CN1796342A - Refining method of coarse piperyene - Google Patents
Refining method of coarse piperyene Download PDFInfo
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- CN1796342A CN1796342A CN 200410093599 CN200410093599A CN1796342A CN 1796342 A CN1796342 A CN 1796342A CN 200410093599 CN200410093599 CN 200410093599 CN 200410093599 A CN200410093599 A CN 200410093599A CN 1796342 A CN1796342 A CN 1796342A
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- pentadiene
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Abstract
This invention is a process for the refinery of crude m-pentadiene, which is obtained through the separation of the by-product C5 fraction of ethane manufacturing via petroleum pyrolysis, including the steps of: 1) directing the crude m-pentadiene into an extractive rectification column, and collecting an overhead product of a mixed stream substantially enriched in cyclopentene and cyclopententane, and a bottom product of a mixed stream substantially enriched in m-pentadiene and the extractant, which is dimethyl formamide, N-methyl pyrrolidone, ethyl hydrazine or an aqueous solution of ethyl hydrazine containing 5-15 wt.% water; 2) directing the said bottom stream into a refinery column, and colleting an overhead product of the refined m-pentadiene, and a bottom product of the extractant, which is recovered and recycled. This invention ensures a high recovery and refinery rate to obtain refined m-pentadiene product with purity higher than 95%, and also obtains a mixture of cyclopentene and cyclopententane with a high utility value, which largely reduces the amount of the effluent liquids during the refinery course. The whole refinery course is much more environmentally friendly with the recovery and recycle of the extractant.
Description
Technical field
The present invention relates to a kind of process for purification of coarse piperyene, particularly separate the coarse piperyene that obtains, by the method for the refining m-pentadiene of extracting rectifying by petroleum cracking system ethylene by-product C 5 fraction.
Background technology
The a considerable amount of C 5 fractions of by-product are rich in diolefins such as m-pentadiene, isoprene and cyclopentadiene 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.Major ingredient in the mixing carbon five (hereinafter to be referred as coarse piperyene) of the enrichment m-pentadiene that is obtained by carbon five separating technologies is m-pentadiene, cyclopentenes and pentamethylene, wherein the content of m-pentadiene is between 65～75wt%, and the total content of cyclopentenes and pentamethylene is generally about 18wt%.Remaining part mainly is 2-methyl-2-butene and a spot of other C5 hydro carbons and the above hydrocarbon compound of C6 of trace, and plurality of impurities such as dicyclopentadiene, stopper and other polymkeric substance.Because the purity of coarse piperyene product is not high enough, can only be used for making m-pentadiene petro-resin usually, as more further purification then can be used as elastomeric raw material to more than the 95wt%, its value will improve greatly.On the other hand, cyclopentenes that contains in the coarse piperyene and pentamethylene also have the wide industrial purposes, cyclopentenes is a kind of important polymerization single polymerization monomer and fine chemical material, pentamethylene is harmless to atmospheric ozonosphere, can substitute halogenated hydrocarbon (CFCs) and make whipping agent, and the mixture of cyclopentenes and pentamethylene can directly be used as solvent.
Because the boiling point of m-pentadiene and cyclopentenes, pentamethylene is very approaching, and also have multiple other impurity, can't realize the refining purification of coarse piperyene with common distillation technology.Can realize its refining purification in theory by precise distillation, but rectifying tower requires that very high stage number is arranged, and requires very large reflux ratio during operation, is very uneconomic in industrial application.Patent US 4,031, and 151 propose to adopt adsorption separation technologies to come compartment pentadiene and other impurity, 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 parsing belong to a kind of astable material exchange process, difficult to realize stable industrialization operation.Chinese patent ZL02111085.9 has proposed a kind of method of purifying and refining piperyene, and this method has adopted takes off heavy component impurity earlier to coarse piperyene, and then carries out the flow process of extracting rectifying.Taking off heavy and extracting rectifying in two steps, a considerable amount of m-pentadienes have entered in the waste material, are m-pentadiene product more than 95% though this method has obtained purity, and the yield of m-pentadiene is lower, only is 60～75%.Simultaneously, produced a fairly large number of by product, the total amount of by product accounts for 30～40wt% of coarse piperyene amount.These by products still contain a certain amount of m-pentadiene, but because purity is very low, almost do not have utility value, have very much the cyclopentenes of using value and pentamethylene also to go out of use in addition in the by product, fail to obtain to recycle.
Summary of the invention
The invention provides a kind of process for purification of coarse piperyene, this coarse piperyene is obtained by the separation of petroleum cracking system ethylene by-product C 5 fraction, the technical problem that it will solve is to make with extra care purification with higher yield, and recycles cyclopentenes and the pentamethylene that contains in the coarse piperyene.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of process for purification of coarse piperyene, this coarse piperyene is obtained by the separation of petroleum cracking system ethylene by-product C 5 fraction, wherein contains m-pentadiene, cyclopentenes and pentamethylene, and treating process comprises:
1) coarse piperyene enters extractive distillation column and carries out extracting rectifying, and the extractant feed temperature is 25～120 ℃, and coarse piperyene is 1 with the feed weight ratio of extraction agent: (6～20).Working pressure is 0～0.2MPa, and tower still temperature is 70～250 ℃, and tower top temperature is 40～60 ℃, and the cat head rate of distillating is 15%～70%, and reflux ratio is 2～30.Cat head gets the mixture of enrichment cyclopentenes and pentamethylene, and the tower still gets the material of enrichment m-pentadiene and extraction agent, and extraction agent is that dimethyl formamide, N-Methyl pyrrolidone, acetonitrile or water-content are any in the acetonitrile solution of 5～15wt%;
2) above-mentioned tower still material enters rectifying tower and carries out rectifying, and working pressure is 0～0.2MPa, and tower still temperature is 70～180 ℃, and tower top temperature is 38～60 ℃, and reflux ratio is 0.5～5, and cat head gets the m-pentadiene purified product, and the tower still gets extraction agent, the extraction agent recycled.
Said process 1 described extractant feed temperature is preferably 40～80 ℃; Coarse piperyene is preferably 1 with the feed weight ratio of extraction agent: (8～16); Working pressure is preferably normal pressure; Tower still temperature is preferably 75～125 ℃, and tower top temperature is preferably 43～48 ℃.
It is fixed that the process 1 described cat head rate of distillating is that the content according to cyclopentenes in the coarse piperyene and pentamethylene comes, and generally is controlled at the percentage ratio a little more than this content, and promptly 15%～70%, be preferably 20%～35%.
Said process 1 described reflux ratio is preferably 4～8; Extraction agent is preferably the acetonitrile solution that dimethyl formamide, N-Methyl pyrrolidone or water-content are 5～15wt%.
Said process 2 described working pressures are preferably normal pressure; Tower still temperature is preferably 80～110 ℃, and tower top temperature is preferably 40～44 ℃; Reflux ratio is preferably 1～4.
Usually, the table composed as follows of above-mentioned coarse piperyene is listed:
| Component | Content (wt%) |
| M-pentadiene | 60～74 |
| Cyclopentenes+pentamethylene | 15～25 |
| Other C5 and C6 hydro carbons, other impurity | Surplus |
Wherein, the total content of other C5 and C6 hydro carbons and other impurity is lower, generally about 5wt%.
Technical scheme provided by the invention has mainly comprised two steps, and wherein step 1 is the most key.The present invention separates the material beyond the m-pentadiene with it by having selected ideal extraction agent and suitable extracting rectifying operational condition; The rectifying of step 2 is separated the m-pentadiene product with extraction agent, obtain the m-pentadiene purified product, and separating and recovering extractant.Through these two steps, obtained highly purified m-pentadiene product, cat head obtains the hydrocarbon mixture based on cyclopentenes and pentamethylene simultaneously, and wherein the total content of cyclopentenes and pentamethylene reaches more than the 80wt%.This hydrocarbon mixture can be directly as the raw material of fine chemistry industry, as be used for product such as synthesis of glutaraldehyde, or use as organic solvent.
The extractive distillation column that step 1 adopts can be packing tower or sieve-tray tower, and its theoretical plate number is generally 40～80; Step 2 is a kind of simple rectifyinges, because the boiling point of the extraction agent that the present invention selects is all apparently higher than the boiling point of m-pentadiene, the theoretical plate number of rectifying tower is generally got 5～20 and got final product.
Compared with prior art, the invention has the advantages that the refining yield that has improved m-pentadiene greatly, and the m-pentadiene purified product has very high purity equally, purity can reach more than 95% usually.Also obtained having the cyclopentenes and the pentamethylene hydrocarbon mixture of higher using value simultaneously, this discharging of waste liquid amount that makes treating process produce greatly reduces, and used in addition extraction agent fully obtains reclaiming the back recycled, and whole process is beneficial to environmental protection.
Below will the invention will be further described by specific embodiment.
In an embodiment, cat head distillates rate D/F and is defined as:
Embodiment
The coarse piperyene that each embodiment uses is formed listed as table 1:
Table 1.
| Component | Content (wt%) |
| M-pentadiene | 73.5 |
| Cyclopentenes | 16.9 |
| Pentamethylene | 6.7 |
| Other C5 hydro carbons and the above hydro carbons of C6, other impurity | Surplus |
[embodiment 1～7]
Form and to enter an extractive distillation column after coarse piperyene as table 1 is preheated to 30～40 ℃ and carry out extracting rectifying, extractive distillation column is a packing tower, and theoretical plate number is 45.Coarse piperyene enters extractive distillation column with the flow of 400g/h from the 32nd block of column plate, and extraction agent is from the 4th column plate charging.Each embodiment extractive distillation column is operated under normal pressure, the feed weight of the concrete extraction agent that uses, m-pentadiene and extraction agent than and tower still and tower top temperature see Table 2.The main composition of each embodiment extracting rectifying column overhead discharging material sees Table 3, and this material is collected as cyclopentenes and pentamethylene hydrocarbon mixture product.
Extracting rectifying Tata still material enters subsequently and carries out rectifying in the rectifying tower, and rectifying tower is a packing tower, and theoretical plate number is 7, and opening for feed is positioned at the 5th block of plate, and each embodiment rectifying tower is operated under normal pressure, and other operational condition sees Table 4.Rectifying Tata still obtains extraction agent, and extraction agent is sent the extractive distillation column recycled back to, and cat head discharging material is collected as the m-pentadiene purified product.Purity, the m-pentadiene product yield of each embodiment m-pentadiene purified product see Table 5.
Table 2
| Extraction agent | The extractant feed temperature (℃) | Extraction agent/coarse piperyene (weight ratio) | Tower still/tower top temperature (℃) | Reflux ratio | D/F (％) | |
| Embodiment 1 | DMF | 40 | 16 | 125/48 | 20 | 24 |
| Embodiment 2 | DMF | 50 | 12 | 116/45 | 6 | 26 |
| Embodiment 3 | DMF | 80 | 10 | 114/45 | 4 | 27 |
| Embodiment 4 | DMF | 50 | 12 | 116/45 | 6 | 31 |
| Embodiment 5 | DMF | 60 | 8 | 98/43 | 8 | 29 |
| Embodiment 6 | Acetonitrile solution | 45 | 12 | 75/45 | 6 | 28 |
| Embodiment 7 | N-Methyl pyrrolidone | 50 | 12 | 160/45 | 8 | 28 |
Annotate: DMF is a dimethyl formamide; The water-content of acetonitrile solution is 10wt%.
Table 3.
| Cyclopentenes (wt%) | Pentamethylene (wt%) | M-pentadiene (wt%) | Other impurity | |
| Embodiment 1 | 68.3 | 26.4 | 1.5 | Surplus |
| Embodiment 2 | 65.1 | 25.3 | 2.2 | Surplus |
| Embodiment 3 | 62.4 | 24.2 | 3.0 | Surplus |
| Embodiment 4 | 57.6 | 22.3 | 10.0 | Surplus |
| Embodiment 5 | 59.5 | 23.3 | 4.4 | Surplus |
| Embodiment 6 | 60.1 | 23.2 | 7.0 | Surplus |
| Embodiment 7 | 60.0 | 23.9 | 10.1 | Surplus |
Table 4.
| Tower still temperature (℃) | Tower top temperature (℃) | Reflux ratio | |
| Embodiment 1 | 100 | 44 | 4 |
| Embodiment 2 | 110 | 44 | 2 |
| Embodiment 3 | 100 | 44 | 3 |
| Embodiment 4 | 100 | 44 | 1 |
| Embodiment 5 | 100 | 43 | 2 |
| Embodiment 6 | 80 | 40 | 4 |
| Embodiment 7 | 203 | 44 | 4 |
Table 5.
| M-pentadiene purified product purity (%) | M-pentadiene yield (%) | |
| Embodiment 1 | 95.4 | 99.5 |
| Embodiment 2 | 96.4 | 99.2 |
| Embodiment 3 | 95.8 | 98.9 |
| Embodiment 4 | 95.6 | 95.8 |
| Embodiment 5 | 97.0 | 98.3 |
| Embodiment 6 | 95.7 | 97.3 |
| Embodiment 7 | 98.0 | 96.1 |
Claims (9)
1, a kind of process for purification of coarse piperyene, this coarse piperyene is obtained by the separation of petroleum cracking system ethylene by-product C 5 fraction, wherein contains m-pentadiene, cyclopentenes and pentamethylene, and treating process comprises:
1) coarse piperyene enters extractive distillation column and carries out extracting rectifying, the extractant feed temperature is 25～120 ℃, coarse piperyene is 1 with the feed weight ratio of extraction agent: (6～20), working pressure is 0～0.2MPa, tower still temperature is 70～250 ℃, tower top temperature is 40～60 ℃, the cat head rate of distillating is 15%～70%, reflux ratio is 2～30, cat head gets the mixture of enrichment cyclopentenes and pentamethylene, the tower still gets the material of enrichment m-pentadiene and extraction agent, and extraction agent is a dimethyl formamide, N-Methyl pyrrolidone, acetonitrile or water-content are any in the acetonitrile solution of 5～15wt%;
2) above-mentioned tower still material enters rectifying tower and carries out rectifying, and working pressure is 0～0.2MPa, and tower still temperature is 70～180 ℃, and tower top temperature is 38～60 ℃, and reflux ratio is 0.5～5, and cat head gets the m-pentadiene purified product, and the tower still gets extraction agent, the extraction agent recycled.
2, the process for purification of coarse piperyene according to claim 1 is characterized in that process 1 described extractant feed temperature is 40～80 ℃.
3, the process for purification of coarse piperyene according to claim 1 is characterized in that the process 1 described coarse piperyene and the feed weight ratio of extraction agent are 1: (8～16).
4, the process for purification of coarse piperyene according to claim 1 is characterized in that process 1 described working pressure is a normal pressure.
5, the process for purification of coarse piperyene according to claim 1 is characterized in that process 1 described tower still temperature is 75～125 ℃, and tower top temperature is 43～48 ℃.
6, the process for purification of coarse piperyene according to claim 1 is characterized in that the process 1 described cat head rate of distillating is 20%～35%.
7, the process for purification of coarse piperyene according to claim 1 is characterized in that process 1 described reflux ratio is 4～8.
8, the process for purification of coarse piperyene according to claim 1 is characterized in that process 1 described extraction agent is that dimethyl formamide, N-Methyl pyrrolidone or water-content are the acetonitrile solution of 5～15wt%.
9, the process for purification of coarse piperyene according to claim 1 is characterized in that process 2 described working pressures are normal pressure, and tower still temperature is 80～110 ℃, and tower top temperature is 40～44 ℃, and reflux ratio is 1～4.
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| 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 |
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| 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 |
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