乙醇缩合制高碳醇（C6+醇）多相催化剂研究进展

doi:10.16085/j.issn.1000-6613.2022-0507

化工进展 ›› 2023, Vol. 42 ›› Issue (1): 194-203.DOI: 10.16085/j.issn.1000-6613.2022-0507

乙醇缩合制高碳醇（C₆₊醇）多相催化剂研究进展

薛马晨¹(), 杨伯伦¹(), 夏春谷², 朱刚利²^,³()

^1.西安交通大学化学工程与技术学院，陕西西安 710049
^2.中国科学院兰州化学物理研究所，甘肃兰州 730000
^3.中国科学院大学，北京 100049

收稿日期:2022-03-28 修回日期:2022-07-11 出版日期:2023-01-25 发布日期:2023-02-20
通讯作者: 杨伯伦,朱刚利
作者简介:薛马晨（1993—），男，博士研究生，研究方向为工业催化。E-mail：xuemachen@stu.xjtu.edu.cn。
基金资助:
国家自然科学基金(21773270);江苏省自然科学基金(BK20201194);中国科学院青年创新促进会基金(2018453);兰州化物所青年科技工作者合作基金(HZJJ20-05)

Progress in heterogeneous catalyst for ethanol upgrading to higher (C₆₊) alcohols

XUE Machen¹(), YANG Bolun¹(), XIA Chungu², ZHU Gangli²^,³()

^1.School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China
^2.Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
^3.University of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-03-28 Revised:2022-07-11 Online:2023-01-25 Published:2023-02-20
Contact: YANG Bolun, ZHU Gangli

摘要/Abstract

摘要：

以乙醇为原料制备其他高附加值化工产品近期得到了广泛关注，特别是乙醇基于Guerbet反应缩合制备高碳醇（C₆₊）的过程更成为这一领域的研究热点。本文着重报道了近年来乙醇转化为高碳醇过程的几种典型的多相催化剂，包括羟基磷灰石（HAP）、类水滑石（LDHs）以及各种负载型金属催化剂的研究开发现状，分析比较了各类催化剂的优势与不足，结合反应机理针对催化剂对高碳醇选择性不高的原因进行了讨论，对理想催化剂的设计和改进进行了展望，指出应该通过促进Guerbet反应中的羟醛缩合过程增加高碳醇的选择性。金属负载型催化剂对该反应控制步骤的加速作用显著，而金属位点和载体表面酸碱活性位点的精细调控以及特定催化剂形貌结构的控制合成则是该领域未来的研究重点。

关键词: 高碳醇, 生物燃料, 多相反应, 催化剂, Guerbet反应

Abstract:

Conversion of ethanol to other high value-added chemicals has attracted extensive attention recently, especially upgrading to higher alcohols (C₆₊) through Guerbet reaction. The research and development status of several typical heterogeneous catalysts, including hydroxyapatite (HAP), hydrotalcite (LDHs) and supported metal catalysts, for the conversion of ethanol to higher alcohols in recent years are reviewed in this paper. Their advantages and disadvantages are comprehensively compared and analyzed. The reasons for the low selectivity for higher alcohols of current catalysts are discussed based on the reaction mechanism. The design and improvement to obtain an ideal catalyst are prospected. It is pointed out that the higher alcohols selectivity could be improved by promoting the aldol reaction step in Guerbet reaction. The metal-supported catalyst can accelerate the rate-limiting step significantly. Fine regulation of metal, acid and base active sites distribution on the support surface and the controlled synthesis of catalyst with specific structures will be the focus of future research in this field.

Key words: higher alcohols, biofuel, heterogeneous reaction, catalyst, Guerbet reaction

中图分类号:

TQ032.4

薛马晨, 杨伯伦, 夏春谷, 朱刚利. 乙醇缩合制高碳醇（C₆₊醇）多相催化剂研究进展[J]. 化工进展, 2023, 42(1): 194-203.

XUE Machen, YANG Bolun, XIA Chungu, ZHU Gangli. Progress in heterogeneous catalyst for ethanol upgrading to higher (C₆₊) alcohols[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 194-203.

图/表 12

图1 Guerbet反应过程

图2 乙醇缩合反应中不同碳数的产品质量分数随反应进度的关系（虚线是理想阶梯增长模型预测的值）[12]

图3 乙醇在HAP上反应生成丁醇的机理[14]

图4 乙醇在HAP（0001）表面的Guerbet缩合路径[16]（虚线框内是最佳反应路径，数字表示活化能，单位为kJ/mol）

图5 羟醛缩合过程

图6 Cu7.6、Cu2.8和Cu1.0催化剂的CO2-TPD曲线和反应结果[18]

表1 用于乙醇缩合反应的部分催化剂总结

序号	催化剂	反应条件	转化率/%	选择性/%		参考文献
序号	催化剂	反应条件	转化率/%	丁醇	C₆₊醇	参考文献
1	CaC₂	10%（摩尔分数）催化剂，6h，0.1MPa Ar，315℃	50	26.8	52.2	[23]
2	Ca(OCH₂CH₃)	10%（摩尔分数）催化剂，8h，0.1MPa Ar，315℃	28	34	47	[24]
3	FeNiO _x	1.25%（质量分数）催化剂，0.8% LiOH，24h，0.5MPa N₂，230℃	37	71	20	[25]
4	Ni-Sn	3.3%（质量分数）催化剂，NaOH，0.1MPa H₂，24h，250℃	46.6	23	53.6	[26]

图7 乙醇在CaC2上生成丁醇的机理以及CaC2的变化过程[23]

图8 乙醇在介孔和无孔Ni/BAP上的反应路径[34]

表2 用于乙醇缩合反应的部分金属负载型催化剂总结

序号	催化剂	反应条件	转化率/%	选择性/%		参考文献
序号	催化剂	反应条件	转化率/%	丁醇	C₆₊醇	参考文献
1	Ag/MgAl-LDO	LHSV=6h^-1，250°C，2MPa N₂	53.7	57.3	13.8	[31]
2	3Cu1Ce/AC	LHSV=4h^-1，250°C，2MPa N₂	46.2	41.3	19.7	[20]
3	3Cu1Ce/AC	4%（质量分数）催化剂，250℃，48h，0.1MPa N₂	39.1	55.2	20.3	[20]
4	Pd@UiO-66	LHSV=4h^-1，250°C，2MPa N₂	49.8	48.6	～20	[32]

图9 不同催化剂Ag 3d的XPS光谱（1~4的Ag粒径分别为7.4nm、17.9nm、22.4nm、34.1nm）和Ag-O-Al密度对选择性的影响[36]

图10 不同催化剂上乙醇的转化和Ni 2p XPS表征结果[40]

参考文献 40

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乙醇缩合制高碳醇（C₆₊醇）多相催化剂研究进展

Progress in heterogeneous catalyst for ethanol upgrading to higher (C₆₊) alcohols

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