CN104276915B - A kind of separation method of C9~C10 cuts - Google Patents
A kind of separation method of C9~C10 cuts Download PDFInfo
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Abstract
A kind of separation method of C9~C10 cuts, including：Raw material rectification under vacuum in vacuum rectification tower separates, and tower top must be enriched with styrene, methyl styrene cut, and tower reactor obtains remaining cut；Kettle material enters depolymerization rectifying column and carries out depolymerization rectifying, and tower top must be rich in cyclopentadiene cut, and side line obtains the material of methyl cyclopentadiene, and tower reactor obtains indenes and remaining dicyclopentadiene mixed fraction；Tower reactor cut enters vacuum rectification tower and carries out rectification under vacuum, and tower top must be rich in the mixed fraction of indenes and dicyclopentadiene, and tower reactor obtains heavy constituent impurity；Cut rich in indenes and dicyclopentadiene enters depolymerization rectifying column and carries out depolymerization rectifying, and tower top obtains cyclopentadiene cut, and tower reactor must be rich in indenes cut.The present invention obtains the cyclopentadiene and methyl cyclopentadiene of high-purity while high-quality Petropols raw material is obtained；Rectifying separation process dimerization reaction is greatly reduced, and avoids the generation of polymer, makes one way product yield higher, also solves the contradiction of dicyclopentadiene and indenes separation difficulty.
Description
Technical field
The invention belongs to petrochemical industry, and more particularly to one kind is by petroleum cracking Crude products.deep process C9~C10 cuts
Separation Application way, i.e., C9~C10 cuts are obtained into the raw material of high-quality Petropols by the methods of depolymerization, separation.
Background technology
C9~C10 cuts be naphtha or Pyrolysis Reaction of Gas Oil accessory substance is extracted isolate C 5 fraction, C6~C8 cuts after
Remaining cut, account for the 10%~20% of ethylene yield.C9~C10 fractional compositions are complicated, there are about the 150 various ingredients cuts,
Mainly contain component and the cyclopentadiene such as more than C9 aromatic hydrocarbons, styrene, methyl styrene, dicyclopentadiene (DCPD), indenes, naphthalenes
(CPD), methyl cyclopentadiene (MCPD) various forms autohemagglutination, interpolymerized dimer, wherein again with methyl styrene and bicyclic penta 2
The content highest of alkene.The content height of dicyclopentadiene in Petropols raw material is prepared, then resin yield is high, darkens, molecule
Amount reduces.Dicyclopentadiene amount is more in C9~C10 cuts, is the principal element for influenceing resin form and aspect.Increase styrene contains
Amount can improve color and luster, improve yield, but can reduce the softening point of resin and the intermiscibility with other resins.Methyl styrene contains
Amount does not interfere with yield, but too high levels can damage form and aspect.Softening point is typically the higher the better, increases the content of indenes and can improve resin
Softening point, but content easy coking more than 20%.It is general that the diversity and complexity of this component are different from C9 polymerization
One pack system polymerization, the molecular weight of polymerizate is not in normal distribution, while C9 heavy components are more, and intrinsic colour is deeper,
So gained resin is necessarily low-grade resin.Therefore, C9~C10 cuts have industrially been had begun in certain temperature range
Carry out it is coarse-fine evaporate, raw material is cut into 3 phenylethylene, dicyclopentadiene class and indene fraction sections, then polymerize, obtaining property
The stable resin of energy.
Patent 200610130712.0 discloses a kind of method that C9 raw materials utilize, and this method cuts into C9 raw material rectifying
Phenylethylene Petropols, dicyclopentadiene resinoid oil and three fraction sections of indene Petropols, by these three fraction section roots
According to product requirement, heat polymerization kettle is added.Heat polymerization kettle is connected for four kettles, and material continues through four reactions successively
Kettle.By the material after four kettles series connection hot polymerization, distillation removes solvent therein, that is, obtains petroleum resin products.Patent
200610144206.7 disclose a kind of C9 +The method that fraction seperation utilizes, this method is by C9 +Cut is divided into richness with rectification under vacuum
Cut containing styrene and tower bottom distillate；Atmospheric distillation is carried out after described tower bottom distillate is heated into 180~380 DEG C again, by normal
Pressure rectifying tower top isolates cyclopentadiene cut, methyl cyclopentadiene cut to bottom of towe, rich in dicyclopentadiene cut, indenes successively
Content higher cut and heavy end.When kettle temperature is heated to more than 180 DEG C, depolymerization easily occurs for dicyclopentadiene in this method,
C when if temperature reaches 260 DEG C9 +Thermal polymerization can occur for the polymer monomer in cut, so as to add other dimerization in material
The generation of thing and polymer, it not only have impact on the separation of material but also add the loss of material..
The B1 of US 6,258,989 disclose a kind of method of drippolene integrated treatment, and this method heats drippolene
It is dicyclopentadiene to make cyclopentadiene therein, and the material then is cut into C5~C9 using the method for rectifying and C10+ evaporates
Segmentation, C5~C9 cuts obtain the products such as benzene, toluene and dimethylbenzene by Hydrogenation, and C10+ cuts isolate bicyclic penta by rectifying
Diene and fuel oil.US 4,522,688 is disclosed a kind of produces CPD's and MCPD only by depolymerization C9~C10 fraction seperations
Method.
It follows that in the prior art to C9~C10 cuts using merely by depolymerization separation come produce CPD and
MCPD, or the raw material as Petropols only is cut into the rectifying of C9 raw materials, C9 raw materials are not utilized sufficiently；And
During rectification under vacuum C9 raw materials, because DCPD concentration is higher, the ratio shared by styrene, methyl styrene and indenes is relatively
Low, DCPD and methyl styrene and indenes boiling point are more or less the same, under a reduced pressure more closely, wanting to obtain high level
Cut then needs larger reflux ratio, while also loses more methyl styrene.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of by petroleum cracking Crude products.deep process C9~C10 cuts
Separation method, the present invention are reducing rectifying cutting difficulty, while obtaining high-quality Petropols raw material, are improving C9~C10 cuts
Comprehensive utilization ratio.
A kind of separation method of C9~C10 cuts of the present invention, including:
（1）Through vacuum rectification tower, tower top obtains entering rich in styrene, methyl styrene cut, kettle material C10 raw materials
Next processing unit.Bottom temperature is 80~120 DEG C, and tower top temperature is 50~67 DEG C, and reflux ratio is 3~10, tower top pressure
For -80~-90KPaG.
（2）Step（1）Obtained kettle material is separated into depolymerization rectifying column, and tower top obtains CPD cuts, and side line obtains
MCPD cuts, kettle material enter next processing unit.De-polymerization temperature is 160~220 DEG C, and tower top temperature is 37~50 DEG C, side
Line temperature is 65~80 DEG C, and reflux ratio is 1~5, and tower top pressure is 0~10KPaG.
（3）Step（2）Obtained kettle material is separated into vacuum rectification tower, and tower top obtains being rich in dicyclopentadiene
With the cut of indenes, tower reactor obtains heavy constituent.Bottom temperature is 105~160 DEG C, and tower top temperature is 56~78 DEG C, and reflux ratio is 1~7,
Tower top pressure is -80~-90KPaG.
（4）Step（3）Obtained tower top material carries out depolymerization rectifying, and tower top obtains being rich in cyclopentadiene cut, and tower reactor is
Indenes.De-polymerization temperature is 160~210 DEG C, and tower top temperature is 35~49 DEG C, and reflux ratio is 1~5, and tower top pressure is 0~10KPaG.
Above-mentioned steps（1）The bottom temperature is preferably 90~105 DEG C, and tower top temperature is preferably 54~59 DEG C, reflux ratio
Preferably 5~8, tower top pressure is preferably -82~-88KPaG..
Above-mentioned steps（2）The de-polymerization temperature is preferably 180~210 DEG C, and tower top temperature is preferably 41~44 DEG C, side line temperature
Preferably 68~72 DEG C of degree, reflux ratio is preferably 2~4, and tower top pressure is preferably 2~8KPaG.
Above-mentioned steps（3）The bottom temperature is preferably 105~135 DEG C, and tower top temperature is preferably 60~70 DEG C, reflux ratio
Preferably 2~5, tower top pressure is preferably -82~-88KPaG.
Above-mentioned steps（4）The de-polymerization temperature is 170~190 DEG C, and tower top temperature is 41~44 DEG C, and reflux ratio is 1~3,
Tower top pressure is 2~8KPaG.
Beneficial effect
Compared with prior art, the advantage of the invention is that obtaining high-purity while high-quality Petropols raw material is obtained
Cyclopentadiene and methyl cyclopentadiene；Rectifying separation process dimerization reaction is greatly reduced, and whole flow process is believed that and do not deposited substantially
In recycle stock, the generation of polymer is avoided, makes one way product yield higher；Meanwhile the improvement of flow also solve it is bicyclic
The contradiction of pentadiene and indenes separation difficulty.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention, and wherein raw material C9~C10 cuts W1 initially enters the first rectification under vacuum
Tower 1（Theoretical cam curve 25）Rectification under vacuum, tower top obtain styrene, methyl styrene cut W2, and tower reactor cut W3 enters the first solution
Poly- rectifying column 2（Theoretical cam curve 20）Depolymerization rectifying is carried out, tower top obtains dicyclopentadiene cut W4, and side line obtains methyl cyclopentadiene
Cut W5, tower reactor cut W6 enter the second vacuum rectification tower 3（Theoretical cam curve 25）Rectification under vacuum is carried out, tower top obtains indenes and bicyclic
Pentadiene mixed fraction W7, tower reactor periodically discharge heavy constituent material W8.W7 enters the second depolymerization rectifying column 4（Theoretical cam curve 15）
Depolymerization rectifying is carried out, tower top obtains cyclopentadiene cut W9, and tower reactor obtains indenes cut W10.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
In the present embodiment, cyclopentadiene yield, methyl cyclopentadiene yield, styrene, methyl styrene yield and indenes
Yield is respectively defined as：
Wherein：
Unit interval dicyclopentadiene mole of feed amount=W1 flow × dicyclopentadiene mole percent；
Unit interval cyclopentadiene mole load=（W4 flow × W4 cyclopentadiene mole percents+W9 flow
× W9 cyclopentadiene mole percents）；
Unit interval double methyl cyclopentadiene mole of feed amount=W1 flow × bis- methyl cyclopentadienes mole percent；
Unit interval methyl cyclopentadiene mole load=W5 flow × methyl cyclopentadiene mole percent；
Unit interval styrene, methyl styrene mole of feed amount=W1 flow × W1 styrene, methyl styrene rub
That percentage；
Unit interval styrene, methyl styrene mole load=W2 flow × W25 styrene, methyl styrene rub
That percentage；
Unit interval indenes molar product inlet amount=W1 flow × W1 indenes mole percents；
Unit interval indenes molar product load=W10 flow × W10 indenes mole percents.
【Embodiment 1~10】
（1）C9~C10 cuts are evaporated under reduced pressure by the first vacuum rectification tower 1, tower top obtains styrene, methylbenzene
Ethene cut, tower reactor obtain remaining cut；Wherein bottom temperature is 80~120 DEG C, and tower top temperature is 50~67 DEG C, reflux ratio 3
~10, tower top pressure is -80~-90KPaG.；
（2）By step（1）The tower reactor cut of gained enters the depolymerization rectifying of the first depolymerization rectifying column 2, and tower top obtains cyclopentadiene
Cut, side line obtain methyl cyclopentadiene, and tower reactor obtains remaining cut；Wherein, bottom temperature is 160~220 DEG C, and tower top temperature is
37~50 DEG C, side stream temperature is 65~80 DEG C, and reflux ratio is 1~5, and tower top pressure is 0~10KPaG；
（3）By step（2）The tower reactor cut of gained is evaporated under reduced pressure into the second vacuum rectification tower 3, and tower top obtains bicyclic
Pentadiene and indenes mixed fraction, tower reactor obtain heavy constituent；Wherein, bottom temperature is 105~160 DEG C, and tower top temperature is 56~78 DEG C,
Reflux ratio is 1~7, and tower top pressure is -80~-90KPaG；
（4）By step（3）Overhead fraction cyclopentadiene cut is obtained by the depolymerization rectifying of the second depolymerization rectifying column 4, tower top,
Bottom of towe obtains indenes cut；Wherein, depolymerization reaction temperature is 160~210 DEG C, and tower top temperature is 35~49 DEG C, and reflux ratio is 1~5, tower
Pressure on top surface is 0~10KPaG.
Accompanying drawing 1 is shown in the technological process of embodiment 1~10, and raw material is C9~C10 cuts of petroleum cracking ethylene by-product, main
Form and be shown in Table 1.
Each embodiment the first vacuum rectification tower 1, the first depolymerization rectifying column 2, the second vacuum rectification tower 3 and the second depolymerization essence
The process condition for evaporating tower 4 is shown in Table 2,3,4 and 5 respectively.Analyzed respectively using gas chromatography material W2, W4, W5, W9 and
W10 composition, the content of enriched composition is shown in Table 6 in each material.In conjunction with the yield of the flow rate calculation product of each material, as a result see
Table 7.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Although the present invention discloses preferred embodiment as above, so it is not limited to present disclosure, any ripe
Know this those skilled in the art, do not departing from the present invention main spirits and context in, when can make it is various change and retouching, therefore invent
Protection domain should be defined by the basic right claimed range applied for a patent.
Claims (9)
1. a kind of separation method of C9~C10 cuts, it is characterised in that this method comprises the following steps:
（1）C9~C10 cuts are passed through into the first vacuum rectification tower（1）It is evaporated under reduced pressure, tower top obtains styrene, methylbenzene second
Alkene cut, tower reactor obtain remaining cut；Wherein, bottom temperature be 80~120 DEG C, tower top temperature be 50~67 DEG C, reflux ratio be 3~
10, tower top pressure is -80~-90KPaG；
（2）By step（1）The tower reactor cut of gained enters the first depolymerization rectifying column（2）Depolymerization rectifying, tower top obtain cyclopentadiene and evaporated
Point, side line obtains methyl cyclopentadiene, and tower reactor obtains remaining cut；Wherein, bottom temperature is 160~220 DEG C, tower top temperature 37
~50 DEG C, tower top pressure is 0~10KPaG, and side stream temperature is 65~80 DEG C, and reflux ratio is 1~5；
（3）By step（2）The tower reactor cut of gained enters the second vacuum rectification tower（3）It is evaporated under reduced pressure, tower top obtains bicyclic penta
Diene and indenes mixed fraction, tower reactor obtain heavy constituent；Wherein, bottom temperature is 105~160 DEG C, and tower top temperature is 56~78 DEG C, tower
Pressure on top surface is -80~-90KPaG, and reflux ratio is 1~7；
（4）By step（3）Overhead fraction pass through the second depolymerization rectifying column（4）Depolymerization rectifying, tower top obtain cyclopentadiene cut, tower
Bottom obtains indenes cut；Wherein, depolymerization reaction temperature be 160~210 DEG C, tower top temperature be 35~49 DEG C, tower top pressure be 0~
10KPaG, reflux ratio are 1~5.
2. the separation method of C9~C10 cuts according to claim 1, it is characterised in that：The step（1）In tower reactor
Temperature is 90~105 DEG C, and tower top temperature is 54~59 DEG C, and tower top pressure is -82~-88KPaG.
3. the separation method of C9~C10 cuts according to claim 1, it is characterised in that：The step（1）In backflow
Than for 5~8.
4. the separation method of C9~C10 cuts according to claim 1, it is characterised in that：The step（2）In tower reactor
Temperature is 180~210 DEG C, and tower top temperature is 41~44 DEG C, and tower top pressure is 2~8KPaG, and side stream temperature is 68~72 DEG C.
5. the separation method of C9~C10 cuts according to claim 1, it is characterised in that：The step（2）In backflow
Than for 2~4.
6. the separation method of C9~C10 cuts according to claim 1, it is characterised in that：The step（3）In tower reactor
Temperature is 105~135 DEG C, and tower top temperature is 60~70 DEG C, and tower top pressure is -82~-88KPaG.
7. the separation method of C9~C10 cuts according to claim 1, it is characterised in that：The step（3）In backflow
Than for 2~5.
8. the separation method of C9~C10 cuts according to claim 1, it is characterised in that：The step（4）In depolymerization
Reaction temperature is 170~190 DEG C, and tower top temperature is 41~44 DEG C, and tower top pressure is 2~8KPaG.
9. the separation method of C9~C10 cuts according to claim 1, it is characterised in that：The step（4）In backflow
Than for 1~3.
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| CN108865259B (en) * | 2018-06-09 | 2022-08-05 | 濮阳市联众兴业化工有限公司 | Method for decoloring and deodorizing cracking carbon nine |
| CN111548246A (en) * | 2020-04-23 | 2020-08-18 | 广东新华粤石化集团股份公司 | Method for preparing high-purity dicyclopentadiene from cracking carbon nine fraction |
| CN114426445A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Comprehensive utilization method of carbon nine-carbon ten-fraction as byproduct in ethylene preparation through petroleum cracking |
| CN115124403B (en) * | 2022-09-01 | 2022-12-06 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for separating cracked carbon nine by single-tower rectification in petroleum resin system |
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| CN101190868A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Separation utilization method for preparing ethene by-product C9+ fractioning by cracking |
| CN102010285A (en) * | 2010-11-02 | 2011-04-13 | 宁波职业技术学院 | Method for extracting methyl cyclopentadiene from ethylene cracked C9 heavy fractions |
| CN102399123A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene and dimethylcyclopentadiene |
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| US4522688A (en) * | 1982-10-29 | 1985-06-11 | Maruzen Petrochemical Co., Ltd. | Process for recovery of cyclopentadienes |
| CN101190868A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Separation utilization method for preparing ethene by-product C9+ fractioning by cracking |
| CN101186552A (en) * | 2007-11-22 | 2008-05-28 | 山东东昌精细化工科技有限公司 | Technique for separating cyclopentadiene and methylcyclopentadiene |
| CN102399123A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene and dimethylcyclopentadiene |
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