Synthesis of Oxide Materials by Hydrothermal Hydrolysis

TRAVAUX 48, Proceedings of the 37 th International ICSOBA Conference and
XXV Conference «Aluminium of Siberia», Krasnoyarsk, Russia, 16 – 20 September, 2019
AA28 - Synthesis of Oxide Materials by Hydrothermal Hydrolysis of

Aluminum Chloride Hexahydrate
Nikolay Dobrynkin1, Marina Batygina2 and Aleksandr Noskov3
1. Senior researcher
2. Engineer
3. Vice-director
Federal Research Center Boreskov Institute of Catalysis, Novosibirsk, Russia
Corresponding author: [email protected], [email protected]
Abstract
In the present work, the processes of aluminum oxyhydroxides synthesis by hydrothermal

hydrolysis in water solutions and in solid phase are considered. The process studies were
conducted using a batch type autoclave at temperatures from 443 to 503 K at a pressure of 1.6 -2.3
MPa with the variation of such parameters as temperature, pressure, residence time of the reaction
mixture in the reactor, flow velocity of the displacing gas during hydrolysis; number of washes,
time and rate of hydrothermal decomposition products centrifugation, time and temperature of
aluminium hydroxide drying. It is shown that Al-O-H product formed by hydrothermal hydrolysis
of aluminum chloride hexahydrate AlCl3* 6 H2O, and urea jointly in water solutions is a highly
dispersed (nano) γ-AlOOH (boehmite). Hydrothermal process of self-hydrolysis of aluminum
chloride hexahydrate in solid phase with the use of crystalline water is lead to formation of
bayerite (mainly) and aluminum oxychlorides with a total Cl content of not more than 4 %.
Keywords: alumina production, hydrolysis, hydrothermal synthesis, bayerite, boehmite.
1. Introduction
Currently, for the production of alumina from high-silicon raw materials, mainly kaolin, alkaline
technologies are widely used. The proposed promising technologies are based on acidic methods
for processing of kaolins and clays use sulfuric, hydrochloric and nitric acids, but they are
multistage and high-cost [1].
The most advanced technology includes the leaching of raw materials with a solution of
hydrochloric acid in an autoclave, separation of the resulting pulp, crystallization of aluminum
chloride hexahydrate from clarified aluminum chloride solution with gaseous hydrogen chloride,
calcining aluminum chloride hexahydrate to produce gamma-alumina and its final
recrystallization in alkali solution to obtain metallurgical grade alumina. However, this
technology can be significantly simplified by replacing the operations of crystallization and
calcination of aluminum chloride hexahydrate by the decomposition operation to obtain
aluminum hydroxide, which is directed to alkaline recrystallization. The method of hydrothermal
hydrolysis of aluminum chloride hexahydrate is most suitable for replacing the existing
energy-consuming multi-stage high-temperature methods of aluminum chloride decomposition
[2].
The advantages of the hydrothermal hydrolysis method of producing Al-O-H products are:
1. Single-stage process;
2. Low energy consumption;
3. Chemical and phase purity of the product;
4. Low level of aggregation;
5. The ability to control the size, morphology and structure of the obtained Al-O-H products;
6. The possibility of using this method for high-silica raw materials of various origin.
401
Important features of the hydrolysis of aluminum chlorides in solutions at elevated temperatures

(373-773 K) are [3]:
(a) The incompleteness of the second and third hydrolysis steps;
(b) The formation of soluble multicore aluminum oxychloride complexes forming colloidal
solutions;
(c) The strong dependence of the hydrolysis depth on the acidity of the medium and on the
presence of additional components in the solution.
Based on the literature data, boehmite (or its modification - pseudo-boehmite) is the only Al-O-H
product that can be obtained under mentioned hydrothermal conditions (temperature 433-513 K
and pressure 0.6-2.4 MPa) in the presence of additional components that enhance hydrolysis. The
output of boehmite is a quantitative estimate of the depth of hydrolysis of aluminum chloride. 100
% yield of boehmite indicates complete hydrolysis of aluminum chloride [4].
At the same time, there are no data about the possibility of hydrothermal hydrolysis with the
production of Al-O-H products from crystalline aluminum chloride hexahydrate in solid phase—
that is, in the process of self-hydrolysis involving lattice water of the crystalline hydrate.
The purpose of this work was to determine the possibility of carrying out the process of complete
hydrolysis of aluminum chloride hexahydrate at elevated pressures and temperatures under
hydrothermal conditions with the production of alumina products.
2. Experimental
The hydrolysis in water phase was performed under hydrothermal conditions with aqueous
solutions of AlCl3.6H2O (analytical grade with ≥ 98 % purity) with concentration of 3.0–30.0 wt.
%., which was obtained from commercial source and used without purification. Carbamide of
analytically pure grade with concentration of 8.5 – 20.2 wt % was served as an additive
accelerating the hydrolysis. The solution volume was 30–60 mL. Experiments were performed at
a temperature of 160 – 200 °C and pressure of 0.6–1.6 MPa in a 200-mL autoclave reactor, which
was a part of the laboratory experimental setup, described early [5].
The characteristics of the installation enabled experiments on hydrothermal hydrolysis at

temperatures of 423–523K and pressures of 0.1–5.0 MPa, with the measurement error and
parameter adjustment accuracy of no worse than 3 % under the conditions of an inert gas flowing
through the reactor. The pressure in the system was provided by the flow of argon delivered to the
reactor inlet and varied with upstream and downstream high-pressure gas controllers, with the
pressure corresponding to the saturated water vapor pressure at the prescribed temperature of
experiment.
The reactor outlet was connected to a trap filled with distilled water to catch gaseous products
carried away by the flow of argon. The argon flow rate was maintained constant and equal to
0.00125 m3 h–1. The experiment duration was 1 to 10 h.
The resulting insoluble hydrolysis products were washed several times with distilled water, with
the subsequent centrifugation of the sediment. The centrifugation was performed in the course of
8 min at a rotor speed of 2600 rpm. Further, the washed samples were dried at T = 353 K for 5 h.
The composition and content of the insoluble precipitate was determined by weighing, X-ray
fluorescence method, X-ray diffraction (XRD) analyses and 27Al MAS NMR.
402
The complete hydrolysis of AlCl3 occurs at a ratio AlCl3/(NH2)2CO= 0.67 at a temperature of

433-513 K and a pressure of 0.6 - 2.4 MPa in aqueous solutions with the yield of 100 % a highly
dispersed γ-AlOOH (boehmite).
The possibility of hydrothermal self-hydrolysis of aluminum chloride hexahydrate with the

removal of HCl from the reaction zone to produce bayerite was established for the first time. The
most effective process of self-hydrolysis takes place at a temperature of 513 K and a pressure of
1.5 MPa. While bayerite is the main product of the self-hydrolysis of AlCl3.6H2O in solid phase.
In all cases, the total content of Cl in the products of hydrolysis does not exceed 4 % wt.
5. Acknowledgements
This work was conducted within the framework of budget project No.
АААА-А17-117041710077-4 for Boreskov Institute of Catalysis.
The authors are also grateful to Prof. O. Lapina, Ph.D. Kh.Khabibulin, Ph.D. V. Ushakovand
leading engineer I. Kraevskaya I.L. for the for the assistance in carrying out the study.
6. References
1. Panov A.A., et.al. The state and prospects of development of acidic methods for
producing alumina. Proceedings of the 4-th International Congress "Non-Ferrous Metals
& Minerals", Krasnoyarsk, Russia, 5- September 2012, 272-277.
2. Batygina M. V., Dobrynkin N. M., Noskov A. S. Synthesis of nano-sized boehmite by
hydrolysis of aluminum chloride hexahydrate under hydrothermal conditions. Tsvetnye
Metally (Non-Ferrous Metals).Vol. 2(890), (2017), 51-55.
3. Glinka, N.L., Obshchaya khimiya (General Chemistry), Moscow: Knorus, 2019, 752.
4. Suchanek, W.L., Hydrothermal Synthesis of Alpha Alumina (α‐Al2O3) Powders: Study
of the Processing Variables and Growth Mechanisms. J. Am. Ceram. Soc. Vol. 93, No. 2,
(2010), 399–412.
5. Batygina M.V., Dobrynkin N.M., Noskov A.S. Synthesis of Boehmite and Hematite by
Joint Hydrolysis of Carbamide, Aluminum Chloride, and Iron(III) Chloride under
Hydrothermal Conditions. Russian Journal of Applied Chemistry. Vol.89, No11, (2016),
1763-1768.
6. Duan J., Gregory J.Coagulation by hydrolysing metal salts. Advances in Colloid and
Interface Science. Vol. 100/102, (2003), 475–502.
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Synthesis of Oxide Materials by Hydrothermal Hydrolysis

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TRAVAUX 48, Proceedings of the 37 th International ICSOBA Conference and

XXV Conference «Aluminium of Siberia», Krasnoyarsk, Russia, 16 – 20 September, 2019

AA28 - Synthesis of Oxide Materials by Hydrothermal Hydrolysis of

In the present work, the processes of aluminum oxyhydroxides synthesis by hydrothermal

Keywords: alumina production, hydrolysis, hydrothermal synthesis, bayerite, boehmite.

Important features of the hydrolysis of aluminum chlorides in solutions at elevated temperatures

The characteristics of the installation enabled experiments on hydrothermal hydrolysis at

The complete hydrolysis of AlCl3 occurs at a ratio AlCl3/(NH2)2CO= 0.67 at a temperature of

The possibility of hydrothermal self-hydrolysis of aluminum chloride hexahydrate with the

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