CN101643379A - Preparation method of high-purity 1,3-pentadiene - Google Patents
Preparation method of high-purity 1,3-pentadiene Download PDFInfo
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- CN101643379A CN101643379A CN200910018227A CN200910018227A CN101643379A CN 101643379 A CN101643379 A CN 101643379A CN 200910018227 A CN200910018227 A CN 200910018227A CN 200910018227 A CN200910018227 A CN 200910018227A CN 101643379 A CN101643379 A CN 101643379A
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Abstract
The invention relates to a preparation method of high-purity 1,3-pentadiene, belonging to the technical field of chemical industry. Byproduct C-5 fractions of ethylene, which is prepared by petroleumcracking, are taken as raw materials and polymerized by a polymerization tank and enter an extraction tower to be extracted and separated, and materials taking the 1,3-pentadiene and an extracting agent as main materials are obtained in a tower kettle and finally enter a resolving tower to be resolved and rectified so as to obtain a high-purity 1,3-pentadiene product. The invention prepares the high-purity 1,3-pentadiene, also obtains a mixture of cyclopentene and cyclopentane with higher application additional values and has high purification precision and easy industrialization performance.
Description
(1) technical field
The invention belongs to chemical technology field, particularly a kind of preparation method of high purity m-pentadiene.
(2) background technology
The a considerable amount of C of by-product in the process of petroleum cracking system ethene
5Fraction, C
5Be rich in diolefins such as isoprene, cyclopentadiene and m-pentadiene in the fraction.These diolefin chemical property are active, are the valuable sources of chemical utilization.With the difference on hydrocarbon cracking raw material, cracking severity and the separation degree, C
5Diolefin content can be different in the fraction, but total content is between 40～60%.Therefore, separation utilizes C
5Fraction is for the economic benefit that improves ethylene unit, and the comprehensive utilization petroleum resources have far reaching significance.
Both at home and abroad early to the diolefin development and use, particularly isoprene, cyclopentadiene (dicyclopentadiene) are widely used, because m-pentadiene purity is usually between 65%～70%, and contain 20%～25% cyclopentenes, pentamethylene component, cyclopentadiene about 2% and alkynes composition, neither easily separatedly go out the high purity m-pentadiene, have influence on the polymerization of m-pentadiene again, kill catalyzer.Usually can only be used for making m-pentadiene petro-resin, comprehensive utilization value is single, if can further purify to the high purity m-pentadiene more than 95%, removes alkynes and cyclopentadiene, then can be as the synthetic rubber raw material, and using value improves greatly.
(3) summary of the invention
The present invention provides a kind of preparation method that can improve yield and reclaim the high purity m-pentadiene of pentamethylene and cyclopentenes in order to remedy the deficiencies in the prior art.
The present invention is achieved through the following technical solutions:
A kind of preparation method of high purity m-pentadiene is a raw material with the C 5 fraction of petroleum cracking ethylene by-product, it is characterized in that: comprise the steps:
(1) C 5 fraction enters polymerization tank and carries out polymerization, and feeding temperature is 20～40 ℃, and polymerization time is 20～50 hours, 70～130 ℃ of polymerization temperatures, and by gas chromatographic detection as can be known, the content of cyclopentadiene is between 0.05～0.08 in the C 5 fraction after polymerization;
(2) C 5 fraction that comes out from polymerization tank enters extraction tower and carries out extracting and separating, the extractant feed temperature is 20～100 ℃, the input material volume ratio of C 5 fraction and extraction agent is 1: 4～15, working pressure is 0～0.25MPa, tower still temperature is 60～160 ℃, tower top temperature is 39～58 ℃, the cat head rate of distillating is 10～60%, reflux ratio is 5～35, cat head obtains the hydrocarbon mixture based on cyclopentenes and pentamethylene, the tower still obtains the material based on m-pentadiene and extraction agent, and extraction agent is dimethyl formamide, acetonitrile, N-Methyl pyrrolidone, N-N-formyl morpholine N-;
(3) tower still material enters Analytic Tower and resolves rectifying in the step (2), and working pressure is 0～0.25MPa, and tower still temperature is 100～200 ℃, tower top temperature is 35～55, and reflux ratio is 1～7, and cat head obtains the high purity m-pentadiene, the tower still obtains extraction agent, and extraction agent is capable of circulation to be applied mechanically.
Preferred process of the present invention is:
In the step (1), described polymerization time is 24～36 hours, and polymerization temperature is 100～120 ℃; In the step (2), described extractant feed temperature is 35～70 ℃, and the input material volume ratio of C 5 fraction and extraction agent is 1: 6～12, tower still temperature is 90～140 ℃, and tower top temperature is 44～49 ℃, and working pressure is a normal pressure, the cat head rate of distillating is 25～40%, and extraction agent is a dimethyl formamide; In the step (3), described tower still temperature is 135～165, and tower top temperature is 39～43 ℃, and working pressure is a normal pressure, and reflux ratio is 2～5.
(volume fraction) composed as follows of the C 5 fraction of petroleum cracking system ethylene by-product:
Isoprene: 2.2455%; 2-amylene: 0.4379%; 2-methyl-2-butene: 0.7051%; M-pentadiene: 68.4548%; Cyclopentadiene: 0.3456%; Cyclopentenes: 15.9485%; Pentamethylene: 8.3947%; C6 heavy constituent: 0.5%.
The relative volatility of material component in the presence of solvent sees Table 1.
Table 1:
| Form | Boiling point (℃) | Solvent-free | Dimethyl formamide |
| Isoprene | ??34.07 | ??1 | ??1 |
| The 2-amylene | ??36.35 | ??0.930 | ??1.605 |
| The 2-methyl-2-butene | ??18.57 | ??0.867 | ??1.396 |
| Instead-1,3-pentadiene | ??42.03 | ??0.775 | ??0.763 |
| Suitable-1,3-pentadiene | ??44.07 | ??0.725 | ??0.706 |
| Cyclopentadiene | ??42.50 | ??0.811 | ??0.623 |
| Cyclopentenes | ??44.24 | ??0.719 | ??0.914 |
| Pentamethylene | ??49.26 | ??0.610 | ??1.166 |
Adopt method of the present invention to obtain (volume fraction) composed as follows of product:
M-pentadiene＞95%, cyclopentenes+pentamethylene: 2%, cyclopentadiene＜5ppm, sulphur content＜20ppm, heavy constituent: 2%, alkynes＜50ppm.
In sum, the present invention has obtained the high purity m-pentadiene more than 95% with higher yield, wherein cyclopentadiene content is less than 5ppm, and obtained using the higher cyclopentenes of added value and the mixture of pentamethylene, preparation high purity m-pentadiene possesses purification precision height, is easy to industrialized advantage from the m-pentadiene raw material.
The present invention takes first polymerization, the method for one-time extractive rectification then, and preparation high purity m-pentadiene from raw material has purification precision height, is easy to the advantage of suitability for industrialized production.
(4) description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is a technological process apparatus synoptic diagram of the present invention;
Fig. 2 is a process flow sheet of the present invention.
(5) embodiment
Embodiment 1:
C 5 fraction enters polymerization tank, and feeding temperature is 20 ℃, and polymerization temperature is 70 ℃, and polymerization time is 24 hours.C 5 fraction after polymerization enters extractive distillation column, 25 ℃ of feeding temperatures, working pressure 0.1MPa, reflux ratio 7, be preheated to 60 ℃ earlier before the extraction agent dimethyl formamide charging that cat head adds, with the material quantity volume ratio for being 4: 1, the removed overhead cyclopentenes, pentamethylene and light constituent, tower still obtain extraction agent and m-pentadiene material, to extract Tata still material and enter Analytic Tower, working pressure is a normal pressure, and tower still temperature is 120 ℃, and tower top temperature is 39 ℃, reflux ratio is 1, cat head obtains high purity m-pentadiene and a small amount of cyclopentenes, pentamethylene, the tower still obtains extraction agent, the extraction agent recycled.Resultant high purity m-pentadiene volume content is as follows: m-pentadiene＞95%, cyclopentenes+pentamethylene＜2%, cyclopentadiene＜5ppm, sulphur content＜20ppm, heavy constituent＜2%, alkynes＜50ppm.
Embodiment 2:
C 5 fraction enters polymerization tank, and feeding temperature is 30 ℃, and polymerization temperature is 100 ℃, and polymerization time is 30 hours.C 5 fraction after polymerization enters extractive distillation column, 20 ℃ of feeding temperatures, working pressure 0.15MPa, reflux ratio 8, be preheated to 70 ℃ earlier before the extraction agent dimethyl formamide charging that cat head adds, with the material quantity volume ratio for being 5: 1, the removed overhead cyclopentenes, pentamethylene and light constituent, tower still obtain extraction agent and m-pentadiene material, to extract Tata still material and enter Analytic Tower, working pressure is a normal pressure, and tower still temperature is 140 ℃, and tower top temperature is 41 ℃, reflux ratio is 2, cat head obtains high purity m-pentadiene and a small amount of cyclopentenes, pentamethylene, the tower still obtains extraction agent, the extraction agent recycled.Resultant high purity m-pentadiene volume content is as follows: m-pentadiene＞95%, cyclopentenes+pentamethylene＜2%, cyclopentadiene＜5ppm, sulphur content＜20ppm, heavy constituent＜2%, alkynes＜50ppm.
Embodiment 3:
C 5 fraction enters polymerization tank, and feeding temperature is 40 ℃, and polymerization temperature is 130 ℃, and polymerization time is 36 hours.C 5 fraction after polymerization enters extractive distillation column, 20 ℃ of feeding temperatures, working pressure 0.20MPa, reflux ratio 9, the extraction agent dimethyl formamide feeding temperature that cat head adds is preheated to 75 ℃ earlier, with the material quantity volume ratio for being 6: 1, the removed overhead cyclopentenes, pentamethylene and light constituent, tower still obtain extraction agent and m-pentadiene material, to extract Tata still material and enter Analytic Tower, working pressure is a normal pressure, and tower still temperature is 160 ℃, and tower top temperature is 42 ℃, reflux ratio is 3, cat head obtains high purity m-pentadiene and a small amount of cyclopentenes, pentamethylene, the tower still obtains extraction agent, the extraction agent recycled.Resultant high purity m-pentadiene volume content is as follows: m-pentadiene＞95%, cyclopentenes+pentamethylene＜2%, cyclopentadiene＜5ppm, sulphur content＜20ppm, heavy constituent＜2%, alkynes＜50ppm.
Claims (8)
1. the preparation method of a high purity m-pentadiene is a raw material with the C 5 fraction of petroleum cracking ethylene by-product, it is characterized in that: comprise the steps:
(1) C 5 fraction enters polymerization tank and carries out polymerization, and feeding temperature is 20～40 ℃, and polymerization time is 20～50 hours, 70～130 ℃ of polymerization temperatures;
(2) C 5 fraction that comes out from polymerization tank enters extraction tower and carries out extracting and separating, the extractant feed temperature is 20～100 ℃, the input material volume ratio of C 5 fraction and extraction agent is 1: 4～15, working pressure is 0～0.25MPa, tower still temperature is 60～160 ℃, tower top temperature is 39～58 ℃, the cat head rate of distillating is 10～60%, reflux ratio is 5～35, cat head obtains the hydrocarbon mixture based on cyclopentenes and pentamethylene, the tower still obtains the material based on m-pentadiene and extraction agent, and extraction agent is dimethyl formamide, acetonitrile, N-Methyl pyrrolidone, N-N-formyl morpholine N-;
(3) tower still material enters Analytic Tower and resolves rectifying in the step (2), and working pressure is 0～0.25MPa, and tower still temperature is 100～200 ℃, and tower top temperature is 35～55 ℃, and reflux ratio is 1～7, and cat head obtains the high purity m-pentadiene, and the tower still obtains extraction agent.
2. the preparation method of high purity m-pentadiene according to claim 1 is characterized in that: in the step (1), described polymerization time is 24～36 hours, and polymerization temperature is 100～120 ℃.
3. the preparation method of high purity m-pentadiene according to claim 1 and 2 is characterized in that: in the step (2), described extractant feed temperature is 35～70 ℃.
4. the preparation method of high purity m-pentadiene according to claim 1 and 2 is characterized in that: in the step (2), the input material volume ratio of described C 5 fraction and extraction agent is 1: 6～12.
5. the preparation method of high purity m-pentadiene according to claim 1 and 2 is characterized in that: in the step (2), described tower still temperature is 90～140 ℃, and tower top temperature is 44～49 ℃, and working pressure is a normal pressure.
6. the preparation method of high purity m-pentadiene according to claim 1 and 2 is characterized in that: in the step (2), the described cat head rate of distillating is 25～40%
7. the preparation method of high purity m-pentadiene according to claim 1 and 2 is characterized in that: in the step (2), described extraction agent is a dimethyl formamide.
8. the preparation method of high purity m-pentadiene according to claim 1 and 2 is characterized in that: in the step (3), described tower still temperature is 135～165 ℃, and tower top temperature is 39～43 ℃, and working pressure is a normal pressure, and reflux ratio is 2～5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418695A (en) * | 2013-08-23 | 2015-03-18 | 中国石油天然气股份有限公司 | Method for preparing polymer-grade piperylene by acetonitrile method |
| CN104558327A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Polypentadiene and preparation method thereof |
| CN104725182A (en) * | 2015-02-04 | 2015-06-24 | 新疆独山子天利实业总公司 | Purification method of m-pentadiene crude product separated from byproduct C5 in ethylene preparation process by petroleum cracking |
| CN105481631A (en) * | 2014-09-19 | 2016-04-13 | 中国石油化工股份有限公司 | Rectification method for 1,3-piperlene |
| CN105585412A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing polymer-grade piperylene |
-
2009
- 2009-08-31 CN CN200910018227A patent/CN101643379A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418695A (en) * | 2013-08-23 | 2015-03-18 | 中国石油天然气股份有限公司 | Method for preparing polymer-grade piperylene by acetonitrile method |
| CN104418695B (en) * | 2013-08-23 | 2017-03-01 | 中国石油天然气股份有限公司 | Method for preparing polymer-grade piperylene by acetonitrile method |
| CN104558327A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Polypentadiene and preparation method thereof |
| CN104558327B (en) * | 2013-10-17 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of poly- pentadiene and preparation method thereof |
| CN105481631A (en) * | 2014-09-19 | 2016-04-13 | 中国石油化工股份有限公司 | Rectification method for 1,3-piperlene |
| CN105481631B (en) * | 2014-09-19 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of process for purification of pentadiene |
| CN105585412A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing polymer-grade piperylene |
| CN104725182A (en) * | 2015-02-04 | 2015-06-24 | 新疆独山子天利实业总公司 | Purification method of m-pentadiene crude product separated from byproduct C5 in ethylene preparation process by petroleum cracking |
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Application publication date: 20100210 |