CN104761428A - Prepolymerization method for separating cracking C5 - Google Patents

Prepolymerization method for separating cracking C5 Download PDF

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Publication number
CN104761428A
CN104761428A CN201410003159.9A CN201410003159A CN104761428A CN 104761428 A CN104761428 A CN 104761428A CN 201410003159 A CN201410003159 A CN 201410003159A CN 104761428 A CN104761428 A CN 104761428A
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China
Prior art keywords
pentadiene
isoprene
prepolymerization
carbon
cyclopentadiene
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Pending
Application number
CN201410003159.9A
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Chinese (zh)
Inventor
孙长明
罗恒志
柳玉新
刘相杨
林慧忠
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FUSHUN YIKESI NEW MATERIAL Co Ltd
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FUSHUN YIKESI NEW MATERIAL Co Ltd
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Priority to CN201410003159.9A priority Critical patent/CN104761428A/en
Publication of CN104761428A publication Critical patent/CN104761428A/en
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Abstract

The invention discloses a prepolymerization method for separating cracking C5, and relates to the technical field of separation methods of the cracking C5. The method comprises the following steps: sending the above C5 raw material into a C4 removal tower, rectifying to obtain a heavy component containing isoprene, dicyclopentadiene and m-pentadiene, carrying out a dimerization reaction on the heavy component in a prepolymerization sphere tank at 50-60DEG C for 3-5d to make cyclopentadiene become dicyclopentadiene, and separating prepolymerized materials to produce isoprene and m-pentadiene. The method can reduce self polymerization of isoprene and m-pentadiene or copolymerization of isoprene, m-pentadiene and cyclopentadiene in the reaction process, controls the total loss content of isoprene, cyclopentadiene and m-pentadiene smaller than 1%, improves the product yield and reduces the production cost. Compared with traditional methods, the method disclosed in the invention has the advantages of low polymerization temperature, no need of steam heating in the reaction process, steam consumption reduction and production cost reduction.

Description

Separating cracked carbon five prepolymerization method
[technical field]
The present invention relates to the separation method of cracking c_5, in particular, the present invention relates to a kind of separating cracked carbon five prepolymerization method.
[background technology]
Can go out a kind of C5 fraction by by-product in petroleum cracking process of producing ethylene, in all cracking of ethylene by-product materials, C5 fraction occupies higher proportion.Cyclopentadiene, isoprene and m-pentadiene that total amount is 40 ~ 60wt% is contained in C5 fraction, these three kinds of diolefin chemical property are active, can react with gas chromatography, all have been widely used in resin, rubber, medicine or agriculture and other field of fine chemical.At present, be separated produce cyclopentadiene, isoprene and m-pentadiene be C5 fraction main be also the Application way of most economic worth.C5 fraction complicated component, permitted multi-component boiling point close, or easily form azeotrope, and three kinds of easier autohemagglutinations of diolefin or mutually poly-and then generation dipolymer, therefore they respectively cannot be isolated highly purified product in C5 fraction by simple rectifying.In prior art, almost all carbon five separating technology is all first carry out preliminary separation (this process is called pre-separation or pre-treatment by industrial custom) to raw material, and then carry out the process such as rectifying or extracting rectifying respectively to obtain highly purified product to initial gross separation material.
In order to solve carbon five be separated time, the time high temperature that cyclopentadiene aggregates into dicyclopentadiene can cause isoprene and m-pentadiene autohemagglutination, or isoprene, m-pentadiene and cyclopentadiene copolymerization (the loss sum 6-10% of isoprene, cyclopentadiene and m-pentadiene), the yield of isoprene, cyclopentadiene and m-pentadiene is reduced greatly.Therefore, the cyclopentadiene in the present invention's low temperature, long-time prepolymerization carbon five, reduces the loss of isoprene, cyclopentadiene and m-pentadiene, improves carbon five and has divided from the isoprene of process, cyclopentadiene and m-pentadiene yield, thus reduce production cost.Traditional process is that the cracking c_5 that tank field is come enters decarburization four tower, tower top takes off carbon four and carbon five light constituent, tower reactor obtains the heavy constituent relatively such as isoprene, cyclopentadiene, m-pentadiene, the material of tower reactor enters polymerization reaction kettle or pipeline reactor carries out high temperature polymerization, polymeric kettle temperature control 80-110 DEG C, carbon five per ton consumes 0.3-0.5t steam, is separated from polymeric kettle material out again.This mode also exists following shortcoming: 1, generally can only control the cyclopentadiene after being polymerized at 2-3%; 2, conventional art general control polymerization temperature 80-110 DEG C, isoprene and m-pentadiene autohemagglutination can be made, or isoprene, m-pentadiene and cyclopentadiene copolymerization (the loss sum 6-10% of isoprene, cyclopentadiene and m-pentadiene), the yield of isoprene, cyclopentadiene and m-pentadiene is reduced greatly., product income is low; 3, need steam heating in reaction process, increase production cost; 4, high temperature polymerization can produce a lot of oligopolymer, and oligopolymer easily blocks polymerization reaction kettle or pipeline reactor, and load is produced in impact, seriously causes production to carry out.
[summary of the invention]
The object of the invention is to the deficiency effectively overcoming above-mentioned technology, provide a kind of separating cracked carbon five prepolymerization method, the method is convenient to carbon five separation, reduces the loss of isoprene, m-pentadiene and cyclopentadiene, reduces steam consumption, lower production cost.
Technical scheme of the present invention is achieved in that the method comprises the following steps:
1) by take away pump, the carbon Wuyuan of tank field material is delivered to decarburization four tower and carry out rectifying, tower top takes off carbon four, carbon five light constituent, tower reactor obtains the relative heavy constituents such as isoprene, cyclopentadiene, m-pentadiene and dicyclopentadiene, wherein bottom temperature controls at 60-90 DEG C, and tower top temperature controls at 40-50 DEG C;
2) heavy constituent of tower reactor extraction is expected to carry out heat exchange by the interchanger that is connected with decarburization four tower and carbon Wuyuan, then this heavy constituent is delivered to prepolymerization spherical tank, carry out prepolymerization;
3) described step 2) in heavy constituent in prepolymerization spherical tank, there is dimerization reaction, wherein cyclopentadiene generation dimerization reaction generate dicyclopentadiene, during dimerization reaction, temperature controls at 50-60 DEG C, and time controling is 3-5 days;
4) material after prepolymerization is separated, produces isoprene, m-pentadiene, dicyclopentadiene.
Described step 2) in, after described heavy constituent and carbon Wuyuan expect to carry out heat exchange, the temperature of carbon Wuyuan material is 35-45 DEG C.
In described step 3), during dimerization reaction, temperature controls at 55-60 DEG C.
Beneficial effect of the present invention is: the content of cyclopentadiene can control at <1% by one, the present invention, the cyclopentadiene when being separated the material after prepolymerization is avoided certainly to be polymerized to dicyclopentadiene, affect the effect of extracting of solvent, even likely cause production to carry out, therefore the content of cyclopentadiene is more low better; Two, conventional art general control polymerization temperature 80-110 DEG C, isoprene and m-pentadiene autohemagglutination can be caused, or isoprene, m-pentadiene and cyclopentadiene copolymerization (the loss sum 6-10% of isoprene, cyclopentadiene and m-pentadiene), and polymerization temperature of the present invention is at 55-60 DEG C, isoprene and m-pentadiene autohemagglutination can be reduced during reaction, or isoprene, m-pentadiene and cyclopentadiene copolymerization, control the loss content sum <1% of isoprene, cyclopentadiene and m-pentadiene, improve product yield, reduce production cost; Three, compared with conventional art, polymerization temperature of the present invention is low, and reaction process does not need steam heating, can reduce steam consumption, reduces production cost; Four, compared with conventional art, polymerization temperature of the present invention is low, and high temperature polymerization can produce a lot of oligopolymer, oligopolymer easily blocks polymerization reaction kettle or pipeline reactor, load is produced in impact, and seriously cause production to carry out, the present invention then there will not be above-mentioned situation.
[accompanying drawing explanation]
Fig. 1 is specific embodiments of the invention figure.
[embodiment]
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
With reference to shown in Fig. 1, present invention is disclosed a kind of separating and cracking tower five prepolymerization method, concrete, the method comprises the following steps:
1) carbon Wuyuan material is contained in carbon Wuyuan batch can 10, by being connected to the take away pump on carbon Wuyuan batch can 10, carbon Wuyuan material in tank field is delivered in decarburization four tower 20 and carries out rectifying, the tower top of decarburization four tower 20 takes off carbon four, carbon five light constituent and most of alkynes, tower reactor obtains heavy constituent, and this heavy constituent mainly comprises isoprene, cyclopentadiene and m-pentadiene, wherein, bottom temperature controls at 60-90 DEG C, and tower top temperature controls at 40-50 DEG C;
2) heavy constituent of tower reactor extraction expected to carry out heat exchange with carbon Wuyuan by the interchanger 30 be connected with decarburization four tower 20, carbon five material temperature entered in decarburization four tower 20 is raised, after heavy constituent and carbon Wuyuan expect to carry out heat exchange, the temperature of carbon Wuyuan material is 35-45 DEG C; After this, the heavy constituent after heat exchange is delivered to prepolymerization spherical tank 40 inner, carry out prepolymerization;
3) step 2) in heavy constituent in prepolymerization spherical tank 40, there is dimerization reaction, wherein, cyclopentadiene generation dimerization reaction generate dicyclopentadiene, during dimerization reaction, temperature controls at 50-60 DEG C, and time controling is 3-5 days;
4) material after prepolymerization is separated, produces isoprene, m-pentadiene, dicyclopentadiene.
By above-mentioned step, the present invention can make the cyclopentadiene in carbon five fully aggregate into dicyclopentadiene, reduce the polymerization of isoprene and m-pentadiene simultaneously, improve the yield of isoprene and m-pentadiene in cracking c_5, traditional technology generally can only control the content of the cyclopentadiene after being polymerized at 2-3%, this kind of technique of the present invention then can control the content <1% of the cyclopentadiene after being polymerized, the cyclopentadiene when being separated the material after prepolymerization is avoided certainly to be polymerized to dicyclopentadiene, affect the effect of extracting of solvent, production is even likely caused to carry out, therefore the content of cyclopentadiene is more low better, in addition, conventional art general control polymerization temperature 80-110 DEG C, isoprene and m-pentadiene autohemagglutination can be made, or isoprene, m-pentadiene and cyclopentadiene copolymerization (isoprene, the loss sum 6-10% of cyclopentadiene and m-pentadiene), make isoprene, the yield of cyclopentadiene and m-pentadiene reduces greatly, and polymerization temperature of the present invention is at 55-60 DEG C, isoprene and m-pentadiene polymerization can be reduced during reaction, control isoprene, cyclopentadiene and m-pentadiene loss content sum <1%, improve product yield, reduce production cost.
Embodiment 2
Composition graphs 1, present invention is disclosed a kind of separating and cracking tower five prepolymerization method, concrete, the method comprises the following steps:
1) by take away pump, the carbon Wuyuan material in carbon Wuyuan batch can 10 is delivered to decarburization four tower 20 and carry out rectifying, tower top takes off carbon four, carbon five light constituent, tower reactor obtains the relative heavy constituent of isoprene, dicyclopentadiene and m-pentadiene, wherein bottom temperature controls at 60-90 DEG C, and tower top temperature controls at 40-50 DEG C;
2) heavy constituent of tower reactor extraction is expected to carry out heat exchange with carbon Wuyuan by the interchanger 30 be connected with decarburization four tower 20, then this heavy constituent is delivered to prepolymerization spherical tank 40, carry out prepolymerization; After described heavy constituent and carbon Wuyuan expect to carry out heat exchange, the temperature of carbon Wuyuan material is 35-45 DEG C;
3) described step 2) in heavy constituent in prepolymerization spherical tank 40, there is dimerization reaction, wherein cyclopentadiene generation dimerization reaction generate dicyclopentadiene, during dimerization reaction, temperature controls at 55-60 DEG C, and time controling is 3-5 days;
4) material after prepolymerization is separated, produces isoprene, m-pentadiene, dicyclopentadiene.
By above-mentioned step, the present invention can make the cyclopentadiene in carbon five fully aggregate into dicyclopentadiene, reduce the polymerization of isoprene and m-pentadiene simultaneously, improve the yield of isoprene and m-pentadiene in cracking c_5, traditional technology generally can only control the content of the cyclopentadiene after being polymerized at 2-3%, this kind of technique of the present invention then can control the content <1% of the cyclopentadiene after being polymerized, the cyclopentadiene when being separated the material after prepolymerization is avoided certainly to be polymerized to dicyclopentadiene, affect the effect of extracting of solvent, production is even likely caused to carry out, therefore the content of cyclopentadiene is more low better, in addition, conventional art general control polymerization temperature 80-110 DEG C, isoprene and m-pentadiene autohemagglutination can be caused, or isoprene, m-pentadiene and cyclopentadiene copolymerization (the loss sum 6-10% of isoprene, cyclopentadiene and m-pentadiene), and polymerization temperature of the present invention is at 55-60 DEG C, isoprene and m-pentadiene polymerization can be reduced during reaction, control the content <1% of isoprene and m-pentadiene participation polymerization, improve product yield, reduce production cost.
Compared with conventional art, polymerization temperature of the present invention is low, and reaction process does not need steam heating, can reduce steam consumption, reduces production cost; Further, high temperature polymerization can produce a lot of oligopolymer, and oligopolymer easily blocks polymerization reaction kettle or pipeline reactor, and load is produced in impact, and seriously cause production to carry out, the present invention then there will not be above-mentioned situation.
Described above is only preferred embodiment of the present invention, and above-mentioned specific embodiment is not limitation of the present invention.In technological thought category of the present invention, can occur various distortion and amendment, all those of ordinary skill in the art, according to describing retouching, the amendment made above or equivalent replacing, all belong to the scope that the present invention protects.

Claims (3)

1. separating cracked carbon five prepolymerization method, is characterized in that: the method comprises the following steps:
1) by take away pump, the carbon Wuyuan of tank field material is delivered to decarburization four tower and carry out rectifying, tower top takes off carbon four, carbon five light constituent, tower reactor obtains the heavy constituent of isoprene, dicyclopentadiene and m-pentadiene, and wherein bottom temperature controls at 60-90 DEG C, and tower top temperature controls at 40-50 DEG C;
2) heavy constituent of tower reactor extraction is expected to carry out heat exchange by the interchanger that is connected with decarburization four tower and carbon Wuyuan, then this heavy constituent is delivered to prepolymerization spherical tank, carry out prepolymerization;
3) described step 2) in heavy constituent in prepolymerization spherical tank, there is dimerization reaction, wherein cyclopentadiene generation dimerization reaction generate dicyclopentadiene, during dimerization reaction, temperature controls at 50-60 DEG C, and time controling is 3-5 days;
4) material after prepolymerization is separated, produces isoprene, m-pentadiene, dicyclopentadiene.
2. separating cracked carbon five prepolymerization method according to claim 1, is characterized in that: described step 2) in, after described heavy constituent and carbon Wuyuan expect to carry out heat exchange, the temperature of carbon Wuyuan material is 35-45 DEG C.
3. separating cracked carbon five prepolymerization method according to claim 1, is characterized in that: in described step 3), during dimerization reaction, temperature controls at 55-60 DEG C.
CN201410003159.9A 2014-01-03 2014-01-03 Prepolymerization method for separating cracking C5 Pending CN104761428A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412165A (en) * 2001-10-12 2003-04-23 中国石油化工股份有限公司 Separation method of cracked C5 fraction
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412165A (en) * 2001-10-12 2003-04-23 中国石油化工股份有限公司 Separation method of cracked C5 fraction
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
柯良德尔著,张平生等译: "《粗苯加工新方法》", 30 September 1982, 冶金工业出版社 *
菜世干等主编: "《石油化工工艺学》", 31 July 2006, 中国石化出版社 *
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Application publication date: 20150708