ДЕЗАКТИВАЦИЯ И РЕГЕНЕРАЦИЯ HZSM-5 ПРИ АРОМАТИЗАЦИИ ПАРОВ ПИРОЛИЗА ГОРЮЧИХ СЛАНЦЕВ: ОТ ПРИРОДЫ КОКСА К ИНТЕГРАЛЬНОЙ ПРОИЗВОДИТЕЛЬНОСТИ КАТАЛИЗАТОРА
DOI:
https://doi.org/10.66960/jof.3093-8899.00042Ключевые слова:
HZSM-5, дезактивация, кокс, регенерация, пиролизные пары, моноароматические углеводороды, TPO, интегральная производительностьАннотация
Представлен критический обзор механизмов дезактивации и регенерации HZSM-5 применительно к двухстадийной ароматизации паров пиролиза горючих сланцев. Показано, что оценка катализатора по одному свежему циклу систематически переоценивает технологическую ценность материалов с высокой начальной кислотностью, если она сопровождается быстрым блокированием микропор и ростом полиароматического кокса. Предложена многоуровневая модель состояния катализатора, объединяющая количество кокса, его локализацию, степень конденсации, потерю микропористого объёма, изменение доступной Brønsted/Lewis-кислотности и восстановление структуры после окислительной регенерации. Для периодического пиролиза предложена адаптация принципа коррекции на временную изменчивость состава подаваемых паров: сравнение активности должно проводиться при эквивалентной накопленной нагрузке паров или с параллельным контрольным образцом свежего катализатора. Основным показателем предлагается интегральная производительность Σm(МАУ)/mкат,0 за серию реакция–регенерация, дополненная коэффициентом восстановления активности и удельным образованием кокса. На основе литературы по сланцам, пиролизным маслам и другим сложным углеводородным потокам сформирована программа не менее пяти циклов с характеристикой свежего, отработанного и регенерированного HZSM-5 методами XRD, N2-адсорбции, NH3-TPD/пиридин-FTIR и TGA/TPO; рамановская спектроскопия предлагается для независимой оценки степени упорядоченности углеродистых отложений. Научный вклад настоящего обзора состоит в переходе от статического понятия «активность катализатора» к измеримой карте состояния и накопленной производительности, а также в формировании рабочего окна регенерации, ограниченного с одной стороны неполным удалением кокса, а с другой — необратимой деалюминацией и потерей кислотности.
Библиографические ссылки
Williams P.T., Chishti H.M. Influence of residence time and catalyst regeneration on the pyrolysis–zeolite catalysis of oil shale. Journal of Analytical and Applied Pyrolysis. 2001;60(2):187–203. DOI: 10.1016/S0165-2370(00)00198-4. DOI: https://doi.org/10.1016/S0165-2370(00)00198-4
Chang Z. et al. Production of aromatic hydrocarbons from catalytic pyrolysis of Huadian oil shale using ZSM-5 zeolites as catalyst. Journal of Analytical and Applied Pyrolysis. 2021;159:104990. DOI: 10.1016/j.jaap.2020.104990. DOI: https://doi.org/10.1016/j.jaap.2020.104990
Yang Q. et al. Continuous catalytic pyrolysis of waste oil to aromatics: Exploring the structure-performance relations of ZSM-5 based on different scale-up forms. Chemical Engineering Journal. 2023;475:146259. DOI: 10.1016/j.cej.2023.146259. DOI: https://doi.org/10.1016/j.cej.2023.146259
Nyembe N., Isa Y.M. Design rules for hierarchical ZSM-5 zeolites in catalytic fast pyrolysis: Linking porosity and acidity to selectivity and deactivation resistance. Chemical Engineering and Processing - Process Intensification. 2026;227:110940. DOI: 10.1016/j.cep.2026.110940. DOI: https://doi.org/10.1016/j.cep.2026.110940
Bensafi B., Chouat N., Djafri F. The universal zeolite ZSM-5: Structure and synthesis strategies. A review. Coordination Chemistry Reviews. 2023;496:215397. DOI: 10.1016/j.ccr.2023.215397. DOI: https://doi.org/10.1016/j.ccr.2023.215397
Lok C.M., Van Doorn J., Aranda Almansa G. Promoted ZSM-5 catalysts for the production of bio-aromatics, a review. Renewable and Sustainable Energy Reviews. 2019;113:109248. DOI: 10.1016/j.rser.2019.109248. DOI: https://doi.org/10.1016/j.rser.2019.109248
Daligaux V., Richard R., Manero M.-H. Deactivation and regeneration of zeolite catalysts used in pyrolysis of plastic wastes—A process and analytical review. Catalysts. 2021;11(7):770. DOI: 10.3390/catal11070770. DOI: https://doi.org/10.3390/catal11070770
Argyle M.D., Bartholomew C.H. Heterogeneous catalyst deactivation and regeneration: A review. Catalysts. 2015;5:145–269. DOI: 10.3390/catal5010145. DOI: https://doi.org/10.3390/catal5010145
Guisnet M., Magnoux P. Deactivation by coking of zeolite catalysts. Prevention of deactivation. Optimal conditions for regeneration. Catalysis Today. 1997;36:477–483. DOI: 10.1016/S0920-5861(96)00238-6. DOI: https://doi.org/10.1016/S0920-5861(96)00238-6
Guisnet M., Magnoux P. Organic chemistry of coke formation. Applied Catalysis A: General. 2001;212:83–96. DOI: 10.1016/S0926-860X(00)00845-0. DOI: https://doi.org/10.1016/S0926-860X(00)00845-0
Fals J. et al. Deactivation and regeneration dynamics in hierarchical zeolites: Coke characterization and impact on catalytic cracking of vacuum gas oil. Heliyon. 2024;10:e37813. DOI: 10.1016/j.heliyon.2024.e37813. DOI: https://doi.org/10.1016/j.heliyon.2024.e37813
Chen T.-S., Wang P.-F., Du Z.-Y., Liao Y.-H. Comparative effects of mesopores and framework defects on the deactivation of HZSM-5 catalyst during alkylphenol dealkylation. Chemical Engineering Science. 2023;275:118712. DOI: 10.1016/j.ces.2023.118712. DOI: https://doi.org/10.1016/j.ces.2023.118712
Anekwe I.M.S. et al. Stability, deactivation and regeneration study of a newly developed HZSM-5 and Ni-doped HZSM-5 zeolite catalysts for ethanol-to-hydrocarbon conversion. Catalysis Communications. 2024;186:106802. DOI: 10.1016/j.catcom.2023.106802. DOI: https://doi.org/10.1016/j.catcom.2023.106802
Liu X. et al. Catalytic pyrolysis of nonedible oils for the production of renewable aromatics using metal-modified HZSM-5 catalysts. ACS Omega. 2022;7:18953–18968. DOI: 10.1021/acsomega.2c02011. DOI: https://doi.org/10.1021/acsomega.2c02011
Wang J. et al. Aromatic hydrocarbon production and catalyst regeneration in pyrolysis of oily sludge using ZSM-5 zeolites as catalysts. Energy & Fuels. 2017;31:11681–11689. DOI: 10.1021/acs.energyfuels.7b01855. DOI: https://doi.org/10.1021/acs.energyfuels.7b01855
Kariim I., Swai H., Kivevele T. Bio-oil upgrading over ZSM-5 catalyst: A review of catalyst performance and deactivation. International Journal of Energy Research. 2023;2023:4776962. DOI: 10.1155/2023/4776962. DOI: https://doi.org/10.1155/2023/4776962
Li Y. et al. ZSM-5 zeolite for catalytic cracking of non-edible oil: Strategies for coke suppression. Catalysts. 2026;16:834. DOI: 10.3390/catal16090834. DOI: https://doi.org/10.3390/catal16090834
He L. et al. Mechanisms of sulfur and nitrogen transformation during Longkou oil shale pyrolysis. Energy. 2021;232:120977. DOI: 10.1016/j.energy.2021.120977. DOI: https://doi.org/10.1016/j.energy.2021.120977
Yung M.M. et al. Restoring ZSM-5 performance for catalytic fast pyrolysis of biomass: Effect of regeneration temperature. Catalysis Today. 2019;323:76–85. DOI: 10.1016/j.cattod.2018.06.025. DOI: https://doi.org/10.1016/j.cattod.2018.06.025
Heracleous E. et al. Characterization of deactivated and regenerated zeolite ZSM-5-based catalyst extrudates used in catalytic pyrolysis of biomass. Journal of Catalysis. 2019;380:108–122. DOI: 10.1016/j.jcat.2019.10.019. DOI: https://doi.org/10.1016/j.jcat.2019.10.019
Luna-Murillo B. et al. Catalytic fast pyrolysis of biomass: Catalyst characterization reveals the feed-dependent deactivation of a technical ZSM-5-based catalyst. ACS Sustainable Chemistry & Engineering. 2021;9(1):291–304. DOI: 10.1021/acssuschemeng.0c07153. DOI: https://doi.org/10.1021/acssuschemeng.0c07153
Stanton A.R., Iisa K., Mukarakate C., Nimlos M.R. Role of biopolymers in the deactivation of ZSM-5 during catalytic fast pyrolysis of biomass. ACS Sustainable Chemistry & Engineering. 2018;6(8):10030–10038. DOI: 10.1021/acssuschemeng.8b01333. DOI: https://doi.org/10.1021/acssuschemeng.8b01333
Eschenbacher A. et al. Impact of ZSM-5 deactivation on bio-oil quality during upgrading of straw-derived pyrolysis vapors. Energy & Fuels. 2019;33(1):397–412. DOI: 10.1021/acs.energyfuels.8b03691. DOI: https://doi.org/10.1021/acs.energyfuels.8b03691
Kalogiannis K.G., Stefanidis S.D., Lappas A.A. Catalyst deactivation, ash accumulation and bio-oil deoxygenation during ex situ catalytic fast pyrolysis of biomass in a cascade thermal-catalytic reactor system. Fuel Processing Technology. 2019;186:99–109. DOI: 10.1016/j.fuproc.2018.12.008. DOI: https://doi.org/10.1016/j.fuproc.2018.12.008
Hernández-Giménez A.M. et al. Deactivation and regeneration of solid acid and base catalyst bodies used in cascade for bio-oil synthesis and upgrading. Journal of Catalysis. 2022;405:641–651. DOI: 10.1016/j.jcat.2021.09.029. DOI: https://doi.org/10.1016/j.jcat.2021.09.029
Vitolo S., Bresci B., Seggiani M., Gallo M.G. Catalytic upgrading of pyrolytic oils over HZSM-5 zeolite: behaviour of the catalyst when used in repeated upgrading–regenerating cycles. Fuel. 2001;80(1):17–26. DOI: 10.1016/S0016-2361(00)00063-6. DOI: https://doi.org/10.1016/S0016-2361(00)00063-6
Li Y. et al. Control of coke deposition in solid acid catalysis through the doping of transition metal combined with the assistance of H2: a review. Applied Catalysis A: General. 2021;626:118340. DOI: 10.1016/j.apcata.2021.118340. DOI: https://doi.org/10.1016/j.apcata.2021.118340
Yao N.-Y. et al. Coke formation on different metal-modified (Co, Mo and Zr) ZSM-5 in the catalytic pyrolysis of cellulose to light aromatics. Journal of Analytical and Applied Pyrolysis. 2024;179:106516. DOI: 10.1016/j.jaap.2024.106516. DOI: https://doi.org/10.1016/j.jaap.2024.106516
Hu J. et al. Synthesis of HZSM-5@activated carbon for improving aromatic production from catalytic pyrolysis of biomass. Chemical Engineering Journal. 2024;494:153031. DOI: 10.1016/j.cej.2024.153031. DOI: https://doi.org/10.1016/j.cej.2024.153031
Zhong S. et al. Selective production of aromatics from catalytic fast pyrolysis of cassava residues over vanadium modified ZSM-5: Experimental and kinetic study. Journal of Analytical and Applied Pyrolysis. 2024;177:106334. DOI: 10.1016/j.jaap.2023.106334. DOI: https://doi.org/10.1016/j.jaap.2023.106334
Qiao J. et al. Methanol to aromatics: isolated zinc phosphate groups on HZSM-5 zeolite enhance BTX selectivity and catalytic stability. RSC Advances. 2020;10:5961–5971. DOI: 10.1039/C9RA09657D. DOI: https://doi.org/10.1039/C9RA09657D
Shim H., Hong J., Ha K.-S. Efficient utilization of hydrocarbon mixture to produce aromatics over Zn/ZSM-5 and physically mixed with ZSM-5. Catalysts. 2022;12(5):501. DOI: 10.3390/catal12050501. DOI: https://doi.org/10.3390/catal12050501
Wang W., Luo Z., Li S., Xue S., Sun H. Novel micro-mesoporous composite ZSM-5 catalyst for aromatics production by catalytic fast pyrolysis of lignin residues. Catalysts. 2020;10(4):378. DOI: 10.3390/catal10040378. DOI: https://doi.org/10.3390/catal10040378
Chen H. et al. Catalytic fast pyrolysis of rice straw to aromatic compounds over hierarchical HZSM-5 produced by alkali treatment and metal-modification. Journal of Analytical and Applied Pyrolysis. 2018;131:76–84. DOI: 10.1016/j.jaap.2018.02.009. DOI: https://doi.org/10.1016/j.jaap.2018.02.009
Hernández-Giménez A.M. et al. Effect of mesoporosity, acidity and crystal size of zeolite ZSM-5 on catalytic performance during the ex-situ catalytic fast pyrolysis of biomass. ChemCatChem. 2021;13:1207–1219. DOI: 10.1002/cctc.202001778. DOI: https://doi.org/10.1002/cctc.202001778
Qiao K. et al. Catalytic fast pyrolysis of cellulose in a microreactor system using hierarchical ZSM-5 zeolites treated with various alkalis. Applied Catalysis A: General. 2017;547:274–282. DOI: 10.1016/j.apcata.2017.07.034. DOI: https://doi.org/10.1016/j.apcata.2017.07.034
Jia L.Y. et al. Catalytic fast pyrolysis of biomass: superior selectivity of hierarchical zeolites to aromatics. Green Chemistry. 2017;19:5442–5459. DOI: 10.1039/C7GC02309J. DOI: https://doi.org/10.1039/C7GC02309J
Chen H. et al. Controlled synthesis of hierarchical ZSM-5 for catalytic fast pyrolysis of cellulose to aromatics. Journal of Materials Chemistry A. 2018;6:21178–21185. DOI: 10.1039/C8TA08930B. DOI: https://doi.org/10.1039/C8TA08930B
Yang K. et al. Preparation of nanocrystalline ZSM-5 and its catalytic performance in fast pyrolysis of cellulose to produce aromatic hydrocarbons. Microporous and Mesoporous Materials. 2022;331:111679. DOI: 10.1016/j.micromeso.2022.111679. DOI: https://doi.org/10.1016/j.micromeso.2022.111679
Sun H. et al. Porosity roles of micro-mesostructured ZSM-5 in catalytic fast pyrolysis of cellulolytic enzyme lignin for aromatics. Energy Conversion and Management. 2021;247:114753. DOI: 10.1016/j.enconman.2021.114753. DOI: https://doi.org/10.1016/j.enconman.2021.114753
Du H. et al. Ex-situ catalytic upgrading of vapors from microwave-assisted pyrolysis of bamboo with chemical liquid deposition modified HZSM-5 to enhance aromatics production. Journal of Analytical and Applied Pyrolysis. 2020;149:104857. DOI: 10.1016/j.jaap.2020.104857. DOI: https://doi.org/10.1016/j.jaap.2020.104857
Dai G. et al. Enhancement of aromatics production from catalytic pyrolysis of biomass over HZSM-5 modified by chemical liquid deposition. Journal of Analytical and Applied Pyrolysis. 2018;134:439–445. DOI: 10.1016/j.jaap.2018.07.010. DOI: https://doi.org/10.1016/j.jaap.2018.07.010
Rahman M.M., Liu R., Cai J. Catalytic fast pyrolysis of biomass over zeolites for high quality bio-oil – a review. Fuel Processing Technology. 2018;180:32–46. DOI: 10.1016/j.fuproc.2018.08.002. DOI: https://doi.org/10.1016/j.fuproc.2018.08.002
Liang J., Shan G., Sun Y. Catalytic fast pyrolysis of lignocellulosic biomass: critical role of zeolite catalysts. Renewable and Sustainable Energy Reviews. 2021;139:110707. DOI: 10.1016/j.rser.2021.110707. DOI: https://doi.org/10.1016/j.rser.2021.110707
Liu R. et al. Multi-scale complexities of solid acid catalysts in the catalytic fast pyrolysis of biomass for bio-oil production – a review. Progress in Energy and Combustion Science. 2020;80:100852. DOI: 10.1016/j.pecs.2020.100852. DOI: https://doi.org/10.1016/j.pecs.2020.100852
Valle B. et al. Selective production of aromatics by crude bio-oil valorization with a nickel-modified HZSM-5 zeolite catalyst. Energy & Fuels. 2010;24:2060–2070. DOI: 10.1021/ef901231j. DOI: https://doi.org/10.1021/ef901231j
Mullen C.A., Boateng A.A. Catalytic pyrolysis-GC/MS of lignin from several sources. Fuel Processing Technology. 2010;91:1446–1458. DOI: 10.1016/j.fuproc.2010.05.022. DOI: https://doi.org/10.1016/j.fuproc.2010.05.022
Zheng Y. et al. Study on aromatics production via the catalytic pyrolysis vapor upgrading of biomass using metal-loaded modified H-ZSM-5. Journal of Analytical and Applied Pyrolysis. 2017;126:169–179. DOI: 10.1016/j.jaap.2017.06.011. DOI: https://doi.org/10.1016/j.jaap.2017.06.011
Carlson T.R. et al. Aromatic production from catalytic fast pyrolysis of biomass-derived feedstocks. Topics in Catalysis. 2009;52:241–252. DOI: 10.1007/s11244-008-9160-6. DOI: https://doi.org/10.1007/s11244-008-9160-6
Yu Y. et al. The role of shape selectivity in catalytic fast pyrolysis of lignin with zeolite catalysts. Applied Catalysis A: General. 2012;447–448:115–123. DOI: 10.1016/j.apcata.2012.09.012. DOI: https://doi.org/10.1016/j.apcata.2012.09.012
Luan P. et al. Ex-situ catalytic fast pyrolysis of waste polycarbonate for aromatic hydrocarbons: Utilizing HZSM-5/modified HZSM-5. Journal of Analytical and Applied Pyrolysis. 2024;182:106667. DOI: 10.1016/j.jaap.2024.106667. DOI: https://doi.org/10.1016/j.jaap.2024.106667
Liu H., Qiu Y., Shan R., Zhang J., Yuan H., Chen Y. Catalytic pyrolysis of polyethylene over bimetallic-modified ZSM-5: Role of alkaline sites on structure regulation, thermal behavior and aromatics production. Fuel. 2025;395:135180. DOI: 10.1016/j.fuel.2025.135180. DOI: https://doi.org/10.1016/j.fuel.2025.135180
Wu Z. et al. Boosting aromatic production from catalytic pyrolysis of polyethylene by co-feeding CO₂ over Zn-modified HZSM-5 zeolite. Journal of the Energy Institute. 2026;127:102602. DOI: 10.1016/j.joei.2026.102602. DOI: https://doi.org/10.1016/j.joei.2026.102602
Gu B. et al. Catalytic fast pyrolysis of sewage sludge over HZSM-5: A study of light aromatics, coke, and nitrogen migration under different atmospheres. Industrial & Engineering Chemistry Research. 2020;59(39):17537–17545. DOI: 10.1021/acs.iecr.0c01170. DOI: https://doi.org/10.1021/acs.iecr.0c01170
Geng R. et al. Structure evolution of Zn species on fresh, deactivated, and regenerated Zn/ZSM-5 catalysts in ethylene aromatization. ACS Catalysis. 2022;12(23):14735–14747. DOI: 10.1021/acscatal.2c04074. DOI: https://doi.org/10.1021/acscatal.2c04074
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