C4二醇的发酵生产及其化学催化升级为高价值化学品的研究进展

doi:10.1016/S1872-2067(23)64512-7

催化学报 ›› 2023, Vol. 52: 99-126.DOI: 10.1016/S1872-2067(23)64512-7

C4二醇的发酵生产及其化学催化升级为高价值化学品的研究进展

Abhishek R. Varma^a, Bhushan S. Shrirame^a, Sunil K. Maity^a^,^*(), Deepti Agrawal^b, Naglis Malys^c, Leonardo Rios-Solis^d, Gopalakrishnan Kumar^e, Vinod Kumar^f^,^g^,^h^,^*()

^a印度海得拉巴理工学院化学工程系, 特伦甘纳桑加雷迪, 印度
^bCSIR-印度石油研究所材料资源效率处, 生物化学和生物技术区, 北阿坎德邦德拉敦, 印度
^c考纳斯理工大学化学技术学院有机化学系, 考纳斯, 立陶宛
^d伦敦大学学院生物化学工程系, 伦敦, 英国
^e延世大学土木与环境工程学院, 首尔, 韩国
^f克兰菲尔德大学水能源与环境学院, 克兰菲尔德, 英国
^g印度鲁尔基理工学院生物科学与生物工程系, 北阿坎德邦, 印度
^h碳源可再生能源有限公司, 爱丁堡, 英国

收稿日期:2023-07-17 接受日期:2023-08-28 出版日期:2023-09-18 发布日期:2023-09-25
通讯作者: *电子信箱: sunil_maity@che.iith.ac.in (S. K. Maity),Vinod.Kumar@cranfield.ac.uk (V. Kumar).

Recent advances in fermentative production of C4 diols and their chemo-catalytic upgrading to high-value chemicals

Abhishek R. Varma^a, Bhushan S. Shrirame^a, Sunil K. Maity^a^,^*(), Deepti Agrawal^b, Naglis Malys^c, Leonardo Rios-Solis^d, Gopalakrishnan Kumar^e, Vinod Kumar^f^,^g^,^h^,^*()

^aDepartment of Chemical Engineering, Indian Institute of Technology Hyderabad, Kandi, Sangareddy 502284, Telangana, India
^bBiochemistry and Biotechnology Area, Material Resource Efficiency Division, CSIR-Indian Institute of Petroleum, Dehradun 248005, Uttarakhand, India
^cDepartment of Organic Chemistry, Faculty of Chemical Technology, Kaunas University of Technology, Radvilėnų Street 19, LT-50254 Kaunas, Lithuania
^dDepartment of Biochemical Engineering, University College London, Gower Street, London WC1E 6BT, United Kingdom
^eSchool of Civil and Environmental Engineering, Yonsei University, Seoul 03722, Republic of Korea
^fSchool of Water, Energy and Environment, Cranfield University, Cranfield MK43 0AL, United Kingdom
^gDepartment of Bioscience and Bioengineering, Indian Institute of Technology Roorkee, Uttarakhand 247667, India
^hC-Source Renewables Limited, Summit House, 4-5 Mitchell Street, Edinburgh, EH6 7BD, United Kingdom

Received:2023-07-17 Accepted:2023-08-28 Online:2023-09-18 Published:2023-09-25
Contact: *E-mail: sunil_maity@che.iith.ac.in (S. K. Maity),Vinod.Kumar@cranfield.ac.uk (V. Kumar).
About author:Dr. Sunil K. Maity is currently working as a Professor in the Department of Chemical Engineering, Indian Institute of Technology Hyderabad, India. He also served about two and half years as an Assistant Professor at the National Institute of Technology Rourkela, India, from 2007 to 2010. Prof. Maity received his B.Tech. degree in Chemical Engineering from University College of Science and Technology, University of Calcutta, India in 1999, followed by M.Tech. degree in 2002 and Ph.D. in 2007 from the Department of Chemical Engineering, Indian Institute of Technology Kharagpur. His research interests mainly focus on biorefinery for biofuels and renewable chemicals, heterogeneous catalysis and chemical reaction engineering, and techno-economic analysis using Aspen Plus and pinch technology. He published three edited books, ten book chapters, forty peer-reviewed journal articles, and has organized several national and international conferences.
Dr. Vinod Kumar is a Senior Lecturer in Microbial Technology and Biorefining at Cranfield University (CU). He is a Fellow of Higher Education Academy (FHEA). Dr. Kumar earned his M.Sc. (Chemistry) and PhD (Biochemical Engineering & Biotechnology) degree from Indian Institute of Technology Delhi, India. He graduated in B.Sc. (Hons) Chemistry from Hindu College, University of Delhi, India. The research activities of Dr. Kumar are at nexus of Metabolic/Pathway Engineering, Bioprocessing and Waste Valorization. His work leads to development of low carbon biomanufacturing technologies for overproduction of platform/commodity chemicals and fuels from carbonaceous agro-industrial waste streams rich in renewable carbon, with a circular economy approach. He has 130+ publications in peer reviewed high-quality journals/publishers attracting a cumulative citation of 4004 with an h-index ~35 till date. Dr. Kumar is Associate Editor for 3Biotech, and Microbial Cell Factories and Editor for Food and Bioproducts Bioprocessing and sits on Editorial Board of Chemical Engineering Journal. He also holds Visiting Faculty position for two premier institutes in India: Indian Institute of Technology Delhi and Roorkee.

摘要/Abstract

摘要：

化石资源的过度消耗导致能源和环境污染问题, 迫切需要科研人员开发出可持续、低能耗、绿色低碳的化学品生产技术. 生物技术利用“细胞工厂”, 以生物质等可再生资料为原料生产基础化学品, 是以化石资源为原料的合成方法的潜在替代方案. 然而, 利用生物技术生产全系列石化产品存在其自身的局限性, 因此, 人们对集成/混合方法越来越感兴趣, 该方法先采用生物技术对生物质升级, 再通过化学催化的途径使其转化为含有活性官能团的产物.

本文主要综述了C4二醇的三种重要结构异构体, 2,3-、1,3-和1,4-丁二醇的生物生产方法, 目前这些异构体主要通过石化路线生产, 全球市场需求不断增长. 首先, 从集成方法的原理出发, 总结了上述二醇的生物法生产现状, 包括底物、微生物、发酵技术和代谢/途径工程和发酵技术. 然后, 全面总结了C4二醇催化升级以生产系列产物的最新研究进展, 讨论了催化剂中不同活性位点对催化活性、产物选择性和催化剂稳定性的影响. 此外, 给出了集成方法的具体实例, 解决开发C4二醇生物生产工艺的相关挑战, 强调通过直接催化转化方法对其升级所存在的困难. 最后, 对C4二醇的发酵生产及其化学催化升级为高价值化学品的相关研究进行总结, 对未来发展进行展望, 并指出将生物催化和化学催化方法相结合对于拓宽生物质升级转化产物范围具有重要作用.

关键词: 丁二醇, 发酵, 代谢工程, 多相催化, 1,3-丁二烯, 3-丁烯-1-醇, 3-丁烯-2-醇, 甲乙酮

Abstract:

The current era is witnessing the transition from a fossil-dominated economy towards sustainable and low-carbon green manufacturing technologies at economical prices with reduced energy usage. The biological production of chemical building blocks from biomass using cell factories is a potential alternative to fossil-based synthesis. However, microbes have their own limitations in generating the whole spectrum of petrochemical products. Therefore, there is a growing interest in an integrated/hybrid approach where products containing active functional groups obtained by biological upgrading of biomass are converted via chemo-catalytic routes. The present review focuses on the biological production of three important structural isomers of C4 diols, 2,3-, 1,3-, and 1,4-butanediol, which are currently manufactured by petrochemical route to meet the soaring global market demand. The review starts with justifications for the integrated approach and summarizes the current status of the biological production of these diols, including the substrates, microorganisms, fermentation technology and metabolic/pathway engineering. This is followed by a comprehensive review of recent advances in catalytic upgrading of C4 diols to generate a range of products. The roles of various active sites in the catalyst on catalytic activity, product selectivity, and catalyst stability are discussed. The review also covers examples of integrated approaches, addresses challenges associated with developing end-to-end processes for bio-based production of C4 diols, and underlines existing limitations for their upgrading via direct catalytic conversion. Finally, the concluding remarks and prospects emphasise the need for an integrated biocatalytic and chemo-catalytic approach to broaden the spectrum of products from biomass.

Key words: Butanediols, Fermentation, Metabolic engineering, Heterogeneous catalysis, 1,3-Butadiene, 3-Buten-1-ol, 3-Buten-2-ol, Methyl ethyl ketone

Abhishek R. Varma, Bhushan S. Shrirame, Sunil K. Maity, Deepti Agrawal, Naglis Malys, Leonardo Rios-Solis, Gopalakrishnan Kumar, Vinod Kumar. C4二醇的发酵生产及其化学催化升级为高价值化学品的研究进展[J]. 催化学报, 2023, 52: 99-126.

Abhishek R. Varma, Bhushan S. Shrirame, Sunil K. Maity, Deepti Agrawal, Naglis Malys, Leonardo Rios-Solis, Gopalakrishnan Kumar, Vinod Kumar. Recent advances in fermentative production of C4 diols and their chemo-catalytic upgrading to high-value chemicals[J]. Chinese Journal of Catalysis, 2023, 52: 99-126.

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Butanediol	Molar mass (g/mol)	Boiling point (°C)	Melting point (°C)	Density (g/cm³)	Vapor pressure (Pa)	Heat capacity (J/(mol·°C ))
1,4-BDO	90.12	230	20.1	1.02	1.4@25 °C	202.34@25 °C
2,3-BDO	90.12	177	19	0.967	23@20 °C	227.2@27 °C
1,3-BDO	90.12	207	‒77	1.01	8@20 °C	227.2@27 °C
1,2-BDO	90.12	192	‒42	1.002	2.7@20 °C	240.4@25 °C

Butanediol	Molar mass (g/mol)	Boiling point (°C)	Melting point (°C)	Density (g/cm³)	Vapor pressure (Pa)	Heat capacity (J/(mol·°C ))
1,4-BDO	90.12	230	20.1	1.02	1.4@25 °C	202.34@25 °C
2,3-BDO	90.12	177	19	0.967	23@20 °C	227.2@27 °C
1,3-BDO	90.12	207	‒77	1.01	8@20 °C	227.2@27 °C
1,2-BDO	90.12	192	‒42	1.002	2.7@20 °C	240.4@25 °C

Microorganism	Genotype	Substrate	Fermentation mode	Titer (g/L)	Yield (g/g)	Productivity (g/(L·h))	Ref.
Klebsiella pneumoniae	wild type	glucose	fed-batch	150.0	0.48	3.95	[162]
Serratia marcescens	ΔswrW	sucrose	fed-batch	152.0	0.46	2.67	[163]
Klebsiella oxytoca	ΔaldA	glucose	fed-batch	130.0	0.48	1.63	[164]
Klebsiella pneumoniae	wild type	glycerol	fed-batch	70.0	0.39	0.47	[165]
Paenibacillus polymyxa	wild type	glucose	fed-batch	111.0	—	2.06	[166]
Bacillus licheniformis	wild type	glucose	fed-batch	144.7	0.40	1.14	[167]
Klebsiella pneumoniae	↑budA ↑budB	glucose	fed-batch	101.5	0.34	2.54	[168]
Klebsiella oxytoca	ΔldhA	glucose	fed-batch	115.0	0.41	2.27	[169]
Saccharomyces cerevisiae	Δpdc1Δpdc5, point mutation in mth1, ↑alsS↑alsD↑bdh1	glucose	fed-batch	96.2	0.28	0.39	[170]
Bacillus amyloliquefaciens	↑bdh ↑gapA	glucose	fed-batch	132.9	0.45	2.95	[171]
Klebsiella pneumoniae	ΔadhEΔldhA	glucose	fed-batch	116	0.49	2.23	[172]
Klebsiella oxytoca	↑budC	glucose	fed-batch	142.5	0.42	1.47	[173]
Enterobacter cloacae	mutant strain	glucose	fed-batch	110.9	0.39	1.98	[174]
Bacillus licheniformis	ΔbudC	glucose	fed-batch	123.7	—	2.95	[29]
Klebsiella oxytoca	ΔadhEΔackA-ptaΔldhAME	glucose	fed-batch	117.4	0.49	1.20	[175]
Enterobacter cloacae	ΔldhΔptsGΔbdhΔfrdA↑bdh↑galP	glucose/xylose	fed-batch	152.0	0.49	3.50	[176]
Klebsiella oxytoca	ΔldhAΔpflBΔbudC↑bdh	glucose	fed-batch	106.7	0.40	3.10	[28]
Bacillus subtilis	↑alsS ↑alsD ↑budC ↑udhAΔuppΔacoAΔbdhAΔptaΔldh	glucose	fed-batch	103.7	0.49	0.46	[177]
Saccharomyces cerevisiae	↑alsS↑alsD↑BDH1↑PDC1↑noxEΔPDC	glucose	fed-batch	154.3	0.40	1.98	[178]
Klebsiella sp.	random mutant	sucrose	fed-batch	119.4	0.40	1.84	[179]
Saccharomyces cerevisiae	↑alsS ↑alsD ↑BDH1 ↑noxEΔadh1ΔPDC	glucose	fed-batch	178.0	0.34	1.88	[180]
Enterobacterludwigii	Wild type	VHP cane sugar	fed-batch	111.0	0.40	1.11	[181]
Bacillus licheniformis	ΔbudC	glucose	fed-batch	123.0	0.41	1.71	[182]
Enterobacter ludwigii	random mutant	xylose	fed-batch	71.1	0.40	0.94	[27]
Enterobacter ludwigii	random mutant	glucose	fed-batch	144.5	0.47	1.51	[22]
Klebsiella oxytoca	wild type	molasses	repeated batch	118.0	0.42	2.40	[183]
Klebsiella pneumoniae	wild type	jerusalem artichoke	fed-batch/SSF	84.0	0.29	2.10	[184]
Enterobacter cloacae	wild type	cassava powder	fed-batch/SSF	93.9	—	2.00	[185]
Enterobacter aerogenes	ΔldhAΔscrR	sugarcane molasses	fed-batch	98.7	0.37	2.74	[186]
Bacillus licheniformis	wild type	inulin	fed-batch/SSF	103.0	—	3.43	[187]
Bacillus licheniformis	wild type	apple pomace	fed-batch	113.0	0.49	0.69	[188]
Klebsiella oxytoca	ΔpduCΔldhA	crude glycerol	fed-batch	131.5	0.44	0.84	[189]
Enterobacter cloacae	mutant strain	sugarcane molasses	fed-batch	90.8	0.36	1.66	[174]
Enterobacter cloacae	ΔldhΔptsGΔbdhΔfrdA↑bdh↑galP	corn stover	fed-batch	119.4	0.48	2.30	[176]
Enterobacter cloacae	Wild type	corncob-derived xylose	fed-batch	81.4	0.39	0.72	[190]
Saccharomyces cerevisiae	↑alsS ↑alsD ↑BDH1 ↑noxEΔadh1ΔPDC	cassava	fed-batch	132.0	0.32	1.92	[180]
Enterobacter ludwigii	random mutant	sugarcane bagasse	fed-batch	63.5	0.36	0.84	[27]
Enterobacter ludwigii	random mutant	brewer’s spent grains	fed-batch	118.5	0.43	1.65	[25]
Enterobacter ludwigii	random mutant	bread waste	fed-batch	138.8	0.48	1.45	[22]
ME: metabolic evolution

Microorganism	Genotype	Substrate	Fermentation mode	Titer (g/L)	Yield (g/g)	Productivity (g/(L·h))	Ref.
Klebsiella pneumoniae	wild type	glucose	fed-batch	150.0	0.48	3.95	[162]
Serratia marcescens	ΔswrW	sucrose	fed-batch	152.0	0.46	2.67	[163]
Klebsiella oxytoca	ΔaldA	glucose	fed-batch	130.0	0.48	1.63	[164]
Klebsiella pneumoniae	wild type	glycerol	fed-batch	70.0	0.39	0.47	[165]
Paenibacillus polymyxa	wild type	glucose	fed-batch	111.0	—	2.06	[166]
Bacillus licheniformis	wild type	glucose	fed-batch	144.7	0.40	1.14	[167]
Klebsiella pneumoniae	↑budA ↑budB	glucose	fed-batch	101.5	0.34	2.54	[168]
Klebsiella oxytoca	ΔldhA	glucose	fed-batch	115.0	0.41	2.27	[169]
Saccharomyces cerevisiae	Δpdc1Δpdc5, point mutation in mth1, ↑alsS↑alsD↑bdh1	glucose	fed-batch	96.2	0.28	0.39	[170]
Bacillus amyloliquefaciens	↑bdh ↑gapA	glucose	fed-batch	132.9	0.45	2.95	[171]
Klebsiella pneumoniae	ΔadhEΔldhA	glucose	fed-batch	116	0.49	2.23	[172]
Klebsiella oxytoca	↑budC	glucose	fed-batch	142.5	0.42	1.47	[173]
Enterobacter cloacae	mutant strain	glucose	fed-batch	110.9	0.39	1.98	[174]
Bacillus licheniformis	ΔbudC	glucose	fed-batch	123.7	—	2.95	[29]
Klebsiella oxytoca	ΔadhEΔackA-ptaΔldhAME	glucose	fed-batch	117.4	0.49	1.20	[175]
Enterobacter cloacae	ΔldhΔptsGΔbdhΔfrdA↑bdh↑galP	glucose/xylose	fed-batch	152.0	0.49	3.50	[176]
Klebsiella oxytoca	ΔldhAΔpflBΔbudC↑bdh	glucose	fed-batch	106.7	0.40	3.10	[28]
Bacillus subtilis	↑alsS ↑alsD ↑budC ↑udhAΔuppΔacoAΔbdhAΔptaΔldh	glucose	fed-batch	103.7	0.49	0.46	[177]
Saccharomyces cerevisiae	↑alsS↑alsD↑BDH1↑PDC1↑noxEΔPDC	glucose	fed-batch	154.3	0.40	1.98	[178]
Klebsiella sp.	random mutant	sucrose	fed-batch	119.4	0.40	1.84	[179]
Saccharomyces cerevisiae	↑alsS ↑alsD ↑BDH1 ↑noxEΔadh1ΔPDC	glucose	fed-batch	178.0	0.34	1.88	[180]
Enterobacterludwigii	Wild type	VHP cane sugar	fed-batch	111.0	0.40	1.11	[181]
Bacillus licheniformis	ΔbudC	glucose	fed-batch	123.0	0.41	1.71	[182]
Enterobacter ludwigii	random mutant	xylose	fed-batch	71.1	0.40	0.94	[27]
Enterobacter ludwigii	random mutant	glucose	fed-batch	144.5	0.47	1.51	[22]
Klebsiella oxytoca	wild type	molasses	repeated batch	118.0	0.42	2.40	[183]
Klebsiella pneumoniae	wild type	jerusalem artichoke	fed-batch/SSF	84.0	0.29	2.10	[184]
Enterobacter cloacae	wild type	cassava powder	fed-batch/SSF	93.9	—	2.00	[185]
Enterobacter aerogenes	ΔldhAΔscrR	sugarcane molasses	fed-batch	98.7	0.37	2.74	[186]
Bacillus licheniformis	wild type	inulin	fed-batch/SSF	103.0	—	3.43	[187]
Bacillus licheniformis	wild type	apple pomace	fed-batch	113.0	0.49	0.69	[188]
Klebsiella oxytoca	ΔpduCΔldhA	crude glycerol	fed-batch	131.5	0.44	0.84	[189]
Enterobacter cloacae	mutant strain	sugarcane molasses	fed-batch	90.8	0.36	1.66	[174]
Enterobacter cloacae	ΔldhΔptsGΔbdhΔfrdA↑bdh↑galP	corn stover	fed-batch	119.4	0.48	2.30	[176]
Enterobacter cloacae	Wild type	corncob-derived xylose	fed-batch	81.4	0.39	0.72	[190]
Saccharomyces cerevisiae	↑alsS ↑alsD ↑BDH1 ↑noxEΔadh1ΔPDC	cassava	fed-batch	132.0	0.32	1.92	[180]
Enterobacter ludwigii	random mutant	sugarcane bagasse	fed-batch	63.5	0.36	0.84	[27]
Enterobacter ludwigii	random mutant	brewer’s spent grains	fed-batch	118.5	0.43	1.65	[25]
Enterobacter ludwigii	random mutant	bread waste	fed-batch	138.8	0.48	1.45	[22]
ME: metabolic evolution

Microorganism	Genotype	Substrate	Fermentation mode	Titer (g/L)	Yield (g/g)	Productivity (g/(L·h))	Ref.
E. coli	↑phaA↑phaB↑bld	glucose	fed-batch	9.05	—	0.08	[40]
E. coli	↑phaA↑phaB↑bld	glucose	fed-batch	15.7	0.19	0.16	[41]
E. coli	↑AKR↑DERA ↑PDC ΔadhEΔldhAΔpflBδyqhDΔeutGΔadhPΔyjgBΔilvBΔpoxBΔpta	glucose	fed-batch	2.4	0.058	—	[43]
E. coli	↑bld^L273T↑yqhD↑phaA↑phaB↑pntA↑pntB↑sfp↑yqhD	glucose	fed-batch	13.4	0.29	0.42	[36]
E. coli	↑thl↑hbd↑tesB ↑car↓fabD↓accAΔeddΔpfkB	glucose	fed-batch	22.7	0.40	0.32	[42]
E. coli	↑phaA↑phaB↑bld ↑yqhDΔadhEΔldhAΔpoxBΔpta-ackAΔpyciA	glucose	fed-batch	23.1	0.25	0.64	[44]
C. necator	↑bld↑yqhD↑dra↑PDC↑phaABΔphaC1	CO₂	fed-batch	3.0	0.20	0.025	[47]
Cell free in vitro synthesis	↑ADH ↑NOX↑DERA↑AKR↑FDH	ethanol	batch	7.7	0.83*	0.16	[48]

C4二醇的发酵生产及其化学催化升级为高价值化学品的研究进展

Recent advances in fermentative production of C4 diols and their chemo-catalytic upgrading to high-value chemicals

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Metrics

Microorganism	Genotype	Substrate	Fermetation mode	Titer (g/L)	Yield (g/g)	Productivity (g/(L·h))	Ref.
E. coli	ΔadhEΔpflBΔldhAΔmdhΔarcAΔlpdA Kp.lpdD354K gltAR163L↑sucCD↑sucD↑4hbd/↑sucA↑adh(025B) ↑Cat2	glucose	fed-batch	18.0	0.37	0.15	[18]
E. coli	not available	glucose	fed-batch	29.0	0.25	0.60	[54]
E. coli	not available	glucose	fed-batch	99.0	0.35	2.10	[54]
E. coli	not available	glucose	fed-batch	>125.0	>0.40	>3.50	[51]
E. coli	ΔxylAΔyjhHΔyagE↑xdh↑xylX↑mdlC	xylose	batch	0.44	0.042	—	[60]
E. coli	ΔxylAΔyagEΔyjhH↑xylB↑xylC↑xylD↑xylX↑kivd(V461I)↑yqhD	xylose + glucose	fed-batch	9.2	0.22	0.26	[62]
E. coli	ΔxylAΔyagEΔyjhH↑xylB↑xylC↑xylD↑xylX↑kivd(V461I)↑yqhD↑atoB↑mvaS↑mvaE	xylose + glucose	fed-batch	12.0	0.26	0.40	[62]
E. coli	↑araC↑araD↑araA↑araB↑kivd↑yqhD	arabinose + glucose	fed-batch	15.6	0.22	0.22	[62]
E. coli	ΔgarLΔuxaC↑udh↑garD↑ycbC↑kivd↑yqhD	galactouronic acid + glucose	fed-batch	16.5	0.33	0.18	[62]
E. coli	ΔxylAΔyagEΔyjhH↑xylBC↑xylD↑kivD↑yqhD↑ppdA-C-B (S301AQ336AV300M)	xylose	batch	0.21	—	—	[61]
E. coli*	↑gldABC(S302AQ337A)	erythritol	batch	16.1	0.009	0.81	[191]
E. coli*	↑pddABC(S301AQ336A)	erythritol	batch	11.9	0.006	0.6	[191]
E. coli*	↑gldABC(S302AQ337A)	erythritol	batch	34.5	—	—	[63]

Catalyst	Acidity (μmol/g)	Reaction conditions			X (%)	Selectivity (%)				Ref.
Catalyst	Acidity (μmol/g)	WHSV (h^‒1)	T (°C)	N₂ (mL/min)	X (%)	MEK	BD	IBA	Others	Ref.
AlP	930	1.5	250	—	100	78.1	6.9	13.4	C₈-C₁₂: 1.5	[74]
ZrP	840	400	250	—	11.2	65.8	3.5	23.5	C₈-C₁₂: 4.1	[74]
γ-Al₂O₃	189	10	250	25	82.8	73.3	3.2	2.8	C₈-C₁₂: 19.9	[73]
H-BEA	220	10	250	25	81.6	51.9	4.6	16.3	C₈-C₁₂: 26.1, 3B2OL: 0.2
deAl BEA¹	43				75.9	50.5	4.2	17.4	C₈-C₁₂: 27.6, 3B2OL: 0.2
Zr-BEA	270				80	25.7	2.3	7.2	C₈-C₁₂: 63.1, 3B2OL: 0.1
2%P/HZSM-5	1407	4	180	12.5	~100	~75	—	~15	—	[75]
1%B/HZSM-5	963.8	4	180	12.5	97.2	68.4	1.2	16.8	—	[71]
1%B/HZSM-5	963.8	4	200	12.5	100	69.7	1.4	20.1	—	[71]
a-CP²	—	1780³	324.5	10	~100	~32	~20	5	3B2OL: ~16	[76]
P/SiO₂_9.8⁴	—	0.04	180	10	100	49.2	21.4	11.8	BT: 2.9	[77]

Catalyst	Acidity	Basicity	Reaction conditions			X (%)	Selectivity (%)				Ref.
Catalyst	Acidity	Basicity	WHSV (h^‒1)	T (°C)	N₂ (mL/min)	X (%)	3B2OL	MEK	IBA	Others	Ref.
ZrO₂^a	—	—	1	325	45^c	62.5	48.6	16	1.3	IBO: 7.8, acetoin: 14.9, others: 11.4	[78]
ZrO₂^b	—	—	1	325	45	76.4	43.8	17.9	1.1	IBO: 7.4, acetoin: 11.4, others: 18.4	[78]
CaO/ZrO₂^a	—	211.3^d	1.06	350	80^c	~60	~70	—	—	—	[80]
SrO/ZrO₂^a	—	—				~60	~78	—	—
BaO/ZrO₂^a	—	—				~75	~75	—	—
MgO/ZrO₂^a	—	—				~40	~70	—	—
2K_P/SiO₂_20	30.2^f	21.14^f	1.2	400	100	64	78^e	9		BTO: 10, acetoin + BDOn: 2	[70]
1.75 Cs_P/SiO₂_20	24^f	—	1.2	400	100	46	50^e	10		BTO: 28.6, acetoin + BDOn: 6	[70]
1.82 Na_P/SiO₂- 17.2^g	18.15^f	3.63^f	1.11	180	100	94.6	53.7	17.4	1.5	BD: 13.5, acetoin + BDOn: 1.9, BTO: 4.4	[77]
3Sc_0.5Yb_1.5O₃	—	—	1.06	411	45^c	99.2	35.3	14.9	6.3	BD: 9.2, IBO: 5.9, others: 28.4	[67]
Nd₂O₃	—	—	1.06	425	45^c	87.8	35.2	16.9	4.0	BD: 0.0, IBO: 6.0, others: 37.9	[67]

Catalyst	Acidity (mmol_NH3/g)	Basicity (mmol_CO2/g)	Reaction conditions			X (%)	Selectivity (%)					Ref.
Catalyst	Acidity (mmol_NH3/g)	Basicity (mmol_CO2/g)	WHSV (h^-1)	T (°C)	N₂ (mL/min)	X (%)	BD	MEK	IBA		Others	Ref.
Sc₂O₃	—	—	1.06	411	45^a	100	88.3	1.1	0.1		3B2OL: 0.8, IBO: 0.3, Others: 9.4	[67]
Lu₂O₃	—	—		425		99	23.2	23.1	1.8		3B2OL: 5.0, IBO: 0.8, Others: 46.1
CeO₂	—	—		425		100	0.5	39.2	2.4		3B2OL: 0.5, IBO: 0.6, Others: 56.8
γ-Al₂O₃	0.24	0.059	11.8	450	100	100	28	56.9	3.3		C₃: 1.4, Others: 10.4	[84]
γ-Al₂O₃	—	—	395	350	75^b	13	60	11	13		BTO: 15	[83]
GdPO₄	—	—	30^c	300	100	100	~50	~38	~12		—	[85]
NdPO₄	—	—				100	~55	~35	~10		—
LaPO₄	—	—				~95	~50	~40	~9		—
2K_P/SiO₂_20	30.2^f	21.14^f	1.2	400	100	64	78^d	9^e			BDOn + Actn: 2 BTO: 10	[70]
1.5Cs_P/SiO₂_20	—	—	1.2	400	100	83	50	12			BDOn + Actn: 4 BTO: 7.3	[70]
10%CsH₂PO₄/CARiACT Q10	—	—	0.99	404	30	>99.9	91.9	7.0		0.3	3B2OL: 0.2, Butenes: 0.4, Others: 0.2	[86]

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Catalyst	Acidity	Reaction condition			X (%)	Selectivity (%)			Ref.
Catalyst	Acidity	WHSV (h^‒1)	T (°C)	N₂ (mL/min)	X (%)	THF		Others	Ref.
Fixed-bed reactor
2.5 wt% Yb₂O₃/ZrO₂	98.2	53.7	310	30	—	~80	BTO: ~20		[97]
m-ZrO₂	114.5	53.7	310	30	—	~78	BTO: ~22		[97]
Al₂O₃	—	2.4	325	26	100	97.4	3B1OL: 0.1, Others: 2.5		[112]
t-ZrO₂	—				99.9	96.8	3B1OL: 0.7, GBL: 0.3, Others: 2.3
Yb/SiO₂	—				100	98.3	3B1OL: 0.2, GBL: 0.1, Others: 1.4
Yb/t-ZrO₂	—				77.1	50.7	3B1OL: 39.4, GBL: 0.8, Others: 9.1
AMW	—	1.0	375	30	97	99	Others: 1		[192]
CaO-ZrO₂^a	261	1.02	350	30	99.1	79.6	3B1OL: 18.1, GBL: 1.1, Others: 1.2		[107]
Batch reactor
Amberlyst-15	—	100 °C, 900 mL pure 1,4-BDO, 5 g catalyst, 1 h			29.32, 45.7^b	Selective^c	1%		[96]
Bu₄PBr	—	220 °C, 0.04 mL 1,4-BDO, 0.58 g of catalyst, 15 min			100	72%	BD: 27, Butanal: 1		[114]
HnbMoO₆	1.9^d	140 °C, 3 mL water solvent, 900 mL 1,4-BDO, 0.05 g catalyst, 3 h			19	> 99	< 1%		[193]
HZSM-5	200				50	> 99	< 1%		[193]
HZSM-5 (23)	—	225 °C, 17 bar N₂, 1,4-dioxane solvent, 0.7 mol 1,4-BDO/L, 10 g catalyst, 3 h			93.8	99.6	< 1%		[99]
H-Y (5.1)	—				89.5	99.3
H-Mordenite (90)	—				88.2	99.7
H-Beta (25)	—				90.3	99.9
Ferrierite (20)	—				80.2	99.5
4.6CuO/nano ZSM-5	—	170 °C, 2.5 g catalyst, 50 g 1,4-BDO, 3 h			100	> 99	< 1%		[100]

Catalyst	Acidity	Reaction condition			X (%)	Selectivity (%)			Ref.
Catalyst	Acidity	WHSV (h^‒1)	T (°C)	N₂ (mL/min)	X (%)	THF		Others	Ref.
Fixed-bed reactor
2.5 wt% Yb₂O₃/ZrO₂	98.2	53.7	310	30	—	~80	BTO: ~20		[97]
m-ZrO₂	114.5	53.7	310	30	—	~78	BTO: ~22		[97]
Al₂O₃	—	2.4	325	26	100	97.4	3B1OL: 0.1, Others: 2.5		[112]
t-ZrO₂	—				99.9	96.8	3B1OL: 0.7, GBL: 0.3, Others: 2.3
Yb/SiO₂	—				100	98.3	3B1OL: 0.2, GBL: 0.1, Others: 1.4
Yb/t-ZrO₂	—				77.1	50.7	3B1OL: 39.4, GBL: 0.8, Others: 9.1
AMW	—	1.0	375	30	97	99	Others: 1		[192]
CaO-ZrO₂^a	261	1.02	350	30	99.1	79.6	3B1OL: 18.1, GBL: 1.1, Others: 1.2		[107]
Batch reactor
Amberlyst-15	—	100 °C, 900 mL pure 1,4-BDO, 5 g catalyst, 1 h			29.32, 45.7^b	Selective^c	1%		[96]
Bu₄PBr	—	220 °C, 0.04 mL 1,4-BDO, 0.58 g of catalyst, 15 min			100	72%	BD: 27, Butanal: 1		[114]
HnbMoO₆	1.9^d	140 °C, 3 mL water solvent, 900 mL 1,4-BDO, 0.05 g catalyst, 3 h			19	> 99	< 1%		[193]
HZSM-5	200				50	> 99	< 1%		[193]
HZSM-5 (23)	—	225 °C, 17 bar N₂, 1,4-dioxane solvent, 0.7 mol 1,4-BDO/L, 10 g catalyst, 3 h			93.8	99.6	< 1%		[99]
H-Y (5.1)	—				89.5	99.3
H-Mordenite (90)	—				88.2	99.7
H-Beta (25)	—				90.3	99.9
Ferrierite (20)	—				80.2	99.5
4.6CuO/nano ZSM-5	—	170 °C, 2.5 g catalyst, 50 g 1,4-BDO, 3 h			100	> 99	< 1%		[100]

Catalyst	Acidity	Basicity	Reaction condition			X (%)	Selectivity (%)
Catalyst	Acidity	Basicity	WHSV (h^‒1)	T (°C)	N₂ (mL/min)	X (%)	3B1OL	THF	GBL	Others	Ref.
ZrO₂	—	—	6	350	73^a	86.4	48.0	44.9	—	7.1	[103]
1.5 Na-ZrO₂	0	396	1.8	325	73^a	18.7	71.8	20.8	2.1	5.3	[104]
1.5 Li-ZrO₂	—	—				19.1	63.5	27.9	1.0	7.5
1.5 K-ZrO₂	—	—				19.0	63.6	26.9	3.9	5.6
1.5P/ZrO₂	142	103				99.9	11.4	80.6	0.6	7.4
CaO/ZrO₂	295	496	3.3	350	30	92.6	65.4	11.3	—	23.3	[105]
SrO/ZrO₂	127	211				84.1	45.1	33.7	—	21.2
BaO/ZrO₂	72	164				74.3	35.9	40.8	—	23.3
12.5CaO/ZrO₂^b	251	486	1.02	350	30	94.6	68.9	9.8	6.3	15	[107]
CeO₂	—	—	0.1662	400	73 ^a	87.6	68.1	3.7	—	BD: 1.7, others: 26.5	[40]
CeO₂	—	—	0.073	425	29 ^a	74	57.1	17.4	3.0	2B1OL: 7.5, others: 15	[108]
CeO₂-N	—	—	1.02^c	375	—	78.5	55.0	3.3	2.4	39.2	[111]
CeO₂-AH	—	—				91.7	51.4	4.2	3.1	41.3
CeO₂	—	—				94.5	63.2	3.0	0.9	32.9
Yb/ZrO₂	281^d	281^d	2.5	325	26	50.8	86.5	4.3	1.1	8.1	[112]
Yb₂O₃	—	—	22.17	375	30	33.9	87.6	1.3	0.9	2B1OL: 7.5	[82]
Sc₂O₃	—	—	22.17	375	30	20.6	70	22.8	1.7	2B1OL: 1.5	[82]
Mg₇Yb₃ oxide	116	260.5	1.08	350	—	90.4	78.6	—	—	21.7	[113]

Catalyst	Acidity	Basicity	Reaction condition			X (%)	Selectivity (%)
Catalyst	Acidity	Basicity	WHSV (h^‒1)	T (°C)	N₂ (mL/min)	X (%)	3B1OL	THF	GBL	Others	Ref.
ZrO₂	—	—	6	350	73^a	86.4	48.0	44.9	—	7.1	[103]
1.5 Na-ZrO₂	0	396	1.8	325	73^a	18.7	71.8	20.8	2.1	5.3	[104]
1.5 Li-ZrO₂	—	—				19.1	63.5	27.9	1.0	7.5
1.5 K-ZrO₂	—	—				19.0	63.6	26.9	3.9	5.6
1.5P/ZrO₂	142	103				99.9	11.4	80.6	0.6	7.4
CaO/ZrO₂	295	496	3.3	350	30	92.6	65.4	11.3	—	23.3	[105]
SrO/ZrO₂	127	211				84.1	45.1	33.7	—	21.2
BaO/ZrO₂	72	164				74.3	35.9	40.8	—	23.3
12.5CaO/ZrO₂^b	251	486	1.02	350	30	94.6	68.9	9.8	6.3	15	[107]
CeO₂	—	—	0.1662	400	73 ^a	87.6	68.1	3.7	—	BD: 1.7, others: 26.5	[40]
CeO₂	—	—	0.073	425	29 ^a	74	57.1	17.4	3.0	2B1OL: 7.5, others: 15	[108]
CeO₂-N	—	—	1.02^c	375	—	78.5	55.0	3.3	2.4	39.2	[111]
CeO₂-AH	—	—				91.7	51.4	4.2	3.1	41.3
CeO₂	—	—				94.5	63.2	3.0	0.9	32.9
Yb/ZrO₂	281^d	281^d	2.5	325	26	50.8	86.5	4.3	1.1	8.1	[112]
Yb₂O₃	—	—	22.17	375	30	33.9	87.6	1.3	0.9	2B1OL: 7.5	[82]
Sc₂O₃	—	—	22.17	375	30	20.6	70	22.8	1.7	2B1OL: 1.5	[82]
Mg₇Yb₃ oxide	116	260.5	1.08	350	—	90.4	78.6	—	—	21.7	[113]