Research progress in olefin hydration process and the catalysts

doi:10.16085/j.issn.1000-6613.2022-1590

Abstract

Abstract:

Researches of the mechanism, process and catalysts for various olefin hydration reactions were reviewed. The latest progress in the processes and catalysts of cyclohexene hydration to produce cyclohexanol, propylene hydration to produce isopropanol, and high-carbon olefin hydration to produce high-carbon alcohol were summarized in detail, together with the development trend of olefin hydration reaction in the future. The reaction pathways of olefin hydration could be mainly divided into direct and indirect ones, and the reaction mechanisms were mainly the electrophilic addition mechanism of martensitic rule, the electrophilic addition mechanism of anti-martensitic rule and the radical mechanism. The olefin hydration catalysts are changing from liquid acid, alkali, transition metal salt or oxygen salt, to molecular sieve, solid acid, synthetic resin, photocatalyst and enzyme catalyst. In the future, photocatalysis and enzyme catalysis will be the key research directions of olefin hydration technology, and the optimization of reaction equipment parameters, the enhancement of catalyst performance, and the improvement of material mixing and mass transfer are the development trends of olefin hydration process optimization.

Key words: olefin, hydration, alcohol, molecular sieve, catalyst, selectivity

摘要：

综合介绍了多种烯烃水合反应的机理、生产工艺及催化剂的研究成果。分类详细归纳了环己烯、丙烯、高碳烯烃等通过水合反应生产相应产物醇的生产工艺和催化剂的最新研究进展，并分析了烯烃水合技术的未来发展趋势。分析发现：烯烃水合反应的路径主要分为直接路径和间接路径；其反应机理主要有马氏规则的亲电加成机理、反马氏规则的亲电加成机理、自由基反应机理等；烯烃水合反应用催化剂从液体酸、碱，过渡金属盐或氧盐，不断向分子筛、固体酸、合成树脂、光催化剂、酶催化剂方向发展。未来，光催化和生物酶催化是烯烃水合科技研究的重点方向；而反应设备参数优化、提升催化剂性能、强化物料混合效果、改善传质过程等，则是烯烃水合生产工艺优化的发展趋势。

关键词: 烯烃, 水合, 醇, 分子筛, 催化剂, 选择性

CLC Number:

HAN Hengwen, HAN Wei, LI Mingfeng. Research progress in olefin hydration process and the catalysts[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3489-3500.

韩恒文, 韩伟, 李明丰. 烯烃水合反应工艺与催化剂研究进展[J]. 化工进展, 2023, 42(7): 3489-3500.

Figures/Tables 12

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烯烃水合方法	催化剂	反应机理	合成产物	优点/缺点
强酸水解	硫酸	马氏规则亲电加成、直接路径	乙醇、异丙醇等，长链则为仲、叔醇	简单、廉价/腐蚀、易重排生成仲醇
过渡金属催化烯烃水合反应	过渡金属（钯）盐	反马氏规则、直接路径	苯乙醇	特定醇的合成/过程复杂、催化剂昂贵
酸酯化-水解	硫酸、三氯化铝、固体酸、合成树脂	马氏规则亲电加成、间接路径	异丙醇、环己醇等	过程较复杂、消耗蒸汽、腐蚀严重、副产物多
硼氢化-氧化水解	双氧水、碱	反马氏规则、间接路径（硼烷化、氧化水解）	伯醇	原子利用率高，不宜重排/环境影响大
烯烃串联羟基化	乙腈、乙酸钾	自由基-极性反应	芳基醇	需加热、碱催化受限制
光催化烯烃水合	光，二苯二硫醚（Ph-S-S-Ph）	反马氏规则、自由基（争议）	伯醇、仲醇、叠氮醇	原料易得、方法简单/难控制、催化剂贵、需氢供体
酶催化烯烃水合	丙氨酸磷酸核糖醇连接酶	反马氏规则	芳香基取代醇	条件温和、转化率高，绿色无污染

烯烃水合方法	催化剂	反应机理	合成产物	优点/缺点
强酸水解	硫酸	马氏规则亲电加成、直接路径	乙醇、异丙醇等，长链则为仲、叔醇	简单、廉价/腐蚀、易重排生成仲醇
过渡金属催化烯烃水合反应	过渡金属（钯）盐	反马氏规则、直接路径	苯乙醇	特定醇的合成/过程复杂、催化剂昂贵
酸酯化-水解	硫酸、三氯化铝、固体酸、合成树脂	马氏规则亲电加成、间接路径	异丙醇、环己醇等	过程较复杂、消耗蒸汽、腐蚀严重、副产物多
硼氢化-氧化水解	双氧水、碱	反马氏规则、间接路径（硼烷化、氧化水解）	伯醇	原子利用率高，不宜重排/环境影响大
烯烃串联羟基化	乙腈、乙酸钾	自由基-极性反应	芳基醇	需加热、碱催化受限制
光催化烯烃水合	光，二苯二硫醚（Ph-S-S-Ph）	反马氏规则、自由基（争议）	伯醇、仲醇、叠氮醇	原料易得、方法简单/难控制、催化剂贵、需氢供体
酶催化烯烃水合	丙氨酸磷酸核糖醇连接酶	反马氏规则	芳香基取代醇	条件温和、转化率高，绿色无污染

工艺	公司	国家	年份	催化剂
均相催化环己烯水合工艺	菲利普石油公司	美国	1974	硫酸、苯磺酸
非均相催化环己烯水合工艺	杜邦	美国	1980	全氟磺酸树脂
苯-环己烯-环己醇工艺	旭化成集团	日本	1990	Ru/HZSM-5
引进旭化成工艺+改进工艺	神马集团	中国	1998	Ru/HZSM-5

工艺	公司	国家	年份	催化剂
均相催化环己烯水合工艺	菲利普石油公司	美国	1974	硫酸、苯磺酸
非均相催化环己烯水合工艺	杜邦	美国	1980	全氟磺酸树脂
苯-环己烯-环己醇工艺	旭化成集团	日本	1990	Ru/HZSM-5
引进旭化成工艺+改进工艺	神马集团	中国	1998	Ru/HZSM-5

项目	维巴工艺	德山曹达工艺	德士古工艺
反应条件
反应物相态	气相	液相	气液混合相
催化剂种类	固体磷酸	钨、钼系杂多酸	阳离子交换树脂
反应压力/MPa	2.0~2.5	20.5~25.0	6.0~8.0
反应温度/℃	180~260	240~280	130~160
丙烯纯度（φ）/%	≥99	95	92
水/烯摩尔比	0.6~0.8	25.0~27.0	12.5~15.0
反应结果
丙烯单程转化率/%	5~6	50~75	60~70
异丙醇选择性/%	98~99	92~96	98~99
设备腐蚀程度	较严重	无	无
催化剂稳定性	磷酸流失	非常好	不耐高温
催化剂寿命	>12个月	半永久性	>8个月