CN111499487A - Industrial production process for preparing high-purity cyclopentadiene - Google Patents
Industrial production process for preparing high-purity cyclopentadiene Download PDFInfo
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- CN111499487A CN111499487A CN202010332692.5A CN202010332692A CN111499487A CN 111499487 A CN111499487 A CN 111499487A CN 202010332692 A CN202010332692 A CN 202010332692A CN 111499487 A CN111499487 A CN 111499487A
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- cyclopentadiene
- dicyclopentadiene
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000009776 industrial production Methods 0.000 title claims abstract description 10
- 238000005336 cracking Methods 0.000 claims abstract description 66
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 239000003112 inhibitor Substances 0.000 claims abstract description 41
- 239000003085 diluting agent Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 40
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 20
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 16
- 238000010790 dilution Methods 0.000 claims description 15
- 239000012895 dilution Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 10
- 229940094933 n-dodecane Drugs 0.000 claims description 10
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 9
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 9
- 230000008016 vaporization Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000000066 reactive distillation Methods 0.000 abstract description 8
- 238000004939 coking Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004230 steam cracking Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003250 fulvenyl group Chemical class C1(=CC=CC1=C)* 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an industrial production process for preparing high-purity cyclopentadiene by depolymerizing dicyclopentadiene, which takes dicyclopentadiene as a raw material, adds diluent 1 and polymerization inhibitor 1 into the dicyclopentadiene to be uniformly mixed, then carries out depolymerization, rectification and separation in a reactive distillation column 1, collects crude cyclopentadiene at the top of the column, then adds the crude cyclopentadiene, diluent 2 and polymerization inhibitor 2 into an evaporation kettle, heats and vaporizes, passes steam through a cracking tube to carry out tubular cracking, carries out secondary depolymerization, rectification and separation in the reactive distillation column 2 after cracking, and collects high-purity cyclopentadiene at the top of the column. The process solves the problems of coking, bumping and low purity of the prior art, obtains the cyclopentadiene with high purity, has high yield and has high industrial application value.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to an industrial production process for preparing high-purity cyclopentadiene by depolymerizing dicyclopentadiene.
Background
Dicyclopentadiene (DCPD) is a dimer of Cyclopentadiene (CPD). DCPD is colorless crystal at room temperature, is light yellow oily liquid containing impurities, has camphor smell, has melting point of 32 ℃ and boiling point of 170 ℃, is soluble in most organic solvents, and is depolymerized into CPD at high temperature, and the CPD is easily dimerized into DCPD at room temperature. DCPD is mainly from the by-product of petroleum cracking, and the C5 fraction with naphtha or light diesel oil as cracking material has high yield. The DCPD has two isomers of bridged ring type and hanging ring type in the space structure, and the DCPD and monomer CPD thereof have conjugated double bonds and active hydrogen on methylene, and are main raw materials for producing unsaturated polyester polymers. DCPD is mainly used for preparing hydrogenated high-grade petroleum resin, is mainly used as an adhesive of sanitary materials, is used for preparing cyclopentadiene, glutaraldehyde and ferrocene, is copolymerized with ethylene and the like to prepare a high molecular product, is polymerized dicyclopentadiene (PDCPD) resin, is used for preparing high-energy fuel and the like. DCPD with the mass content of more than 90 percent is in short supply in the market at present and is partially dependent on import.
Cyclopentadiene (CPD), also known as 1, 3-Cyclopentadiene and cyclopentadienes, is a colorless, transparent, strongly odoriferous liquid having a melting point of-97.542 ℃ and a boiling point of 41-42 ℃, and is an important by-product of the cracking of C5 fractions to ethylene. Cyclopentadiene is readily dimerized to dicyclopentadiene at room temperature and depolymerized to cyclopentadiene at high temperatures, and therefore is usually present as a dimer. Because cyclopentadiene contains conjugated double bonds, has active property and high chemical reaction activity, can be subjected to reactions such as hydrogenation, halogenation, addition, polymerization, condensation, reduction and the like, is easy to react with unsaturated compounds to generate various cyclic compounds, and can also be condensed with aldehyde and ketone to generate high-value-added products such as colored fulvene derivatives and the like. Cyclopentadiene has been widely used in the fields of resins, plastics, rubbers, perfumes, agricultural chemicals, epoxy resins, curing agents, flame retardants, catalysts, solvents, and the like. In addition, cyclopentadiene can react with transition metal salt to produce metallocene compound, which is the main raw material for electrically synthesizing ferrocene. The purity of cyclopentadiene directly influences the quality of synthesized downstream products, and most reaction conditions require the use of high-purity cyclopentadiene, so that the preparation of high-purity cyclopentadiene has profound significance for the expansion of the application field of cyclopentadiene.
Because dicyclopentadiene has a self-polymerization phenomenon in the high-temperature cracking process, coking blockage is formed due to self-polymerization, and impurities are generated along with side reactions, so that the yield and the purity of the product are negatively influenced. Because high-temperature depolymerization is needed, the problems of coking, bumping, incomplete depolymerization, low purity and the like can be generated in the industrial production process, and a new industrial production process is urgently needed to solve the problems.
Disclosure of Invention
Therefore, the invention provides an industrial production process for preparing high-purity cyclopentadiene by depolymerizing dicyclopentadiene, which can be used for industrially producing cyclopentadiene in large scale, and the prepared cyclopentadiene has high purity and high yield. The process solves the problems of coking, bumping and low purity of the existing process.
The technical scheme of the invention is as follows:
an industrial production process for preparing high-purity cyclopentadiene by depolymerizing dicyclopentadiene uses dicyclopentadiene as a raw material, and comprises the following steps of adding diluent 1 and polymerization inhibitor 1 into dicyclopentadiene, uniformly mixing, carrying out depolymerization, rectification and separation in a reactive rectification tower 1, controlling the temperature of a tower kettle to be 170-.
Further, dicyclopentadiene is used as a raw material, and the method comprises the following steps of firstly adding a diluent 1 and a polymerization inhibitor 1 into dicyclopentadiene, uniformly mixing, then carrying out depolymerization, rectification and separation in a reactive distillation tower 1, controlling the temperature of a tower kettle to be 190-.
The method further comprises the following steps of adding diluent 1 and polymerization inhibitor 1 into dicyclopentadiene, uniformly mixing, performing depolymerization, rectification and separation in a reactive rectification tower 1, controlling the temperature of a tower kettle to be 220 ℃, the temperature of a tower top to be 41-45 ℃, the pressure of the tower top to be 14-16KPaG, the reflux ratio to be 8, the feeding rate to be 3L/min, collecting crude cyclopentadiene at the tower top, adding the crude cyclopentadiene, diluent 2 and polymerization inhibitor 2 into an evaporation kettle, heating and vaporizing, allowing steam to pass through a cracking pipe heated to about 320 ℃, performing tubular cracking, performing secondary depolymerization, rectification and separation in the reactive rectification tower 2, controlling the temperature of the tower kettle to be 230 ℃, the temperature of the tower top to be 41-42 ℃, the pressure of the tower top to be 16KPaG, and the reflux ratio to be 12, and collecting high-purity cyclopentadiene at the tower top.
Further, the diluent 1 is composed of n-dodecane and n-hexane in a mass ratio of (10-15) to (1-3), and the raw materials are diluted to 20% -30% in mass fraction.
Further, the diluent 2 is composed of n-hexadecane and n-hexane in a mass ratio of (5-10) to (1-3), and the raw materials are diluted to 10-15% by mass.
Further, the polymerization inhibitor 1 consists of hydroquinone and aniline in a mass ratio of (5-8) to (0.5-2), and the addition amount is 0.01-0.015 percent of the mass of the raw materials before dilution.
Further, the polymerization inhibitor 2 consists of 2, 6-di-tert-butyl-p-methylphenol and chloranil in the mass ratio of (1-5) to (5-1), and the adding amount is 0.005-0.01 percent of the mass of the raw materials before dilution.
Further, the diluent 1 is composed of n-dodecane and n-hexane in a mass ratio of 10:3, and the raw materials are diluted to 20% by mass.
Further, the diluent 2 is composed of n-hexadecane and n-hexane in a mass ratio of 5:1, and the raw materials are diluted to a mass fraction of 15%.
Further, the polymerization inhibitor 1 is composed of hydroquinone and aniline in a mass ratio of 10:1, and the addition amount is 0.01% of the mass of the raw materials before dilution.
Further, the polymerization inhibitor 2 is composed of 2, 6-di-tert-butyl-p-methylphenol and chloranil in a mass ratio of 1:1, and the addition amount is 0.01% of the mass of the raw materials before dilution.
Furthermore, the inside of the cracking tube is of a net structure, or the cracking tube is composed of a plurality of cracking tubes with uniform thickness and smaller diameter.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses the diluent and the polymerization inhibitor, can dilute the concentration of the dicyclopentadiene, and the polymerization inhibitor plays a role in synergy, properly reduces the depolymerization rate, and avoids the occurrence of self-polymerization reaction due to overhigh concentration of the cyclopentadiene caused by overhigh depolymerization rate, thereby effectively controlling the depolymerization and inhibiting the generation of coking phenomenon in the high-temperature cracking process.
2. The invention uses the tubular reactor, can greatly improve the reaction temperature, lead the depolymerization reaction to be more thorough, and improve the reaction yield and the purity of the product.
3. The invention uses the method of low-temperature cracking to obtain a crude product, and then high-temperature cracking, rectification and separation to obtain a high-purity product.
4. The cracking tube is internally provided with a net structure, or consists of a plurality of cracking tubes with uniform thickness and smaller diameter, so that the cracking tube can prevent the phenomenon of 'bumping' at high temperature and avoid the damage of equipment or the influence of product quality.
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
Example 1
Firstly, adding diluent 1 (n-dodecane and n-hexane in a mass ratio of 10: 3) and polymerization inhibitor 1 (hydroquinone and aniline in a mass ratio of 10: 1) into dicyclopentadiene, uniformly mixing, controlling the use amount of the diluent 1 to dilute the raw materials to 20% by mass and the use amount of the polymerization inhibitor 1 to be 0.01% by mass of the raw materials before dilution, then carrying out depolymerization, rectification and separation in a reactive rectification tower 1, controlling the tower bottom temperature to be 190-200 ℃, the tower top temperature to be 41-45 ℃, the tower top pressure to be 13-16KPaG, the reflux ratio to be 8, the feeding rate to be 3L/min, collecting to obtain crude cyclopentadiene at the tower top, then adding the crude cyclopentadiene and diluent 2 (n-hexadecane and n-hexane in a mass ratio of 10: 3), the polymerization inhibitor 2(2, 6-di-tert-butyl-methyl phenol and tetrachlorobenzoquinone in a mass ratio of 1: 1) into an evaporation kettle, diluting the raw materials to 15% by mass, adding the polymerization inhibitor 2 to be 0.01% by mass before dilution, heating the polymerization inhibitor to a steam cracking kettle to obtain a high-purity-96% by reflux ratio, heating the cracking kettle to obtain a high-purity-220%, carrying out secondary cracking reaction, detecting, and carrying out secondary cracking reaction, wherein the high-purity detection is carried out secondary cracking reaction, the cracking kettle is carried out cracking at the cracking reaction, the cracking kettle at the tower top temperature is carried out a secondary cracking reaction, the secondary cracking kettle is carried out at the secondary cracking reaction, the secondary.
Example 2
Firstly, adding diluent 1 (n-dodecane and n-hexane in a mass ratio of 15: 1) and polymerization inhibitor 1 (hydroquinone and aniline in a mass ratio of 4: 1) into dicyclopentadiene, uniformly mixing, controlling the use amount of the diluent 1 to dilute the raw materials to 20% by mass and the use amount of the polymerization inhibitor 1 to be 0.01% by mass of the raw materials before dilution, then carrying out depolymerization, rectification and separation in a reactive rectification tower 1, controlling the tower bottom temperature to be 180: 190 ℃, the tower top temperature to be 41-43 ℃, the tower top pressure to be 15KPaG, the reflux ratio to be 6, the feeding rate to be 5L/min, collecting crude cyclopentadiene at the tower top, then adding the crude cyclopentadiene and diluent 2 (n-hexadecane and n-hexane in a mass ratio of 5: 1), the polymerization inhibitor 2(2, 6-di-tert-butyl-p-methylphenol and tetrachlorobenzoquinone in a mass ratio of 5: 1) into an evaporation kettle, diluting the raw materials to 15% by mass, adding the polymerization inhibitor 2 to 0.01% by mass before dilution, heating the distillation to a steam cracking kettle, carrying out secondary pyrolysis separation in a high-purity-cracking rectification tower top to be 2, controlling the steam cracking temperature to be 220, carrying out secondary cracking separation to be 12 ℃ and carrying out secondary cracking at the tower top to obtain a high-purity detection, and the high-purity detection, wherein the purity of 2 is controlled to be 2, and the purity of 2 is controlled.
Example 3
Firstly adding a diluent 1 (n-dodecane and n-hexane in a mass ratio of 10: 1) and a polymerization inhibitor 1 (hydroquinone and aniline in a mass ratio of 15: 1) into dicyclopentadiene, uniformly mixing, controlling the tower bottom temperature to be 200 ℃, the tower top temperature to be 41-43 ℃, the tower top pressure to be 13KPaG, the reflux ratio to be 8, the feeding rate to be 1L/min, carrying out depolymerization and rectification separation in a reactive distillation tower 1, controlling the tower top temperature to be 13-43 ℃, the tower top pressure to be 13KPaG, collecting crude cyclopentadiene at the tower top, then adding the crude cyclopentadiene and the diluent 2 (n-hexadecane and n-hexane in a mass ratio of 5: 1), the polymerization inhibitor 2(2, 6-di-tert-butyl-p-methylphenol and tetrachlorobenzoquinone in a mass ratio of 1: 5) into an evaporation kettle, diluting the raw material to be 10%, the adding amount of the diluent 2 to be 0.01% of the mass of the raw material before dilution, carrying out rectification, heating and vaporizing the crude cyclopentadiene to be heated to be 300 ℃ through a steam cracking tower top, controlling the purity to be 97-21, carrying out cracking separation in a high-purity-cracking distillation tower top, detecting that the cracking kettle is 12.42 ℃, and carrying out secondary cracking at the cracking reaction at the tower top temperature to obtain the high-purity of a cracking kettle.
Example 4
Firstly adding diluent 1 (n-dodecane and n-hexane are in a mass ratio of 10: 1) and polymerization inhibitor 1 (hydroquinone and aniline are in a mass ratio of 10: 1) into dicyclopentadiene, uniformly mixing, controlling the tower bottom temperature to be 200 ℃, the tower top temperature to be 41-43 ℃, the tower top pressure to be 15KPaG, the reflux ratio to be 7, the feeding rate to be 2L/min, collecting crude cyclopentadiene at the tower top in a reactive distillation tower 1, controlling the tower bottom temperature to be 200 ℃, the tower top temperature to be 41-43 ℃, the tower top pressure to be 15KPaG, feeding the crude cyclopentadiene and the diluent 2 (n-hexadecane and n-hexane) to be 7, controlling the reflux ratio to be 7, feeding the crude cyclopentadiene at the feeding rate to be 2L/min, adding the crude cyclopentadiene and the diluent 2 (n-hexadecane and n-hexane are in a mass ratio of 5: 1), the polymerization inhibitor 2(2, 6-di-tert-butyl-p-methylphenol and tetrachlorobenzoquinone to be in a mass ratio of 1: 1) into an evaporation kettle, diluting the raw material with the raw material, rectifying the raw material to be 2, heating and vaporizing the raw material, heating the raw material to be vaporized, heating the steam to be heated to be carried out cracking in a cracking tower top of a cracking tower, controlling the cracking reaction kettle to be 99.7 ℃, the cracking temperature to be 12 ℃, detecting the cracking temperature to be 12.
Example 5
Firstly adding diluent 1 (n-dodecane and n-hexane are in a mass ratio of 5: 1) and polymerization inhibitor 1 (hydroquinone and aniline are in a mass ratio of 5: 2) into dicyclopentadiene, uniformly mixing, controlling the tower bottom temperature to be 220 ℃, the tower top temperature to be 41-43 ℃, the tower top pressure to be 15KPaG, the reflux ratio to be 8, the feeding rate to be 3L/min, carrying out depolymerization and rectification separation in a reactive distillation tower 1, controlling the tower top temperature to be 4 ℃, the tower top temperature to be 41-43 ℃, the tower top pressure to be 15KPaG, collecting crude cyclopentadiene at the tower top, then adding crude cyclopentadiene and diluent 2 (n-hexadecane and n-hexane are in a mass ratio of 5: 1), polymerization inhibitor 2(2, 6-di-tert-butyl-methyl phenol and tetrachlorobenzoquinone are in a mass ratio of 1: 3) into an evaporation kettle, diluting the raw material to be 15%, the adding amount of 2 to be 0.01% of the mass before dilution of the raw material, carrying out rectification, heating and vaporizing the raw material, heating the steam is heated to a cracking tower top, the cracking kettle is heated to be 96.42 ℃, carrying out cracking separation, controlling the cracking temperature to be 42 ℃, carrying out secondary cracking reaction, and obtaining the crude cyclopentadiene at the cracking in the cracking kettle, and carrying out secondary cracking at the cracking reaction distillation tower top temperature to be 16-38 ℃ to obtain the secondary cracking.
Comparative example 1
Firstly adding a diluent 1 (n-dodecane and n-hexane in a mass ratio of 10: 3) and a polymerization inhibitor 1 (hydroquinone and aniline in a mass ratio of 10: 1) into dicyclopentadiene, uniformly mixing, wherein the using amount of the diluent 1 is 20% of the mass of the raw materials, the using amount of the polymerization inhibitor 1 is 0.01% of the mass of the raw materials before dilution, then carrying out depolymerization, rectification and separation in a reactive distillation tower 1, controlling the temperature of a tower kettle to be 190-200 ℃, the temperature of a tower top to be 41-45 ℃, the pressure of the tower top to be 13-16KPaG, the reflux ratio to be 8, the feeding rate to be 3L/min, collecting the cyclopentadiene at the tower top, the yield to be 98.2%, and the purity to be 96.12% by gas chromatography detection.
Comparative example 2
Adding dicyclopentadiene, a diluent 2 (composed of n-hexadecane and n-hexane in a mass ratio of 10: 3) and a polymerization inhibitor 2 (composed of 2, 6-di-tert-butyl-p-methylphenol and tetrachlorobenzoquinone in a mass ratio of 1: 1) into an evaporation kettle, wherein the dosage of the diluent 2 is that the raw materials are diluted to the mass fraction of 15%, and the dosage of the polymerization inhibitor 2 is 0.01% of the mass of the raw materials before dilution. Heating for vaporization, and making steam pass through a cracking tube heated to about 330 ℃, wherein the interior of the cracking tube is of a net structure for tubular cracking, performing secondary depolymerization and rectification separation in a reactive distillation tower 2 after cracking, controlling the temperature of a tower kettle to be 220-230 ℃, the temperature of a tower top to be 41-43 ℃, the pressure of the tower top to be 16KPaG, and the reflux ratio to be 12, and collecting high-purity cyclopentadiene at the tower top, wherein the yield is 97.6%, and the purity is 95.21% by gas chromatography detection.
Comparative example 3
Firstly adding a diluent 1 (n-dodecane and n-hexane in a mass ratio of 10: 3) and a polymerization inhibitor 1 (hydroquinone and aniline in a mass ratio of 10: 1) into dicyclopentadiene, uniformly mixing, wherein the amount of the diluent 1 is 20% by mass of the raw materials, the amount of the polymerization inhibitor 1 is 0.01% by mass of the raw materials before dilution, then carrying out depolymerization, rectification and separation in a reactive rectification tower 1, controlling the temperature of a tower kettle to be 190-200 ℃, the temperature of a tower top to be 41-45 ℃, the pressure of the tower top to be 13-16KPaG, the reflux ratio to be 8, the feeding rate to be 3L/min, collecting crude cyclopentadiene at the tower top, then carrying out secondary depolymerization, rectification and separation in a reactive rectification tower 2, controlling the temperature of the tower kettle to be 220-.
The yield and the purity of the cyclopentadiene obtained in the embodiments 1-5 of the invention are both higher than those of the comparative examples 1-3, which shows that the process conditions provided by the invention effectively inhibit the self-polymerization reaction of the cyclopentadiene, the side reaction in the high-temperature cracking process and no bumping, so that the obtained cyclopentadiene has higher purity and yield and has higher industrial application value.
Claims (8)
1. An industrial production process for preparing high-purity cyclopentadiene by depolymerizing dicyclopentadiene is characterized in that dicyclopentadiene is used as a raw material, and the process comprises the following steps of adding diluent 1 and polymerization inhibitor 1 into dicyclopentadiene, uniformly mixing, carrying out depolymerization, rectification and separation in a reactive rectification tower 1, controlling the temperature of a tower kettle to be 170-17 KPaG, the temperature of a tower top to be 40-48 ℃, the pressure of the tower top to be 10-17KPaG, the reflux ratio to be 5-8, the feeding rate to be 1-5L/min, collecting crude cyclopentadiene at the tower top, adding the crude cyclopentadiene, the diluent 2 and the polymerization inhibitor 2 into an evaporation kettle, heating and vaporizing, leading steam to pass through a cracking pipe heated to be about 300-330 ℃, carrying out tubular cracking, carrying out secondary depolymerization and separation in the reactive rectification tower 2 after cracking, controlling the temperature of the tower kettle to be 230 ℃, the temperature of the tower top to be 41-43 ℃, the pressure of the tower top to be 12-18KPaG, controlling the reflux ratio to be 8-12, and collecting high-purity cyclopentadiene at the tower top.
2. The industrialized production process for preparing high-purity cyclopentadiene by depolymerizing dicyclopentadiene as claimed in claim 1, wherein dicyclopentadiene is used as a raw material, the method comprises the steps of adding diluent 1 and polymerization inhibitor 1 into dicyclopentadiene, uniformly mixing, carrying out depolymerization, rectification and separation in a reactive rectification column 1, controlling the temperature of a column bottom to be 190-.
3. The industrial production process of dicyclopentadiene depolymerizing to prepare high-purity cyclopentadiene as claimed in claim 1, wherein dicyclopentadiene is used as a raw material, and comprises the steps of adding diluent 1 and polymerization inhibitor 1 into dicyclopentadiene, uniformly mixing, performing depolymerization, rectification and separation in a reactive rectification column 1, controlling the temperature of a column bottom to be 220 ℃, the temperature of a column top to be 41-45 ℃, the pressure of the column top to be 14-16KPaG, the reflux ratio to be 8, the feeding rate to be 3L/min, collecting crude cyclopentadiene at the column top, adding the crude cyclopentadiene, diluent 2 and polymerization inhibitor 2 into an evaporation kettle, heating and vaporizing, allowing steam to pass through a cracking tube heated to about 320 ℃, performing tubular cracking, performing secondary depolymerization and separation in the reactive rectification column 2, controlling the temperature of the column bottom to be 230 ℃, the temperature of the column top to be 41-42 ℃, the pressure of the column top to be 16KPaG, and collecting high-purity cyclopentadiene at the column top, wherein the reflux ratio is 12.
4. The industrial process for producing high-purity cyclopentadiene by depolymerizing dicyclopentadiene according to any one of claims 1 to 3, characterized by: the diluent 1 is composed of n-dodecane and n-hexane in a mass ratio of (10-15) to (1-3), and the raw materials are diluted to 20-30% by mass.
5. The industrial process for producing high-purity cyclopentadiene by depolymerizing dicyclopentadiene according to any one of claims 1 to 4, characterized by: the diluent 2 is composed of n-hexadecane and n-hexane in a mass ratio of (5-10) to (1-3), and the raw materials are diluted to 10-15% by mass.
6. The industrial process for producing high-purity cyclopentadiene by depolymerizing dicyclopentadiene according to any one of claims 1 to 5, characterized by: the polymerization inhibitor 1 consists of hydroquinone and aniline in a mass ratio of (5-8) to (0.5-2), and the addition amount of the polymerization inhibitor is 0.01-0.015 percent of the mass of the raw materials before dilution.
7. The industrial process for producing high-purity cyclopentadiene by depolymerizing dicyclopentadiene according to any one of claims 1 to 6, characterized by: the polymerization inhibitor 2 consists of 2, 6-di-tert-butyl-p-methylphenol and chloranil in the mass ratio of (1-5) to (5-1), and the adding amount is 0.005-0.01 percent of the mass of the raw materials before dilution.
8. The industrial process for producing high-purity cyclopentadiene by depolymerizing dicyclopentadiene according to any one of claims 1 to 7, characterized by: the inside of the cracking tube is of a net structure, or the cracking tube consists of a plurality of cracking tubes with uniform thickness and smaller diameter.
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| CN114085138A (en) * | 2021-11-16 | 2022-02-25 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer and intermediate thereof |
| CN114085138B (en) * | 2021-11-16 | 2023-12-29 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer and intermediate thereof |
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