Ind. Eng. Chem. Res.

2000, 39, 4173-4177 4173

Bench-Scale Decomposition of Aluminum Chloride Hexahydrate to

Produce Poly(aluminum chloride)
Kyun Young Park,* Yong-Woon Park, Sung-Ho Youn, and Sun-Young Choi
Department of Chemical Engineering, Kongju National University, 182 Shinkwandong,
Chungnam 314-701, Korea

Partial thermal decomposition of aluminum chloride hexahydrate was carried out in a rotary
glass tube at temperatures of 230-260 °C. The decomposition solid product was dissolved in
water to produce a ploy(aluminum chloride) (PAC) solution. The effects of the decomposition
temperature, the rotation speed of the tube, and the feed rate of aluminum chloride hexahydrate
on the properties and morphology of the basic chloride resulting from the decomposition were
investigated. The basicity of the PAC obtained by dissolving the decomposition solid product in
water was related to the extent of decomposition by the linear equation Y ) 2.025 + 1.063X,
where Y is the basicity (%) and X is the extent of decomposition (%). The PAC solution prepared
by the present method showed a flocculation capacity comparable to that of an existing PAC
made from aluminum hydroxide and hydrochloric acid.

Introduction. decomposition degree on the basicity of the PAC solution

was investigated. In the present work, the decomposi-
Poly(aluminum chloride), PAC, has been widely used tion was carried out continuously in a rotary glass tube
in water treatments as a flocculating agent, along with 8 cm in diameter and 100 cm in length, with the feed
the alum referring to a commercial aluminum sulfate rate of aluminum chloride varying between 250 and 650
hydrate. It is a partially hydrolyzed aluminum chloride g/h. The effects of the decomposition temperature, the
solution, the aluminum content of which is about 10 wt rotation speed of the tube, and the feed rate of alumi-
%, expressed as Al2O3. PAC is known to provide faster num chloride hexahydrate on the properties and mor-
flocculation and stronger flocs than alum in some pholgy of the basic chloride resulting from the decom-
applications.1 It has been produced commercially by position were investigated. The PAC solution obtained
dissolving aluminum hydroxide in hydrochloric acid in by dissolving the basic chloride in water was tested on
autoclaves at elevated temperatures and pressures. the water taken from a river using a jar tester.
Recently, we reported a new method of PAC production,2
in which aluminum chloride hexahydrate (AlCl3‚6H2O)
is partially decomposed at about 200 °C under atmo- Experimental Section
spheric pressure and the resulting basic chloride in solid A schematic drawing of the experimental apparatus
form is dissolved in water. The dissolution of the basic is shown in Figure 1. The aluminum chloride hexahy-
chloride is simple and can be performed locally at the drate is charged by a screw feeder into a rotating glass
place where the flocculant is needed. This is an advan- tube 8 cm in diameter and 100 cm in length. The tube
tage from the viewpoint of transportation cost. With the is heated by an electrical heater over the length of 50
conventional method, in which PAC is produced as a cm, between 30 and 80 cm from the inlet. The tube
solution containing more than 90 wt % of water, an slopes down to the outlet by 1.8°. Three glass rods, each
extra evaporation step is required to obtain PAC in solid 1 cm in diameter, equivalent to the flights in commercial
form. rotary kilns, are located on the interior of the tube to
There have been other studies on thermal decomposi- lift and shower the solids through the gas space. The
tion of aluminum chloride hexahydrate.3-5 All of these temperature in the gas space was measured by a
studies are, however, associated with the production of thermocouple travelling in the axial direction. Another
alumina by complete decomposition of the chloride and thermocouple was located very close to the outside wall
focus on the transition mechanism of morphology and of the cylinder. The decomposition products leaving the
crystal structure of the alumina at temepratures of decomposition cylinder are routed to a solid-gas sepa-
400-1400 °C. For the production of PAC, the aluminum rator equipped with a filter. The solid product or the
chloride is not completely decomposed, but partially basic chloride drops by gravity from the separator to a
decomposed at a lower temperature of about 200 °C. In graduated cylinder on a balance. At the same time, the
our previous work,2 the partial decomposition of alu- gaseous products containing the hydrochloric acid and
minum chloride hexahydrate was performed in a 50- water vapors evolved during the decomposition are
cm3 flask immersed in a silicon oil bath. The formation passed through a condenser to condense the acid vapors.
of a basic chloride was identified by IR spectrometry, Any acid vapors remaining uncondensed are finally
the decomposition kinetics were studied in the temper- removed by caustic soda in two packed columns in
ature range of 140-200 °C, and the effect of the series.
The aluminum chloride hexahydrate used is of re-
* Author to whom correspondence should be addressed. agent grade from Junsei Chemical Co., and the particle
E-mail: [email protected]. Fax: 82-41-858-2575. shape is cylindrical with a aspect ratio of about 3.0. The
Tel.: 82-41-850-8637. extent of decomposition of the chloride was determined
10.1021/ie000029b CCC: $19.00 © 2000 American Chemical Society
Published on Web 10/06/2000
4174 Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000

Figure 1. Schematic drawing of the experimental apparatus.

by subjecting the solids (or basic chlorides) leaving the

decomposer to complete decomposition in a separate
furnace at 1000 °C. From the weight loss on the further
decomposition and from the fact that complete decom-
position of aluminum chloride hexahydrate (2AlCl3‚
6H2O ) Al2O3 + 6HCl + 9H2O) reduces the virgin
chloride to 21.1% of its initial weight, the extent of
decomposition can be determined as follows:

Extent of decomposition (%) )

1-
[ W - Wf
(Wf/0.211 - Wf) ]
× 100 (1)

where W is the weight of the basic chloride charged to

the furnace and Wf is the weight after it was completely
decomposed. The basic aluminum chloride was dissolved
in water at 80 °C to yield a poly(aluminum chloride) Figure 2. Extent of decomposition vs cumulative weight of solid
product at various temperatures (feed rate, 350 g/h; rotation speed,
solution. The volume of water was controlled so that the 3 rpm).
aluminum content of the solution was about 10 wt %
on the Al2O3 basis. wall temperature of 250 °C, the temperature in the gas
The basicity of the PAC solution, which is defined as space was measured between the two ends. The maxi-
the equivalent ratio in percentage of OH to Al present mum gas temperature was about 200 °C. This temper-
in the solution, was determined by following the pro- ature level was maintained in the zone of 20 cm in
cedure described in KS (Korean Standard) M 1510-1981. length. Actual temperature of the chlorides being de-
For the flocculation test, the PAC solution of 10 wt % composed must be between the wall temperature and
Al2O3 was diluted by 100 times. A predetermined the gas temperature. Figure 2 shows the extents of
volume of the diluted solution was added to 1 L of the decomposition of solid product leaving the decomposer
water to be tested, with vigorous agitation for 1 min. against cumulative weight of the solid produced, at the
Then, about 20 min of agitation followed at a reduced three temperatures of 230, 250 and 260 °C. In every
rpm of 20. After the flocs settled, the turbidity of the case, the extent of decomposition showed a transient
water was measured by a turbidity meter. behavior in the initial period, then reached a steady
value. The extents of decomposition at the steady state
Results and Discussion were 32, 47, and 55%, respectively. At a steady state,
the fraction of cross section occupied by the solids was
Effects of Decomposition Variables on the Ex- measured at 8%. The volume of the solids in the
tent of Decomposition. The effect of the temperature constant-temperature zone of 20 cm in length is calcu-
on the extent of decomposition was studied over a range lated at 80.4 cm3. Assuming that this is an approximate
of 230 to 260 °C, with the feed rate of aluminum chloride volume for the decomposition and the solid flow pattern
hexahydrate at 350 g/min. and the rotation speed of the is plug flow axially,6 the residence time is roughly
tube at 3 rpm. The temperature is the wall temperature calculated at 11 min. Using the activation energy of 55.5
mid-way between two ends of the heated zone. At the kJ/mol and the preexponential factor of 297.6 s-1, which
 Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000 4175

Figure 3. Effect of rotation speed of the decomposer on the extent Figure 4. Effect of feed rate of Chloride on the extent of
of decomposition (feed rate, 350 g/h; wall temp, 250 °C). decomposition (wall temp, 250 °C; rotation speed, 3 rpm).
were determined previously in the laboratory-scale
experments,2 the extents of decomposition were esti-
mated by the following simple model to be 28.9, 43.2,
and 51.3%, respectively, for 230, 250 and 260 °C.
dX
) Ae-E/RT(1 - X) (2)
dt
where X is the fractional extent of decomposition, t
is the time, A is the preexponential factor, E is the
activation energy and T is the temperature. Considering
that the decomposition should have also occurred to
some extent outside the zone assumed for the estima-
tion, model prediction based on the kinetic data is in
good agreement with experimental data.
The rotation speed of the tube was varied from 1.5 to
6 rpm, holding the feed rate at 350 g/h and the wall
temperature at 250 °C. As shown in Figure 3, the extent
of decomposition decreased as the speed is increased
from 1.5 to 3 rpm, probably due to the residence time
becoming shorter with the speed increase. A further
increase of the rotation speed to 6 rpm, however, had
little effect on the extent of decomposition despite the
reduction in residence time. A possible explanation for
the reason is that the increase of the speed may have
increased the frequency of the solids touching the hotter
wall, resulting in an increase of the solids temperature
on the average and consequently the rate constant
increased so as to compensate for the influence of the
reduction in residence time.
Figure 4 shows the effect of the feed rate on the extent
of decomposition. The feed rate was varied from 260 to
650 g/h, with the rotation speed of the tube kept
constant at 3 rpm and the wall temperature at 250 °C.
The extent of decomposition decreased gradually with
increasing the feed rate. The data showed a considerable
scattering; the extent of decomposition differed by as
high as 10% at the same feed rate. Such a scattering of
data may be due to the formation of agglomerates of
chloride particles. Many agglomerates were found in the
entrance of the decomposing tube. Some of the water
Figure 5. Cross-sectional images of the decomposition product.
vapors formed during the decomposition may have
diffused back toward the inlet of the decomposer and the agglomerates. The agglomeration was irregular,
condensed on the incoming aluminum chloride hexahy- which might have brought about the scattering of the
drate particles, thereby forming agglomerates. The data.
decomposition behavior of the agglomerates should be SEM Investigation of the Basic Chloride. Figure
different from those of individual free particles, because 5 shows the scanning electron microscopic images of the
of internal resistances to mass and heat transfers. The cross sections of basic chloride particles produced at two
influence of the agglomeration on the extent of decom- decomposition temperatures of 230 and 260 °C, with the
position will depend on the number, size and shape of rotation speed of the decomposer kept at 6 rpm. By
4176 Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000

Figure 6. Correlation between extent of decomposition and

basicity. Figure 7. Comparison of flocculation capacity between present
and conventional PACs.
investigation of the images, the decomposition may have
occurred from the outside toward the center, not uni- The aluminum content of the PAC solution was 10 wt
formly throughout the cross section. At the decomposi- % on the Al2O3 basis, and its basicity was 50.0%. For
tion temperature of 230 °C, an annular layer, the comparison, a PAC solution of the same aluminum
thickness of which is about one-third the radius of the content and basicity, but made by the existing method
particle, existed outside (Figure 5a). By eye inspection, from aluminum hydroxide and hydrochloric acid, was
the outer layer appears to have undergone more severe obtained from a manufacturer. One gram of each PAC
decomposition than the inner zone. To verify this solution was dissolved in 100 mL of distilled water.
conjecture, local weight ratios of Cl to Al were measured Figure 7 shows the changes in the pH and turbidity of
using energy-dispersive X-ray (EDX). The ratio was 3.36 the treated water with variations in the volume of the
in the center of the section and 1.57 at a point close to diluted PAC solution added to 1 L of the raw water.
the edge. The ratio of virgin aluminum chloride hexahy- With a dosage of 5 mL, the turbidity of the water was
drate is 3.94 by stoichiometry. In the course of the dropped to 3.3 NTU with the present PAC and 4.7 NTU
decomposition, the chlorine is removed as HCl, while with the conventional PAC. A further increase of the
the aluminum remains unremoved: therefore, the ratio dosage to 10 mL increased the turbidity to 27.2 and 48.8
would decrease with an increase of the decomposition. NTU, respectively; over-dosage of a flocculant leads to
The lower ratio measured near the edge indicates that deflocculation.7 The pH of the treated water was a little
the decomposition was more severe than in the center. lower with the conventional PAC. We heard from the
With the increase of the temperature to 260 °C, the manufacturer that a small amount of hydrosulfuric acid
outer layer became thicker and bigger cracks were was added in the manufacture of that PAC. This may
formed, as shown in Figure 5b. The weight ratios of Cl be the reason for the pH being lower. This level of
to Al were measured at 3.52 in the center and 1.40 near flocculation test is sufficient for the purpose of this
the edge. The increase of the temperature increased the paper. A more elaborate evaluation of the flocculating
decomposition near the edge, but affected little the capacity of the PAC may be necessary in the future.
decomposition in the center. The ratio in the center even
became a little higher with the temperature increase. Conclusion
The increment, however, may be within the error limits
of analysis. It is more reasonable to say that the The partial decomposition of aluminum chloride
temperature increase had no effect on the extent of hexahydrate was performed successfully on a bench
decomposition in the center. The average ratio of Cl to scale. The effects of various operating variables on the
Al over the cross section was 3.0 for the wall tempera- extent of decomposition were studied. Increasing the
ture of 230 °C and 1.7 for 260 °C, respectively. The decomposition temperature from 230 to 260 °C increased
decomposition was considered to have proceeded like a the extent of decomposition from 32 to 55%, at a feed
shrinking core. rate of 350 g/h and a rotation speed of 3 rpm. By SEM
Evaluation of the PAC Solution. The basicity of a and EDX analyses, the decomposition appeared to have
PAC solution is an important specification. The basicity proceeded from the outside toward the center of a
of commercial-grade PAC is around 50%. In Figure 6, particle, like a shrinking core. The extent of decomposi-
the correlation between the basicity and the extent of tion decreased as the rotation speed was increased from
decomposition is indicated. The basicity increases with 1.5 to 3 rpm, probably because of a decrease in the
increasing the extent of decomposition. The correlation residence time. A further increase of the rotation speed
can be represented by the linear equation Y ) 2.025 + to 6 rpm, however, had little effect on the extent of
1.063X, where Y is the basicity (%) and X is the extent decomposition. A possible explanation for this observa-
of decomposition (%), with a correlation coefficient of tion is that the increase in the speed may have increased
0.77. the frequency with which the solids touched the hotter
The PAC solution prepared by the present method wall, resulting in an increase in the average tempera-
was tested on some water taken from the Kum river ture of the solidsand, consequently, an increase in the
using a jar tester. The turbidity of the water was 55.3 rate constant so as to compensate for the influence of
NTU, the pH was 7.35, and the temperature was 26 °C. the reduction in residence time. The correlation between
 Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000 4177

the basicity of the PAC obtained by dissolving the (2) Park, K. Y.: Kim, J.; Jeong, J.: Choi, Y. Y. Production of
decomposition solid product in water and the extent of Poly(aluminum chloride) and Sodium Silicate from Clay. Ind. Eng.
decomposition could be represented by the linear equa- Chem. Res. 1997, 36, 2646.
(3) Petzold, D.; Naumann, R. J. Thermoanalytical Studies on
tion Y ) 2.025 + 1.063X, where Y is the basicity (%) the Decomposition of Aluminum Chloride Hexahydrate. Thermal
and X is the extent of decomposition (%), with a Anal. 1981, 20, 71.
correlation coefficient of 0.77. The PAC solution pre- (4) Marchessaux, P.; Plass, L.; Reh, L. Thermal Decomposition
pared by the present method showed a flocculation of Aluminum Chloride Hexahydrate for Alumina Production. Light
capacity comparable to that of an existing PAC made Met. 1979, 189.
from aluminum hydroxide and hydrochloric acid. (5) Park, K. Y.; Jeong, J. Manufacture of Low-Soda Alumina
from Clay. Ind. Eng. Chem. Res. 1996, 35, 4379.
(6) Walas, S. M. Chemical Reactors. In Perry’s Chemical
Acknowledgment Engineers’ Handbook, 7th ed.; Green, D. W., Maloney, J. O., Eds.;
McGraw-Hill: New York, 1980.
The authors acknowledge the financial support of the (7) Hughes, M. A. Coagulation and Flocculation. In Solid-
R&D Management Center for Energy and Resources. Liquid Separation, 3rd ed.; Svarovsky, L., Ed.; Butterworth-
Heinemann, Ltd.: Cambridge, U.K., 1990.
Literature Cited Received for review January 6, 2000
Revised manuscript received August 3, 2000
(1) Heitner, H. I. Flocculating Agents. In Encyclopedia of Accepted August 4, 2000
Chemical Technology; Jacqueline, I. K., Howe-grant, M., Eds.; John
Wiley & Sons: New York, 1994. IE000029B