CN100503526C - Method for refining crude piperyene - Google Patents
Method for refining crude piperyene Download PDFInfo
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- CN100503526C CN100503526C CNB2005100259197A CN200510025919A CN100503526C CN 100503526 C CN100503526 C CN 100503526C CN B2005100259197 A CNB2005100259197 A CN B2005100259197A CN 200510025919 A CN200510025919 A CN 200510025919A CN 100503526 C CN100503526 C CN 100503526C
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Abstract
This invention relates to a method for refined producing crude pentadiene, comprising: (1) conduct the first extractive distillation of crude pentadiene with extractant, where the extractant is one of dimethyl formamide, acetonitrile or acetonitrile solution with 5-15wt% water. The top distillation tower collects the trans-pentadiene material containing other hydrocarbons, and the distillation tower collects the rest pentadiene and extractant material; (2)distill the tower bottom material of the procedure(1) and collect the refined pentadiene product at the top of the distillation tower, at the bottom of the tower collects the extractant; (3) conduct the second extractive distillation of the top material of procedure(2) with extractant which is the same with that of procedure(1), at the bottom of the tower collects the trans-pentadiene and extractant material, the rest hydrocarbons are discharged from the top of the tower; (4) the bottom material of procedure(3) is sent to the refined distillation tower for distillation, at the top of the tower collects the refined trans-pentadiene product, and at the bottom collects the extractant. This invention can produce some high-purity trans-pentadiene during the pentadiene refining process.
Description
Technical field
The present invention relates to a kind of method of refining crude piperyene, particularly the method that adopts extracting rectifying to come refining crude piperyene.
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.The content of m-pentadiene is between 65～75wt% 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, and remaining part mainly is other C5 and above hydrocarbon compound and other impurity of C6.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 be worth and will improve greatly to more than the 95wt%.U.S. Pat 4,031,151 and Chinese patent ZL02111085.9 a kind of method of purifying and refining piperyene has been proposed separately, the final m-pentadiene product purity that obtains can both reach more than the 95wt%.
M-pentadiene exists cis and trans two kinds of isomer, and cis and trans two kinds of isomer ratios between two are generally 1 in the m-pentadiene that is obtained by five fractions of petroleum cracked carbon: between (1.5～3).For the polyreaction of differential responses condition, two kinds of isomer of m-pentadiene can present different chemical property, all help cis-isomeride generation polymerization as alfin sodium catalyst and free-radical emulsion polymerization.Have only trans-isomer(ide) to react in more conditions, and cis-isomeride does not participate in reaction, as adopt the polyreaction of anionic catalyst, Ziegler-Natta catalyst or transition-metal catalyst, by asking that the reaction of pentadiene and cis-butenedioic anhydride produces methyl tetrahydro phthalic anhydride etc.
When having only list kind m-pentadiene isomer to participate in reaction, another kind of isomer exists as inert media, this obvious negative influence that brought to reaction, as make yield, catalyst efficiency and product purity reduce, and the energy consumption increase etc.Sometimes, the sort of isomer of not participating in reaction also is used as refuse and is handled, and this not only causes the waste of resource, returns environmental protection and brings pressure.So, if can obtain highly purified single trans comparatively widely m-pentadiene isomer of m-pentadiene isomer, particularly purposes of planting, industrial be that economic worth is arranged very much.
Yet owing to piperyene cis, both boiling-point differences of trans-isomer(ide) are 1.9 ℃, the refining m-pentadiene product that method obtained of existing refining crude piperyene is two kinds of mixture of isomers.Though also have the separation method of some piperyene cis, trans-isomer(ide) in the prior art, for want of economy and do not have industrial utility value.
Summary of the invention
The invention provides a kind of method of refining crude piperyene, it adopts industrial extracting rectifying commonly used, distillation technology, when obtaining the m-pentadiene purified product, can also obtain highly purified pure trans m-pentadiene with higher yield, remedied the defective that prior art exists well.
Below be technical scheme of the present invention:
A kind of method of refining crude piperyene, described coarse piperyene obtains by separating in the petroleum cracking C 5 fraction, and this method comprises following process:
1) the coarse piperyene raw material carries out the extracting rectifying first time in the presence of extraction agent.Extraction agent is that dimethyl formamide, acetonitrile or water-content are any in the acetonitrile solution of 5～15wt%.The extractant feed temperature is 20～80 ℃, and material 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 20～70%, and reflux ratio is 1～30.Cat head must contain the trans m-pentadiene material of other hydrocarbons, and the tower still gets the material of remaining m-pentadiene and extraction agent;
2) process 1) the tower still material that obtains enters rectifying tower and carries out rectifying.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.Cat head gets the m-pentadiene purified product, and the tower still gets extraction agent and recycled;
3) process 1) the cat head material that obtains carries out the extracting rectifying second time in the presence of extraction agent.Extraction agent is that dimethyl formamide, acetonitrile or water-content are any in the acetonitrile solution of 5～15wt%.The extractant feed temperature is 20～80 ℃, and material 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 40～90%, and reflux ratio is 2～30.The tower still gets the material of trans m-pentadiene and extraction agent, and other hydrocarbons is discharged by cat head;
4) process 3) the tower still material that obtains enters rectifying tower and carries out rectifying.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.Cat head gets trans m-pentadiene purified product, and the tower still gets extraction agent and recycled.
Said process 1) or process 3) described extractant feed temperature is preferably 25～50 ℃; Material 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 ℃; The cat head rate of distillating is preferably between 45～55%; Reflux ratio is preferably 4～8; Extraction agent is preferably dimethyl formamide.
Said process 2) or process 4) described working pressure is preferably normal pressure; Tower still temperature is preferably 80～110 ℃; Tower top temperature is preferably 40～44 ℃.
Technical scheme provided by the invention has mainly comprised four steps.Step 1 is an extracting rectifying process, the existence of extraction agent has increased the relative volatility between cis and the trans m-pentadiene, add and cooperate suitable operational condition, by the m-pentadiene in the overhead product material can be trans-isomer(ide) basically entirely, and remaining a part of trans-isomer(ide) and all cis-isomerides are present in and enter in the extraction agent in the tower still material.Therefore hydrocarbons except that m-pentadiene is also distillated by cat head, after the rectifying by step 2 reclaims out with extraction agent, can obtain the higher m-pentadiene purified product of purity by the rectifying tower cat head.This m-pentadiene product is the isomer of cis mostly, and can be used for any is not the occasion that is only participated in reaction by trans-isomer(ide).Step 3 is extracting rectifying processes second time, and the extraction agent of employing can be identical with step 1.By the extracting rectifying in this step, the material in the coarse piperyene raw material except that m-pentadiene is all discharged by cat head, and trans m-pentadiene and extraction agent are by the extraction of tower still.Once more extraction agent is reclaimed out by step 4 then, can obtain the pure trans m-pentadiene of higher degree at last by the rectifying tower cat head.
Step 1 and 3 extractive distillation columns that adopt can be packing tower or sieve-tray tower, and the theoretical plate number of extractive distillation column generally should be advisable with 40～60 theoretical stages more than 30.Certainly higher theoretical plate number can make separating effect desirable more, but the practicality of industry then can decrease.Step 2 and 4 rectifying are comparatively simple, because there are enough boiling-point differences in extraction agent and material that the present invention selects.The theoretical plate number of rectifying tower can select 10～20.
Positive effect of the present invention is to provide a kind of ideal coarse piperyene process for purification, and it can obtain the highly purified pure trans m-pentadiene that a part has higher economic worth when having realized the m-pentadiene product purification.And adopt technology such as extracting rectifying, rectifying also very general in industrial use, therefore method provided by the invention is easy to realize industrial applications, has overcome the defective that prior art exists well.
Below will the invention will be further described by specific embodiment, effect of the present invention is not limited to the data that embodiment shows.Extractive distillation column adopts higher theoretical plate number and adopts the bigger extraction agent and the charge ratio of material obviously can obtain better effect, but this can reduce the economy of industrial application.
In an embodiment, cat head distillates rate D/F and is defined as:
Embodiment
The coarse piperyene raw material that each embodiment uses is from five fractions of petroleum cracked carbon, and its composition is listed as table 1:
Table 1.
| Component | Content (wt%) |
| Trans-m-pentadiene | 46 |
| Cis-m-pentadiene | 26 |
| The above hydro carbons of other C5 and C6 | Surplus |
[embodiment 1～5]
One, forms as entering first extractive distillation column behind coarse piperyene raw material preheating to 40～50 of table 1 ℃ and carry out extracting rectifying.Extractive distillation column is a packing tower, and theoretical plate number is 45.The coarse piperyene raw material enters extractive distillation column with the speed of 3900g/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, and other main extracting rectifying operational condition sees Table 2.
Two, the tower still material of first extractive distillation column enters and carries out rectifying in first rectifying tower to reclaim extraction agent.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 main distillation operation condition sees Table 3.Rectifying Tata still obtains extraction agent, and extraction agent recycled, cat head obtain the m-pentadiene purified product, and product purity sees Table 6.
Three, the cat head material of first extractive distillation column enters second extractive distillation column and carries out extracting rectifying.Extractive distillation column is a packing tower, and theoretical plate number is 45.The coarse piperyene raw material enters extractive distillation column with the speed of 1950g/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, and other main extracting rectifying operational condition sees Table 4.The tower still gets the material of trans m-pentadiene and extraction agent, and other hydrocarbons is discharged by cat head
Four, the tower still material of second extractive distillation column enters and carries out rectifying in second rectifying tower to reclaim extraction agent.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 main distillation operation condition sees Table 5.Rectifying Tata still obtains extraction agent, and extraction agent recycled, cat head obtain pure trans m-pentadiene purified product.
The purity and the yield of pure trans m-pentadiene purified product see Table 6.
Table 2
| Extraction agent | The extractant feed temperature (℃) | Raw material/extraction agent (weight ratio) | Tower still/tower top temperature (℃) | Reflux ratio | D/F (％) | |
| Embodiment 1 | DMF | 25 | 1/16 | 125/48 | 20 | 20 |
| Embodiment 2 | DMF | 50 | 1/12 | 116/44 | 4 | 45 |
| Embodiment 3 | DMF | 80 | 1/12 | 116/43 | 6 | 55 |
| Embodiment 4 | DMF | 50 | 1/8 | 98/44 | 8 | 50 |
| Embodiment 5 | Acetonitrile solution | 45 | 1/12 | 75/44 | 6 | 52 |
Annotate: DMF is a dimethyl formamide; The water-content of acetonitrile solution is 10wt%.
Table 3.
| Tower still temperature (℃) | Tower top temperature (℃) | Reflux ratio | |
| Embodiment 1 | 110 | 44 | 4 |
| Embodiment 2 | 101 | 44 | 2 |
| Embodiment 3 | 100 | 44 | 3 |
| Embodiment 4 | 100 | 44 | 2 |
| Embodiment 5 | 80 | 40 | 4 |
Table 4.
| Extraction agent | The extractant feed temperature (℃) | Raw material/extraction agent (weight ratio) | Tower still/tower top temperature (℃) | Reflux ratio | D/F (％) | |
| Embodiment 1 | DMF | 50 | 1/16 | 125/48 | 4 | 90 |
| Embodiment 2 | DMF | 50 | 1/12 | 116/43 | 6 | 53 |
| Embodiment 3 | DMF | 50 | 1/10 | 114/43 | 6 | 40 |
| Embodiment 4 | DMF | 50 | 1/8 | 98/43 | 4 | 48 |
| Embodiment 5 | Acetonitrile solution | 25 | 1/12 | 75/42 | 6 | 53 |
Annotate: DMF is a dimethyl formamide; The water-content of acetonitrile solution is 10wt%.
Table 5.
| Tower still temperature (℃) | Tower top temperature (℃) | Reflux ratio | |
| Embodiment 1 | 110 | 44 | 4 |
| Embodiment 2 | 101 | 42 | 2 |
| Embodiment 3 | 100 | 42 | 3 |
| Embodiment 4 | 100 | 42 | 2 |
| Embodiment 5 | 80 | 40 | 4 |
Table 6.
| M-pentadiene product purity (%) | Trans m-pentadiene product purity (%) | Trans m-pentadiene product yield (%) | |
| Embodiment 1 | 91.2 | 98.0 | 21.3 |
| Embodiment 2 | 90.1 | 97.1 | 14.3 |
| Embodiment 3 | 88.1 | 78.6 | 47.8 |
| Embodiment 4 | 91.8 | 88.0 | 49.5 |
| Embodiment 5 | 87.5 | 77.4 | 47.8 |
Claims (10)
1, a kind of method of refining crude piperyene, described coarse piperyene obtains by separating in the petroleum cracking C 5 fraction, and this method comprises following process:
1) the coarse piperyene raw material carries out the extracting rectifying first time in the presence of extraction agent, extraction agent is a dimethyl formamide, acetonitrile or water-content are any in the acetonitrile solution of 5～15wt%, the extractant feed temperature is 20～80 ℃, material 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 20～70%, reflux ratio is 1～30, cat head must contain the trans m-pentadiene material of other hydrocarbons, and the tower still gets the material of remaining m-pentadiene and extraction agent;
2) process 1) the tower still material that obtains enters rectifying tower and carries out rectifying, and working pressure is 0～0.2MPa, and tower still temperature is 70～180 ℃, tower top temperature is 38～60 ℃, reflux ratio is 0.5～5, and cat head gets the m-pentadiene purified product, and the tower still gets extraction agent and recycled;
3) process 1) the cat head material that obtains carries out the extracting rectifying second time in the presence of extraction agent, extraction agent is a dimethyl formamide, acetonitrile or water-content are any in the acetonitrile solution of 5～15wt%, the extractant feed temperature is 20～80 ℃, material 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 40～90%, reflux ratio is 2～30, the tower still gets the material of trans m-pentadiene and extraction agent, and other hydrocarbons is discharged by cat head;
4) process 3) the tower still material that obtains enters rectifying tower and carries out rectifying, and working pressure is 0～0.2MPa, and tower still temperature is 70～180 ℃, tower top temperature is 38～60 ℃, reflux ratio is 0.5～5, and cat head gets trans m-pentadiene purified product, and the tower still gets extraction agent and recycled.
2, the method for refining crude piperyene according to claim 1 is characterized in that process 1) or process 3) described extractant feed temperature is 25～50 ℃.
3, the method for refining crude piperyene according to claim 1 is characterized in that process 1) or process 3) described material is 1 with the feed weight ratio of extraction agent: (8～16).
4, the method for refining crude piperyene according to claim 1 is characterized in that process 1) or process 3) described working pressure is normal pressure.
5, the method for refining crude piperyene according to claim 1 is characterized in that process 1) described tower still temperature is 75～125 ℃, tower top temperature is 43～48 ℃.
6, the method for refining crude piperyene according to claim 1 is characterized in that process 1) the described cat head rate of distillating is 45～55%, reflux ratio is 4～8.
7, the method for refining crude piperyene according to claim 1 is characterized in that process 1) or process 3) described extraction agent is dimethyl formamide.
8, the method for refining crude piperyene according to claim 1 is characterized in that process 2) or process 4) described working pressure is normal pressure.
9, the method for refining crude piperyene according to claim 1 is characterized in that process 2) described tower still temperature is 80～110 ℃, tower top temperature is 40～44 ℃.
10, the method for refining crude piperyene according to claim 1 is characterized in that process 4) described tower still temperature is 80～110 ℃, tower top temperature is 40～44 ℃.
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| CNB2005100259197A CN100503526C (en) | 2005-05-18 | 2005-05-18 | Method for refining crude piperyene |
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| CNB2005100259197A CN100503526C (en) | 2005-05-18 | 2005-05-18 | Method for refining crude piperyene |
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| CN100503526C true CN100503526C (en) | 2009-06-24 |
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| CN104418694B (en) * | 2013-08-23 | 2016-04-06 | 中国石油天然气股份有限公司 | Method for preparing high-purity piperylene by acetonitrile method |
| CN113999100B (en) * | 2021-10-29 | 2023-10-13 | 万华化学集团股份有限公司 | Method for preparing methyl heptenone and applying raw materials |
| CN115572274B (en) * | 2022-11-11 | 2023-03-17 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as raw material |
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