Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu‐MCM‐41 catalysts

Abstract

The synthesis and utilization of mesoporous Cu‐MCM‐41 catalysts for hydrogenation of dimethyl oxalate to ethylene glycol is described in this article. Physicochemical properties of these Cu‐MCM‐41 catalysts have been investigated by N2‐physisorption, X‐ray diffraction, inductively coupled plasma, N2O titration, transmission electron microscopy, temperature programmed reduction, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. It was found that the copper loading significantly influenced the pore structure and copper surface area of the catalyst. High catalytic performance is obtained over a 20Cu‐MCM‐41 catalyst with a full DMO conversion and EG yield of 92% at a LHSV of 3.0 h−1. The catalytic performance of optimized 20Cu‐MCM‐41 catalyst could be attributed to the fine copper dispersion and large copper surface areas. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2530–2539, 2013

A copper-phyllosilicate core-sheath nanoreactor for carbon–oxygen hydrogenolysis reactions

“…The DMO hydrogenation reaction to EtOH comprises several continuous reactions (Table 1), including DMO hydrogenation to MG, MG hydrogenation to ethylene glycol (EG) and deep hydrogenation of EG to EtOH 33,34 . Confinement of reactants and reaction intermediates within such nanochannels could prolong the contact time of these species with the active sites inside the CuPSNTs 35 , which favours the deep hydrogenation reaction and leads to a higher selectivity to EG or ethanol.…”

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

“…The dissociation of MN on metal surfaces has also been investigated by several groups [7][8][9][10]12]. Peck and co-workers performed A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT 4 auger electron spectroscopy (AES), low-energy electron diffraction (LEED), and temperature-programmed desorption (TPD) studies on MN dissociation on Pt(111) and Pt-Sn alloys [9,10]. They found that the activation of MN is very facile to produce adsorbed CH 3 [7,8].…”

“…However, due to the shrink of oil resources and the continuous increase of EG demand, an alternative EG synthesis technology called coal to ethylene glycol (CTEG) has attracted substantial attention [1,[4][5][6]. CO catalytic coupling with methyl nitrite (MN) to dimethyl oxalate (DMO) is the crucial step in the conversion of inorganic C1 to organic C2 in CTEG, and thus it is considered to be one of the most important applications in C1 chemistry [5].…”

New Catalysts for Coal to Ethylene Glycol

“…Due to the high reaction activity and low cost, Cu-based catalyst has been widely used in DMO hydrogenation to EG. [33][34][35][36] …”

“…The other supports can be divided into two categories: simple oxides (TiO 2 , [52] ZnO, [53] Al 2 O 3 , [54] ZrO 2 [55] etc.) and molecular sieves (SBA-15, [56] ZSM-5, [57] MCM-41, [58] HMS, [59] etc.). The effect of TiO 2 crystal phase and the interaction between Cu and TiO 2 were systematically investigated by Dai group.…”