Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts
Article PDF

Keywords

methyl glycolate, ethylene glycol, copper-containing catalysts, gas-phase oxidation

How to Cite

Varvarin, A. M., Levytska, S. I., Mylin, A. M., Zinchenko, O. Y., & Brei, V. V. (2022). Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts. Catalysis and Petrochemistry, (33), 59-65. https://doi.org/10.15407/kataliz2022.33.059

Abstract

The gas-phase oxidation of ethylene glycol and methanol mixture into methyl glycolate С2H6O2+CH3OH+O2 = C3H6O3+2H2О over synthesized copper-containing catalysts was studied.  Methyl glycolate can be considered as raw material for obtaining biodegradable polyglycolide. The CuO-containing samples were synthesized by impregnation of granular oxide-supports (γ-Al2O3, SiO2 and MgO-ZrO2) with the calculated amount of aqueous solution of Cu(NO3)2·3H2O followed by heat treatment at 400 °C. In such way the supported CuO-MexOy /Al2O3 (Me = Mg, Ti, Cr, Co, Zn, Zr, Ag) samples have been prepared. Catalytic experiments were performed in a stainless-steel flow reactor with a fixed bed of catalyst at 200-270 °C and atmospheric pressure. Oxygen of air was used as an oxidant. The reaction products were analyzed using 13C NMR spectroscopy and gas chromatography. It was found that СuO/Al2O3 catalyst provides ~ 100% ethylene glycol conversion with 56% selectivity towards methyl glycolate at 220 °С. The main by-products are methoxymethanol, 1,1-dimethoxymethane, methyl methoxyacetate, and methyl formate. Use of silica as catalyst support leads to a significant decrease of the ethylene glycol conversion to 57 % for CuO/SiO2, but methyl glycolate selectivity does not change significantly. Promotion of СuO/Al2O3 with MgO increases methyl glycolate yield to 64%. According to the scheme of ethylene glycol sequential oxidation the increase in selectivity for methyl glycolate over CuO-MgO/Al2O3 catalyst is caused by the basic sites that promote intramolecular Cannizzaro rearrangement of the intermediate reaction product  glyoxal hemiacetal to methyl glycolate. It’s found that mixed CuO-CrO3 oxide supported by γ-Al2O3 provides 80 % methyl glycolate selectivity with 95-100% ethylene glycol conversion at 200-210 °C.

https://doi.org/10.15407/kataliz2022.33.059
Article PDF

References

De Clercq R., Makshina E., Sels B.F., Dusselier M. Catalytic gas-phase cyclization of glycolate esters: a novel route toward glycolide-based bioplastics. ChemCatChem. 2018. 10 (24). 5649-5655.

Nair L.S., Laurencin C.T. Biodegradable polymers as biomaterials. Prog. Polym. Sci. 2007. 32. 762–798.

Lee S.Y., Kim J.C., Lee J.S., Kim Y.G. Carbonylation of formaldehyde over ion exchange resin catalyst. 1. Batch reactor studies. Ind. Eng. Chem. Res. 1993. 32. 253-259.

Sun Y., Wang H., Shen J., Liu H., Liu Z. Highly effective synthesis of methyl glycolate with heteropolyacids as catalysts. Catal. Com. 2009. 10. 678-681.

Нe D., Huang W., Liu J., Zhu Q. Condensation of formaldehyde and methyl formate to methyl glycolate and methyl metoxy acetate using heteropolyacids and their salts. Catal. Today.1999. 51. 127-134.

Wang K., Yao J., Wang Y., Wang G. Catalytic systems containing p-toluenesulfonic acid for coupling reaction of formaldehyde and methyl formate. J. Natur. Gas Chem. 2007. 16. 286-292.

Wang B., Xu Q., Song H., Xu G. Synthesis of methyl glycolate by hydrogenation of dimethyl oxalate over Cu-Ag/SiO2 catalyst. J. Natur. Gas Chem. 2007. 16. 78-80.

Zhu J., Cao L., Li C., Zhao G., Zhu T., Hu W., Sun W., Lu Y. Nanoporous Ni3P evolutionarily structured onto a Ni foam for highly selective hydrogenation of dimethyl oxalate to methyl glycolate. ACS Appl. Mater. Interfaces. 2019. 11. 37635-37643.

Yin A., Guo X., Dai W., Fan K. High activity and selectivity of Ag/SiO2 catalyst to hydrogenation of dimethyloxalate. Chem. Commun. 2010. 46. 4348-4350.

Zheng J., Lin H., Wang Y.-n., Zheng X., Duan X., Yuan Y. Efficient low-temperature selective hydrogenation of esters on bimetallic Au-Ag/SBA-15 catalyst. J. Catal. 2013. 297. 110-118.

Hu M., Yan Y., Duan X., Ye L., Zhou J., Lin H., Yuan Y. Effective anchoring of silver nanoparticles onto N-doped carbon with enhanced catalytic performance for the hydrogenation of dimethyl oxalate to methyl glycolate. Catal. Commun. 2017. 100. 148-152.

Abbas M., Chen Z., Chen J. Shape and size controlled synthesis of Cu nanoparticles-wrapped on RGO nanosheets catalyst and their outstanding stability and catalytic performance in the hydrogenation reaction of dimethyl oxalate. J. Mater. Chem. A. 2018. 6. 19133-19142.

Ye R.-P., Lin L., Wang L.-C., Ding D., Zhou Z., Pan P., Xu Z., Liu J., Adidharma H., Radosz M., Fan M., Yao Y.-G. Perspectives on the active sites and catalyst design for the hydrogenation of dimethyl oxalate. ASC Catal. 2020. 10 (8). 4465-4490.

Кiyoura T., Kogure Y. Synthesis of hydroxyacetic acid and its esters from glyoxal catalysed by multivalent metal ions. Appl. Catal. A. 1997. 156. 97-104.

Feng L., Li G., Yan Y., Hou W., Zhang Y., Tang Y. Direct conversion of C6 sugars to methyl glycerate and glycolate in methanol. RSC Adv. 2018. 8. 30163-30170.

Ke Y.-H., Qin X.-X., Liu C.-L., Yang R.-Z., Dong W.-S. Oxidative esterification of ethylene glycol in methanol to form methyl glycolate over supported Au catalysts. Catal. Sci. Technol. 2014. 4. 3141-3150.

Levytska S.I. Investigation of glucose isomerization into fructose on MgO-ZrO2 catalyst in flow mode. Catalysis and Petrochemistry. 2017. N26. 46-52. [in Ukrainian].

Mylin A.M., Brei V.V. Selective conversion of glycerol–ethanol mixture into ethyl lactate over СеO2/Al2O3-catalyst. Ukr. J. Chem. 2016. 82(2). 79-83. [in Ukrainian].

Sharanda M.E., Mylin A.M., Zinchenko O.Yu., Brei V.V. Vapor-phase oxidation of propylene glycol-methanol mixture to methyl lactate on CeO2/Al2O3 catalyst. Catalysis and Petrochemistry. 2021. N31. 92-97. [in Ukrainian].

Brei V.V., Levytska S.I., Prudius S.V. To the question on oxidation at a surface of oxides: TPR oxidation of cyclohexanol. Catalysis and Petrochemistry. 2022. N33. 1-9.