生物质基甘油缩醛和缩酮的合成研究进展

doi:10.3969/j.issn.1673-5854.2019.06.009

摘要/Abstract

摘要：

甘油作为一种重要的生物质基平台化合物，可以和羰基化合物在酸性催化剂的作用下发生缩合反应生成缩醛和缩酮,缩醛和缩酮可广泛应用于燃料添加剂、香料、兽药制剂、塑化剂和多元醇等领域。从甘油缩醛和缩酮的合成机理出发，简单比较了传统的液体酸催化剂与固体催化剂的催化性能，重点介绍了丙酮甘油缩酮、环己酮甘油缩酮、苯甲醛甘油缩醛、甘油甲醛缩醛和甘油乙酰丙酸酯缩酮等几种重要甘油缩醛和缩酮的合成工艺，并概述了其生产技术，最后展望了生物质基甘油缩醛和缩酮的开发应用前景。

关键词: 甘油, 缩醛, 缩酮, 连续流反应

Abstract:

As an important biomass-based platform compound, glycerol can be condensed with carbonyl compounds under the action of acidic catalysts to form acetals and ketals. Acetals and ketals are widely used in the fields of fuel additives, perfumes, veterinary medicine preparations, plasticizers and polyols. The catalytic performance of traditional liquid acid catalyst and solid catalyst was compared based on the synthesis mechanism of glyceryl acetal and ketal; then, the synthesis processes of several important glycerol acetals and ketals such as solketal, cyclohexanone glycerol ketal, benzaldehyde glycerol acetal, glycerol formal and glycerol levulinate ketal were introduced, and their production technology was summarized; finally, the development and application prospects of bio-based glycerol acetal and ketal are prospected.

Key words: glycerol, acetal, ketal, continuous flow reaction

中图分类号:

TQ35

肖泽,常春,白净,陈俊英,李攀,韩秀丽. 生物质基甘油缩醛和缩酮的合成研究进展[J]. 生物质化学工程, 2019, 53(6): 51-58.

Ze XIAO,Chun CHANG,Jing BAI,Junying CHEN,Pan LI,Xiuli HAN. Progress in the Synthesis of Biomass-based Glycerol Acetals and Ketals[J]. Biomass Chemical Engineering, 2019, 53(6): 51-58.

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催化剂catalyst		原料及比例 raw material and ratio	反应条件 reaction condition	结果 result	参考文献 reference
液体酸 liquid acid	H₂SO₄	n(乙酰丙酸乙酯)/n(甘油)5:1 n(ethyl levulinate)/n(glycerol)5:1	4 kPa, 110 ℃, 26 min	甘油转化率>99%,五元环选择性100% glycerol conversion rate 99%, five-membered ring selectivity 100%	[15]
液体酸 liquid acid	对甲苯磺酸 p-toluene sulphonic acid	n(丙酮)/n(甘油)3:1 n(acetone)/n(glycerol)3:1	2 h	甘油转化率85%,五元环选择性97% glycerol conversion 85%, five-membered ring selectivity 97%	[16]
固体酸 solid acid	β沸石 β-zeolite	n(丙酮)/n(甘油)6:1 n(acetone)/n(glycerol)6:1	60 ℃, 4 h	甘油转化率94.26% glycerol conversion 94.26%	[17]
	木质素磺酸基质子酸 lignosulfonate-based protonic acid	n(乙酰丙酸甲酯)/n(甘油)4:1 n(methyl levulinate)/n(glycerol)4:1	100 ℃, 1 h	甘油转化率100% glycerol conversion 100%	[18]
	磷钨酸活性炭 phosphotungstic acid activated carbon	n(甘油)/n(苯甲醛)1.1:1 n(glycerol)/n(benzaldehyde) 1.1:1	2 h	六元环缩醛产率96.4% five-membered ring acetal yield 96.4%	[19]
	Cs_2.5H_0.5PW₁₂O₄₀	n(甲醛)/n(甘油)1.2:1 n(formaldehyde)/n(glycerin) 1.2:1	70 ℃	甘油转化率90% glycerol conversion 90%	[20]
	Amberlyst-15树脂 Amberlyst-15 resin	n(丙酮)/n(甘油)2:1 n(acetone)/n(glycerol)2:1	70 ℃, 1 h	甘油转化率95% glycerol conversion 95%	[21]
	蒙脱石K10-H⁺ montmorillonite K10-H⁺	n(甘油)/n(环戊酮)1:10 n(glycerol)/n(cyclopentanone) 1:10	60 ℃, 2 h	五元环缩酮产率81.4% five-membered ring ketal yield 81.4%	[22]
	SO₄/SnO₂	n(环己酮)/n(甘油)1.05:1 n(cyclohexanone)/n(glycerol)1.05:1	90~130 ℃, 1 h	五元环缩酮产率97.5% five-membered ring ketal yield 97.5%	[23]

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