Synthesis of complex alumina-cobalt systems using thermally activated gibbsite product

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Abstract

Using the methods of X-ray phase, thermal, microscopic, adsorption, and chemical analyses, the possibility of obtaining high-percentage mixed alumina-cobalt spinels by hydrochemical treatment under room or hydrothermal conditions of powder suspensions of the product of centrifugal thermal activation of gibbsite in aqueous solutions of cobaltous nitrate is studied and shown. Thermal treatment of hydrochemical interaction products, viz. xerogels in the range of 350–850°C, is established to lead to the formation of Co3O4 and CoAl2O4 spinel phases with their different ratio depending on the synthesis conditions. Thus, hydrochemical treatment of suspensions at room temperature provides, after calcination, the predominant formation of the Co3O4 phase while hydrothermal treatment at 150°C leads to a deeper interaction of suspension components at the treatment stage, forming CoAl2O4 after thermal treatment. It is noted that the maximum content of spinel of CoAl2O4 type (90% according to H2-TPR data) is observed for the hydrothermal product calcined at 850°C. The considered method is concluded to allow obtaining complex alumina-cobalt compounds with different phase ratio, reducing the number of initial reagents, preparation stages, completely excluding effluents, as well as reducing the total amount of nitrates by 75 wt.%, as compared to the nitrate classical co-precipitation scheme.

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About the authors

A. V. Zhuzhgov

G. K. Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences

Author for correspondence.
Email: zhuzhgov@catalysis.ru
Russian Federation, Novosibirsk

A. S. Gorkusha

G. K. Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences; Novosibirsk State University

Email: zhuzhgov@catalysis.ru
Russian Federation, Novosibirsk; Novosibirsk

E. A. Suprun

G. K. Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences

Email: zhuzhgov@catalysis.ru
Russian Federation, Novosibirsk

A. I. Lysikov

G. K. Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences; Novosibirsk State University

Email: zhuzhgov@catalysis.ru
Russian Federation, Novosibirsk; Novosibirsk

L. A. Isupova

G. K. Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences

Email: zhuzhgov@catalysis.ru
Russian Federation, Novosibirsk

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2. Fig. 1. Powder diffractograms of comparison samples of aluminum hydroxides and oxides: a - pseudobemite synthesized by the classical nitrate precipitation method; b - well-oxidized bemite (1), well-oxidized bayerite (2); c - Al(150)-110 hydration product of CTA-GB in aqueous medium (without presence of Co2+ cations), representing pseudobemite; d - products of heat treatment at 550°C of bemite/pseudobemite and bayerite, representing low-temperature modifications of γ-Al2O3 (1) and η-Al2O3 (2), respectively.

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3. Fig. 2. Powder diffractograms of aluminocobalt systems after low-temperature drying at 110°C and heat treatment in the range of 350-850°C: a - comparison sample CoAl-CoAl-110, synthesized by conventional co-precipitation method using nitrate technology; b - comparison sample CoAl-CoAl-550, obtained by heat treatment of CoAl-CoAl-110 at 550°C; c - products of hydrothermal treatment of CTA-GB in Co2+ solutions in the concentration range of 10-20 wt%: 1 - 1°CoAl(150)-110, 2 - 15CoAl(150)-110, 3 - 2°CoAl(150)-110; d - products of room-temperature and hydrothermal treatment of CTA-HB in Co2+ solutions with stoichiometric concentration of ~33 wt%: 1 - 33CoAl(150)-110, 2 - 33CoAl(25)-110; e - products of heat treatment of samples in the range of 350-850°C of hydrochemical interaction of CTA-GB in Co2+ solutions with stoichiometric concentration in ~33 wt%: 1 - CoAl(25)-350, 2 - CoAl(25)-550, 3 - CoAl(25)-850, 4 - CoAl(150)-550, 5 - CoAl(150)-850.

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4. Fig. 3. Thermal analysis data: a - initial CTA-GB, b - Al(150)-110, c - 1°CoAl(150)-110, d - 15CoAl(150)-110, e - 2°CoAl(150)-110, f - 33CoAl(25)-110, g - 33CoAl(150)-110.

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5. Fig. 4. TPV-H2 curves: a - 33CoAl(25)-350, b - 33CoAl(25)-550, c - 33CoAl(150)-550, d - 33CoAl(25)-850, e - 33CoAl(150)-850.

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6. Fig. 5. Desorption curves of pore size distribution: a - 33CoAl(25)-350 (1), 33CoAl(150)-350 (2); b - 33CoAl(25)-550 (1), 33CoAl(150)-550 (2); c - 33CoAl(25)-850 (1), 33CoAl(150)-850 (2).

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7. Fig. 6. Electron images of 33CoAl(25)-850 sample particles at different magnifications: 50 (a), 10 (b), 5 (c), 2 μm (d).

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8. Fig. 7. Electron images of 33CoAl(150)-850 sample particles at different magnifications: 50 (a), 10 (b), 5 (c), 2 μm (d).

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