United States Patent Office 2,703,272

Patented Mar. 1, 1955

1. 2
from the solution from which the solid constituents have
2,703,272 been removed is substantially free of lead, i. e., contains
PROCESS FOR PRODUCING POTASSUM CHILO. than five parts-per-million of lead with a good crystal
yield.
SE
RTSUBSTANTIALLY FREE OF LEAD M. The water insoluble adsorbent material in the aqueous
potassium chloride feed solution are preferably the in
Charles H. Fuchsman, Carlsbad, N. Mex, assignor to from soluble impurities present in muriate of potash produced
International Minerals & Chemical Corporation, a cor bad, New Sylvinite ore such as is mined and refined at Carls
poration of New York Mexico. The water insoluble adsorbent mate
O rials contained in sylvinite ore mined at Carlsbad, New
No Drawing. Application December 24, 1949 Mexico, are principally montmorillonite-type clays. How
Serial No. 135,040 ever, other solid constitutents may be employed. In
soluble absorbent materials such as fuller's earth, paper
7 Claims. (CI. 23-89) pulp, magnesium silicate and the like may be added to
5 potassium chloride feed solutions.
This invention relates to a process for producing sub While the precise form of the lead impurities present
stantially pure potassium chloride crystals and has par in the muriate of potash solution prepared from ores such
ticular reference to a process for preparing potassium as Sylvinite is unknown, the lead is thought to be in a
chloride substantially free of lead. combined, charged, or ionized state. As used herein in
Certain commercial consumers of potassium chloride 20 the description and claims, the word "lead' is used in the
and potash require a pure material substantially free of sense of combined, charged, or ionized lead.
lead. Among these may be mentioned the safety appli From the foregoing it is apparent that the principles
ance manufacturers and the producers of chemically of the instant novel process as previously mentioned may
pure potassium hydroxide. Caustic potash producers be employed with several different variations. For ex
using the mercury cathode cell require for optimum re 25 ample, the amount of lead removed with the insoluble
sults a chemical grade potassium chloride of exceptional constituents of muriate of potash produced from Sylvinite
purity. Purity specifications on refined potassium chlo ore at Carlsbad is increased by either of the following
ride require that the lead content not exceed five parts methods or a combination of both.
per-million. The use of potash for safety appliances also
requires a substantially lead free material. 30 1. Heating of an aqueous solution of muriate of potash
Heretofore, potassium chloride has been concentrated prior to the removal of the insoluble constituents.
by subjecting ores containing potassium chloride such 2. Adjustment of the pH of the aqueous solution of
as sylvinite to froth flotation and then to crystallization muriate of potash to between about 8.0 and about
treatments. However, the potassium chloride produced 11.0 prior to the removal of the insoluble constit
uents.
by flotation processes contains more than five parts-per 35
million of lead, and unlike other trace impurities lead Either of these procedures is effective when used on
is known to concentrate in potassium chloride crystallizing aqueous muriate of potash solutions which are saturated
Ep aqueous solution containing minute concentrations ever,
O ea.
or less than saturated at atmospheric temperatures. How
as the potassium chloride concentration is increased
It is an object of the present invention, to provide a 40 above these concentrations (i. e., a solution saturated at
simple economical process for the removal of lead from elevated temperatures) a greater proportion of lead is
potassium chloride. found in the liquid phase and partially nullifies the tem
It is a further object of the invention to provide a perature effect. Since commercial applications usually
process for the production of refined potassium chloride involve potassium chloride solutions saturated at ele
having a lead content of less than five parts-per-million. 45 vated temperatures, it is preferred that a combination of
It is a further object of the invention to minimize lead still further elevating the temperature and pH adjust
impurities in the potassium chloride crystals by reducing ment be employed in order to remove the lead from
the quantity of lead in the hot aqueous solution from the potassium chloride solution.
which the potassium chloride is crystallized. ... In the preferred embodiment of the invention, "doubly
Additional objects will be apparent on a fuller under 50 centrifuged muriate of potash' is dissolved in water at
inding of the process as hereinafter described in de room temperature or an elevated temperature. The re
tail. sultant muriate of potash solution may be saturated or
It has been discovered that in an aqueous unsaturated less than saturated as long as the potassium chloride con
potassium chloride solution, containing lead and water centration does not increase with temperature (i. e., the
insoluble adsorbent material, the solubility of lead de solution is unsaturated at the higher temperature at which
creases as the temperature is increased. The proportion 55 the solid impurities are to be removed) and the required
of lead retained in the suspended water insoluble solids temperature increase is within practical operating limits.
is increased at elevated temperature. When the insoluble As herein used the term "doubly centrifuged muriate
solids are separated from a boiling potassium chloride of potash” means muriate of potash having substantially
solution, the potassium chloride crystallized upon evap 60 the following analysis: K-51.5, Mg-0.11, Na-0.33,
oration of the resultant solution contains less than five C-47.3, SO4-0.21, Pb-0.0009, Ca-0.04, Insoluble
parts-per-million of lead. 0.36, all per cent by weight dry basis.
This retrograde solubility temperature relationship While "doubly centrifuged muriate of potash' is pre
holds for aqueous potassium chloride solutions saturated ferred, "singly centrifuged muriate of potash' may also be
or less than saturated at atmospheric temperatures in employed. By the term "singly centrifuged muriate of
which the potassium chloride concentration is constant 65 potash' as herein used is meant muriate of potash of
so that the solution becomes unsaturated upon heating. substantially the following analysis: K-50.3, Mg-0.15,
On the other hand, the solubility of lead increases as Na-1.08, C-47.1, SO4-0.82, Pb-0.0009, Ca-0.05,
the temperature increases in hot saturated aqueous po Insoluble-0.37, all per cent by weight dry basis. How
tassium chloride solutions, i. e., saturation is maintained 70 ever, it is not intended to limit the process to muriates of
with rising temperature through the presence of excess potash of these analyses. The feed material employed
solid phase potassium chloride. :.
The invention embodies the further discovery that the
is E. impure muriate of potash containing lead com
pounds.
equilibrium existing between the lead content of the Preferably sufficient sodium hydroxide is added to the
suspended solid constituents and of the liquor is altered 75 muriate of potash solution to obtain a pH of between
by varying the hydrogen ion concentration. If the hy about 9.5 and about 11.0. Although sodium hydroxide
drogen ion concentration of the unsaturated boiling potas is preferred, any inorganic alkali metal compound or
sium chloride solution is decreased, prior to removal of alkaline earth metal compound may be employed to ad
the solid constituents, the concentration of lead in the just the pH. The term "alkali metal compound' in
solution is decreased, and is increased with respect to the cludes ammonia. Thus, the caustic may be supplied as
solid constituents. The potassium chloride crystallized 80 sodium hydroxide, potassium hydroxide, sodium car
 2,703,272 4.
3 Table II
bonate, potassium carbonate, ammonia, calcium hydrox
ide, barium hydroxide and the like. Obviously, caustic. Pb (p. p. m.)
which will introduce impurities which will contaminate Filtered liquor-------------------------------- 0.18
the final product, should not be added. While adjust 1st crystals---------------------------------- 1.80
ment to a pH of between about 9.5 and about 11.0 is pre-, 2nd mother liquor--------------------------- 0.00
ferred, less favorable but successful results are obtained 2nd crystals--------------------------------- 0.05
by, adjusting to a pH of between about 8.0. and about 9.5. EXAMPLE III
A higher pH can be used for more complete lead re
moval, however for practical purposes the above pH 10 To study the effect of pH on the lead content of the
range is preferred. The alkaline mixture is heated to. potassium chloride crystals, two solutions containing 500
any elevated temperature in excess of that at which the grams of "doubly centrifuged muriate of potash' dis
particular solution is saturated and filtered or settled and solved in 1000 grams of distilled water were prepared.
decanted immediately. The purity of the potassium chlo The first solution was used as a control. To the second
ride crystals ultimately produced is equally high, re solution was added 354 milligrams of chemically pure
gardless of whether the insoluble lead impurities are re sodium hydroxide. Each sample was heated to boiling
moved by filtration or by settling and decantation of and then filtered immediately. The pH and the lead
clarified liquid from the solid impurities. In the pre content of the filtrates were determined. Table III indi
ferred embodiment, in which sodium hydroxide is used cates the pH of each filtrate and the parts-per-million
to adjust the pH to between about 9.5 and about 11.0, 20 of lead found in each. Potassium chloride crystals ob
the crystallized potassium chloride produced from the tainable from the filtrate produced by following the proc
clarified solution contains less than five parts-per-million ess of experiment two usually contain less than 1 part-per
of lead, with an economically acceptable crystal yield. million of lead while those from filtrate obtained by fol
The length of time which the alkaline mixture is main lowing the process of experiment one usually contain
tained at an elevated temperature or at the boiling point 25 6-10 parts-per-million of lead.
prior to the removal of solid impurities is not critical. Table III
The following examples are intended merely as ill
lustrations of the instant novel process and are not in
tended to be in limitation thereof. Pb in filtrate
(p. p. m.) pH
EXAMPLE I
0.53 6.6
In order to illustrate the effect of removing the water 0.06 9.8
insoluble impurities from a hot as compared to a cold
solution of muriate of potash, two 20 per cent aqueous When the "singly centrifuged muriate of potash' from
solutions of "doubly centrifuged muriate of potash, with 35
the flotation plant was used instead of the "doubly cen
analysis as indicated, were prepared. In test number trifuged muriate of potash," additional caustic soda was
one, the muriate of potash was dissolved at room tem needed to raise the pH to the preferred range of 9.5 to
perature. In test number two, muriate of potash was 10.0. This is reasonably explained by the fact that as
dissolved while keeping the solution boiling. Both previously shown the magnesium content of the "singly
samples were immediately filtered to remove insolu 40
centrifuged muriate of potash" is much higher than it is
ble impurities and then boiled to remove water ap after repulping and recentrifuging. Consequently, the
proximately equal to one-third of the weight of the effect of the originally added caustic is somewhat can
original solution. The concentrated solutions were then celled by the buffering action of the magnesium. If prior
cooled slowly and the resultant potassium chloride crys to removal of solid impurities the pH of the hot solu
tals filtered off at room temperature. The data in Table 45 tion is increased to between about 8.1 and about 8.7
I indicates that crystals produced from the liquor which by using the same amount of caustic soda as hereinbe
has been heated prior to the removal of solid impurities fore stated, there is a buffering action due to the presence
contain only one part-per-million of lead, whereas the of soluble magnesium impurities thus preventing the
crystals produced from the unheated liquor contain 8.9 solution from reaching a pH of between about 9.5 and
parts-per-million of lead. about 10.0. In this case the lead concentration in the
liquor does not exceed about 0.4 part-per-million. How
Table I ever, if the pH is raised to between about 9.5 and about
10.0 which is above the buffering range of magnesium,
the lead content of the liquor is reduced to about 0.06
Pb in evaporated
liquor (p. p.m.)
Pb in crystals
(p. p. m.) part-per-million. The potassium chloride crystallized
from the high pH liquors contains less than 2 parts-per
No. 1 cold-------------------
No. 2 hot--------------------
0.43
0.19 g million of lead.
Having now fully described and illustrated the charac
ter of the invention, what is desired to be secured by
60 Letters Patent is:
1. A process for producing potassium chloride sub
EXAMPLE II stantially free from lead by removing lead impurities
from an aqueous potassium chloride solution containing
An 18 per cent aqueous solution of "doubly centrifuged lead impurities and water insoluble adsorbent material
muriate of potash" of analysis indicated was prepared 65 selected from the group consisting of fuller's earth, mag
while keeping the solution boiling, and insoluble solids nesium silicate, and water insoluble impurities present
were filtered from the hot solution. Water was then in sylvinite ore mined at Carlsbad, New Mexico, which
removed by evaporation until the solution was 58 per process utilizes an inorganic alkaline compound as the
cent of its original weight. The potassium chloride crys sole added reagent and which process comprises heating
tals were filtered off. The mother liquor was then evap said potassium chloride solution to an elevated tempera
orated to 79 per cent of its original weight, and a second ture, adjusting the pH of the hot solution to between
set of potassium chloride crystals was removed. about 8.0 and about 11.0 with an inorganic alkaline
An inspection of Table II shows that although lead compound, removing solids from the hot solution, said
has a marked tendency to concentrate in the solid potas solids containing said lead impurities, removing water
sium chloride, most of the lead is removed with the solid 75 from the solution to obtain a saturated solution with re
impurities while the potassium chloride is in solution. spect to potassium chloride at an elevated temperature,
The filtered liquor from which solid impurities have been cooling the resultant saturated solution and crystallizing
removed contans only 0.18 part-per-million of lead. Sub potassium chloride therefrom, the resultant crystalline
stantially all of the lead remaining in this liquor is in potassium chloride being substantially free from lead im
corporated into the potassium chloride crystallized from 80 purities. -
it, and the filtrate from which the crystals have been 2. A process for producing potassium chloride sub
separated is substantially free of lead. Upon further stantially free from lead by removing lead impurities
concentration of this filtrate very pure potassium chloride from an aqueous potassium chloride solution containing
staining 0.05 part-per-million of lead crystallizes there lead impurities and water insoluble adsorbent materials
0. 85 present in sylvinite ore mined at Carlsbad, New Mexico,
 2,703,272
5
which process utilizes an inorganic alkaline compound solution to a temperature6higher than the temperature
as the sole added reagent and which process comprises
heating said potassium chloride solution to an elevated at which the solution is substantially saturated with re
spect to potassium chloride, but lower than the boiling
temperature, adjusting the pH of the hot solution to point of the solution, adjusting the pH of the resultant
between about 8.0 and about 11.0 with an inorganic al hot solution to between about 8.0 and about 11.0 with
kaline compound, removing solids from the hot solu an inorganic alkaline compound, removing solids from
tion, said solids containing said lead impurities, remov the hot solution, said solids holding adsorbed lead im
ing water from the solution to obtain a saturated solu purities, removing water from the solution to obtain a
tion with respect to potassium chloride at an elevated
temperature, cooling the resultant saturated solution and 10 saturated solution with respect to potassium chloride at
an elevated temperature, cooling the resultant saturated
crystallizing potassium chloride therefrom, the resultant solution, and crystallizing potassium chloride therefrom,
crystalline potassium chloride being substantially free the resultant crystalline potassium chloride being sub
from lead impurities. stantially free of lead impurities.
3. A process for producing potassium chloride sub 5. The process of claim 4 in which the pH is ad
stantially free of lead by removing lead impurities from 15 justed to between about 9.5 and about 11.0.
an aqueous potassium chloride solution containing lead 6. The process of claim 5 in which the inorganic al
impurities and water insoluble adsorbent material select kaline compound is sodium hydroxide.
ed from the group consisting of fuller's earth, magnesium 7. The process of claim 5 in which the inorganic al
silicate, and water insoluble impurities present in syl kaline compound is potassium hydroxide.
vinite ore mined at Carlsbad, New Mexico, which process 20
utilizes an inorganic alkaline compound as the sole added References Cited in the file of this patent
reagent, and which process comprises heating said solu
tion to an elevated temperature, maintaining the solu UNITED STATES PATENTS
tion saturated with respect to potassium chloride at the 1,873,329 Ritchie et al. ---------- Aug. 23, 1932
elevated temperature, adjusting the pH of the resultant 25 2,470,822 Johnson et al. ---------- May 24, 1949
hot saturated solution to between about 8.0 and about 2,613,133 Anderson -------------- Oct. 7, 1952
11.0 with an inorganic alkaline compound, removing
solids from the hot solution, said solids holding ad OTHER REFERENCES
sorbed lead impurities, cooling the saturated solution, "Catalog of Baker's Analyzed C. P. Chemicals,” Jan.
and crystallizing potassium chloride therefrom, the re 30 1935, page 95. Published by J. T. Baker Chem. Co.
sultant crystalline potassium chloride being substantially
free of lead impurities. “Manual on Fertilizer Manufacture,' by V. Sauchelli,
4. A process for producing potassium chloride sub pages 73, 74 (Apr. 1946). The Davison Chem. Corp.,
stantially free of lead by removing lead impurities from
an aqueous potassium chloride solution containing lead 35 Baltimore 3, Md.
"Handbook of Chem. and Physics,” 27th ed., pages
impurities and water insoluble adsorbent material select
ed from the group consisting of fuller's earth, magnesium 398-399. Chemical Rubber Pub. Co., Cleveland, Ohio.
silicate, and water insoluble impurities present in syl Cable PrintingbyandE. W.
“Manures,” Bell, 1897 ed., pages 68, 69. The
Publishing Co., Ltd., London.
vinite ore mined at Carlsbad, New Mexico, which process "Inorganic and Theoretical Chem.” by J. W. Mellor,
utilizes an inorganic alkaline compound as the sole 40 9. & 1927 ed., pages 568, 569. Longmans, Green and
added reagent, and which process comprises heating said O. N. Y.