油酸甲酯烯烃复分解合成1-癸烯的工艺优化

doi:10.3969/j.issn.1673-5854.2021.05.002

生物质化学工程 ›› 2021, Vol. 55 ›› Issue (5): 8-14.doi: 10.3969/j.issn.1673-5854.2021.05.002

油酸甲酯烯烃复分解合成1-癸烯的工艺优化

舒恒毅¹^,³, 郑志锋³^,⁴, 李水荣⁴, 刘守庆¹^,³, 何宏舟², 黄元波²^,³^,*()

1. 西南林业大学材料科学与工程学院, 云南昆明 650224
2. 集美大学机械与能源工程学院, 福建厦门 361021
3. 林业生物质资源高效利用技术国家地方联合工程研究中心; 西南地区林业生物质资源高效利用国家林业和草原局重点实验室, 西南林业大学, 云南昆明 650224
4. 厦门市现代农业生物质高值化技术重点实验室(厦门大学); 福建省生物质高值化技术工程研究中心(厦门大学); 厦门大学能源学院, 福建厦门 361102

收稿日期:2020-07-29 出版日期:2021-09-30 发布日期:2021-09-13
通讯作者: 黄元波 E-mail:youthshow@163.com
作者简介:黄元波, 副教授, 硕士生导师, 主要从事生物质能源与材料研究教学工作; E-mail: youthshow@163.com
舒恒毅(1994-), 男, 云南曲靖人, 硕士生, 主要从事生物质能源与化学转化研究工作
基金资助:
国家自然科学基金资助项目(31860190);国家重点研发计划项目(2016YFD0600802);云南省研发经费投入补助项目(2017YB236)

Process Optimization of Synthesis of 1-Decene by Olefin Metathesis of Methyl Oleate

Hengyi SHU¹^,³, Zhifeng ZHENG³^,⁴, Shuirong LI⁴, Shouqing LIU¹^,³, Hongzhou HE², Yuanbo HUANG²^,³^,*()

1. School of Materials Science & Engineering, Southwest Forestry University, Kunming 650224, China
2. School of Mechanical & Energy Engineering, Jimei University, Xiamen 361021, China
3. National Local Joint Engineering Research Center for Efficient Utilization of Forestry Biomass Resources; Key Laboratory for Highly-Efficient Utilization of Forest Biomass Resources in the Southwest China, National Forestry and Grassland Administration, Southwest Forestry University, Kunming 650224, China
4. Xiamen Key Laboratory for High-valued Conversion Technology of Agricultural Biomass(Xiamen University); Fujian Provincial Engineering and Research Center of Clean and High-valued Technologies for Biomass; College of Energy, Xiamen University, Xiamen 361102, China

Received:2020-07-29 Online:2021-09-30 Published:2021-09-13
Contact: Yuanbo HUANG E-mail:youthshow@163.com

摘要/Abstract

摘要：

以油酸甲酯（MO）为植物油脂模型物，通过烯烃复分解反应制备1-癸烯，以油酸甲酯转化率和1-癸烯得率为评价指标，探究了反应底物、催化剂类型、反应温度、反应时间、催化剂用量和MO与反应底物物质的量之比对烯烃复分解反应制备1-癸烯的影响，最后通过正交试验设计优化得到最佳工艺条件。结果表明：反应底物丁香酚和Grubbs第二代催化剂C2有利于本反应体系，最佳工艺条件为反应温度0℃，反应时间40 min，催化剂C2用量1%，n（MO）：n（丁香酚）1：10，在此条件下MO转化率和1-癸烯得率分别为96%和78%。

关键词: 油酸甲酯, 烯烃交叉复分解, 钌络合催化剂, α-烯烃

Abstract:

1-Decene was prepared through olefin metathesis reaction using methyl oleate (MO) as the vegetable oil model chemistry, the conversion rate of methyl oleate and yield of 1-decene were used as evaluation indicators to explore the effect of reaction temperature, reaction time, catalyst dosage and molar ratio of substrates to MO, finally the optimal conditions were obtained by orthogonal experiment design. The results showed that the substrate eugenol and Grubbs second-generation catalyst (C2) were beneficial to the reaction system. The optimal conditions were reaction temperature 0℃, reaction time 40 min, catalyst dosage 1%, molar ratio of MO and eugenol 1:10, under these conditions the conversion rate of MO and the yield of 1-decene were 96% and 78%, respectively.

Key words: methyl oleate, olefin cross-metathesis, ruthenium-complex catalyst, α-olefin

中图分类号:

TQ35
S216

舒恒毅, 郑志锋, 李水荣, 刘守庆, 何宏舟, 黄元波. 油酸甲酯烯烃复分解合成1-癸烯的工艺优化[J]. 生物质化学工程, 2021, 55(5): 8-14.

Hengyi SHU, Zhifeng ZHENG, Shuirong LI, Shouqing LIU, Hongzhou HE, Yuanbo HUANG. Process Optimization of Synthesis of 1-Decene by Olefin Metathesis of Methyl Oleate[J]. Biomass Chemical Engineering, 2021, 55(5): 8-14.

图/表 6

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表2

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参考文献 22

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烯烃底物 olefin substrate	MO转化率/% MO conversion	1-癸烯得率/% 1-decene yield
乙酸烯丙酯allyl acetate	2	1
烯丙基缩水甘油醚allyl glycidyl ether	27	8
丙烯酸甲酯methyl acrylate	93	16
2-甲氧基丙烯2-methoxypropylene	61	0
丙烯腈acrylonitrile	21	6
苯乙烯styrene	59	21
丁香酚eugenol	93	14
烯丙基三甲基硅烷allyltrimethylsilane	96	17
氯丙烯allyl chloride	44	16
丙烯醇allyl alcohol	40	9

序号 No.	A 反应温度/ ℃ reaction temperature	B 反应时间/min reaction time	C 催化剂用量/% amount of catalyst	D n(MO)∶n(丁香酚) n(MO)∶n(eugenol)	MO转化率/% MO conversion	1-癸烯得率/% 1-decene yield
1	0	20	0.5	1∶3	91	50
2	0	40	1	1∶10	96	78
3	0	60	3	1∶20	99	77
4	20	20	1	1∶20	99	6
5	20	40	3	1∶3	99	17
6	20	60	0.5	1∶10	92	46
7	40	20	3	1∶10	96	14
8	40	40	0.5	1∶20	95	34
9	40	60	1	1∶3	78	9
k′₁	95.3	95.3	92.7	89.3
k′₂	96.7	96.7	91	94.7
k′₃	89.7	89.7	98	97.7
R′	7	7	7	8.4
k₁^″	68.3	23.3	43.3	25.3
k₂^″	23	43	31	46
k₃^″	19	44	36	39
R^″	49.3	20.7	12.3	20.7

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油酸甲酯烯烃复分解合成1-癸烯的工艺优化

Process Optimization of Synthesis of 1-Decene by Olefin Metathesis of Methyl Oleate

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