CN115433053A - Co-production method of tetracyclododecene and norbornene - Google Patents
Co-production method of tetracyclododecene and norbornene Download PDFInfo
- Publication number
- CN115433053A CN115433053A CN202211083207.0A CN202211083207A CN115433053A CN 115433053 A CN115433053 A CN 115433053A CN 202211083207 A CN202211083207 A CN 202211083207A CN 115433053 A CN115433053 A CN 115433053A
- Authority
- CN
- China
- Prior art keywords
- ethylene
- tetracyclododecene
- dicyclopentadiene
- norbornene
- tcd
- 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.)
- Granted
Links
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 title claims abstract description 71
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000005977 Ethylene Substances 0.000 claims abstract description 74
- 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 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims description 40
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000012043 crude product Substances 0.000 abstract description 31
- 239000006227 byproduct Substances 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000004088 simulation Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/10—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond in hydrocarbons containing no six-membered aromatic rings
-
- 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
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
-
- 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
- C07C2603/86—Ring systems containing bridged rings containing four rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a co-production method of tetracyclododecene and norbornene, which comprises the following steps of reacting dicyclopentadiene solution with ethylene in a tubular reactor to obtain a co-product of tetracyclododecene and norbornene. The invention simplifies the production flow, omits the process of preparing NB, directly uses dicyclopentadiene to react with ethylene by adopting specific process parameters, simultaneously produces TCD and NB, produces few by-products when the concentration of TCD in the crude product is higher, the concentration of NB in the crude product is 47.68 percent, the concentration of TCD is 43.03 percent, the concentration of the by-products is only 1.02 percent, the crude product is rectified under normal pressure to obtain NB with the purity of more than 99.8 percent, and is continuously rectified under reduced pressure to obtain TCD with the purity of more than 99.5 percent. The co-production method provided by the invention simplifies the production flow, omits the process of preparing NB, greatly reduces the equipment investment, energy consumption and unit consumption of production and has very low cost.
Description
Technical Field
The invention belongs to the technical field of production of tetracyclododecene and norbornene, and relates to a co-production method of tetracyclododecene and norbornene.
Background
The cycloolefin copolymer is a high polymer material with the characteristics of high transparency, low birefringence, low water absorption, high rigidity, high heat resistance, high refractive index, good water vapor tightness and the like, is used for medical optical parts and high-end medicine packaging materials, is an amorphous thermoplastic high polymer material which draws high attention in the industry and academia in recent years, and has wide application prospects in the fields of optics, electronics, medicine packaging and the like.
And Tetracyclododecene (TCD) and Norbornene (NB) are important monomers for preparing the cyclic olefin copolymer. At present, NB is prepared by rectification and purification after dicyclopentadiene (DCPD) reacts with ethylene (E), ethylene is greatly excessive, a small amount of TCD is generated as a byproduct, and rectification and purification of NB and recovery of ethylene require a large amount of equipment and generate a large amount of energy consumption. TCD is prepared by rectification and purification after DCPD and NB react, NB is greatly excessive, and simultaneously a plurality of useless byproducts are generated, and the higher the concentration of TCD in the crude product is, the more byproducts are generated, and the higher the cost of raw materials is; while reducing the concentration of TCD in the crude product can reduce the by-products, recovery of NB can result in significant energy consumption.
In the existing production process, NB needs to be prepared first and then reacts with DCPD to prepare TCD, and the crude product has a lot of byproducts when the concentration of TCD is high. When NB is synthesized, ethylene is greatly excessive and needs to be recovered, and the rectification and purification of NB consumes a large amount of energy, when TCD is synthesized, NB is greatly excessive and needs to be rectified and recovered, and a large amount of byproducts are remained after the rectification and purification of TCD, so that the cost of TCD is very high.
Therefore, how to find a more suitable production process to solve the above problems in producing tetracyclododecene and norbornene has become one of the problems to be solved by many front-line researchers and research and development type enterprises in the industry.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a method for co-producing tetracyclododecene and norbornene, which can simultaneously produce tetracyclododecene and norbornene, greatly simplify the production process, reduce the equipment investment, energy consumption and unit consumption of the production, and have low cost.
The invention provides a method for co-producing tetracyclododecene and norbornene, which comprises the following steps:
1) Reacting the dicyclopentadiene solution with ethylene in a tubular reactor to obtain a co-product of the tetracyclododecene and the norbornene.
Preferably, the mass fraction of the dicyclopentadiene solution is 60-90%;
the solvent of the dicyclopentadiene solution comprises one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane.
Preferably, the ethylene comprises liquid ethylene;
the mass content of the tetracyclododecene in the co-product is 30-65%;
the mass content of norbornene in the co-product is 35-48%.
Preferably, the liquid ethylene is obtained by low-temperature treatment of ethylene;
the temperature of the liquid ethylene is less than or equal to-5 DEG C
Preferably, the purity of the dicyclopentadiene is not less than 90%;
the purity of the ethylene is not less than 99%.
Preferably, the ethylene is in a supercritical state before and during the reaction;
the step 1) specifically comprises the following steps:
and (2) continuously placing the ethylene and the solvent in a tubular reactor, switching the solvent into a dicyclopentadiene solution, introducing the dicyclopentadiene solution into the tubular reactor, and reacting to obtain a co-product of the tetracyclododecene and the norbornene.
Preferably, the solvent comprises one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane;
the ethylene reaching the supercritical state is to make the ethylene reach a stable supercritical state at the reaction temperature.
Preferably, the molar ratio of ethylene to dicyclopentadiene is (1.3-1.6): 1;
the pressure of the reaction is such that ethylene is in a supercritical state;
the reaction pressure is more than or equal to 10MPa.
Preferably, the reaction temperature is 220-260 ℃;
the retention time of the dicyclopentadiene solution and the ethylene in the tubular reactor is 2-4 h.
Preferably, the concentration of tetracyclododecene in the co-product is controlled by varying the molar ratio of ethylene to dicyclopentadiene;
the reaction also comprises a rectification step;
the rectification comprises normal pressure rectification and reduced pressure rectification.
The invention provides a co-production method of tetracyclododecene and norbornene, which comprises the following steps of reacting dicyclopentadiene solution with ethylene in a tubular reactor to obtain a co-product of tetracyclododecene and norbornene. Compared with the prior art, the invention aims at the problems of more steps, more equipment investment, large raw material and energy consumption and high cost in the existing TCD production process. The invention creatively provides a co-production method of Tetracyclododecene (TCD) and Norbornene (NB), which simplifies the production flow, omits the process of preparing NB, adopts specific process parameters to directly react dicyclopentadiene (DCPD) and ethylene (E), simultaneously produces TCD and NB, produces few by-products when the concentration of TCD in a crude product is higher, the concentration of NB in the crude product is 47.68 percent, the concentration of TCD is 43.03 percent, the concentration of the by-products is only 1.02 percent, the crude product is rectified under normal pressure to obtain NB with the purity of more than 99.8 percent, and is continuously rectified under reduced pressure to obtain TCD with the purity of more than 99.5 percent.
The co-production method provided by the invention simplifies the production flow, omits the process of preparing NB, directly uses DCPD and ethylene to react and simultaneously produce TCD and NB, has few by-products when the concentration of TCD in the crude product is higher, greatly reduces the equipment investment, energy consumption and unit consumption of production, and has low cost.
Experimental results show that the co-production method provided by the invention has the advantages that the TCD concentration in the crude product is very high, the rectification is facilitated, the purification cost is reduced, the content of byproducts is very low, and the raw material cost is facilitated to be reduced.
Detailed Description
For a further understanding of the present invention, the following description of the preferred embodiments of the present invention is given in conjunction with the examples, but it is to be understood that these descriptions are only intended to further illustrate the features and advantages of the present invention, and not to limit the claims of the present invention.
All starting materials for the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and analytical purity or conventional purity used in the technical field of tetracyclododecene production is preferably employed in the present invention.
The invention provides a co-production method of Tetracyclododecene (TCD) and Norbornene (NB), which comprises the following steps:
1) And introducing the dicyclopentadiene solution and ethylene into a tubular reactor, and reacting to obtain a co-product of the tetracyclododecene and the norbornene.
In the present invention, the mass fraction of the dicyclopentadiene (DCPD) solution is preferably 60% to 90%, more preferably 65% to 85%, and still more preferably 70% to 80%.
In the present invention, the solvent of the dicyclopentadiene solution preferably includes one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane, more preferably cyclohexane, toluene, xylene, n-pentane or n-hexane.
In the present invention, the ethylene (E) preferably comprises liquid ethylene.
In the present invention, the liquid ethylene is preferably obtained by subjecting ethylene to a low-temperature treatment.
In the present invention, the temperature of the liquid ethylene is preferably-5 ℃ or lower, more preferably-8 ℃ or lower, and still more preferably-10 ℃ or lower.
In the present invention, the purity of the dicyclopentadiene is preferably not less than 90%, more preferably not less than 92%, more preferably not less than 95%.
In the present invention, the purity of the ethylene is preferably not less than 99%, more preferably not less than 99.3%, and still more preferably not less than 99.5%.
In the present invention, the ethylene is in a supercritical state before and during the reaction. That is, in the present invention, before the reaction, ethylene is already in a supercritical state, and after the system is in a stable state, the reaction is carried out. During the reaction, ethylene is continuously introduced to keep the pressure of the system stable, and the ethylene is also in a supercritical state during the reaction.
In the present invention, the step 1) specifically preferably includes:
and (2) continuously placing the ethylene and the solvent in a tubular reactor, switching the solvent into a dicyclopentadiene solution, introducing the dicyclopentadiene solution into the tubular reactor, and reacting to obtain a co-product of the tetracyclododecene and the norbornene. Among them, it is more preferable that the system be stabilized after the ethylene reaches the supercritical state.
In the present invention, the solvent preferably includes one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane, and more preferably cyclohexane, toluene, xylene, n-pentane or n-hexane.
In the present invention, it is particularly preferable that the ethylene is brought into a supercritical state, and the ethylene is brought into a stable supercritical state at the reaction temperature.
In the present invention, the molar ratio of ethylene to dicyclopentadiene is preferably (1.3 to 1.6): 1, more preferably (1.35 to 1.55): 1, more preferably (1.4 to 1.5): 1.
in the present invention, the pressure of the reaction is such that ethylene is in a supercritical state. Specifically, the pressure of the reaction is preferably 10MPa or more, more preferably 11MPa or more, and still more preferably 12MPa or more.
In the present invention, the temperature of the reaction is preferably 220 to 260 ℃, more preferably 225 to 255 ℃, more preferably 230 to 250 ℃, and more preferably 235 to 245 ℃.
In the present invention, the residence time of the feedstock in the tubular reactor is preferably from 2 to 4 hours, more preferably from 2.4 to 3.6 hours, more preferably from 2.8 to 3.2 hours.
In the present invention, it is preferred to control the concentration of tetracyclododecene in the co-product by varying the molar ratio of ethylene to dicyclopentadiene.
In the present invention, the reaction preferably includes a rectification step after the reaction.
In the present invention, the rectification preferably includes atmospheric rectification and vacuum rectification. Specifically, the crude product is rectified under normal pressure to obtain NB, and the rectification under reduced pressure is continued to obtain TCD.
In the present invention, the mass content of tetracyclododecene in the co-product is preferably 30% to 65%, more preferably 35% to 60%, more preferably 40% to 55%, more preferably 45% to 50%.
In the present invention, the mass content of norbornene in the co-product is preferably 35% to 48%, more preferably 37% to 45%, and still more preferably 40% to 43%.
The invention is a complete and refined integral process flow, better ensures the structure and stable synthesis of the co-product, and improves the yield and the purity of the co-product, and the co-production method of the tetracyclododecene and the norbornene can specifically comprise the following steps:
preparing Dicyclopentadiene (DCPD) solution by using a solvent, and introducing ethylene (E) gas into a low-temperature intermediate tank to change into a liquid phase. The solvent and ethylene are pumped into the tubular reactor by a liquid phase metering pump according to a certain flow rate, the solvent and the ethylene stay for a period of time at a certain temperature, and the pressure in the reactor is regulated by a back pressure valve. And after the system is stable, the solvent is switched into a DCPD solution, timing reaction is started, and after the reaction system is stable, the co-product of the tetracyclododecene and the norbornene is obtained.
Sampling and detecting the content of each component in the crude product by using gas chromatography. And (3) rectifying the crude product at normal pressure to obtain NB with the purity of more than 99.8%, and continuing to rectify under reduced pressure to obtain TCD with the purity of more than 99.5%.
Specifically, the solvent is one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane, and cyclohexane is preferred.
Specifically, the purity of the DCPD is not less than 90%;
specifically, the purity of the ethylene is not less than 99%;
specifically, the mass fraction of the DCPD solution is 60-90%, preferably 85-90%, and when the mass fraction exceeds 90%, the reactor is at risk of blockage.
Specifically, the temperature of the low-temperature intermediate tank is less than or equal to-5 ℃, and preferably less than or equal to-5 ℃.
Specifically, the reaction temperature is 220-260 ℃, preferably 230-240 ℃.
Specifically, the molar ratio of ethylene to DCPD is 1.3.
Specifically, the pressure in the reactor is more than or equal to 10MPa, so that the ethylene is in a supercritical state, and preferably 10-12 MPa.
Specifically, the residence time of the reaction raw materials in the reactor is preferably 2 to 4 hours, and more preferably 2.5 to 3.5 hours.
Wherein the length, inner diameter and volume of the tubular reactor are not required. The flow rates of the solvent and ethylene were calculated from the reactor volume, temperature, pressure, residence time, ethylene to DCPD molar ratio, DCPD solution concentration using Aspen software simulation. The rectification conditions of the crude product are not required, such as the number of tower plates, the reflux ratio and the like.
The invention provides a method for co-producing tetracyclododecene and norbornene. The invention simplifies the production flow, omits the process of preparing NB, directly uses dicyclopentadiene (DCPD) to react with ethylene (E) by adopting specific process parameters, simultaneously produces TCD and NB, has few by-products when the concentration of TCD in the crude product is higher, has 47.68 percent of NB concentration in the crude product, 43.03 percent of TCD concentration and only 1.02 percent of by-product concentration, obtains NB with the purity of more than 99.8 percent by normal pressure rectification of the crude product, and continuously carries out reduced pressure rectification to obtain TCD with the purity of more than 99.5 percent.
The co-production method provided by the invention simplifies the production flow, omits the process of preparing NB, directly uses DCPD and ethylene to react and simultaneously produce TCD and NB, has few by-products when the concentration of TCD in the crude product is higher, greatly reduces the equipment investment, energy consumption and unit consumption of production, and has low cost.
Experimental results show that the co-production method provided by the invention has the advantages that the TCD concentration in the crude product is very high, the rectification is facilitated, the purification cost is reduced, the content of byproducts is very low, and the raw material cost is facilitated to be reduced.
To further illustrate the present invention, the method for co-producing tetracyclododecene and norbornene is described in detail in the following with reference to the following examples, but it should be understood that these examples are carried out in the light of the technical scheme of the present invention, and that the detailed embodiments and specific procedures are given, which are only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
Preparing a DCPD cyclohexane solution with the mass fraction of 90%, and introducing ethylene gas into an intermediate tank at the temperature of-5 ℃ to change into a liquid phase. Cyclohexane (3.477 ml/min) and ethylene (2 ml/min) were fed into a tubular reactor (reactor internal volume 2352 ml) by a liquid phase metering pump, and the flow rates of cyclohexane and ethylene were calculated by simulation using Aspen software based on reactor volume, temperature, pressure, residence time, ethylene to DCPD molar ratio, DCPD solution concentration, etc. The reaction temperature is 230 ℃, the molar ratio of ethylene to DCPD is 1.5, the raw materials stay in the reactor for 3h, the pressure in the reactor is adjusted to 10MPa by a back pressure valve, the cyclohexane is switched to 90 percent of DCPD cyclohexane solution after the system is stabilized, the timing reaction is started, and a sample is taken after the reaction system is stabilized to detect the content of each component in the crude product by using a gas chromatography. See table 1.
And (3) rectifying the crude product at normal pressure to obtain NB with the purity of more than 99.8%, and continuing to rectify under reduced pressure to obtain TCD with the purity of more than 99.5%.
The main reaction is as follows:
the side reactions are as follows:
Example 2
Preparing a DCPD cyclohexane solution with the mass fraction of 90%, and introducing ethylene gas into an intermediate tank at the temperature of-5 ℃ to change into a liquid phase. Cyclohexane (2.608 ml/min) and ethylene (1.5 ml/min) were fed into a tubular reactor (reactor internal volume 2352 ml) using a liquid phase metering pump, and the flow rates of cyclohexane and ethylene were calculated by simulation using Aspen software based on reactor volume, temperature, pressure, residence time, ethylene to DCPD molar ratio, DCPD solution concentration, etc. The reaction temperature is 230 ℃, the molar ratio of ethylene to DCPD is 1.5, the raw materials stay in the reactor for 4h, the pressure in the reactor is adjusted to 10MPa by using a back pressure valve, the cyclohexane is switched to 90 percent of DCPD cyclohexane solution after the system is stabilized, the timing reaction is started, and after the reaction system is stabilized, a sample is taken and the gas chromatography is used for detecting the content of each component in the crude product. See table 1.
And (3) rectifying the crude product at normal pressure to obtain NB with the purity of more than 99.8%, and continuing to rectify under reduced pressure to obtain TCD with the purity of more than 99.5%.
Example 3
Preparing a DCPD cyclohexane solution with the mass fraction of 90%, and introducing ethylene gas into a tundish at the temperature of minus 5 ℃ to change into a liquid phase. Cyclohexane (5.210 ml/min) and ethylene (3 ml/min) were fed into a tubular reactor (reactor internal volume 2352 ml) using a liquid phase metering pump, and the flow rates of cyclohexane and ethylene were calculated by simulation using Aspen software based on reactor volume, temperature, pressure, residence time, ethylene to DCPD molar ratio, DCPD solution concentration, etc. The reaction temperature is 230 ℃, the molar ratio of ethylene to DCPD is 1.5, the raw materials stay in the reactor for 2h, the pressure in the reactor is adjusted to 10MPa by using a back pressure valve, the cyclohexane is switched to 90 percent of DCPD cyclohexane solution after the system is stabilized, the timing reaction is started, and after the reaction system is stabilized, a sample is taken and the gas chromatography is used for detecting the content of each component in the crude product. See table 1.
And rectifying the crude product at normal pressure to obtain NB with the purity of more than 99.8%, and continuously rectifying under reduced pressure to obtain TCD with the purity of more than 99.5%.
Comparative example 1
Preparing a mixed raw material solution of cyclohexane with a mass fraction of 6.25%, NB 80% and DCPD by 13.75%, pumping cyclohexane (10.089 ml/min) into a tubular reactor (with a volume of 2352ml in the reactor) by a liquid phase metering pump, keeping the reaction temperature at 230 ℃, keeping the molar ratio of NB to DCPD at 8, keeping the raw material in the reactor for 3h, adjusting the pressure in the reactor to 10MPa by a back pressure valve, switching the cyclohexane into the mixed raw material solution after the system is stabilized, starting a timing reaction, sampling after the reaction system is stabilized, and detecting the content of each component in the crude product by using gas chromatography. And rectifying the crude product at normal pressure to obtain NB with the purity of more than 99.8%, and continuously rectifying under reduced pressure to obtain TCD with the purity of more than 99.5%. See table 1.
The experimental data are shown in table 1, and table 1 is a comparative data table of the gas chromatography detection results of the crude products produced in the examples of the present invention and the comparative examples.
TABLE 1 gas chromatography test results for crude product
| Main component | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| NB | 47.68％ | 42.75％ | 50.85％ | 50.29％ |
| TCD | 43.03％ | 47.69％ | 40.17％ | 34.30％ |
| Cyclohexane | 7.77％ | 7.78％ | 7.76％ | 6.83％ |
| Cyclopentadiene | 0.07％ | 0.05％ | 0.09％ | 0.09％ |
| DCPD | 0.43％ | 0.32％ | 0.48％ | 0.16％ |
| Polymer and method of producing the same | 1.02％ | 1.41％ | 0.65％ | 8.33％ |
The invention simplifies the production flow, omits the process of preparing NB, directly uses DCPD and ethylene to react and simultaneously produce TCD and NB, has few by-products when the concentration of TCD in the crude product is higher, greatly reduces the equipment investment, energy consumption and unit consumption of production, and has low cost. While NB in the comparative example was recovered as a raw material, the TCD concentration was low and the by-product was high.
The present invention is described in detail above with respect to a method for co-producing tetracyclododecene and norbornene, and the principles and embodiments of the present invention are described herein with reference to specific examples, which are intended to be included as an aid in understanding the principles of the present invention and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A method for co-producing tetracyclododecene and norbornene, comprising the steps of:
1) Reacting the dicyclopentadiene solution with ethylene in a tubular reactor to obtain a co-product of the tetracyclododecene and the norbornene.
2. The co-production method according to claim 1, wherein the mass fraction of the dicyclopentadiene solution is 60-90%;
the solvent of the dicyclopentadiene solution comprises one or more of cyclohexane, toluene, xylene, n-pentane and n-hexane.
3. The co-production process of claim 1, wherein the ethylene comprises liquid ethylene;
the mass content of the tetracyclododecene in the co-product is 30-65%;
the mass content of norbornene in the co-product is 35-48%.
4. A co-production process according to claim 3, wherein said liquid ethylene is obtained by cryogenic treatment of ethylene;
the temperature of the liquid ethylene is less than or equal to-5 ℃.
5. The co-production process according to claim 1, wherein the purity of the dicyclopentadiene is not less than 90%;
the purity of the ethylene is not less than 99%.
6. A co-production process according to claim 1, wherein the ethylene is in a supercritical state before and during the reaction;
the step 1) specifically comprises the following steps:
and (2) continuously placing the ethylene and the solvent in a tubular reactor, switching the solvent into a dicyclopentadiene solution, introducing the dicyclopentadiene solution into the tubular reactor, and reacting to obtain a co-product of the tetracyclododecene and the norbornene.
7. The co-production process of claim 6, wherein the solvent comprises one or more of cyclohexane, toluene, xylene, n-pentane, and n-hexane;
the ethylene reaching the supercritical state is to make the ethylene reach a stable supercritical state at the reaction temperature.
8. The co-production process according to claim 1, wherein the molar ratio of ethylene to dicyclopentadiene is (1.3-1.6): 1;
the pressure of the reaction is such that ethylene is in a supercritical state;
the reaction pressure is more than or equal to 10MPa.
9. A co-production process according to claim 1, wherein the reaction temperature is 220-260 ℃;
the retention time of the dicyclopentadiene solution and the ethylene in the tubular reactor is 2-4 h.
10. The co-production process according to claim 1, wherein the concentration of tetracyclododecene in the co-product is controlled by varying the molar ratio of ethylene to dicyclopentadiene;
the reaction also comprises a rectification step;
the rectification comprises normal pressure rectification and reduced pressure rectification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211083207.0A CN115433053B (en) | 2022-09-06 | 2022-09-06 | Co-production method of tetracyclododecene and norbornene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211083207.0A CN115433053B (en) | 2022-09-06 | 2022-09-06 | Co-production method of tetracyclododecene and norbornene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115433053A true CN115433053A (en) | 2022-12-06 |
| CN115433053B CN115433053B (en) | 2024-10-11 |
Family
ID=84246266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211083207.0A Active CN115433053B (en) | 2022-09-06 | 2022-09-06 | Co-production method of tetracyclododecene and norbornene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115433053B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115806460A (en) * | 2022-12-09 | 2023-03-17 | 杭州睿丰融创科技有限公司 | Method for reducing by-products in production process of tetracyclododecene |
| CN116854555A (en) * | 2023-07-10 | 2023-10-10 | 天津大学 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
| CN118491441A (en) * | 2024-07-18 | 2024-08-16 | 拓烯科技(衢州)有限公司 | Combined production device and process of norbornene and tetracyclododecene |
| CN118652157A (en) * | 2024-08-20 | 2024-09-17 | 淄博鲁华泓锦新材料集团股份有限公司 | Process for producing norbornene and tetracyclododecene |
| CN118652157B (en) * | 2024-08-20 | 2024-10-22 | 淄博鲁华泓锦新材料集团股份有限公司 | Process for producing norbornene and tetracyclododecene |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10287592A (en) * | 1997-04-10 | 1998-10-27 | Nippon Zeon Co Ltd | Crude tetracyclododecene mixture and its production, production of purified tetracyclododecene and apparatus for producing the same |
| WO2000034344A1 (en) * | 1998-12-09 | 2000-06-15 | The B.F.Goodrich Company | In mold addition polymerization of norbornene-type monomers using group 10 metal complexes |
| JP2001139500A (en) * | 1999-11-10 | 2001-05-22 | Nippon Petrochem Co Ltd | Simultaneous production of both norbornene and high- purity tetracyclododecene |
| JP2001139502A (en) * | 1999-11-10 | 2001-05-22 | Nippon Petrochem Co Ltd | Method for continuous production of tetracyclododecene |
| JP2003137820A (en) * | 2001-10-26 | 2003-05-14 | Nippon Zeon Co Ltd | Method for simultaneously producing norbornene and tetracyclododecene |
| CN102015819A (en) * | 2008-02-29 | 2011-04-13 | 日本瑞翁株式会社 | Crystalline norbornene ring-opening polymer hydride and molded article of same |
| CN103664470A (en) * | 2012-09-26 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing norbornene |
-
2022
- 2022-09-06 CN CN202211083207.0A patent/CN115433053B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10287592A (en) * | 1997-04-10 | 1998-10-27 | Nippon Zeon Co Ltd | Crude tetracyclododecene mixture and its production, production of purified tetracyclododecene and apparatus for producing the same |
| WO2000034344A1 (en) * | 1998-12-09 | 2000-06-15 | The B.F.Goodrich Company | In mold addition polymerization of norbornene-type monomers using group 10 metal complexes |
| CN1554680A (en) * | 1998-12-09 | 2004-12-15 | ס�ѵ�ľ��ʽ���� | In mold addition polymerization composition of norbornene-type monomers and its crosslinking addition polymer |
| JP2001139500A (en) * | 1999-11-10 | 2001-05-22 | Nippon Petrochem Co Ltd | Simultaneous production of both norbornene and high- purity tetracyclododecene |
| JP2001139502A (en) * | 1999-11-10 | 2001-05-22 | Nippon Petrochem Co Ltd | Method for continuous production of tetracyclododecene |
| JP2003137820A (en) * | 2001-10-26 | 2003-05-14 | Nippon Zeon Co Ltd | Method for simultaneously producing norbornene and tetracyclododecene |
| CN102015819A (en) * | 2008-02-29 | 2011-04-13 | 日本瑞翁株式会社 | Crystalline norbornene ring-opening polymer hydride and molded article of same |
| CN103664470A (en) * | 2012-09-26 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing norbornene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115806460A (en) * | 2022-12-09 | 2023-03-17 | 杭州睿丰融创科技有限公司 | Method for reducing by-products in production process of tetracyclododecene |
| CN115806460B (en) * | 2022-12-09 | 2024-03-08 | 杭州睿丰融创科技有限公司 | Method for reducing byproducts in tetracyclododecene production process |
| CN116854555A (en) * | 2023-07-10 | 2023-10-10 | 天津大学 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
| CN116854555B (en) * | 2023-07-10 | 2024-02-06 | 天津大学 | Method for preparing dimethylbridge octahydronaphthalene or derivative thereof in gradient pressurizing manner |
| CN118491441A (en) * | 2024-07-18 | 2024-08-16 | 拓烯科技(衢州)有限公司 | Combined production device and process of norbornene and tetracyclododecene |
| CN118491441B (en) * | 2024-07-18 | 2024-09-24 | 拓烯科技(衢州)有限公司 | Combined production device and process of norbornene and tetracyclododecene |
| CN118652157A (en) * | 2024-08-20 | 2024-09-17 | 淄博鲁华泓锦新材料集团股份有限公司 | Process for producing norbornene and tetracyclododecene |
| CN118652157B (en) * | 2024-08-20 | 2024-10-22 | 淄博鲁华泓锦新材料集团股份有限公司 | Process for producing norbornene and tetracyclododecene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115433053B (en) | 2024-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115433053A (en) | Co-production method of tetracyclododecene and norbornene | |
| CN115385769A (en) | Method for reducing byproducts in process of synthesizing tetracyclododecene compound | |
| CN109665934B (en) | Method for preparing dicyclopentadiene | |
| CN109180531B (en) | Method for obtaining MDI-50 with prolonged shelf life | |
| CN105254610A (en) | Method for preparing difluoro piperonal by utilizing continuous flow microchannel reactor | |
| CN112876452A (en) | Preparation method and reaction device of lactide | |
| CN106588590A (en) | Refinement method for polyoxymethylene dimethyl ether | |
| CN104263796A (en) | Preparation method of R-1-aminotetralin | |
| CN106588598A (en) | Polyformaldehyde dimethyl ether refinement method | |
| CN208883750U (en) | A kind of serialization prepare glycine around pipe reaction device | |
| CN107955012B (en) | Product preparation and separation system for byproduct with boiling point lower than that of product and raw material, and treatment method and application thereof | |
| CN108947774A (en) | A kind of method and device of separating isopropanol | |
| CN110407725A (en) | A kind of preparation method of 2 mercapto ethanol | |
| CN115806460B (en) | Method for reducing byproducts in tetracyclododecene production process | |
| CN106588596A (en) | Method for purifying polyoxymethylene dimethyl ether | |
| CN115814737A (en) | Device and method for continuously preparing tetrafluoroethane-beta-sultone | |
| CN114146441A (en) | Reflux automatic control device and method for intermittent vacuum rectification of high-purity alpha-thiophene derivative | |
| CN116261559A (en) | Method and device for purifying intermediate in maltol grignard section | |
| CN109988055A (en) | A kind of preparation method of high-purity cyclopentadiene and methyl cyclopentadiene | |
| CN111039802A (en) | Process for preparing aromatic diether diamine | |
| CN101805631B (en) | Variable pressure steam stripping method of C5 fraction extraction solvent | |
| CN112279823A (en) | Method for preparing methyl glycidyl ether from epichlorohydrin by-product | |
| CN111747925A (en) | Nicotine purification method | |
| CN114436751A (en) | Preparation method of methylcyclopentene | |
| CN117164422A (en) | Recovery method of norbornene process byproducts and production method of norbornene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |