2646 Ind. Eng. Chem. Res.

1997, 36, 2646-2650

Production of Poly(aluminum chloride) and Sodium Silicate from

Clay
Kyun Young Park*
Department of Chemical Engineering, Kongju National University, 182 Shinkwandong,
Chungnam 314-701, Korea

Jin-Kwon Kim
Department of Chemistry, Kongju National University, 182 Shinkwandong, Chungnam 314-701, Korea

Jinki Jeong and Young Youn Choi

Department of Materials Development, Korea Institute of Geology, Mining and Materials, P.O. Box 14,
Taedok Science Town, Taejon, Korea

A novel process is proposed for the extraction of aluminum from clay, by which the aluminum
is recovered as poly(aluminum chloride) solution requiring energy much less than that for the
recovery as alumina, and the volume of the siliceous residue left after the aluminum was
extracted from the clay can be reduced by 70% by extracting the silicon from the residue as
sodium silicate solution. The poly(aluminum chloride) solution was made by partially decompos-
ing the aluminum chloride hexahydrate, an intermediate product leading to alumina on complete
decomposition, and subsequently dissolving the resultant basic chloride in water at 90 °C. About
80% of the silicon in the siliceous residue could be recovered as sodium silicate by leaching the
residue with 20 wt % NaOH for 1 h at 100 °C under atmospheric pressure. The maximum
molar ratio of SiO2:Na2O of the sodium silicate solution thus obtained was 3.0:1.

Introduction sumption and the waste volume considerably. By this

Non-bauxite aluminum ores, including kaolinic clay,
have been considered as alternative sources for alumina.
Among various methods proposed for producing alumina
from non-bauxite sources, the HCl method is known to
be the most promising (Peters and Johnson, 1974). By
the HCl method, the ore is treated by hydrochloric acid
leaching. The resulting solution, which contains iron
and aluminum, is subjected to a purification step in
which iron is removed by solvent extraction. Aluminum
values in the purified liquor is recovered as aluminum
chloride hexahydrate (AlCl3‚6H2O) by crystallization.
The chloride is then thermally decomposed and calcined
at about 1100 °C to produce alumina.
The process of alumina production from clay based
on the HCl method, however, appears to have no
apparent economic advantage over the Bayer process,
although the comparison between the two processes is
difficult because the Bayer process is well refined and
the HCl process is not. The decomposition of aluminum
chloride hexahydrate is highly endothermic, requiring
a supply of considerable heat volumes. In comparison
with the Al2O3 calcination from aluminum hydroxide
according to the Bayer process, the specific heat re-
quirement and the specific waste gas volume are four
times as high (Marchessaux et al., 1979). This must
be a problem of the HCl process. Another problem
associated with the HCl process is that bulky residues
are generated; about two-thirds by weight of the clay
charged for the acid leaching remains undissolved, the
major component of which is silica. Utilization of this
residue should be important, but has received little
attention.
A new process is proposed for the recovery of alumi-
num from clay, which would reduce the energy con-
* Author to whom correspondence should be addressed. Tel,
82-416-50-8637; FAX, 82-416-50-8589.
S0888-5885(96)00786-5 CCC: $14.00
process, as shown in Figure 1, the aluminum is recov-
ered in the form of poly(aluminum chloride) used as a
flocculating agent in water treatments, and the volume
of the solid waste is reduced by extracting the silicon
from the residue in the form of sodium silicate solution
used as adhesives and for the production of precipitated
silicas and synthetic zeolites. The poly(aluminum chlo-
ride) is produced by partially decomposing the alumi-
num chloride hexahydrate at a temperature of 200 °C,
much lower than the decomposition temperature re-
quired for alumina, and subsequently dissolving the
resulting basic chloride in water. This is a new method
for the production of poly(aluminum chloride). The
sodium silicate solution is produced by leaching the
siliceous residue with NaOH under atmospheric pres-
sure.
Experimental Section
The clay samples were obtained from Sancheong,
Korea. The chemical analysis of the clay is shown in
Table 1. Mineralogical X-ray diffraction analyses were
made using Cu KR radiation. The principal mineral
was halloysite. Minor minerals found were: kaolinite,
feldspar, quartz, and montmorillonite.
Preparation of Samples. The clay was calcined at
750 °C for 2 h, then leached at 105 °C for an hour with
105% of stoichiometric requirement of 26 wt % hydro-
chloric acid in a closed 1-L flask with mechanical
stirring and refluxing. The clay charged for leaching
weighed about 200 g. Following the leaching, the slurry
was filtered and the residue washed three times with
water and dried. The filtrate was passed to a solvent
extraction step, in which iron is removed with an
organic phase containing 15 vol % Alamine 336 (a
tertiary amine), 10 vol % decyl alcohol, and 75 vol %
kerosene. The extraction was carried out at a phase
ratio of 4:1, aqueous/organic. By this solvent extraction,
© 1997 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997 2647

Figure 2. Experimental apparatus for partial decomposition of

AlCl3‚6H2O.

Table 3. Chemical Analysis of Impurities in AlCl3‚6H2O

component content (wt ppm)
Si 30
Na 180
Fe 5
Mg <1
Ca 15
K 90
Ti <1

equipped with a pH meter. The pH decreased with the

acid gas being absorbed. The pH indicates the amount
of hydrogen chloride evolved or the extent of decomposi-
Figure 1. Block diagram for production of poly(aluminum tion. When the pH arrived at a predetermined value,
chloride) and sodium silicate from clay. the decomposition was stopped. The resultant material,
a basic chloride, was taken out of the decomposition
Table 1. Composition of Clay flask and weighed. IR spectra of the basic chloride were
compound wt % compound wt % measured on an IR spectrophotometer (Bomem MB
Al2O3 37.86 K2O 1.53
series) after pressing the samples into KBr pellets. The
SiO2 44.03 MgO 0.78 basic chloride was then dissolved in hot water at 90 °C.
Fe2O3 1.46 TiO2 0.20 One hour was enough for the dissolution. The resulting
CaO 1.85 MnO 0.02 poly(aluminum chloride) solution was analyzed for
Na2O 0.33 H 2O 11.32 aluminum content and basicity. The basicity, which is
defined as the equivalent ratio in percentage of OH to
Table 2. Composition of the Siliceous Residue
Al present in a poly(aluminum chloride) solution, was
compound wt % compound wt % determined by following the procedure described in KS
SiO2 79.58 MgO 0.095 (Korean standard) M 1510-1981. NMR spectra of the
Al2O3 11.48 Na2O 0.099 solution were measured to determine the structures of
CaO 0.15 TiO2 0.16 Al species in the solution.
Fe2O3 0.33 ignition loss 7.62 Production of Sodium Silicate. The siliceous resi-
due was leached with an NaOH solution in a 1-L flask
the iron content was reduced from 0.4 wt % to less than with mechanical stirring and refluxing. The weight of
5 ppm. The purified pregnant solution was sparged the residue charged was about 100 g. The molar ratio
with HCl gas to 26% to produce aluminum chloride of Na in the NaOH solution to Si in the residue was
hexahydrate crystals. The crystals were separated from varied from 0.4 to 1.0, the leaching temperature from
the mother liquor by vacuum filtering, washing with 25 to 100 °C, the leaching time from 30 to 120 min, and
36% HCl, and vacuum drying. This procedure for the the NaOH concentration from 10 to 50 wt %. After
preparation of aluminum chloride hexahydrate is the leaching, the undissolved solids were removed using a
same as that used by the Bureau of Mines (Eisele, 1980). vacuum filter. The filtrate, a sodium silicate solution,
Chemical analyses for the siliceous residue and the was then analyzed for chemical composition.
aluminum chloride hexahydrate are shown in Tables 2
and 3, respectively. Results and Discussion
Production of Poly(aluminum chloride). The
aluminum chloride hexahydrate was thermally decom- Poly(aluminum chloride). The aluminum chloride
posed in a 50-cc flask immersed in a silicon oil bath. hexahydrate was subject to decomposition for 180 min
The schematic drawing of the experimental apparatus at temperatures of 140, 160, 180, and 200 °C. The
is shown in Figure 2. About 5 g of the chloride was extent of decomposition, which is defined as the ratio
spread on the bottom of the flask and then heated to a of the weight loss at a given time to the weight loss on
temperature of 150-200 °C with a flow of nitrogen gas complete decomposition, is presented as a function of
through the flask at a rate of 40 cc/min. Hydrogen time in Figure 3. It is apparent that the temperature
chloride gas and water vapor evolved with decomposi- had a significant influence on the rate of decomposition.
tion. They were absorbed by water in a 1-L flask At 140 °C, the extent of decomposition reached 4.8% in
2648 Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997
Figure 3. Extent of decomposition with time at different decom-
position temperatures.
Figure 4. Arrhenius plot for thermal decomposition of aluminum
chloride hexahydrate at different temperatures.
35 min and showed little increase thereafter. At the
higher temperatures of 160, 180, and 200 °C, the extent
of decomposition increased continuously with time and
reached 44.5, 79.3, and 83.7%, respectively, at the end
of the run. The decomposition rate is modeled by
dX
) Ae-E/RT(1 - X)
dt
where X is the instantaneous extent of decomposition,
t is the time, A is the preexponential factor, and E is
the activation energy for decomposition. Upon integra-
tion and rearrangement, one obtains eq 2. An Arrhe-
ln [ -ln(1 - X)
t ]
) ln A -
E 1
RT ()
nius plot (Figure 4) was constructed from the data in
Figure 3 using eq 2. From the straight line drawn to
fit the data at 160, 180, and 200 °C, the activation
energy and the preexponential factor were calculated
to be 55.5 kJ/mol and 297.6 s-1, respectively. The data
at 140 °C were scattered over a broad range and fall
below the line, implying the decomposition rate repre-
sented by equation 1 may not be applicable at 140 °C.
The decomposition was too slow at that temperature;
therefore, no further investigation was made.
The X-ray diffraction patterns at different extents of
decomposition are reproduced in Figure 5, from which
Figure 5. X-ray diffraction pattern at different extents of
decomposition.
Figure 6. IR spectra of the solid material resulted from decom-
position at different extents of decomposition.
it is obvious that at the extent of decomposition of 63.8%
the patterns changed markedly, indicating the material
had become almost amorphous. Figure 6 shows the IR
spectra of the solid material that resulted from the de-
composition at various extents of decomposition ranging
0-63.8%. The absorption peak at 1640 cm-1 is due to
the presence of chemically bound water, and those at
600, 800, and 1200 cm-1 are due to the water molecule
(1) coordinated to the aluminum atom (Nakamoto, 1978).
At the decomposition of 33.4% a new peak appeared at
980 cm-1 which is the stretching mode of Al-OH
(Naumann et al., 1979), indicating the formation of basic
aluminum chloride. When the extent of decomposition
reached 63.8%, the peak at 1640 cm-1 was reduced
considerably and also the peak at 800 cm-1 disappeared.
(2)
The basic aluminum chloride was dissolved in water
at 90 °C for an hour to yield a poly(aluminum chloride)
solution. The volume of water was controlled so that
the aluminum content of the solution ranged 8.4-13.4
wt % on the Al2O3 basis. The basic chloride was
completely dissolved to give a clear solution at decom-
positions lower than 63.8%. With a further increase of
decomposition to 78.5%, the solution became opaque due
to incomplete dissolution. For the range of aluminum
content in discussion the solubility was not affected by
the volume of water. Figure 7 shows the 27Al NMR
spectra of an aqueous solution of the basic aluminum
chloride made with the extent of decomposition at
53.0%. The Al2O3 content of the solution was 9.5 wt %.
The narrow resonance at 0 ppm indicates the presence

Figure 7. 27Al NMR spectra of an aqueous solution of the basic
aluminum chloride made at an extent of decomposition of 53.0%.
Figure 8. Basicity of poly(aluminum chloride) solution with
different extents of decomposition.
of octahedral Al3+ monomers. The broad resonance over
0-10 ppm is assigned to the dimers and larger polymers
resulting from dimer condensation (Brinker and Scher-
er, 1990). The ratio of the area under the broad
resonance curve to the one under the narrow resonance
curve, which indicates the molar ratio of polymers to
monomers in the solution, increased with increasing the
extent of decomposition. The basicity of the poly-
(aluminum chloride) solution increased with increasing
the extent of decomposition (Figure 8). The basicity of
45%, the level of commercial-grade poly(aluminum
chloride), was obtained at an extent of decomposition
at about 40%.
Sodium Silicate. Figure 9 shows silica extraction
by 20 wt % NaOH solution for varying leaching tem-
peratures with a solid concentration of 40.0 wt %. The
leaching time was held at 1 h. Silica extractions of 56.1,
71.0, 80.0, 82.0, and 82.0% were obtained at tempera-
tures of 25, 40, 60, 80, and 100 °C, respectively. The
leaching temperature was not actually the temperature
of the leaching solution, but the temperature of the
water bath in which the leaching flask is immersed. On
feeding the residue to the flask, the solution tempera-
ture, initially at 25 °C, rose to 47 °C in 2.5 min, dropped
to 26 °C in 10 min, and returned gradually to the initial
temperature (Figure 10). The initial rise in temperature
indicates that the dissolution of silica was very active
during the initial 10 min. Such a high-dissolution rate
Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997 2649
Figure 9. Extraction of Si at various leaching temperatures with
a leaching time of 1 h.
Figure 10. History of leaching solution temperature with the
water bath temperature at 25 °C; 20 wt % NaOH; 40 wt % solids.
may be due to the nature of the silica remaining after
the aluminum was extracted from the clay, an alumi-
nosilicate material, and also to the large BET area of
280 m2/g of the residue. The leaching time of 1 h may
be more than sufficient; for the leaching temperature
of 100 °C, little change was detected in the extraction
of silica over the leaching time of 0.5-2.0 h.
The molar ratio of Na in the NaOH solution to Si in
the residue was varied from 0.4 to 1.0 with a leaching
time of 1 h at the temperature of 100 °C. As shown in
Figure 11, the extraction of silica increased almost
linearly with the ratio up to 0.55, equivalent to 30.4 g
of pure NaOH per 100 g of the residue, beyond which
additional increase in the ratio (or the amount of NaOH)
extracted only 1-2%. The molar ratio of SiO2/Na2O of
the resulting sodium silicate solution was shown in
Figure 12. The SiO2/Na2O ratio of the silicate solution
was almost constant at 3.0, until the molar ratio of Na
in the leaching solution to Si in the residue increased
to 0.55, and then the SiO2/Na2O decreased continuously
down to 1.8 at the Na/Si ratio of 1.0. The concentration
of NaOH in the leaching solution was varied from 10.0
to 50.0 wt % with the Na/Si ratio kept constant at 0.55.
The concentration of NaOH had no effect on the Si
extraction.
Table 4 shows an analysis of the impurities contained
in the sodium silicate solution. The major impurity was
aluminum at 0.31 wt %, and the minor impurities were
calcium, titanium, and iron at 70, 70, and 15 ppm,
2650 Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997

at 160 °C, but this method is limited to ratios of 2.5-

2.7 or lower (Weldes and Lange, 1969). Compared to
the pressure leaching, the leaching of the siliceous
residue with NaOH under atmospheric pressure gave
a higher SiO2/Na2O ratio of 3.0, even at a lower
temperature of 100 °C. The impurities in the solution,
as shown in Table 4, may have limited the SiO2/Na2O
ratio to 3.0; the metal ions are known to link silicate
ions together to form an insoluble precipitate (Iler,
1979). The sodium silicate produced has been tested
to give zeolites on specification. Additional work must
follow to see if it is suitable for other applications.

Conclusion
A novel process is proposed for the extraction of
aluminum from clay, by which the aluminum is recov-
ered as poly(aluminum chloride) solution requiring
Figure 11. Effect of the Na/Si ratio on Si extraction; 20 wt % energy much less than that for the recovery as alumina
NaOH; temperature, 100 °C; leaching time, 1 h. and the volume of the siliceous residue left after the
aluminum was extracted from the clay can be reduced
by 70% by extracting the silicon from the residue as
sodium silicate solution. The poly(aluminum chloride)
solution was made by partially decomposing the alu-
minum chloride hexahydrate, an intermediate product
leading to alumina on complete decomposition, and
subsequently dissolving the resultant basic chloride in
water at 90 °C. The basicity of the poly(aluminum
chloride) solution increased with increasing the extent
of decomposition, and the basicity of 45%, required for
commercial grade poly(aluminum chloride) solution, was
obtained at a decomposition of about 40%. The basic
aluminum chloride was soluble in water at the extents
of decomposition up to 63.8%. About 80% of the silicon
was recovered from the siliceous residue as sodium
silicate by leaching the residue with 20 wt % NaOH for
1 h at 100 °C under atmospheric pressure. The maxi-
mum molar ratio of SiO2/Na2O of the sodium silicate
Figure 12. Effect of the Na/Si on SiO2/Na2O in the sodium silicate solution thus obtained was 3.0.
solution; 20 wt % NaOH; temperature 100 °C; leaching time, 1 h.
Literature Cited
Table 4. Chemical Analysis of Impurities in the Sodium
Silicate Solution Brinker, C. J.; Scherer, G. W. Sol-Gel Science; Academic Press,
Inc.: New York, 1990.
component wt % Eisele, J. A. Producing Alumina From Clay by the Hydrochloric
Al 0.31 Acid Process. A Bench-Scale Study, U.S. Bureau of Mines RI
Fe 0.0015 8476, 1980.
Mg 0.0001 Iler, R. K. The Chemistry of Silica; John Wiley & Sons: New York,
Ca 0.007 1979.
Ti 0.007 Marchessaux, P.; Plass, L.; Reh, L. Thermal Decomposition of
Aluminum Hexahydrate Chloride for Alumina Production.
Table 5. Chemical Analysis of the Undissolved Solid Light Met. 1979, 189.
compound wt % compound wt % Nakamoto, K. Infrared and Raman Spectra of Inorganic and
Coordination Compounds, 3rd ed.; Wiley-Interscience: New
SiO2 50.73 Fe2O3 0.98
York, 1978.
Al2O3 31.41 Na2O 1.12
CaO 0.37 TiO2 0.46 Naumann, R.; Petzold, D.; Paulik, F.; Paulik, J. J. Investigation
MgO 0.26 ignition loss 12.14 of Thermal Decomposition of Aluminum Chloride Hexahydrate
under Dynamic and Quasi-isothermal Condition. Therm. Anal.
respectively. About 30 wt % of the siliceous residue 1979, 15, 47.
charged for leaching remained undissolved. The chemi- Peters, F. A.; Johnson, P. W. Revised and Updated Cost Estimates
cal analysis of the undissolved solid is shown in Table for Producing Alumina from Domestic Raw Materials, U.S.
5. As seen from the table, the major components are Bureau of Mines IC 8648, 1974.
silicon and aluminum. The sodium content is 1.12 wt Weldes, H. H.; Robert Lange, K. Properties of Soluble Silicates.
Ind. Eng. Chem. 1969, 61, 29.
%, indicating that loss of NaOH may be tolerable in the
production of sodium silicate solution from the siliceous
Received for review December 9, 1996
residue.
Revised manuscript received April 7, 1997
Sodium silicates have been produced commercially for Accepted April 15, 1997X
over 100 years by fusion of sand with soda ash at
temperatures of about 1300 °C followed by dissolution IE9607863
of the glass in water. Sodium silicate solutions with
SiO2/Na2O ratios up to 4.0 can be made by this method.
Other methods are also used to a lesser degree, such as XAbstract published in Advance ACS Abstracts, June 1,
pressure leaching of sand with NaOH in an autoclave 1997.