CN1911877A - Method of preparing cyclopentene by continuous hydrogenation of cyclopentadiene - Google Patents
Method of preparing cyclopentene by continuous hydrogenation of cyclopentadiene Download PDFInfo
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- CN1911877A CN1911877A CN 200510028611 CN200510028611A CN1911877A CN 1911877 A CN1911877 A CN 1911877A CN 200510028611 CN200510028611 CN 200510028611 CN 200510028611 A CN200510028611 A CN 200510028611A CN 1911877 A CN1911877 A CN 1911877A
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Abstract
The continuous cyclopentadiene hydrogenating process to prepare cyclopentene is one continuous catalytic hydrogenation reaction of the mixture of cyclopentadiene, solvent and hydrogen in a fixed bed catalyst bed. The catalyst includes gamma-Al2O3 as carrier and Pa as active component. The solvent is any one of benzene, toluene, cyclohexane, ethanol, methanol, tertiary amyl alcohol and tertiary butyl alcohol. The molar ratio between cyclopentadiene and hydrogen is 1 to 1.5-3.5, and the reaction system has pressure of 0.9-1.5 MPa and temperature of 30-55 deg.c. The reacted liquid is discharged partially and externally circulated partially with the weight ratio being 1 to 6-12, and the externally circulated liquid after being cooled is mixed with cyclopentadiene material and solvent before being mixed with hydrogen in venturi ejector, atomized into gas-liquid mixture and reacted in the catalyst bed. The catalyst load is 4-7/hr accounted in liquid phase material, and the reacted heat is transferred via external circulation.
Description
Technical field
The present invention relates to a kind of method for preparing cyclopentenes by the cyclopentadiene selective hydrogenation.
Background technology
Cyclopentenes is the intermediate of quite a lot of fine chemical product, as can be used as high added value medicine intermediates such as producing cyclopentanol, bromocyclopentane, chlorocyclopentane, chaulmoogric acid, and cyclopentenes also is the main raw material of poly-cycloolefin high molecular polymer.Cyclopentenes can be obtained by several different methods in the prior art, however the tool industrial applications prospect of the method for producing with cyclopentadiene hydrogenating.As U.S. Pat 3,994,986 employing dicyclopentadiene depolymerization are cyclopentadiene, then two-stage hydrogenation continuous production cyclopentenes.The employing tubular reactor is a hydrogenator, and the mol ratio of first section hydrogen and cyclopentadiene is (1～1.5): 1, the second section ratio is (1～7): 1.Going out hydrogen through a gas-liquid separator separates after the reactant cooling is recycled.Because cyclopentadiene hydrogenating reaction is strong exothermal reaction, thereby beds occurs temperature runaway easily and causes catalyst deactivation in the shortening process.Mostly adopt the method for settling heat-exchanger rig in hydrogenator to remove the reaction heat of a large amount of generations in the prior art, the defective of this method is that the homogeneity of reactor internal cooling has been subjected to certain restriction.Exist local excessive to heat up by inference in beds, thereby caused the part catalyst deactivation, and cyclopentadiene very easily produces dimerization reaction generation dicyclopentadiene in this high-temperature zone, this all will reduce the yield of cyclopentenes.
Summary of the invention
The invention provides a kind of method by the continuous hydrogenation of cyclopentadiene preparing cyclopentene, the technical problem that it will solve is to adopt better heat-exchange method to remove the reaction heat that the cyclopentadiene hydrogenating process produces, thereby make reaction can obtain higher cyclopentenes yield, to overcome the defective that prior art exists.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of method by the continuous hydrogenation of cyclopentadiene preparing cyclopentene, this method comprise and will carry out catalytic hydrogenation reaction by the fixed bed catalyst bed continuously after cyclopentadiene, solvent and the hydrogen mixing.Catalyzer is with γ-Al
2O
3Being carrier, is active ingredient with Pa, and Pa content is 0.2～0.6wt%.Solvent is taken from any in benzene, toluene, hexanaphthene, ethanol, methyl alcohol, tertiary amyl alcohol or the trimethyl carbinol, and the weight ratio of cyclopentadiene and solvent is 1: (5～10), the mol ratio of cyclopentadiene and hydrogen are 1: (1.5～3.5).Reacting system pressure is 0.9～1.5MPa, and temperature of reaction is 30～55 ℃.The discharging of reaction solution part, part outer circulation.Reaction solution cooling back and the cyclopentadiene raw material and the solvent of outer circulation enter beds with hydrogen by the gas-liquid mixture that the venturi-type eductors mixed aerosol nebulizes then.The load of catalyzer is counted 4～7hr with liquid phase material
-1, the weight ratio of the load of reaction solution and outer circulation amount is 1: (4～12), reaction heat is removed by the outer circulation reaction solution.
Above-mentioned temperature of reaction is preferably 40～50 ℃; Solvent is preferably taken from any in methyl alcohol, the trimethyl carbinol or the tertiary amyl alcohol; The load of catalyzer is preferably 5～6hr in liquid phase material
-1The load of reaction solution and the weight ratio of internal circulating load are preferably 1: (5～10); The mol ratio of cyclopentadiene and hydrogen is preferably 1: (2～2.5).
One of key problem in technology of the present invention is to return hydrogenator after a part of outer circulation cooling with reaction solution, by partial reaction liquid is mixed with fresh reaction raw materials after reactor external application interchanger cools off again, enters reactor then system is lowered the temperature.After mixing, next atomizing of having adopted venturi-type eductors to carry out material makes that the mixing of liquid-liquid, liquid-gas storeroom is more even, and make gas-liquid two-phase reach high dispersing, form the very big gas-liquid interface that contacts, thereby strengthened the mass-transfer efficiency of gas-liquid phase greatly.Experiment shows that after having taked these two technical measures, the temperature of each point more becomes evenly in the system, in the beds, reacts also easier carrying out.Advantage compared with prior art of the present invention is that reaction yield obviously improves, and is that the cyclopentenes yield of calculating benchmark is 80～90% with the cyclopentadiene.
Below will the invention will be further described by specific embodiment, owing to the invention is characterized in terms of existing technologies and remove reaction heat with returning hydrogenator after the reaction solution part outer circulation cooling, the content of other parts and prior art do not have the difference of essence, therefore will pay attention to enumerating this part processing parameter in an embodiment.
In an embodiment:
Catalyst loading=unit catalyst volume, unit time (hour) liquid phase material is by catalysis
The volume of bed * 100%
Description of drawings
Accompanying drawing is a process flow diagram of the present invention.
Each mark is defined as in the accompanying drawing:
1---hydrogenator; 2---venturi-type eductors; 3---the raw material make-up tank; 4---the reaction solution storage tank; 5---the outer circulation interchanger; 6---the product storage tank; M1---raw material cyclopentadiene; M2---solvent; M3---raw hydrogen; M4---outer circulation reaction solution; M5---reaction solution discharging; M6---product discharging.
Embodiment
[embodiment 1～8]
The technical process of various embodiments of the present invention as shown in drawings, reactor 1 is fixed-bed reactor, the reactor inner top is settled a venturi-type eductors 2.The incoming stock make-up tank of raw material cyclopentadiene M1, solvent M2 and outer circulation reaction solution M4 mixes.Thorough mixing atomizing in venturi-type eductors 2 is carried out hydrogenation reaction for behind the vaporific gas-liquid mixture by the fixed bed catalyst bed from the liquid phase material of raw material make-up tank and raw hydrogen M3.The reaction solution that goes out autoreactor enters reaction solution storage tank 4, carries out the heat exchange cooling through the outer circulation heat exchanger then.Be divided into two portions through the refrigerative reaction solution, one is outer circulation part M4, and it is two for discharging M5, and M4 returns raw material make-up tank 3, and M5 enters product storage tank 6.Product discharging M6 removes refining separation circuit, and by obtaining refining cyclopentenes product behind the refining separation circuit, solvent then returns and applies mechanically.
Catalyzer is with γ-Al
2O
3Being carrier, is active ingredient with Pa, and Pa content is 0.2～0.6wt%.The volume of hydrogenation reaction is 50 liters, and loaded catalyst is 20 kilograms.Solvent adopts the trimethyl carbinol, and it is 1 listed that other processing condition of each embodiment see Table.
[embodiment 9]
Desolventize adopt methyl alcohol outer all the other with embodiment 1～8, it is 1 listed that other processing condition see Table.
[embodiment 10]
Desolventize adopt tertiary amyl alcohol outer all the other with embodiment 1～8, it is 1 listed that other processing condition see Table.
The reaction result of each embodiment sees Table 2.
Table 1.
| CPD/ solvent (weight ratio) | CPD/H 2(mol ratio) | Reaction pressure (MPa) | Temperature of reaction (℃) | Catalyst loading (hr -1) | M5/M4 (weight ratio) | |
| Embodiment 1 | 1∶5 | 1∶3.2 | 1.2 | 55 | 7.0 | 1∶10 |
| | 1∶8 | 1∶2.1 | 1.2 | 46 | 6.0 | 1∶5 |
| | 1∶8 | 1∶2.1 | 0.9 | 45 | 5.5 | 1∶8 |
| | 1∶8 | 1∶2.1 | 1.5 | 43 | 5.5 | 1∶8 |
| | 1∶8 | 1∶2.1 | 1.2 | 43 | 5.5 | 1∶8 |
| | 1∶8 | 1∶2.4 | 1.2 | 50 | 3.5 | 1∶12 |
| Embodiment 7 | 1∶8 | 1∶1.5 | 1.2 | 40 | 5.5 | 1∶4 |
| Embodiment 8 | 1∶10 | 1∶1.9 | 1.2 | 30 | 4.0 | 1∶8 |
| Embodiment 9 | 1∶8 | 1∶2.1 | 1.2 | 44 | 5.0 | 1∶8 |
| Embodiment 10 | 1∶8 | 1∶2.1 | 1.2 | 46 | 5.5 | 1∶8 |
(annotate: CPD is a cyclopentadiene in the table, and M5 is the reaction solution load, and M4 is a reaction solution outer circulation amount.)
Table 2.
| CPD transformation efficiency (%) | Cyclopentenes yield (%) | |
| Embodiment 1 | 82.8 | 81.3 |
| | 83.3 | 84.5 |
| | 84.9 | 88.8 |
| | 97.6 | 90.0 |
| | 97.4 | 92.7 |
| | 95.2 | 90.9 |
| Embodiment 7 | 80.9 | 82.1 |
| Embodiment 8 | 97.7 | 91.5 |
| Embodiment 9 | 96.8 | 90.8 |
| Embodiment 10 | 98.2 | 89.0 |
Claims (6)
1, a kind of method by the continuous hydrogenation of cyclopentadiene preparing cyclopentene, this method comprise and will carry out catalytic hydrogenation reaction by the fixed bed catalyst bed continuously after cyclopentadiene, solvent and the hydrogen mixing that catalyzer is with γ-Al
2O
3Be carrier, with Pa is active ingredient, Pa content is 0.2～0.6wt%, solvent is taken from any in benzene, toluene, hexanaphthene, ethanol, methyl alcohol, tertiary amyl alcohol or the trimethyl carbinol, the weight ratio of cyclopentadiene and solvent is 1: (5～10), the mol ratio of cyclopentadiene and hydrogen are 1: (1.5～3.5).Reacting system pressure is 0.9～1.5MPa, temperature of reaction is 30～55 ℃, the discharging of reaction solution part, part outer circulation, reaction solution cooling back and the cyclopentadiene raw material and the solvent of outer circulation, enter beds with hydrogen by the gas-liquid mixture that the venturi-type eductors mixed aerosol nebulizes then, the load of catalyzer is counted 4～7hr with liquid phase material
-1, the weight ratio of the load of reaction solution and outer circulation amount is 1: (4～12), reaction heat is removed by the outer circulation reaction solution.
2, the method for preparing cyclopentene according to claim 1 is characterized in that described solvent takes from any in methyl alcohol, the trimethyl carbinol or the tertiary amyl alcohol.
3, the method for preparing cyclopentene according to claim 1 is characterized in that described temperature of reaction is 40～50 ℃
4, the method for preparing cyclopentene according to claim 1 is characterized in that described catalyst loading counts 5～6hr with liquid phase material
-1
5, the method for preparing cyclopentene according to claim 1 is characterized in that the load of described reaction solution and the weight ratio of internal circulating load are 1: (5～10).
6, the method for preparing cyclopentene according to claim 1, the mol ratio that it is characterized in that described cyclopentadiene and hydrogen is 1: (2～2.5).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311761A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Low hydrogen-oil ratio hydrotreating method and reactor |
| CN102399121A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Preparation method of cyclopentane and methylcyclopentane |
| CN102850174A (en) * | 2012-08-29 | 2013-01-02 | 宁波职业技术学院 | Method for preparing cyclopentene from ethylene cracking C9 heavy fraction |
| CN103342624A (en) * | 2013-07-24 | 2013-10-09 | 上海派尔科化工材料有限公司 | Preparation method of high purity cyclopentene |
| CN109865519A (en) * | 2017-12-01 | 2019-06-11 | 中国石化扬子石油化工有限公司 | A kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application |
| CN111889036A (en) * | 2019-05-05 | 2020-11-06 | 中国石油集团工程股份有限公司 | Cyclopentadiene fixed bed catalytic hydrogenation reaction device, system and method |
-
2005
- 2005-08-09 CN CN 200510028611 patent/CN1911877A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311761A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Low hydrogen-oil ratio hydrotreating method and reactor |
| CN102311761B (en) * | 2010-07-07 | 2014-01-01 | 中国石油化工股份有限公司 | Low hydrogen-oil ratio hydrotreating method and reactor |
| CN102399121A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Preparation method of cyclopentane and methylcyclopentane |
| CN102850174A (en) * | 2012-08-29 | 2013-01-02 | 宁波职业技术学院 | Method for preparing cyclopentene from ethylene cracking C9 heavy fraction |
| CN103342624A (en) * | 2013-07-24 | 2013-10-09 | 上海派尔科化工材料有限公司 | Preparation method of high purity cyclopentene |
| CN103342624B (en) * | 2013-07-24 | 2014-12-17 | 上海派尔科化工材料有限公司 | Preparation method of high purity cyclopentene |
| CN109865519A (en) * | 2017-12-01 | 2019-06-11 | 中国石化扬子石油化工有限公司 | A kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application |
| CN109865519B (en) * | 2017-12-01 | 2021-11-30 | 中国石化扬子石油化工有限公司 | Ruthenium modified activated carbon supported nickel catalyst, preparation method and application thereof |
| CN111889036A (en) * | 2019-05-05 | 2020-11-06 | 中国石油集团工程股份有限公司 | Cyclopentadiene fixed bed catalytic hydrogenation reaction device, system and method |
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Effective date of registration: 20070608 Address after: Shanghai City, Jinshan District Jinyi Road, No. 48 Applicant after: Shanghai Petrochemical Co., Ltd., SINOPEC Co-applicant after: Sinopec Corp. Address before: Shanghai City, Jinshan District Jinyi Road, No. 48 Applicant before: Shanghai Petrochemical Co., Ltd., SINOPEC |
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