CN109894145A - A kind of fischer-tropsch synthetic catalyst and its preparation and application containing zeolite molecular sieve - Google Patents
A kind of fischer-tropsch synthetic catalyst and its preparation and application containing zeolite molecular sieve Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst and preparation method thereof of highly selective liquefaction of the F- T synthesis containing zeolite molecular sieve.The catalyst is made of zeolite beta molecular sieve carrier and active component Ru, and the beta molecular sieve with meso-hole structure is directly prepared using hydrothermal synthesis method, and active component Ru is loaded on molecular sieve carrier by infusion process.By changing the ingredient proportion of silicon source and silicon source in mixed liquor, the Acidity of molecular sieve can be effectively adjusted.By optimizing the mesopore orbit size of molecular sieve and the acidity of molecular sieve in the synthesis process, when which is used for Fischer-Tropsch synthesis can synthetic gasoline with high selectivity, C in product5+Selectivity up to 90% or more.In catalyst of the present invention, beta molecular sieve is not required to any last handling process, the activity in synthesis syngas conversion reactor can not only can be improved directly as carrier to load metal Ru active component, the catalyst, the selectivity of gasoline component in reaction product can also be greatly improved.
Description
Technical field
The present invention relates to a kind of catalyst containing zeolite molecular sieve and its preparation to convert highly selective system in synthesis gas with it
Application in oil.
Background technique
In recent years, with being becoming tight the day of petroleum resources, the continuous soaring and modern society of crude oil price is to petrol and diesel oil
The increasingly increase of equal liquid fuels demand, the competition of countries on petroleum resource are more fierce.In conjunction with China's richness coal, oil-poor, few gas
The fundamental realities of the country, develop coal-to-oil industry under petroleum resources international situation with keen competition, there is very important status.It adopts
The coal oil utilization of resources can be realized with direct coal liquefaction technology, but direct coal liquefaction technology needs a large amount of hydrogen, and it is big to consume energy,
The economic benefit is not high.Use producing synthesis gas from coal coupling Fischer-Tropsch synthesis for coal-to-oil industry provide a high financial profit,
It is easier to the technology path realized.
Traditional Fischer-Tropsch synthesis follows carbide surface mechanism of polymerization, and the selectivity of every kind of product all has a pole
Limit value, i.e. product obey Anderson-Schulz-Flory (ASF) distribution.According to the regularity of distribution, gasoline component in product
Selectivity only up to reach 48%, far from the Strategic Demand for reaching coal oil.The activity of traditional fischer-tropsch synthetic catalyst
Group is divided into Fe, Co, Ru, and the sequence of hydrogenation capability is Ru > Co > Fe, and Ru is in higher steam partial pressure or other oxic gas
Higher activity can be maintained in atmosphere；Carrier mostly uses metal oxide, such as Al2O3、SiO2、TiO2Deng.In the effect of the catalyst
Under, product is mostly linear paraffin, and the selectivity of gasoline component is high and inferior quality (octane number is low) of gasoline, and generates a large amount of
Wax, process flow is complex.
Molecular sieve carrier has highly acid and unique duct shape selectivity, and weight in product can be reduced by hydrocracking reaction
The selectivity of matter component wax etc., improves the selectivity of gasoline；Also it can increase isohydrocarbon in product by the way that isomerization reaction occurs
Ratio improves the quality (improving octane number) of gasoline.It, will for the selectivity and quality for improving gasoline in Fischer-Tropsch synthesis product
Active component in fischer-tropsch synthetic catalyst is combined with zeolite molecular sieve, converts high selectivity gasoline group for synthesis gas
Divide by more and more extensive concern.Li et al. people by the confinement of Ru nanoparticle in the duct of SBA-15 molecular sieve, due to molecule
The duct shape selectivity of sieve, the selectivity of product can break through the limitation of ASF distribution；And in this study, relative to Ru nanoparticle
Size changes the influence being distributed to product, and the influence that the duct confinement effect of SBA-15 molecular sieve is distributed product is more significant
(J.Phys.Chem.C,2008,112(26),9706–9709).Wang et al. handles ZSM-5 molecular sieve, warp using NaOH solution
After alkali process, mesopore orbit structure is formed by certain destruction inside the ZSM-5 molecular sieve, at the same time ZSM-5 molecule
There are a degree of decreases for the acidity of sieve；It is closed using the ZSM-5 molecular sieve supported active metals Ru after alkali process for Fischer-Tropsch
At reaction, which can significantly improve C in product under ZSM-5 molecular sieve mesopore orbit and acid synergistic effect5-11's
Selectivity (Angew.Chem.Int.Ed.2011,50,5200-5203).In addition, Wang et al. handles beta using NaOH solution
Molecular sieve makes the structure of beta molecular sieve by a degree of destruction, so that the beta molecular sieve with meso-hole structure is obtained,
The acidity of beta molecular sieve is reduced simultaneously；Beta molecular sieve carrier load Ru after alkali process is used to synthesize syngas conversion reactor,
The selectivity of gasoline component in product can be significantly improved and promote gasoline quality, C5-11Selectivity up to 77% (ACS
Catal.2012,2,441-449)。
In above-mentioned catalyst synthesis, molecular sieve has to pass through post-processing and is just able to achieve the mesh for being effectively improved selectivity of product
's；And molecular sieve, after post-processing, the skeleton of molecular sieve can undergo desiliconization, dealumination process, make its internal structure by serious
It destroys.Beta molecular sieve carrier in the present invention can directly construct mesoporous hole using polymer template agent during hydrothermal synthesis
Road, the template only serve the effect of pore-foaming agent, and when removing will not destroy the skeleton structure of molecular sieve.In addition, changing template
Molecular weight or dosage adjusting to molecular sieve mesopore orbit size can be achieved, change the throwing of silicon source and silicon source in synthesis process
Material ratio, can easily and effectively regulatory molecule sieve acidity；By effective adjusting to molecular sieve pore passage size and acidity, can obtain
It must be used for the beta molecular sieve carrier of F- T synthesis Efficient Conversion.The synthetic operation of catalyst is easy in the present invention, synthesis
Beta molecular sieve itself has mesopore orbit structure, and being not required to any post-treatment condition can be directly used for synthesis syngas conversion reactor, and
Highly selective under higher activity it can obtain gasoline component.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst that highly selective liquefaction is converted for synthesis gas, the catalyst pair
Fischer-Tropsch synthesis has the characteristics that high conversion, highly selective.
The purpose of the present invention is to provide the preparation method that a kind of synthesis gas converts highly selective liquefaction catalyst, this method
Have the characteristics that it is easy to operate, repeated it is strong, universality is high.
To achieve the goals above, the technical solution adopted by the present invention is that: one kind converting highly selective system for synthesis gas
The catalyst of oil, including zeolite molecular sieve carrier and active component Ru, the content of the Ru in terms of metal is 0.1~5wt%, with boiling
The content of the carrier of stone molecular sieve meter is 95~99.9wt%, and the carrier is zeolite molecular sieve beta.
A kind of preparation method converting highly selective liquefaction catalyst for synthesis gas provided by the invention, specific steps
Are as follows:
1) preparation of beta molecular sieve
Silicon source, silicon source, highly basic, template, water etc. are mixed to get homogeneous mixture, in the mixture each substance respectively with
SiO2、Al2O3、M2O、P、H2The molar ratio of O meter is 10~100SiO2:Al2O3: 0.5~50M2O:0.5~100T:100~
10000H2O, wherein M2O is alkali metal, and P is template；After 2-20h is stirred at room temperature in said mixture, it is transferred to have and gathers
In the hydrothermal synthesis kettle of tetrafluoroethene liner, it is transferred in baking oven after water heating kettle sealing, constant temperature keeps 36- at 120-250 DEG C
360h；After hydro-thermal process, the solid in water heating kettle is filtered, 3-10 times is washed with deionized to filtrate pH=6-9, will filter
The dry 4-24h in 60-150 DEG C of baking oven of solid afterwards, then roasts 2-12h under 300-800 DEG C of air atmosphere in Muffle furnace,
Obtain beta molecular sieve；
2) preparation of the molecular sieve carried Ru catalyst of beta
0.05-13.52g ruthenium precursor solution is taken to form homogeneous solution in 10-150ml deionized water, into the solution
Carrier is added and forms homogeneous mixture, in the mixture on the basis of catalyst, the content of the Ru in terms of metal is 0.1~
5wt%, the content of the carrier in terms of zeolite molecular sieve are 95~99.9wt%；The mixture of formation is heated at 40-90 DEG C and is stirred
Mix until solvent is evaporated, by obtained solid in 60-120 DEG C of baking oven dry 4-24h, then 150-500 DEG C in Muffle furnace
1-10h is roasted in air atmosphere, obtains the molecular sieve carried Ru catalyst Ru/beta of beta.
Silicon source in step 1) is one or more of fumed silica, silica solution, tetraethyl orthosilicate, sodium metasilicate；
Silicon source is one or more of sodium metaaluminate, aluminium hydroxide, aluminium powder, aluminum nitrate；Highly basic is sodium hydroxide, sodium oxide molybdena, hydrogen-oxygen
Change one or more of potassium, potassium oxide；Template be different molecular weight polydiallyldimethyl ammonium chloride solution (PDADMA),
One or more of polydiene diethylammonium chloride solution (PDADEA) of different molecular weight；Ruthenium presoma in step 2) is
RuCl3·3H2O、Ru(NO)(NO3)3、Ru2Cl4(CO)6、Ru(Ac)3One or more of.
The preferred 4-10h of mixing time in step 1).Step 1) hydrothermal temperature is 160-220 DEG C, crystallization time 72-
120h。
Maturing temperature is 400-600 DEG C in step 1), time 3-8h.
In step 2) on the basis of catalyst, the content of the Ru in terms of metal is 0.5~3wt%, the load in terms of molecular sieve
The content of body is 97~99.5wt%.
The temperature of evaporation solvent is 50-70 DEG C in step 2)；Maturing temperature is 200-350 DEG C, calcining time 2-5h.
Catalyst provided by the invention is used for Fischer-Tropsch synthesis, carries out reduction pretreatment, reduction to catalyst before reaction
Temperature is 100-600 DEG C, preferably 200-400 DEG C；Recovery time is 1-10h, preferably 2-5h；Reduction can in pure hydrogen atmosphere into
Row, can also carry out in the gaseous mixture of hydrogen and inert gas.
Catalyst provided by the invention is used for Fischer-Tropsch synthesis, and reaction evaluating condition is as follows:
Using fixed bed reactors, 150-300 DEG C of reaction temperature, preferably 180-250 DEG C；Reaction pressure 1-5MPa, preferably
1.8-2.5MPa；H in unstripped gas2Molar ratio with CO is 0.5~5, preferably 0.5~2.5；Gas volume air speed 500-10000h-1, preferably 1200-4000h-1。
The beneficial effects of the present invention are embodied in:
1) low in raw material price used in catalyst preparation provided by the invention, synthetic operation is easy, is conducive to advise greatly
Mould production and use；
2) present invention can directly synthesize the beta molecular sieve with meso-hole structure using hydrothermal synthesis method, do not need it is any after
Treatment process can be directly used as the high performance carrier materials of F- T synthesis.
3) catalyst provided by the invention can pass through the duct of the molecular-weight adjusting molecular sieve of change template in preparation
Structure, the SiO of the proportion adjustment molecular sieve by changing silicon source and silicon source2/Al2O3Than optimizing the acidity of molecular sieve；
4) catalyst provided by the invention is used in Fischer-Tropsch synthesis, and reactivity is high, does not have the weight such as paraffin in product
Matter hydrocarbon generation, isoparaffin ratio is very high up to 85%, and in oil product for the selectivity of gasoline, i.e., oil product octane number is high, has
The good capability of antidetonance.
Detailed description of the invention
Fig. 1 is molecular sieve carried Ru catalyst (1wt%Ru/30-beta-1, the 1wt% of beta with different meso-hole structures
Ru/30-beta-2 and 1wt%Ru/30-beta-3) physical absorption result.
Fig. 2 is molecular sieve carried Ru catalyst (1wt%Ru/30-beta-1, the 1wt% of beta with different meso-hole structures
Ru/30-beta-2 and 1wt%Ru/30-beta-3) Fischer-Tropsch synthesis evaluation result.
Fig. 3 is with different SiO2/Al2O3It is Ru catalyst (1wt%Ru/30- more molecular sieve carried than the beta of (acidity)
Beta-1,1wt%Ru/50-beta-1 and 1wt%Ru/70-beta-1) physical absorption result.
Fig. 4 is with different SiO2/Al2O3It is Ru catalyst (1wt%Ru/30- more molecular sieve carried than the beta of (acidity)
Beta-1,1wt%Ru/50-beta-1 and 1wt%Ru/70-beta-1) Fischer-Tropsch synthesis evaluation result.
Fig. 5 be the molecular sieve carried various sizes of Ru nano-particle catalyst of beta (0.5wt%Ru/30-beta-1,
1wt%Ru/30-beta-1 and 3wt%Ru/30-beta-1) Fischer-Tropsch reaction evaluation result.
Specific embodiment
Embodiment 1
1) by 0.75g NaAlO2, 2.50g NaOH, 7.21g fumed silica, 150ml deionized water, 20.0g poly- two
Alkene dimethylammonium chloride ammonium salt solution (PDADMA, Mw=50000~100000, P1) be uniformly mixed, 4h is stirred at room temperature；By above-mentioned mixing
Liquid is transferred in water heating kettle, is transferred in 200 DEG C of baking ovens after water heating kettle sealing, constant temperature keeps 72h；After hydro-thermal process, by hydro-thermal
Solid filtering in kettle, is washed with deionized to pH=7, filtered solid is dried 10h in 120 DEG C of baking ovens, then
550 DEG C of roasting 4h, obtain 30-beta-1 in Muffle furnace.
2) RuCl of 10wt% is weighed3·3H2O solution 0.52g, is diluted to 10ml with deionized water, 1.98g is taken to walk
The rapid 30-beta-1 1) obtained is added in above-mentioned mixed solution, is placed in 60 DEG C of water-baths until solution is evaporated；The solid that will be obtained
It is placed in 120 DEG C of baking ovens dry 10h, then is placed in 300 DEG C of Muffle kiln roasting 2h to get 1wt%Ru/30-beta-1 is arrived.
Embodiment 2
1) by 0.75g NaAlO2, 2.50g NaOH, 7.21g fumed silica, 150ml deionized water, 20.0g poly- two
Alkene dimethylammonium chloride ammonium salt solution (PDADMA, Mw=400000~500000, P2) be uniformly mixed, 4h is stirred at room temperature；By above-mentioned mixing
Liquid is transferred in water heating kettle, is transferred in 200 DEG C of baking ovens after water heating kettle sealing, constant temperature keeps 72h；After hydro-thermal process, by hydro-thermal
Solid filtering in kettle, is washed with deionized to pH=7, filtered solid is dried 10h in 120 DEG C of baking ovens, then
550 DEG C of roasting 4h, obtain 30-beta-2 in Muffle furnace.
2) RuCl of 10wt% is weighed3·3H2O solution 0.52g, is diluted to 10ml with deionized water, 1.98g is taken to walk
The rapid 30-beta-2 1) obtained is added in above-mentioned mixed solution, is placed in 60 DEG C of water-baths until solution is evaporated；The solid that will be obtained
It is placed in 120 DEG C of baking ovens dry 10h, then is placed in 300 DEG C of Muffle kiln roasting 2h to get 1wt%Ru/30-beta-2 is arrived.
Embodiment 3
1) by 0.75g NaAlO2, 2.50g NaOH, 7.21g fumed silica, 150ml deionized water, 20.0g poly- two
Alkene dimethylammonium chloride ammonium salt solution (PDADMA, 50%P1+ 50%P2, wherein P1, Mw=40000~100000；P2, Mw=400000
~500000) it is uniformly mixed, 4h is stirred at room temperature；Above-mentioned mixed liquor is transferred in water heating kettle, is transferred to 200 after water heating kettle sealing
In DEG C baking oven, constant temperature keeps 72h；After hydro-thermal process, the solid in water heating kettle is filtered, is washed with deionized to pH=7, it will
Filtered solid dry 10h in 120 DEG C of baking ovens, then 550 DEG C of roasting 4h in Muffle furnace, obtain 30-beta-3.
2) RuCl of 10wt% is weighed3·3H2O solution 0.52g, is diluted to 10ml with deionized water, 1.98g is taken to walk
The rapid 30-beta-3 1) obtained is added in above-mentioned mixed solution, is placed in 60 DEG C of water-baths until solution is evaporated；The solid that will be obtained
It is placed in 120 DEG C of baking ovens dry 10h, then is placed in 300 DEG C of Muffle kiln roasting 2h to get 1wt%Ru/30-beta-3 is arrived.
Embodiment 4
1) by 0.75g NaAlO2, 4.00g NaOH, 12.02g fumed silica, 150ml deionized water, 20.0g is poly-
Diene dimethylammonium chloride ammonium salt solution (PDADMA, Mw=50000~100000, P1) be uniformly mixed, 4h is stirred at room temperature；It will be above-mentioned mixed
It closes liquid to be transferred in water heating kettle, be transferred in 200 DEG C of baking ovens after water heating kettle sealing, constant temperature keeps 72h；After hydro-thermal process, by water
Solid filtering in hot kettle, is washed with deionized to pH=7, filtered solid is dried 10h in 120 DEG C of baking ovens, so
550 DEG C of roasting 4h in Muffle furnace afterwards, obtain 50-beta-1.
2) RuCl of 10wt% is weighed3·3H2O solution 0.52g, is diluted to 10ml with deionized water, 1.98g is taken to walk
The rapid 50-beta-1 1) obtained is added in above-mentioned mixed solution, is placed in 60 DEG C of water-baths until solution is evaporated；The solid that will be obtained
It is placed in 120 DEG C of baking ovens dry 10h, then is placed in 300 DEG C of Muffle kiln roasting 2h to get 1wt%Ru/50-beta-1 is arrived.
Embodiment 5
1) by 0.75g NaAlO2, 5.60g NaOH, 16.82g fumed silica, 150ml deionized water, 20.0g is poly-
Diene dimethylammonium chloride ammonium salt solution (PDADMA, Mw=50000~100000, P1) be uniformly mixed, 4h is stirred at room temperature；It will be above-mentioned mixed
It closes liquid to be transferred in water heating kettle, be transferred in 200 DEG C of baking ovens after water heating kettle sealing, constant temperature keeps 72h；After hydro-thermal process, by water
Solid filtering in hot kettle, is washed with deionized to pH=7, filtered solid is dried 10h in 120 DEG C of baking ovens, so
550 DEG C of roasting 4h in Muffle furnace afterwards, obtain 70-beta-1.
2) RuCl of 10wt% is weighed3·3H2O solution 0.52g, is diluted to 10ml with deionized water, 1.98g is taken to walk
The rapid 70-beta-1 1) obtained is added in above-mentioned mixed solution, is placed in 60 DEG C of water-baths until solution is evaporated；The solid that will be obtained
It is placed in 120 DEG C of baking ovens dry 10h, then is placed in 300 DEG C of Muffle kiln roasting 2h to get 1wt%Ru/70-beta-1 is arrived.
Embodiment 6
1) by 0.75g NaAlO2, 2.50g NaOH, 7.21g fumed silica, 150ml deionized water, 20.0g poly- two
Alkene dimethylammonium chloride ammonium salt solution (PDADMA, Mw=50000~100000, P1) be uniformly mixed, 4h is stirred at room temperature；By above-mentioned mixing
Liquid is transferred in water heating kettle, is transferred in 200 DEG C of baking ovens after water heating kettle sealing, constant temperature keeps 72h；After hydro-thermal process, by hydro-thermal
Solid filtering in kettle, is washed with deionized to pH=7, filtered solid is dried 10h in 120 DEG C of baking ovens, then
550 DEG C of roasting 4h, obtain 30-beta-1 in Muffle furnace.
2) RuCl of 10wt% is weighed3·3H2O solution 0.26g, is diluted to 10ml with deionized water, 1.99g is taken to walk
The rapid beta-30Si/Al 1) obtained2-P1It is added in above-mentioned mixed solution, is placed in 60 DEG C of water-baths until solution is evaporated；It will obtain
Solid be placed in 120 DEG C of baking ovens dry 10h, then be placed in 300 DEG C of Muffle kiln roasting 2h to get to 0.5wt%Ru/30-
beta-1。
Embodiment 7
1) by 0.75g NaAlO2, 2.50g NaOH, 7.21g fumed silica, 150ml deionized water, 20.0g poly- two
Alkene dimethylammonium chloride ammonium salt solution (PDADMA, Mw=50000~100000, P1) be uniformly mixed, 4h is stirred at room temperature；By above-mentioned mixing
Liquid is transferred in water heating kettle, is transferred in 200 DEG C of baking ovens after water heating kettle sealing, constant temperature keeps 72h；After hydro-thermal process, by hydro-thermal
Solid filtering in kettle, is washed with deionized to pH=7, filtered solid is dried 10h in 120 DEG C of baking ovens, then
550 DEG C of roasting 4h, obtain 30-beta-1 in Muffle furnace.
2) RuCl of 10wt% is weighed3·3H2O solution 1.56g, is diluted to 10ml with deionized water, 1.94g is taken to walk
The rapid 30-beta-1 1) obtained is added in above-mentioned mixed solution, is placed in 60 DEG C of water-baths until solution is evaporated；The solid that will be obtained
It is placed in 120 DEG C of baking ovens dry 10h, then is placed in 300 DEG C of Muffle kiln roasting 2h to get 3wt%Ru/30-beta-1 is arrived.
Catalyst performance test
The catalyst 1.0g prepared in embodiment 1-7 is seated in fixed bed reactors respectively, it is anti-to carry out F- T synthesis
Answer catalytic performance test.H is used first2Reduction treatment, temperature are 300 DEG C, and pressure is normal pressure.Fischer-Tropsch synthesis condition are as follows:
180-240 DEG C of reaction temperature, reaction pressure 1.8-2.2MPa, synthesis gas volume space velocity 1200-3000h-1, H2It is with CO molar ratio
2.Gaseous product uses gas-chromatography on-line analysis, and the product liquid being collected into uses gas-chromatography offline analysis.
Claims (10)
1. a kind of catalyst for Fischer-Tropsch synthesis, it is characterised in that: the catalyst is that synthesis gas conversion is highly selective
The catalyst of gasoline processed；Catalyst includes zeolite molecular sieve carrier and active component Ru.
2. catalyst described in accordance with the claim 1, it is characterised in that: the content of the Ru in terms of metal is 0.1~5wt%, institute
Stating carrier is zeolite molecular sieve beta.
3. a kind of preparation method of the fischer-tropsch synthetic catalyst according to claim 1 or 2 containing zeolite molecular sieve, feature exist
In synthesis step is as follows:
1) preparation of beta molecular sieve
Silicon source, silicon source, highly basic, template, water etc. are mixed to get homogeneous mixture, each substance is respectively with SiO in the mixture2、
Al2O3、M2O、P、H2The molar ratio of O meter is 10~100SiO2:Al2O3: 0.5~50M2O:0.5~100T:100~10000H2O,
Wherein M2O is alkali metal, and P is template；After 2-20h is stirred at room temperature in said mixture, it is transferred to polytetrafluoroethylene (PTFE)
In the hydrothermal synthesis kettle of liner, it is transferred in baking oven after water heating kettle sealing, constant temperature keeps 36-360h at 120-250 DEG C；At hydro-thermal
After reason, the solid in water heating kettle is filtered, is washed with deionized 3-10 times to filtrate pH=6-9, by filtered solid in
Then dry 4-24h in 60-150 DEG C of baking oven roasts 2-12h in Muffle furnace to get beta is arrived under 300-800 DEG C of air atmosphere
Molecular sieve；
2) preparation of the molecular sieve carried Ru catalyst of beta
It takes 0.05-13.52g ruthenium precursor solution to form homogeneous solution in 10-150ml deionized water, is added into the solution
Carrier forms homogeneous mixture, and in the mixture on the basis of catalyst, the content of the Ru in terms of metal is 0.1~5wt%；Shape
At mixture at 40-90 DEG C heating stirring until solvent is evaporated, by obtained solid in 60-120 DEG C of baking oven dry 4-
For 24 hours, 1-10h then is roasted in 150-500 DEG C of air atmosphere in Muffle furnace, obtains the molecular sieve carried Ru catalyst of beta
Ru/beta。
4. the preparation method of catalyst according to claim 3, it is characterised in that: the silicon source in step 1) is gas phase dioxy
One or more of SiClx, silica solution, tetraethyl orthosilicate, sodium metasilicate；Silicon source is sodium metaaluminate, aluminium hydroxide, aluminium powder, nitric acid
One or more of aluminium；Highly basic is one or more of sodium hydroxide, sodium oxide molybdena, potassium hydroxide, potassium oxide；Template is
The polydiene diethylammonium chloride solution of the polydiallyldimethyl ammonium chloride solution (PDADMA) of different molecular weight, different molecular weight
One or more of (PDADEA)；Ruthenium presoma in step 2) is RuCl3·3H2O、Ru(NO)(NO3)3、Ru2Cl4
(CO)6、Ru(Ac)3One or more of.
5. the preparation method of catalyst according to claim 3, it is characterised in that: step 1) hydrothermal temperature is 160-220
DEG C, crystallization time 72-120h.
6. the preparation method of catalyst according to claim 3, it is characterised in that: maturing temperature is 400- in step 1)
600 DEG C, time 3-8h.
7. the preparation method of catalyst according to claim 3, it is characterised in that: Ru's in step 2) in terms of metal contains
Amount is 0.5~3wt%.
8. the preparation method of catalyst according to claim 3, it is characterised in that: the temperature of evaporation solvent is in step 2)
50-70℃；Maturing temperature is 200-350 DEG C, calcining time 2-5h.
9. a kind of application of catalyst described in accordance with the claim 1, it is characterised in that: restore to catalyst before reaction pre-
Processing, reduction temperature are 100-600 DEG C, preferably 200-400 DEG C；Recovery time is 1-10h, preferably 2-5h；Reduction can be in pure hydrogen
It carries out, can also be carried out in the gaseous mixture of hydrogen and inert gas in atmosphere.
10. the application of catalyst according to claim 9, it is characterised in that: catalyst reaction evaluation is anti-using fixed bed
Answer device, 150-300 DEG C of reaction temperature (preferably 180-250 DEG C)；Reaction pressure 1-5MPa (1.8-2.5MPa)；H in unstripped gas2With
The molar ratio of CO is 0.5~5 (preferably 0.5~2.5)；Gas volume air speed 500-10000h-1(preferably 1200-4000h-1)。
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