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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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Published online: 16 Mar 2012.

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Informative Report No. 4

TI-2 Chemical Industry Committee

ith the development of the lected, dried and liquified in equipment

electric dynamo, in the late 1800's, This report, published as Informa- similar to that for the diaphragm cells.
the electrolytic process for the produc- tive Report No. 4 of the Air Pollution
Control Association's TI-2 Chemical Mercury Cells
tion of chlorine and caustic soda be- Committee, began to move through
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came a commercial possibility. The the 14 step approval procedure, as Mercury cell installations are on the
first practical cell was patented in 1886. outlined in the March 1963 Journal, increase in the United States because
Today, this process accounts for most on January 10, 1963. Comments of the high purity NaOH which they
made by members of the Technical produce.
of the chlorine and sodium hydroxide Council were considered in the
produced in the United States. preparation of the final report. It is Brine is electrolyzed to produce chlo-
Chlorine production in the United now published as representing the rine at the anode and sodium or potas-
States has climbed from a meager three "best thinking of the Association." sium metal at the cathode, which is
It is an extremely timely and informa- a pool of mercury. The alkali metal
tons per day in 1892 to 14,000 tons tive report.
per day in 1959; of this total only forms an amalgam with the mercury
one to two percent is from a nonelec- from which hydroxide is sub sequently
trolytic source, namely, the nitric acid formed by reaction with water. The
partially dried, it is further dried by mercury is circulated by rocking, pump-
process. contact with sulfuric acid. Depending
Caustic soda production in the United ing or other mechanical means.
upon the technique used, the spent
States is expected to hit an all time high sulfuric acid can either be reclaimed or The chlorine gas is collected, dried,
of approximately 19,000 tons per day discharged to the sewer through a suit- and liquified in equipment similar
in 1965. This can be compared with able neutralizer. The chlorine gas is to that for the diaphragm cells.
a daily production of 850 tons in 1919. then liquified by compression and cool- Nitric Acid Process
Approximately 94.6% of the caustic ing.
soda manufactured in 1959 was made Presently in the United States there
There is a small amount of non- is only one plant producing chlorine
electrolytically. Most of the remaining condensable gas remaining after the
5.4% was produced by the lime-soda by the nitric acid process. However,
final cooler. It consists of air and some it is worthy of note since it has a
process. chlorine and is called "blow gas" considerable chlorine capacity.
The Processes or "sniff gas." At some plants there There are two main considerations for
are nearby chlorination operations in using this process: (1) an outlet for
Chlorine Production which this gas is used for its chlorine NaNO3, which is produced as a co-
content. When the blow gas cannot product with chlorine; and (2) a
Electrolytic Diaphragm Cells be so used, it is given a final treatment ready supply of nitric acid. The
Electrolytic diaphragm cells vary to remove the chlorine before venting. process involves the following reac-
considerably in size and shape; how- This final treatment may be passage tions :
ever, all commercial installations oper- through an alkaline scrubber or an ab-
ate on the same principles. Chlorine sorption-desorption recovery unit. In 3 NaCl + 4 HNO3 = 3 NaN0 3 + Cl2
and alkali are produced as co-products one type of recovery unit the chlorine + NOC1 -|- 2 H2O
with hydrogen as a by-product. Chlo- is dissolved in brine and later driven 2 NOC1 + O2 = Cl2 + N2O4
rine is liberated at the anode. At the from solution by acidification. In
cathode, an alkali solution forms and another type of unit the chlorine is Sodium chloride (NaCl) is reacted
hydrogen is liberated. The alkali absorbed on silica gel, from which it with nitric acid (HN03) to form sodium
formed depends upon the raw material is subsequently recovered by heating. nitrate (NaN03) which is removed by
fed. Either KC1 or NaCl, as a satu- Still other types are known which use crystallization and processed as a
rated brine, may be used. other solvents or absorbents but are final product. Gases leaving the reac-
The chlorine gas, about 98% Cl2, similar in principle to the above. tor containing chlorine (Cl2), nitrosyl
leaves the cells hot and is sent to cool- chloride (NOC1), and moisture (H2O)
ers. Cooling the cell gas condenses Fused Electrolytic Cells are dried and the NOC1 oxidized with
water saturated with chlorine. This Chlorine is also produced from fused oxygen to form chlorine (CI2) and nitro-
water passes to the sewer through a MgCl2 as a co-product in the produc- gen dioxide (N2O4). The chlorine and
limestone pit. It is not a source of tion of magnesium, and from fused NaCl nitrogen dioxide are then liquified,
air pollution. as a co-product with metallic sodium. with non-condensables and oxygen re-
After the chlorine is cooled and thus In these cases, the chlorine gas is col- turning to the system. Chlorine is

88 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
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
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chloride BP concentrated in evaporators to 73%

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
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
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
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

March 1964 / Volume 14, No. 3 89

Diaphragm Type
Sludge formation may be appreciably
or Mercury Type reduced in the future by modifications
Plus Decomposer _^,Sodium Hydrox to divert blowby, according to a paper
(50% Standard Gr.)
Blow Gas to
presented at the SAE Automotive
Process or
Recovery Unit
5 0 % Caustic
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
Sodium Hydroxide Institute in San Antonio, Texas, de-
scribes four approaches which elim-
Fusion inate to a marked extent combustion
Sodium Hydroxide Pot by-products, commonly called "blowby
(73% High Grade)
gases," from reaching the crankcase.
Sodium Hydroxide Blowby is a mixture of fuel, gases,
Sodium Hydroxid
acidic wrater and insolubles. When
(Flake) these gases contact engine lubricants, a
chemical reaction takes place forming
In the paper, the authors outline four
Air Pollution Control Aspects which contain chlorine will cause no
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techniques developed at the laboratory

air pollution as long as they are kept which divert the gases after they pass
Chlorine alkaline. Care must be taken that they the bottom compression piston ring
are not discharged into a ditch or sewer but before they reach the crankcase.
The cells, coolers, and driers are oper- that also receives acid wastes, as this
ated under a slight vacuum so that if might cause a chlorine release. 90% Blowby Diverted
there are any leaks, air leaks into the Treatment of the blow gas to remove Using these techniques, better than
system instead of chlorine leaking its chlorine has been described. 90% of the blowby can be diverted,
out into the cell rooms. An accidental Sodium Hydroxide thus prolonging lubricant life and also
circuit power failure can cause an extending component performance. In
imbalance in which chlorine could es- This is a non-volatile material. experiments conducted at the U. S.
cape to the atmosphere. This can be Mists or droplets of caustic solution Army Fuels and Lubricants Research
quickly corrected by re-balancing the might be blown into the air during badly Laboratory in San Antonio, the prin-
system. Failure of the compressor upset conditions but these will settle in ciple of blowby diversion has been
that supplies the draft for the chlorine the immediate area. proved feasible.
lines can also cause gas leakage until Kiln burning of calcium carbonate The diversion systems designed by
the cells are shut down. (from the lime-soda process) causes some the Institute staff are simple and can
To prevent air pollution during these dust formation. This can be con- be readily adapted to various engine
emergencies, the chlorine lines from the trolled by the conventional dust collect- and piston designs. As a result, ac-
cells and liquifiers are either tied into ing equipment. ceptable performance can be obtained
a high stack for dispersion of the gas REFERENCES with a lower quality oil. Using a high
or tied to a scrubber to remove the quality lubricant will result in greatly
chlorine. In the latter case, the gas 1. Chemical Engineers Handbook, Thirdimproved performance.
Edition. J. Perry, Editor.
from the scrubber usually is vented to a 2. Dangerous Properties of Industrial Ma- Other significant features of blowby
tall stack. terials, N. Sax. diversion include reduced engine wear,
Air used for transferring liquid chlo- 3. Industrial Chemicals; Faith, Keyes, especially piston ring wear. In ad-
rine is also vented through this same and Clark. Reprinted with permission dition, the blowby is routed back into
from Faith, Keyes, and Clark—Indus-
scrubber—stack system. trial Chemical copyright 1957. John the combustion chamber and reburned,
The several aqueous waste streams Wiley and Sons, Inc. decreasing the air pollution rate.

Consulting Engineer Consulting Engineer Engineers and Consultants
Environmental Engineering
Water—Wastes—Refuse APPLICATION ENGINEERING Air Pollution Evaluation and Control
Services for Utilities and Industrials
Air Pollution Control FOR
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90 Journal of the Air Pollution Control Association