CN108484348B - Adiabatic tubular reaction method for synthesizing ethylidene norbornene - Google Patents
Adiabatic tubular reaction method for synthesizing ethylidene norbornene Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
- C07C5/2506—Catalytic processes
- C07C5/2556—Catalytic processes with metals
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- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Abstract
The invention discloses a heat insulation pipe type reaction method for synthesizing ethylidene norbornene, which comprises the following steps: synthesizing by adopting a multi-side-line feeding heat-insulating tube type reactor; the reactor is divided into at least 2 reaction sections, the front end of each reaction section is provided with a feed inlet, the feed inlet at the front end of the first reaction section is a main line feed inlet, and the rest are lateral line feed inlets, and the method comprises the following steps: 1) feeding vinyl norbornene as a raw material into the first reaction section from a main line feeding port; 2) only throwing the solid alkali catalyst into a reaction channel of the reaction section from a main feeding hole, or throwing the solid alkali catalyst into the reaction channel of the corresponding reaction section from the main feeding hole and a lateral line feeding hole; 3) and separating the mixture flowing out of the tail end discharge hole to obtain the ethylidene norbornene. The method has the advantages of high reaction rate, high selectivity and adjustable Z/E ratio of the product, and can directly obtain high-quality pure ENB.
Description
Technical Field
The invention relates to a heat-insulating tube type reaction process for synthesizing ethylidene norbornene, namely a method for directly preparing high-purity ethylidene norbornene by catalyzing isomerization of vinyl norbornene by using solid base in a multi-side-line feeding heat-insulating tube type reactor.
Background
Ethylidene Norbornene (ENB) has two cis-and trans-isomers. The cis-boiling point is 147.35 ℃, the trans-boiling point is 148.57 ℃, the freezing point is-80 ℃, the relative density is 0.90(15/4 ℃), the refractive index is 1.4856(30 ℃), the flash point is 38 ℃, and the liquid is colorless and transparent liquid at normal temperature, has strong camphor-like smell and has larger volatility in air. At present, ENB is mainly applied to the synthesis of Ethylene Propylene Diene Monomer (EPDM), and the polymerization reaction activity is high; the secondary reaction opportunities of branching rubber molecules and generating gel are less; the product has high vulcanization speed, is the first-choice third monomer of EPDM, and needs different isomerization ratios (cis-ENB/trans-ENB, Z/E for short) according to different requirements of EPDM. In recent years, the application of ENB is further expanded to the fields of downstream elastomer materials and similar various norbornene compounds with wide market prospects. Thus, ENB is a petrochemical product with extremely wide use.
The main source of ENB is the catalytic isomerization of Vinylnorbornene (VNB), in which a basic catalyst is mainly used. The solid base is used for catalyzing the isomerization reaction of VNB, which belongs to the heterogeneous catalysis reaction process, the process is carried out on the surface of a solid catalyst, reactants in a fluid phase need to be transferred to the surface of the solid catalyst, the generated reaction product needs to be transferred in the opposite direction, a certain heat effect is necessarily generated while the chemical reaction is carried out, and then heat transfer exists between the solid catalyst and the fluid. The chemical reaction heat of the VNB isomerized ENB is 1.6kcal/mol, the adiabatic tube heat exchanger is selected to effectively utilize the reaction heat to improve the reaction temperature, so that the outside can obtain higher reaction rate by providing little energy, the catalyst is inactivated even if the temperature is too high, and the isomerization ratios of products are different at different reaction temperatures to meet different subsequent polymerization requirements.
Chinese patent CN104098422 discloses a tubular fixed bed reactor device for producing ethylidene norbornene by isomerizing vinyl norbornene. The device comprises a reactor cylinder and a tube nest filled with a solid base catalyst, a plurality of heat exchange sections are arranged at the same time, reaction heat is removed by using a cooling medium, the VNB isomerization reaction is carried out under the conditions that the temperature is 0-50 ℃, the pressure is 0.2-0.3 MPa and the residence time is 8-12 h to obtain the ENB, the highest conversion rate reaches 99.8%, but the selectivity is not mentioned. The process has long reaction time and low efficiency, and the solid alkali catalyst is easy to inactivate when meeting water and oxygen, so the reactor has a complex structure and is not suitable for replacing the catalyst.
Chinese patent CN104058912 discloses a method for utilizing a catalyst in an ethylidene norbornene heterogeneous synthesis process, which comprises the steps of firstly adopting 2 or more serially connected stirred reactors to form a multi-stage stirred reactor group, gradually passing a fresh VNB raw material through the reactors filled with the catalyst, arranging a graded cyclone between the reactors to carry out solid-liquid separation, and continuously discharging liquid from the last-stage stirred reactor to obtain a product ENB. The reaction time of each stage of stirring reaction kettle is 6-8 h, the unloading time is 1-3 h, the reaction temperature is 15-65 ℃, and the concentration of the catalyst is 1-5%. However, the device adopts the traditional kettle type stirring, the heat removal capability is low, the temperature is not easy to control, the time of the whole reaction process is long, and the efficiency is low.
US4727204 reports the preparation and use of a solid base. In general N2Was added to a 100ml flask and heated at a constant temperature, and 0.4 wt% of a solid base catalyst (theoretical base amount: 4.13 mmol.g)-1) The reaction was stirred together and VNB was converted to ENB in 99.62% yield at 20 ℃ for 5 hours.
The reaction process of Zhang Changye et al (Jilin science and technology, 1997, 5 (3): 17-24) and Dingyuan et al (Jilin institute of chemical engineering, 2001, 18 (3): 12-14) in the literature is as follows: a certain amount of VNB sample was placed in a 100ml four-necked flask in high purity N2Adding a certain amount of Na-KOH/gamma-Al under the atmosphere2O3And (3) stirring the catalyst for 3-6 h at 10-25 ℃ to obtain an Ethylidene Norbornene (ENB) product, wherein the isomerization conversion rate of vinyl norbornene of the solid super-strong base reaches 99.6%, and the selectivity of ethylidene norbornene reaches 99.8%.
Disclosure of Invention
The invention aims to solve the technical problem of providing a heat-insulating tube type reaction method for synthesizing ethylidene norbornene, which has the advantages of high reaction rate, high selectivity and adjustable Z/E ratio of a product, and can directly obtain high-quality pure ENB.
In order to solve the technical problems, the invention provides a heat-insulating tubular reaction method for synthesizing ethylidene norbornene, which adopts a multi-side-line feeding heat-insulating tubular reactor for synthesis; the reactor is divided into at least 2 reaction sections, the front end of each reaction section is provided with a feed inlet, the feed inlet at the front end of the first reaction section is a main line feed inlet, and the rest are lateral line feed inlets, and the method comprises the following steps:
1) feeding vinyl norbornene with inlet temperature of-10-80 deg.c as material into the reaction channel of the first reaction section from the main line feeding port;
2) only throwing the solid alkali catalyst into a reaction channel of the reaction section from a main feeding hole, or throwing the solid alkali catalyst into the reaction channel of the corresponding reaction section from the main feeding hole and a lateral line feeding hole;
the adding amount of the solid base catalyst is 0.1-5 wt% of the raw materials by mass percent;
the residence time of the feedstock in the entire reactor was: 0.5 h-2 h;
the material temperature at the outlet of the reactor is 10-120 ℃;
the reaction pressure is as follows: 0.1MPa to 2 MPa;
3) and separating the mixture flowing out of the tail end discharge hole to obtain the ethylidene norbornene.
As an improvement of the adiabatic tube reaction method for synthesizing ethylidene norbornene of the present invention:
the solid base catalyst in the step 2) is prepared by loading basic Ammonium Aluminum Carbonate (AACH) carrier precursor on metal (Na, K) and metal hydroxide (NaOH, KOH), the base strength is 20-33, and the base content is 5mmol.g-1～15mmol.g-1。
As a further improvement of the adiabatic tube reaction method for synthesizing ethylidene norbornene of the present invention, the preparation method of the solid base catalyst comprises the following steps in sequence:
roasting basic Ammonium Aluminum Carbonate (AACH) in inert gas atmosphere at the roasting temperature of 300-800 ℃ for 4-8 h to prepare a carrier (a carrier with high specific surface area of 500 m)2/g～1000m2/g)；
Secondly, mixing metal and metal hydroxide according to a molar ratio of 0.5-5: 1 to obtain a mixture A;
thirdly, stirring the mixture A and the carrier according to the mass ratio of 30: 3-15 in an inert gas atmosphere at the temperature of 360-600 ℃ for reaction for 1-5 h to obtain the solid base catalyst (the solid base catalyst with high alkali content and medium alkali strength).
As a further improvement of the adiabatic tube reaction method for synthesizing ethylidene norbornene of the present invention:
in the second step, the metal is Na and K, and the metal hydroxide is NaOH and KOH.
As a further improvement of the adiabatic tube reaction method for synthesizing ethylidene norbornene of the present invention:
the number of the lateral line feed inlets is 1-4.
As a further improvement of the heat-insulating tubular reaction method for synthesizing ethylidene norbornene of the present invention,
each reaction section is a heat-insulating pipe type reaction vessel.
Namely, each reaction section is sleeved in a heat-insulating pipe sleeve, the pipe sleeve can effectively reduce the heat loss, the temperature is increased by utilizing the released reaction heat, so that the isomerization reaction is carried out at a higher reaction rate, and the isomerization ratio is different along with the difference of the reaction temperature, thereby achieving the purpose of adjusting.
In the invention, the preparation method of the vinyl norbornene comprises the following steps: in general N2(high purity N)2) Under the condition, the vinyl norbornene is subjected to water removal and oxygen removal by utilizing a molecular sieve until the water content is lower than 10 ppm. In the process of removing water and oxygen and after the process is finished, high-purity N is always introduced2。
In the invention, the alkali strength and the alkali quantity of the solid alkali are measured by a Hammett indicator method, and the isomerization ratio of the obtained product is detected by a chromatogram.
The solid alkali obtained by the method has high alkali content and no specific requirement on the strength of the solid alkali; the catalyst is applied to the catalytic isomerization reaction of vinyl norbornene, the solid base catalyst is low in dosage, high in catalytic activity, high in product selectivity, adjustable in Z/E ratio of the product and significant for industrial application. In the isomerization reaction of the invention, the isomerization ratio Z/E of the product ENB can be regulated and controlled by adding the catalyst in batches, which specifically comprises the following steps: when the number of times is small, the isomerization ratio is large; on the contrary, when the adding amount is small and the adding times are large, the isomerization ratio is small; and the reaction selectivity is high, the temperature rise is easy to control, the catalyst dosage is small, and after the reaction is finished, the catalyst can be separated by conventional filtration.
In the invention, the ethylidene norbornene with the purity of more than 99 percent is prepared by contacting the vinyl norbornene and the high-efficiency solid base catalyst without further purification.
The method has the advantages of continuous process, convenient operation and good device tightness, the raw material VNB enters the reaction section after being subjected to water and oxygen removal through the molecular sieve, the catalyst can also be stored in a container without water and oxygen and enters the reaction section through the feed pump for reaction, and the contact with moisture and oxygen can be avoided in the whole process, so that the high-efficiency utilization of the catalyst is realized.
In conclusion, the invention provides a heat-insulating tubular reaction process for synthesizing ethylidene norbornene. The process takes solid alkali as a catalyst to prepare ethylidene norbornene in a multi-side-line feeding adiabatic tube type reactor. The catalyst is added in batches in the process, so that the possibility of catalyst inactivation caused by local overheating is avoided, the reaction heat is effectively utilized, the using amount of the catalyst is small, the preparation process is simple and easy to control, the reaction rate is high, the selectivity is high, the Z/E of the product is adjustable, the high-quality and pure ENB is directly obtained, the subsequent purification processes such as rectification and the like are not needed, and the economic benefit is good.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic view of the structure of an adiabatic tube reactor for synthesizing ethylidene norbornene.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
A heat-insulating pipe type reactor for synthesizing ethylidene norbornene is disclosed in figure 1, and comprises 5 reaction sections, wherein the front end of each reaction section is provided with a feed inlet, the feed inlet at the front end of the first reaction section is provided with a main line feed inlet, the rest are side line feed inlets, each feed inlet is provided with a respective catalyst feed pump (solid base catalyst feed pump) and a static mixer, a stop valve is arranged at each catalyst feed pump (solid base catalyst feed pump), and the stop valve is used for opening and closing the catalyst material entering the static mixer from the catalyst feed pump. The tail end of each reaction section is provided with a discharge port, and the front section of the discharge port is provided with a check valve; the check valve is used for automatically preventing media at the discharge ports from flowing reversely, and each discharge port can also be used as a sampling port: sampling and detecting each reaction section to obtain reaction data so as to adjust the process parameters.
At the beginning, the catalyst entering from the solid base catalyst feed pump (solid base catalyst feed pump 1) and the reaction mass entering from the VNB feed pump are mixed at the static mixer (static mixer 1) and enter the first reaction section. Then, the catalyst entering from the solid base catalyst feed pump (solid base catalyst feed pump 2-5) and the reaction material discharged from the discharge port of the previous reaction section are mixed at the corresponding static mixer (static mixer 2-5) and then enter the reaction section (second reaction section-fifth reaction section).
Remarks explanation: the static mixer is part of its corresponding reaction section.
The preparation method of the solid base catalyst comprises the following steps:
and roasting 20g of AACH in an inert gas atmosphere at the roasting temperature of 500 ℃ for 4h to obtain the carrier. Weighing 5.18g (0.235mol) of Na and 1.8g (0.045mol) of NaOH to prepare a mixture, putting the mixture and a carrier into a stirring kettle to be stirred, adjusting the temperature to 500 ℃ in an inert gas atmosphere, reacting for 1h, and cooling to obtain the solid base catalyst A. The alkali strength is 26 and the alkali content is 10mmol-1。
In general N2(high purity N)2) Under the condition, removing water and oxygen from vinyl norbornene by using a molecular sieve until the water content is lower than 10 ppm; thus obtaining the vinyl norbornene after removing water and oxygen by molecular sieve. Description of the drawings: in the course of removing water and removing oxygen and after the above-mentioned process is completed, high-purity N is passed through2。
VNB in the following examples 1 to 8 means the above-mentioned vinylnorbornene after water removal by molecular sieve;
the solid base catalysts in examples 1 to 8 below were all prepared as described above.
Example 1, a adiabatic tubular reaction method for synthesizing ethylidene norbornene:
VNB with inlet temperature of-10 ℃ is directly conveyed into a tubular reaction device from a main line feed inlet at a constant flow rate, 1 wt% of solid base catalyst is respectively conveyed into the tubular reaction device from feed inlets 1, 2, 3, 4 and 5, the total amount is 5wt%, the solid base catalyst enters a reaction section after being mixed by a static mixer and reacts in the tubular reactor, the outlet temperature is 10 ℃, the reaction pressure is 2MPa, and the retention time is 2 h. Through gas chromatographic analysis, the conversion rate is 99.6%, the selectivity is 99.9%, the purity is 99.5%, and the isomerization ratio Z/E is 8.5.
Example 2, a adiabatic tubular reaction process for the synthesis of ethylidene norbornene:
VNB with the inlet temperature of-10 ℃ is directly conveyed into a tubular reaction device from a main line feed inlet at a constant flow rate, 5wt% of solid base catalyst (namely, the solid base catalyst accounts for 5% of the weight of the VNB) is conveyed into the tubular reaction device from a feed inlet 1, the total amount is 5wt%, the solid base catalyst is mixed by a static mixer and then enters a reaction section, the reaction is carried out in the tubular reactor, the outlet temperature is 20 ℃, the reaction pressure is 2MPa, and the retention time is 2 h. Through gas chromatographic analysis, the conversion rate is 99.7%, the selectivity is 99.1%, the purity is 98.8%, and the isomerization ratio Z/E is 8.6.
Example 3, a adiabatic tubular reaction process for the synthesis of ethylidene norbornene:
VNB with the inlet temperature of 80 ℃ is directly conveyed into a tubular reaction device from a main line feed inlet at a constant flow rate, 3 wt% and 2 wt% of solid base catalyst are respectively conveyed into the tubular reaction device from feed inlets 1 and 2, the total amount is 5wt%, the VNB enters a reaction section after being mixed by a static mixer and reacts in the tubular reactor, the outlet temperature is 120 ℃, the reaction pressure is 0.5MPa, and the retention time is 2 h. Through gas chromatographic analysis, the conversion rate is 99.3%, the selectivity is 86.2%, the purity is 85.6%, and the isomerization ratio Z/E is 3.4.
Example 4, a adiabatic tubular reaction process for the synthesis of ethylidene norbornene:
VNB with the inlet temperature of 80 ℃ is directly conveyed into a tubular reaction device from a main line feed inlet at a constant flow rate, 1 wt% of solid base catalyst is respectively conveyed into the tubular reaction device from feed inlets 1, 2, 3, 4 and 5, the total amount is 5wt%, the solid base catalyst enters a reaction section after being mixed by a static mixer and reacts in the tubular reactor, the outlet temperature is 110 ℃, the reaction pressure is 1MPa, and the retention time is 2 h. By gas chromatographic analysis, the conversion rate was 99.7%, the selectivity was 88.7%, the purity was 88.4% and the isomerization ratio Z/E was 3.2.
Example 5 a method for the isomerization of vinyl norbornene to ethylidene norbornene:
VNB with the inlet temperature of 60 ℃ is directly conveyed into a tubular reaction device from a main line feed inlet at a constant flow rate, 5wt% of solid base catalyst is respectively conveyed into the tubular reaction device from a feed inlet 1, the total amount is 5wt%, the solid base catalyst enters a reaction section after being mixed by a static mixer and reacts in the tubular reactor, the outlet temperature is 95 ℃, the reaction pressure is 1MPa, and the retention time is 0.5 h. Through gas chromatographic analysis, the conversion rate is 99.8%, the selectivity is 99.7%, the purity is 99.5%, and the isomerization ratio Z/E is 4.5.
Example 6 a method for the isomerization of vinyl norbornene to ethylidene norbornene:
VNB with the inlet temperature of 60 ℃ is directly conveyed into a tubular reaction device from a main line feed inlet at a constant flow rate, 2.5 wt% of solid base catalyst is respectively conveyed into the tubular reaction device from feed inlets 1, 2, 3, 4 and 5, the total amount is 2.5 wt%, the solid base catalyst enters a reaction section after being mixed by a static mixer and reacts in the tubular reactor, the outlet temperature is 90 ℃, the reaction pressure is 1MPa, and the retention time is 1 h. Through gas chromatographic analysis, the conversion rate is 99.9%, the selectivity is 99.9%, the purity is 99.8%, and the isomerization ratio Z/E is 4.2.
Example 7 a method for the isomerization of vinyl norbornene to ethylidene norbornene:
VNB with the inlet temperature of 70 ℃ is directly conveyed into a tubular reaction device from a main line feed inlet at a constant flow rate, 2.5 wt% of solid base catalyst is respectively conveyed into the tubular reaction device from feed inlets 1, 2, 3, 4 and 5, the total amount is 2.5 wt%, the solid base catalyst enters a reaction section after being mixed by a static mixer and reacts in the tubular reactor, the outlet temperature is 100 ℃, the reaction pressure is 1MPa, and the retention time is 1 h. Through gas chromatographic analysis, the conversion rate is 99.8%, the selectivity is 99.1%, the purity is 98.9%, and the isomerization ratio Z/E is 3.9.
Example 8, a method for the isomerization of vinyl norbornene to ethylidene norbornene:
VNB with the inlet temperature of 30 ℃ is directly conveyed into a tubular reaction device from a main line feed inlet at a constant flow rate, 2.5 wt% of solid base catalyst is respectively conveyed into the tubular reaction device from feed inlets 1, 2, 3, 4 and 5, the total amount is 2.5 wt%, the solid base catalyst enters a reaction section after being mixed by a static mixer and reacts in the tubular reactor, the outlet temperature is 45 ℃, the reaction pressure is 1MPa, and the retention time is 1 h. Through gas chromatographic analysis, the conversion rate is 99.2%, the selectivity is 99.8%, the purity is 99.0%, and the isomerization ratio Z/E is 6.1.
Comparative example 1 VNB with inlet temperature 60 ℃ was directly fed into the tubular reactor at constant flow rate from the main line feed inlet, feed inlets 1, 2, 3, 4, 5 did not feed solid base catalyst into the tubular reactor, outlet temperature was 60 ℃, reaction pressure was 1MPa, residence time was 1 h. The conversion was 0% and the selectivity 0% by gas chromatography.
Comparative example 2, 20g of AACH was calcined under an inert gas atmosphere at a calcination temperature of 500 ℃ for 4 hours to obtain a carrier. The solid base catalyst in example 6 was replaced with this carrier, and the rest was the same as example 6; the results obtained were: the exit temperature was 60 ℃, the conversion was 4%, the selectivity was 38%, the purity was 1.5% and the isomerization ratio Z/E was 5.3.
Comparative example 3, the calcination of AACH in the catalyst preparation process is cancelled, namely, AACH is directly used as a carrier to react with Na and NaOH; the method comprises the following specific steps:
weighing 5.18g (0.235mol) of Na and 1.8g (0.045mol) of NaOH to prepare a mixture by using 20g of AACH as a carrier, putting the mixture and the carrier into a stirring kettle for stirring, adjusting the temperature to 500 ℃ under the atmosphere of inert gas, reacting for 1h, and cooling to obtain the solid base catalyst.
The solid base catalyst prepared by the method replaces the solid base catalyst in the example 6, and the rest is equal to the solid base catalyst in the example 6; the results obtained were: the exit temperature was 70 ℃, the conversion was 35.5%, the selectivity was 96.4%, the purity was 34.2% and the isomerization ratio Z/E was 4.9.
The parameters of the above case and the resulting ratio are shown in table 1 below.
TABLE 1
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (3)
1. A heat-insulating tubular reaction method for synthesizing ethylidene norbornene is characterized in that: synthesizing by adopting a multi-side-line feeding heat-insulating tube type reactor; the reactor is divided into at least 2 reaction sections, the front end of each reaction section is provided with a feed inlet, the feed inlet at the front end of the first reaction section is a main line feed inlet, and the rest are lateral line feed inlets, and the method comprises the following steps:
1) feeding vinyl norbornene with the inlet temperature of-10-80 ℃ into the first reaction section from a main line feeding port as a raw material;
2) only throwing the solid alkali catalyst into a reaction channel of the reaction section from a main feeding hole, or throwing the solid alkali catalyst into the reaction channel of the corresponding reaction section from the main feeding hole and a lateral line feeding hole;
the adding amount of the solid base catalyst is 0.1-5 wt% of the raw materials by mass percent;
the residence time of the feedstock in the entire reactor was: 0.5-2 h;
the material temperature at the outlet of the reactor is 10-120 ℃;
the reaction pressure is as follows: 0.1MPa to 2 MPa;
the solid base catalyst is prepared by metal and metal hydroxide loaded basic ammonium aluminum carbonate carrier precursor,the alkali strength is 20-33, and the alkali content is 5mmol-1~15 mmol.g-1；
The preparation method of the solid base catalyst comprises the following steps in sequence:
roasting basic ammonium aluminum carbonate in an inert gas atmosphere at the roasting temperature of 300-800 ℃ for 4-8 h to prepare a carrier;
secondly, mixing metal and metal hydroxide according to a molar ratio of 0.5-5: 1 to obtain a mixture A;
the metal is Na and K, and the metal hydroxide is NaOH and KOH;
thirdly, stirring and reacting the mixture A and the carrier for 1-5 hours at 360-600 ℃ in an inert gas atmosphere according to the mass ratio of 30: 3-15 to obtain solid base catalyst powder;
3) and separating the mixture flowing out of the tail end discharge hole to obtain the ethylidene norbornene.
2. The method according to claim 1, wherein the reaction is carried out in a thermal insulation tube type for synthesizing ethylidene norbornene:
the number of the reaction sections is 2-5, and the number of the lateral line feed inlets is 1-4.
3. The method according to claim 2, wherein the reaction is carried out in a thermal insulation tube type for synthesizing ethylidene norbornene:
each reaction section is a heat-insulating pipe type reaction vessel.
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| CN104058912A (en) * | 2014-07-01 | 2014-09-24 | 上海华畅环保设备发展有限公司 | Method and device for utilizing catalyst in ethylidene norbornene isosynthesis technology |
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