CN103285919A - Hydrogenation catalyst and preparation method and application thereof - Google Patents
Hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a hydrogenation catalyst and a preparation method and application thereof. The hydrogenation catalyst contains polyether-ether-ketone and active components, namely nano-cluster particles loaded on the polyether-ether-ketone. The hydrogenation catalyst provided by the invention has high activity and selectivity, can effectively improve the selectivity of the cyclohexene and the conversion rate of benzene when being used for preparing cyclohexene by benzene hydrogenation especially, and furthermore, can well avoid the problem that an active component in a conventional hydrogenation catalyst runs off so as to improve the stability of the hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and its preparation method and application.
Background technology
It is important Organic Chemicals that cyclohexene reaches by its downstream product adipic acid of deriving, nylon 6, nylon 66, polyamide, polyester, has important industrial use and vast market prospect.By adopting benzene selective hydrogenation can prepare the important source material cyclohexene of synthetic other multiple fine chemicals.
The method of traditional mode of production cyclohexene generally is divided into two classes.One class is to be the rapid synthetic route of multistep of raw material with benzene, earlier makes cyclohexane or cyclohexane halide by benzene, then cyclohexane is made cyclohexanol and is dewatered and form cyclohexene or the cyclohexane halide dehydrohalogenation is formed cyclohexene.Another kind of is to be the one-step method synthetic route of raw material with benzene, namely generates corresponding cyclohexene with benzene for the raw material partial hydrogenation, and this synthetic route is paid close attention to widely owing to the technology simple and fast.
In the prior art, the most technology of preparation of hydrogenation catalyst that benzene selective hydrogenation prepares cyclohexene is comparatively complicated, and selection of catalysts is lower.For example, WO93/16971 discloses technology and the hydrogenation catalyst that a kind of benzene partial hydrogenation is produced cyclohexene, and described hydrogenation catalyst is the loaded catalyst that contains ruthenium and complex carrier, but there is selective low and the problem that the by-product cyclic hexane is more of cyclohexene in it.Because the hydrogenation activity of the relative much bigger metal platinum with supply of reserves is higher, and its industry service life greater than 5 years, therefore, cyclohexene selectively reaches 48% when having report to propose composite catalyst with platinum/nylon to be used for benzene hydrogenation.But, the problem that the catalyst for preparing according to the method for such polymer powder loadization exists poor stability and active component easily to run off.
Summary of the invention
The objective of the invention is to overcome prior art hydrogenation catalyst lower, the selective relatively poor problem of activity and provide a kind of activity and selectively all preferably and catalyst stability preferably, be specially adapted to benzene selective hydrogenation and prepare hydrogenation catalyst of cyclohexene and its preparation method and application.
Because the hydrogenation activity of platinum is higher, therefore in the prior art, the someone attempts platinum nano-cluster particle is embedded in the photosensitive polyimide film, to attempt to improve its catalytic activity and selective.But, find that in use benzene makes the polyimide film swelling of hydrogenation catalyst and the generation catalytic reaction that contacts with the activated centre of catalyst surface.But because described polyimide film has light sensitivity, under UV-irradiation, can take place crosslinked, in case control improper, thereby can appreciable impact benzene influence the yield of cyclohexene with contacting of catalyst.
To achieve these goals, the invention provides a kind of hydrogenation catalyst, wherein, described hydrogenation catalyst contains polyether-ether-ketone and the active component nano-cluster particle that loads on the polyether-ether-ketone.
The present invention also provides a kind of hydrogenization catalyst preparation method, wherein, this method is included under the existence of first solvent of the precursor compound that can dissolve polyether-ether-ketone and active component and under reducing condition, precursor compound, the polyether-ether-ketone of active component and the conditioning agent that plays peptizaiton are mixed, and the hydrogenation catalyst that precipitation obtains containing polyether-ether-ketone and loads on the active component nano-cluster particle on the polyether-ether-ketone in second solvent of insoluble solution polyether-ether-ketone and described active component.
The present invention also provides described hydrogenation catalyst to prepare application in the cyclohexene at benzene selective hydrogenation.
The present inventor finds unexpectedly, with active component nano-cluster particulate load on polyether-ether-ketone, both can guide contacting of benzene and activity of hydrocatalyst component, improve the selective of cyclohexene, can also solve the losing issue of catalyst activity component well, thereby improve the stability of hydrogenation catalyst.
Other features and advantages of the present invention will partly be described in detail in the specific embodiment subsequently.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that the specific embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, described hydrogenation catalyst contains polyether-ether-ketone and the active component nano-cluster particle that loads on the polyether-ether-ketone.
According to the present invention, as long as although make described active component nano-cluster particulate load at polyether-ether-ketone, but, under the preferable case, on the one hand for described active component nano-cluster particle is loaded in the polyether-ether-ketone better, on the other hand, guarantee to make benzene to contact with the activated centre smoothly, under the preferable case, be 1 in the described active component nano-cluster particle of metal and the mass ratio of polyether-ether-ketone: 1.5-15, more preferably under the situation, the present inventor finds, be 1 in the described active component nano-cluster particle of metal and the mass ratio of polyether-ether-ketone: during 2.5-5, the catalytic effect of hydrogenation catalyst is better.
Can prepare littler, the dispersed better nano-scale particle of active component of grain diameter according to method of the present invention, and make described active component nano-cluster particulate load on polyether-ether-ketone, under the preferable case, the average particulate diameter of described hydrogenation catalyst is the 15-50 nanometer, and the average particulate diameter of described active component nano-cluster particle is the 3-5 nanometer.
The present invention is not particularly limited described active component, can be used in the active component that selective catalytic benzene hydrogenation prepares cyclohexene for various, and under the preferable case, described active component is selected from one or more in platinum, ruthenium, rhodium and the palladium.
The present invention is not particularly limited described polyether-ether-ketone, can be the various polyether-ether-ketones of this area routine, under the preferable case, in order under the condition of milder, to prepare described hydrogenation catalyst, described polyether-ether-ketone is the polyether-ether-ketone that contains trifluoromethyl in the molecular structure, and the number-average molecular weight of described polyether-ether-ketone is 50,000-80,000.The polyether-ether-ketone that contains trifluoromethyl in the described molecular structure can be commercially available also and can prepare according to the method for well known to a person skilled in the art, for example: can prepare according to following method: G.L.Tullos, P.E.Cassidy, A.K.St.Clair, " Polymers derived from hexafluoroacetone:12F-poly (ether ketone) " Macromolecules, 1991,24,6059-6064.Concrete reaction equation is as follows:
Concrete preparation method comprises: will be above-mentioned in the flask with three necks,round bottom that is equipped with agitating device, condenser pipe, water knockout drum and argon protective device react that (the two fluorine monomers shown in the formula (1) are generally excessive under by the catalysis of bis-phenol at Anhydrous potassium carbonate shown in the two fluorine monomers shown in the formula (1) and the formula (2); the mol ratio of the bis-phenol shown in itself and the formula (2) can be 1.2-3: 1); with N; the N-dimethylacetylamide is as solvent, with toluene as the band aqua.Stir, be warming up to 140-150 ℃, band water back flow reaction 1-3h.Be warming up to 160-170 ℃ then, after toluene is steamed fully, reacted 6-8 hour.Reaction pours into reactant liquor in the 10 weight % aqueous hydrochloric acid solutions after finishing, and obtains white powder, boils twice with deionized water, uses the methyl alcohol extracting again 40-48 hour, obtains the polyether-ether-ketone shown in the formula (3).
According to the present invention, hydrogenization catalyst preparation method is included under the existence of first solvent of the precursor compound that can dissolve polyether-ether-ketone and active component and under reducing condition, precursor compound, the polyether-ether-ketone of active component and the conditioning agent that plays peptizaiton are mixed, and the hydrogenation catalyst that precipitation obtains containing polyether-ether-ketone and loads on the active component nano-cluster particle on the polyether-ether-ketone in second solvent of insoluble solution polyether-ether-ketone and described active component.
According to the present invention, under the preferable case, be 1 in the described precursor compound of metal and the mass ratio of polyether-ether-ketone: 1.5-15 under the situation, is 1 in the described precursor compound of metal and the mass ratio of polyether-ether-ketone: 2.5-5 more preferably.
According to the present invention, described conditioning agent has reaction speed and control active component nano particle size, the effect that makes its dispersion and be not easy to reunite, under the preferable case, in order to prepare the stable active component nanometer particle that loads on the polyether-ether-ketone, and guarantee the catalytic activity of this nano particle, and the mass ratio of the contained reactive metal in the precursor compound of described conditioning agent and active component is preferably 0.1-1.5: 1, and 0.1-0.8 more preferably: 1; Described conditioning agent is preferably potassium hydroxide and/or NaOH.
According to the present invention, described reducing condition refers to make the precursor compound of described active component to be reduced to the condition of the valence state of the active component that can play catalytic action, is generally the metallic state that described precursor compound is reduced to active component.For example, can be by adding reducing agent, for example, hydrogen, carbon monoxide, pure steam, hydrazine, formaldehyde and sodium borohydride etc. are preferably hydrogen.The temperature of described reduction is 80-400 ℃, is preferably 100-350 ℃.Under the preferable case, described reducing condition is heating using microwave, the selectable range of the condition of described heating using microwave is wideer, as long as can satisfy the metal simple-substance that the precursor compound that makes active component is reduced to active component, polyether-ether-ketone is decomposed to get final product, under the preferable case, the power of heating using microwave is 500-800W, more preferably 600-750W.The time of common described heating using microwave is 0.1-10 minute.More preferably under the situation, being blended under the stirring condition of the precursor compound of described active component, polyether-ether-ketone and conditioning agent carried out, and described mixing speed can be 20-200 rev/min, is preferably 100-150 rev/min, mixing time is 0.1-6 hour, is preferably 0.5-4 hour.
According to the present invention, described first solvent is the solvent that can dissolve the precursor compound of polyether-ether-ketone and active component, described second solvent is the solvent of insoluble solution polyether-ether-ketone and described active component, under the preferable case, described polyether-ether-ketone is the polyether-ether-ketone that contains trifluoromethyl in the molecular structure, and the number-average molecular weight of described polyether-ether-ketone is 50,000-80,000; Therefore, under the preferable case, described first solvent is selected from dimethyl sulfoxide (DMSO), N, dinethylformamide and N, one or more in the N-dimethylacetylamide; Described second solvent is selected from one or more in methyl alcohol, ethanol, ethylene glycol and the acetone.In addition, the present invention is not particularly limited the consumption of described first solvent and second solvent, can suitably regulate according to polyether-ether-ketone and amount thereof.
According to the present invention, the precursor compound of described active component is preferably selected from one or more in chloroplatinic acid, chloroplatinate, the acid of chlorine rhodium, chlorine rhodate, ruthenium hydrochloride and the ruthenium hydrochloride salt.Described chloroplatinate, chlorine rhodate, ruthenium hydrochloride salt are preferably their sodium salt and/or sylvite.
According to the present invention, in order the hydrogenation catalyst that obtains to be easier to play the contact action in guiding benzene and activated centre, adding pore-foaming agent when this method also is included in the precursor compound of active component, polyether-ether-ketone and the conditioning agent that plays peptizaiton mixed.For example, described pore-foaming agent can be in alcohol, alkane and the alkene one or more.Preferably, described pore-foaming agent is the aliphatic alcohol of C3-C8 and/or the alkane of C6-C20.Among the present invention, the instantiation of described pore-foaming agent can for but be not limited to: isopropyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, sec-butyl alcohol, isoamyl alcohol, tert-pentyl alcohol, neopentyl alcohol, n-amyl alcohol, n-hexyl alcohol, 2-ethyl-1-hexanol, isooctanol, normal heptane, normal octane, isooctane, n-decane, dodecane, the tetradecane and hexadecane.The selectable range of the amount of described pore-foaming agent is wideer, is preferably the 10-30 weight % of polyether-ether-ketone weight.
The present invention also provides the application of described hydrogenation catalyst in hydrogenation reaction.Be specially adapted to benzene selective hydrogenation and prepare cyclohexene.Hydrogenation catalyst of the present invention is used for can significantly improving the selective of cyclohexene in the method that hydrogenation reaction, particularly benzene selective hydrogenation prepare cyclohexene.Except adopting hydrogenation catalyst of the present invention, described benzene selective hydrogenation prepares the condition of cyclohexene can carry out with reference to prior art well-known to those skilled in the art.
More than describe preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in the above-mentioned specific embodiment under reconcilable situation, can make up by any suitable manner, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible compound modes.
In addition, also can carry out any combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will describe the present invention by embodiment.
Among the following embodiment, measure the average particulate diameter of hydrogenation catalyst and the average particulate diameter of active component nano-cluster by ESEM.
Used polyether-ether-ketone is the polyether-ether-ketone that has trifluoromethyl in the molecular structure among the following embodiment, and according to G.L.Tullos, P.E.Cassidy, A.K.St.Clair, " Polymers derived from hexafluoroacetone:12F-poly (ether ketone) " Macromolecules, 1991,24, the 6059-6064 disclosed method prepares, and the number-average molecular weight of the polyether-ether-ketone for preparing is 5-6 ten thousand.
Among the present invention, adopt gas chromatograph (to purchase in Shanghai Precision Scientific Apparatus Co., Ltd, model is GC128) carry out in the system analysis that each is formed, undertaken quantitatively by proofreading and correct normalization method, all can carry out with reference to prior art, calculate the evaluation index such as selective of conversion ratio, the cyclohexene of benzene on this basis.
The conversion ratio of benzene (%)=(molal quantity of the benzene that consumes in the reaction/be provided to the molal quantity of the benzene feedstock in the reaction) * 100%.
Cyclohexene selective (%)=(molal quantity of the benzene that consumes in the molal quantity/reaction of the cyclohexene of generation) * 100%.
Embodiment 1
Present embodiment is used for the preparation of explanation hydrogenation catalyst provided by the invention.
With 0.53g six hydration chloroplatinic acids, (mass ratio of platinum and polyether-ether-ketone is 1: 1.5 in the six hydration chloroplatinic acids 0.285g polyether-ether-ketone and 0.13g potassium hydroxide aqueous solution (mass percent concentration is 15 weight %) mix with 50 milliliters of DMSO, the mass ratio of platinum is 0.1: 1 in potassium hydroxide and the six hydration chloroplatinic acids), under agitation, the mixed solution that adopts heating using microwave (microwave power is 700W) to obtain, when solution stops reaction when yellow becomes dark brown, and described mixture mixed with 50 milliliters of acetone, precipitation obtains the polyether-ether-ketone particle of load active component nano-cluster particle, then, place it in 110 ℃ the drying box dryly, obtain hydrogenation catalyst C1.The average particulate diameter that records described active component nano-cluster particle is 3.5 nanometers, and the average particulate diameter of hydrogenation catalyst C1 is 25 nanometers.And be 7.2 weight % by the content that spectrofluorimetry obtains active component Pt in the described hydrogenation catalyst.
Embodiment 2
Present embodiment is used for the preparation of explanation hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares hydrogenation catalyst, and different is that the consumption of polyether-ether-ketone is 0.475g (mass ratio of platinum and polyether-ether-ketone is 1: 2.5 in the six hydration chloroplatinic acids), obtains hydrogenation catalyst C2.The average particulate diameter that records described active component nano-cluster particle is 3.3 nanometers, and the average particulate diameter of hydrogenation catalyst C2 is 20 nanometers.And be 7.6 weight % by the content that spectrofluorimetry obtains active component Pt in the described hydrogenation catalyst.
Embodiment 3
Present embodiment is used for the preparation of explanation hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares hydrogenation catalyst, and different is that the consumption of polyether-ether-ketone is 0.95g (mass ratio of platinum and polyether-ether-ketone is 1: 5 in the six hydration chloroplatinic acids), obtains hydrogenation catalyst C3.The average particulate diameter that records described active component nano-cluster particle is 4.1 nanometers, and the average particulate diameter of hydrogenation catalyst C3 is 26.2 nanometers.And be 7.5 weight % by the content that spectrofluorimetry obtains active component Pt in the described hydrogenation catalyst.
Embodiment 4
Present embodiment is used for the preparation of explanation hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares hydrogenation catalyst, and different is that the consumption of potassium hydroxide aqueous solution is 1g (mass ratio of platinum and potassium hydroxide is 1: 0.8 in the six hydration chloroplatinic acids), obtains hydrogenation catalyst C4.The average particulate diameter that records described active component nano-cluster particle is 3.2 nanometers, and the average particulate diameter of hydrogenation catalyst C4 is 24 nanometers.And be 7.2 weight % by the content that spectrofluorimetry obtains active component Pt in the described hydrogenation catalyst.
Embodiment 5
Present embodiment is used for the preparation of explanation hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares hydrogenation catalyst, and different is that the consumption of potassium hydroxide aqueous solution is 2.28 grams (mass ratio of platinum and potassium hydroxide is 1: 1.8 in the six hydration chloroplatinic acids), obtains hydrogenation catalyst C5.The average particulate diameter that records described active component nano-cluster particle is 4.5 nanometers, and the average particulate diameter of hydrogenation catalyst C5 is 28 nanometers.And be 7 weight % by the content that spectrofluorimetry obtains active component Pt in the described hydrogenation catalyst.
Embodiment 6
Present embodiment is used for the preparation of explanation hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares hydrogenation catalyst, different is, with 0.6g chlordene rhodium acid sodium dodecahydrate, 0.3g polyether-ether-ketone and 0.67g sodium hydrate aqueous solution (mass percent concentration is 15 weight %) and 50 milliliters of N, dinethylformamide mixes that (mass ratio of rhodium and polyether-ether-ketone is 1: 3 in the chlordene rhodium acid sodium dodecahydrate, the mass ratio of rhodium and NaOH is 1: 1 in the chlordene rhodium acid sodium dodecahydrate), under agitation, the mixed solution that adopts heating using microwave (microwave power is 650W) to obtain, microwave heating time is 2 minutes, and described mixture mixed with 50 milliliters of ethylene glycol, precipitation obtains the polyether-ether-ketone particle of load active component nano-cluster particle.Then, place it in 110 ℃ the drying box dryly, obtain hydrogenation catalyst C6.The average particulate diameter that records described active component nano-cluster particle is 3 nanometers, and the average particulate diameter of hydrogenation catalyst C6 is 18.5 nanometers.And be 7.9 weight % by the content that spectrofluorimetry obtains active component Rh in the described hydrogenation catalyst.
Embodiment 7
Present embodiment is used for the preparation of explanation hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares hydrogenation catalyst, and different is, adds isooctanol when six hydration chloroplatinic acids, polyether-ether-ketone and potassium hydroxide aqueous solution are mixed with DMSO, and the addition of isooctanol is 20 weight % of polyether-ether-ketone quality.Obtain hydrogenation catalyst C7.The average particulate diameter that records described active component nano-cluster particle is 3.2 nanometers, and the average particulate diameter of hydrogenation catalyst C7 is 18 nanometers.And be 7.7 weight % by the content that spectrofluorimetry obtains active component Pt in the described hydrogenation catalyst.
Embodiment 8
Present embodiment is used for the preparation of explanation hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares hydrogenation catalyst, and different is that the mass ratio of platinum and polyether-ether-ketone is 1: 15 in the six hydration chloroplatinic acids, obtains hydrogenation catalyst C8.The average particulate diameter that records described active component nano-cluster particle is 8 nanometers, and the average particulate diameter of hydrogenation catalyst C8 is 55 nanometers.And be 6 weight % by the content that spectrofluorimetry obtains active component Pt in the described hydrogenation catalyst.
Comparative Examples 1
This Comparative Examples is used for the preparation of explanation reference hydrogenation catalyst.
Method according to embodiment 1 prepares hydrogenation catalyst, and different is, replaces polyether-ether-ketone with polyvinylpyrrolidone, obtains reference hydrogenation catalyst B1.The average particulate diameter of described hydrogenation catalyst B1 is 60 nanometers.And be 4.5 weight % by the content that spectrofluorimetry obtains active component Pt in the described reference hydrogenation catalyst.
EXPERIMENTAL EXAMPLE 1-8
This EXPERIMENTAL EXAMPLE is used for the explanation benzene selective hydrogenation and prepares cyclohexene.
In the stainless steel autoclave of sweeping the 0.5L that blows in advance with nitrogen fully, add 120 ml waters; add hydrogenation catalyst and 40 milliliters of benzene that 6 grams are prepared by embodiment 1-8 respectively; and introducing hydrogen; be that 5.0MPa and reaction temperature are 150 ℃ and down react (and carrying out) by stirring (500 rev/mins) under nitrogen protection at Hydrogen Vapor Pressure; after reaction was finished, the cooling autoclave took out oil phase; use the gas chromatograph analytic product, the result is as shown in table 1.
Comparative Examples 2
This Comparative Examples is used for the explanation benzene selective hydrogenation and prepares cyclohexene.
Method according to EXPERIMENTAL EXAMPLE 1-8 prepares cyclohexene, and different is, employing be the reference hydrogenation catalyst B1 of Comparative Examples 1.The result is as shown in table 1.
Table 1
| The embodiment numbering | Reaction time/minute | Conversion ratio/the % of benzene | Selective/the % of cyclohexene |
| Embodiment 1 | 50 | 46.2 | 73.5 |
| Embodiment 2 | 50 | 46.5 | 74.2 |
| Embodiment 3 | 50 | 45.8 | 72.6 |
| Embodiment 4 | 50 | 46.9 | 74.6 |
| Embodiment 5 | 50 | 45.1 | 71.9 |
| Embodiment 6 | 50 | 47.7 | 75.5 |
| Embodiment 7 | 50 | 47.2 | 75.1 |
| Embodiment 8 | 50 | 44.9 | 70.9 |
| Comparative Examples 2 | 50 | 38.9 | 66.1 |
According to the result in the table 1 as can be known, adopt hydrogenation catalyst provided by the invention to be used for reaction that benzene selective hydrogenation prepares cyclohexene and can significantly improve the selective of the conversion ratio of benzene and cyclohexene in the short period of time.
Claims (15)
1. a hydrogenation catalyst is characterized in that, described hydrogenation catalyst contains polyether-ether-ketone and the active component nano-cluster particle that loads on the polyether-ether-ketone.
2. hydrogenation catalyst according to claim 1 wherein, is 1 in the described active component nano-cluster particle of metal and the mass ratio of polyether-ether-ketone: 1.5-15.
3. hydrogenation catalyst according to claim 2 wherein, is 1 in the described active component nano-cluster particle of metal and the mass ratio of polyether-ether-ketone: 2.5-5.
4. according to any described hydrogenation catalyst among the claim 1-3, wherein, the average particulate diameter of described hydrogenation catalyst is the 15-55 nanometer.
5. according to any described hydrogenation catalyst among the claim 1-3, wherein, described polyether-ether-ketone is the polyether-ether-ketone that contains trifluoromethyl in the molecular structure, and the number-average molecular weight of described polyether-ether-ketone is 50,000-80,000.
6. according to any described hydrogenation catalyst among the claim 1-3, wherein, described active component is selected from one or more in platinum, ruthenium, rhodium and the palladium.
7. hydrogenization catalyst preparation method, it is characterized in that, this method is included under the existence of first solvent of the precursor compound that can dissolve polyether-ether-ketone and active component and under reducing condition, precursor compound, the polyether-ether-ketone of active component and the conditioning agent that plays peptizaiton are mixed, and the hydrogenation catalyst that precipitation obtains containing polyether-ether-ketone and loads on the active component nano-cluster particle on the polyether-ether-ketone in second solvent of insoluble solution polyether-ether-ketone and described active component.
8. preparation method according to claim 7 wherein, is 1 in the described precursor compound of metal and the mass ratio of polyether-ether-ketone: 1.5-15.
9. preparation method according to claim 8 wherein, is 1 in the described precursor compound of metal and the mass ratio of polyether-ether-ketone: 2.5-5.
10. preparation method according to claim 7, wherein, described conditioning agent is potassium hydroxide and/or NaOH; Described conditioning agent is 0.1-1.5 with mass ratio in the precursor compound of the active component of metal: 1, be preferably 0.1-0.8: 1.
11. according to any described preparation method among the claim 7-9, wherein, described polyether-ether-ketone is the polyether-ether-ketone that contains trifluoromethyl in the molecular structure, the number-average molecular weight of described polyether-ether-ketone is 50,000-80,000; Described first solvent is selected from dimethyl sulfoxide (DMSO), N, dinethylformamide and N, one or more in the N-dimethylacetylamide; Described second solvent is selected from one or more in methyl alcohol, ethanol, ethylene glycol and the acetone.
12. preparation method according to claim 7, wherein, described reducing condition comprises heating using microwave, and the power of heating using microwave is 500-800W.
13. preparation method according to claim 7, wherein, this method adds pore-foaming agent when also being included in the precursor compound of active component, polyether-ether-ketone and the conditioning agent that plays peptizaiton being mixed.
14. according to any described preparation method among the claim 7-10, wherein, the precursor compound of described active component is selected from one or more in chloroplatinic acid, chloroplatinate, the acid of chlorine rhodium, chlorine rhodate, ruthenium hydrochloride, ruthenium hydrochloride salt, the acid of chlorine palladium and the chloropalladate.
15. the hydrogenation catalyst for preparing according to any described method among any or the claim 7-14 among the claim 1-6 prepares application in the cyclohexene at benzene selective hydrogenation.
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