CN102249839A - Method for preparing norbornene in loop reactor - Google Patents
Method for preparing norbornene in loop reactor Download PDFInfo
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- CN102249839A CN102249839A CN2011101276161A CN201110127616A CN102249839A CN 102249839 A CN102249839 A CN 102249839A CN 2011101276161 A CN2011101276161 A CN 2011101276161A CN 201110127616 A CN201110127616 A CN 201110127616A CN 102249839 A CN102249839 A CN 102249839A
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Abstract
The invention discloses a method for preparing norbornene in a loop reactor. The method disclosed by the invention comprises the following steps of: (1) heating and pre-decomposing dicyclopentadiene in a heat exchanger to partially or wholly decompose the dicyclopentadiene into cyclopentadiene, wherein the temperature for heating and pre-decomposing is in a range of 120-240 DEG C and the absolute pressure is in a range of 5-30 MPa; (2) transporting the heated and pre-decomposed product of the step (1) into the loop reactor through the heat exchanger, adding ethylene into the loop reactor at the same time and reacting to obtain the norbornene, wherein the reaction conditions are as follows: the temperature is in a range of 180-300 DEG C, the absolute pressure of an outlet of the loop reactor is in a range of 5-30 MPa, the mol ratio of the ethylene to the dicyclopentadiene which is not heated and pre-decomposed is 1-20 to 1, the recycle ratio is 100-300 to 1, and the temperature and the pressure of the ethylene in the process of adding the ethylene into the loop reactor are the same as those in the reaction conditions. According to the method provided by the invention, the safety of the preparation process can be remarkably improved and higher selectivity and conversion rate of the cyclopentadiene can be realized.
Description
Technical field
The present invention relates to method by the mixture reaction production norbornylene of ethene and cyclopentadiene (CPD) reaction or ethene and dicyclopentadiene (DCPD) and cyclopentadiene (CPD).
Background technology
Nineteen forty-one, L. M.Joshel and L. W. Butz have described the synthetic of norbornylene first.The reaction of synthesing norborene is the Diels-Alder reaction, cyclopentadiene
Two two bond ruptures, 2 and 3 form two keys, 1 and 4 and ethene condensation, the generation norbornylene:
The reaction of ethene and cyclopentadiene is a strong exothermal reaction, Δ H °
298=-22kcal/mol perfect gas.Compare with ethene, cyclopentadiene is the product more responsive to these explosive reactions.Propositions such as the M. Ahmed of Union Carbide Corporation: cyclopentadiene can recur thermopositive reaction through heating under following temperature under pressure:
250 ℃, form dicyclopentadiene oligopolymer (Δ H=-66kcal/mol);
340 ℃, oligopolymer is converted into polymkeric substance (Δ H=-80kcal/mol);
440 ℃, polymer unwinds generates a large amount of gases (Δ H=-90 kcal/mol).
According to the different sources of cyclopentadiene, these temperature can have 30 ℃ variation, but agnogenio.These factors have increased the possibility of norbornylene production process blast, therefore, how to improve the security of norbornylene production process, are that the planner of every cover production equipment must consider.
In addition, under these reaction conditionss, other side reaction may take place also, as:
1, cyclopentadiene and norbornylene carry out diels-alder reaction, generate tetracyclododecane TCD,
2, dicyclopentadiene and cyclopentadiene carry out diels-alder reaction, generate cyclopentadiene tripolymer (CPD Trimer is to call TM in the following text),
American documentation literature US2340908 has disclosed at 200 ℃, carries out the reaction of dicyclopentadiene and ethene under the absolute pressure 50-100bar condition.U.S. Pat 3007977 has disclosed the method by the mixture synthesing norborene of cyclopentadiene and dicyclopentadiene, has adopted the mixture that is considered to help controlling reaction conditions.
American documentation literature US3763253 has disclosed a kind of method of production norbornylene of highly selective, comprising:
1. with the mixture of light alkene and dicyclopentadiene, about more than 190 ℃ in temperature, especially at about 200-325 ℃, be under the condition of 2-40 to the mol ratio of dicyclopentadiene at alkene for example, alkene is caused in the reactor under excessive;
2. keep the condition of reactor temperature, pressure and the residence time, make reactant and product keep gas phase, especially temperature is at 200-325 ℃, and pressure is 6.8-136pa and residence time 0.5-20 minute, to help generating norbornylene;
3. recovery norbornylene
Germany Patent document DD215078A1 discloses a kind of method of continuous production norbornylene, and according to the method, its reaction conditions not only can make reactant ethylene and cyclopentadiene keep gas phase, also can make norbornylene also be in gas phase; Under the pressure of the temperature of 523-613 ° of K and 2-20MPa, the cyclopentadiene of 1mol and the ethene of 1-25mol are reacted.Its process comprises mixes and two processes of reaction, mixing temperature 433-473 ° K, and residence time 10-30 minute, the higher-boiling compound that forms in the mixing zone was extracted out from the bottom; In the reaction zone after the mixing zone, generate the reaction of norbornylene, extract reaction product from the reaction zone top out; And product is separated by two sections distillation zones.
Germany Patent document DD140874A1 and DE203313C have disclosed a kind of method of continuous production norbornylene, have adopted the reaction of carrying out dicyclopentadiene and/or cyclopentadiene and ethene under reactant and product norbornylene all are in the condition of gas phase.Method like this, the dicyclopentadiene of 1mol is mixed with the ethene of 2-50mol, at 250-340 ℃, react under the 2-20MPa, in reaction pressure and be lower than under 190 ℃ the temperature excessive ethene was introduced in the past at reaction zone, pass the liquid dicyclopentadiene, then react at reaction zone, obtain norbornylene, and norbornylene is drawn from the reaction zone top with gaseous state.
German Patent DD244257A3 relates to a kind of method by dicyclopentadiene and ethene synthesing norborene, and the two tubes that its reaction compartment is placed with one heart is divided into an interior space of mainly carrying out annular space He another main synthesing norborene of dicyclopentadiene dissociative reaction.
Chinese patent literature CN1284052A relates to the method for a kind of dicyclopentadiene and ethene synthesing norborene, the reactor at its reaction place is a upright shaft type barrel type reactor, comprise a kind of equipment that injects reactant, two pipes of placing with one heart of its homotaxis.Preheating is to make it partly to be decomposed into cyclopentadiene before entering reaction zone for dicyclopentadiene, and ethene makes it to be under the temperature and pressure condition of reaction zone before entering reaction zone.The space that ethene advances between two pipes of placing with one heart of inside reactor with supercritical state enters reactor, and the mixture of dicyclopentadiene and cyclopentadiene enters reactor from the interior pipe of two pipes of placing with one heart of inside reactor.Increase the speed of ethene by the nozzle form at concentric tube top.Quicken at narrow orifice by ethene, make reactant reach well blend, thereby disperse dicyclopentadiene.Singulation by remaining dicyclopentadiene is improved dispersion, produces postcritical cyclopentadiene.Form strong mixing zone in reactor head.
In the above method, part has adopted dicyclopentadiene and/or cyclopentadiene and ethene to be pre-mixed, and introduces the method that reaction zone reacts again, and this method can reduce the risk of the bad side reaction that may cause of reaction zone mass transfer; Part has adopted by adding the method for strongly mixing condition, makes to mix and be reflected in the same reactor to carry out.But what they used all is still formula, tower or similar still formula and tower reactor.For ethene by relating to High Temperature High Pressure and reaction system is divided into the heterogenetic reaction system with such one of cyclopentadiene prepared in reaction norbornylene, how to take into account the safe secret worry that mixing between a plurality of phase materials and High Temperature High Pressure are brought, become norbornylene production and realize industrialized bottleneck.
In addition, some is in fact but very difficult in industrial realization by the synthetic method of dicyclopentadiene or cyclopentadiene synthesing norborene, because the reactive behavior of ethene is low, it needs harsh operational condition.These conditions are very near the blast pyrolysated condition of dicyclopentadiene/cyclopentadiene.This also just why several cover attempt the reason that the full scale plant of synthesing norborene is forced to stop production owing to blast.
Summary of the invention
The purpose of this invention is to provide a kind of safe method that in annular-pipe reactor, prepares norbornylene.
For achieving the above object, the technical solution used in the present invention is: the described method for preparing norbornylene in annular-pipe reactor comprises the steps:
(1) dicyclopentadiene heats predecomposition partly or wholly being decomposed into cyclopentadiene in interchanger, and the temperature of described heating predecomposition is that 120 ℃-240 ℃, absolute pressure are 5-30MPa;
(2) the heating predecomposition product with step (1) is transported in the annular-pipe reactor by described interchanger, adds ethene simultaneously and obtain norbornylene to react in annular-pipe reactor, and described reaction conditions is as follows:
Temperature: 180 ℃-300 ℃,
The absolute pressure in the exit of annular-pipe reactor: 5-30MPa,
Ethene is 1-20 with the mol ratio of heating predecomposition dicyclopentadiene before: 1,
Recycle ratio is 100-300: 1;
The temperature and pressure of described ethene when adding annular-pipe reactor is identical with temperature and pressure in the described reaction conditions.
Further, in the step of the present invention (2), ethene is 2-10 with the mol ratio of heating predecomposition dicyclopentadiene before: 1.
Further, the present invention earlier was dissolved in inert organic solvents with dicyclopentadiene before dicyclopentadiene is joined interchanger, described inert organic solvents be in straight chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon, the aromatic hydrocarbons any or appoint several mixtures.
Further, inert organic solvents of the present invention is a toluene.
Compared with prior art, the invention has the beneficial effects as follows: the present invention is by being applied to annular-pipe reactor the production process of ethene and dicyclopentadiene/cyclopentadiene prepared in reaction norbornylene, thereby the safety coefficient of norbornylene production process is improved greatly.Simultaneously because the advantage of annular-pipe reactor aspect mass transfer and heat transfer, make the production method of norbornylene involved in the present invention have the material choice and the monomer conversion of higher cyclopentadiene.In the methods of the invention, annular-pipe reactor has made it to have concurrently withstand voltage, the fast advantage of conducting heat of mass transfer, mixing advantage and the tubular reactor of tank reactor because of the structure of its uniqueness.Participate in by the multi phase state material for such one of ethene and dicyclopentadiene/cyclopentadiene prepared in reaction norbornylene, the reaction down of high temperature, high pressure, and with the inflammable and explosive reaction of strong heat release, simple relatively still formula or the tubular reactor of annular-pipe reactor has remarkable advantages in the reaction process.
Embodiment
The reaction system that production method of the present invention relates to comprises ethene and two kinds of raw materials of dicyclopentadiene, and ethene is 1-20 with the mol ratio of heating predecomposition dicyclopentadiene before: 1, and preferred ratio is 2-10: 1.Dicyclopentadiene charging separately also may be dissolved in charging in the inert organic solvents.Selectable inert organic solvents be in straight chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon, the aromatic hydrocarbons any or appoint several mixtures.Preferred inert organic solvents is a toluene.Dicyclopentadiene partly or wholly is converted into cyclopentadiene by heating predecomposition before entering annular-pipe reactor, the predecomposition product is the mixture of cyclopentadiene (CPD) or dicyclopentadiene (DCPD) and cyclopentadiene (CPD).Heating predecomposition is carried out in interchanger, and its temperature is 120 ℃-240 ℃, and absolute pressure is 5-30MPa.Ethene heated earlier before entering annular-pipe reactor, make its temperature and pressure reach the interior temperature and pressure of annular-pipe reactor, and then the ethene that will be under this temperature and pressure joined in the annular-pipe reactor.Have the two-way raw material to enter annular-pipe reactor: one tunnel charging is the ethene after heating, and another road charging is the product of dicyclopentadiene after heating predecomposition.This two-way raw material adds annular-pipe reactor by volume pump, gives thorough mixing by static mixer when entering annular-pipe reactor.Reaction conditions in the annular-pipe reactor is as follows:
Temperature: 180 ℃-300 ℃
Exit absolute pressure: 5-30MPa
Ethene is 1-20 with the mol ratio of heating predecomposition dicyclopentadiene before: 1;
Recycle ratio is 100-300: 1;
Above reaction conditions makes that at least a component is in supercritical state in the system, and wherein, ethene is in supercritical state.
Material is discharging after the circulation primary at least in annular-pipe reactor.
Annular-pipe reactor is applied to the preparation of norbornylene, can significantly improves the security of process.Simultaneously, owing to good heat transfer, the mass transfer effect that annular-pipe reactor had, can obtain the selectivity and the transformation efficiency of higher cyclopentadiene.
Below further specify the present invention with specific embodiment.
Embodiment 1:
The length of the annular-pipe reactor that present embodiment uses is 30 centimetres, and internal diameter is 2 centimetres, and the ingress is provided with static mixer.Dicyclopentadiene partly or entirely was decomposed into cyclopentadiene by interchanger heating predecomposition before entering annular-pipe reactor, its processing condition are 240 ℃, 5MPa.The temperature of ethene when entering annular-pipe reactor is that 180 ℃, absolute pressure are 5MPa.The predecomposition product of ethene and dicyclopentadiene passes through the volume pump charging respectively, and gives thorough mixing by static mixer when entering annular-pipe reactor.Wherein, the feed flow rates of ethene is 6.24mL/s, and the feed flow rates of the predecomposition product of dicyclopentadiene is 1.41mL/s, is 1 to annular-pipe reactor ethene that adds and the mol ratio that heats predecomposition dicyclopentadiene before.The temperature of annular-pipe reactor is 180 ℃, and the exit absolute pressure is 5MPa; The material recycle ratio is 100: 1, and the outlet material flow rate is 3.14mL/s, and wherein the content of norbornylene is 29.3mol%, and the selectivity of cyclopentadiene is 71%, and transformation efficiency is 58.4%.Remove that the thick product concentration of norbornylene is 75w% behind the ethene.
Embodiment 2:
The length of the annular-pipe reactor that present embodiment uses is 30 centimetres, and internal diameter is 2 centimetres, and the ingress is provided with static mixer.Dicyclopentadiene partly or entirely was decomposed into cyclopentadiene by interchanger heating predecomposition before entering annular-pipe reactor, its processing condition are 120 ℃, 8MPa.The temperature of ethene when entering annular-pipe reactor is that 220 ℃, absolute pressure are 10MPa.The predecomposition product of ethene and dicyclopentadiene passes through the volume pump charging respectively, and gives thorough mixing by static mixer when entering annular-pipe reactor.Wherein, the feed flow rates of ethene is 4.64mL/s, and the feed flow rates of the predecomposition product of dicyclopentadiene is 0.75mL/s, is 2 to annular-pipe reactor ethene that adds and the mol ratio that heats predecomposition dicyclopentadiene before.The temperature of annular-pipe reactor is that 220 ℃, exit absolute pressure are 10MPa; The material recycle ratio is 100: 1, and the outlet material flow rate is 3.14mL/s, and wherein the content of norbornylene is 45.9mol%, and the selectivity of cyclopentadiene is 93%, and transformation efficiency is 99.2%.Remove that the thick product concentration of norbornylene is 95w% behind the ethene.
Embodiment 3:
The length of the annular-pipe reactor that present embodiment uses is 30 centimetres, and internal diameter is 2 centimetres, and the ingress is provided with static mixer.Dicyclopentadiene partly or entirely was decomposed into cyclopentadiene by interchanger heating predecomposition before entering annular-pipe reactor, its processing condition are 150 ℃, 13MPa.The temperature of ethene when entering annular-pipe reactor is 260 ℃, and absolute pressure is 15MPa.The predecomposition product of ethene and dicyclopentadiene passes through the volume pump charging respectively, and gives thorough mixing by static mixer when entering annular-pipe reactor.Wherein, the feed flow rates of ethene is 3.27mL/s, and the feed flow rates of the predecomposition product of dicyclopentadiene is 0.11mL/s, is 16 to annular-pipe reactor ethene that adds and the mol ratio that heats predecomposition dicyclopentadiene before.The temperature of annular-pipe reactor is that 260 ℃, exit absolute pressure are 15MPa.The material recycle ratio is 200: 1, and the outlet material flow rate is 3.14mL/s, and wherein the content of norbornylene is 5.93mol%, and the selectivity of cyclopentadiene is 95%, and transformation efficiency is 99.8%.Remove that the thick product concentration of norbornylene is 96w% behind the ethene.
Embodiment 4:
The length of the annular-pipe reactor that present embodiment uses is 30 centimetres, and internal diameter is 2 centimetres, and the ingress is provided with static mixer.Dicyclopentadiene partly or entirely was decomposed into cyclopentadiene by interchanger heating predecomposition before entering annular-pipe reactor, its processing condition are 210 ℃, 18MPa.The temperature of ethene when entering annular-pipe reactor is 300 ℃, and absolute pressure is 20MPa.The predecomposition product of ethene and dicyclopentadiene passes through the volume pump charging respectively, and gives thorough mixing by static mixer when entering annular-pipe reactor.Wherein, the feed flow rates of ethene is 2.74mL/s, and the feed flow rates of the predecomposition product of dicyclopentadiene is 0.11mL/s, is 20 to annular-pipe reactor ethene that adds and the mol ratio that heats predecomposition dicyclopentadiene before.The temperature of annular-pipe reactor is that 300 ℃, exit absolute pressure are 20MPa.The material recycle ratio is 200: 1, and the outlet material flow rate is 3.14mL/s, and wherein the content of norbornylene is 4.76mol%, and the selectivity of cyclopentadiene is 96%, and transformation efficiency is 99.3%.Remove that the thick product concentration of norbornylene is 97w% behind the ethene.
Embodiment 5:
The length of the annular-pipe reactor that present embodiment uses is 30 centimetres, and internal diameter is 2 centimetres, and the ingress is provided with static mixer.Dicyclopentadiene partly or entirely was decomposed into cyclopentadiene by interchanger heating predecomposition before entering annular-pipe reactor, its processing condition are 200 ℃, 24MPa.The temperature of ethene when entering annular-pipe reactor is 240 ℃, and absolute pressure is 25MPa.The predecomposition product of ethene and dicyclopentadiene passes through the volume pump charging respectively, and gives thorough mixing by static mixer when entering annular-pipe reactor.Wherein, the feed flow rates of ethene is 1.61mL/s, and the feed flow rates of the predecomposition product of dicyclopentadiene is 0.44mL/s, to annular-pipe reactor ethene that adds and mol ratio=5 of heating predecomposition dicyclopentadiene before.The temperature of annular-pipe reactor is that 240 ℃, exit absolute pressure are 25MPa.The material recycle ratio is 300: 1, and the outlet material flow rate is 3.14mL/s, and wherein the content of norbornylene is 19.3mol%, and the selectivity of cyclopentadiene is 97%, and transformation efficiency is 99.7%.Remove that the thick product concentration of norbornylene is 98w% behind the ethene.
Embodiment 6:
The length of the annular-pipe reactor that present embodiment uses is 30 centimetres, and internal diameter is 2 centimetres, and the ingress is provided with static mixer.Dicyclopentadiene partly or entirely was decomposed into cyclopentadiene by interchanger heating predecomposition before entering annular-pipe reactor, its processing condition are 190 ℃, 30MPa.The temperature of ethene when entering annular-pipe reactor is 280 ℃, and absolute pressure is 30MPa.The predecomposition product of ethene and dicyclopentadiene passes through the volume pump charging respectively, and gives thorough mixing by static mixer when entering annular-pipe reactor.Wherein, the feed flow rates of ethene is 1.61mL/s, and the feed flow rates of the predecomposition product of dicyclopentadiene is 0.22mL/s, to annular-pipe reactor ethene that adds and mol ratio=10 of heating predecomposition dicyclopentadiene before.The temperature of annular-pipe reactor is that 280 ℃, exit absolute pressure are 30MPa.The material recycle ratio is 300: 1, and the outlet material flow rate is 3.14mL/s, and wherein the content of norbornylene is 9.4mol%, and the selectivity of cyclopentadiene is 94%, and transformation efficiency is 99.9%.Remove that the thick product concentration of norbornylene is 95w% behind the ethene.
Embodiment 7:
The length of the annular-pipe reactor that present embodiment uses is 30 centimetres, and internal diameter is 2 centimetres, and the ingress is provided with static mixer.Before dicyclopentadiene is joined interchanger, dicyclopentadiene is dissolved in inert organic solvents toluene, be made into the toluene solution that concentration is the dicyclopentadiene of 96w%.Before entering annular-pipe reactor, concentration is that the toluene solution of the dicyclopentadiene of 96w% heats predecomposition by interchanger under 180 ℃, 14MPa condition, makes dicyclopentadiene partly or entirely be decomposed into cyclopentadiene.The temperature of ethene when entering annular-pipe reactor is that 240 ℃, absolute pressure are 15MPa.Ethene and concentration be the toluene solution of predecomposition product of dicyclopentadiene of 96w% respectively by the volume pump charging, and when entering annular-pipe reactor, give thorough mixing by static mixer.Wherein, the feed flow rates of ethene is 1.61mL/s, and concentration is that the feed flow rates of toluene solution of predecomposition product of the dicyclopentadiene of 96w% is 0.27mL/s, and the mol ratio of the dicyclopentadiene before ethene that annular-pipe reactor adds and heating predecomposition is 8.The temperature of annular-pipe reactor is 240 ℃, and the exit absolute pressure is 15MPa.The material recycle ratio is 150: 1, and the outlet material flow rate is 3.14mL/s, and wherein the content of norbornylene is 12.0mol%, and the selectivity of cyclopentadiene is 97%, and transformation efficiency is 99.3%.Remove that the thick product concentration of norbornylene is 98w% behind the ethene.
Claims (4)
1. a method for preparing norbornylene in annular-pipe reactor is characterized in that, comprises the steps:
(1) dicyclopentadiene heats predecomposition partly or wholly being decomposed into cyclopentadiene in interchanger, and the temperature of described heating predecomposition is that 120 ℃-240 ℃, absolute pressure are 5-30MPa;
(2) the heating predecomposition product with step (1) is transported in the annular-pipe reactor by described interchanger, adds ethene simultaneously and obtain norbornylene to react in annular-pipe reactor, and described reaction conditions is as follows:
Temperature: 180 ℃-300 ℃,
The absolute pressure in the exit of annular-pipe reactor: 5-30MPa,
Ethene is 1-20 with the mol ratio of heating predecomposition dicyclopentadiene before: 1,
Recycle ratio is 100-300: 1;
The temperature and pressure of described ethene when adding annular-pipe reactor is identical with temperature and pressure in the described reaction conditions.
2. method according to claim 1 is characterized in that: in the described step (2), ethene is 2-10 with the mol ratio of heating predecomposition dicyclopentadiene before: 1.
3. method according to claim 1 and 2, it is characterized in that: before dicyclopentadiene is joined interchanger, earlier dicyclopentadiene is dissolved in inert organic solvents, described inert organic solvents be in straight chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon, the aromatic hydrocarbons any or appoint several mixtures.
4. method according to claim 3 is characterized in that: described inert organic solvents is a toluene.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664470A (en) * | 2012-09-26 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing norbornene |
| CN104262074A (en) * | 2014-08-27 | 2015-01-07 | 无锡阿科力科技股份有限公司 | Production technique of norbornene |
| CN104692993A (en) * | 2015-02-13 | 2015-06-10 | 浙江大学 | Method for synthesizing norbornene by micro-channel reactor |
| CN105481625A (en) * | 2015-12-07 | 2016-04-13 | 上海派尔科化工材料股份有限公司 | Norbornene production method |
| CN117402034A (en) * | 2023-12-13 | 2024-01-16 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for continuously producing norbornene |
| WO2024125138A1 (en) * | 2022-12-14 | 2024-06-20 | 中国石油天然气股份有限公司 | Preparation method for norbornene |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664470A (en) * | 2012-09-26 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing norbornene |
| CN104262074A (en) * | 2014-08-27 | 2015-01-07 | 无锡阿科力科技股份有限公司 | Production technique of norbornene |
| CN104262074B (en) * | 2014-08-27 | 2016-06-29 | 无锡阿科力科技股份有限公司 | The production technology of norborene |
| CN104692993A (en) * | 2015-02-13 | 2015-06-10 | 浙江大学 | Method for synthesizing norbornene by micro-channel reactor |
| CN104692993B (en) * | 2015-02-13 | 2017-06-06 | 浙江大学 | By the method for micro passage reaction synthesing norborene |
| CN105481625A (en) * | 2015-12-07 | 2016-04-13 | 上海派尔科化工材料股份有限公司 | Norbornene production method |
| WO2024125138A1 (en) * | 2022-12-14 | 2024-06-20 | 中国石油天然气股份有限公司 | Preparation method for norbornene |
| CN117402034A (en) * | 2023-12-13 | 2024-01-16 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for continuously producing norbornene |
| CN117402034B (en) * | 2023-12-13 | 2024-03-29 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for continuously producing norbornene |
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Application publication date: 20111123 |