Patented Nov.

19, 1940 2,222,330

UNITED STATES PATENT OFFICE

2,222,330
PROCESS OF SALT PURFCATION
Arthur J. Weinig, Golden, Colo., assignor to
Potash Company of America, Denver, Colo, a
corporation of Colorado
No Drawing. Application June 25, 1937,
Serial No. 150,341
5 Claims. (C. 209-166)
This invention relates to a method of separat fying Sodium and potassium salts, such as sodium
ing gangue matter from the valuable constitu chloride and potassium chloride artificially pro
ents of Sylvinite ore and the like. duced or recrystallized in industrial operations,
It is a primary object of the present inven where Such compositions have impurities of the
tion to provide a simple, efficient and economical type described herein as being amenable to the 5
process in which gangue matter may be effective present treatment.
The present invention relates to the use of cer
ly separated from associated sodium chloride, or
potassium chloride, or both, and removed as an tain reagents by which certain compositions are
impurity from the treatment. Selectively floated for their separation from
O It has been found that potassium chloride and halides with which they have been associated 0.
Sodium chloride constituents of Sylvinite ores in their natural or artificial formation.
may be separated effectively by froth flotation, The separation of the present invention in
and in my c0pending applications, Serial Nos. volves the use of a pulp formed by Suspending
38,319, and 81,729, I have disclosed treatments the valuable constituents under treatment in a
5 of this character. In these applications, gangue Saturated Solution thereof, and then subjecting 5
is floated with one chloride in a treatment in Such pulp to the action of a flotation reagent,
volving the separation of such chloride from the which in the presence of agitation and aeration
other chloride in the pulp. Selectively carries the gangue matter to the Sur
The present process is designed to have ap face as a froth to be subsequently removed as a
20 plication in conjunction with, or independently reject product, while the valuable constituents
of treatments of the type disclosed in the afore are collected and recovered as a non-floated resi
Said applications. due of the treatment.
Thus, where potassium chloride is to be re Many compositions classed as insoluble gangles
covered as a froth concentrate, I have discov may be floated by the present process, and in 25
25 ered that the flotation separation can be im particular, such gangue constituents of Sylvinite
proved by first separating gangue constituents ores and the like, as clays, gypsum, anhydrite,
from a pulp in which the valuable constituents iron oxide, manganese oxide, polyhalite, lang
of Sylvinite ore are suspended, and thereafter beinite, leonite and glaserite, are acted on by the
floating off the potassium chloride in a substan reagent and carried to the surface in a froth. 30
30 tially pure condition for its separation from the Numerous reagents and reagent combinations
Sodium chloride content. Similarly, a reversal may be utilized in the present process. For ex
of these operations will be effective also. In the ample, such compositions as oleic acid (red oil),
flotation of Sylvite, reagents of the type disclosed coconut oil Soaps, palm kernel oil soaps, resin
in application No. 38,319 are used, namely an al Soaps, cresylic acid and phenol oils, or mixtures 3.5
kali salt of a sulfated alcohol, or an alkali Salt thereof are effective for this purpose.
of a sulfated aliphatic alcohol, having from 5 to The amount of reagent used in the treatEnent
14 carbon atoms in the molecule, such as sodium will be determined by the properties of the par
lauryl sulfate or Sodium octyl sulfate for example. ticular pulp treated, and a rather close control
Under certain conditions, it may be desirable is advisable to attain best results. Generally, a
to make a market product of the sodium chloride range of from to 10 lbs. reagent per ton of 40
reject of an operation of the type disclosed in ore treated will give good results.
application No. 81,729, in which potassium chlo The reagent selected must act both as a frother
ride constituents of Sylvinite ore are purified and collector. Most of the aforementioned re
While a sodium chloride and gangue mixture Sep agent compositions act both as frothers and co
45 arated therefron is produced as a Waste prod lectors, and in any given operation, if greater 45
uct. The present process is effective for this pur Selectivity is required than is afforded by a soap
pose, the gangue matter contained in the reject or fatty acid, or mixture thereof, a modifier such
product being readily floated off from the pre as cresylic acid may be used effectively in Small
viously associated sodium chloride content, with quantities, to improve collection.
50 the result that the sodium chloride constitutes The advantages of cresylic acid in a flotation 50
a substantially pure residue of the operation. operation of this character have been described
It will be apparent to those skilled in the art, in my co-pending application Serial No. 123,484,
that the process may be utilized further in puri and reside primarily in improving selectivity
fying natural Salt by froth flotation, and the While reducing operating COSt and increasing
55 process also has application in cleaning and puri plant capacity. In the present process, cresylic
 2 2,222,380
acid may be used as a collector or as a modifier taken very Well, there is a great shortage of KCl
for another frother and collector reagent com in the products. The solution was analyzed for
position, and it will be understood that where KCl and it was found to contain 52.9 grams KC
cresylic acid acts as a modifier, relatively small per litre or for the two litres of solution used,
amounts thereof will suffice to produce the de 105.8 grams of KCl dissolved. Thus where the
sired rest. Solution of the pulp is not saturated with respect
In preparing the pulp of the treatment, the to KCl, any KCl contained as an impurity of
Sylvinite ore, or other similar gangue-contain NaCl may be separated therefrom automatically
ing material, is reduced to a suitable degree of in an operation of this type.
fineness in any convenient manner, and is then A repetition of the operation in which the so 0.
introduced into a saturated solution of the same
lution of the pulp was saturated with respect to
material. While the fineness of the grind Will both sodium chloride and potassium chloride gave
differ with different substances and treatment the following product analysis:
problems, a 48-mesh product may be taken as
5 a standard. Per - Per- Per
The pulp is introduced into a suitable froth cent cent cent
flotation cell and Subjected to agitation and aera weight KCl Insol.
tion in the presence of one of the above-men
tioned reagents, or combinations of reagent, and Foth concentrate-------------------------
Flotation tailing--------------------------- 6.5
93.5 2.8
6,0 3.3
0.43
20 the process is continued until the separation is 20
substantially complete. The duration of the This test indicates that the solution must be
treatment will vary, but as a general rule, 10 to kept unsaturated with respect to KCl if KCl is
15 minutes is sufficient time to complete the to be completely separated from the salt product.
separation.
25 The final solution analyzed 135.5 grams KCl per
The amount of the reagent used in the treat litre
ment also will vary and the range of from which is the saturation point for KCl for
the temperature
to 10 lbs. of reagent per ton of ore will produce excess NaCl. existing and in the presence of
best results. It Will be understood that the ef From the foregoing it is apparent that if in
ficiency of the operation is in part determined
30 by reagent cost, and Small additions of cresylic pure Salt is Subjected to flotation, the gangues 3.
acid to oleic acid or soaps, used as the reagent float easily and are thereby separated from the
will reduce the quantity of the latter required for salt. When potassium chloride is an impurity of
the salt, it dissolves and replaces salt in the
good selectivity, and thereby reduce operating Solution. The proper control requires that the
CoStS. -
35 The temperature control features of the type Solution be maintained unsaturated with respect
to KCl during the flotation operation.
disclosed and claimed in my Patent No. 2,105,294. In order to render this operation workable,
of January 11, 1938, may be employed effective a certain temperature (ordinarily 70 F.) must
ly in the present process. Advantage is takeni of
the different solubility characteristics of sodium be maintained to establish a saturation point for
KC. Having this, a quantity of Solution nearly
chloride and potassium chloride to effect a sep Saturated KCl must be removed from the 40
aration by causing one or the other to go into circuit andwith
solution in connection with certain flotation sepa of solution. After toSeparation
cooled cause KCl to crystallize out
of the crystallized
rations. potassium chloride, the Solution is heated and
To afford a better understanding of the scope returned
45 and effectiveness of the present process, refer circuit istomaintained
the flotation circuit, or the fiotation
at a higher temperature
ence will be made to certain illustrative opera than the separated Solution returned thereto,
tions, in which various applications of the proc and in either instance this returned solution
ess to different treatment problems are cited.
In the first of these, potassium chloride is is again dissolves
repeated.
potassium chloride and the cycle
50 dissolved. When Sodium chloride containing it is
treated in a Saturated sodium chloride solution. when From the foregoing, it will be apparent that
KCl containing gangue and Some NaCl as
The salt of the treatment was analyzed as foll an impurity is to be treated by the present proc
lows: 1.5% insolubles (gangues), 13.9%. KCl and ess, the solution of the pulp should be saturated
84.5% NaCl.
55 The pulp was prepared by introducing 800 with respect to KCl and not saturated with re 55
grams of this ore into 2000 c. c. of a saturated spect to NaCl.
The reagents have no affinity for KCl and
NaCl solution containing no KC). One quarter
pound of Coconut oil soap per ton of solid Salt none for NaCl, so long as there is no lead or
was employed as the reagent of the treatment. bismuthin the solution, and carry up the gangues
60 in the froth while the NaCl is dissolved in the
The products of this test analyzed as follows: solution. (0
In this operation a controlled tempera
Per Pe- Per ture is also required.
cent cent cent Where the treated material consists of a
KCl NaCl Insol. single halide and gangue only and not of a more
65 Froth concentrate-------- complex composition, the cleaning may be ef
Flotation tailing--------- fected by reagent control alone. Thus the final
reject NaCl and gangue product of an operation
Subsequent analysis of the product tabulated for separating potassium chloride from Sylvinite
as 2.1% KCl disclosed the same to be polyhalite ores for example, may be effectively refined by
70 present in the ore, and not KC). This finding is introducing the product into a saturated solu
consistent With other operations in which the tion of the same material and subjecting the
reagents have been found to have no affinity resulting pulp to a froth flotation treatment in
for KC. the presence of a reagent comprising .07 pound
It will be noted that while the total weight of coconut oil soap and 10 pound oleic acid (red
S products recovered checks the original weight . oil) perton of Sodium chloride solids in the pulp.
 2,222,880 3.
The residue of this operation is substantially In order to employ a generic expression to
pure NaCl of good market grade. designate the various reagents shown to be ef
A third operation will illustrate the Wide ap fective for the present invention, as well as
plication of the present invention to different equivalents thereof not specifically described,
materials. Prior to the flotation operation in the notation "a composition of the class char
which potassium chloride constituents are sepa acterized by oleic acid' Salt Water Soaps, and
rated as a froth concentrate by the action of alkali resinates has been selected.
the aforesaid sulfonated alcohol reagents, and Features described but not claimed herein
after classification, the pulp may be entered into have been claimed in my several co-pending ap
O : fotation innachine and subjected to agitation plications hereinbefore referred to, and other
alind aeration in the presence of a reagent such as copending applications, as follows:
oleic acid, or palm kernel oil Soap in an amount The temperature control features of the pres
preferably not exceeding 1 lb. per ton of ore ent process are described and claimed in Patent
treated, which causes the gangue constituents No. 2,105,294;
and potash minerals other than KCl to rise and The use of the class of reagents comprising 5
collect in the froth. oleic acid, coconut oil Soap, palm kernel oil and
The cleaned pulp is then subjected to the alkali resinates for floating sodium chloride and
flotation action in which a sulfated alcohol re gangue constituents of Sylvinite ores has been
agent is employed. The froth product of this described and claimed in my co-pending appli
secondary flotation is KCl Solids Substantially cation, Serial No. 173,431, while the use of the 20
free from impurities. alkali resinate reagents for the same purpose has
The use of the foregoing treatment permits a been claimed Specifically in Patent No. 2,105,295;
closer reagent control to attain maximum Selec The use of cresylic acid compositions with the
tivity in the secondary operation, and any gangue reagents described in the preceding paragraph
not removed in the first operation which is is described and claimed in application, Serial
carried into the froth of the secondary operation No. 123,484;
will be of such insignificant quantity that it will The milling treatmentS in an operation in
not appreciably reduce the grade of the con which potassium chloride is floated are described
centrate. and claimed in application Serial No. 38,316;
The foregoing examples demonstrate the Wide and 3.
application of the present process commercially. The milling treatments in an operation in
It may be used in connection with a separation which Sodium chloride and gangue are floated
of the valuable constituents of Sylvinite Ore, are described and claimed in application Serial
either at the beginning of the treatment to re No. 81,729, and also in my co-pending applica
move gangues before the halides are separated, tion, Serial No. 28,983. 35
or as a treatment subsequent to such separation Changes and modifications may be availed of
to refine an impure concentrate of the Separa within the Spirit and Scope of the invention as
tion. defined in the hereunto appended claims.
While the purification of NaCl may be car What claim and desire to Secure by Letters
- O ried out in an operation of the above Stated Patent is:
character, it is obvious that the proceSS Inay be 1. In a process for the purification of an Ore
used to great advantage in the purification of containing mixed chlorides of Sodium and potas
sat obtained from natural formations, in which sium having insoluble gangue matter as an im
gangues are present as an impurity. purity thereof, the improvement which comprises
By combining solubility and reagent control, introducing Such a composition in finely-divided 45
the concentrate of the process may be obtained condition into a saturated Solution of such com
in a high degree of purity to Satisfy market position to form a pulp, and purifying the com
standards. In addition the individual particles position by subjecting the pulp so formed to the
are surface coated by the fatty acid or equivalent action of an alkali resinate in a froth flotation
it) reagents to a sufficient degree to render them treatment, whereby Such gangue constituents are
Substantially water-repellent, which results in selectively collected in a froth separate from
a product that may be conveniently stored or other solid constituents of the composition.
snipped without appreciable caking. 2. In a proceSS for the purification of an ore
As there does not appear to be any recognized containing mixed chlorides of sodium and potas
s term that may be used to designate all the na sium having insoluble gangue matter as an im 5.
terials amenable to the present process, the ex purity thereof, the improvement which comprises
pression “a material of the class characterized introducing Such a composition in finely-divided
by Sylvinite ore' will be used in the Speci condition into a Saturated Solution of such con
fication to designate the materials herein de position to form a pulp, and purifying the com
scribed and their equivalents, which may be position by subjecting the pulp so formed to the
treated by the present process. frothing and collecting action of a composition
It will be apparent that the Saturated Solution containing an alkali resinate and cresylic acid
herein described may be varied in composition in a froth flotation treatment, whereby such
to a considerable degree without impairing the gangue constituents are selectively collected in
effectiveness of the treatment. Therefore Where a froth separate from other solid constituents of
“saturated solution' is used in the description the composition.
and cairns it is intended to designate a solution 3. In a process for the treatment of a sodium
saturated with respect to one composition and chloride compositill containing gangue mate
which may also contain a saturation or partial rial and Some potassium chloride as impurities
Saturation of another composition. thereof, the improvement which comprises in C
Where the term "alkali resinate' is used in the troducing such a composition in finely-divided
specification, it is intended to designate a re condition into a Solution Saturated with respect
agent of the type described and claimed in my to Sodium chloride to form a pulp, and purify
Patent No. 2,105,295 of January 1, 1938 for ing the composition by Subjecting the pulp so
Fiotation process. formed to the frothing and collecting action of
 4 2,222,880
an alkali resinate, in a froth flotation treat ly collected in a froth separate from the potas
ment, whereby such potassium chloride impuri sium chloride.
ties are dissolved and gangue constituents are se 5. In a process for the treatment of Sylvinite
lectively collected in a froth separate from the ore containing insoluble gangue matter as an im- .
Sodium chloride. purity thereof, the improvement which comprises
4. In a process for the treatment of a potas introducing such Sylvinite ore infinely-divided
sium chloride composition containing gangue condition into a saturated solution of the ore
material and some sodium chloride as impurities to form a pulp, purifying the ore by subjecting
thereof, the improvement which comprises in the pulp so formed to the action of an alkali
O troducing such a composition in finely-divided resinate, in a froth flotation treatment, where o
condition into a solution Saturated with respect by such garague constituents are selectively col
to potassium chloride to form a pulp, and puri of theincomposition,
lected a froth separate from other constituents
and separating the residual
fying the composition by Subjecting the pulp so Solids of the initial flotation treatment in a sec
5 formed to the frothing and collecting action of ond froth flotation treatment by the action of a s
an alkali resinate, in a froth flotation treatment, reagent having a selective affinity for one of
whereby such sodium chloride constituents are the constituents.
dissolved and gangue constituents are selective ARTHUR. J. WENIG.