CN1445206A - Method for purifying and refining piperyene - Google Patents
Method for purifying and refining piperyene Download PDFInfo
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- CN1445206A CN1445206A CN 02111085 CN02111085A CN1445206A CN 1445206 A CN1445206 A CN 1445206A CN 02111085 CN02111085 CN 02111085 CN 02111085 A CN02111085 A CN 02111085A CN 1445206 A CN1445206 A CN 1445206A
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Abstract
A process for purifying pentadiene includes such steps as rectifying to remove heavy components, extraction rectifying under existance of polymerizing inhibitor for removing light components, and rectifying for removing extractant which can be reused. Its advantage is high purity of product.
Description
Technical field
The method that the petroleum cracking system of the present invention relates to ethylene by-product carbon five separates the further purification of m-pentadiene that obtains particularly is extraction agent carries out the extracting rectifying purification to above-mentioned m-pentadiene method with the dimethyl formamide.
Background technology
The a considerable amount of C 5 fractions of by-product are rich in diolefins such as isoprene, cyclopentadiene and m-pentadiene in the process of petroleum cracking system ethene in the C 5 fraction.These diolefin chemical property are active, are the valuable sources of chemical utilization.Since in three kinds of C 5 dienes the isoprene market development early and be widely used, so general C 5 fraction separation process scheme is only separated utilization isoprene wherein.Along with petrochemical complex, the particularly development of Speciality Petrochemicals, the applied research of m-pentadiene and dicyclopentadiene is also quite successful, its market requirement increases day by day, and therefore the technology of exploitation obtains m-pentadiene and dicyclopentadiene product with removing the further rectifying separation of heavy component material in the flow process in recent years.Contain plurality of impurities such as dicyclopentadiene, stopper and other polymkeric substance in the m-pentadiene product that is obtained by carbon five separating technologies, m-pentadiene concentration is about 75%.Because the purity of product is not high enough, can only be used for making m-pentadiene petro-resin usually, as more further more than the purification to 95%, then can be used as elastomeric raw material, it is worth greatly and improves.But other material and its boiling point that contain in the above-mentioned m-pentadiene raw material are very approaching, and common distillation technology can't be realized it is carried out purification.Can realize purification by precise distillation in theory, but rectifying tower requiring to have very high stage number and require that very large reflux ratio is arranged when operation, is very uneconomic industrial being applied.Patent US 4,031, and 151 propose to adopt adsorption separation technologies to come the purification m-pentadiene, but the surface acidity that the shortcoming of this method is sorbent material has katalysis, the easy inactivation of sorbent material to the polymerization of alkene, diolefin.In addition, because absorption and desorb belong to a kind of astable material exchange process, difficult to realize stable industrialization operation.
Summary of the invention
Technical problem to be solved by this invention provides a kind of industrialized purifying and refining piperyene method that is easy to, and the m-pentadiene that obtains after being separated by petroleum cracking by-product carbon five is by purification, and purity will reach more than 95%.
It below is the concrete technical scheme that the present invention solves the problems of the technologies described above.
A kind of method of purifying and refining piperyene may further comprise the steps:
1) the m-pentadiene raw material carries out rectifying separation and removes heavy constituent, and the working pressure of rectifying tower is 0.03～0.5MPa, and tower still temperature is 35～100 ℃, and reflux ratio is 1～8, gets the m-pentadiene material from cat head;
2) the cat head material that obtains in the step 1) is carried out extracting rectifying to remove light component in the presence of stopper, the tower internal pressure of extractive distillation column is 0.03～0.5MPa, tower still temperature is 100～180 ℃, reflux ratio is 1～10, the m-pentadiene raw material is 1: 2～1: 10 with the weight rate ratio of extractant feed, the tower still obtains the material of m-pentadiene and extraction agent, and the extraction agent that is adopted is a kind of in the aqueous solution of dimethyl formamide, N-Methyl pyrrolidone, acetonitrile or acetonitrile; 3) the tower still material that step 2) obtains removes extraction agent through rectifying and gets highly purified m-pentadiene product, and the extraction agent recovery is returned the extracting rectifying process and recycled.
In above-mentioned steps 2) in, the m-pentadiene raw material is preferably in the middle part charging of extractive distillation column, and extraction agent is preferably in its top feed of tower; Extraction agent preferably is preheated to 20～80 ℃ earlier before entering the extraction agent rectifying tower.
The main purpose of step 1) is to remove polymkeric substance and the heavy constituent of carbon more than six that generate in storage process in the material, and the working pressure of rectifying tower is preferably 0.08～0.3MPa, and tower still temperature is preferably 50～80 ℃, and reflux ratio is preferably 2～6; Step 2) main purpose is to remove in the material light component such as cyclopentenes, the tower internal pressure of extractive distillation column is preferably 0.08～0.3MPa, tower still temperature is preferably 110～160 ℃, reflux ratio is preferably 3～8, the m-pentadiene raw material is preferably 1: 4 with the weight rate ratio of extractant feed～and 1: 8, and extraction agent preferably adopts dimethyl formamide.
In step 2) in the described extracting rectifying process, adopting a kind of for extraction agent all is feasible in the aqueous solution of methylformamide, N-Methyl pyrrolidone, acetonitrile or acetonitrile, is that then separating effect is even more ideal for extraction agent but the contriver finds to adopt dimethyl formamide.
Above-mentioned steps 2) in, what the stopper that is adopted can be in ONP, oil of mirbane, furfural, N-Methyl pyrrolidone, thanomin or the Sodium Nitrite is a kind of.
When industrial applications, the structure of rectifying tower can adopt column plate tower or packing tower usually.
Compared with prior art, the invention has the advantages that process stabilizing, easy to operate, facility investment and running cost are lower, are highly susceptible to industrial applications, petroleum cracking system ethylene by-product carbon five is separated the m-pentadiene that obtains carry out purification.The purity of m-pentadiene is more than 95% after purifying, and the yield of product generally can reach 60～75%.
Embodiment
The present invention is further illustrated below by embodiment, and in an embodiment, product yield is defined as:
The m-pentadiene raw material is that petroleum cracking system ethylene by-product carbon five separates the m-pentadiene that obtains, and it consists of (wt.%):
Along amylene-2 0.03
2-methyl butene-2 0.12
M-pentadiene 71.78
Cyclopentadiene 0.20
Cyclopentenes 17.01
Pentamethylene 9.58
Other carbon 0.87
Total carbon six 0.41[embodiment 1～8]
It is that 0.6 meter packing tower carries out rectifying that the m-pentadiene raw material enters packed height, to remove polymkeric substance and the heavy constituent of carbon more than six that generate in the storage process, the working pressure of rectifying tower is 0.03～0.5MPa, tower still temperature is 35～100 ℃, reflux ratio is 1～8, obtains the m-pentadiene material from cat head.
With packed height is that 1.5 meters packing tower is the extractive distillation column that removes light component, above-mentioned m-pentadiene material through removing heavy component is from the middle part charging of tower, the extraction agent dimethyl formamide is preheated to 20～80 ℃ of its top feed from tower, carries out extracting rectifying to remove light component in the presence of the stopper Sodium Nitrite.The weight rate of the tower internal pressure of each embodiment extractive distillation column, tower still temperature, reflux ratio and m-pentadiene raw material and extractant feed process data such as compares and sees Table 1.The tower still obtains the material of m-pentadiene and extraction agent.
It is to carry out intermittence or continuous rectification in 0.6 meter the packing tower that the material that above-mentioned tower still is obtained m-pentadiene and extraction agent enters packed height, and the highly purified m-pentadiene of cat head output, tower still extraction agent recycle after through regeneration.The yield and the purity of each embodiment product see Table 2.
Table 1.
Annotate: feed rate ratio=extractant feed weight rate/m-pentadiene raw material feed weight flow.Table 2.
| Tower internal pressure (MPa) | Tower still temperature (℃) | Reflux ratio | The feed rate ratio | |
| Embodiment 1 | ????0.1 | ????120 | ????1 | ????6 |
| Embodiment 2 | ????0.1 | ????121 | ????7 | ????6 |
| Embodiment 3 | ????0.1 | ????127 | ????5 | ????10 |
| Embodiment 4 | ????0.08 | ????115 | ????3 | ????7 |
| Embodiment 5 | ????0.08 | ????120 | ????5 | ????9 |
| Embodiment 6 | ????0.2 | ????130 | ????5 | ????5 |
| Embodiment 7 | ????0.3 | ????138 | ????7 | ????7 |
| Embodiment 8 | ????0.5 | ????142 | ????8 | ????5 |
| Yield (%) | Product purity (%) | |
| Embodiment 1 | ????65 | ????96.08 |
| Embodiment 2 | ????69 | ????95.67 |
| Embodiment 3 | ????64 | ????95.71 |
| Embodiment 4 | ????67 | ????96.12 |
| Embodiment 5 | ????73 | ????95.84 |
| Embodiment 6 | ????64 | ????96.41 |
| Embodiment 7 | ????69 | ????95.37 |
| Embodiment 8 | ????66 | ????95.02 |
Claims (7)
1, a kind of method of purifying and refining piperyene, may further comprise the steps: 1) the m-pentadiene raw material carries out rectifying separation and removes heavy constituent, and the working pressure of rectifying tower is 0.03～0.5MPa, and tower still temperature is 35～100 ℃, reflux ratio is 1～8, gets the m-pentadiene material from cat head; 2) the cat head material that obtains in the step 1) is carried out extracting rectifying to remove light component in the presence of stopper, the tower internal pressure of extractive distillation column is 0.03～0.5MPa, tower still temperature is 100～180 ℃, reflux ratio is 1～10, the m-pentadiene raw material is 1: 2～1: 10 with the weight rate ratio of extractant feed, the tower still obtains the material of m-pentadiene and extraction agent, and the extraction agent that is adopted is a kind of in the aqueous solution of dimethyl formamide, N-Methyl pyrrolidone, acetonitrile or acetonitrile; 3) the tower still material that step 2) obtains removes extraction agent through rectifying and gets highly purified m-pentadiene product, and the extraction agent recovery is returned the extracting rectifying process and recycled.
2, the method for purifying and refining piperyene according to claim 1 is characterized in that step 2) the m-pentadiene raw material is in the charging of the middle part of extractive distillation column, and extraction agent is in its top feed of tower.
3, the method for purifying and refining piperyene according to claim 1 is characterized in that step 2) extraction agent is preheated to 20～80 ℃ earlier before entering the extraction agent rectifying tower.
4, the method for purifying and refining piperyene according to claim 1, the working pressure that it is characterized in that the rectifying tower described in the step 1) is 0.08～0.3Mpa, and tower still temperature is 50～80 ℃, and reflux ratio is 2～6.
5, the method for purifying and refining piperyene according to claim 1, it is characterized in that step 2) described in the tower internal pressure of extractive distillation column be 0.08～0.3MPa, tower still temperature is 110～160 ℃, reflux ratio is 3～8, and the m-pentadiene raw material is 1: 4～1: 8 with the weight rate ratio of extractant feed.
6, according to the method for claim 1,2,3,4 or 5 described purifying and refining piperyenes, it is characterized in that step 2) in the extraction agent that adopted be dimethyl formamide.
7, according to the method for claim 1,2,3,4 or 5 described purifying and refining piperyenes, it is characterized in that step 2) described in stopper be a kind of in ONP, oil of mirbane, furfural, N-Methyl pyrrolidone, thanomin or the Sodium Nitrite.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393676C (en) * | 2005-12-26 | 2008-06-11 | 山东玉皇化工有限公司 | Method for producing high-purity cyclopentadiene and cyclopentane by coarse piperyene |
| CN104418695A (en) * | 2013-08-23 | 2015-03-18 | 中国石油天然气股份有限公司 | Method for preparation of polymer grade m-pentadiene by acetonitrile method |
| 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 |
| CN105622327A (en) * | 2014-11-28 | 2016-06-01 | 中国石油天然气股份有限公司 | Method for separating petroleum cracking C5 fraction through acetonitrile process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331830C (en) * | 2004-12-24 | 2007-08-15 | 中国石化上海石油化工股份有限公司 | Refining separation method for coarse piperyene |
-
2002
- 2002-03-19 CN CNB021110859A patent/CN1168689C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393676C (en) * | 2005-12-26 | 2008-06-11 | 山东玉皇化工有限公司 | Method for producing high-purity cyclopentadiene and cyclopentane by coarse piperyene |
| CN104418695A (en) * | 2013-08-23 | 2015-03-18 | 中国石油天然气股份有限公司 | Method for preparation of polymer grade m-pentadiene by acetonitrile method |
| CN104418695B (en) * | 2013-08-23 | 2017-03-01 | 中国石油天然气股份有限公司 | A kind of method that acetonitrile method prepares polymer grade piperyene |
| 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 |
| CN105622327A (en) * | 2014-11-28 | 2016-06-01 | 中国石油天然气股份有限公司 | Method for separating petroleum cracking C5 fraction through acetonitrile process |
| CN105622327B (en) * | 2014-11-28 | 2019-01-18 | 中国石油天然气股份有限公司 | A kind of method of acetonitrile method separation five fractions of petroleum cracked carbon |
| 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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