CN114773140A - Method for preparing dicyclopentadiene by cracking carbonine - Google Patents
Method for preparing dicyclopentadiene by cracking carbonine Download PDFInfo
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- CN114773140A CN114773140A CN202210600555.4A CN202210600555A CN114773140A CN 114773140 A CN114773140 A CN 114773140A CN 202210600555 A CN202210600555 A CN 202210600555A CN 114773140 A CN114773140 A CN 114773140A
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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 44
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005336 cracking Methods 0.000 title claims abstract description 16
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 10
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000295 fuel oil Substances 0.000 claims description 9
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 6
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 claims description 5
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 claims description 5
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 claims description 5
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000012691 depolymerization reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 125000002619 bicyclic group Chemical group 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- -1 methyl dicyclopentadiene Chemical compound 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Images
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing dicyclopentadiene by cracking carbonine, which relates to the technical field of chemical preparation and comprises the following steps: s1: raw material preparation, S2: depolymerizing, namely feeding the raw material in S1 into a high-temperature depolymerization kettle for reaction, and performing negative pressure operation, wherein a reflux heater is 360 ℃ and-10 kpa, so that the entering dicyclic ring is depolymerized, and gas-phase cyclopentadiene is generated at the top of the tank; s3: separating, namely cooling the gas-phase cyclopentadiene generated at the top of the tank in the S2 to 100 ℃, introducing the gas-phase cyclopentadiene into a separation tower, performing negative pressure operation, extracting re-liquefied heavy components, polymerized dicyclopentadiene and the like from a tower kettle, extracting carbon nine components with lower boiling points from a side line, and extracting cyclopentadiene from a tower top; s4: and (3) performing polymerization reaction, namely cooling and liquefying the cyclopentadiene prepared by the S3, polymerizing by using the process to prepare dicyclopentadiene, and performing depolymerization and polymerization purification to obtain a high-purity product, wherein the produced resin has better quality in strength and ageing resistance.
Description
Technical Field
The invention belongs to the technical field of chemical preparation, and particularly relates to a method for preparing dicyclopentadiene through carbon nine cracking.
Background
The cracking carbon nine has complex components due to the characteristics of the production process. A large amount of components with approximate boiling points exist near the dicyclopentadiene, so that the influence on the purity of the product is large in the process of preparing the high-purity dicyclopentadiene, and the dicyclopentadiene product with the purity meeting the requirement cannot be obtained.
In the existing dicyclopentadiene extraction process from the cracked C.sub.H, the reaction temperature is low (generally 180-200 ℃), the single-pass conversion rate of dicyclopentadiene is low, the product purity is insufficient, in order to improve the yield of the device, a reaction raw material circulation heating mode is usually adopted to improve the reaction time, but the problem that other C.sub.H active components (such as methyl styrene and the like) are polymerized due to overlong residence time in a high-temperature zone is caused, and a large amount of C.sub.H active components are polymerized into heavy components.
Disclosure of Invention
The embodiment of the application provides a preparation method for preparing dicyclopentadiene by cracking carbon nine, overcomes the defects of low conversion rate of a single process and insufficient product purity in the existing preparation process, and avoids a large amount of polymerization of carbon nine active components while ensuring the yield of the dicyclopentadiene.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for preparing dicyclopentadiene by cracking carbonine comprises the following steps:
s1: preparing raw materials, mixing cyclopentadiene, benzene, toluene, ethylbenzene, p-xylene, styrene, o-xylene, propenyl benzene, mesitylene, pseudocumene, methyl ethylbenzene, methyl styrene, ethyl vinyl benzene, dicyclopentadiene, indene, methyl indene, naphthalene and methyl naphthalene according to the component ratio
S2: depolymerizing, namely feeding the raw material in S1 into a high-temperature depolymerization kettle for reaction, and performing negative pressure operation, wherein a reflux heater is at 360 ℃ and-10 kpa, so that the entering double rings are depolymerized, heavy oil which cannot be depolymerized and has a higher boiling point is extracted from the tower kettle, the heavy oil is extracted to a tank area after being cooled to below 60 ℃, and gas-phase cyclopentadiene is generated at the top of the tank;
s3: separating, namely cooling the gas-phase cyclopentadiene generated at the top of the tank in the S2 to 100 ℃, introducing the gas-phase cyclopentadiene into a separation tower, performing negative pressure operation, extracting re-liquefied heavy components, polymerized dicyclopentadiene and the like from a tower kettle, extracting carbon nine components with lower boiling points from a side line, and extracting cyclopentadiene from a tower top;
s4: and (3) performing polymerization reaction, namely cooling and liquefying the cyclopentadiene prepared by the S3, controlling the temperature to be 60-90 ℃, directly feeding the cyclopentadiene into a polymerization kettle, maintaining the temperature of the polymerization kettle by adopting hot water at 80-90 ℃, removing the reaction heat, and polymerizing to prepare the dicyclopentadiene.
As a preferred scheme, the raw materials in the step S1 are calculated by weight percentage as shown in the following table:
| composition (I) | Content/%) |
| Cyclopentadiene | 0.12 |
| Benzene and its derivatives | 1.52 |
| Toluene | 0.58 |
| Ethylbenzene production | 2.72 |
| Para xylene | 1.54 |
| Styrene (meth) acrylic acid ester | 4.08 |
| Ortho-xylene | 4.25 |
| Propenyl benzene | 0.62 |
| Mesitylene | 4.12 |
| Unsym-trimethyl benzene | 3.15 |
| Methyl ethyl benzene | 8.18 |
| Methyl styrene | 9.59 |
| Ethylvinylbenzene | 3.49 |
| Dicyclopentadiene | 29.61 |
| Indene | 10.52 |
| Methyl indene | 2.55 |
| Naphthalene | 12.15 |
| Methylnaphthalene | 1.21 |
。
As a preferable scheme, the weight percentage of each raw material in the step S1 is as follows:
| composition (I) | Content/% |
| Cyclopentadiene | 0.2 |
| Benzene and its derivatives | 1.8 |
| Toluene | 0.3 |
| Ethylbenzene production | 2.3 |
| Para xylene | 1.20 |
| Styrene (meth) acrylic acid ester | 3.05 |
| Ortho-xylene | 4.01 |
| Propenyl benzene | 0.52 |
| Mesitylene | 4.02 |
| Unsym-trimethyl benzene | 3.5 |
| Methyl ethyl benzene | 8.02 |
| Methyl styrene | 8.58 |
| Ethylvinylbenzene | 3.52 |
| Dicyclopentadiene | 30.65 |
| Indene | 11.52 |
| Methyl indene | 2.66 |
| Naphthalene | 13.52 |
| Methylnaphthalene | 1.52 |
。
As a preferable scheme, the weight percentage of each raw material in the step S1 is as follows:
preferably, the sulfur content concentration in the cyclopentadiene is 200ppm, and the chlorine content concentration in the benzene is 0.1 ppm; the concentration of nitrogen content in the toluene was 150 ppm.
Preferably, the feeding conditions in step S2 are as follows: the feeding amount is 2t/h, the feeding is carried out at normal temperature, and the system is pumped.
Preferably, after the liquid level of the depolymerization reactor reaches 50% in the step S2, the temperature is raised cyclically, and the final temperature of the depolymerization reactor is controlled between 350 and 360 ℃.
As a preferable scheme, in the step S3, the gas phase at the top of the separation tower is liquefied and then enters a reflux tank, and a reflux of the separation tower is established;
wherein the reaction process is as follows:
one or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
the process depolymerizes dicyclopentadiene and methyl dicyclopentadiene to generate cyclopentadiene and methyl cyclopentadiene by gas-phase mixed-state thermal depolymerization, and obtains dicyclopentadiene and other products by cooling, refluxing, purifying and separating the depolymerized and vaporized gas-phase products in a separation tower and then performing temperature-controlled polymerization reaction and other processes, thereby avoiding the large amount of polymerization of the carbon nine active components while ensuring the yield of dicyclopentadiene.
2. The existing crude cyclopentadiene with lower purity can only be used as an effective component of carbon five or carbon nine polymer resin to produce resin products with general quality. After the depolymerization and repolymerization purification process, a high-purity product is obtained, and the produced resin has better quality in strength and aging resistance, and is a new technology for breaking the bottleneck in the future.
Drawings
FIG. 1 is a schematic diagram of a reaction scheme;
Detailed Description
In order to better understand the technical solution, the technical solution will be described in detail with reference to the drawings and the specific embodiments.
Dicyclopentadiene (PDCPD) is an environment-friendly and novel engineering plastic and is prepared by organic metal catalytic polymerization of dicyclopentadiene (DCPD). The dicyclopentadiene is derived from the byproducts of ethylene production by petroleum cracking and carbon 5 in coal coking. The PDCPD has high modulus, high impact resistance and high creep resistance, shows excellent comprehensive mechanical property compared with other engineering plastics, has heat resistance superior to PU, PVC, PE, PP and other materials, has dimensional stability superior to PU, has creep resistance superior to nylon products, has good environmental adaptability, and can be applied to the fields of chemical anti-corrosion pipe fittings, sports equipment parts, large-scale electrical equipment shells and the like. In particular, in the automotive industry, PDCPDs can be used in place of metal or glass fiber reinforced plastic for vehicle housings, bumpers, and other parts, thereby reducing vehicle fuel consumption and increasing vehicle load capacity. In addition, the vehicle shell can realize more diversified and personalized appearance design, and the A-level surface roughness can be achieved without any treatment before the shell is sprayed with paint.
The main reaction conditions are as follows: the main reaction conditions are as follows:
| item | Unit | Parameter(s) |
| Temperature of feed | ℃ | 15-25 |
| Amount of feed | kg/h | 3000 |
| Depolymerization kettle temperature | ℃ | 180 |
| Pressure of depolymerization kettle | KPa(A) | 20-25 |
| Pressure of the separation column | KPa(A) | 30-40 |
| Temperature of tower and kettle of separation tower | ℃ | 210-215 |
| Overhead temperature of the separation column | ℃ | 70-75 |
| Side line draw temperature of separation column | ℃ | 150-155 |
| Pressure of polymerization vessel | MPa | 0.7-0.8 |
| Temperature of the polymerization vessel | ℃ | 80-90 |
The preparation method of each example is as follows
As shown in figure 1 of the drawings, in which,
a method for preparing dicyclopentadiene by cracking carbonine comprises the following steps:
s1: preparing raw materials, namely mixing and feeding cyclopentadiene, benzene, toluene, ethylbenzene, p-xylene, styrene, o-xylene, propenyl benzene, mesitylene, pseudocumene, methyl ethylbenzene, methyl styrene, ethyl vinyl benzene, dicyclopentadiene, indene, methyl indene, naphthalene and methyl naphthalene according to the component ratio; wherein:
s2: depolymerizing, namely feeding the raw material in S1 into a high-temperature depolymerization kettle for reaction, and performing negative pressure operation, wherein a reflux heater is 360 ℃ and-10 kpa, so that depolymerization reaction is performed on the entering double rings, heavy oil which cannot be depolymerized and has a high boiling point is extracted from the tower kettle, the heavy oil is extracted into a tank area after being cooled to below 60 ℃, and gas-phase cyclopentadiene is generated at the top of the tank;
s3: separating, namely cooling the gas-phase cyclopentadiene generated at the top of the tank in the S2 to 100 ℃, introducing the gas-phase cyclopentadiene into a separation tower, performing negative pressure operation, extracting re-liquefied heavy components, polymerized dicyclopentadiene and the like from a tower kettle, extracting carbon nine components with lower boiling points from a side stream, and extracting cyclopentadiene from a tower top;
s4: and (3) performing polymerization reaction, namely cooling and liquefying the cyclopentadiene prepared by the step S3, controlling the temperature to be 60-90 ℃, directly feeding the cyclopentadiene into a polymerization kettle, maintaining the temperature of the polymerization kettle by adopting hot water at the temperature of 80-90 ℃, removing the reaction heat, and polymerizing to prepare the dicyclopentadiene.
As a preferable scheme, the feeding conditions in step S2 are: the feeding amount is 2t/h, the feeding is carried out at normal temperature, and the system is pumped.
Preferably, in step S2, after the liquid level of the depolymerization reactor reaches 50%, the temperature is raised cyclically, and the final temperature of the depolymerization reactor is controlled to be 350 to 360 ℃.
Preferably, in step S3, the gas phase at the top of the separation column is liquefied and then enters a reflux tank to establish reflux of the separation column;
wherein the reaction process is as follows:
the specific operation steps of the process comprise the following steps:
the normal temperature raw materials enter a negative pressure depolymerization kettle of 20-25KPa, a small amount of heat transfer oil is introduced into the depolymerization kettle, and the mixture is heated and continuously stirred to maintain the temperature of 170-175 ℃; the heavy oil which is extracted from the bottom of the tank and can not be depolymerized and has a higher boiling point is partially heated by the preheater (200 ℃) and returns to the depolymerization kettle to be used as a thermal cycle material, and the other part is directly extracted to the heavy oil product tank. By the operation, the energy consumption of a heat source of the depolymerization kettle can be greatly reduced, and the blockage phenomenon caused by direct temperature rise of the depolymerization kettle is greatly reduced. Depolymerized gas-phase cyclopentadiene and partial heavy component materials generated at the top of the tank enter a cooler and a gas-liquid separation tank, and the gas-liquid phase materials after cooling and separation all enter a separation tower.
The separation tower is operated under the negative pressure of 30-40KPa, the tower kettle is heated to 210-215 ℃ by heat conducting oil to produce re-liquefied heavy components and partially polymerized dicyclopentadiene, and the part of the material is not recovered, but returns to the inlet of the depolymerization kettle to be used as a circulating material, so that the operation can greatly improve the conversion rate and avoid the loss of effective components. Carbon nine components with lower boiling points are extracted from the side line of the tower at 150 ℃ and directly enter a corresponding product tank. A built-in cooler is arranged at the tower top for cooling to 70-75 ℃, and the gas-phase cyclopentadiene comes out from the tower top and enters a condenser to be changed into a liquid phase; the built-in cooler on the top of the tower can make full use of the heat source in the tower, and the cooled material is used as a self-refluxing material in the tower for mass and heat transfer, so that a reflux tank and a reflux pump in the traditional process are reduced, and the cost is saved.
The gas-phase cyclopentadiene from the top of the tower is controlled to be 60-70 ℃ by a heat exchanger, the hot material enters a polymerization kettle again and is subjected to temperature maintenance and reaction heat removal by adopting hot water at the temperature of 80-90 ℃, and finally polymerized dicyclopentadiene enters a product tank as a product.
Compared with the traditional process, the process has the advantages that most of heavy components are collected in the depolymerization kettle, and the subsequent heavy component removal pressure is reduced; the traditional direct heating method is changed on the heating mode of the depolymerization kettle, negative pressure operation is adopted, materials at the bottom of the tank are heated and then circularly enter the kettle, so that the probability of blockage caused by direct temperature rise of the depolymerization kettle can be greatly reduced, and the production can be operated more efficiently for a long time.
In the separation process, the prior process that the cyclopentadiene is extracted from the top of the tower to the reflux tank and then flows back to the tower is changed, and a cooler is arranged in the top of the tower, so that the equipment consumption can be reduced, more importantly, the retention time of the gas-phase cyclopentadiene is reduced, the reaction with other components is avoided, the purity of the cyclopentadiene is increased, and the conversion rate is greatly improved.
In the final polymerization process, the gas-phase cyclopentadiene with higher purity is kept to enter a polymerization kettle at the temperature of 60-70 ℃ and is polymerized at the temperature of 80-90 ℃, so that dimerization and trimerization reactions generated at high temperature are avoided. In order to improve the conversion rate of the whole dicyclopentadiene, the technology of heavy oil circulation of a depolymerization kettle and material circulation of a tower kettle of a separation tower is designed, effective components possibly lost in the subsequent technology are recovered to the maximum extent, and the whole conversion rate is finally over 90 percent.
Comparison of new and old process experiments
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. A method for preparing dicyclopentadiene by cracking carbonine is characterized in that: the method comprises the following steps:
s1: preparing raw materials, mixing cyclopentadiene, benzene, toluene, ethylbenzene, p-xylene, styrene, o-xylene, propenyl benzene, mesitylene, pseudocumene, methyl ethylbenzene, methyl styrene, ethyl vinyl benzene, dicyclopentadiene, indene, methyl indene, naphthalene and methyl naphthalene according to the component ratio
S2: depolymerizing, namely feeding the raw material in S1 into a high-temperature depolymerization kettle for reaction, and performing negative pressure operation, wherein a reflux heater is at 360 ℃ and-10 kpa, so that the entering double rings are depolymerized, heavy oil which cannot be depolymerized and has a higher boiling point is extracted from the tower kettle, the heavy oil is extracted to a tank area after being cooled to below 60 ℃, and gas-phase cyclopentadiene is generated at the top of the tank;
s3: separating, namely cooling the gas-phase cyclopentadiene generated at the top of the tank in the S2 to 100 ℃, introducing the gas-phase cyclopentadiene into a separation tower, performing negative pressure operation, extracting re-liquefied heavy components, polymerized dicyclopentadiene and the like from a tower kettle, extracting carbon nine components with lower boiling points from a side stream, and extracting cyclopentadiene from a tower top;
s4: and (3) performing polymerization reaction, namely cooling and liquefying the cyclopentadiene prepared by the S3, controlling the temperature to be 60-90 ℃, directly feeding the cyclopentadiene into a polymerization kettle, maintaining the temperature of the polymerization kettle by adopting hot water at 80-90 ℃, removing the reaction heat, and polymerizing to prepare the dicyclopentadiene.
2. The method for preparing dicyclopentadiene by cracking cabochytene according to claim 1, characterized in that: the raw materials in the step S1 are calculated according to the following weight percentage:
3. the method for preparing dicyclopentadiene by cracking nineteen carbon atoms according to claim 2, wherein the method comprises the following steps: the sulfur content concentration of the cyclopentadiene is 200ppm, and the chlorine content concentration of the benzene is 0.1 ppm; the concentration of nitrogen in the toluene was 150 ppm.
4. The method for preparing dicyclopentadiene by cracking cabochytene according to claim 2, characterized in that: the feeding conditions in the step S2 are as follows: the feeding amount is 2t/h, the feeding is carried out at normal temperature, and the system is pumped.
5. The method for preparing dicyclopentadiene by cracking cabochytene according to claim 2, characterized in that: and (S2), circularly heating after the liquid level of the depolymerization reaction kettle reaches 50%, and finally controlling the temperature of the depolymerization reaction kettle between 350 and 360 ℃.
6. The method for preparing dicyclopentadiene by cracking cabochytene according to claim 2, characterized in that: the gas phase at the top of the separation tower in the step S3 is liquefied and then enters a reflux tank to establish reflux of the separation tower;
wherein the reaction process is as follows:
7. the method for preparing dicyclopentadiene by cracking cabochytene according to claim 1, characterized in that: the weight percentage of each raw material in the step S1 is calculated as follows:
8. the method for preparing dicyclopentadiene by cracking nineteen carbon atoms according to claim 1, wherein the method comprises the following steps: the raw materials in the step S1 are calculated according to the following weight percentage:
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597205A (en) * | 2008-06-06 | 2009-12-09 | 上海宝钢化工有限公司 | A kind of method from coking byproduct production dicyclopentadiene |
| CN102010285A (en) * | 2010-11-02 | 2011-04-13 | 宁波职业技术学院 | Method for extracting methyl cyclopentadiene from ethylene cracked C9 heavy fractions |
| CN106699497A (en) * | 2016-11-21 | 2017-05-24 | 烟台大学 | Method for preparing cyclopentadiene through gas-phase depolymerization of dicyclopentadiene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597205A (en) * | 2008-06-06 | 2009-12-09 | 上海宝钢化工有限公司 | A kind of method from coking byproduct production dicyclopentadiene |
| CN102010285A (en) * | 2010-11-02 | 2011-04-13 | 宁波职业技术学院 | Method for extracting methyl cyclopentadiene from ethylene cracked C9 heavy fractions |
| CN106699497A (en) * | 2016-11-21 | 2017-05-24 | 烟台大学 | Method for preparing cyclopentadiene through gas-phase depolymerization of dicyclopentadiene |
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Application publication date: 20220722 |