You are on page 1of 8

United States Patent 1191] [11] 4,339,312

Brooks et al. [45] Jul. 13, 1982


[54] CONTINUOUS PROCESS FOR THE DIRECT 3,824,172 7/1974 Hodges ............................. .. 204/269
CONVERSION OF POTASSIUM CHLORIDE 3,878,072 4/1975 Cook etal. 204/95
TO POTASSIUM CHLORATE BY 3,883,406 5/1975 OBrien et a1. 204/95
ELECTROLYSIS 3,940,323 2/1976 Cook .... ..... .. 204/95
3,943,042 3/1976 Cook ............ .. 204/95
[75] Inventors: Wayne E. Brooks, Bryan, Tex.; 3,948,748 4/1976 Messner et al. 204/95
Jimmie R. Hodges, Downingtown, 4,046,653 9/1977 deNora et a1. 204/95
Pa.; Morris P. Walker, Benton, Ky. 4,075,077 2/1978 Hodges ............................. .. 204/269

[73] Assignee: Pennwalt Corporation, Philadelphia, Primary ExaminerHoward S. Williams


Pa. >
[57] ABSTRACT
[21] Appl. No.: 185,972
A continuous closed-loop process for directly produc
[22] Filed: ' Sell- 10, 1980 ing potassium chlorate by electrolysis of an aqueous
[51] Int. C1.3 .................... C25B 1/14; (325B 1/26 potassium chloride solution with a metal anode is de
[52] U_s_ CL _________________ u scribed. The process provides surprising advantages in
[58] Field of Search ........................................ .. 204/95 efficiency by comparison with conventional double
Y _ decomposition processes for producing potassium chlo
[56] References Clted rate from electrolyzed sodium chloride.
U.S. PATENT DOCUMENTS
3,329,594 7/1967 Anthony et a1. .................... .. 204/95 10 Claims, 3 Drawing Figures

STEAM

. VAPOR
0 CELL o
KCI BRINE CELLS IS] F _ LIQUOR 200 F 10%? H20
STRIPPING
2a * Hg VAC
Lsou111c| COND
MOTHER 11011011 m -=:- E;
I |08F if 5.:
_; f?vMOTHER LIQUOR
RESATURATION " '

20% 1110, l '

SLURQRY
'08 F
((VACUUM cooum; CYCLONE
CRYSTALLIZER

CENlR|FUGE-~
US. Patent Jul. 13, 1982 Sheet 2 of3 4,339,312

SOLID KC!

SOLID KCHOB

0c 30C 50C s0c 70c 80C 00% 3 B


| | | I l I | | | I r '
048l2162024283236404448525660
KCIOE, (GRAMS PER I00 GRAMS H20)

Fig . 2
4,339,312
1 2
out, chlorine is produced at theanode while alkali metal
CONTINUOUS PROCESS FOR THE DIRECT hydroxide forms at the cathode. The chlorine and hy
CONVERSION OF POTASSIUM CHLORIDE TO droxyl ions are thus free to react chemically to form
POTASSIUM CHLORATE BY ELECTROLYSIS alkali metal hypochlorite, as is shown by the following
equation illustrating the process with potassium:
FIELD OF THE INVENTION
This invention relates to the production :of alkali
metal chlorates, in particular, potassium chlorate, di
rectly by the electrolysis of an aqueous solution of the
corresponding chloride. 10 W

BACKGROUND OF THE INVENTION


Historically, commercial quantities of potassium
chlorate have been produced by the double decomposi
l
3 KClO + 3 K_Cl + 3 HOH
tion of sodium chlorate and potassium chloride;
The hypochlorite rapidly converts to form chlorate;

The sodium chlorate used in this process has ordinarily


been produced directly by the electrolysis of an aqueous
sodium chloride solution in an electrolytic cell. To each The reversible nature of the formation of alkali metal
batch of sodium chlorate produced potassium chloride hypochlorite accounts for signi?cant process inef?cien
is added stoichiometrically; the resulting KClO3/NaCl cies where oxygen is liberated into the cell liquor when
solution is cooled; and the KClO3 crystals that form are the hypochlorite decomposes instead of disproportion
separated from the solution. The industry practice has ating into the chloride and the chlorate. Prior to the
been to boil down the remaining solution, or mother 25 advent of metal anodes, the direct production of potas
liquor, to adjust the water concentration to the level sium chlorate was uneconomical because the low solu
employed in the electrolytic cell and to return the con bility of KClO3 in water at the temperature previously
centrated liquor to the cell for further electrolysis with employed (e.g. 4-5% in H2O at 30 C.) limited the re
the NaCl added by the above reaction to produce more covery of KClO3 when compared with the yields avail
sodium chlorate according to the reaction 30 able in the conventional double decomposition process.
US. Pat. No. 4,046,653 discloses a process for pro
ducing sodium or potassium chlorate by the direct elec
Since the separation of KClO3 is not 100% ef?cient, trolysis of the corresponding chloride at temperatures
potassium ions will inevitably be present in the concen of 90ll0 C. The working example that discloses the
trated liquor returned to the cell, necessitating the oper 35 electrolysis of potassium chloride starts with a solution
ation of the cell at high temperatures to prevent the containing 300 g per liter of solution as a starting elec
crystallization of the potassium. These hightempera trolyte, achieving concentrations of 90 g/l potassium
tures and the potassium ions present cause very rapid chloride and 210 g/l potassium chlorate at steady state
wear results in high equipment costs, while labor costs operating conditions. While this patent discloses the
are elevated by the fact this process is carried out in a discharge of an equal volume of electrolyte from the
batch, rather than on a continuous, basis. cell as the KC] brine is fed in, we have determined that
US. Pat. No. 3,883,406, the disclosure of which is it is not possible to operate a closed loop process in
fully incorporated herein by reference, is directed to a accordance with this patent using only a saturated brine
process for recovering electrolytically produced alkali without adding additional solid KCl directly to the cell
metal chlorates obtained by the direct electrolysis of 45 electrolyte and that the results stated are not signi?
sodium chloride to sodium chlorate in diaphragmless cantly different from those expected from the electroly
cells equipped with dimensionally stable anodes of a sis of sodium chloride. In contrast, our process pro;
valve metal, such as titanium, coated with a noble metal duces surprising results in ef?ciency increases not ac
and/or oxide thereof. The discussion of the prior art in counted for by the heavier weight of potassium chlo
this patent explains that NaCl is less soluble than Na 50 rate.
Cl03 at the temperatures conventionally used, so that
during the concentration and evaporative cooling steps SUMMARY OF THE INVENTION
of the prior art, NaCl crystals separate from the cell We have invented a continuous closed-loop process
liquor ?rst and are removed by ?ltration or centrifuga for directly producing potassium chlorate by electroly
tion. This NaCl may then be redissolved and returned to 55 sis of an aqueous potassium chloride solution, providing
the cell. US. Pat. No. 3,883,406 itself discloses pro the ?rst practical metal anode process for producing
cesses wherein solutions are achieved having chlorate potassium chlorate by electrolysis and providing sur
concentrations in excess of 700 grams NaClO3 per liter prising advantages in ef?ciency by comparison with the
and chloride concentrations as low as 40 grams NaCl conventional double decomposition process for produc
per liter. At the high chlorate/chloride concentrations ing potassium chlorate from sodium chloride.
obtained, evaporative cooling causes the chlorate to This invention provides a continuous closed-loop
crystallize ?rst if suf?cient vacuum is applied. The par process for the direct production by electrolysis of
ticular advantages of the process disclosed in US Pat. potassium chlorate from potassium chloride, wherein an
No. 3,883,406 are achieved by electrolyzing the NaCl aqueous solution of potassium chloride is electrolyzed
solution to produce a ratio of NaClOgzNaCl of at least 65 in a suitable electrolytic cell having a metal cathode and
5:1 and preferably at least 7:1. a metal anode coated with a precious metal or a pre
When the direct electrolysis of alkali metal chlorides cious metal oxide. The base of the metal anode may be
to alkali metal chlorates in. aqueous solution is carried a metal selected from the group consisting of titanium,
4,339,312
3 4
zirconium, tantalum and hafnium, with titanium being inefficiencies of the prior art double decomposition
preferred. The coating may be a precious metal, for process.
example platinum, etc.; an alloy, for example platinum Another important feature of this invention is the
iridium alloy, etc.; an oxide, for example ruthenium provision of a process for producing potassium chlorate
oxide, titanium oxide, etc., including mixtures thereof; that can be practiced in the same apparatus used to
or a platinate, for example lithium platinate, calcium convert sodium chloride to sodium chlorate electrolyti
platinate, etc. After the solution has been subjected to cally, while providing unexpected increases in current
electrolysis and at least part of the potassium chloride in efficiency and power consumption.
the solution has been converted to potassium chlorate, Yet another feature of the invention is that it provides
the solution is removed as an ef?uent from the cell and 10 a process for producing potassium chlorate that may be
is cooled until crystals of the chlorate form. This cool practiced within a wide range of operating conditions
ing may be adiabatic, e.g. under a vacuum, or it may be without detriment to the efficiency of the process.
carried out by refrigeration. After the crystals have These features and other advantages of this invention
formed, they are removed from the effluent by conven will be apparent to persons skilled in this art from read
tional means. The ef?uent that remains is enriched by ing the speci?cation and the claims appended hereto.
adding a controlled amount of potassium chloride to the
effluent either as solid potassium chloride or as a con BRIEF DESCRIPTION OF THE DRAWINGS
centrated potassium chloride brine. This enriched ef?u FIG. 1 is a flow diagram depicting the process of this
ent is then returned to the electrolytic cell as part of the invention.
aqueous solution for further electrolysis, at a volume FIG. 2 is an equilibrium phase diagram showing
rate equal to the rate at which the unenriched ef?uent is graphically the parameters of the broad scope of this
removed from the cell for cooling crystallization. invention. .
In particular, this invention involves a process FIG. 3 is an equilibrium phase diagram depicting the
wherein the ef?uent removed from the electrolytic cell more preferred parameters of operation of the process
contains about 820% by weight KCl and about 820% 25 according to this invention.
by weight KClO3, in the .ratio of about 0.5-2.5 parts by
weight KCl to each part by weight KClO3. In particu DETAILED DESCRIPTION OF THE
lar, the effluent may contain about 10% KClO3 by INVENTION
weight and less than about 15% KCl by weight. The 30 In this invention potassium chloride is converted by
invention further comprehends electrolytic cell ef?u direct electrolysis into potassium chlorate in electro
ents which contain about 10-14% KClO3 and 10-16% lytic cells using titanium anodes, for example. We em
by weight KCl. As will be discussed further below, the ploy in our process cells as disclosed in either U.S. Pat.
operation parameters of the process in accordance with No. 3,824,172 or U.S. Pat. No. 4,075,077, the disclosures
this invention are described in FIGS. 2 and 3 of the 35 of which are hereby incorporated fully by reference.
drawings. The process according to this invention may The cells are operated individually or in groups em
be particularly carried out within the area HIJK as set' ploying series or parallel ?ow, so that the ?nal cell
forth in FIG. 2. product contains 820% KClO3 and 820% KCl. These
In addition to the above characteristics and attributes, solutions preferably have a ratio of chloride to chlorate
the process in accordance with our invention may also of at least about 05:1 and not more than about 2.5:1.
include a step, interposed in the process at the point FIG. 1 shows the steps of the process by reference to
after which the effluent is removed from the electro the apparatus components and general process condi
lytic cell and before the effluent is subjected to cooling tions we employ.
crystallization, wherein any elemental chlorine present When the cell product, or ef?uent, is removed from
in the effluent is stripped therefrom. In carrying out the45 the cell or cells, it may optionally be passed through a
process in accordance with this invention, which is stripper to remove dissolved elemental chlorine from
exothermic in nature, we have found that the tempera the ef?uent before it is cooled. The stripped ef?uent
ture of the electrolytic cell can be controlled when the liquor then passes to a cooling crystallizer, which may
cell is equipped with coils or, preferably, when the cell be operated either under a vacuum or with refrigera
liquor is passed through a heat exchanger through 50 tion. Preferably, the ef?uent is cooled under a high
which is passed water at a temperature which is above vacuum (28 in. Hg) to a temperature of about 100 F.
the temperature at which the KClO3 will crystallize (38 C.) at which point KClO3 crystals form as a slurry
from aqueous solutions when it is present in the concen at the bottom of the crystallizer. The KClO3 product is
trations selected for use in the process. This may be rendered from the slurry by a conventional cyclone and
accomplished in an intermediate step, either before or 55 a centrifuge. The mother liquor ef?uent, now a dilute
after crystallizing the KClO3 from the ef?uent. After KCl solution with some residual KClO3 in it, passes
operation of the cell over a period of time, the concen through a resaturator, where solid KCl (or KCl brine) is
trations of KCl and KClO3 in the electrolyte will reach added to restore the concentration of KCl in the liquor
an equilibrium. In the resaturation or enriching step that to its pre-electrolysis concentration. This enriched li
is part of the invention herein, suf?cient solid KCl, or 60 quor is then returned to the electrolytic cell, completing
KCl brine, is added to the ef?uent to restore the KCl the closed-loop process. Of course, water may also be
concentration in the enriched ef?uent that is returned to added to the liquor in the resaturator to control cell
the cell to the level of KCl concentration in the equilib concentrations. In carrying out this process persons
rium solution electrolyzed in the cell. skilled in this art will adjust the electrolyte pH, use
One of the main features of this invention is the provi 65 suitable buffering agents, e.g., sodium dichromate, and
sion for the ?rst time of a practical continuous closed otherwise optimize process conditions, in light of the
loop process for the direct conversion of potassium disclosures of U.S. Pat. Nos. 3,824,172 and 4,075,077
> chloride to potassium chlorate, without the attendant and conventional practices in this art.
4,339,312
_-5 6
The equilibriumuphase diagrams FIGS. 2 and 3 illus > The particular, and surprising, advantages of the
trate the parameters of Operation of this process. In process according to our invention are illustrated by the
FIG. 2, area ABC represents the theoretical range cov following Table 1: "
TABLE 1
COMPARISON OF ELECTROLYSIS
- - KCIO3 VERSUS NaClO3
pI-I = 6.5
Na2Cr207 = 5.0 g/l .
Current h , Power Usage % Oxygen ,
Density Temperature DC . KWH/Ion in Cell Gas Cell Voltage
Amps/inz F. KClO3 NaClO3 KC103 NaClO3 KCIO3 NaClOg
1.5 ' ' 167 3,642 4,532 1.022 2.98 3.082 3.378
2.0 ' 167 3,781 4,925 1.418 2.98 3.191 3.797
2.5 167 3,920 5,318 1.022 2.98 ' 3.300 4.080
% Overall Current Efficiency:
KCIO3 ; |00.so
NaClO; = 83.03

Ordinarily, whether a process is closed-loop or con


20 tinuous is not of great importance, where the batch
ered by our process. Outside of area ABC it is not possi process is easily and cheaply carried out. However, I
ble to perform the steps of electrolysis (line AB) crystal when the ?ndings of Table I are considered, it is appar
lization (line BC) and resaturation with solid KCl and ent that the direct production of KClO3 from KCl is
KC] brine (line CA). Realistically the process ismost unexpectedly more ef?cient than the production of
practicable within _the area DEFG, while smaller area NaClO3 (and thus KCIO; by the double decomposition
HIJK represents the desired range of operation for the method) from NaCl under analogous process condi
continuous closed-loop process of this invention. tions. Our process may be carried out with the same
FIG. 3 depicts the operation within the area HIJK of equipment as the process disclosed in US. Pat. No.
FIG. 2, with the theoreticaland practical limits of a 3,883,406, but with results that provide ef?ciencies,
particular process set-up added for emphasis. The area 30 based on electric power usage, of KClO3 production
RbFaMR represents the theoretical limits of operation hitherto unavailable. Table I shows that under the same
for the particular process design depicted, while area conditions of temperature and current density, the elec
RdFcMR represents the practical limits of that same trolysis of KCl to KClO3 in accordance with our pro
design. Points R, F and M delimit the process described cess is 12% more ef?cient, consumes 25% less power
in the Example below. Line A (connecting points R and per ton of product and produces signi?cantly less oxy
F) represents the electrolytic conversion of KCl to gen in the cell gas, as compared] with the electrolysis of
KClO3; line ,B (connecting points F and M) represents NaCl to NaClO3.
the vacuum ?ash crystallization of KClO3 (at a tempera We have learned, subsequent to our making of this
ture of about 100 F., as indicated above); and line C invention, that the efficiency of our process is further
(connecting points M andR) represents the resaturation 40 enhanced by ensuring that the apparatus in which the
of the effluent liquor with solid KCl, thus closing the process is carried out is constructed so that all portions
material balance. Where crystallization is performed of the system which come into contact with the effluent
under refrigeration rather than evaporative cooling are substantially devoid of nickel and other transition
under a vacuum, the crystallization line B on FIG. 3 elements, in particular copper, manganese, zinc and
will more closely approximate dM than line FM de 45 cobalt. It has been determined that the oxygen content
picted. This, and other, modi?cations of the process are of the cell gas, which negatively correlates with the
apparent to persons skilled in this art from an examina ef?ciency of conversion of chloride to chlorate (the
tion of FIGS. 2 and 3. oxygen being liberated by the undesired decomposition
The following example is a representative illustration of the hypochlorite intermediate), is signi?cantly re
of the process according to this invention as demon 50 duced from usual levels when the nickel and other tran
strated in FIG. 3: sition metals loadings in the cell liquor are kept below 1
EXAMPLE ppm
Another re?nement is the control of the water tem
A pilot cell (as disclosed in US Pat. No. 3,824,172) of perature, in the exchanger at a temperature which is
5000 amperes capability was operated for 22 days to 55 above the temperature in which KClO3 will crystallize
produce a liquor concentration of 150 g/l KClO3 and from aqueous solution when present in a particular
175 g/l KCl (13% KClO3 and 15.3% KC] respectively). concentration chosen for operation of the process. The
The material was passed through a crystallizer tank electrolytic conversion of potassium chloride to potas
operated at 100 F. The recycle liquor was returned to sium chlorate is known to be exothermic, but in the past,
a saturator tank where solid KCl was added to achieve 60 workers in this art have preferred to rely upon the rapid
the material balance. Solid KClO3 was removed from movement of the electrolyte itself through the cell to
the crystallizer tank, washed and analyzed. The cell provide cooling. We have found that the process yields
liquor was maintained at 75 C. by a heat exchanger on may be increased by permitting additional residence
the circulating liquor. Hot water was used as the cool time in the cell, if the liquor is cooled, not with cold
ing media to prevent chlorate crystallization in the ex 65 water, but with water that has a temperature which is
changer and the cell. The power consumption during selected to be below the equilibrium'temperature of the
this period averaged 3800 KWH (DC) per ton of cell, which is ordinarily about 167 F. (75 C.), but
KClO3 produced. above the temperature at which KClO3 will crystallize
4,339,312
7 8
from the solution along the walls of the cell. This (d) cooling said effluent until crystals of the chlorate
method also has the advantage of reducing power con form;
sumption for cooling over either refrigerative cooling (e) removing said chlorate crystals from said effluent;
or providing cooling by rapid transport of electrolyte (f) enriching said effluent by adding a controlled
through the cell. 7 . 5 amount of potassium chloride thereto; and
The foregoing description of our invention has been (g) returning and adding. the enriched effluent to said
directed to particular embodiments in accordance with electrolytic cell for further electrolysis, at a vol
the requirements of the Patent Act and for purposes of ume rate equal to the rate at which the unenriched
explanation and illustration. It will be apparent, how~ effluent is removed from the cell in step (c).
10 2. The process of claim 1, wherein the ef?uent con
ever, to those skilled in the art that many modi?cations
tains about 8-20% by weight KC] and about 820% by
and changes in both apparatus and procedure may be weight KClO3, in the ratio of about 0.5-2.5 parts by
made without departing from the scope and spirit of the weight KCl to each part by weight KClO3, and wherein
invention. For example, it is apparent that persons the process is carried out within the area DEFG set
skilled in the art may modify the particular apparatus set 1 forth in FIG. 2.
up disclosed in order to satisfy the needs of any particu 3. The process of claim 1, wherein the ef?uent con
lar ?eld installation or to use equipment of equivalent tains about 8-20% by weight KCl and about 820% by
function to the equipment disclosed. It is further appar weight KC103, in the ratio of about 0.5-2.5 parts by
ent that persons of ordinary skill in this art will, on the weight KCl to each part by weight KClO3, and wherein
basis of this disclosure, be able to practice the invention 20 the process is carried out within the area HIJK set forth
within a broad range of process conditions. These, and in FIG. 2.
other, modi?cations of the process according to this 4. The process of claim 3, wherein the ef?uent con
invention will be apparent to those skilled in the art. It tains about 10% KClQ; by weight, and less than about
is our intention in the following claims to cover all such 15% KCl by weight.
equivalent modi?cations and variations as fall within 2 5 5. The process of claim 3, wherein the effluent con
the true scope and spirit of the invention. tains about lO-l4% by weight KCIO; and about
What is claimed is: 10-16% by weight KCl.
1. A continuous closed-loop process for the direct 6. The process of claim 3, 4 or 5, further including
production by electrolysis of potassium chlorate from stripping any elemental chlorine present in said ef?uent
potassium chloride, comprising the steps of: 30 obtained from step (h) before carrying out step (c).
(a) electrolyzing an aqueous solution of potassium 7. The process of claim 3, 4 or 5, wherein the ef?uent
chloride in an electrolytic cell having a metal cath is subjected in step (b) to evaporative cooling.
8. The process of claim 3, 4 or 5, wherein enriching
ode and a coated metal anode, said coating com step (d) comprises adding sufficient solid KC] to the
prising a precious metal, a precious metal alloy, a 35 ef?uent to restore the KC] concentration in the en
precious metal oxide or a platinate, riched ef?uent returned to the cell to the level of KCl
(b) passing said aqueous solution through a heat ex-' concentration in the aqueous solution of step (a).
changer using a heated cooling medium which is at 9. The process of claim 3, 4 or 5, wherein the anode
a temperature which is below the equilibrium tem comprises a base of a metal selected from the group
peratur of said aqueous solution in said cell but 40 consisting of titanium, zirconium, tantalum and haf
above the temperature at which potassium chlorate nium, coated with a material selected from the group
crystallizes from solutions of the concentration consisting of platinum, platinum-iridium alloys and ru
selected for the process; thenium oxide.
(0) removing from said cell an ef?uent solution con 10. The process of claim 1 wherein the cooling me
taining potassium chlorate formed by said electrol- 45 dium is hot water.
ysis of potassium chloride;

50

55

60

65

You might also like