Selective Oxidation of Methanol to Dimethoxymethane over V/Ce⁃Al2O3 Catalysts

doi:10.19894/j.issn.1000-0518.210531

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (9): 1429-1436.DOI: 10.19894/j.issn.1000-0518.210531

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Selective Oxidation of Methanol to Dimethoxymethane over V/Ce⁃Al₂O₃ Catalysts

Dan ZHANG¹^,², Run-Mei SHANG², Zhen-Tao ZHAO², Jun-Hua LI¹^,²(), Jin-Juan XING²

^1.School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun 113001，China
^2.College of Chemistry and Materials Engineering，Bohai University，Jinzhou 121013，China

Received:2021-11-10 Accepted:2022-03-01 Published:2022-09-01 Online:2022-09-08
Contact: Jun-Hua LI
About author:lijunhua0521@163.com
Supported by:
the National Natural Science Foundation of China(21606117);the key R&D Projects in Liaoning Province(2018?479?14)

Abstract

Abstract:

Bifunctional 20V/Ce-Al₂O₃（mass percent 20% V₂O₅） catalysts are prepared by simply co-precipitation of 20V₂O₅/Al₂O₃ with Ce to improve the acidity of catalyst effectively，and tested for partial oxidation of methanol. The structural properties are characterized by X-ray diffraction（XRD），scanning electron microscopy （SEM-EDS）， Raman spectroscopy （Raman）， H₂ temperature-programmed reduction（H₂-TPR） and NH₃ temperature-programmed desorption （NH₃-TPD） techniques，respectively. The characterization results confirm that the incorporation of Ce in catalyst enhances the surface acidity， which is the key factor to improve the selectivity of DMM，and the interaction between vanadium oxide and the support is enhanced and the redox ability of the catalysts is reduced at the same time. The experimental results show that the catalyst 20V/8Ce-Al₂O₃ with mass percent 8% CeO₂ exhibits the best catalytic performance and the reaction temperature has a great influence on the methanol oxidation products. Low temperature is more favourable for the formation of DMM. For the catalyst 20V₂O₅/8Ce-Al₂O₃，the methanol conversion and the DMM selectivity are 23.6% and 99.9% at 170 ℃，respectively. The selectivity of DMM is 99.9% after 5 runs. The study provides valuable reference for improving the acidity of catalyst.

Key words: Partial oxidation, Catalyst, Modification, Methanol, Dimethoxymethane

CLC Number:

O643.3

Dan ZHANG, Run-Mei SHANG, Zhen-Tao ZHAO, Jun-Hua LI, Jin-Juan XING. Selective Oxidation of Methanol to Dimethoxymethane over V/Ce⁃Al₂O₃ Catalysts[J]. Chinese Journal of Applied Chemistry, 2022, 39(9): 1429-1436.

Figures/Tables 10

Fig.1 XRD patterns of 20V/Al2O3 （a），20V/4Ce-Al2O3（b），20V/8Ce-Al2O3，20V/4Ce-Al2O3（c），20V/12Ce-Al2O3（d），20V/16Ce-Al2O3 （e） and 20V/20Ce-Al2O3 （f）

Fig.2 SEM （A，B，C，D） and EDS （E，F，G，H，I） images of catalystsA，B. SEM images of 20V/Al2O3；C，D. SEM image of 20V/12Ce-Al2O3；E. EDS image of 20V/12Ce-Al2O3；F. Al；G. O；H. V；I. Ce

Fig.3 FT-IR spectra of 20V/Al2O3 （a）， 20V/4Ce-Al2O3 （b）， 20V/8Ce-Al2O3 （c），20V/12Ce-Al2O3（d）， 20V/16Ce-Al2O3 （e） and 20V/20Ce-Al2O3 （f）

Fig.4 Raman spectra of 20V/Al2O3 （a）， 20V/4Ce-Al2O3 （b）， 20V/8Ce-Al2O3 （c）， 20V/12Ce-Al2O3 （d）， 20V/16Ce-Al2O3 （e） and 20V/20Ce-Al2O3 （f）

Fig.5 H2-TPR profiles of 20V/Ce-Al2O3 catalysts with different amount of CeO2

Fig.6 NH3-TPD profiles of 20V/Al2O3 （a），20V/4Ce-Al2O3 （b），20V/8Ce-Al2O3 （c），20V/12Ce-Al2O3 （d），20V/16Ce-Al2O3 （e） and 20V/20Ce-Al2O3 （f）

Table 1 Catalytic performance of catalysts with different amount of CeO2 at 170 ℃

催化剂 Catalyst	甲醇转化率 Methanol conversion/%		产物选择性 Product selectivity/%
催化剂 Catalyst	After 1 h	After 12 h	DMM	FA	MF
20V/Al₂O₃	83.8	66.8	0.0	98.3	1.7
20V/4Ce?Al₂O₃	50.1	40.5	35.6	64.4	0.0
20V/8Ce?Al₂O₃	23.6	22.1	99.9	0.0	0.0
20V/12Ce?Al₂O₃	20.3	19.2	99.9	0.0	0.0
20V/16Ce?Al₂O₃	18.6	17.9	99.9	0.0	0.0
20V/20Ce?Al₂O₃	17.0	16.6	99.9	0.0	0.0

Fig.7 Effect of reaction temperature on catalytic performance of 20V/8Ce-Al2O3Reaction conditions：WHSV=2.37 h-1；V（O2）∶V（N2）=1∶4；p=0.1 MPa

Fig.8 Reusability of 20V/8Ce-Al2O3 catalystReaction conditions：Temperature=170 ℃； WHSV=2.37 h-1；V（O2）∶V（N2）=1∶4； p=0.1 MPa

Fig.9 （A） XRD，（B） NH3-TPD and （C） H2-TPR patterns before and after reaction for 20V/8Ce-Al2O3 catalyst

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Selective Oxidation of Methanol to Dimethoxymethane over V/Ce⁃Al₂O₃ Catalysts

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