CN103769113A - Supported binary metal oxide nano-catalyst and preparation method thereof - Google Patents
Supported binary metal oxide nano-catalyst and preparation method thereof Download PDFInfo
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- CN103769113A CN103769113A CN201310662665.4A CN201310662665A CN103769113A CN 103769113 A CN103769113 A CN 103769113A CN 201310662665 A CN201310662665 A CN 201310662665A CN 103769113 A CN103769113 A CN 103769113A
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Abstract
The invention discloses a supported binary metal oxide nano-catalyst and a preparation method of the supported binary metal oxide nano-catalyst. The preparation method comprises the following steps: (1) performing ultrasonic immersing on Ti0.5Sn0.5O2 composite oxide into Ce(NO3)3 solution, performing oil bath to evaporate out water, performing vacuum drying, grinding and roasting so as to obtain CeO2/Ti0.5Sn0.5O2 nano-catalyst; (2) performing ultrasonic immersing on the CeO2/Ti0.5Sn0.5O2 nano-catalyst obtained in the step (1) into Fe(NO3)3 solution, performing oil batch to evaporate out water, performing vacuum drying, grinding and roasting to obtain supported binary metal oxide nano-catalyst of Fe2O3/CeO2/CeO2/Ti0.5Sn0.5O2. The nano-catalyst and the preparation method provided by the invention have the advantages of adoption of cheap and easily available raw materials, simple method and equipment, low energy consumption, small pollution and potential industrial application and the like, large-scale production can be realized and the catalytic performance is excellent.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to nano material of binary metal load and preparation method thereof.
Background technology
NO
xelimination is one of the important topic polluted that controls environment, and CO Reduction of NO
xbe to eliminate the important reaction of automobile exhaust pollution thing, the general catalyst adopting is that noble metal (Rh, Pt and Pd) loads on TiO
2, Al
2o
3, ZrO
2and CeO
2on carrier, the activity that these catalyst are done well in CO+NO reaction.But consider the practicality of noble metal and expensive price, be difficult to large scale application; Base metal and metal oxide have been widely used and have revealed good activity at pyrometric scale at present simultaneously, have made up the shortcoming of the easy high temperature deactivation of noble metal.
Ferrum-based catalyst shows good activity in CO+NO reaction, for example, and Fe
2o
3, ferrous metal oxide, iron ion exchange material and high degree of dispersion ferrum-based catalyst.In early days, Shelef etc. has reported Al
2o
3and ZrO
2metal oxide supporting catalyst active order in NO+CO reaction is: Fe
2o
3>Cu
2o>Cr
2o
3>NiO>Co
3o
4>MnO>V
2o
5.Visible, Fe
2o
3specific activity better.In addition due to Fe
2o
3there is good heat endurance, in catalytic reaction, there is good application prospect.
CeO
2as the carrier of environmental protection catalyst, it shows the character of many uniquenesses and is subject to people's attention.CeO
2in three-way catalyst, commonly use as improver.It not only can promote the dispersion of active component and improve the activity of active component, but also can strengthen depositing oxygen storage capacity and improving the heat endurance of catalyst of catalyst.
If can be by ferrous metal oxide, CeO
2fully merge and load on Ti
0.5sn
0.5o
2on composite oxides, as CO Reduction of NO
xcatalyst will there is good catalytic effect.
Summary of the invention
The object of the present invention is to provide a kind of load binary metal oxide nanocatalyst and preparation method thereof, by adopting simple method to prepare high activity, high-temperature stability is good, has high NO and eliminate the load binary metal oxide nanocatalyst of performance; The raw material adopting is easy to get, simple to operate, without especial equipment requirements, makes it have good application prospect at catalytic field.
Technical solution of the present invention is as follows:
A preparation method for load binary metal oxide nanocatalyst, it comprises the steps:
(1) by Ti
0.5sn
0.5o
2composite oxides are put into Ce (NO
3)
3ultrasonic immersing 1.5～2h in solution, supersonic frequency is 2000～5000Hz; And then adopt 115～130 ℃ of oil baths to stir evaporating water; Vacuum drying 8～11h at 90～100 ℃, grinds, and the lower 500 ℃ of roasting 3.5～4h of air atmosphere, obtain CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into Fe (NO
3)
3ultrasonic immersing 1.5～2h in solution, supersonic frequency is 2000～5000Hz; And then adopt 115～130 ℃ of oil baths to stir evaporating water; Proceeding to vacuum drying 8～11h at 90～100 ℃, grinding, the lower 500 ℃ of roasting 3.5～4h of air atmosphere, obtain Fe
2o
3/ CeO
2/ Ti
0.5sn
0.5o
2load binary metal oxide nanocatalyst.
Further preferred version as load binary metal oxide nanocatalyst preparation method of the present invention is:
(1) by Ti
0.5sn
0.5o
2composite oxides are put into Ce (NO
3)
3ultrasonic immersing 1.5h in solution, supersonic frequency is 2000～3000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, grinds, and the lower 500 ℃ of roasting 4h of air atmosphere, obtain CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into Fe (NO
3)
3ultrasonic immersing 2h in solution, supersonic frequency is 2000～3000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Proceeding to vacuum drying 10h at 90～100 ℃, grinding, the lower 500 ℃ of roasting 3.5～4h of air atmosphere, obtain Fe
2o
3/ CeO
2/ Ti
0.5sn
0.5o
2load binary metal oxide nanocatalyst,
The Fe that the present invention is prepared
2o
3/ CeO
2/ Ti
0.5sn
0.5o
2the pore diameter range of load binary metal oxide nanocatalyst be 10～20nm, it is good especially that it is applied in CO Reduction of NO process effect, has the thermal stability the best of self simultaneously, particle diameter is little, pore-size distribution is more even, the large (～80m of specific area
2/ the advantage such as g).
Preferred Ce (NO in the present invention
3)
3solution concentration is 0.1～0.2molL
-1, Fe (NO
3)
3solution concentration is 0.1～0.2molL
-1.
The vacuum adopting in preparation method of the present invention is 300～500Pa.
It is above-mentioned that to be ground to 160～200 mesh sieves proper.
Ti in the present invention
0.5sn
0.5o
2the preparation method of composite oxides is by TiCl
4solution and SnCl
45H
2o is that 1:1 mixes by Ti:Sn mol ratio, is uniformly mixed solution 1～2h, then slowly at the uniform velocity drips while stirring weak aqua ammonia to mixed solution, until pH=10 makes its precipitation completely, leaves standstill 24～36h; Then weak aqua ammonia washing suction filtration for gained being precipitated, then dry 12～16h in 110～120 ℃ of baking ovens, grind; Then 550 ℃ of roasting 4～5h in Muffle furnace, obtain Ti
0.5sn
0.5o
2composite oxides.
Fe of the present invention
2o
3/ CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst method for testing performance: the Fe that the present invention is prepared
2o
3/ CeO
2/ Ti
0.5sn
0.5o
2after nanocatalyst compressing tablet, cross 60-80 mesh sieve; Then put into microreactor, nanocatalyst consumption of the present invention is 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1.Testing result shows, at 350 ℃, the conversion ratio of NO reaches 100%.Adopt the cerium modified ferrotitanium tin catalyst activity of seldom measuring just fine, can effectively save material.
Advantage of the present invention:
1. the composite oxide supported ferric oxide catalyst of titanium tin that adopts the cerium oxide modification of minute quantity in the present invention, has good catalytic activity, and raw material cheapness, and requirement is few; Method is simple; Production equipment is simple and easy; Technological operation is easy; Pollute few.
2. the Fe that the present invention prepares
2o
3/ CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst is better than the heat endurance of the catalyst of noble metal; And there is higher activity; Be applied to CO Reduction of NO
xin process, the conversion ratio of NO reaches more than 98%, selectively reaches 100%.
Accompanying drawing explanation
Fig. 1 is 1%CeO prepared by the present invention
2/ Ti
0.5sn
0.5o
2and 6%Fe
2o
3/ 9%CeO
2/ Ti
0.5sn
0.5o
2the N of nanocatalyst
2adsorption isotherm.
Fig. 2 is 1%CeO prepared by the present invention
2/ Ti
0.5sn
0.5o
2and 6%Fe
2o
3/ 9%CeO
2/ Ti
0.5sn
0.5o
2the pore size distribution result figure of nanocatalyst.
Fig. 3 is the XRD collection of illustrative plates of the nanocatalyst prepared of the present invention, and wherein (a) is x%CeO
2/ Ti
0.5sn
0.5o
2catalyst XRD collection of illustrative plates, (b) is 6%Fe
2o
3/ x%CeO
2/ Ti
0.5sn
0.5o
2catalyst XRD collection of illustrative plates.
Fig. 4 is the LRS collection of illustrative plates of the nanocatalyst prepared of the present invention, and wherein (a) is x%CeO
2/ Ti
0.5sn
0.5o
2the LRS collection of illustrative plates of catalyst, (b) is 6%Fe
2o
3/ x%CeO
2/ Ti
0.5sn
0.5o
2the LRS collection of illustrative plates of catalyst.
Fig. 5 is 6%Fe prepared by the present invention
2o
3/ x%CeO
2/ Ti
0.5sn
0.5o
2the EPR collection of illustrative plates of catalyst.
Fig. 6 is 6%Fe prepared by the present invention
2o
3/ x%CeO
2/ Ti
0.5sn
0.5o
2the NO of catalyst eliminates reactivity and selectivity diagram.
Specific embodiment
Below in conjunction with instantiation, the present invention is described further, but protection scope of the present invention is not limited to the scope that embodiment represents.
Principle of the present invention is as follows: due to the K of titanium tin hydroxide
spdifference, in order to guarantee two kinds of Ar ion mixings precipitation evenly, joins weak aqua ammonia in the mixed solution of two kinds of ions very lentamente, makes its precipitation completely, and then aging, roasting obtains the Ti of bigger serface
0.5sn
0.5o
2composite oxides, and as carrier, adopt the method for ultrasonic immersing, load C eO respectively
2and Fe
2o
3, make modified component and active component Fe
2o
3be dispersed in carrier surface, prepare nanocatalyst.
1, Ti
0.5sn
0.5o
2the preparation of composite oxides: by TiCl
4solution and SnCl
45H
2o is that 1:1 mixes by Ti:Sn mol ratio, is uniformly mixed solution 1h, then slowly at the uniform velocity drips while stirring weak aqua ammonia to mixed solution, until pH=10 makes its precipitation completely, leaves standstill 24h, age overnight.Then weak aqua ammonia washing suction filtration for gained being precipitated, then dry 12h in 110 ℃ of baking ovens, grind; Then 550 ℃ of roasting 4h in Muffle furnace, obtain Ti
0.5sn
0.5o
2composite oxides, for subsequent use.
2,6%Fe
2o
3/ Ti
0.5sn
0.5o
2the preparation of nanocatalyst: by 1g Ti
0.5sn
0.5o
2composite oxides are put into 7.04ml as carrier, 0.1molL
-1fe (NO
3)
3ultrasonic immersing 2h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 6%Fe
2o
3/ Ti
0.5sn
0.5o
2nanocatalyst is as basic sample.
3, catalyst catalytic performance detects: by the 6%Fe obtaining
2o
3/ Ti
0.5sn
0.5o
2nanocatalyst compressing tablet is crossed 60～80 mesh sieves, and then compressing tablet is put into microreactor, catalyst amount 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1; When result shows 350 ℃ of reaction temperatures, catalyst n O conversion ratio is 70%.
Embodiment 2
1, Ti
0.5sn
0.5o
2the preparation of composite oxides: by TiCl
4solution and SnCl
45H
2o is that 1:1 mixes by Ti:Sn mol ratio, is uniformly mixed solution 2h, then slowly at the uniform velocity drips while stirring weak aqua ammonia to mixed solution, until pH=10 makes its precipitation completely, leaves standstill 36h, age overnight.Then weak aqua ammonia washing suction filtration for gained being precipitated, then dry 16h in 120 ℃ of baking ovens, grind; Then 550 ℃ of roasting 5h in Muffle furnace, obtain Ti
0.5sn
0.5o
2composite oxides, for subsequent use.
2,6%Fe
2o
3/ 1%CeO
2/ Ti
0.5sn
0.5o
2the preparation of binary metal oxide nanocatalyst comprises the steps:
(1) by 1g Ti
0.5sn
0.5o
2composite oxides are put into 0.88ml0.1molL as carrier
-1ce (NO
3)
3ultrasonic immersing 1.5h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 1%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) 1%CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into 7.04ml0.1molL
-1fe (NO
3)
3ultrasonic immersing 2h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 6%Fe
2o
3/ 1%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst.
3, catalyst catalytic performance detects: by the 6%Fe obtaining
2o
3/ 1%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst compressing tablet is crossed 60～80 mesh sieves, and then compressing tablet is put into microreactor, catalyst amount 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1; When result shows 350 ℃ of reaction temperatures, catalyst n O conversion ratio is 100%.Active fine.
Embodiment 3
1, Ti
0.5sn
0.5o
2the preparation of composite oxides is with embodiment 1.
2,6%Fe
2o
3/ 3%CeO
2/ Ti
0.5sn
0.5o
2the preparation of binary metal oxide nanocatalyst comprises the steps:
(1) by 1g Ti
0.5sn
0.5o
2composite oxides are put into 2.64ml0.1molL as carrier
-1ce (NO
3)
3ultrasonic immersing 1.5h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 3%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) 3%CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into 7.04ml0.1molL
-1fe (NO
3)
3ultrasonic immersing 2h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 6%Fe
2o
3/ 3%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst.
3, catalyst catalytic performance detects: by the 6%Fe obtaining
2o
3/ 3%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst compressing tablet is crossed 60～80 mesh sieves, and then compressing tablet is put into microreactor, catalyst amount 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1; When result shows 350 ℃ of reaction temperatures, catalyst n O conversion ratio is 100%.Active fine.
Embodiment 4
1, Ti
0.5sn
0.5o
2the preparation of composite oxides is with embodiment 1.
2,6%Fe
2o
3/ 6%CeO
2/ Ti
0.5sn
0.5o
2the preparation of binary metal oxide nanocatalyst comprises the steps:
(1) by 1g Ti
0.5sn
0.5o
2composite oxides are put into 5.28ml0.1molL as carrier
-1ce (NO
3)
3ultrasonic immersing 1.5h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 6%CeO
2/ Ti
0.5Sn
0.5o
2nanocatalyst;
(2) 6%CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into 7.04ml0.1molL
-1fe (NO
3)
3ultrasonic immersing 2h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 6%Fe
2o
3/ 6%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst.
3, catalyst catalytic performance detects: by the 6%Fe obtaining
2o
3/ 6%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst compressing tablet is crossed 60～80 mesh sieves, and then compressing tablet is put into microreactor, catalyst amount 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1; When result shows 350 ℃ of reaction temperatures, catalyst n O conversion ratio is 100%, is selectively 100%, active fine.
Embodiment 5
1, Ti
0.5sn
0.5o
2the preparation of composite oxides is with embodiment 1.
2,6%Fe
2o
3/ 9%CeO
2/ Ti
0.5sn
0.5o
2the preparation of binary metal oxide nanocatalyst comprises the steps:
(1) by 1g Ti
0.5sn
0.5o
2composite oxides are put into 7.92ml0.1molL as carrier
-1ce (NO
3)
3ultrasonic immersing 1.5h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 9%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) 9%CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into 7.04ml0.1molL
-1fe (NO
3)
3ultrasonic immersing 2h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 6%Fe
2o
3/ 9%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst.
3, catalyst catalytic performance detects: by the 6%Fe obtaining
2o
3/ 9%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst compressing tablet is crossed 60～80 mesh sieves, and then compressing tablet is put into microreactor, catalyst amount 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1; When result shows 350 ℃ of reaction temperatures, catalyst n O conversion ratio is 100%.Active fine.
Embodiment 6
1, Ti
0.5sn
0.5o
2the preparation of composite oxides is with embodiment 1.
2,9%CeO
2/ Ti
0.5sn
0.5o
2the preparation of nanocatalyst: by 1g Ti
0.5sn
0.5o
2composite oxides are put into 7.92ml0.1molL as carrier
-1ce (NO
3)
3ultrasonic immersing 1.5h in solution, supersonic frequency is 2000Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10h at 90～100 ℃, vacuum is 400Pa; Ground 160 mesh sieves.The lower 500 ℃ of roasting 4h of air atmosphere, obtain 9%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
3, catalyst catalytic performance detects: by the 6%Fe obtaining
2o
3/ 9%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst compressing tablet is crossed 60～80 mesh sieves, and then compressing tablet is put into microreactor, catalyst amount 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1; When result shows 350 ℃ of reaction temperatures, catalyst n O conversion ratio is 20%.Active poor.
Embodiment 7
1, Ti
0.5sn
0.5o
2the preparation of composite oxides is with embodiment 1.
2,6%Fe
2o
3/ 6%CeO
2/ Ti
0.5sn
0.5o
2the preparation of binary metal oxide nanocatalyst comprises the steps:
(1) by 1g Ti
0.5sn
0.5o
2composite oxides are put into 5.28ml0.1molL as carrier
-1ce (NO
3)
3ultrasonic immersing 2h in solution, supersonic frequency is 3000Hz; And then adopt 115 ℃ of oil baths to stir evaporating water; Vacuum drying 11h at 90～100 ℃, vacuum is 300Pa; Ground 200 mesh sieves.The lower 500 ℃ of roasting 3.5h of air atmosphere, obtain 6%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) 6%CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into 7.04ml0.1molL
-1fe (NO
3)
3ultrasonic immersing 1.5h in solution, supersonic frequency is 5000Hz; And then adopt 130 ℃ of oil baths to stir evaporating water; Vacuum drying 8h at 90～100 ℃, vacuum is 500Pa; Ground 180 mesh sieves.The lower 500 ℃ of roasting 3.5h of air atmosphere, obtain 6%Fe
2o
3/ 6%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst.
3, catalyst catalytic performance detects: by the 6%Fe obtaining
2o
3/ 6%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst compressing tablet is crossed 60～80 mesh sieves, and then compressing tablet is put into microreactor, catalyst amount 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1; When result shows 350 ℃ of reaction temperatures, catalyst n O conversion ratio is 100%, is selectively 100%.
Embodiment 8
1, Ti
0.5sn
0.5o
2the preparation of composite oxides is with embodiment 1.
2,6%Fe
2o
3/ 3%CeO
2/ Ti
0.5sn
0.5o
2the preparation of binary metal oxide nanocatalyst comprises the steps:
(1) by 1g Ti
0.5sn
0.5o
2composite oxides are put into 2.64ml0.1molL as carrier
-1ce (NO
3)
3ultrasonic immersing 2h in solution, supersonic frequency is 5000Hz; And then adopt 130 ℃ of oil baths to stir evaporating water; Vacuum drying 8h at 90～100 ℃, vacuum is 500Pa; Ground 200 mesh sieves.The lower 500 ℃ of roasting 3.5h of air atmosphere, obtain 3%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) 3%CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into 7.04ml0.1molL
-1fe (NO
3)
3ultrasonic immersing 1.5h in solution, supersonic frequency is 3000Hz; And then adopt 115 ℃ of oil baths to stir evaporating water; Vacuum drying 11h at 90～100 ℃, vacuum is 300Pa; Ground 200 mesh sieves.The lower 500 ℃ of roasting 3.5h of air atmosphere, obtain 6%Fe
2o
3/ 3%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst.
3, catalyst catalytic performance detects: by the 6%Fe obtaining
2o
3/ 3%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst compressing tablet is crossed 60～80 mesh sieves, and then compressing tablet is put into microreactor, catalyst amount 25mg, the volume composition of reaction gas: CO10%, NO5% and He85%.Product (separates O through 13X molecular sieve+5A molecular sieve
2, N
2with CO) (separate N with Paropak Q
2o and CO
2) detect air speed 12000mLg after separation with thermal conductivity detector (TCD)
-1h
-1; When result shows 350 ℃ of reaction temperatures, catalyst n O conversion ratio is 100%.Active fine.
Detection example: the nanocatalyst preparing is carried out to collection of illustrative plates, Performance Detection:
1, Fig. 1 is 1%CeO
2/ Ti
0.5sn
0.5o
2and 6%Fe
2o
3/ 9%CeO
2/ Ti
0.5sn
0.5o
2the N of nanocatalyst
2adsorption isotherm, Fig. 2 is 1%CeO
2/ Ti
0.5sn
0.5o
2and 6%Fe
2o
3/ 9%CeO
2/ Ti
0.5sn
0.5o
2the pore size distribution result figure of nanocatalyst.All adsorption isotherms are IV type as seen from Figure 1, Figure 2, show that distinctive time stagnant ring of meso-hole structure is positioned at p/p
0in=0.7～0.85 scope, show that sample is really made up of mesoporous, pore size distribution curve further shows that resulting materials pore-size distribution is narrower, and aperture is between 10～20nm.
2, by the x%CeO preparing
2/ Ti
0.5sn
0.5o
2and 6%Fe
2o
3/ x%CeO
2/ Ti
0.5sn
0.5o
2catalyst carries out X-ray diffraction analysis and obtains XRD collection of illustrative plates (as shown in Figure 3).
As can be seen from Figure 3, for all sample catalysts, all there is Ti
0.5sn
0.5o
2the characteristic diffraction peak of carrier, does not observe the characteristic diffraction peak of iron oxide crystal; In the time that the carrying capacity of iron oxide is 6%, iron oxide high degree of dispersion is at Ti as seen from the figure
0.5sn
0.5O
2carrier surface.In the time of content≤6% of cerium oxide, do not observe crystalline phase CeO
2characteristic diffraction peak, but in the time that the carrying capacity of cerium oxide is 9%, 28.6 and 47.8
oplace has detected very weak crystalline phase CeO
2characteristic diffraction peak, CeO is described
2be gathered into crystalline phase at catalyst surface.
3, in order further to prove that iron oxide and cerium oxide are at Ti
0.5sn
0.5o
2the state of carrier surface, carries out LRS test to the sample of different loads amount.
The x%CeO that invention is prepared
2/ Ti
0.5sn
0.5o
2and 6%Fe
2o
3/ x%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst carry out Laser Roman spectroscopic analysis of composition and obtain LRS collection of illustrative plates (as shown in Figure 4).
As shown in Figure 4, for xCeTS(x%CeO
2/ Ti
0.5sn
0.5o
2) sample (Fig. 4 (a)), in the time of carrying capacity≤6% of cerium oxide, do not observe crystalline ceric oxide phase character scattering peak, only there is Ti
0.5sn
0.5o
2feature scattering peak, lay respectively at 248,428 and 607cm
-1.But in the time that the content of cerium is 9%, at 460cm
-1there is a very weak scattering peak in place, is attributed to crystalline phase CeO
2feature scattering.And (Fig. 4 (b)), also can observe this peak after load 6% iron oxide.There is not the feature scattering peak of cupric oxide.The above results explanation cerium oxide energy high degree of dispersion is at Ti
0.5sn
0.5o
2carrier surface, this is consistent with XRD result.
4, in order to study Fe
3+the existence of ion in catalyst, has carried out electron paramagnetic resonance (EPR) test to sample.
Test result as shown in Figure 5, as can be seen from the figure, 1%CeO
2/ Ti
0.5sn
0.5o
2there is a wide signal in the spectrogram of sample, this signal is to be caused by instrumental background, illustrates that can not cause any signal adding of cerium oxide.For the 6%Fe of cerium oxide modification
2o
3/ Ti
0.5sn
0.5o
2sample, g=4.29 signal peak obviously weakens and 2.00 place's signal peaks disappear, and illustrates that the iron species of exclusive state reduce, and adding of cerium oxide promoted iron oxide to become cluster by exclusive state.It should be noted that, along with the increase of cerium oxide carrying capacity, almost there is not obvious variation in EPR spectrogram, may be that a small amount of cerium oxide just can make the iron species of exclusive state become cluster, but continuation increases the carrying capacity of cerium oxide, the state of iron oxide does not change.Illustrate that iron oxide is to exist at carrier surface with exclusive state and polymeric form, the modification of cerium promotes the state of iron to become polymeric form by exclusive state.
5, nanocatalyst of the present invention is active detects
To 6%Fe of the present invention
2o
3/ x%CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst carries out NO to be eliminated reactivity and selectively detects and obtain Fig. 6.As can be seen from the figure, 6%Fe
2o
3/ x%CeO
2/ Ti
0.5sn
0.5o
2the NO conversion ratio of catalyst and the carrying capacity of reaction temperature and cerium oxide are closely related.In the time that the carrying capacity of cerium oxide is 1%, the conversion ratio of NO is significantly increased in whole temperature range, and the conversion ratio of NO reaches 100% 350 ℃ time.Along with the further increase of cerium oxide content, the conversion ratio of NO is almost constant.In conjunction with EPR result, it may be the state that just can change iron oxide species due to a small amount of cerium oxide, the carrying capacity that continues to increase cerium oxide, the state of iron oxide remains unchanged, this consistent with Cu-Ce-Al catalyst system [Appl.Catal.A:General360 (2009) 26-52].This has further proved the supposition above us, cerium oxide add the state that has changed iron, be transformed into polymeric form by exclusive state, and then changed the activity of catalyst, so the iron species of polymeric form are active species.In conjunction with EPR result, the carrying capacity that increases cerium oxide does not further increase the content of the iron of polymeric form, and this is also to cause activity there is no the reason increasing.But, N
2selective increase along with the increase of cerium oxide content, illustrate that promote better NO to change into N adding of cerium oxide
2.
Claims (8)
1. a preparation method for load binary metal oxide nanocatalyst, is characterized in that: comprise the steps:
(1) by Ti
0.5sn
0.5o
2composite oxides are put into Ce (NO
3)
3ultrasonic immersing 1.5 ~ 2 h in solution, supersonic frequency is 2000 ~ 5000 Hz; And then adopt 115 ~ 130 ℃ of oil baths to stir evaporating water; Vacuum drying 8 ~ 11 h at 90 ~ 100 ℃, grind, and lower 500 ℃ of roasting 3.5 ~ 4 h of air atmosphere, obtain CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into Fe (NO
3)
3ultrasonic immersing 1.5 ~ 2 h in solution, supersonic frequency is 2000 ~ 5000 Hz; And then adopt 115 ~ 130 ℃ of oil baths to stir evaporating water; Proceeding to vacuum drying 8 ~ 11 h at 90 ~ 100 ℃, grinding, lower 500 ℃ of roasting 3.5 ~ 4 h of air atmosphere, obtain Fe
2o
3/ CeO
2/ Ti
0.5sn
0.5o
2load binary metal oxide nanocatalyst.
2. the preparation method of load binary metal oxide nano material according to claim 1, is characterized in that: comprise the steps:
(1) by Ti
0.5sn
0.5o
2composite oxides are put into Ce (NO
3)
3ultrasonic immersing 1.5 h in solution, supersonic frequency is 2000 ~ 3000 Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Vacuum drying 10 h at 90 ~ 100 ℃, grind, and lower 500 ℃ of roasting 4 h of air atmosphere, obtain CeO
2/ Ti
0.5sn
0.5o
2nanocatalyst;
(2) CeO step (1) being obtained
2/ Ti
0.5sn
0.5o
2nanocatalyst is put into Fe (NO
3)
3ultrasonic immersing 2 h in solution, supersonic frequency is 2000 ~ 3000 Hz; And then adopt 120 ℃ of oil baths to stir evaporating water; Proceeding to vacuum drying 10 h at 90 ~ 100 ℃, grinding, lower 500 ℃ of roasting 3.5 ~ 4 h of air atmosphere, obtain Fe
2o
3/ CeO
2/ Ti
0.5sn
0.5o
2load binary metal oxide nanocatalyst.
3. the preparation method of load binary metal oxide nano material according to claim 1 and 2, is characterized in that: described Ce (NO
3)
3solution concentration is 0.1 ~ 0.2 molL
-1, Fe (NO
3)
3solution concentration is 0.1 ~ 0.2 molL
-1.
4. the preparation method of load binary metal oxide nano material according to claim 1 and 2, is characterized in that: described vacuum is 300 ~ 500 Pa.
5. the preparation method of load binary metal oxide nano material according to claim 1 and 2, is characterized in that: described in be ground to 160 ~ 200 mesh sieves.
6. the preparation method of load binary metal oxide nano material according to claim 1 and 2, is characterized in that: described Ti
0.5sn
0.5o
2the preparation method of composite oxides is by TiCl
4solution and SnCl
45H
2o is by Ti: Sn mol ratio is to mix at 1: 1, is uniformly mixed solution 1 ~ 2 h, then slowly at the uniform velocity drips while stirring weak aqua ammonia to mixed solution, until pH=10 make its precipitation completely, leaves standstill 24 ~ 36 h; Then weak aqua ammonia washing suction filtration for gained being precipitated, then dry 12 ~ 16 h in 110 ~ 120 ℃ of baking ovens, grind; Then 550 ℃ of roasting 4 ~ 5 h in Muffle furnace, obtain Ti
0.5sn
0.5o
2composite oxides.
7. the load binary metal oxide nano material that the preparation method of the load binary metal oxide nano material of employing as described in claim 1 ~ 6 obtains, is characterized in that: aperture is 10 ~ 20nm.
8. an application for load binary metal oxide nano material as claimed in claim 7, is characterized in that: it is in CO Reduction of NO
xin application.
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