catalКатализ в промышленностиKataliz v promyshlennosti1816-03872413-6476LLC "KALVIS"10.18412/1816-0387-2025-2-79-86catal-1160Research ArticleКАТАЛИЗ В ХИМИЧЕСКОЙ И НЕФТЕХИМИЧЕСКОЙ ПРОМЫШЛЕННОСТИCATALYSIS IN CHEMICAL AND PETROCHEMICAL INDUSTRYПаровая конверсия метанола в водородсодержащий газ на нанесенных Pt-содержащих катализаторахMethanol Steam Reforming to Hydrogen-Containing Gas over Supported Platinum-Containing CatalystsКузнецоваА. Д.KuznetsovaA. D.ctls@kalvis.ruРогожниковВ. Н.RogozhnikovV. N.ctls@kalvis.ruСнытниковП. В.SnytnikovP. V.ctls@kalvis.ruБадмаевС. Д.BadmaevS. D.ctls@kalvis.ruИнститут катализа СО РАН, Новосибирск; Новосибирский государственный университетРоссияBoreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk; Novosibirsk State UniversityRussian FederationИнститут катализа СО РАН, НовосибирскРоссияBoreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, NovosibirskRussian Federation2025280320252527986Copyright © LLC "KALVIS", 20252025LLC "KALVIS"LLC "KALVIS"https://www.catalysis-kalvis.ru/jour/about/submissions#copyrightNoticehttps://www.catalysis-kalvis.ru/jour/article/view/1160

Изучены и сопоставлены свойства нанесенных Pt-содержащих гранулированных (Pt/Ce0,75Zr0,25O2) и блочных структурированных (Pt/Ce0,75Zr0,25O2 /η-Al2O3/FeCrAl) катализаторов в отношении реакции паровой конверсии метанола в синтез-газ для питания твердо- оксидных топливных элементов. Сравнительные исследования показали, что активная Pt/Ce0,75Zr0,25O2 система более эффективно работает на блочном структурированном носителе. В частности, катализатор 0,15 мас.% Pt/8 мас.% Ce0,75Zr0,25O2 /6 мас.% η-Al2O3/FeCrAl при атмосферном давлении, температуре 400 °С, скорости подачи реакционной смеси (30 об.% СН3ОН, 35 об.% Н2О, 35 об.% N2) 60 л/(гкат·ч) обеспечивает полную конверсию метанола в синтез-газ с суммарным содержанием Н2 и СО ~60 об.% и производительность по синтез-газу ~85 л (Н2+СО)/(гкат · ч).

The catalytic properties of supported Pt-containing granular (Pt/Ce0.75Zr0.25O2) and structured (Pt/Ce0.75Zr0.25O2-δ/η-Al2O3/FeCrAl) catalysts for methanol steam reformong to syngas were studied and compared. Comparative studies prove that the active Pt/Ce0.75Zr0.25O2 system in the structured catalyst operates more efficiently than in the granular catalyst. In particular, the structured catalyst 0.15 wt. % Pt/8 wt. % Ce0.75Zr0.25O2-δ/6 wt. % η-Al2O3/FeCrAl at atmospheric pressure, temperature 400 °C, and the reaction mixture (30 vol. % CH3OH, 35 vol. % H2O, 35 vol. % N2) feed rate of 60 L/(gcat·h), provided complete conversion of methanol to syngas with a total H2 and CO content of ~60 vol. % and syngas productivity of ~85 L(H2+CO)/(gcat·h).

метанолпаровая конверсиясинтез-газплатинананесенные катализаторыблочные структурированные носителиFeCrAlmethanol steam reformingsyngasplatinumsupported catalystsstructured supportsFeCrAlReferencesАгарков Д.А., Бредихин С.И. Твердооксидные топливные элементы (ТОТЭ) и энергоустановки // Энергоэксперт. 2021. Т. №3. С. 6–8.Агарков Д.А., Бредихин С.И. Твердооксидные топливные элементы (ТОТЭ) и энергоустановки // Энергоэксперт. 2021. Т. №3. С. 6–8.Kirillov V.A., Kuzin N.A., Amosov Y.I., Kireenkov V. V., Sobyanin V.A. Catalysts for the conversion of hydrocarbon and synthetic fuels for onboard syngas generators // Catal. Ind. 2011. Vol. 3, № 2. P. 176–182. https://doi.org/10.1134/S2070050411020073.Kirillov V.A., Kuzin N.A., Amosov Y.I., Kireenkov V. V., Sobyanin V.A. Catalysts for the conversion of hydrocarbon and synthetic fuels for onboard syngas generators // Catal. Ind. 2011. Vol. 3, № 2. P. 176–182. https://doi.org/10.1134/S2070050411020073.Потемкин Д.И., Усков С.И., Горлова А.М., Кириллов В.А., Шигаров А.Б., Брайко А.С., Рогожников В.Н., Снытников П.В., Печенкин А.А., Беляев В.Д., Пименов А.А., Собянин В.А. Низкотемпературная паровая конверсия природного газа в метано-водородные смеси // Катализ в промышленности. 2020. Т. 20, № 3. С. 184–189. https://doi.org/10.18412/1816-0387-2020-3-184-189.Потемкин Д.И., Усков С.И., Горлова А.М., Кириллов В.А., Шигаров А.Б., Брайко А.С., Рогожников В.Н., Снытников П.В., Печенкин А.А., Беляев В.Д., Пименов А.А., Собянин В.А. Низкотемпературная паровая конверсия природного газа в метано-водородные смеси // Катализ в промышленности. 2020. Т. 20, № 3. С. 184–189. https://doi.org/10.18412/1816-0387-2020-3-184-189.Бадмаев С.Д., Беляев В.Д., Потемкин Д.И., Снытников П.В., Собянин В.А., Хартон В.В. Разложение метанола в синтез-газ на нанесенных Pt-содержащих катализаторах // Катализ в промышленности. 2023. Т. 23, № 2. С. 26–33. https://doi.org/10.18412/1816-0387-2023-2-26-33.Бадмаев С.Д., Беляев В.Д., Потемкин Д.И., Снытников П.В., Собянин В.А., Хартон В.В. Разложение метанола в синтез-газ на нанесенных Pt-содержащих катализаторах // Катализ в промышленности. 2023. Т. 23, № 2. С. 26–33. https://doi.org/10.18412/1816-0387-2023-2-26-33.Ranjekar A.M., Yadav G.D. Steam Reforming of Methanol for Hydrogen Production: A Critical Analysis of Catalysis, Processes, and Scope // Ind. Eng. Chem. Res. 2021. Vol. 60, № 1. P. 89–113. https://doi.org/10.1021/acs.iecr.0c05041.Ranjekar A.M., Yadav G.D. Steam Reforming of Methanol for Hydrogen Production: A Critical Analysis of Catalysis, Processes, and Scope // Ind. Eng. Chem. Res. 2021. Vol. 60, № 1. P. 89–113. https://doi.org/10.1021/acs.iecr.0c05041.Sá S., Silva H., Brandão L., Sousa J.M., Mendes A. Catalysts for methanol steam reforming-A review // Appl. Catal. B Environ. 2010. Vol. 99, № 1–2. P. 43–57. https://doi.org/10.1016/j.apcatb.2010.06.015.Sá S., Silva H., Brandão L., Sousa J.M., Mendes A. Catalysts for methanol steam reforming-A review // Appl. Catal. B Environ. 2010. Vol. 99, № 1–2. P. 43–57. https://doi.org/10.1016/j.apcatb.2010.06.015.Анализ мирового рынка метанола в 2019 - 2023 гг, прогноз на 2024 - 2028 гг // ООО "БизнесСтат", Москва, 2023. С. 50.Анализ мирового рынка метанола в 2019 - 2023 гг, прогноз на 2024 - 2028 гг // ООО "БизнесСтат", Москва, 2023. С. 50.Irena and Methanol Intitute, Innovation Outlook : Renewable Methanol // International Renewable Energy Agency., 2021. P. 122.Irena and Methanol Intitute, Innovation Outlook : Renewable Methanol // International Renewable Energy Agency., 2021. P. 122.Yang W.W., Ma X., Tang X.Y., Dou P.Y., Yang Y.J., He Y.L. Review on developments of catalytic system for methanol steam reforming from the perspective of energy-mass conversion // Fuel. 2023. Vol. 345. P. 23. https://doi.org/10.1016/j.fuel.2023.128234.Yang W.W., Ma X., Tang X.Y., Dou P.Y., Yang Y.J., He Y.L. Review on developments of catalytic system for methanol steam reforming from the perspective of energy-mass conversion // Fuel. 2023. Vol. 345. P. 23. https://doi.org/10.1016/j.fuel.2023.128234.Sá S., Silva H., Brandão L., Sousa J.M., Mendes A. Catalysts for methanol steam reforming—A review // Appl. Catal. B Environ., 2010. Vol. 99, № 1–2. P. 43–57. https://doi.org/10.1016/J.APCATB.2010.06.015.Sá S., Silva H., Brandão L., Sousa J.M., Mendes A. Catalysts for methanol steam reforming—A review // Appl. Catal. B Environ., 2010. Vol. 99, № 1–2. P. 43–57. https://doi.org/10.1016/J.APCATB.2010.06.015.Mrad M., Gennequin C., Aboukaïs A., Abi-Aad E. Cu/Zn-based catalysts for H2 production via steam reforming of methanol // Catal. Today., 2011. Vol. 176, № 1. P. 88–92. https://doi.org/10.1016/j.cattod.2011.02.008.Mrad M., Gennequin C., Aboukaïs A., Abi-Aad E. Cu/Zn-based catalysts for H2 production via steam reforming of methanol // Catal. Today., 2011. Vol. 176, № 1. P. 88–92. https://doi.org/10.1016/j.cattod.2011.02.008.Yong S.T., Ooi C.W., Chai S.P., Wu X.S. Review of methanol reforming-Cu-based catalysts, surface reaction mechanisms, and reaction schemes // Int. J. Hydrogen Energy. 2013. Vol. 38, № 22. P. 9541–9552. https://doi.org/10.1016/j.ijhydene.2013.03.023.Yong S.T., Ooi C.W., Chai S.P., Wu X.S. Review of methanol reforming-Cu-based catalysts, surface reaction mechanisms, and reaction schemes // Int. J. Hydrogen Energy. 2013. Vol. 38, № 22. P. 9541–9552. https://doi.org/10.1016/j.ijhydene.2013.03.023.Iwasa N., Masuda S., Ogawa N., Takezawa N. Steam reforming of methanol over Pd/ZnO: Effect of the formation of PdZn alloys upon the reaction // Appl. Catal. A, Gen. 1995. Vol. 125, № 1. P. 145–157. https://doi.org/10.1016/0926-860X(95)00004-6.Iwasa N., Masuda S., Ogawa N., Takezawa N. Steam reforming of methanol over Pd/ZnO: Effect of the formation of PdZn alloys upon the reaction // Appl. Catal. A, Gen. 1995. Vol. 125, № 1. P. 145–157. https://doi.org/10.1016/0926-860X(95)00004-6.Iwasa N., Mayanagi T., Ogawa N., Sakata K., Takezawa N. New catalytic functions of Pd-Zn, Pd-Ga, Pd-In, Pt-Zn, Pt-Ga and Pt-in alloys in the conversions of methanol // Catal. Letters. 1998. Vol. 54, № 3. P. 119–123. https://doi.org/10.1023/A:1019056728333.Iwasa N., Mayanagi T., Ogawa N., Sakata K., Takezawa N. New catalytic functions of Pd-Zn, Pd-Ga, Pd-In, Pt-Zn, Pt-Ga and Pt-in alloys in the conversions of methanol // Catal. Letters. 1998. Vol. 54, № 3. P. 119–123. https://doi.org/10.1023/A:1019056728333.Papavasiliou J., Avgouropoulos G., Ioannides T. Production of hydrogen via combined steam reforming of methanol over CuO-CeO2 catalysts // Catal. Commun. 2004. Vol. 5, № 5. P. 231–235. https://doi.org/10.1016/j.catcom.2004.02.009.Papavasiliou J., Avgouropoulos G., Ioannides T. Production of hydrogen via combined steam reforming of methanol over CuO-CeO2 catalysts // Catal. Commun. 2004. Vol. 5, № 5. P. 231–235. https://doi.org/10.1016/j.catcom.2004.02.009.Liu Y., Hayakawa T., Suzuki K., Hamakawa S. Production of hydrogen by steam reforming of methanol over Cu/CeO2 catalysts derived from Ce1 xCuxO2 x precursors // Catal. Commun. 2001. Vol. 2, № 6–7. P. 195–200. https://doi.org/10.1016/S1566-7367(01)00033-4.Liu Y., Hayakawa T., Suzuki K., Hamakawa S. Production of hydrogen by steam reforming of methanol over Cu/CeO2 catalysts derived from Ce1 xCuxO2 x precursors // Catal. Commun. 2001. Vol. 2, № 6–7. P. 195–200. https://doi.org/10.1016/S1566-7367(01)00033-4.Patel S., Pant K.K. Activity and stability enhancement of copper-alumina catalysts using cerium and zinc promoters for the selective production of hydrogen via steam reforming of methanol // J. Power Sources. 2006. Vol. 159, № 1. P. 139–143. https://doi.org/10.1016/j.jpowsour.2006.04.008.Patel S., Pant K.K. Activity and stability enhancement of copper-alumina catalysts using cerium and zinc promoters for the selective production of hydrogen via steam reforming of methanol // J. Power Sources. 2006. Vol. 159, № 1. P. 139–143. https://doi.org/10.1016/j.jpowsour.2006.04.008.Iwasa N., Masuda S., Takezawa N. Steam reforming of methanol over Ni, Co, Pd and Pt supported on ZnO // React. Kinet. Catal. Lett. 1995. Vol. 55, № 2. P. 349–353. https://doi.org/10.1007/BF02073070.Iwasa N., Masuda S., Takezawa N. Steam reforming of methanol over Ni, Co, Pd and Pt supported on ZnO // React. Kinet. Catal. Lett. 1995. Vol. 55, № 2. P. 349–353. https://doi.org/10.1007/BF02073070.Shanmugam V., Neuberg S., Zapf R., Pennemann H., Kolb G. Hydrogen production over highly active Pt based catalyst coatings by steam reforming of methanol: Effect of support and co-support // Int. J. Hydrogen Energy., 2020. Vol. 45, № 3. P. 1658–1670. https://doi.org/10.1016/j.ijhydene.2019.11.015.Shanmugam V., Neuberg S., Zapf R., Pennemann H., Kolb G. Hydrogen production over highly active Pt based catalyst coatings by steam reforming of methanol: Effect of support and co-support // Int. J. Hydrogen Energy., 2020. Vol. 45, № 3. P. 1658–1670. https://doi.org/10.1016/j.ijhydene.2019.11.015.Takezawa N., Iwasa N. Steam reforming and dehydrogenation of methanol: Difference in the catalytic functions of copper and group VIII metals // Catal. Today. 1997. Vol. 36, № 1. P. 45–56. https://doi.org/10.1016/S0920-5861(96)00195-2.Takezawa N., Iwasa N. Steam reforming and dehydrogenation of methanol: Difference in the catalytic functions of copper and group VIII metals // Catal. Today. 1997. Vol. 36, № 1. P. 45–56. https://doi.org/10.1016/S0920-5861(96)00195-2.Silva L.P.C., Terra L.E., Coutinho A.C.S.L.S., Passos F.B. Sour water–gas shift reaction over Pt/CeZrO2 catalysts // J. Catal. 2016. Vol. 341. P. 1–12. https://doi.org/10.1016/j.jcat.2016.05.024.Silva L.P.C., Terra L.E., Coutinho A.C.S.L.S., Passos F.B. Sour water–gas shift reaction over Pt/CeZrO2 catalysts // J. Catal. 2016. Vol. 341. P. 1–12. https://doi.org/10.1016/j.jcat.2016.05.024.Ruiz J.A.C., Passos F.B., Bueno J.M.C., Souza-Aguiar E.F., Mattos L. V., Noronha F.B. Syngas production by autothermal reforming of methane on supported platinum catalysts // Appl. Catal. A Gen. 2008. Vol. 334, № 1–2. P. 259–267. https://doi.org/10.1016/j.apcata.2007.10.011.Ruiz J.A.C., Passos F.B., Bueno J.M.C., Souza-Aguiar E.F., Mattos L. V., Noronha F.B. Syngas production by autothermal reforming of methane on supported platinum catalysts // Appl. Catal. A Gen. 2008. Vol. 334, № 1–2. P. 259–267. https://doi.org/10.1016/j.apcata.2007.10.011.Badmaev S.D., Belyaev V.D., Konishcheva M. V., Kulikov A. V., Pechenkin A.A., Potemkin D.I., Rogozhnikov V.N., Snytnikov P. V., Sobyanin V.A. Catalysts and Catalytic Processes for the Production of Hydrogen-Rich Gas for Fuel Cell Feeding // Chem. Probl. 2019. Vol. 17, № 2. P. 193–204. https://doi.org/10.32737/2221-8688-2019-2-193-204.Badmaev S.D., Belyaev V.D., Konishcheva M. V., Kulikov A. V., Pechenkin A.A., Potemkin D.I., Rogozhnikov V.N., Snytnikov P. V., Sobyanin V.A. Catalysts and Catalytic Processes for the Production of Hydrogen-Rich Gas for Fuel Cell Feeding // Chem. Probl. 2019. Vol. 17, № 2. P. 193–204. https://doi.org/10.32737/2221-8688-2019-2-193-204.Rogozhnikov V.N., Salanov A.N., Potemkin D.I., Glotov A.P., Boev S. V., Snytnikov P. V. Synthesis and studies of structured support Ce0.75Zr0.25O2/θ Al2O3/FeCrAl // Mater. Lett., 2021. Vol. 283. P. 128855. https://doi.org/10.1016/j.matlet.2020.128855.Rogozhnikov V.N., Salanov A.N., Potemkin D.I., Glotov A.P., Boev S. V., Snytnikov P. V. Synthesis and studies of structured support Ce0.75Zr0.25O2/θ Al2O3/FeCrAl // Mater. Lett., 2021. Vol. 283. P. 128855. https://doi.org/10.1016/j.matlet.2020.128855.Shoynkhorova T.B., Simonov P.A., Potemkin D.I., Snytnikov P. V., Belyaev V.D., Ishchenko A. V., Svintsitskiy D.A., Sobyanin V.A. Highly dispersed Rh-, Pt-, Ru/Ce0.75Zr0.25O2–Δ catalysts prepared by sorption-hydrolytic deposition for diesel fuel reforming to syngas // Appl. Catal. B Environ., 2018. Vol. 237. P. 237–244. https://doi.org/10.1016/j.apcatb.2018.06.003.Shoynkhorova T.B., Simonov P.A., Potemkin D.I., Snytnikov P. V., Belyaev V.D., Ishchenko A. V., Svintsitskiy D.A., Sobyanin V.A. Highly dispersed Rh-, Pt-, Ru/Ce0.75Zr0.25O2–Δ catalysts prepared by sorption-hydrolytic deposition for diesel fuel reforming to syngas // Appl. Catal. B Environ., 2018. Vol. 237. P. 237–244. https://doi.org/10.1016/j.apcatb.2018.06.003.

The authors declare that there are no conflicts of interest present.