CN111548246A - Method for preparing high-purity dicyclopentadiene from cracking carbon nine fraction - Google Patents

Method for preparing high-purity dicyclopentadiene from cracking carbon nine fraction Download PDF

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CN111548246A
CN111548246A CN202010325393.9A CN202010325393A CN111548246A CN 111548246 A CN111548246 A CN 111548246A CN 202010325393 A CN202010325393 A CN 202010325393A CN 111548246 A CN111548246 A CN 111548246A
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dicyclopentadiene
fraction
rectifying tower
temperature
carbon
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刘阳
梁国强
陈炳琳
左洪亮
林茂生
杨圣儒
黄杰
苏秋万
谭庆
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Guangdong Xinhuayue Petrochemical Inc Co
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Guangdong Xinhuayue Petrochemical Inc Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/50—Diels-Alder conversion
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes

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Abstract

The invention relates to the field of dicyclopentadiene preparation, and more particularly relates to a method for preparing dicyclopentadiene from a cracking carbon-nine fraction, which comprises the following steps: (1) inputting the cracked carbon nine fraction into a rectifying tower T1, feeding a material and an inert solvent collected from the top of a rectifying tower T1 into a reactor R1 through a preheater E1 for cracking, wherein the temperature of the reactor R1 is 280-300 ℃; (2) the cracked material in the step (1) enters a rectifying tower T2 through a condenser E2 for rectification, and liquid-phase cyclopentadiene is obtained from the top of the tower; (3) enabling the liquid-phase cyclopentadiene obtained in the step (2) to enter a dimerization reaction kettle for dimerization reaction; (4) and (4) rectifying the polymerization product obtained in the step (3) in a rectifying tower T3 to obtain dicyclopentadiene from a lateral line.

Description

Method for preparing high-purity dicyclopentadiene from cracking carbon nine fraction
Technical Field
The invention relates to the field of dicyclopentadiene preparation, and particularly relates to a method for preparing high-purity dicyclopentadiene from cracked C-nine fraction.
Background
Cyclopentadiene (CPD) is a highly reactive cyclic conjugated diene that exists as a dimer dicyclopentadiene at ambient temperatures. Dicyclopentadiene (DCPD) is an important chemical raw material, and the largest application of dicyclopentadiene is to prepare hydrogenated high-grade petroleum resin and replace part of phthalic anhydride to produce unsaturated polyester, and the dicyclopentadiene is used for manufacturing paint, coating, printing ink, pipelines, storage tanks, sanitary wares, ships, anticorrosion equipment and the like. The dicyclopentadiene can be used as raw material to produce various special fine chemicals, such as high-energy fuel, pesticide, perfume, solidifying agent and medical intermediate. The high-purity dicyclopentadiene can be used as a third monomer of the ethylene propylene rubber, and can also be used for preparing the third monomer of the ethylene propylene rubber, such as ethylidene norbornene and a catalyst. The ultra-high purity dicyclopentadiene can be used for producing reaction injection molding engineering plastic polydicyclopentadiene (PDCDP), and the product can replace certain metals and engineering plastics. It is widely used in civil engineering, construction, vehicles, ships and machinery. Reaction of dicyclopentadiene with ethylene produces norbornene, which is the primary starting material for Cyclic Olefin Copolymers (COC).
Cracking raw materials obtained by cracking petroleum, gasoline and the like to prepare ethylene are separated into light fractions with more than eight carbons to obtain a considerable amount of carbon nine and carbon ten fractions, and the materials called the carbon nine and carbon ten fractions are generally from a gasoline component separation device in an ethylene combined device. The material has complex components and contains more than 100 components, such as dicyclopentadiene, dimers of cyclopentadiene and methylcyclopentadiene, nona-carbon aromatics, indenes, naphthalene compounds and the like. Since it is very difficult to separate these substances from each other, the materials have not been reported to be effectively utilized so far, and are industrially used as a fuel in many cases. This not only causes a great waste of petroleum resources, but also is very harmful to environmental protection. In fact, most of the substances contained in the solution are highly valuable, such as dicyclopentadiene.
In the prior art, the preparation process of high-purity dicyclopentadiene is mainly realized by separating ethylene cracking carbon five and cracking carbon nine, and dicyclopentadiene separated from cracking carbon five fraction has the purity of about 85 percent and relatively low purity. The purity of dicyclopentadiene cracked and separated by cracking carbon nine fraction is more than 95 percent, the dicyclopentadiene produced by liquid phase depolymerization and rectification by using ethylene cracking carbon nine as a raw material is produced by the main process technology of dicyclopentadiene with higher purity at present, the yield of dicyclopentadiene produced by the technology is low, cyclopentadiene and dicyclopentadiene and other C5 types generated by long retention time of liquid phase reaction materials in a reactor can generate polymerization reaction, so that the materials in the reactor are easy to polymerize to generate polymers, and meanwhile, the cyclopentadiene produced by liquid phase depolymerization is difficult to reach the high purity dicyclopentadiene. The invention adopts the methods of solvent protection and high-temperature gas phase depolymerization to produce the high-purity dicyclopentadiene, and well solves the problems of low product yield, coking of a reactor and low product purity.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a method for preparing dicyclopentadiene from a pyrolysis carbon nine fraction, which comprises the following steps:
(1) inputting the cracked carbon nine fraction into a rectifying tower T1, collecting a dicyclopentadiene-rich material and an inert solvent from the top of a rectifying tower T1, feeding the dicyclopentadiene-rich material and the inert solvent into a reactor R1 through a preheater E1 for cracking, wherein the temperature of the reactor R1 is 280-300 ℃;
(2) quenching the cracked material in the step (1) through a condenser E2, and then feeding the quenched material into a rectifying tower T2 for rectification to obtain liquid-phase cyclopentadiene from the top of the tower;
(3) allowing the liquid-phase cyclopentadiene obtained in the step (2) to enter a dimerization reaction kettle for dimerization reaction;
(4) and (4) rectifying the polymerization product obtained in the step (3) in a rectifying tower T3 to obtain dicyclopentadiene from a lateral line.
As a preferable technical scheme of the invention, the boiling point of the inert solvent is 90-120 ℃.
As a preferable technical scheme of the invention, the mass ratio of the inert solvent to the material extracted from the top of the rectifying tower T1 is (0.8-1.5): 1.
as a preferable technical scheme of the invention, the cracking carbon nine fraction in the step (1) is C of a byproduct of ethylene preparation by gasoline cracking9～C12And (6) cutting.
As a preferable technical scheme of the invention, the temperature of the dimerization reaction kettle is 50-60 ℃, and the pressure is 500-600 kPa.
As a preferable technical scheme of the invention, the pressure of the rectifying tower T1 is 9-11 kPa, the temperature of the bottom of the tower is 140-150 ℃, and the temperature of the top of the tower is 90-120 ℃.
As a preferable technical scheme of the invention, the cracking retention time in the step (1) is 5-10 s.
As a preferable technical scheme of the invention, the bottom temperature of the rectifying tower T2 is 110-130 ℃, and the top temperature is 38-60 ℃.
As a preferable technical scheme, the top temperature of the rectification T3 is 84-89 ℃, the side-draw temperature is 90-94 ℃, and the bottom temperature is 100-110 ℃.
In a second aspect, the present invention provides dicyclopentadiene produced in a process for producing dicyclopentadiene from a cracked carbon nine fraction.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing dicyclopentadiene from the cracked carbon nine fraction is safe and feasible, the coking phenomenon does not occur in the whole process, and the service life of the reactor is prolonged; the dicyclopentadiene obtained by the method has the component yield of not less than 95 percent and the purity of not less than 99 percent, and realizes high-efficiency production.
Drawings
FIG. 1 is a flow chart of the apparatus and process of the present invention.
1-9 are all materials related to the invention, wherein: 1-cracking C nine fraction; 2-a dicyclopentadiene-rich material; 3-an inert solvent; 4-cyclopentadiene; 5-dicyclopentadiene; 6-light component; 7-heavy component; 8-carbon nine material containing inert solvent; 9-high boiling carbon nine fraction.
T1-T3-rectifying tower; e1-preheater; r1-reactor; e2-condenser; R2A, R2B-dimerization reactor.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
In a first aspect of the present invention, there is provided a method for preparing highly pure dicyclopentadiene from a pyrolysis carbon-nine fraction, the method for preparing dicyclopentadiene from the pyrolysis carbon-nine fraction comprising the steps of:
(1) inputting the cracked carbon nine fraction into a rectifying tower T1, feeding the material extracted from the tower top and an inert solvent into a reactor R1 for cracking through a preheater E1, wherein the temperature of the reactor R1 is 280-300 ℃;
(2) quenching the cracked material in the step (1) through a condenser E2, and then feeding the quenched material into a rectifying tower T2 for rectification to obtain liquid-phase cyclopentadiene from the top of the tower;
(3) allowing the liquid-phase cyclopentadiene obtained in the step (2) to enter a dimerization reaction kettle R2 for dimerization reaction to obtain crude dicyclopentadiene;
(4) and (4) rectifying the polymerization product obtained in the step (3) in a rectifying tower T3 to obtain dicyclopentadiene from a lateral line.
Step (1)
In one embodiment, the pressure of the rectifying tower T1 is 9-11 kPa, the bottom temperature is 140-150 ℃, and the top temperature is 90-120 ℃. The tower top extraction amount is 45-50 wt% of the T1 feeding amount.
Preferably, the pressure of the rectification column T1 is 10 kPa.
Preferably, the temperature of the tower top is 90-120 ℃. The material extracted from the top of the rectifying tower T1 is a material rich in dicyclopentadiene (corresponding to the number 2 in the attached drawing of the specification); a high boiling point carbon nine fraction (corresponding to the number 9 in the attached drawing of the specification) is extracted from the bottom of the tower.
In one embodiment, the temperature of the preheater E1 is 170-190 ℃; preferably, the temperature of the preheater E1 is 180-190 ℃.
In one embodiment, the reactor R1 temperature is 280 ℃ to 300 ℃; preferably, the reactor R1 temperature is 285 ℃ to 295 ℃.
In one embodiment, the pyrolysis residence time is 5 to 10 s; preferably, the lysis residence time is 8 s.
In one embodiment, the flow rate of the input cracked carbon nine fraction of the rectifying tower T1 is 7.5-8.5T/h; more preferably, the flow rate of the input cracked carbon nine fraction of the rectifying tower T1 is 8T/h.
In one embodiment, the overhead flow rate of the rectifying tower T1 is 3.6-4.2T/h; preferably, the overhead flow velocity of the rectifying tower T1 is 4.0T/h.
In one embodiment, the cracking carbon nine-fraction is C of a byproduct of ethylene production by gasoline cracking9～C12And (6) cutting.
The cracking C nine-fraction comprises 24-26 wt% of dicyclopentadiene, 20-22 wt% of styrene and homologues thereof and 8-10 wt% of C11H14Polycycloolefin, 1-2.5 wt% C12H16Polycycloolefin, 12-13.5 wt% of indene segment homologues and 32-33 wt% of other components.
In one embodiment, the inert solvent has a boiling point of 90 to 120 ℃.
Preferably, the inert solvent comprises at least one of C9 aliphatic alkane, toluene, C9 cycloalkane.
The inert solvent corresponds to the number 3 in the drawings of the specification.
Preferably, the mass ratio of the inert solvent to the material extracted from the top of the rectifying tower T1 is (0.8-1.5): 1; more preferably, the mass ratio of the inert solvent to the material extracted from the top of the rectifying tower T1 is 1: 1.
the high depolymerization temperature is beneficial to depolymerization of the dimer, the depolymerization is thorough, and the yield of the product is improved, however, the high temperature is unfavorable for the reactor, the service life of the reactor is influenced, and meanwhile, the high temperature is easier to form high polymer, and the coking is aggravated. In order to further improve the yield of the product, the cracking retention time is set to be 5-10 s, and the depolymerized active monomers are allowed to stay for a longer time and to form insoluble substances under a high-temperature condition, so that pipelines are blocked. The applicant unexpectedly finds that the generation of coking can be reduced by introducing a certain inert solvent before depolymerization, probably because the inert solvent with the boiling point of 90-120 ℃ can dilute the concentration of active components such as cyclopentadiene and dicyclopentadiene on one hand, and can form a protective film on the wall of the vessel on the other hand, so that the direct contact of materials and the vessel wall is avoided, and the generation of coking is reduced. The inert solvent plays a role in the subsequent rectification process all the time, reduces the probability of repolymerization of the monomer, and improves the purity and yield of the product.
Step (2)
The cracked material obtained in the step (1) enters a condenser E2, and in one embodiment, the outlet temperature of the condenser E2 is 65-75 ℃.
The cracked material in the step (1) enters a rectifying tower T2 through a condenser E2 for rectification, and liquid-phase cyclopentadiene is obtained from the top of the tower; and a carbon nine material solvent separation and recovery system containing inert solvent at the bottom of the tower.
Wherein, the cyclopentadiene of the liquid phase corresponds to the number 4 in the attached drawing of the specification, and the carbon nine material containing the inert solvent corresponds to the number 8 in the attached drawing of the specification.
In one embodiment, the temperature of the bottom of the rectifying tower T2 is 110-130 ℃, and the temperature of the top of the rectifying tower T2 is 38-60 ℃.
In one embodiment, the pressure of the rectification column T2 is 105 to 115 kPa; more preferably, the pressure of said rectification column T2 is 110 kPa.
In one embodiment, the input flow rate of the rectifying tower T2 is 7.4-8.4T/h; more preferably, the input flow rate of the rectifying column T2 is 8T/h.
In one embodiment, the overhead flow rate of the rectifying tower T2 is 1.9-2.1T/h; preferably, the overhead flow rate of the rectifying tower T2 is 2T/h.
Step (3)
In one embodiment, the temperature of the dimerization reactor is 50 to 60 ℃ and the pressure is 500 to 600 kPa.
Preferably, the dimerization reactor pressure is 550 kPa.
In one embodiment, the dimerization reaction time is 23 to 25 hours; preferably, the dimerization reaction time is 24 h.
In one embodiment, the dimerization reactor R2 comprises n reactors, with n reactors operating in a shift operation, where n.gtoreq.2. For example, n-2, or n-3, or n-4; from the viewpoints of economic efficiency, cost, yield and the like, n is preferably 4.
Step (4)
In one embodiment, the dicyclopentadiene after polymerization is fed to the rectification column T3 at a flow rate of 2 to 6T/h.
In a preferred embodiment, the dicyclopentadiene after polymerization is fed to the rectification column T3 at a flow rate of 4T/h.
In one embodiment, the vacuum distillation is carried out in a rectification column T3, the rectification column T3 has a pressure of-89 to-91 kPa; preferably, the rectification column T3 pressure is-90 kPa.
In one embodiment, the rectifying tower T3 has a top temperature of 84-89 ℃, a side draw temperature of 90-94 ℃ and a bottom temperature of 100-110 ℃.
A substance extracted from the side line in the rectifying tower T3 is dicyclopentadiene; the substance extracted from the tower top is light component; the extracted substance at the bottom of the tower is a heavy component.
Examples
Example 1
Example 1 of the present invention provides a method for preparing dicyclopentadiene from a pyrolysis carbon nine fraction, which comprises the following steps:
(1) inputting the cracked carbon nine fraction into a rectifying tower T1 at 8T/h, controlling the pressure of the rectifying tower T1 to be 9kPa, the temperature of the bottom of the tower to be 145 +/-5 ℃ and the temperature of the top of the tower to be 115 +/-5 ℃; obtaining a material rich in dicyclopentadiene at the tower top at 3.6t/h, and introducing the material and an inert solvent into a reactor R1 for cracking through a preheater E1, wherein the cracking retention time is 5s, the temperature of the preheater E1 is controlled to be 155 +/-5 ℃, and the temperature of the reactor R1 is controlled to be 290 +/-5 ℃;
(2) quenching the cracked material obtained in the step (1) by a condenser E2, feeding the quenched material into a rectifying tower T2 for rectification, controlling the pressure of the rectifying tower T2 to be 105kPa, the temperature of the tower bottom to be 115 +/-5 ℃, and the temperature of the tower top to be 38-45 ℃, and obtaining liquid-phase cyclopentadiene from the tower top; the outlet temperature of the condenser E2 is 65-70 ℃; the input flow rate of the rectifying tower T2 is 8T/h; the tower top extraction flow speed of the rectifying tower T2 is 2T/h.
(3) Allowing the liquid-phase cyclopentadiene obtained in the step (2) to enter a dimerization reaction kettle R2 for dimerization reaction at 55 +/-5 ℃ for 23 hours, wherein the pressure of the dimerization reaction kettle is 500 kPa; the dimerization reactor R2 comprises two reactors (R2A and R2B), and the two reactors are operated alternately;
(4) and (4) intermittently rectifying the polymerization product obtained in the step (3) in a rectifying tower T3 at a rate of 4T/h to obtain dicyclopentadiene, wherein the pressure of a rectifying tower T3 is-89 kPa, the top temperature of the rectifying tower T3 is 84-89 ℃, the side-draw temperature is 90-94 ℃, and the bottom temperature is 105 +/-5 ℃.
The cracking carbon nine-cut fraction comprises 25.26 wt% of dicyclopentadiene, 20.52 wt% of styrene and homologues thereof and 8.39 wt% of C11H14Polycycloolefins, 1.35 wt% C12H16Polycycloolefin, 12.35 wt% indene segment homologue and 32.13 wt% other components C9 and C10.
The inert solvent is n-heptane; the mass ratio of the inert solvent to the material extracted from the top of the rectifying tower T1 is 1: 1.
the dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Example 2
Example 1 of the present invention provides a method for preparing dicyclopentadiene from a pyrolysis carbon nine fraction, which comprises the following steps:
(1) inputting the cracking carbon nine-fraction into a rectifying tower T1 at 8T/h, controlling the pressure of the rectifying tower T1 to be 9kPa, the temperature of the bottom of the rectifying tower to be 145 +/-5 ℃, the temperature of the top of the rectifying tower to be 115 +/-5 ℃, and controlling the reflux ratio to be 1.2: 1; obtaining a material rich in dicyclopentadiene at the tower top at 3.6t/h, and introducing the material and an inert solvent into a reactor R1 for cracking through a preheater E1, wherein the cracking retention time is 10s, the temperature of the preheater E1 is controlled to be 155 +/-5 ℃, and the temperature of the reactor R1 is controlled to be 290 +/-5 ℃;
(2) quenching the cracked material obtained in the step (1) by a condenser E2, feeding the quenched material into a rectifying tower T2 for rectification, controlling the pressure of the rectifying tower T2 to be 105kPa, the temperature of the tower bottom to be 115 +/-5 ℃, and the temperature of the tower top to be 38-45 ℃, and obtaining liquid-phase cyclopentadiene from the tower top; the outlet temperature of the condenser E2 is 65-70 ℃; the input flow rate of the rectifying tower T2 is 8T/h; the tower top extraction flow speed of the rectifying tower T2 is 2T/h.
(3) Allowing the liquid-phase cyclopentadiene obtained in the step (2) to enter a dimerization reaction kettle R2 for dimerization reaction at 55 +/-5 ℃ for 23 hours, wherein the pressure of the dimerization reaction kettle is 500 kPa; the dimerization reactor R2 comprises two reactors (R2A and R2B), and the two reactors are operated alternately;
(4) and (4) intermittently rectifying the polymerization product obtained in the step (3) in a rectifying tower T3 at a rate of 4T/h to obtain dicyclopentadiene, wherein the pressure of a rectifying tower T3 is-89 kPa, the top temperature of the rectifying tower T3 is 84-89 ℃, the side-draw temperature is 90-94 ℃, and the bottom temperature is 105 +/-5 ℃.
The cracking carbon nine-cut fraction comprises 25.26 wt% of dicyclopentadiene, 20.52 wt% of styrene and homologues thereof and 8.39 wt% of C11H14Polycycloolefins, 1.35 wt% C12H16Polycycloolefin, 12.35 wt% indene segment homologue and 32.13 wt% other components C9 and C10.
The inert solvent is toluene; the mass ratio of the inert solvent to the materials extracted from the top of the tower is 1: 1.
example 3
Example 1 of the present invention provides a method for preparing dicyclopentadiene from a pyrolysis carbon nine fraction, which comprises the following steps:
(1) inputting the cracking carbon nine-fraction into a rectifying tower T1 at 8T/h, controlling the pressure of the rectifying tower T1 to be 9kPa, the temperature of the bottom of the rectifying tower to be 145 +/-5 ℃, the temperature of the top of the rectifying tower to be 105 +/-5 ℃, and controlling the reflux ratio to be 1.2: 1; obtaining a material rich in dicyclopentadiene at the tower top at 3.6t/h, and introducing the material and an inert solvent into a reactor R1 for cracking through a preheater E1, wherein the cracking retention time is 10s, the temperature of the preheater E1 is controlled to be 155 +/-5 ℃, and the temperature of the reactor R1 is controlled to be 290 +/-5 ℃;
(2) quenching the cracked material obtained in the step (1) by a condenser E2, feeding the quenched material into a rectifying tower T2 for rectification, controlling the pressure of the rectifying tower T2 to be 105kPa, the temperature of the tower bottom to be 115 +/-5 ℃, and the temperature of the tower top to be 38-45 ℃, and obtaining liquid-phase cyclopentadiene from the tower top; the outlet temperature of the condenser E2 is 65-70 ℃; the input flow rate of the rectifying tower T2 is 8T/h; the tower top extraction flow speed of the rectifying tower T2 is 2T/h.
(3) Allowing the liquid-phase cyclopentadiene obtained in the step (2) to enter a dimerization reaction kettle R2 for dimerization reaction at 55 +/-5 ℃ for 23 hours, wherein the pressure of the dimerization reaction kettle is 500 kPa; the dimerization reactor R2 comprises two reactors (R2A and R2B), and the two reactors are operated alternately;
(4) and (4) intermittently rectifying the polymerization product obtained in the step (3) in a rectifying tower T3 at a rate of 4T/h to obtain dicyclopentadiene, wherein the pressure of a rectifying tower T3 is-89 kPa, the top temperature of the rectifying tower T3 is 84-89 ℃, the side-draw temperature is 90-94 ℃, and the bottom temperature is 105 +/-5 ℃.
The cracking carbon nine-cut fraction comprises 25.26 wt% of dicyclopentadiene, 20.52 wt% of styrene and homologues thereof and 8.39 wt% of C11H14Polycycloolefins, 1.35 wt% C12H16Polycycloolefin, 12.35 wt% indene segment homologue and 32.13 wt% other components C9 and C10.
The inert solvent is n-heptane; the mass ratio of the inert solvent to the materials extracted from the top of the tower is 1: 1.
the dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Example 4
Embodiment 4 of the present invention provides a method for preparing dicyclopentadiene from a pyrolysis carbon nine fraction, which is similar to embodiment 3 in the specific embodiment, except that the mass ratio of the inert solvent to a material extracted from the top of a rectifying tower T1 is 0.2: 1.
the dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Example 5
Embodiment 5 of the present invention provides a method for preparing dicyclopentadiene from a pyrolysis carbon nine fraction, which is similar to embodiment 3 in the specific embodiment except that the temperature of the reactor R1 is controlled to 295-300 ℃.
The dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Example 6
Example 6 of the present invention provides a process for producing dicyclopentadiene from a cracked carbonine fraction in the same manner as in example 3 except that the cracking residence time is 2 s.
The dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Example 7
Example 7 of the present invention provides a process for producing dicyclopentadiene from a cracked carbonine fraction in the same manner as in example 3 except that the cracking residence time is 15 s.
The dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Example 8
Embodiment 8 of the present invention provides a method for preparing dicyclopentadiene from a pyrolysis carbon nine fraction, which is performed in the same manner as embodiment 3, except that the weight ratio of the inert solvent to the overhead material of the rectification column T1 is 3: 1.
the dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Example 9
Example 9 of the present invention provides a process for producing dicyclopentadiene from a cracked carbonine fraction in the same manner as in example 3 except that the inert solvent is chloroform.
The dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Example 10
Example 10 of the present invention provides a process for producing dicyclopentadiene from a cracked carbonine fraction in the same manner as in example 3 except that the inert solvent is n-nonane.
The dicyclopentadiene is prepared by the method for preparing the dicyclopentadiene from the cracking carbon nine fraction.
Performance evaluation
1. Purity: the purity of cyclopentadiene obtained from the top of the rectifying column T2 in step (2) in examples 1 to 3 was measured by gas chromatography, and the purity of dicyclopentadiene obtained from the side of the rectifying column T3 in step (4) in examples 1 to 10 was measured by gas chromatography.
2. Yield: the yield of dicyclopentadiene obtained in step (4) in examples 1 to 10 was measured in terms of mass yield, which means that the mass of an actually obtained product is a percentage of the total amount of the product monomer in the raw materials.
3. Coking: whether or not coking occurs in the reactor R1 in the step (1) in examples 1 to 10 was observed.
Table 1 results of performance testing
Figure BDA0002463019620000101
From the test results in table 1, it can be seen that the method for preparing dicyclopentadiene from cracked carbon nine fraction provided by the invention is safe and feasible, the product yield and purity are high, the utilization rate of raw materials is improved, the coking phenomenon does not occur in the whole process, and the service life of the reactor is prolonged.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (10)

1. A method for preparing high-purity dicyclopentadiene from a cracking carbon nine fraction is characterized by comprising the following steps of:
(1) inputting the cracked carbon nine fraction into a rectifying tower T1, collecting a dicyclopentadiene-rich material and an inert solvent from the top of a rectifying tower T1, feeding the dicyclopentadiene-rich material and the inert solvent into a reactor R1 through a preheater E1 for cracking, wherein the temperature of the reactor R1 is 280-300 ℃;
(2) the cracked material in the step (1) enters a rectifying tower T2 through a condenser E2 for rectification, and liquid-phase cyclopentadiene is obtained from the top of the tower;
(3) enabling the liquid-phase cyclopentadiene obtained in the step (2) to enter a dimerization reaction kettle for dimerization reaction;
(4) and (4) rectifying the polymerization product obtained in the step (3) in a rectifying tower T3 to obtain dicyclopentadiene from a lateral line.
2. The method for preparing dicyclopentadiene from the pyrolysis of carbon nine fraction according to claim 1, wherein the inert solvent has a boiling point of 90 to 120 ℃.
3. The method for preparing dicyclopentadiene from cracked carbon nine fraction according to claim 1 or 2, wherein the mass ratio of the inert solvent to the material extracted from the top of the rectifying tower T1 is (0.8-1.5): 1.
4. the method for preparing dicyclopentadiene from the cracked carbon nine fraction as claimed in claim 3, wherein the cracked carbon nine fraction in step (1) is C of the by-product of ethylene production by gasoline cracking9～C12And (6) cutting.
5. The method for preparing dicyclopentadiene from the pyrolysis of the carbon nine fraction according to claim 1 or 2, wherein the temperature of the dimerization reactor is 50 to 60 ℃ and the pressure is 500 to 600 kPa.
6. The method for preparing dicyclopentadiene from the cracked carbon nine fraction as recited in claim 1 or 2, wherein the pressure of said rectifying tower T1 is 9-11 kPa, the temperature of the bottom of the tower is 140-150 ℃, and the temperature of the top of the tower is 90-120 ℃.
7. The method for preparing dicyclopentadiene from cracking carbonine fraction according to claim 1 or 2, wherein the cracking residence time in the step (1) is 5-10 s.
8. The method for preparing dicyclopentadiene from the cracked carbon nine fraction according to claim 1 or 2, wherein the temperature of the bottom of the rectifying tower T2 is 110-130 ℃ and the temperature of the top of the rectifying tower T2 is 38-60 ℃.
9. The method for preparing dicyclopentadiene from cracked carbon nine fraction according to claim 1 or 2, wherein the temperature of the top of the rectifying tower T3 is 84-89 ℃, the temperature of the side draw is 90-94 ℃ and the temperature of the bottom of the rectifying tower is 100-110 ℃.
10. Dicyclopentadiene produced by the method for producing high-purity dicyclopentadiene from a pyrolysis carbonine fraction according to any one of claims 1 to 9.
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