CN114656319B - 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; and polymerizing cyclopentadiene to obtain dicyclopentadiene. The polyionic liquid catalyst/diluent adopts an acidic group as an anion structure of a polyionic liquid monomer, provides a catalytic effect for catalyzing DCPD depolymerization, promotes DCPD cracking under the catalytic effect of the polyionic liquid, reduces DCPD isomerization phenomenon at low temperature, improves DCPD degradation selectivity, reduces DCPD coking phenomenon, and improves dicyclopentadiene yield.
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, and is mainly derived from a byproduct C5 fraction of ethylene prepared by petroleum pyrolysis, and the main way is that Cyclopentadiene (CPD) in the C5 fraction is obtained by polymerization and separation. The dicyclopentadiene has lower purity due to side reactions during the polymerization. And because the boiling point of the byproduct is close to that of dicyclopentadiene, impurities such as isopropenyl norbornene in dicyclopentadiene products are difficult to remove in a common rectification mode to obtain dicyclopentadiene with higher purity. In the prior art, the method for obtaining high-purity dicyclopentadiene generally comprises the steps of depolymerizing dicyclopentadiene at high temperature, cracking the dicyclopentadiene into monomer cyclopentadiene, separating the cyclopentadiene, and polymerizing the cyclopentadiene to obtain the high-purity dicyclopentadiene.
Chinese patent CN103664472a discloses a method for preparing high purity dicyclopentadiene, which takes crude dicyclopentadiene as raw material, and adds diluent in the depolymerization process, and dicyclopentadiene and diluent are mixed according to the proportion of 0.5-5 and then enter into depolymerization rectifying tower; under normal pressure, the depolymerization temperature is 160-200 ℃, the reflux ratio is 0.5-5, and the depolymerization time is 1-3h. High-purity Cyclopentadiene (CPD) is obtained at the top of the tower, and then the cyclopentadiene passes through a tubular reactor, the reaction temperature is 40-120 ℃, the reaction pressure is 0.1-1.5MPa, the residence time is 4-10h, and finally the dicyclopentadiene with the purity of more than 99% is obtained. The diluent is byproduct C9-C10 components of an ethylene cracking device or byproduct C9-C10 components of an aromatic hydrocarbon reforming device. The industrial process is complex, high-pressure reaction is carried out in the reaction process, the requirement on equipment is too high, and danger hidden danger is carried out.
Chinese patent CN112679307a discloses a method for preparing high purity dicyclopentadiene from crude dicyclopentadiene, which comprises the steps of: (1) the raw dicyclopentadiene material enters a fixed bed reactor to carry out selective hydrogenation reaction, and the catalyst is a Pd-based catalyst modified by Pt and Pb; (2) feeding the hydrogenated material into a depolymerization reaction rectifying tower, depolymerizing to generate cyclopentadiene, and polymerizing (3) cyclopentadiene through a first-stage polymerization reactor, a second-stage polymerization reactor and a third-stage polymerization reactor to obtain dicyclopentadiene. However, the preparation of the Pt metal catalyst in the patent has high cost, and has certain danger and difficult operation in the catalytic hydrogenation process.
Chinese patent CN112679297a discloses a method for preparing high purity dicyclopentadiene, which comprises the steps of: (1) feeding the raw material of the crude dicyclopentadiene into a depolymerization reaction rectifying tower, and depolymerizing to generate a mixture of cyclopentadiene and isoprene; (2) feeding a mixture of cyclopentadiene and isoprene into a catalyst bed filled with oxalic acid, wherein the catalyst of the catalyst bed is a strong acid cation exchange resin type catalyst, and removing isoprene to obtain cyclopentadiene through an addition esterification reaction and the adsorption of the catalyst bed; (3) the cyclopentadiene is polymerized by a first-stage polymerization reactor, a second-stage polymerization reactor and a third-stage polymerization reactor to obtain dicyclopentadiene. In this way, dicyclopentadiene is completely cracked, but at the same time, impurities (other dimers) are cracked, and although isoprene is treated by using a chemical adsorption process part, the purity of a cyclopentadiene product is still affected by a small amount of Isoprene (IP) contained in the product, and the product is difficult to separate from cyclopentadiene.
The depolymerization temperature of the patent is higher, and the yield of the product is lower, which is unfavorable for industrial production.
Ionic liquids (ionic liquids) are liquid substances consisting entirely of ions, which are liquid at room temperature or at low temperatures and are therefore also known as room temperature/low temperature molten salts, or liquid organic salts. In theory, the ionic liquid can be 10 in variety 18 Many.
Polyionic liquids generally have excellent ionic conductivity, chemical stability, nonflammability, etc., characteristics as compared to nonionic polymers. Since the cationic (anionic) groups are "immobilized" on the polymer backbone, the glass transition temperature is correspondingly reduced and the ionic mobility is correspondingly reduced compared to ionic liquids, resulting in an increase in viscosity and a decrease in conductivity, e.g., typically 1X 10 for ionic liquids -2 S·cm -1 About, and the conductivity of the polyionic liquidOften less than 1X 10 -6 S.cm-1. The methods for increasing the conductivity of the polyionic liquid mainly comprise two methods: (1) increasing the concentration of carrier ions; (2) changing the structure of the electrolyte to increase the ion mobility. Generally, polycationic ionic liquids are less ion conductive than polyanionic ionic liquids.
The characteristics of the polyionic liquid lead the polyionic liquid to be preliminarily applied in the fields of (quasi) solid electrolyte, fuel cell polyelectrolyte membrane, stimulus response material, carbon material, electrochemistry, catalysis and the like, and have wide application prospect. However, no related documents or patents have been found to use ionic liquids for 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 to carry out catalytic depolymerization, so that the cracking effect of crude dicyclopentadiene is effectively improved, the cracking is quicker and more stable, the selectivity is higher, and the yield of dicyclopentadiene products is improved.
The technical scheme adopted 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; and polymerizing cyclopentadiene to obtain dicyclopentadiene.
Wherein:
the structural formula of the polyionic liquid is as follows:
wherein: r is R 1 is-BF 4 - 、-PF 6 -、-PO 4 3 -、-SO 3 H or-SO 3 - ；R 2 is-BF 4 - 、-PF 6 - 、-PO 4 3- 、-SO 3 H、-SO 3 -or-H; r is R 3 is-BF 4 -、-PF 6 -、-SO 3 - or-SO 3 H is formed; x is-CH 2 Or O, n is 1 or 2. Preferably, R 1 is-SO 3 - ，R 2 is-SO 3 -，R 3 is-SO 3 H is formed; or R is 1 is-SO 3 -，R 2 is-SO 3 H，R 3 is-SO 3 -。
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 to 150 ℃, preferably 50 to 90 ℃.
The content of dicyclopentadiene in the crude dicyclopentadiene is 80-85wt.%.
The catalytic depolymerization reaction and polymerization of the invention are all carried out under normal pressure.
The preparation process of the polyionic liquid comprises the following steps: under the action of an initiator, imidazole compounds, benzene compounds and brominated compounds are subjected to copolymerization reaction to obtain a polyion liquid precursor, and the polyion liquid precursor is then mixed with H 2 SO 4 And (3) reacting the solution, washing and drying to obtain the polyionic liquid.
The molar ratio of the imidazole compound to the benzene compound to the brominated 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-butyl imidazole; the benzene compound is sodium styrene sulfonate; the bromo-compound is 1, 8-triethylene glycol diyl-3, 3' -divinyl imidazole bromide [ EG ] 3 (VIM) 2 ]Br 2 And 1, 8-dioctyl-3, 3' -divinylimidazole bromide [ O (Vim) 2 ]Br 2 。
The copolymerization reaction temperature is 80-85 ℃, and the copolymerization reaction time is 20-24h; the initiator is azodiisobutyronitrile.
Taking a polyion liquid SAPILs as an example, the preparation process is as follows:
first, 1, 3-propane sultone was dissolved in tetrahydrofuran and put into a flask. Then, 1-vinylimidazole, tetrahydrofuran solution was added to the flask. Stirring at room temperature to react to obtain white solid, washing, and vacuum drying at 60-65deg.C for 10-12h to obtain 1-ethylene-3- (3-sulfopropyl) imidazole (VSim);
1-ethylene-3- (3-sulfopropyl) imidazole (VSim), sodium styrene sulfonate NaSS, 1, 8-triethylene glycol diyl-3, 3' -divinylimidazole bromide [ EG ] 3 (VIM) 2 ]Br 2 Crosslinking agent and H 2 Mixing O, adding initiator AIBN, and copolymerizing at 80-85 deg.c for 20-24 hr to obtain precursor SAPILs; cooling and drying the precursor of the SAPILs, and H 2 SO 4 And (3) carrying out solution reaction, washing and drying the formed SAPILs to obtain the canary yellow polyion liquid SAPILs.
The beneficial effects of the invention are as follows:
the invention takes crude dicyclopentadiene as raw material, polyion liquid as catalyst and diluent to carry out catalytic depolymerization reaction. The polyionic liquid catalyst/diluent adopts an acidic group as an anion structure of the polyionic liquid monomer, so that a catalytic effect is provided for catalyzing DCPD depolymerization by the polyionic liquid catalyst/diluent, and the acidic group can generate active H + And H is + Critical for the cleavage of the C-C bond, it can attack the bridging carbon on the DCPD carbocyclic ring, resulting in cleavage of the C-C bond. Under the catalysis of polyionic liquid, the cracking of DCPD is promoted, 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.
Detailed Description
The 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 crude dicyclopentadiene (DCPD) with the content of 80wt.% and rectifying to obtain high-purity Cyclopentadiene (CPD);
(2) Dimerization of Cyclopentadiene (CPD) obtained in the step (1) is carried out to obtain dicyclopentadiene with high purity.
The structural formula of the polyionic liquid is as follows:
the preparation of the polyionic liquid is as follows:
first, 1, 3-propane sultone (12.21 g,0.1 mol) was dissolved in 20mL tetrahydrofuran and placed in a 100mL round bottom flask. Then, 1-vinylimidazole (9.41 g,0.1 mol), 5mL of tetrahydrofuran solution was slowly added to the flask. Stirring at room temperature for reaction for 24 hours to obtain white solid, washing with diethyl ether, and vacuum drying at 65 ℃ for 10 hours to obtain 1-ethylene-3- (3-sulfopropyl) imidazole (VSim);
the SAPILs are synthesized by adopting a free radical copolymerization and acidification two-step method: first, 1-ethylene-3- (3-sulfopropyl) imidazole (VSim) (1.05 g,4.875 mmol), sodium styrene sulfonate NaSS (1.00 g,4.875 mmol), 1, 8-triethylene glycol diyl-3, 3' -divinyl imidazole bromide [ EG ] 3 (VIM) 2 ]Br 2 (0.12 g,0.25 mmol) crosslinker and 5mL H 2 O was added to a 50mL double neck 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 initiator AIBN (0.11 g,5 wt.%) was added to the flask at 82℃N 2 Stirring for 22 hours in the atmosphere, and copolymerizing to obtain a precursor of the SAPILs; the sapins precursor was cooled to room temperature, washed with excess methanol and water multiple times, dried under vacuum at 60 ℃ for 12H, then the sapins precursor and 100ml 1m H 2 SO 4 The solution was added to a 250mL beaker equipped with a magnetic stirrer, stirred at room temperature for 24 hours, the sapis formed was washed with excess water several times until the pH of the wash was neutral, and dried under vacuum at 65 ℃ for 10 hours to give 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 82wt.% and rectifying to obtain high-purity Cyclopentadiene (CPD);
(2) Dimerization of Cyclopentadiene (CPD) obtained in the step (1) is carried out to obtain dicyclopentadiene with high purity.
The structural formula of the polyionic liquid is as follows:
the preparation process is as follows:
first, 1, 3-propane sultone (12.21 g,0.1 mol) was dissolved in 20mL tetrahydrofuran and placed in a 100mL round bottom flask. Then, 1-vinylimidazole (9.41 g,0.1 mol), 5mL of tetrahydrofuran solution was slowly added to the flask. Stirring at room temperature for reaction for 24 hours to obtain white solid, washing with diethyl ether, and vacuum drying at 60 ℃ for 12 hours to obtain 1-ethylene-3- (3-sulfopropyl) imidazole (VSim);
the SAPILs are synthesized by adopting a free radical copolymerization and acidification two-step method: first, 1-ethylene-3- (3-sulfopropyl) imidazole (VSim) (1.05 g,4.875 mmol), sodium styrene sulfonate NaSS (1.00 g,4.875 mmol), 1, 8-triethylene glycol diyl-3, 3' -divinyl imidazole bromide [ EG ] 3 (VIM) 2 ]Br 2 (0.12 g,0.25 mmol) crosslinker and 5mL H 2 O was added to a 50mL double neck 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 initiator AIBN (0.11 g,5 wt.%) was added to the flask at 80℃N 2 Stirring for 24 hours under the atmosphere, and copolymerizing to obtain the precursor of the SAPILs; the sapins precursor was cooled to room temperature, washed with excess methanol and water multiple times, dried under vacuum at 60 ℃ for 12H, then the sapins precursor and 100ml 1m H 2 SO 4 The solution was added to a 250mL beaker equipped with a magnetic stirrer, stirred at room temperature for 24 hours, the resulting sapis washed with excess water several times until the pH of the wash was neutral, and dried under vacuum at 60 ℃ for 12 hours to give canary yellow polyionic liquid sapis of the above structure in a total yield of about 84%.
The mass ratio of the polyionic liquid to the crude dicyclopentadiene, the catalytic depolymerization reaction temperature, the polymerization temperature, 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 polyion liquid catalyst is not added in the catalytic depolymerization process, and the rest conditions are the same as in example 1; the purity of the dicyclopentadiene product is 87.6 percent, and the yield of the dicyclopentadiene product is 80.2 percent.
Comparative example 2
The polyion liquid catalyst is not added in the catalytic depolymerization process, and the rest conditions are the same as in example 6; the purity of the dicyclopentadiene product is 86.5%, and the yield of the dicyclopentadiene product is 81.4%.
Claims (7)
1. A preparation method of high-purity dicyclopentadiene is characterized by comprising the following steps of: 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; polymerizing cyclopentadiene to obtain dicyclopentadiene;
the structural formula of the polyionic liquid is as follows:
wherein: r is R 1 is-SO 3 - ，R 2 is-SO 3 - ，R 3 is-SO 3 H is formed; or R is 1 is-SO 3 - ，R 2 is-SO 3 H，R 3 is-SO 3 - The method comprises the steps of carrying out a first treatment on the surface of the X is-CH 2 N is 1.
2. The method for producing high-purity dicyclopentadiene according to claim 1, wherein the method is characterized in that: the preparation process of the polyionic liquid comprises the following steps: under the action of an initiator, imidazole compounds, benzene compounds and brominated compounds are subjected to copolymerization reaction to obtain a polyion liquid precursor, and the polyion liquid precursor is then mixed with H 2 SO 4 Reacting, washing and drying the solution to obtain polyionic liquid;
the imidazole compound is 1-ethylene-3- (3-sulfopropyl) imidazole, 1-ethylene-3- (4-sulfobutyl) imidazole or 1-vinyl-3-butyl imidazole; the benzene compound is sodium styrene sulfonate; the bromo-compound is 1, 8-triethylene glycol diyl-3, 3 '-divinyl imidazole bromide and 1, 8-dioctyl-3, 3' -divinyl imidazole bromide.
3. The method for producing high-purity dicyclopentadiene according to claim 2, wherein: the molar ratio of the imidazole compound to the benzene compound to the brominated compound is 19-20:19-20:1.
4. A process for producing high-purity dicyclopentadiene according to claim 3, wherein: the copolymerization reaction temperature is 80-85 ℃, and the copolymerization reaction time is 20-24h; the initiator is azodiisobutyronitrile.
5. The method for producing high-purity dicyclopentadiene according to claim 1, wherein: the mass ratio of the polyion liquid to the crude dicyclopentadiene is 1:10-1:0.1.
6. The method for producing high-purity dicyclopentadiene according to claim 1, wherein: the catalytic depolymerization reaction temperature is 145-148 ℃.
7. The method for producing high-purity dicyclopentadiene according to claim 1, wherein: the polymerization temperature is 0-150 ℃.
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| 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 |
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| 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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| CN114656319A (en) | 2022-06-24 |
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