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Preferential Synthesis of Ethanol from Syngas Via Dimethyl Oxalate Hydrogenation Over an Integrated Catalyst Chemcomm Chemical Communications Rsc.Li/Chemcomm

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Preferential Synthesis of Ethanol from Syngas Via Dimethyl Oxalate Hydrogenation Over an Integrated Catalyst Chemcomm Chemical Communications Rsc.Li/Chemcomm Showcasing research from Professor Yujun Zhao’s laboratory As featured in: at Tianjin University, Tianjin, China. Volume 55 Number 39 14 May 2019 Pages 5527–5672 Preferential synthesis of ethanol from syngas via dimethyl oxalate hydrogenation over an integrated catalyst ChemComm Chemical Communications rsc.li/chemcomm The cooperation of Fe5 C2 and CuZnO–SiO2 remarkably inhibited the formation of byproducts, resulting in a significantly high ethanol yield of about 98%. It opens a new route for the preferential synthesis of ethanol from syngas via hydrogenation of dimethyl oxalate. ISSN 1359-7345 COMMUNICATION Ying He et al . Enantioselective iridium catalyzed α-alkylation of azlactones by a tandem asymmetric allylic alkylation/aza-Cope rearrangement See Yujun Zhao et al ., Chem . Commun ., 2019, 55 , 5555. rsc.li/chemcomm Registered charity number: 207890 ChemComm COMMUNICATION Preferential synthesis of ethanol from syngas via dimethyl oxalate hydrogenation over an Cite this: Chem. Commun., 2019, 55, 5555 integrated catalyst† Received 27th March 2019, Accepted 11th April 2019 Xin Shang, Huijiang Huang, Qiao Han, Yan Xu, Yujun Zhao, * Shengping Wang and Xinbin Ma DOI: 10.1039/c9cc02372k rsc.li/chemcomm An integrated catalyst that contains Fe5C2 and CuZnO–SiO2 with a (B553 K) is necessary for the synthesis of ethanol via DMO hydro- dual-bed configuration was designed for the preferential synthesis of genation, the formation of C3–4OH via the Guerbet reaction would ethanol via dimethyl oxalate hydrogenation. The cooperation of the two be highly facilitated by the surface basic sites on the Cu-based catalyst components remarkably inhibited the formation of various catalysts.17 Li’s group18 achieved a high ethanol yield of 95% by byproducts, resulting in a significantly high ethanol yield of about 98%. using a bifunctional catalyst (Cu nanoparticle inlaid mesoporous Al2O3) and 1,4-dioxane instead of methanol as the solvent. The Ethanol has attracted wide attention due to its important influence of the support has also been reported by the same group.19 applications in chemical production and potential to replace These works provide a meaningful instruction for developing a new gasoline as an environmentally friendly fuel.1 Production of technology for ethanol production. Although Cu-based catalysts ethanol from syngas has been proposed and considered as a perform well in the conversion of DMO, further improvement of promising process other than fermentation of biomass or their selectivity to ethanol is still a big challenge for a process with hydration of ethylene. Direct synthesis of ethanol from syngas the presence of methanol from an industrial viewpoint.20,21 over Rh-based,2 Mo-based,3 Cu-based4 or modified F–T synthesis Recently, Liu et al.22 developed a molybdenum carbide catalyst catalysts5 has made great advances in recent years. However, poor for the hydrogenation of DMO to ethanol with an ethanol yield of selectivity of ethanol limits its industrial application. Thus, a new 70% at 473 K. They found that high activity of Mo2C-based catalysts synthesis route of ethanol from syngas via dimethyl ether (DME) in C–C cleavage can lead to the decomposition of DMO and lower and methyl acetate (MA) is developed.6,7 DME synthesized from ethanol selectivity. In our previous work, a highly efficient iron syngas is carbonylated to MA by zeolite catalysts8,9 and MA is carbide catalyst was prepared for DMO hydrogenation to ethanol sequentially hydrogenated to ethanol by Cu-based catalysts.10 A with a selectivity of 90%.23 Meanwhile, it was found that the relatively higher yield of ethanol makes it promising for industrial presence of Fe5C2 leads to the formation of ethanol via the 11 production of ethanol from syngas. hydrogenation of intermediate MA instead of EG. The Fe5C2 Another ethanol production process from syngas via the catalyst exhibited a different reaction path in comparison with hydrogenation of dimethyl oxalate (DMO) has been proposed as the Cu-based catalyst (Scheme 1). an alternative method.12 Cu-based catalysts have been widely In addition, some bifunctional catalysts or integrated systems for investigated in the hydrogenation of DMO with a selectivity of the conversion of C1 molecules to lower olefins24 or liquid fuels25 ethylene glycol (EG) of up to 95%.13,14 The synergy of Cu species have been reported, but the concept of integrated catalysis has never 0 + (Cu and Cu )forH2 dissociation and CQOadsorptiononCu-based been reported in the selective synthesis of ethanol via DMO hydro- catalysts was reported to be responsible for the higher catalytic genation. Since Fe5C2 is an effective catalyst for DMO conversion performance in DMO hydrogenation.15 When the hydrogenation of and MA is the key intermediate product in the consecutive hydro- DMO was performed at higher temperature and H2/DMO, more genation system, coupling of Fe5C2 and a copper-based catalyst ethanol can be formed with a selectivity of 83% by deep hydrogena- could be a rational strategy to ensure a higher ethanol selectivity in tion of EG on a Cu-based catalyst.16 As higher reaction temperature DMO hydrogenation. Herein, an integrated catalyst that contains Fe5C2 and CuZnO–SiO2 with a dual-bed configuration is fabricated Key Laboratory for Green Chemical Technology of Ministry of Education, for the hydrogenation of DMO and a significantly high selectivity to Collaborative Innovation Center of Chemical Science and Engineering, School of ethanol (98%) was achieved, which is beyond all of the reported Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China. E-mail: [email protected] results. The effect of the integration manner and the reaction paths † Electronic supplementary information (ESI) available: Experimental details and over the integrated catalyst were also well investigated. The achieve- characterization data. See DOI: 10.1039/c9cc02372k ments suggest a promising prospect for its practical application. This journal is © The Royal Society of Chemistry 2019 Chem. Commun., 2019, 55, 5555--5558 | 5555 Communication ChemComm The major products change to ethanol and MA in these two cases and the selectivity of ethanol was significantly improved from 40–60% to 80–90%. These results suggested a cooperation effect of the integrated catalyst, such that the Fe5C2 catalyst ensures the conversion of DMO and Cu-based catalysts prompt the further hydrogenation of intermediate MA to ethanol. The absence of methyl glycolate (MG) and EG implied that Fe5C2 is active enough for the conversion of DMO and MG, preventing the formation of EG via the DMO/MG hydrogenation on a Cu-based catalyst. Obviously, the formation of C3–4OH has also been efficiently inhibited by the integrated catalyst. To further understand how the integrated catalyst performs Scheme 1 The reaction pathway of the hydrogenation of DMO on the in the hydrogenation of DMO, the mass ratio of two components Fe5C2 and Cu-based catalyst. (Fe5C2 and CuZnO–SiO2) was tuned to investigate its effect on the catalytic performance. As shown in Fig. 2, when various mass ratios of Fe5C2 to CuZnO–SiO2 were applied in the hydrogenation, To gain an insight into the effect of Fe5C2, the performance the product distribution changed significantly under the same of Cu-based catalysts before and after the introduction of Fe C 5 2 reaction conditions. When the mass ratio of Fe5C2 to CuZnO–SiO2 was investigated in the hydrogenation of DMO. And the sole increased from 1/5 to 5/5, the selectivity of ethanol kept increasing, Fe5C2 catalyst was also tested in the hydrogenation for comparison. accompanied by a drastic decrease of EG and C3–4OH selectivity. As shown in Fig. 1, with Cu–SiO as the sole catalyst, ethanol, EG 2 Inthisrangeofmassratios,theamountofFe5C2 was not yet and C3–4OH were the major products. The selectivity of ethanol was enough to provide active sites for the conversion of DMO or MG, so very low (58.7%) and a considerable amount of EG was produced unreacted DMO or MG was hydrogenated to EG on the CuZnO– due to relatively lower reaction temperature (533 K). C3–4OH SiO2 catalyst bed, leading to the generation of C3–4OH as well on (10.5%) was formed as a result of the Guerbet reaction over the 17 the basic sites of CuZnO–SiO2. However, as Fe5C2/CuZnO–SiO2 surface basic sites of the catalyst (Fig. S3, ESI†). The selectivity of increased further (from 5/2 to sole Fe5C2), there was a significant ethanol over the sole CuZnO–SiO2 was similar to that of Cu–SiO2, decrease of the ethanol selectivity (from 90.5% to 75.9%) accom- and the higher selectivity of C3–4OH (21.8%) could be ascribed to panied by an increase of MA. In fact, a ratio of 5/2 presented better the formation of more basic sites because of the introduction of Zn ethanol selectivity than any other ratio. Therefore, it can be (Fig. S3, ESI†).ThesoleFeC was also tested for the hydrogenation 5 2 concluded that Fe5C2 plays an important role in the total conver- of DMO under the same conditions and the obtained ethanol sion of DMO and MG, due to the extremely high selectivity to MA in selectivity was 75.9% with MA as the major by-product. These the hydrogenation of MG (as shown in Scheme 1). But it presented results indicated that it was quite a different reaction pathway over relatively lower activity in the hydrogenation of MA than the Fe C catalysts with which DMO was first hydrogenated to MA 5 2 CuZnO–SiO2 catalyst. A cooperative effect is enhanced by an instead of EG on the Fe5C2 surface. However, further hydrogenation optimal ratio which ensures the complete conversion of DMO/ of MA to ethanol on Fe C was difficult, so a higher selectivity to MA 5 2 MG into MA/ethanol on Fe5C2 and inhibits the formation of (24.1%) was obtained.
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