United States Patent [191 [11] 4,239,735

Eisele et al. [45] Dec. 16, 1980

[54] REMOVAL OF IMPURITES FROM CLAY Attorney, Agent, or Firm-William S. Brown; Donald A.
Gardiner
[75] Inventors: Judith A. Eisele, Verdi; Donald J.
[57] ABSTRACT
Bauer; Paul R. Bremner, both of
Reno, all of Nev. A method for producing substantially pure alumina
from kaolin clay by removing in a soluble form impuri
[73] Assignee: - The United States of America, as ties which contaminate the alumina while the aluminum
represented by the Secretary of the is maintained in an insoluble form. This is accomplished
Interior, Washington, DC. by leaching calcined kaolin clay with at least 36 weight
percent hydrochloric acid to dissolve the impurities and
[211 Appl. No.: 72,957 convert the aluminum to insoluble aluminum chloride
[22] Filed: Sep. 6, 1979 and maintaining the hydrochloric acid concentration in
the leach liquor at at least 36 weight percent by the
[5 ll Int. Cl.3 .............................................. .. C01F 7/22 injection of hydrochloric acid gas. The insoluble alumi
[52] US. Cl. ................................... .. 423/ 126; 423/132 num chloride is then separated from the dissolved impu
[58] Field of Search .............................. .. 423/ 126, 32 rities and subjected to a second leaching step to solubi
lize and separate it from the silica gangue. Substantially
References Cited pure A1Cl3-6H2O crystals are recovered from solution
U.S. PATENT DOCUMENTS and converted to alumina by conventional means. In an
alternate embodiment, the process may be practiced on
558,725 4/1896 Gooch .. .. . .. . . . . . .. 423/126
uncalcined clay and includes the addition of a source of
1,490,021 10/
4/ 1924
1930 Pedemonte
Masin ....... .. ?uoride ions, such as H2SiF6, to the at least 36 weight
1,777,570 percent hydrochloric acid leach liquor. An optional
1,798,261 preleaching step utilizing 2N to 6N mineral acid is also
2,413,709 3/1931
6/1974
l/ 1947 Hois?eld
Hoffman................................ .. 423/132
Belsky
3,816,605 disclosed.

Primary» Examiner—Herbert T. Carter 18 Claims, N0 Drawings

 4,239,735
1 2
such as P205, MgO, CaO, K20 and Fc2O3, are removed
REMOVAL OF IMPURITES FROM CLAY from kaolin clay as soluble matter before the aluminum
in the clay is solubilized. As a result the level of impuri
DESCRIPTION ties in the liquor from which AlCl3.6H2O is crystallized
Technical Field is greatly reduced. The method of the present invention
comprises the steps of leaching calcined kaolin clay
The present invention relates generally to‘ the separa with hydrochloric acid maintained at a concentration of
tion and recovery of substantially pure alumina from
aluminiferous materials and, speci?cally, to a method not less than 36 weight percent and a temperature of
for the removal of impurities which contaminate alu about 50° to 110° C., preferably about 90° to 95° C., to
mina recovered from kaolin clay. form a leach solution containing insoluble matter. So
long as the concentration of hydrochloric acid is main
Background Art tained at at least 36%, such as by the injection of hydro
In recent years an increasing emphasis has been chloric acid gas, the AlCl3.6H2O solubility is depressed
placed on the utilization of domestic resources for the 15 and it remains in insoluble form while the impurities
production of aluminum in an attempt to reduce this remain soluble at the high acid concentration and can be
country’s dependence on imported bauxite ore. Some readily separated from the insoluble AlCl3.6H2O by
domestic clay resources have been found to be valuable ?ltering and washing the ?lter cake with 36% hydro
sources of this important metal. In particular, cell-grade chloric acid. The insoluble aluminum chloride in the
alumina can be produced from domestic kaolin clay ?lter cake may be solubilized in conventional manner,
deposits. However, other substances found in the kaolin such as by dissolving in water or in 26 weight percent
clay tend to contaminate the alumina and are not readily HCl solution.
separated from it using currently available processes.
The leaching of kaolin clay with hydrochloric acid to BEST MODE FOR CARRYING OUT THE
recover the aluminum in the clay as AlC13.6H2O is well INVENTION
known, as is the use of hydrochloric acid gas to precipi The preferred method of the present invention com
tate aluminum chloride from water suspensions of cal prises leaching calcined kaolin clay with 36 weight
cined clay. See, e.g. U.S. Pat. Nos. 1,519,880; 2,189,376; percent hydrochloric acid at a temperature of about 50°
and 2,217,099. Alumina is recoverable from the alumi to 110° C., preferably 90° to 95° C., during or after
num chloride by conventional techniques, such as ther which time hydrochloric acid gas is injected into the
mal decomposition and the like. However, dif?cult to leach solution to maintain a constant hydrochloric acid
remove impurities such as P205, MgO, K20, CaO and concentration of at least 36 weight percent; cooling the
Fe2O3 are also leached from the clay and prevent the resulting leach solution, which contains unreacted clay
ultimate recovery of pure alumina. While iron, which is solids and insoluble aluminum chloride, to room tem
likely to be the major contaminant, is readily removed perature; ?ltering the solution and washing the ?lter
from the leach liquor by solvent extraction or other 35
cake with 36 weight percent hydrochloric acid to re
conventional means, and potassium can be removed by move substantially all of the impurities as soluble mate
controlling the acidity of the leach liquor, other con rials while maintaining the aluminum chloride in insolu
taminants, such as CaO, MgO and P205, present more ble form; further contacting the ?lter cake with water
complicated and expensive removal problems. These or about 26 weight percent hydrochloric acid to solubi
problems are compounded somewhat by the repeated
recycling of the leach liquor which commonly occurs lize the aluminum chloride content thereof; ?ltering the
during presently known continuous aluminum extrac resulting aluminum chloride solution; and sparging the
tion processes such as those disclosed in the aforemen solution with hydrochloric acid gas to recover substan
tioned US. Patents. Such recycling tends to concen tially pure AlCl3.6H2O crystals.
trate impurities to levels which seriously contaminate 45 The method of the present invention removes the
the alumina. Furthermore, prior art processes for the major portion of the impurities from the clay prior to
production of alumina from clay present additional the solubilization of the aluminum and thus increases
disadvantages, such as lengthy processing times, in the purity of the alumina ultimately recovered from the
volved processing steps and excessive energy consump clay. Contamination of the aluminum by impurities such
tion. 50 as P205, MgO, K20, CaO and Fe2O3 is substantially
avoided in the practice of the present process by the
DISCLOSURE OF THE INVENTION utilization of at least 36 weight percent hydrochloric
Accordingly, it is an object of the present invention acid to leach the calcined kaolin clay. At this concentra
to provide a hydrochloric acid leaching method tion, the impurities are soluble, while the solubility of
whereby the impurities which contaminate alumina 55 the aluminum is depressed. In fact, AlCl3.6H2O is virtu
may be removed from kaolin clay quickly, effectively ally insoluble in 36% hydrochloric acid. At lower hy
and inexpensively to produce substantially pure alu drochloric acid concentrations, however, the solubility
mina. of the aluminum increases, as does the likelihood that
It is an additional object of the present invention tosubstantial amounts of aluminum could be lost when the
provide a method of removing the impurities from kao 60 impurities, which are also soluble at lower concentra
lin clay prior to solubilization of the aluminum in the tions, are removed. Therefore, to insure the recovery of
clay. the maximum amount of aluminum possible from the
Other objects and advantages will become apparent clay, it is important that the hydrochloric acid concen
from the following description and appended claims. tration be maintained.
Briefly stated, in accordance with the aforesaid ob 65 The starting material for the method of the present
jects, a method for producing substantially pure alu invention is kaolin clay which has been calcined by
mina from aluminiferous raw materials, such as calcined conventional means known to those skilled in the art.
kaolin clay, is provided whereby alumina contaminants, An alternate embodiment of the process, discussed
 4,239,735
3 4
hereinbelow, allows conservation of the energy re 12%, of the P105, MgO, K20, CaO and Fe2O3 impuri
quired to calcine the clay and therefore permits the use ties originally present‘inthe clay and typically contain
of an untreated kaolin clay starting material. ing more than 90% of the aluminum originally present.
In the preferred process, the calcined kaolin clay is Sparging the AlCl3 solutiontwith. hydrochloric acid gas
placed in a leaching vessel to which is added a solution results in the recovery of the aluminum chloride as
of at least 36 weight percent hydrochloric acid. At least substantially pure AlCl3.6‘H2O crystals. It is possible to
100 ml to 500 ml, and preferably at least 150 ml, of 36% recycle the liquor frornvthis step for use in the prior step
hydrochloric acid is required to leach the impurities of solubilizingaluminum chloride to separate it from the
from each 50 g of clay. Since the reaction between the silica tails.-'= xi‘: '
calcined kaolin clay and the hydrochloric acid gener The energy required to calcine the clay can be saved
ates water, it is necessary to inject hydrochloric acid gas by utilizing an alternate embodiment of the present
to maintain the acid concentration at at least 36 weight process. In this embodiment raw, uncalcined kaolin clay
percent. Injection of the hydrochloric acid gas into the is leached with hydrochloric acid maintained at a con
leach solution typically occurs during the leaching pro centration of at least 36 weight percent by the injection
cess and may be continued afterwards to insure the of hydrochloric acid gas, as in the first step of the pre
required acidity of the solution. In the preferred em ferred embodiment;'to which has been added H2SiF6 or
bodiment of the process, heat is applied to the leaching any other appropriate source of fluoride ions, such as
vessel to bring the temperature to about 50° to 110° C. CaFg, Na2SiF6 or HF. The reaction of the clay with the
and preferably to about 90° to 95° C. Although the hydrochloric acid in the presence of fluoride ions gener
reaction between the hydrochloric acid and the clay 20 ates more heat than the reaction conducted in the ab
generates heat and is self sustaining, the reaction pro sence of ?uoride ions and, therefore, the external appli
ceeds too slowly for practical commercial purposes cation of heat to the leaching vessel is not as bene?cial
unless heat is applied. The calcined clay is leached with in the preferred embodiment. A I'IZSlF? concentration
36 weight percent hydrochloric acid for about 15 min of about 0.05 to 1.0, preferably 0.2, moles F ion per mole
utes to 4 hours, preferably 1 to 2 hours, during which 25 of aluminum in the kaolin clay sample has been found to
time hydrochloric acid gas is injected to maintain the effectively assist in the removal of impurities from un
HCl concentration at at least 36 weight percent. calcined clay prior to the solubilization of the alumi
The resulting reaction mixture, which consists of num. As in the preferred process, the impurities are
leach solution and solid AlCl3.6H2O and silica tails, is soluble in the strong acid, but the aluminum remains
then preferably cooled to room temperature. The con 30 insoluble. ‘
tinued injection of hydrochloric acid gas during cooling In some cases it may be desirable to remove certain of
insures that the concentration will be maintained at at the impurities prior to performing the at least 36% hy
least 36% so that little or no aluminum will dissolve in drochloric acid leach process of the preferred embodi
the cooling leach liquor. The cooled reaction mixture is ment. If it is desired to perform this preleaching step,
then ?ltered and the ?lter cake washed with 36 weight 35 raw uncalcined kaolin clay is contacted with a dilute
percent hydrochloric acid to wash out substantially all mineral acid, the resulting solids are ?ltered,'washed
of the soluble impurities, which include P205, Fe2O3, and contacted with a solution of about 26 weight per
K20, MgO and C210. The ?ltrate and wash solution cent hydrochloric acid and H1SiF6 (or other source of
contain more than 86% to 94% of the impurities in the ?uoride ions, e.g., CaFg, Na2SiF6, HF). Dilute mineral
clay which most commonly contaminate alumina while acid concentrations of about 2 N have been found to
only a minor amount of the aluminum, about 1% to 2%, remove more than 30% of the P205 and MgO from the
is found therein. clay while removing only about 5% of the aluminum. A
The substantially uncontaminated AlCl3.6H2O in the preleach mineral acid concentration of about 6 N will
?lter cake is then solubilized by conventional means to remove about 50% of these impurities; however, this
separate it from the silica gangue portion thereof. A 45 concentration also leaches about 14% of the aluminum
preferred process includes contacting the ?lter cake with the impurities. Although hydrochloric acid is pre
with suf?cient water for a period of about 15 minutes to ferred for use in the dilute mineral acid preleach, other
4 hours, preferably 1 to 2 hours, to dissolve the AlCl3.6 mineral acids, such as nitric acid and sulfuric acid, are
H2O. The application of heat is not required; however, also suitable.
it may be desired to apply suf?cient heat to decrease the The following Examples are intended to be illustra
viscosity of the resulting solution. This may be accom tive of the present invention and are not intended to
plished, for example, by contacting the ?lter cake with limit its scope in any way.
elevated temperature water at about 25° to 100° C.
Alternatively, the ?lter cake may be contacted with a EXAMPLE I
solution of 26% hydrochloric acid to render the alumi 55 50 g of calcined kaolin clay was leached with 150 ml
num chloride soluble. In this case enough heat must be of 36 weight percent HCl for 2 hours at 90° C., during
applied to the aluminum chloride-hydrochloric acid which time HCl gas was injected into the leach solution
solution to drive off the hydrochloric acid content, at to maintain the concentration of the HCl at 36%. The '
which point the solubility of the aluminum chloride will resulting solids containing leach solution was then
be enhanced. It has been found that solubilizing the cooled to room temperature while the injection of HCl
aluminum with 26% hydrochloric acid is most effective gas was continued to insure saturation of the solution.
when the aluminum chloride-hydrochloric acid solu After cooling, the solution was ?ltered and the ?lter
tion is maintained at about 95° C. for about 2 hours. cake washed with 36% HCl. The ?ltrate and wash
The resulting solution containing the dissolved alumi solutions were collected and labelled “Strong Acid”.
num chloride is separated from the insoluble silica 65 The remaining‘?ltercake, was leached with 200 ml of
gangue by ?ltering and subsequently washing the ?lter hot water for 1 hour, theresulting solution and solids
cake with water. This AlCl3 solution is substantially. ?ltered and the ?lter cake washed with water. The
pure, containing only a minor amount, about 6% to water leach and wash solutions were collected and
 4,239,735
r 5 6
labelled “Water”, The ?lter cake constituted the “Resi ' -continued
due”. Analysis of the.“Strong Acid" and “Water? solu
tions and the dried residue yielded the-following ‘results: Percent Elements in Leaches
Al ‘P205 Fe2O3 K10 MgO CaO
Residue’ 7 I

_ Percent F‘
Al ‘r205 Fe2O3
Strong Acid 1.3.’ ,»86_ ' 88
.Water 97 l4_ l2
Residue l.5
' EXAMPLE II
50 g of calcined clay was leached with 150 ml of‘36
weight percent HCl and 20ml of 30 percent H2SiF6 for
4 hours. No heat was applied; however, the heat gener
ated by the reaction caused the temperature torise to
78° C. HCl gas was injected during the leach‘period but
. > was discontinued while the solids containing leach solu
tion cooled-‘back to room temperature. As a result, the
?nal HCl concentration in the leach liquor was less than
36%. The solution was ?ltered and the ?lter cake
washed with 36% ‘HCl; The ?ltrate and wash solutions
‘were collected and labelled “Strong Acid”. The re 25
maining filter cake was leached with 150 ml of 26%
HCl at 95°“C; for 2 hours. The‘resultingsolution ‘and
solids were ?ltered and the ?lter cake washed with
water.’ The 26% HCl'leach and water wash solutions
were collected and labelled “Weak Acid”. The ?lter
cake constituted the"‘Residue”. Analysis of the “Strong
Acid” and “Weak Acid” solution and the “Residue”
yielded the results set forth below; Titration of the
second leach solution showed‘ that it contained 7% free
HCl. .
‘ in Leaches
K20 Mgo CaQ
v optional. preleaching step is illustrated by the
9l= .94 94-.
following examples.
9_ 6 g .. 6 EXAMPLE IV
'50 g'of uncalcined kaolin clay was leached with 150
ml of ‘2 N HCl for 2 hours at the boiling point. The
resulting‘ solids containing leach solution was ?ltered
and the ?lter cake washed. The ?ltrate and wash solu
tion constituting the preleach, were collected and ana
lyzed. The ?lter cake was then subjected to a leaching
process as described above to remove the remaining
impurities and solubilize the aluminum. Analysis of the
preleach ?ltrate and wash solution showed the follow
ing percentages of impurities and aluminum removed
during preleaching:
The use of 2 N HNO3 and 2 N H2804 yielded similar
results.
EXAMPLE V
50 g of uncalcined kaolin clay was leached as in Ex
ample IV except that 150 ml of 6 N HCl was used.
Analysis of the preleach ?ltrate and wash solution
35 showed the following percentages of impurities and
aluminum removed during preleaching:

‘ ‘Percent Elements in Leaches

Al P205 ’ FezOgv KZIO MgO CaO
40
‘Strong Acid 7 92 97 as 94 ‘94
Wéak Acid 91 s 3 12 6 6
Residue 2 1
We‘claim:
' l. A method for producing substantially pure alumina
from aluminum-containing calcined kaolin clay, com
EXAMPLE III 45
prising‘the steps of:
50 g of raw kaolin was leached with 150 ml of 36 (a) contacting the calcined clay with a solution com
weight percent HCl and 20 ml of 30% H2SiF6 for 2 prising at least 36 weight percent hydrochloric
hours at 95° C. HCl gas was injected into the solids acid, whereby said acid reacts with said clay to
containing leach solution during leaching, cooling and 50 form soluble and insoluble reaction products, said
after cooling to room temperature to insure saturation insoluble products containing a major proportion
with HCl. The solution was then ?ltered and the ?lter of the aluminum content of said clay;
cake washed with 36% BC]. The ?ltrate and wash (b) maintaining said concentration of hydrochloric
solutions were collected and labelled “Strong Acid”. acid at at least 36 weight percent;
The remaining ?lter cake was leached with 200 ml hot (0) separating the solids portion of the clay-reaction
water for 1 hour. The resulting solution and solids were product-acid mixture from the liquid portion;
?ltered and the ?lter cake washed with water. The ((1) washing said solids portion with a solution having
water leach and wash solutions were collected and a concentration of at least 36 weight percent hy
labelled “Water”. The ?lter cake constituted the “Resi drochloric acid;
due”. The “Strong Acid”, “Water” and “Residue” 60 (e) solubilizing the aluminum contained in said solids
were analyzed, as in Examples I and II, and yielded the portion by contacting with water having a temper
results set forth below. ature of about 25° to 100“ C., or with a solution
comprising about 26 weight percent hydrochloric
acid and applying suf?cient heat to drive off the
Percent Elements in Leaches hydrochloric acid content of the resulting solution,
Al P205 Fe1O3 K20 MgO CaO to separate it from the remainder thereof;
Strong Acid 2 94 98 91 91 85 (t) precipitating said aluminum as substantially un
Water 91 6 2 9 9 15 contaminated crystals of AlCl3.6H2O; and
 7
(g) converting said crystals of AlCl3.6H2O to alu
minim _ ._ . . , . ..
2. A method as claimed in claim 1 wherein said clay
hydrochloric acid reaction mixture is heated toa'tem
perature inthe range from about '50“ to 110° C.
3. A method as claimed in claim 1 wherein said clay
hydrochloric acid reaction mixture is heated to a‘ tem
perature in the range from about 90° to 95° C.
4. A method as claimed in claims 1 or 2 wherein said
at least 36 weight percent hydrochloric acid concentra
tion is maintained for a period of about 15 minutes to 4
hours. ,‘
5. A method as claimed in claims 1 or 2 wherein said
at least 36 weight percent hydrochloric acid concentra
tion is maintained for a period of about 1 to 2 hours.
6. A method, as claimed in claim 1, wherein said
solids portion is separated from said liquid portion by
?ltering.
7. A method, as claimed in claim 1, wherein said 20
aluminum chloride crystals are precipitated by sparging
said aqueous aluminum chloride solution with hydro
chloric acid gas.
8. A method for producing substantially pure alumina 25
from aluminum-containing uncalcined kaolin clay, com
prising the steps of:
(a) contacting the uncalcined clay with a solution
comprising at least 36 weight percent hydrochloric
acid and a source of ?uoride ions, whereby said
acid reacts with said clay to form soluble and insol
uble reaction products, said insoluble products
containing a major proportion of the aluminum
content of said clay;
(b) maintaining said concentration of hydrochloric
acid at at least 36 weight percent;
(c) separating the solids portion of the clay-reaction
product-acid mixture from the liquid portion;
(d) washing said solids portion with at least 36 weight
percent hydrochloric acid;
(e) solubilizing the aluminum contained in said solids
portion by contacting with water having a temper
ature of about 25° to 100° C., or with a solution
comprising about 26 weight percent hydrochloric
acid and applying suf?cient heat to drive off the
4,239,?35 8
‘ hydrochloric acid-content of- the resulting solution,
. to separate'it from the remainder thereof;
(f)“precipitating ‘said aluminum as'substantially un
contaminated crystals of AlCl3.6H2O; and
-5 (g) converting said crystals of AlCl3.6H2O to alu
' >~~~~m1na. -- ‘ -
9. A method, as claimed in claim 8, wherein said
. source ofit'luoride ions is selectedfrom the group con
sisting of -H2SiF6, CaF2, HF and Na2SiF6.
10. A method, as claimed in claim 8, wherein said
source of fluoride ions is H2SiF6.
11. A method, as claimed in claim 8, including the
p
step of maintaining said clay-hydrochloric acid reaction
mixture at a temperature in the range from about 50° to
110“v C. . ¢ » .
12. A method, as claimed in “claims 8m 9, vwherein
said at least 36 weight percent hydrochloric acid 'con
centration is maintained for a period of about 15 minutes
, . to 4 hours. . . . - - /
13. A method, as claimedlintclaims 8>.or 9, wherein
said‘ at least 36 weight percent hydrochloric acid con
centration is-maintained fora period plfaabout l to 2
hours. . '. ' . at,” ‘
.
14. A method, as claimedxin claim 8, ,Wherein said
solids portion ,is separated from said liquid portion by
?ltering. _ V, . > I _ .
15. .A method, as claimed in claim..8,=.wherein said
aluminum chloride crystals are precipitated ,by sparging
said aqueous aluminum chloride solution with hydro
chloric acid gas. _ ' _ q i _.
16. A method as claimed in claims ,8 or 9, further
including the ‘steps of contacting said uncalcined clay
prior to step (a) ‘with a solution of a'dilute mineral acid
for a period of about 1 to 2 hours while maintaining said
35 solution at its boiling point to form liquid and solid
‘ ' portions, said liquid portion containing alumina contam
inating impurities and said solid portion containing a
major portion of the aluminum content of said clay and
separating the liquid and solid portions.
17. A method as claimed in claim 16, wherein said
acid is selected from the group consisting of HCl,
HNO3 and H2504.
‘18. A method as ‘claimed in claim 17, wherein the
concentration of said acid is in the range from 2 N to 6
45 N. I '
II! It 1i i i
‘so i
55
65