离子液体中异丁烷/2-丁烯烷基化反应机理研究

王丽红; 李瑞; 刘鹰; 胡瑞生

离子液体中异丁烷/2-丁烯烷基化反应机理研究

内蒙古大学化学化工学院, 内蒙古呼和浩特 010021

基金项目:

国家自然科学基金 21266015, 20806036

详细信息

中图分类号: TE624.9
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- 被引次数: 0
出版历程
- 收稿日期: 2015-12-30
- 修回日期: 2016-04-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-06-10

Reaction mechanism of isoparaffin alkylation in the presence of ionic liquid

School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China

More Information

Corresponding author: Tel & Fax: 0471-4992981, E-mail: celiuy@imu.edu.cn

摘要

摘要: 以复合离子液体[Et₃NH]Cl-AlCl₃-CuCl为催化剂, 在连续搅拌釜式反应器中进行了异丁烷与2-丁烯烷基化反应; 利用氘代异丁烷同位素示踪法研究了催化反应机理。结果表明, 在离子液体中异丁烷烷基化的反应诱导期较短; 三甲基戊烷产物主要源于异丁烷的自烷基化、丁烷/丁烯的直接烷基化以及C₁₂⁺中间体的裂化反应, 而大部分二甲基己烷是仲丁基碳正离子与丁烯加成的产物。
- 离子液体 /
- 异丁烷 /
- 烷基化 /
- 反应机理
Abstract: The alkylation of isobutane with butene catalyzed by [Et₃NH]Cl-AlCl₃-CuCl ionic liquid was carried out in a continuous stirred autoclave reactor; deuterated isobutane was used as an isotope tracer to investigate the reaction mechanism of alkylation. The results indicate that the induction period of alkylation catalyzed by Cl-AlCl₃-CuCl is less than 30min. Tri-methyl-pentanes are primarily produced from the self-alkylation of isobutane, the alkylation of isobutane with 2-butene and the cracking of C₁₂⁺ intermediates, whereas the undesired di-methyl-hexane is mainly formed from the addition reaction between sec-C₄⁺ and 2-butene.
- ionic liquids /
- isobutane /
- alkylation /
- reaction mechanism

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图 1 异丁烷/2-丁烯连续烷基化反应装置示意图

Figure 1 Schematic diagram of the continuous stirred tank reactor for the alkylation of isobutane with 2-butene

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图 2 H₂SO₄催化异丁烷和2-丁烯反应产物分布随时间的变化

Figure 2 Product distribution with time on stream for the alkylation of isobutane with 2-butene catalyzed by H₂SO₄

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图 3 CIL催化异丁烷和2-丁烯反应产物分布随时间的变化

Figure 3 Product distribution with time on stream for the alkylation of isobutane with 2-butene catalyzed by CIL

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图 4 CIL中的烷基化阶段气相2-丁烯的加入量 (B) 与气相异丁烷的消耗量 (S)

Figure 4 Consumption of isobutane (S) and amount of 2-butene added (B) during the alkylation of isobutane with 2-butene catalyzed by CIL

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图 5 异丁烷m/z=41.0丰度峰随反应时间的变化

Figure 5 (a) Mass spectrum of i-C₄H₁₀ and i-C₄D₁₀; (b) Relative abundance of i-C₄D₁₀ at m/z=41.0 with time on stream for the alkylation catalyzed by CIL

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图 6 离子液体催化C₄烷基化反应机理

Figure 6 Proposed reaction mechanism for the alkylation of isobutane with 2-butene catalyzed by CIL

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表 1 异丁烷/2-丁烯烷基化C₈产物分布^a

Table 1 Product distribution of isobutane/ 2-butene alkylation ^a

Component	Molecular weight	H₂SO₄	[Et₃NH]Cl-AlCl₃-CuCl
Alkane
TMP (C₈H₈D₁₀)	124	-	0.05
2, 2, 4-TMP (C₈H₁₈)	114	9.13	13.63
TMP (C₈H₅D₁₃)	127	-	0.04
2, 2-DMH (C₈H₁₈)	114	-	0.01
2, 4-DMH (C₈H₁₈)	114	3.2	2.71
2, 5-DMH (C₈H₁₈)	114	4.51	2.28
2, 2, 3-TMP (C₈H₁₈)	114	0.92	1.66
TMP (C₈H₉D₉)	123	-	0.12
TMP (C₈H₁₆D₂)	116	-	0.24
3, 3-DMH (C₈H₁₈)	114	-	0.01
2, 3, 4-TMP (C₈H₁₈)	114	6.01	13.72
2, 2, 3-TMP (C₈H₁₈)	114	8.12	11.43
TMP (C₈D₁₈)	132	-	0.02
^a the mixture of i-C₄D₁₀ (5g), i-C₄H₁₀ (50g) was used as the feed and sampling was made after continuous reaction for 30min

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表 2 不同催化剂中异丁烷/2-丁烯烷基化副产物的分布

Table 2 Side-product distribution of isobutane/ 2-butene alkylation

Component	Molecular weight	H₂SO₄	[Et₃NH]Cl-AlCl₃-CuCl
C₄H₁₀	59	5.23
C₄H₉D	59		0.36
C₅H₁₂	72	2.73	0.16
C₆H₁₄	86	4.48	0.30
C₇H₁₆	100	5.21	1.14
C₆D₁₄	100	-	0.04
C₈H₁₆	112	17.36	1.01
C₁₂H₂₄D₂	172	-	0.16
C₁₂H₁₂D₁₄	184	-	0.08
C₁₂H₁₈D₈	178	-	0.02
C₁₂H₁₂D₁₄	184	-	0.05
C₁₂H₂₆	170	11.84	23.62

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