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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front Chem Sci Eng    2012, Vol. 6 Issue (4) : 415-422    https://doi.org/10.1007/s11705-012-1214-4
RESEARCH ARTICLE
Influence of crystalline phase of Li-Al-O oxides on the activity of Wacker-type catalysts in dimethyl carbonate synthesis
Yadong GE, Yuanyuan DONG, Shengping WANG, Yujun ZHAO, Jing LV, Xinbin MA()
Key Laboratory for Green Chemical Technology (Ministry of Education), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
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Abstract

The catalysts supported on LiAl5O8 (spinel) for vapor phase synthesis of dimethyl carbonate (DMC) from methyl nitrite (MN) have been studied. Their catalytic activities on supports prepared by different methods were evaluated in a continuous reactor. The samples were characterized by powder X-ray diffraction, N2 adsorption-desorption isotherms, fourier transform infrared spectroscopy and temperature-programmed reduction of H2. Li/Al molar ratio and calcination temperature greatly influence the structure of crystalline phase of Li-Al-O oxides. Desirable LiAl5O8 (spinel) was formed at 800°C, while LiAl5O8 (primitive cube) formed at 900°C is undesirable for the reaction. A high Li/Al molar ratio, which was related with LiAlO2, also slowed the reaction rate. The electron transfer ability and the interaction with active component are the important properties of the spinel-based supports. The CuCl2-PdCl2/LiAl5O8 (spinel) with better electron transfer ability and low Pd2+ reduction temperature exhibited a better catalytic ability.
Keywords Wacker-type catalyst      dimethyl carbonate      methyl nitrite      spinel     
Corresponding Author(s): MA Xinbin,Email:xbma@tju.edu.cn   
Issue Date: 05 December 2012
 Cite this article:   
Yujun ZHAO,Jing LV,Xinbin MA, et al. Influence of crystalline phase of Li-Al-O oxides on the activity of Wacker-type catalysts in dimethyl carbonate synthesis[J]. Front Chem Sci Eng, 2012, 6(4): 415-422.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-012-1214-4
https://academic.hep.com.cn/fcse/EN/Y2012/V6/I4/415
Calcination temperature /°CSpecific surface area /(m2·g–1)Pore volume /(cm3·g–1)Pore diameter /nm
700128.80.338.8
800103.20.309.5
90080.10.2811.7
Tab.1  Textural properties of the supports calcined at different temperatures
Fig.1  Nitrogen adsorption-desorption isotherms and pore size distribution for supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.1  Nitrogen adsorption-desorption isotherms and pore size distribution for supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.1  Nitrogen adsorption-desorption isotherms and pore size distribution for supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.1  Nitrogen adsorption-desorption isotherms and pore size distribution for supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.1  Nitrogen adsorption-desorption isotherms and pore size distribution for supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.1  Nitrogen adsorption-desorption isotherms and pore size distribution for supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.2  SEM micrographs of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.2  SEM micrographs of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.2  SEM micrographs of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.2  SEM micrographs of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.2  SEM micrographs of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.2  SEM micrographs of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.3  The XRD patterns of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.3  The XRD patterns of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.3  The XRD patterns of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.3  The XRD patterns of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.3  The XRD patterns of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.3  The XRD patterns of supports calcined at different temperatures: (a) 700°C, (b) 800°C, and (c) 900°C
Fig.4  Effects of supports calcined at different temperatures on catalysts: (a) Pd-Cu/LiAl-700, (b) Pd-Cu/LiAl-800, and (c) Pd-Cu/LiAl-900
Fig.4  Effects of supports calcined at different temperatures on catalysts: (a) Pd-Cu/LiAl-700, (b) Pd-Cu/LiAl-800, and (c) Pd-Cu/LiAl-900
Fig.4  Effects of supports calcined at different temperatures on catalysts: (a) Pd-Cu/LiAl-700, (b) Pd-Cu/LiAl-800, and (c) Pd-Cu/LiAl-900
Fig.4  Effects of supports calcined at different temperatures on catalysts: (a) Pd-Cu/LiAl-700, (b) Pd-Cu/LiAl-800, and (c) Pd-Cu/LiAl-900
Fig.4  Effects of supports calcined at different temperatures on catalysts: (a) Pd-Cu/LiAl-700, (b) Pd-Cu/LiAl-800, and (c) Pd-Cu/LiAl-900
Fig.4  Effects of supports calcined at different temperatures on catalysts: (a) Pd-Cu/LiAl-700, (b) Pd-Cu/LiAl-800, and (c) Pd-Cu/LiAl-900
Fig.5  The XRD patterns of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.5  The XRD patterns of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.5  The XRD patterns of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.5  The XRD patterns of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.5  The XRD patterns of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.5  The XRD patterns of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.6  TEM images of LiAl-0.15
Fig.6  TEM images of LiAl-0.15
Fig.6  TEM images of LiAl-0.15
Fig.6  TEM images of LiAl-0.15
Fig.6  TEM images of LiAl-0.15
Fig.6  TEM images of LiAl-0.15
SupportsLi/Al (molar) ratioCalcination at 800°C
LiAl-0.050.05γ-Al2O3 + LiAl5O8
LiAl-0.100.10γ-Al2O3 + LiAl5O8
LiAl-0.150.15γ-Al2O3 + LiAl5O8
LiAl-0.200.20LiAl5O8 + LiAlO2
LiAl-0.250.25LiAl5O8 + LiAlO2
Tab.2  The composition of supports with different Li/Al (molar) ratios
Fig.7  The FTIR spectra of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.7  The FTIR spectra of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.7  The FTIR spectra of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.7  The FTIR spectra of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.7  The FTIR spectra of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.7  The FTIR spectra of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.8  Nitrogen adsorption-desorption isotherms and pore size distribution for the supports with different Li/Al ratios: (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.8  Nitrogen adsorption-desorption isotherms and pore size distribution for the supports with different Li/Al ratios: (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.8  Nitrogen adsorption-desorption isotherms and pore size distribution for the supports with different Li/Al ratios: (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.8  Nitrogen adsorption-desorption isotherms and pore size distribution for the supports with different Li/Al ratios: (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.8  Nitrogen adsorption-desorption isotherms and pore size distribution for the supports with different Li/Al ratios: (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.8  Nitrogen adsorption-desorption isotherms and pore size distribution for the supports with different Li/Al ratios: (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
SupportsSpecific surface area /(m2·g–1)Pore volume /(cm3·g–1)Pore diameter /nm
γ-Al2O3178.40.335.9
LiAl-0.05134.30.337.8
LiAl-0.10126.00.338.3
LiAl-0.15103.20.309.5
LiAl-0.20?97.60.309.9
LiAl-0.25?70.00.2512.3?
Tab.3  Textural properties of the supports with different Li/Al (molar) ratios
Fig.9  H-TPR profiles of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.9  H-TPR profiles of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.9  H-TPR profiles of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.9  H-TPR profiles of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.9  H-TPR profiles of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.9  H-TPR profiles of (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.10  Effects of supports with different Li/Al ratios on STY and . (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.10  Effects of supports with different Li/Al ratios on STY and . (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.10  Effects of supports with different Li/Al ratios on STY and . (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.10  Effects of supports with different Li/Al ratios on STY and . (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.10  Effects of supports with different Li/Al ratios on STY and . (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
Fig.10  Effects of supports with different Li/Al ratios on STY and . (a) Li/Al-0.05, (b) LiAl-0.10, (c) LiAl-0.15, (d) Li/Al-0.20, and (e) Li/Al-0.25
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