A Study of Methyl Formate Production from Carbon Dioxide Hydrogenation in Methanol over a Copper Zinc Oxide Catalyst

Abstract

A preliminary study of the production of methyl formate (MF) from CO 2 hydrogenation in liquid methanol was carried out over a Cu/ZnO/Al 2 O 3 based catalyst which was synthesized by a precipitation technique following a well established route. The effects of amine concentration, hydrogen pressure, temperature, CO and water addition on the activity and selectivity of MF were investigated. It is of interest to note that the addition of 1% trimethylamine can dramatically increase the initial turnover frequency with the MF being the major product. It is evident that the formation of CO 2 -amine adduct promotes the catalytic hydrogenation of CO 2 on the surface of the catalyst.

Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol

“…A few approaches have been reported to produce MF from CO 2 , for instance, by photocatalytic reduction of CO 2 , and CO 2 hydrogenation in the presence of methanol (eq ). The latter was demonstrated using both homogeneous − and heterogeneous catalysts. ,,, Generally, heterogeneous catalysis offers great advantages to transform a large amount of reactant(s) with increased space-time-yield and benefits from process intensification associated with continuous operation, more facile product/catalyst separation, and catalyst regeneration. In fact, an efficient heterogeneous catalyst that promotes such a reaction would be key in developing the continuous synthesis of thermodynamically unstable formic acid starting from CO 2 and H 2 , since MF can serve as an intermediate and methanol can also be produced by CO 2 hydrogenation …”

“…Only Cu and Au supported on metal oxides were reported as heterogeneous catalysts for the CO 2 hydrogenation to MF under batch rather than flow conditions. ,,, Interestingly, Ag has not been investigated so far despite its similarity to Cu in terms of hydrogenation activity. , Other metals such as Ru, Ni, and Pd were reported as promoters to Cu/ZnO/Al 2 O 3 catalyst positively influencing the yield of MF . Among Au catalysts, the ZrO 2 supported ones show higher activities compared to those supported on CeO 2 and TiO 2 ; this difference was ascribed to the amphoteric nature of the support, i.e., the acidic and basic sites promoting the adsorption of CO 2 and desorption of formic acid intermediate, respectively .…”

“…However, to date, the roles of metal and support as well as reaction mechanisms including the type of reactive surface species have not been clarified. It has been proposed that MF is formed by a reaction of CH 3 OH with either surface formates or formic acid intermediates. ,, This was supported by the lack of MF production in the absence of CH 3 OH 17 despite the formation of formate species on the catalyst surface as suggested by ex situ IR studies. , Therefore, it remains a challenge to determine the reactive intermediates and active sites that control the catalytic activity in the MF synthesis under reaction conditions.…”

Research Progress on Carbon Dioxide Reduction Coupled with the Formation of C−O Bonds to Oxygenated Compounds

“…This might be related to the hydrogen molecular activation ability and transfer ability of the promoters. In 2011, the group [86] also studied the hydrogenation of carbon dioxide to methyl formate over Cu/ZnO/Al 2 O 3 catalyst. This research group investigated the effects of amine concentration, hydrogen molecular pressure, temperature, CO and H 2 O addition on this reaction.…”

Transformation of sodium bicarbonate and CO2 into sodium formate over NiPd nanoparticle catalyst

“…Preti et al investigated CO 2 hydrogenation in the presence of neat NEt 3 to form HCOOH/NEt 3 adducts over gold black (Preti et al, 2011 ). Tsang and co-workers explored the possibility of using copper zinc oxide catalyst for the methyl formate production from CO 2 (Kerry Yu and Tsang, 2011 ). There were several investigations on the heterogenization of homogeneous catalysis by immobilizing ruthenium complex catalysts on silica and polystyrene resin (Baiker, 2000 ; Zhang et al, 2004 ).…”