CN107879880A - A kind of separation method of chemical grade isoprene - Google Patents
A kind of separation method of chemical grade isoprene Download PDFInfo
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- CN107879880A CN107879880A CN201610867789.XA CN201610867789A CN107879880A CN 107879880 A CN107879880 A CN 107879880A CN 201610867789 A CN201610867789 A CN 201610867789A CN 107879880 A CN107879880 A CN 107879880A
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- tower
- isoprene
- chemical grade
- extractant
- separation method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
Abstract
A kind of separation method of chemical grade isoprene, including step：1) the light dydrocarbon raw material that cyclopentadiene is stripped of by pretreatment enters knockout tower progress extracting rectifying, extractant separation, removes light light dydrocarbon and recovery extractant in material；2) step 1) obtains the material progress rectifying rich in isoprene and obtains chemical grade isoprene product with separation removal heavy constituent impurity, tower top；Compared with prior art, the advantage of the invention is that reducing residence time of the isoprene in separation process in separation process, reduce the loss of isoprene, while reduce equipment investment and separating energy consumption, there is significant economic benefit.
Description
Technical field
The present invention relates to a kind of separation method of chemical grade isoprene, more particularly to by petroleum cracking ethylene by-product
Material after C 5 fraction pretreatment removing cyclopentadiene is raw material, and synchronous progress disintegration is separated with solvent using extracting rectifying
The method of classes and grades in school isoprene.
Background technology
Cracking c_5 (C5) cut is the accessory substance during naphtha and other heavy hydrocarbon cracking ethylene preparations, and content is about
For 12%~20% or so of ethylene yield.In C 5 fraction be mainly alkane, monoolefine, diolefin and alkynes, wherein content compared with
More isoprene (IP), pentadiene (PD) and cyclopentadiene (CPD), accounts for the 40%~60% of C 5 fraction yield.Isoamyl
Diene accounts for 15%-25% in C5 fraction, in synthetic rubber, medical pesticide intermediate and synthetic lubricant fluid additive, rubber
The producer mask of glue vulcanizing agent has been widely used, and exploitation prospect is very wide.
But because C 5 fraction forms complexity, boiling point is close between component, and relative volatility is small, and is easily formed between component
Azeotropic so that the separation process of C 5 fraction becomes complex.At present, it is domestic typically first to remove C 5 fraction using hot process for dimerization
In most CPD, the method being then combined using extracting rectifying and conventional distillation isolates chemical grade IP, two-part extraction
The method that rectifying and conventional distillation are combined isolates polymer grade IP, and conventional extractant is dimethylformamide (DMF), acetonitrile
And 1-METHYLPYRROLIDONE (NMP) (CAN).
Except routine extraction rectifying method (DMF methods, ACN methods, NMP methods) outside, in order to reduce energy consumption, improve product yield,
Researchers develop different novel process.Admittedly special company of the U.S. can form binary with pentane using isoprene and be total to
The characteristics of boiling thing have developed the azeotropic distillation method of separating isoprene.This method, which is suitable for pentane, can be used as isoprene
The solvent of polymerisation does not have influential situation azeotropic distillation in the presence of pentane on isoprene polymerization reaction.Whole stream
Journey only needs lightness-removing column and weight-removing column, and lightness-removing column removes component of the boiling point than azeotropic mixture low boiling point, and weight-removing column removing boiling point is than altogether
Boil the high component of thing boiling point.Compared with extraction fractional distillation, azeotropic distillation preferably solves extraction fractional distillation due to using molten
Agent and the various problems directly relevant with solvent such as solvent loss, toxicity, recovery, decomposition and environmental protection for bringing.Do not appear in
(presence of solvent makes system be in higher temperature) isoprene, pentadiene and cyclopentadiene, alkynes etc. is easy under high temperature
Inhibition and the explosion phenomenon of concentration alkynes etc..But the shortcomings that its is maximum is：Obtained product is isoprene and pentane
Azeotropic mixture, the higher isoprene of purity can not be obtained, further purification and regeneration need higher column plate and larger time
Ratio is flowed, it is economically uneconomical.
Ruan is carefully strong etc. to develop a kind of selective catalytic hydrogenation removing alkynes to substitute the production technology of the second extraction cells.
I.e. in C5Before cut carries out extract and separate, the micro-alkyne in selective hydrogenation removing isoprene is carried out using catalyst, entered
And substitute the second extraction cells.Compared with traditional two-section extraction flow, the technique uses selective hydrogenation reactor, operates bar
The selectivity of part mild catalytic agent, activity and stability are higher；Second extraction larger due to eliminating the energy consumption in whole flow process
Take unit so that its energy consumption and production cost significantly decline：Improvement part is due to without using solvent, making polymerization grade isoprene
Dimethylamine is free of in product, quality is improved, and reduces the solvent load in whole flow process.On this basis, by that will react
Rectifying introduces pre- weight-removing column, can save the hot dipolymer reactor of generally use, make flow more simplified.But selection hydrogenation process
In have part isoprene and lost because of hydrogenation, reduce the yield of isoprene
Patent CN1709842 discloses a kind of azeotropic superfractionation/extractive distillation coupling technique.This method first takes azeotropic superfinishing
Evaporate and obtain the isoprene-pentane azeotropic mixture for meeting polymer grade requirement by taking off light unit and de- weight unit, then with extraction
Distillation separates pentane and isoprene, obtains polymerization grade isoprene.Process synthesis azeotropic superfractionation and extraction essence
The advantage evaporated, the object of extractive distillation processing is only the mixture of isoprene and pentane so that solvent processing and high temperature
The problems such as polymerization of lower product, is alleviated significantly.Isoamyl two is can only obtain in addition, also solving using azeotropic superfractionation merely
Alkene and pentane mixture, and the deficiency of pure isoprene can not be obtained, high-purity isoprene and pentane can be produced simultaneously.
Liao Lihua etc. have studied a kind of using the NMP containing NaSCN as extractant, the method for separation of extractive distillation isoprene.
This method can reduce the theoretical cam curve and solvent ratio of the first and second extractive distillation columns needs, and C5 is separated using this method,
The purity of isoprene, dicyclopentadiene and pentadiene be respectively 99.90%, 98.90% and 90.30%. yields be respectively
98.86%th, 94.99% and 98.93%, it is improved than traditional DMF methods and NMP methods.But in extractive distillation with salt in reality
In application process, the problems such as recovery and crystallization of salt also be present, need to be further improved.
As can be seen here, chemical grade isoprene is prepared using the C 5 fraction of petroleum cracking ethylene by-product in the prior art
Shi Wufa takes into account the problem of energy consumption is with isoprene yield, purity.
The content of the invention
The present invention provides a kind of separation method of chemical grade isoprene, to be stripped of the C5 fraction of cyclopentadiene as original
Material, using group technology, the method for separation chemistry grade isoprene.The present invention is prepared to extraction fractional distillation in the prior art to be polymerize
Grade isoprene technique is improved, and is solved when extraction fractional distillation prepares chemical grade isoprene in the prior art, high energy consumption, is subtracted
The polymerization of few isoprene, while equipment investment is reduced, reduce cost of investment.It is the concrete technical scheme of the present invention below：
A kind of separation method of chemical grade isoprene, is mainly included the following steps that：
1) the light dydrocarbon raw material that cyclopentadiene is stripped of by pretreatment enters knockout tower progress separation of extractive distillation, knockout tower
Knockout tower is divided into two parts in left and right by top by a baffle plate, while removes extractant, and extractant is dimethylformamide.Raw material
With extractant feed weight than controlling as 1：4~1：8, extractant feed temperature is 50~70 DEG C, bottom temperature control for 150~
170 DEG C, tower top temperature is controlled as left 30~40 DEG C of tower, right 32~42 DEG C of tower, operating pressure control for 0.02~
0.06Mpa, reflux ratio are controlled as left tower 1.5~3.5, right tower 1.5~2.5, tower top discharge respectively raffinate carbon-5 fraction with
Isoprene and heavy constituent mixtures of impurities material, tower reactor obtain extractant, and extractant recycles；
2) isoprene and heavy component impurity material obtained by step 1) enters rectifying column and carries out rectifying, removes heavy component
Impurity, obtain chemical grade isoprene.Bottom temperature control is 80~100 DEG C, and tower top temperature control is 50~60 DEG C, operation pressure
Power control is 0.05~0.2Mpa, and reflux ratio control is 10~20, and tower top obtains chemical grade isoprene product, and tower reactor obtains weight
Component impurity.
Above-mentioned steps 1) raw material with extractant feed weight is 1 than preferably control：5~1：6, extractant feed temperature
Preferably 60~65 DEG C, bottom temperature is preferably controlled as 155~165 DEG C, and tower top temperature is preferably controlled as left tower 34~36
DEG C, right 36~38 DEG C of tower, operating pressure preferably controls preferably is controlled as left tower 2~3 for 0.03~0.05Mpa, reflux ratio,
Right tower 1.7~2.0.
Above-mentioned steps 1) the knockout tower Internal baffle is highly the 0.8~0.9 of knockout tower.
Above-mentioned steps 2) bottom temperature preferably controlled as 85~90 DEG C, and tower top temperature is preferably controlled as 54~56 DEG C,
Operating pressure preferably controls preferably to be controlled as 14~16 for 0.08~0.12Mpa, reflux ratio.
During preparing chemical grade isoprene using the method for extracting rectifying in the prior art, because needing to reclaim extraction
Agent is, it is necessary to set the separation of stripper progress extractant and isoprene, so preparing chemical grade isoprene process in separation
In, extractant usage amount is larger, and part energy consumption concentrates on the removal process of extractant.Simultaneously according to C 5 diene polymerisation
Kinetics understand, isoprene residence time in whole separation process is longer, isoprene unavoidably occur from
Poly- or copolymerization, so as to add the loss of isoprene, have impact on the yield of isoprene and the economy of light dydrocarbon separator
Property.With the continuous development of light dydrocarbon isolation technics, the advance for embodying light dydrocarbon isolation technics is mainly reflected in light dydrocarbon material diene
The yield of hydrocarbon and the energy consumption of whole separation process.Inventor it has been investigated that, can design the extraction of chemical grade isoprene
Rectifying and the recovery of extractant is taken to be carried out in same seat knockout tower, by setting up baffle plate in separation column, by knockout tower
Into the part of left and right two and the region of knockout tower bottom three, knockout tower upper right is isoprene and weight light dydrocarbon and extraction for part
Agent DMF separation (equivalent to a part for former stripper) is taken, left side is the separation of light C5 and isoprene in thick isoprene
(equivalent to former extractive distillation column), tower bottom are public stripping zone.Knockout tower upper left-hand and knockout tower bottom are referred to as point
From tower king-tower, middle part charging of the raw material (the thick isoprene come from light dydrocarbon separation and culture unit) on the left of knockout tower, extraction
Agent DMF is taken to be fed near the tower top on the left of knockout tower.
Compared with prior art, the significant progress of the present invention is：One side extracting rectifying and extractant recovery can be one
Carried out in seat knockout tower, so as to eliminate stripper section, reduce equipment investment, reduce energy consumption, reduce solvent loss, the opposing party
Surface current journey, which shortens, reduces residence time of the isoprene in tower reactor, reduces the dimerization of isoprene, improves isoprene
Yield, isoprene total recovery can improve 2-3%.
Below by specific embodiment, the invention will be further described, and the yield of isoprene is determined in embodiment
Justice is：
Brief description of the drawings
Fig. 1 is a kind of process chart of the separation method of chemical grade isoprene
Embodiment
Embodiment【1~10】
The technological process of embodiment 1~10 is shown in that Fig. 1, raw material W1 are the light dydrocarbon raw material that pretreatment is stripped of cyclopentadiene, its
Main composition is shown in Table 1.
The process condition of knockout tower 1 and weight-removing column 2 is shown in Table 2, table 3 respectively, using in gas chromatography analysis product
Isoprene forms, and calculates isoprene yield with reference to each mass flow, the results are shown in Table 4.
Table 1.
Table 2.
Table 3
Table 4.
| Chemical grade isoprene content (wt%) | Chemical grade isoprene yield % | |
| Embodiment 1 | 98.5 | 97.0 |
| Embodiment 2 | 98.6 | 97.5 |
| Embodiment 3 | 98.7 | 98.0 |
| Embodiment 4 | 98.8 | 98.5 |
| Embodiment 5 | 98.9 | 99.0 |
| Embodiment 6 | 99.0 | 98.5 |
| Embodiment 7 | 99.1 | 98.5 |
| Embodiment 8 | 99.2 | 98.0 |
| Embodiment 9 | 99.3 | 97.5 |
| Embodiment 10 | 99.3 | 97.0 |
Claims (8)
1. a kind of separation method of chemical grade isoprene, it is characterised in that comprise the steps of：
1) the light dydrocarbon raw material that cyclopentadiene is stripped of by pretreatment enters knockout tower progress extracting rectifying, extractant separation, point
Knockout tower is divided into two parts in left and right by a baffle plate from tower top, while removes extractant, extractant is dimethylformamide；
Raw material is 1 than control with extractant feed weight：4~1：8, extractant feed temperature is 50~70 DEG C, and bottom temperature control is
150~170 DEG C, tower top temperature is controlled as left 30~40 DEG C of tower, right 32~42 DEG C of tower, operating pressure control for 0.02~
0.06Mpa, reflux ratio are controlled as left tower 1.5~3.5, right tower 1.5~2.5, tower top discharge respectively raffinate carbon-5 fraction with
Isoprene and heavy constituent mixtures of impurities material, tower reactor obtain extractant, and extractant recycles；
2) isoprene and heavy component impurity material obtained by step 1) enters rectifying column and carries out rectifying, and removing heavy component is miscellaneous
Matter, obtain chemical grade isoprene；Bottom temperature control is 80~100 DEG C, and tower top temperature control is 50~60 DEG C, operating pressure
Control as 0.05~0.2Mpa, reflux ratio control is 10~20, and tower top obtains chemical grade isoprene product, and tower reactor is recombinated
Part impurity.
A kind of 2. separation method of chemical grade isoprene according to claim 1, it is characterised in that the step 1) original
Material is 1 than control with extractant feed weight：5~1：6.
A kind of 3. separation method of chemical grade isoprene according to claim 1, it is characterised in that the step 1) extraction
It is 60~65 DEG C to take agent feeding temperature.
A kind of 4. separation method of chemical grade isoprene according to claim 1, it is characterised in that the step 1) tower
Kettle temperature control is 155~165 DEG C, and tower top temperature is controlled as left 34~36 DEG C of tower, right 36~38 DEG C of tower, operating pressure control
It is made as 0.03~0.05Mpa.
5. the separation method of a kind of chemical grade isoprene according to claim 1, it is characterised in that step 1) is described to return
Stream is than being controlled as left tower 2~3, right tower 1.7~2.0.
A kind of 6. separation method of chemical grade isoprene according to claim 1, it is characterised in that described point of step 1)
Highly it is the 0.8~0.9 of knockout tower from tower Internal baffle.
A kind of 7. separation method of chemical grade isoprene according to claim 1, it is characterised in that the step 2) tower
Kettle temperature control is 85~90 DEG C, and tower top temperature control is 54~56 DEG C.
A kind of 8. separation method of chemical grade isoprene according to claim 1, it is characterised in that the step 2) behaviour
It is 0.08~0.12Mpa to make Stress control, and reflux ratio control is 14~16.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516777A (en) * | 2022-03-02 | 2022-05-20 | 青岛伊科思技术工程有限公司 | Energy-saving method of isoprene refining system |
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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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| CN1469765A (en) * | 2000-09-20 | 2004-01-21 | �����ɷ� | Method and device for carrying out the distillative separation of C5+ cuts |
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| CN102951984A (en) * | 2011-08-17 | 2013-03-06 | 中国石油化工股份有限公司 | Method for separation of C5 fraction and preparation of polymer grade isoprene |
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| CN114516777A (en) * | 2022-03-02 | 2022-05-20 | 青岛伊科思技术工程有限公司 | Energy-saving method of isoprene refining system |
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