on standby.
The cell gas scrubber uses 20% NaOH (Figure 5) . It was designed
to handle the plant output for ten minutes. Normally 1,200 GPM are
recirculated through the spray heads and back to one of the tanks.
The other is maintained on standby. When cell gas is released to the
scrubber, the effluent temperature rises and the partially neutralized
caustic will be diverted to the waste disposal system. The system
then operates on a once through basis and the caustic entering the
spray chamber is maintained at 207=..
The temperature switch alarms at 130°F and actuates the valves
at 140°F. The recirculation stream normally operates at 100 to 110°F
and will be heated to 185° as it reacts with chlorine. Should the
tank return valve fail to close, the piping is arranged so flow is
preferentially to waste disposal. Should the tank return valve and
the valve to waste both close, the spray chamber has an overflow to
waste. If the system misoperates and stays on recirculation, the
cell gas load can be handled for only about 5 minutes because
caustic depletion and overheating will occur. This still gives
ample time for an orderly cell room shutdown.

TEST OF THE OPERATING UNIT

When installation was completed the system was tested to be sure
it afforded adequate protection. The tail gas scrubber is in con
tinuous operation so evaluation posed no problem. Gases leaving the
stack have routinely been tested at 1-4 ppm.
A test of the cell gas scrubber required a programmed shut down
of the compressor while the cell rooms were still operating. The
scrubber was designed to handle cell room gases at full rate for ten
minutes. As a test the compressor was to be shut down for three
minutes. This would allow two minutes to restart the compressor and
still leave five minutes to shut down the cell room in case the com
pressor could not be restarted.
Prior to the testi the composition of cell gas was analyzed, the
level and concentration of caustic in the tanks were measured, and a
gas sampler was installed on the scrubber outlet. The gas to be
sampled was drawn through a series of Smith-Greenburg impingers.
The first three contained potassium iodide solution and the fourth
was packed with silica gel. The impingers were located within four
feet of the scrubber stack outlet. Pertinent data recorded are com
pared to design operation in Table I. The major departure from
design was temperature. This resulted because the caustic solution

272
had just been made up by diluting 50% NaOH and was still hot when the
test was run.
The off gas flow rate was related to the incoming flow rate by
assuming the incoming inert gases (CO, H2, & O2) were present in
the exit. The scrubber removed more than 99% of all the chlorine
entering the system. The gases would cause no problem for personnel
on or off the plant site. At the flow rate of caustic used, 1,160
gpm, each of the two reservoirs holding 12,000 gallons would handle
the cell room effluent for ten minutes.

SUMMARY
A dual chlorine destruction system was installed and tested at
Kaiser's chlorine manufacturing facility in Gramercy, Louisiana.
Tail gases, remaining after liquefaction, contain primarily air
with substantial amounts of CO2 as well as chlorine and hydrogen.
The initial concentration of caustic used must be kept below 12.5 wt X
to avoid solid carbonate formation. Scrubber efficiencies for a dip
tube sprayer are better than 99.97„.
To handle cell gas during emergency shut downs, a spray tower
with once through liquid flow is employed. The spent caustic concen
tration must be kept above 8 wt % to maximize mass transfer rates.
The input caustic concentration must be "kept below 20 wt % to avoid
overheating or wastage of caustic. A plant test has indiciated that
during an emergency shut down, the scrubber can remove better than
99% of the chlorine entering for up to ten minutes. We believe this
is adequate protection.

273
 CELL GAS CHLORINE PLANT UNCONDENSED
RELIEF TAIL GAS

LIQUEFIER

POWER
COMPRESSOR
COOLER DRYERS LIQUID
CHLORINE I

QT5
CELL ROOM
FIGURE 1

ORIGINAL DESTHUC1IOH STSTEM MASS TRANSFER COEFFICIENT

STACK

CAUSTIC CONCENTRATION-

r—®-
9 20

CAUSTIC CONCENTRATION -*T %

CAUSTIC TANKS
1212,000
HI. % GAL
NaOH
iIrom J, E. Vivian - ScOThesis MIT - 1945
FIGURE 3

274
 REVISED SYSTEM TAIL GAS ABSORBER

SEPARATE CELL
GAS RELIEF

LIQUEFIER

CHECK VALVES

SEQUENTIAL [ COMPRESSOR
POWER TRIP y k COOLER DRYERS

CELL ROOM FIGURE 4 LIQUID

CHLORINE
CELL GAS ABSORBER

CELL GAS OVERFLOW

y
TO WASTE DISPOSAL

-®—* ®-

20% CAUSTIC X% CAUSTIC

12.000 GAL. 12,000 GAL.

FIGURE 5

275
 TABLE I
COMPARISON OF DESIGN VS TEST CONDITIONS

ITEM DESIGN OBSERVED

Caustic Flow Rate 1200 gpm 1155 gpm
Initial Caustic Cone. 20 wt 7. 18.5 wt %
Final Caustic Cone. 10 wt % Not Reliable
Initial Caustic Temp. 105°F 126°F
Final Caustic Temp. 185°F 208°F
Gas to Scrubber
H20 7500 SCFM 7150 SCFM
Inerts 150 134
CI2 4500 3920
Efficiency Above 99% 99.9%

276
 REFERENCES
1. ) Vivian, J. E., "Absorption of Chlorine in Water and Caustic".
Sc.D. Thesis, MIT, 1945.
2. ) Perry, Chilton, Kirkpatrick, "Perry's Chemical Engineers
Handbook", McGraw-Hill, 4th ed. p. 14-39.
3. ) Vivian, op cit, Figure 19.

277
 RECOVERY OF CHLORINE FROM WASTE GAS - PILOT EXPERIMENT
F. HINE , M. YASUDA and M. HIGUCHI
Nagoya Institute of Technology, Nagoya 466a Japan
Pilot experiments for electrochemical recovery of
chlorine from waste gas containing weak chlorine
have been carried out. Operation of the cell at
high temperatures such as 70°C with high flow rate
of the catholyte is preferable because the cathodic
process is controlled by diffusion of cupric ions
in the vicinity of the cathode surface. The ele
ctric power consumption is estimated to be about
1,700 KWH/t-Cl2.
I. INTRODUCTION
Chlorine from waste gas at chlor-alkali plants should be recovered.
A new electrochemical process with a depolarized cathode has been an
nounced in a previous report (1). This process resembles the Kyoto-
type HC1 cell (2,3). The cathode reaction consists of the electro
chemical reduction of cupric chloro-complex ions (designated as Cu(II),
hereafter) into cuprous ions (Cu(l)), and Cu(l) is oxidised simultane
ously by dissolved chlorine in the catholyte. Although the chemistry
of this process is simple, the cell design is complicated. Use of the
chlorine absorber, in which absorption and chemical reaction of weak
chlorine with the catholyte effluent containing cuprous ions take place
simultaneously, would be more practical.
A small pilot cell (20 cm2 electrode area) has been operated for
several months in the laboratory.
II. FLOWSHEET OF SYSTEM
A small pilot cell made of Lucite resin consists of an anode and
cathode compartment with a PVC fibre fabric diaphragm. The graphite
electrode, both anode and cathode, is W mm wide and 50 mm long, or 20
cm of effective area. A metal oxide coated Ti anode was also examined,
but no significant advantage was observed.
The Luggin probe connected with the saturated calomel reference
electrode was placed 1 to 2 mm from the electrode surface. Therefore,
the potentials observed>involve some IR-drops between the working ele
ctrode and the Luggin. These data would be preferable for calculation
of the cell voltage. The terminal voltage was recorded continuously,
and agreed well with the balance of the anode and cathode potentials.
The electrode-to-diaphragm a pacings were varied from 1 mm to 20 mm:
most experiments were carried out with 10 mm spacing, that is, the dis
tance between the anode and the cathode was 20 mm. The IR-drops were
calibrated with the conductivity data shown in Figs. 10 and 11.

278
 The flowsheet of the system
used Is shown in Fig.l. The
electrolyte is pumped up to the
level tank about 1.5 m above the
cell, and is sent to the anode
and cathode compartments.
Chlorine is recovered from the
anolyte effluent. Since the
electrolyte after dechlorination
contains a small amount of
chlorine, it is sent to the top
of the chlorine absorber, or to
the oatholyte reservior.
The catholyte effluent con
taining Cu(I) is sent to the
chlorine absorber, where Cu(I)
is oxidised into Cu(II) by weak
gas. The off-gas of the
chlorine absorber is washed with
fresh water or alkali solution,
and the purge gas is swept out.
-VTE CADfeLYTE
The flowsheet in this fig RVIOR -g RESERVIOR
ure is useful for practical
operation. In the laboratory,
recovered chlorine was absorbed
with the catholyte effluent, Fig.l. A flowsheet for practical
and thus chlorine was recycled. operation, also for exp
erimental works.

III. RESULTS
1. Anode Potential.
The anodic process is chlorine
formation and is independent of the
flow rate of electrolyte, but
□ too depends much on the temperature.
a 40.0 The higher the operating tempera
0 22.8 ture the lower is the chlorine
overvoltage (Fig.2).
2. Electrolyte Composition.
Since the conductivity of the
mixed solution consisting of HC1
and CuCli is high at 5-7 N HC1
(Fig. 10), the HC1 concentration is
Fig.2. Polarisation curves. kept constant at 6 M.
5.4M HC1 ♦ 1.3M CuCla As shown in Fig.2, the cathode
4.05 cm/sec (Re . 900) polarisation curve showed the

279
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08Z
in concentrated HC1 solution was limited at about 1.5M CuCla, and hence,
the electrolytic solution consisting of 6 M HC1 and 1.4 M CuCl2 was used.
The conductivity lowers with increase in the CuClz concentration (Figs.
10 and 11).
3. Catholyte Flow Rate.
Since the cathodic process is controlled by diffusion, the catholyte
flow rate very much Influences the polarization behavior as shown in Fig.
5. At ♦0.1 v vs. SCE, for example, the current density is a linear
function of the flow rate (Fig.6), and hence, the catholyte flow rate
should be maintained as high as possible.
At less noble potentials than about -0.2 v vs. SCE, copper deposi
tion at the cathode takes place (Fig.2), and is a problem of cell opera
tion. Therefore, the cathode potential should be no less than 0 v vs.
SCE.
<f. Temperature.
The cathode process is affected very much by the operating temp
erature as shown in Fig. 7, that is, the current density at a given
potential (♦0.1 v vs. SCE, for example) increases with temperature as
shown in Fig.8.
5. Cell Voltage.
The cell voltage involves the anodic and cathodic polarisations
and the IR-drops between two electrodes, and the data recorded are in
agreement with the balance of the polarisation data of two electrodes
with the Luggin probe.

i■ O0rI

Fig. 7. Cathode potential vs. Fig.8. Current density vs. temp

current density. erature at O.lv vs. SCE.
16.3 cm/sec. 16.3 cm/sec.

281
Pig.9. Call voltage vs. temperature Fig. 10. Conductivity of mixed
at 50 a/dm*. 5.kH HC1 ♦ solutions of HC1 and CuClt
1.3M CuCl2. 16.3 cm/sec. at 80°C.
Since both anodic and cathodic
processes are influenced by the
operating temperature , the cell volt
age is also a function of temperature
as shown in Fig. 9. That is, the
higher the temperature, the loner the
cell voltage.
In the range loner than W°C,
the cathode potential is less noble
than -0.2 v vs. SCE at relatively
high current densities such as 50
a/dm , and copper deposition takes
place at the cathode surface with an
increase of cell voltage as shown by
CiCIt CCNCXNTIUTION IM) the closed points in Fig. 9.
Fig. 11. Conductivity of mixed IV. DISCUSSION
solutions of 5.6 M HC1
and CuCla. The electrolytic solution having
high conductivity should be used so
as to keep cell voltage low. As
shown in Figs. 10 and 11, the maximum conductivity is achieved in 5-7 M
HC1 at high temperatures, but the conductivity lowers with increase in
the CuCls concentration. On the other hand, the cathode process
requires high concentration of Cu(H) as described above. Therefore,
the anode-to-cathode spacing should be designed as small as possible to
keep IR-drops small, that is, 1-2 mm between the electrode and the dia
phragm could be a minimum size applicable in practice.

282
 Suppose that,
Electrolyte 6M HC1 * 1.5M CuCla
10.8 mhos/cm at ?0°C
Temperature 70°C
Anode-to-cathode
Current density 50 a/dm*
the IR-drop In the electrolyte would be 0.02 v, which Is acceptable.
The catholyte flow rate Is an Important factor for this process.
More than 15 cm/sec of the flow rate Is preferable from the view point
of electrochemical science, but this requires work Input for practical
operation due to narrow spacing between the cathode and the diaphragm.
Recirculation of the catholyte with an additional pump to Increase the
Reynolds number In the vicinity of the cathode would be applicable but
has not been carried out In the laboratory.
At high temperatures such as 70 - 80°C, the diffusion current
density Increases, no copper deposition occurs at relatively high
current densities such as 50 a/dm , the conductivity of the electrolyte
Increases, and hence the cell voltage lowers considerably. Cell
performance Is good, and only failure of the construction materials of
the system In the corrosive environment Is a problem.
The weight loss of the graphite anode Is negligible. The side
reactions such as C02 formation and H2O discharge would not take place
In such concentrated add solutions (4), In other words, the anodic
process consists of the chlorine evolution alone, and the current effi
ciency Is more than 97% In normal operation.
The metal oxide coated Tt anode Is also applicable. The anode
polarisation and the cell voltage are lower compared to the graphite
anode, but only by 50-100 mv. Since the graphite anode Is not corroded
In this system, we conclude that graphite Is the best and the metal oxide
anode Is no longer employed from the economical view-point.
Suppose that the terminal voltage Is 2.2 v at 50 a/dm2 and ?0°C
under possible flow rate of the catholyte, say 15 cm/sec. The electric
power consumption Is then estimated to be 1,680 KWH/t-Cla compared to
2,900 KWH for the modern diaphragm-type chlor-alkall cells and 3,200 KWH
for amalgam-type cells.
Copper deposition on the cathode surface due to poor operation Is
a problem. If copper deposition takes place, the electrolytic circuit
should be swltched-off , and the electrolytic solution should be circulated
continuously for a few minutes so as to dissolve deposited copper. The
cell can then be re-operated.
In conclusion, the process, the cell design, and operation of the
system are simple with considerably small power consumption for unit
production or recovery of chlorine.

283
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V
 THE USE OF COMPUTER MODELING
IN DEVELOPING CHLOR-ALKALI PLANT DESIGNS
Edwin L. Sokol
Colin S. McLarty

Hooker Chemical Corporation

MPO Box 8
Niagara Falls, New York 14302

ABSTRACT
This paper outlines the benefits accruing from and the problems
associated with computer modeling of chlor-alkali plant designs.
The features needed to reflect a meaningful simulation of an
actual plant are discussed.
An example of a computer simulation of a chlorine liquefaction
system is presented. It exhibits the relationship between design
parameters such as liquid chlorine product purity and liquefaction
pressure and temperature.
The simulation of an entire diaphragm cell chlor-alkali plant
is also discussed.

285
INTRODUCTION
The use of computer modeling of chemical processes is well
documented and a number of commercial programs are available
for lease or direct purchase. Therefore, this paper is not
addressed to the detailed mechanics of computer modeling but
to how computer modeling can aid in the design of chlor-alkali
plants.
Several years ago Hooker Chemical Corporation purchased a
commercially available chemical plant simulation program,
which was fitted with especially prepared physical property
data for the components encountered in chlorine processing.
The program is operational on our in-house computer and
is now used to evaluate all our chlor-alkali plant designs.
For those engaged in chlorine plant design and operation,
and for those contemplating the writing or purchase of a
computer plant simulation program, the following comments
will prove of interest.
Computer Design Benefits:
The reason a computer is used in design is because the user
believes that it will provide certain benefits. These
benefits may be speed, calculation accuracy, etc. Many
times the benefits contemplated at the inception of a plan
to use computers in plant design never materialize. Having
experienced the process of setting up a computer simulation
program we feel the following are some of the actual benefits
which have been realized.
(1) Probably the major advantage of computer calculation
is that it facilitates the following of trace impurities
in the chlorine stream throughout complex process
arrangement replete with many recycle streams. This
point will be expanded later.

(2) Computer calculations give assurance that correct physical

property data has been used in computation.

286
(3) Computer simulation facilitates the evaluation of alternate
process conditions or arrangements in sufficient detail to
uncover subtleties that might later prove important.
(4) The process of preparing the process input data forces a
logical review of the process and interacting forces.
(5) The computer simulation program permits less experienced
personnel to perform sophisticated calculations.
(6) . The input data is concise and can be easily reviewed by
supervisory personnel. The input data contains a complete
statement of the calculations. It reveals the flow sheet,
control schemes, input data and calculation instructions.
(7) The output data is in a readable form which permits quick
checks for accuracy. The output data can be used by
anyone without interpretation.

Computer Program Criteria:

To obtain the above benefits, care must be exercised in selecting

the commercial simulation program or in establishing the design
criteria for the plant design program you want to have
developed. For a program to be used in chlor alkali design we
considerered these two criteria to be important.
First, the program should have a physical property data system which
can accurately reflect the solubility of trace components in
chlorine. This need for accurate distribution of a few PPM of
impurities in the chlorine process streams can not be over
emphasized. For example, trace quantities of water can
concentrate somewhere in the process to a level where corrosion
to process equipment results. Therefore, the computer simulation
system must accurately reflect water solubility in chlorine
and also distribute water between liquid and gas phases. This will
permit calculation of the water level at various critical spots in
the system even when the system is complicated by internal recycle
streams.
Other components of concern in the PPM level are oxygen, nitrogen,
carbon dioxide, bromine and certain organics.

287
Not all commercial simulations are programmed to reflect
accurately the solubility of trace components. Some programs
are based on simplified physical property relationships which
allow rapid calculation techniques but are not suitable for the
accuracy that we feel is necessary for chlorine plant design.
Secondly, the simulation program should be very flexible. It
should be possiblle to revise a process model quickly and
investigate only areas of interest. For example it should not
be necessary to run an entire plant model complete with
compressors and intercoolers if the process section under
consideration is the liquefaction system.
Before giving some specific examples, it might be well to
point out some of the problems associated with computer
modeling.
Problems :
The need for highly accurate physical property data will
make the initial calculation and check of the property
constants used in the program tedious. However, failure to
spend the time, money and effort on this phase of the
computer program development will greatly reduce the programs
effectiveness.
As with any tool, there is a certain learning period which
must be endured. With computer modeling this can be a
frustrating and expensive time. Even after this period is
survived, a stray comma or period in the wrong place in the
input data can negate an entire process run.
Some examples of how computer modeling is used in chlor-
alkali plant design will illustrate some of the points
mentioned above.
Chlorine Processing:
The basic process steps of chlorine processing from the
electrolytic cell to the liquid product storage tank are well
established - cooling, drying compression and staged
liquefaction at decreasing temperature levels. These general
process steps are shown in Fig. 1. In the past, process
conditions such as liquefaction system pressure was limited
because the only suitable compressor was a sulfuric acid sealed
Nash. Today with non- lubricated reciprocating compressors or
centrifugal machines available to handle dry chlorine gas
and other advances, the process designer has complete freedom
in selecting process conditions.

288
To illustrate how a computer model helps evaluate various
design alternates and some of the other points previously
discussed, let us look at a typical two stage liquefaction
system as shown in Figure 2. In this process compressed
chlorine cell gas enters as stream No. 1. It is partially
cooled and condensed in the primary condenser. Dilution
air is added to the primary vent gas as stream No. 12.
The mixed gas stream No. 13 is further cooled and
additional chlorine is condensed in the secondary
liquefier. The vent stream, No. 6, is analyzed for H2
concentration and this data is used to control the
quantity of dilution air. The combined product stream
No. 8, might be the final product, or we could
continue on and flash this combined liquid to a
lower pressure thereby producing liquid product stream
No. 11. The flash gas from this operation might leave
the process as stream No. 16 or recycle back to
liquefaction as stream No. 15.
Using this simple process scheme lets look at four
variations which we will call cases A through D. Case
A will operate at 40 FS16 liquefaction pressure and
appropriate liquefaction temperatures and end with
stream 8 as product liquid. Case B will operate at
100 PSIG and higher liquefaction temperatures and also
end with stream No. 8 product liquid. Case C will be
the same as Case B but will continue on to flash stream
No. 8 to 40 PSIG and have all flash gas leave as
stream 16. Case D will be the same as C except that
all flash gas will be recycled as stream No. 15.
The process operating data for these various
alternatives are given in Table I.

TABLE I
SYSTEM PROCESS DATA A B C D
Liquefaction Pressure (PSIG) 40 100 100 100
Primary Liquefaction Temp. (°F) 10 60 60 60
Secondary Liquefaction Temp. (°F) -40 -40 -40 -40
Flash Pressure (PSIG) none none 40 40
Flash Gas Recycle none none none yes

289
Computer Flow Sheet :
Figure 3 illustrates the computer flow sheet for the process
given in Figure 2. Titles such as SETSC4 and FLASH 3 are the
names of standard operational process models in the program
that call for certain calculation procedures that simulate
the process equipment. The stream numbers are the same as
Figure 2 and it is quite easy to see the process flow sheet
in the computer flow sheet. This one computer flow sheet
serves for all alternates.
Once the initial input data is prepared for Case A all the
other cases can be run by merely changing a few numbers.
An example of the complete input data for Case A is given in
the appendix. As stated previously, a person familiar with
the computer system can reconstruct the entire problem from
this concise tabulation.
A typical output sheet as it comes from the computer is also
given in the appendix . Anyone having the process flow diagram
and the output data can understand and check the results.
Comparison of Results:
To continue our example we can evaluate the four cases
using a typical cell gas composition. At this point we can
reemphasize that the computer program can be operated by an
engineer with little speciallized knowledge of computer
programming.
Table II contains a summary of a few interesting parameters
from the run results.
TABLE II
LIQUEFACTION SYSTEM COMPARISON
A B C D
% Cl2 Liquefied 97.9 99.0 94.4 99.0
%(V/V) Cl2 in Product 99.3 99.1 99.6 99.5
PPM (Vol) Oxygen 470 840 50 50
Product Temperature (°F) 7.9 50.3 27.7 26.7
Heat Duty (BTU/Hr. x 10"6)
Primary 8.08 7.00 7.00 6.88
Secondary 2.93 4.75 4.75 5.07
Dil. Air (SCFM) 277 351 351 327

290
At this time, it is not important how the results from these
various alternatives are weighted to decide a final process
selection. This depends on individual plant conditions,
management desires and other factors. The important point is
that a complete comparative energy and material balance,
including an analysis of product quality, can be obtained on
any alternate process in a matter of minutes.
Overall Plant Balance
The computer simulation program has also proved very useful in
calculating overall plant material balances. Figure 4 shows a
box diagram of one possible overall plant arrangement. As can
be seen from inspection, there are a number of recycle streams.
These recycle streams add complexity to the calculations and make
the calculation procedure very laborious.
With the current emphasis regarding ecology and energy
conservation, future plants will have even more recycle streams.
The calculation of overall balances are tedious. It is quite
important to follow items such as sulphate levels and excess
caustic in various brine streams throughout the process.
To make a complete balance and then have a request to change
one little variable in one of the process steps can be very
discouraging. Having the overall balance on a computer file
where it is only necessary to change a number or patch in a new
process step can alleviate a lot of frustration.
Overall plant balances are rather large networks of computer
flow sheets for each process step. Figure 5 illustrates how the
brine treatment box in Figure 4 would appear in our computer
simulation. This is then tied together with other similar type
simulations representing the other process steps to yield the
overall system. In the overall calculations, the number of
components increase from about 6 or 7 when considering the chlorine
system alone to 15 or 16. Once the network is complete and
tested it is an easy process to change process variables or to
patch in additional process steps.
Conclusion:
The computer simulation system permits thorough evaluation of
various process alternates. With growing emphasis on product
purity, energy conservation and zero pollution plants, the
computer simulation system will be a necessary tool for
effective plant design.

291
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 APPENDIX
COMPUTER OUTPUT DATA

STREAM VARIABLES — RUN I FINAL

STREAM NUMBER 1 .00 2.00 3.00 4.00 5.00

VAPOR FRACTION 1.00 0.09 1.00 0.00 0.72
TEMPERATURE DEG. F 100.00 10.00 10.00 10.00 -40.00
PRESSW:E PS I A 114.70 54.70 54.70 54.70 54.70
ENTHALPY BTU/LBMOL 1 6504. 6S 8420. 19 12930.08 7963.92 6876.49
TOTAL LBKOL/HR 1000. 00 1000.00 91 .88 908. 12 138.45
CL2 LBMOL/HR 960.00 960.00 58.37 901 . 63 58.37
H2o LBMOL/HR 0.00 0.00 0.00 0.00 0.00
COS LBK3L/HR 15.00 1 5.00 9.32 5. 66 9.32
ce LBMOL/HR 1.00 1.00 0.96 0.04 0.96
He LBi'.vL/HR 4.00 4.00 4.00 0.00 4.00
as LBK3L/HR 12.00 12.00 11.58 0.42 21 .36
N2 LBM3L/HR 6.00 8.00 7. 65 0.35 44.44

298
 SIMULATION OF A SALT CRYSTALLIZER DURING PERIODS OF
POSITIVE AND NEGATIVE EVAPORATION
I R WILLIAMS
ICI Australia Limited
ALKALI FACTORY,
OSBORNE, SOUTH AUSTRALIA 5017

ABSTRACT
A model of the evaporation, salt deposition and sal;
redissolving taking place in a crystal lizer is presented, based
on previously published relationships for heat transfer, mass
transfer and evaporation. The model is able to predict the
operation of a crystallizer during periods of positive and
negative evaporation and is reasonably successful in predicting
water evaporation from an evaporimeter.
Conventional meteorological data available from most
stations is used as the input data for the model.
The model can be easily adapted to simulate concentrating
ponds and continuous crystallizer operation and thus is a useful
tool in the design and investigation of Saltfields.

INTRODUCTION
Salt production by solar evaporation of seawater brines is
a widely used method of obtaining salt, but still today, the
design and operation of saltfields is largely an art based
upon prior experience and a small amount of technical data.
Even if sufficient meteorological, brine salinity and seepage
data is available there are few ways (other than by experience
and trial) to predict the operation of the field before it is
built or to predict the effect of different operating methods.
In this paper, a simulation model is presented, based on
previously published evaporation studies by other workers,
which has successfully simulated the operation of a salt
crystallizer over a six month period covering both positive and
negative (excess rainfall) periods of evaporation. The model
has also been applied to water evaporimeters and although not
as accurate as for brine, a reasonable simulation is still
obtained.

299
 THEORY OF EVAPORATION
The process of water evaporation can be represented by the
Dalton equation (Dalton, 1802) which is written:
E = k(Pw - Pa) (1)
where E = evaporation rate,
K = mass transfer coefficient, a function of wind
speed
Pw= vapour pressure at the water surface
Pa= partial pressure of water vapour in air.
From this equation it can be seen that the water surface
temperature (Tw) is important in determining evaporation rate.
Angstrom, (Angstrom, 1920) first recognized the importance of
the total energy balance and subsequently further theories of
evaporation were developed on the energy balance concept.
The problem of reconciling these two theories of evaporation
was solved independantly by two workers H L Penman (Penman, 1948)
and J Ferguson (Ferguson, 1952) and combined mass transfer -
energy balance equations were developed depending on only four
meteorological parameters, viz. net gain in radiant energy Qa,
air temperature Ta, humidity and wind. The equations are
described in detail by Bonython (ref. 1).
The equation used in this study is from Ferguson's work
namely:
E = K(Pw - Pa) - the Dalton equation
h/LK = 0.5 (2)
and Qa - r(Tw - Ta) = LK (Pw - Pa) + h(Tw - Ta) (3)
where Tw and Ta are the water surface and air temperatures
respectively,
r = emission coefficient for black body radiation,
h = heat transfer coefficient between water and air
and Qa = net gain of radiant energy.
It can be seen that as Pw is a function of Tw, the equations
can be solved iteratively for the evaporation rate, E.

DEVELOPMENT OF THE MODEL

As there is a large amount of data available on water and

brine evaporation, it was decided that an approximate analytical
model should be built ie, the model would reflect both the
internal and external changes in the system, using approximations
where exact representation was difficult or impossible.

300
 On this basis, the following discrete parts of
the model were developed.

1. Calculation of The Net Gain in Radiant Energy (Qa)

The net gain in radiant energy depends on short-wave
insolation and reflection, long-wave radiation emitted from
the absorbing surface and back radiation from the atmosphere,
and can be calculated over long periods with reasonable
accuracy from published meteorological data for the area
in question. However, most saltfields and weather stations
are equipped with instruments that can improve the accuracy
of this calculation and hence it was decided to use a
calculation based on daily meteorological measurements. The
data needed is the total short wave insolation (measured by a
solarimeter) , the hours of bright sunshine, the air humidity
and air temperature.
The exchange of radiant energy at a surface is shown in
Figure 1 where:
Qi = incoming short-wave radiation
Qr = reflected short-wave radiation
Ra = incoming long-wave radiation
Rw = outgoing long-wave radiation
Rr = reflected long-wave radiation from the water surface.
Of these five variables, Qi can be measured by a
solarimeter, Qr can be calculated from the solar altitude
and reflection data published by other workers (ref. 1, 2),
and the long-wave radiation balance (Rw + Rr - Ra) can be
calculated from the air temperature, the air humidity and
the percentage cloud cover. For this model, the percentage
cloud cover was taken as:
inn ( i hours bright sunshine )
100 ^ 1 - aax. floers of senshine ^

Hence, Qa can be calculated from: Qa = Qi-Qr-Ql (A)

where QI (the net outgoing long-wave radiation) =Rw+Rr-Ra (5)
It should be noted that Qi and Qr act only over daylight
hours whereas QI acts continuously.
Typical values of these variables for Adelaide are
given in Table 1.

301
Table 1
Average Radiation Values
Qi Qr Ql
raid summer 5000 470 1400 cal cm "2 week "'i
mid winter 1600 350 1000 "
A detailed treatment of the derivation of Qa is given
in Appendix 1.

Calculation of Evaporation From Water or Brine

As mentioned before, the evaporation part of the model
is based on Ferguson's combined mass and heat balance
relationship's ie,
E = 2h (Pw - Pa)/L -(6)
Qa - (r+h) (Tw-Ta) - 2h (Pw-Pa) = 0 -(7)
where Pw = func (Tw) for water
and Pw = func (Tb,^ ) for brine, Tb and^
being the temperature and density of brine respectively.
In the model, the heat balance equation is solved for
Ta or Tb the surface temperature of the evaporating medium
by the Newton-Raphson iteration, having previously calculated
the radiation coefficient r and the heat transfer coefficient
h.
Bonython (ref. 1) quotes the radiation coefficient as
being :
r = 40-(273.16+Ta)3 cal cm"2 hr"l OR-1 (8)
wherecris the Stefan-Boltzmann constant.
The Latent heat of water as a function of temperature
is well known, but for brine there is little published data
on the subject. Specifically the latent heat of brine is
the latent heat of water corrected for heat of dilution
changes or heat of crystallization changes, as the case may
be, but as these latter two values only total IX of the
latent heat of the water removed, they have been ignored and
it is assumed that the latent heat of brine is identical to
that for water.

302
 Several workers (refs. 3, 4, 5) give data on both
mass and heat transfer coefficients for water as a function
of wind speed but both values also depend on the pond
dimensions and only Bonython (refs. 1, 4, 6, 7, 8) gives
data on the effect of pond size. All the data quoted was
tested in the simulation model and it was decided that
Sutton's equation (ref. 3) best fitted the data used for
model confirmation. Hence the relationship chosen was:
h = 35-301 F.v°-78 (Note 1) (8)
where h = mass transfer coefficient cal cm-2 hr-1 oq-1
v = wind speed m.sec "1 at 10m above the surface,
and F is a factor derived from Bonython1 s work (refs. 1 , 8)
giving the effect of pond size. This factor is shown in
Figure 2.
Having evaluated Tw (or Tb) and h, the saturation
vapour pressure is calculated and then evaporation from the
equation:
E = 7.HDL.2h (Pw - Pa)/L cm week -1 (9)
which differs from equation 6 by the factor 7HDL, where HDL
is the hours of daylight/day, and allows for the assumption
that significant evaporation only takes place during daylight.
This assumption is valid when it is remembered that Qi is the
quantity most influencing solar evaporation.
A detailed treatment of latent heat, vapour pressure and
evaporation is given in Appendix 2.

Mass Balance Relationships

This is the most difficult part of brine evaporation to
simulate as the mass balance is effected by rain, evaporation,
seepage, rate of salt dissolving, wind effects on mixing and
diffusion through different density layers. The data collected
during the experiment gave the best guide to what happens
during positive and negative evaporation and it was on this
basis that the mass balance relationships were chosen.
Note 1: Measurements at other heights can be corrected to
10m by the 1/7 power law.

303
 The relationships for brine density and composition,
although rather complex, were fairly easily formulated as
there is a large amount of published data on the subject.
The data chosen was from Bonython (refs. 10, 11) and the
assumption was made that throughout the operation of a
crystallizer the relationship between sodium and magnesium
follows that for concentrated seawater. This assumption
is correct for a brine concentrating pond, but if a salt
bed is present an error occurs . in the magnesium balance,
however, the salt balance is not affected.
For the purpose of the model, it is assumed that the
brine consists of three layers of equal depth and that rain
and evaporation act in the top layer and seepage on the bottom
layer. Salt is deposited from the top layer and if the bottom
layer reaches an unsaturated condition redissolving will occur.
No accurate data on brine diffusion could be found so for
the model, the simple diffusion system described in Appendix 3
was chosen, which is based on the measured data.
>
Throughout the simulation the concentration of Mg ++ and
NaCl were chosen as base variables and from these, the
density, volume and vapour pressure were calculated. The mass
balance was performed at 20°C for simplicity, as the data
was available for this temperature. Simulation was done on a
weekly basis using average brine composition values for the
start and finish of the week and the amount of salt deposited
or dissolved at the end of the week was obtained from a salt
mass balance.
A detailed description of the mass balance and equations
describing density and composition are given in Appendix 3.

EVAPORATION DATA
The evaporation data for model building and confirmation
was obtained from the ICI Australia Limited Saltfields at Dry
Creek, near Adelaide, South Australia. This field operates on
solar evaporation of seawater and produces some 400 000 tons of
salt a year. Many previous evaporation studies have been done
at this site by other workers (such as Bonython) and it is an
ideal site for data collection as (a) it is a well instrumented
field and (b) the data on seepage, brine composition and salt
density was available, experiment was conducted fT-om May
to November 1970.

304
 The field is idle during the winter months (May-August)
and as it was simple to obtain data on a crystallizer during this
period, it was decided that a crystallizer should be left
unharvested but flooded at the end of the saltmaking season and
data would be collected during the period of negative evaporation
(May-August) and continue during part of the positive evaporation
period (September-November in this case). This was the main
source of data, but in addition, data was collected from a
nearby crystallizer containing no solid salt, but flooded with
maiden brine and also from water evaporimeters 10ft and 3ft in
diameter respectively.
In total, the following data in Table 2 was collected:
Table 2
Data Collected During Saltfields Trial May-November 1970
Daily Weekly or after Monthly
Rain 0.2 in
Max air temp. Brine density & brine Salt depth
Min air temp. temp of top, middle at 27 points
Ave. air humidity & bottom brine layers in crys.
Ave. wind speed at 12 points in crys.
Ave. wind direction
Water evaporation
Oft St." 10ft tank)
Rainfall
Total solar radiation
Total hours bright sunshine
Evaporimeter temperatures
In addition, several sets of brine density and temperature
measurements were taken at 8 hourly intervals for up to 3 days
to trace the approach to equilibrium after heavy periods of rain,
and salt density and quantity measurements were made on the
crystallizer at the end of the experiment.
Model Data
For each week of the simulation, the following data is
supplied to the model:
a. day number on which the week starts
b. total short-wave insolation (from solarimeter)
c. average wind speed in mph (at a height of 3ft in this case)
d. average air humidity in mm Hg
e. average air temperature in °F calculated from Tmax + Tmin
2

305
f. average % cloud cover (calculated from hours of bright sunshine)
g. total rainfall in inches.

In addition the following general data was supplied.

latitude in degrees, seepage in cm/week and the pond size
factor F.
Simulation of water evaporation in an evaporimeter needed
no further data, but for crystallizer simulation the following
data for the first day is needed:
a. total crystallizer depth in cm
b. total salt depth in cm
c. top, middle and bottom brine densities at 20°C in gm ml"l
d. average brine temperature.
At present, the model simulates a batch crystallizer
operation, but the mass balance section can easily be adapted
to simulate continuous operation if brine inflow and outflow
data is supplied.

SIMULATION RESULTS
Apart from intermediate meteorological data, the model
simulates water evaporation from both an evaporimeter and a
crystallizer in cm/week, crystallizer total depth, brine and
salt depth, and brine density and surface temperature. The
test and simulated data is given in figures 4 to 8.
Figure 4 gives water evaporation in cm week"'' for a 3ft diam
Australian Standard Evaporimeter which is similar to a class A
pan except that the water surface is at ground level. Figure
5 is the same measurement from a 10ft diameter evaporimeter which
was built at Dry Creek in 1951 to study brine evaporation in pans.
Figures 6 and 7 give the simulated and measured results on BO
crystallizer which contained the layer of salt. In figure 7,
the brine depth is the depth assuming no salt layer is present
ie, total depth - (1-salt voids). salt depth.
Figure 8 shows the simulated brine height of C4 crystallizer
which contained brine only. It should be mentioned that this
crystallizer was "decanted" and "retopped" with maiden brine
three times during the experiment and the measured brine height
has been corrected to elliminate the step changes in brine
height after decantation. All data is corrected to 20°C.

306
 The actual dimensions of these crystallizers are:
BO 800 ft x 648 ft
C4 800 ft x 419 ft

DISCUSSION OF RESULTS
It should be noted that simulation is a technique by
which a sufficiently accurate representation of a system can
be achieved so that a decision can be made on its operation.
In this regard, the simulation is certainly successful. Taking
BO for example, the simulated total crystallizer depth and
brine depth agree very closely with the measured data. C4 shows
similar good agreement between simulated and actual brine
depths .
Simulation of salt bed depth is very difficult because
during deposition and redissolving, the voids content changes.
During redissolving, the voids content of the salt bed
increases as dissolving takes place throughout the entire bed;
seepage actually enhancing this phenomenon. The simulation
results do not account for this as they assume a constant
voidage. Hence, the simulated salt depth initially decreases
at a greater rate than the actual salt depth although the
amount of salt present in the bed will be similar for each
curve. The salt bed remains rigid up to a certain point during
redissolving, but gradually begins to breakup and eventually
collapses into a mass of unattached crystals. This was observed
during the experiment and is shown dramatically in figure 6.
At this time, measurement of the salt bed depth becomes difficult
and significant errors are expected. Once salt deposition
recommences, the bed again becomes rigid and there is good
agreement in the rate of change of salt bed depth for both the
simulated and measured results; the fairly constant difference
being caused by bed collapse. A further small error that can
occur results from the fact that seepage is not necessarily
constant duriqg the experimental period and would probably be
higher during the period that the bed was not rigid. Again,
no allowance was made for this in the simulation model.
As explained above, there are good reasons for the anomaly
in salt depth ie, the measurements show a decrease in depth and
the simulation shows a slight increase in depth over the
experiment. There is further evidence however, that the
simulation is correct ie, that there is an increase in the
quantity of solid salt present. At the start of the experiment
the average brine density was 1.225 ( 29° Be) at 20°C and at
the completion of the experiment the average brine density was
1.237 (30.5° Be).

307
 As no brine had been added to the crystallizer during the
experiment which would artificially increase the density, and
the crystallizer was close to saturation at the start of the
experiment, the increase in density can only be explained by
an increase in the amount of salt deposited.
The simulated water evaporation does not show the same good
agreement with measured data as do the salt cry stallizers.
During the period of low evaporation (May-August) the simulated
evaporation is lower than actual for both evaporimeters, but
better agreement is obtained as evaporation increases. During
the period of low evaporation, the ratio between simulated and
actual evaporation is about 0.57 for the 3ft diam evaporimeter
and 0.70 for the 10ft evaporimeter. 3onython (ref. 11) shows
the same effect, his ratios being as follows:
3ft evaporimeter 10ft evaporimeter
Winter 0.66 0.83 (Calculated/Measured)
Summer 0.32 1.01 " "
He goes into detail trying to explain the difference but
concludes that the 3ft diameter evaporimeter is not a suitable
size for evaporation measurements and a larger diameter tank
should be used if the results are to be used for comparison with
large evaporating ponds.
The experiment also showed up the reduction in actual brine
evaporation from large ponds when compared with water evaporation
in evaporimeters. This is demonstrated in figure 9 where the
calculated brine and measured water evaporation rates are
presented.
1 . Voidage
After the experiment was concluded crystallizer BO was
drained and 10 sections approximately 18" sq were cut from it.
The salt density as measured from these samples was 73.3 lb ft
which corresponds to an SG- of 1.19 and a voidage of OA55.
This density was close to the average figure for the field of
76 - 5 lb ft"3 which has been obtained over several years.
Although the actual salt voidage changed during the experimental
period (as previously mentioned), it was decided to use this
measured voidage for the simulation. Other users of the
simulation model could obviously use different voidage values.

308
2. Salt Depth and Quantity
The salt bed depth was also calculated from the 10 samples
taken for density measurements and the average salt depth at
the end of the experiment was 14.5 cm which is close to the
final value of 13.7 cm on the last day of the experiment, the
difference arising from (a) possible errors in the salt bed
measurements during the experiment and (b) the extra evaporation
occurring in the week between the end of the experiment and the
taking of the density samples.
It is worth noting that the salt bed was originally level
at the start of the experiment, but after the experimental period
of 6 months, the upwind average depth was 15.4 cm and the
downwind average depth was 12.9 cm. The depth difference of
2.5 cm was caused by the rainwater and hence weaker brine being
pushed to the downwind side of the crystallizer by the prevailing
wind, and thus causing more salt dissolving in this area. This
effect of wind on density distribution was well demonstrated
during the experiment.
The calculated quantity of salt at the end of the experiment
was 8110 tons which compared well with the harvested amount of
7640 tons.
FURTHER OBSERVATIONS FROM THE EXPERIMENTAL DATA
It has been mentioned previously that the data obtained
during the experiment provided an insight into the problems of
density distribution, salt dissolving and brine diffusion
occurring in a crystallizer subjected to both evaporation and
rain. In general, the following observations were made during
the experiment:
a. A rainfall of less than 0.1 in shows up as a decrease in
brine density evenly distributed throughout the brine.
b. A large rainfall disturbance of 0.2 in or greater in 24
hours shows up as a less dense layer on the brine surface
which will flow to the down-wind side of the crystallizer
under the. influence of the prevailing wind where it will
remain for up to two days. During weeks with a large
rainfall (eg, 1-3 inches) the density gradient through
the brine depth was large although only small changes in
the bottom density were observed. The wind velocity and
direction changes helped to mix the brine, but still after
a week of dry weather a slight density gradient could still
be observed.

309
 c. It would be expected that the ratio
change in salt bed depth (ds)
change in total crys. depth (dD)
would be constant for both salt deposition and salt
dissolving if the crystal lizer was a perfect mixer.
However, this is not so and during the experiment the
following values were observed:
period of salt dissolving ds/dD = -0.17
period of salt deposition ds/dD = -0.33
As expected however, the value of ds/dD for deposition
is almost identical to theoretical value of -0.329
calculated at the salting specific gravity of 1.126 and
a voidage of 0.455.

DECANTATION
It is well known that although decantation of the weak top
layer of brine after rain will remove some salt in solution, the
resulting solid salt yield can be increased with decantation
because the crystal lizer can be returned to a salting condition
more rapidly. Decantation was not practised on BO crystal lizer
during the experiment, but it was decided that a simple
decantation model should be built into the rain simulation model;
this is described in Appendix 3. It was assumed that decantation
would occur if the rainfall in the week concerned was>1.9 in.
The results of this simulation for BO are shown in figure 10,
although there is no experimental confirmation available.

CONCLUSION
It has been demonstrated that simulation can be applied to
the operation of a crystal lizer with reasonable accuracy and
that published data on evaporation and brine composition is
suitable for the building of simulation models. The simulation
presented in this paper has been conducted over the most difficult
period to simulate ie, the period of salt redissolving , but still
it has been successful; even moreso during the more normal period
of salt deposition.

310
 It is believed that this model could be simply adapted to
the simulation of continuously operating ponds and crystal lizers
and could be used to predict such values as (a) salt yield, (b)
pond/crystal lizer ratio, (c) effect of decantation of rain and (d)
effect of storing unharvested salt in a flooded crystallizer
during a rainy season. The meteorological data is fairly easy
to obtain and if an operating field is to be simulated, the required
data could be assumed with reasonable accuracy from previous
records.

311
 APPENDIX T

CALCULATION OP THE NET GAIN IN RADIANT ENERGY

The basic equation is:
Qa = Qi/(7 . HDL) - Qr - Ql (l)
1. Calculation of Lon^ware Radiation Loss Ql
Prom Geiger (ref. 2)
Ql = (Ta + 273.l6)i(-(l-RP(0.78-O.148.10 -°•o68Pa).cF (2)

The factor SF allows for the back radiation from the

atmosphere which is reflected from the water surface. Its
value lies between 0.95 and 1, but has been set at 1 in the
simulation. CF is a factor allowing for the percentage
cloud cover and is explained fully in ref. 1. As the type
of clouds had not been monitored in the experiment it was
decided for simplicity that:
% cloud cover = 10o(l - -SS§ ) (3)
( max hours of sunshine)
The maximum hours of sunshine for any area and day of
the year is found from published data and the hours of bright
sunshine (HBS) was recorded on a sunshine meter. Prom ref. 1
CF can be calculated as follows:
CF = 0.16 + 0.02 (100 - C) for C>90?S (4a)
CF = 0.28 + 0.64 log10 (100 - C) for C<90# (4b)
where C is the % cloud cover.
2. Calculation of the Reflected Short-wave Radiation Qr
Qr = 0.01. REF . Qi/(7.IIDL) — (5)
where REF is the average % reflection over a day.
Firstly, the solar altitude is calculated as a function
of the time of the day, the day of the year and the latitude
from:
cos (ZD) = sin(LAT)sin(DEC)+cos(LAT)cos(DEC)cos(HA) (6)
where: ZD = 90-altitude = zenith distance of sun
LAT = latitude
DEC = solar declination
HA = hour angle (time from local noon in degrees) .

312
 The data on DEC was obtained from ref. 12 and for the
Southern Hemisphere is:
DOY < 81 DEC = -23.27 cos (DOY+9) (7a)
82-172 DEC = 23.27 sin( (DOY-81) 90/91) (7b)
173-265 DEC = 23.27 cos( (DOY-172) 90/93) (7c)
266-355 DEC = -23.27 sin( (DOY-265) 90/91) (7d)
356-365 DEC = -23.27 cos (DOY-356) (7e)
where DOY = day of year.
Once the solar altitude is known the instantaneous
reflection from the water or brine surface can be calculated
from curves shown in figure 3> Test runs on the data showed
that Geiger's curve for moving water (ref. 2) gave the best
results, but there is little to choose between the different
curves at the latitude of Dry Creek (34°50's). The equations
for Geiger's curve are:
PER = 3.2587 + 535.4066/( ALT + 5.1851), ALT<20° — (8a)
PER = 4.1701 + 97.4119 /(ALT - 16. 7525) , ALT >20° (8b)
where PER = % reflection (instantaneous).
The average % reflection for the day is calculated by
integrating the instantaneous value of reflection from 8 hours
before local noon to 8 hours after local noon in 10 minute
intervals. The calculation of REF is performed at day 3 of
the week to represent the average for the week.

313
 APPENDIX 2

CALCULATION OF EVAPORATION
The evaporation equations used are:
Qa - r(Tw - Ta) = Lk (Pw - Pa) + h (Tw - Ta)
h/Lk = 0.5
E = 2h (Pw - Pa)/L=k(Pw - Pa)
Calculation of Vapour Pressure and Latent Heat
The vapour pressure of brine and water can be represented
by the following equation which is in the form of the
Clapeyron - Clausius equation and based on the data given by
Bonython in ref. 1:
Pw = exp(18. 0446-5332. ll/(Tw+273.16)+6.64/> -3. 494/02))
The latent heat for both brine and water is taken as:
L = 596.4 - 0.50225. Tw
Calculation of Heat Transfer Coefficient
The chosen equation was based on the work of Sutton
(ref. 3) and Bonython (refs. 1,8) and is:
h = 35.3801 .P. v0*?8
where P is the pond size factor given in figure 2 which
depends on the average downwind dimension of the pond.
The wind speed v is at 10m above ground level, but can
be corrected to 10m by the 1/7 power law for wind shear:
v (at 10m) = v (at height a metres) (l0)l/7 (
At present, the model accepts wind velooiiy in mph
measured at a height of 3ft, and F = 1 for both BO and C4
crystallizers.
Calculation of Evaporation
The solution for E is obtained by the Newton-Raphson
iteration on equation (1) for the value of Tw and Pw and
then solving for E in equation (3).
Note: The change in sensible heat is neglected as it has
very little effect as 3hown by Bonython (ref. 11).

314
 APPENDIX 3

CRYSTALLIZER MASS BALANCE

1 . Assumptions
a. The relationship between concentration of Mg++, NaCl and
H2O follow the relationship for concentrated seawater up
to the point of Mg++ deposition. The simulation is not
valid past the point of Mg++ deposition. The system
temperature is assumed to be 20°C.
b. The voidage of the salt bed is constant.
0. The seepage is saturated with respect to NaCl at the Mg++
concentration in the bottom brine layer.
2. Unsaturated Brine
The data used is given in Ref . 9.
The NaCl saturation point for seawater ooours at the
following condition: Mg++ = 1 .05$ w/w
NaCl = 22. w/w
/O = 1.216 gm ml-1 at 20°C
Relationship between Mg++, NaCl and density:
NaCl % w/w = 108 (/«»-l), <1.10 (1a)
NaCl % w/w = 99.305/0- 98.43, /i >1.10 (1b)
NaCl % w/w = 21.328 Mg % w/w (2)
Mg % w/w = 0.047085 . NaCl % w/w (3)
3. Saturated Brine
The data used is given in ref. 10
a. Relationship between Mg++, NaCl and density:
/a ■= 1.208307 + 0.004543 Mg + 0.0026519 Mg2 (4a)
Mg =-1176.5571 + 1848.9973/9 - 724.1533 /» 2 (4b)
NaCl= 29.0085 - 7.06.53 Mg + O.642 Mg2 — (5a)
Mg = 8.448252 - 0.505409 NaCl - O.OO7787 NaCl2 (5b)
4. Evaporation Relationships for Saturated and Unsaturated Brine
EV = 73.0212 - 76.7949/fog (6
VB = (82.24 - 0.9711 •EV)/0.8224 (7;

315
/o = 1.208307 + 0.34887/(73. 021 2-W)
+0.0026519 ( 76.7949/(73.0212-BV)z) (8)

where :EV » evaporation gm/l00gm of original brine at/o ■ 1.216

VB ■ volume of brine remaining after EV in ml/lOOml of
original brine.
Diffusion of Brine and Dissolving of Salt
It is assumed that the brine consists of three layers of
equal depth and that at the end of the week the following
situation will be achieved:
New Top Layer: 2/3 old top layer, 1/3 old middle layer.
New Middle Layer: 1/3 old top, 1/3 old middle, 1/3 old bottom
layers
New Bottom Layer: 2/3 old bottom layer, 1/3 old middle layer
If at any time, the top layer density e xoeeds that of the
bottom layer then complete mixing is assumed. The three
layers are adjusted to equal height at the start of the next
week after evaporation and seepage is accounted for.
If at any time, the bottom layer becomes unsaturated,
then it is assumed that salt dissolving will occur (if a
salt bed is present) and the NaCl cone entration in the bottom
layer will increase to: (saturation concentration + starting
oonoentration)/2 .
Seepage
It is assumed that seepage acts continuously and is
saturated with respeot to NaCl at the Mg++ concentration
ooourring in the bottom layer. The seepage for both BO
and C4 crystallizers is between 0.1*97 and 0.203 cm/week
(from previous tests) and is set at 0.203 in this simulation.

316
 APPENDIX U.

MODEL DETAILS
The model is written in FI»/1 and requires a total of 60K
bytes of store in an IBM System 360/50 Computer. Saoh
simulation run takes approximately 3 minutes to run including
compilation and evaporimeter simulation.
The model listing is not included in the paper, but can be
supplied on request to the author.
Model Procedures:
a. KVAP: The main procedure which reads the data, oalls
other procedures, calculates evaporation and the
mass balance, and prints the weekly results.
b. METCALC:A procedure which calculates the reflected short-wave
radiation, the net loss in long-wave radiation, the
heat transfer coefficient, the latent heat and the
surface temperature of the evaporating medium.
o. PSAL: A procedure which calculates density and % w/w
Mg++ from % w/w NaCl.
d. PMAG: A procedure which calculates density and % w/w NaCl
from % w/w Mg++.
e. PDENS: A procedure which c alculates % w/w Mg++ and NaCl
from density.

317
Nomenclature
ALT Solar altitude deg
C Cloud over %
C? Cloud factor dimensionless
DEC Solar declination deg
5 Water evaporation cm week
EV Evaporation of brine at/0=1.2l6 gm m-1 gm/lOOgm of
original solution
F Pond dimension factor dimensionless
HA Hour angle deg
HDL Hours of daylight per day hour
L Latent heat of evaporation cal gm
LAT Latitude deg
Mg llg concentration % w/w
NaCl NaCl % w/w
P Vapour pressure mm Hg
PER Instantaneous reflection of %
short-wave radiation
Qa Net gain in radiant energy cal cm-2 hr ~'
Qi Short-wave insolation cal cm-2 week -1
Qr Reflected short-wave radiation "
Ql Loss in long-wave radiation cal cm-2 hr-^
Ra Long-wave radiation from atmosphere "
Rw ■ ■ " " surface "
Rr " " " " atmosphere ■
reflected
REP Short-wave radiation reflected in a %
day (average)
RF Long-wave radiation from atmosphere factor of unity
absorbed
T Temperature deg C
VB Volume of bittern remaining after EV ml/lOOml of
original solution
ZD Solar zenith distance deg
h Heat transfer coefficient (water- cal cm"2 hr-1
air system) °C~1
k Mass Transfer coefficient (water- gm cm-2 hr"1
air svstem) mm Hg~^
r Bmmission coefficient for black body cal cm-2 hr-1
radiation OK"1
v Wind speed at 10m above ground m sec-^
s-o Density gm ml-1
O1- Stefan-Boltzmann Constant cal cm-2 hr~^
Subscripts: °¥r^
a Air
b Brine
w Water

318
 Mr M C Nicholson of ICI Australia Limited for assistance in
the model theory and much of the original programming work.
Mr R K Sullivan of ICI Australia Limited for assistance in
model refinement.

References
1. Bonython C.W. , Second Symposium on Salt, Northern Ohio
Geological Society 1966.
2. Geiger, R, "The Climate Near the Ground", Harvard Press, 1950.
3. dePlers P., Cailland A., Charuit P., Third Symposium on Salt,
Northern Ohio Geological Society, 1966.
4. Bonython C.W. , ICI Australia Lijnited, Osborne Report 0/114
5. ft N " 0/1053
6. ■ ■ " 0/218
7. * ■ " 0/903
8. II ■ " 0/1349
9. 11 n " 0/213
10. 9 ■ " 0/427
11. ■ * Trans .Roy .Soc. S.Aust., 73(2) Dec 1950,pp198-219
12. 1954 Almanac

319
320
 0 I 2 3 5 T~
LOGlO (DOWNWIND LENGTH, FT)
Figure 2 POND SIZE FACTOR

Figure 3A SOLAR ALTITUDE (DEG) Figure 3B SOLAR ALT (DEG)

REFLECTION OF SHORT WAVE INSOLATION

321
 52

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322
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323
 THE EFFECTS OF OXYGEN CONTAINING ANIONS
ON CHLORINE ANODE EFFICIENCY
E. H. Cook and M. P. Grotheer,
Hooker Chemicals and Plastics Corporation,
Box 344, Niagara Falls, New York 14302

The economic incentive for building integrated chemical

plants are improved if sodium chloride brine containing
other inorganic anions can be resaturated with sodium
chloride and fed to a diaphragm chlorine cell. The role of
oxygen containing anions such as chlorate, sulfate, chromate,
phosphate, nitrate and perchlorate on the efficiency of the
anodic chlorine reaction has been studied. Results with
both metal anodes and graphite anodes are compared.
In an integrated chemical plant many streams can be recycled for
increased economics of processing and more effective pollution control.
The incentives for utilizing chlor-alkali cells in these integrated
plants can be improved if sodium chloride brines containing other
inorganic anions can be resaturated and fed to a diaphragm chlorine
cell.
Some of the more common sources of brine contamination that might be
encountered are listed below:
(1) Recycled anolyte - build up of sulfates and chlorates.
(2) Resaturation using salt from a caustic evaporator - sulfate build up.
(3) Use of salt from chlorate processes.
(4) Direct uses of cell liquor for neutralization and recycle.
(5) Brines from saline water conversion plants.
(6) High sulfate salt deposits. Brine wells.
(7) Phosphate treatment to inhibit sulfate dissolution.
(8) Corrosion inhibitor of brine lines - e.g. chromate and phosphate.
Sodium sulfate impurities have long been known to be detrimental to
the operation of a chlor-alkali cell using graphite anodes. The results
obtained by Murray and Kirscher are shown in Figure 1. (1)
In this present study, we reviewed the effect of several oxygen
containing anions on chlorine anode efficiency with particular emphasis
on using anodes with noble metal or noble metal oxide coatings. These
results were obtained using laboratory cells which operated at current
loads up to 200 amperes.

R. L. Murray and M. S. Kirscher, Trans. Electrochem. Soc,

86 (1944) p. 83 ff.

324
 Differences in chlor-alkali cell operating characteristics are
known to exist between cells using metal anodes and cells using graphite
anodes. Under normal operating conditions cells with metal anodes have
higher current efficiencies (less oxygen in chlorine cell gas) than
cells using graphite anodes. Figure 2 shows a comparison between metal
anodes and graphite anodes when the effect of sodium chloride concentra
tion on current efficiency was studied. In these studies sodium
sulfate was added to simulate a brine obtained from sea salt. These
results showed that metal anodes would operate more efficiently in
dilute brines than cells using graphite anodes. (2) Even a lower
anolyte pH was not sufficient to cause the anode efficiency of a
graphite anode to approach that of a metal coated anode. In the
electrolysis of dilute brines using metal anodes the only apparent
penalty would be that of an increase in cell voltage.
Our interest is studying the effect of oxygen containing anions on
the anode efficiency in diaphragm cells started when we were asked to
look at the feasibility of using a dilute sodium chloride brine contain
ing small amounts of sodium chlorate as a feed for diaphragm cells.
These dilute brines would be saturated with salt and then fed to a cell.
The presence of sodium chlorate made this brine of questionable value
as a brine feed for diaphragm cells. This skepticism resulted from the
well established effects of sulfate on anode efficiency and from the
years associating the presence of chlorates with low anode efficiency
and high graphite consumption.
It has long been recognized that the presence of chlorates in the
caustic effluent of a diaphragm chlorine cell was related to the in
efficiency of cell operation. Normally chlorates are produced by the
back migration of caustic into the anolyte compartment where it reacts
with dissolved chlorine to produce chlorate by a combination of chemical
and electrochemical processes.
The net effect is a decrease in chlorine efficiency and in the case
of cells operating with a graphite anode, a corresponding increase in
graphite consumption is observed. Because of this relationship many
operators of chlor-alkali cells have considered the presence of
chlorates to be a cause of cell inefficiency when in fact we show that
it is only the result of cell inefficiency.

(2) J. E. Currey, M. P. Grotheer and E. H. Cook,

U.S. Patent 3,745,101 (July 10, 1973)

325
 Figure 3 shows the results of experiments on the effects of chlorate
addition to the chlor-alkali cell anolyte. These results were obtained
on a laboratory cell using a graphite anode. (3)
As long as the anolyte pH was that of a normal chlor-alkali cell
and as long as sufficient chloride ion was available for mass transport
at the anode, the presence of chlorate was not detrimental to the anode
current efficiency. These efficiencies are based on chlorine gas
analysis in an operating diaphragm chlor-alkali cell.
This illustrates the necessity of maintaining an adequate sodium
chloride concentration in the anolyte and also the fact that additions
of sodium chlorate to the anolyte do not adversely affect the anode
efficiency. In fact as the sodium chlorate concentration in the
anolyte was increased lower concentrations of sodium chloride could be
tolerated.
This last result was somewhat surprising. However, it might be
explained by reasoning that the main source of oxygen evolution is the
electrolysis of water. By increasing the sodium chlorate concentration,
the activity coefficient of water decreases due to the increase in salt
concentration and less water is available at the anode surface for the
electrolytic production of oxygen. The important thing is the condi
tions at the anode surface. At 60°C the CCi2 content of the cell gas was
17. or less. At higher anolyte pH values and at higher temperature the
current efficiency decreased as evidenced by an increase in the CO2 and
O2 content of the Cl^ cell gas. However, at 80°C, current efficiencies
of 957. could be attained. Material balance around the cell confirmed
that all of the chlorine was produced from the chloride ion and not by
any reaction between chlorate and chloride.
Similar results with chlorate containing brine were observed with
diaphragm cells using metal anodes. With metal anode cells we could
increase the temperature to 90°C and the anolyte pH to about 4.0 with
a current efficiency of 95-967..
Figure 4 shows that unlike graphite the gas efficiency using metal
anodes was not affected by the presence of sodium sulfate in the anolyte.
The slight decrease in efficiency is attributed to the dilution of the
brine.

(a) M. P. Grotheer, J. E. Currey and E. H. Cook,

U.S. Patent 3,516,918 (June 23, 1970).
(b) M. P. Grotheer, J. E. Currey and E. H. Cook,
U.S. Patent 3,553,088 (Jan. 5, 1971).
(c) M. P. Grotheer and E. H. Cook,
U.S. Patent 3,464,901 (Sept. 2, 1969).

326
 Figure 5 shows similar results obtained using a Pt-Ir coated
titanium anode.
Figure 6 shows results obtained with sodium nitrate addition.
Figure 7 shows results obtained with sodium phosphate additions.
It was surprising that phosphate did not show any detrimental effect
because previous observations using graphite anodes indicated that
phosphate additions were detrimental to cells using graphite anodes.
Figure 8 shows the effects of chromate.
Figure 9 shows the effects of perchlorate.
None of the anions studied appear to have an adverse affect on the
anode current efficiency using metal anodes. Platinum-iridium coated
anodes were used for Figures 5-9. These tests were of relatively
short duration and any effects on consumption rate were not determined.
It is assumed that consumption rates will be somewhat proportional to
the current efficiency.
We are not certain why the metal anode coatings are superior to
graphite in sulfate containing solutions. One possible explanation may
be the presence of the oxide coating that exists on the surface of noble
metal anodes when polarized to the potential necessary to evolve
chlorine. A noble metal coating is known to be covered by an oxide
layer under these conditions.
Balashova and his co-workers showed that sulfate adsorbs on a
platinum anode up to a potential of about 0.5 volts (NHE), followed by
a desorption of sulfate at more anodic potentials. This desorption was
explained by the fact that above this potential adsorbed ions are
displaced by adsorbed oxygen which forms on the surface. (4)

(a) N. A. Balashova and V. E. Kazarinov,

Elektrokhimiya Vol. 1, No. 5 (1965) p. 512-516.
(b) V. E. Kazarinov and N. A. Balashova
Doklady Akademii Navk SSSR Vol. 157 No. 5 (1964) p. 1174-1177.
(c) A. N. Frumkin, N. A. Balashova and V. E. Kazarinov,
J. Electrochem Soc, 113 (1966) p. 1011 ff.
(d) N. A. Balashova, A. M. Kossaya and N. T. Gorokhova,
Elektrokhimiya, Vol. 3, No. 5 (1967) pp. 656-659.
(e) M. I. Kulezneva and N. A. Balashova,
Elektrokhimiya, Vol. 6, No. 7 (1970) pp. 1057-1060.

327
 Studies by Krishtalic and Fliskii using graphite anodes show that
sulfate ion continues to adsorb with increasing anodic polarization. (5)
It was speculated by these authors that the increased attack on
graphite was associated with adsorption of sulfate. This is believed
to accelerate the discharge of water molecules.
Therefore we conclude that the difference in behavior between
graphite and metal anodes (especially in respect to sulfate ions) is
associated with the degree of adsorption of the sulfate ion on the
anode.
Ions such as chlorate that probably do not adsorb on graphite do not
adversely affect anode efficiency on either graphite or metal anodes.
The important difference between metal anodes and graphite as far as
adsorption is concerned in probably the oxide film that forms on the
metal anode surface and lessens ion adsorption.

ACKNOWLEDGEMENT

The authors wish to thank Professor B. E. Conway, University of

Ottawa, for helpful discussions on the surface chemistry of noble metal
anodes. Also M. Tarjanyi of Hooker Chemical and Plastics Corporation
for helpful discussions on the surface chemistry of graphite anodes.
The authors also wish to thank D. J. Snyder, R. Falvo, R. Granieri
and G. E. Cise for performing the experimental work discussed in this
paper.

(a) N. M. Flisskii, I. E. Veselovskaya and R. V. Dzhagatspanyan,

Russian Journal Physical Chem Vol. 33 No. 8 (1960)
pp. 1901-1903.
(b) L. I. Krishtalik, G. L. Melikova and E. G. Kalinina,
Russian Journal Physical Chem Vol. 34, No. 7 (1961)
pp. 1543-1547.
(c) I. E. Vesselovskaya, M. M. Fliskii, R. V. Dzhagatspanyan and
L. V. Morochko, Russian Journal Physical Chem Vol. 36, No. 10
(1963) pp. 2179-2183.

328
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331
 ENERGY CONSIDERATIONS IN HYDROGEN COLLECTION
Louis W. Condra, Jr.
Dow Chemical U. S. A.
Texas Division
Freeport, Texas 77541

Larger chlorine plants and higher energy prices

have intensified the long-standing challenge to
effectively utilize by-product electrolytic
hydrogen. Energy supplies, ecological require
ments, and world-wide competition are demanding
the maximum utilization of raw materials and
by-products .

For years the prophets of doom have

predicted that the world cannot produce enough food for
the rapidly increasing population. It now appears that
this dreary prediction has been overshadowed by the fear
that the national energy supply will soon be exhausted.
This gloomy outlook is not totally justified. These
prophets of doom fail to recognize that the solution to
the energy problem depends not only on developing
alternate sources of energy, but on devising new methods
of energy conservation.
The first thing that comes to mind when we
speak of new energy systems is nuclear power. Even so,
in the United States less than four percent of the
electricity is supplied by nuclear power, and in turn
electricity accounts for only 10 percent of the total
energy consumed. The remaining 90 percent can be
switched to nuclear power by the production of hydrogen
through the electrolysis or dissociation of water.
Hydrogen is being proposed by many as the most probable
fuel of the future.
We do not have to wait for this fuel of
the future. Large quantities of by-product hydrogen are
produced by many plants. One major source of hydrogen
is the chlorine cell. Hydrogen was once considered an
undesirable by-product of chlor-alkali production. The
relatively low heating value per unit volume and the
wide explosive range with air have often obscurred the
merits of hydrogen.

332
 In the past, the amount of chlorine, and
therefore hydrogen, produced at a given location was
generally small. The low price of energy limited the
profitability of using the hydrogen and it was often vent
ed to the atmosphere. The production of ammonia has been
a significant use for this by-product hydrogen. This
process required a supply of nitrogen from the air by
liquefaction and separation or by combustion. In the
early 1960's reformer catalysts and centrifugal compres
sors for high pressures were developed. Between 1964 and
1969 more than forty plants with capacities exceeding
34,000 tons of ammonia per day were built in the United
States alone. As a point of reference, this is equivalent
to hydrogen from more than 425 million pounds per day of
chlorine. By 1970 most of the small ammonia plants had
been abandoned, and only a relatively small amount of
electrolytic hydrogen was being used for ammonia
production.
Today energy shortages, ecology require
ments, and world-wide competition all demand the maximum
utilization of raw materials and by-products. Just what
is the value of by-product hydrogen? To answer this
rather basic question, many factors must be considered.
Its value depends not only upon the cost to deliver it to
the point of use but also upon the cost of any alternate
fuel or raw material.
All the factors of good engineering and
good economics apply. The interesting point is that
these factors often give unexpected answers today.
Let us consider the by-product hydrogen
from a plant that produces one thousand tons of chlorine
per day. Figure 1 shows a simplified flow sheet for
collecting 56,864 pounds of hydrogen produced each day.
The design is set primarily by pressure requirements.
For this study I have assumed a maximum of four inches
of water pressure at the cells, a slightly positive
pressure at the suction of the compressor, and a dis
charge pressure of 35 psig. It has also been assumed
that the hydrogen is to be used near the point of
collection. The estimated cost of this system is
$1,200,000.
The gross heating value of hydrogen is 324
BTU per standard cubic foot or 60,958 BTU per pound.
Thus with a 95% collection efficiency, the hydrogen has

333
a heat value of 3.3 billion BTU per day.
When hydrogen is burned as fuel its value
can be defined as the value of the fuel it replaces.
Table I shows the cost to collect hydrogen for burning in
an existing boiler. Costs are shown for various energy
values. Figure 2 shows the return on investment before
taxes. For an energy cost of $1.00 per million BTU the
collection costs are $0,092 per thousand standard cubic
feet of hydrogen. This yields a 71% return on investment.
If an existing unit is not available, a
package boiler that will produce approximately 100,000
pounds per hour of 150 psig steam can be added to the
basic system for $800,000. Operating costs for this
expanded system are shown in Table II with the ROI shown
in Figure 3. For an energy cost of $1.00 per million BTU
these values are $0,126 per thousand standard cubic feet
of hydrogen and 36% ROI.
The value of electrolytic hydrogen as a raw
material is not easily determined, since it depends upon
the value of the product as well as the value of alternate
raw materials or alternate sources of hydrogen. The most
common source of hydrogen today is the catalytic reforming
of hydrocarbons. Natural gas is the preferred feed stock
since it requires lower capital and lower operating costs
than LPG or naphtha .
A methane reformer that produces hydrogen
in volume equal to the 1000 ton chlorine plant will cost
$5,000,000. Table III shows the operating costs with the
various energy costs; for example, $0,519 per thousand
standard cubic feet of hydrogen for an energy value of
$1.00 per million BTU. Figure 4 compares the cost of
reformer hydrogen with our basic collection system. The
lower line shows the collection costs for the hydrogen.
The middle line shows the collection costs plus the fuel
value of the electrolytic hydrogen. The cost for reformer
hydrogen is shown by the top line.
By-product hydrogen from a 1000 ton per day
chlorine plant has a daily heating value equivalent to
3.5 million standard cubic feet of natural gas, 25,000
gals, of oil, 135 tons of coal, or 160 cords of wood. As
energy prices continue to skyrocket, yesterday's
nuisance becomes today's advantage.

334
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341
 Present and Future Concepts of Chlorine
Control Systems for Disinfection of Potable
Water and Wastewater

Geo. Clifford White

556 Spruce St., San Francisco, CA 94ll8
Abstract: The development of present techniques is
largely the result of the demand created by the regula
tory agencies. For potable water the impetus was for a
scheme that would produce a safe water that was palat
able. The search for such a scheme led to the develop
ment of the amperometric tltrator and the continuous
amperometric chlorine residual recorder. These analytical
instruments made it possible to control most Free Residual
chlorination processes. Owing to the degradation of our
water supplies more selective and sophisticated analytical
instruments are needed for the production of safe palatable
water and properly disinfected sewage effluents. We need
an additional array of analytical Instruments. These in
clude: detection of free chlorine residual as undlssoci-
ated H0C1, detection of monochloramlne and free chlorine
in the presence of both, a continuous chlorine demand
monitor, an ammonia nitrogen analyzer sensitive to 0.1
mg/l, and a sulfite ion detector to 0.1 mg/l.
INTRODUCTION
HISTORICAL BACKGROUND
The first use of chlorine in the field of sani
tary engineering was at Brewster, N. Y. In I89A the Woolf
process was used for the on-site manufacture of chlorine
to disinfect the Brewster sewage plant effluent for the
protection of the Croton drainage area of the New York City
water supply. The Woolf process was based on the elec
trolysis of a brine solution. This installation operated
successfully for 17 years until it was destroyed by fire
in 1911. The first chlorination of a water supply was a
chloride of lime installation at Boonton, N. J., in 1908
for the Jersey City water supply. This installation was
replaced by the first Wallace and Tiernan direct feed
chlorinator on February 22, 1913. On February 1 of the
same year the Ornstein chlorinator as manufactured by the
Electro Bleach Gas Company was installed at the Wilming
ton Delaware treatment plant. These were the early begin
nings of chlorination of potable water and wastewater.
The Ornstein chlorinator metered chlorine gas

342
Into an absorption tower, water flowing into the top of
this tower absorbed the chlorine gas and formed a hypo-
chlorous acid solution which flowed by gravity to the
point of application. The Wallace and Tiernan direct feed
chlorinator metered the chlorine gas under a controlled
discharge pressure. The gas was applied directly to the
point of application under pressure through a porous dif-
fuser. The gas was quickly absorbed into the water flow
provided the conditions were right. The direct gas feed
chlorinator concept was In for a lot of trouble right from
the start, but then so was the patented ornsteln gravity
solution flow chlorinator. Wallace and Tiernan bought the
Ornsteln patent and proceeded to make a compromise chlori
nator which was a hybrid, combining the principles of
direct feed under pressure and the discharging of chlorine
soluticji under pressure. This solution feed chlorinator
utilized for the first time the aspirator Injection con
cept. This chlorinator did not solve all the problems of
metering minute quantities of chlorine under variable
temperature conditions, so Mr. C. F. Wallace, a prolific
inventor, developed the Visible Vacuum species of chlori-
nators. The first of these units began appearing on the
market about 1920. They were expensive compared to the
direct feed units but they were an Instant success. There
were two generations of these chlorinators. The second
generation appeared in 1939. They were available with a
variety of ancillary automatic control devices and
chlorine metering capacities up to 300 lb/day and later
750 lb/day. A special group were available in capacities
up to 6000 lb/day.
When plastics first became available the entire
concept of chlorinatlon changed back to spring loaded dia
phragms similar to the original direct feed units. The
present species of plastic chlorinators however still use
the vacuum principle of metering chlorine gas.
The metering of chlorine gas for the treatment
of potable water and wastewater Is unique in several ways.
First it is metered under a vacuum as compared to indus
trial processes which are metered under pressure. Second,
the gas is usually applied in proportion to a variable
flow rate and sometimes to a variable dosage requirement.
Third, the quantities metered are very small: - ounces
per hour as compared to industrial applications where
quantities are spoken of in terms of hundreds of lb/hour.
Fourth, the range of chlorine feed rate required by many
installations may exceed the capability of the chlorine
metering device (rotameter) now used in all makes of
chlorinators. These situations are solved by using more

343
than one unit to expand the rangeablllty .
The annual chlorine consumption for potable
water and wastewater combined is only 3 to k percent of
the total chlorine productlon(l) . However, the number of
chlorinator installations and cylinder handling facilities
for these uses outnumber industrial installations by a
factor of at least 50 or 100 to 1.
POTABLE WATER
CONTEMPORARY PRACTICES
Prom the very beginning of chlorination of
potable water in the USA, disinfection became classified
as a process, just as sedimentation and filtration were
considered processes. However, there was a great deal of
sentiment against the use of chlorine because of the off
flavors it produced in the treated water. It was the
search for a palatable chlorinated drinking water which
led to the discovery of the breakpoint phenomenon which
in turn led to the development of the Free Residual chlori
nation process. This process of applying chlorine, if
properly controlled, provides the consumer with the most
palatable water. There are of course exceptions. This
process will not work on all waters.
FREE RESIDUAL PROCESS
This process is based on the fact that free
residual chlorine which is hypochlorous acid (H0C1) im
parts a negligible off -flavor to the water and is by far
the most germicidal of all the chlorine compounds as com
pared to mono and dichloramlne. The Free Residual process
is inhibited by the presence of ammonia nitrogen and
organic nitrogen. If these two compounds were not present
in water, chlorine would be a perfect disinfecting agent.
Chlorine reacts rapidly with ammonia nitrogen to form
monochloramlne and dichloramlne. It reacts very slowly
with organic nitrogen to form a class of compounds
described as N-Chloro compounds. All of these chloro-
nitrogen compounds Impart an off -flavor to the treated
water, depending upon their concentration. These com
pounds when considered as a group are called combined
chlorine compounds. The sum of the free and combined
chlorine residual is called total chlorine residual.
In the free residual process, sufficient chlor
ine Is added to destroy the ammonia nitrogen. This is
approximately 10 parts of chlorine by weight to 1 part
NH3-N. Fig. 1 illustrates what happens to the chlorine
residual with respect to dosage in the presence of

344
ammonia nitrogen. The breakpoint phenomenon is indi
cated by the dip in the curve. It is the point where
there exists an irreducible minimum of chlorine residual
made up of nearly equal amounts of mono and dichloramine
with a trace of free chlorine. Beyond the dip there will
be found increasing amounts of free residual chlorine
(H0C1) together with the nuisance residuals of dichlora
mine and a possibility of some nitrogen trichloride.
Proper control will mitigate against the formation of
nitrogen trichloride which Imparts an offensive odor to
the water. It is the nuisance residuals beyond the dip
which cause the taste and odor complaints. The Free
Residual process must be controlled so that the free
residual is at least 85 percent of total chlorine
residual .
If organic nitrogen is present in the untreated
water it compounds the problem of nuisance residuals.
Pig. 2 illustrates the effect of this compound. It is to
be noted that water containing a significant amount
(0.5 mg/l) of organic nitrogen will produce a higher con
centration of combined chlorine residual and the break
point is less well defined. This is the result of the
slowness of the reaction between free chlorine and organic
nitrogen. Control of the Free Residual process is the
same whether or not organic nitrogen is a factor, but com
plications may arise due to the formation of N-Chloro
compounds and excessive amounts of nitrogen trichloride.
This depends largely upon the amount of organic nitrogen
present.
SEARCH FOR CONTROL
After Griffin(2) discovered the breakpoint
phenomenon and determed that there was a difference in the
kinds of chlorine compounds formed, various techniques
were tried with orthotolldine to differentiate between
free and combined residual chlorine. First came Laux's
flash test and then the orthotolidine-arsenlte procedure.
These techniques resulted in only fair approximations of
free residual. They could not be put to practical use
to control chlorine metering equipment.
The most significant progress came when Dr.
Henry Marks(3) developed the amperometric titrator Ca.
19^2. This is a laboratory instrument which can differen
tiate quantitatively free chlorine, combined chlorine,
total chlorine, monochloramine, and dichloramine residuals.
This instrument led to the development of the continuous
chlorine residual recorder capable of measuring either
free or total chlorine residual. This device was first

345
placed on the market by Wallace and Tlernan circa 1948(1)
(P. 129).
MODERN CONCEPT OF CONTROL
The modern approach to controlling the chlorina-
tion process is to provide a chlorination facility capable
of adding sufficient chlorine to the raw water so that a
substantial free chlorine residual will persist throughout
the treatment plant. The chlorine residual in the
finished water is controlled as it leaves the plant by
means of dechlorination. The addition of dechlorinatlng
agent is controlled by the use of an amperometric chlorine
residual analyzer(4). This system works extremely well
for nearly all surface waters that are moderately polluted.
Grossly polluted waters high in organic nitrogen and con
taining excessive chlorine consuming Industrial wastes do
present problems in controlling the Free Residual process.
FUTURE REQUIREMENTS
The control of the Free Residual process is
directly related to the nitrogen problem. The nitrogen
problem consists of the presence of ammonia nitrogen and
more especially to organic nitrogen in the untreated or
"raw" water. The closer the water supply is to the source
of pollution the greater the concentration of these com
pounds. Since chlorine reacts with ammonia nitrogen on a
weight basis of 10 to 1, a slight shift in the concentra
tion of this compound requires a tenfold shift in the
chlorine dosage to maintain the proper control. Further
more there is the added requirement that the proper free
residual chlorine must be 85 percent of the free plus com
bined residual. Improper control results in taste and
odor problems In the distribution system. This situation
immediately suggests the need for analytical instrumenta
tion to monitor the ammonia nitrogen content In the raw
water supply. Monitoring organic nitrogen would not serve
any practical purpose as its quantitative relationship to
the Free Residual process is not predictable. The proper
way to deal with the organic nitrogen problem is by the
protection of -our water supplies. Pollution of these
waters should not be allowed to raise the organic nitrogen
level above about 0.3 mg/l.
One additional factor to be considered in the
control of the Free Residual process is the dissociation
of free residual chlorine, H0C1. An aqueous solution of
chlorine dissociates into two species; H0C1 and 0C1 ion.
The distribution of these two species is pH dependent.
At pH 7.5 the distribution is about equal. Below 7.5
H0C1 concentration increases, above 7.5 0C1~ increases.

346
This is important because H0C1 has a much greater germi
cidal efficiency (about 100:1) than does the 0C1 ion.
This is graphically illustrated by Fig. 3. The point to
be made here is that at pH 7.5 it requires a titrable free
chlorine residual of 2 mg/l to produce 1 mg/l of undlsso-
clated H0C1 - the germicidal agent. This 13 a very im
portant consideration because microbiologists, bacteriolo
gists and virologists dealing with the germicidal efficien
cy of free chlorine are now oriented to the procedure of
reporting bacteria and virus destruction based on the
residual concentration of undlssoclated H0C1. This elimi
nates the complication of reporting titrable free residual
at a specified pH.
This situation immediately suggests the need
for analytical control equipment capable of measuring
undlssoclated H0C1 while ignoring the 0C1 ion. Such a
piece of equipment would be highly desirable for potable
water chlorination.
Present chlorine residual analyzers are avail
able in two difference arrangements; one which is specific
for free chlorine without the use of chemicals, and one
which can measure either free or total chlorine. The
latter employs the principle of I2 release at pH4 to
measure total chlorine residual by the addition of potas
sium iodide to the sample. The analyzers which measure
free chlorine in the presence of combined chlorine are of
two types, one operates without the need for chemicals.
This type reads out the free chlorine directly. The other
type uses the addition of potassium bromide to the sample
at a reduced pH so that free bromine is released quantita
tively by the free chlorine present without interference
from combined chlorine. This unit then measures the free
bromine released.
It would be desirable and most helpful to the
art of potable water chlorination if we had one additional
analyzer which would be specific for chloramine. With
this instrument and the others presently available the
water works operator with the troublesome water could
monitor free chlorine, chloramine and total chlorine.
This would tell the operator all he needed to know about
the chlorination process. Multiplying and dividing
Instrumentation is available now to convert the free
chlorine and total chlorine residuals into a ratio signal
output and warn the operator of the critical ratio point.
The chloramine (combined) residual would indicate rather
sharply the magnitude of the nuisance residual factor
Appropriate instrumentation could then be used to express
the radio of free to combined residual. This would provide

347
valuable historical Information for solving taste and odor
problems. This should be considered as worthwhile Instru
mentation.
Up to this point the discussion of future
requirements has been concerned with analytical instru
ments capable of continuously recording various fractions
of the chlorine residual. Also up to this point control
of the Free Residual process is based on a feedback system
using residual control by dechlorination of the treated
water. Prechlorination is usally controlled by flow pacing
plus a daytime and a nighttime dosage change to offset the
loss of H0C1 during sunlight hours. The ultimate in con
trol would be the installation of an ammonia nitrogen
recorder on the raw water. This Information would be com
bined with the flow pacing signal to control the chlorine
dosage. Therefore with a raw water ammonia analyzer the
chlorine dosage could be changed in the proper amount to
take care of changes in the ammonia nitrogen content of
the untreated water. As pointed out above, a shift of
0.1 mg/l NH3-N concentration requires a l.o mg/l chlorine
dosage change to maintain the free residual chlorine at a
given level.
Another concept as an alternative to shifting
the chlorine dosage in accordance with changes in concen
tration of NH3 - N is to simply measure the chlorine
demand on a continuous basis. The most promising method
for continuous analysis is some type of coulometric
analysis .
Coulometry - The coulometric principle is a "Faradaic"
method of measurement. The instruments are in essence,
continuous titrators wherein the titrating reagent is
continuously generated in the quantity demanded by the
analyzed constituent In the stream. In such a system the
sample and reagent flow in known and carefully controlled
rates through an electrolytic cell. The cell contains
two pairs of electrodes. One pair serves as the chlorine
residual detecting system and the other pair serves to
electrolyze the reagent as it passes through the cell.
The detecting electrodes control the current delivered to
the electrolyzer by appropriate circuitry so that the
generation of reagent is controlled to the exact end
point of the reaction between the chlorine residual In
the sample and the reagent generated by the electrolyzer.
Thus the concentration of the chlorine in the sample is
directly proportional to the current flowing in the
electrolyzer, based on Faraday's law(5)(6).

348
 Messrs. Kobayashl and Okuda of Japan have been
working on several schemes for the continuous measurement
of chlorine demand in untreated potable water supplies(7).
Fig. 4 is a schematic illustration of the apparatus they
used for their chlorine consumption test. That they
measured chlorine consumption in the presence of UV radia
tion is irrelevant to the measuring apparatus for the
purpose of this discussion.
Chlorine is continuously generated by the elec
trolysis of hydrochloric acid. The chlorine-acid mixture
and water sample are fed at fixed rates to a stirred-tank
reactor and mixed together under irradiation with an
ultraviolet light submerged in the reactor.
The chlorine concentration in the chlorine -
hydrochloric acid-water sample mixture is continuously
measured amperometrically in the chlorine detector. The
output signal of the detector is amplified and fed into a
controller which regulates the chlorine-generating current
so as to provide a constant chlorine concentration in the
reactor at some predetermined level. The chlorine con
sumption of the sample is proportional to the difference
between the chlorine-generating current of the sample
(measured at a steady rate reaction) and the chlorine -
generating current of chlorine demand-free water.
The concept of continuous chlorine demand
analysis is not entirely new. Wallace and Tlernan Co. of
Belleville, N. J., developed (Ca 1955) a packaged chlori-
natlon system whereby the dosage was controlled on the
basis of continuous measurement of the chlorine demand of
the untreated water. Lack of consumer demand and instru
mentation difficulties led to an early abandonment of
this feed-forward process, not the least of which was due
to the success of automatic residual control (feedback
control) .
The need for reviving interest in the develop
ment of this type of equipment is much greater now than
it was 20 years ago. Consumer demands for better tasting
water, and regulatory agency demands for safer water re
quire the best possible control methods for the disinfec
tion process.
Recent correspondence with Mr. T. Okuda of Japan
indicates that he and his colleagues are investigating a
new type of chlorine residual measuring device. This is
described as a "gaseous -chlorine detector" similar to the
aqueous detector used in the experiments shown in

349
pig. H(8) . Mr. Okuda believes that such a detector,
properly modified, will be able to measure either free
chlorine or chloramine in the presence of each other.
Such an analytical instrument would be a valuable contri
bution to the art of chlorinatlon. It would satisfy one
of the requirements for future analytical equipment
described above.
WASTEWATER CHLORINATION
CONTEMPORARY PRACTICES
Wastewater chlorinatlon Is primarily for disin
fection. Usually, however, a disinfection system is laid
out in such a way that the standby equipment is made avail
able for prechlorination or intermediate chlorinatlon to
eliminate odors or prevent septiclty of the wastewater.
The present concept of disinfection is based on
the coliform bacteria concentration in the treated efflu
ent after a suitable contact time with the chlorine.
Recent studies have stressed the fact that one of the basic
requirements of a proper disinfection system is a chlori
natlon installation controlled by the chlorine resldual(9).
CHEMISTRY OF WASTEWATER CHLORINATION
As It affects the chemistry of the chlorinatlon
process, there are two types of wastewater effluents; one
that Is nitrified and one that is not. Most of the efflu
ents today fall in the latter category. Effluents from
most sewage plants whether they be primary or seconday
treated effluents contain from 15 to 30 mg/l ammonia nitro
gen. Since disinfection can be achieved with chlorine
dosages in the range of 10 - 20 mg/l, all of the residual
formed will be combined chlorine. It is only in those
plants with highly nitrified effluents having ammonia
nitrogen concentrations of 2.0 mg/l or less will there be
any free chlorine residual after chlorinatlon. Therefore
practically all wastewater systems measure the chlorine
as total residual.
This total residual Is made up of two fractions
which can be differentiated into monochloramine and
dlchloramine using the forward titration procedure with
an amperometric endpoint. The monochloramine may be a
true compound but the dlchloramine does not display proper
characteristics to be considered a true compound. It is
thought that the fraction which titrates as dlchloramine
is probably an organic chloramine formed by the reaction
between the chlorine and organic nitrogen in the waste
water. This fraction displays remarkable stability and

350
very little If any germicidal efficiency. Pure dichlora-
mlne Is very unstable and Is a better disinfectant than
monochloratnine . It has been demonstrated that a combined
chlorine residual loses its germicidal efficiency with
time(10). It is theorized that in the presence of signifi
cant amounts of organic nitrogen the monochloramlne formed
after the initial mix of wastewater and chlorine solution
reacts slowly with the organic nitrogen to produce an
organic chloramine with lesser germicidal efficiency. It
also seems that this lesser reactive fraction, which per
sists for many hours, is the component which is toxic to
fish. Therefore it would be desirable to have an analyzer
capable of recording the monochloramlne fraction and
ignoring the nuisance residual which presently titrates as
dichloramlne.
MODERN CONTROL SYSTEM
Fig. 5 illustrates a modern control system
using currently available chlorine residual analyzers.
The chlorinator receives two separate signals (compound-
loop control), each of which can change the chlorine feed
rate. One signal is from the plant flow meter and the
other is from the residual analyzer. The analyzer located
at the end of the contact chamber monitors the residual
some 30 minutes or so after the chlorine is applied. This
analyzer can be used to automatically reposition the set
point of the control analyzer if desired.
FUTURE REQUIREMENTS FOR CONTROL
It would be highly desirable if we could add one
additional signal to the system shown In Fig. 5. This
could be either a chlorine demand factor or an ammonia
nitrogen factor. This signal and the flow pacing signal
would be fed into a signal multiplier. Such a system is
illustrated in Fig. 6. The residual control signal would
remain as is but would have less work to do. At this
point it would be desirable for the control analyzer to be
specific for monochloramlne. The monitor analyzer should
be arranged to record total chlorine residual.
Nitrogen Removal. If present trends continue, chlorine
will be used more and more for nitrogen removal and for
polishing effluents from tertiary treatment plants and
water reclamation plants. Both applications involve the
Free Residual process described above for potable water
treatment. This means that an ammonia nitrogen recorder
would have to be used instead of chlorine demand apparatus.
For these situations the signals from the NH-7 - N
recorder and the effluent flow meter would be fed into a
signal multiplier. The output of the multiplier would

351
drive the chlorine metering orifice positioner. The
control analyzer- would have to be able to measure free
chlorine in the presence of chloramine (combined residual) .
It would be desirable to monitor both free and combined
residual or free and total residual. This provides closer
control of the process, whether it be for nitrogen removal
or for the Free Residual process. It amounts to the same
thing. Improper control wastes chlorine, causes excess
formation of nitrogen chloride and an excess of toxic
chlorine residuals.
DECHLORINATION
That chlorine residuals in wastewater effluents,
free or combined, In excess of 0.1 mg/l are toxic to fish
has caused sufficient alarm to require some dischargers,
particularly in California, to dechlorinate the effluents.
Obviously, controlling a chlorinatlon process to such a
low concentration is not practical using the chlorine
residual control method. The most popular chemical for
dechlorination is sulfur dioxide. It is easy to handle,
uses the same type of control equipment as chlorine and
is not expensive (15 cents/lb). Current practice is to
add a slight excess of sulfur dioxide 30 that the
chlorine residual is always zero. Fortunately sulfur-
dioxide residuals which appear as the sulfite ion (SOj)
are not toxic to fish in the 1-5 mg/l range or higher.
However we do need to be careful about excessive H2SO3
residuals for fear of oxygen depletion in the receiving
waters. Fig. 7 Illustrates a typical feedforward
dechlorination system using sulfur dioxide. It is manda
tory that an effluent flow signal be provided. The
monitor residual used for the chlorinatlon process becomes
the control signal for the dechlorination system. Proof
of proper and continuous dechlorination is the problem due
to the lack of appropriate analytical equipment. For
the system shown, the dechlorinated sample which is dis
charging to waste continuously Is diverted for about
5 to 7 minutes per hour to the monitor analyzer. The
sulfonator control is secured during this time Interval.
The dechlorinated sample will appear as a trace on the
chlorine residual chart as proof of zero chlorine residual.
The ideal system would be one which could be
controlled from an analyzer specific for measuring the
sulfite Ion concentration. The S05 residual would be
maintained at about 0.5 - 0.75 mg/l which should be
practical for the accuracy of such control equipment.
Until such analytical equipment is available we
will have to use inferential means of proving

352
dechlorination. Some possibilities for continuous proof
of dechlorination is to bias the zero of a chlorine
residual analyzer by adding a known and constant amount
of hypochlorite to the sample before it passes through
the measuring cell. Another method that has a higher
degree of reliability is to chlorinate a minor but con
stant flow of dechlorinated effluent. Record this flow,
record the chlorine applied and record the chlorine
residual. This information can be analyzed by multiplying
and dividing Instruments to read out the chlorine residual
in the dechlorinated effluent.
Another method for control of chlorine residuals,
proposed from time to time, is ORP (Oxidation-Reduction-
Potential). It must be emphasized that ORP is a quali
tative rater than a quantitative measure of chlorine
residual. This method can, in clean water, differentiate
between free and combined residual - but not quantita
tively. It has been further suggested that ORP be used in
wastewater on a differential basis for controlling
chlorination; i.e., control by comparing the difference
between the ORP before and after chlorination. ORP is
satisfactory for controlling end points of certain chemi
cal processes but it is not very promising for the quanti
tative control of trace amounts of chlorine In potable
water and wastewater. Our efforts should be directed
toward equipment which will measure concentrations of
specific chlorine compounds.
SUMMARY
For the proper control of the Free Residual
process in potable water chlorination there is need
for analyzers capable of detecting free chlorine residual
as undlssoclated H0C1 and chloramine . in the presence
of each other without interference from each other.
There is need for an analyzer which can con
tinuously monitor the chlorine demand of any potable water,
wastewater or reclaimed water.
There is need for an analyzer which can con
tinuously measure the monochloramlne fraction of the total
chlorine residual in a wastewater effluent.
There is need for an analyzer which can con
tinuously monitor the ammonia nitrogen content of any
potable water or wastewater to within 0.1 mg/l.

353
 There is need for an analyzer which can con
tinuously monitor the concentration of sulfite ion
(SO^) within 0.1 mg/l in dechlorinated wastewater efflu
ents .
These analytical instruments will provide the
operating personnel with the necessary tools of the
trade to meet the future requirements of potable water,
reuse water and wastewater discharges.

354
 REFERENCES

1. White, 0. C, "Handbook of Chlorination"

Van Nostrand Relnhold, New York, N. Y., 1972.
2. Griffin, A. E., "observations on Breakpoint
Chlorination", Jour. AWWA, 32:11&7 (1940).
3. Marks, H. C, and Glass, J. R., "A New Method
for Determining Residual Chlorine",
Jour. AWWA, 34:1227 (1942).
4. White, G. C, "Chlorination and Dechlorination:
A Scientific and Practical Approach",
Jour. AWWA, 60:5^0, (May, 1968) .
5. Jones, R. H., and Joyce, R. J., "Instrumentation
for Continuous Analysis", Jour. AWWA 63:713,
(June, 1961).
6. Siggia, Sidney, "Continuous Analysis of Chemical
Process Systems", John Wiley and Sons, Inc.,
New York, N. Y. (1959) .
7. Kobayashl, T., and Okuda, T., "A Continuous
Method of Monitoring Water Quality by Chlorine
Consumption Under Ultraviolet Radiation",
Water Research Vol. 6, pp 197-209, (Feb., 1972).
8. Okuda, T., Private Communication Feb. 6, 1973,'
and Jan. 11, 1974, Tokyo, Japan.
9. White, G. C, "Disinfection Practices in the
San Francisco Bay Area", Jour. W.P.C.F., p 89,
(Jan., 1974).
10. Selleck, R. E., Collins, H. F., and White, G. C,
"Kinetics of Wastewater Chlorination in Continuous
Flow Processes". Paper presented at 5th
International Water Pollution Research Conference,
San Francisco, 1970.

355
 Fit.2
Rel»tionship Between Ammoni» enP Orgenic Nitrogen
■nP Chlorine

356
99 per cent destruction of E. coll at 2-6°C.
PlB.3
Co«p»rlton or Hypochloroua AciP, Hypochlorite Xon
tnP Monochloruine

357
 Magnetic
Stirrer Sample Pump HCI Pump

Chlorine DeMnP Honltorlng Syite«

Chlorinator Control n
Anolyzer I

Chlorine
Metering
Orifice -

ru.5
MoPern Chlorine Control System for weeteweter
Dlllnfeatlon

358
 Chlorine Demand . Chlorinator Monitor
or Analyzer-^
Ammonia Nitrogen
Analyze^
"n=fy Set Points
Sianol ;
& ©

Rolio -Sample Lines—''I

Station
Flow Signal-^ ^Injector Pump
Sample Pump Sample Pump-£

Effluent Metering Contact Chamber

Device / Mlxh ixlng
CI, Diffuser- -/ Devi ice
Fig.6
Puturt Chlorine Control 3yite« Tor HutmMr
Disinfection
Ratio Station
Sulfonator,

SO,
Metering
Orifice

SO, Diffuser
rit.7
•e•p-Porv»rP SpstM for Doohlerlnotlon of
KutMiter Effluent!

359
 REDOX* CONTROL OF SULFHYDRATE ADDITION
FOR MERCURY SULFIDE FORMATION
L. K. Norton
Monsanto Industrial Chemicals Company
Sauget, Illinois 62201

ABSTRACT
Formation of mercuric sulfide is a sensitive
reaction. Excess sulfhydrate redissolves mer
curic sulfide as the polysulfide while a deficit
of sulfhydrate does not allow for reaction with
all dissolved mercury. A control system that
maintains optimum sulfhydrate concentration in
mercury cell chlor-alkali waste water is des
cribed. Redox concepts, the control system,
past and potential problems and a brief descrip
tion of process parameters are presented.

In late 1970, it was recognized in this country that

essentially all mercury had to be removed from mercury cell
chlor-alkali plant waste streams prior to their discharge
to public waterways. The formation of insoluble mercury
sulfide and subsequent removal was undertaken by many plants
as the process for removing essentially all mercury from
their discharges.
Formation of insoluble mercury sulfide was thought to
be a straight forward reaction but this has been proven not
to be true. An excess of sulfhydrate will react with pre
viously formed mercury sulfide to redissolve it as a poly
sulfide. A deficit of sulfhydrate will not allow for
reaction with all dissolved mercury present.
Several approaches have been used to limit and hope
fully control the amount of excess sulfhydrate present in
treated solutions. The use of large holding ponds which
allow for sulfhydrate removal over an extended time period
and batch operations of continuing intermittent periods of
sulfhydrate addition and wet chemical analysis are two
approaches .

* (Reduction-Oxidation Potentials abbreviated, also known

as Oxidation Reduction Potential or ORP)

360
 At Sauget, Illinois, Monsanto uses a closed loop Redox
control system to continuously control the amount of sulf-
hydrate so as to form only the insoluble mercury sulfide
and not the polysulfide.

Redox Concepts
Use of Redox as a control is based on the concept of
adding a reducing agent (sulf hydrate) to waste water and
changing its nature from oxidizing (to mercury) to that of
reducing (to mercury) . As this change occurs there is a
corresponding exchange of electrons that develop specific
potentials. These potentials are Reduction-Oxidation po
tentials that can be measured by a Redox cell. Actually,
these potentials are the difference of electrical potential
between a noble-metal electrode and a reference electrode
that comprise the Redox cell. These measured potentials
are a function of the standard potential associated with
each reactant, relative ion concentrations, temperature and
the number of electrons transferred.
The well known Nernst equation can be used to describe
the oxidation-reduction potential as a function of the
above variables. Modification of the Nernst equation to
account for the electrochemical potential of the reference
electrode and a collection of constants results in an equa
tion of the following form:
ORP = EQ - 0. 0591 log (ox) - REF
n (red)
where
ORP = the potential indicated by the measuring
devices .
EQ ■ the standard potential associated with the
various reactants as listed in electro
chemical tables at the standard condition
as measured against a standard hydrogen
electrode .
n ■ number of electrons transferred.
(ox) = molar concentration of the oxidized form of
a substance.

361
 (red) = molar concentration of the reduced form
of a substance.
REF ■ the standard potential of the reference
electrode to the same standard as EQ .
In addition to use in the Nernst equation standard ED
potentials may be used to calculate the "Overall" potential
and the "Equivalence Point" potential between reactants.
Significance of the "Overall" potential is that a
positive value indicates that the reaction will go spon
taneously. The overall potential is calculated by sub
tracting the EQ of the oxidized reactant from the EQ of
the reduced reactant.
The reaction between sulfhydrate ion and mercuric ion
would be analyzed as follows: 1 1 2 , 3
Hg + HS" + OH" = HgS + H20 + 2e EQ = + 0.77 V
Hg = Hg ++ + 2e EQ = - 0.852V

In order for the reaction to occur spontaneously the EQ for

mercury must be subtracted from the Eo for sulfhydrate thus
making the overall potential a large positive value.
EQ (Sulfhydrate) = + 0.77 V
E0 (Mercury) = -(-0.852V)

EQ (Overall) = + 1.622V
Mercury is thus the oxidized reactant, and the equation is
wr i 1 1 en as :
Hg + HS" + OH- = HgS + H20 + 2e
Hg ++ + 2e = Hg

Hg + HS" + OH" = HgS + H20

Significance of the "Equivalence Point" potential is
that it is produced whenever the concentration of both
reactants are equal. This will also be either at or near
the optimum set point potential for mercury and sulfhydrate
reaction as the concentration of both reactants will be

362
small and will be approaching each other. Equivalence point
potential is calculated by dividing the sum of the two reac-
tant EQ values by two and subtracting the standard potential
of the reference electrode. The calculated equivalence
point for the reaction of sulfhydrate ion with the mercuric
ion is :
ORP = Ep(Sulfhydrate) + En(Mercuric) - REF (Silver/
2 Silver Chloride)
ORP = + 0.77 V + (-0.852 V) - (-0.199 V)
2
ORP = + 0.157 V or + 157 mv (Millivolts) (American
Convention)
This would be -157 mv in European Convention.
Note, at a Redox reading of +157 millivolts (Silver /Silver
Chloride reference American Convention) the concentration
of mercuric ion will be equal to the concentration of sulf
hydrate ion, so +157 mv should be used as the Redox control
set point so as to avoid polysulfide formation.
The attached Figure No. 1 illustrates a Redox curve
which is a graphic representation of the Nernst equation.
Notice that near the equivalence point there is a large
change in potential for small incremental changes in con
centration; thus a Redox curve is similar to a pH curve
with the equivalence point similar in location to a pH
value of 7.

The Control System

The Redox control system consists of a submersion assembly,
a Redox transmitter, a potential to current converter, an
ampere to air transducer, a recording controller, a rever
sing relay, a control valve and two positive displacement
air regulated pumps. The system functions by comparing a
measured Redox potential of the waste water after sulf
hydrate addition to a preferred Redox potential set point.
Deviation between measured and set point potential causes
the controller to make adjustments to the volumetric
pumping rate of feed pump. This control system has been in
service since November, 1970. Original installation cost,
including all labor and materials except pumps, was $3,000.
Average annual maintenance cost has been $2,200, primarily
as instrument mechanic labor.

363
 Past and Potential Problems
Past problems of control have been the establishing of
the optimum set point, obtaining true solution Redox
readings and having an "immediate" controlled reactant
system response to the Redox controller. Actions taken to
establish the optimum set point have been the development
of a Redox curve by laboratory titration of actual inplant
material. This titration resulted with the development of
an "S" curve by plotting millivolts of a Redox reading ver
sus some amount of the reactant added. A similar curve
could be developed by experimenting with the field Redox
set point and having the treated material analyzed for both
reactants. Optimum set point of actual inplant material
has been found to be +160 mv. False solution Redox readings,
whatever the cause, are indicated by normal Redox control
system response and a continuing laboratory analysis of an
excess of one reactant. The false solution Redox readings
were found by placing the electrode pair (silver /silver
chloride reference and the gold electrode) into standard
Redox solutions and reading the transmitted Redox value.
Transmitted Redox values were then manually adjusted to
correspond to the standard if they were not in agreement.
Standard Redox solutions are usually saturated quinhydrone
at pH4 and pH8. Two different pH solutions should be used
to make sure that a non-drifting final measurement is
attained .
The problem of not having an "immediate" response of
the controlled reactant system has been solved by strategi
cally placing control valves, by varying solution strengths
and by properly adjusting control instruments. The con
trolled reactant automatic control valve was relocated so
as to assure that there was neither line drainage nor
siphoning on automatic control valve closure. Solution
strength of the 45% by weight NaHS raw material was cut
to about 10% by weight so as to assist in control as well
as reduce the freezing point of the controlled reactant.
Controller is presently adjusted to a reset setting of
about 7 while the proportional band is set at about 250.
The term "immediate" will depend upon the rate of chemical
reaction, which for mercury with sulfhydrate is proposed to
be instantaneous.
Potential problems in addition to those above would be
system components failures and insufficient knowledge of
the involved chemistry. Component failure has occurred at
least once in the silver /silver chloride reference electrode
and potentially could occur in any of the many components

364
in the system. Of course, no solution can be found for
components failure but the leads and the control loop can
be checked by impressing a millivolt signal on the system.
Instrument readings of 20%, 50% and 80% presently corres
pond respectively to impressed signals of -300 mv., 0 mv . ,
and +300 mv.
Chemistry of the process measuring electrode and the
solution can affect the meaning and significance of Redox
readings. The measuring electrode has to be sufficiently
noble so as not to react with the solution. Surface of
the measuring electrode may be desensitized due to coating
and/or a memory effect. Coatings may be from material in
either the raw materials and/or untreated waste water.
Memory effects can result from exposure to either strong
oxidants or reductants. The pH and temperature can affect
both the measuring electrode and solution chemistry. Other
oxidants and reductants may also affect Redox readings and
the shape of the Redox curve.
Knowledge of the critical process chemistry and the
critical electrode chemistry are important, but all of the
process chemistry doesn't have to be known in order to de
sign and perfect a Redox control system.

Mercury Treatment Process

Critical operations of the Monsanto chlor-alkali waste
water treatment process at Sauget, Illinois, are pH control,
Redox control, settling and filtration. pH is considered
optimal at a value of 7.5 to 8.5 because of materials of
construction. The Redox control system has been previously
described and can best be summarized as, "the heart of the
mercury treatment process."
Sulfhydrate addition under Redox control is made to
the untreated waste water in the stilling well of an old
clarifier. Solids are allowed to settle from the treated
waste water in the clarifier before it passes to filtration.
At 200 gpm (pumping limit) loading on the clarifier would
be 0.281 GPM/ft2 and residence time would be about 7 hours.
Overflow from the clarifier is then pumped through one or
two sand filters, an activated carbon filter and finally a
polish filter. The packed filters are nine foot in dia
meter.
One gravel filter is backwashed once per shift with
treated and filtered waste water while the activated carbon

365
filter is backwashed once per week with city water. Five
micron cartridge filters are used to polish the filtered
waste water and are changed out at a 30 psig pressure drop.
All treated waste water is held until a final chemical
analysis is made of its mercury content. Decision to dis
charge treated waste water or recycle it for further treat
ment is based on a final wet chemical analysis.
Lowest mercury content of treated waste water to date
has been 20 ppb with normal operations averaging between 20
to 30 ppb.

REFERENCES

1. "ORP Measurement in Waste Treatment" by T.J. Kehoe and

R.H. Jones, Beckman Reprint pH-4337, Reprinted from
Water and Sewage Works , August, 1960.

2. "Oxidation Potentials" by W.M. Latimer, Ph.D. Prentice-

Hall, Inc., New York, 1938, pp. 293-301.

3. "Electrochemical Engineering" by C.L. Mantell, Ph.D.,

4th Edition, McGraw-Hill Book Company, New York, 1960,
pp. 45-47.

366
 FIGURE NO. 1
REDOX CURVE

INCREASING AMOUNT OF
REACTANT ADDITION

367
MODERN CENTRIFUGAL COMPRESSORS FOR CHLORINE SERVICE
R. M. Salzmann - DELAVAL Turbine Inc.
P. O. Box 251 Trenton, New Jersey 08602

ABSTRACT
When Carl Wilhelm Scheele discovered chlorine two
hundred years ago, he could not have foreseen its wide
variety of uses today. While growing demand has fos
tered successful large scale production, the disagreeable
nature of the gas has continued to challenge the ingenuity
of process and machinery designers. The particular ef
fects of chlorine on multistage centrifugal compressor
operation, the problems which can occur and the methods
of dealing with them are the subjects of this paper. Ex
perience and changing technology have resulted in im
provements which have increased the reliability of mod
ern centrifugal compressors and their adaptability to
chlorine process requirements.

With increasing plant size, centrifugal compressors were in

troduced into chlorine service some fifteen years ago. In the inter
vening period, multistage machines have been built for chlorine
plants capable of producing from 150 to 1500 tons per day of product.
Although the path to their successful application has not been free
of problems, the overall flexibility and reliability of centrifugal
compressors is attested to by their continued predominant use in
new and expanded production facilities.

The compressor's role in the process stream is an important

one. The electrolysis of brine in either diaphragm or mercury cells
results in the collection of chlorine gas at graphite anodes. The cell
pressure is maintained slightly below ambient, and the gas is essen
tially saturated with water vapor. It contains a variety of other un
desirable impurities as well, generally including salts and other
organics, metallic traces, residue from cell construction materials
and a small percentage of hydrogen. The cell gas is cooled, either
by direct contact in a packed tower or indirectly using a heat ex
changer, cleaned, and dried in a series of sulfuric acid drying
towers before entering the compressor, where its pressure is in
creased to a level suitable for liquification or distribution to user
plants as a gas.

368
 Modern chlorine compressor application, design, operating and
maintenance procedures have evolved from the combined experiences
of plant operators and equipment manufacturers, who together have
brought about substantial improvements to both the process and the
machinery. In discussing some of the difficulties which can occur
and the means available to deal with them, an understanding of the
basic parameters governing the centrifugal compressor, the process,
and the inter- relationships between them is required. These have
been dealt with by other authors and will not be repeated except as
necessary for clarity.

Perhaps the most persistent problem encountered by many

plant operators is caused by the corrosive nature of chlorine and
its processing upstream of the compressor. Decreasing plant
throughput over a period of time can result from a buildup of ma
terial in process components, including the stationary internal flow
passages of the compressor. These deposits occur when residual
moisture, which is not eliminated in the coolers, drying towers and
demisters, combines with chlorine to attack iron in the process
equipment and compressor to form ferric chloride, which tends to
collect and trap salt particles and other contaminants carried over
from the brine or cell construction materials. The widths of dif-
fuser and return channels in the compressor are thus reduced, ad
versely affecting its performance characteristics. For a given
volume flow to pass through a restricted diffuser passage, it must
travel a shorter path, lessening its ability to convert the velocity
head imparted by the rotating impeller to pressure. The irregular
surfaces can also cause flow separation and additional friction losses.
These effects are compounded in successive compressor stages,
each having to swallow a volume flow increasingly greater than its
design and developing correspondingly less velocity head. The
cumulative effect of fouling is therefore to shift the overall perfor
mance curve in the direction of reduced pressure differential and
capacity at constant speed as illustrated in Figure 1. Since the com
pressor discharge pressure required for liquification or other
process use is controlled, flow must be reduced to maintain the
minimum acceptable level, eventually resulting in plant shutdown if
the buildup continues.
Three approaches to the fouling problem are available -- re
duce the carryover of contaminants in the cell gas, compensate for
anticipated capacity reduction in sizing the compressor train, or
prevent the buildup on critical surfaces.

369
 Plant designers and operators have made substantial progress
in the control of brine purity and the installation of well designed
cooling and drying systems, including high efficiency demisters and
filters which are currently available. These and other refinements
to cell gas treatment have generally resulted in increased plant
turn-around intervals.

The variations in chlorine production processes and equipment

from one plant to another have shown widely varying rates and de
grees of compressor fouling. For this reason, the amount of ad
ditional flow capacity built into chlorine compressors is largely
based on experience and requires cooperation between the plant de
signer and compressor manufacturer. Fouling factors from vir
tually nothing to as much as 25% excess capacity have been used.
Of course, oversizing the compressor increases its initial cost, as
well as that of the driver and other auxiliary equipment. Operating
costs, in terms of power, will also be somewhat higher since throt
tling at the compressor suction or recycling excess flow will be re
quired to maintain the desired discharge pressure when the machine
is not fouled. These costs, however, are normally small if the ad
ded margin does, in fact, extend the time between plant shutdowns.
Where variable speed drivers are used, fouling may be compensated
for to some extent by increasing speed.

The prevention of buildup on critical compressor surfaces is an

approach for which the possibility of success has increased in the
past several years, with the development of materials and methods
of application suitable for coating the basic iron or steel stationary
internal compressor parts.
A short term laboratory study (1) has been made, investigating
several promising materials. These were applied to carbon steel
test pieces and exposed to a flow of moist chlorine gas at approxi
mately 200°F. for 40 hours. The test materials included samples
coated with a fluorinated polymer, a polyvinylidene fluoride resin,
and an electrodeposited chrome-nickel alloy infused with a polytetra
fluorethylene, together with a carbon steel control piece. Figure 2
shows some results of these tests. The uncoated steel piece, of
course, experienced severe corrosion and had a heavy buildup of
ferric chloride after very little exposure. The fluorinated polymer
showed no buildup of ferric chloride, but the edges of the sample
were corroded where the coating was inadequate. Since this ma-

. 370
terial can be applied only in a very thin layer, it may be eroded in
actual service or damaged during handling, exposing the base metal
to attack. The polyvinylidene fluoride resin can be applied in signi
ficantly greater thickness with the dimensional accuracy required
for compressor internals. This sample showed no buildup of ferric
chloride or corrosion. The coating of electrodeposited chrome-
nickel alloy infused with polytetra fluorethylene proved too porous
and suffered corrosion and ferric chloride buildup.

These results indicate that by the proper application of existing

materials technology, the prevention of buildup on sensitive flow
passages is a reasonable probability. The next step requires the
installation of test pieces in an existing chlorine compressor, in
cooperation with plant operators, at a location where a significant
degree of fouling is known to occur.

Compressor interstage and balance drum labyrinth seals can

also be a cause for concern in chlorine service. Until the recent
past, these had been made of stainless or carbon steel, depending
on the adjoining rotating material. Erosion and/or corrosion of the
labyrinth teeth, which are typically 0. 015 inch wide at the tip, opens
running clearances and increases the recirculation flow around the
unit. This flow naturally uses a portion of the machines' capacity
and reduces throughput correspondingly. In the case of the balance
drum seals, increasing the pressure drop through the balance line
to the compressor suction causes the pressure differential across
the drum to decrease. This increases the axial load carried by the
thrust bearing. For this reason, compressor balance drums and
thrust bearings should be sized so that increasing clearance by a
factor of two or three times the normal running clearance will not
overload the bearing.

A number of substitute labyrinth materials have been suggested

over the years, including some by chlorine plant operators. A study
of the available materials resulted in the selection of a ceramic-
teflon compound that could be machined accurately and was unaf
fected by the gas. It was also easily abraded and sufficiently tough
to withstand the pressures and temperatures encountered in chlorine
service.
A satisfactory means of mounting this material for use in com
pressor installations was required, and a development program (2)

371
led to a steel-backed, pressure-supported retaining arrangement.
The use of bonding agents and purely mechanical means to hold the
ceramic-teflon in place proved unreliable for the anticipated oper
ating conditions. Also, since most such materials are structurally-
poor, they should not be used in this type of service without metal
backing.
Interstage and balance drum labyrinths utilizing this patented,
pressure- supported design (Figure 3) have been installed in a num
ber of chlorine compressors. The several years of operating ex
perience accumulated to date has been uniformly good, and recur
ring maintenance costs to users in terms of both hardware and
downtime has been minimized. Based on this record, similar laby
rinths, buffered with dry air, are now being installed, replacing the
more traditional segmented carbon rings as shaft end seals (Figure
4).
The use of ceramic -teflon interstage and balance drum seals
has also reduced another risk faced by chlorine plant operators.
It is well known that chlorine can react with iron and ignite at a
temperature generally believed to be between 400 and 500°F. Al
though every effort is made by compressor designers and operators
to assure that even under abnormal circumstances there will be no
contact between rotating and stationary parts, the possibilities of
foreign material entry, sustained surging of the compressor, or
severe vibration due to imbalance or misalignment cannot be totally
eliminated. Running contact between metals inevitably generates
heat which may not be dissipated quickly enough from the small
labyrinths to prevent the ignition temperature from being exceeded.
Contact between ceramic-teflon labyrinths and steel, should it occur,
generates significantly less heat, owing to the ease with which it is
abraded, improving the compressor's tolerance of abnormal upsets
and reducing the user's risk.

Although the relatively low acoustic velocity of chlorine gas

limits the rotating speed of centrifugal compressors due to Mach
number considerations, most multistage units still operate between
the first and second lateral critical speeds. Proper rotor balancing
procedures are necessary to insure smooth, long-term operation.
The correct technique, referred to as "progressive balancing", re
quires that each impeller and balance drum to be installed on the

372
shaft be individually balanced, dynamically. The rotor is then in
dicated for runout and check balanced after each of these items is
mounted. Any significant change in the measured runout indicates
that the component is not mounted squarely on the shaft and must be
adjusted before checking the rotor balance. Unbalance found during
any of the check balancing operations should be corrected only on the
last impeller or other component mounted. This method can produce
a well balanced rotor using commonly available low speed balance
machinery. However, the practice of balancing fully assembled ro
tors in such machines, and making corrections at the first and last
stage impellers is not suitable for high speed rotating machinery.
Balancing assembled rotors should only be done at a speed above
the first lateral rotor critical, correcting at the plane of unbalance.

Another important requirement for reliable compressor opera

tion is good alignment between the shafts of all equipment in the com
pressor train, taking into account the relative thermal movement of
the shafts at normal operating conditions. Although all rotating ma
chinery can tolerate some misalignment, it is one of the moet fre
quently occurring causes of operating problems.

Hydraulically mounted coupling hubs have become an attractive

feature of modern centrifugal compressor designs. With this method
no keys are used which, in addition to eliminating stress concen
tration factors that reduce the torque transmitting capability of a
given shaft by at least a factor of two, reduces the difficulty of
mounting the hub squarely and concentric with the shaft. Since the
hub is symetrical, it will tend to expand uniformly.

To mount the coupling hub hydraulically, the shaft end is drilled

to provide a passage for high pressure oil, from a small hand pump,
to be injected into the area between the tapered shaft and coupling
bore. After the hub is pushed manually onto the shaft and the con
tact checked, hydraulic pressure is applied to expand the hub while
it is pushed up onto the shaft taper with jackscrews to a predeter
mined locatioq providing the desired interference fit (Figure 5).
Relieving the pressure allows the hub to shrink on the shaft, after
which the tools can be removed and a check nut installed to protect
the mounting adaptor threads. The procedure is reversed for re
moval of the hub and it is expanded with hydraulic pressure until it
backs off against the jacking tools. Note that since no heat is re
quired, these operations can be performed safely at the unit site.

373
 In addition to the basic compressor design features, a variety
of auxiliary equipment, such as vibration probes, temperature and
pressure sensors, etc. , is available, which can forewarn the opera
tor of certain types of potential trouble. Provisions for the instal
lation of shaft vibration pickups and axial rotor position indicators,
for example, has become increasingly common. Their use in de
tecting changes from "normal" operating conditions can indicate
unbalance, misalignment and thrust bearing wear or load changes
and permit the operator to plan corrective action or schedule pre
ventive maintenance. The pressure differential across the com
pressor balance piping may also be measured to detect significant
changes in flow which may be due to increasing running clearances
in the balance drum or shaft seal areas, and buffer air pressure to
the seals can be monitored to assure a positive differential over gas
pressure in the case to prevent chlorine leakage.

Of course, the value of all such devices depends upon their

being regularly checked and properly maintained. This is especially
true in the corrosive environments typical of chlorine plants. Pro
tective devices which are not kept in good working order can, at
best, cause unnecessary shutdowns, and, at worst, instill a false
sense of security with severe consequences.

In addition to the normal or design conditions of operation, it

is important that the user be aware of the compressor's reaction to
anticipated variations in the process or "off-design" modes of op
eration.

For example, in some plants the compressor must be brought

on line with essentially air in the system, chlorine concentration
gradually increasing as the cell begins to produce. This type of
"bootstrap" startup must be provided for in the pressure control
and piping systems to avoid prolonged periods of compressor sur
ging which can cause heat buildup in the machine and possible me
chanical damage, depending on its severity.

The familiar equation relating compressor head and pressure

ratio shows that the differential pressure developed in a compres
sor stage at fixed speed decreases with gas molecular weight.
Thus, low chlorine concentrations mean that each succeeding stage
must handle a larger volume flow than that for which it was de
signed. Since impeller head decreases with increasing volume
flow, this effect is compounded and it is apparent that serious

374
mis-matching of the compressor stages can occur. Depending on
the specific design, a minimum chlorine concentration is reached
at which the first compressor stage is approaching its surge flow
while the last stage is approaching its maximum or choke flow.
Figure 6 shows the effect of various chlorine-air mixtures on the
performance of a six stage, three section compressor, designed
for a 98% chlorine mixture. In this case, the minimum concentra
tion which can be handled through the entire machine is approxi
mately 30% chlorine. Operating below this level at initial startup
requires venting or recycling a portion of the flow from an inter
mediate point, provision for which can be made in the piping and
control systems by the plant designer with assistance from the
manufacturer. Note also that for this compressor, design discharge
pressure is reached at about 83% chlorine concentration.
It should be apparent that the design and application of multi
stage centrifugal compressors must take into account the potential
problems peculiar to chlorine service, while at the same time,
provide sufficiently flexible machinery to meet the requirements
of the variety of process designs which are in use today or can be
anticipated in the future.

Current practice generally limits maximum gas temperatures |

to between 25 0 and 300°F. , which means that for all but the lowest
differential pressures, intercooling is required at one or more
points during the gas compression. The number of intercooling
points required and their locations depends upon the temperatures
to which the gas can be precooled and intercooled as well as the re
quired pressure ratio across the machine. The ideal stage arrange
ment should result in approximately equal discharge temperatures
from each compression section.

The compression of a 98% chlorine-air mixture from -2 to

100 psig, for example, may be done in five or six stages of com
pression and at least one intercooling point. If the gas is precooled
to -30°F. and can be intercooled to 40°F. , a five stage compres
sor, cooled between the third and fourth stages, results in nearly
equal discharge temperatures from each section of about 210°F. A
six stage machine, intercooled, between the third and fourth stages
would have section discharge temperatures of 175°F. and 250°F.
respectively, an acceptable but less desirable arrangement. When
the inlet and intercooling temperatures are the same, however, an

375
equal number of stages in each section gives the optimum result.
Increasing temperatures require additional cooling. For the same
-2 to 100 psig pressure differential and 90°F. suction and inter-
cooling, the six stage compressor intercooled between the third and
fourth stages would have section discharge temperatures of about
325°F. , excessive by accepted standards. The addition of a second
intercooling point and arranging the unit in three sections of two
stages each reduces the exit temperatures to a reasonable 245°F.

Centrifugal compressor manufacturers have recognized the

need for the kind of flexibility the foregoing exercise illustrates.
In addition to cast compressor frames which continue to be widely
used, machinery designs are available today which are entirely
fabricated, eliminating any restriction on the designer in optimizing
the compressor arrangement for a particular application. Fabri
cated compressors of the type shown in Figure 7 can be built with
as many as three intercooling points, a wide variety of nozzles sizes
and orientations, and aerodynamic internals specifically suited to the
conditions of chlorine service. As the demand for chlorine continues
to grow, the need for larger compressor trains can be anticipated.
Machines capable of handling at least twice the capacity of those in
service today are already available for use when economic conditions
justify larger facilities.

In conclusion, much has been accomplished in the past fifteen

years to maximize the utility of multistage centrifugal compressors
in chlorine service, while avoiding potential pitfalls. With con
tinuing effort, it is certain that further improvements can and will
be made, assuring the use of modern centrifugal compressors,
tailored to the needs of chlorine plant designers and operators, now
and in the future.

REFERENCES

1. DELAVAL Turbine Inc. Materials Engineering Report MAT-31

A. H. Miller, 5 July 1972
2. DELAVAL Turbine Inc. Research & Development Report CD-11
J. A. Silvaggio, Jr., 19 August 1969

376
 DISCHARGE
PRESSURE

WEIGHT FLOW

FIGURE I. EFFECT OF FOULING ON COMPRESSOR PERFORMANCE

377
UNCOATED CARBON STEEL FLUORINATED POLYMER

ELECTRODEPOSITED Ni-Cr
POLYVINYLIDENE ALLOY INFUSED WITH A
FLUORIDE RESIN POLYTETRA FLUORETHYLENE

FIGURE 2. EFFECT OF MOIST CHLORINE GAS

ON TEST MATERIALS

378
379
380
381
130 t-% DISCHARGE
PRESSURE

120 h

110 -

100 -

90 -

80 -

70 -

60 -

50 -

40 -
% CHLORINE
30 - CONCENTRATION

20 -

10 _L
20 30 40 50 60 70 80 90 100 110 120
% WEIGHT FLOW

FIGURE 6. EFFECT OF CHLORINE- AIR MIXTURES ON

CENTRIFUGAL COMPRESSOR PERFORMANCE
AT CONSTANT SPEED

382
FIGURE 7. FABRICATED CHLORINE COMPRESSOR
SIX STAGE, DOUBLE INTERCOOLED

383
 ELECTROLTSIS OF AQUEOUS SODIUM CHLORIDE SOLUTIONS
WITH A MERCURY CATHODE AT 20 to 50 KA/m2
I. T. RODEANU
Turda Chemical Works ; ROMANIA
Experimental data is presented to show the
possibility of developing a pressurized elec
trolytic cell for the electrolysis of aqueous
sodium chloride solutions at high current
densities using a mercury cathode.
The electrolysis of aqueous NaCl solutions with a
mercury cathode proves to be an electrode process. The
theoretic value of the electrode potential in all the
stages of undertaken research / laboratory, pilot plant,
industry / remains a constant e0. The overvoltage of the
process totalises the voltage drop brought abaut by the
passing of the current at the limiting line between the
electrolyte and the surface of the electrodes , by the
physical and chemical phenomena caused by the change of
the medium immediately surrounding the electrodes, phe
nomena accompanying the electrolysis process and finally
eaused by the industrial technologic .hydrodynamic and
constructive medium in which it takes place.
In industrial working conditions through of the den
sity increase of the current, the electrode potential mo
re negative values of the cathode and more positive of
the anode, in disagreement to Tafel's equation and the
equations drawn from it. At the same conditions the
voltage drop in the electrolyte to submit to not Ohm's
law.flJThe causa do this fact is an unavoidable conse
quence of the disturbance of the kynetic field by agen
ts, discovered by us, not depending on the nature of the
microclimate of basic electrochemical process, but de
pending to the rate of the dominant electrode process
which is the slowest and in additional of the babbles
chlorine-electrolyte medium.
In the conditions of the current density increase
Id > It 1.
in which:
I*a = Kja C„ + „„
NaT:Cl~ is rate of the depositing
Jt ' Kt / CNa;Cl " ^Cl' is transport rate

384
of the ions of the double technological layer /Sd/ to
give a name to us [2j .
The overvoltsge of the electrode potential is given
by equation 2
- RT , , Sd nV . .
eNa+;Cl- F ln ' gNa;Cl 0NaPl' im
in which
Sd
CN - the concentration of the sodium or
*
chlorine in the double technological
layer
C„ ,C1 - the concentration of the sodium or
' chlftrine in the volume of the cathodic
or electrolytic medium
and IR-drop through the electrolytic medium, according to
the fallowing equation:

e Ce+gS Ce+g
in which
1 * is the interpolar distance
C - the conductivity of the electrolytic
* medium /electrolyte and bubbles chlorine/
S = the effective area
Dc * current density
EXPERIMENTAL
The experiments were carried through in a laboratory
electrolyzer having an a/b construction ratio 5/1 made
of organic glass with on anode monobloc ,with possibility
for observing and measuring the technological parameters
The use of the one piece anode has allowed to carry thr
ough the experiments, in conditions that can be repeated
CATHODIC POTENTIAL
In intensive working conditions, the slow stage of
the electrode process is represented by the transporta
tion of the sodium from double cathodic technological
layer into the mass /volume/ of the amalgam. As the elee
trode potential is depending on the sodium content of
of the double cathodic technological layer, the variation
of latter will evidently lead to the change of the elee-
trode potential .
By expressing the total rate of the process as a fun

385
etion of the dominant partial process, in hydrodynamic
working conditions we hare the rate of the deposit must
be smaller or at the utmost equal to the rate of the
transport process .keeping the same symbols
Kd * <"Na+ *t ' cNa cNa '
one obtains y
cSd „ gd ' CNa+ * Kt * CNa .

From the interpretation of the above equations on

notices that for a given value of the sodium content of
the double cathodic technological layer, the current's
density can not have any value and dependes greatly on
the constant of transport rate of the sodium from the
double cathodic technological layer in the amalgam mass.
From this point of view the development in optimum con
ditions of the process forces us to reconsider all tech
nologic jhydrodynamic and constructive agents, such as:
the display of the technological process under a higher
temperature , the adoption of some mechanical devices lea
ding to the homogenization of the cathodic sodium, the
adoption of a turbulent flowing rote, etc. , insuring the
transportation of the sodium from the double cathodic
technological layer with a higher speed into the amal
gam mass.
For a given value of obtained from experimental
data, the sodium content of the double cathodic technoi
logical layer and implicitely the overvoltage electrode
process take the values schown in figures 1 and 2 , ac
cording to the increase Dc ,with the constructive factor
a/b and to the medium content of the sodium in the amal
gam. For this calculation one hsa not taken an increase
of Kt due to increase of Be, because these were not
experimental data at on industrial scale. The data ob
tained in the lab stage are not reproducing the indus
trial process and are therefore inconclusive.
By interpreting figures 1 and 2 one notices that the
optimum working field may be thus chosen as to have the
sodium content of the double cathodic technological la
yer quantitatively lower as the content of sodium ions
deposited at current densities up to 30 KA/m*.
ANODIC POTENTIAL
The slow stage of the anodic process in working con

386
ditions under monobloc anode ,may be due to the solubi
lization rate of the chlorine in the electrolyte as well
as to the limitation of the filling degree X of the
electrolyte with chlorine bubbles.
The permanent stage of the process is characterized
by the deposit of a number of chlorine ions, in proporti
on to the density of the current and their transformati
on into atoms. The atoms have a tendency of forming mo
lecules.
CI" + Cl~ ■ Cl2 5.
The atoms as well as the chlorine molecules are sol
ved in the electrolyte and have a tendency of diffusing
into it, the atoms all ending up by forming molecules,
which in their turn agglomerate giving birth to chlorine
bubbles. Displaced into the neighbourhood of the anode
the chlorine bubbles mixed to the electrolyte form the
double anodic technological layer. There is not known
way of determining the value of the chlorine atoms and
molecules in the electrolyte according to the density
of the current or to the aptitude of the anode's sur
face, in given hydrodynamic conditions ?to cooperate to
the formation of chlorine bubbles an its surface. On
interpretation of the process may be draw from relation
ship 5 meaning that simultaneonsley to the increase of
the deposit rate ,the number of chlorine atoms passing
into a molecular state increases and the concentration
of atomic chlorine decreases.
In optimum working conditions, the rate of the depo
siting process must be lower or at the utmost equal to
the rate of the transportation process in the electro
lyte of the chlorine deposited on the anode. Two of the
known agents favour this process: the decrease of the
concentration of the electrolyte in the NaCl immediately
neighbouring the electrode to a degree depending on the
increase of the density of the eurrent, and secondly
the hydrodynamic regime in which takes place.
The apparition of the chlorine in the electrolyte
under on osmotic pressure Posm. is determined by the
agglomeration of the CI? chlorine molecules with the
forming of gaseous bubbles having on inner pressure P.
This bubble can only appear and grow if the pressure
P exceeld the hydrostatic pressure due to the superfi
cial tension of the bubble's surface? ■ 4«7d in which
<T is the capillary constant of the electrolyte and
d - the initial diameter of the bubble

387
 P-Ph + ¥ «•
The formation of the double anodic technological la
yer in the neighbourhood of the anode is an unavoidable
consequence of the passing of Cl~ into CI?, a process
favoured in industrial working condition by the construe
tive factor a/b,the increase of the current's density
and other agents.
The display of the electrolytic process under mono-
bloc anode calls for the adoption of hydrodynamic work
ing conditions »f the electrolyte's flow that should
avoid the association of the chlorine molecules solved
as bubbles on the anode's surface and a limited associ
ation in the electrolyte up to a filling degree X=5-»10%
The supplementary value of the anodic potential A Ea
expressed versus the concentration of the solved chlori
ne actually in bubbles-form in current densities up to
30 KA/m? is shown in Figure 5.
By interpreting the data one notices that the over-
voltage of the anodic potential changes very little
with the increase of the concentration of the solved
chlorine in the electrolyte and takes very high values
with the appearence of the molecular chlorine associated
in bubbles form. Under this aspect the display of by
process in a hydrodynamic climate of a more intensive
flawing of the electrolyte so as to have the whole quan
tity of freed chlorine entirely absorbent into electro
lyte or limited to a filling degree limited between 5
to 10 % as well as the adoption of a constructive factor
a/b = 1 proves to be favourable to the decrease of the
overvoltage of the anodic potential.
VOLTAGE DROP THROUGH THE ELECTROLYTE
The conductivity of NaCl solutions increase lineary
with the increase of the sodium chloride content. This
fact determines an increase of the number of active iona
per cm proportional to the concentration. On the other
hand, the conductivity of the electrolyte does not chan
ge with the increase of the chlorine concentration up
to the solubility limit. With the formation of chlorine
bubbles the conductivity take different values according
to the filling degree.
By limiting the carrying through of the electrolysis
process under monobloc anode to a total absortion of
the chlorine deposited at the anode in the electrolyte

388
and in a second variant to a filling degree with chlori
ne bubbles of a maximum X = 5* 10 % ,the value of the
voltage drop in the electrolyte at • diatanee between
the electrodes limited between 3 to 5 mm as resulting
from the interpretation of Ohm's law, for current densi
ties up to 30 KA/m2, are shown in Figure 4
Measurements undertaken under a charge going up te
23 KA/wfi do not shown a linear increase of the specific
resistance of the electrolyte for an increase of the
density of the current. The values obtained at 60o, as
shewn in Figure 4 for distance of 5 and 3 mm between the
electrodes, are placed under the line 1, pointing out
under the circumstances to a higher conductivity of the
electrolyte /la and 3 a / in disagreement with the
data obtained by Schmidt and Helzinger for the distance
of 3 ma. This gap could no louger be observed with the
apparition of the chlorine bubbles ,a fact which to our
belief has left its mark on the research work of Schmidt
and Holsinger [3] .
The influence of the natere of different agents on
the conductivity of the electrolyte is not entirely
known. We are referring to the influence of the solved
chlorine, as well as to the increase of the number of
ions transported with the increase of the density of the
current whieh in this case lowers the specific resistan
ce of the electrolytic medium under 1.8ilcm.
The anodes built of carbon steel covered with tita
nium activated, obtained through electrolytic deposit and
corresponding processing prove advantageous from many
points of view for the display of the electrolysis pro
cess under monobloc anode. The resistance to corrosion,
the fact of their being neutral , constant interpolar
distance, provide an economic long working duration.
Compared to the electrolysis carried out with perfo
rated anodes, the electrolsis under anode monobloc ,
excepting the limitation of the filling degree with
chlorine bubbles, does not require ani changes.Moreover
it offers the possibility of displayting the process
under pressure.
Figure 5 gives the dependency of electrolyte's con
ductivity with the increase of the pressure in the in
terval 1-15 atm. ,registering a maxim between 8 and 10
atm. Over 15 atm. the coductivity of the electrolyte
does not depend on the pressure. The same behaviour was
found for an addition of 1.6 g C12/1.

389
Following the parallel evolution of the curves it is to
be supposed that in the interval 8-10 atm. the active
number of ions increases, independently of the content
of solved chlorine ,which helps to a slight increase of
the conductivity of the electrolyte.
The display of the electrolysis process under mono-
bloc anode depends on a more favourable certain filling
degree to the limit of the solubility of the chlorine
in the electrolyte, a fact which ultimately requires the
adoptation of an electrolyzer with a construction form
allowing the use of a higher electrolyte flow, without
bringing about an increase of the overvoltage of the
process. Among the construction factors corresponding
to this view is the ratio a/b.
Granting the due importance to the studied and deve-
lopping the electrolysis process of sodium chloride
with mercury cathode and monobloc anode under a current
density of De ■ 25 ICA/M2 we fina the optimum domain
through a compromise established between the technologic
hydrdynamic and constructive factors.
Figure 6 gives the dependency of the technologic /
pressure , concentration drop, chlorine content of the
electrolyte /,hydrodynamie /potential of the velocity
of flow and the Reynolds regime of the electrolyte/and
the constructive factor a/b.
The interpretation of the obtained data point out
the positive influence of the constructive factor a/b on
the display of the electrolysis process under a flowing
rate Re < 11600, corresponding to a velocity we » 1 m/sec.
and to a higher pressure than 2 atm. which in this case
bear a greater influence on the yeld of the process ac
cording to the absorbed chlorine and the concentration
drop in NaCl of the electrolyte.
Quantitatively the electrolysis of sodium chloride
under monobloc anode remains bound to the mass transport
G>Na+*Cl- from tne •lsctrolyta to the electrodes, to the
surface S and the mass taken out of the cathodic and
electrolytic medium GNa;Cl by the volume unit V,both
processes taking place in the time unit t.
1 dQNa+;Cl- 1 daNa;Cl -
s dt v art—
The conditions for the taking place of the process
is that the mass transport from the electrodes should

390
be smaller or at the utmost equal to the mass transport
from electrolytic medium. When this is not c*he,case,
the process is disturbed by agents alien to the basic
electrochemical process and becomes not economic. The
electrolyte plays a double role : a medium for the
carrying out of the process and a means of transportati4
on for the deposited chlorine. There ensues a close de
pendency between the density of the current and the
constructive factor a/b, the velocity potential w and
the flowing rate or regime of the electrolyte Re, the
pressure p, the concentration Cji8Cl»the temperature T
at which takes place, and other parameters. The optimum
domain presents a compromise between at least seven
agents influencing the overvoltage of the electrolysis
process
AS - f/ Dc, a/b, w, fie, p, CNaC1, T / 8.
A mathematical model representing faithfully the
dependence degree of the overvoltage to the above agente
can not be found owing to the limits between which it
variantes but especially because of the different ef
fect displayed on the causes which added together bring
about the overvoltage of the process.
Thus the constructive factor a/b in given working
conditions or in the conditions of the current's densi
ty increase , shows itself with a less negative influence
on the cathodic potential as compared to the influence
on the anodic potential
The display of the electrolysis process in on opti
mum domain imposes the adoption of an agent a/b>l
for the cathodic space and a/b<l for the anodic space.
This fact was placed at the basis of the view according
to which the electrolysis process takes place in a cros
sed current, amalgam-electrolyte , under an angle of 90°.
From the construction point of view, the electrolyzer
Rj and aggregate cells Rj fulfills this condition. The
electrolyser R5 Figure 7 consists of a vat with ebonite
set bords through which mercury flows in a layer 3 to 5
mm with a speed depending on the slope thus calculated
as to have the enrichment in sodium not disturbing the
process, a monobloc anode consisting of a steel plate
covered by a titanium activated , rigid by set at a dis
tance of 5-5 mm of the surface of the cathode serveing
meanwhile as a lid , and four valves attached to the
body of the electrolyser to let out the brine, let out
the electrolyte with chlorine, introduce the mercury

391
and evacuate the amalgam. The whole electrolyser is
supported by adjustable brackets to provide a suitable
slope for the free flow of the cathode.
The aggregate cells R4 Figure 8 unites in a single
construction a great number of electrolysers .consisting
of vats superposed at a convenient distance isolated and
partitioned , having on the lower surface of the closing
plates and the lower side of the vats } excepting the last
one, a layer of titanium activated which forms the anode
The vats are set in a rigid frame forming the sides and
the ends through which the electrolysers are fed with
electrolyte and mercury and the worn-out electrolyte and
the sodium amalgam is taken out.
The process taken place simultaneously in all the
superposed electrolysers forming the unit in technologic
hydrolynamic conditions, shown in Figure 9, thus chosen as
to run smoothly without any extra energy consution in
a field of current density between 20—30 KA/m2, tempe
rature 60-80°C and on electrolyte concentration between
270 and 310 g/1 NaCl at athmospheric pressure or still
better under pressure
The vati forming the electrolysers have slopes in
both ways and convenient apertures at the ends to let
in the mercury and take out the amalgam in conditions
in which the working of the electrolyser R3 takes place
and of the flowing of the amalgam from one vat into the
other in the working conditions of the electrolytic
unit H4. In both cases the amalgam is favourably intre-
rupted and stirred by traverse and deepen grooves in
the vats to omogenize the sodium content. Thresholds
are placed in the grooves to partition the anodic space
respectively the interpolar space through which the
electrolyte runs, leaving a free passage for mercury ea-»
thode helps to keep the interpolar distance constant*
After corresponding enrichement in sodium and to avoid
the decomposition of the amalgam in the electrolyser,
it is taken out submitted to decomposition process and
introduced again into the system. Meanwhile the electro
lyte containing absorbed chlorine is degassed by strip
ping, brought back into the circuit up to a concentra
tion gradient of Cjf^n-^ of minimum 40 g/1, after which it
is submitted to a saturation and purification process.
The inactive parts of the electrolyser R3 and of the
unit R4 such as : the sides and ends of the vats , the
inner parts through which the feeding with electrolyte

392
takes place as well as the in lets and outlets of the
mercury and amalgam are protected by anti corrosion
materials and it is understood that anodic plate is also
isolated from the electrolyser vat known methods. The
anodic and cathodic bars are rigidly conected to the co
vering plate of the vat, and the lower part of the latter
in the case of the electrolytic unit having the anodic
vats in the middle, in way ensuring a uniform repartiti*
on of the current on the service able surface of the
unit.
Less dependent on the adopted constructive ratio a/b
the electrolyser R3 and the unit R4 can a charge betwe
en 250 and 500 KA.
An electrolysis plant made of a number of 40 electro-
lysers R3 and of the same value as an electrolytic unit
R4 consisting of a same number of superposed vats,worked
under a current density of 25 KA/m^ has a voltage balan
ce and technical data shown on table 1 and table 2.
By developing the process under a pressure of 8 to
10 atm. the resistance of the electrolytic medium decre
ase by 0.217Jl.cm, a fact conferring the electrolyte a
higher conductivity in this domain and evidently a decre
ase of the voltage drop in the electrolyte of about 170
■V under the values resulting from the interpretation of
the dependency of the voltage drop in the electrolyte
on the density of the current.
Sodium hydroxide solutions as we lias chlorine in
gaseous form are obtained in specific outfilts of the
desamalgamation and degassing processes.
The electrolysis of NaCl aqueous solutions with a
mercury cathode at 20 - 30 KA/m2, proves to be very ad
vantageous economicaly for high density working current
as* far its very important productive capacity. It is
estimated that 30 such electrolysis cell aggregate R4
might be equivalent to Dow Chemical Company production.
At the same time 112 cell aggregates of this type
should give a chlorine output which were higher that the
whole world production.
CONCLUSIONS
the experiments undertaken show the possibility
developping the electrolytic process of the aqueous
sodium chloride solutions with a mercury cathode under
pressure and at densities of current between 20-30 KA/m'

393
in a technologic, hydrodynamic and constructive climat
suitable to this purpose. The overvoltage of the catho—
die and anodic potential remains strictly bound to the
rate of the dominant electrode process which is the
slowest. The condition for the electrolysis process ta
king place in an optimum domain of the voltage drop ia
that the rate of the depositing process should be smal
ler or at the utmost equal to the transportation rate
of the sodium and chlorine atoms of the double techno
logical layer in the mass of amalgam and respectively
electrolyte .
in idustrial working conditions, a minimal overvol
tage of the electrode potential is obtained through a
compromise of the technological, hydrodynamic and con
structive factors, especially of the a/b ratio, so as to
ensure a permanent equilibrium between the quantity of
Ka+ and Cl~ ions deposited and neutralized on the elec
trodes according to the density of current at which
one works, and to the sodium and chlorine atoms content
in double technological layer, in the volume of amalgam
respectively of electrolyte.
The ratio between the atomic and molecular chlorine
solved in the electrolyte .taking part at the formation
of double technological layer at the anode is unknown.
Up to the limit of solvability, the chlorine solved in
the electrolyte has a favourable influence on the con
ductivity of the medium. The increase of the density of
current acts in the same way,afect explained by the
increase of the number of active ions in the solution
transported to wards the electrodes.
The conductivity of the electrolyte takes different
values according to the increase of the peessure in the
interval of 1 to 15 atm. marking a maximum between 8
and 10 atm. Over 15 &tm. the conductivity of the elec
trolyte does not depend on the pressure. Through an
addition of chlorine the conductivity of the electroly
te increases slightly giving for the field of our re
search, 1-20 atm. a curve parallel to the first one.
REFERENCES
1 / Rodeanu I. T. Denki Kagaku,41,No.5 /1975/
2 / Rodeanu I. T. Dissertation for the Doctor degree
Iassy, March 1970
3 / Schmidt and Holzinger, Chemie lng.Techn.35,1,
/196V

394
 Fig.l
Dependency of the
potenti.nL anodic
overvoltage. on the
sodium content of
the doable cathodic
technological layer
~ Sd
^ Ha

Dc.tO-3 Hjrrfi

an* Fi-g
Dependency of cathodic
-MO potential overvoltage
■too on the sodium content
-40 of the double cathodic
~2te. -eo layer for a construction
-«0 ratio of a/b»5
-20

Tig . 3.
Dependency of anodic
potential overvoltage on
the concentration dagreo
of chlorine solved, and
in bubble form.

395
 FLg.V
Dcpendcncj of the
voltage drop in tha
electroljtc on the
distance between
the- electrodes and
the filling degree *fiih
chlorine bubbles-

1-5mmi id-bmrn experimentally obtained carve

a«iimm
5.5mm', 3a -1mm experimentally obtained curve
k • 5mm X. 5% gaseous chlorcne in bubble form
5 *5mm X«)0% gaseaus chlorine in bubble form

Fiq. 5.
0,"i7 -I
0,i,6-| Dependency of the conduduitj
0,1(5 of the electrolyte on the
O.Mi pressure increase.

0.H2H
-1—1—1—1—1—1—1—1—1—1—
t H t 8 10 « (8 18 eo
p-atm

Tig. 6.
Dependency of tehnologlc
and hydrodjnamic agents
on construction elements

396
 figure 7- Clectrolyser R3
l-vat,2-iid,3-olectrol\(ta inlet hood,
4-clectrolyte outlet hcad,5-mercury
Inlet heqa,6-amalgam outlet head,
7-power current barojS- isolation.
9- Pt-Ti monobloc anodo, 10-eboniia-
sot surface, It-assembling head,
12-support.

riqurefi-CeUs aggregate Ri,

1-vai, 2-oloclrol\jto inlet ,3-o,lectrolyte outlet ft -mercury inlet ,5-amalgom outlet,
6-powr current bare fi»ing,7-obonite-6et 6ur|aco,8-rigide {ramo,9-Pt-Ti anode.

M
to
Dc«g500OA/m'| r*o
M

i l I T i + b I 5" •'-To
figure 9 Optimal operation |iold o| monobloc anode electrolysis process
Tabela I
Vottago balance [Eloctroly6er R3 and aggregate B„].
mV
o'Na 1810
o'Cl 1310
E»-d".3mm (160-1380
AC, 31
&£a 1.8
JCciTt activated 'lO
tcotsept tintr. 4&3
E^contacto rigide H.2
Ec. -Tl aoe
002

397
 Table 2
TECHNICAL DATA OF ELECTROLYSES ft- AND CELLS
AQOREOATE R.
Characteristics

Number of cells installed 40 1

Number of cells in operation 40 1
Rated / KA / 2 300 250 - 500
Anodic area / ■ / - 10 400 800
Current dens ity / KA/mV 30 25 25
Current efficiency % 98-99 98-99
Short-circuiting switches
unit 9 5 10
Power DC k»h/t Cl2 3,260 3,260
Cathodic width / m / 2 2 2
Cathodic length / m / 5 5 10
Cathodic area Am2 / 10 400 . 800
Floor space / m2/t Cl2 / 0.0053 13. 10-4 7. 10-*
Mercury / kg/t CW 0.218 0.218
Copper / kg/t Cl2 / 1.2
Sodium content entering
decomposer / % 7 0.3 0.300

398

■
DEPOLARIZATION AND INHIBITION OP AMALGAM DECOMPOSITION
AND DESIGN APROACH TO MERCURY CELL DECOMPOSERS
M.M. Jaksic, I.M. Csonke and R.T. Atanesoski
Electrochemistry Department, Institute of Chemistry,
Technology and Metallurgy, Karnegijeva VIV,
Belgrade, Yugoslavia

Depolarization of sodium amalgam decomposition on grap

hite cathode of decomposers of mercury cells is impor
tant both to reduce the volume of the latter and thus a
mercury content of electrolysers and to produce caustic
soda of higher concentration.
Considerable depolarization effects have been achieved
both with molybdenized1 and cobaltized graphite (Fig.l).
The former has been obtained in situ during the pro
cess by cathodic reduction of alkali molybdates or
peroxymolybdates, and the latter both by chemical and
electrochemical cobalt deposition on graphite surfa
ces. The Tafel lines achieved on metalized graphite
exibit nearly the same slopes as the ones on metals
themselves, but are shifted to more positive potential
values, thus changing the polarization characteristics
of carrying graphite cathode. Thereby their mixed po
tentials with sodium amalgam anode were also shifted
to considerably larger values, thus increasing either
the decomposer's capacity or the concentration of pro
duced caustic soda. It would be worthy to note that in
practical decomposer work of industrial scale the con
centration of caustic soda at equal temperature and
all other process parameters kept constant was incre
ased from 48% to 65% NaOH (no heating).
The design procedures for sodium amalgam decomposition

399
towers given independently by F. Hine and I. Rousar-7
were simplified and used for optimisation and scale-up
of their dimensions. The whole approach is given in the
paper.
On the other hand, the Inhibition of sodium amalgam de
composition is of essential importance for wort of the
mercury cell electrolyser.
Such inhibitors would provide in extremly small contents
more stable cell work resulting in minimized hydrogen
evolution, that is esspecially important in case of ap
pearance of impurities in brine (Mg, Or - ions and
others). Several alcohols, esspecially polyalcohols and
certain organic cationic compounds, which provide the
potential of zero charge (p.z«c) of the mercury and
amalgam electrodes to be shifted to more positive values,
have been found as suitable inhibitors for the mercury
cells. Further improvements has to be done to stabilize
such compounds from chlorination by introducing fluorine
in the molecules of the latter and thus to provide their
longer life time in the course of use as inhibitors of
chlorine cells. However the practical effect now obta
ined woeld be to redece hydrogen content of the cell
immediately as imperities of the brine suddenly appear.

Fig. 1. Polarization characteristics of sodium amalgam

decomposition. •, anode polarization of sodium amalgam
decomposition. Tafel plot of experimental results for
various cathodes at 80°C:V, plain graphite ; A. -mo lyb-
denized graphite ; A and n , two cobaltized graphites
prepared on different methods.
References
1) M.M. Jafcsic and I.M. Csonfca.Electrochem.Technol. ,
it, 49 (1966)
2) F. Hine, ibid., 2, 79 (1964)
5) I. RouSsr, paper presented at 143rd Meeting of the
Electrochemical Society, Chicago, 1973
400
401
 INDEX
A Depolarized cathode, 278
Air pad mining, 68, 75
Amalgam decomposition, 399
Anode adjustment, 145
Anode efficiency, 324
B Diaphragms, 153, 194, 205,
Brine impurities, 115
Brine purification, 60, 97
C Electroactive coatings, 162,
Cell design, 150, 203, 260,
399
Cell room safety, 235, 246
Cell voltage, 138, 212, 259,
281, 385
Centrifugal chlorine com
pressor, 9
Centrifugal compressor, 368
Chlorine cell, future of,
147, 187
Chlorine compression, 368
Chlorine demand, 6
Chlorine destruction, 267
Chlorine emission control,
244, 247
Chlorine, history of, 1, 20,
35
Chlorine liquefaction, 232,
289
Chlorine plant development,
44
Chlorine purification, 231,
269, 279
Chlorine quality, 233
Compressor design, 368
Computer modeling, 285
Cupric chloro- complex ions,
278
Current efficiency, 324
D N
Dechlorination, 352
Depolarization, 399
403
Diaphragm cell design, 215
Diaphragm cell material bal
ance, 140, 213
Diaphragm cells, 10, 152,
191, 198, 209, 218, 285,
324
220, 261
E
174
Electrolyte conductivity, 282
H
HC1 electrolysis, 278
Hydraulic fracturing, 76
Hydrochloric acid electro
lysis, 257, 349
Hydrogen, 332
M
Mass transfer, 270
Mass transport, 390
Material balances, 261, 290,
304
Mathematical modeling, 299,
391
Mercury butter, 111
Mercury cells, 10, 39, 111,
120, 145, 151, 190, 384,
399
Mercury emission control, 136
Mercury impurities, 114
Mercury recovery, 120, 131
Mercury sulfide, 360
Metal anodes, 158, 174, 211,
220, 278, 326
Morphology, 178
Negative evaporation, 301
 Oxychlorination , 257 Salt crystallization, 299
Oxygen containing anions, Salt, trace metals in, 86
324 Single well mining, 65
Solar salt, 86, 299
P Solution mining, 60, 63, 74
Strontium, 111
Plant design, 196, 222, 237, Sulfhydrate, 360
247, 270, 285, 332
Pollution abatement, 13, 120, T
133, 148
Pollution control, 60 Tail gas, 268, 278
Positive evaporation, 301
Pressurized electrolysis, W
384
Water purification, 342
R Waste water treatment, 127,
131, 342, 365
Redox, 361

404

9 bt60^0i3, ps 7180