CN101244976B - Method for producing polymerization level isoprene - Google Patents
Method for producing polymerization level isoprene Download PDFInfo
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- CN101244976B CN101244976B CN2007100639570A CN200710063957A CN101244976B CN 101244976 B CN101244976 B CN 101244976B CN 2007100639570 A CN2007100639570 A CN 2007100639570A CN 200710063957 A CN200710063957 A CN 200710063957A CN 101244976 B CN101244976 B CN 101244976B
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Abstract
The invention relates to a method for preparing polymerization grade isoprene which belongs to the technical field of separating 5 carbon stream, and provides a method for preparing polymerization grade isoprene in order to solve the problems of a second extraction unit in the existing carbonium 5 separation process, such as high energy consumption, complex operation, harsh operation demand and big extraction solvent loss, etc.; the method adopts a distillation method to remove isoprene and uses an azeotropy distillation method to remove alkyne; a polymerization grade isoprene product is obtained with no need of two times extraction and the second extraction unit and a solvent refining tower are omitted. The method for preparing the polymerization grade isoprene is simple in operation, easy in operation and low in production cost; the energy consumption of the polymerization grade isoprene product unit of the invention is about 20 percent of the existing second extraction unit in the same treating load of the raw material; m-pentadiene is produced from a pre-deheavy tower kettle and does not enter an extraction and distillation unit; the throughput of the extraction and distillation tower, an absorption tower and a de-heavy tower is reduced by 50 percent with the energy consumption being reduced by 50 percent correspondingly, and construction cost and production cost are greatly reduced.
Description
Technical field
The present invention relates to the isolating method of a kind of C5 fraction, more particularly, the present invention relates to the method that a kind of separating cracked carbon-5 fraction is produced the polymerization grade isoprene product.
Background technology
Diolefins such as isoprene, cyclopentadiene and m-pentadiene are rich in a considerable amount of C5 fractions of by-product in the C5 fraction in the process of petroleum cracking system ethene.These diolefin chemical property are active, are important chemical material.Because petroleum hydrocarbon cracking raw materials, cracking severity and separation degree is different, diolefin content is different in the cracked C 5 fraction, and total content is between 40～60%.Therefore, separate and utilize C5 fraction to improving the economic benefit of ethylene unit, the comprehensive utilization petroleum resources have far reaching significance.
Cracked C 5 fraction contain more than 20 kind of boiling point close, easily form the component of azeotrope each other, from wherein isolating the higher C 5 diene of comprehensive utilization value, technology is comparatively complicated.C5 fraction contains for example alkynes such as crotonylene and valylene, these alkynes content are generally in 0.1～2% scope, because their chemical property is active, it is the main detrimental impurity of reaction of C 5 diene product and polymerization process, therefore remove alkynes wherein effectively, this step is the important step of cracked C 5 fraction separating technology.
In order to produce the polymerization grade isoprene product, generally adopt the two-section extraction rectificating method in the prior art, the existing employed extraction solvent of industrialized cracked C 5 fraction method has dimethyl formamide (DMF), acetonitrile etc.For example in carbon five separation process of China's research and development, first extraction cells removes alkane and the monoolefine in the cracked C 5 fraction, make chemical grade isoprene, second extraction cells removes alkynes and cyclopentadiene wherein, alkynes mainly is crotonylene and valylene, but second extraction cells exists problems, (1) in such two-section extraction rectificating method, operating equipment is more, the energy consumption of second extraction cells is very high, needs strict operation, and the simmer down to operation in some equipment of (2) alkynes brings unsafe factor, there is black bits latch up phenomenon in (3) second extraction cells, solvent recovery unit has a large amount of burnt matter, and is difficult to cleaning, and (4) solvent-oil ratio is big, increase production cost, had problem of environmental pollution simultaneously.
Summary of the invention
The present invention is directed to that existing second extraction cells is taken off the energy consumption height of existence, operational difficulty, easily stopped up, solvent loss is big and uneasy congruent problem, a kind of method of one-section abstraction distillation separation cracking carbon 5-cut fraction is proposed, this method is utilized rectificating method to remove cyclopentadiene and is utilized the azeotropic distillation method to remove alkynes, does not need second extraction cells just can obtain the polymerization grade isoprene product.
Concrete technical scheme is as follows.
The method of producing polymerization grade isoprene that the present invention proposes may further comprise the steps:
(1) pretreatment unit: cracked C 5 fraction enters the light constituent of pre-lightness-removing column from removed overhead carbon containing four, alkynes and alkane, the material of tower still extraction enters dipolymer reactor and carries out dimerization reaction, make cyclopentadiene dimerization wherein become dicyclopentadiene, enter pre-weight-removing column then, from the material of cat head extraction based on isoprene, from the material of tower still extraction based on m-pentadiene and dicyclopentadiene, the cat head material is sent into the extracting rectifying unit;
(2) extracting rectifying unit: the material from pre-weight-removing column cat head enters the extractive distillation column middle part, extraction solvent enters extractive distillation column from top, through the extracting rectifying effect from cat head extraction C 5 alkane and monoolefine, the solvent that contains isoprene, alkynes and cyclopentadiene is from the extraction of tower still, the solvent of this hydrocarbonaceous enters Analytic Tower, from resolving cat head extraction isoprene, alkynes and cyclopentadiene, use from the solvent cycle of Analytic Tower still extraction
Or enter first Analytic Tower from the solvent of the hydrocarbonaceous of extractive distillation column still and resolve the recovery solvent, first Analytic Tower and the second Analytic Tower serial operation, first gas of resolving the cat head extraction enters the bottom of second Analytic Tower, the liquid of the second Analytic Tower still enters from the first Analytic Tower cat head, from the second parsing cat head extraction isoprene, alkynes and cyclopentadiene, use from the solvent cycle of the first Analytic Tower still extraction; The material of resolving cat head from Analytic Tower or second enters the bottom of weight-removing column, from cat head extraction isoprene, makes cyclopentadiene content in the isoprene less than 1ppm, tower still extraction cyclopentadiene and the isoprene of carrying secretly;
(3) polymerization grade isoprene unit: make material enter the decylization pentadiene reactor that MALEIC ANHYDRIDE is housed from weight-removing column top, cyclopentadiene and maleic acid anhydride reactant in decylization pentadiene reactor so that the cyclopentadiene content in the isoprene less than 1ppm; The material that comes out from decylization pentadiene reactor enters azeotropy rectification column with iso-pentane as entrainer, isolate iso-pentane and alkynes from cat head, from tower still or tower still side line extraction polymerization grade isoprene product, make alkynes content in the isoprene less than 50ppm; Material from the azeotropic distillation column overhead enters the hydrogenator that catalyzer is housed, through shortening with the alkynes hydrogenation and removing; The material that comes out from hydrogenator enters knockout drum, and the liquid circulation of telling in the knockout drum lower end is returned azeotropy rectification column and used, and the compressed hydrogenator that loops back of the gas that the upper end emits uses.
In the present invention, the boiling point of isoprene and valylene (valylene) is 34 ℃, adopts the conventional distillation method not separate between them.Yet iso-pentane can form azeotrope with crotonylene and valylene respectively, does not form azeotrope with isoprene, and the boiling point of the azeotrope that iso-pentane and valylene form is 26.3 ℃, and azeotropic consists of the iso-pentane of 63.8 quality %.The boiling point of the azeotrope that iso-pentane and crotonylene form is lower.Thereby utilize iso-pentane can remove alkynes in the isoprene as entrainer.
Method of the present invention can further include step: merge from the material of pre-weight-removing column T-102 tower still with from the material of weight-removing column T-204 tower still, send into carbon five and steam tower T-401, steam tower T-401 cat head extraction carbon five hydrocarbon at carbon five, from tower still extraction dicyclopentadiene, cat head carbon five hydrocarbon enter the m-pentadiene treating tower, from the material of cat head extraction isoprene containing, this material enters dipolymer reactor R-101 or pre-weight-removing column T-102, and the tower still obtains the m-pentadiene product.
Selectively, method of the present invention can further include step: send into carbon five from the material of pre-weight-removing column tower still and steam tower, steam column overhead extraction carbon five hydrocarbon at carbon five, from tower still extraction dicyclopentadiene, cat head carbon five hydrocarbon enter the m-pentadiene treating tower, from the material of cat head extraction isoprene containing, this material and merge from the material of weight-removing column tower still and to enter dipolymer reactor or pre-weight-removing column, the tower still obtains the m-pentadiene product.
Preferably, pre-weight-removing column T-102 has 70～130 number of theoretical plates, and reflux ratio is 5～20, and tower top temperature is 40～60 ℃, from the middle part charging.
Preferably, weight-removing column T-204 has 70～150 number of theoretical plates, and reflux ratio is 7～20, and tower top temperature is 40～60 ℃, from underfeed.
Preferably, described azeotropy rectification column has 70～200 theoretical stages, and from tower middle part charging, the weight ratio of isoprene material and iso-pentane is 20: 0.5～5, and reflux ratio is 50～120.
Palladium catalyst or nickel catalyzator are housed in hydrogenator, and reaction conditions is: reaction pressure 1.0～5.0MPa, 20～150 ℃ of temperature of reaction, liquid hourly space velocity 0.1～10h
-1Owing to contain a large amount of iso-pentane and a spot of alkynes, isoprene from the material of azeotropic distillation cat head, the purpose of carrying out shortening in this hydrogenator is exactly alkynes and the complete hydrogenation and removing of isoprene with wherein, therefore can use industrial normally used hydrogenation with palladium catalyst or nickel catalyzator, for example the various hydrogenation catalysts produced of Beijing Chemical Research Institute.There is no particular limitation to hydrogenation conditions, those skilled in the art can freely select according to general knowledge, as long as it is just passable that the crotonylene in the iso-pentane, valylene and the isoprene carried secretly are hydrogenated into alkane substantially, the crotonylene hydrogenation becomes butane, its boiling point is very low, can emit by emptying on the return tank of azeotropy rectification column, valylene and isoprene are hydrogenated into iso-pentane, do not need to separate again.
In separation method of the present invention, any solvent that extractive distillation column can use this area to use for example uses acetonitrile, dimethyl formamide or N-Methyl pyrrolidone as solvent.
Highly purified isoprene is when being used for polyreaction, a spot of alkynes can consume polymerizing catalyst in large quantities, and bring disadvantageous color to polymerisate, therefore the general requirement alkynes that is used for the polymeric high purity isoprene less than 50ppm and cyclopentadiene less than 1ppm, adopt separation method of the present invention, do not need to carry out second section extraction and just can obtain the polymerization grade isoprene product.
In the present invention, concentration all in mass, per-cent is meant mass percent, ppm is meant * 10
-6(mass concentration).
Method of the present invention is compared with existing C5 fraction separation process, has the following advantages:
1. the method for producing polymerization grade isoprene of the present invention only adopts the one-section abstraction rectificating method, does not need for the second time that extraction rectifying method just can obtain the polymerization grade isoprene product, because there is not the second extracting rectifying unit, thereby can omit the solvent treatment tower.The purpose of solvent treatment tower is exactly the dicyclopentadiene that removes in the circulating solvent, avoid making the cyclopentadiene content in the isoprene product be higher than 1ppm during extracting rectifying in the second time, obviously, there is not such problem in method of the present invention, does not just need the solvent treatment tower.
2. the equipment that method of the present invention is used is few, simple to operate, easy handling, and construction cost and production cost reduce.
3. handle under the load at identical raw material, in polymerization grade isoprene of the present invention unit the needed heat energy consumption of azeotropic distillation part be about existing second extraction cells the heat energy consumption 20%.Because m-pentadiene from the extraction of pre-weight-removing column tower still, does not enter the extracting rectifying unit, the treatment capacity of extractive distillation column, Analytic Tower and weight-removing column reduces by 50%, and correspondingly energy consumption also reduces by 50%, and therefore, production cost reduces greatly.
Description of drawings
Fig. 1 is the synoptic diagram of the existing cracked C 5 fraction separation process of China.
Fig. 2 is a schematic flow sheet of producing the method for polymerization grade isoprene of the present invention.
Nomenclature:
In Fig. 1, the pre-lightness-removing column of T-101; The R-101 dipolymer reactor; The pre-weight-removing column of T-102; T-201 first extraction tower; T-202, T-203 one collection Analytic Tower; The T-204 weight-removing column; T-301 second extraction tower; The T-302 lightness-removing column; T-303 two collection Analytic Towers; T-304 vacuum analysis tower; T-401 carbon five steams tower; T-402 m-pentadiene treating tower; T-403 dicyclopentadiene treating tower; The E-501 solvent regeneration tower; The burnt matter dilution of V-501 tower; T-501 solvent treatment tower;
In Fig. 2, R-301 decylization pentadiene reactor; 1 azeotropy rectification column; The R-302 hydrogenator; The V-301 knockout drum; All the other symbols are identical with implication among Fig. 1.
Embodiment
Below in conjunction with the further method of producing polymerization grade isoprene of the present invention of accompanying drawing.
With reference to Fig. 1, C5 fraction separation method by Beijing Chemical Research Institute's research has the commerical test device in Kingsoft construction, adopt the two-section extraction rectificating method, comprise 5 unit altogether, i.e. raw materials pretreatment unit, first extraction cells, second extraction cells, m-pentadiene and dicyclo refined unit and solvent recovery unit.The raw materials pretreatment unit removes most of alkynes and light constituent in pre-lightness-removing column T-101, through dipolymer reactor R-101 cyclopentadiene is transformed into dicyclopentadiene, removes in pre-weight-removing column T-102.In first extraction cells, the first extraction tower T-201 adopts solvent removal alkane and monoolefine, the solvent that contains isoprene is resolved the recovery solvent through a collection Analytic Tower T-202 and T-203, the material that parses contains components such as isoprene, alkynes (being mainly crotonylene, valylene), m-pentadiene, a small amount of cyclopentadiene, cyclopentenes, pentamethylene, isolates isoprene, alkynes, micro-cyclopentadiene through weight-removing column T-204 from cat head.In second extraction cells, utilize solvent in the second extraction tower T-301, valylene and cyclopentadiene to be extracted in the solvent once more, cat head is isolated isoprene and crotonylene, this material enters lightness-removing column T-302 general crotonylene (isoprene: 34 ℃ wherein, crotonylene: 27 ℃) isolate, solvent reclaims solvent through normal pressure Analytic Tower T-303 and decompression Analytic Tower T-304.M-pentadiene and dicyclo refined unit obtain m-pentadiene product and dicyclo product through decarburization five tower T-401, m-pentadiene treating tower T-402 and dicyclo treating tower T-403.Solvent recovery unit at first utilizes regeneration still E-501 to remove wherein burnt matter, burnt matter is emitted through dilution in V-501, utilize water and dicyclo azeotropic to steam wherein dicyclo at solvent treatment tower T-501 then, the cyclopentadiene that the recovery solvent of avoiding entering second extraction cells has in the isoprene product that the dicyclo component makes production is defective.
Explain one embodiment of the invention below with reference to Fig. 2.The method of producing polymerization grade isoprene that the present invention proposes may further comprise the steps:
(1) pretreatment unit: cracked C 5 fraction enters the light constituent of pre-lightness-removing column T-101 from removed overhead carbon containing four, alkynes and alkane, the material of tower still extraction enters dipolymer reactor R-101 and carries out dimerization reaction, make cyclopentadiene dimerization wherein become dicyclopentadiene, enter pre-weight-removing column T-102 then, from the material of cat head extraction based on isoprene, from the material of tower still extraction based on m-pentadiene and dicyclopentadiene, the cat head material is sent into the extracting rectifying unit;
(2) extracting rectifying unit: the material from pre-weight-removing column T-102 cat head enters extractive distillation column T-201 from the middle part, extraction solvent enters extractive distillation column T-201 from top, through extracting rectifying from cat head extraction C 5 alkane and monoolefine, contain isoprene, the solvent of alkynes and cyclopentadiene is from the extraction of tower still, the solvent of this hydrocarbonaceous enters the first Analytic Tower T-202 and resolves the recovery solvent, the first Analytic Tower T-202 and the second Analytic Tower T-203 serial operation, the gas of the first Analytic Tower T-202 top extraction enters the bottom of the second Analytic Tower T-203, the liquid of the second Analytic Tower T-203 still enters from the first Analytic Tower T-202 cat head, from the second Analytic Tower T-203 top extraction isoprene, alkynes and cyclopentadiene, use from the solvent cycle of the first Analytic Tower T-202 still extraction, enter the bottom of weight-removing column T-204 from the material on second Analytic Tower T-203 top, from cat head extraction isoprene, tower still extraction cyclopentadiene and the isoprene of carrying secretly;
(3) polymerization grade isoprene unit: make material enter the decylization pentadiene reactor R-301 that MALEIC ANHYDRIDE is housed from weight-removing column T-204 top, cyclopentadiene and maleic acid anhydride reactant in decylization pentadiene reactor R-301 so that the cyclopentadiene content in the isoprene less than 1ppm; The material that comes out from decylization pentadiene reactor R-301 enters azeotropy rectification column 1 with iso-pentane as entrainer, isolate iso-pentane and alkynes from cat head, from tower still side line extraction polymerization grade isoprene product, make alkynes content in the isoprene less than 50ppm; Material from azeotropy rectification column 1 cat head enters the hydrogenator R-302 that catalyzer is housed, through shortening with the alkynes hydrogenation and removing; The material that comes out from hydrogenator R-302 enters knockout drum V-301, and the liquid circulation of telling in the lower end is returned azeotropy rectification column and used, and the compressed hydrogenator R-302 that loops back of the gas of emitting in the upper end uses.
Method of the present invention may further include step: merge from the material of pre-weight-removing column T-102 tower still with from the material of weight-removing column T-204 tower still, send into carbon five and steam tower T-401, steam tower T-401 cat head extraction carbon five hydrocarbon at carbon five, from tower still extraction dicyclopentadiene, cat head carbon five hydrocarbon enter m-pentadiene treating tower T-402, from the material of cat head extraction isoprene containing, this material enters dipolymer reactor R-101 or pre-weight-removing column T-102, and the tower still obtains the m-pentadiene product.Perhaps, send into carbon five from the material of pre-weight-removing column T-102 tower still and steam tower T-401, be sent to dipolymer reactor R-101 or pre-weight-removing column T-102 from the material of weight-removing column 2 tower stills and from the material merging of m-pentadiene treating tower T-402 cat head.These materials that circulate can reclaim wherein isoprene to improve the isoprene yield of whole device, certainly this step that is not absolutely necessary.The material that steams tower T-401 tower still from carbon five enters dicyclopentadiene treating tower T-403, and the tower still obtains the dicyclopentadiene product.This part is identical with China existing cracked C 5 fraction tripping device, does not specifically describe here.Certainly those skilled in the art can be according to practical situation by these three rectifying tower of calculation Design.
Extract partial solvent out from the second Analytic Tower T-203 tower still and be sent to solvent reclamation still E-501, the decompression heating steams solvent, the solvent cycle utilization, and the residue of the solvent reclamation still E-501 solvent cut jar V-501 that fell regularly emits.Solvent reclamation still and regeneration condition are identical with existing regeneration still, and it is just passable to separate burnt matter by underpressure distillation, does not specifically describe here.But compared with prior art, the present invention does not need the solvent treatment tower.
Cracked C 5 fraction with Yanshan Petrochemical company is a raw material, utilizes separation method of the present invention to carry out cracked C 5 fraction and separates, during the turnover material composition of raw material composition and each operating gear is listed in the table below.
(1) pretreatment unit: 31, the cracked C 5 fraction of 000kg/h enters pre-lightness-removing column T-101 middle part, pre-lightness-removing column T-101 has 80 theoretical stages, reflux ratio is 22, tower top temperature is 45 ℃, from removed overhead carbon containing four, the light constituent of alkynes and alkane, the material of tower still extraction enters dipolymer reactor R-101, under 80～85 ℃, carry out dimerization reaction, make cyclopentadiene dimerization wherein become dicyclopentadiene, enter pre-weight-removing column T-102 then, pre-weight-removing column T-102 has 85 theoretical stages, and reflux ratio is 10, tower top temperature is 50 ℃, from the material of cat head extraction based on isoprene, from the material of tower still extraction based on m-pentadiene and dicyclopentadiene, the cat head material is sent into the extracting rectifying unit;
(2) extracting rectifying unit: the material from pre-weight-removing column T-102 cat head enters extractive distillation column T-201 from the middle part, extractive distillation column T-201 has 110 theoretical stages, reflux ratio is 2, extraction solvent enters extractive distillation column T-201 from top, solvent is a dimethyl formamide in the present embodiment, but the present invention is not limited to it, the charging mass flux ratio of solvent and carbon five hydrocarbon chargings is 5.5, through the extracting rectifying effect from cat head extraction C 5 alkane and monoolefine, contain isoprene, the solvent of alkynes and cyclopentadiene is from the extraction of tower still, the solvent of this hydrocarbonaceous enters the first Analytic Tower T-202 and resolves the recovery solvent, the first Analytic Tower T-202 and the second Analytic Tower T-203 serial operation, the gas of the first Analytic Tower T-202 top extraction enters the bottom of the second Analytic Tower T-203, the liquid of the second Analytic Tower T-203 still enters from the first Analytic Tower T-202 cat head, from the second Analytic Tower T-203 top extraction isoprene, alkynes and cyclopentadiene, use from the solvent cycle of the first Analytic Tower T-202 still extraction, regenerate from the second Analytic Tower T-203 tower still extraction a small amount of solvent regeneration unit that desolvates, the first Analytic Tower T-202 and the second Analytic Tower T-203 have 15 theoretical stages respectively, the reflux ratio of the second Analytic Tower T-203 is 1, and tower top temperature is 50 ℃; Enter the bottom of weight-removing column T-204 from the material of the second Analytic Tower T-203 cat head, weight-removing column T-204 has 100 theoretical stages, and reflux ratio is 15, and tower top temperature is 45 ℃, from cat head extraction isoprene, and tower still extraction cyclopentadiene and the isoprene of carrying secretly;
(3) polymerization grade isoprene unit: the material from weight-removing column T-204 top enters the decylization pentadiene reactor R-301 that MALEIC ANHYDRIDE is housed, cyclopentadiene and maleic acid anhydride reactant in decylization pentadiene reactor R-301 so that the cyclopentadiene content in the isoprene less than 1ppm; Make from the material of decylization pentadiene reactor R-301 and iso-pentane and enter azeotropy rectification column 1 as entrainer, azeotropy rectification column 1 has 100 theoretical stages, reflux ratio is 50, the charging mass flux ratio of iso-pentane and isoprene is 1: 20, tower top temperature is 45 ℃, isolate iso-pentane and alkynes from cat head,, make alkynes content in the isoprene less than 50ppm from tower still extraction isoprene; Enter the hydrogenator R-301 that the palladium catalyst that the Beijing Chemical Research Institute produces is housed from the material of azeotropy rectification column 1 cat head, with the alkynes hydrogenation and removing, hydrogenation pressure is 3.0Mpa through shortening, and hydrogenation temperature is 45～60 ℃, and the volume hourly space velocity is 3h
-1, by analysis, the material behind the hydrogenation does not contain alkynes and alkene substantially; The material that comes out from hydrogenator R-301 enters knockout drum V-301, and the liquid circulation of telling from knockout drum V-301 lower end is returned azeotropy rectification column 1 and used, and the compressed hydrogenator R-301 that loops back of the hydrogen of telling from the upper end uses.
Merge from the material of pre-weight-removing column T-102 tower still with from the material of weight-removing column T-204 tower still, send into carbon five and steam tower T-401, steam tower T-401 cat head extraction carbon five hydrocarbon at carbon five, from tower still extraction dicyclopentadiene, cat head carbon five hydrocarbon enter m-pentadiene treating tower T-402, and from the material of cat head extraction isoprene containing, this material enters dipolymer reactor R-101 or pre-weight-removing column T-102, can certainly be sent to head tank, the tower still obtains the m-pentadiene product.Perhaps, send into carbon five from the material of pre-weight-removing column T-102 tower still and steam tower T-401, be sent to dipolymer reactor R-101 or pre-weight-removing column T-102 from the material of weight-removing column T-204 tower still and from the material merging of m-pentadiene treating tower T-402 cat head.The material that steams tower T-401 tower still from carbon five enters dicyclopentadiene treating tower T-403, and the tower still obtains the dicyclopentadiene product.This part is identical with China existing cracked C 5 fraction tripping device, does not specifically describe here.Certainly those skilled in the art can be according to practical situation by these three rectifying tower of calculation Design.
Extract partial solvent out from the second Analytic Tower T-203 tower still and be sent to solvent reclamation still E-501, the decompression heating steams solvent, the solvent cycle utilization, and the residue of the solvent reclamation still E-501 solvent cut jar V-501 that fell regularly emits.Solvent reclamation still and regeneration condition are identical with existing regeneration still, and it is just passable to separate burnt matter by underpressure distillation, does not specifically describe here.But compared with prior art, the present invention does not need the solvent treatment tower.
The turnover material of table main device is formed
Claims (7)
1. a method of producing polymerization grade isoprene is characterized in that, said method comprising the steps of:
(1) pretreatment unit: cracked C 5 fraction enters the light constituent of pre-lightness-removing column from removed overhead carbon containing four, alkynes and alkane, the material of tower still extraction enters dipolymer reactor and carries out dimerization reaction, make cyclopentadiene dimerization wherein become dicyclopentadiene, enter pre-weight-removing column then, from the material of cat head extraction based on isoprene, from the material of tower still extraction based on m-pentadiene and dicyclopentadiene, the cat head material is sent into the extracting rectifying unit;
(2) extracting rectifying unit: the material from pre-weight-removing column cat head enters the extractive distillation column middle part, extraction solvent enters extractive distillation column from top, through the extracting rectifying effect from cat head extraction C 5 alkane and monoolefine, the solvent that contains isoprene, alkynes and cyclopentadiene is from the extraction of tower still, the solvent of this hydrocarbonaceous enters Analytic Tower, from resolving cat head extraction isoprene, alkynes and cyclopentadiene, use from the solvent cycle of Analytic Tower still extraction
Or enter first Analytic Tower from the solvent of the hydrocarbonaceous of extractive distillation column still and resolve the recovery solvent, first Analytic Tower and the second Analytic Tower serial operation, first gas of resolving the cat head extraction enters the bottom of second Analytic Tower, the liquid of the second Analytic Tower still enters from the first Analytic Tower cat head, from the second parsing cat head extraction isoprene, alkynes and cyclopentadiene, use from the solvent cycle of the first Analytic Tower still extraction; Enter the bottom of weight-removing column from resolving the cat head or second material of resolving cat head, from cat head extraction isoprene, tower still extraction cyclopentadiene and the isoprene of carrying secretly;
(3) polymerization grade isoprene unit: make material enter the decylization pentadiene reactor that MALEIC ANHYDRIDE is housed from weight-removing column top, cyclopentadiene and maleic acid anhydride reactant in decylization pentadiene reactor so that the cyclopentadiene content in the isoprene less than 1ppm; The material that comes out from decylization pentadiene reactor enters azeotropy rectification column with iso-pentane as entrainer, isolate iso-pentane and alkynes from cat head, from tower still or tower still side line extraction polymerization grade isoprene product, make alkynes content in the isoprene less than 50ppm; Material from the azeotropic distillation column overhead enters the hydrogenator that catalyzer is housed, through shortening with the alkynes hydrogenation and removing; The material that comes out from hydrogenator enters knockout drum, and the liquid circulation of telling in the knockout drum lower end is returned azeotropy rectification column and used, and the compressed hydrogenator that loops back of the gas that the upper end emits uses;
Described extractive distillation column uses acetonitrile, dimethyl formamide or N-Methyl pyrrolidone as solvent.
2. the method for producing polymerization grade isoprene as claimed in claim 1, it is characterized in that, merge from the material of pre-weight-removing column tower still with from the material of weight-removing column tower still, send into carbon five and steam tower, steam column overhead extraction carbon five hydrocarbon, from tower still extraction dicyclopentadiene at carbon five, cat head carbon five hydrocarbon enter the m-pentadiene treating tower, from the material of m-pentadiene treating tower cat head extraction isoprene containing, this material enters dipolymer reactor or pre-weight-removing column, and the tower still obtains the m-pentadiene product.
3. the method for producing polymerization grade isoprene as claimed in claim 1, it is characterized in that, send into carbon five from the material of pre-weight-removing column tower still and steam tower, steam column overhead extraction carbon five hydrocarbon at carbon five, from tower still extraction dicyclopentadiene, cat head carbon five hydrocarbon enter the m-pentadiene treating tower, from the material of cat head extraction isoprene containing, this material and merge from the material of weight-removing column tower still and to enter dipolymer reactor or pre-weight-removing column, the tower still obtains the m-pentadiene product.
4. the method for producing polymerization grade isoprene as claimed in claim 1 is characterized in that, pre-weight-removing column has 70～130 number of theoretical plates, and reflux ratio is 5～20, and tower top temperature is 40～60 ℃, from the middle part charging.
5. the method for producing polymerization grade isoprene as claimed in claim 1 is characterized in that, weight-removing column has 70～150 number of theoretical plates, and reflux ratio is 7～20, and tower top temperature is 40～60 ℃, from underfeed.
6. the method for producing polymerization grade isoprene as claimed in claim 1, it is characterized in that described azeotropy rectification column has 70～200 theoretical stages, from tower middle part charging, the weight ratio of isoprene material and iso-pentane is 20: 0.5～5, and reflux ratio is 50～120.
7. the method for producing polymerization grade isoprene as claimed in claim 1, it is characterized in that palladium-based catalyst or nickel-base catalyst are housed, and reaction conditions is: reaction pressure 1.0～5.0MPa in hydrogenator, 20～150 ℃ of temperature of reaction, liquid hourly space velocity 0.1～10h
-1
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| CN102021015B (en) * | 2009-09-10 | 2013-05-01 | 中国石油化工集团公司 | Tar dissolving method for extracting C4 hydrocarbon and C5 hydrocarbon by using dimethylformamide as solvent |
| CA2783976A1 (en) * | 2009-12-18 | 2011-06-23 | Danisco Us Inc. | Purification of isoprene from renewable resources |
| AR101431A1 (en) * | 2013-06-05 | 2016-12-21 | Gtc Technology Us Llc | PROCESS AND APPARATUS TO SEPARATE DI-OLEFINS C₅ FROM PIRÓISIS NAFTAS |
| CN107879880A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of separation method of chemical grade isoprene |
| CN107879881A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of separation method of polymerization grade isoprene |
| CN107879879A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | The method for preparing polymerization grade isoprene |
| US10906852B2 (en) * | 2017-04-27 | 2021-02-02 | Sabic Global Technologies B.V. | Removal of alkyne impurities from diolefin containing mixtures through cracking over CuO/Al2O3 based materials |
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| US4647344A (en) * | 1983-10-21 | 1987-03-03 | Basf Aktiengesellschaft | Recovery of isoprene from a C5 -hydrocarbon mixture |
| CN1709842A (en) * | 2004-06-18 | 2005-12-21 | 南京工业大学 | Method for separating cracked carbon 5 using azeotropic super fractionation and extractive distillation coupling |
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| US4647344A (en) * | 1983-10-21 | 1987-03-03 | Basf Aktiengesellschaft | Recovery of isoprene from a C5 -hydrocarbon mixture |
| CN1709842A (en) * | 2004-06-18 | 2005-12-21 | 南京工业大学 | Method for separating cracked carbon 5 using azeotropic super fractionation and extractive distillation coupling |
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