CN104525192A - 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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- CN104525192A CN104525192A CN201410804446.XA CN201410804446A CN104525192A CN 104525192 A CN104525192 A CN 104525192A CN 201410804446 A CN201410804446 A CN 201410804446A CN 104525192 A CN104525192 A CN 104525192A
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- benzene
- cyclohexene
- ruthenium
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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, relate 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 the production of adipic acid, nylon 6, nylon66 fiber, polyamide and other fine chemicals, has huge industrial economy and is worth and wide market prospects.Then prepared the route of nylon-6 and nylon-66 by producing cyclohexene with benzene selective hydrogenation, there is the advantages such as raw material abundance, high financial profit, environmental friendliness and production safety and extensively concerned because of it.But, from thermodynamics, the standard Gibbs free energy change generating cyclohexene due to benzene selective hydrogenation is-23kJ/mol, and that benzene complete hydrogenation generates cyclohexane is then-98kJ/mo1, thermodynamics is analyzed benzene hydrogenation and more easily generate cyclohexane, it is very difficult that this route prepares cyclohexene.From the thirties in last century, many researchers are devoted to develop the producing cyclohexene with benzene selective hydrogenation catalyst be suitable for.1988, Asahi Kasei Corporation achieved the industrialization of producing cyclohexene with benzene selective hydrogenation first.The four phase reaction systems that this system is made up of water, oil, hydrogen and solid catalyst, need add reaction dressing agent and excellent catalyst and just can reach the selective and yield of higher cyclohexene.
In order to break the technology restriction of producing cyclohexene with benzene selective hydrogenation catalyst, the nineties in 20th century rises, Duo Jia unit of China, as Zhengzhou University, Fudan University, Dalian Inst of Chemicophysics, Chinese Academy of Sciences etc., starts the exploitation of the catalyst of a large amount of liquid phase producing cyclohexene with benzene selective hydrogenation.The Zinc modified ruthenium unsupported catalyst of industrial use produces cyclohexene.Unsupported catalyst is primarily of preparations such as coprecipitation, infusion process, chemical reduction methods, and best with Ru-Zn catalyst performance, patent has CN 1597098, CN 1337386, CN1446625 etc.These catalyst mostly need ruthenium trichloride raw material alkaline chemical precipitation or adopt alkali liquid washing, and complex steps, output waste liquid is more, and in its catalyst prepared, Zn content is higher.The present invention is directed to above-mentioned shortcoming, propose direct hydrogen reducing in zinc salt solution and prepare the preparation method of Ru-Zn catalyst.
Summary of the invention
The object of the invention is to prepare in producing cyclohexene with benzene selective hydrogenation catalyst preparation process to overcome prior art the defect needing co-precipitation step under precipitating reagent exists, provide a kind of preparation method of producing cyclohexene with benzene selective hydrogenation catalyst, particularly a kind of benzene selective hydrogenation Liao ?the preparation method of auxiliary agent catalyst.
Technical scheme of the present invention is: for achieving the above object, the present invention's direct hydrogen reducing in ruthenium salt and zinc salt solution prepare Liao ?auxiliary agent catalyst, its step is as follows:
The step of a kind of preparation method of non-loading type producing cyclohexene with benzene selective hydrogenation catalyst is as follows: be dissolved in the salting liquid of metal promoter by the presoma of ruthenium, above-mentioned solution is loaded in autoclave, at 130-170 DEG C, liquid-phase reduction 2-20 hour under 800-1200r/min, 4-6MPa Hydrogen Vapor Pressure, the pressed powder obtained, through washing, obtains ruthenium-auxiliary agent catalyst.
Preferably, the presoma of described ruthenium is ruthenium trichloride.
Preferably, the salting liquid of described metal promoter is white vitriol.
Preferably, the concentration of salt solution of described metal promoter is 0.1-1mol/L.
Preferably, the mass ratio of the presoma of described ruthenium and the salting liquid of metal promoter is 0.015-0.025:1.
In the present invention, the ruthenium presoma used is ruthenium trichloride, and the slaine of auxiliary agent is white vitriol, and metal salt concentrations adjuvant used during reduction is 0.1-1mol/L, and the good recovery time is 3-18 hour.
Use catalyst prepared by method of the present invention, when reacting for producing cyclohexene with benzene selective hydrogenation, under optimal conditions, during benzene conversion ratio 43%, cyclohexene selective higher than 82%, reaches the level of industrial applications.
Compared with prior art, the invention has the advantages that: in ruthenium salt and aqueous metal salt direct hydrogen reducing prepare Liao ?auxiliary agent catalyst, for producing cyclohexene with benzene selective hydrogenation reaction there is high selectivity.The simple low consumption of preparation process, with low cost, auxiliary agent content is low, excellent catalytic effect, has good industrial applications prospect.
Detailed description of the invention
Embodiment 1
Get 1.6g RuCl
3xH
2o is dissolved in 60g 0.75mol/L ZnSO
4in the aqueous solution, load in 250mL autoclave, in 150 DEG C, 1000r/min, 5MPa H
2take out after lower reduction 6h, adopt decantation washing, with 300mL water washing 4-6 time, namely obtain Ru-Zn catalyst.
The catalyst of preparation is used under the following conditions producing cyclohexene with benzene selective hydrogenation reaction: get the above-mentioned catalyst of 0.12g, 0.65g ZrO
2powder, 8.4g ZnSO
47H
2o, 70ml water, 35ml benzene, in reactor, at 150 DEG C, gets upper oil phase after reacting certain hour under 1200r/min, 5.0MPa hydrogen pressure, adopts gas chromatographic analysis product composition, the results are shown in table.
Embodiment 2
With embodiment 1, by RuCl
3xH
2o is dissolved in 0.1mol/L ZnSO
4in solution.
Embodiment 3
With embodiment 1, by RuCl
3xH
2o is dissolved in 1.0mol/L ZnSO
4in solution.
Embodiment 4
With embodiment 1, at 170 DEG C, 800r/min, 4MPa H
2lower reduction 3h.
Embodiment 5
With example 1, at 130 DEG C, 1200r/min, 6MPa H
2lower 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 provides.
From above data, adopt hydrogen reducing one-step method in ruthenium salt of the present invention and zinc salt solution prepare ruthenium zinc catalyst be applied to producing cyclohexene with benzene selective hydrogenation reaction there is good catalytic performance.This preparation method introduces a small amount of Zn (Zn/Ru=0.02-0.04) in ruthenium-based catalyst, facilitates cyclohexene and optionally improves.More than 81.5% cyclohexene can be obtained selective when benzene conversion ratio 40-43%.According to industrial requirement, when benzene conversion ratio 40%, the selective catalyst higher than 80% of cyclohexene just has industrial applications to be worth, and the catalyst that thus prepared by the present invention can meet industrial production needs.
Claims (5)
1. a preparation method for producing cyclohexene with benzene selective hydrogenation catalyst, is characterized in that, its step is as follows: be dissolved in the salting liquid of metal promoter by the presoma of ruthenium, is loaded by above-mentioned solution in autoclave, at 130-170
oliquid-phase reduction 2-20 hour under C, 800-1200 r/min, 4-6 MPa Hydrogen Vapor Pressure, the pressed powder obtained, through washing, obtains ruthenium-auxiliary agent catalyst.
2. method according to claim 1, is characterized in that the presoma of described ruthenium is ruthenium trichloride.
3. method according to claim 1, is characterized in that the salting liquid of described metal promoter is white vitriol.
4. method according to claim 1, is characterized in that the concentration of salt solution of described metal promoter is 0.1-1 mol/L.
5. method according to claim 1, is characterized in that the mass ratio of the presoma of described ruthenium and the salting liquid of metal promoter is 0.015-0.025:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109433201A (en) * | 2018-12-10 | 2019-03-08 | 郑州师范学院 | Producing cyclohexene with benzene selective hydrogenation Ru@Y2O3Catalyst and its preparation method and application |
| 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 |
| CN115430422A (en) * | 2022-09-29 | 2022-12-06 | 北京旭阳科技有限公司 | Preparation method of spherical twin crystal ruthenium catalyst, catalyst prepared by preparation method, and method for preparing cyclohexene by using catalyst |
Families Citing this family (1)
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| CN111620872B (en) * | 2020-05-19 | 2021-02-09 | 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109433201A (en) * | 2018-12-10 | 2019-03-08 | 郑州师范学院 | Producing cyclohexene with benzene selective hydrogenation Ru@Y2O3Catalyst and its preparation method and application |
| 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 |
| CN115430422A (en) * | 2022-09-29 | 2022-12-06 | 北京旭阳科技有限公司 | Preparation method of spherical twin crystal ruthenium catalyst, catalyst prepared by preparation method, and method for preparing cyclohexene by using catalyst |
| 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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