CN114656319A - Preparation method of high-purity dicyclopentadiene - Google Patents
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Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of high-purity dicyclopentadiene. Taking crude dicyclopentadiene as a raw material, taking polyion liquid as a catalyst and a diluent, and carrying out catalytic depolymerization reaction and rectification to obtain cyclopentadiene; then polymerizing the cyclopentadiene to obtain the dicyclopentadiene. The polyion liquid catalyst/diluent disclosed by the invention adopts an acidic group as an anionic structure of a polyion liquid monomer, so that a catalytic action is provided for catalyzing depolymerization of DCPD, cracking of DCPD is promoted under the catalytic action of polyion liquid, and simultaneously, the isomerization phenomenon of DCPD is reduced at low temperature, the selectivity of DCPD degradation is improved, the coking phenomenon of DCPD is reduced, and the yield of dicyclopentadiene is improved.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of high-purity dicyclopentadiene.
Background
Dicyclopentadiene (DCPD) is an important fine chemical raw material, mainly comes from a C5 fraction which is a byproduct in the preparation of ethylene by petroleum cracking, and is obtained by polymerizing and separating Cyclopentadiene (CPD) in a C5 fraction. The purity of dicyclopentadiene is low due to side reactions during the polymerization. And because the boiling point of the by-product is closer to that of dicyclopentadiene, dicyclopentadiene with higher purity is obtained, impurities such as isopropenyl norbornene and the like in the dicyclopentadiene product are difficult to remove by a common rectification mode. In the prior art, the method for obtaining high-purity dicyclopentadiene is generally that dicyclopentadiene is firstly depolymerized at high temperature and is cracked into monomer cyclopentadiene, and the high-purity dicyclopentadiene can be obtained by polymerizing the separated cyclopentadiene.
Chinese patent CN103664472A discloses a method for preparing high-purity dicyclopentadiene, which takes crude dicyclopentadiene as a raw material, adds a diluent in the depolymerization process, mixes the dicyclopentadiene and the diluent according to the proportion of 0.5-5, and then enters a depolymerization rectifying tower; under normal pressure, the depolymerization temperature is 160-200 ℃, the reflux ratio is 0.5-5, and the depolymerization time is 1-3 h. High-purity Cyclopentadiene (CPD) is obtained at the tower top, the cyclopentadiene passes through a tubular reactor, the reaction temperature is 40-120 ℃, the reaction pressure is 0.1-1.5MPa, the retention time is 4-10h, and the dicyclopentadiene with the purity of more than 99 percent is finally obtained. The diluent is a byproduct C9-C10 component of an ethylene cracking device or a byproduct C9-C10 component of an aromatic hydrocarbon reforming device. The industrial process of the patent is complex, high-pressure reaction is accompanied in the reaction process, the requirement on equipment is high, and the danger hidden danger is accompanied.
Chinese patent CN112679307A discloses a method for preparing high-purity dicyclopentadiene by taking crude dicyclopentadiene as a raw material, which comprises the following steps: firstly, feeding a crude dicyclopentadiene raw material into a fixed bed reactor to perform selective hydrogenation reaction, wherein the catalyst is a Pt and Pb modified Pd catalyst; feeding hydrogenated material into depolymerization rectifying tower to depolymerize to produce cyclopentadiene, and polymerizing cyclopentadiene in the first polymerization reactor, the second polymerization reactor and the third polymerization reactor to obtain dicyclopentadiene. However, in the patent, the preparation cost of the Pt metal catalyst is high, and certain dangerousness exists in the catalytic hydrogenation process, so that the operation is difficult.
Chinese patent CN112679297A discloses a preparation method of high-purity dicyclopentadiene, which comprises the following steps: feeding a crude dicyclopentadiene raw material into a depolymerization reaction rectifying tower, and depolymerizing to generate a mixture of cyclopentadiene and isoprene; secondly, sending the mixture of cyclopentadiene and isoprene into a catalyst bed layer filled with oxalic acid, wherein the catalyst of the catalyst bed layer is a strong acid cation exchange resin type catalyst, and removing isoprene to obtain cyclopentadiene through addition esterification reaction and adsorption of the catalyst bed layer; and polymerizing cyclopentadiene in a first-stage polymerization reactor, a second-stage polymerization reactor and a third-stage polymerization reactor to obtain dicyclopentadiene. In this way, dicyclopentadiene is cracked completely, but impurities (other dimers) are also cracked, and although isoprene is treated by a chemical adsorption process part, the purity of cyclopentadiene products is affected by a small amount of Isoprene (IP) contained in the products, and the cyclopentadiene products are difficult to separate from cyclopentadiene.
The depolymerization temperature of the above patent is high, and the yield of the product is low, which is not favorable for industrial production.
Ionic liquids (ionic liquids) are liquid substances that are composed entirely of ions and are liquids at room temperature or at low temperatures, and are therefore also called room temperature/low temperature molten salts, or liquid organic salts. Theoretically, the ionic liquid can have the species of 1018There are a plurality of.
Polyionic liquids generally have superior ionic conductivity, chemical stability, and nonflammability compared to nonionic polymers. Since the cationic (anionic) groups are "fixed" to the polymer backbone, the ionic mobility is correspondingly reduced as the glass transition temperature is increased as compared to that of ionic liquids, resulting in increased viscosity and decreased conductivity, e.g., ionic liquids typically having a conductivity of 1X 10-2S·cm-1On the other hand, the conductivity of polyionic liquids is often lower than 1X 10-6S cm-1. There are two main methods for increasing the conductivity of polyionic liquids: (1) increasing the concentration of carrier ions; (2) the structure of the electrolyte is changed to increase the ionic mobility. Generally, the ionic conductivity of polycationic ionic liquids is lower than that of polyanionic ionic liquids.
The properties of the polyion liquid enable the polyion liquid to be primarily applied to the fields of (quasi-) solid electrolyte, fuel cell polyelectrolyte membranes, stimulus response materials, carbon materials, electrochemistry, catalysis and the like, and the polyion liquid has wide application prospects. However, no relevant documents and patents have been found to date for the use of ionic liquids in the preparation of dicyclopentadiene.
Disclosure of Invention
The invention aims to provide a preparation method of high-purity dicyclopentadiene, which takes polyion liquid as a catalyst and a diluent for catalytic depolymerization, effectively improves the cracking effect of crude dicyclopentadiene, leads the cracking to be more rapid and stable and has higher selectivity, and improves the yield of dicyclopentadiene products.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the high-purity dicyclopentadiene comprises the following steps: taking crude dicyclopentadiene as a raw material, taking polyion liquid as a catalyst and a diluent, and carrying out catalytic depolymerization reaction and rectification to obtain cyclopentadiene; then polymerizing the cyclopentadiene to obtain the dicyclopentadiene.
Wherein:
the structural formula of the polyion liquid is as follows:
wherein: r1is-BF4 -、-PF6-、-PO4 3-、-SO3H or-SO3 -；R2is-BF4 -、-PF6 -、-PO4 3-、-SO3H、-SO3-or-H; r3is-BF4-、-PF6-、-SO3 -or-SO3H; x is-CH2Or O and n are 1 or 2. Preferably, R1is-SO3 -，R2is-SO3-，R3is-SO3H; or R1is-SO3-，R2is-SO3H，R3is-SO3-。
The mass ratio of the polyion liquid to the crude dicyclopentadiene is 1:10-1: 0.1.
The catalytic depolymerization reaction temperature is 145-148 ℃.
The polymerization temperature is 0-150 ℃, preferably 50-90 ℃.
The content of dicyclopentadiene in the crude dicyclopentadiene is 80-85 wt.%.
The catalytic depolymerization reaction and the polymerization of the present invention are carried out under normal pressure.
The preparation process of the polyion liquid comprises the following steps: under the action of an initiator, performing copolymerization reaction on an imidazole compound, a benzene compound and a bromo-compound to obtain a polyion liquid precursor, and then mixing the polyion liquid precursor with H2SO4And (3) reacting the solution, washing and drying to obtain the polyion liquid.
The molar ratio of the imidazole compound, the benzene compound and the bromo-compound is 19-20:19-20: 1.
The imidazole compound is 1-ethylene-3- (3-sulfopropyl) imidazole, 1-ethylene-3- (4-sulfobutyl) imidazole or 1-vinyl-3-butylimidazole; the benzene compound is sodium styrene sulfonate; the brominated compound is 1, 8-triethylene glycol diyl-3, 3' -divinylimidazole bromide [ EG3(VIM)2]Br2And 1, 8-dioctyl-3, 3' -divinylimidazolium bromide [ O (vim)2]Br2。
The copolymerization reaction temperature is 80-85 ℃, and the copolymerization reaction time is 20-24 h; the initiator is azobisisobutyronitrile.
Taking the polyion liquid SAPILs as an example, the preparation process is as follows:
first, 1, 3-propanesultone was dissolved in tetrahydrofuran and placed in a flask. Then, the 1-vinylimidazole, tetrahydrofuran solution was added to the flask. Stirring at room temperature to react to obtain white solid, washing, and vacuum drying at 60-65 deg.C for 10-12h to obtain 1-ethylene-3- (3-sulfopropyl) imidazole (VSIm);
1-ethylene-3- (3-sulfopropyl) imidazole (VSIm), sodium styrenesulfonate NaSS, 1, 8-triethylene glycol diyl-3, 3' -divinylimidazole bromide [ EG3(VIM)2]Br2Crosslinking agent and H2Mixing O, adding an initiator AIBN, carrying out copolymerization reaction for 20-24h at the temperature of 80-85 ℃, and obtaining a precursor of the SAPILs after copolymerization; cooling and drying the SAPILs precursor, and reacting with H2SO4And (4) reacting the solution, washing and drying the formed SAPILs to obtain the canary yellow polyion liquid SAPILs.
The invention has the following beneficial effects:
the invention takes crude dicyclopentadiene as a raw material and takes polyion liquid as a catalyst and a diluent to carry out catalytic depolymerization reaction. The polyion liquid catalyst/diluent adopts an acidic group as an anion structure of a polyion liquid monomer, so as to provide a catalytic action for catalyzing the depolymerization of DCPD, and the acidic group can generate active H+And H is+Is critical for the cleavage of the C-C bond, which attacks the bridge on the DCPD carbocycleCarbon, resulting in the cleavage of the C-C bond. Under the catalytic action of the polyionic liquid, the cracking of the DCPD is promoted, the isomerization phenomenon of the DCPD is reduced at low temperature, the degradation selectivity of the DCPD is improved, the coking phenomenon of the DCPD is reduced, and the yield of dicyclopentadiene is improved.
Detailed Description
The present invention is further described below with reference to examples.
Examples 1 to 8
The preparation method of the high-purity dicyclopentadiene comprises the following steps:
(1) taking polyion liquid as a catalyst and a diluent, carrying out catalytic depolymerization on 1000g of 80 wt.% crude dicyclopentadiene (DCPD), and rectifying to obtain high-purity Cyclopentadiene (CPD);
(2) dimerizing Cyclopentadiene (CPD) obtained in the step (1) to obtain high-purity dicyclopentadiene.
The structural formula of the polyion liquid is as follows:
the polyion liquid is prepared as follows:
first, 1, 3-propanesultone (12.21g, 0.1mol) was dissolved in 20mL tetrahydrofuran and placed in a 100mL round bottom flask. Then, 1-vinylimidazole (9.41g, 0.1mol), 5mL of tetrahydrofuran solution was slowly added to the flask. Stirring and reacting for 24h at room temperature to obtain a white solid, washing with diethyl ether, and vacuum drying at 65 ℃ for 10h to obtain 1-ethylene-3- (3-sulfopropyl) imidazole (VSIm);
synthesizing SAPILs by adopting a two-step method of free radical copolymerization and acidification: first, 1-ethylene-3- (3-sulfopropyl) imidazole (VSIm) (1.05g, 4.875mmol), sodium styrenesulfonate NaSS (1.00g, 4.875mmol), 1, 8-triethylene glycol diyl-3, 3' -divinylimidazolium bromide [ EG3(VIM)2]Br2(0.12g, 0.25mmol) crosslinker and 5mL H2O was added to a 50mL two-necked round bottom flask equipped with a magnetic stirrer. After stirring at room temperature for 0.5h, the mixture was gradually heated to 80 ℃ and then charged into a flaskIn which the initiator AIBN (0.11g, 5 wt.%) was added, N at 82 ℃ C2Stirring for 22h under the atmosphere, and copolymerizing to obtain SAPILs precursors; cooling the precursor of SAPILs to room temperature, washing with excess methanol and water for several times, vacuum drying at 60 deg.C for 12h, and mixing with 100mL of 1M H2SO4The solution was added to a 250mL beaker equipped with a magnetic stirrer, stirred at room temperature for 24 hours, the resulting SAPILs were washed several times with excess water until the pH of the washing solution was neutral, and vacuum-dried at 65 ℃ for 10 hours to obtain the polyionic liquid.
Example 9
The preparation method of the high-purity dicyclopentadiene comprises the following steps:
(1) taking polyion liquid as a catalyst and a diluent, carrying out catalytic depolymerization on 1500g of crude dicyclopentadiene (DCPD) with the content of 82 wt.%, and rectifying to obtain high-purity Cyclopentadiene (CPD);
(2) dimerizing Cyclopentadiene (CPD) obtained in the step (1) to obtain high-purity dicyclopentadiene.
The structural formula of the polyion liquid is as follows:
the preparation process comprises the following steps:
first, 1, 3-propanesultone (12.21g, 0.1mol) was dissolved in 20mL tetrahydrofuran and placed in a 100mL round bottom flask. Then, 1-vinylimidazole (9.41g, 0.1mol), 5mL of tetrahydrofuran solution was slowly added to the flask. Stirring and reacting for 24h at room temperature to obtain a white solid, washing with diethyl ether, and vacuum drying at 60 ℃ for 12h to obtain 1-ethylene-3- (3-sulfopropyl) imidazole (VSIm);
synthesizing SAPILs by adopting a two-step method of free radical copolymerization and acidification: first, 1-ethylene-3- (3-sulfopropyl) imidazole (VSIm) (1.05g, 4.875mmol), sodium styrenesulfonate NaSS (1.00g, 4.875mmol), 1, 8-triethylene glycol diyl-3, 3' -divinylimidazolium bromide [ EG3(VIM)2]Br2(0.12g, 0.25mmol) crosslinker and 5mL H2O was added to a 50mL two-necked round bottom flask equipped with a magnetic stirrer. In thatAfter stirring at room temperature for 0.5h, the mixture was gradually heated to 80 ℃ and the initiator AIBN (0.11g, 5 wt.%) was added to the flask, N, at 80 ℃2Stirring for 24 hours under the atmosphere, and copolymerizing to obtain a precursor of the SAPILs; cooling the precursor of SAPILs to room temperature, washing with excess methanol and water for several times, vacuum drying at 60 deg.C for 12h, and mixing with 100mL of 1M H2SO4The solution was added to a 250mL beaker equipped with a magnetic stirrer, stirred at room temperature for 24 hours, and the resulting SAPILs were washed several times with excess water until the pH of the washing solution was neutral, and vacuum-dried at 60 ℃ for 12 hours to obtain canary yellow polyionic liquid SAPILs of the above structure with a total yield of about 84%.
The mass ratio of polyion liquid to crude dicyclopentadiene, the temperature of catalytic depolymerization reaction, the temperature of polymerization, the product yield and the purity in examples 1 to 9 of the present invention are shown in table 1.
TABLE 1 operating conditions and product yield and purity data for examples 1-9
Comparative example 1
The catalytic depolymerization process is not added with a polyion liquid catalyst, and the rest conditions are the same as in example 1; the purity of the obtained dicyclopentadiene product is 87.6 percent, and the product yield is 80.2 percent.
Comparative example 2
The catalytic depolymerization process is carried out without adding polyion liquid catalyst, and the rest conditions are the same as in example 6; the purity of the obtained dicyclopentadiene product is 86.5 percent, and the yield of the product is 81.4 percent.
Claims (10)
1. A preparation method of high-purity dicyclopentadiene is characterized by comprising the following steps: taking crude dicyclopentadiene as a raw material, taking polyion liquid as a catalyst and a diluent, and carrying out catalytic depolymerization reaction and rectification to obtain cyclopentadiene; then polymerizing the cyclopentadiene to obtain the dicyclopentadiene.
2. The method for producing high-purity dicyclopentadiene according to claim 1, characterized in that: the structural formula of the polyion liquid is as follows:
wherein: r1is-BF4 -、-PF6 -、-PO4 3-、-SO3H or-SO3 -；R2is-BF4 -、-PF6 -、-PO4 3-、-SO3H、-SO3 -or-H; r3is-BF4 -、-PF6 -、-SO3 -or-SO3H; x is-CH2Or O and n are 1 or 2.
3. The method for producing high-purity dicyclopentadiene according to claim 2, characterized in that: r is1is-SO3 -，R2is-SO3 -，R3is-SO3H; or R1is-SO3 -，R2is-SO3H，R3is-SO3 -。
4. The method for producing high-purity dicyclopentadiene according to claim 3, characterized in that: the preparation process of the polyion liquid comprises the following steps: under the action of an initiator, performing copolymerization reaction on an imidazole compound, a benzene compound and a bromo-compound to obtain a polyion liquid precursor, and then mixing the polyion liquid precursor with H2SO4And (3) reacting the solution, washing and drying to obtain the polyion liquid.
5. The method for producing high-purity dicyclopentadiene according to claim 4, characterized in that: the molar ratio of the imidazole compound, the benzene compound and the bromo-compound is 19-20:19-20: 1.
6. The method for producing high-purity dicyclopentadiene according to claim 5, characterized in that: the imidazole compound is 1-ethylene-3- (3-sulfopropyl) imidazole, 1-ethylene-3- (4-sulfobutyl) imidazole or 1-vinyl-3-butylimidazole; the benzene compound is sodium styrene sulfonate; the brominated compounds are 1, 8-triethylene glycol diyl-3, 3 '-divinylimidazole bromide and 1, 8-dioctyl-3, 3' -divinylimidazole bromide.
7. The method for producing high-purity dicyclopentadiene according to claim 5, characterized in that: the copolymerization reaction temperature is 80-85 ℃, and the copolymerization reaction time is 20-24 h; the initiator is azobisisobutyronitrile.
8. The method for producing high-purity dicyclopentadiene according to claim 1, characterized in that: the mass ratio of the polyion liquid to the crude dicyclopentadiene is 1:10-1: 0.1.
9. The method for producing high-purity dicyclopentadiene according to claim 1, characterized in that: the catalytic depolymerization reaction temperature is 145-148 ℃.
10. The method for producing high-purity dicyclopentadiene according to claim 1, characterized in that: the polymerization temperature is 0-150 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5321177A (en) * | 1991-04-18 | 1994-06-14 | Maruzen Petrochemical Co., Ltd. | Process for the vapor-phase thermal cracking of dicyclopentadiene and a process for the manufacture of high purity dicyclopentadiene |
| CN103664472A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing high-purity dicyclopentadiene |
| CN108017758A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of modified dicyclopentadiene hydrogenated petroleum resin and preparation method thereof |
| CN109665934A (en) * | 2017-10-16 | 2019-04-23 | 中国石油化工股份有限公司 | A method of preparing dicyclopentadiene |
| CN112679297A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Preparation method of high-purity dicyclopentadiene |
| CN112679307A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method for preparing high-purity dicyclopentadiene by taking crude dicyclopentadiene as raw material |
| CN112759501A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of polymer-grade dicyclopentadiene |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5321177A (en) * | 1991-04-18 | 1994-06-14 | Maruzen Petrochemical Co., Ltd. | Process for the vapor-phase thermal cracking of dicyclopentadiene and a process for the manufacture of high purity dicyclopentadiene |
| CN103664472A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing high-purity dicyclopentadiene |
| CN108017758A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of modified dicyclopentadiene hydrogenated petroleum resin and preparation method thereof |
| CN109665934A (en) * | 2017-10-16 | 2019-04-23 | 中国石油化工股份有限公司 | A method of preparing dicyclopentadiene |
| CN112679297A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Preparation method of high-purity dicyclopentadiene |
| CN112679307A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method for preparing high-purity dicyclopentadiene by taking crude dicyclopentadiene as raw material |
| CN112759501A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of polymer-grade dicyclopentadiene |
Non-Patent Citations (3)
| Title |
|---|
| CHEN, BIHUA等: "Poly(ionic liquid)s with superior swelling and enrichment properties in solvents", POLYMER CHEMISTRY, vol. 12, no. 18, pages 2731 - 2742 * |
| 李丹东等: "离子液体中的化学反应", 辽宁石油化工大学学报, vol. 24, no. 2, pages 27 - 34 * |
| 陈晓伟等: "离子液体催化C5馏分中二烯烃的聚合反应", 石油化工, vol. 36, no. 3, pages 232 - 236 * |
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