CN112759501A - Preparation method of polymer-grade dicyclopentadiene - Google Patents
Preparation method of polymer-grade dicyclopentadiene Download PDFInfo
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- 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 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 68
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 76
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000032050 esterification Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 5
- 238000000066 reactive distillation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000006471 dimerization reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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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
- 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
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
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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 belongs to the field of preparation of polymer-grade dicyclopentadiene, and particularly relates to a preparation method of polymer-grade dicyclopentadiene, which comprises the following steps: 1) feeding the crude dicyclopentadiene raw material into a depolymerization reaction rectifying tower, and depolymerizing to generate a mixture of cyclopentadiene and isoprene; 2) feeding the mixture of cyclopentadiene and isoprene generated by depolymerization into a catalyst bed filled with oxalic acid, wherein the catalyst of the catalyst bed is a molecular sieve adsorption type catalyst, and removing isoprene to obtain cyclopentadiene through addition esterification and the adsorption action of the catalyst bed; 3) cyclopentadiene is polymerized in the first polymerization reactor, the second polymerization reactor and the third polymerization reactor successively to obtain dicyclopentadiene. The method takes the crude dicyclopentadiene separated from the ethylene by-product C5 fraction as a raw material, adopts the combined technology of depolymerization and rectification and chemical adsorption to prepare the high-purity dicyclopentadiene, has simple and effective technology, effectively removes isoprene in cyclopentadiene, and obtains the polymer-grade dicyclopentadiene with the content of more than 99 percent.
Description
Technical Field
The invention relates to a preparation method of polymer-grade dicyclopentadiene, in particular to a method for preparing polymer-grade dicyclopentadiene by taking crude dicyclopentadiene separated from an ethylene byproduct C5 fraction as a raw material and adopting a combined process of depolymerization and rectification and chemical adsorption.
Background
Dicyclopentadiene (DCPD) is an important fine chemical raw material, mainly comes from a C5 fraction which is a byproduct in ethylene preparation by petroleum cracking, and is obtained by polymerizing and separating Cyclopentadiene (CPD) in a C5 fraction. Because of side reaction in the polymerization process, the purity of the obtained crude dicyclopentadiene product is about 80 percent, the crude dicyclopentadiene product is usually used for producing resin or replacing part of phthalic anhydride to produce unsaturated polyester, and the added value is not high; the ultra-high purity (more than 99 percent) dicyclic ring can be used for producing reaction injection molding engineering plastics polydicyclopentadiene (PDCPD), and the product can replace certain metal and engineering plastics, be widely used in the aspects of civil engineering, construction, vehicles, ships and machinery, and greatly improve the value.
At present, crude dicyclopentadiene is mainly used as a raw material in industry, high-purity (purity > 95%) dicyclopentadiene is obtained through a depolymerization-dimerization method, and ultrahigh-purity dicyclopentadiene (purity > 99%) can be obtained under optimized conditions. For example, CN102060649A discloses a method for preparing polymer-grade dicyclopentadiene, which uses a high-temperature carrier, wherein dicyclopentadiene is depolymerized, but polymers are aggregated therein, and thus coking is easy, and the device cannot be operated for a long time in industrial application. U.S. Pat. No. 4, 5321177A discloses a process for producing polymer grade dicyclopentadiene by depolymerizing dicyclopentadiene in a tubular reactor in such a way that the dicyclopentadiene is cracked more completely, but impurities (other dimers) are cracked at the same time, and a small amount of Isoprene (IP) contained in the product affects the purity of the cyclopentadiene product, and the cyclopentadiene is difficult to separate from cyclopentadiene, so that the polymer grade dicyclopentadiene is difficult to obtain. In order to solve the problems, CN105585415A develops the development and research of the reactive distillation technology in the separation of cracking C5 fraction, two reactive distillation towers are adopted to combine the reaction and the distillation, and the purity and the yield of the dicyclopentadiene are improved by adjusting the operating parameters of the reactive distillation towers to control the reaction direction and the reaction depth. However, because both IP and CPD are easy to generate polymerization reaction, and the difference between the dimerization rate of CPD and the copolymerization rate of IP and CPD is not large, the reaction depth is difficult to control, and in order to ensure the purity of dicyclopentadiene, more unpolymerized IP and CPD are discharged from the top of the tower to circulate, thereby affecting the yield and greatly increasing the energy consumption.
Therefore, the existing technology for removing the impurity (isoprene) in the cyclopentadiene still has obvious defects, and the high purity and the high yield of the dicyclopentadiene cannot be simultaneously met.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of polymer-grade dicyclopentadiene, which takes crude dicyclopentadiene separated from an ethylene byproduct C5 fraction as a raw material, adopts a depolymerization rectification and chemical reaction adsorption combined process to prepare the polymer-grade dicyclopentadiene, utilizes the chemical reaction adsorption process to remove main impurity isoprene after the depolymerization of the crude dicyclopentadiene, and then obtains the polymer-grade dicyclopentadiene through a proper dimerization process.
The technical scheme of the invention is as follows: a preparation method of polymer-grade dicyclopentadiene comprises the following steps:
1) feeding the crude dicyclopentadiene raw material into a depolymerization reaction rectifying tower, and depolymerizing in the depolymerization reaction rectifying tower to generate a mixture of cyclopentadiene and isoprene;
depolymerization reaction conditions in the depolymerization reaction rectifying tower are as follows: the method comprises the following steps of (1) carrying out normal pressure treatment, wherein the temperature of the top of the tower is 35-45 ℃, the temperature of a tower kettle is 150-200 ℃, and the reflux ratio is 1-5;
2) feeding the mixture of cyclopentadiene and isoprene generated by depolymerization in the step 1) into a catalyst bed filled with oxalic acid, wherein the catalyst forming the catalyst bed is a molecular sieve adsorption type catalyst, and removing isoprene through addition esterification reaction and adsorption of the catalyst bed to obtain cyclopentadiene;
reaction conditions in the catalyst bed: the mass space velocity is 1-10 hr-1The reaction temperature is 20-80 ℃, and the reaction pressure is 0.1-1.0 MPa;
3) polymerizing cyclopentadiene obtained in the step 2) sequentially through a first-stage polymerization reactor, a second-stage polymerization reactor and a third-stage polymerization reactor to obtain dicyclopentadiene;
reaction conditions in the first-stage polymerization reactor: the retention time is 3-8 hr, the reaction temperature is 30-60 ℃, and the reaction pressure is 0.3-1.0 MPa;
reaction conditions in the two-stage polymerization reactor: the retention time is 3-6 hr, the reaction temperature is 60-90 ℃, and the reaction pressure is 0.3-1.0 MPa;
reaction conditions in the three-stage polymerization reactor: the residence time is 1-5 hr, the reaction temperature is 90-120 ℃, and the reaction pressure is 0.3-1.0 MPa.
In the step 1), the top temperature of the depolymerization reaction rectifying tower is preferably 39-42 ℃, and more preferably 40-42 ℃; the temperature of the tower kettle is preferably 175-185 ℃, and more preferably 180-183 ℃; the reflux ratio is preferably 2 to 3, more preferably 2.5 to 2.8. Preferably, the depolymerization reaction conditions in the depolymerization reaction rectification tower are as follows: the temperature of the tower top is 40-42 ℃, the temperature of the tower kettle is 180-183 ℃, and the reflux ratio is 2.5-2.8 under normal pressure.
In the step 1), the crude dicyclopentadiene raw material is depolymerized in a depolymerization reaction rectifying tower to generate a mixture of cyclopentadiene and isoprene and also generate heavy components, the mixture of cyclopentadiene and isoprene is discharged from the top of the depolymerization reaction rectifying tower, and the heavy components are discharged from the bottom of the tower.
In step 2), the catalyst forming the catalyst bed is preferably 13X molecular sieve.
In the step 2), the mass space velocity in the catalyst bed layer is preferably 3-6 hr-1More preferably 4 to 5hr-1(ii) a The reaction temperature is preferably 40-50 ℃, and more preferably 43-45 ℃; the reaction pressure is preferably 0.4 to 0.7MPa, more preferably 0.5 to 0.6 MPa. As a preferable scheme, the reaction conditions in the catalyst bed are as follows: the mass space velocity is 4-5 hr-1The reaction temperature is 43-45 ℃, and the reaction pressure is 0.5-0.6 MPa.
In the step 3), the residence time in the first-stage polymerization reactor is preferably 4-6 hr, more preferably 4.5-5 hr; the reaction temperature is preferably 40-50 ℃, and more preferably 45-48 ℃; the reaction pressure is preferably 0.5 to 0.8MPa, more preferably 0.6 to 0.75 MPa. As a preferred scheme, the reaction conditions in the first-stage polymerization reactor are as follows: the retention time is 4.5-5 hr, the reaction temperature is 45-48 ℃, and the reaction pressure is 0.6-0.75 MPa.
In the step 3), the residence time in the two-stage polymerization reactor is preferably 4-5 hr, more preferably 4.5-5 hr; the reaction temperature is preferably 70-80 ℃, and more preferably 73-78 ℃; the reaction pressure is preferably 0.5 to 0.8MPa, more preferably 0.6 to 0.75 MPa. As a preferred scheme, the reaction conditions in the two-stage polymerization reactor are as follows: the retention time is 4.5-5 hr, the reaction temperature is 73-78 ℃, and the reaction pressure is 0.6-0.75 MPa.
In the step 3), the residence time in the three-stage polymerization reactor is preferably 2-4 hr, more preferably 2.5-3 hr; the reaction temperature is preferably 100-110 ℃, and more preferably 105-110 ℃; the reaction pressure is preferably 0.5 to 0.8MPa, more preferably 0.6 to 0.75 MPa. As a preferred scheme, the reaction conditions in the two-stage polymerization reactor are as follows: the residence time is 2.5-3 hr, the reaction temperature is 105-110 ℃, and the reaction pressure is 0.6-0.75 MPa.
In the step 3), the first-stage polymerization reactor, the second-stage polymerization reactor and the third-stage polymerization reactor are all tubular polymerization reactors.
The invention relates to a method for preparing polymer-grade dicyclopentadiene by using crude dicyclopentadiene separated from an ethylene byproduct C5 fraction as a raw material. In the preparation process of polymerization-grade dicyclopentadiene, because dimers of IP and CPD contained in the raw materials also carry out depolymerization reaction in the reactive distillation tower, a small amount of Isoprene (IP) is contained in a tower top product of the depolymerization reactive distillation tower, and the purity of the cyclopentadiene product is influenced. The invention adopts a depolymerization and rectification and chemical reaction adsorption combined process to obtain the high-purity cyclopentadiene without isoprene through addition esterification reaction and adsorption of a catalyst bed layer. In addition, in the separation process, in the depolymerization and rectification tower, the tower kettle carries out depolymerization reaction, the depolymerization product directly rises to the rectification section in a gaseous state for rectification and refining, and the rectification section does not need an additional stripping section to realize the gasification of the material, so that the process flow of the depolymerization product in the system is extremely short, and the generation of polymers is avoided.
The catalyst bed layer in the fixed bed reactor adopts a molecular sieve adsorbent, and the surface property of the catalyst bed layer is adjusted by loading a metal substance, so that the aim of adsorption and separation is fulfilled. The inventor finds that the 13X molecular sieve has better adsorption selectivity, the adsorption selectivity is further improved through modification, and due to the difference of molecular structures and larger difference of acid-base property of molecular surfaces, under the combined action of physical adsorption and chemical adsorption, the 13X molecular sieve can adsorb and fix isoprene on the surface of a catalyst during the catalytic addition reaction of diolefin and acetic acid, so that only isoprene molecules are adsorbed on the surface of the catalyst in a chemical adsorption form under proper conditions, and isoprene in cyclopentadiene can be effectively removed.
Drawings
FIG. 1 is a schematic process flow diagram of a polymer-grade dicyclopentadiene preparation method of the present invention.
Detailed Description
The process for preparing high purity DCPD according to the present invention is described in further detail below with reference to the accompanying drawings and specific examples. It should be noted that technical features or combinations of technical features described in the following embodiments should not be considered as being isolated, and they may be combined with each other to achieve better technical effects.
[ examples 1 to 10 ]
The technological process of the embodiment 1-10 is shown in figure 1, a raw material W1 firstly enters a reaction rectifying tower for depolymerization, rectification and separation, the theoretical plate number of the reaction rectifying tower is 25, a mixed material W2 of CPD and IP is obtained at the tower top, and heavy component impurities are periodically discharged at the tower bottom. And depolymerizing the raw material W1 to generate a mixed material W2 of CPD and IP, feeding the mixed material into a fixed bed reactor from the top of a reaction rectifying tower, removing the IP by a chemical method to obtain a high-purity CPD finished product W3, and performing dimerization reaction by a three-section polymerization reactor to finally obtain a DCPD finished product W4.
The raw material W1 is a DCPD-rich material, the main composition of which is shown in table 1, the process conditions of the depolymerization and rectification tower, the fixed bed reactor, the first-stage polymerization reactor, the second-stage polymerization reactor and the third-stage polymerization reactor in each example are shown in tables 2, 3, 4, 5 and 6 respectively, the composition of the product is analyzed by gas chromatography after the reaction is finished, and the yield and the purity of the DCPD product are shown in table 7. The product yield of DCPD is defined as:
TABLE 1 Main Components of the raw materials (W1)
| Components | Content (wt.%) |
| CPD | 0.3 |
| DCPD | 84.0 |
| NB (interpolymer of IP and CPD) | 9.5 |
| Others | 6.2 |
TABLE 2 depolymerization distillation separation reaction conditions in depolymerization distillation column of each example
| Temperature at the top of column (. degree.C.) | Column bottom temperature (. degree. C.) | Reflux ratio | |
| Example 1 | 35 | 150 | 1 |
| Example 2 | 39 | 175 | 2 |
| Example 3 | 39.5 | 177 | 2.2 |
| Example 4 | 40.8 | 180 | 2.1 |
| Example 5 | 40.5 | 179 | 2.5 |
| Example 6 | 41.0 | 181 | 2.5 |
| Example 7 | 41.2 | 182 | 2.8 |
| Example 8 | 41.6 | 183 | 3 |
| Example 9 | 42 | 185 | 4 |
| Example 10 | 45 | 200 | 5 |
TABLE 3 reaction conditions in the fixed bed reactor of each example
| Reaction temperature (. degree.C.) | Reaction pressure (MPa) | Mass space velocity (hr)-1) | |
| Example 1 | 60 | 1.0 | 10 |
| Example 2 | 50 | 0.8 | 8.0 |
| Example 3 | 48 | 0.7 | 6.0 |
| Example 4 | 44 | 0.6 | 5.0 |
| Example 5 | 45 | 0.65 | 5.5 |
| Example 6 | 46 | 0.55 | 4.5 |
| Example 7 | 42 | 0.45 | 3.5 |
| Example 8 | 43 | 0.5 | 4.0 |
| Example 9 | 40 | 0.4 | 3.0 |
| Example 10 | 20 | 0.1 | 1.0 |
TABLE 4 reaction conditions in the one-stage polymerization reactor of each example
| Reaction temperature (. degree.C.) | Reaction pressure (MPa) | Residence time (hr) | |
| Example 1 | 30 | 0.3 | 8.0 |
| Example 2 | 40 | 0.4 | 7.0 |
| Example 3 | 42 | 0.5 | 6.0 |
| Example 4 | 43 | 0.55 | 5.5 |
| Example 5 | 45 | 0.6 | 5.0 |
| Example 6 | 44 | 0.7 | 5.0 |
| Example 7 | 46 | 0.65 | 4.5 |
| Example 8 | 48 | 0.75 | 4.5 |
| Example 9 | 50 | 0.8 | 4.0 |
| Example 10 | 60 | 1.0 | 3.0 |
TABLE 5 reaction conditions in the two-stage polymerization reactor of each example
| Reaction temperature (. degree.C.) | Reaction pressure (MPa) | Residence time (hr) | |
| Example 1 | 60 | 0.3 | 3.0 |
| Example 2 | 70 | 0.4 | 4.0 |
| Example 3 | 72 | 0.5 | 4.2 |
| Example 4 | 75 | 0.55 | 4.5 |
| Example 5 | 78 | 0.6 | 4.4 |
| Example 6 | 76 | 0.7 | 4.6 |
| Example 7 | 73 | 0.65 | 4.8 |
| Example 8 | 77 | 0.75 | 4.9 |
| Example 9 | 80 | 0.8 | 5.0 |
| Example 10 | 90 | 1.0 | 6.0 |
TABLE 6 reaction conditions in three-stage polymerization reactors for the examples
| Reaction temperature (. degree.C.) | Reaction pressure (MPa) | Residence time (hr) | |
| Example 1 | 90 | 0.3 | 5.0 |
| Example 2 | 100 | 0.4 | 4.0 |
| Example 3 | 102 | 0.5 | 3.5 |
| Example 4 | 105 | 0.55 | 3.2 |
| Example 5 | 104 | 0.6 | 3.0 |
| Example 6 | 108 | 0.7 | 2.4 |
| Example 7 | 106 | 0.65 | 2.8 |
| Example 8 | 110 | 0.75 | 2.2 |
| Example 9 | 115 | 0.8 | 2.0 |
| Example 10 | 120 | 1.0 | 1.0 |
TABLE 7 DCPD product yield and product purity obtained in each example
| DCPD Single pass yield (%) | DCPD purity (%) | |
| Example 1 | 78.4 | 99.1 |
| Example 2 | 79.5 | 99.1 |
| Example 3 | 82.3 | 99.2 |
| Example 4 | 80.0 | 99.4 |
| Example 5 | 86.1 | 99.3 |
| Example 6 | 86.2 | 99.2 |
| Example 7 | 85.7 | 99.3 |
| Example 8 | 85.3 | 99.5 |
| Example 9 | 83.6 | 98.5 |
| Example 10 | 81.7 | 98.3 |
Claims (7)
1. A preparation method of polymer-grade dicyclopentadiene is characterized by comprising the following steps:
1) feeding the crude dicyclopentadiene raw material into a depolymerization reaction rectifying tower, and depolymerizing in the depolymerization reaction rectifying tower to generate a mixture of cyclopentadiene and isoprene;
depolymerization reaction conditions in the depolymerization reaction rectifying tower are as follows: the method comprises the following steps of (1) carrying out normal pressure treatment, wherein the temperature of the top of the tower is 35-45 ℃, the temperature of a tower kettle is 150-200 ℃, and the reflux ratio is 1-5;
2) feeding the mixture of cyclopentadiene and isoprene generated by depolymerization in the step 1) into a catalyst bed filled with oxalic acid, wherein the catalyst forming the catalyst bed is a molecular sieve adsorption type catalyst, and removing isoprene through addition esterification reaction and adsorption of the catalyst bed to obtain cyclopentadiene;
reaction conditions in the catalyst bed: the mass space velocity is 1-10 hr-1The reaction temperature is 20-80 ℃, and the reaction pressure is 0.1-1.0 MPa;
3) polymerizing cyclopentadiene obtained in the step 2) sequentially through a first-stage polymerization reactor, a second-stage polymerization reactor and a third-stage polymerization reactor to obtain dicyclopentadiene;
reaction conditions in the first-stage polymerization reactor: the retention time is 3-8 hr, the reaction temperature is 30-60 ℃, and the reaction pressure is 0.3-1.0 MPa;
reaction conditions in the two-stage polymerization reactor: the retention time is 3-6 hr, the reaction temperature is 60-90 ℃, and the reaction pressure is 0.3-1.0 MPa;
reaction conditions in the three-stage polymerization reactor: the residence time is 1-5 hr, the reaction temperature is 90-120 ℃, and the reaction pressure is 0.3-1.0 MPa.
2. The preparation method according to claim 1, wherein in the step 1), the temperature of the top of the depolymerization rectifying tower is 39-42 ℃, the temperature of the bottom of the tower is 175-185 ℃, and the reflux ratio is 2-3.
3. The method according to claim 1, wherein in the step 2), the catalyst forming the catalyst bed is 13X molecular sieve.
4. The method of claim 1, wherein in step 2), the mass space velocity in the catalyst bed is 3-6 hr-1The reaction temperature is 40-50 ℃, and the reaction pressure is 0.4-0.7 MPa.
5. The method according to claim 1, wherein in the step 3), the residence time in the first stage polymerization reactor is 4 to 6hr, the reaction temperature is 40 to 50 ℃, and the reaction pressure is 0.5 to 0.8 MPa.
6. The method according to claim 1, wherein in the step 3), the residence time in the two-stage polymerization reactor is 4 to 5hr, the reaction temperature is 70 to 80 ℃, and the reaction pressure is 0.5 to 0.8 MPa.
7. The method according to claim 1, wherein the residence time in the three-stage polymerization reactor in step 3) is 2 to 4hr, the reaction temperature is 100 to 110 ℃, and the reaction pressure is 0.5 to 0.8 MPa.
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