MoO<sub>3</sub>-SnO<sub>2</sub>催化剂上二甲醚低温氧化高选择性制备甲酸甲酯

引用本文: 刘广波, 张清德, 韩怡卓, 椿范立, 谭猗生. MoO₃-SnO₂催化剂上二甲醚低温氧化高选择性制备甲酸甲酯[J]. 燃料化学学报, 2013, 41(2): 223-227. shu

Citation: LIU Guang-bo, ZHANG Qing-de, HAN Yi-zhuo, TSUBAKI Noritatsu, TAN Yi-sheng. Low-temperature oxidation of dimethyl ether to methyl formate with high selectivity over MoO₃-SnO₂ catalysts[J]. Journal of Fuel Chemistry and Technology, 2013, 41(2): 223-227. shu

MoO₃-SnO₂催化剂上二甲醚低温氧化高选择性制备甲酸甲酯

通讯作者: 谭猗生.Tel:0351-4044287;Fax:0351-4044287;E-mail:tan@sxicc.ac.cn。

基金项目:
国家自然科学基金(20903114, 20773154) (20903114, 20773154)

山西省自然科学基金(2010011015-1) (2010011015-1)

科技部自主研究课题(2010BWZ001) (2010BWZ001)

中国科学院山西煤炭化学研究所青年人才基金(2011SQNRC15)。 (2011SQNRC15)

摘要: 定向设计并制备了多功能MoO₃-SnO₂催化剂,在常压连续流动固定床反应器上实现了二甲醚低温氧化高选择性制备甲酸甲酯的过程。考察了机械混合法、共沉淀法及沉淀浸渍法等不同制备方法对催化剂性能的影响。在沉淀浸渍法制备的MoO₃-SnO₂催化剂上,常压、160℃反应条件下,甲酸甲酯选择性达94.1%,DME转化率也达到了33.9%,并且产物中无CO_x生成。采用NH₃-TPD、CO₂-TPD及H₂-TPR对催化剂进行了表征,结果表明,表面酸性、碱性及氧化性的不同是造成催化剂反应性能差异的原因。另外,通过采用XRD、Raman及TEM对催化剂结构进行表征发现,晶粒粒径及金属氧化物MoO₃的存在状态等结构的差异是造成催化剂活性不同的主要原因。较小晶粒的催化剂和表面存在的低聚态MoO₃是致使催化剂活性提高的主要原因。

关键词:

English

Low-temperature oxidation of dimethyl ether to methyl formate with high selectivity over MoO₃-SnO₂ catalysts

1.
1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;

Corresponding author: 谭猗生.Tel:0351-4044287;Fax:0351-4044287;E-mail:tan@sxicc.ac.cn。

Received Date: 14 October 2012
Fund Project:
国家自然科学基金(20903114, 20773154)

山西省自然科学基金(2010011015-1)

科技部自主研究课题(2010BWZ001)

中国科学院山西煤炭化学研究所青年人才基金(2011SQNRC15)。

Abstract: Low-temperature oxidation of dimethyl ether (DME) to methyl formate (MF) with high selectivity was realized in a continuous flow fixed-bed reactor over the multifunctional MoO₃-SnO₂ catalysts designed and prepared intentionally. The effect of the preparation methods including mechanical mixing, co-precipitation and co-precipitation-impregnation on the catalyst activity was investigated. The results showed that the selectivity to MF reaches 94.1% at 160℃ over the catalyst prepared by co-precipitation-impregnation, with DME conversion of 33.9% and absence of CO_x in the products. The results of NH₃-TPD, CO₂-TPD and H₂-TPR characterizations indicated that the catalysts prepared by various methods are also obviously different in the surface acidic, alkaline and redox properties. The results of Raman, XRD and TEM revealed that MoO₃ structure and particle sizes have a significant influence on the catalyst activity; small particle size and oligomeric MoO₃ may be responsible for the high activity of the MoO₃-SnO₂ catalysts from co-precipitation-impregnation in the selective oxidation of DME to MF at low temperature.

Key words:

1. [1] WANG D, HAN Y , TAN Y , TSUBAKI N. Effect of H₂O on Cu-based catalyst in one-step slurry phase dimethyl ether synthesis[J]. Fuel Process Technol, 2009, 90(3): 446-451.[1] WANG D, HAN Y , TAN Y , TSUBAKI N. Effect of H₂O on Cu-based catalyst in one-step slurry phase dimethyl ether synthesis[J]. Fuel Process Technol, 2009, 90(3): 446-451.
2. [2] SAN X , ZHANG Y, SHEN W , TSUBAKI N. New synthesis method of ethanol from dimethyl ether with a synergic effect between zeolite and metallic catalyst[J]. Energy Fuels, 2009, 23(5): 2843-2844.[2] SAN X , ZHANG Y, SHEN W , TSUBAKI N. New synthesis method of ethanol from dimethyl ether with a synergic effect between zeolite and metallic catalyst[J]. Energy Fuels, 2009, 23(5): 2843-2844.
3. [3] LIU G , ZHANG Q , HAN Y , TAN Y . Direct oxidation of dimethyl ether to ethanol over WO₃/HZSM-5 catalysts[J]. Catal Commun, 2012, 26: 173-177.[3] LIU G , ZHANG Q , HAN Y , TAN Y . Direct oxidation of dimethyl ether to ethanol over WO₃/HZSM-5 catalysts[J]. Catal Commun, 2012, 26: 173-177.
4. [4] HIROSHI Y, KENJI A, ATSUSHI M, KAORU F. Oxidation dimerization of dimethyl ether with solid catalysts[J]. Appl Catal, 1989, 53(1): L5-L9.[4] HIROSHI Y, KENJI A, ATSUSHI M, KAORU F. Oxidation dimerization of dimethyl ether with solid catalysts[J]. Appl Catal, 1989, 53(1): L5-L9.
5. [5] ZHANG Q , TAN Y , YANG C , HAN Y . MnCl₂ modified H₄SiW₁₂O₄0/SiO₂ catalysts for catalytic oxidation of dimethyl ether to dimethoxymethane[J]. J Mol Catal A, 2007, 236(1/2): 149-155.[5] ZHANG Q , TAN Y , YANG C , HAN Y . MnCl₂ modified H₄SiW₁₂O₄0/SiO₂ catalysts for catalytic oxidation of dimethyl ether to dimethoxymethane[J]. J Mol Catal A, 2007, 236(1/2): 149-155.
6. [6] LIU H , CHEUNG P, IGLESIA E. Structure and support effects on the selective oxidation of dimethyl ether to formaldehyde catalyzed by MoOx domains[J]. J Catal, 2003, 217(1): 222-232.[6] LIU H , CHEUNG P, IGLESIA E. Structure and support effects on the selective oxidation of dimethyl ether to formaldehyde catalyzed by MoOx domains[J]. J Catal, 2003, 217(1): 222-232.
7. [7] 黄秀敏,徐奕德,申文杰. 负载型MoO_x和VO_x催化剂上二甲醚选择氧化制甲醛的反应[J].催化学报,2004, 25(4): 267-271. HUANG Xiu-min, XU Yi-de, SHEN Wen-jie. Selective oxidation of dimethyl ether to formaldehyde over supported MoO_x and VO_x catalysts[J]. Chinese Journal of Catalysis, 2004, 25(4): 267-271.[7] 黄秀敏,徐奕德,申文杰. 负载型MoO_x和VO_x催化剂上二甲醚选择氧化制甲醛的反应[J].催化学报,2004, 25(4): 267-271. HUANG Xiu-min, XU Yi-de, SHEN Wen-jie. Selective oxidation of dimethyl ether to formaldehyde over supported MoO_x and VO_x catalysts[J]. Chinese Journal of Catalysis, 2004, 25(4): 267-271.
8. [8] AI M. Dimerization of formaldehyde to methyl formate on SnO₂-WO₃ catalysts[J]. Appl Catal, 1984, 9(3): 371-377.[8] AI M. Dimerization of formaldehyde to methyl formate on SnO₂-WO₃ catalysts[J]. Appl Catal, 1984, 9(3): 371-377.
9. [9] GONCALVES F, MEDEITOS P, EON J, APPEL L. Active sites for ethanol oxidation over SnO₂-supported molybdenum oxides[J]. Appl Catal A, 2000, 193(1/2): 195-202.[9] GONCALVES F, MEDEITOS P, EON J, APPEL L. Active sites for ethanol oxidation over SnO₂-supported molybdenum oxides[J]. Appl Catal A, 2000, 193(1/2): 195-202.
10. [10] CHEUNG P, LIU H , IGLESIA E. Kinetics and mechanism of dimethyl ether oxidation to formaldehyde on supported molybdenum oxides domains[J]. J Phys Chem B, 2004, 108(48): 18650-18658.[10] CHEUNG P, LIU H , IGLESIA E. Kinetics and mechanism of dimethyl ether oxidation to formaldehyde on supported molybdenum oxides domains[J]. J Phys Chem B, 2004, 108(48): 18650-18658.
11. [11] HERRMANN J M, VILLAIN F, APPEL L. Characterization of Mo-Sn-O system by means of Raman spectroscopy and electrical conductivity measurements[J]. Appl Catal A, 2003, 240(1/2): 177-182.[11] HERRMANN J M, VILLAIN F, APPEL L. Characterization of Mo-Sn-O system by means of Raman spectroscopy and electrical conductivity measurements[J]. Appl Catal A, 2003, 240(1/2): 177-182.

扫一扫看文章

计量

PDF下载量: 440
文章访问数: 1273
HTML全文浏览量: 117

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

MoO₃-SnO₂催化剂上二甲醚低温氧化高选择性制备甲酸甲酯

通讯作者: 谭猗生.Tel:0351-4044287;Fax:0351-4044287;E-mail:tan@sxicc.ac.cn。

English

Low-temperature oxidation of dimethyl ether to methyl formate with high selectivity over MoO₃-SnO₂ catalysts

Corresponding author: 谭猗生.Tel:0351-4044287;Fax:0351-4044287;E-mail:tan@sxicc.ac.cn。

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

MoO3-SnO2催化剂上二甲醚低温氧化高选择性制备甲酸甲酯

通讯作者: 谭猗生.Tel:0351-4044287;Fax:0351-4044287;E-mail:tan@sxicc.ac.cn。

English

Low-temperature oxidation of dimethyl ether to methyl formate with high selectivity over MoO3-SnO2 catalysts

Corresponding author: 谭猗生.Tel:0351-4044287;Fax:0351-4044287;E-mail:tan@sxicc.ac.cn。

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

MoO₃-SnO₂催化剂上二甲醚低温氧化高选择性制备甲酸甲酯

Low-temperature oxidation of dimethyl ether to methyl formate with high selectivity over MoO₃-SnO₂ catalysts

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs