CN1911876A - Method of preparing methyl cyclo penlene by continuous hydrogenation of methyl cyclo pentadiene - Google Patents
Method of preparing methyl cyclo penlene by continuous hydrogenation of methyl cyclo pentadiene Download PDFInfo
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- CN1911876A CN1911876A CN 200510028608 CN200510028608A CN1911876A CN 1911876 A CN1911876 A CN 1911876A CN 200510028608 CN200510028608 CN 200510028608 CN 200510028608 A CN200510028608 A CN 200510028608A CN 1911876 A CN1911876 A CN 1911876A
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- methyl
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- cyclopentadiene
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Abstract
The continuous methyl cyclopentadiene hydrogenating process to prepare methyl cyclopentene is one continuous catalytic hydrogenation reaction of the mixture of methyl 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 reaction system has pressure of 0.9-1.5 MPa and temperature of 60-100 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 methyl 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 3-6.0/hr accounted in liquid phase material, and the reacted heat is transferred via external circulation. The present invention has high yield.
Description
Technical field
The present invention relates to a kind of method for preparing methyl cyclopentene by the methyl cyclopentadiene selective hydrogenation.
Background technology
Methyl cyclopentene is the intermediate of quite a lot of fine chemical product, as can be used for producing various sterilants, resin intermediate etc.Methyl cyclopentene can be obtained by several different methods in the prior art, however the tool industrial applications prospect of the method for producing with the methyl cyclopentadiene hydrogenation.Reference by methyl cyclopentadiene hydrogenation preparing methyl cyclopentene is rare, but because the reaction of it and cyclopentadiene hydrogenating preparing cyclopentene is essentially identical, so the latter has identical reference value.As U.S. Pat 3,994,986 to have introduced the depolymerization of a kind of employing dicyclopentadiene be cyclopentadiene, then the method for two-stage hydrogenation continuous production cyclopentenes.Its adopts tubular reactor is 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 (methyl) 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.In beds, exist local excessive to heat up by inference, thereby caused the part catalyst deactivation, and (methyl) cyclopentadiene very easily produces dimerization reaction and generates two (methyl) cyclopentadiene in this high-temperature zone, and this all will reduce the yield of (methyl) cyclopentenes.
Summary of the invention
The invention provides a kind of method by methyl cyclopentadiene continuous hydrogenation system methyl cyclopentene, the technical problem that it will solve is to adopt better heat-exchange method to remove the reaction heat that methyl cyclopentadiene hydrogenation process produces, thereby make reaction can obtain higher methyl cyclopentene 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 methyl cyclopentadiene continuous hydrogenation system methyl cyclopentene, this method comprise and will carry out catalytic hydrogenation reaction by the fixed bed catalyst bed continuously after methyl 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 methyl cyclopentadiene and solvent is 1: (5～10), the mol ratio of methyl cyclopentadiene and hydrogen are 1: (1.5～3.0).Reacting system pressure is 0.9～1.5MPa, and temperature of reaction is 60～100 ℃.The discharging of reaction solution part, part outer circulation.Reaction solution cooling back and the methyl 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 3～6.0hr 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 60～75 ℃; Solvent is preferably taken from any in methyl alcohol, the trimethyl carbinol or the tertiary amyl alcohol; The load of catalyzer is preferably 4～6hr 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 methyl 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 methyl cyclopentene yield that calculates benchmark can reach about 90% with the methyl 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 methyl 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 methyl 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 methyl cyclopentene 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.
| MCPD/ solvent (weight ratio) | MCPD/H 2(mol ratio) | Reaction pressure (MPa) | Temperature of reaction (℃) | Catalyst loading (hr -1) | M5/M4 (weight ratio) | |
| Embodiment 1 | 1∶10 | 1∶2.0 | 1.2 | 72 | 3.5 | 1∶8 |
| Embodiment 2 | 1∶8 | 1∶1.5 | 1.2 | 92 | 3.0 | 1∶4 |
| Embodiment 3 | 1∶8 | 1∶2.2 | 1.5 | 69 | 5.5 | 1∶8 |
| Embodiment 4 | 1∶8 | 1∶2.2 | 0.9 | 74 | 5.5 | 1∶8 |
| Embodiment 5 | 1∶8 | 1∶2.2 | 1.2 | 68 | 5.5 | 1∶8 |
| Embodiment 6 | 1∶8 | 1∶2.5 | 1.2 | 81 | 5.5 | 1∶12 |
| Embodiment 7 | 1∶8 | 1∶2.2 | 1.2 | 75 | 4.2 | 1∶5 |
| Embodiment 8 | 1∶5 | 1∶3.0 | 1.2 | 60 | 6.0 | 1∶10 |
| Embodiment 9 | 1∶8 | 1∶2.2 | 1.2 | 75 | 5.5 | 1∶8 |
| Embodiment 10 | 1∶8 | 1∶2.2 | 1.2 | 74 | 5.5 | 1∶8 |
Table 2.
| MCPD transformation efficiency (%) | Methyl cyclopentene yield (%) | |
| Embodiment 1 | 94.4 | 90.3 |
| Embodiment 2 | 89.2 | 89.4 |
| Embodiment 3 | 93.3 | 92.1 |
| Embodiment 4 | 92.8 | 90.1 |
| Embodiment 5 | 95.2 | 90.4 |
| Embodiment 6 | 94.9 | 89.9 |
| Embodiment 7 | 89.0 | 88.6 |
| Embodiment 8 | 88.7 | 89.2 |
| Embodiment 9 | 93.0 | 90.6 |
| Embodiment 10 | 95.8 | 91.8 |
(annotate: MCPD is a methyl cyclopentadiene in the table, and M5 is the reaction solution load, and M4 is a reaction solution outer circulation amount.)
Claims (6)
1, a kind of method by methyl cyclopentadiene continuous hydrogenation system methyl cyclopentene, this method comprise and will carry out catalytic hydrogenation reaction by the fixed bed catalyst bed continuously after methyl 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 benzene, toluene, hexanaphthene, ethanol, methyl alcohol, any in the tertiary amyl alcohol or the trimethyl carbinol, the weight ratio of methyl cyclopentadiene and solvent is 1: (5～10), the mol ratio of methyl cyclopentadiene and hydrogen is 1: (1.5～3.0), reacting system pressure is 0.9～1.5MPa, temperature of reaction is 60～100 ℃, it is characterized in that the discharging of reaction solution part, the part outer circulation, reaction solution cooling back and the methyl 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 3～6.0hr 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 system methyl 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 system methyl cyclopentene according to claim 1 is characterized in that described temperature of reaction is 60～75 ℃
4, the method for system methyl cyclopentene according to claim 1 is characterized in that described catalyst loading counts 4～6hr with liquid phase material
-1
5, the method for system methyl 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 system methyl cyclopentene according to claim 1, the mol ratio that it is characterized in that described methyl cyclopentadiene and hydrogen is 1: (2～2.5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200510028608 CN1911876A (en) | 2005-08-09 | 2005-08-09 | Method of preparing methyl cyclo penlene by continuous hydrogenation of methyl cyclo pentadiene |
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|---|---|---|---|
| CN 200510028608 CN1911876A (en) | 2005-08-09 | 2005-08-09 | Method of preparing methyl cyclo penlene by continuous hydrogenation of methyl cyclo pentadiene |
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Cited By (4)
| 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 |
| CN103420776A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for methyl cyclopentene |
| CN106040158A (en) * | 2016-07-18 | 2016-10-26 | 天津鲁华化工有限公司 | Venturi tube used in hydrogenation reaction of dicyclopentadiene and use method of venturi tube |
| CN114436738A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of high-purity methylcyclopentene |
-
2005
- 2005-08-09 CN CN 200510028608 patent/CN1911876A/en active Pending
Cited By (7)
| 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 |
| CN103420776A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for methyl cyclopentene |
| CN103420776B (en) * | 2012-05-22 | 2016-07-27 | 中国石油化工股份有限公司 | A kind of method preparing methyl cyclopentene |
| CN106040158A (en) * | 2016-07-18 | 2016-10-26 | 天津鲁华化工有限公司 | Venturi tube used in hydrogenation reaction of dicyclopentadiene and use method of venturi tube |
| CN106040158B (en) * | 2016-07-18 | 2018-01-12 | 天津鲁华化工有限公司 | A kind of Venturi tube and its application method being used in dicyclopentadiene hydrogenated reaction |
| CN114436738A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of high-purity methylcyclopentene |
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