CN104923222A - Preparation method of catalyst for cyclohexene prepared by selective benzene hydrogenation, and catalyst prepared by method - Google Patents
Preparation method of catalyst for cyclohexene prepared by selective benzene hydrogenation, and catalyst prepared by method Download PDFInfo
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- CN104923222A CN104923222A CN201510382821.0A CN201510382821A CN104923222A CN 104923222 A CN104923222 A CN 104923222A CN 201510382821 A CN201510382821 A CN 201510382821A CN 104923222 A CN104923222 A CN 104923222A
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- 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
Abstract
The invention relates to a preparation method of a catalyst for cyclohexene prepared by selective benzene hydrogenation. The method comprises the following steps: uniformly mixing a surfactant dissolved in water in advance with the water solution of ruthenium salt and zinc salt so as to obtain a mixture; adding an alkaline liquid in the mixture in a dripping manner so as to generate sedimentation, and performing reduction with a reducing agent so as to form nanometer ruthenium and zinc with stable surfactant; filtering the prepared nanometer ruthenium and zinc, and washing the filtered nanometer ruthenium and zinc so as to obtain the highly dispersed nanometer ruthenium-zinc catalyst, wherein based on total weight of the catalyst, the catalyst comprises 70-95 wt% of ruthenium, and 5-30 wt% of zinc. In the preparation of the catalyst, the particle diameter of ruthenium and zinc particles is 1-5nm. The catalyst prepared by the method disclosed by the invention has higher activity, higher yield of cyclohexene, and longer service life. The method disclosed by the invention is simple in preparation process and high in repeatability.
Description
The application is the applying date is on September 13rd, 2011, and application number is 201110270359.7, and denomination of invention is the divisional application of the application for a patent for invention of " preparation method of the catalyst of producing cyclohexene with benzene selective hydrogenation and the catalyst prepared by the method ".
Technical field
The preparation method that the present invention relates to a kind of catalyst of producing cyclohexene with benzene selective hydrogenation and the catalyst prepared by the method.
Background technology
Cyclohexene, as the intermediate of organic synthesis, is widely used in the production of adipic acid, nylon-6, nylon-66, polyamide, polyester and other fine chemicals.Cyclohexene and downstream product thereof, have important industrial use and wide market prospects, and preparing cyclohexene from benzene added with hydrogen has huge industrial economy and is worth.
At present, the production of nylon-6, nylon-66, what generally adopt both at home and abroad is benzene complete hydrogenation: namely first generate cyclohexane by benzene complete hydrogenation, then generates the mixture route of cyclohexanone and cyclohexanol via cyclohexane oxidation.Because cyclohexane oxidation belongs to radical reaction, can only operate under lower conversion ratio.Technological process is long, and step is many, and yield is low, and energy consumption is large, and easily causes environmental pollution.
Partial hydrogenation of benzene: namely produce cyclohexene by partial hydrogenation of benzene, then cyclohexene hydration obtains the route of cyclohexanol, is the new technology abroad proposed the nineties in 20th century.By contrast, this process safety is efficient, carbon atom utilization rate 100%, and hydrogen depletion few 1/3, without discarded object and environmental pollution, has the features such as atom economy benefit and environmental friendliness, represent the developing direction of this technical field.But the where the shoe pinches of partial hydrogenation of benzene route is: benzene hydrogenation is a successive reaction, be difficult to rest on the intermediate product cyclohexene stage.Partial hydrogenation of benzene produces cyclohexene, normally adopts ruthenium zinc as catalyst, under aqueous systems, carries out hydrogenation reaction.At present, there is the scheme much preparing ruthenium zinc catalyst, as being supported on carrier by ruthenium zinc, as silica, aluminium oxide, barium sulfate and zirconia etc. (JP-A-57-130926, JP-A-61-40226, CN01122208.5, CN200510017578.9).But, consider that while introducing carrier, impurity also may be introduced thereupon, may cause the service life reduction of catalyst like this.Therefore, we have developed a kind of carrier that can be removed by washing.
Summary of the invention
In order to solve the problem, an object of the present invention is to provide a kind of preparation method of catalyst of new producing cyclohexene with benzene selective hydrogenation, the method adopts surfactant as carrier, prevents the reunion of ruthenium zinc nano particle, can form stable nanometer ruthenium zinc catalyst; After reaction, by washing removing surfactant, the nanometer ruthenium zinc catalyst of high dispersive can be obtained, thus improve the activity and selectivity of catalyst.
Therefore, the invention provides a kind of preparation method of catalyst of producing cyclohexene with benzene selective hydrogenation, the method comprises the following steps:
(1) by the aqueous solution Homogeneous phase mixing of the surfactant that is dissolved in advance in water and ruthenium salt and zinc salt, then use alkali lye to make it precipitation, then with reducing agent reduction, form the nanometer ruthenium zinc of surfactants stabilize;
(2) filtered by obtained nanometer ruthenium zinc, wash, obtain the nanometer ruthenium zinc catalyst of high dispersive, wherein, based on the gross weight of catalyst, ruthenium is 70 ~ 95 % by weight, and zinc is 5 ~ 30 % by weight.
Wherein, in step (1), described ruthenium salt be selected from ruthenium bromide, ruthenic chloride, nitric acid ruthenium and acetic acid ruthenium one or more; Described zinc salt be selected from zinc sulfate, zinc chloride, zinc acetate and zinc nitrate one or more; The concentration of the aqueous solution of described ruthenium salt and zinc salt is 0.001 ~ 0.1mol/L, preferably 0.01 ~ 0.05mol/L separately;
Described surfactant be selected from Sodium Polyacrylate, dodecyl sodium sulfate, perfluoro octyl sulfonic acid sodium, softex kw and PVP one or more; The weight ratio of described surfactant and metal Ru and zinc total amount is 100:1 ~ 0.1:1, preferred 20:1 ~ 1:1;
Described alkali be selected from NaOH, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, caustic alcohol and potassium ethoxide one or more; The concentration of described alkali lye is 0.01 ~ 100mol/L, preferably 0.1 ~ 10mol/L;
Described precipitation temperature is 25 ~ 100 DEG C, preferably 50 ~ 80 DEG C; Sedimentation time is 0.1 ~ 10 hour, preferably 1 ~ 2 hour;
Described reducing agent is H
2or NaBH
4deng, be preferably H
2.As use H
2when making reducing agent, pressure is 0.1 ~ 4MPa, preferably 2 ~ 4MPa; Recovery time is 0.1 ~ 20 hour, preferably 12 ~ 15 hours; Reduction temperature is 40 ~ 200 DEG C, preferably 100 ~ 200 DEG C;
In the catalyst of preparation, the particle diameter of metal Ru zinc particle is 1 ~ 10nm, preferably 1 ~ 5nm.
Another object of the present invention is to provide the catalyst of the producing cyclohexene with benzene selective hydrogenation prepared by said method.
The catalyst of the producing cyclohexene with benzene selective hydrogenation prepared according to said method is used for the reaction of producing cyclohexene with benzene selective hydrogenation by following method:
(1) preparation of slurries: slurries are made up of deionized water, catalyst of the present invention, zirconium dioxide and zinc sulfate, the weight ratio of catalyst and zirconium dioxide is 1:0.01 ~ 1:10; The weight ratio of zinc sulfate and deionized water is 1% ~ 25%, and the weight ratio of catalyst and deionized water is 0.1% ~ 10%;
(2) benzene hydrogenation: add benzene in obtained slurries, the weight ratio of benzene and slurries is 1:2 ~ 5, then passes into hydrogen and reacts, and wherein, hydrogen-pressure 1 ~ 5MPa, reaction temperature 100 ~ 200 DEG C, mixing speed is 500 ~ 1000r/min.
Beneficial effect of the present invention also comprises the following aspects:
1, surfactant is one or more mixture.
2, surfactant prevents ruthenium zinc nano particle from reuniting, and catalytic activity is high, and the life-span is long.
3, method for preparing catalyst is simple, and repeatability is excellent, and nano-metal particle narrow diameter distribution, domain size distribution is mainly 3-5 nanometer.
4, the filtrate after filtering can recycle.
5, by washing removing surfactant, the nanometer ruthenium zinc catalyst of high dispersive can be obtained.
Accompanying drawing explanation
Fig. 1 is the TEM figure of catalyst prepared by embodiment 2;
Fig. 2 is the grain size distribution of catalyst prepared by embodiment 2;
Fig. 3 is the TEM figure of catalyst prepared by comparative example 1;
Fig. 4 is the grain size distribution of catalyst prepared by comparative example 1.
Detailed description of the invention
Below in conjunction with embodiment, invention is described further.
Embodiment 1
4g PVP is dissolved in the water, adds 0.5g RuCl wherein
3nH
2the aqueous solution of O (Ru content 40% (weight)) and 0.08g ZnSO
47H
2the aqueous solution (PVP: Ru=20:1 (weight)) of O, Homogeneous phase mixing.Then in above-mentioned solution, drip the NaOH aqueous solution of 4ml 10mol/L, stir 3 hours at 60 DEG C, aged overnight.Then the solution obtained is joined in 60ml autoclave, at 150 DEG C, with the H of 5MPa
2reduce 15 hours, filter, i.e. obtained anti-applications catalyst after washing three times.
Embodiment 2
1g Sodium Polyacrylate is dissolved in the water, adds 0.5g RuCl wherein
3nH
2the aqueous solution of O (Ru content 40% (weight)) and 0.08g ZnSO
47H
2the aqueous solution (Sodium Polyacrylate: Ru=5:1 (weight)) of O, Homogeneous phase mixing.Then in above-mentioned solution, drip the NaOH aqueous solution of 4ml 10mol/L, stir 3 hours at 60 DEG C, aged overnight.Then solution is joined in 60ml autoclave, at 150 DEG C, with the H of 5MPa
2reduce 15 hours, filter, i.e. obtained anti-applications catalyst after washing three times.
Embodiment 3
2.7g dodecyl sodium sulfate is dissolved in the water, adds 0.5g RuCl wherein
3nH
2the aqueous solution of O (Ru content 40% (weight)) and 0.08g ZnSO
47H
2the aqueous solution (dodecyl sodium sulfate: Ru=13.5:1 (weight)) of O, Homogeneous phase mixing.Then in above-mentioned solution, drip the NaOH aqueous solution of 4ml 10mol/L, stir 3 hours at 60 DEG C, aged overnight.Then the solution obtained is joined in 60ml autoclave, at 150 DEG C, with the H of 5MPa
2reduce 15 hours, filter, i.e. obtained anti-applications catalyst after washing three times.
Embodiment 4
5.2g perfluoro octyl sulfonic acid sodium is dissolved in the water, adds 0.5g RuCl wherein
3nH
2the aqueous solution of O (Ru content 40% (weight)) and 0.08g ZnSO
47H
2the aqueous solution (perfluoro octyl sulfonic acid sodium: Ru=26:1 (weight)) of O is dissolved in the water, Homogeneous phase mixing.Then in above-mentioned solution, drip the NaOH aqueous solution of 4ml 10mol/L, stir 3 hours at 60 DEG C, aged overnight.Then the solution obtained is joined in 60ml autoclave, at 150 DEG C, with the H of 5MPa
2reduce 15 hours, filter, i.e. obtained anti-applications catalyst after washing three times.
Embodiment 5
3.6g softex kw is dissolved in the water, adds 0.5g RuCl wherein
3nH
2the aqueous solution of O (Ru content 40% (weight)) and 0.08g ZnSO
47H
2the aqueous solution (softex kw: Ru=18:1 (weight)) of O, Homogeneous phase mixing.Then in above-mentioned solution, drip the NaOH aqueous solution of 4ml10mol/L, stir 3 hours at 60 DEG C, aged overnight.Then the solution obtained is joined in 60ml autoclave, at 150 DEG C, with the H of 5MPa
2reduce 15 hours, filter, i.e. obtained anti-applications catalyst after washing three times.
Comparative example 1
By 0.5g RuCl
3nH
2o (Ru content 40% (weight)) and 0.08g ZnSO
47H
2o is dissolved in 30ml water, in solution, then drip the NaOH aqueous solution of 4ml 10mol/L, stirs 3 hours, aged overnight at 60 DEG C.Then the solution obtained is joined in 60ml autoclave, at 150 DEG C, with the H of 5MPa
2reduce 15 hours, filter, i.e. obtained anti-applications catalyst after washing three times.
Comparative example 2
By 0.5g RuCl
3nH
2o (Ru content 40% (weight)) and 0.08g ZnSO
47H
2o is dissolved in 30ml water, then in solution, adds 1g ZrO
2, drip the NaOH aqueous solution of 4ml 10mol/L in the most backward solution, stir 3 hours at 60 DEG C, aged overnight.Then the solution obtained is joined in 60ml autoclave, at 150 DEG C, with the H of 5MPa
2reduce 15 hours, filter, i.e. obtained anti-applications catalyst after washing three times.
Test case
Catalyst prepared by embodiment 1 ~ 5 and comparative example 1 ~ 2 is used for preparing cyclohexene from benzene added with hydrogen reaction respectively under the following conditions:
Be add 28mL water, 0.5g ZrO in the autoclave high-pressure reactor of 60mL at volume
2, 1.44gZnSO
47H
2o, the consumption of the catalyst that embodiment 1 ~ 5 and comparative example 1 obtain is respectively 0.1g, and the consumption of the catalyst of comparative example 2 is 0.6g.Then in reactor, add 14mL benzene, seal post-reactor hydrogen exchange 3 times, be then filled with the hydrogen of 3MPa, be slowly heated to 150 DEG C, adjustment hydrogen valve, make system reach 5MPa, after 60min, reaction completes.Reaction result is evaluated.
The evaluation result of table 1 catalyst performance
Table 1 shows catalyst of the present invention and has higher activity and higher cyclohexene productive rate.
In addition, use TEM instrument to observe embodiment 2 and comparative example 1 gained catalyst or measure, result is see Fig. 1 ~ 4.As can be seen from Fig. 1 ~ 4, by adding catalyst that Sodium Polyacrylate prepares as surfactant than the catalyst not adding surfactant and prepare, there is less particle diameter.
Claims (7)
1. a preparation method for the catalyst of producing cyclohexene with benzene selective hydrogenation, it comprises the following steps:
(1) by the aqueous solution Homogeneous phase mixing of the surfactant that is dissolved in advance in water and ruthenium salt and zinc salt, then drip alkali lye and make it precipitation, then with reducing agent reduction, form the nanometer ruthenium zinc of surfactants stabilize;
(2) filtered by obtained nanometer ruthenium zinc, washing, obtains the nanometer ruthenium zinc catalyst of high dispersive,
Wherein, based on the gross weight of catalyst, ruthenium is 70 ~ 95 % by weight, and zinc is 5 ~ 30 % by weight.
2. preparation method according to claim 1, wherein, described ruthenium salt be selected from ruthenium bromide, ruthenic chloride, nitric acid ruthenium and acetic acid ruthenium one or more; Described zinc salt be selected from zinc sulfate, zinc chloride, zinc acetate and zinc nitrate one or more; The concentration of the aqueous solution of described ruthenium salt and zinc salt is 0.001 ~ 0.1mol/L separately.
3. preparation method according to claim 1, wherein, described surfactant be selected from Sodium Polyacrylate, dodecyl sodium sulfate, perfluoro octyl sulfonic acid sodium, softex kw and PVP one or more; The weight ratio of described surfactant and metal Ru and zinc total amount is 100:1 ~ 0.1:1.
4. preparation method according to claim 1, wherein, described alkali be selected from NaOH, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, caustic alcohol and potassium ethoxide one or more; Concentration 0.01 ~ the 100mol/L of described alkali lye.
5. preparation method according to claim 1, wherein, described reducing agent is H
2or NaBH
4.
6. preparation method according to claim 1, wherein, in the catalyst of preparation, the particle diameter of metal Ru zinc particle is 1 ~ 5nm.
7. the catalyst of producing cyclohexene with benzene selective hydrogenation prepared of the method according to any one of claim 1 ~ 6.
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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 |
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CN102744084B (en) * | 2012-07-23 | 2013-10-09 | 郑州天长化工技术有限公司 | Catalyst system for preparing cyclohexene by benzene selective hydrogenation, and method for preparing cyclohexene by benzene selective hydrogenation by catalyzing with catalyst system |
CN102744085B (en) * | 2012-07-23 | 2013-10-09 | 郑州大学 | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation |
CN104941637B (en) * | 2015-05-20 | 2018-06-22 | 上海交通大学 | Metallic catalyst and preparation method and the application on producing cyclohexene with benzene selective hydrogenation |
CN108101029A (en) * | 2017-12-25 | 2018-06-01 | 信利光电股份有限公司 | A kind of preparation method of graphene-Nano-Zinc water-setting gel electrode |
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CN1795983A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | Catalyst in use for hydrogenation reaction of benzene selection, preparartion method and application |
CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
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CN1795983A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | Catalyst in use for hydrogenation reaction of benzene selection, preparartion method and application |
CN1676215A (en) * | 2005-01-11 | 2005-10-05 | 中国神马集团有限责任公司 | Catalyst for producing cycloolefine by partial hydrogenation of mononuclear aromatics, and its preparing method and use |
CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
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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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