CN105439801B - The preparation method of hexamethylene - Google Patents
The preparation method of hexamethylene Download PDFInfo
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- CN105439801B CN105439801B CN201410427734.8A CN201410427734A CN105439801B CN 105439801 B CN105439801 B CN 105439801B CN 201410427734 A CN201410427734 A CN 201410427734A CN 105439801 B CN105439801 B CN 105439801B
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Abstract
The present invention relates to a kind of preparation method of hexamethylene, mainly solves operating condition harshness, the longer technical problem of flow in the technology of existing producing cyclohexane by adding hydrogen in benzene.The present invention is using the material rich in methyl cyclopentane as raw material, raw material and catalyst haptoreaction generation hexamethylene at 50~100 DEG C, wherein used catalyst is at least one of anhydrous aluminum halide, reaction raw materials and the technical scheme that catalyst weight ratio is 1~10 preferably solve the problem, can apply in the industrial production of hexamethylene.
Description
Technical field
The present invention relates to a kind of hexamethylene preparation method.
Background technology
Hexamethylene is the primary raw material for manufacturing cyclohexanol and cyclohexanone, and further produces adipic acid and acyl in oneself
Amine, they are the primary raw materials for producing polyamide and nylon.In addition, hexamethylene is also used as industrial solvent on a small quantity.
Hexamethylene is initially to be directly separated acquisition by crude distillation to carry out industrial, but its purity is only 85% left
It is right.Henry boolean oil company of the U.S. and Philips Petroleum Co. report a kind of light fraction oil by petroleum distillate through overweight
After the series of steps such as whole, rectifying, hydrogenation and isomery, the method for wherein methyl cyclopentane isomerization generation hexamethylene can obtain
The higher hexamethylene of purity is obtained, but product purity can not meet the needs of polyamide production.
With the development that polyamide produces, hexamethylene requirement is increased rapidly, therefore is obtained with producing cyclohexane by adding hydrogen in benzene
To developing rapidly, this method is big in 150~250 DEG C and 23~53 typically using nickel as catalyst (CN1546230, CN1210759)
Under air pressure, benzene hydrogenation generation hexamethylene.Also there is the method that producing cyclohexane by benzene hydrogenation is carried out using noble metal catalyst
(CN1457923).Hexamethylene yield is produced close to 100% using benzene hydrogenation method, and product purity is very high, is current production hexamethylene
The main method of alkane, but this method has the shortcomings that operating condition is harsh, and flow is longer.
The content of the invention
The technical problems to be solved by the invention be existing producing cyclohexane by adding hydrogen in benzene technology in operating condition it is harsh, stream
A kind of longer technical problem of journey, there is provided new hexamethylene production method.This method has that catalyst price is low, reaction condition temperature
And the advantages of.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of preparation method of hexamethylene, with richness
Material containing methyl cyclopentane is reaction raw materials, reaction raw materials and catalyst haptoreaction generation hexamethylene at 50~100 DEG C,
Wherein used catalyst is at least one of anhydrous aluminum halide, and reaction raw materials and catalyst weight ratio are 1~10.
In above-mentioned technical proposal, at least one in the preferred anhydrous Aluminum chloride of anhydrous aluminum halide catalyst or ALUMINIUM BROMIDE ANHYDROUS
Kind.More preferably using anhydrous Aluminum chloride and the mixture of ALUMINIUM BROMIDE ANHYDROUS, now there is more preferable selectivity to n-hexane.When
During using the mixture of anhydrous Aluminum chloride and ALUMINIUM BROMIDE ANHYDROUS, the weight ratio preferably 0.5 of anhydrous Aluminum chloride and ALUMINIUM BROMIDE ANHYDROUS~
2。
In above-mentioned technical proposal, reaction temperature is preferably 50~100 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably self-formed from reaction pressure.
In above-mentioned technical proposal, the methyl cyclopentane content in reaction raw materials is preferably 20~100wt%.
In above-mentioned technical proposal, the weight ratio preferably 1~10 of reaction raw materials and anhydrous aluminum halide catalyst.
In above-mentioned technical proposal, it is preferred to use tank reactor is reacted.
In above-mentioned technical proposal, it is preferred to use stirring makes reaction raw materials be sufficiently mixed with catalyst.
In above-mentioned technical proposal, mixing speed is preferably 100~1000 revs/min.
In above-mentioned technical proposal, the reaction time is preferably 1~24 hour.
The most important reaction that the invention is related to is methyl cyclopentane isomerization ring expansion generation hexamethylene, methyl cyclopentane
Ring expansion isomerization reaction meets carbonium ion mechanism, and the rate-determining steps of the reaction are the generations of methyl cyclopentane carbonium ion,
So the higher strong acid center of density is advantageous to the progress of the reaction.In addition, the isomery between methyl cyclopentane and hexamethylene is anti-
Reversible reaction is should be, and is limited by thermodynamical equilibrium, the equilibrium concentration of hexamethylene is higher at a lower temperature, if reaction temperature
Reach balance less than 80 DEG C, the conversion ratio of methyl cyclopentane can reach more than 70%.Anhydrous aluminum halide is typical Louis
Acid catalyst, carbonium ion intermediate is combined to form with methyl cyclopentane in the reaction, methyl can be promoted in a mild condition
The isomerization reaction generation hexamethylene of pentamethylene.Compared with benzene hydrogenating catalyst, anhydrous aluminum halide catalyst price is relatively low, has
Larger advantage.
Using method provided by the invention, under catalyst action, reaction temperature (T) is 50~100 DEG C, reaction pressure
(P) be normal pressure or self-formed from reaction pressure, methyl cyclopentane (MCP) content in reaction raw materials is 20~100%, reaction raw materials with
The weight ratio (R) of anhydrous aluminum halide catalyst is 1~10, is reacted using tank reactor, makes reaction raw materials using stirring
It is sufficiently mixed with catalyst, mixing speed is 100~1000 revs/min (rpm), under the reaction time (t) 1~24 hour (h)
The conversion ratio of methyl cyclopentane is more than 60%, and hexamethylene (CH) selectivity of product is more than 99%, and reaction condition is gentle, product yield
Height, achieve good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
In the closed tank reactors of 50ml, in anhydrous Aluminum chloride (AlCl3) under catalyst action, reaction temperature 100
DEG C, using methyl cyclopentane as reaction raw materials, reaction raw materials and AlCl3Weight than 10, mixing speed be 1000 revs/min, instead
The conversion ratio of methyl cyclopentane is 63.2% after answering 24 hours, and cyclohexane product is selectively 99.1%.
For ease of comparing, catalyst, reaction condition and reaction result are listed in table 1.
【Embodiment 2】
In the closed tank reactors of 50ml, in anhydrous Aluminum chloride (AlCl3) under catalyst action, reaction temperature 70
DEG C, using methyl cyclopentane as reaction raw materials, reaction raw materials and AlCl3Weight than 3, mixing speed be 800 revs/min, reaction
The conversion ratio of methyl cyclopentane is 74.2% after 18 hours, and cyclohexane product is selectively 99.2%.
For ease of comparing, catalyst, reaction condition and reaction result are listed in table 1.
【Embodiment 3】
In the closed tank reactors of 50ml, in anhydrous Aluminum chloride (AlCl3) under catalyst action, reaction temperature 50
DEG C, using methyl cyclopentane as reaction raw materials, reaction raw materials and AlCl3Weight than 1, mixing speed be 1000 revs/min, reaction
The conversion ratio of methyl cyclopentane is 80.5% after 20 hours, and cyclohexane product is selectively 99.1%.
For ease of comparing, catalyst, reaction condition and reaction result are listed in table 1.
【Embodiment 4】
In the closed tank reactors of 50ml, in anhydrous Aluminum chloride (AlCl3) under catalyst action, reaction temperature 60
DEG C, to be the richest in cyclopentane as reaction raw materials (wherein for methyl cyclohexane weight content for 20%, remaining is n-hexane), reaction is former
Material and AlCl3Weight than 1, mixing speed is 500 revs/min, and the conversion ratio of methyl cyclopentane is after reaction 10 hours
70.0%, cyclohexane product is selectively 99.3%.
For ease of comparing, catalyst, reaction condition and reaction result are listed in table 1.
【Embodiment 5】
In the closed tank reactors of 50ml, in ALUMINIUM BROMIDE ANHYDROUS (AlBr3) under catalyst action, reaction temperature 70
DEG C, using methyl cyclopentane as reaction raw materials, reaction raw materials and AlBr3Weight than 3, mixing speed be 800 revs/min, reaction
The conversion ratio of methyl cyclopentane is 60.5% after 18 hours, and cyclohexane product is selectively 99.4%.
For ease of comparing, catalyst, reaction condition and reaction result are listed in table 1.
【Embodiment 6】
In the closed tank reactors of 50ml, in ALUMINIUM BROMIDE ANHYDROUS (AlBr3) under catalyst action, reaction temperature 72
DEG C, using methyl cyclopentane as reaction raw materials, reaction raw materials and AlBr3Weight than 1, mixing speed be 100 revs/min, reaction
The conversion ratio of methyl cyclopentane is 64.4% after 24 hours, and cyclohexane product is selectively 99.5%.
For ease of comparing, catalyst, reaction condition and reaction result are listed in table 1.
【Embodiment 7】
In the closed tank reactors of 50ml, in ALUMINIUM BROMIDE ANHYDROUS (AlBr3) under catalyst action, reaction temperature 70
DEG C, it is reaction to be the richest in cyclopentane as reaction raw materials (wherein for methyl cyclohexane weight content for 60%, remaining is normal heptane)
Raw material, reaction raw materials and AlBr3Weight than 4, mixing speed is 1000 revs/min, methyl cyclopentane after reaction 24 hours
Conversion ratio is 70.9%, and cyclohexane product is selectively 99.1%.
For ease of comparing, catalyst, reaction condition and reaction result are listed in table 1.
【Embodiment 8】
In the closed tank reactors of 50ml, in anhydrous Aluminum chloride (AlCl3) and ALUMINIUM BROMIDE ANHYDROUS (AlBr3) mix and urge
(weight is than 1 for agent：1) under acting on, reaction temperature is 70 DEG C, and using methyl cyclopentane as reaction raw materials, reaction raw materials are urged with mixing
For the weight of agent than 3, mixing speed is 800 revs/min, and the conversion ratio of methyl cyclopentane is 68.7% after reacting 18 hours, ring
Hexane selectivity of product is 99.6%.
For ease of comparing, catalyst, reaction condition and reaction result are listed in table 1.
Table 1
Note：R represents the weight ratio of reaction raw materials and catalyst in table.
Claims (5)
1. the preparation method of hexamethylene, using the material rich in methyl cyclopentane as reaction raw materials, the reaction raw materials at 50~100 DEG C
Hexamethylene is generated with catalyst haptoreaction, wherein used catalyst is at least one of anhydrous aluminum halide, and reaction raw materials are with urging
Agent part by weight is 1~10；
Wherein, reaction raw materials are made to be sufficiently mixed with catalyst using stirring, mixing speed is 100~1000 revs/min；
Wherein, the reaction time is 1~24 hour.
2. the preparation method of hexamethylene according to claim 1, it is characterised in that anhydrous aluminum halide catalyst selects anhydrous chlorine
Change at least one of aluminium or ALUMINIUM BROMIDE ANHYDROUS.
3. the preparation method of hexamethylene according to claim 1, it is characterised in that reaction pressure is self-formed from reaction pressure.
4. the preparation method of hexamethylene according to claim 1, it is characterised in that the methyl cyclopentane content in reaction raw materials
For 20~100wt%.
5. the preparation method of hexamethylene according to claim 1, it is characterised in that reacted using tank reactor.
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| CN112573981B (en) * | 2019-09-30 | 2023-04-07 | 中国石油化工股份有限公司 | Process for the preparation of cyclohexane |
| CN112573989A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Preparation method and preparation device of halogen-free cyclohexane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329585A (en) * | 1998-12-01 | 2002-01-02 | 菲利浦石油公司 | Isomerization method of hydrocarbons |
| CN101851530A (en) * | 2009-03-31 | 2010-10-06 | 中国石油化工股份有限公司 | Paraffin isomerization method of reducing benzene content |
| CN102666448A (en) * | 2009-12-07 | 2012-09-12 | 巴斯夫欧洲公司 | Method for isomerizing a saturated, branched, and cyclical hydrocarbon |
-
2014
- 2014-08-27 CN CN201410427734.8A patent/CN105439801B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329585A (en) * | 1998-12-01 | 2002-01-02 | 菲利浦石油公司 | Isomerization method of hydrocarbons |
| CN101851530A (en) * | 2009-03-31 | 2010-10-06 | 中国石油化工股份有限公司 | Paraffin isomerization method of reducing benzene content |
| CN102666448A (en) * | 2009-12-07 | 2012-09-12 | 巴斯夫欧洲公司 | Method for isomerizing a saturated, branched, and cyclical hydrocarbon |
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