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

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

Abstract

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

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

CLC Number:

TQ072

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.

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.

Figures/Tables 15

References 33

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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

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

Cu/SiO₂-Al₂O₃催化1,2-丁二醇加氢脱氧制备1-丁醇

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Figures/Tables 15

References 33

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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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