CN116283468A - Method for removing dicyclopentadiene from ethylene cracking carbon nine fraction - Google Patents
Method for removing dicyclopentadiene from ethylene cracking carbon nine fraction Download PDFInfo
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- CN116283468A CN116283468A CN202211680125.4A CN202211680125A CN116283468A CN 116283468 A CN116283468 A CN 116283468A CN 202211680125 A CN202211680125 A CN 202211680125A CN 116283468 A CN116283468 A CN 116283468A
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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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- 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 phenol modified petroleum resin and a preparation method thereof. The method comprises the following steps: s1, placing the pyrolysis carbon nine in a rectifying tower, rectifying and separating the pyrolysis carbon nine, and obtaining a light component dicyclopentadiene enrichment liquid at the top of the rectifying tower; s2, placing the dicyclopentadiene enrichment solution into a distillation tower for reduced pressure distillation, and obtaining dicyclopentadiene distillate at the top of the distillation tower; s3, introducing dicyclopentadiene distillate into a gasifier, and gasifying the dicyclopentadiene distillate to obtain cyclopentadiene monomers; s4: cooling the cyclopentadiene monomer to 90 ℃ for liquefaction, introducing the cyclopentadiene monomer into a separation tower, adding negative pressure, and extracting the cyclopentadiene monomer from the top of the separation tower; s5: cooling the cyclopentadiene monomer to 50 ℃, cooling and liquefying, and then introducing the cyclopentadiene monomer into a polymerization kettle for polymerization reaction to obtain dicyclopentadiene. The method for removing dicyclopentadiene from the ethylene pyrolysis carbon nine fraction can improve the purity and the yield of dicyclopentadiene.
Description
Technical Field
The invention relates to the technical field of dicyclopentadiene preparation, in particular to a method for removing dicyclopentadiene from ethylene cracking carbon nine fraction.
Background
The C9-C10 fraction is the residual fraction of naphtha or light diesel oil pyrolysis byproducts after the C5 fraction and the C6-C8 fraction are extracted and separated. The C9-C10 fraction has complex composition and more than 150 components, mainly contains components such as aromatic hydrocarbon, styrene, methyl styrene, dicyclopentadiene (DCPD), indene, naphthalene and the like, and various forms of self-polymerized and inter-polymerized dimers of Cyclopentadiene (CPD) and Methyl Cyclopentadiene (MCPD), wherein the content of the methyl styrene and the dicyclopentadiene is the highest, and the dicyclopentadiene can be used for synthesizing important intermediates of perfumes, medicines and the like, and plays a very important role.
At present, a method combining thermal dimerization with azeotropic distillation or solvent extraction distillation is widely used in industry, namely, the characteristic that cyclopentadiene is easier to dimerize than other C5 fractions is utilized to dimerize into dicyclopentadiene (DCPD), and the characteristic that the boiling point of dicyclopentadiene is obviously higher than that of other C5 hydrocarbons is utilized to separate the dicyclopentadiene from the C5 fractions through distillation. In the process of rectifying the C9 raw material under reduced pressure, dicyclopentadiene is prepared by adopting a rectification and polymerization mode at present, and also a direct extraction or extraction mode is adopted. However, the current manner of polymerization by distillation results in lower yields and purities, wasting a significant amount of C9 fractions.
Disclosure of Invention
Based on this, it is necessary to provide a process for removing dicyclopentadiene from an ethylene cracking carbon nine fraction.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a process for removing dicyclopentadiene from an ethylene cracking carbon nine fraction comprising the steps of:
s1, placing pyrolysis carbon nine in a rectifying tower, rectifying and separating the pyrolysis carbon nine, wherein a light component dicyclopentadiene enrichment liquid is obtained at the top of the rectifying tower, and a heavy component in the pyrolysis carbon nine is obtained at the bottom of the rectifying tower;
s2, placing the dicyclopentadiene enrichment liquid into a distillation tower for reduced pressure distillation, obtaining dicyclopentadiene distillate at the top of the distillation tower, and obtaining residual fraction at the bottom of the distillation tower;
s3, introducing the dicyclopentadiene distillate into a gasifier, and gasifying the dicyclopentadiene distillate to obtain cyclopentadiene monomers;
s4: cooling the cyclopentadiene monomer to 90 ℃ for liquefaction, introducing the cyclopentadiene monomer into a separation tower, adding negative pressure, extracting a small amount of heavy components in the cyclopentadiene monomer from the tower bottom of the separation tower, extracting carbon nine components with lower boiling points from the side line of the separation tower, and extracting the cyclopentadiene monomer from the tower top of the separation tower;
s5: cooling the cyclopentadiene monomer to 50 ℃, cooling and liquefying, then introducing the cyclopentadiene monomer into a polymerization kettle, keeping the temperature of the polymerization kettle at 80-90 ℃, and reacting for 1-4h to obtain dicyclopentadiene.
According to the method for removing dicyclopentadiene from the ethylene pyrolysis carbon nine fraction, the pyrolysis carbon nine is firstly subjected to rectification separation, dicyclopentadiene is primarily separated, then the enriched liquid is subjected to reduced pressure distillation to obtain dicyclopentadiene distillate, and other fractions are further removed; gasifying the distillate to obtain monomer, liquefying and separating the monomer again, polymerizing, separating high-purity cyclopentadiene monomer before polymerizing, and obtaining dicyclopentadiene with high yield and purity up to 94% or more and 92% or more.
In one embodiment, in the step S5, the polymerization kettle uses hot water at 80-90 ℃ to maintain the temperature and remove the heat of reaction.
In one embodiment, the temperature of the gasifier in the step S3 is 199 ℃ to 210 ℃.
In one embodiment, the vacuum degree of the top of the rectifying tower in the step S1 is-65 kpa to-55 kpa, and the temperature of the top of the rectifying tower is controlled to be 90 ℃ to 100 ℃.
In one embodiment, the heavy component extracted from the bottom of the separation tower in step S4 is recycled into the rectification tower.
In one embodiment, in the step S2, the temperature of the distillation column bottom is 80-120 ℃, the temperature of the column top is 50-74 ℃, and the pressure of the column top is-80-90 kpa g.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a method for removing dicyclopentadiene from an ethylene cracking carbon nine fraction, which comprises the following steps:
s1, placing the pyrolysis carbon nine in a rectifying tower, rectifying and separating the pyrolysis carbon nine, obtaining a light component dicyclopentadiene enrichment liquid at the top of the rectifying tower, and obtaining a heavy component in the pyrolysis carbon nine at the tower bottom of the rectifying tower. The dicyclopentadiene enrichment liquid can be primarily separated from the cracking carbon nine by adopting primary rectification separation, and part of heavy components are removed.
S2, placing the dicyclopentadiene enrichment liquid into a distillation tower for reduced pressure distillation, obtaining dicyclopentadiene distillate at the top of the distillation tower, and obtaining the residual fraction at the bottom of the distillation tower. And (3) performing reduced pressure distillation on the dicyclopentadiene enrichment liquid, further separating out dicyclopentadiene, and removing the residual components in the enrichment liquid.
S3, introducing dicyclopentadiene distillate into a gasifier, and gasifying the dicyclopentadiene distillate to obtain cyclopentadiene monomers. And heating dicyclopentadiene to obtain cyclopentadiene monomer.
S4: cooling the cyclopentadiene monomer to 90 ℃ for liquefaction, introducing the cyclopentadiene monomer into a separation tower, adding negative pressure, extracting polymerization liquid from the tower bottom of the separation tower, wherein the polymerization liquid comprises heavy components obtained by re-liquefying the cyclopentadiene monomer and the polymerized cyclopentadiene monomer, extracting carbon nine components with lower boiling points from the side line of the separation tower, and extracting the cyclopentadiene monomer from the tower top of the separation tower. The cyclopentadiene monomer is liquefied and separated again, and further purified. (cyclopentadiene+dicyclopentadiene (bridge) is more than or equal to 97%)
S5: cooling the polymerization solution and cyclopentadiene monomer to 50 ℃, cooling and liquefying, then introducing the polymerization solution and cyclopentadiene monomer into a polymerization kettle, keeping the temperature of the polymerization kettle at 80-90 ℃, and reacting for 1-4h to obtain dicyclopentadiene.
According to the method for removing dicyclopentadiene from the ethylene pyrolysis carbon nine fraction, the pyrolysis carbon nine is firstly subjected to rectification separation, dicyclopentadiene is primarily separated, then the enriched liquid is subjected to reduced pressure distillation to obtain dicyclopentadiene distillate, and other fractions are further removed; gasifying the distillate to obtain monomer, liquefying and separating the monomer again, polymerizing, separating high-purity cyclopentadiene monomer before polymerizing, and obtaining dicyclopentadiene with high yield and purity up to 94% or more and 92% or more.
In one embodiment, in step S5, the polymerization vessel is maintained at a temperature of 80℃to 90℃with hot water and the heat of reaction is removed.
In one embodiment, the gasifier temperature in step S3 is 199 ℃ -210 ℃.
In one embodiment, the vacuum degree of the top of the rectifying tower in the step S1 is-65 kpa to-55 kpa, and the temperature of the top of the rectifying tower is controlled to be 90 ℃ to 100 ℃.
In one embodiment, the heavy component extracted from the bottom of the separation tower in step S4 is recycled to the rectifying tower. The heavy components are separated again in a circulating way, the raw materials are recycled, and the monomers can be purified repeatedly, so that the purity of the reactants of the polymerization reaction is ensured to be higher, and the purity and the yield of the product are improved.
In one embodiment, in step S2, the temperature of the distillation tower bottom is 80-120 ℃, the temperature of the tower top is 50-74 ℃, and the pressure of the tower top is-80-90 KPaG.
Through testing, the dicyclopentadiene prepared by the preparation method has the purity of more than 94 percent. The yield of dicyclopentadiene can reach 92% by adopting the following formula. The content of dicyclopentadiene and its monomers in the pyrolysis carbon nine fraction of the pre-test raw material was 20%.
Yield = dicyclopentadiene mass/mass content of dicyclopentadiene and monomer in the ethylene-cracking carbon nine fraction produced 100%.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. A process for removing dicyclopentadiene from an ethylene cracking carbon nine fraction comprising the steps of:
s1, placing pyrolysis carbon nine in a rectifying tower, rectifying and separating the pyrolysis carbon nine, wherein a light component dicyclopentadiene enrichment liquid is obtained at the top of the rectifying tower, and a heavy component in the pyrolysis carbon nine is obtained at the bottom of the rectifying tower;
s2, placing the dicyclopentadiene enrichment liquid into a distillation tower for reduced pressure distillation, obtaining dicyclopentadiene distillate at the top of the distillation tower, and obtaining residual fraction at the bottom of the distillation tower;
s3, introducing the dicyclopentadiene distillate into a gasifier, and gasifying the dicyclopentadiene distillate to obtain cyclopentadiene monomers;
s4: cooling the cyclopentadiene monomer to 90 ℃ for liquefaction, introducing the cyclopentadiene monomer into a separation tower, adding negative pressure, extracting a small amount of heavy components in the cyclopentadiene monomer from the tower bottom of the separation tower, extracting carbon nine components with lower boiling points from the side line of the separation tower, and extracting the cyclopentadiene monomer from the tower top of the separation tower;
s5: cooling the cyclopentadiene monomer to 50 ℃, cooling and liquefying, then introducing the cyclopentadiene monomer into a polymerization kettle, keeping the temperature of the polymerization kettle at 80-90 ℃, and reacting for 1-4h to obtain dicyclopentadiene.
2. The process for removing dicyclopentadiene from an ethylene cracking carbon nine fraction according to claim 1, wherein: in the step S5, the polymerization kettle adopts 80-90 ℃ hot water to maintain the temperature and remove the reaction heat.
3. The process for removing dicyclopentadiene from an ethylene cracking carbon nine fraction according to claim 1, wherein: the temperature of the gasifier in the step S3 is 199-210 ℃.
4. The process for removing dicyclopentadiene from an ethylene cracking carbon nine fraction according to claim 1, wherein: the vacuum degree of the top of the rectifying tower in the step S1 is-65 kpa to-55 kpa, and the temperature of the top of the rectifying tower is controlled to be 90 ℃ to 100 ℃.
5. The process for removing dicyclopentadiene from an ethylene cracking carbon nine fraction according to claim 1, wherein: and (4) recycling heavy components extracted from the tower bottom of the separation tower in the step (S4) into the rectifying tower.
6. The process for removing dicyclopentadiene from an ethylene cracking carbon nine fraction according to claim 1, wherein: in the step S2, the temperature of the tower bottom of the distillation tower is 80-120 ℃, the temperature of the tower top is 50-74 ℃, and the pressure of the tower top is-80-90 KPaG.
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