CN106699497B - Method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene - Google Patents
Method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene Download PDFInfo
- Publication number
- CN106699497B CN106699497B CN201611023023.XA CN201611023023A CN106699497B CN 106699497 B CN106699497 B CN 106699497B CN 201611023023 A CN201611023023 A CN 201611023023A CN 106699497 B CN106699497 B CN 106699497B
- Authority
- CN
- China
- Prior art keywords
- dcpd
- depolymerizer
- stage
- gas
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene. The method has the advantages that the depolymerizers are designed in a segmented series connection mode, and the temperature is controlled in a segmented mode, so that on one hand, the depolymerization time is shortened, and the possibility of coking is reduced, the service life of the depolymerizers is prolonged to the maximum extent, and meanwhile, the energy consumption for depolymerization is reduced by adopting the method; on the other hand, the method further improves the depolymerization rate of DCPD and the yield of CPD, respectively reaches the highest depolymerization rate of DCPD of 99.9% and the highest yield of CPD of 99.5%, especially the yield of CPD is improved by 5% under the condition of prolonging the service life compared with the prior art, and the service life of the depolymerizer is prolonged to more than 1200 h.
Description
Technical Field
A method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene belongs to the field of chemical industry.
Background
Dicyclopentadiene and cyclopentadiene are abbreviated as DCPD and CPD, respectively, in the present invention. CPD is an important byproduct in the ethylene industry, is widely applied to the fields of rubber, pesticides, resin and the like, and has high application value. CPD is susceptible to dimerization at room temperature to produce DCPD, so when CPD is used, DCPD needs to be depolymerized first, and the depolymerization reaction is:
this reaction is endothermic and therefore the heat required for depolymerization is provided to the right.
The method for depolymerizing DCPD comprises a liquid-phase depolymerization method and a gas-phase depolymerization method. The liquid phase depolymerization is carried out in a common rectifying tower kettle, and has the defects that a large amount of polymer is generated by heating DCPD in the kettle for a long time, the yield of CPD is low, and the method is not feasible economically. The conversion rate of DCPD by the gas-phase depolymerization method is higher, but due to overhigh temperature, the material is easy to generate coking phenomenon, so that the reactor is blocked, and great difficulty is brought to the operation.
Zhengxinsheng mentions a process for depolymerizing DCPD into CPD by diluting DCPD with water vapor in the research of 'gas-phase depolymerization process of high-purity DCPD refining method', adopts a high temperature of more than 350 ℃, and water and DCPD are emulsified after depolymerization by adopting the process, so that the DCPD is difficult to separate from the water, the DCPD yield is reduced, and a large amount of DCPD is contained in the discharged waste water to bring a large amount of pollution to the environment. Lexing's paper published in petrochemical 2001, 11 (study on the gas phase depolymerization Process of dicyclopentadiene) mentions the use of N2Gas phase depolymerization of DCPD with N as diluent gas2The consumption is large, the entrainment quantity of DCPD is large, the economic waste is caused, and the DCPD is not deoxidized and is not reacted with N2Thorough mixing by a static mixer, the depolymerization rate of DCPD can only reach 98%, and coking can occur up to 500 hours after depolymerization. The depolymerization process of DCPD is improved in the 11 th stage of 2008 of Lixing in petrochemical industry, and the used N2The dosage is reduced, but the N in the tail gas is not recycled2Direct evacuationEconomic waste and air pollution are caused, DCPD deoxidation treatment is still not carried out, and coking phenomenon can occur after depolymerization is carried out for 1000 hours. Neither patent CN1150942A (Van Weiyun 1997, a method for preparing high purity cyclopentadiene) nor patent CN1389444A (Liu Jingu 2003, a method for preparing high purity cyclopentadiene and dicyclopentadiene) mention the use of N2The depolymerization rate and yield of DCPD as a dilution shielding gas were not high. Patent CN1129686 adopts N2As the diluted protective gas, because depolymerization is carried out at 350 ℃ and DCPD is not deoxidized, severe coking occurs when the reactor is operated for more than 1000h, and a reaction tube is blocked, so that depolymerization cannot be carried out.
Disclosure of Invention
In order to solve the defects of the prior art, avoid coking of a depolymerizer and prolong the service time of the depolymerizer, the invention provides a method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene. The method has the advantages that the depolymerizers are designed in a segmented series connection mode, and the temperature is controlled in a segmented mode, so that on one hand, the depolymerization time is shortened, and the possibility of coking is reduced, the service life of the depolymerizers is prolonged to the maximum extent, and meanwhile, the energy consumption for depolymerization is reduced by adopting the method; on the other hand, the method further improves the depolymerization rate of DCPD and the yield of CPD, respectively reaches the highest depolymerization rate of DCPD of 99.9% and the highest yield of CPD of 99.5%, especially the yield of CPD is improved by 5% under the condition of prolonging the service life compared with the prior art, and the service life of the depolymerizer is prolonged to more than 1200 h.
The principle of the invention is as follows:
compared with the prior art, the invention uses N2As diluent gas, the diluent gas is divided into two parts and enters a depolymerization reactor, one part is mixed with DCPD through a static mixer and then enters, and the other part is bypassed by N2Tangentially from the inlet of the depolymerization reactor.
Researches find that the higher the temperature of the DCPD material is, the better the depolymerization effect is, but the higher the depolymerization temperature is, the DCPD material is easy to generate coking phenomenon to block a depolymerizer, and meanwhile, the coking phenomenon of the DCPD material is also related to the depolymerization reaction time, and the longer the depolymerization reaction time is, the easier the coking is; therefore, the depolymerization reactor in the method is formed by connecting a first-stage depolymerizer and a second-stage depolymerizer in series, the temperature is controlled in a segmented manner, and the temperature of the first-stage depolymerizer is controlled by 240-; the temperature of the second-stage depolymerizer is controlled at 280 ℃ and 300 ℃, so that the depolymerization temperature can be flexibly and effectively controlled, the material is partially depolymerized after passing through the first-stage depolymerizer, the concentration of DCPD is reduced, DCPD with relatively low concentration can achieve more sufficient depolymerization effect under the condition of higher temperature of the second-stage depolymerizer, and meanwhile, the residence time of the material in the first-stage depolymerizer and the second-stage depolymerizer is shortened.
N in the tail gas2Can be recycled, not only saves N2The cost is reduced, and N is reduced2Entrainment losses to the product CPD due to direct discharge and consequent environmental pollution.
The specific method steps of the present invention are shown in fig. 1.
A method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene comprises the following steps:
step 1, pretreatment
Filtering liquid material DCPD to remove impurity and deoxygenating, then vaporizing the deoxygenated DCPD, at the same time making N2Heating to 200-300 deg.C and dividing into two paths, one heated N2Mixed with vaporized DCPD in a molar ratio of 1:1, and the other by-pass N2Charging into a first-stage depolymerizer in advance;
N in the step 12The mixed gas with the DCPD is filled from the inlet of the first-stage depolymerizer and then is output from the outlet of the first-stage depolymerizer and enters the second-stage depolymerizer;
wherein the temperature of the first-stage depolymerizer is controlled to be 240-270 ℃, the temperature of the second-stage depolymerizer is controlled to be 280-300 ℃, and the residence time of the mixed gas in the step after passing through the two-stage depolymerizers is 5-7 s;
Cooling the pyrolysis material discharged from the second-stage depolymerizer in the step 2 to 50-54 ℃, then carrying out gas-liquid separation, controlling the gas-liquid separation temperature at 110-120 ℃, and separating and removing impurity liquid;
step 4, cooling to obtain CPD
Cooling the CPD gas discharged in the step (3) to below 40 ℃, introducing the CPD gas into a low-temperature bath, controlling the temperature of the low-temperature bath to below 0 ℃, and generating CPD in a container of the low-temperature bath;
wherein, N in the above step2Pressure maintenance of 1.013X 105Pa。
Preferably, N in the tail gas discharged in the step 42Can be recycled.
Preferably, the cooling liquid of the low-temperature bath in the step 4 is frozen saline or ice water.
The method uses the raw materials with the DCPD content of more than 80 percent, and under the conditions that the depolymerization temperature is 280-300 ℃ and the retention time is 5-7s, the first-stage depolymerizer and the second-stage depolymerizer can continuously operate for 1200h without coking, the depolymerization rate is kept above 99 percent, and the CPD yield reaches 98 percent.
In order to prolong the running time and improve the DCPD conversion rate and the CPD yield on the premise of ensuring no decoking, the invention mainly provides the following innovation points: firstly, adding a deoxygenator before depolymerizing the raw material, wherein the deoxygenator contains a 13X molecular sieve, so that the oxygen content in the raw material is reduced to the minimum, and the generation of subsequent coking is reduced; two and N2Two flows of the raw materials enter a depolymerization reactor, one flow of the raw materials is fully mixed with the gasified raw materials through a static mixer and then enters the depolymerization reactor, the other flow of the raw materials directly enters the depolymerization reactor from an inlet of the depolymerization reactor in a tangential mode, and N is formed at the position of a tube wall2The surrounding atmosphere minimizes the chance of contact between the feedstock and the vessel wall, thereby reducing the occurrence of coking and extending the run time. Thirdly, the depolymerization reactor is formed by connecting a first-stage depolymerization reactor and a second-stage depolymerization reactor in series, the temperature is controlled in a sectional manner, and the temperature of the first-stage depolymerization reactor is controlled by 240-; the temperature of the second-stage depolymerizer is controlled by 280 ℃ and 300 ℃, so the depolymerization temperature can be flexibly and effectively controlled, the material is partially depolymerized after passing through the first-stage depolymerizer, the concentration of DCPD is reduced, and a higher depolymerization rate can be achieved after passing through the second-stage depolymerizer,compared with a single depolymerization reactor, the depolymerization temperature is reduced, the retention time of the depolymerization reaction in the depolymerization reactor is shortened, the generation of coking is reduced to the maximum extent, and the CPD yield is obviously improved. Fourthly, N in tail gas2Can be recycled, not only saves N2The cost is reduced, and N is reduced2Entrainment losses to the product CPD due to direct discharge and consequent environmental pollution.
Drawings
Fig. 1 is a flow diagram of DCPD depolymerization.
Wherein, 1 is a DCPD deoxygenator, 2 is a DCPD vaporizer, and 3 is N2Preheater, 4 by-pass N 25 is a static mixer, 6 is a first-stage depolymerizer, 7 is a second-stage depolymerizer, 8 is a water condenser, 9 is a gas-liquid separator, 10 is a water condenser, 11 is a low-temperature bath, and 12 is a recycling N 213 is N2Pressure tank, 14 is a DCPD feed metering pump.
Detailed Description
A method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene is shown in figure 1, and comprises the following steps:
step 1, pretreatment
Filtering liquid material DCPD by a DCPD deoxygenator to remove impurities and deoxygenating, then vaporizing the deoxygenated DCPD by a DCPD vaporizer, and simultaneously N2The preheater adds N2Heating to 200-300 deg.C and dividing into two paths, one heated N2Enters a static mixer to be mixed with vaporized DCPD according to the molar ratio of 1:1, and bypasses N2Charging into a first-stage depolymerizer in advance;
N in the step 12The mixed gas with the DCPD is filled from the inlet of the first-stage depolymerizer and then is output from the outlet of the first-stage depolymerizer and enters the second-stage depolymerizer;
wherein the temperature of the first-stage depolymerizer is controlled to be 240 ℃ and 270 ℃, the temperature of the second-stage depolymerizer is controlled to be 280 ℃ and 300 ℃, and the retention time of the mixed gas passing through the two-stage depolymerizers is 5-7 s;
Cooling the cracking material discharged from the second-stage depolymerizer in the step 2 to 50-54 ℃ through a water condenser, then introducing into a gas-liquid separator for gas-liquid separation, controlling the gas-liquid separation temperature at 110-120 ℃, and separating and removing impurity liquid;
step 4, cooling to obtain CPD
And (3) cooling the CPD gas discharged in the step (3) to below 40 ℃ through a water condenser, then introducing the CPD gas into a low-temperature bath, controlling the temperature of the low-temperature bath to below 0 ℃, and then producing the CPD in a container of the low-temperature bath.
Wherein, N in the above step2Pressure maintenance of 1.013X 105Pa, and simultaneously discharging N in tail gas in the step 42Cyclically use and access N again2A preheater.
The control points in the method are explained in detail as follows:
the source of the raw material DCPD is China petrochemical Shanghai petrochemical company Limited, and the composition (mass fraction) is as follows: CPD0.34%, C60.10%,<C103.40 percent, polymer 0.44 percent, DCPD 84.45 percent,>C101.45%；N2is of industrial grade, steel bottle.
The DCPD deoxygenator 1 is made of a phi 32X 400 glass tube, a 13X molecular sieve is arranged in the DCPD deoxygenator, and the temperature is controlled to be normal temperature.
The DCPD vaporizer is made of a stainless steel tube with the material of phi 14 multiplied by 2 multiplied by 400, a thermocouple is inserted in the DCPD vaporizer, an electric heating tape is wound outside the DCPD vaporizer, a heat preservation asbestos layer is wound outside the electric heating tape, the outermost layer is bound by iron sheets, and the temperature is controlled to be 125 ℃.
3 is N2The preheater is made of a phi 14 multiplied by 2 multiplied by 400 stainless steel pipe, a thermocouple is inserted in the stainless steel pipe, an electric heating tape is wound outside the stainless steel pipe, a heat preservation asbestos layer is wound outside the electric heating tape, the outermost layer is wrapped by iron sheets, and the temperature is controlled at 300 ℃.
4 is a bypass N2Before feeding, the raw materials are firstly passed through a bypass channel N2，N2The inlet is tangentially fed, and N is formed at the pipe wall2The surrounding atmosphere minimizes the chance of feed contact with the walls, thereby reducing the generation of coke.
5 is a static mixer made of phi 14X 2X 100 stainless steel tube with stainless steel wire net inside.
6 is a section of depolymerizer made of phi 18X 2.5X 1200 stainless steel tube, inserted with phi 3 thermocouple tube, wound with electric heating tape, wound with heat-insulating asbestos layer, and wrapped with iron sheet at the outermost layer. Controlling the temperature to 240 ℃ and 270 ℃.
7 is a stainless steel tube of 18X 2.5X 1200 diameter of two-section depolymerizer, a thermocouple tube of 3 diameter is inserted, an electric heating tape is wound outside, a heat preservation asbestos layer is wound outside the electric heating tape, and the outermost layer is bound by iron sheet. The temperature is controlled at 280 ℃ and 300 ℃. The discharge port of the depolymerization reactor is sealed by using an external mantle fiber, and a welded phi 3 thermocouple well is arranged in the middle of the screw cap; the opening at the side edge is welded with a phi 8 pipe.
8 is a water condenser, and the temperature of the depolymerized material to be cooled is 52 +/-2 ℃.
9 is a gas-liquid separator, a 500 mL ground flask is used at the lower part, a phi 32X 400 glass tube is used at the upper part, a 4X 4 theta ring filler with the height of 320mm is arranged in the glass tube, and the middle opening of the glass tube is used as a feed inlet of the cooled depolymerized material. The temperature of the gas-liquid separator is controlled to be 115 +/-5 ℃; the feed port temperature was controlled at 52. + -. 2 ℃.
10 is a water condenser, and the temperature is controlled below 40 ℃.
12 is N2Recycling pipeline, N can be closed after the pressure in the pipeline is maintained to a certain pressure2And an air source valve.
13 is N2And (4) a pressure tank.
14 is a DCPD feeding metering pump, and the actual feeding time is about 100-200mL/h, namely the retention time is about 5-7 s.
Analysis and calculation method
The analysis of the raw materials and the products adopts a gas chromatography analyzer: SP3400 chromatograph, 10% squalane, 50m long quartz capillary tube and hydrogen flame detector. Conditions are as follows: the initial temperature is 45 ℃, the heating rate is 18 ℃/min, the final temperature is 100 ℃, the vaporization temperature is 230 ℃, and the detection temperature is 230 ℃.
Depolymerization rate of DCPD:
C=（F1-F2）/ F1×100%；
wherein: c-depolymerization rate of DCPD F1The mass (Kg) of DCPD fed in F2The mass (Kg) of the depolymerized DCPD.
Selectivity of CPD: mass of CPD in product/mass of product
Yield of CPD: DCPD depolymerization Rate × CPD Selectivity
Residence time
τ=VP/(n1+n2)×R×(273+T)
Tau is the residence time s and V is the effective volume m of the reactor3；
T is reaction temperature ℃, R is general gas constant
n1= (material feed amount × material density)/material molecular weight;
n2=N2amount of feed
P=1.013×105Pa (1 atmosphere)
The following specific examples were run all in accordance with the depolymerization process and apparatus described above.
Example 1
Carbon ten with 80 percent of DCPD content is used as a raw material, the process flow of the invention is applied, and the temperature of a first-stage depolymerizer is controlled to 240 ℃; the temperature of the two-stage depolymerizer is controlled to be 300 ℃, and the retention time is 7s, N (N)2) In the condition of/n (DCPD) =1:1, a 1200-hour continuous operation experiment was performed, and the analysis result of the product shows that the depolymerization rate of DCPD is 99.7%, the yield of CPD is 99.0%, and no coking material is generated.
Example 2
Carbon ten with 80 percent of DCPD content is used as a raw material, the process is applied, and a first-stage depolymerizer controls the temperature to be 270 ℃; the temperature of the two-stage depolymerizer is controlled to be 300 ℃, and the retention time is 7s, N (N)2) In the condition of/n (DCPD) =1:1, a 1200-hour continuous operation experiment is carried out, and the DCPD depolymerization rate of the product is 99.9 percent, the CPD yield is 99.5 percent, and no coking material is generated.
Example 3
Carbon ten with 80 percent of DCPD content is used as a raw material, the process is applied, and the temperature of a first-stage depolymerizer is controlled to 240 ℃; the temperature of the two-stage depolymerizer is controlled to be 280 ℃, and the retention time is 5s, N (N)2) (DCPD) =1:1, the product analysis results DCPD depolymerization rate 99.1%, CPD yield 98.4% without coke formation.
Example 4
Carbon ten with 80 percent of DCPD content is used as a raw material, the process is applied, and a first-stage depolymerizer controls the temperature to be 270 ℃; the temperature of the two-stage depolymerizer is controlled to be 280 ℃, and the retention time is 5s, N (N)2) In the condition of/n (DCPD) =1:1, a 1200-hour continuous operation experiment is carried out, and the DCPD depolymerization rate of the product is 99.6 percent, the CPD yield is 98.9 percent, and no coking material is generated.
Example 5
Carbon ten with 80 percent of DCPD content is used as a raw material, the process is applied, and a first-stage depolymerizer controls the temperature to be 250 ℃; the temperature of the two-stage depolymerizer is controlled to be 300 ℃, and the retention time is 7s, N (N)2) In the condition of/n (DCPD) =1:1, a 1200-hour continuous operation experiment is carried out, and the DCPD depolymerization rate of the product is 99.4%, the CPD yield is 98.8% and no coking material is generated.
Example 6 carbon ten with 93% DCPD content was used as the starting material, the process of the invention was applied, and the temperature was controlled at 260 ℃ in a first stage depolymerizer; the temperature of the two-stage depolymerizer is controlled to be 290 ℃, and the retention time is 7s, N (N)2)In the condition of/n (DCPD) =1:1, a 1200-hour continuous operation experiment is carried out, and the DCPD depolymerization rate of the product is 99.7 percent, the CPD yield is 99.5 percent, and no coking material is generated.
While the specification has described the preparation of the catalyst in detail and specifically, it is apparent that other obvious variations and modifications will occur to persons skilled in the art upon reading the foregoing description. Therefore, the present invention is not limited to the specific embodiments herein, and all that does not depart from the spirit and scope of the present invention is intended to be included within the present application.
Claims (3)
1. A method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene comprises the following steps:
step (1), pretreatment
Filtering liquid material DCPD to remove impurity and deoxygenating, then vaporizing the deoxygenated DCPD, at the same time making N2Heating to 200-300 deg.C and dividing into two paths, one heated N2Mixed with vaporized DCPD in a molar ratio of 1:1, and the other by-pass N2Charging into a first-stage depolymerizer in advance;
it is characterized in that the preparation method is characterized in that,
step (2), depolymerizing CPD with DCPD
Adding N in the step (1)2The mixed gas with the DCPD is filled from the inlet of the first-stage depolymerizer and then is output from the outlet of the first-stage depolymerizer and enters the second-stage depolymerizer;
wherein the temperature of the first-stage depolymerizer is controlled to be between 240 ℃ and 270 ℃, the temperature of the second-stage depolymerizer is controlled to be between 280 ℃ and 300 ℃, and the residence time of the mixed gas in the step passing through the first-stage depolymerizer and the second-stage depolymerizer is between 5 and 7 seconds;
step (3), cooling to remove impurities
Cooling the pyrolysis material discharged from the second-stage depolymerizer in the step (2) to 50-54 ℃, then carrying out gas-liquid separation, controlling the gas-liquid separation temperature at 110-120 ℃, and separating and removing impurity liquid;
step (4), cooling to obtain CPD
Cooling the CPD gas discharged in the step (3) to below 40 ℃, then introducing the CPD gas into a low-temperature bath, controlling the temperature of the low-temperature bath to below 0 ℃, and then generating CPD in a container of the low-temperature bath;
wherein, N in the above step2Pressure maintenance of 1.013X 105Pa。
2. The method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene according to claim 1, characterized in that N in the tail gas discharged in step (4)2Can be recycled.
3. The method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene according to claim 1 or 2, wherein the low-temperature bath coolant in step (4) is frozen brine or ice water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611023023.XA CN106699497B (en) | 2016-11-21 | 2016-11-21 | Method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611023023.XA CN106699497B (en) | 2016-11-21 | 2016-11-21 | Method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106699497A CN106699497A (en) | 2017-05-24 |
| CN106699497B true CN106699497B (en) | 2020-03-31 |
Family
ID=58941069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611023023.XA Active CN106699497B (en) | 2016-11-21 | 2016-11-21 | Method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106699497B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517907A (en) * | 2020-05-27 | 2020-08-11 | 江西省驰邦药业有限公司 | Cyclopentadiene microchannel cracking reactor and method thereof |
| CN114773140A (en) * | 2022-05-30 | 2022-07-22 | 濮阳市联众兴业化工有限公司 | Method for preparing dicyclopentadiene by cracking carbonine |
| CN115043699A (en) * | 2022-07-15 | 2022-09-13 | 辽宁北化鲁华化工有限公司 | Method for preparing high-purity dicyclopentadiene through industrial cracking carbon nine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1129686A (en) * | 1995-02-22 | 1996-08-28 | 中国石化齐鲁石油化工公司 | Method and equipment for preparing cyclopentadiene by depolymerizing dicyclopentadiene |
| CN204874341U (en) * | 2015-07-21 | 2015-12-16 | 淄博鲁华泓锦新材料股份有限公司 | Dicyclopentadiene refining plant |
-
2016
- 2016-11-21 CN CN201611023023.XA patent/CN106699497B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1129686A (en) * | 1995-02-22 | 1996-08-28 | 中国石化齐鲁石油化工公司 | Method and equipment for preparing cyclopentadiene by depolymerizing dicyclopentadiene |
| CN204874341U (en) * | 2015-07-21 | 2015-12-16 | 淄博鲁华泓锦新材料股份有限公司 | Dicyclopentadiene refining plant |
Non-Patent Citations (1)
| Title |
|---|
| 双环戊二烯气相解决工艺的改进;李兴存等;《石油化工》;20081231;第37卷(第11期);第1152-1154页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106699497A (en) | 2017-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106699497B (en) | Method for preparing cyclopentadiene by gas-phase depolymerization of dicyclopentadiene | |
| MX2014007151A (en) | Methods for deoxygenating biomass-derived pyrolysis oil. | |
| US10081590B2 (en) | Device and process for producing undecylenic acid methyl ester using methyl ricinoleate as raw material | |
| CN106242961B (en) | Production of chloroacetic acid equipment | |
| Kunnakorn et al. | Performance of sodium A zeolite membranes synthesized via microwave and autoclave techniques for water–ethanol separation: Recycle-continuous pervaporation process | |
| CN113527252A (en) | Method for synthesizing vinylene carbonate for electrolyte | |
| CN111620759B (en) | Method for preparing styrene by gas phase dehydration of phenethyl alcohol | |
| CN112142547B (en) | Method for removing residual oxygen in product stream of ethane catalytic oxidative dehydrogenation to ethylene | |
| CN1045949C (en) | Method and apparatus for producing cyclopentadience by depolymerizing dicyclopentadience | |
| CN114100551B (en) | Production device and production process of dimeric thiohexafluoroacetone | |
| CN109336728A (en) | A kind of process for effectively purifying of 1,2,4,5- durene | |
| CN115677461A (en) | Method for continuously producing 4-oxoisophorone by using tower reactor | |
| CN210994350U (en) | Reaction device for preparing methyl ethyl ketone by dehydrogenating sec-butyl alcohol | |
| TW201033173A (en) | Method and apparatus for purifying paraffin | |
| CN214181843U (en) | Chloroform rectifier unit | |
| CN105623706B (en) | Crude oil continuous still dewatering | |
| CN214514487U (en) | Material reinforced mixed trans-1, 2-dichloroethylene production device | |
| CN105237399B (en) | The reactive distillation process of heavy constituent residual liquid in a kind of carbonylation production process of acetic acid | |
| US2913502A (en) | Process for the preparation of 1, 4-dibromobutane | |
| CN114315507B (en) | Process for preparing 1-chloro-3, 3, 3-trifluoropropene and/or Z-1, 3-dichloro-3, 3-difluoropropene | |
| CN217220230U (en) | Butane separation device for refining carbon four raw materials | |
| CN112028017B (en) | Dehydrogenation separation purification process for carbon monoxide raw material gas | |
| CN214319159U (en) | Energy-saving separation process device for high-purity monomethylamine and dimethylamine | |
| CN214514486U (en) | Trans-1, 2-dichloroethylene preparation system | |
| CN210495269U (en) | Toluene liquid-phase air oxidation process decomposition desalting liquid light-weight removal device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210331 Address after: 113004 north side of Shuangmian Road, Dongzhou District, Fushun City, Liaoning Province (Haixin Industrial Park) Patentee after: FUSHUN HUAXING PETROLEUM CHEMICAL Co.,Ltd. Address before: 264005, Yantai University, Yantai, Laishan, Shandong Province, No. 32 Qingquan Road Patentee before: Yantai University |
|
| TR01 | Transfer of patent right |