Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts
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 polygly...
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| Datum: | 2022 |
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2022
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| author | Varvarin, Anatolii M. Levytska, Svitlana I. Mylin, Artur M. Zinchenko, Oleksii Yu. Brei, Volodymyr V. |
| author_facet | Varvarin, Anatolii M. Levytska, Svitlana I. Mylin, Artur M. Zinchenko, Oleksii Yu. Brei, Volodymyr V. |
| author_sort | Varvarin, Anatolii M. |
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| datestamp_date | 2023-01-20T10:00:52Z |
| description | 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. |
| first_indexed | 2026-03-12T15:50:15Z |
| format | Article |
| id | oai:katalizorgua:article-82 |
| institution | Catalysis and petrochemistry |
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| language | English |
| last_indexed | 2026-03-12T15:50:15Z |
| publishDate | 2022 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
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| spelling | oai:katalizorgua:article-822023-01-20T10:00:52Z Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts Varvarin, Anatolii M. Levytska, Svitlana I. Mylin, Artur M. Zinchenko, Oleksii Yu. Brei, Volodymyr V. methyl glycolate, ethylene glycol, copper-containing catalysts, gas-phase oxidation метилгліколат, етиленгліколь, мідьвмісні каталізатори, газо-фазне окиснення 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. 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. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2022-10-26 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/82 10.15407/kataliz2022.33.059 Catalysis and petrochemistry; No. 33 (2022): Catalysis and petrochemistry; 59-65 Каталіз та нафтохімія; № 33 (2022): Каталіз та нафтохімія; 59-65 2707-5796 2412-4176 10.15407/kataliz2022.33 en https://kataliz.org.ua/index.php/journal/article/view/82/71 Copyright (c) 2022 Catalysis and petrochemistry |
| spellingShingle | метилгліколат етиленгліколь мідьвмісні каталізатори газо-фазне окиснення Varvarin, Anatolii M. Levytska, Svitlana I. Mylin, Artur M. Zinchenko, Oleksii Yu. Brei, Volodymyr V. Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_alt | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_full | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_fullStr | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_full_unstemmed | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_short | Vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over CuO-containing catalysts |
| title_sort | vapor-phase oxidation of ethylene glycol methanolic solution into methyl glycolate over cuo-containing catalysts |
| topic | метилгліколат етиленгліколь мідьвмісні каталізатори газо-фазне окиснення |
| topic_facet | methyl glycolate ethylene glycol copper-containing catalysts gas-phase oxidation метилгліколат етиленгліколь мідьвмісні каталізатори газо-фазне окиснення |
| url | https://kataliz.org.ua/index.php/journal/article/view/82 |
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