CN112679302A - Method for preparing high-purity dicyclopentadiene from carbon five fraction - Google Patents
Method for preparing high-purity dicyclopentadiene from carbon five fraction 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 54
- 238000000034 method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- 208000005374 Poisoning Diseases 0.000 claims abstract description 5
- 231100000572 poisoning Toxicity 0.000 claims abstract description 5
- 230000000607 poisoning effect Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 72
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 24
- 238000012691 depolymerization reaction Methods 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 abstract description 13
- 239000006227 byproduct 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
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 22
- 238000000066 reactive distillation Methods 0.000 description 5
- 238000006471 dimerization reaction Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 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
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000004939 coking Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 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
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention belongs to the field of preparation of dicyclopentadiene, and particularly relates to a method for preparing high-purity dicyclopentadiene from carbon five fraction, which comprises the following steps: feeding a crude dicyclopentadiene raw material separated by cracking a carbon five fraction into a fixed bed reactor for selective hydrogenation reaction, wherein a catalyst is a Ni catalyst subjected to poisoning treatment; 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. The method takes crude dicyclopentadiene separated from ethylene byproduct C5 fraction as a raw material, and adopts a selective hydrogenation process to convert norbornene into a relatively stable substance by hydrogenation, so that side reactions of the raw material in a depolymerization rectifying tower can be effectively eliminated, and high-purity dicyclopentadiene with the content of more than 99% can be obtained.
Description
Technical Field
The invention relates to a dicyclopentadiene method, in particular to a method for preparing high-purity dicyclopentadiene from carbon five fraction.
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. As a side reaction exists in the polymerization process, the purity of the obtained crude dicyclopentadiene product is about 80 percent, and the main byproduct is norbornene (copolymer of cyclopentadiene and isoprene). The crude dicyclopentadiene 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, the industry mainly uses crude dicyclopentadiene as raw material to obtain high-purity (purity > 95%) DCPD by depolymerization-dimerization method, and can obtain ultra-high-purity DCPD (purity > 99%) under optimized conditions. For example, CN102060649A discloses a method for preparing high purity dicyclopentadiene, which uses a high temperature carrier, in which dicyclopentadiene is depolymerized, but polymers are aggregated therein, and thus coking is easy, and the apparatus cannot be operated for a long time in industrial applications. U.S. Pat. No. 4, 5321177A discloses a process for producing high purity dicyclopentadiene by depolymerizing dicyclopentadiene in a tubular reactor, which is a more complete way to crack DCPD, but also cracks Norbornene (NB), and a small amount of Isoprene (IP) contained in the product affects the purity of cyclopentadiene product, and the cyclopentadiene product is difficult to separate from cyclopentadiene, so that high purity 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 method for preparing high-purity dicyclopentadiene from an ethylene byproduct C5 fraction, which takes crude dicyclopentadiene separated from an ethylene byproduct C5 fraction as a raw material, adopts a selective hydrogenation process to hydrogenate norbornene into relatively stable substances, can effectively eliminate side reactions of the raw material in a depolymerization reaction rectifying tower, and obtains the high-purity dicyclopentadiene through a proper dimerization process.
The technical scheme of the invention is as follows:
a process for preparing high purity dicyclopentadiene from a carbon five fraction comprising the steps of:
1) feeding a crude dicyclopentadiene raw material into a fixed bed reactor, and carrying out selective hydrogenation reaction on NB (interpolymer of isoprene and cyclopentadiene) in the raw material, wherein the catalyst is a Ni catalyst subjected to poisoning treatment;
the catalyst bed reaction conditions are as follows: hydrogen to hydrocarbon molar ratio of 1: (1-2) the mass space velocity is 6-20 hr-1The reaction temperature is 0-40 ℃, and the reaction pressure is 1.0-3.0 MPa;
2) feeding the hydrogenated material obtained in the step 1) into a depolymerization reaction rectifying tower, and depolymerizing the material in the depolymerization reaction rectifying tower to generate cyclopentadiene;
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;
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 catalyst forming the catalyst bed layer is preferably subjected to poisoning treatment on Ni-Mo/Al2O3、Ni-Mo/Si2Any one of O2.
In step 1), the hydrogen/hydrocarbon molar ratio in the catalyst bed is preferably 1: (1.2-1.5); the preferred mass space velocity is 10-15 hr-1(ii) a The reaction temperature is preferably 15-25 ℃; the reaction pressure is preferably 1.5 to 2.5 MPa.
In the step 2), the top temperature of the depolymerization reaction rectifying tower is preferably 40-43 ℃, and more preferably 41-42 ℃; the temperature of the tower kettle is preferably 175-185 ℃, and more preferably 180-183 ℃; the reflux ratio is preferably 2 to 4, more preferably 2.5 to 3. Preferably, the depolymerization reaction conditions in the depolymerization reaction rectification tower are as follows: the temperature of the tower top is 41-42 ℃, the temperature of the tower kettle is 180-183 ℃, and the reflux ratio is 2.5-3 under normal pressure.
In the step 2), the hydrogenated crude dicyclopentadiene raw material is depolymerized in a depolymerization reaction rectifying tower to generate a small amount of heavy components, the cyclopentadiene is discharged from the top of the depolymerization reaction rectifying tower, and the heavy components are discharged from the bottom of the tower.
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 high-purity dicyclopentadiene by taking crude dicyclopentadiene separated from an ethylene byproduct C5 fraction as a raw material. In the preparation process of high-purity dicyclopentadiene, if raw materials are directly cracked, main impurities Norbornene (NB) can also generate depolymerization reaction in a reactive distillation tower, and a product at the top of the depolymerization reactive distillation tower contains a small amount of IP, so that the purity of a cyclopentadiene product is influenced. The invention adopts a combined process of firstly selecting hydrogenation and then depolymerizing and rectifying to obtain the high-purity DCPD. By selective hydrogenation reaction and maintaining proper hydrogenation process conditions, NB in the raw material can be subjected to selective hydrogenation reaction to generate a dihydro product with relatively stable property, so that only DCPD in a subsequent reaction rectifying tower is subjected to depolymerization reaction, and the top product cannot generate IP to influence the purity of CPD. 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 key point of hydrogenation is the adsorption selectivity of the catalyst, and the DCPD and the NB can be chemically adsorbed on the surface of the catalyst and then carry out addition reaction with hydrogen atoms adsorbed on the surface of the catalyst, but because the reaction activation energy of the two substances is different, and the adsorption capacity of the NB and the DCPD on the surface of the catalyst is different, the NB double bond in the raw material is more active than that of the DCPD double bond, the reaction activity is higher, and the NB double bond hydrogenation product is more stable than that of the CP double bond hydrogenation product in thermodynamics, so that the NB double bond preferentially reacts. The inventor finds that the surface active sites of the catalyst are reduced after poisoning treatment in a certain mode, so that the difference between the adsorption selectivity and the hydrogenation activity of double bonds of NB and DCPD is more obvious, and the selective hydrogenation of NB can be used as a main reaction under certain conditions, thereby meeting the requirement of subsequent separation.
Drawings
FIG. 1 is a schematic process flow diagram of the process for preparing high purity dicyclopentadiene 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 process flow of the embodiment 1-10 is shown in figure 1, a raw material W1 firstly enters a fixed bed reactor to carry out hydrogenation reaction to obtain a hydrogenation product W2, W2 then enters a depolymerization rectifying tower to be separated, the theoretical plate number of the reaction rectifying tower is 15, a high-purity CPD finished product W3 is obtained at the top of the tower, and heavy component impurities are periodically discharged from the bottom of the tower. And carrying out dimerization reaction through a three-section polymerization reactor to finally obtain a DCPD finished product W4.
The raw material W1 is a DCPD-rich material, and its main composition is shown in table 1, in each example, the process conditions of sequentially passing through a fixed bed reactor, a depolymerization rectification column, a first-stage polymerization reactor, a second-stage polymerization reactor and a third-stage polymerization reactor are shown in tables 2, 3, 4, 5 and 6, respectively, after the reaction is finished, the composition analysis of the product is performed by gas chromatography, and the DCPD product yield and product purity 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 reaction conditions in the fixed bed reactor of each example
| Reaction temperature (. degree.C.) | Hydrogen to hydrocarbon ratio (mol ratio) | Reaction pressure (MPa) | Mass space velocity (hr-1) | |
| Example 1 | 40 | 1 | 3.0 | 6 |
| Example 2 | 25 | 1.2 | 2.5 | 10 |
| Example 3 | 23 | 1.3 | 2.2 | 11 |
| Example 4 | 21 | 1.25 | 2.4 | 12 |
| Example 5 | 22 | 1.35 | 2.1 | 12.5 |
| Example 6 | 24 | 1.4 | 2.0 | 14 |
| Example 7 | 17 | 1.45 | 1.8 | 13.5 |
| Example 8 | 19 | 1.5 | 1.6 | 13 |
| Example 9 | 15 | 1.7 | 1.5 | 15 |
| Example 10 | 0 | 2 | 1.0 | 20 |
TABLE 3 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 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 | 77.2 | 99.2 |
| Example 2 | 78.3 | 99.2 |
| Example 3 | 81.1 | 99.4 |
| Example 4 | 78.8 | 99.5 |
| Example 5 | 84.9 | 99.4 |
| Example 6 | 85.0 | 99.3 |
| Example 7 | 84.8 | 99.4 |
| Example 8 | 84.2 | 99.5 |
| Example 9 | 82.5 | 98.5 |
| Example 10 | 80.7 | 98.3 |
Claims (7)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN118619803A (en) * | 2024-08-12 | 2024-09-10 | 淄博鲁华泓锦新材料集团股份有限公司 | Production process of norbornene |
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| CN105585415A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | A method of preparing high-purity dicyclopentadiene through reactive distillation |
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- 2019-10-18 CN CN201910992617.9A patent/CN112679302A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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Application publication date: 20210420 |