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CN1379005A - Process for oligomerizing isobutylene in ionic liquid [Hmim] +BF-(4) - Google Patents

Process for oligomerizing isobutylene in ionic liquid [Hmim] +BF-(4) Download PDF

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CN1379005A
CN1379005A CN02111529A CN02111529A CN1379005A CN 1379005 A CN1379005 A CN 1379005A CN 02111529 A CN02111529 A CN 02111529A CN 02111529 A CN02111529 A CN 02111529A CN 1379005 A CN1379005 A CN 1379005A
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ionic liquid
hmim
oligomerization
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product
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CN1183066C (en
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张鹏荣
陈雯雯
杨帆
邹刚
汤杰
何呜元
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East China Normal University
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Abstract

一种异丁烯在离子液体[Hmim]+BF4 －,即四氟硼酸甲基咪唑盐中齐聚的方法,属有机化学反应方法的技术领域,在兼作溶剂和催化剂的离子液体[Hmim]+BF4 －中,异丁烯经一步齐聚、重力沉降、分液,制得齐聚产品,转化率52～95%,产物中二聚体占17～82%,其中2,4,4－三甲基－1－戊烯选择性为74～78%,三聚体占16～81%,四聚体2%,有工艺简单、催化剂可反复循环使用、环境友好等优点,使用该方法制备的产品适用于制造高品质油品的添加剂及高级醛、醇等。A method for the oligomerization of isobutene in ionic liquid [Hmim] + BF 4 － , i.e. methylimidazolium tetrafluoroborate, which belongs to the technical field of organic chemical reaction methods. 4 - In the process of one-step oligomerization, gravity sedimentation, and liquid separation, isobutene is used to obtain oligomerized products, with a conversion rate of 52-95%, and dimers in the product account for 17-82%, of which 2,4,4-trimethyl The selectivity of -1-pentene is 74-78%, the trimer accounts for 16-81%, and the tetramer accounts for 2%. It has the advantages of simple process, recyclable catalyst, and environmental friendliness. The product prepared by this method is suitable for Additives and higher aldehydes, alcohols, etc. for the manufacture of high-quality oil products.

Description

Iso-butylene is at ionic liquid [Hmim] +BF 4-The method of middle oligomerisation
Technical field
The present invention relates to a kind of iso-butylene at ionic liquid [Hmim] +BF 4 -, i.e. the method for oligomerisation in the Tetrafluoroboric acid methylimidazole salt belongs to the technical field of organic chemical reactions method.
Background technology
The isobutene oligomerisation product is widely used at petrochemical industry.As dimer 2,4,4-trimethylammonium-1-amylene, 2,4,4-trimethylammonium-2-amylene can make the additive of high-quality oil product by the reduction hydrogenation; Corresponding nine carbon aldehyde can be obtained by hydroformylation reaction, nine carbon alcohol can be made through going back principle again.
The isobutene oligomerisation method of background technology adopts acidic oxides such as zeolite, sieve and silica-sesquioxide to realize as catalyzer mostly.European patent (patent No. EP 536839) has been reported and has been utilized SiO 2/ Al 2O 3Make catalyzer, in the autoclave pressure, under 60～65 ℃ of conditions, carry out the method for isobutene oligomerisation, isobutene conversion is 85%, and dimer accounts for 62% in the product, and tripolymer accounts for 33%, and the tetramer accounts for 1%.In background technology,, but still there is catalyzer short problem in work-ing life though catalyzer and product separation are not difficult.
Ionic liquid is the eco-friendly novel material of greatly being paid close attention in recent years of a class, have good stability, non-volatile, with advantages such as organic intermiscibility is adjustable.Wherein [Hmim] +BF 4 -Being that the Tetrafluoroboric acid methylimidazole salt has certain acidity, is solvent, is again an acidic catalyst, in this ion liquid system, carry out the oligomerisation reaction of iso-butylene, product and ionic liquid, can recycle because ionic liquid does not almost have loss through volatilization repeatedly very easily by gravity separation, and loss of catalytic activity not, thereby can solve the existing catalyst life problem of background technology, this reaction process does not produce pollution simultaneously, is greenization.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of environmental friendliness and the simple isobutene oligomerisation method of technology.The present invention solves this technical problem by the following technical programs: a kind of iso-butylene is at ionic liquid [Hmim] +BF 4 -The method of middle oligomerisation is characterized in that, ionic liquid [Hmim] +BF 4 -Be placed in the autoclave pressure with iso-butylene, airtight, to stir, oligomerisation reaction is carried out in heating, leaves standstill, gravity settling, separatory gets oligomerization product, ionic liquid [Hmim] +BF 4 -With the weight ratio of iso-butylene be 10: 1, ionic liquid [Hmim] +BF 4 -Double as solvent and catalyzer, the oligomerisation reaction skeleton symbol is: Ionic liquid [Hmim] +BF 4 -Recycle.
Now describe content of the present invention in detail.A kind of iso-butylene is at ionic liquid [Hmim] +BF 4 -The method of middle oligomerisation is characterized in that,
Implementation step:
Ionic liquid [Hmim] with 30 parts of weight +BF 4 -Add in the autoclave pressure with the iso-butylene of 3 parts of weight, airtight, stir, heating, control reaction temperature is 45～110 ℃, reacts 10～50 hours, reaction solution is cooled to 30 ℃, leaves standstill gravity settling, tell the upper strata oligomerization product by separatory, the ionic liquid of lower floor recycles, transformation efficiency 52～95%, dimer accounts for 17～82% (wherein 2,4,4-trimethylammonium-1-amylene selectivity is 74～78%) in the product, tripolymer accounts for 16～81%, the tetramer 2%.
Compare with background technology, the present invention has the following advantages:
1. ionic liquid [Hmim] +BF 4 -Being catalyzer, is again solvent, can recycle repeatedly, and catalytic activity and selectivity do not change.
2. environmental friendliness, ionic liquid [Hmim] +BF 4 -Non-volatile in reaction, free of losses really realizes cleaner production.
3. technology is simple, and separatory can obtain product after reaction mixture only needed gravity settling.
Embodiment
Embodiment 1: with 30g ionic liquid [Hmim] +BF 4 -Add in the autoclave pressure with the 3g iso-butylene, airtight, stir, heating, control reaction temperature is 45 ℃, reacts 48 hours, reaction solution is cooled to 30 ℃, leaves standstill gravity settling, tell the upper strata oligomerization product by separatory, the ionic liquid of lower floor recycles, transformation efficiency 52%, dimer accounts for 82% (wherein 2,4,4-trimethylammonium-1-amylene selectivity is 78%) in the product, tripolymer accounts for 16%, the tetramer 2%.
Embodiment 2: with 30g ionic liquid [Hmim] +BF 4 -Add in the autoclave pressure with the 3g iso-butylene, airtight, stir, heating, control reaction temperature is 70 ℃, reacts 50 hours, reaction solution is cooled to 30 ℃, leaves standstill gravity settling, tell the upper strata oligomerization product by separatory, the ionic liquid of lower floor recycles, transformation efficiency 95%, dimer accounts for 46% (wherein 2,4,4-trimethylammonium-1-amylene selectivity is 74%) in the product, tripolymer accounts for 52%, the tetramer 2%.
Embodiment 3: with 30g ionic liquid [Hmim] +BF 4 -Add in the autoclave pressure with the 3g iso-butylene, airtight, stir, heating, control reaction temperature is 110 ℃, reacts 10 hours, reaction solution is cooled to 30 ℃, leaves standstill gravity settling, tell the upper strata oligomerization product by separatory, the ionic liquid of lower floor recycles, transformation efficiency 73%, dimer accounts for 17% (wherein 2,4,4-trimethylammonium-1-amylene selectivity is 74%) in the product, tripolymer accounts for 81%, the tetramer 2%.
The method that the present invention relates to is applicable to the oligomerisation of iso-butylene, has that technology is simple, catalyzer can recycle repeatedly, advantages of environment protection.Additive that uses the product of this method preparation to be applicable to make high-quality oil product and senior aldehyde, alcohol etc.

Claims (2)

1.一种异丁烯在离子液体[Hmim]+BF4 -中齐聚的方法，其特征在于，把离子液体[Hmim]+BF4 -与异丁烯放在压力釜中，密闭，搅拌，加热，进行齐聚反应，静置，重力沉降，分液，得齐聚产物，离子液体[Hmim]+BF4 -与异丁烯的重量比为10∶1，离子液体[Hmim]+BF4 -兼作溶剂和催化剂，齐聚反应简式为：
Figure A0211152900021
离子液体[Hmim]+BF4 -循环使用。1. a method for oligomerization of isobutene in ionic liquid [Hmim] + BF 4 - is characterized in that, ionic liquid [Hmim] + BF 4 - and isobutene are placed in a pressure vessel, sealed, stirred, heated, and carried out Oligomerization reaction, static, gravity sedimentation, liquid separation, oligomerization product, ionic liquid [Hmim] + BF 4 - the weight ratio of isobutylene is 10:1, ionic liquid [Hmim] + BF 4 - double as solvent and catalyst , the oligomerization reaction formula is:
Figure A0211152900021
Ionic Liquid [Hmim] + BF 4 - Recycle. 2.根据权利要求1所述的一种异丁烯在离子液体[Hmim]+BF4 -中齐聚的方法，其特征在于，2. a kind of isobutylene according to claim 1 is in ionic liquid [Hmim] + BF 4 -The method for oligomerization in, it is characterized in that, 实施步骤：Implementation steps: 将30份重量的离子液体[Hmim]+BF4 -和3份重量的异丁烯加入压力釜中，密闭，搅拌，加热，控制反应温度为45～110℃，反应10～50小时，反应液冷却至30℃，静置，重力沉降，通过分液分出上层齐聚产物，下层的离子液体循环使用，转化率52～95％，产物中二聚体占17～82％，该二聚体中2，4，4-三甲基-1-戊烯选择性为74～78％，三聚体占16～81％，四聚体2％。Add 30 parts by weight of ionic liquid [Hmim] + BF 4 - and 3 parts by weight of isobutylene into the autoclave, seal it, stir, heat, control the reaction temperature to 45-110°C, react for 10-50 hours, and cool the reaction liquid to Stand at 30°C, settle by gravity, separate the oligomerization product in the upper layer by liquid separation, and recycle the ionic liquid in the lower layer, the conversion rate is 52-95%, and the dimer in the product accounts for 17-82%. , The selectivity of 4,4-trimethyl-1-pentene is 74-78%, the trimer accounts for 16-81%, and the tetramer accounts for 2%.
CNB02111529XA 2002-04-28 2002-04-28 A method for the oligomerization of isobutylene in the ionic liquid [Hmim] BF Expired - Fee Related CN1183066C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101190861B (en) * 2006-11-29 2011-07-13 中国石油大学(北京) Method for catalyzing butene oligomerization by using ionic liquid as catalyst
CN107983409A (en) * 2016-10-26 2018-05-04 中国石油化工股份有限公司 The preparation method of low-molecular olefine polymer
CN109433263A (en) * 2018-12-11 2019-03-08 中国科学院过程工程研究所 A kind of method of the ionic liquid-catalyzed isobutene oligomerisation of proton acid type pyridyl group
CN109651436A (en) * 2018-12-11 2019-04-19 万华化学集团股份有限公司 Ionic liquid, ionic liquid loaded Raney nickel and catalysis n-butene or the method for mixing C4 oligomerisation
US11078433B2 (en) 2016-10-14 2021-08-03 Gevo, Inc. Conversion of mixtures of C2—C8 olefins to jet fuel and/or diesel fuel in high yield from bio-based alcohols

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101190861B (en) * 2006-11-29 2011-07-13 中国石油大学(北京) Method for catalyzing butene oligomerization by using ionic liquid as catalyst
US11078433B2 (en) 2016-10-14 2021-08-03 Gevo, Inc. Conversion of mixtures of C2—C8 olefins to jet fuel and/or diesel fuel in high yield from bio-based alcohols
CN107983409A (en) * 2016-10-26 2018-05-04 中国石油化工股份有限公司 The preparation method of low-molecular olefine polymer
CN107983409B (en) * 2016-10-26 2020-10-27 中国石油化工股份有限公司 Preparation method of low molecular weight olefin polymer
CN109433263A (en) * 2018-12-11 2019-03-08 中国科学院过程工程研究所 A kind of method of the ionic liquid-catalyzed isobutene oligomerisation of proton acid type pyridyl group
CN109651436A (en) * 2018-12-11 2019-04-19 万华化学集团股份有限公司 Ionic liquid, ionic liquid loaded Raney nickel and catalysis n-butene or the method for mixing C4 oligomerisation
CN109651436B (en) * 2018-12-11 2021-05-14 万华化学集团股份有限公司 Ionic liquid, ionic liquid-loaded nickel catalyst and method for catalyzing n-butene or mixed C4 oligomerization

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