Journal of the Air Pollution Control Association

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Manufacture of Chlorine and Sodium Hydroxide

To cite this article: (1964) Manufacture of Chlorine and Sodium Hydroxide, Journal of the Air
Pollution Control Association, 14:3, 88-90, DOI: 10.1080/00022470.1964.10468251

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MANUFACTURE of CHLORINE and SODIUM HYDROXIDE
Informative Report No. 4
ith the development of the
electric dynamo, in the late 1800's,
the electrolytic process for the produc-
tion of chlorine and caustic soda be-
came a commercial possibility. The
first practical cell was patented in 1886.
Today, this process accounts for most
of the chlorine and sodium hydroxide
produced in the United States.
Chlorine production in the United
States has climbed from a meager three
tons per day in 1892 to 14,000 tons
per day in 1959; of this total only
one to two percent is from a nonelec-
trolytic source, namely, the nitric acid
process.
Caustic soda production in the United
States is expected to hit an all time high
of approximately 19,000 tons per day
in 1965. This can be compared with
a daily production of 850 tons in 1919.
Approximately 94.6% of the caustic
soda manufactured in 1959 was made
electrolytically. Most of the remaining
5.4% was produced by the lime-soda
process.
The Processes
Chlorine Production
Electrolytic Diaphragm Cells
Electrolytic diaphragm cells vary
considerably in size and shape; how-
ever, all commercial installations oper-
ate on the same principles. Chlorine
and alkali are produced as co-products
with hydrogen as a by-product. Chlo-
rine is liberated at the anode. At the
cathode, an alkali solution forms and
hydrogen is liberated. The alkali
formed depends upon the raw material
fed. Either KC1 or NaCl, as a satu-
rated brine, may be used.
The chlorine gas, about 98% Cl2,
leaves the cells hot and is sent to cool-
ers. Cooling the cell gas condenses
water saturated with chlorine. This
water passes to the sewer through a
limestone pit. It is not a source of
air pollution.
After the chlorine is cooled and thus
88
This report, published as Informa-
tive Report No. 4 of the Air Pollution
Control Association's TI-2 Chemical
Committee, began to move through
the 14 step approval procedure, as
outlined in the March 1963 Journal,
on January 10, 1963. Comments
made by members of the Technical
Council were considered in the
preparation of the final report. It is
now published as representing the
"best thinking of the Association."
It is an extremely timely and informa-
tive report.
partially dried, it is further dried by
contact with sulfuric acid. Depending
upon the technique used, the spent
sulfuric acid can either be reclaimed or
discharged to the sewer through a suit-
able neutralizer. The chlorine gas is
then liquified by compression and cool-
ing.
There is a small amount of non-
condensable gas remaining after the
final cooler. It consists of air and some
chlorine and is called "blow gas"
or "sniff gas." At some plants there
are nearby chlorination operations in
which this gas is used for its chlorine
content. When the blow gas cannot
be so used, it is given a final treatment
to remove the chlorine before venting.
This final treatment may be passage
through an alkaline scrubber or an ab-
sorption-desorption recovery unit. In
one type of recovery unit the chlorine
is dissolved in brine and later driven
from solution by acidification. In
another type of unit the chlorine is
absorbed on silica gel, from which it
is subsequently recovered by heating.
Still other types are known which use
other solvents or absorbents but are
similar in principle to the above.
Fused Electrolytic Cells
Chlorine is also produced from fused
MgCl2 as a co-product in the produc-
tion of magnesium, and from fused NaCl
as a co-product with metallic sodium.
In these cases, the chlorine gas is col-
TI-2 Chemical Industry Committee
lected, dried and liquified in equipment
similar to that for the diaphragm cells.
Mercury Cells
Mercury cell installations are on the
increase in the United States because
of the high purity NaOH which they
produce.
Brine is electrolyzed to produce chlo-
rine at the anode and sodium or potas-
sium metal at the cathode, which is
a pool of mercury. The alkali metal
forms an amalgam with the mercury
from which hydroxide is sub sequently
formed by reaction with water. The
mercury is circulated by rocking, pump-
ing or other mechanical means.
The chlorine gas is collected, dried,
and liquified in equipment similar
to that for the diaphragm cells.
Nitric Acid Process
Presently in the United States there
is only one plant producing chlorine
by the nitric acid process. However,
it is worthy of note since it has a
considerable chlorine capacity.
There are two main considerations for
using this process: (1) an outlet for
NaNO3, which is produced as a co-
product with chlorine; and (2) a
ready supply of nitric acid. The
process involves the following reac-
tions :
3 NaCl + 4 HNO3 = 3 NaN0 3 + Cl2
+ NOC1 -|- 2 H2O
2 NOC1 + O2 = Cl2 + N2O4
Sodium chloride (NaCl) is reacted
with nitric acid (HN03) to form sodium
nitrate (NaN03) which is removed by
crystallization and processed as a
final product. Gases leaving the reac-
tor containing chlorine (Cl2), nitrosyl
chloride (NOC1), and moisture (H2O)
are dried and the NOC1 oxidized with
oxygen to form chlorine (CI2) and nitro-
gen dioxide (N2O4). The chlorine and
nitrogen dioxide are then liquified,
with non-condensables and oxygen re-
turning to the system. Chlorine is
Journal of the Air Pollution Control Association
 Technical Data then removed in a fractionator. The
Physical N2O4 from the fractionator may be
Name Properties Odor Toxicity Miscellaneous sold or converted to nitric acid for
reuse.
Chlorine Green-yel- Strong Strong upper respiratory system Bleaches some
low gas pungent irritant; irritant effect on eyes dyes and Sodium Hydroxide Production
BP 34.5° detect- nose and throat. Single, very colors. Cor-
C able at high or prolonged exposure re- rosive to Electrolytic Process
3 ppm suits in pulmonary edema. some metals
MAC for 8 hours of continuous in moist at- Sodium hydroxide is produced in elec-
exposure in work environment mospheres. trolytic cells from sodium chloride with
1 ppm (3 milligrams per cubic
meter). chlorine as a co-product and hydrogen
Sodium White solid None Upper respiratory irritant. Dust Dry solid picks as a by-product. It is produced in
hydrox- BP extremely caustic to skin and up moisture either diaphragm cells or mercury cells,
ide 1390°C eyes, with possibility of ulcer and CO2 depending upon the purity desired.
formation. MAC for dust 2 from air
milligrams per cubic meter of rapidly, (For cell operation, see Chlorine Produc-
air (for continuous 8-hour ex- tion.)
posure in the work environ- The diaphragm cells produce a con-
ment). centration of 10 to 12% NaOH from
Calcium White solid None Moderately caustic to skin, with Dry solid picks
oxide BP resulting dermatitis. Severe up moisture which water is usually evaporated to
2850°C eye irritant. Irritant to mu- and CO2 produce the commercial grades. The
cous membranes in high con- from air. cell liquor passes to nickel lined multi-
centrations. effect evaporators where 50% NaOH
Calcium White solid None Non-toxic
carbon- dec 825°C is produced. Salt is constantly removed
ate and fed back to the brine making sys-
Sodium White solid None Non-toxic tem. The 50% NaOH can further be
chloride BP concentrated in evaporators to 73%
1413°C
Sodium White solid None Non-toxic NaOH. Anhydrous NaOH is produced
carbon- dec by fusion in pots or by continuous
ate 850+ °C evaporation, boiling off essentially all re-
maining water at temperatures of 500
to 600°C.
The mercury cells produce 20 to
70% NaOH directly without the need
for evaporation.
Lime-Soda Process
The lime-soda process depends on
the reaction of calcium hydroxide and
sodium carbonate (soda ash) in solu-
tion to form soluble sodium hydroxide
and insoluble calcium carbonate. It
can be carried out as either a continu-
ous or batch operation. Calcium oxide
and a soda ash solution are mixed and
agitated for about one hour at 85 °C.
The calcium oxide first slakes to the
hydroxide and then reacts with the soda
ash. The slurry from this reaction goes
to a battery of two or three thickeners
SODIUM HYDROXIDE BY THE LIME-SODA PROCESS where the calcium carbonate settles
Oxygen Noncondensables and is drawn off as a thick sludge and
and Oxygen Return
To System the remaining clear solution contains
the desired NaOH. (The solution
Oxidizor —i from the first thickeners contains about
11% NaOH.) This solution can be
Reaction
concentrated by evaporation as de-
Tower scribed above to whatever degree is
desired. The sludge from the first
thickener is pumped to the second one
Liquifier
where hot water and filtrates from the
third unit are added. The liquor from
this unit is generally used to make up
the original sodium carbonate solution.
The third thickener is fed the sludge
from the second. The overflow of the
third is sent to the second and the
Nitrogen
Dioxide sludge, mostly calcium carbonate, is
filtered, washed and sent to a lime kiln
to form calcium oxide which is re-used
Sodium in the initial soda ash-lime mixture.
Nitrate In the lime kiln, there exists the typical
CHLORINE BY THE NITRIC ACID PROCESS dust recovery problem.

March 1964 / Volume 14, No. 3 89

 Hydrogen
Diaphragm Type
or Mercury Type
Plus Decomposer
Water
Blow Gas to
Chlorination
Process or
Recovery Unit
Sodium Hydroxide
(73% High Grade)
CHLORINE-ALKALI HYDROXIDE BY ELECTROLYSIS
Air Pollution Control Aspects
Chlorine
The cells, coolers, and driers are oper-
ated under a slight vacuum so that if
there are any leaks, air leaks into the
system instead of chlorine leaking
out into the cell rooms. An accidental
circuit power failure can cause an
imbalance in which chlorine could es-
cape to the atmosphere. This can be
quickly corrected by re-balancing the
system. Failure of the compressor
that supplies the draft for the chlorine
lines can also cause gas leakage until
the cells are shut down.
To prevent air pollution during these
emergencies, the chlorine lines from the
cells and liquifiers are either tied into
a high stack for dispersion of the gas
or tied to a scrubber to remove the
chlorine. In the latter case, the gas
from the scrubber usually is vented to a
tall stack.
Air used for transferring liquid chlo-
rine is also vented through this same
scrubber—stack system.
The several aqueous waste streams
NEW TECHNIQUES DEVELOPED
TO REDUCE SLUDGE FORMATION
_^,Sodium Hydrox
(50% Standard Gr.)
5 0 % Caustic
Storage
Sodium Hydroxide
(737.)
Fusion
Pot
Sodium Hydroxide
Sodium Hydroxid
(Solid)
(Flake)
which contain chlorine will cause no
air pollution as long as they are kept
alkaline. Care must be taken that they
are not discharged into a ditch or sewer
that also receives acid wastes, as this
might cause a chlorine release.
Treatment of the blow gas to remove
its chlorine has been described.
Sodium Hydroxide
This is a non-volatile material.
Mists or droplets of caustic solution
might be blown into the air during badly
upset conditions but these will settle in
the immediate area.
Kiln burning of calcium carbonate
(from the lime-soda process) causes some
dust formation. This can be con-
trolled by the conventional dust collect-
ing equipment.
REFERENCES
1. Chemical Engineers Handbook, Thirdimproved performance.
Edition. J. Perry, Editor.
2. Dangerous Properties of Industrial Ma- Other significant features of blowby
terials, N. Sax.
3. Industrial Chemicals; Faith, Keyes,
and Clark. Reprinted with permission
from Faith, Keyes, and Clark—Indus-
trial Chemical copyright 1957. John
Wiley and Sons, Inc.
Sludge formation may be appreciably
reduced in the future by modifications
to divert blowby, according to a paper
presented at the SAE Automotive
Engineering Congress January 15. The
paper, by R. D. Quillian, Jr., Nelson T.
Meckel and John V. Moffitt of the U. S.
Army Fuels and Lubricants Research
Laboratory at Southwest Research
Institute in San Antonio, Texas, de-
scribes four approaches which elim-
inate to a marked extent combustion
by-products, commonly called "blowby
gases," from reaching the crankcase.
Blowby is a mixture of fuel, gases,
acidic wrater and insolubles. When
these gases contact engine lubricants, a
chemical reaction takes place forming
sludge.
In the paper, the authors outline four
techniques developed at the laboratory
which divert the gases after they pass
the bottom compression piston ring
but before they reach the crankcase.
90% Blowby Diverted
Using these techniques, better than
90% of the blowby can be diverted,
thus prolonging lubricant life and also
extending component performance. In
experiments conducted at the U. S.
Army Fuels and Lubricants Research
Laboratory in San Antonio, the prin-
ciple of blowby diversion has been
proved feasible.
The diversion systems designed by
the Institute staff are simple and can
be readily adapted to various engine
and piston designs. As a result, ac-
ceptable performance can be obtained
with a lower quality oil. Using a high
quality lubricant will result in greatly
diversion include reduced engine wear,
especially piston ring wear. In ad-
dition, the blowby is routed back into
the combustion chamber and reburned,
decreasing the air pollution rate.

WILLIAM T. INGRAM
CARL R. FLODIN JACKSON & MORELAND, INC.
Consulting Engineer Consulting Engineer Engineers and Consultants
Environmental Engineering
Planning—Design—Research
CONTROL EQUIPMENT
Water—Wastes—Refuse APPLICATION ENGINEERING Air Pollution Evaluation and Control
Services for Utilities and Industrials
Air Pollution Control FOR
Industrial Health DUSTS-FUMES-GASES-MISTS . DESIGN, SPECIFICATION, AND EVALU-
Laboratory Services EVALUATIONS-SPECIFICATIONS ATION OF SYSTEMS AND EQUIPMENT
Offices: CONSULTATION FOR PILOT UNITS . SUPERVISION OF CONSTRUCTION
East Coast AND OPERATION
AND FULL-SCALE INSTALLATIONS
7 North Drive AIR SAMPLING SURVEYS
Whitestone, N.Y. 11357 2744 MONTEREY ROAD . PUBLIC RELATIONS
West Coast SAN MARINO, CALIFORNIA, 91108
90 Panoramic Way MUrray 2-1800
Boston—Washington—New York
Walnut Creek, Calif; AREA CODE 213

90 Journal of the Air Pollution Control Association