CN1137072C - Process for separating mixture containing 4-methyl-1-pentene and 4-methyl-2-pentene - Google Patents

Process for separating mixture containing 4-methyl-1-pentene and 4-methyl-2-pentene Download PDF

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CN1137072C
CN1137072C CNB001321617A CN00132161A CN1137072C CN 1137072 C CN1137072 C CN 1137072C CN B001321617 A CNB001321617 A CN B001321617A CN 00132161 A CN00132161 A CN 00132161A CN 1137072 C CN1137072 C CN 1137072C
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methyl
pentene
amylene
separation method
compound
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CN1359885A (en
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张明森
柯丽
杨菁
冯炎
贺黎明
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
China Petrochemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention discloses a method for separating 4-methyl-1-pentene from 4-methyl-2-pentene. The difference of the relative volatility of 4-methyl-1-pentene, cis-4-methyl-2-pentene and trans-4-methyl-2-pentene is changed by adding one or a plurality of third components additionally, and the separation efficiency of the components is improved. After the separation of one component in the components reaches certain requirements, and the added third components are respectively separated from another two components.

Description

A kind of separating mixture that contains 4-methyl-1-pentene and 4-methyl-2-amylene
The present invention relates to a kind of method that is used to separate the close material of boiling point, specifically, the present invention relates to the separation method of 4-methyl-1-pentene and 4-methyl-2-amylene in a kind of propylene dimerization product.
4-methyl-1-pentene (being called for short 4MP1) is the very excellent high alpha-olefin of a kind of performance.As a kind of polymerization single polymerization monomer, it both can homopolymerization prepare poly(4-methyl-1-pentene), also can prepare linear low density polyethylene (LLDPE) with ethylene copolymer.The moulded parts of poly(4-methyl-1-pentene) has high-clarity, high heat-resisting, high impact properties, electrical specification is good and resistance to chemical attack, advantage such as nontoxic, therefore be widely used in fields such as optics, medicine equipment, automobile, aviation, have very high using value.Indexs such as the shock resistance of linear low density polyethylene (LLDPE), tear strength, optical property all are better than the linear low density polyethylene with the preparation of 1-butylene or 1-alkene.
At present, unique method that can adapt to the large-scale commercial production 4-methyl-1-pentene is a propylene dimerization.In fixed-bed reactor, sodium and/or the potassium catalyzer generation selective dimerisation reaction of working load on salt of wormwood or graphite obtains the dimerisation products 4-methyl-1-pentene.Also carried out more research for the method for the synthetic 4-methyl-1-pentene of propylene dimerization abroad, as US2986588, GB912824, GB933253, EP083083, clear 58-14736, clear 58-114737, clear 58-114738, flat 3-2043 or the like.
Prepare in the process of 4-methyl-1-pentene at propylene dimerization, can produce more by product, as cis and trans 4-methyl-2-amylene (being called for short 4MP2), 1-hexene, cis and trans 2-hexene etc.Therefore, must separate, just can obtain meeting the 4-methyl-1-pentene of purity requirement product.Present industrial separation 4-methyl-1-pentene generally all adopts rectification method.But in above-mentioned by product, cis and trans 4-methyl-2-amylene are because very close with the 4-methyl-1-pentene structure, and it is very little that boiling point differs, and therefore separate 4-methyl-1-pentene and 4-methyl-2-amylene and be the emphasis in the sepn process of propylene dimerization product.
Table 1 has been listed the boiling point of related substance in the propylene dimerization product.Table 1
The material title Boiling point/℃
4～Methyl-1-pentene 53.88
Suitable, 4-methyl-2-amylene 56.30
Instead, 4-methyl-2-amylene 58.55
The 1-hexene 63.49
Suitable, the 2-hexene 68.84
Instead, 2-hexene 67.87
2,3-dimethyl-1-butylene 56
2,3-dimethyl-2-butylene 73
The 4-methyl-1-pentene boiling point is 53.88 ℃, and the boiling point of suitable 4-methyl-2-amylene is 56.3 ℃, only differs 2.42 ℃.If 4-methyl-1-pentene and suitable-4-methyl-2-amylene are handled as true liquid, 95% 4-methyl-1-pentene and suitable-4-methyl of 5%-2-amylene simulation mixture passes through rectifying separation, obtain 99.5% 4-methyl-1-pentene at cat head, obtain suitable-4-methyl-2-amylene of 99.0% at the bottom of tower, its rectifying tower needs 107 blocks of theoretical trays approximately as calculated.The way that present industrial separation 4-methyl-1-pentene and 4-methyl-2-amylene adopts is to use a plurality of super rectifying tower,
The object of the present invention is to provide the separation method of a kind of 4-methyl-1-pentene and 4-methyl-2-amylene.
To describe technical scheme of the present invention in detail below.
The present invention improves the separation efficiency of described component by adding another or multiple the 3rd component to change 4-methyl-1-pentene and suitable, anti--4-methyl-relative volatility difference of 2-amylene.
Separation method of the present invention increases the difference of the relative volatility of 4-methyl-1-pentene and 4-methyl-2-amylene, increased the separation efficiency of described two components, and after a kind of separation of component reached certain requirement therein, the 3rd component that will add again separated with other two components respectively.Can be on full scale plant according to the implantation site that adds of extraction agent, extraction agent and being separated on the same tower of a component are wherein finished.
The 3rd component wherein of the present invention can be a kind of in alcohol compound, tertiary amine compounds, halogenated hydrocarbon compound, aromatic hydrocarbons or the halogenated aryl hydrocarbon compounds or their mixture.
Wherein said alcohol compound can be represented with following general structure:
ROH
Wherein R is C 1-C 10Alkyl, preferred C 1-C 4Alkyl, most preferably be selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and the trimethyl carbinol.
Wherein said tertiary amine compounds can be represented with following general structure:
R 1R 2R 3N
R 1, R 2, R 3Identical or different, be selected from C 1-C 6Alkyl; Be preferably selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl.
Wherein said tertiary amine compounds most preferably is selected from Trimethylamine 99, triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine.
Wherein said halogenated hydrocarbon compound can be represented with following general structure:
(R 4)X n
Wherein said R 4Be C 1-C 6Alkyl, be preferably selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl.Wherein X is F, Cl or Br.N is the natural number that satisfies described halogenated hydrocarbon compound valence state.
Wherein said halogenated hydrocarbon compound most preferably uses methylene dichloride, trichloromethane, tetracol phenixin, monochloroethane, 1,2-ethylene dichloride, 1,1-ethylene dichloride, 1, vinyl trichloride, zellon.
Wherein said aromatic hydrocarbons or halogenated aryl hydrocarbon compounds can be represented with following general structure:
R wherein 5Can be selected from H, methyl, ethyl, propyl group, nitro, cyano group.N is the natural number of 1-6.
The 3rd component of the present invention should meet the following conditions:
1. described the 3rd component has and 4-methyl-1-pentene and the complete compatible character of 4-methyl-2-amylene.
2. it is enough big that the boiling point of described the 3rd component and 4-methyl-1-pentene and 4-methyl-2-amylene differs.
Compare with the separation method of 4-methyl-2-amylene with existing 4-methyl-1-pentene, the present invention has following beneficial effect:
1. the separation method of 4-methyl-1-pentene and 4-methyl-2-amylene adopts two super rectifying tower rectifying separation in the existing industrial production, and required column plate is more, and is all comparatively strict to the requirement of equipment and operational condition.And use method of the present invention, 4-methyl-1-pentene and 4-methyl-2-amylene separate and the 3rd component all only needs to use common separation column to finish with separating of above-mentioned two components.
2. use method of the present invention can significantly improve relative volatility poor of 4-methyl-1-pentene and 4-methyl-2-amylene, thereby improve the separation efficiency of 4-methyl-1-pentene and 4-methyl-2-amylene greatly.
3. use method of the present invention to improve the production efficiency of propylene dimerization.
4. owing to need not use super rectifying tower, the present invention is minimized the production cost of propylene dimerization.
Describe the present invention further below by embodiment, the present invention is more in depth understood with promotion.But the present invention is not subjected to the restriction of these embodiment.Those skilled in the art can make amendment or improve under the guide of spirit of the present invention the present invention, all belong to apparent.Protection scope of the present invention proposes in claims.
Embodiment
Comparative Examples 1
Will be by weight percentage, content is that 84.225% 4-methyl-1-pentene, content are that 4-methyl-2-amylene mixture 35ml of 15.775% joins in two mouthfuls of bottles of 100ml, be heated to boiling reflux, after waiting to reflux 1 hour, from sampling spot sampling analysis 4-methyl-1-pentene and 4-methyl-2-amylene content.Because the sample size of sampling spot is seldom, therefore, can think its liquid phase is formed influence not quite, ignore.The composition of this sample is the gas phase that balances each other with the raw material that adds and forms.The results are shown in Table 2.
Embodiment 1
Except that adding the 35ml tetracol phenixin in initial raw material, other condition is with comparative example 1.Experimental result sees Table 2.
Embodiment 2
Except that adding the 35ml benzene in initial raw material, other condition is with comparative example 1.Experimental result sees Table 2.
Embodiment 3
Except that adding the 35ml Virahol in initial raw material, other condition is with comparative example 1.Experimental result sees Table 2.
Embodiment 4
Except that adding the 35ml Tri-n-Propylamine in initial raw material, other condition is with comparative example 1.Experimental result sees Table 2.
Table 2 is that the gas phase behind adding the 3rd component is formed table.
Table 2
The 3rd component Gas phase is formed Gas phase is formed 4MP1 content increased value
4MP1 4MP2
Comparative Examples 1 86.8275 13.1725 2.6025％
Embodiment 1 Tetracol phenixin 89.2567 10.7433 5.0317％
Embodiment 2 Benzene 87.2968 12.7032 3.0718％
Embodiment 3 Virahol 87.4067 12.5993 2.8602％
Embodiment 4 Tri-n-Propylamine 87.0852 12.9148 2.8602％
The result shows: when not adding the 3rd component (Comparative Examples 1), the gas phase that balances each other with stock liquid consists of 4MP1:86.8275%, 4MP2:13.1725%, promptly represent effect through a theoretical stage, to consist of 4MP1:84.225%, the 4MP2:15.7755% mixture is purified to 4MP1:86.8275%, 4MP2:13.1725%.4MP1 content increased value is 2.6025 percentage points.When adding the 3rd component, after the separation through a theoretical stage, the increased value of 4MP1 content all has raising in various degree.It is the most obvious wherein to add tetracol phenixin, and the increased value of 4MP1 content is 5.0317%, is 1.93 times of added-time not.
Comparative Examples 2
Reaction conditions is with Comparative Examples 1, and only the initial material with Comparative Examples 1 changes in weight ratio, contains 4MP1:90.8767%, 4MP2:9.1233%.
Embodiment 5
Except that adding the 35ml zellon in initial raw material, other condition is with comparative example 2.Experimental result sees Table 3.
Embodiment 6
Remove in initial raw material and add outside 35ml 1,1,1 trichloroethane, other condition is with comparative example 2.Experimental result sees Table 3.
Embodiment 7
Remove and add 35ml 1 in initial raw material, outside the 2-propylene dichloride, other condition is with comparative example 2.Experimental result sees Table 3.
Embodiment 8
Except that adding the 35ml toluene in initial raw material, other condition is with comparative example 2.Experimental result sees Table 3.
Embodiment 9
Except that adding the 35ml oil of mirbane in initial raw material, other condition is with comparative example 2.Experimental result sees Table 3.
Table 3 is that the gas phase behind adding the 3rd component is formed table.
Table 3
The 3rd component Gas phase is formed Gas phase is formed 4MP1 content increased value
4MP1 4MP2
Comparative Examples 2 92.0782 7.9218 1.2015％
Embodiment 5 Zellon 92.6831 7.3169 1.8071％
Embodiment 6 1,1,1 trichloroethane 94.2449 5.7551 3.3682％
Embodiment 7 1, the 2-propylene dichloride 92.4547 7.5453 1.578％
Embodiment 8 Toluene 92.4314 7.5686 1.5547％
Embodiment 9 Oil of mirbane 92.7343 7.2657 2.8602％
The result shows, when not adding the 3rd component in initial material, through the separation of a theoretical stage, 4MP1 content brings up to 92.0782% from 90.87675%, has improved 1.2015%.After adding the 3rd component, the content improvement value of 4MP1 all has increase in various degree.Wherein, the most remarkable to add 1, the improvement value of 4MP1 is 3.3682%, is 2.8 times of added-time not.

Claims (6)

1. one kind contains 4-methyl-1-pentene and 4-methyl-2-amylene separating mixture, it is characterized in that, in the mixture of 4-methyl-1-pentene and 4-methyl-2-amylene, add the 3rd component, poor with the relative volatility that changes 4-methyl-1-pentene and 4-methyl-2-amylene;
Wherein said the 3rd component is in alcohol compound, tertiary amine compounds, halogenated hydrocarbon compound, aromatic hydrocarbons or the halogenated aryl hydrocarbon compounds-kind or their mixture;
Wherein said alcohol compound is represented with following general structure: ROH; Wherein R is C 1-C 10Alkyl;
Wherein said tertiary amine compounds is represented with following general structure:
R 1R 2R 3N
R 1, R 2, R 3Identical or different, be selected from C 1-C 6Alkyl;
Wherein said halogenated hydrocarbon compound is represented with following general structure:
(R 4)X n
R wherein 4Be C 1-C 6Alkyl; X is F, Cl or Br; N is the natural number that satisfies described halogenated hydrocarbon compound valence state;
Wherein said aromatic hydrocarbons or halogenated aryl hydrocarbon compounds are represented with following general structure:
Figure C0013216100021
R wherein 5Be selected from H, methyl, ethyl, propyl group, nitro, cyano group; N is the natural number of 1-6.
2. separation method according to claim 1 is characterized in that, R is C in the described alcohol compound 1-C 4Alkyl.
3. separation method according to claim 1 is characterized in that, described alcohol compound is for being selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol.
4. separation method according to claim 1 is characterized in that described tertiary amine compounds is selected from Trimethylamine 99, triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine.
5. separation method according to claim 1 is characterized in that, the R in the halogenated hydrocarbon compound 4Be selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl.
6. separation method according to claim 1 is characterized in that, halogenated hydrocarbon compound is selected from methylene dichloride, trichloromethane, tetracol phenixin, monochloroethane, 1,2-ethylene dichloride, 1,1-ethylene dichloride, 1, vinyl trichloride.
CNB001321617A 2000-12-19 2000-12-19 Process for separating mixture containing 4-methyl-1-pentene and 4-methyl-2-pentene Expired - Lifetime CN1137072C (en)

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