CN104525192B - Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene - Google Patents
Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene Download PDFInfo
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- CN104525192B CN104525192B CN201410804446.XA CN201410804446A CN104525192B CN 104525192 B CN104525192 B CN 104525192B CN 201410804446 A CN201410804446 A CN 201410804446A CN 104525192 B CN104525192 B CN 104525192B
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- Prior art keywords
- ruthenium
- benzene
- cyclohexene
- selective hydrogenation
- catalyst
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 87
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 229960001763 zinc sulfate Drugs 0.000 claims 1
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000010908 decantation Methods 0.000 abstract description 2
- 239000003929 acidic solution Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- -1 Zinc modified ruthenium Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- QORYBJZFIBBDSH-UHFFFAOYSA-N ruthenium zinc Chemical compound [Zn].[Zn].[Zn].[Ru] QORYBJZFIBBDSH-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing a catalyst used in the preparation of cyclohexene by virtue of selective hydrogenation of benzene. The method comprises the following steps of dissolving a ruthenium precursor in an aqueous solution of metal salt of an additive, placing an acidic solution into an autoclave, carrying out hydrogen reduction on a liquid phase for a certain time at a certain temperature, taking out and washing with water for multiple times by virtue of a decantation method to obtain the ruthenium-additive catalyst for selective hydrogenation of benzene with uniform particle size. When the prepared ruthenium-based catalyst is used in the reaction for preparing cyclohexene by virtue of selective hydrogenation of liquid-phase benzene, the conversion rate of benzene is 43%, and the selectivity of cyclohexene can reach 82%. The preparation method has the advantages of simplicity in steps, easily available raw materials, low cost and environment-friendly process and has good industrial application value.
Description
Technical field
The invention belongs to chemical technology field, it is related to a kind of preparation method of producing cyclohexene with benzene selective hydrogenation catalyst.
Background technology
Cyclohexene is important organic intermediate, is widely used in adipic acid, nylon 6, nylon66 fiber, polyamide and other essences
The production of thin chemicals, has huge industrial economy and is worth and wide market prospect.Right by producing cyclohexene with benzene selective hydrogenation
Prepare the route of nylon-6 and nylon -66 afterwards, because it has raw material abundance, high financial profit, environmental friendliness and production safety etc.
Advantage and extensively concerned.But, from thermodynamically, because benzene selective hydrogenation generates the standard gibbs free energy change of cyclohexene
For -23kj/mol, that benzene complete hydrogenation generates hexamethylene is then -98kj/mo1, and thermodynamically analysis benzene hydrogenation is easier to generate
Hexamethylene, it is very difficult that this route prepares cyclohexene.From the thirties in last century, many researcheres are devoted to exploitation and are suitable for
Producing cyclohexene with benzene selective hydrogenation catalyst.1988, Asahi Kasei Corporation achieved the work of producing cyclohexene with benzene selective hydrogenation first
Industry.The four phase reaction systems that this system is made up of water, oil, hydrogen and solid catalyst, need to add reaction dressing agent and excellent
Different catalyst can be only achieved higher cyclohexene selectivity and yield.
In order to break the technical limitations of producing cyclohexene with benzene selective hydrogenation catalyst, from the nineties in 20th century, many lists of China
Position, such as Zhengzhou University, Fudan University, Dalian Inst of Chemicophysics, Chinese Academy of Sciences etc., have started substantial amounts of liquid phase benzene and have selected
The exploitation of the catalyst of hydrogenation cyclohexene.Industrial using Zinc modified ruthenium unsupported catalyst produce cyclohexene.Unsupported
Type catalyst is mainly prepared by coprecipitation, infusion process, chemical reduction method etc., and optimal with ru-zn catalyst performance, patent has cn
1597098th, cn 1337386, cn1446625 etc..These catalyst need mostly by ruthenium trichloride raw material alkaline chemical precipitation or employing
Alkali liquid washing, complex steps, output waste liquid is more, and in its catalyst of preparing, zn content is higher.The present invention is directed to above-mentioned
Shortcoming, proposes the preparation method that direct hydrogen reducing in zinc salt solution prepares ru-zn catalyst.
Content of the invention
The invention aims to overcoming prior art to prepare in producing cyclohexene with benzene selective hydrogenation catalyst preparation process
Need the defect of co-precipitation step in the presence of precipitant, there is provided a kind of preparation side of producing cyclohexene with benzene selective hydrogenation catalyst
Method, particularly a kind of preparation method of benzene selective hydrogenation ruthenium auxiliary agent catalyst.
The technical scheme is that for achieving the above object, the present invention direct hydrogen in ruthenium salt and zinc salt solution
Ruthenium auxiliary agent catalyst is prepared in reduction, and its step is as follows:
A kind of step of the preparation method of non-loading type producing cyclohexene with benzene selective hydrogenation catalyst is as follows: by the presoma of ruthenium
It is dissolved in the saline solution of metal promoter, above-mentioned solution is loaded in autoclave, in 130-170 DEG C, 800-1200r/min, 4-
Liquid-phase reduction 2-20 hour under 6mpa Hydrogen Vapor Pressure, the pressed powder obtaining, through washing, obtains final product ruthenium-auxiliary agent catalyst.
Preferably, the presoma of described ruthenium is ruthenium trichloride.
Preferably, the saline solution of described metal promoter is zinc sulphate heptahydrate.
Preferably, the concentration of salt solution of described metal promoter is 0.1-1mol/l.
Preferably, the mass ratio of the saline solution of the presoma of described ruthenium and metal promoter is 0.015-0.025:1.
In the present invention, the ruthenium presoma being used is ruthenium trichloride, and the slaine of auxiliary agent is zinc sulphate heptahydrate, institute during reduction
The metal salt concentrations of used additives are 0.1-1mol/l, and the preferable recovery time is 3-18 hour.
Using the catalyst of method of the present invention preparation, when reacting for producing cyclohexene with benzene selective hydrogenation, optimizing
Under conditions of, during benzene conversion ratio 43%, the selectivity of cyclohexene is higher than 82%, reaches the level of industrial applications.
Compared with prior art, it is an advantage of the current invention that: direct hydrogen reducing system in ruthenium salt and aqueous metal salt
Standby ruthenium auxiliary agent catalyst, has high selectivity for producing cyclohexene with benzene selective hydrogenation reaction.The simple low consumption of preparation process, cost
Cheap, auxiliary agent content is low, excellent catalytic effect, has good industrial applications prospect.
Specific embodiment
Embodiment 1
Take 1.6g rucl3·xh2O is dissolved in 60g 0.75mol/l znso4In aqueous solution, load in 250ml autoclave,
In 150 DEG C, 1000r/min, 5mpa h2Take out after lower reduction 6h, using decantation washing, with 300ml water washing 4-6 time, that is,
Obtain ru-zn catalyst.
The catalyst of preparation is used for producing cyclohexene with benzene selective hydrogenation reaction under the following conditions: take the above-mentioned catalysis of 0.12g
Agent, 0.65g zro2Powder, 8.4g znso4·7h2O, 70ml water, 35ml benzene in reactor, at 150 DEG C, 1200r/min,
5.0mpa hydrogen takes upper oil phase after pressure reaction certain time, and using gas chromatographic analysiss product composition, result is listed in table.
Embodiment 2
With embodiment 1, by rucl3·xh2O is dissolved in 0.1mol/l znso4In solution.
Embodiment 3
With embodiment 1, by rucl3·xh2O is dissolved in 1.0mol/l znso4In solution.
Embodiment 4
With embodiment 1, in 170 DEG C, 800r/min, 4mpa h2Lower reduction 3h.
Embodiment 5
With example 1, in 130 DEG C, 1200r/min, 6mpa h2Lower reduction 18h.
Following table is the benzene selective hydrogenation reaction result of embodiment 1-5.In table, zn/ru mass ratio is measured by xrf and is given.
From data above, ruthenium zinc is prepared using hydrogen reducing one-step method in the ruthenium salt of the present invention and zinc salt solution and urges
Agent is applied to producing cyclohexene with benzene selective hydrogenation reaction and has good catalytic performance.This preparation method introduces a small amount of zn
(zn/ru=0.02-0.04) in ruthenium-based catalyst, promote cyclohexene and optionally improve.In benzene conversion ratio 40-43%
More than 81.5% cyclohexene selectivity can be obtained.According to industrial requirement, the selectivity of cyclohexene in benzene conversion ratio 40%
Catalyst higher than 80% just has industrial applications to be worth, thus the catalyst of present invention preparation disclosure satisfy that commercial production needs
Will.
Claims (3)
1. a kind of preparation method of producing cyclohexene with benzene selective hydrogenation catalyst is it is characterised in that its step is as follows: before ruthenium
Drive body to be dissolved in the saline solution of metal promoter, above-mentioned solution is loaded in autoclave, in 130-170 DEG C, 800-1200 r/
Liquid-phase reduction 2-20 hour under min, 4-6 mpa Hydrogen Vapor Pressure, the pressed powder obtaining, through washing, obtains final product ruthenium-auxiliary agent catalyst,
The presoma of described ruthenium is ruthenium trichloride, and the saline solution of described metal promoter is solution of zinc sulfate.
2. method according to claim 1 is it is characterised in that the concentration of salt solution of described metal promoter is 0.1-1
mol/l.
3. method according to claim 1 is it is characterised in that the saline solution of the described presoma of ruthenium and metal promoter
Mass ratio is 0.015-0.025:1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410804446.XA CN104525192B (en) | 2014-12-22 | 2014-12-22 | Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410804446.XA CN104525192B (en) | 2014-12-22 | 2014-12-22 | Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene |
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| CN104525192A CN104525192A (en) | 2015-04-22 |
| CN104525192B true CN104525192B (en) | 2017-01-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620872A (en) * | 2020-05-19 | 2020-09-04 | 南京纽邦生物科技有限公司 | Synthetic method of tetramethyluric acid and special catalyst thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104998631A (en) * | 2015-07-06 | 2015-10-28 | 湖北大学 | Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof |
| CN109433201B (en) * | 2018-12-10 | 2021-09-14 | 郑州师范学院 | Preparation of cyclohexene Ru @ Y by selective hydrogenation of benzene2O3Catalyst, preparation method and application thereof |
| CN113042043A (en) * | 2021-03-24 | 2021-06-29 | 内蒙古瑞翔拓创新材料有限公司 | Ruthenium-based hydrogenation catalyst, aqueous solution of ruthenium-based hydrogenation catalyst, and preparation method and application of aqueous solution |
| CN115430422B (en) * | 2022-09-29 | 2023-07-21 | 北京旭阳科技有限公司 | Preparation method of spherical twin crystal ruthenium catalyst, catalyst prepared by using spherical twin crystal ruthenium catalyst and method for preparing cyclohexene by using spherical twin crystal ruthenium catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4331839A1 (en) * | 1993-09-20 | 1995-03-23 | Basf Ag | Process for the preparation of cyclohexene by partial hydrogenation of benzene |
| DE4423725A1 (en) * | 1994-07-08 | 1996-01-11 | Basf Ag | Process for the continuous production of cyclohexene by partial hydrogenation of benzene |
| JPH09208499A (en) * | 1996-02-07 | 1997-08-12 | Mitsubishi Chem Corp | Production of cycloolefin |
| JP4025411B2 (en) * | 1997-04-16 | 2007-12-19 | 旭化成ケミカルズ株式会社 | Method for producing cycloolefin |
| JPH1129503A (en) * | 1997-07-08 | 1999-02-02 | Asahi Chem Ind Co Ltd | Production of cycloolefin |
| JP5306586B2 (en) * | 2006-09-07 | 2013-10-02 | 旭化成ケミカルズ株式会社 | Method for producing cyclohexene |
| CN103191732B (en) * | 2012-01-10 | 2016-04-27 | 武汉优立克新材料科技有限公司 | A kind of method of partial hydrogenation of benzene cyclohexene catalyst and production cyclohexene |
| CN103721709B (en) * | 2013-12-23 | 2015-08-12 | 浙江大学 | A kind of preparation method of producing cyclohexene with benzene selective hydrogenation catalyst |
| CN104190417B (en) * | 2014-07-21 | 2017-01-25 | 复旦大学 | Preparation method of ruthenium-based bimetallic catalyst for preparing cyclohexene by partial hydrogenation of benzene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111620872A (en) * | 2020-05-19 | 2020-09-04 | 南京纽邦生物科技有限公司 | Synthetic method of tetramethyluric acid and special catalyst thereof |
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