July 15, 1958 M. B.

CARUS 2,843,537
PRODUCTION OF POTASSIUM PERMANGANATE
Filed Jan. 9, 1957 3. Sheets-Sheet 1

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INVENTOR:
2. MILTON B. CARUS
BY
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ATT'YS
July 15, 1958 M. B. CARUs - 2,843,537
PRODUCTION OF POTASSIUM PERMANGANATE
Filed Jan. 9, 1957 3. She
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INVENTOR:
MILTON B. CARUS
 July 15, 1958 M. B., CARUS 2,843,537
PRODUCTION OF POTASSIUM PERMANGANATE
Filed Jan. 9, 1957 3. Sheets-Sheet 3
F. G. 7

FIG.9

39

OconTENT 9
PERCEN

INVENTOR:
7O and: Efficiency cent le, MILTON B. CARUS
2?----ee, 2-4-2-4----e. 162-2
United States Patent Office 2,843,537
Patented July 15, 1958
Rikistars:

2
Figure 2 is a perspective view of a preferred cell or
cell bank as employed in the invention;
Figure 3 is an enlarged fragmentary perspective and
2,843,537 sectional view of the cell;
PRODUCTION OF POTASSUM PERMANGANATE
5 Figure 4 is a further enlarged fragmentary section illus
trating the assembly and construction of the electrodes to
Milton B. Carus, La Sale, Ill., assignor to Carus Chemi form an individual cell of the cell bank;
cal Company, La Sale, ii., a corporation of ilii.ois Figure 5 is an enlarged bottom plan view of an electrode
Application January 9, 1957, Serial No. 633,211 taken on line 5-5 of Figure 4;
O Figure 6 is an enlarged top plan view of a base or end
6. Caims. (C. 204-82) electrode taken online 6-6 of Figure 4;
Figure 7 is a further enlarged fragmentary plan view of
a cathode element of the electrode, corresponding to a
view taken on line 5-5 of Figure 4;
This invention relates to the production of potassium 5 Figure 8 is a side elevation of the element of Figure 7;
permanganate, and particularly, to an improved and ifigure 9 is an enlarged cross-sectional view of a di
very efficient continuous type process for the production vider taken on line 9-9 of Figure 5;
of potassium permanganate by electrolytic oxidation of Figure 10 is an enlarged cross-sectional view illustrat
potassium manganate. ing the construction of one of the dividers, taken on line
The prior methods for producing potassium perman 20 10-10 of Figure 5;
ganate by electrolytic oxidation of potassium manganate Figure 11 is an enlarged fragmentary bottom plan view
include a batch type method in which potassium manga of a top or end electrode taken on line 11-11 of Figure
nate solution is agitated or passed in gravity flow in 3; and
parallel streams through banks of cells having separate Figure 12 is a graph of the anode efficiency versus the
cathodes and anodes. Another method involves passing 25 proportion of oxygen in the gases produced in the cell.
potassium manganate solution in gravity flow in Series The new process of the present invention involves pro
through a number of adjacent dipolar cells. The potas viding an aqueous potassium hydroxide solution of po
sium manganate feed solution is prepared by dissolving tassiurn manganate, mixing, or diluting the Solution with
potassium manganate in aqueous potassium hydroxide, product soilution, electrolytically oxidizing the resulting
producing a concentrated Solution containing on the order 30 solution, and crystallizing the resulting solution to produce
of 100-225 grams per liter of potassium manganate. crystals of potassium permanganate and a mother liquor
This solution is charged to a cell and subjected to elec being the aforementioned product solution. The process
trolysis until oxidized to the endpoint, or, in the case of may be carried out continuously in a most advantageous
oxidation in a number of cells in series, the solution is manner. Reference to potassium manganate herein means
partly oxidized, potassium permanganate produced is 35 KMnO, wherein manganese has a valence of six.
crystallized, and electrolysis is continued, by a second pass A result of the new process is that concentrated potas
through the cells. This process is repeated until oxidation sium manganate solution may be prepared in the first in
is complete. Potassium permanganate is removed between stance, which is most desirable in manufacturing opera
passes to prevent crystallization in the cells. tions, from the standpoint of the solubility of potassium
The prior methods suffer in the low crystal purity of 40 manganate in aqueous potassium hydroxide solution and
the potassium permanganate product, especially due to to keep solution volumes within practical limits for handl
the presence of double salts of potassium permanganate ing and processing. At the same time, it has been found
and potassium manganate, requiring recrystallization op in accordance with the invention that the feed solution
erations and involved recovery procedures. Complica to the electrolytic cell is most advantageously performed
tions arise due to crystallization in the cells, cell and 45 with dilute potassium manganate solution. Double salt
conversion efficiencies are often poor, and the power formation is avoided, and the purity of the permanganate
consumption is often high. The construction of the elec is much improved.
trolytic cells and their operation necessitate sizeable in The dilution of the manganate solution is accom
stallations and considerable capital investment, Space re plished by mixing with mother liquors or the like which
quirements, operating cost and labor. 50 are products of the electrolysis. This mixing also serves
The present invention has for its object to provide an to recycle potassium manganate remaining after the oxi
improved process for producing potassium permanganate, daticii. Very importantly also, part of the mother
overcoming the disadvantages previously encountered. iiquors is used to produce the concentrated manganate
Another object is to provide a new and improved process Solution, which provides a quantity of potassium perman
which may be operated continuously to constantly and re 55 ganate therein in a substantial concentration which serves
liably produce a high quality product. to prevent hydrolysis of the concentrated potassium man
An additional object is to produce potassium permanga ganate. At the same time, potassium hydroxide is con
nate crystals directly in high purity, without double Saits, tinuously recycled and reused, with part of the mother
while reducing finishing and recovery operations markedly. liquor being removed from the circulation for removal
Another object is to provide a process having high 60 of the potassium hydroxide produced in the process.
oxidation and electrolytic efficiencies. The new overall process is thus preferably a cyclic
An additional object is to provide a process which process of electrolytically oxidizing potassium manganate,
utilizes concentrated potassium manganate solution yet crystallizing the CXidation product to produce potassium
avoids the prior disadvantages which resulted from sup permanganate crystals and mother liquor, removing part
plying the concentrated solution to the cell. 65 of the mother liquor for removal of the potassium hydrox
These and other objects, advantages and functions of ide produced, adding potassium manganate and water to
the invention will be apparent on reference to the specifi the remaining part of the mother liquor, and cycling the
cation and to the accompanying drawings, in which like resulting solution to the electrolytic oxidation.
parts are identified by like reference characters in each The electrolytic oxidation of the potassium manganate
of the views, and in which: 70 solution containing potassium permanganate is carried out
Figure 1 is a schematic representation of a preferred to produce a quantity of potassium permanganate within
form of the invention, illustrating the new process; its solubility in the solution or electrolyte after oxidation,
 2,843,537
3 4
Crystallization of the latter solution produces crystals of water is employed in the preparation of the leaching solu
potassium permanganate of high purity, and the mother tion in the first mixing tank 1. From the evaporation
liquor remaining is used again in the process with the of liquor, potassium hydroxide is recovered which may be
aforementioned considerable advantages. used in the production of potassium manganate. Potas
Referring to Figure 1 of the drawings, the process com sium manganate and potassium permanganate are sepa
mences with the preparation of aqueous potassium hy rated in the evaporation, and they may be supplied to
droxide solution of potassium manganate in a leaching the first mixing tank.
tank it. Fresh potassium manganate is supplied to the The operating units schematically illustrated in Figure
process, and recovered and recycled potassium manganate 1 are conventional, with the exception of the cell 7, sub
is added thereto. The manganate is leached or dissolved 0 sequently described. The crystallizer 5 illustrated and
in aqueous potassium hydroxide solution which consti eployed in the exemplary process herein is a Struthers
tutes mother liquors from the process, containing potas Wells 10 foot diameter suspension container having a
sium hydroxide, potassium manganate and potassium per capacity of about 7000 gallons. The pump 10 connected
manganate. In dissolving the manganate, wash waters to the riser 9 from the crystallizer has a capacity of 3000
are utilized, including the permanganate wash water. 15 gallons per minute. The vaporizer 11 is a Struthers Wells
The wash waters replace the water withdrawn from the vaporizer having a diameter of 8/2 feet.
cyclic process, reducing the potassium hydroxide concen The new process is preferably and very advantageously
tration of the mother liquors to the desired degree for high
cell efficiency.
carried out with the new electrolytic cell or cell bank 7
illustrated in Figures 2 through 10. The construction
The leach solution is pumped by a pump 2 from the and operation of the cell and the electrolytic oxidation
tank 1 to a filter 3, for removal of insoluble materials. process constituting a new and improved process per se
The filtrate passes to a second mixing tank 4, where it form the subject matter of my copending application,
is diluted or blended with a further quantity of mother Serial Number 633,212, filed January 9, 1957, wherein
liquor produced in the process. In continuous operation, they are claimed.
a storage tank, not shown, may be provided between the Figure 2 illustrates a complete cell 7 composed of a
first and second mixing tanks, 1 and 4. The quantities bank or column of dipolar electrodes 15 in side-by-side
of mother liquor supplied to the first and second mixing relationship and secured together to form a plurality of
tanks and 4 are withdrawn from a subsequent crystal individual closed cells. Any two adjacent electrodes form
lizer 5, adjacent the top of the solution therein. The one cell, as will appear. The cell bank 7 in the embodi
materials supplied to the second mixing tank 4 are heated 30 ment illustrated is also divided into three cell sections
with live steam, but other heating means can be em 16a, 16b, and 6c. The feed solution is supplied to the
ployed. The solution is then removed and pumped by cell bank 7 in series-parallel, that is, feed solution passes
a pump 6 to an electrolytic cell 7. The solution from through cells in each cell section in series, and the three
the second tank 4 constitutes the electrolyte in the cell, cell sections are fed in parallel. In the particular em
and it passes through the cell in regulated flow for oxida bodiment illustrated, it is found that division of the cell
tion of the potassium manganate to potassium perman bank 7 into three sections of twenty individual cells each
ganate according to the following equation: is preferable due to the resistance to fiow, which becomes
electro. Cathode -- Anode Substantial with more than twenty cells in series.
KMnO4 -- HO -3
KOH-4H. KMnO The feed solution is thus supplied through a main pipe
or conduit 17 to three groups of parallel section feed
The oxidized solution from the cell 7 is conveyed to conduits 18a, 18b, and 18c, which enter the first cell of
a gas separator 8, where the gases produced are vented each of the sections of twenty cells. The oxidized solu
from the solution and continuously analyzed for oxygen tion exits from the twentieth or last cell of each section
proportion. The solution is then conveyed to a riser 9 through parallel groups of conduits 19a, 19b, and 19c,
connected to the crystallizer 5, and it is pumped upwardly from whence they are conveyed to the gas separator 8
in the riser together with a large volume of liquor from by a discharge conduit 20. Between each feed and outlet
the crystallizer by a pump 60. The contents of the conduit and its respective manifold is a 4-foot section of
riser discharge into a vaporizer i, which is maintained glass pipe, e. g., 18aa or 19aa, for electrical insulation
under reduced pressure, or evacuated, by condenser and purposes. The electrodes 15 are clamped together in
vacuum equipment represented at 12. Evaporation and gas-tight union by tie rods 2 or the like. The end, or
consequent cooling of the solution takes place in the top and bottom, electrodes 22 and 23 are insulated by
vaporizer. insulating sheets 24 and 25, preferably constructed of
The cooled solution in the vaporizer is supersaturated ebony asbestos. Bus bars 26 and 27 are electrically con
with potassium permanganate, and it descends into the nected to the respective end electrodes 22 and 23, adja
crystallizer 5 at a point adjacent the bottom thereof. cent one extremity thereof, and the bus bars are con
The Supersaturation is released in the crystallizer, crystals nected to a source of D. C. power, preferably about
of potassium permanganate forming on the nuclei or 140-170 volts, depending upon the current desired. The
crystals present in the crystallizer. This results in a individual cells and the electrodes 5 thus have a voltage
quantity of potassium permanganate crystals and a body applied to them in series, so that the potential across each
of saturated mother liquor in the crystallizer. of the sixty cells is one-sixtieth of the total voltage. In
Mother liquor is withdrawn from the upper portion of this connection, it will be apparent that the cell dimensions
the crystallizer, as previously described, and potassium. and the corresponding applied voltage and total current
permanganate crystals are withdrawn in a slurry from are determined from practical considerations and accord
the lower portion, by means of a pump 13. The potas ing to the power available. The electrolytic oxidation
sium permanganate crystals are separated and washed process performed in the cell is fundamentally only a
with water in a centrifuge 14, after which they are dried function of the current density at the electrodes.
by conventional means not shown. The mother liquor Figures 4-8 illustrate in detail the construction of the
from the centrifuge is recycled to the crystallizer. A por
tion of the liquor in the crystallizer 5 is also withdrawn electrodes 15 and their assembly. The electrodes are
and conveyed to an evaporator, for recovery of the potas 70 dipolar, and each constitutes both an anode 28 and a
sium hydroxide produced in the electrolytic oxidation and cathode 29, except for the top and bottom electrodes 22
removal of miscellaneous salts and impurities, by conven and 23 which necessarily perform only a single function.
tional methods. Two adjacent electrodes form a cell together, of the
Recovered and by-product materials are reused insofar anode of one and the cathode of the other. The elec
as possible. Thus, the potassium permanganate wash 75 trolyte of the solution to be oxidized and being oxidized
 2,843,587
5 6
flows between the anode and cathode of adjacent elec cell, illustrated as the lowermost or first cell in the cell
trodes. bank 7. In assembly of the cell, the electrode as illus
In the oxidation, it is necessary that the current density trated in Figure 5 may be visualized as rotated over onto
at the cathode 29 be much higher than that at the anode the surface of the electrode of Figure 6, in the manner of
28. The current density must be high at the cathode to closing a book. In the construction of the cells, border
avoid reduction of potassium permanganate there. The ing spacers and sealing or closure members 38 are pro
current density must be low at the anode, so that the vided around the edges of the electrodes, and flow dividers
anode efficiency is high, with gocod oxidation of potassium 39 are emplaced on the surfaces of the electrodes. In
manganate to potassium permanganate and low oxygen assembling the cell, the spacers and the dividers are
production. Previously, the anode constituted a bare O assembled together with the cathode surface 29, and sealed
metal sheet, and the cathode was a smaller bare metal and adhered thereto by plastic junctions, for example, by
sheet, or was covered by a perforated insulating material applying polystyrene in a solvent Such as toluene at the
such as Transite to decrease the effective area of the junctions, and evaporating the solvent. Prior to assem
cathode and increase the current density. Also, dia bly, a coating of heavy tarry material 40 is provided on
phragms had been provided between the electrodes. 5 the exposed edges of the border pieces 38 and the dividers
However, such perforate materials were unsatisfactory, 39, for effecting a tight seal when the plates are stacked
as the openings therein rapidly became plugged with and bolted or clamped together. It will be observed in
solids. The electrode 15 illustrated functions very well Figure 6 that the screens 32 are located on the surface of
to provide the necessary current density, and interference the base sheet 30 by means of a template or the like, to
by solid deposits is greatly reduced. The surface of the 20 leave uncovered or exposed areas 41 on the surface of
cathode 29 is constructed to preclude such fouling. The the base sheet which correspond to the locations of the
anode need be flushed only after periods of one to six border pieces 38 and the dividers 39, for assembling the
weeks to remove solids therefrom. cell with the pieces therein.
The electrode 15 is constructed of materials which are
25
Figure 3 illustrates the manner in which the feed
resistant to the alkaline manganate solutions at the ten conduits 18 a-c and the discharge conduits 19a-c are con
peratures employed under electrolysis conditions. Thus, nected to the cells. They pass through the end border
a base sheet 30 of 11-gauge hot-rolled steel may be em pieces 38 and communicate with the interior of the cells.
ployed. The base sheet of each of the top and bottom The feed and discharge conduits are non-conductive ma
electrodes 22 and 23 extends outwardly from the cell at terial, preferably tetrafluoroethylene polymer. Figure 9
the ends to provide a flange portion 31 on each for mount 30 illustrates the slightly tapered construction of the dividers
ing the bus bars 26 and 27. 39, which is for the purpose of giving more tolerance to
The anode surface 28 of the electrode is provided with the fabricated screens 32 in assembling the cell.
one or more preferably Monel metal wire screens 32, The more specific description herein and in the example
which are electrically connected to each other and to the refers particularly to a cell 7 which is constructed with
base sheet 30 by spot welding or the like at the edges and electrodes 15 having ends 48 inches wide and sides 96
at a number of points over the surface of the anode. inches long, including the bordering spacers 38 and ex
At the cathode surface 29 of the electrode, a sheet of cluding the extensions 3:1. This area is decreased by the
22-gauge cold-rolled steel 33 is electrically connected to spacers 38, which are 2 inches wide, and they are 14
the base sheet 30, as by welding. The 22-gauge sheet 33 40
inches in depth. The dividers 39 have a width of 1 inch
is stamped or blanked out to provide partly severed and at the base and /2 inch at the top, and they are 14 inches
integral or connected perpendicularly outwardly project deep. The distance between the cathode of one electrode
ing conductive metal elements 34, as illustrated in Figures 15 and the anode of the adjacent electrode is 78 inch,
4, 5, 7 and 8, leaving corresponding perforations or open surface to surface, providing a liquid stream of approxi
ings 35 in the sheet. The spaces between the conductive mately the same thickness or depth. Two superimposed
elements 34 at the cathode surface are filled with an in 45 anode wire screens 32 are provided, 8 mesh (U. S. Sieve
sulating or non-conductive material 36, which may be a Series) and .047 gauge Monel metal. The cathode ele
synthetic organic resin or other material having the re ment extremities 37 are 4 inch long, and the elements 34
quisite resistance to the conditions of electrolysis. Poly extend 346 inch from the surface of the cathode sheet 33.
styrene is preferably and very satisfactorily employed. About 5000 cathode elements are provided. The con
Another thermoplastic resin contemplated for use is tetra 50 ductive cathode area is 930 square centimeters, and that
fluoroethylene polymer. of the anode is 140,000 square centimeters (ratio of
In the construction of the electrode, the anode Screens 1:150).
32 and the cathode sheet 33 are connected to the base The cells are preferably operated with the anodes 28
sheet 30, and the spaces between the conductive elements below the cathodes 29, but in principle, their positions
34 are filled with polystyrene molding powder, which is could be reversed. The flow of solution to be oxidized or
heated and plasticized to completely fill and Seal the electrolyte is illustrated with reference to the dividers in
spaces. Then, the polystyrene is milled off to expose the Figure 5. Figures 5 and 11, respectively, illustrate the
steel tips or extremities. 37 of the conductive elements, feed to and discharge from the cell bank 7. The liquid
presenting the appearance illustrated in Figure 5. 60
enters through the feed conduits 18a-c above the first
In this manner, a small cathode area is exposed, consist electrode 15 in each cell section 16a-c, in the channel
ing of the extremities of the conductive elements uni defined by the end divider 39a and the end border piece
formly distributed at spaced points throughout the surface 38. The channel is insulated by a strip 29a of ebony
of the cathode 29. In the illustrative embodiment, 4% of asbestos on the surface of the cathode 29. The liquid
the cathode surface is metal corresponding to the exposed passes through the cell in tortuous flow around the dividers
edges of the elements, and the remainder is polystyrene. 65 and exits through an opening 42 in the opposite end of
The reverse side of the electrode 15, constituting the the electrode from the feed end. The liquid passes
anode, preferably has a considerably increased conductive through the opening into the next adjacent cell, which is
area, by virtue of the screens 32 and the substantial addi above the preceding cell in the series fiow, in the embodi
tional surface afforded thereby. One or more, and pref ment illustrated. The arrangement of the dividers 39,
erably two screens 32 are employed, and more may be 0 and the corresponding liquid flow, in the next adjacent
used if desired. The screens perform an additional bene cell is a mirror image of the arrangement illustrated, so
ficial function in producing turbulence or agitation in the that the opening 42 communications with a duplicate
electrolyte flowing through the cell, very favorably affect channel to that illustrated as formed by the end divider
ing the efficiency of conversion at the anode. 39a and the border piece 38, which is at the opposite end
Figures 5 and 6 illustrate the assembly of one individual in the next cell. Liquid flow in the next cell then pro
 2,843,537
8
ceeds in the opposite direction to discharge through an portions of manganate and permanganate are selected
other opening like the opening 42 in the first cell, at the so that under the operating conditions, the quantity of
opposite end of the next electrode. The liquid flow pro potassium permanganate produced in the cell 7 is within
ceeds back and forth in series from one cell to the next and does not exceed its solubility in the solution or elec
until the liquid passes through the last or twentieth cell trolyte after oxidation. There is then no problem of crys
in each cell section. The liquid then exits at the same tallization in the cell.
end of the cell bank 7 as the feed end, through the dis
charge conduits 19a-c, which project into the end of the C. The solution is oxidized at a temperature of about 55
to 80° C. The initial solution enters the cell at a
cell in the area corresponding to the discharge opening 42 preferred temperature of about 55° C. to 75° C., and the
which is present in the preceding cells (see Figure 11). O temperature increases in the cell about 3-5° C. Higher
The cell design and the flow pattern are established to temperatures are avoided because the cell efficiency de
provide cocurrent flow of liquid and gases, so that the Cea SCS.
cell is operated in forced circulation without gas binding. The process is operated to produce an oxidized solu
The gases discharge evenly and continuously together with tion preferably containing about 30 to 70 grams per liter
the oxidized solution through the discharge conduit 20, of potassium permanganate,
5
further preferably 45 to 55
and the mixture is conducted to the gas separator 8. The
gases are vented off and analyzed continuously for oxygen concentration is preferably about potassium
grams per liter. The resulting manganate
15 to 50 grams per
content, on the basis of which the operation is regulated, liter, further preferably, 20 to 30 grams per liter, 15 to 20
as subsequently described. To achieve this cocurrent
flow, the base of the cell as represented is at an angle 6 20 grams being substantially the endpoint of electrolytic
oxidation. It is preferable to avoid increasing the amount
with the horizontal, illustrated as about 30° in Figure 1.
This view is a representation of the narrow side or end of of potassium manganate remaining, to avoid an adverse
effect on the purity of the product crystals and to mini
the cell. Thus, the spacer 38a of each electrode adjacent mize the second salts to be handled. By the endpoint
the discharge opening 42 is at the upper edge, and the is Ineant the potassium manganate concentration at which
opposite spacer 38b is at the lower edge. Liquid flow in 25 the rate of oxidation of the manganate decreases rapidly.
each cell is from the area adjacent the lower edge to the The potassium hydroxide concentration increases in pro
area adjacent the upper edge with the gas ascending there portion to the permanganate production, with one mole
with. Because the feed to each cell enters at the high of potassium hydroxide being produced for each mole of
edge 38a, a by-pass opening 43 is provided in the end permanganate produced. The proportions of the ma
divider 39a at its upper end (see Figure 10). The open 30
terials after oxidation are, consistently with the initial
ing by-passes or vents the gas not conducted by the liquid proportions,
from that area. In providing the cocurrent flow, the cell within its solubility such that the potassium permanganate is
can also be arranged with the electrodes extending at dif in the solution.
ferent angles or vertically. In this connection, the production of a solution of
While the apparatus and arrangement of parts illus greater potassium permanganate concentration tends to
trated are preferred, it will be apparent that variations reduce the anode efficiency. The production of potassium
may be made within the scope of the invention. permanganate is further regulated by the quantity present
In carrying out the process, the potassium hydroxide in the starting solution, described above. Also, it is
concentration in the first mixing tank or leacher should preferable to provide at least about 5° C. of superheat
be strong enough to prevent Substantial potassium man 40 in the electrolyte, to prevent possible crystallization of
ganate hydrolysis. It should not be too strong, because permanganate in the cell due to local supersaturation.
later in the process, cell efficiency and crystal purity are The feed solution is supplied to the cell 7 described
impaired. It is preferred that the potassium hydroxide at a rate of about 40 to 75 gallons per minute, preferably
concentration be about 70 to 150 grams per liter, prefer 45 to 65 gallons per minute. The flow is sufficient to
ably 80 to 120 grams per liter. 45 create turbulence around the anode 28, preferably about
The potassium manganate concentration should not 4 to 6 inches per second over the anode. The flow rate
be too high, as otherwise, hydrolysis increases, with the is also correlated with the oxidation rate, as determined
production of permanganate and manganese dioxide. by the current supplied, and the temperature of the
With low manganate concentrations, excessive amounts Solution, which determines its capacity for permanganate.
of liquid must be handled. It is preferred that the Thus, for example, at a current of 1200 amperes and
potassium manganate concentration be about 100 to 200 corresponding production of 12 pounds of permanganate
grams per liter, and 120 to 180 grams per liter is further per minute, with the solution at 62° C., a flow rate of
preferred. about 60 G. P. M. is selected.
It is also preferred to provide as much potassium The cathode current density is preferably from 50 to
permanganate as possible in the leach liquid, to prevent 55 400 times the anode current density, further preferably,
hydrolysis of the concentrated manganate. Thus, a so 100 to 200: 1. To provide such current density ratios, the
lution containing about 100 grams per liter of potassium conductive surface areas of the cathode and anode bear
hydroxide and about 150 grams per liter of potassium an inverse ratio to each other, i. e., 1:50 to 400. The
manganate is preferably saturated with potassium per cathode current density for the embodiment illustrated
manganate, representing about 50 grams per liter thereof. 60 is preferably 0.4 to 2.0 amperes per square centimeter,
The leach solution is made up at about 50° C. to 60 further preferably, 0.6-1.5 amperes per square centimeter.
C., is filtered, and is then charged to the second mixing The anode current density is preferably 0.003 to 0.014
tank 4. There, the leach solution is diluted with several ampere per square centimeter, further preferably, 0.005
volumes of mother liquor from the crystallizer 5, the to 0.009 ampere per square centimeter. The exposed
proportions depending upon the quantities of materials cathode Surface represented by the extremities 37 of the
present in the two liquids. The mixture is heated, such conductive element 34, and the exposed anode surface
as with live steam, as necessary to provide a temperature represented by the screens 32 and the adjacent surface
of preferably about 55° C. to 75° C. of the base sheet 30 are determined to provide the proper
The solution thus prepared for electrolytic oxidation current densities. The voltage across each cell is deter
preferably contains potassium hydroxide in a concentra 70 mined by the current density and the cell resistance. In
tion of 80 to 180, preferably. 120 to 150, grams per liter. the illustrated embodiment, the resistance is low, and the
The potassium manganate concentration is preferably individual cell voltage is in the range of about 2.3 to 2.8
about 35 to 80 grams per liter, and further preferably, After the Start of operation, the operating conditions
50 to 60 grams per liter. The potassium permanganate for the ceil or electrolysis conditions are regulated bas
is preferably below about 35 grams per liter. The pro 75 ically in the invention according to the production of
 2,843,537
9
oxygen in the cell, which is determined by analysis of tallizer, and wash waters. The solution is prepared at
the effluent gases. To operate in this manner, it is first 50° C. to 60° C. and has the following composition:
necessary to determine the cathode efficiency under given 100 grams per liter KOH
conditions of current density and operating temperature. 150 grams per liter K2MnOA
This is determined in a known manner by determination 50 grams per liter KMnO4
of the production of hydrogen and comparison with the
theoretical production. At the same time, the optimum 14 gallons per minute of the solution is filtered through
cathode current density is determined. the filter 3 to remove impurities and insoluble materials,
At a given current density and operating temperature, and is then conducted to the second mixing tank 4.
the cathode efficiency remains relatively constant when 10 In the second mixing tank, the leach solution is con
the feed conditions, that is, the solution flow rate or tinuously mixed in the proportion of one part by volume
the composition of the solution, are varied. At a given to about three parts by volume of mother liquor from
cathode efficiency, the oxygen proportion in the effluent the crystallizer 5, the mother liquor being at 38° C. and
gases (H2 and O2) corresponding to various anode effi having the following composition:
5 135 g./I. KOH
ciencies is calculated. A curve is plotted of the anode
efficiency versus the oxygen content for the cathode effi 25 g/l. K2MnO4
ciency at which the cell will be operated, as illustrated in 25 g/l. KMnO4.
Figure 12 of the drawings. Live steam is introduced into the second tank until the
In operation, the oxygen proportion in the discharged 20 temperature is 65 C. The resulting solution for oxida
gases is measured, from which the anode efficiency is tion has the following composition:
determined according to the graph. The invention oper 120 g./1. KOH
ates at an anode efficiency in the vicinity of 90-92%.
The efficiency will decrease when the flow of electrolyte 53 g/l. KMnO4
is too low, the concentration of manganate in the feed is 30 g./l. KMnO,
25
too low, or deposits accumulate on the anode. Accord The solution is continuously pumped from the second
ingly, if the oxygen content indicates a substantially lower tank 4 by the pump 6 to the cell 7 at a rate of 50 gal
efficiency, indicating greater electrolysis of water, the lons per minute, in three parallel streams through the
rate of feed is increased to supply more manganate for three cell sections i6a-c. D. C. power is connected to
oxidation and return to the expected anode efficiency. 30 the cell, 155 volts and 1150 amperes. The resulting cath
The same result is accomplished, alternatively, by in ode current density is 1.3 amperes per square centineter,
creasing the concentration of manganate in the feed. and the resulting anode current density is .009 ampere
In another alternative, the current density can be re per square centimeter. The temperature of the effluent
duced, by reducing the voltage, to regain the expected from the cell is 68-70° C.
anode efficiency. When the change is not great, the The oxidized solution flows to the gas separator 8,
change in cathode efficiency may be disregarded, espe where the gases are vented. The gases are continuously
cially at a high cathode efficiency. Otherwise, a different analyzed for oxygen by a Beckman oxygen analyzer, and
curve on the graph is used, to correspond to the resulting the percentage of oxygen in the gases is recorded con
different cathode efficiency. Thus, the operation of the tinuously. The cell should operate at an anode efficiency
cell is controlled simply and reliably according to the pro 40 of about 90-92% and a cathode efficiency of about 89%,
duction of oxygen in the cell. When deposits on the corresponding to an average oxygen production of about
anode increase to the point that the operation loses effi 4-5%, as illustrated in Figure 12. If the oxygen content
ciency, the cells are cleaned. increases to above 6%, the leach solution flow is in
The oxidation product solution is conducted from the creased to about 16 G. P. M., and it then usually comes
gas separator 8 to the riser 9 connected to the crystal down again. If it does not but keeps on climbing, the
lizer 5, as previously described. The pump 10 circul cell must be shut down and flushed out, after which its
lates the mother liquor and the fresh product solution operation is again brought back to normal. When the
at a rate of 3000 gallons per minute, the vaporizer is at leach solution flow rate is increased in the foregoing man
an absolute pressure of about 35 mm. Hg, and the tem ner, the quantity of mother liquor mixed therewith in the
perature in the vaporizer 11 and in the crystallizer 5 is second tank 4 is kept constant, as is the flow rate to the
about 38° C. in the illustrative embodiment. However, cell 7. This results in an increased manganate con
these conditions can be varied. Thus, a greater Vacuum centration in the feed solution to the cell.
may be employed with consequent increased evaporation Operating in this manner, the product from the cell
and cooling in the vaporizer. An increased quantity of has the following average composition:
potassium permanganate then crystallizes in the crystal 55 128 g/l. KOH
lizer, and the mother liquors contain a lesser concentra 24 g/l. K2MnO4
tion of potassium permanganate.
Mother liquors are circulated to the mixing tanks 1 and 53 g/l. KMnO,
4, as described, the proportions being adjusted to pro The warm product solution is mixed with the crystal
vide the compositions previously described. A quantity 60 lizer solution, which is at 38° C., and is pumped there
of liquid is also removed from the crystallizer for remov with up the riser S at the rate of 3000 gallons per minute.
ing the potassium hydroxide formed in the process and The absolute pressure in the vaporizer is about 35 mm.
for removal of impurities. The crystallized potassium Hg, and about 3.5 gallons per minute of water are vapor
permanganate product is pumped from the bottom of the ized, cooling the solution in the riser from about 38.5
crystallizer by the pump 13 in about 30% solids slurry. 65 C. to 37.8 C.
The further processing is as previously described. Crystallization takes place in the crystallizer, to leave
The following example illustrates operation of the proc a mother liquor having about the following composition:
ess according to the invention, but it is to be understood
that the invention is not limited to the particular equip 135 g/l. KOH
ment, proportions, conditions and procedures given 70
25 g/l. K2MnO4
therein. 25 g./1. KMnO,
Example 6 G. P. M. of mother liquor are continuously recycled
A leach solution is prepared in the first mixing tank 1 from the crystallizer to the first tank E, and 36 G. P. M.
from fresh potassium manganate of about 82-90% purity, of mother liquor are continuously recycled to the second
and from recovered salts, mother liquor from the crys 75 tank 4.8 G. P. M. of mother liquor are conducted from
 2,843,537
12
the crystallizer to the evaporators. 125 grams of KMnO, tion to produce crystals of potassium permanganate and
per liter of the leach solution is oxidized to 99 grams of a mother liquor, removing part of the mother liquor
KMnO4, which is recovered from the centrifuge 4 (11.5 for removal of the potassium hydroxide produced, adding
lbs. produced/min.). potassium manganate and water to the remaining part
The potassium permanganate crystals in the centrifuge of the mother liquor, and cycling the resulting solution
14 are washed with water, and the wash is reused in to said electrolytic oxidation.
making up the solution in the leach tank 1. The crystals 4. The process for producing potassium permanganate
are dried by hot air at 120° C. The potassium perman which comprises electrolytically oxidizing an aqueous po
ganate thus produced has a purity of 99.40%. The yield tassium hydroxide solution containing about 35 to 80
of potassium permanganate on the basis of the potassium 0 grams per liter of potassium manganate and about 80 to
manganate consumed is about 99% in the cell 7. The i80 grams per liter of potassium hydroxide to produce
overall yield of potassium permanganate based upon the a solution containing about 15 to 50 grams per liter of
fresh potassium manganate supplied to the process is potassium manganate, about 30 to 70 grams per liter of
about 98%. potassium permanganate, and potassium hydroxide in a
The cell operates at an overall electrolytic efficiency of 15
correspondingly increased concentration, crystallizing the
82% (potassium permanganate produced compared to resulting solution to produce crystals of potassium per
the current required). The power requirement is low, manganate and a mother liquor, removing part of the
being 0.25 D. C. kilowatts per pound of saleable potas mother liquor for removal of the potassium hydroxide
sium permanganate produced. produced, adding potassium manganate to a second part
The invention thus provides a new and improved proc 20
of the mother liquor to increase the concentration of the
ess for producing potassium permanganate which is well manganate to about 100 to 200 grams per liter, diluting
adapted for continuous or semi-continous operation. The the resulting solution with a third part of the mother
process directly produces high quality permanganate in liquor and providing additional water in the resulting solu
high yields. The electrolytic and conversion efficiencies 25 tion to produce a solution containing about 35 to 80 grams
are high. The apparatus is compact and greatly simpli per liter of potassium manganate and about 80 to 180
fied, and it is easily operated with few personnel. Capital grams per liter of potassium hydroxide, and cycling the
investment, maintenance, and operating costs are consid solution then resulting to said electrolytic oxidation.
erably reduced. 5. The process for producing potassium permanganate
The invention is hereby claimed as follows: 30 which comprises providing an aqueous solution contain
1. The process for producing potassium permanganate ing about 100 to 200 grams per liter of potassium
which comprises providing a concentrated aqueous potas manganate and about 70 to 150 grams per liter of po
sium hydroxide solution of potassium manganate, diluting tassium hydroxide, diluting the solution with aqueous
the Solution with aqueous potassium hydroxide product potassium hydroxide product solution containing potas
Solution containing potassium manganate in a lower con sium manganate in a lower concentration, the potassium
centration, the potassium manganate concentration in the 35 manganate concentration in the resulting solution being
resulting Solution being such that subsequent electrolytic such that subsequent electrolytic oxidation produces a
oxidation produces a quantity of potassium permanganate quantity of potassium permanganate within its solubility
within its solubility in the solution after oxidation, elec in the solution after oxidation, electrolytically oxidizing
trolytically oxidizing the resulting solution to produce an 40 the resulting solution to produce an aqueous potassium
aqueous potassium hydroxide solution containing potas hydroxide solution containing potassium permanganate in
sium permanganate in an increased concentration and po an increased concentration and potassium manganate in
tassium manganate in a decreased concentration, and a decreased concentration, and crystallizing the resulting
crystallizing the resulting solution to produce crystals of solution to produce crystals of potassium permanganate
potassium permanganate and a mother liquor being said and a mother liquor being said product solution.
product solution. 6. The process for producing potassium permanganate
2. The process for producing potassium permanganate which comprises providing an aqueous solution contain
which comprises electrolytically oxidizing an aqueous po ing about 100 to 200 grams per liter of potassium
tassium hydroxide solution of potassium manganate to manganate and about 70 to 150 grams per liter of po
produce a solution containing potassium manganate in a tassium hydroxide, and potassium permanganate, dilut
decreased concentration, potassium permanganate in an : ing the solution with aqueous potassium hydroxide prod
increased concentration, and potassium hydroxide in an uct solution containing potassium manganate in a lower
increased concentration, the proportions of materials in concentration and also containing potassium permanga
the solution before and after oxidation being such that nate, the potassium permanganate concentration being
the potassium permanganate quantity resulting is within below about 35 grams per liter in the resulting solution
its solubility in the solution after oxidation crystallizing and the potassium manganate concentration being about
the resulting Sciution to produce crystals of potassium 35 to 80 grams per liter therein, electrolytically oxidiz
permanganate and a mother liquor, removing part of the ing the resulting solution at a temperature of about 55
mother liquor for removal of the potassium hydroxide C. to 80° C. to produce an aqueous potassium hydroxide
produced, adding potassium manganate to a second part solution containing about 30 to 70 grams per liter of po
of the mother liquor to produce a concentrated manga tassium permanganate and about 15 to 50 grams per liter
60
nate solution, diluting the concentrated solution with a of potassium manganate, the proportions of materials in
third part of the mother liquor, providing additional water the solution before and after oxidation being such that
in the resulting solution, and cycling the solution then re the potassium permanganate quantity resulting is within
Sulting to said electrolytic oxidation. its solubility in the solution after oxidation, and crystal
3. The process for producing potassium permanganate lizing the resulting solution to produce crystals of po
which comprises electrolytically oxidizing an aqueous po tassium permanganate and a mother liquor being said
tassium hydroxide solution containing about 35 to 80 product solution.
grams per liter of potassium manganate to produce a solu
tion containing about 15 to 50 grams per liter of potassi References Cited in the file of this patent
un manganate, and potassium permanganate and potas 70
sium hydroxide in correspondingly increased concentra UNITED STATES PATENTS
tions, the proportions of materials in the solution before 1,291,751 Brewster -------------- Jan. 21, 1919
and after oxidation being such that the potassium per
manganate quantity resulting is within its solubility in the FOREIGN PATENTS
Solution after oxidation crystallizing the resulting solu- 75 848,514 France ---------------- July 24 1939