June 30, 1970 G, J, CRANE 3,518,173

CONTINUOUS MANUFACTURE OF CHLORATES AND PERCHLORATES

Fied Dec. 26, 1967

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United States Patent Office
3,518,173
CONTINUOUS MANUEFACTURE OF CHLORATES
AND PERCHLORATES
George J. Crane, Islington, Ontario, Canada; Ernest
Arthur Du Wernet and Selma Leslie Crane, execu
tors of the last will of said George J. Crane, de
ceased, assignor to Huron Nassau Ltd., Nassau,
Bahama Islands, a corporation of the Bahamas
Continuation-in-part of application Ser. No. 362,720,
Apr. 27, 1964. This application Dec. 26, 1967, Ser.
No. 693,551
Int, C. C01b 11/26
U.S. C. 204-95 4 Claims
ABSTRACT OF THE DISCLOSURE
The operation of a plurality of multipolar electrolytic
cells in the production of an alkali metal chlorate or
perchlorate, particularly sodium chlorate or perchlorate,
by the electrolysis of an electrolyte comprising an aque
ous solution of an alkali metal chloride on a continuous 20
basis. In the continuous operation, the electrolyte is par
tially electrolysed in a first cell and further electrolysed
in subsequent cells, in each cell the electrolyte being
continuously recirculated through the cell from a cell
tank to effect electrolysis, a small proportion of the re
circulating volume of the electrolyte in each cell being
continuously passed serially between the cells, fresh elec
trolyte being continuously fed to the first cell and elec
trolysed electrolyte being continuously withdrawn from
the last cell of the series. By the improved operation of
the multipolar cell according to the present invention, the
overall efficiency of the process for the production of
the alkali metal chlorate or perchlorate is substantially
increased.
This application is a continuation-in-part of U.S. appli
cation No. 362,720 filed Apr. 27, 1964, now abandoned.
The present invention relates to the production of
alkali metal chlorates and perchlorates by the electroly
sis of an electrolyte comprising an aqueous solution con
taining an alkali metal chloride in multipolar electrolytic
cells. In particular the present invention relates to the
production of such alkali metal chlorates and perchlo
rates in which the multipolar cells are operated upon a
continuous basis, and in which the electrolyte is partially
electrolysed in each of a series of cells, a small portion
of the electrolysed electrolyte from each cell being serial
ly continuously passed to the next adjacent cell for fur
ther electrolysis.
The electrolytic production of an alkali metal chlorate
or perchlorate particularly sodium chlorate or perchlorate
has heretofore been effected by the electrolysis of an
electrolyte comprising an aqueous solution containing an
alkali metal chloride suitably at a pH in the range 6-7
and more preferably in the range 6.5-6.8, the electrolyte
usually containing electrolytic aids such as acid chro
mate. While initially such electrolysis was conducted in
monopolar electrolytic cells, it has been found that the
electrolysis of the electrolyte in multipolar electrolytic
cells has many advantages over operation in monopolar
electrolytic cells. However, while it is conventional to
operate monopolar electrolytic cells on a continuous basis
effecting partial electrolysis of the electrolyte during a
single pass of electrolyte in each cell, due inter alia to
volume and electric power consideration it has hereto
fore been considered commercially necessary to operate
the electrolysis in multipolar electrolytic cells on a batch
basis even allowing for the recognized disadvantages of
batch operations such as loss of time in stopping and
starting the process including emptying and filling the
3,518,173
Patented June 30, 1970
2
cell tanks in which the multipolar cells are normally lo
cated.
A multipolar electrolytic cell with which the present
invention is concerned, is an electrolytic cell which con
sists of a number of cell units which are electrically
connected in series but through which the electrolyte
flows in parallel. It is formed from a pair of monopolar
electrodes which have the same polarity on all surfaces
and through which surfaces current enters or leaves the
O cell at the same polarity relative to the surrounding elec
trolyte. Dividing the space between the monopolar elec
trodes are a plurality of spaced intermediate bipolar elec
trodes which are at a positive polarity on one side and
a negative polarity on the other side with respect to the
electrolyte. In such a cell the total voltage impressed be
tween the two monopolar electrodes which is typically of
the order of 100 to 250 volts is taken up by the bipolar
electrodes such that the sum of the difference between
the voltage on adjacent bipolar electrodes is equal to the
aforesaid total voltage. Thus, for instance, in a cell con
taining 24 bipolar electrodes operating at a voltage of
100 volts between the monopolar electrodes there would
be a difference of 4 volts across each pair of adjacent
electrodes (which form a cell unit) and there would be
25 individual separate electrolytic cell units between each
pair of monopolar electrodes each of which units oper
ates at a different voltage. The multipolar electrolytic
cell in the production of the alkali metal chlorates and
perchlorates is normally located in a tank which contains
30 the electrolyte, the electrolyte being recirculated in par
allel through the cell units conventionally from the bot
tom of the cell to the top of the cell and back into the
tank during which pass through the cell it is subjected
to electrolytic action i.e. electrolysis. During its residence
time in the tank the relatively slow chlorate producing
reaction involving the combination of the hypochlorous
acid and the hypochlorite ion according to the equation
2HClO--OCl =ClO-2HCl takes place, the hypo
chlorous acid and hypochlorite ions being generated by
40 a relatively fast reaction occurring in the electrolytic cell.
In conventional batch operation of the multipolar electro
lytic cell system for the production of sodium chlorate
and perchlorate, the recirculation of the electrolyte
through the cell from the tank is continued until the de
45 sired concentration of sodium chlorate or perchlorate is
obtained in the electrolyte in the tank whence the cell
operation is then shut down, the electrolyte removed
from the tank and sent for further processing for the
recovery of the sodium chlorate and perchlorate, the cell
50 tank and the cell cleaned and then filled up with fresh
brine solution for subsequent batch operation. The com
pletion of the electrolysis process normally takes from
5 days to 2 weeks depending upon the liquid capacity of
the tank in relation to the electric power applied to the
55 multipolar cell. During the process, the electrolyte is
enriched periodically with more brine when a chlorate is
manufactured or with a chlorate solution when a perchlo
rate is manufactured. In addition, water is periodically
added to replace that which has been electrolysed or
60 evaporated during the process. In a typical chlorate plant
a number of multipolar electrolytic cells and their tanks
will be present all of which are operated upon a batch
basis and the usual output from a single tank varies from
200-2000 tons per year depending upon its size.
65 In contrast to the multipolar electrolytic cell with which
the present invention is concerned, in a monopolar cell
each cell is an integral unit having monopolar electrodes
only and in each cell unit there is a separate flow in and
out of the electrolyte and a separate flow of electricity
70 from and to each cell unit.
In monopolar cell operation with all the cells in series
the total volume of electrolyte is typically of the order
 3,518,173
3 4.
of 2000 cubic feet and from this point of view, it would
be extremely difficult to operate monopolar cells on a
batch basis as in a batch system using for instance 40
cells, there would have to be 40 separate operations and
40 storage tanks and it has become in the operation of
monopolar cells standard practice to operate monopolar
cells with the electrolyte flow in series, the electrolyte
passing between the electrodes of each cell once only.
In contrast to the 2000 cubic foot flow of electrolyte in
the monopolar cell system, in a multipolar cell System
having say 4 cells the electrolyte volume would be some
thing in the order of 20,000 cubic feet and in view of
the relatively large volume involved and inherently in
a multipolar electrolytic cell, you have a large tank for
each cell each with a volume of electrolyte greater than
the total of the monopolar cells, it has not heretofore
been considered necessary or even desirable to operate
these multipolar electrolytic cells in series and it has
been considered conventional to operate multipolar elec
trolytic cells in the production of alkali metal chlorates
and perchlorates on a batch basis of about 8-14 days
per batch per cell.
In similar vein, operation of 40 monopolar cells in
series which typically operate at 50 kw. involves 2,000
kw. in the whole system. However, with a single multi
polar electrolytic cell operation there is somewhere be
tween 1,200-2,500 kw. loading and it will be readily
seen that from the electrical point of view, a single
multiplar cell operating on a batch basis is equivalent to
a plurality of monopolar cells operating upon a series
basis.
Thus, heretofore, it has not been considered to be
worthwhile to operate multipolar electrolytic cells in the
production of an alkali metal chlorate or perchlorate
on a continuous basis because a single multipolar elec
trolytic cell operating on a batch basis is involved with a
volume of electrolyte substantially in excess of the volume
of electrolyte which can be handled by a plurality of
monopolar electrolytic cells operating in series, and fur
ther a single multipolar cell operating on a batch basis
involves the same electrical loading as a plurality of
monopolar electrolytic cells operating in series. In par
ticular, it has heretofore been considered that a multipolar
electrolytic cell operating on a batch basis is equivalent
to a plurality of monopolar electrolytic cells operating
upon a series basis and there is no equivalency whatso
ever between operating a monopolar cell System on a
continuous basis and operating a multipolar cell system
on a continuous basis as completely different considera
tions are involved. However, while as aforesaid operation
of a multipolar cell on a continuous basis has not hereto
fore been considered to be economically advantageous,
it has been considered that there are decided disadvan
tages to operating a multipolar electrolytic cell in the
production of an alkali metal perchlorate or chlorate on
a continuous basis and up to the present invention all
major sodium chlorate and perchlorate producers in the
United States and Canada who were producing sodium
chlorate and sodium perchlorate using monopolar cells
and multipolar cells have been running their monopolar
cells on a series basis and their multipolar cells on a
batch principle. In particular, it was theretofore con
sidered to be disadvantageous to operate multipolar elec
trolytic cells in the production of sodium chlorate or
perchlorate on a continuous basis as after every batch
operation in the multipolar electrolytic cell operation the
cell had to be pumped clear and washed out thoroughly
to remove the accumulation of graphite dust and crud
and it was thus considered in view of the fact that this
cleaning was necessary there Would be no advantage in
operating continuously, because each cell would have
to be periodically emptied and cleaned out anyway, so
batch operation of the multipolar electrolytic cells seemed
the natural way to effect the operation. Thus, to operate
on a continuous basis, it would be necessary to provide
each multipolar cell with some means of removing the
graphite dust and crud during the operation of the cell
which would entail capital expenditure in research which
was not heretofore considered to be worthwhile.
5 Further, operating the multipolar electrolytic cell on a
batch basis, the electrolyte starts out with a pure brine
and finishes up with an electrolyte containing a mixture
of sodium chloride and sodium chlorate. The electric
power requirement is a function of the voltage across the
O cell and the voltage is a function of the sodium chloride
concentration and hence batchwise operation it was con
sidered would give greatest efficiency because with series
electrolytic flow the average sodium chloride concentra
tion is lower than that with batch operation.
In summary therefore, as the state of the art stood
before the present invention, it was generally considered
that operation on a continuous basis of multipolar elec
trolytic cell in the production of sodium chlorate and
perchlorate was not necessary and there were obvious, on
20 the face of it, disadvantages in effecting such a process
and the teaching of the prior art is against using a con
tinuous operation.
It has now been found according to the present inven
tion that there are advantages to operating a multipolar
electrolytic cell on a continuous basis which far outweigh
the aforesaid disadvantages set forth heretofore which
advantages were not obvious before the present inven
tion. Further, applicants have found that the optimum
advantages are to be obtained by operating the multi
30 polar cells on a continuous basis and in particular effect
ing partial electrolysis of the brine in each of the multi
polar electrolytic cells and continuously passing a small
proportion, usually of the order of 10%, of the recir
culating volume of electrolyte in each of the multipolar
35 electrolytic cells to a subsequent cell for further elec
trolysis, fresh electrolyte being added to the first of the
electrolytic cells and electrolysed electrolyte being re
moved from the last of the electrolytic cells.
According to the present invention therefore, there is
40 provided in the production of a compound selected from
an alkali metal chlorate and an alkali metal perchlorate
particularly sodium chlorate and sodium perchlorate
which includes electrolysing an electrolyte comprising
an aqueous solution of an alkali metal chloride in a
plurality of multipolar electrolytic cells in which the
electrolyte is continuously recirculated through each cell
during electrolysis from an individual cell tank the im
provement which comprises providing a continuous serial
flow of a small proportion of the volume of electrolyte
50 recirculating in each cell tank between said cells, partially
electrolysing the electrolyte in the first of said cells and
effecting further partial electrolysis of said electrolyte in
each of the Subsequent cells of said series, continuously
introducing fresh electrolyte into the cell tank of said
55 first cell and continuously removing electrolysed elec
trolyte from the cell tank of the last of said cells of said
whereby to effect the process on a continuous
aSS.
Thus, applicants have found in contrast to convention
60 all thinking in the operation of multipolar cells for the
production of sodium chlorate and sodium perchlorate it
has now been unexpectedly found that continuous opera
tion according to the present invention gives greater ef
ficiency than batch operation because it is possible by
continuous operation to control and maintain constant
the temperature of the electrolyte, its pH and the hypo
chlorite content of the electrolyte in each stage of the
process, i.e. in each multipolar electrolytic cell system.
In particular, with batch operation initially the tem
perature of the brine is at ambient temperautre, for in
stance 20 C. and at 20 C. to operate the process more
power, i.e. kilowatts are required than operating at a tem
perature of 40 C. Therefore, when operating on a batch
basis until the temperature of the electrolyte reaches 40
C. the efficiency of the process is not optimum. On the
 3,518,173
5 6
other hand, operating on a continuous basis as according the preceding cell without necessitating an overall shut
to the present invention makes is possible to maintain the down.
temperature of the liquor in all the tanks at optimum op Finally a substantial advantage according to the inven
erating temperature, e.g. 40 C. and therefore the process tion is whereas when the cells are operated on a batch
is always operating at this optimum temperature and this basis, they require a wash-down and particular removal
increases the efficiency of the process. Further in the proc procedure every week or two, when operating according
ess starting with fresh brine, the pH changes extremely to the present invention this problem is removed and the
rapidly because the sodium chloride must first break down graphite and crud level in the cells are no substantial
into sodium hypochlorite and hypochlorous acid before problem. Thus, due to the continuous removal of the
forming the sodium chlorate. The product is thus initially 10 product from the top level of the electrolyte the harmful
a strong base and a weak acid and in practical terms when particles are continuously removed as formed and are
fresh brine is put into the electrolytic cell with an adjusted pumped out to the product collector tank. They do not
pH of 6.8, as is required in the process, after 20 minutes have time to settle or coagulate and no down time is re
operation the pH would be about 8 and more acid must quired for washing. Further operation is consistently bet
be added quickly to bring the pH close to 6.8 so that 5. ter because the cells do not clog with extraneous mate
the electrolyte contains the correct proportions of hypo rial which is unexpected and effectively increases the an
chlorous acid and sodium hypochlorite. If the propor nual cell output capacity by some 2% because of shut
tions are incorrect, power consumption increases as much. down elimination.
as 50% because the sodium chlorate is made by different The present invention will be further illustrated by way
chemical route. In contarst thereto, operating on a con 20 of the accompanying drawing which is a perspective side
tinuous basis it is possible to automatically maintain the elevation of three multipolar electrolytic cells and their
pH of the electrolyte and the hypochlorite content of the associated tank the third of which is partially broken
electrolyte essentially constant and thus avoid excessive away adapted for operation according to the present in
power consumption. vention.
Again, operation of the multipolar electrolytic cell ac 25 Referring to the drawing there is provided a third mul
cording to the present invention and the production of tipolar electrolytic cell 1 disposed in a tank 2 on a block
sodium chlorate and perchlorate on a continuous basis 3, the tank 2 containing the electrolyte surrounding the
has the advantage of reducing the loss of time required cell wall, the electrolyte being cooled by means of coils
to empty and replenish the multipolar cells operating on 4 disposed therein through which coils 4 water is passed
a batch basis and further avoid the use of large storage 30
via lines 5 and 6. The electrolyte is passed into the elec
containers which are necessary in a batch process and trolytic cell 1 through inlets 7 in a block 8 attached to the
equalizes out the voltage considerations which are re outside walls of the cell 1 and pass upwardly through
quired due to the changing composition of the electrolyte the cell 1 either by natural circulation or by means of a
on a batch basis. In particular, during the emptying of a pump (not shown) and back into the cell tank 2 via the
cell tank after completion of a batch process, the entire outlets 9 in the block 10 also attached to the outside of
facility on the same circuit must be disconnected and since the walls in the cell 1.
emptying and filling the tank requires approximately 1 to Located in the cell 1 are a pair of monopolar elec
3 hours a typical plant of 4 to 8 cell tanks on one circuit trodes 11 one of which is connected to the positive of
will incur a lost production time of 5-15%. 40 an electrical supply by means of a copper conductor 12
Further, operating the electrolysis in the multipolar and the other of which is connected to another monopolar
electrolytic cells on a batch basis means that the elec electrode 11a in the second cell 1a by means of the cop
trolyte in each of the cell tanks must be separately an per conductor 13. Between the monopolar electrodes 11
alyzed and controlled by adding the various materials in the cell 1 are bipolar electrodes 14 which effectively
such as water, brine, acid chromate, and soluble calcium divide the cell up into a series of cell units each of which
salts when they become depleted in the electrolyte and 45 has an inlet 7 and an outlet 9 in communication therewith
further as the electrolyte becomes enriched in the sodium Such that the electrolyte recirculating through the cell 1
chlorate the voltage necessary for maintaining the cur passes in parallel throught the cell units formed between
rent flow through the cell is increased. As an example a the electrodes 14 and also between the adjacent elec
freshly filled tank would require only 100 volts for a full trodes 14 and 11. During passage through the cell 1 the
production rate but the same tank when electrolysis is 50 electrolyte which comprises an aqueous solution contain
finished would require about 120 volts. Since this varia ing sodium chloride and other electrolytic aids at a pH
tion takes place across each cell tank the voltage supply of approximately 6.8, is partially electrolysed to produce
must be variable over the relatively large range. This in hypochlorous acid and sodium hypochlorite which then
creases the capital cost of equipment and increases the 55
converts slowly to sodium chlorate in the cell tank 2.
peak amount for electrical energy and hence the cost per Disposed beneath the outlet 9 in the block 10 is a
kw. hr. of electric power will increase. By operating on a trough 15 which collects the effluent from the outlet 9
continuous basis it is possible to operate each cell at a before passage to the tank 2 by means of overflowing
substantially constant voltage depending upon the concen from the trough 15 and a small proportion of the electro
tration of sodium chloride in each cell tank and thus the lyte is continuously removed from the tank 2 accord
demand for electrical energy will remain substantially 60 ing to the present invention by means of the scoop 16
constant there being no peak demand. at the end of the arm 17 which is adapted to rotate on
Again according to the present invention when operat the axis 18 in the direction shown by the arrows. The
ing a multipolar electrolytic cell on a batch basis the elec electrolyte on rotation of the arm 17 is passed into the
trolyte will remain in each cell for something of the 65 channel member 19 from whence it is taken for further
order of 5 days to 2 weeks whereas with the process of processing for the recovery of the sodium chlorate from
the present invention the electrolyte remains in each cell the liquor. Electrolyte passes into the cell tank 2 from
tank for only a few hours and further the accurate con- . the cell tank 2a by means of channel wires 19a bridging
the cell tanks 2 and 2a and supplied from a trough 15a
trol of each cell tank as is possible according to the pres
ent invention decreases the operating hazard through re 70 in the cell tank 2a by means of scoops 16a which remove
electrolyte from the trough 15a on rotation of the arm
duction of foam containing hydrogen or oxygen. Still 17a on the axis 18a in a similar manner as aforesaid.
further, by operating on a continuous basis according to The second multipolar cell 1a and its associated tank
the present invention should a cell operation fail, or other 2a are of the same structure as the multipolar cell 1 and
wise become unmanageable it can be taken out of op its associated tank 2 as is the first multipolar cell 1b and
eration and bypassed with the electrolysed effluent from 75 its associated tank 2b, the only difference being that the
 3,518,173
7 8
monopolar electrode 11b in the first cell 1b is connected ditions of operation of each of the five cells is given in the
to a negative source of power through the copper con following table:
TABLE
Feature No. 1 Cell No. 2 Cell No. 3 Cell No. 4 Cell No. 5 Cell
EICO and NaClO in electrolyte (g.p.l.).-------- 3 3 3 3.2 3.3
NaCl, g.p.. in electrolyte---------- 288, 6 265.6 240.7 23.6 185
NaClO3, g.p.l. in electrolyte 56. 115 177.5 243.5 312
Voltage to ground--------- -210 -106 O -H110 --222
CaCl2, g.p.l. in electrolyte. .. 2 .. 2 .. 2 2 .. 2
Sodium dichromate in electrolyte 0.2 0.2 0.2 0.2 0.2
Flow, U.S. g.p.m. ------------------------------ 3.2 to 13, 2 to 12.9 to 12, 5 to 12.2

ductor 20 and the cell tank 2b is applied with a fresh
aqueous solution of sodium chloride by means of line
21 and a pump (not shown).
In operation the electrolyte in each cell recirculates
around the cooling coils 4 and through the cell between
the electrodes where it undergoes partial electrolysis.
The rotating scoops 16, 16a and 16b continuously trans
fer electrolyte from the trough 15, 15a and 15b into the
channel members 19, 19a and 19b whereby a small pro
portion usually in the order of 10% is transferred con
tinuously to the next cell tank, fresh brine in an equal
volume being introduced through line 21 into the first
tank 2b. In a typical cell with 10.0 bipolar cell units oper
ating at 10,000 amps the recirculation rate of the electro
lyte in any particular cell tank will be of the order of
500-800 gallons per minute and there will be a forward
transfer flow from cell to cell of something of the order
of 10 gallons per minute. The drawings of the present
invention are of course simplified drawings for the pur
poses of understanding the present invention and thus
there are only three cell units so shown with their associ
ated cell tanks and the number of electrodes in the cells
of course does not represent the conventional actual num
ber which as aforesaid is of something of the order of
100 electrodes or more.
The present invention will be further illustrated by way
of the following example.
EXAMPLE
Five multipolar electrolytic cells were set up for serial
flow of electrolyte substantially as shown in the accom
panying drawing, each cell containing 120 graphite elec
trodes, five of which were monopolar electrodes and the
rest, bipolar electrodes. The volume of electrolyte re
circulating in each cell was approximately 20,000 cubic
feet the temperature of the recirculating electrolyte was
maintained at about 40 C. and the pH of the electrolyte
was maintained at 6.8 by the periodic automatic injec
tion of the hydrochloric acid therein, the ratio of hypo
chlorous acid to sodium hypochlorite in the recirculating
electrolyte in each cell being maintained automatically
by maintenance of said pH at about 1 to 2. Brine con
taining 310 grams per litre of sodium chloride a trace of
calcium chloride and a small amount, 0.2-- or -0.1 gram
per litre, of sodium dichromate was fed at a rate of 13.5
U.S. gallons per minute to the first cell. The relevant con
From the last cell numbered 5 a liquor was obtained
at a rate of 11.8 U.S. gallons per minute containing 1.85
grams per litre of sodium chloride, 312 grams per litre
of sodium chlorate, 0.2 gram per litre of calcium chloride
and 0.2 gram per litre of sodium dichromate which was
then for further processing. The cells were all operated
at a current of 900 amperes and the voltage to ground
was periodically reversed to even out anode and cathode
Wea.
I claim:
1. In the production of a compound selected from an
alkali metal chlorate and an alkali metal perchlorate
which includes electrolysing an electrolyte comprising
an aqueous solution of an alkali metal chloride in a plu
rality of multipolar cells in which the electrolyte is con
tinuously recirculated through each cell during electroly
sis from an individual cell tank the improvement which
comprises providing a continuous serial flow of a small
30 proportion of the volume of electrolyte recirculating in
each cell tank between said cells partially electrolysing
the electrolyte in the first of said cells and effecting fur
ther partial electrolysis of said electrolyte in each of the
subsequent cells of said series continuously introducing
35 fresh electrolyte into the cell tank of the first cell and
continuously removing electrolysed electrolyte from the
cell tank of the last of said cells of said series whereby
to effect the process on a continuous basis.
2. The process as claimed in claim 1 in which the
40 alkali metal is sodium.
3. The process as claimed in claim 1 in which up to
10% of the recirculating electrolyte in a cell tank by vol
ume is continuously removed and passed into the cell.
4. The process as claimed in claim 1 in which the
small proportion of electrolyte is removed from the Sur
face of the electrolyte in the cell tank.
References Cited
UNITED STATES PATENTS
50
3,287,251 11/1966 Horne et al. --------- 204-95
DANIEL E. WYMAN, Primary Examiner
J. M., HICKEY, Assistant Examiner
55
U.S. C. X.R.
204-82