Ind. Eng. Chem. Prod. Res. Dev.

1983, 22, 105-110 105

parameters. An extension of the foregoing work to en-
compass dynamic filtration could perhaps be of use in
industrial applications.
Acknowledgment
We acknowledge with thanks the support of this project
by both Saint-Gobain Recherche and Everitube and the
cooperation and advice of Drs. J. J. Massol, F. Naudin, and
A. Sabouraud.
Registry No. A1C13, 7446-70-0; Ca(OH)2,1305-62-0.
Literature Cited
Daimon, M.; Roy, D. M. Cem. Concr. Res. 1978, 8(6),753.
Daimon, M.; Roy, D. M. Cem. Concr. Res. 1979, 9(1), 103.
Lindstrom, T.; Shemark, C. Das Papier 1975, 29(12), 519.
Nardin, M.; Papirer, E.; Schukz, J. J . C o / M Interface Sci. 1982, 88(1), 204.
Papirer, E.; Dovergne, G.; Siffert, E.; Leroy, P. Clays Clay Miner. 1976. 24,
101.
Robinson, M.; Pask, J. A.; Fuerstenau, D. W. J. Am. Ceram. SOC.1984, 47,
516.
Schultz, J.; Papirer, E.; Nardin, M. Ind. Eng. Chem. Prod. Res. D e v . 1983a.
Part 1 in this issue.
Schukz, J.; Papirer, E.; Nardin, M. Ind. Eng. Chem. Prod. Res. D e v . l983b.
Pari 2 in this issue.
Schuitz, J.; Papirer, E.; Nardin, M. Ind. Eng. Chem. Prod. Res. D e v . 1 9 8 3 ~ .
Part 3 in this issue.
Touray, J. C.; Thomassin, J. H.; Baiiiif, P.; Scherrer, S.;Champomier. F.;
Naudin, F. J . Non-Cryst. Solids 1980 38, 643.
Received for review February 19, 1982
Accepted August 23, 1982

Bench-Scale Studies To Recover Alumina from Clay by a

Hydrochloric Acid Process

J. A. Elsele," D. J. Bauer, and D. E. Shanks

Reno Research Center, Bureau of Mines, U.S. Department of the Interior, Reno, Nevada 89572

As part of its goal of producing cellgrade alumina from clay, the Bureau of Mines, US. Department of the Interior,
conducted bench-scale cyclic tests of the Bureau's proposed clay-HCI leaching-HCI sparging process and in-
vestigated in detail the crystallization of aluminum chloride hexahydrate. The composition of recycled leaching
liquor was determined for two HCI sparging crystallization conditions: 36% HCI and 26% HCI. Crystallization
research showed that cell-grade alumina could not be produced without a recrystallization step.

Introduction Table I. Composition of Calcined Clay

Alumina feed for electrolytic cells in the production of compd or compd or
aluminum metal is obtained from bauxite by the Bayer element 9i element 9i
process. The United States has very little bauxite and is 43.0 cy203 0.014
dependent on imports. As part of its goal of decreasing 3.27 ZnO 0.012
dependence on foreign resources, the Bureau of Mines 1.26 NiO 0.0079
implemented a program for producing cell-grade alumina 0.087 MnO 0.0037
from domestic aluminous material. 0.087 CUO <0.005
The United States has more than 3 billion tons of 0.063 so4 0.18
0.034 F 0.025
high-grade kaolinitic clay that cannot be treated by the 0.032 SiO, 51.8
Bayer process because of high SiOz content (Bureau of
Mines, 1967). Extensive research has been conducted to
had defined this parameter, a bench-scale test program was
devise an acid process to recover alumina (Peters and
undertaken to obtain this information. Process liquor was
Johnson, 1974). The most promising process is HCl
recycled until the impurity level approached steady state,
leaching of the clay and crystallization of A1C13.6Hz0
which allowed an accurate projection to be made of the
(ACH) by sparging with HC1 gas (Bengtson et al., 1978). impurity content of the liquor when varying size bleeds-
The Bureau of Mines performed bench-scale and mi-
treams are taken in the process.
niplant-scale research to provide essential information for
Since less than 10% of the impurities were removed
design of a 25-ton-per-day HC1 process pilot plant from the liquor by cocrystallization with ACH, the com-
(Bengtson et al., 1980; Eisele, 1980; Maysilles et al., 1981;
Poppleton and Sawyer, 1977; Shanks et al., 1981). In this position of the recycle liquors was not greatly affected by
the mode of crystallization. A crude crystallization step
process, calcined clay is leached with 26% HC1 and the
was made during each cycle and provided a mother liquor
clarified liquor is treated by solvent extraction to remove
iron. The purified pregnant liquor is evaporated to in- for recycling to leaching. The mode of crystallization
greatly influenced crystal growth and purity. After im-
crease the A1Cl3concentration, and ACH is crystallized by purity concentrations were determined in the liquors, more
injecting HC1 gas. The crystals are calcined to alumina, exacting crystallization tests were performed on simulated
and HCl is recovered from the offgases. liquors to determine the quantity of impurities in the ACH
An important parameter is the purity of the product crystals for a given liquor composition.
alumina. Data on the purity of alumina produced by a
continuous process can bnly be obtained by knowledge of Materials, Equipment, and Procedures
the concentration of impurity elements in the feed stream 1. Leaching-Recycling Tests. Unit operations used
going to crystallization. Since none of the previous work in the leaching-recycling tests are shown in Figure 1 and
This article not subject to US. Copyright. Published 1983 by the American Chemical Society
106 Ind. Eng. Chem. Prod. Res. Dev., Vol. 22, No. 1, 1983

Minus IO-mesh
calcined clay
oxidized by injecting chlorine gas into the solution until
the solution EMF was 650 mV; at this point the Fez+was
<5 ppm.
I h a t 105 "C (e) Solvent Extraction. Iron was extracted from the
oxidized liquor with an organic phase containing 15 vol %
Tailing Alamine 336 (a tertiary amine), 10 vol % decyl alcohol, and
75 vol '70 kerosine. (Reference to specific trade names or
companies is for identification only and does not imply
Evaporate t o
2 5 % AIC13 endorsement by the Bureau of Mines.) Solvent extraction
at I O 8 OC was performed in separatory funnels. The feed liquor was
extracted at a phase ratio of 41, aqueous-to-organic(A/O).
The organic phase was stripped with 0.1 N HC1 at a
phase ratio of 4:3, O/A. The stripped organic phase was
stored until the next cycle. The pregnant liquor was
poured through a column of activated carbon to remove
traces of organic material.
(f) Evaporation to 30% AlCl,. The purified pregnant
Iron Evaporate t o liquor was evaporated to increase the concentration of
3 0 % AICI3
at 113 OC
AlCI, to 30%. The concentrated liquor was the sparger

z Samples
feed from which ACH was crystallized. Sparger feed was
analyzed by atomic absorption spectrophotometry for
Fez03,NazO, K,O, CaO, MgO, MnO, CuO, NiO, PbO, and
Crz03. AlCl,, Sod2-, and Pz05were analyzed by wet-
chemical methods, and F was analyzed with a specific ion
t
I
-
' Volume and
acid adjustment
F i l t e r and wash
AICI~.BHzO
36% H C I
wash
electrode.
(g) Sparging with HCl Gas. Although AlC13 is very
soluble in solutions containing negligible amounts of free

Q Calcination
5 h at 1,100 " C

A l 2 O 3 product

Figure 1. Flowsheet of operations for bench-scale clay-HC1 leach-

ing-HC1 sparging process.
will be described in detail below.
(a) Leaching. Kaolinitic clay obtained from the Thiele
Kaolin Co., Sandersville,GA, was calcined at 750 "C before
sizing to -10 mesh. Analysis of the calcined clay is given
in Table I.
The clay was leached with 105% of the stoichiometric
requirement of 26% HCI in a 4-L glass reaction vessel
fitted with a condenser. For the first cycle, reagent grade
36% HC1 was diluted to 26%. For subsequent cycles, the
combined mother liquor and acid wash liquors were ad-
justed to the required acid concentration and volume for
leaching.
To start the first cycle, 800 g of clay and 3 L of HC1 were
used. For each subsequent cycle, the amount of clay was
decreased by a factor that represented the loss of liquor
that resulted from sampling. The only exiting materials
were the ACH crystals and the small amount of liquor not
washed out of the clay tailing, which contained less than
2 % of the soluble components.
(b) Filtering and Washing. The residue was separated
from the pregnant liquor and washed in a centrifuge. The
residue was washed three times with 0.1% HC1. Total
wash volume was approximately 3 L. The wash volume
is greater than would be used in a pilot plant, but it en-
sured that 98% of the solubilized aluminum was recovered
from the residue. The pregnant solution and washes were
clarified by filtration.
(c) Evaporation to 25% AlCl,. Because a large volume
of washing solution was used, the combined filtrate was
concentrated by evaporation to 25% AlCl, and had a
volume between 1.5 and 2.5 L.
(d) Oxidation. Although most of the iron in the
leaching liquor was in the ferric form, a small amount of
nonextractable ferrous iron was present. The Fez+was
HC1, solubility decreases when HC1 concentration increases
(Brown et al., 1979). According to equilibrium solubility
data, at 26% HC1 approximately 85% of the contained
AlCl, is crystallized from 30% AlCl, solution, and more
than 99% is crystallized a t 36% HCl.
Bench-scale sparging with HCl gas to 26% resulted in
about 70% crystallization of AlCl,. Sparging to 36% HC1
resulted in about 90% crystallization. Since 85% crys-
tallization with 26% HCl in the mother liquor was not
achieved, two sets of runs were made. In one run of 20
cycles, the feed was sparged to 36% HC1. In the second
run of 10 cycles, the feed was sparged to 26% HC1. The
results were compared, and the effect of acid strength on
ACH crystal purity was determined.
Sparging was done in a 4-L glass vessel surrounded by
a water-cooled jacket. HC1 gas was introduced through
a glass tube at the bottom of the vessel while the contents
were gently agitated. The total crystallization time was
3 h, and the temperature averaged 50 OC.
(h) Filtering and Washing the ACH Crystals. The
ACH crystals were separated from the mother liquor by
vacuum filtering. The objective was to wash the crystals
as clean as possible, rather than to minimize wash volume.
Each batch of crystals was washed three times with 36%
HC1. About 99% of the mother liquor was removed, and
no significant amounts of aluminum were dissolved. The
crystals were vacuum-dried on the filter, transferred to
glass pans, and dried at 95 "C for 12 to 24 h. The dried
crystals were weighed, and a portion was removed for
calcining.
(i) Calcination. Two-hundred-fifty grams of the ACH
crystals was slowly heated to expel most of the HC1. The
temperature was raised to 1100 OC and maintained for 5
h. Fifty grams of Alz03was produced. Alumina samples
were analyzed by X-ray fluorescence for Fez03, NazO,CaO,
SO,, NiO, TiOz, V205,CuO, MnO, ZnO, C1, and Pz05.
Although X-ray fluorescence is not an accurate method for
determining low levels of P,06, it was adequate for the
levels encountered. Cr203and SiOz were analyzed spec-
trographically, and MgO was analyzed by atomic absorp-
tion analysis after dissolution of the sample.
 Ind. Eng. Chem. Prod. Res. Dev., Vol. 22, No. 1, 1983 107

Table 11. The Composition of Sparger Feed from 20 Cycles, 36% HCl in Mother Liquor, %a

impurity
cycle Na,O K,O CaO MgO P,O, SO, F MnO CuO NiO PbO Cr,O,
1 0.006 0.013 0.008 0.015 0.020 0.002 0.004 <0.0001 0.0030 0.001 0.003
5 0.032 0.062 0.043 0.077 0.061 0.11 0.007 0.015 0.0004 0.0094 0.004 0.012
10 0.047 0.087 0.083 0.13 0.084 0.22 0.011 0.016 0.0013 0.015 0.006 0.017
15 0.072 0.14 0.106 0.18 0.115 0.29 0.005 0.021 0.0019 0.020 0.010 0.026
20 0.078 0.15 0.117 0.22 0.120 0.35 0.005 0.023 0.0032 0.021 0.009 0.026
The chemical compositions of the impurities were not determined, but in most cases they are probably chlorides. They
are reported as oxides to conform t o industry practice. All cycles contained 30% AlCl, and 40.002% Fe,O,.

Table 111. The Composition of Sparger Feed From 10 Cycles, 26% HC1 in Mother Liquor, %a

impurity
cycle Na,O K,O CaO MgO P,O, SO, F MnO CuO NiO PbO Cr,O,
1 0.006 0.014 0.011 0.021 0.018 0.03 0.001 0.001 0.0004 0.002 0.001 0.003
5 0.020 0.043 0.032 0.055 0.048 0.11 0.002 0.004 0.0008 0.006 0.004 0.010
10 0.042 0.074 0.057 0.10 0.077 0.18 0.03 0.006 0.0006 0.009 0.005 0.017
a The chemical compositions of the impurities were not determined, but in most cases they are probably chlorides. They
are reported as oxides to conform to industry practice. All cycles contained 30% AlCl, and 90.002% Fe,O,.

(j) Acid Adjustment. The combined mother liquor and

HC1 washes after crystallization were adjusted to give the I KEY
correct amount of HC1 for leaching calcined clay in the
next cycle. The amounts of clay and acid needed for each -0- 25 oc
....0 .... 45 oc
succeeding leaching cycle were calculated on the decrease
65OC
in weight of sparger feed due to sample removal. Even -A-

though the volume decrease was small for each cycle by

the 20th cycle, only 438 g of clay was leached, compared
with 800 g for the first cycle.
2. Draft-Tube Crystallization Tests. Hydrogen
chloride sparging crystallization of ACH is based on the
low AlCl, solubility in concentrated HC1. Figure 2 shows
the effects of HCl concentration and temperature on the
solubility of AlC1, (Brown et al., 1979).
A bench-scale, draft-tube crystallizer was designed and
constructed to study the behavior of impurities during
crystallization. Top and side views are illustrated in Figure
3.
Aluminum chloride solutions were crystallized in a J
40

400-gal continuous crystallizer in the Boulder City Engi-
neering Laboratory (BCEL) miniplant and in the bench-
scale crystallizer. Two feeds were sparged to 26% HC1 in
each crystallizer. One sparger feed was a one-cycle preg-
nant liquor. The other sparger feed was made by dis-
solving ACH crystallized from the first sparger feed in
deionized water. There was little difference between
crystals produced by the two types of crystallizers. This
indicated that a batch, bench-scale crystallizer can be used
to predict the purity of crystals produced in larger scale
equipment.
Aluminum chloride liquors were prepared to match the
compositions of selected cycles of the leaching-recycle
study. Commercial ACH crystals were dissolved in dis-
tilled water, and the impurity levels were adjusted to the
composition of the appropriate cycle.
In each crystallization experiment, the crystallizer vessel
was charged with 2.0 L of 30% aluminum chloride liquor.
Nitrogen and hydrogen chloride gases were mixed in a
packed column and injected at 1 / 2 in. above the propeller
blades into the aluminum chloride liquor. Sparging with
HC1 continued until the HC1 concentration in the mother
liquor was 26%.
The ACH crystals were separated from the mother li-
quor by vacuum filtration through a coarse fritted glass
disk. Entrained mother liquor was removed from the
crystals by a displacement wash with 1.0 L of 26% HC1
saturated with AlCl,, followed by one displacement wash
HCI CONCENTRATION, percent
Figure 2. The effects of HC1 concentration and temperature on the
solubility of AlCl,.
and two reslurry washes of 36% HC1. After washing, the
ACH crystals were dried under infrared heat lamps. The
crystals were screened through US. Standard stainless
steel screens to determine crystal size distribution.
The liquid samples and redissolved ACH crystals were
analyzed for FezO3, Na20, K 2 0 , CaO, MgO, MnO, CuO,
NiO, PbO, and Cr203by atomic absorption spectroscopy,
and for AlCl,, P205,Sod2-, and F- by wet-chemical meth-
ods.
Results and Discussion: Leaching-Recycling
(1) 36% HCl Sparging Test. During the 20-cycle run,
an average of 95% of the aluminum was leached. Ap-
proximately 92% of the AlCl, was crystallized from the
mother liquor by sparging to 36% HC1.
Table I1 gives the analyses of sparger feeds for selected
cycles. The impurity concentrations, except for iron, in-
creased with each cycle, but not at constant rates and not
at the same rates. At 20 cycles, the concentration of MgO
was increasing at the greatest rate, whereas the concen-
tration of NazO had almost reached a constant value.
(2) 26% HCl Sparging Test. During the 10-cycle run,
an average of 95% of the aluminum was leached. An
average of 76% of the contained AlCl, was crystallized
from the mother liquor by sparging to 26% HC1.
108 Ind. Eng. Chem. Prod. Res. Dev.. Vol. 22. No. 1. 1983

Table N. Analyses of Alumina Produced in Recycling Tests,

cycle Fe,O, K,O CaO MgO P,O, NiO TiO, CrA CUO SiO,
1, 36%HCI 0.007 0.023 0.003 0,010 0.014 0.001
0.001 0.012 0.02
<0.002
1, 26%HCI 0.004 0.008 0.001 0.006 0.007 0.001
0.001 0.009 0.004
<0.002
5, 36%HCI 0,009 0.042 0.004 0.023 0.035 0.003
0.003 0.012 0.03
0.04
5, 26%HCI 0.003 0,011 0,002 0.027 0.030 0.002
0.001 0.008 0.01
<0.002
10,36%HC1 0.003 0.042 0.003 0.053 0.037 0.003
0.001 0.012 0.02
0.01
10, 26%HCI 0.003 0.014 0,002 0.038 0.025 0.002
0.001 0.006 0.02
0.11
15, 36% HCI 0.004 0.032 0.004 0,080 0.064 0.002
0.005 0.014 0.03
0.08
20, 36%HCl 0.004 0.024 0.005 0.066 0.047 0.005
0.001 0.013 0.03
0.004
Bayer 0.02 0.003 0.016 0.003 <0.005 <0.005
0.004 0.012 ND
0.004
specifications 0.03 0.005 0.06 0.002 0.001 0.005
0.005 0.01 0.002
0.025
Alumina from all cycles contained <0.003% ZnO, <0.001% V,O,, 60.002% MnO,, <0.03% Na,O, <0.009% SO,, and
<0.02% CI.

~ ~~~

KEY
.20 "C
40 ' C
085- 60 T
0"
a" Cmd,f,onr

FRONT Y E W

PHOSPHORUS IN SPARGER FEED. nersenl P2Os

Figure 4. The effect of temperature and phosphorus concentration

Figure 3. Bench-scale ACH crystallizer
Table 111gives the analyses of sparger feed for selected
cycles. In 10 cycles, the "leveling off" of impurity disso-
lution was not apparent. Impurity concentration for a
given cycle w&slegs for the 26% HC1 test than for the 36%
HC1 test The greater mass of the sparger feed in the 26%
HC1 test produced a dilution effect. The increased feed
mass resulted from circulation of 24% of the AICI, in the
26% HC1 test, compared with 8% circulation in the 36%
HC1 test.
(3) Alumina Purity. Table IV gives the analyses of
alumina produced from liquors of selected cycles from both
26% and 36% HC1 sparging.. The analysis for alumina
produced by the Bayer process and the specifications for
cell-grade alumina, as defined by several major aluminum
producers, are also shown. The S O z analyses are erratic,
hut the alumina produced by an HC1 process is nominally
acceptable with regard to SiOa content. Four impurities
exceed the specifications, even in the first cycle: KzO,
MgO, Pz05,and Crz03. Alumina produced from 26%, HC1
in sparger feed on phosphorus content of ACH.
sparging was cleaner than that from 36% HCI sparging.
Subsequent crystallization studies showed that slowing the
crystallization rate decreased the potassium and chromium
content to acceptable levels. Since phosphorus and mag-
nesium always exceeded the specified maximum concen-
trations, the crystallization step was studied to determine
if crystals of adequate purity could he produced, or if a
recrystallization step was necessary (Shanks et al., 1981).
(4)Crystallizer Configuration and Gas Flow Rate.
In initial studies, the spacing and dimensions of the
crystallizer draft tube and propeller were not major factors.
Pockets of high HCI concentration were prevented from
forming by mixing the HC1 with an inert carrier gas.
Doubling the HC1 flow rate from 1.3 to 2.6 L/min doubled
the phosphorus and magnesium concentration in the ACH
crystals. Decreasing the flow rate helow 1.3 L/min had
no effect on crystal purity. One and three-tenths liters per
minute was used in subsequent tests.
(5) Effects of Sparger Feed Phosphorus and Mag-
nesium Concentrations on Purity of ACH Crystals.
The effect of phosphorus and magnesium concentration
in sparger feed on the concentration of phosphorus and
magnesium in ACH crystals is plotted in Figures 4 and 5
for temperatures of 20.40, and 60 "C. The advantage of
operating a t 60 "C rather than 20 or 40 "C is shown. A t
sparger feed concentrations greater than 0.12% Pz05and
temperatures of 40 and 60 "C, the amount of phosphorus
incorporated into the ACH crystals is not linearly pro-
portional to the amount in the sparger feed. This fact is
significant for a process utilizing a recrystallization step.
The first crystallization can he made from impure liquor
without significantly increasing the Pz06content of the
ACH going to the recrystallization step.
 Ind. Eng. Chem. Prod. Res. Dev., Vol. 22, No. 1, 1983 109

.
I I I
KEY Conditions

A
20 oc

4 0 OC
p Ooo8-
AIC13 feed concenlralion
Final HCI concentration
30%
26%

0
60 "C a

Conditions:
AIC13 f e e d concentration;
30%
- Final HCI concentration:
2 6 '10

I I I I
0
0 005 0 010 0015 0020 0025
MAGNESIUM IN SPARGER FEED, percent MgO

Figure 7. The effect of magnesium concentration in sparger feed

on magnesium content of ACH at 60 'C.

/$2
Conditions
AICIs feed concentration 30%
Temperature 60 OC
Final HCI concentration

- B /. 0
//

z
-.- KEY
--C 1st stage
2d stage
Single stage
1 .

M A G N E S0.08
I U M IN SPARGER
0 16 F E E D , percent
0.24 MgO

Figure 5. The effect of temperature and magnesium concentration

in sparger feed on magnesium content of ACH.

I Conditions I
6
PHOSPHORUS IN SPARGER FEED, percent P205

Figure 8. Phosphorus content of ACH from two-stage crystalliza-

tion compared to single-stage crystallization.
0 oc
e 0004
I I I
Conditions
AlCl3 feed concentration 30%
Temperature 60 C'
Final HCI concentra1ion
p OC
1st stage 15% / -

-
2d stage 2 6 %
J
/
+ /'
I I I I

-.- /.
0 0 005 0 010 0015 0020 0025 KEY /'
/
PHOSPHORUS IN SPARGER FEED, percent P2O5 Is1 stage /'
i
Figure 6. The effect of phosphorus concentration in sparger feed :: 00 .......2dSinglestagestage /' -
on phosphorus content of ACH at 60 OC. I I
/

5
When ACH is decomposed to alumina, there is a 4.73- z
z
fold increase in concentration of impurities. To produce P
alumina that meets specifications of 0.001% P205and = 00

0.002% MgO, the P205and MgO content of ACH cannot

exceed 0.00021% and 0.00042%, respectively. The chem-
ical compositions of the impurities in the ACH were not
determined but are reported as oxides to conform to alu-
mina industry practice. The maximum allowable con-
centration of phosphorus and magnesium in sparger feed
can be determined graphically. Figures 6 and 7 are en-
largements of the low-concentration portions of Figures
4 and 5 and show the intersection of phosphorus and
magnesium specification with the 60 "C curves. The
maximum permissible concentrations in sparger feed are
0.003% P205and 0.01% MgO. Since the concentration
of P205and MgO in cycle 1 liquor was about 0.02%, a
recrystallization step was necessary.
(6) Crystal Growth and Aluminum Chloride Con-
centration. Most crystallization tests were performed in
a single stage, but some were performed in two stages to
MAGNESIUM IN SPARGER FEED, percent MgO
Figure 9. Magnesium content of ACH from two-stage crystalliza-
tion compared to single-stage crystallization.
simulate the proposed Kaiser pilot-plant flowsheet
(Bengtson et al., 1980). In the two stage tests (Figures 8
and 9), the ACH crystals were removed in two batches, the
first batch when HC1 concentration was 15%, and the
second batch when HC1 concentration was 26%. The
results for single-stage crystallization are shown for com-
parison.
The crystals produced in the first and second stages are
more contaminated than the crystals obtained in a single
110 Ind. Eng. Chem. Prod. Res. Dev., Vol. 22, No. 1, 1983
0 Oler I I
Temperature 60
KEY
bo5
-2- MgO
- 200
IO 20
AICI, CONCENTRATION OF SPARGER FEED, percent
Figure 10. The effect of AlC1, concentration on phosphorus and
magnesium content of ACH.
stage of sparging. The impurity content of the single-stage
crystals would be expected to be the average of the im-
purity contents of the first- and second-stage crystals. A
possible explanation is that the major portion of the
phosphorus and magnesium is incorporated in the crystals
during the early stage of crystal growth, and relatively little
is incorporated during the subsequent, slower, crystal
growth stage. If the process is interrupted by removing
all the crystals (at 15% HCl), nucleation must occur again
for the crystals produced during sparging from 15% to
26% HC1. Both sets of crystals will contain more im-
purities than if crystal growth had proceeded without in-
terruption in a single stage. The second-stage ACH
crystals contained significantly more phosphorus than
either first-stage or single-stage ACH crystals. The most
obvious differences in conditions were that second-stage
crystallization began in a solution containing 15% AlCl,
and that the total weight of crystals recovered was less.
To define the effect of AlC1, concentration on crystal
purity, a series of tests was made in which the phosphorus
and magnesium concentrations were constant a,nd the
AlCl, concentration was varied. Figure 10 shows that AlCl,
concentration is an important parameter and should be
30% at the start of crystallization so that the amount and
purity of ACH recovered from solution is maximized.
In another test, MC13feed containing no impurities was
sparged, and as soon as crystallization was observed, 0.12%
P205and 0.22% MgO were added. The ACH contained
OC
one-third of the phosphorus and one-half of the magne-
sium usually incorporated into crystals sparged from liquor
of this composition. Seeding with pure ACH to provide
clean nuclei for crystal growth may produce significantly
cleaner crystals from contaminated liquors.
Conclusions
Bench-scale leaching and recycling tests determined the
composition of aluminum chloride liquors in the clay-HC1
leaching-HC1 sparging process. Specifications for all im-
purities except P2O5 and MgO can be met by crystallizing
from a liquor that simulates 20 cycles. Specifications for
P205and MgO were not met even by crystallizing from a
first-cycle liquor, corresponding to discarding all the
mother liquor from crystallization as a bleedstream. A
recrystallization step must be included in the process
flowsheet. Significantly cleaner crystals may possibly be
produced by a seeding technique.
Registry No. AlCl,, 7446-70-0; A1,0,, 1344-28-1.
Literature Cited
Bengtson, K. 6.; Chaberka, P.; Malm, L. E.; McLaughlin, A. E.; Nunn, R. F.;
Stein, D. L. "Alumina Process Feaslbillty Study and Preliminary Pilot Plant
Deslgn. Task 1 Report: Comparlson of Six Processes"; BuMines Open
Flle Rept. Pb-286 638, Sept. 1977; 267 pp. [Available for consultation at
the Bureau of Mines libraries in Tuscaloosa, AL, Avondale, MD, Twin Cit-
ies, MN, Rolla, MO, Boulder Cky and Reno, NV, Albany, OR, and Salt Lake
City, UT, at the National Library of Natural Resources, U.S. Department of
the Interior, Washington, D C and from National Technical Information
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Piant Design. Task 3 Report: Preliminary Design of 25 Ton Per Day Pilot
Plant, vol. 1, Process Technology and Costs"; BuMines Open File Rept.
PB81-125031, Nov 1979; 231 pp. [Available as In preceding reference,
except PB8 1- 125031.]
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ity of Aluminum Chloride in Aqueous Hydrochloric Acid Solutions"; Bu-
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Bureau of Mines "Potential Sources of Aluminum": BuMines I C 8335, 1967;
148 pp.
Eisele, J. A. "Producing Alumina From Clay by the Hydrochloric Acid Process,
A Bench-Scale Study"; BuMlnes R I 8476, 1980; 20 pp.
Maysilles, J. H.; Traut, D. E.; Sawyer, D. L., Jr. "Aluminum Chloride Hexa-
hydrate Crystallization by HCI Gas Sparging, Alumina Recovery by the
Clay/Hydrochloric Acid Process"; BuMines R 1 8590, 1981; 20 pp.
Peters, F. A.; Johnson, P. W. "Revised and Updated Cost Estimates for Pro-
ducing Alumina From Domestic Raw Materials"; BuMlnes I C 8648, 1974;
51 PP.
Poppleton, H. 0.;Sawyer, D. L. "Hydrochloric Acid Leaching of Calcined
Kaolin to Produce Alumina"; Light Metals, TMS Light Metals Committee,
published by the Metallurgical Society of AIME, P.O. Box 430, Warren-
dale, PA, Vol. 2, 1977; pp 103-1 14.
Shanks, D. E.; Eisele, J. A.; Bauer, D. J. "Hydrogen Chloride Sparging Crys-
tallization of Aluminum Chloride Hexahydrate"; BuMines R I 8593, 1981;
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Received for review March 24, 1982
Revised manuscript received August 2, 1982
Accepted August 15, 1982