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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
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
WILLIAM T. INGRAM
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