CN104058914B - The method of diolefine in separating cracked carbon 5 fraction - Google Patents
The method of diolefine in separating cracked carbon 5 fraction Download PDFInfo
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Abstract
The present invention's problems such as the longer and energy consumption of separation of polymeric grade isoprene product process flow is higher in order to the m-pentadiene method of purification process that solves prior art and exist is complicated and energy consumption is higher, from cracked C 5 fraction, propose in the charging of m-pentadiene treating tower, to add raffinate to reduce cyclopentadiene content in m-pentadiene product, improve product quality.Cracked C 5 fraction, decarburization six refining through de-heavy reactive distillation, de-light, extraction and parsings, isoprene product purification, decarburization five, m-pentadiene and process acquisition polymerization grade isoprene product, m-pentadiene product and the dicyclopentadiene product such as dicyclopentadiene is refining successively is also proposed.It is short that method of the present invention has flow process, and energy consumption is low, build and running cost low, product quality advantages of higher.
Description
Technical field
The present invention relates to a kind of separation method of cracked, C 5 fraction, more particularly, the present invention relates to a kind of method adopting reaction rectification technique and abstraction technique separating cracked carbon 5 fraction.
Background technology
In a considerable amount of C5 fraction of the byproduct in process of petroleum cracking ethene, in C5 fraction, be rich in the diolefins such as isoprene, cyclopentadiene and m-pentadiene.These diolefin chemical property are active, are important industrial chemicals.Due to the difference of petroleum hydrocarbon cracking raw materials, cracking severity and separation degree, in cracked C 5 fraction, diolefin content is different, and total content is between 40% ~ 60%.Therefore, be separated and utilize C5 fraction to the economic benefit improving ethylene unit, comprehensive utilization petroleum resources have far reaching significance.
Cracked C 5 fraction contains the component that more than 20 kind of boiling point is close, easily form azeotrope each other, and from wherein isolating the higher C 5 diene of comprehensive utilization value, technique is comparatively complicated.C5 fraction contains the such as alkynes such as crotonylene and valylene, these alkynes content are generally in 0.1 ~ 2% scope, because their chemical property is active, be the main detrimental impurity of the reaction of C 5 diene product and polymerization process, therefore the alkynes effectively removed wherein is the important step of cracked C 5 fraction separating technology.
In order to the isoprene product of high-purity, generally adopt two-section extraction rectificating method in the prior art, the extraction solvent that existing industrialized cracked C 5 fraction separation method uses has dimethyl formamide (DMF), acetonitrile etc.Such as in carbon five separation process of Beijing Chemical Research Institute's exploitation, first feed material preparation units is utilized to carry out pre-treatment to carbon Wuyuan material, remove carbon fourth class light constituent wherein and most of alkynes, make cyclopentadiene become dicyclopentadiene, in pre-weight-removing column, remove the heavy constituents such as m-pentadiene; Then use DMF to make extraction solvent, in the first extraction cells, remove the alkane in cracked C 5 fraction and monoolefine, obtained chemical grade isoprene; In the second extraction cells, remove alkynes wherein and cyclopentadiene, alkynes is crotonylene and valylene mainly; M-pentadiene product and dicyclopentadiene product is produced by rectifying in another one unit; Finally attach a solvent recovery unit.Obviously, this separation process is long, equipment is many, energy consumption is high, especially the second extraction cells also exists problems: (1) is in such two-section extraction rectificating method, operating equipment is more, the energy consumption of the second extraction cells is very high, needs strictly to operate, 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 large, add production cost, there is problem of environmental pollution simultaneously.Water azeotropic treating tower recycling design is adopted in solvent recovery unit, first by the solvent to be regenerated heavy constituent such as pressure reducing and steaming Jiao Zhi in solvent reclamation tank, the logistics that gas phase is formed enters water azeotropic treating tower, water is added in this tower, water and dicyclopentadiene is made to form azeotrope, azeotropic boiling point is 97 DEG C, dicyclopentadiene and solvent DMF is separated like this.Owing to adding water, solvent DMF is hydrolyzed and generates dimethylamine and formic acid, formic acid promotes that again solvent accelerates hydrolysis, causes solvent loss and blocks tower and pipeline thereof.
In order to improve the various side reactions occurred in cyclopentadiene reaction, Chinese patent application CN200910087775.6 proposes a tubular reactor with revolving fragment.Chinese patent CN200810057745.6 proposes the method for cyclopentadiene in reactive distillation separating cracked carbon five, in the method, reactive distillation column does not specially arrange conversion zone, but by the residence time on each column plate, the residence time of these column plates is shorter, and arbitrarily can not regulate the residence time.Chinese patent CN200710178913.2 proposes to hang a dipolymer reactor with it at rectifying tower, and needs pump initiatively to make liquid-flow, hangs dipolymer reactor and this rectifying tower is complicated.
In order to propose, containing the purity of m-pentadiene in m-pentadiene material, to propose various method.Chinese patent application CN200510131162.X and Chinese patent application 200410093599.4 propose to extract and resolving containing m-pentadiene material, obtain polymer grade piperyene, process is very complicated, energy consumption is very high undoubtedly, production cost is expensive, and does not industrially generally also need so high purity.
In sum, still there is a lot of area for improvement in the prior art of separation of carbon five diolefine, the m-pentadiene method of purification that searching process is simple and energy consumption is lower and from cracked C 5 fraction the method for separating isoprene product all there is the requirement of economic worth and technical progress.
Summary of the invention
The present invention's problems such as the longer and energy consumption of separation of polymeric grade isoprene product process flow is higher in order to the m-pentadiene method of purification process that solves prior art and exist is complicated and energy consumption is higher, from cracked C 5 fraction, propose a kind of carbon five raffinate that utilizes and assist rectifying m-pentadiene material to put forward highly purified method and to utilize the method for separation of polymeric grade isoprene product of the method.
Concrete technical scheme is as follows.
An object of the present invention is to provide the method for cyclopentadiene in a kind of compartment pentadiene, carbon five raffinate that material and cracked C 5 fraction extraction separation device containing m-pentadiene are produced enters m-pentadiene treating tower simultaneously, through azeotropic distillation process, the logistics of cyclopentadiene is contained from described m-pentadiene treating tower overhead extraction, from described m-pentadiene treating tower bottom side take-off containing m-pentadiene product, contain the logistics of dicyclopentadiene from tower reactor extraction; Described carbon five raffinate contain Skellysolve A, 2-methyl-2-butene and 2-amylene first time extraction tower tower top material; Described azeotropic distillation refers to the rectifying utilizing Skellysolve A and cyclopentadiene azeotropic, 2-methyl-2-butene and cyclopentadiene azeotropic and 2-amylene and cyclopentadiene azeotropic.
Preferably, described m-pentadiene treating tower has 50 ~ 100 pieces of number of theoretical plates, and reflux ratio is 15 ~ 35, and tower top temperature is 40 ~ 65 DEG C.The charge-mass ratio that the described material containing m-pentadiene and described carbon five are raffinated oil is 1:1 ~ 10:1, more preferably 2:1 ~ 6:1.
Another object of the present invention is to provide the method for diolefine in a kind of separating cracked carbon 5 fraction, comprises the following steps:
(1) de-heavy: to make cracking c_5 raw material, through overheated dipolymer reactor, hot dimerization reaction occur, then de-heavy reactive distillation column is entered, or cracking c_5 raw material directly enters de-heavy reactive distillation column without overheated dipolymer reactor, through reactive distillation processes, from the logistics of overhead extraction isoprene containing and more light constituent, from the logistics of tower reactor extraction extraction containing cyclopentadiene, m-pentadiene and more heavy constituent; Described reactive distillation makes cyclopentadiene be the process of dicyclopentadiene while referring to and carry out rectifying in rectifying tower;
(2) de-light: to make the logistics of the heavy reactive distillation column overhead of autospasy to enter lightness-removing column, through rectifying, from the light constituent that lightness-removing column overhead extraction volatility is larger than isoprene, from the logistics of tower reactor extraction isoprene containing;
(3) extraction and parsing: the logistics comprising isoprene from lightness-removing column tower reactor enters in the middle part of extraction tower, extraction solvent enters from extraction tower top, through extracting rectifying process, the raffinate of C 5 alkane and monoolefine is comprised from extraction tower overhead extraction, Analytic Tower is entered from the logistics of tower reactor extraction, through the resolving analytically isoprene logistics of column overhead extraction based on isoprene, the logistics of Analytic Tower tower reactor extraction loops back extraction tower;
(4) isoprene is refined: the isoprene logistics based on isoprene of analytically column overhead extraction enters in the middle part of isoprene product tower, through rectifying from isoprene product column overhead extraction isoprene product, contain the logistics of cyclopentadiene and m-pentadiene from the extraction of isoprene product tower tower reactor;
(5) decarburization five: make the logistics of the heavy reactive distillation column tower reactor of autospasy to enter decarburization five tower, through rectifying, contains carbon five logistics of m-pentadiene, contains the logistics of dicyclopentadiene from tower reactor extraction from the extraction of described decarburization five column overhead;
(6) m-pentadiene is refined: make from described decarburization five column overhead containing m-pentadiene carbon five logistics and enter m-pentadiene treating tower from a part of raffinate of extraction tower tower top simultaneously, through azeotropic distillation process, the logistics of cyclopentadiene is contained from described m-pentadiene treating tower overhead extraction, from described m-pentadiene treating tower bottom side take-off containing m-pentadiene product, contain the logistics of dicyclopentadiene from tower reactor extraction; Described carbon five raffinate contain Skellysolve A, 2-methyl-2-butene and 2-amylene first time extraction tower tower top material; Described azeotropic distillation refers to the rectifying utilizing Skellysolve A and cyclopentadiene azeotropic, 2-methyl-2-butene and cyclopentadiene azeotropic and 2-amylene and cyclopentadiene azeotropic.In the present invention, described carbon five raffinate is exactly the material of extraction tower overhead extraction.When C5 fraction adopts twice extraction cells, carbon five raffinate is the material of the first extraction tower tower top, and therefore Unify legislation is the material of first time extraction tower tower top in the claims.The logistics containing cyclopentadiene of overhead extraction can turn back in cracked C 5 fraction raw material.
Described m-pentadiene treating tower has 50 ~ 100 pieces of number of theoretical plates, and reflux ratio is 15 ~ 35, and tower top temperature is 40 ~ 65 DEG C.The charge-mass ratio that the described material containing m-pentadiene and described carbon five are raffinated oil is 1:1 ~ 10:1, more preferably 2:1 ~ 6:1.
As a technical scheme of the present invention, in separating cracked carbon 5 fraction of the present invention, the method for diolefine is further comprising the steps:
(7) decarburization six: make from described decarburization five tower tower reactor containing dicyclopentadiene logistics and merge from the logistics containing dicyclopentadiene of described m-pentadiene treating tower tower reactor, then decarburization six tower is entered, through rectifying, from the logistics of described decarburization six column overhead extraction carbon containing six, contain the logistics of dicyclopentadiene from tower reactor extraction, turn back to the tower reactor of described decarburization five tower from a part for the logistics of the carbon containing six of overhead extraction to regulate the bottom temperature of described decarburization five tower;
(8) dicyclopentadiene is refined: make the logistics containing dicyclopentadiene from described decarburization six tower tower reactor enter dicyclopentadiene treating tower, through rectification under vacuum process, from described dicyclopentadiene treating tower overhead extraction dicyclopentadiene product, from the heavy constituent that tower reactor extraction volatility is less than dicyclopentadiene.
Containing a large amount of isoprene from the logistics of isoprene product tower tower reactor extraction, also containing m-pentadiene and cyclopentadiene, in order to improve the yield of carbon five diolefine, also as a preferred technical scheme, make to turn back to cracked C 5 fraction raw material from the logistics containing cyclopentadiene and m-pentadiene of described isoprene product tower tower reactor extraction, also can be incorporated in the charging of decarburization five tower.
There is tank reactor there is back-mixing to solve cyclopentadiene reaction in cracked C 5 fraction that prior art exists, also there is side reaction and existing reactive distillation column and there is the problems such as the residence time is non-adjustable in tubular reactor, the bottom of described de-heavy reactive distillation column arranges dimerization reaction section, in the bottom of described de-heavy reactive distillation column, one dividing plate is set, dividing plate is offered a hole, a cylindrical shell is upwards connected along described bore edges, the space for material stop is formed between described cylindrical shell and tower wall, inner or outer setting U-tube road at described de-heavy reactive distillation column, the one end on U-tube road is connected with the bottom in described space, the other end is connected with the rectifying section below described dividing plate, rectifying section below the liquid stopped in described space is flowed into by described U-tube road, arrange a passage on the top on described U-tube road to be communicated with the gas phase on liquid level in described space, dimerization reaction is there is and generates dicyclopentadiene in cyclopentadiene in described space, from the logistics of described de-heavy reactive distillation column overhead extraction isoprene containing, the logistics of m-pentadiene is contained from tower reactor extraction.
For the number of theoretical plate of described de-heavy reactive distillation column and tower plate structure and form, there is no particular limitation, and industrial practice also proves, only can reach rectifying separation object component just can for reactive distillation column.Those skilled in the art can according to spirit of the present invention, the number of theoretical plate of selective rectification section aptly and operational condition, according to the height of the depth adjustment conversion zone of dimerization reaction, can regulate the residence time.As a preferred technical scheme, described de-heavy reactive distillation column has 80 ~ 180 pieces of number of theoretical plates, and reflux ratio is 10 ~ 30, and tower top temperature is 40 ~ 60 DEG C.
In described de-heavy reactive distillation column, can according to the degree of cyclopentadiene, regulate the height in the described space for material stop to be 1 ~ 4 hour to make material in the residence time in described space.Concrete regulating measure is such as regulating the height of U-tube.
In order to better, alkynes in C5 fraction is removed, various ways is there is in prior art, before or after the first extraction cells, such as set up selec-tive hydrogenation unit hydrogenation, below setting up hydrogenation unit and carry out alkynes hydrogenation etc. at pre-lightness-removing column are carried out to the alkynes in C5 fraction, also have the reflux ratio by strengthening pre-lightness-removing column and increase overhead extraction amount to remove alkynes as much as possible.Set up the complicacy that hydrogenation unit can increase system, strengthen reflux ratio and will increase energy consumption, increasing overhead extraction amount will make isoprene rate of loss increase, in order to address these problems, as alternative and preferred technical scheme, the present invention proposes following technical scheme: arrange hydrogenation catalyst bed in the upper end of described lightness-removing column, in hydrogenation catalyst bed, be provided with gas rising passway pass through for the rectifying gas phase under it, hydrogen inlet is provided with in hydrogenation catalyst bed lower end, pass into hydrogen from hydrogen inlet and make hydrogen by hydrogenation catalyst bed, the rectifying liquid phase flowed downward above hydrogenation catalyst bed is by hydrogenation catalyst bed, flow into the rectifying section below hydrogenation catalyst bed afterwards, the logistics of carbon four is comprised from de-light hydrogenation rectifying tower overhead extraction through hydrogenation reaction and rectifying, the logistics of isoprene is comprised from de-light hydrogenation tower bottom of rectifying tower extraction.
There is no particular limitation for the catalyzer used for lightness-removing column of the present invention, and those skilled in the art can select according to production cost and the easily acquired of catalyzer.For example, the catalyzer used can be noble metal catalyst, such as palladium-based catalyst or platinum based catalyst, example comprises palladium/aluminum oxide, palladium/gac or palladium/silicon-dioxide more specifically, auxiliary agent can also be contained in palladium-based catalyst, not only active ingredient can add auxiliary agent as silver, and carrier also can add auxiliary agent as lanthanum.The catalyzer used also can be non-precious metal catalyst, such as nickel-base catalyst, cobalt-base catalyst or copper-based catalysts, example comprises Raney's nickel, thunder Buddhist nun cobalt, Lei Nitong, loading type nickel-based catalyst if nickel/aluminum oxide, load type cobalt-base catalyst are if cobalt/aluminum oxide, copper-based catalysts are as copper-zinc-Al catalysts more specifically.The preparation method of catalyzer can in conventional manner, such as pickling process, coprecipitation method, vapour deposition process, spraying method etc.For openly abundant, and the example of exemplarily property, introduce CN1188494C in full here.For example, described hydrogenation catalyst can be used in Al
2o
3, SiO
2, on the carrier such as ZnO, take precious metal as the loaded catalyst of active constituent; Preferred catalyzer take aluminum oxide as carrier, with the gross weight of catalyzer for benchmark, comprises the I B-group metal at least one periodic table of elements, and its weight content is 0.1%-10%; Group VIII metal at least one periodic table of elements, its weight content is 0.008%-1%; At least one basic metal, its weight content is 0.01%-5%; Being more preferably I B-group metal is at least one in copper and silver, and wherein copper at least accounts for 90% of I B-group metal; Group VIII metal is palladium; Basic metal is potassium.Described catalyzer prepares by method below: the salpeter solution oxide impregnation alumina supporter first using the salpeter solution of the salt of I B-group metal and the salt of group VIII metal, then uses the aqueous impregnation of alkali metal compound; In the temperature range of 50 ~ 200 DEG C, carry out drying after each step dipping, in the temperature range of 250 ~ 650 DEG C, carry out roasting.
For the number of theoretical plate of described lightness-removing column and the structure of column plate and form, there is no particular limitation, and industrial practice also proves, only can reach rectifying separation object component just can for reactive distillation column.Those skilled in the art can according to spirit of the present invention, the number of theoretical plate of selective rectification section aptly and operational condition, as a preferred technical scheme, described lightness-removing column has 80 ~ 120 pieces of number of theoretical plates, reflux ratio is 5 ~ 20, tower top temperature is 40 ~ 60 DEG C, and the liquid phase air speed of hydrogenation catalyst bed is 0.5 ~ 10h
-1, hydrogen is 1 ~ 8:1 with the mol ratio entering the alkynes in the liquid phase material of hydrogenation catalyst bed.
About extraction tower and Analytic Tower, there is no particular limitation in the present invention, can use structure formation and the operational condition of prior art, the technical characteristic of existing document can be introduced here.For example, the stage number of extraction tower is 70 ~ 150 pieces, tower internal pressure is 0.01 ~ 0.3MPa, bottom temperature is 100 ~ 150 DEG C, tower top temperature is 40 ~ 80 DEG C, and trim the top of column ratio is 4 ~ 15, and solvent ratio is 5 ~ 11, obtain monoolefine and alkane by tower top, the solvent material of the C 5 dienes such as isoprene must be rich in by tower reactor; Kettle material is through resolving, and the solvent cycle that tower reactor obtains uses.
Any solvent that described extraction solvent can be suitable for, for example, described extraction solvent is dimethyl formamide, acetonitrile or N-Methyl pyrrolidone.
In separation method of the present invention, extraction section need regenerate continuously or off and on the extraction pipeline of analytically tower tower reactor extraction solvent can go regeneration, the solvent after regeneration adds in extraction solvent continuously or off and on.
The renovation process of extraction solvent can use the one of prior art, and as a preferred technical scheme, the solvent that the need of extraction are regenerated enters the matter tower that comes unstuck, and through rectifying, from the solvent-laden logistics of overhead extraction, contains the waste material of colloid from tower reactor extraction; Make the solvent-laden logistics from matter column overhead of coming unstuck enter de-dimer tower, through rectifying, the solvent after described de-dimer column overhead extraction regeneration, from tower reactor extraction containing dimeric logistics.
Be not particularly limited for the theoretical plate number of described come unstuck matter tower and de-dimer tower and reflux ratio, those skilled in the art know, number of theoretical plate is larger, and reach identical separation object, required reflux ratio is less, vice versa.Further, need the composition of the solvent of regeneration also to have an impact to the separation of solvent and recovery, for example, when the content of carbon five hydrocarbon and water is higher, de-number of theoretical plate required for dimer tower and/or reflux ratio also higher.When needing the colloid that contains in regenerated solvent higher, the number of theoretical plate required for matter of coming unstuck tower and/or reflux ratio also higher.For de-dimer tower, if when the dimer content entering this tower is higher, this tower also needs higher number of theoretical plate and/or reflux ratio.For example, matter of coming unstuck tower has 10 ~ 20 pieces of number of theoretical plates, adopts the reflux ratio of 1 ~ 6.De-dimer tower has 20 ~ 40 pieces of number of theoretical plates, adopts the reflux ratio of 1 ~ 7.
For the operating parameters of three vacuum rectification tower, provide optimum condition here.Preferably, described in the come unstuck tower top pressure of matter tower be 0.002MPa ~ 0.004MPa, tower top temperature is 55 DEG C ~ 80 DEG C, and tower reactor pressure is 0.007MPa ~ 0.01MPa, and bottom temperature is 80 DEG C ~ 100 DEG C.The tower top pressure of described de-dimer tower is 0.008MPa ~ 0.02MPa, and tower top temperature is 80 DEG C ~ 100 DEG C, and tower reactor pressure is 0.018MPa ~ 0.03MPa, and bottom temperature is 88 DEG C ~ 115 DEG C.
About described isoprene product tower, there is no particular limitation.As preferred technical scheme, described weight-removing column has 80 ~ 180 pieces of number of theoretical plates, and reflux ratio is 10 ~ 30, and tower top temperature is 40 ~ 60 DEG C.
Described decarburization five tower has 40 ~ 100 pieces of number of theoretical plates, and reflux ratio is 5 ~ 20, and tower top temperature is 40 ~ 60 DEG C, and bottom temperature is 95 ~ 120 DEG C, and reflux ratio is 0.5 ~ 3.
Carbon five hydrocarbon that decarburization five tower top obtains, deliver to m-pentadiene treating tower to refine, described m-pentadiene treating tower has 40 ~ 100 pieces of number of theoretical plates, tower top temperature is 40 ~ 60 DEG C, bottom temperature is 50 ~ 70 DEG C, reflux ratio is 20 ~ 40, and side take-off m-pentadiene product, tower top discharging turns back to C5 fraction raw material.
Described decarburization six tower has 20 ~ 60 pieces of number of theoretical plates, and tower top temperature is 10 ~ 50 DEG C, and bottom temperature is 80 ~ 120 DEG C, and reflux ratio is 1 ~ 3, negative-pressure operation, and tower internal pressure is-0.05 ~-0.10MPa.
For dicyclopentadiene treating tower, tower top temperature is 50 ~ 75 DEG C, and bottom temperature is 90 ~ 110 DEG C, and tower internal pressure is-0.05 ~-0.12MPa, and reflux ratio is 0.8 ~ 2.
In de-light hydrogenation rectificating method of the present invention, utilize the principle of rectifying, the larger component of relative volatility such as carbon Four composition, iso-pentane and 2-butyne etc. and component such as the valylene etc. that forms the lower azeotrope of azeotropic point are tending towards moving to rectifier, and less component such as isoprene, m-pentadiene and the cyclopentadiene etc. of relative volatility are tending towards moving to rectifying tower bottom.The result of rectifying is that most of alkynes shifts to rectifier.Hydrogenation catalyst bed is set at rectifier, at this, alkynes is hydrogenated into alkene or alkane, and isoprene loses because concentration is lower less or loss is very micro-.Because of hydrogenation, concentration reduces alkynes, alkynes below hydrogenation catalyst bed is more easily moved up, thus reduce the alkynes content of tower bottom of rectifying tower, be easy to reach very low level from the logistics of tower reactor extraction alkynes content wherein after extraction process, such as, be less than 50ppm.Those skilled in the art can easily expect, in the method, requires relatively low, because when this position hydrogenation, isoprene content is very low to selectivity of catalyst.
In cracked, C 5 fraction separation method of the present invention, make use of the principle of reactive distillation fully, in described de-heavy reactive distillation column, cyclopentadiene generation dimerization reaction generates dicyclopentadiene, because the relative volatility of dicyclopentadiene is less, thus be more tending towards moving to tower reactor, thus reach utilization reaction promotion rectifying, simultaneously because the dicyclopentadiene generated constantly shifts to tower reactor, thus be more conducive to constantly carrying out of cyclopentadiene reaction, can effectively avoid cyclopentadiene and isoprene, m-pentadiene reacts generation dimer, namely the X3 alleged by those skilled in the art.Be conducive to the loss reducing isoprene, m-pentadiene like this, the quality of raising m-pentadiene product, dicyclopentadiene product and color.But in existing autoclave or tubular type dipolymer reactor, the dicyclopentadiene that cyclopentadiene reaction generates can not be removed in time, under certain temperature and pressure, cyclopentadiene and dicyclopentadiene are tending towards reaching chemical equilibrium, cyclopentadiene can not be reduced to very low degree, cyclopentadiene and isoprene, m-pentadiene generation dimerization reaction generate X3, cause isoprene, m-pentadiene to lose, the quality variation of m-pentadiene product and dicyclopentadiene product.Industrial production is verified, and the generation of X3 is mainly derived from dimerization reaction process.In the method for the invention, the effect making full use of reactive distillation overcomes the drawback of industrial production existence.
In separation process of the present invention, isoprene product tower utilizes reactive distillation to make the cyclopentadiene in overhead product reach the requirement of polymerization grade isoprene product, is generally less than 1ppm(quality).In pre-lightness-removing column, most alkynes is hydrogenated to alkene or alkane, on a small quantity from overhead extraction, is less than 50ppm(quality to make alkynes content in isoprene product column overhead product), alkynes generally refers to 2-butyne and valylene.Therefore polymerization grade isoprene product is obtained in isoprene product column overhead.Thus eliminate the second extraction cells.
Because isoprene product tower has the effect that reactive distillation removes cyclopentadiene, therefore to the cyclopentadiene in the solvent of regeneration and dicyclopentadiene content not requirement, they can be contained.But in existing two-section extraction separating cracked carbon 5 fraction flow process, first solvent due to regeneration circulates and adds in the second extraction cells, utilize the method for extraction to be removed by the cyclopentadiene in isoprene and be less than 1ppm(quality), so just require regenerate solvent in cyclopentadiene and dicyclopentadiene content very low, such as be less than 1ppm(quality respectively) and 0.2 quality %, otherwise cyclopentadiene can not be made to be less than 1ppm(quality through the second extraction process product isoprene).
By cracked, C 5 fraction separation method of the present invention and existing two-section extraction or with selec-tive hydrogenation unit one-section abstraction method compared with, obviously, it is short that method of the present invention has flow process, and energy consumption is low, build and running cost low, product quality advantages of higher.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the method representing diolefine in separating cracked carbon 5 fraction of the present invention;
Fig. 2 is the schematic diagram of the method representing alkynes in de-light hydrogenation distillation separation cracking C 5 fraction of the present invention;
Fig. 3 is the schematic diagram of the method representing cyclopentadiene in reactive distillation separating cracked carbon 5 fraction of the present invention.
Nomenclature:
1, de-heavy reactive distillation column; 2, lightness-removing column; 3, extraction tower; 4, Analytic Tower; 5, isoprene product tower; 6, decarburization five tower; 7, m-pentadiene treating tower; 8, decarburization six tower; 9, dicyclopentadiene treating tower; 10, matter of coming unstuck tower; 11, de-dimer tower; 1-1, condenser; 1-2, liquid block umbrella; 1-3, gas phase rising passway; 1-4, dividing plate; 2-1, the second condenser; 2-2, the first condenser; 2-3, backflow distributor; 2-4, liquid block umbrella; 2-5, gas phase rising passway; 2-6, hydrogenation catalyst bed; 2-7, dividing plate.
Embodiment
Explain the present invention further below in conjunction with accompanying drawing, in separating cracked carbon 5 fraction of the present invention, the method for diolefine is as shown in Figure 1:
The method of diolefine in separating cracked carbon 5 fraction, comprises the following steps:
(1) de-heavy: to make cracking c_5 raw material directly enter de-heavy reactive distillation column 1, through reactive distillation processes, from the logistics of overhead extraction isoprene containing and more light constituent, from the logistics of tower reactor extraction extraction containing cyclopentadiene, m-pentadiene and more heavy constituent; Described reactive distillation makes cyclopentadiene be the process of dicyclopentadiene while referring to and carry out rectifying in rectifying tower;
(2) de-light: to make the logistics of autospasy heavy reactive distillation column 1 tower top to enter lightness-removing column 2, through rectifying, from the light constituent that lightness-removing column 2 overhead extraction volatility is larger than isoprene, from the logistics of tower reactor extraction isoprene containing;
(3) extraction and parsing: the logistics comprising isoprene from lightness-removing column 2 tower reactor enters in the middle part of extraction tower 3, extraction solvent enters from extraction tower 3 top, through extracting rectifying process, the raffinate of C 5 alkane and monoolefine is comprised from extraction tower 3 overhead extraction, Analytic Tower 4 is entered from the logistics of tower reactor extraction, through the resolving analytically isoprene logistics of tower 4 overhead extraction based on isoprene, the logistics of Analytic Tower 4 tower reactor extraction loops back extraction tower 3;
(4) isoprene is refined: analytically the isoprene logistics based on isoprene of tower 4 overhead extraction enters in the middle part of isoprene product tower 5, through rectifying from isoprene product column overhead extraction isoprene product, contain the logistics of cyclopentadiene and m-pentadiene from the extraction of isoprene product tower tower reactor; Tower reactor extraction logistics can turn back in cracked C 5 fraction raw material, to improve the yield of carbon five diolefine, also can be incorporated in the charging of decarburization five tower 6.
(5) decarburization five: make the logistics of autospasy heavy reactive distillation column 1 tower reactor to enter decarburization five tower 6, through rectifying, contains carbon five logistics of m-pentadiene, contains the logistics of dicyclopentadiene from tower reactor extraction from described decarburization five tower 6 overhead extraction;
(6) m-pentadiene is refined: make from described decarburization five tower 6 tower top containing m-pentadiene carbon five logistics and enter m-pentadiene treating tower 7 from a part of raffinate of extraction tower 3 tower top simultaneously, through azeotropic distillation process, the logistics of cyclopentadiene is contained from described m-pentadiene treating tower 7 overhead extraction, from described m-pentadiene treating tower 7 bottom side take-off containing m-pentadiene product, contain the logistics of dicyclopentadiene from tower reactor extraction; Described carbon five raffinate contains the material of extraction tower 3 tower top of Skellysolve A, 2-methyl-2-butene and 2-amylene; Described azeotropic distillation refers to the rectifying utilizing Skellysolve A and cyclopentadiene azeotropic, 2-methyl-2-butene and cyclopentadiene azeotropic and 2-amylene and cyclopentadiene azeotropic.Can turn back to cracked C 5 fraction raw material from the logistics of m-pentadiene treating tower 7 overhead extraction, to reclaim isoprene and cyclopentadiene etc. wherein.
(7) decarburization six: make from described decarburization five tower 6 tower reactor containing dicyclopentadiene logistics and merge from the logistics containing dicyclopentadiene of described m-pentadiene treating tower 7 tower reactor, then decarburization six tower 8 is entered, through rectifying, from the logistics of described decarburization six tower 8 overhead extraction carbon containing six, contain the logistics of dicyclopentadiene from tower reactor extraction, turn back to the tower reactor of described decarburization five tower 8 from a part for the logistics of the carbon containing six of overhead extraction to regulate the bottom temperature of described decarburization five tower 6;
(8) dicyclopentadiene is refined: make the logistics containing dicyclopentadiene from described decarburization six tower 8 tower reactor enter dicyclopentadiene treating tower 9, through rectification under vacuum process, from described dicyclopentadiene treating tower 9 overhead extraction dicyclopentadiene product, from the heavy constituent that tower reactor extraction volatility is less than dicyclopentadiene.
(9) to come unstuck matter: the solvent that the need of extraction are regenerated enters the matter tower 10 that comes unstuck, through rectifying, from the solvent-laden logistics of overhead extraction, from the waste material of tower reactor extraction containing colloid;
(10) de-dimer: make the solvent-laden logistics from matter tower 10 tower top that comes unstuck enter de-dimer tower 11, through rectifying, the solvent after described de-dimer tower 11 overhead extraction regeneration, from tower reactor extraction containing dimeric logistics.
Composition graphs 2, the structure of the de-heavy reactive distillation column 1 described in explaining in further detail and form, but the present invention is not limited to the structure represented by Fig. 2.Cracking c_5 raw material is made to enter in the middle part of de-heavy reactive distillation column 1, condenser 1-1 is connected at the top of described de-heavy reactive distillation column 1, dimerization reaction section is set in bottom, in the bottom of described de-heavy reactive distillation column, one dividing plate 1-4 is set, dividing plate 1-4 offers a hole, a cylindrical shell is upwards connected along described bore edges, cylindrical shell forms gas phase rising passway 1-3, liquid is set above cylindrical shell and blocks umbrella 1-2, the space for material stop is formed between described cylindrical shell and tower wall, inner or outer setting U-tube road at described de-heavy reactive distillation column, the one end on U-tube road is connected with the bottom in described space, the other end is connected with the rectifying section below described dividing plate, rectifying section below the liquid stopped in described space is flowed into by described U-tube road, arrange a passage on the top on described U-tube road to be communicated with the gas phase on liquid level in described space, dimerization reaction is there is and generates dicyclopentadiene in cyclopentadiene in described space, from the logistics of described de-heavy reactive distillation column overhead extraction isoprene containing, the logistics of m-pentadiene is contained from tower reactor extraction.
For described de-heavy reactive distillation column 1, more particularly, in described de-heavy reactive distillation column 1 bottom, one dividing plate 1-4 is set, dividing plate 1-4 offers a hole, described hole upwards connects a cylindrical shell, formed between described cylindrical shell and tower wall from above the space that stops of the liquid material that flows down of column plate.Inner or outer setting U-tube road at described de-light hydrogenation rectifying tower, the one end on U-tube road is connected with the bottom in above-mentioned space, the other end is connected with the rectifying section below dividing plate 1-4, the rectifying section below described U-tube road inflow dividing plate 1-4 is passed by the liquid in described space, arrange a passage on the top on described U-tube road to be communicated with the gas-phase space above described space, U-tube can be avoided like this to produce siphonage, make the liquid level in U-tube identical with the liquid level in described space, thus the residence time of liquid in described space can be controlled.Be provided with on rising passway and block umbrella 1-2 and directly flow down from rising passway 1-3 to avoid dirty liquid material.
Composition graphs 3, explain structure and the form of described lightness-removing column 2 in more detail, but the present invention is not limited to the structure represented by Fig. 3, cracking c_5 raw material is made to enter in the middle part of lightness-removing column 2, the upper end of described lightness-removing column 2 arranges hydrogenation catalyst bed 2-6, in hydrogenation catalyst bed, be provided with gas rising passway 2-5 pass through for the rectifying gas phase under it, be provided with hydrogen inlet in hydrogenation catalyst bed lower end and make hydrogen upwards by hydrogenation catalyst bed 2-6, the rectifying liquid phase flowed downward above hydrogenation catalyst bed 2-6 passes downwardly through hydrogenation catalyst bed 2-6, flow into the rectifying section below hydrogenation catalyst bed 2-6 afterwards, the logistics of carbon four is comprised from the overhead extraction of lightness-removing column 2 through hydrogenation reaction and rectifying, the logistics of isoprene is comprised from the tower reactor extraction of lightness-removing column 2.
For described lightness-removing column 2, more particularly, in described lightness-removing column 2 upper end, one dividing plate 2-7 is set, dividing plate 2-7 offers a hole, described hole upwards connects a cylindrical shell 2-5, between described cylindrical shell 2-5 and the tower wall of lightness-removing column 2, described hydrogenation catalyst bed 2-6 is set, space is left between described hydrogenation catalyst bed 2-6 and described dividing plate 2-7, hydrogen inlet and described space pass to mutually and make hydrogen enter this space, then hydrogen is upwards by hydrogenation catalyst bed 2-6, inner or outer setting U-tube road at described lightness-removing column, the one end on U-tube road and the described spatial joins passing into hydrogen, the other end is connected with the rectifying section below hydrogenation catalyst bed 2-6, rectifying section below hydrogenation catalyst bed 2-6 is flowed into by described U-tube road by the liquid of hydrogenation catalyst bed 2-6, arrange a passage on the top on described U-tube road to be communicated with the gas-phase space above hydrogenation catalyst bed-6, U-tube can be avoided like this to produce siphonage, make the liquid level in U-tube identical with the liquid level in hydrogenation catalyst bed, thus hydrogenation catalyst submergence can be controlled in a liquid.Remaining hydrogen through hydrogenation catalyst bed and the gas phase by rising passway 2-5 flow to the first condenser 2-2 on the top of lightness-removing column, most of component is in addition to the hydrogen under this condensation, the liquid part extraction of condensation, a part is back to top of tower, top of tower is provided with backflow distributor 2-3, backflow material be distributed in above hydrogenation catalyst bed by backflow distributor 2-3, be provided with on rising passway block umbrella 2-4 with avoid reflux liquid material directly flow down from rising passway 2-5.The liquid material of backflow flows from top to bottom in hydrogenation catalyst bed, and final liquid flow to the rectifying section below hydrogenation catalyst bed by U-tube.In the first condenser 2-2, do not have the hydrogen of condensation and small part hydrocarbon to enter the second condenser 2-1, through further condensation, the hydrocarbon major part entered is condensed, and by the liquid extraction of condensation, uncooled gas is hydrogen and a small amount of hydrocarbon, can use through pressurization cycle.
The catalyzer used is such as the hydrogenation catalyst BC-A-20(cobalt/aluminium oxide catalyst of Beijing Chemical Research Institute's production, cobalt contents is 25wt%, prepared by pickling process) and hydrogenation catalyst BC-A-30(nickel/aluminum oxide, nickel content is 15wt%, pickling process preparation), BC-A-31(copper-zinc-Al catalysts, copper content is 35wt%, Zn content is 55wt%, and surplus is aluminum oxide, coprecipitation method prepare), BC-A-32(palladium/aluminum oxide, palladium content is 0.3wt%, prepared by spraying method) etc.
In the present invention, if do not particularly not pointed out, degree is mass percentage content.
Embodiment 1
With the cracked C 5 fraction of certain factory for raw material, utilize hydrogenation distillation and separation method of the present invention to carry out cracked C 5 fraction separation, the turnover logistics composition of raw material composition and each operating gear is listed in the following table.
(1) de-heavy: cracking c_5 raw material to be entered in the middle part of de-heavy reactive distillation column 1, the flow of cracking c_5 raw material is 6.3 tons/hour, described de-heavy reactive distillation column has 110 pieces of number of theoretical plates, reflux ratio is 15, tower top temperature is 45 DEG C, comprise the logistics of isoprene from de-heavy reactive distillation column 1 overhead extraction through reactive distillation processes, de-heavy reactive distillation column 1 tower reactor extraction is containing the logistics of m-pentadiene, and in the dimerization reaction section of bottom, the residence time of liquid is 2 hours;
(2) de-light: the logistics comprising isoprene of de-heavy reactive distillation column 1 overhead extraction enters in the middle part of lightness-removing column 2, the upper end of described lightness-removing column 2 arranges hydrogenation catalyst bed, the hydrogenation catalyst BC-A-30 that catalyzer adopts Beijing Chemical Research Institute to produce, the loadings of catalyzer is 9m
3the mol ratio of hydrogen and total alkynes is 1.1, in hydrogenation catalyst bed, be provided with gas rising passway pass through for the rectifying gas phase under it, be provided with hydrogen inlet in hydrogenation catalyst bed lower end and make hydrogen by hydrogenation catalyst bed, the rectifying liquid phase flowed downward above hydrogenation catalyst bed is by hydrogenation catalyst bed, flow into the rectifying section below hydrogenation catalyst bed afterwards, comprise the logistics of carbon four through hydrogenation reaction and rectifying from lightness-removing column 2 overhead extraction, comprise the logistics of isoprene from the extraction of lightness-removing column 2 tower reactor; Described de-light hydrogenation rectifying tower has 100 pieces of number of theoretical plates, and reflux ratio is 15, and tower top temperature is 50 DEG C;
(3) extraction and resolve: described in comprise isoprene logistics enter in the middle part of extraction tower 3, extraction solvent enters from extraction tower 3 top, extraction tower 3 has 90 pieces of theoretical stages, reflux ratio is 3, extraction solvent enters extraction tower 3 from top, solvent is dimethyl formamide in the present embodiment, but the present invention is not limited to it, the feedstock quality throughput ratio of solvent and the charging of carbon five hydrocarbon is 5.5, through extracting rectifying process, the raffinate of C 5 alkane and monoolefine is comprised from extraction tower 3 overhead extraction, Analytic Tower 4 is entered from the logistics of tower reactor extraction, Analytic Tower has 40 blocks of theoretical trays, reflux ratio is 1, tower top temperature is 50 DEG C, through the resolving analytically isoprene logistics of tower 4 overhead extraction based on isoprene, the logistics of Analytic Tower tower reactor extraction loops back extraction tower 3,
(4) isoprene is refined: analytically the isoprene logistics of tower 4 overhead extraction enters in the middle part of isoprene product tower 5, isoprene product tower has 160 pieces of number of theoretical plates, reflux ratio is 20, tower top temperature is 48 DEG C, through reactive distillation processes from isoprene product tower 5 overhead extraction polymerization grade isoprene product, comprise the logistics of dicyclopentadiene from the extraction of isoprene product tower 5 tower reactor.
(5) decarburization five: make the logistics of autospasy heavy reactive distillation column 1 tower reactor to enter decarburization five tower 6, through rectifying, contains carbon five logistics of m-pentadiene, contains the logistics of dicyclopentadiene from tower reactor extraction from described decarburization five tower 6 overhead extraction; Described decarburization five tower has 60 pieces of number of theoretical plates, and reflux ratio is 10, and tower top temperature is 52 DEG C, and bottom temperature is 105 DEG C, and reflux ratio is 1.2.
(6) m-pentadiene is refined: make the 1500kg/h from described decarburization five tower 6 tower top contain carbon five logistics of m-pentadiene and enter m-pentadiene treating tower 7 from the 300kg/h raffinate of extraction tower 3 tower top simultaneously, through azeotropic distillation process, the logistics of cyclopentadiene is contained from described m-pentadiene treating tower 7 overhead extraction, from described m-pentadiene treating tower 7 bottom side take-off containing m-pentadiene product, contain the logistics of dicyclopentadiene from tower reactor extraction; Described carbon five raffinate contains the material of extraction tower 3 tower top of Skellysolve A, 2-methyl-2-butene and 2-amylene; Described azeotropic distillation refers to the rectifying utilizing Skellysolve A and cyclopentadiene azeotropic, 2-methyl-2-butene and cyclopentadiene azeotropic and 2-amylene and cyclopentadiene azeotropic.Can turn back to cracked C 5 fraction raw material from the logistics of m-pentadiene treating tower 7 overhead extraction, to reclaim isoprene and cyclopentadiene etc. wherein.Described m-pentadiene treating tower has 70 pieces of number of theoretical plates, and tower top temperature is 45 DEG C, and bottom temperature is 61 DEG C, and reflux ratio is 30, and side take-off m-pentadiene product, tower top discharging turns back to C5 fraction raw material.
Can with reference to prior art about decarburization six tower, dicyclopentadiene treating tower and solvent treatment part, according to spirit of the present invention, those skilled in the art can design suitable operational condition.
As can be seen from table below, the method for separating cracked carbon 5 fraction of the present invention can obtain polymerization grade isoprene product, not only makes separation process shorten, and the quality index of polymerization grade isoprene product is fully guaranteed.Add or do not add the quality index contrast of the m-pentadiene product of side take-off in raffinate situation as can be seen from m-pentadiene treating tower, adding the cyclopentadiene content reduction contained in m-pentadiene product in raffinate situation, improve m-pentadiene quality.
Turnover material composition (quality %) of table main device
Turnover material composition (quality %) of continued main device
Claims (18)
1. the method for cyclopentadiene in a compartment pentadiene, it is characterized in that, carbon five raffinate that material and cracked C 5 fraction extraction separation device containing m-pentadiene are produced enters m-pentadiene treating tower simultaneously, through azeotropic distillation process, the logistics of cyclopentadiene is contained from described m-pentadiene treating tower overhead extraction, from described m-pentadiene treating tower bottom side take-off containing m-pentadiene product, contain the logistics of dicyclopentadiene from tower reactor extraction; Described carbon five raffinate contain Skellysolve A, 2-methyl-2-butene and 2-amylene first time extraction tower tower top material; Described azeotropic distillation refers to the rectifying utilizing Skellysolve A and cyclopentadiene azeotropic, 2-methyl-2-butene and cyclopentadiene azeotropic and 2-amylene and cyclopentadiene azeotropic.
2. the method for claim 1, is characterized in that, described m-pentadiene treating tower has 50 ~ 100 pieces of number of theoretical plates, and reflux ratio is 15 ~ 35, and tower top temperature is 40 ~ 65 DEG C.
3. the method for claim 1, is characterized in that, described is 1:1 ~ 10:1 containing the material of m-pentadiene and the charge-mass ratio of described carbon five raffinate.
4. method as claimed in claim 3, is characterized in that, described is 2:1 ~ 6:1 containing the material of m-pentadiene and the charge-mass ratio of described carbon five raffinate.
5. the method for diolefine in separating cracked carbon 5 fraction, is characterized in that, said method comprising the steps of:
(1) de-heavy: to make cracking c_5 raw material, through overheated dipolymer reactor, hot dimerization reaction occur, then de-heavy reactive distillation column is entered, or cracking c_5 raw material directly enters de-heavy reactive distillation column without overheated dipolymer reactor, through reactive distillation processes, from the logistics of overhead extraction isoprene containing and more light constituent, from the logistics of tower reactor extraction containing cyclopentadiene, m-pentadiene and more heavy constituent; Described reactive distillation makes cyclopentadiene be the process of dicyclopentadiene while referring to and carry out rectifying in rectifying tower;
(2) de-light: to make the logistics of the heavy reactive distillation column overhead of autospasy to enter lightness-removing column, through rectifying, from the light constituent that lightness-removing column overhead extraction volatility is larger than isoprene, from the logistics of tower reactor extraction isoprene containing;
(3) extraction and parsing: the logistics comprising isoprene from lightness-removing column tower reactor enters in the middle part of extraction tower, extraction solvent enters from extraction tower top, through extracting rectifying process, the raffinate of C 5 alkane and monoolefine is comprised from extraction tower overhead extraction, Analytic Tower is entered from the logistics of tower reactor extraction, through the resolving analytically isoprene logistics of column overhead extraction based on isoprene, the logistics of Analytic Tower tower reactor extraction loops back extraction tower;
(4) isoprene is refined: the isoprene logistics based on isoprene of analytically column overhead extraction enters in the middle part of isoprene product tower, through rectifying from isoprene product column overhead extraction isoprene product, contain the logistics of cyclopentadiene and m-pentadiene from the extraction of isoprene product tower tower reactor;
(5) decarburization five: make the logistics of the heavy reactive distillation column tower reactor of autospasy to enter decarburization five tower, through rectifying, contains carbon five logistics of m-pentadiene, contains the logistics of dicyclopentadiene from tower reactor extraction from the extraction of described decarburization five column overhead;
(6) m-pentadiene is refined: make from described decarburization five column overhead containing m-pentadiene carbon five logistics and enter m-pentadiene treating tower from a part of raffinate of extraction tower tower top simultaneously, through azeotropic distillation process, the logistics of cyclopentadiene is contained from described m-pentadiene treating tower overhead extraction, from described m-pentadiene treating tower bottom side take-off containing m-pentadiene product, contain the logistics of dicyclopentadiene from tower reactor extraction; Described carbon five raffinate contain Skellysolve A, 2-methyl-2-butene and 2-amylene first time extraction tower tower top material; Described azeotropic distillation refers to the rectifying utilizing Skellysolve A and cyclopentadiene azeotropic, 2-methyl-2-butene and cyclopentadiene azeotropic and 2-amylene and cyclopentadiene azeotropic.
6. method as claimed in claim 5, it is characterized in that, described m-pentadiene treating tower has 50 ~ 100 pieces of number of theoretical plates, and reflux ratio is 15 ~ 35, and tower top temperature is 40 ~ 65 DEG C.
7. method as claimed in claim 5, is characterized in that, for described m-pentadiene treating tower, described is 1:1 ~ 10:1 containing the material of m-pentadiene and the charge-mass ratio of described carbon five raffinate.
8. method as claimed in claim 7, is characterized in that, for described m-pentadiene treating tower, described is 2:1 ~ 6:1 containing the material of m-pentadiene and the charge-mass ratio of described carbon five raffinate.
9. method as claimed in claim 5, it is characterized in that, described method is further comprising the steps:
(7) decarburization six: make from described decarburization five tower tower reactor containing dicyclopentadiene logistics and merge from the logistics containing dicyclopentadiene of described m-pentadiene treating tower tower reactor, then decarburization six tower is entered, through rectifying, from the logistics of described decarburization six column overhead extraction carbon containing six, contain the logistics of dicyclopentadiene from tower reactor extraction, turn back to the tower reactor of described decarburization five tower from a part for the logistics of the carbon containing six of overhead extraction to regulate the bottom temperature of described decarburization five tower;
(8) dicyclopentadiene is refined: make the logistics containing dicyclopentadiene from described decarburization six tower tower reactor enter dicyclopentadiene treating tower, through rectification under vacuum process, from described dicyclopentadiene treating tower overhead extraction dicyclopentadiene product, from the heavy constituent that tower reactor extraction volatility is less than dicyclopentadiene.
10. method as claimed in claim 5, is characterized in that, makes to turn back to cracked C 5 fraction from the logistics containing cyclopentadiene and m-pentadiene of described isoprene product tower tower reactor extraction.
11. methods as claimed in claim 5, it is characterized in that, the bottom of described de-heavy reactive distillation column arranges dimerization reaction section, in the bottom of described de-heavy reactive distillation column, one dividing plate is set, dividing plate is offered a hole, a cylindrical shell is upwards connected along described bore edges, the space for material stop is formed between described cylindrical shell and tower wall, inner or outer setting U-tube road at described de-heavy reactive distillation column, the one end on U-tube road is connected with the bottom in described space, the other end is connected with the rectifying section below described dividing plate, rectifying section below the liquid stopped in described space is flowed into by described U-tube road, arrange a passage on the top on described U-tube road to be communicated with the gas phase on liquid level in described space, dimerization reaction is there is and generates dicyclopentadiene in cyclopentadiene in described space, from the logistics of described de-heavy reactive distillation column overhead extraction isoprene containing, the logistics of m-pentadiene is contained from tower reactor extraction.
12. methods as described in claim 5 or 11, is characterized in that, described de-heavy reactive distillation column has 80 ~ 180 pieces of number of theoretical plates, and reflux ratio is 10 ~ 30, and tower top temperature is 40 ~ 60 DEG C.
13. methods as claimed in claim 11, is characterized in that, regulate the height in the described space for material stop to be 1 ~ 4 hour to make material in the residence time in described space.
14. methods as claimed in claim 5, it is characterized in that, in the upper end of described lightness-removing column, hydrogenation catalyst bed is set, in hydrogenation catalyst bed, be provided with gas rising passway pass through for the rectifying gas phase under it, hydrogen inlet is provided with in hydrogenation catalyst bed lower end, pass into hydrogen from hydrogen inlet and make hydrogen by hydrogenation catalyst bed, the rectifying liquid phase flowed downward above hydrogenation catalyst bed is by hydrogenation catalyst bed, flow into the rectifying section below hydrogenation catalyst bed afterwards, the logistics of carbon four is comprised from de-light hydrogenation rectifying tower overhead extraction through hydrogenation reaction and rectifying, the logistics of isoprene is comprised from de-light hydrogenation tower bottom of rectifying tower extraction.
15. methods as claimed in claim 14, it is characterized in that, described lightness-removing column has 80 ~ 120 pieces of number of theoretical plates, and reflux ratio is 5 ~ 20, and tower top temperature is 40 ~ 60 DEG C, and the liquid phase air speed of hydrogenation catalyst bed is 0.5 ~ 10h
-1, hydrogen is 1 ~ 8:1 with the mol ratio entering the alkynes in the liquid phase material of hydrogenation catalyst bed.
16. methods as claimed in claim 5, it is characterized in that, described extraction solvent is dimethyl formamide, acetonitrile or N-Methyl pyrrolidone.
17. methods as claimed in claim 5, is characterized in that, the solvent extraction part that described extraction tower and Analytic Tower use regenerates, and the solvent after regeneration is added in circulating solvent and used.
18. methods as claimed in claim 17, it is characterized in that, the solvent that the need of extraction are regenerated enters the matter tower that comes unstuck, and through rectifying, from the solvent-laden logistics of overhead extraction, contains the waste material of colloid from tower reactor extraction; Make the solvent-laden logistics from matter column overhead of coming unstuck enter de-dimer tower, through rectifying, the solvent after described de-dimer column overhead extraction regeneration, from tower reactor extraction containing dimeric logistics.
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| CN101244974A (en) * | 2007-02-15 | 2008-08-20 | 中国石油化工股份有限公司 | Method for one-section abstraction distillation separation cracking carbon 5-cut fraction |
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| SU763312A1 (en) * | 1977-03-14 | 1980-09-15 | Предприятие П/Я А-1148 | Method of isolating piperilene |
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| CN101302134A (en) * | 2007-05-11 | 2008-11-12 | 中国石油化工股份有限公司 | Method for separating cracked carbon-5 fraction by front-end alkyne removal one-stage extraction |
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