CN103861591B - Selective oxidation removes load type nano gold catalyst and the Synthesis and applications thereof of CO - Google Patents
Selective oxidation removes load type nano gold catalyst and the Synthesis and applications thereof of CO Download PDFInfo
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- CN103861591B CN103861591B CN201210551593.1A CN201210551593A CN103861591B CN 103861591 B CN103861591 B CN 103861591B CN 201210551593 A CN201210551593 A CN 201210551593A CN 103861591 B CN103861591 B CN 103861591B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention is a kind of high activity, high selectivity and the load type gold catalyst and preparation method thereof of selective oxidation CO in the stable hydrogen-rich gas of reactivity worth.Active component is Au, and carrier is LaMO
3-M
xo
ycomposite oxides, wherein M=Al, Fe, Mn, Co, Ni or Ga.LaMO
3-M
xo
ycomposite oxides adopt infusion process or coprecipitation preparation, and rare metal La is incorporated into M
xo
yon oxide, through 700-1000 ° of C roasting to make La and M
xo
ym element " original position " in oxide generates LaMO
3perovskite structure.LaMO
3-M
xo
ycomposite oxides support Au catalyst, have preparation process and are simple and easy to large-scale production, catalytic activity and selective high, under hydrogen rich gas atmosphere in CO Selective Oxidation, can complete oxidation CO be CO in very wide temperature of fuel cell window
2.
Description
Technical field
The present invention relates to catalyst technical field, particularly relate to a kind of high activity, high selectivity and the preparation method of the load type nano gold catalyst of selective oxidation CO in the stable hydrogen-rich gas of reactivity worth.
Background technology
Fuel cell is Proton Exchange Membrane Fuel Cells (PEMFC) especially, is one of most important application places of current Hydrogen Energy, and it is a kind of fuel cell of clean, efficient, green, environmental protection, has fabulous application prospect.Because the key position Pt electrode of PEMFC anode is easy to be poisoned by CO, thus the content of CO in hydrogen-rich gas must be controlled at least below 50ppm.Within the scope of general work temperature 60 ~ 120 ° of C of fuel cell, at rich H
2in gas, selective oxidation removes CO(CO-PROX) be the method for the most simple and effective solution fuel cell electrode poisoning problem.
Pt, Au catalyst of support type is the noble metal CO selective oxidation catalyst of most study.Adopt ion-exchange as (USPatent6,168,772 and 5,702,838) are disclosed, by Pt load on A, Y zeolite, although the loading of its Pt is up to 3 ~ 6%, be only 2000 ~ 8000h in air speed
-1time, its optimum operating temperature still needs 200 ° of about C.Compare Pt catalyst, nano-Au catalyst has unique low temperature active to CO oxidation and to H
2oxidation activity is lower, is more preferably CO selective oxidation catalyst.Compare with the result of patent report with existing document, University Of Yantai An Lidun professor etc. has invented a series of Al with higher CO oxidation activity
2o
3, Fe
2o
3, TiO
2deng the Au catalyst (CN00122829.3, CN03138786.1, CN201010189525.6, CN201010516171.1) of oxide supported; And, by by LaFeO
3, LaCoO
3, LaNiO
3deng perovskite or spinel structure transition metal oxide be incorporated into Al
2o
3surface, to form composite oxides (CN200410024509.6, CN200910019345.0), greatly enhance the stable storing performance of load type nano gold catalyst, but its catalyst series is to H
2oxidation activity higher equally, thus its CO oxidation selectivity in CO-PROX is poor.
Au catalyst is difficult to obtain higher CO oxidation selectivity in CO-PROX reaction, and main cause has two: 1, the adsorption capacity of Au to CO is more weak, as easy as rolling off a log desorption when temperature is higher; 2, when temperature is higher than 60 ° of C, H on Au catalyst
2oxidation rate be increased sharply, and higher than the oxidation rate of CO.The present invention is directed to above two reasons, design has been prepared at M
xo
y(M=Al, Fe, Mn, Co, Ni, Ga metal) oxide surface introduces La element, makes La and M through high-temperature roasting
xo
yin oxide, M element " original position " generates LaMO
3perovskite type metal oxide; Pass through LaMO
3-M
xo
ycomposite oxide supported Au catalyst, improves the adsorption strength of CO on Au position, and greatly reduces H on catalyst
2oxidation rate, thus the temperature window transformed completely by CO on Au catalyst is widened to temperature of fuel cell interval.
Summary of the invention
Technical problem solved by the invention is, provides the preparation method of the load type nano gold catalyst of CO selective oxidation under a kind of high activity and the hydrogen-rich gas selective, reactivity worth is stable.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A nano catalyst of selective oxidation CO in the hydrogen-rich gas that high activity, high selectivity and reactivity worth are stable, is characterized in that: active component is Au, and carrier is at M
xo
yoxide surface " original position " generates La system LaMO
3(M=Al, Fe, Mn, Co, Ni, Ga metal) perovskite type metal oxide and obtained complex carrier.Noble metal Au accounts for the 0.1-3% of complex carrier weight content, LaMO in complex carrier
3with M
xo
yweight ratio be 1: 99-1: 1.
Wherein, composite oxide carrier adopts infusion process or coprecipitation preparation, and the precursor solution of La is impregnated into M
xo
yon oxide or the precursor salt solution of La and M under the effect of alkali after co-precipitation, after aging, drying, in 700-1000 ° of C roasting, to make LaMO
3perovskite metal oxide is at M
xo
ysurface is formed.
The load of Au adopts anion infusion process or deposition-precipitation method.Wherein, anion infusion process first regulates the pH value of chlorauric acid solution to 6-11, then poured into by complex carrier and leave standstill aging, through washing, dry, and finally reduction and obtain finished catalyst in roasting or hydrogen stream in atmosphere; Deposition-precipitation method is added in chlorauric acid solution by above-mentioned complex carrier, regulates solution ph to maintain 5-10, reaction 1-6h, then after filtration or centrifugal, washing, dry, and finally also reduction and obtained finished catalyst in roasting or hydrogen in atmosphere.
The above-mentioned adjust ph mentioned aqueous slkali used, comprises NaOH, Na
2cO
3, KOH, K
2cO
3, (NH
4)
2cO
3in one or more the aqueous solution.
The present invention adopts LaMO
3modification M
xo
ypreparation load type nano gold catalyst, its essential characteristic is: LaMO
3perovskite type metal oxide " original position " is incorporated into M
xo
yoxide surface, improves the adsorption strength of reacting gas CO on Au position, greatly reduces competitive reaction gas H simultaneously
2oxidation rate, thus improve the CO oxidation selectivity of catalyst, significantly widened the temperature window of catalyst complete oxidation CO.
Desirable (existing without steam and carbon dioxide) or under simulating practical gas (water and carbon dioxide exist) condition, LaMO
3-M
xo
ythe Au catalyst that composite oxides support all has more excellent stable reaction performance.
Compared with the prior art, have the following advantages:
Although 1 preparation method is simple, in prepared catalyst, the domain size distribution of Au is narrower, and particle is less, and average grain diameter is at about 2nm;
2, in hydrogen-rich gas, the activity and selectivity of CO selective oxidation is high, has significantly widened the temperature window of Au catalyst complete oxidation CO in temperature of fuel cell interval;
3, in desirable or that simulation is practical gas, this catalyst has good stable reaction performance.
4, during this catalyst can also be applied to containing a certain amount of steam air CO oxidation reaction in, there is good reactivity equally.
Accompanying drawing explanation
Fig. 1 is 1%Au/20%LaAlO prepared by embodiment 1
3-Al
2o
3the HRTEM photo of (being abbreviated as Au/20%LA) catalyst and domain size distribution statistical chart thereof;
Fig. 2 is the 20%LaAlO by different temperatures roasting in embodiment 1
3-Al
2o
3the XRD figure of Au catalyst prepared by complex carrier
Fig. 3 is the activity and selectivity of Au catalyst in CO-PROX reaction prepared by comparative example 1,2 and embodiment 1
Catalytic reaction condition: fixed-bed micro-reactor, tube inner diameter 6mm; Unstripped gas consists of CO: O
2: H
2: He=1: 1: 40: 58, unstripped gas air speed is 60,000mlg
-1cath
-1.
Fig. 4 is the 1%Au/LaAlO adopting embodiment 1 method to prepare
3-Al
2o
3the stability of (letter is Au/LA) catalyst in CO-PROX reaction
Reaction condition: 80 ° of C, air speed: 60,000mL/g/h, normal pressure.Each reactor feed gas is as follows:
PROX:1%CO+1%O
2+40%H
2+He；
PROX+H
2O:1%CO+1%O
2+40%H
2+10%H
2O+He；
PROX+H
2O+CO
2：1%CO+1%O
2+40%H
2+10%H
2O+20%CO
2+He。
Fig. 5 is that the reaction speed of Au catalyst under differential responses atmosphere adopting comparative example and embodiment 1 method to prepare compares
Reaction condition: normal pressure, 80 ° of C, reactor feed gas is as follows:
CO oxidation reaction: 2%CO+2%O
2+ 96%He;
H
2oxidation reaction: 40%H
2+ 2%O
2+ 58%He;
CO-PROX reacts: 2%CO+2%O
2+ 40%H
2+ 56%He.
Detailed description of the invention
Comparative example 1
1%Au/Al
2o
3preparation:
Anion infusion process: measure chlorauric acid solution (9.56g/L) 1.06ml, drips NaOH solution (1M) to solution ph to 6-11, then adds water 0.3mL, by 1.0006gAl
2o
3carrier is poured into and is left standstill aging 2-12h, after abundant washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/Al
2o
3finished catalyst;
Deposition-precipitation method: by 1.0006gAl
2o
3carrier is poured in 10.6ml chlorauric acid solution (0.956g/L), drip NaOH solution (1M) adjust pH and maintain between 5-10, in 40-80 DEG C of reaction 1-6h, after centrifugal or filtration, washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/Al
2o
3finished catalyst.
Comparative example 2
4.5%Au/Fe
2O
3-WGC：
Au/Fe prepared by the coprecipitation that WGC provides
2o
3catalyst is the CO-PROX Au catalyst that a kind of reactivity is higher, as comparative catalyst of the present invention.
Embodiment 1
1,20%LaAlO
3-Al
2o
3preparation:
Infusion process: weigh 1.070gLa (NO
3)
3.6H
2o is fully dissolved in 2.9ml deionized water, pours 2.0008gAl into
2o
3carrier (α or γ type), stirs, and leaves standstill 10h, then in the dry 12h of 100-150 ° of C, finally calcines 2-12h through 700-1000 ° of C and obtains 20wt.%LaAlO
3/ Al
2o
3complex carrier;
Coprecipitation: weigh 1.070gLa (NO
3)
3.6H
2o and 11.6960gAl (NO
3)
3.9H
2o is dissolved in 25mL deionized water, be added drop-wise under stirring condition in the NaOH solution of 50mL6mol/L and (also NaOH solution can be added drop-wise in the mixed solution of La, Al), be added dropwise to complete rear continuation and stir 2-5h and aging 2-12h, then after filtering washing, in the dry 12h of 100-150 ° of C, calcine 2-12h through 700-1000 ° of C and obtain 20wt.%LaAlO equally
3/ Al
2o
3complex carrier.
2,1%Au/20%LaAlO
3-Al
2o
3preparation:
Anion infusion process: measure chlorauric acid solution (9.56g/L) 1.06ml, drips NaOH solution (1M) to solution ph to 6-11, then adds water 0.3mL, by 1.0006g20wt.%LaAlO
3/ Al
2o
3complex carrier is poured into and is left standstill aging 2-12h, after abundant washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaAlO
3-Al
2o
3finished catalyst, letter is 1%Au/20%LA;
Deposition-precipitation method: by 1.0006g20wt.%LaAlO
3/ Al
2o
3complex carrier is poured in 10.6ml chlorauric acid solution (0.956g/L), drip NaOH solution (1M) adjust pH and maintain between 5-10, in 40-80 DEG C of reaction 1-6h, after centrifugal or filtration, washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaAlO
3-Al
2o
3finished catalyst.
Embodiment 2
1,20%LaFeO
3-Fe
2o
3preparation:
Infusion process: weigh 0.7131gLa (NO
3)
3.6H
2o is fully dissolved in 1.4ml deionized water, pours 1.7318gFe into
2o
3carrier (α or γ type), stirs, and leaves standstill 10h, then in the dry 12h of 100-150 ° of C, finally calcines 2-12h through 700-1000 ° of C and obtains 20wt.%LaFeO
3/ Fe
2o
3complex carrier;
Coprecipitation: weigh 0.7131gLa (NO
3)
3.6H2O with 8.7451gFe (NO
3)
3.9H
2o is dissolved in 25mL deionized water, be added drop-wise under stirring condition in the NaOH solution of 50mL6mol/L and (also NaOH solution can be added drop-wise in the mixed solution of La, Fe), be added dropwise to complete rear continuation and stir 2-5h and aging 2-12h, then after filtering washing, in the dry 12h of 100-150 ° of C, calcine 2-12h through 700-1000 ° of C and obtain 20wt.%LaFeO equally
3/ Fe
2o
3complex carrier.
2,1%Au/20%LaFeO
3-Fe
2o
3preparation:
Anion infusion process: measure chlorauric acid solution (19.13g/L) 0.53ml, drips NaOH solution (1M) to solution ph to 6-11, by 1.0006g20wt.%LaFeO
3/ Fe
2o
3complex carrier is poured into and is left standstill aging 2-12h, after abundant washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaFeO
3-Fe
2o
3finished catalyst;
Deposition-precipitation method: by 1.0006g20wt.%LaFeO
3/ Fe
2o
3complex carrier is poured in 10.6ml chlorauric acid solution (0.956g/L), drip NaOH solution (1M) adjust pH and maintain between 5-10, in 40-80 DEG C of reaction 1-6h, after centrifugal or filtration, washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaFeO
3-Fe
2o
3finished catalyst.
Embodiment 3
1,20%LaMnO
3-MnO
2preparation:
Infusion process: weigh 0.7162gLa (NO
3)
3.6H
2o is fully dissolved in 1.6ml deionized water, pours 1.7272gMnO into
2carrier, stirs, and leaves standstill 10h, then in the dry 12h of 100-150 ° of C, finally calcines 2-12h through 700-1000 ° of C and obtains 20wt.%LaMnO
3/ MnO
2complex carrier;
Coprecipitation: weigh 0.7162gLa (NO
3)
3.6H
2o and 5.6126gMn (NO
3)
24H
2o is dissolved in 25mL deionized water, be added drop-wise under stirring condition in the NaOH solution of 50mL6mol/L and (also NaOH solution can be added drop-wise in the mixed solution of La, Mn), be added dropwise to complete rear continuation and stir 2-5h and aging 2-12h, then after filtering washing, in the dry 12h of 100-150 ° of C, calcine 2-12h through 700-1000 ° of C and obtain 20wt.%LaMnO equally
3/ MnO
2complex carrier.
2,1%Au/20%LaMnO
3-MnO
2preparation:
Anion infusion process: measure chlorauric acid solution (19.13g/L) 0.53ml, drips NaOH solution (1M) to solution ph to 6-11, by 1.0006g20wt.%LaMnO
3/ MnO
2complex carrier is poured into and is left standstill aging 2-12h, after abundant washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaMnO
3-MnO
2finished catalyst;
Deposition-precipitation method: by 1.0006g20wt.%LaMnO
3/ MnO
2complex carrier is poured in 10.6ml chlorauric acid solution (0.956g/L), drip NaOH solution (1M) adjust pH and maintain between 5-10, in 40-80 DEG C of reaction 1-6h, after centrifugal or filtration, washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaMnO
3-MnO
2finished catalyst.
Embodiment 4
1,20%LaCoO
3-Co
3o
4preparation:
Infusion process: weigh 0.7046gLa (NO
3)
3.6H
2o is fully dissolved in 1.4ml deionized water, pours 1.7306gCo into
3o
4carrier, stirs, and leaves standstill 10h, then in the dry 12h of 100-150 ° of C, finally calcines 2-12h through 700-1000 ° of C and obtains 20wt.%LaCoO
3/ Co
3o
4complex carrier;
Coprecipitation: weigh 0.7046gLa (NO
3)
3.6H
2o and 6.2752gCo (NO
3)
3.6H
2o is dissolved in 25mL deionized water, be added drop-wise under stirring condition in the NaOH solution of 50mL6mol/L and (also NaOH solution can be added drop-wise in the mixed solution of La, Co), be added dropwise to complete rear continuation and stir 2-5h and aging 2-12h, then after filtering washing, in the dry 12h of 100-150 ° of C, calcine 2-12h through 700-1000 ° of C and obtain 20wt.%LaCoO equally
3/ Co
3o
4complex carrier.
2,1%Au/20%LaCoO
3-Co
3o
4preparation:
Anion infusion process: measure chlorauric acid solution (19.13g/L) 0.53ml, drips NaOH solution (1M) to solution ph to 6-11, by 1.0006g20wt.%LaCoO
3/ Co
3o
4complex carrier is poured into and is left standstill aging 2-12h, after abundant washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaCoO
3-Co
3o
4finished catalyst;
Deposition-precipitation method: by 1.0006g20wt.%LaCoO
3/ Co
3o
4complex carrier is poured in 10.6ml chlorauric acid solution (0.956g/L), drip NaOH solution (1M) adjust solution ph and maintain between 5-10, in 40-80 DEG C of reaction 1-6h, after centrifugal or filtration, washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaCoO
3-Co
3o
4finished catalyst.
Embodiment 5
1,20%LaNiO
3the preparation of-NiO:
Infusion process: weigh 0.7052gLa (NO
3)
3.6H
2o is fully dissolved in 1.4ml deionized water, pours 1.7217gNiO carrier into, stirs, and leaves standstill 10h, then in the dry 12h of 100-150 ° of C, finally calcines 2-12h through 700-1000 ° of C and obtains 20wt.%LaNiO
3/ NiO complex carrier;
Coprecipitation: weigh 0.7052gLa (NO
3)
3.6H
2o and 6.7026gNi (NO
3)
2.6H
2o is dissolved in 25mL deionized water, be added drop-wise under stirring condition in the NaOH solution of 50mL6mol/L and (also NaOH solution can be added drop-wise in the mixed solution of La, Ni), be added dropwise to complete rear continuation and stir 2-5h and aging 2-12h, then after filtering washing, in the dry 12h of 100-150 ° of C, calcine 2-12h through 700-1000 ° of C and obtain 20wt.%LaNiO equally
3/ NiO complex carrier.
2,1%Au/20%LaNiO
3the preparation of-NiO:
Anion infusion process: measure chlorauric acid solution (19.13g/L) 0.53ml, drips NaOH solution (1M) to solution ph to 6-11, by 1.0006g20wt.%LaNiO
3/ NiO complex carrier is poured into and is left standstill aging 2-12h, after abundant washing, in the dry 2-24h of 50-110 ° of C, finally under 100-500 ° of C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaNiO
3-NiO finished catalyst;
Deposition-precipitation method: by 1.0006g20wt.%LaNiO
3/ NiO complex carrier is poured in 10.6ml chlorauric acid solution (0.956g/L), drip NaOH solution (1M) adjust solution ph and maintain between 5-10, in 40-80 DEG C of reaction 1-6h, after centrifugal or filtration, washing, in the dry 2-24h of 50-110 ° of C, finally at 100-500 DEG C in air in roasting or hydrogen stream reductase 12-6h obtain 1%Au/20%LaNiO
3-NiO finished catalyst.
Although carried out detailed, concrete description to the preparation of catalyst in description, obviously this area researcher still can infer other apparent change and content after having read the description of description above.Therefore, the invention is not restricted to specific embodiment in literary composition, allly also should to be included in the application with the not contrary content of spirit and scope of the invention.
Claims (6)
1. selective oxidation removes the load type nano gold catalyst of CO, it is characterized in that: active component is Au, and carrier is at M
xo
ythe complex carrier that oxide surface " original position " generates one or two or more kinds in La system perovskite type metal oxide and obtains, La system perovskite type metal oxide is LaMO
3, wherein M=Al, Fe, Mn, Co, Ni or Ga, x be 1,2 or 3, y be 1,2,3 or 4.
2. according to nano catalyst according to claim 1, it is characterized in that: noble metal Au accounts for the 0.1-3% of complex carrier weight content, LaMO in complex carrier
3with M
xo
yweight ratio be 1:99-1:1.
3. a preparation method for the nano catalyst described in claim 1 or 2, is characterized in that: La system LaMO
3perovskite type metal oxide and M
xo
ycomplex carrier be adopt infusion process or coprecipitation preparation, the precursor solution of La is impregnated into M
xo
yon oxide or the precursor salt solution of La and M under the effect of alkali after co-precipitation, through aging, dry, and 700-1000 DEG C of roasting, to make LaMO
3perovskite metal oxide is at M
xo
ysurface is formed; Then, on above-mentioned complex carrier, support the salting liquid of noble metal Au with anion infusion process or deposition-precipitation method, obtain finished catalyst through aging, washing, drying, activation process.
4., according to preparation method according to claim 3, it is characterized in that:
1) preparation of complex carrier:
Infusion process: by M
xo
yoxide joins in the precursor salt solution of La, stirs, and leaves standstill 2-12h, then dries 2-24h, final 700-1000 DEG C of calcining 2-12h for 100-150 DEG C;
Coprecipitation: the precursor salt solution of La and M is mixed, and then be added drop-wise in aqueous slkali or aqueous slkali is added drop-wise in the mixed solution of La, M, stir 2-5h and aging 2-12h; Then 2-24h, final 700-1000 DEG C of calcining 2-12h is dried for 100-150 DEG C;
Wherein, the precursor salt solution of La is the solution containing one or more lanthanum nitrates, lanthanum chloride, lanthanum oxalate or lanthanum sulfate, and the salting liquid of M metal is also the solution containing one or more its nitrate, chlorate, oxalates or sulfate;
2) Precious Metals-Gold catalyst preparing: adopt anion infusion process or deposition-precipitation method;
Wherein, when adopting anion infusion process, first regulate the pH value of chlorauric acid solution to 6-11, complex carrier is poured into and leaves standstill aging 2-12h, after fully washing, 50-110 DEG C of dry 2-24h, reductase 12-6h in roasting or hydrogen stream in air at 100-500 DEG C, obtained finished catalyst;
Deposition-precipitation method is added in chlorauric acid solution by above-mentioned complex carrier, regulate solution ph to maintain 5-10,40-80 DEG C of reaction 1-6h, filter or centrifugal, deionized water washing, drying afterwards, roasting or reduction treatment, with anion infusion process, finally also obtain finished catalyst;
Said adjust ph aqueous slkali used comprises NaOH, Na
2cO
3, KOH, K
2cO
3, (NH
4)
2cO
3in one or more the aqueous solution.
5. according to preparation method according to claim 4, it is characterized in that: the precursor solution of La is impregnated into M
xo
yon oxide or the precursor salt solution of La and M under the effect of alkali after co-precipitation, after aging, dry, roasting, M
xo
ysurface " original position " forms one deck LaMO
3perovskite metal oxide; Wherein, M
xo
ybe respectively α-Al
2o
3, γ-Al
2o
3, α-Fe
2o
3, γ-Fe
2o
3, MnO
2, Co
3o
4, NiO, α-Ga
2o
3, γ-Ga
2o
3one in metal oxide or two kinds, LaMO
3be respectively LaAlO
3, LaFeO
3, LaMnO
3, LaCoO
3, LaNiO
3, LaGaO
3one in perofskite type oxide or two kinds.
6. the application of catalyst according to claim 1 in hydrogen-rich gas in CO selective oxidation, the feature of its concrete reaction condition is: reaction gas consists of 0.5 ~ 2%CO, 0.5 ~ 2%O
2, H
2balance, reaction pressure is normal pressure, reaction temperature-30 ~ 160 DEG C.
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