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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