CN102516010B - Method and equipment for separating diolefin component in oil cracking ethylene byproduct carbon-5 fraction - Google Patents
Method and equipment for separating diolefin component in oil cracking ethylene byproduct carbon-5 fraction Download PDFInfo
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- CN102516010B CN102516010B CN 201110380610 CN201110380610A CN102516010B CN 102516010 B CN102516010 B CN 102516010B CN 201110380610 CN201110380610 CN 201110380610 CN 201110380610 A CN201110380610 A CN 201110380610A CN 102516010 B CN102516010 B CN 102516010B
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Abstract
The invention provides a separation method of diolefin in carbon-5 aiming at the problem of high content of cyclopentadiene in isoprene when the diolefin in carbon-5 is separated by utilizing the post-heating dimerization method. The method comprises the following steps of: carrying out thermal dimerization reaction for two times, carrying out heavy removal for two times and removing the cyclopentadiene in the carbon-5 by using a special thermal dipolymer reactor. The content of the cyclopentadiene in the isoprene prepared by adopting the method is below 1 percent (weight), and meanwhile, thecontent of cyclopentadiene in produced piperylene is less than 1 percent (weight); and the content of an isoprene autopolymer or an isoprene copolymer in dicyclopentadiene can reach the level of a post-heating dimerization carbon-5 separation technology. The invention also discloses equipment for implementing the separation method at the same time.
Description
Technical field
The present invention relates to a kind of method and apparatus for separating of the diolefin component in the C5 fraction of petroleum cracking ethylene by-product.
Background technology
The C5 fraction of the quite a lot of quantity of by-product in the petroleum cracking ethylene process, output generally is about 10%～20% of ethylene yield.Contain more than 30 kind of hydrocarbon component in the C5 fraction, wherein tool utility value is three diolefins: m-pentadiene, isoprene, cyclopentadiene.These diolefins, because its specific molecule structure, chemical property is active, is important chemical material.Because the difference on petroleum hydrocarbon cracking raw materials, cracking severity and the separation degree, diolefin content is different in the C5 fraction, but total amount is between 40%～60%.Therefore, separate and utilize C5 fraction for the economic benefit that improves ethylene unit, the comprehensive utilization petroleum resources have profound significance.
The main ingredient boiling point of C5 fraction is close, easily generates azeotrope each other again in addition, and it is higher therefrom to isolate the satisfactory C 5 diene difficulty of purity, and method is comparatively complicated.The key of C 5 diene sepn process is isoprene and the separating of cyclopentadiene, and the boiling-point difference under both normal pressures is 7.45 ℃, and also can increase both separating difficulties with other carbon five hydrocarbon azeotropic.
At present, the industrial higher C 5 diene of comprehensive utilization value of from cracked C 5 fraction, isolating, generally adopt extraction rectifying method, this method advantage is to remove micro-cyclopentadiene and alkynes, shortcoming is that this method flow is long, and facility investment is big, operational difficulty, energy consumption is higher, is the approach that people avoid as far as possible.The present more employing of industrial simple separation diolefin method be after heat dimerization separation method, this method is the cracking c_5 raw material to be sent into take off the isoprene tower, the cat head separation obtains thick isoprene, the tower reactor material enters hot dipolymer reactor and carries out dimerization reaction, and reacting rear material is refining m-pentadiene and the dicyclopentadiene product of obtaining further.The advantage of this method is to have solved in the past in the isolation technique raw material earlier through hot dipolymer reactor production dicyclopentadiene during with the separating ring pentadiene, isoprene generation autohemagglutination and with cyclopentadiene generation copolymerization, influence the problem of dicyclopentadiene purity and subsequent applications; But it is higher that this method is separated the content of cyclopentadiene in the isoprene that obtains, and reaches more than the 4wt%, influenced the subsequent applications of isoprene.
The hot dipolymer reactor that present industrial separating carbon 5 fraction uses mainly contains horizontal reactor and tubular reactor, horizontal reactor wherein, built-in traverse baffle, and with the tube bank heat exchange, the subject matter that exists is that material occurs taking a shortcut and mixes during Flow of Goods and Materials and disturb, heat exchange is inhomogeneous, causes the bad or local overheating phenomenon of part cyclopentadiene polymerization; Tubular reactor then exists temperature control to be difficult for, operation, maintenance inconvenience.
In sum, industrially need that exploitation is a kind of more simply can to solve the high problem of cyclopentadiene content in the isoprene at present, can reduce the method and apparatus of the separating carbon 5 fraction of isoprene autohemagglutination in the dicyclopentadiene or multipolymer again.
Summary of the invention
For solving prior art separation method complexity, the not good problem of separating effect, the invention provides a kind of method for separating of diolefin component in the C5 fraction of petroleum cracking ethylene by-product, use this method can reduce greatly the content of the cyclopentadiene in the isolated isoprene, and can reduce the generation of isoprene autohemagglutination in the dicyclopentadiene or multipolymer.The present invention also provides a cover to implement the specific equipment of the inventive method simultaneously.
For achieving the above object, separation method of the present invention mainly may further comprise the steps:
(1) lightness-removing column is sent in the C5 fraction of petroleum cracking ethylene by-product, from removed overhead carbon four hydro carbons light constituents;
(2) material that comes out from the lightness-removing column tower reactor enters first stage reactor and carries out hot dimerization reaction, makes the hot dimerization of cyclopentadiene wherein become dicyclopentadiene;
(3) material that comes out of first stage reactor enters first weight-removing column, and cat head obtains being rich in the material of isoprene and m-pentadiene, and tower reactor obtains being rich in the material of dicyclopentadiene;
The cat head material of (4) first weight-removing columns enters after cooling and takes off the isoprene tower, and cat head obtains cyclopentadiene content less than the thick isoprene product of 1wt%, and tower reactor obtains containing the rich m-pentadiene material of cyclopentadiene;
(5) the tower reactor material that takes off the isoprene tower enters second stage reactor, makes the cyclopentadiene in the material further carry out hot dimerization reaction;
(6) material that comes out of second stage reactor enters second weight-removing column, and cat head obtains being rich in the material of m-pentadiene, and tower reactor obtains being rich in the material of dicyclopentadiene;
The cat head material of (7) second weight-removing columns enters after cooling and takes off the m-pentadiene tower and make with extra care, and tower reactor obtains cyclopentadiene content less than the m-pentadiene product of 1wt%;
The material that is rich in dicyclopentadiene of (8) first weight-removing column tower reactors and the second weight-removing column tower reactor merges, enter and take off the dicyclopentadiene tower and remove light constituent, obtain purity greater than the dicyclopentadiene product of 85wt%, wherein, X1 content is less than 8.5wt% in the dicyclopentadiene, and X2 content is less than 5wt%; Described X1: the multipolymer of isoprene autopolymer+isoprene and cyclopentadiene; X2: the component that weighs than X1 in the C5 fraction.
Further, in the described step (2), described first stage reactor is in series by several hot dipolymer reactors, wherein, the first hot dipolymer reactor front end is provided with preheater, the rear end of each hot dipolymer reactor is equipped with water cooler, and the temperature of reaction of hot dipolymer reactor is 70～120 ℃, and reaction pressure is 0.70～0.90MPa.
Further, in the described step (3), the operational condition of described first weight-removing column is: the theoretical plate number preferable range is 20～60, and tower top temperature is 40～60 ℃, 80～110 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 1～10, from the middle part charging.
Further, the operational condition of taking off the isoprene tower in the described step (4) is: the theoretical plate number preferable range is 70～120, and tower top temperature is 40～60 ℃, 50～70 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 10～20, from the middle part charging.
Further, in the described step (5), described second stage reactor is in series by several hot dipolymer reactors, and the quantity of the hot dipolymer reactor that it comprises is less than the quantity of hot dipolymer reactor in the described first stage reactor; Wherein, the first hot dipolymer reactor front end is provided with preheater, and the rear end of each hot dipolymer reactor is equipped with water cooler, and the temperature of reaction of hot dipolymer reactor is 80～130 ℃, and reaction pressure is 0.80～1.00MPa.
Further, in the described step (6), the operational condition of described second weight-removing column is: the theoretical plate number scope is 15～50, and tower top temperature is 40～70 ℃, 50～80 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 1～8, from the middle and upper part charging.
Further, in the described step (7), described operational condition of taking off the m-pentadiene tower is: the theoretical plate number scope is 80～120, and tower top temperature is 40～80 ℃, 60～90 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 20～40, from the middle part charging.
Further, in the described step (8), described operational condition of taking off the dicyclopentadiene tower is: the theoretical plate number preferable range is 10～40, tower top temperature is 60～130 ℃, and column bottom temperature is 90～150 ℃, pressure is-0.05～-0.07MPa, reflux ratio is 1～10, from the middle part charging
Further behind the decylization pentadiene tower in technique scheme the dicyclopentadiene weight-removing column is set, makes and take off dicyclopentadiene Tata still material and enter the dicyclopentadiene weight-removing column and remove heavy constituent, obtain the dicyclopentadiene product.X1 content is less than 7wt% in the dicyclopentadiene product, and X2 content is less than 0.6wt%.The operational condition of dicyclopentadiene weight-removing column: the theoretical plate number preferable range is 20～50, and tower top temperature is 70～130 ℃, 90～150 ℃ of column bottom temperatures, pressure be preferably-0.07～-0.09MPa, reflux ratio is 0.5～5, from the middle part charging.
A kind of equipment of implementing above-mentioned separation method, comprise by the processing step in the above-mentioned separation method continuous lightness-removing column, first stage reactor, first weight-removing column, take off isoprene tower, second stage reactor, second weight-removing column, take off the m-pentadiene tower, take off the dicyclopentadiene tower, first stage reactor wherein and second stage reactor are in series by several hot dipolymer reactors.
Further, in described first stage reactor and second stage reactor, also before first hot dipolymer reactor, material preheater is set, behind each hot dipolymer reactor, is provided with the water cooler for the material cooling.
Further, described hot dipolymer reactor comprises: reacting cylinder body, be arranged on the opening for feed of reacting cylinder body lower end, be arranged on the reacting cylinder body bottom and be positioned at the charging vibroshock of opening for feed top, be successively set on some grades of heat-exchanger rigs of charging vibroshock top and be arranged on the discharge port of reacting cylinder body upper end; Aspect ratio 20:1～the 50:1 of described reacting cylinder body, the external diameter of described charging vibroshock is identical with the internal diameter of reactor shell.
Further, described heat-exchanger rig is the heat exchange coiled pipe, described heat exchange coiled pipe is arranged in the described reacting cylinder body by the pipe bracing or strutting arrangement, heat exchange coiled pipe and the coaxial setting of reacting cylinder body, and its external diameter is 1/2～2/3 of reacting cylinder body internal diameter, the pitch of heat exchange coiled pipe is 300-500mm, and the layout of heat exchange coiled pipe highly is 2/3～4/5 of reacting cylinder body height, and the diameter of coiled pipe is 30-80mm.
Further, described vibroshock comprises: be arranged on the multi-layer porous silk screen in the mesh wire stents screen net structure of forming and the two-stage baffle plate of meeting the flow direction of material setting; The silk screen that described screen net structure is evenly equipped with diamond-shaped meshes by some layers piles up and forms, and the phase differential of the mesh of adjacent two layers silk screen is 90 degree; The external diameter of described mesh wire stents is identical with the reacting cylinder body internal diameter; Below screen net structure in 400～1000mm space, be evenly equipped with one-level baffle plate and secondary baffle plate along the axial direction due of reacting cylinder body; Described secondary baffle plate is and the ring baffle of the coaxial setting of reacting cylinder body that its external diameter is 1/2～4/5 of reacting cylinder body internal diameter; Described one-level baffle plate is and the plectane of the coaxial setting of reacting cylinder body that its diameter is 1/3～1/2 of reacting cylinder body diameter; Material enters reactor from hot dipolymer reactor bottom feed mouth, by the inflow vibroshock from descending all around of one-level baffle plate; Endoporus and outer space by the secondary baffle plate evenly flows in the screen net structure of vibroshock again, and flow out in the duct of forming through each layer of screen net structure mesh again.
Further, described screen thickness is 1～2mm, and the major axis spacing of described each mesh is 20～24mm, and the minor axis spacing is 8～12mm.
The invention has the beneficial effects as follows:
1, by adopting two sections hot dimerization reactions, secondarys to take off heavily, make the dimerization reaction condition gentleer, react easier stable control, not only reduced the content of cyclopentadiene in isoprene, the m-pentadiene, and reduced autohemagglutination or the copolymerization of isoprene in hot dipolymer reactor.
2, adopt and to take off the method that the dicyclopentadiene weight-removing column is set behind the dicyclopentadiene tower, reduced the content of heavy constituent in the dicyclopentadiene (X2).
3, the content that utilizes cyclopentadiene in the thick isoprene that the present invention produces satisfies its follow-up application demand less than 1wt%; The content of cyclopentadiene is less than 1wt% in the m-pentadiene, satisfied when producing the high-grade pentadiene petroleum resin raw material the wherein control requirement of cyclopentadiene content, isoprene autohemagglutination in the dicyclopentadiene and the content of multipolymer reach the state of the art that the C5 fraction of after heat dimerization separates, and reduced heavy constituent wherein (X2) content, widened the range of application of dicyclopentadiene.The invention solves the high problem of cyclopentadiene content in the isoprene that after heat dimerization C5 fraction separation method exists.
4, the hot dipolymer reactor reacting cylinder body for separating of in employed first stage reactor and the second stage reactor in the equipment of the diolefin component in the C5 fraction of petroleum cracking ethylene by-product among the present invention designs larger ratio of height to diameter, use special charging vibroshock and use to be arranged on the reactor center coiled pipe and carry out heat exchange, disturbance and the air-teturning mixed phenomenon of material fluid have been reduced, strengthened the heat exchange effect, make operation, it is easier to control, make the cyclopentadiene transformation efficiency higher, and effectively reduce the generation of isoprene autopolymer or multipolymer, avoided hot dipolymer reactor material back-mixing in the past, take a shortcut, heat exchange is inhomogeneous, causes the bad or local overheating phenomenon of part cyclopentadiene polymerization.
5, the employed equipment of method of the diolefin component in the separation petroleum cracking ethylene by-product disclosed in this invention C5 fraction is simple, easy and simple to handle, construction investment and production cost are all lower, are the methods that is suitable for more economically for the enterprise based on production carbon five resins.
Description of drawings
Fig. 1 is method flow of the present invention;
Fig. 2 is the first stage reactor structural representation;
Fig. 3 is hot dipolymer reactor structural representation;
Fig. 4 is the vibroshock structural representation;
Fig. 5 is the separation method schema among the embodiment 1.
Embodiment
As shown in Figure 1, the present invention is a kind of mainly comprises following step for separating of the diolefin component method in the C5 fraction of petroleum cracking ethylene by-product:
(1) cracked C 5 fraction enters lightness-removing column 1, and from the removed overhead carbon four hydro carbons light constituents of lightness-removing column 1, the rest materials component is deposited in the tower reactor of lightness-removing column 1;
(2) material that comes out from the tower reactor of lightness-removing column 1 enters first stage reactor 2 and carries out hot dimerization reaction, makes the hot dimerization of cyclopentadiene wherein become dicyclopentadiene; First stage reactor is that three to five hot dipolymer reactors are in series, and is provided with material preheater before the first hot dipolymer reactor, is equipped with water cooler behind each hot dipolymer reactor, is used for the cooling material.Each hot dipolymer reactor temperature of reaction is 70～120 ℃, and reaction pressure is 0.70～0.90MPa, and each hot dipolymer reactor temperature of reaction is preferably 80～100 ℃.Reaction pressure is preferably 0.80～0.90MPa.
(3) material that is rich in dicyclopentadiene that produces in the step (2) enters first weight-removing column 3, and wherein light material is separated with dicyclopentadiene; Cat head at first weight-removing column 3 obtains being rich in isoprene and m-pentadiene material; Tower reactor obtains being rich in the material of dicyclopentadiene; The operational condition of first weight-removing column 3: the theoretical plate number preferable range is 20～60, and tower top temperature is 40～60 ℃, 80～110 ℃ of column bottom temperatures, and positive pressure operation is from the middle part charging.Reflux ratio is 1～10, is preferably 1～5.
The cat head material of (4) first weight-removing columns 3 enters after cooling and takes off isoprene tower 4, the cat head that takes off isoprene tower 4 obtains cyclopentadiene content less than the thick isoprene product of 1wt%, and the tower reactor of taking off isoprene tower 4 obtains containing the rich m-pentadiene material of cyclopentadiene; Take off isoprene tower operational condition: the theoretical plate number preferable range is 70～120, and tower top temperature is 40～60 ℃, 50～70 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 10～20, is preferably 15～20, from the middle part charging.
(5) the tower reactor material that takes off isoprene tower 4 enters in the second stage reactor 5, makes cyclopentadiene wherein further carry out hot dimerization reaction; Second stage reactor 5 is that two or three hot dipolymer reactors are in series, and is provided with preheater before first reactor, is equipped with water cooler behind each reactor.Each reactor reaction temperature is 80～130 ℃, and reaction pressure is 0.80～1.00MPa.It is 90～110 ℃ that the reactor reaction temperature is preferably, and reaction pressure is preferably 0.90～1.00MPa.
(6) material that is obtained by step (5) cat head that enters second weight-removing column, 6, the second weight-removing columns 6 obtains being rich in the material of m-pentadiene, and the tower reactor of second weight-removing column 6 obtains being rich in the material of dicyclopentadiene; The operational condition of second weight-removing column: the theoretical plate number preferable range is 15～50, and tower top temperature is 40～70 ℃, 50～80 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 1～8, is preferably 4～8.From the middle and upper part charging.
The cat head material of (7) second weight-removing columns 2 enters to take off in the m-pentadiene tower 7 after cooling and makes with extra care, and obtains the content of cyclopentadiene in the tower reactor of taking off m-pentadiene tower 7 less than the m-pentadiene product of 1wt%; Take off the operational condition of m-pentadiene tower: the theoretical plate number preferable range is 80～120, and tower top temperature is 40～80 ℃, 60～90 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 20～40, is preferably 20～30.From the middle part charging.
(8) two portions that will be obtained by the tower reactor of the tower reactor of first weight-removing column 1 and second weight-removing column 6 material of being rich in dicyclopentadiene merges, and enters to take off the dicyclopentadiene tower and remove light constituent, can obtain purity greater than the dicyclopentadiene product of 85wt%.X1 content is less than 8.5wt% in this dicyclopentadiene, and X2 content is less than 5wt%, wherein X1: the isoprene autopolymer adds the multipolymer of isoprene and cyclopentadiene; X2: the component that weighs than X1 in the C5 fraction.Take off the operational condition of dicyclopentadiene tower: the theoretical plate number preferable range is 10～40, and tower top temperature is 60～130 ℃, 90～150 ℃ of column bottom temperatures, pressure be preferably-0.05～-0.07MPa, reflux ratio is 1～10, from the middle part charging.Preferably, the dicyclopentadiene weight-removing column also is set after taking off the dicyclopentadiene tower, X1 content is less than 7wt% in the dicyclopentadiene that this tower of process obtains after taking off and weighing, X2 content is less than 0.6wt%, and the operational condition of dicyclopentadiene weight-removing column: the theoretical plate number preferable range is 20～50, and tower top temperature is 70～130 ℃, 90～150 ℃ of column bottom temperatures, pressure is preferably-0.07～-0.09Mpa, reflux ratio is 0.5～5, from the middle part charging.
Separating device by the cracking c_5 diolefin among the present invention among Fig. 1 mainly comprises: the lightness-removing column 1 of being connected in series successively, first stage reactor 2, one section weight-removing column 3, take off isoprene tower 4, second stage reactor 5, two sections weight-removing columns 6, take off m-pentadiene tower 7, take off dicyclopentadiene tower 8 and dicyclopentadiene weight-removing column 9.Wherein first stage reactor 2 and second stage reactor 5 are the set of reactors that a plurality of hot dipolymer reactors are in series, and wherein, first stage reactor 2 is in series by three to five hot dipolymer reactors usually; Second stage reactor 5 is in series by two or three hot dipolymer reactors usually, and first stage reactor 2 and second stage reactor 5 are except the different amts of the hot dipolymer reactor that is cascaded, and the structure formation of other composition is basic identical.Be the concrete structure of two set of reactors of example explanation with the first stage reactor device.As shown in Figure 2, first stage reactor 2 comprises: feed preheater 201, the first hot dipolymer reactor 202, the first reaction mass water cooler 203, the second hot dipolymer reactor 204, the second reaction mass water cooler 205, the 3rd hot dipolymer reactor 206, the 3rd reaction mass water cooler 207, the 4th hot dipolymer reactor 208, the 4th reaction mass water cooler 209, the 5th hot dipolymer reactor 210, the 5th reaction mass water cooler 211.Wherein, feed exchanger 201 is used for before material carries out hot dimerization reaction, namely enters into before the first hot dipolymer reactor 202 the material preheating, makes material reach cyclopentadiene dimerization reaction optimum temps.Be arranged on the reaction mass water cooler behind each hot dipolymer reactor, be used to reacted material cooling, the best feeding temperature of control subsequent reactor.The structure of second stage reactor 5 and first stage reactor 2 are basic identical, before its first hot dipolymer reactor, also be provided with feed exchanger the material that enters is carried out preheating, behind each hot dipolymer reactor, also be provided with the reaction mass interchanger and be used to reacted material cooling.The hot dipolymer reactor that comprises in first, second section reactor assembly is the hot dipolymer reactor of two～level Four heat-exchanger rig and charging vibroshock.Its concrete structure is shown in Figure 3, comprising: reacting cylinder body 311, the aspect ratio 20:1～50:1 of reacting cylinder body 311 is preferably 25:1～35:1.Be arranged on the opening for feed 301 of reacting cylinder body 311 lower ends and the discharge port 308 on top, be arranged on the bottom of reacting cylinder body 311, be positioned at the charging vibroshock 302 of opening for feed 301 tops, first heat-exchanger rig 312 that is successively set on charging vibroshock 302 tops and second heat-exchanger rig 309; The external diameter of charging vibroshock 302 is identical with the internal diameter of reactor shell 311.First and second heat-exchanger rigs are the heat exchange coiled pipe, are arranged in the reacting cylinder body 311 by first and second bracing or strutting arrangements 313,310 respectively, and two heat exchange coiled pipes are provided with refrigerant entrance 304,306 and refrigerant exit 305,307.The external diameter of two heat-exchanger rigs should be 1/2～2/3 of reacting cylinder body 311 internal diameters; The pitch of heat exchange coiled pipe is 300-500mm, the heat exchange coiled pipe typically have a diameter from 30-80mm.The concrete progression that heat-exchanger rig highly is set according to reacting cylinder body 311 arranges two～level Four heat-exchanger rig usually.The total height of heat-exchanger rig should be 2/3～4/5 of reacting cylinder body 311 height.
As shown in Figure 4, charging vibroshock 302 is formed with the two-stage baffle plate of meeting the flow direction of material setting by being arranged on screen net structure multi-layer porous in the mesh wire stents.The silk screen number of plies in the screen net structure can be set according to the actual needs of producing, and is preferably 20～30 layers; Each layer silk screen is stacked or along its axial equally spaced layout, constitutes screen net structure.Every layer of silk screen 403 thick 1～2mm, usually drawn by thick stainless steel plate and form, mesh on it is uniform diamond hole, the major axis spacing of each mesh is 20～24mm, minor axis spacing 8～12mm, phase place 90 degree that are of the mesh on the adjacent two layers silk screen 403 are arranged, i.e. the major axis of adjacent two layers screen mesh vertical setting mutually, and around the multi-layer silk screen 403 and bottom is provided for supporting the mesh wire stents 404 of each layer silk screen 403.The external diameter of mesh wire stents 404 is identical with reacting cylinder body 311 internal diameters.The mesh of silk screen 403 can also adopt other shapes except above-mentioned rhombus, for example: ellipse etc.But need shift to install between the mesh on the adjacent silk screen 403 or as the above-mentioned mode such as set angle layout that is in phase place arrange, make the material that enters into screen net structure need snakelike walking between each layer silk screen 403, make by the material of discharging in the vibroshock 302 close to plug flow.One-level baffle plate 401 and secondary baffle plate 402 are distributed in 400～1000mm space, below of screen net structure along the axial direction due of reacting cylinder body.Wherein, secondary baffle plate 402 is and the stainless steel annular baffle plate of reacting cylinder body 311 coaxial settings that its external diameter is 1/2～4/5 of reacting cylinder body internal diameter.One-level baffle plate 401 is arranged on the below of secondary baffle plate 402, for the stainless steel plectane of reacting cylinder body 311 coaxial settings, its diameter be reacting cylinder body 311 internal diameter 1/3～1/2.One-level baffle plate 401 is fixedlyed connected with secondary baffle plate 402 by one-level baffle plate coupling device 406.Secondary baffle plate 402 links to each other with mesh wire stents 404 by secondary baffle fixing 405.
Material enters reactor from hot dipolymer reactor bottom feed mouth 301, around one-level baffle plate 401 from entering into down vibroshock 302, and continue upwards, endoporus and outer space by secondary baffle plate 402 evenly flow in the screen net structure of vibroshock 302, again through snakelike passing between each layer screen mesh of screen net structure, enter the material of hot dipolymer reactor like this through behind the vibroshock 302, flowing close to plug flow of material is conducive to the carrying out of hot dimerization reaction.Material passes through the heat exchange of multi-stage heat exchanger device again through behind the vibroshock 302, finishes hot dimerization reaction.The structure of above-mentioned hot dipolymer reactor is conducive to the even propelling of material and in time withdrawing from of the reaction heat of material in hot dimerization reaction more, make operation, control more steady.
The quantity that it should be noted that the hot dipolymer reactor in a section and the second stage reactor can be adjusted the quantity of mentioning above being not limited in according to the factors such as particular case of producing.In addition, concrete parameter such as the interchanger progression in the hot dipolymer reactor also can be adjusted according to practical situation, also is not limited to above-described quantity.
Below be to use above-mentioned method and apparatus to separate the specific embodiment of the diolefin component in the C5 fraction of petroleum cracking ethylene by-product.
Embodiment 1
As shown in Figure 5, cracked C 5 fraction enters lightness-removing column 1, carbon containing four hydro carbons light constituents are via the removed overhead of lightness-removing column 1, the lightness-removing column still separates the material that obtains and enters first stage reactor, at temperature of reaction 85-100 ℃, carries out hot dimerization reaction under the reaction pressure 0.75-0.90MPa, make the cyclopentadiene dimerization in the material become dicyclopentadiene, material enters first weight-removing column then, and cat head separates the material that obtains rich isoprene and m-pentadiene, and tower reactor is separated the material that obtains being rich in dicyclopentadiene.First weight-removing column top is separated and is obtained material and enter after cooling and take off the isoprene tower, obtain thick isoprene product export in the cat head separation, separate the rich m-pentadiene material obtain containing cyclopentadiene in tower reactor and enter second stage reactor, at temperature of reaction 90-110 ℃, under the reaction conditions of pressure 0.90-1.0Mpa, make the cyclopentadiene in the material carry out hot dimerization reaction, reacted material enters second weight-removing column, separates the material that obtains being rich in dicyclopentadiene at the second weight-removing column still; Separate the material that obtains being rich in m-pentadiene on second weight-removing column top, enter after cooling and take off the m-pentadiene tower and make with extra care, tower reactor obtains the m-pentadiene product; The material that is rich in dicyclopentadiene in the first weight-removing column still and the second weight-removing column still is merged, enter together and take off the dicyclopentadiene tower and make with extra care, obtain the dicyclopentadiene product.
Wherein, first stage reactor is to be formed by five reactors in series, is provided with preheater before first reactor, a water cooler is set behind every reactor carries out heat exchange, and each DESIGN OF REACTOR two-stage coiled pipe heat exchange, the aspect ratio of hot dipolymer reactor is 30:1.Second stage reactor is to be formed by three reactors in series, is provided with preheater before first reactor, a water cooler is set behind every reactor carries out heat exchange, and each DESIGN OF REACTOR two-stage coiled pipe heat exchange, the aspect ratio of hot dipolymer reactor is 20:1.
Cyclopentadiene content is 0.83wt% in the isoprene product; The content of cyclopentadiene is 0.86wt% in the m-pentadiene product; The purity 85.25% of dicyclopentadiene product, X1 content is 8.09wt% in the dicyclopentadiene, X2 content 4.75wt%.
Each step reaction condition sees Table 3, and the material composition sees Table 4.
Table three:
Table 4
Embodiment 2:
Equipment used and method are basic identical among present embodiment and the embodiment 1, its difference is also to be provided with the dicyclopentadiene weight-removing column after taking off the dicyclopentadiene tower, the tower reactor material that will take off the dicyclopentadiene tower enters and takes off in the dicyclopentadiene weight-removing column heavily, obtain the dicyclopentadiene product in the cat head separation, tower reactor is isolated heavy constituent.The theoretical plate number of this dicyclopentadiene weight-removing column is 40,97 ℃ of tower top temperatures, and 120 ℃ of tower reactor temperature, tower internal pressure control is between-0.08 to-0.09MPa, and reflux ratio is 5.In addition, first stage reactor in the present embodiment is provided with three hot dipolymer reactors and is in series, each hot dipolymer reactor inside all arranges three grades of heat exchange coil pipe devices, aspect ratio is 50:1, second stage reactor arranges two hot dipolymer reactor series connection, hot dipolymer reactor inside arranges level Four heat exchange coil pipe device, and the aspect ratio of hot dipolymer reactor is 40:1, and other operational condition and material are formed identical with embodiment 1.
The purity of dicyclopentadiene product is 87.35%, and X1 content is that 6.52%, X2 content is 0.56% in the dicyclopentadiene.
Claims (12)
1. method for separating of the diolefin component in the C5 fraction of petroleum cracking ethylene by-product is characterized in that described separation method mainly may further comprise the steps:
(1) lightness-removing column is sent in the C5 fraction of petroleum cracking ethylene by-product, from removed overhead carbon four hydro carbons light constituents;
(2) material that comes out from the lightness-removing column tower reactor enters first stage reactor and carries out hot dimerization reaction, makes the hot dimerization of cyclopentadiene wherein become dicyclopentadiene;
(3) material that comes out of first stage reactor enters first weight-removing column, and cat head obtains being rich in the material of isoprene and m-pentadiene, and tower reactor obtains being rich in the material of dicyclopentadiene;
The cat head material of (4) first weight-removing columns enters after cooling and takes off the isoprene tower, and cat head obtains cyclopentadiene content less than the thick isoprene product of 1wt%, and tower reactor obtains containing the rich m-pentadiene material of cyclopentadiene; Described operational condition of taking off the isoprene tower is: the theoretical plate number preferable range is 70～120, and tower top temperature is 40～60 ℃, 50～70 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 10～20, from the middle part charging;
(5) the tower reactor material that takes off the isoprene tower enters second stage reactor, makes the cyclopentadiene in the material further carry out hot dimerization reaction;
(6) material that comes out of second stage reactor enters second weight-removing column, and cat head obtains being rich in the material of m-pentadiene, and tower reactor obtains being rich in the material of dicyclopentadiene;
The cat head material of (7) second weight-removing columns enters after cooling and takes off the m-pentadiene tower and make with extra care, and tower reactor obtains cyclopentadiene content less than the m-pentadiene product of 1wt%; Described operational condition of taking off the m-pentadiene tower is: the theoretical plate number preferable range is 80～120, and tower top temperature is 40～80 ℃, 60～90 ℃ of column bottom temperatures, and positive pressure operation, reflux ratio is 20～40, from the middle part charging;
The material that is rich in dicyclopentadiene of (8) first weight-removing column tower reactors and the second weight-removing column tower reactor merges, and enters to take off the dicyclopentadiene tower and remove light constituent, obtains purity greater than the dicyclopentadiene product of 85wt%; X1 content is less than 8.5wt% in the dicyclopentadiene, and X2 content is less than 5wt%; Described X1: the multipolymer of isoprene autopolymer+isoprene and cyclopentadiene; X2: the component that weighs than X1 in the C5 fraction.
2. according to the described separation method of claim 1, it is characterized in that, in the described step (2), described first stage reactor is in series by several hot dipolymer reactors, wherein, the first hot dipolymer reactor front end is provided with preheater, and the rear end of each hot dipolymer reactor is equipped with water cooler, the temperature of reaction of hot dipolymer reactor is 70～120 ℃, and reaction pressure is 0.70～0.90MPa.
3. according to the described separation method of claim 1, it is characterized in that, in the described step (3), the operational condition of described first weight-removing column is: the theoretical plate number preferable range is 20～60, tower top temperature is 40～60 ℃, 80～110 ℃ of column bottom temperatures, positive pressure operation, reflux ratio is 1～10, from the middle part charging.
4. according to the described separation method of claim 1, it is characterized in that, in the described step (5), described second stage reactor is in series by several hot dipolymer reactors, and the quantity of the hot dipolymer reactor that it comprises is less than the quantity of hot dipolymer reactor in the described first stage reactor; Wherein, the first hot dipolymer reactor front end is provided with preheater, and the rear end of each hot dipolymer reactor is equipped with water cooler, and the temperature of reaction of hot dipolymer reactor is 80～130 ℃, and reaction pressure is 0.80～1.00MPa.
5. according to the described separation method of claim 1, it is characterized in that, in the described step (6), the operational condition of described second weight-removing column is: the theoretical plate number preferable range is 15～50, tower top temperature is 40～70 ℃, 50～80 ℃ of column bottom temperatures, positive pressure operation, reflux ratio is 1～8, from the middle and upper part charging.
6. according to the described separation method of claim 1, it is characterized in that, in the described step (8), described operational condition of taking off the dicyclopentadiene tower is: the theoretical plate number preferable range is 10～40, tower top temperature is 60～130 ℃, and column bottom temperature is 90～150 ℃, pressure is-0.05～-0.07MPa, reflux ratio is 1～10, from the middle part charging; Behind decylization pentadiene tower, the dicyclopentadiene weight-removing column is set, make and take off dicyclopentadiene Tata still material and enter the dicyclopentadiene weight-removing column and remove heavy constituent, the dicyclopentadiene product that obtains, X1 content is less than 7wt% in the dicyclopentadiene product, and X2 content is less than 0.6wt%; The operational condition of dicyclopentadiene weight-removing column: the theoretical plate number preferable range is 20～50, and tower top temperature is 70～130 ℃, 90～150 ℃ of column bottom temperatures, pressure be-0.07～-0.09MPa, reflux ratio is 0.5～5, from the middle part charging.
7. the equipment of each described separation method of enforcement right 1-6, it is characterized in that, comprise by the processing step in the above-mentioned separation method continuous lightness-removing column, first stage reactor, first weight-removing column, take off isoprene tower, second stage reactor, second weight-removing column, take off the m-pentadiene tower, take off the dicyclopentadiene tower, first stage reactor wherein and second stage reactor are in series by several hot dipolymer reactors.
8. according to equipment described in the claim 7, it is characterized in that, in described first stage reactor and second stage reactor, also before first hot dipolymer reactor, material preheater is set, behind each hot dipolymer reactor, be provided with the water cooler for the material cooling.
According to Claim 8 described in equipment, it is characterized in that, described hot dipolymer reactor comprises: reacting cylinder body, be arranged on the opening for feed of reacting cylinder body lower end, be arranged on the reacting cylinder body bottom and be positioned at the charging vibroshock of opening for feed top, be successively set on some grades of heat-exchanger rigs of charging vibroshock top and be arranged on the discharge port of reacting cylinder body upper end; Aspect ratio 20:1～the 50:1 of described reacting cylinder body, the external diameter of described charging vibroshock is identical with the internal diameter of reactor shell.
10. according to equipment described in the claim 9, it is characterized in that, described heat-exchanger rig is the heat exchange coiled pipe, described heat exchange coiled pipe is arranged in the described reacting cylinder body by the pipe bracing or strutting arrangement, heat exchange coiled pipe and the coaxial setting of reacting cylinder body, and its external diameter is 1/2～2/3 of reacting cylinder body internal diameter, and the pitch of heat exchange coiled pipe is 300-500mm, the layout of heat exchange coiled pipe highly is 2/3～4/5 of reacting cylinder body height, and the coiled pipe diameter is 30-80mm.
11., it is characterized in that described vibroshock comprises according to equipment described in the claim 9: be arranged on the multi-layer porous silk screen in the mesh wire stents screen net structure of forming and the two-stage baffle plate of meeting the flow direction of material setting; The silk screen that described screen net structure is evenly equipped with diamond-shaped meshes by some layers piles up and forms, and the phase differential of the mesh of adjacent two layers silk screen is 90 degree; The external diameter of described mesh wire stents is identical with the reacting cylinder body internal diameter; Below screen net structure in 400～1000mm space, be evenly equipped with one-level baffle plate and secondary baffle plate along the axial direction due of reacting cylinder body; Described secondary baffle plate is and the ring baffle of the coaxial setting of reacting cylinder body that its external diameter is 1/2～4/5 of reacting cylinder body internal diameter; Described one-level baffle plate is and the plectane of the coaxial setting of reacting cylinder body that its diameter is 1/3～1/2 of reacting cylinder body diameter.
12. equipment as claimed in claim 11 is characterized in that, described screen thickness is 1～2mm, and the major axis spacing of described each mesh is 20～24mm, and the minor axis spacing is 8～12mm.
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| CN103483135B (en) * | 2013-09-02 | 2015-05-06 | 浙江恒河石油化工股份有限公司 | Preparation method of high-purity ethylidene norbornene (ENB) |
| CN104591948B (en) * | 2013-10-30 | 2018-04-24 | 中石化上海工程有限公司 | It is a kind of to reduce the method that pentadiene process energy consumption is separated from petroleum cracking C5 fractions |
| CN104591949B (en) * | 2013-10-30 | 2018-04-24 | 中石化上海工程有限公司 | A kind of method that pentadiene is separated in the C5 fractions from petroleum cracking |
| CN109665934B (en) * | 2017-10-16 | 2021-10-19 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene |
| CN111747821B (en) * | 2019-03-27 | 2023-03-28 | 中国石油化工股份有限公司 | Process for preparing olefin by oxidative coupling of methane |
| CN111747820B (en) * | 2019-03-27 | 2023-03-28 | 中国石油化工股份有限公司 | Method for producing hydrocarbons |
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| CN100999434A (en) * | 2006-01-11 | 2007-07-18 | 北京化工大学 | 5C separating and comprehensive utilization by acetonitrile solvent method |
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