Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study

doi:10.1016/j.cjche.2015.06.007

Chinese Journal of Chemical Engineering ›› 2016, Vol. 24 ›› Issue (1): 132-139.DOI: 10.1016/j.cjche.2015.06.007

• 第25届中国过程控制会议专栏 • 上一篇下一篇

Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study

Chen Fan¹, Man Luo², Wende Xiao²

1 Key Laboratory of Advanced Control and Optimization for Chemical Processes, Ministry of Education, East China University of Science and Technology (ECUST), Shanghai 200237, China;
2 School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University (SJTU), Shanghai 200240, China

收稿日期:2014-09-08 修回日期:2015-05-04 出版日期:2016-01-28 发布日期:2016-02-23
通讯作者: Wende Xiao
基金资助:
Supported by the National Natural Science Foundation of China (21303102), China Postdoctoral Science Foundation funded project (2012M520900 and 2013T60449).

Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study

Chen Fan¹, Man Luo², Wende Xiao²

1 Key Laboratory of Advanced Control and Optimization for Chemical Processes, Ministry of Education, East China University of Science and Technology (ECUST), Shanghai 200237, China;
2 School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University (SJTU), Shanghai 200240, China

Received:2014-09-08 Revised:2015-05-04 Online:2016-01-28 Published:2016-02-23
Contact: Wende Xiao
Supported by:
Supported by the National Natural Science Foundation of China (21303102), China Postdoctoral Science Foundation funded project (2012M520900 and 2013T60449).

摘要/Abstract

摘要： Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH₃O-NO bond will break with a bond energy of 1.91 eV, and the produced CH₃O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C-H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH₃O andNOtakes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that (i) at lowcoverage, a successive dehydrogenation of the adsorbed CH₃O to CO and H is favored while (ii) at high coverage, hydrogenation of CH₃O to methanol and carbonylation of CH₃O to methyl formate are more preferred. On the basis of the proposed reaction mechanism, two meaningfulways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.

关键词: Methyl nitrite, Catalytic, Non-catalytic, Dissociation, Density functional theory

Abstract: Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH₃O-NO bond will break with a bond energy of 1.91 eV, and the produced CH₃O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C-H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH₃O andNOtakes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that (i) at lowcoverage, a successive dehydrogenation of the adsorbed CH₃O to CO and H is favored while (ii) at high coverage, hydrogenation of CH₃O to methanol and carbonylation of CH₃O to methyl formate are more preferred. On the basis of the proposed reaction mechanism, two meaningfulways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.

Key words: Methyl nitrite, Catalytic, Non-catalytic, Dissociation, Density functional theory

Chen Fan, Man Luo, Wende Xiao. Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study[J]. Chinese Journal of Chemical Engineering, 2016, 24(1): 132-139.

Chen Fan, Man Luo, Wende Xiao. Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study[J]. Chin.J.Chem.Eng., 2016, 24(1): 132-139.

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Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study

Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study

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