CN105618034A - Supported ruthenium nanocluster based catalyst as well as preparation and application thereof - Google Patents
Supported ruthenium nanocluster based catalyst as well as preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a supported ruthenium nanocluster based catalyst as well as preparation and an application thereof. The supported ruthenium nanocluster based catalyst with a special surface structure is prepared by utilizing the effects of water and hydrogen under a certain pressure and ruthenium based metal compound nanoparticles loaded on a carrier. The catalyst has excellent catalytic activity and selectivity for hydrogenation reactions such as Fischer-Tropsch synthesis and the like, is easily separated from a product and has excellent stability.
Description
Technical field
The present invention relates to a kind of support type Ru metal nanometre cluster catalyst based, and preparation method thereof with its application in catalyzing and synthesizing cyclostrophic etc.
Background technology
Interaction between its metal nanoparticle size, surface and interface structure, alloy structure and metal and carrier is had appreciable impact by the preparation method of complex phase metallic catalyst, and then its catalytic performance is made a significant impact. The preparation method of multiphase catalyst includes the methods such as infusion process, colloidal particle sedimentation, oxide nano-particles reduction, before the reduction step, generally first catalyst precursor is carried out high-temperature roasting process.
Fischer-Tropsch synthesis is by synthesis gas (CO and H2Mixture) it is converted into the mixture containing the Hydrocarbon such as Long carbon chain alkane, alkene, alcohol, aldehyde or oxygen-bearing hydrocarbon, it is one of most important reaction in artificial oil technology. Fischer-Tropsch synthesis, generally under the catalytic action of ferrum, cobalt or ruthenium-based catalyst, carries out under 493��593K high temperature. F-T synthesis is strongly exothermic process, and pyroreaction not only consumes more energy, makes product composition wayward, and makes the selectivity of Long carbon chain product in product reduce, and carbochain growth factor reduces, and is unfavorable for improving the economic worth of product. On the other hand, compared with homogeneous catalyst or colloid catalyst, multiphase catalyst has stability height, is prone to the advantages such as product separation and catalyst recovery. Therefore, when other factors are similar, Industrial Catalysis process is generally more likely to select multiphase catalyst. At present it is known that at a lower temperature (lower than 433K) complex phase metallic catalyst catalysis Fischer-Tropsch synthesis catalysis activity non-normally low. Such as, Turner etc. report a kind of Ru/SiO2Multiphase catalyst, its catalysis activity of catalysis F-T synthesis under 423K is 0.19molCOmolRu -1h-1(M.L.Turner, N.Marsih, wait J.Am.Chem.Soc., 2002,124,10456.). Therefore, improve fischer-tropsch reaction multiphase catalyst activity, reduce reaction temperature, the selectivity that increases high carbon number product is a challenging problem.
Summary of the invention
The purpose of the present invention is for providing a kind of support type Ru metal nanometre cluster that the hydrogenations such as F-T synthesis have high catalytic activity and excellent stability catalyst based and its preparation method and application.
Supported ruthenium metal nanometre cluster provided by the invention is catalyst based, and including carrier and loaded to the ruthenium metal nanometre cluster on carrier by precipitation-hydro-thermal hydrogen reduction method, described ruthenium metal nanometre cluster particle diameter is 1��20 nanometer.
Preferably, described ruthenium metal nanometre cluster catalyst based in ruthenium content be 0.1��80% (mass percentage content).
Described ruthenium metal nanometre cluster particle diameter is preferably 1��15 nanometer, more preferably 1��8 nanometer, it is most preferred that be 1��3 nanometer.
Described carrier is metal-oxide, carbon carrier and/or metal carbides; Be selected from aluminium oxide, silicon oxide, magnesium oxide, ferrum oxide, zirconium oxide, Si-Al molecular sieve, nitrogen mix at least one in carbon nanohorn, activated carbon, tungsten carbide, molybdenum carbide.
The preparation method of above-mentioned supported ruthenium base metal nanometer cluster catalyst provided by the invention, includes following steps:
1) in being dispersed with the alkaline aqueous solution of multiphase catalyst carrier, alcoholic solution or its mixed solution, adding the aqueous solution of ruthenium compound, reaction forms ruthenium compound nanoparticle and makes it be deposited on the prepared catalyst precursor of carrier surface;
2) by gained presoma in water in temperature be 353��573K, with hydrogen reducing when pressure is 0.1��21MPa, make ruthenium compound nanoparticle described in described presoma be reduced to ruthenium metal nanometre cluster, prepare the multiphase catalyst being substantially made up of ruthenium metal nanometre cluster and carrier.
Above-mentioned preparation method, step 1) described in carrier be metal-oxide, carbon carrier and/or metal carbides; Be selected from aluminium oxide, silicon oxide, magnesium oxide, ferrum oxide, zirconium oxide, Si-Al molecular sieve, nitrogen mix at least one in carbon nanohorn, activated carbon, tungsten carbide, molybdenum carbide.
In above-mentioned preparation method, step 1) described in ruthenium compound nanoparticle include in ruthenio hydrous metal oxides, ruthenio metal hydroxides and ruthenio basic metal salt compound nanoparticle any one or a few;
In preparation method, the ratio of ruthenium and carrier is 1: 1000 to 1: 0.25 (mass ratio).
In above-mentioned preparation method, described alkaline aqueous solution, alcoholic solution or its mixed solution are containing the aqueous solution of alkali carbonate, alkali metal hydrogencarbonate and/or alkali metal hydroxide, alcoholic solution or its mixed solution.
Above-mentioned alkali carbonate, alkali metal hydrogencarbonate and/or alkali metal hydroxide are preferably sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxid, potassium hydroxide etc.; It is the monohydric alcohol of 1-4, dihydroxylic alcohols, trihydroxylic alcohol or its mixture that described alcohol is preferably carbon atom number. It is furthermore preferred that at least one that described alcohol is in methanol, ethanol, ethylene glycol, glycerol, butanediol.
Above-mentioned preparation method, in step 1) and step 2) between, also product presoma can be separated from system, with water washing and dry. Wherein, described drying dries under 273-370K preferably in vacuum drying oven.
Above-mentioned preparation method, in step 2) after, the catalyst of preparation is separated with system, dries, prepare dry multiphase catalyst.
Above-mentioned preparation method, step 1) in reaction temperature be preferably 263-343K; Step 2) in the temperature of reduction reaction be preferably 290��470K, mode of heating can be microwave heating or common heating.
Supported ruthenium metallic nano cluster catalyst prepared by the present invention can be applicable to catalytic hydrogenation aspect, for instance, it is used for catalyzing and synthesizing cyclostrophic and turns to Hydrocarbon or oxygen-bearing hydrocarbon.
The present invention utilizes the water under certain pressure and hydrogen and the ruthenium compound nanoparticle effect being carried on carrier, and preparation has the supported ruthenium metallic nano cluster catalyst of special surface structure. " precipitation-hydro-thermal hydrogen reduction method " (PHR) of the present invention, utilizes strong interaction (M.A.Henderson, the Surf.Sci.Rep. between water and Ru, 2002,46,1), the accumulation mode of the Ru atom that regulation and control reduction produces, defines special surface texture. The catalyst of the present invention does not observe in the infrared spectrum of the carbon monoxide of ruthenium metal nanometre cluster surface adsorption and is positioned at 1970cm-1The peak (referring to embodiment 1) of neighbouring bridged adsorption CO, its top formula adsorption peak is also much smaller than the peak of multiple ADSORPTION STATE, and these are different from previously reported Ru metallic catalyst, it was shown that it has special surface texture.
The hydrogenations such as F-T synthesis are had the catalysis activity of excellence, selectivity by the supported ruthenium base metal nanometer cluster catalyst prepared by the present invention, and this type of catalyst is prone to separate and have excellent stability with product. Such as, the Ru/ ��-Al of embodiment 1 preparation2O3-PHR catalyst, under 423K, the catalysis activity of catalysis F-T synthesis is up to 17.3molCOmolRu -1h-1, under the 423K of report that is more than before, the catalysis of fischer-tropsch reaction is active; The ratio of the Fischer-Tropsch synthetic medium high carbon number compound obtained by this catalyst is apparently higher than previously reported Ru base multiphase catalyst, and its carbochain growth factor is up to 0.91, and the content of Fischer-Tropsch wax accounts for the 63% of product. The catalytic performance of above-mentioned excellence is cannot to know according to previously reported outcome expectancy.
Accompanying drawing explanation
Fig. 1 is the Ru/ ��-Al of embodiment 1 preparation2O3Transmission electron microscope photo (a and b) of-PHR catalyst and Ru nanocluster size distribution (c).
Fig. 2 is the Ru/ ��-Al of embodiment 1 preparation2O3Scanning transmission electron microscope photo (a) of-PHR catalyst and X-ray energy spectrum (EDS) (b).
Fig. 3 is the Ru/ ��-Al of embodiment 1 preparation2O3The precursor RuO of-PHR catalyst2��xH2O/��-Al2O3(a) and catalyst Ru/ ��-Al2O3The x-ray photoelectron spectroscopy of (b).
Fig. 4 is the infrared diffusing reflectance spectra of the catalyst surface CO absorption that embodiment 1 (a) is prepared with reference examples 2 (b).
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following example. Described method is conventional method if no special instructions. Described raw material all can obtain from open commercial sources if no special instructions.
Embodiment 1, Ru/ ��-Al2O3The preparation of-PHR catalyst (Ru: mass percent is 5%)
1) by 1g ��-Al2O3It is scattered in NaHCO3In aqueous solution (100mL, 0.1M), under agitation by 7.1mLRuCl3��xH2O (20g/L) adds in said mixture, after stirring 1 hour, precipitation is filtered, with water washing, and vacuum drying under 333K, prepare RuO2��xH2O/��-Al2O3Catalyst precursor.
2) by 1gRuO2��xH2O/��-Al2O3It is scattered in 100mL water, above-mentioned mixed system is placed in 300mL autoclave, be filled with hydrogen exchange air, reduction RuO under 423K, 2MPa hydrogen2��xH2O/��-Al2O3, after 2 hours, system being cooled to room temperature, takes out product, solid is vacuum drying under filtration, 333K, prepares Ru/ ��-Al2O3Catalyst. Inductively coupled plasma atomic emission spectrum (ICP-AES) is analyzed and is shown, in catalyst, Ru tenor is 5%; Electron-microscopic analysis (Fig. 1) shows, in catalyst, the mean diameter of Ru nanoparticle is 2.5nm, particle size distribution is 1.5��4nm, in catalyst, Ru nanoparticle crystal formation is hcp, the arrangement of its (100) and (101) interplanar distance respectively 0.233nm and 0.207nm, Ru nanoparticle (101) crystal face forms concavity arcuate structure; X-Ray Energy Spectrum Analysis shows that Ru nanoparticle is scattered in (Fig. 2) on alumina support. X-ray photoelectron spectroscopy analysis shows, prepared RuO2��xH2O/��-Al2O3With Ru/ ��-Al2O3In, Ru3d5/2Electron binding energy respectively 281.7 and 280.0eV, respectively with the Ru3d of ruthenium oxide hydration and metal Ru5/2Electron binding energy consistent (Fig. 3). The carbon monoxide infrared probe test of prepared catalyst adopts normal pressure diffuse-reflectance mode to carry out, and catalyst and CO purge sample with nitrogen after carrying out chemisorbed, then the infrared spectrum of the adsorbed CO of record. Test result shows not observe in the infrared spectrum of the carbon monoxide of ruthenium metal nanometre cluster surface adsorption in catalyst to be positioned at 1970cm-1The peak of neighbouring bridged adsorption CO, these are different from previously reported Ru metallic catalyst.
Ru/ ��-the Al of embodiment 2, embodiment 1 preparation2O3-PHR catalysis Fischer-Tropsch synthesis
300mL autoclave is put into 1gRu/ ��-Al2O3-PHR catalyst (Ru:5%), 100mL hexamethylene, it is filled with synthesis gas (H2: CO=2:1, volume ratio), with 4% nitrogen for interior mark, in 423K, initial pressure is enforcement Fischer-Tropsch synthesis under 3MPa, after reacting 6 hours, system is cooled to room temperature. Gas, product liquid are with gas chromatographic analysis, and solid product FT waxiness amount measures with weight method. In this reaction, CO conversion ratio is 64%, and catalyst activity is 17.3molCOmolRu -1h-1, carbochain growth factor is that 0.91, FT wax accounts for the 63% of product composition.
Experimental result (referring to table 1) shows that fischer-tropsch reaction is had significantly high catalysis activity by catalyst prepared by embodiment 1 at low temperatures, and product medium high carbon number constituent content is significantly high.
Embodiment 3, Ru/SiO2The preparation of-PHR catalyst (Ru: mass percent is 5%)
With SiO2Carrier (AlfaAesar company) replaces the ��-Al in embodiment 12O3, prepare by method in embodiment 1, it is thus achieved that Ru/SiO2Catalyst. Inductively coupled plasma atomic emission spectrum (ICP-AES) is analyzed and is shown, in catalyst, Ru tenor is 5%; Electron-microscopic analysis shows, in catalyst, Ru nano particle diameter is distributed mainly on 1.5��4nm scope.
Embodiment 4, Ru/TiO2The preparation of-PHR catalyst (Ru: mass percent is 0.5%)
1) by 1gTiO2(purchase of STREMCHEMICALS company) is scattered in NaHCO3In aqueous solution (100mL, 0.1M), under agitation by 0.67mlRuCl3��xH2O aqueous solution (20g/L) adds in said mixture, after stirring 1 hour, raises temperature to 333K, continues stirring 1 hour, precipitation filtered, with water washing, and vacuum drying under 333K, prepare RuO2��xH2O/TiO2Catalyst precursor.
2) by 1gRuO2��xH2O/TiO2It is scattered in 100mL water, above-mentioned mixed system is placed in 300mL autoclave, be filled with hydrogen exchange air, reduction RuO under 373K, 2MPa hydrogen2��xH2O/��-Al2O3, after 2 hours, system being cooled to room temperature, takes out product, solid is vacuum drying under filtration, 333K, prepares Ru/TiO2Catalyst. Inductively coupled plasma atomic emission spectrum (ICP-AES) is analyzed and is shown, in catalyst, Ru tenor is 0.5%.
Embodiment 5, Ru/ZSM-5-PHR catalyst (Ru: mass percent is 5%) preparation
1) 1g molecular sieve ZSM-5 (silica alumina ratio is 80, and Tianjin Nan Hua catalyst company limited buys) is scattered in KHCO3In aqueous solution (100mL, 0.1M), under agitation by 7.1mlRuCl3��xH2O (20g/L) adds in said mixture, after stirring 1 hour, precipitation is filtered, with water washing, and vacuum drying under 303K, prepare RuO2��xH2O/ZSM-5 catalyst precursor.
2) by 1gRuO2��xH2O/ molecular sieve ZSM-5 is scattered in 100mL water, is placed in 300mL autoclave by above-mentioned mixed system, is filled with hydrogen exchange air, reduction RuO under 373K, 2MPa hydrogen2��xH2O/��-Al2O3, after 2 hours, system being cooled to room temperature, takes out product, solid is vacuum drying under filtration, 303K, prepared, Ru/ZSM-5 catalyst. Inductively coupled plasma atomic emission spectrum (ICP-AES) is analyzed and is shown, in catalyst, Ru tenor is 5%.
Embodiment 6, Ru/MgO-PHR catalyst (Ru: mass percent is 10%) preparation
1) 1gMgO (purchase of STREMCHEMICALS company) is scattered in NaHCO3In aqueous solution (100mL, 0.1M), under agitation by 14.9mlRuCl3��xH2O (20g/L) adds in said mixture, after stirring 1 hour, precipitation is filtered, with water washing, and vacuum drying under 343K, prepare RuO2��xH2O/MgO catalyst precursor.
2) by 1gRuO2��xH2O/MgO is scattered in 100mL water, is placed in 300mL autoclave by above-mentioned mixed system, is filled with hydrogen exchange air, reduction RuO under 373K, 3MPa hydrogen2��xH2O/��-Al2O3, after 2 hours, system being cooled to room temperature, takes out product, solid is vacuum drying under filtration, 343K, prepares Ru/ ��-Al2O3Catalyst. Inductively coupled plasma atomic emission spectrum (ICP-AES) is analyzed and is shown, in catalyst, Ru tenor is 10%.
Embodiment 7, Ru/C-PHR catalyst (Ru: mass percent is 20%) preparation
1) 1gC (purchase of XC-72RVulcan company) is scattered in NaOH ethylene glycol solution (100mL, 0.25M), under agitation by 33.5mLRuCl3��xH2O (20g/L) adds in said mixture, after stirring 1 hour, precipitation is filtered, with water washing, and vacuum drying under 333K, prepare RuO2��xH2O/C catalyst precursor.
2) by 1gRuO2��xH2O/C is scattered in 100mL water, is placed in 300mL autoclave by above-mentioned mixed system, is filled with hydrogen exchange air, reduction RuO under 373K, 1MPa hydrogen2��xH2O/��-Al2O3, after 2 hours, system being cooled to room temperature, takes out product, solid is vacuum drying under filtration, 333K, prepared, Ru/C catalyst. Inductively coupled plasma atomic emission spectrum (ICP-AES) is analyzed and is shown, in catalyst, Ru tenor is 20%.
Embodiment 8, Ru/ nitrogen mix the preparation of carbon nanohorn-PHR catalyst (Ru: mass percent is 60%)
1) 1g nitrogen is mixed carbon nanohorn (by document J.PowderSource2012,220, prepared by 449 methods) it is scattered in (300mL in KOH ethanol-water solution, ethanol: water=30: 1 (volume ratio), KOH concentration is 0.1M), under agitation by 200mLRuCl3��xH2O (20g/L) adds in said mixture, after stirring 1 hour, precipitation is filtered, with water washing, and vacuum drying under 323K, prepare RuO2��xH2O/ nitrogen mixes carbon nanohorn catalysis agent presoma.
2) by 1gRuO2��xH2O/ nitrogen mixes carbon nanohorn and is scattered in 100mL water, is placed in 300mL autoclave by above-mentioned mixed system, is filled with hydrogen exchange air, reduction RuO under 443K, 2MPa hydrogen2��xH2O/��-Al2O3, after 2 hours, system being cooled to room temperature, takes out product, solid is vacuum drying under filtration, 323K, prepares Ru/ nitrogen and mixes carbon nanohorn catalyst. Inductively coupled plasma atomic emission spectrum (ICP-AES) is analyzed and is shown, in catalyst, Ru tenor is 60%; Electron-microscopic analysis shows, in catalyst, Ru nano particle diameter is distributed mainly on 5��12nm scope.
Ru/ ��-the Al of embodiment 9, embodiment 1 preparation2O3-PHR catalysis Fischer-Tropsch synthesis
300mL autoclave is put into 1gRu/ ��-Al2O3-PHR catalyst (Ru:5%), the mixed liquor of 50mL hexamethylene and 50mL water, it is filled with synthesis gas (H2: CO=2:1, volume ratio), with 4% nitrogen for interior mark, in 423K, initial pressure is enforcement Fischer-Tropsch synthesis under 3MPa, after reacting 6 hours, system is cooled to room temperature. Gas, product liquid are with gas chromatographic analysis, and solid product FT waxiness amount measures with weight method. Experimental result is in Table 1.
Ru/ ��-the Al of embodiment 10, embodiment 1 preparation2O3-PHR catalysis Fischer-Tropsch synthesis
1gRu/SiO put into by 300mL autoclave2Catalyst (Ru:5%), 90mL Hexalin and 10mL water mixed liquid, be filled with synthesis gas (H2: CO=2:1, volume ratio), with 4% nitrogen for interior mark, in 423K, initial pressure is enforcement Fischer-Tropsch synthesis under 3MPa, after reacting 6 hours, system is cooled to room temperature. Gas, product liquid are with gas chromatographic analysis, and solid product FT waxiness amount measures with weight method. Experimental result is in Table 1.
Ru/ ��-the Al of embodiment 11, embodiment 1 preparation2O3-PHR catalysis Fischer-Tropsch synthesis
300mL autoclave is put into 1gRu/ ��-Al2O3-PHR catalyst (Ru:5%), 100mL water, it is filled with synthesis gas (H2: CO=2:1, volume ratio), with 4% nitrogen for interior mark, in 423K, initial pressure is enforcement Fischer-Tropsch synthesis under 3MPa, after reacting 6 hours, system is cooled to room temperature. Gas, product liquid are with gas chromatographic analysis, and solid product FT waxiness amount measures with weight method. Experimental result is in Table 1.
Embodiment 12, respectively with SiO2��TiO2, ZSM-5, MgO, C be carrier, prepare catalyst, catalyst Fischer-Tropsch synthesis by the method that embodiment 1 is similar
300mL autoclave is put into 1g catalyst (Ru:5%), 100mL water, is filled with synthesis gas (H2: CO=2:1, volume ratio), with 4% nitrogen for interior mark, in 423K, initial pressure is enforcement Fischer-Tropsch synthesis under 3MPa, after reacting 6 hours, system is cooled to room temperature. Gas, product liquid are with gas chromatographic analysis, and solid product FT waxiness amount measures with weight method. Experimental result is listed in table 1.
Reference examples 1, it is purchased Ru/Al2O3(Ru: mass percent is 5%) catalysis Fischer-Tropsch synthesis
1gRu/Al put into by 300mL autoclave2O3(purchase of AlfaAesar company) catalyst, 100mL water, it is filled with synthesis gas (H2: CO=2:1, volume ratio), with 4% nitrogen for interior mark, in 423K, initial pressure is enforcement Fischer-Tropsch synthesis under 3MPa, after reacting 6 hours, system is cooled to room temperature. Gas, product liquid are with gas chromatographic analysis, and solid product FT waxiness amount measures with weight method. Experimental result is in Table 1.
Reference examples 2, Ru/ ��-Al2O3The preparation of-H (Ru: mass percent is 5%) catalyst and catalysis Fischer-Tropsch synthesis thereof are by embodiment 1 step 1) prepare RuO2��xH2O/��-Al2O3Catalyst precursor; This presoma is placed in tube furnace with dry hydrogen reductase 12 hour under 423K, prepares comparative catalyst (Ru/ ��-Al2O3-H), inductively coupled plasma atomic emission spectrum (ICP-AES) is analyzed and is shown, in catalyst, Ru tenor is 5%; The carbon monoxide infrared probe test of prepared catalyst adopts normal pressure diffuse-reflectance mode to carry out, and catalyst and CO purge sample with nitrogen after carrying out chemisorbed, then the infrared spectrum of the adsorbed CO of record. Test result shows to be positioned at 1970cm in the infrared spectrum of the carbon monoxide of ruthenium metal nanometre cluster surface adsorption in this catalyst-1The peak of neighbouring bridged adsorption CO is clearly. Implementing Fischer-Tropsch synthesis by condition described in embodiment 2, experimental result is in Table 1.
Table 1, catalyst fischer-tropsch reaction of the present invention activity
Claims (14)
1. a supported ruthenium metal nanometre cluster is catalyst based, and including carrier and loaded to the ruthenium metal nanometre cluster on carrier by precipitation-hydro-thermal hydrogen reduction method, described ruthenium metal nanometre cluster particle diameter is 1��20 nanometer.
2. supported ruthenium metal nanometre cluster as claimed in claim 1 is catalyst based, it is characterised in that the mass percentage content of the catalyst based middle ruthenium of described ruthenium metal nanometre cluster is 0.1��80%.
3. supported ruthenium metal nanometre cluster as claimed in claim 1 is catalyst based, it is characterised in that described ruthenium metal nanometre cluster particle diameter is 1��15 nanometer, it is preferred to 1��8 nanometer, more preferably 1��5 nanometer.
4. supported ruthenium metal nanometre cluster as claimed in claim 1 is catalyst based, it is characterised in that described carrier is metal-oxide, carbon carrier and/or metal carbides.
5. supported ruthenium metal nanometre cluster as claimed in claim 1 is catalyst based, it is characterized in that, described support selected from alumina, silicon oxide, magnesium oxide, ferrum oxide, zirconium oxide, Si-Al molecular sieve, nitrogen mix at least one in carbon nanohorn, activated carbon, tungsten carbide and molybdenum carbide.
6. supported ruthenium metal nanometre cluster as claimed in claim 1 is catalyst based, it is characterised in that described catalyst, after CO absorption and nitrogen purge, does not observe wave number in the infrared spectrum of the CO adsorbed and is positioned at 1970cm-1The peak of bridged adsorption CO.
7. the preparation method that the arbitrary described supported ruthenium metal nanometre cluster of claim 1��6 is catalyst based, comprises the following steps:
1) in being dispersed with the alkaline aqueous solution of multiphase catalyst carrier, alcoholic solution or its mixed solution, adding the aqueous solution of ruthenium compound, reaction forms ruthenium compound nanoparticle and makes it be deposited on the prepared catalyst precursor of carrier surface;
2) gained presoma is 353��573K in temperature in water, with hydrogen reducing when pressure is 0.1��21MPa, makes ruthenium compound nanoparticle described in described presoma be reduced to ruthenium metal nanometre cluster, prepare multiphase catalyst.
8. preparation method as claimed in claim 7, it is characterised in that described ruthenium compound nanoparticle include in ruthenio hydrous metal oxides, ruthenio metal hydroxides and ruthenio basic metal salt compound nanoparticle any one or multiple.
9. preparation method as claimed in claim 7, it is characterised in that described alkaline aqueous solution, alcoholic solution or its mixed solution are containing the aqueous solution of alkali carbonate, alkali metal hydrogencarbonate and/or alkali metal hydroxide, alcoholic solution or its mixed solution.
10. preparation method as claimed in claim 9, it is characterized in that, described alkali carbonate, alkali metal hydrogencarbonate and/or alkali metal hydroxide are selected from one or more in sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxid and potassium hydroxide; Described alcohol is selected from the monohydric alcohol that carbon atom number is 1��4, dihydroxylic alcohols, trihydroxylic alcohol or its mixture.
11. preparation method as claimed in claim 7, it is characterised in that in step 1) and step 2) between, described catalyst precursor is separated from system, with water washing and dry; In step 2) after, the catalyst of preparation is separated with system, dries, prepare dry multiphase catalyst.
12. preparation method as claimed in claim 7, it is characterized in that, step 1) in reaction temperature be 263-343K; Step 2) in the temperature of reduction reaction be 290��470K.
13. the arbitrary catalyst based application in catalytic hydrogenation of described supported ruthenium metal nanometre cluster of claim 1��6.
14. apply as claimed in claim 13, it is characterised in that described supported ruthenium metal nano base cluster catalyst is used for catalyzing and synthesizing cyclostrophic and turns to Hydrocarbon or oxygen-bearing hydrocarbon.
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