FAU分子筛催化γ-戊内酯脱羧制丁烯研究

石油炼制与化工 ›› 2024, Vol. 55 ›› Issue (10): 109-117.

FAU分子筛催化γ-戊内酯脱羧制丁烯研究

乔堉锴^1,2,张新宝¹,李俊杰¹,于伟伟¹,安杰¹,徐仕睿³,朱向学¹,徐龙伢¹,李秀杰¹

1. 中国科学院大连化学物理研究所
2. 中国科学院大学
3. 抚顺东科精细化工有限公司

收稿日期:2024-03-18 修回日期:2024-07-04 出版日期:2024-10-12 发布日期:2024-09-26
通讯作者: 李秀杰 E-mail:xiujieli@dicp.ac.cn
基金资助:
国家自然科学基金;国家自然科学基金资助项目;大连市重点领域创新团队;国家自然科学基金

SELECTIVE PRODUCTION OF BUTENE FROM γ-VALEROLACTONE DECARBOXYLATION OVER FAU ZEOLITE

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Received:2024-03-18 Revised:2024-07-04 Online:2024-10-12 Published:2024-09-26
Contact: Xiujie Li E-mail:xiujieli@dicp.ac.cn

摘要/Abstract

摘要： 生物质基γ-戊内酯脱羧制备丁烯反应为碳四烯烃的可持续生产提供了一条新的途径。针对现有无定形SiO₂-Al₂O₃催化剂只能在低空速下运转的现状，开发了一种高效的NaY分子筛催化剂。因其丰富的Lewis酸与适宜的碱性，可在高空速下实现原料γ-戊内酯的100%转化，同时丁烯选择性高达99.6%。NaY分子筛催化剂显示出良好的反应稳定性和反应-再生循环性能，在连续运转1320 min后，丁烯收率保持在99.4%；经历5次反应-再生循环后，丁烯收率保持在99.2%。在此基础上，通过离子交换法制备LiY，KY，CaY分子筛，对比研究分子筛中金属阳离子种类对分子筛催化脱羧性能的影响。结果表明：NaY分子筛因其适宜的酸碱匹配度，脱羧性能最好；LiY分子筛和KY分子筛次之；CaY分子筛因存在强Br?nsted酸位，催化性能最低。

关键词: γ-戊内酯, 脱羧, 丁烯, NaY分子筛, 离子交换, 生物质

Abstract: The decarboxylation of biomass-based γ-valerolactone (GVL) provides a new pathway for the sustainable production of butene. However, due to the low acidity of the commonly used amorphous SiO₂-Al₂O₃ catalyst, this reaction could only be operated at low weight hourly space velocity (WHSV) condition, which limited its industrial scale-up. An efficient NaY catalyst was developed to address this challenge, which could achieve 100% GVL conversion and 99.6% butene selectivity at high WHSV. After 1 320 minutes on stream, the yield of butene remained at 99.4%. In addition, the yield of butene remained at 99.2% after 5 cycles of regeneration. Furthermore, LiY, KY and CaY were prepared by ion exchange to investigate the effect of metal cations on catalytic performance. The results indicated that NaY showed the best performance due to its balanced acid and base sites, and CaY exhibited poor performance due to the existence of strong Br?nsted acid sites.

Key words: γ-valerolactone, decarboxylation, butylene, NaY zeolite, ion exchange, biomass

乔堉锴张新宝李俊杰于伟伟安杰徐仕睿朱向学徐龙伢李秀杰. FAU分子筛催化γ-戊内酯脱羧制丁烯研究[J]. 石油炼制与化工, 2024, 55(10): 109-117.

参考文献

[1]MASCAL M.Chemicals from biobutanol: technologies and markets[J].Biofuels, Bioproducts and Biorefining, 2012, 6(4):483-493
[2]BENDER M.An Overview of Industrial Processes for the Production of Olefins – C4 Hydrocarbons[J].ChemBioEng Reviews, 2014, 1(4):136-147
[3]AMGHIZAR I，VANDEWALLE L A，VAN GEEM K M， et al.New Trends in Olefin Production[J].Engineering, 2017, 3(2):171-178
[4]ZACHAROPOULOU V，LEMONIDOU A.Olefins from Biomass Intermediates: A Review[J].Catalysts, 2017, 8(1):2-
[5]KOHLI K，PRAJAPATI R，SHARMA B.Bio-Based Chemicals from Renewable Biomass for Integrated Biorefineries[J].Energies, 2019, 12(2):233-
[6]姜涛，兰秀菊.煤制烯烃混合碳四的利用探讨[J].煤化工, 2011, 39(03):5-9
[7]贾向凡，杨震，韩超.国内1-丁烯产能及生产工艺研究[J].[J].化工管理, 2021, (31):150-151
[8]TUCK C O，PéREZ E，HORVáTH I T， et al.Valorization of Biomass: Deriving More Value from Waste[J].Science, 2012, 337(6095):695-699
[9]MANZER L E.Catalytic synthesis of α-methylene-γ-valerolactone: a biomass-derived acrylic monomer[J].Applied Catalysis A: General, 2004, 272(1):249-256
[10]LANGE J-P，VESTERING J Z，HAAN R J.Towards ‘bio-based’ Nylon: conversion of γ-valerolactone to methyl pentenoate under catalytic distillation conditions[J].Chemical Communications, 2007, (33):3488-
[11]HORVáTH I T，MEHDI H，FáBOS V， et al.Valerolactone—a sustainable liquid for energy and carbon-based chemicals[J].Green Chem, 2008, 10(2):238-242
[12]BOND J Q，ALONSO D M，WANG D， et al.Integrated Catalytic Conversion of gamma-Valerolactone to Liquid Alkenes for Transportation Fuels[J].Science, 2010, 327(5969):1110-1114
[13]张战，辛加余，魏灵朝，等.介孔SiO2/Al2O3固体酸催化γ-戊内酯脱羰基制备丁烯[J].过程工程学报, 2014, 14(03):444-449
[14]WANG H T，WU Y S，GUO S， et al.gamma-Valerolactone converting to butene via ring-opening and decarboxylation steps over amorphous SiO2-Al2O3 catalyst[J].Molecular Catalysis, 2020, 497:-
[15]SHAN W，YANG R，JIA Y， et al.Synthesis of Porous Amorphous SiO2-Al2O3 Solid Acid Catalyst for Efficiently Catalyzing GVL Decarboxylation to Butene[J].ChemCatChem, 2024, 16(3):-
[16]LIN L F，SHEVELEVA A M，DA SILVA I， et al.Quantitative production of butenes from biomass-derived gamma-valerolactone catalysed by hetero-atomic MFI zeolite[J].Nature Materials, 2020, 19(1):-
[17]SHERRY H S.The Ion-Exchange Properties of ZeolitesI. Univalent Ion Exchange in Synthetic Faujasite[J].The Journal of Physical Chemistry, 1966, 70(4):1158-1168
[18]SHERRY H S，WALTON H F.The ion-exchange properties of zeolitesII. Ion exchange in the synthetic zeolite Linde 4A[J].The Journal of Physical Chemistry, 1967, 71(5):1457-1465
[19]SHERRY H S.The ion exchange properties of zeolities: IIIRare earth ion exchange of synthetic faujasites[J].Journal of Colloid and Interface Science, 1968, 28(2):288-292
[20]SCHERZER J.The Preparation and Characterization of Aluminum-Deficient Zeolites [M]. Catalytic Materials: Relationship Between Structure and Reactivity. American Chemical Society. 1984: 157-200.
[21]XU J，MOJET B L，LEFFERTS L.Effect of zeolite geometry for propane selective oxidation on cation electrostatic field of Ca2+ exchanged zeolites[J].Microporous and Mesoporous Materials, 2006, 91(1):187-195
[22]WANG L，LIU J，LIN C， et al.Effects of different alkali metal cations in FAU zeolites on the separation performance of CO2/N2O[J].Chemical Engineering Journal, 2022, 431:134257-
[23]BOND J Q，JUNGONG C S，CHATZIDIMITRIOU A.Microkinetic analysis of ring opening and decarboxylation of gamma-valerolactone over silica alumina[J].Journal of Catalysis, 2016, 344:640-656
[24]KHAN T S，GUPTA S，BANDODKAR P， et al.On the role of oxocarbenium ions formed in Bronsted acidic condition on gamma-Al2O3 surface in the ring-opening of gamma-valerolactone[J].Appl Catal a-Gen, 2018, 560:66-72
[25]BéRES A，HANNUS I，KIRICSI I.Acid-base testing of catalysts using 1-butene isomerization as test reaction[J].Reaction Kinetics & Catalysis Letters, 1995, 56(1):55-61
[26]HOWE G W，BIELECKI M，KLUGER R.Base-Catalyzed Decarboxylation of Mandelylthiamin: Direct Formation of Bicarbonate as an Alternative to Formation of CO2[J].Journal of the American Chemical Society, 2012, 134(51):-
[27]WARD J W.The nature of active sites on zeolites: IIIThe alkali and alkaline earth ion-exchanged forms[J].Journal of Catalysis, 1968, 10(1):34-46
[28]WANG X，ZENG J，LU X， et al.High Aluminum Content Beta Zeolite as an Active Lewis Acid Catalyst for γ-Valerolactone Decarboxylation[J].Industrial & Engineering Chemistry Research, 2019, 58(27):11841-11848
[29]KRAPCHO A P，WEIMASTER J F，ELDRIDGE J M， et al.Synthetic applications and mechanism studies of the decarbalkoxylations of geminal diesters and related systems effected in dimethyl sulfoxide by water andor by water with added salts[J].The Journal of Organic Chemistry, 1978, 43(1):138-147
[30]BOND J Q，ALONSO D M，WEST R M， et al.gamma-Valerolactone Ring-Opening and Decarboxylation over SiO2Al2O3 in the Presence of Water[J].Langmuir, 2010, 26(21):16291-16298
[31]BOND J Q，WANG D，ALONSO D M， et al.Interconversion between gamma-valerolactone and pentenoic acid combined with decarboxylation to form butene over silicaalumina[J].Journal of Catalysis, 2011, 281(2):290-299
[32]GUPTA S，ARORA R，SINHA N， et al.Mechanistic insights into the ring-opening of biomass derived lactones[J].RSC Advances, 2016, 6(16):12932-12942
[33]LEE J H，HONG S B.Dehydration of 1, 3-butanediol to butadiene over medium-pore zeolites: Another example of reaction intermediate shape selectivity[J].Applied Catalysis B: Environmental, 2021, (280):119446-