CN102614929A - Catalyst for preparing divinylacetylene by acetylene trimerization - Google Patents
Catalyst for preparing divinylacetylene by acetylene trimerization Download PDFInfo
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- CN102614929A CN102614929A CN2012100608573A CN201210060857A CN102614929A CN 102614929 A CN102614929 A CN 102614929A CN 2012100608573 A CN2012100608573 A CN 2012100608573A CN 201210060857 A CN201210060857 A CN 201210060857A CN 102614929 A CN102614929 A CN 102614929A
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- divinylacetylene
- acetylene
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- ion liquid
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Abstract
The invention relates to a catalyst for preparing divinylacetylene by acetylene trimerization. The catalyst consists of cuprous chloride, organic ion liquid, organic amine hydrochloride and an aid, wherein the aid is N'N-dimethylformamide or N-methyl pyrrolidone; and a mass ratio of the cuprous chloride to the organic ion liquid to the organic amine hydrochloride to the aid is 5.3:(0.2-1.5):(2.0-5.3):(4.1-8.5). Experiments prove that the catalyst has high catalytic activity of ethylene trimerization and selectivity of the divinylacetylene.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of catalyst that the acetylene trimerization prepares divinylacetylene that is used for.
Background technology
Divinylacetylene is a kind of accessory substance of producing neoprene, as organic substance, contains great amount of heat energy.In the traditional handicraft it is directly acted as a fuel, cause the significant wastage of resource.Advanced at present way is that it is used as the house waterproof material; But because divinylacetylene is just as the accessory substance in the neoprene production process; So at present seldom to the research of its application facet; But there are two keys and triple bond in its molecular formula, make it have very wide application potential quality.
Divinylacetylene is mainly derived from the accessory substance of neoprene at present.About 50,000 tons/year of the present neoprene consumption of China, accessory substance divinylacetylene output has only 2000 tons/year, if all use as waterproof material, then supply falls short of demand.Along with the research of divinylacetylene application facet is goed deep into, it is rapidly promoted aspect consumption.On the other hand, rich coal resources in China and price are lower, and along with the continuous maturation of coal system acetylene new technology, acetylene prepares divinylacetylene as cheap industrial chemicals through trimerization reaction, can reduce production costs.
Based on above-mentioned background, the present invention proposes a kind of catalyst that the acetylene trimerization prepares divinylacetylene that is used for.
Summary of the invention
The object of the invention is to provide a kind of catalyst that the acetylene trimerization prepares divinylacetylene that is used for, and this catalyst has good ethylene trimer catalytic activity and divinylacetylene selectivity.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is following:
A kind ofly be used for the catalyst that the acetylene trimerization prepares divinylacetylene; This catalyst is made up of stannous chloride, organic ion liquid, organic amine salt hydrochlorate and auxiliary agent; Said auxiliary agent is N`N-dimethyl formamide or N-methyl pyrrolidone, and wherein the mass ratio of stannous chloride, organic ion liquid, organic amine salt hydrochlorate and auxiliary agent is 5.3:0.2-1.5:2.0-5.3:4.1-8.5.
Concrete, said organic ion liquid is preferably [Bmim] Cl, [Bmim] Br, [Bmim] BF
4, [Bmim] PF
6, [Bmim] OTf (1-butyl-3-methylimidazole fluoroform sulphonate) or [Bmim] [lactate] (1-butyl-3-methylimidazole-L-lactate).
Said organic amine salt hydrochlorate is preferably methylamine hydrochloride, dimethylamine hydrochloride, ethylamine hydrochloride, diethylamine hydrochloride or triethylamine hydrochloride.
Utilize the method for said Preparation of Catalyst divinylacetylene, this method comprises the steps:
1. under obtain solution: the 40-60 ℃ condition; In bubbling reactor, feed nitrogen with deaeration, add organic amine salt hydrochlorate, organic ion liquid and auxiliary agent in proportion, after mixing; Seal this bubbling reactor, continue to feed nitrogen with deaeration (emptying time is no less than 15min);
2. stannous chloride dissolving: be warming up to 60～100 ℃, add stannous chloride in proportion, continue to feed nitrogen, bubbling stirs it is dissolved fully;
3. trimerization reaction: after treating the raw material blending in the bubbling reactor, replace nitrogen, under 60～100 ℃ of conditions, continue bubbling stirring reaction (to quicken three collecting process of acetylene) with acetylene, divinylacetylene, wherein the acetylene air speed is 100～150h
-1
Preferably, before reaction, catalyst is activation 3 h under acetylene atmosphere.
This catalyst is to comprise stannous chloride, organic amine salt hydrochlorate and organic ion liquid and N, dinethylformamide or N-methyl pyrrolidone.Make this catalyst possess good conversion of alkyne and divinylacetylene selectivity through optimizing catalyst proportion, stannous chloride content and preparation condition.
Catalyst according to the invention is a raw material with stannous chloride, organic ion liquid, organic amine salt hydrochlorate and auxiliary agent, is used for the trimerization reaction of catalyzing acetylene, the preparation divinylacetylene.Through evidence, this catalyst has good ethylene trimer catalytic activity and divinylacetylene selectivity.
The specific embodiment
Below through preferred embodiment the present invention is done further explain, but protection scope of the present invention is not limited thereto.
Embodiment 1
A kind ofly be used for the catalyst that the acetylene trimerization prepares divinylacetylene, this catalyst is made up of 40g stannous chloride, 3.1g [Bmim] Br, 30g methylamine hydrochloride and 61.7g N-methyl pyrrolidone.
Utilize the method for above-mentioned Preparation of Catalyst divinylacetylene, this method comprises the steps:
1. obtain solution: under 40 ℃ of conditions; In bubbling reactor, feed nitrogen with deaeration, add organic amine salt hydrochlorate, organic ion liquid and auxiliary agent in proportion, after mixing; Seal this bubbling reactor, continue to feed nitrogen with deaeration (emptying time 30min);
2. stannous chloride dissolving: be warming up to 80 ℃, add stannous chloride in proportion, continue to feed nitrogen, bubbling stirs it is dissolved fully;
3. trimerization reaction: after treating the abundant mixing of raw material in the bubbling reactor, (the acetylene air speed is 110 mlgcat to replace nitrogen with acetylene
-1H
-1), under 80 ℃ of conditions, continue bubbling and stir to quicken three collecting process of acetylene, get divinylacetylene.
Before the reaction, catalyst is activation 3 h under acetylene atmosphere.Table 1 has provided embodiment 1 catalyst corresponding conversion of alkyne and divinylacetylene selective data when reaction 3.0h, 4.0h, 5.5h and 7.0h.Table 1 gives conversion ratio and the selective data of embodiment 2-13 gained catalyst at reaction 3.0h, can be found out that by table 1 catalyst according to the invention has catalytic activity and selectivity preferably.
Embodiment 2
Be with embodiment 1 difference: the quality of used stannous chloride is 60g.
Embodiment 3
Be with embodiment 1 difference: the quality of used stannous chloride is 80g.
Embodiment 4
Be with embodiment 1 difference: auxiliary agent is with N`N-dimethyl formamide replacement N-methyl pyrrolidone.
Embodiment 5
Be with embodiment 1 difference: replace methylamine hydrochloride with dimethylamine hydrochloride.
Embodiment 6
Be with embodiment 1 difference: replace methylamine hydrochloride with ethylamine hydrochloride.
Embodiment 7
Be with embodiment 1 difference: replace methylamine hydrochloride with diethylamine hydrochloride.
Embodiment 8
Be with embodiment 1 difference: replace methylamine hydrochloride with triethylamine hydrochloride.
Embodiment 9
Be with embodiment 1 difference: organic ion liquid is with [Bmim] BF
4Replacement [Bmim] Br.
Embodiment 10
Be with embodiment 1 difference: organic ion liquid is with [Bmim] OTf replacement [Bmim] Br.
Embodiment 11
Be with embodiment 1 difference: auxiliary agent is with N`N-dimethyl formamide replacement N-methyl pyrrolidone, and organic ion liquid is with [Bmim] BF
6Replacement [Bmim] Br.
Embodiment 12
Be with embodiment 1 difference: auxiliary agent is with N`N-dimethyl formamide replacement N-methyl pyrrolidone, and organic ion liquid is with [Bmim] [lactate] replacement [Bmim] Br.
Embodiment 13
Be with embodiment 1 difference: auxiliary agent is replaced methylamine hydrochloride with N`N-dimethyl formamide replacement N-methyl pyrrolidone with diethylamine hydrochloride.
Claims (5)
1. one kind is used for the catalyst that the acetylene trimerization prepares divinylacetylene; It is characterized in that; This catalyst is made up of stannous chloride, organic ion liquid, organic amine salt hydrochlorate and auxiliary agent; Said auxiliary agent is N`N-dimethyl formamide or N-methyl pyrrolidone, and wherein the mass ratio of stannous chloride, organic ion liquid, organic amine salt hydrochlorate and auxiliary agent is 5.3:0.2-1.5:2.0-5.3:4.1-8.5.
2. be used for the catalyst that the acetylene trimerization prepares divinylacetylene according to claim 1, it is characterized in that, said organic ion liquid is [Bmim] Cl, [Bmim] Br, [Bmim] BF
4, [Bmim] PF
6, [Bmim] OTf or [Bmim] [lactate].
3. be used for the catalyst that the acetylene trimerization prepares divinylacetylene according to claim 1, it is characterized in that, said organic amine salt hydrochlorate is methylamine hydrochloride, dimethylamine hydrochloride, ethylamine hydrochloride, diethylamine hydrochloride or triethylamine hydrochloride.
4. utilize the method for the said Preparation of Catalyst divinylacetylene of claim 1, it is characterized in that, comprise the steps:
1. under 40-60 ℃ of condition, in bubbling reactor, feed nitrogen, add organic amine salt hydrochlorate, organic ion liquid and auxiliary agent in proportion, after mixing, seal this bubbling reactor, continue to feed nitrogen with deaeration with deaeration;
2. be warming up to 60～100 ℃, add stannous chloride in proportion, continue to feed nitrogen, bubbling stirs it is dissolved fully;
3. after treating the raw material blending in the bubbling reactor, replace nitrogen with acetylene, under 60～100 ℃ of conditions, continue the bubbling stirring reaction, get divinylacetylene, wherein the acetylene air speed is 100～150h
-1
5. the said method for preparing divinylacetylene of claim 4 is characterized in that, said step 3. in before reaction, catalyst is activation 3 h under acetylene atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100608573A CN102614929A (en) | 2012-03-09 | 2012-03-09 | Catalyst for preparing divinylacetylene by acetylene trimerization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100608573A CN102614929A (en) | 2012-03-09 | 2012-03-09 | Catalyst for preparing divinylacetylene by acetylene trimerization |
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|---|---|
| CN102614929A true CN102614929A (en) | 2012-08-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185562A (en) * | 2017-05-27 | 2017-09-22 | 北京华福工程有限公司 | A kind of catalyst reacted for acetylene dimer and its preparation method and application |
| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB384654A (en) * | 1931-05-27 | 1932-11-28 | Du Pont | Improvements in and relating to acetylene reactions |
| CN101786022A (en) * | 2010-03-17 | 2010-07-28 | 重庆大学 | Catalyst for preparing vinyl acetylene and application method thereof |
-
2012
- 2012-03-09 CN CN2012100608573A patent/CN102614929A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB384654A (en) * | 1931-05-27 | 1932-11-28 | Du Pont | Improvements in and relating to acetylene reactions |
| CN101786022A (en) * | 2010-03-17 | 2010-07-28 | 重庆大学 | Catalyst for preparing vinyl acetylene and application method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185562A (en) * | 2017-05-27 | 2017-09-22 | 北京华福工程有限公司 | A kind of catalyst reacted for acetylene dimer and its preparation method and application |
| CN107185562B (en) * | 2017-05-27 | 2019-10-29 | 北京华福工程有限公司 | A kind of catalyst and its preparation method and application for acetylene dimer reaction |
| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN113559924B (en) * | 2021-07-28 | 2023-10-03 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
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Application publication date: 20120801 |