液体酸耦合体系催化C4烷基化研究进展

doi:10.16085/j.issn.1000-6613.2018-1349

摘要/Abstract

摘要：

综述了近十年来液体酸耦合体系催化C₄烃烷基化反应的最新进展，包括液体超强酸、有机酸-杂多酸、离子液体-酸耦合体系，对比了不同催化体系催化C₄烃烷基化反应过程中的烯烃转化率、三甲基戊烷的选择性和烷基化汽油的研究法辛烷值，总结了不同催化体系的优缺点。重点论述了离子液体-酸耦合体系催化剂中组成离子液体的阴阳离子以及耦合酸类型对C₄烃烷基化反应的影响：有机胺类离子液体较咪唑类有着更为优异的烷基化效果，阴离子和改性离子液体通过形成特定的结构来维持反应体系的酸强度、减少副反应，从而延长催化剂的使用寿命，耦合酸为反应提供酸性位点并与离子液体协同催化。离子液体-酸耦合催化体系具有酸耗低、稳定性好、不易失活且可循环使用等优点，是C₄烷基化催化剂未来的发展方向之一。

关键词: 液体酸, 离子液体, C₄烃, 烷基化, 耦合

Abstract:

The progress in the alkylation of C₄ hydrocarbons catalyzed by liquid acid coupling systems, including liquid super acids， organic acid-heteropoly acids， and ionic liquid-acid coupling systems, in last decade is reviewed. The conversion of olefins， selectivity of trimethylpentane and research octane number of alkylated gasoline during the alkylation of C₄ hydrocarbons catalyzed by different catalytic systems were compared. The advantages and disadvantages of different catalytic systems were also summarized. The effects of the anions and cations of ionic liquids and the coupling acid types on the alkylation of C₄ hydrocarbons in ionic liquid-acid coupling catalysts are mainly discussed. Organic amine ionic liquids have superior alkylation effects to imidazoles. Anions and modified ionic liquids could form specific structures to maintain the acid strength of the reaction systems and reduce side reactions so as to extend the life of the catalysts. The coupling acids provide acidic sites for the reaction and cooperate with ionic liquids. Finally, the ionic liquid-acid coupling catalytic system which has the advantages of low acid consumption, good stability, resistant inactivation and easy recycling， is one of the development directions of the C₄ alkylation catalyst in the future.

Key words: liquid acids, ionic liquids, C₄ hydrocarbons, alkylation, coupling

中图分类号:

TQ072

唐晓东,王治宇,李晶晶,卿大咏,冷曼希,张洪宇. 液体酸耦合体系催化C₄烷基化研究进展[J]. 化工进展, 2019, 38(05): 2339-2346.

Xiaodong TANG,Zhiyu WANG,Jingjing LI,Dayong QING,Manxi LENG,Hongyu ZHANG. Progress in catalytic C₄ alkylation with liquid acid coupled systems[J]. Chemical Industry and Engineering Progress, 2019, 38(05): 2339-2346.

图/表 4

图1 B r o ¨ n s t e d 酸催化剂催化C4烷基化机理

表1 ILs/Acid中不同耦合酸的C4烷基化效果

序号	ILs	Acid	ILs∶ Acid (m/m)	$C 4 =$ 转化率(质量分数)/%	C₈选择性(质量分数)/%	TMP /DMH	参考文献
1	[EMIM]HSO₄	TFOH	11.1∶88.9	>96.0	56.0	10.5	[17]
2	[OMIM]HSO₄	H₂SO₄	16.0∶84.0	98.0	51.3	6.6	[18]
3	[OMIM]HSO₄	TFOH	23.7∶76.3	96.3	75.8	6.8	[18]
4	[MBSIM]OTf	H₂SO₄	46.7∶53.3	91.3	41.0	3.8	[18]
5	[MBSIM]OTf	TFOH	48.3∶51.7	95.2	64.7	5.1	[18]
6	[MBSIM]OTf	CH₃COOH	60.0∶40.0 (v/v)	91.8	67.1	4.1	[19]

表1 ILs/Acid中不同耦合酸的C4烷基化效果

序号	ILs	Acid	ILs∶ Acid (m/m)	$C 4 =$ 转化率(质量分数)/%	C₈选择性(质量分数)/%	TMP /DMH	参考文献
1	[EMIM]HSO₄	TFOH	11.1∶88.9	>96.0	56.0	10.5	[17]
2	[OMIM]HSO₄	H₂SO₄	16.0∶84.0	98.0	51.3	6.6	[18]
3	[OMIM]HSO₄	TFOH	23.7∶76.3	96.3	75.8	6.8	[18]
4	[MBSIM]OTf	H₂SO₄	46.7∶53.3	91.3	41.0	3.8	[18]
5	[MBSIM]OTf	TFOH	48.3∶51.7	95.2	64.7	5.1	[18]
6	[MBSIM]OTf	CH₃COOH	60.0∶40.0 (v/v)	91.8	67.1	4.1	[19]

表2 ILs/Acid中ILs不同阳离子C4烷基化效果

序号	ILs	Acid	ILs∶Acid	$C 4 =$ 转化率 (质量分数)/%	C₈选择性 (质量分数)/%	TMP/DMH	RON	参考文献
1	[EMIM]HSO₄	H₂SO₄	11.1∶88.9(质量比)	>96.0	56.8	11.3	—	[17]
2	[BMIM]HSO₄	H₂SO₄	11.1∶88.9(质量比)	>96.0	58.9	6.2	—	[17]
3	[OMIM]HSO₄	H₂SO₄	11.1∶88.9(质量比)	>96.0	55.2	6.7	—	[17]
4	[BMIM]HSO₄	H₂SO₄	20.9∶79.1(质量比)	90.4	41.0	7.9	—	[18]
5	[OMIM]HSO₄	H₂SO₄	16.0∶84.0(质量比)	98.0	51.3	6.6	—	[18]
6	[DMIPA]HSO₄	TFOH	15.0∶85.0 (体积比)	≈100.0	88.9	12.1	97.4	[21]
7	[MDEA]HSO₄	TFOH	15.0∶85.0 (体积比)	≈100.0	92.1	12.0	97.8	[21]
8	[DEEA]HSO₄	TFOH	15.0∶85.0 (体积比)	≈100.0	87.3	13.5	97.4	[21]
9	[DMEA]HSO₄	TFOH	15.0∶85.0 (体积比)	≈100.0	89.6	12.9	97.7	[21]
10	[MEA]HSO₄	TFOH	25.0∶75.0 (体积比)	≈100.0	87.9	10.4	97.0	[21]
11	[TEA]HSO₄	TFOH	25.0：75.0 (体积比)	≈100.0	91.5	13.5	98.0	[21]

表2 ILs/Acid中ILs不同阳离子C4烷基化效果

序号	ILs	Acid	ILs∶Acid	$C 4 =$ 转化率 (质量分数)/%	C₈选择性 (质量分数)/%	TMP/DMH	RON	参考文献
1	[EMIM]HSO₄	H₂SO₄	11.1∶88.9(质量比)	>96.0	56.8	11.3	—	[17]
2	[BMIM]HSO₄	H₂SO₄	11.1∶88.9(质量比)	>96.0	58.9	6.2	—	[17]
3	[OMIM]HSO₄	H₂SO₄	11.1∶88.9(质量比)	>96.0	55.2	6.7	—	[17]
4	[BMIM]HSO₄	H₂SO₄	20.9∶79.1(质量比)	90.4	41.0	7.9	—	[18]
5	[OMIM]HSO₄	H₂SO₄	16.0∶84.0(质量比)	98.0	51.3	6.6	—	[18]
6	[DMIPA]HSO₄	TFOH	15.0∶85.0 (体积比)	≈100.0	88.9	12.1	97.4	[21]
7	[MDEA]HSO₄	TFOH	15.0∶85.0 (体积比)	≈100.0	92.1	12.0	97.8	[21]
8	[DEEA]HSO₄	TFOH	15.0∶85.0 (体积比)	≈100.0	87.3	13.5	97.4	[21]
9	[DMEA]HSO₄	TFOH	15.0∶85.0 (体积比)	≈100.0	89.6	12.9	97.7	[21]
10	[MEA]HSO₄	TFOH	25.0∶75.0 (体积比)	≈100.0	87.9	10.4	97.0	[21]
11	[TEA]HSO₄	TFOH	25.0：75.0 (体积比)	≈100.0	91.5	13.5	98.0	[21]

表3 不同类型铜基改性体系C4烷基化效果

序号	ILs	Acid	ILs∶ Acid (质量比)	$C 4 =$ 转化率 (质量分数)/%	C₈选择性 (质量分数)/%	TMP/DMH	RON	参考文献
1	[BMIM]HSO₄-CuSO₄	H₂SO₄	11.1∶88.9	>96	77.8	4.8	—	[17]
2	[EMIM]HSO₄-CuCl	H₂SO₄	11.1∶88.9	>96	84.4	14.3	99.0	[17]
3	[Et₃NH]HSO₄-CuCl	H₂SO₄	11.1∶88.9	>96	83.5	12.3	98.7	[17]
4	[EMIM]OTf-CuCl	TFOH	11.1∶88.9	>96	84.9	15.0	99.1	[17]
5	[EMIM]Tf₂N-Cu(OTf)₂	TFOH	11.1∶88.9	>96	80.6	8.5	97.1	[17]
6	[Et₃NH]Cl-1.8AlCl₃-0.5CuCl	—	—	—	71.4	5.5	93.1	[33]
7	[BMIM]Cl-1.8AlCl₃-0.5CuCl	—	—	—	76.6	6.8	94.8	[33]
8	NMA-AlCl₃-CuCl	—	—	—	94.65	15.0	98.4	[34]

表3 不同类型铜基改性体系C4烷基化效果

序号	ILs	Acid	ILs∶ Acid (质量比)	$C 4 =$ 转化率 (质量分数)/%	C₈选择性 (质量分数)/%	TMP/DMH	RON	参考文献
1	[BMIM]HSO₄-CuSO₄	H₂SO₄	11.1∶88.9	>96	77.8	4.8	—	[17]
2	[EMIM]HSO₄-CuCl	H₂SO₄	11.1∶88.9	>96	84.4	14.3	99.0	[17]
3	[Et₃NH]HSO₄-CuCl	H₂SO₄	11.1∶88.9	>96	83.5	12.3	98.7	[17]
4	[EMIM]OTf-CuCl	TFOH	11.1∶88.9	>96	84.9	15.0	99.1	[17]
5	[EMIM]Tf₂N-Cu(OTf)₂	TFOH	11.1∶88.9	>96	80.6	8.5	97.1	[17]
6	[Et₃NH]Cl-1.8AlCl₃-0.5CuCl	—	—	—	71.4	5.5	93.1	[33]
7	[BMIM]Cl-1.8AlCl₃-0.5CuCl	—	—	—	76.6	6.8	94.8	[33]
8	NMA-AlCl₃-CuCl	—	—	—	94.65	15.0	98.4	[34]

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液体酸耦合体系催化C₄烷基化研究进展

Progress in catalytic C₄ alkylation with liquid acid coupled systems

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