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Chlorate Production

CHLORATES, ELECTROLYTIC PRODUCTION

Sodium and potassium chlorate are produced


commercially by electrolysis
of aqueous solutions of the corresponding
chlorides. Other chlorates, which
have only limited commercial use, are made from
sodium chlorate by
metathesis.
The sodium salt, NAClO3, is made in an
electrolytic cell having no
diaphragm and usually having anodes made from
impregnated graphite. A few
cells in this country now use lead dioxide
anodes, while magnetite is also
employed to some extent in European cells.
Anodes may also be made of
platinum or platinum-clad titanium. Mild steel
is widely used for cathodes,
although stainless steel and graphite are also
employed. Steel, plastic, or
concrete are used for cell bodies. Cell covers
are plastic, asbestos-cement,
or some other inert, nonconductive material.

snip

This reaction is favored at temperatures


above 30C and at a pH below 7.
Under alkaline conditions and temperatures below
30C the hypochlorate will

remain unreacted. A typical chlorate cell is


shown in Fig. 1.

Chlorate cells are operated at such a low


temperature that not all of the

heat produced can be carried off by evaporation


of water from the

electrolyte. Therefore, cooling coils are


customarily employed. These coils

are usually of steel, located within the cell,


and are bonded to the cathode
to provide protection against corrosion.
External cooling of circulated

electrolyte may also be used. Owing to the


decrease of overvoltage at

higher temperatures, and its effect on heat


generation, the thermal

conditions are inherently stable and cooling


water may be controlled by a

setting on a hand operated valve. The difference


between the cell voltage

and the theoretical decomposition voltage (2.3


volts) represents the heat

which must be removed from the cell by cooling


methods.

Electrical supply and arrangement of chlorate


cell systems are similar to

those used in chlorine plants. Cells are usually


connected in one or more

electrical series operating at up to 600 volts,


but the electrolyte and

cooling water flows are in parallel.

The cell covers are provided with a gas duct


system to vent the byproduct

gas. Cell gas, principally hydrogen contaminated


with oxygen and chlorine to
the degree that it is usually not recovered, is
vented to the atmosphere. In

some systems air is drawn in over the vapor


space and mixed with the

hydrogen to drop its concentration below the


explosive limit. Cells may

also be sealed and operated with a high hydrogen


content in the vent gas.

Some facilities employ cells having bipolar


electrodes which are arranged

to divide a long narrow cell container into a


large number of parallel

chambers, each being an individual cell. One


side of each electrode is

anodic with the opposite side being the cathode


in the next chamber. Current

is introduced into the first electrode of the


battery and leaves from the

last. This arrangement allows a very simple


electrical bus system and a

compact arrangement of the cells.

No outstanding advantages can be attributed


to any particular cell

design. The operating success of a plant is


usually a function of the
chlorate plant in its entirety. Whereas past
practices have involved cells

containing a large volume of dead space to allow


retention time for the

conversion of hypochlorite to chlorate and


various cascade systems to allow

for liquor flow through groups of cells in


series, present practice tends

toward large cells having no dead space and


simple parallel liquor flow

through individual cells. Advantages of this


trend arise from the greater

electrolyzing capacity per unit area of floor


space and from simplified

operation of the cells. These changes in design


have not resulted in any

apparent loss in current efficiency.

Chlorate cells are not particularly sensitive


to variations in operating

conditions and will produce satisfactorily


within a wide range for each

variable. Thus, it is customary for each


facility to operate it's cells in

such a manner as to obtain maximum fiscal


economy, taking all plant expenses
into consideration. Therefore, it is not
possible to set forth exact

operating data for chlorate cells and the


following table merely contains a

representative range of characteristics based on


the use of graphite anodes.

As in the case of chlorine cells, chlorate


cells must be dismantled at

the end of the useful life of the anodes for


cleaning and anode replacement.

The absence, of a diaphragm in the chlorate cell


makes this repair

relatively simple.

It is customary to add several grams per


liter of sodium chromate to the

electrolyte to assist in maintaining pH on the


acid side and to reduce

corrosion effects on the metallic portions of


the cell (not usable with

lead dioxide anodes). In the event that either


the cell container or the

cooling coils are of metal, they are bonded to


the cathode to provide

cathodic protection against corrosion. Fig. 2 is


a basic flowsheet for
sodium chlorate production.

snip

loss of chlorine from the electrolyte.


Therefore, the stream being returned

to the cells from the rundown tank is acidified


with chlorine or

hydrochloric acid using automatic control based


on pH.

The feed to the crystallization system


contains hypochlorite ion which

must be removed by heating, air blowing, and/or


acid or thiosulfate

treatment. The feed is also made slightly


alkaline with caustic soda

following hypochlorite removal. Failure to


remove hypochlorite and acid will

cause serious corrosion problems in the


evaporator. The liquor is

subsequently filtered to remove anode mud and


other solids. If required by

the concentration of chlorate, the purified


liquor may then be evaporated in
continuous, multi-effect evaporators until
chlorate just starts to

precipitate. The liquor is then transferred to


either an evaporative or a

surface cooled crystallizer where


crystallisation takes place. In some

systems "salting out" of chlorate with sodium


chloride is employed.

Crystallizers may operate at temperatures as


low as -1OC. The slurry

from the crystallizer is continuously


centrifuged to remove chlorate

crystals, with the mother liquor being returned


to the rundown tank.

SNIP

Chlorates are reasonably stable but, since


they are very powerful

oxidizing agents, have a tendency to react


strongly with reducing agents.

Accordingly, great care must be taken that all


equipment and plant
facilities are kept clear of wood, oil,
combustible organic materials,

sulfur, ammonium salts, dust, and easily


oxidizable metals such as aluminum

and magnesium. Moving equipment must either be


run dry or lubricated with

water or fluorinated lubricants. Pump packings


must be of the noncombustible

type. Chlorate solutions are especially


dangerous with respect to materials

that are both absorbent and oxidizable. Rubber


and plastics, although

organic in nature, may be relatively safe for


certain applications provided

that they do not become impregnated with


solution, that they do not exude

organic materials such as oils and plasticizers,


and that their temperature

is kept well below the ignition point. Good


safety practice requires that

employees in chlorate facilities wear a complete


change of clean clothing

every day and that it be washed after each


shift. Clothing should also be

changed immediately in the event that it is


splashed with chlorate solution
since, when dry, chlorate-saturated fabric
becomes violently combustible.

Rubber shoes should also be worn since leather


easily impregnates with

chlorate solutions and becomes hazardous.


Chlorate solution will easily

creep into small cracks and other interstices in


equipment and then form

crystals. Upon crystallization, expansion occurs


which may cause serious

leaks. Chlorate solutions will also creep and


deposit crystals in cell

vents. Therefore, daily washdowns of plant


facilities are advisable.

Sodium chlorate is employed principally for


pulp bleaching (reactant for

chlorine dioxide generation), as a herbicide,


and as an intermediate for

the production of ammonium perchlorate, the


oxidizer for most solid rocket

propellants. Potassium chlorate is used in


matches, flares, and pyrotechnic

devices.
SNIP

Chlorate Cell Characteristics


Cell potential, volts 3.0 - 4.0
Cell current, amperes 1,000 - 30,000
2
Current density, amps/ft 30 - 80 (?)
Current efficiency % 60 - 70
Power consumption, kwh/ton NaClO3 6,000 - 7,000
NaClO3 in electrolite, g/l 150 - 600
NaCl in electrolite, g/l 50 - 200
Sodium chromate in electrolite, g/l 1-7
Temperature, C 30 - 50
pH 6.0 - 7.0
Graphite consumption, lbs/ton NaClO3 15 - 25
Graphite consumption, g/Kg NaClO3 6.8 - 11.4
Life of anodes, years 1-3
Anode-cathode spacing, inches 0.3 - 0.5

References

1) White, N. C., Trans Electrochem SOC., 92, 15 - 21 (1947).


2) Janes, Milton, ibid., 23 - 44.
3) Hampel, Clifford A., and Leppa, P. W., ibid 55 - 65.
4) Mantell, C. L., "Industrial Electrochemistry," 4th Ed., 342 - 347, New
York, McGraw-Hill Book Co Inc, 1960.
5) Kirk, R. E., and Othmer, K. F., Ed., "Encyclopedia of Chemical
Technology." Vol. 3, 707 - 715, New York, The Interscience
Encyclopedia, Inc., 1949.

Joseph B. Heitman
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