Cu/SiO2-Al2O3催化1,2-丁二醇加氢脱氧制备1-丁醇

doi:10.16085/j.issn.1000-6613.2024-2116

摘要/Abstract

摘要：

通过浸渍法制备了一系列负载型金属催化剂，并在高压反应釜中考察了催化剂对1,2-丁二醇加氢脱氧制备1-丁醇的催化活性。Cu/SiO₂-Al₂O₃催化剂对1,2-丁二醇加氢脱氧制备1-丁醇具有较高的催化活性，可以同时获得较高的1,2-丁二醇转化率和1-丁醇选择性。在此基础上，研究了金属负载量、反应温度、反应压力、反应时间等对反应的影响。在反应温度为250℃、反应压力为5MPa的条件下，使用Cu/SiO₂-Al₂O₃催化剂进行反应仅需15min，1,2-丁二醇的转化率便达到50.7%，1-丁醇的选择性达到75.9%。经过3h的反应后1,2-丁二醇完全转化，1-丁醇的选择性提高至88.9%。此外，Cu/SiO₂-Al₂O₃催化剂的活性稳定，在5次循环实验中无明显失活现象。

关键词: 催化剂, 1,2-丁二醇, 1-丁醇, 加氢脱氧, 生物质, 选择性

Abstract:

A series of metal-supported catalysts were prepared via an impregnation method, and their catalytic activities for the hydrodeoxygenation of 1,2-butanediol to 1-butanol were investigated in a batch reactor, among which the Cu/SiO₂-Al₂O₃ catalyst exhibited the highest catalytic activity with both high conversion of 1,2-butanediol and high selectivity to 1-butanol. The effects of metal loading, reaction temperature, H₂ pressure, and reaction time were further studied. Under the reaction conditions of 250℃ and 5MPa H₂ pressure, the Cu/SiO₂-Al₂O₃ catalyst achieved a 75.9% selectivity to 1-butanol and a 50.7% conversion of 1,2-butanediol within only 15 minutes. After 3 hours of reaction, 1,2-butanediol was completely converted, and the selectivity to 1-butanol increased to 88.9%. Additionally, the Cu/SiO₂-Al₂O₃ catalyst exhibited a good stability, as no significant deactivation was observed after five recycle runs.

Key words: catalyst, 1,2-butanediol, 1-butanol, hydrodeoxygenation, biomass, selectivity

中图分类号:

TQ072

李军良, 李悦, 孙道来. Cu/SiO₂-Al₂O₃催化1,2-丁二醇加氢脱氧制备1-丁醇[J]. 化工进展, 2025, 44(S1): 222-231.

LI Junliang, LI Yue, SUN Daolai. Hydrodeoxygenation of 1,2-butanediol to 1-butanol over Cu/SiO₂-Al₂O₃ catalyst[J]. Chemical Industry and Engineering Progress, 2025, 44(S1): 222-231.

图/表 15

参考文献 33

[1]	WU Jing, LIU Hongjuan, YAN Xiang, et al. Efficient catalytic dehydration of high-Concentration 1-butanol with Zn-Mn-Co modified γ-Al₂O₃ in jet fuel production[J]. Catalysts, 2019, 9(1): 93.
[2]	PÉREZ-MACIÁ María Ángeles, Roger BRINGUÉ, IBORRA Montserrat, et al. Thermodynamic equilibrium for the dehydration of 1-butanol to di-n-butyl ether[J]. Chemical Engineering Research and Design, 2015, 102: 186-195.
[3]	付友思, 吴又多, 陈丽杰. Zn²⁺、Ca²⁺和Mn²⁺对丙酮丁醇发酵的协同影响[J]. 化工进展, 2015, 34(10): 3719-3724.
	FU Yousi, WU Youduo, CHEN Lijie. Synergistic effect of Zn²⁺, Ca²⁺, and Mn²⁺ on acetone-butanol fermentation[J]. Chemical Industry and Engineering Progress, 2015, 34(10): 3719-3724.
[4]	KELLA Tatinaidu, VENNATHAN Anjana Anandan, DUTTA Saikat, et al. Selective dehydration of 1-butanol to butenes over silica supported heteropolyacid catalysts: Mechanistic aspect[J]. Molecular Catalysis, 2021, 516: 111975.
[5]	柯啸宇. 邻苯二甲酸二丁酯的合成工艺: CN103030563A[P]. 2013-04-10.
	KE Xiaoyu. Synthesis process of di-n-butyl phthalate (DBP): CN103030563A[P]. 2013-04-10.
[6]	PALLA Venkata Chandra Sekhar, SHEE Debaprasad, MAITY Sunil K. Conversion of n-butanol to gasoline range hydrocarbons, butylenes and aromatics[J]. Applied Catalysis A: General, 2016, 526: 28-36.
[7]	SU Jiantao, YANG Xiaohui, SHI Hui, et al. Heteropolyacid promoted lignin-MOF derived spherical catalyst for catalytic hydrogen transfer of 5-hydroxymethylfurfural[J]. Journal of Colloid and Interface Science, 2024, 669: 336-348.
[8]	CONESA J M, MORALES M V, GARCÍA-BOSCH N, et al. Graphite supported heteropolyacid as a regenerable catalyst in the dehydration of 1-butanol to butenes[J]. Catalysis Today, 2023, 420: 114017.
[9]	JOHN Mathew, ALEXOPOULOS Konstantinos, REYNIERS Marie-Francoise, et al. First-principles kinetic study on the effect of the zeolite framework on 1-butanol dehydration[J]. ACS Catalysis, 2016, 6(7): 4081-4094.
[10]	叶梅芳, 魏怡林, 刘媛媛, 等. 基于HPLC指纹图谱与多成分含量测定的凹叶景天正丁醇部位差异性研究[J]. 医药导报, 2023, 42(6): 904-911.
	YE Meifang, WEI Yilin, LIU Yuanyuan, et al. Study on the regional differences of Sedum aizoon based on HPLC fingerprint and multi-component content determination of n-butanol extracts[J]. Herald of Medicine, 2023, 42(6): 904-911.
[11]	TOMISHIGE Keiichi, FURIKADO Ippei, YAMAGISHI Takashi, et al. Promoting effect of Mo on alcohol formation in hydroformylation of propylene and ethylene on Mo-Rh/SiO₂ [J]. Catalysis Letters, 2005, 103(1): 15-21.
[12]	Shuhei OGO, ONDA Ayumu, YANAGISAWA Kazumichi. Selective synthesis of 1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts[J]. Applied Catalysis A: General, 2011, 402(1/2): 188-195.
[13]	OSMANBEGOVIC Nahla, CHANDGUDE Vijaya, BANKAR Sandip, et al. 1-Butanol separation from aqueous acetone-butanol-ethanol(ABE) solutions by freeze concentration[J]. Crystal Growth & Design, 2023, 23(6): 4147-4153.
[14]	CUI Yuyang, LI Shuaiqi, AN Hualiang, et al. Improvement of ethanol guerbet condensation by acetal hydrolysis[J]. Industrial & Engineering Chemistry Research, 2022, 61(34): 12392-12404.
[15]	SUN Daolai, YAMADA Yasuhiro, SATO Satoshi, et al. Production of aldehydes from 1,2-alkanediols over silica-supported WO₃ catalyst[J]. Applied Catalysis A: General, 2016, 526: 164-171.
[16]	RAJU Suresh, MORET Marc‐Etienne, KLEIN GEBBINK Robertus J M . et al. ChemInform abstract: Rhenium-catalyzed dehydration and deoxydehydration of alcohols and polyols: Opportunities for the formation of olefins from biomass[J]. ChemInform, 2015, 46(11): 281-300.
[17]	ZHANG Liangqing, HUANG Suchang, QIU Jiarong, et al. Selective transformation of biomass-derived substrates to 1,2-butanediol: A comprehensive review and new insights[J]. Industrial Crops and Products, 2023, 202: 116984.
[18]	练彩霞, 李凝, 蒋武, 等. 生物质油催化加氢脱氧(HDO)反应机理及催化剂研究进展[J]. 化工进展, 2020, 39(S1): 153-162.
	LIAN Caixia, LI Ning, JIANG Wu, et al. Research progress on reaction mechanism and catalysts for catalytic hydrodeoxygenation(HDO) of biomass oil[J]. Chemical Industry and Engineering Progress, 2020, 39(S1): 153-162.
[19]	LIU Ben, NAKAGAWA Yoshinao, LI Congcong, et al. Selective C—O hydrogenolysis of terminal C—OH bond in 1,2-diols over rutile-titania-supported iridium-iron catalysts[J]. ACS Catalysis, 2022, 12(24): 15431-15450.
[20]	CHIA Mei, PAGÁN-TORRES Yomaira J, HIBBITTS David, et al. Selective hydrogenolysis of polyols and cyclic ethers over bifunctional surface sites on rhodium-rhenium catalysts[J]. Journal of the American Chemical Society, 2011, 133(32): 12675-12689.
[21]	李帅哲, 聂懿宸, PHIDSAVARD Keomeesay, 等. 非贵金属催化生物质加氢脱氧制备烃基生物燃料的研究进展[J]. 化工进展, 2024, 43(S1): 225-242.
	LI Shuaizhe, NIE Yichen, PHIDSAVARD Keomeesay, et al. Research progress on non-precious metal-catalyzed hydrogenation and deoxygenation of biomass to produce hydrocarbon-based biofuels[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 225-242.
[22]	TOMISHIGE Keiichi, TAMURA Masazumi, NAKAGAWA Yoshinao. Role of Re species and acid cocatalyst on Ir-ReO _x /SiO₂in the C—O hydrogenolysis of biomass-derived substrates[J]. The Chemical Record, 2014, 14(6): 1041-1054.
[23]	AMADA Yasushi, KOSO Shuichi, NAKAGAWA Yoshinao, et al. Hydrogenolysis of 1,2-propanediol for the production of biopropanols from glycerol[J]. ChemSusChem, 2010, 3(6): 728-736.
[24]	SRIFA Atthapon, Nawin VIRIYA-EMPIKUL, ASSABUMRUNGRAT Suttichai, et al. Catalytic behaviors of Ni/γ-Al₂O₃ and Co/γ-Al₂O₃ during the hydrodeoxygenation of palm oil[J]. Catalysis Science & Technology, 2015, 5(7): 3693-3705.
[25]	UEDA Naoyuki, NAKAGAWA Yoshinao, TOMISHIGE Keiichi. Conversion of glycerol to ethylene glycol over Pt-modified Ni catalyst[J]. Chemistry Letters, 2010, 39(5): 506-507.
[26]	HAO Fang, ZHONG Jun, LIU Pingle, et al. Preparation of mesoporous SiO₂-Al₂O₃ supported Co or Mn catalysts and their catalytic properties in cyclohexane nitrosation to ɛ-caprolactam[J]. Journal of Molecular Catalysis A: Chemical, 2011, 351: 210-216.
[27]	LI Chunyu, WU Haihong, CEN Ziyu, et al. Conversion of polyethylene to gasoline: Influence of porosity and acidity of zeolites[J]. Frontiers in Energy, 2023, 17(6): 763-774.
[28]	SUN Daolai, MISU Takuya, YAMADA Yasuhiro, et al. Advantages of using Cu/SiO₂ catalyst for vapor-phase dehydrogenation of 1-decanol into decanal[J]. Applied Catalysis A: General, 2019, 582: 117109.
[29]	何迈, 方萍, 谢冠群, 等. CuO/CeO₂-Al₂O₃催化剂中CuO物种的原位XRD、Raman和TPR表征[J]. 物理化学学报, 2005, 21(9): 997-1000.
	HE Mai, FANG Ping, XIE Guanqun, et al. In situ XRD, Raman and TPR characterization of CuO species in CuO/CeO₂-Al₂O₃ catalysts[J]. Acta Physico-Chimica Sinica, 2005, 21(9): 997-1000.
[30]	SUN Daolai, SAITO Takeshi, YAMADA Yasuhiro, et al. Hydrogenation of γ-valerolactone to 1,4-pentanediol in a continuous flow reactor[J]. Applied Catalysis A: General, 2017, 542: 289-295.
[31]	CHEN Shin-Fu, YEH Chen-Sheng. Influence of alkanethiols adsorption on oxidized copper nanoparticles[J]. Journal of the Chinese Chemical Society, 2002, 49(5): 895-898.
[32]	GHODSELAHI T, VESAGHI M A, SHAFIEKHANI A, et al. XPS study of the Cu@Cu₂O core-shell nanoparticles[J]. Applied Surface Science, 2008, 255(5): 2730-2734.
[33]	ZHAO Binran, LIU Yajun, ZHU Zijun, et al. Highly selective conversion of CO₂ into ethanol on Cu/ZnO/Al₂O₃ catalyst with the assistance of plasma[J]. Journal of CO₂ Utilization, 2018, 24: 34-39.

催化剂	转化率/%	选择性/%
催化剂	转化率/%	丁烯^①	丁醛	2-丁酮	四氢呋喃	1-丁醇	2-丁醇	其他^②
12Cu/SiO₂-Al₂O₃	100.0	0.4	0.2	0.5	0.1	87.0	0.4	11.4
12Ni/SiO₂-Al₂O₃	100.0	0.2	0.0	0.0	0.8	74.7	0.1	24.2
12Cu/H-Beta	100.0	3.6	0.7	1.8	0.2	0.8	3.2	89.7
12Cu/MCM-41	100.0	1.7	1.5	2.3	0.2	79.6	0.3	14.4
12Cu/γ-Al₂O₃	70.8	0.4	0.2	0.5	0.1	35.8	12.4	50.6
12Cu/H-USY	92.3	0.1	0.0	0.0	4.3	0.2	0.0	95.4

催化剂	转化率/%	选择性/%
催化剂	转化率/%	丁烯^①	丁醛	2-丁酮	四氢呋喃	1-丁醇	2-丁醇	其他^②
12Cu/SiO₂-Al₂O₃	100.0	0.4	0.2	0.5	0.1	87.0	0.4	11.4
12Ni/SiO₂-Al₂O₃	100.0	0.2	0.0	0.0	0.8	74.7	0.1	24.2
12Cu/H-Beta	100.0	3.6	0.7	1.8	0.2	0.8	3.2	89.7
12Cu/MCM-41	100.0	1.7	1.5	2.3	0.2	79.6	0.3	14.4
12Cu/γ-Al₂O₃	70.8	0.4	0.2	0.5	0.1	35.8	12.4	50.6
12Cu/H-USY	92.3	0.1	0.0	0.0	4.3	0.2	0.0	95.4

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
12Cu/SiO₂-Al₂O₃	171（450）	0.40（0.71）	6.2（6.3）
12Ni/SiO₂-Al₂O₃	319（450）	0.50（0.71）	6.3（6.3）
12Cu/H-Beta	360	0.42	4.4
12Cu/MCM-41	609	0.72	5.7
12Cu/γ-Al₂O₃	177	0.39	8.8
12Cu/H-USY	457	0.34	2.8

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
12Cu/SiO₂-Al₂O₃	171（450）	0.40（0.71）	6.2（6.3）
12Ni/SiO₂-Al₂O₃	319（450）	0.50（0.71）	6.3（6.3）
12Cu/H-Beta	360	0.42	4.4
12Cu/MCM-41	609	0.72	5.7
12Cu/γ-Al₂O₃	177	0.39	8.8
12Cu/H-USY	457	0.34	2.8

反应时间	转化率/%	选择性/%
反应时间	转化率/%	丁烯^①	丁醛	2-丁酮	四氢呋喃	1-丁醇	2-丁醇	其他^②
5min	9.3	0.7	0.3	0.9	0.2	58.4	2.8	36.7
15min	50.7	0.5	0.5	0.9	0.3	75.9	3.1	17.7
30min	65.3	0.5	0.5	1.0	0.2	78.8	2.5	16.5
1h	74.2	0.6	0.4	1.2	0.2	81.6	2.1	14.0
2h	100.0	2.0	0.4	0.8	0.1	88.3	0.5	9.9
3h	100.0	0.8	0.3	0.7	0.1	88.9	0.4	8.8
4h	100.0	0.7	0.3	0.6	0.1	87.1	0.5	10.7
8h	100.0	3.4	0.3	0.7	0.2	79.0	0.4	16.3

Cu/SiO₂-Al₂O₃催化1,2-丁二醇加氢脱氧制备1-丁醇

Hydrodeoxygenation of 1,2-butanediol to 1-butanol over Cu/SiO₂-Al₂O₃ catalyst

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反应压力/MPa	转化率/%	选择性/%
反应压力/MPa	转化率/%	丁烯^①	丁醛	2-丁酮	四氢呋喃	1-丁醇	2-丁醇	其他^②
4	100.0	1.1	0.7	1.4	0.1	72.1	1.0	23.6
5	100.0	0.8	0.3	0.7	0.1	88.9	0.4	8.8
6	100.0	1.2	0.2	0.5	0.1	86.1	1.0	10.9
7	100.0	1.4	0.3	0.4	0.1	85.3	0.7	11.8

反应温度/℃	转化率/%	选择性/%
反应温度/℃	转化率/%	丁烯^①	丁醛	2-丁酮	四氢呋喃	1-丁醇	2-丁醇	其他^②
200	16.6	0.0	0.1	0.3	0.0	70.3	3.8	25.5
230	72.5	0.4	0.2	0.4	0.0	82.0	3.0	14.0
250	100.0	0.8	0.3	0.7	0.1	88.9	0.4	8.8
280	100.0	5.0	0.9	1.7	0.6	49.6	0.5	41.7

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