Citation: LIU Ya-jie, QING Shao-jun, HOU Xiao-ning, ZHANG Lei, GAO Zhi-xian, XIANG Hong-wei. Synthesis of Cu-Al spinels and its non-isothermal formation kinetics analysis[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(3): 338-348. shu

Synthesis of Cu-Al spinels and its non-isothermal formation kinetics analysis

1.
College of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong 030600, China
2.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
Liaoning Shihua University, Fushun 113001, China

Corresponding author: HOU Xiao-ning, houxn@sxicc.ac.cn GAO Zhi-xian, gaozx@lnpu.edu.cn
Received Date: 13 January 2020
Revised Date: 15 February 2020

Fund Project: The project was supported by the National Natural Science Foundation of China 21673270The project was supported by the National Natural Science Foundation of China (21673270), Scientific and Technologial Innovation Programs of Higher Education Institutions in Shanxi (2019L0880) and Ph. D. Research Funding of Jinzhong University (2019)Scientific and Technologial Innovation Programs of Higher Education Institutions in Shanxi 2019L0880Ph. D. Research Funding of Jinzhong University 2019

Figures(9)

Cu-Al spinels were synthesized by a solid phase method using Cu(OH)₂ and pseudo-boehmite as the raw materials. The effects of synthesis temperature, synthesis time and Cu/Al molar ratio on the formation and properties of Cu-Al spinels were fully investigated by the thermogravimetry(TG/DTG), X-ray diffraction(XRD), H₂ temperature programmed reduction(H₂-TPR). The non-isothermal kinetics of Cu-Al spinel formation process were analyzed using Coats-Redfern method and two diffusion-controlled kinetic models. Characterization results showed that the Cu-Al surface spinels with unsaturated coordination formed easily at the temperature as low as 400℃, and the content of these surface spinel decreased sharply with the synthesis temperature rising. The hardly-reducible spinel Cu²⁺ species and easily-reducible spinel Cu²⁺ species were identified at the synthesis temperature of 700 and 800℃, respectively. The spinel content increased gradually with the synthesis temperature increasing, leading to the formation of Al-rich spinel solid solutions with different Cu/Al molar ratios. At a higher temperature of 1200℃, however, the formation of stoichiometric CuAl₂O₄ spinel was observed. Hence, the spinel reducibility varied dramatically with the synthesis temperature as illustrated by the drastic change of the molar ratio of hardly-reducible spinel Cu²⁺ species and easily-reducible spinel Cu²⁺ species. An appropriate excess of Al³⁺(Cu/Al=1:3) could result in the formation of spinel solid solution with more hardly-reducible spinel Cu²⁺ species, while an excess of Cu²⁺ would lead to the formation of delafossite-type CuAlO₂. Both samples owned low reducibility as compared to the stochiometric CuAl₂O₄ spinel. Besides, a longer synthesis time would favor the spinel formation as well but to a limited extent. Non-isothermal kinetics analysis showed that the formation process of Cu-Al spinel owned three kinetic regions in terms of synthesis temperature, namely 700-850, 850-950 and 950-1200℃, and the apparent activation energies were determined to be 85.2, 304.4 and 38.1 kJ/mol, respectively. The diffusion of reactants via product layer could be considered as an one-dimensional diffusion below 950℃, whereas it was more likely to be a three-dimensional diffusion above 950℃, indicating that the product layer became much thicker.
- Cu-Al spinel,
- solid phase method,
- synthetic conditions,
- non-isothermal kinetics
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