CN103864560B - Method for preparing cyclohexane by benzene hydrogenation - Google Patents
Method for preparing cyclohexane by benzene hydrogenation Download PDFInfo
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- CN103864560B CN103864560B CN201210528113.XA CN201210528113A CN103864560B CN 103864560 B CN103864560 B CN 103864560B CN 201210528113 A CN201210528113 A CN 201210528113A CN 103864560 B CN103864560 B CN 103864560B
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- benzene
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 243
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910016467 AlCl 4 Inorganic materials 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 13
- 230000009466 transformation Effects 0.000 description 13
- 238000005070 sampling Methods 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing cyclohexane by benzene hydrogenation; the benzene and the hydrogen are contacted and reacted for 1 to 8 hours at the temperature of 50 to 100 ℃, the pressure of 0.3 to 2.0Mpa and the stirring speed of 200 to 700 r/min, and then the reaction solution is subjected to reactionSeparating to obtain a hydrogenation product; catalyst consisting of [ RMIm][RuCl4]And [ RMIm][CoCl3]And [ RMIm][AlCl4]Composition, [ RMIm][RuCl4]∶[RMIm][CoCl3]∶[RMIm][AlCl4]The molar ratio of to (B) is 1: 2-4: 6-12; r is ethyl or butyl, MIm is methyl imidazole group addition (based on the mass of benzene, the amount of catalyst is counted by Ru) is 0.001-0.018%, and the amount of dispersing solvent is 1.0-3.0 times of the mass of benzene; the method has 100 percent of benzene conversion rate and 100 percent of cyclohexane selectivity.
Description
Technical field
The present invention relates to a kind of method of preparing cyclohexane by hydrogenating benzene.
Background technology
Hexanaphthene is a kind of important Organic Chemicals, and 90% is used for producing hexanodioic acid, hexanolactam.In addition the fine solvent of hexanaphthene or ether of cellulose, resin, wax, grease, pitch and rubber is the medium of organic synthesis and crystallization, is the remover etc. of coating and varnish.The method of industrial production hexanaphthene can be divided into two classes: the fractionation method for refining of benzene hydrogenation method and petroleum hydrocarbon cut.Current industrial catalytic benzene hydrogenation method is the main production process of hexanaphthene, can be divided into gas-phase catalysis and liquid catalytic again.Catalyzer conventional at present has loaded and metallocene type, reacts and carries out under higher temperature and pressure condition.The metal that supported catalyst uses has Ni, Pt, Pa etc., needs to carry out restoring operation, produce waste water and waste gas, contaminate environment in catalyst production process before using.
Chinese patent CN88105065.2 describes a kind of benzene hydrogenating homogeneous catalyst, and its active metal selects transiting metal nickel or cobalt, preferentially selects metallic nickel, produces waste water in its preparation process, thus needs to detect waste water and process; Use this material dialled of living very much of aluminum alkyls in addition, add the complicacy of production process and the difficulty of operation, all there is potential safety hazard in production and storage process, the use temperature of catalyzer is 180 DEG C, and temperature is higher.
Chinese patent CN200810114879.7 describes a kind of method adopting the ionic-liquid catalyst containing ruthenium to carry out preparing cyclohexane by hydrogenating benzene, in the catalyzer that the reaction carrying out benzene hydrogenation introduced in embodiment 3 uses, Ru content is very large, consumption 10ml according to benzene carries out quality conversion, and in catalyzer, the consumption of Ru is more than 0.2%.Chinese patent CN02157243.7 describes a kind of producing cyclohexane by benzene hydrogenation platinum group catalyst and preparation method thereof, and the reaction conditions of catalyzer is temperature of reaction 150 ~ 600 DEG C, and reaction pressure 2.0 ~ 5.0Mpa, temperature and pressure is all higher.Chinese patent CN200910080080.5 describes a kind of platinum-cobalt dual-metal catalyst with room-temperature benzene hydrogenation activity and preparation method thereof, catalyzer needs to reduce in hydrogen/or rare gas element before using, and then carrying out benzene hydrogenation, the peak rate of conversion of benzene is only 32% in an embodiment.
Chinese patent CN00111762.9 describes a kind of hydrogenation process for preparing cyclohexane by phase change method, and the hot(test)-spot temperature of reactor is 260 ~ 280 DEG C, and catalyzer is palladium content is 0.5%, and temperature is higher, and the consumption of catalyzer is also comparatively large, and catalyzer cost is higher.Chinese patent CN200610169517.9 describes a kind of method preparing hexanaphthene, and adopt nickel system, platinum group or palladium series hydrocatalyst, bottom temperature is 130 ~ 220 DEG C, and tower top working pressure is 0.5 ~ 2.2Mpa, and bottom temperature is higher.Chinese patent CN01136733.4 describes a kind of external coupler of rectifying reaction and synthetic process of preparing cyclohexane by catalyst hydrogenation of benzene, reactor operates at ambient pressure, in reactor, bed temperature is distributed in 130 ~ 180 DEG C, in reactor, the per pass conversion of benzene should remain on 30% ~ 50%, temperature of reaction is higher, and per pass conversion is lower.
Chinese patent CN201010291922.4 describes a kind of method of preparing cyclohexane by hydrogenating benzene, for in current benzene hydrogenation process in reaction system water-content fluctuation adaptability and to suppress carbon distribution generate two aspect requirements, propose under reactor inlet temperature 100 DEG C ~ 320 DEG C, reaction pressure 0.1MPa ~ 4.0MPa condition, hydrogen containing certain mol ratio/benzene gas mixture is passed into reactor and benzene hydrogenating catalyst contact preparation hexanaphthene, temperature of reaction is higher.
The present invention has following advantage: under the effect of environment-friendly catalyzer, realize preparing cyclohexane by hydrogenating benzene, simplify technical process.Catalyzer working conditions is gentle, and convenient operation is 50 ~ 100 DEG C in temperature of reaction, and reaction pressure is 0.3 ~ 2.0Mpa, carries out preparing cyclohexane by hydrogenating benzene under stirring velocity 200 ~ 700 revs/min of conditions.Instant invention overcomes traditional benzene hydrogenating catalyst and be easy to oxidation in storage and use procedure, in catalyzer, there is many defects such as a large amount of inflammable volatile liquid organic solvents.Catalyzer is Preparation and storage under normal temperature and pressure conditions, not containing inflammable volatile liquid organic solvent in finished catalyst, need not carry out nitrogen protection, add the security that catalyzer stores and uses.Catalyzer can need not use through catalyst reduction, simplifies technological operation.Catalyzer of the present invention and product are easy to be separated, and catalyst levels is less, reach the catalytic effect of catalyzer in the past equally, reduce the production cost of hexanaphthene.Add-on (based on the quality of benzene, catalyzer is with the gauge of Ru) is only 0.001 ~ 0.018% and just can realizes benzene conversion rate and be up to 100%, and the selectivity of hexanaphthene reaches 100%.The process conditions of preparing cyclohexane by hydrogenating benzene is gentle, at lower catalyst levels, under lesser temps (50 ~ 100 DEG C) and lower pressure condition, realizes preparing cyclohexane by hydrogenating benzene.
Summary of the invention
The object of this invention is to provide a kind of method of preparing cyclohexane by hydrogenating benzene, solve temperature of reaction of the prior art and reaction pressure high, the problem of low conversion rate.
The method of a kind of preparing cyclohexane by hydrogenating benzene described in invention.Comprise the following steps:
Be 50 ~ 100 DEG C in temperature of reaction, reaction pressure is 0.3 ~ 2.0Mpa, and stirring velocity 200 ~ 700 revs/min, makes benzene contact with hydrogen, and the reaction times is 1 ~ 8 hour, and reaction terminates to carry out separation to reaction solution and obtain hydrogenation products afterwards; Described catalyzer is by [RMIm] [RuCl
4] and [RMIm] [CoCl
3] and [RMIm] [AlCl
4] composition, [RMIm] [RuCl
4]: [RMIm] [CoCl
3]: [RMIm] [AlCl
4] mol ratio be 1: 2 ~ 4: 6 ~ 12, wherein R is ethyl or butyl, and MIm is Methylimidazole group, and catalyst charge is (based on the quality of benzene, catalyzer is with the gauge of Ru) be 0.001 ~ 0.018%, catalyzer dispersion solvent amount is 1.0 ~ 3.0 times of benzene quality.
For realizing goal of the invention, good temperature of reaction is 70 ~ 90 DEG C.
For realizing goal of the invention, good reaction pressure is 0.5 ~ 1.0Mpa.
For realizing goal of the invention, good stirring velocity is 300 ~ 600 revs/min.
For realizing goal of the invention, the good reaction times is 2 ~ 6 hours.
For realizing goal of the invention, good catalyst charge (based on the quality of benzene, catalyzer is with the gauge of Ru) is 0.003 ~ 0.015%.
First in 300ml autoclave, add benzene, then add catalyzer, catalyzer is by [RMIm] [RuCl
4] and [RMIm] [CoCl
3] and [RMIm] [AlCl
4] composition, [RMIm] [RuCl
4]: [RMIm] [CoCl
3]: [RMIm] [AlCl
4] mol ratio be 1: 2 ~ 4: 6 ~ 12, wherein R is ethyl or butyl, MIm is Methylimidazole group, catalyst charge (based on the quality of benzene, catalyzer is with the gauge of Ru) is 0.001 ~ 0.018%, then adds catalyzer dispersion solvent, catalyzer dispersion solvent amount is 1.0 ~ 3.0 times of benzene quality, after nitrogen replacement 3 ~ 5 times, then use hydrogen exchange, then carry out preparing cyclohexane by hydrogenating benzene.Reaction conditions is 50 ~ 100 DEG C in temperature of reaction, reaction pressure is 0.3 ~ 2.0Mpa, stirring velocity 200 ~ 700 revs/min, benzene is contacted with hydrogen, reaction times is 1 ~ 8 hour, and reaction terminates to carry out separation to reaction solution and obtain hydrogenation products afterwards, detects through gas chromatographic analysis, the transformation efficiency of benzene reaches as high as 100%, and the selectivity of hexanaphthene reaches 100%.
Under the effect of environment-friendly catalyzer, realize preparing cyclohexane by hydrogenating benzene, simplify technical process.Catalyzer working conditions is gentle, and convenient operation is 50 ~ 100 DEG C in temperature of reaction, and reaction pressure is 0.3 ~ 2.0Mpa, carries out preparing cyclohexane by hydrogenating benzene under stirring velocity 200 ~ 700 revs/min of conditions.Instant invention overcomes traditional benzene hydrogenating catalyst and be easy to oxidation in storage and use procedure, in catalyzer, there is many defects such as a large amount of inflammable volatile liquid organic solvents.Catalyzer is Preparation and storage under normal temperature and pressure conditions, not containing inflammable volatile liquid organic solvent in finished catalyst, need not carry out nitrogen protection, add the security that catalyzer stores and uses.Catalyzer can need not use through catalyst reduction, simplifies technological operation.
Catalyzer of the present invention and product are easy to be separated, and catalyst levels is less, reach the catalytic effect of catalyzer in the past equally, reduce the production cost of hexanaphthene.Add-on (based on the quality of benzene, catalyzer is with the gauge of Ru) is only 0.001 ~ 0.018% and just can realizes benzene conversion rate and be up to 100%, and the selectivity of hexanaphthene reaches 100%.The process conditions of preparing cyclohexane by hydrogenating benzene is gentle, at lower catalyst levels, under lesser temps (50 ~ 100 DEG C) and lower pressure condition, realizes preparing cyclohexane by hydrogenating benzene.
Embodiment
Embodiment 1
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.001%(is with Ru gauge), add 20ml water again, temperature of reaction 70 DEG C, reaction pressure 1.0MPa, under stirring the condition of 400 revs/min, reaction is after 3 hours, and gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 92.89%, and hexanaphthene selectivity is 100%.
Embodiment 2
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.003%(is with Ru gauge), add 20ml water again, temperature of reaction 80 DEG C, reaction pressure 1.0MPa, react 3 hours under stirring 600 revs/min of conditions, gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 98.12%, and hexanaphthene selectivity is 100%.
Embodiment 3
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.008%(is with Ru gauge), add 40ml water again, temperature of reaction 100 DEG C, reaction pressure 0.8MPa, react 4 hours under stirring the condition of 400 revs/min, gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 99.69%, and hexanaphthene selectivity is 100%.
Embodiment 4
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.005%(is with Ru gauge), add 40ml water again, temperature of reaction 70 DEG C, reaction pressure 1.0MPa, react 4 hours under stirring the condition of 400 revs/min, gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 99.75%, and hexanaphthene selectivity is 100%.
Embodiment 5
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.01%(is with Ru gauge), add 40ml water again, temperature of reaction 70 DEG C, reaction pressure 1.0MPa, react 4 hours under stirring the condition of 400 revs/min, gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 99.97%, and hexanaphthene selectivity is 100%.
Embodiment 6
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.01%(is with Ru gauge), add 60ml water again, temperature of reaction 100 DEG C, hydrogen pressure 0.9MPa, react 4 hours under stirring the condition of 500 revs/min, gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 99.92%, and hexanaphthene selectivity is 100%.
Embodiment 7
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.006%(is with Ru gauge), add 40ml water again, temperature of reaction 100 DEG C, reaction pressure 0.8MPa, react 4 hours under stirring the condition of 500 revs/min, gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 99.89%, and hexanaphthene selectivity is 100%.
Embodiment 8
By catalyst separating used in embodiment 7 out, place after 15 days and use.Measuring 20ml benzene with graduated cylinder pours in reactor, catalyzer adopts isolated catalyzer in embodiment 7, add 40ml water again, in temperature of reaction 100 DEG C of temperature, reaction pressure 1.0MPa, react 4 hours under stirring the condition of 500 revs/min, gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 99.88%, and hexanaphthene selectivity is 100%.
Embodiment 9
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.015%(is with Ru gauge), add 40ml water again, temperature of reaction 80 DEG C, reaction pressure is 2.0MPa, and stirring is react 3 hours under the condition of 300 revs/min, sampling analysis, the transformation efficiency of benzene is 100%, and hexanaphthene selectivity is 100%.
Embodiment 10
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.01%(is with Ru gauge), add 40ml water again, temperature of reaction 80 DEG C, reaction pressure is 0.3MPa, and stirring is react 8 hours under the condition of 200 revs/min, sampling analysis, the transformation efficiency of benzene is 88.64%, and hexanaphthene selectivity is 100%.
Embodiment 11
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.001%(is with Ru gauge), add 40ml water again, temperature of reaction 60 DEG C, reaction pressure 0.7MPa, stirring is react after 1 hour under the condition of 200 revs/min, and gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 37.48%, and hexanaphthene selectivity is 100%.
Embodiment 12
Measuring 20ml benzene with graduated cylinder pours in reactor, catalyst charge is that 0.003%(is with Ru gauge), add 20ml water again, temperature of reaction 80 DEG C, reaction pressure 1.0MPa, react 6 hours under stirring 600 revs/min of conditions, gas chromatographic analysis is carried out in sampling, the transformation efficiency of benzene is 100%, and hexanaphthene selectivity is 100%.
Claims (3)
1. a method for preparing cyclohexane by hydrogenating benzene, is characterized in that: be 70 ~ 90 DEG C in temperature of reaction, and reaction pressure is 0.5 ~ 1.0Mpa, stirring velocity 300 ~ 600 revs/min, benzene is contacted with hydrogen, and the reaction times is 2 ~ 6 hours, and reaction terminates to carry out separation to reaction solution and obtain hydrogenation products afterwards;
Catalyzer is by [RMIm] [RuCl
4] and [RMIm] [CoCl
3] and [RMIm] [AlCl
4] composition, [RMIm] [RuCl
4]: [RMIm] [CoCl
3]: [RMIm] [AlCl
4] mol ratio be 1: 2 ~ 4: 6 ~ 12, wherein R is ethyl or butyl, and MIm is Methylimidazole group, and catalyst charge is based on the quality of benzene, catalyzer is with the gauge of Ru for 0.001 ~ 0.018%, and catalyzer dispersion solvent amount is 1.0 ~ 3.0 times of benzene volume.
2. the method for a kind of preparing cyclohexane by hydrogenating benzene according to claim 1, is characterized in that: the add-on of catalyzer, based on the quality of benzene, catalyzer with the gauge of Ru for 0.003 ~ 0.015%.
3. the method for a kind of preparing cyclohexane by hydrogenating benzene according to claim 1, is characterized in that: catalyzer dispersion solvent is water.
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|---|---|---|---|
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|---|---|---|---|---|
| CN102757298A (en) * | 2011-04-28 | 2012-10-31 | 中国石油天然气股份有限公司 | Method for preparing cyclohexane by benzene hydrogenation |
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| CN102757298A (en) * | 2011-04-28 | 2012-10-31 | 中国石油天然气股份有限公司 | Method for preparing cyclohexane by benzene hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| "Ru-Zn/[BEIM]Cl催化剂的制备及其性能研究";刘俊红;《中国优秀硕士学位论文全文数据库工程科技I辑》;20110115(第01期);B014-635，第13页 * |
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