CN103372446B - A kind of support type perovskite compound and Synthesis and applications thereof - Google Patents

Abstract

The invention relates to a perovskite (ABO _3-δ ; δ=0-1) compound loaded with an inert oxide carrier (SiO ₂ , Al ₂ O ₃ , ZrO ₂ , YSZ, etc.) as an active material. A two-step thermochemical cycle for decomposing CO ₂ to produce CO. The main steps are: (1) the active material first releases oxygen at high temperature; (2) the active material containing a large number of oxygen vacancies reacts with _CO2 at a lower temperature to release CO. The patent of this invention uses perovskite as the active material for the decomposition reaction of _CO2 for the first time. Compared with other active materials, the perovskite active material can release a large amount of oxygen at a lower temperature (16-25ml/ g), producing a considerable amount of CO (20-30ml/g). The invention can use the high-temperature heat generated by solar energy focusing as an energy source, and use _CO2 as a reaction raw material to generate CO, which is clean and pollution-free.

Description

A kind of supported perovskite compound and its preparation and application

technical field

The present invention relates to the decomposition of CO ₂ by a _two -step thermochemical cycle method, and more specifically relates to _perovskite ABO _{3 - δ} ( δ=0-1) compounds are used as active materials to decompose CO ₂ to prepare CO. Such materials can produce considerable amounts of CO at relatively low temperatures, and have broad application prospects in energy saving and emission reduction.

Background technique

Due to the unsustainability of fossil energy, as well as the greenhouse effect and environmental pollution caused by its use, it is urgent to study a clean and environmentally friendly renewable energy system. China is currently the second largest country in terms of CO ₂ emissions, and its CO ₂ emissions are growing rapidly, receiving more and more pressure from the international community. Solar energy has the advantages of being inexhaustible, clean, non-polluting, and renewable. Using solar energy to convert greenhouse gas CO ₂ into chemical fuels that are easy to store has increasingly attracted widespread attention from the international community.

The two-step thermochemical cycle decomposition H ₂ O/CO ₂ technology of metal oxides integrates solar energy storage and chemical fuel preparation, and is one of the hotspots in the field of new energy research and development. The main steps of the reaction are: (1) The active material is first reduced in an inert atmosphere at high temperature (higher than 1400° C.) to release oxygen. (2) Active materials containing a large number of oxygen vacancies react with H ₂ O/CO ₂ at lower temperatures (less than 1200°C) to release H ₂ /CO. The specific expression is as follows:

Thermodynamic calculations show that only a few metal oxides are able to complete this cycle. At present, the systems that have been studied more include iron oxide, ZnO, CeO ₂ , V ₂ O ₅ , SnO ₂ and so on.

Nakamura et al. (SolarEnergy, 1977, 19: 467-475) first proposed the Fe ₃ O ₄ /FeO thermochemical cycle decomposition water hydrogen production system. On this basis, Steinfeld et al. (SolarEnergy, 1999, 65(1): 43- 53) The design principle of solar thermochemical reactor is given, and (Energy & Fuels 2008, 22, 3544-3550) calculates the possibility of Fe ₃ O ₄ /FeO and ZnO/Zn decomposition of CO ₂ . In view of the high decomposition temperature of ferrite, the phase change in the decomposition process is easy to cause sintering and other problems, the composite iron oxide MFe ₂ O ₄ (M=Mg, Cu, Mn, Ni, Co, Zn) and the supported iron oxide Substances (common carriers are ZrO ₂ , YZS) have been developed one after another. The Co _0.67 Fe _2.33 O ₄ /YSZ sample developed by JamesE. Miller et al. (Journal of Material Science, 2008, 43: 4714-4728) can still maintain a hydrogen production activity of 8ml/g after 30 cycles. US Patent (Application No. 20080089834) describes in detail the preparation method of YZS-loaded iron oxide and the specific conditions for its water splitting reaction. The main problem of ferrite is that the reaction rate is too slow, the hydrogen production per unit mass of active material is too low, and the experiment on _CO2 decomposition has not yet been carried out.

Steinfeld et al. (SolarEnergy, 1999, 65(1):59-69) used solar energy to complete the ZnO/Zn cycle process for the first time. The main problem in this process is that Zn vapor and oxygen cannot be separated in time at high temperature, Zn is oxidized again, and in the process of water decomposition, the ZnO layer formed by the reaction of Zn and water will wrap on the surface of Zn to prevent the interaction between Zn and water. Contact, thereby inhibiting the hydrogen production reaction. Volatile oxides such as V ₂ O ₅ , SnO ₂ and GeO ₂ all have the same problem. US Patent (Application No. 20110059009) introduces the reaction device and reaction conditions of V ₂ O ₅ in detail. Likewise, experiments on _CO2 decomposition have not yet been carried out.

Abanades et al. (SolarEnergy, 2006, 80: 1611-1623) completed the CeO ₂ /Ce ₂ O ₃ two-step thermochemical cycle water splitting reaction for the first time. WilliamC.Chueh et al. (Science, 2010, 330: 1797-1800) studied the cycle performance of the CeO ₂ system in detail. The experimental results showed that after 500 cycles, the hydrogen production rate and the hydrogen production rate of the CeO ₂ system were maintained well. . They also used a solar reactor to do a scale-up experiment with 325g CeO ₂ . After many cycles, CeO ₂ still maintained stable activity. The CeO ₂ system is non-volatile, has strong anti-sintering ability, fast H ₂ /CO generation rate, and good cycle performance. It has industrialization prospects and has attracted widespread attention. The main problems in the CeO ₂ system are that the reduction temperature is too high; CeO ₂ has a high molar mass, resulting in low hydrogen production per unit mass; the temperature gradient of the two-step reaction is too large, and heat recovery is difficult.

There is no report on the two-step thermochemical cycle decomposition of H ₂ O/CO ₂ to produce hydrogen in Chinese literature and patents.

It is not difficult to find from the reported work that the two-step thermochemical cycle decomposition of H ₂ O/CO ₂ is still in the primary basic research stage. The main problems existing in the existing active materials are: (1) metal oxides The reduction temperature is high; (2) the amount of oxygen vacancies that can be recycled is less; (3) the cycle performance is poor. Therefore, it is very necessary to develop metal oxide active materials that can give more available oxygen vacancies at lower temperatures and are relatively stable at high temperatures.

The reduction temperature of the active material is lower than the oxygen release temperature of the active materials reported in most literatures, and a relatively large amount of oxygen can be released between 1200°C and 1300°C.

Contents of the invention

The present invention aims to provide the application of perovskite (ABO ₃ ) compounds supported by inert high temperature resistant oxide carriers (SiO ₂ , Al ₂ O ₃ , ZrO ₂ , YSZ, etc.) in the two-step thermochemical cycle decomposition of CO ₂ , A method for preparing CO by decomposing CO ₂ through two-step thermochemical cycles using perovskite (ABO ₃ ) compounds as active materials.

Another object of the present invention is to provide the optimal condition parameters for the CO ₂ decomposition reaction of the perovskite ABO _3-δ (δ=0-1) compound.

To achieve the above object, the present invention provides the following aspects:

A supported perovskite compound, with inert high temperature resistant oxides SiO ₂ , Al ₂ O ₃ , ZrO ₂ or YSZ as a carrier, and the loaded perovskite compound as an active material, the chemical formula of the active material is ABO _3-δ , δ=0-1, where A is one or more of rare earth ions or alkaline earth ions, and B is one or more of transition metal ions, such as Fe, Mn, Cu, Co, Ni , Cr, etc.

The loading amount of the active material is 20-50wt% of the loaded perovskite compound.

In order to improve the reaction rate, one or more transition metal oxides such as Pt, Pd, Rh, Ir, NiO, MoO, CoO, etc. can be selected as co-catalysts to be loaded on the perovskite active material. The loading amount of co-catalysts is 0-5wt% of the supported perovskite compound;

Wherein A is one or more of La, Ce, Sr, Ca, Ba and Bi; B is one or more of Fe, Mn, Cu, Co, Ni and Cr.

The preparation method of the supported perovskite compound: the loading method of the supported perovskite compound can be selected as: direct mechanical mixing, chemical precipitation loading, surfactant template method, or solution combustion method;

Choose the way of mechanical mixing: Weigh the active material and oxide carrier according to the required ratio, mix them thoroughly in a mortar, and bake them in a muffle furnace at 800-900°C for 4-10h;

Select the method of chemical precipitation loading: Weigh the oxide carrier according to the required ratio, suspend it in deionized deionized water, and dissolve A(NO ₃ ) _x and B(NO ₃ ) _y in proportion after passing nitrogen gas for 2 hours. Add NaOH solution to the suspension, the concentration of NaOH solution is 1-3mol/L, until the pH is adjusted to 8.5, the solution is heated to 65°C, and air is introduced at the same time, the solution is centrifugally dried, and roasted at 900°C for 10h;

Select the surfactant template method: weigh the metal salt of the oxide carrier, A(NO ₃ ) _x , B(NO ₃ ) _y according to the required ratio, add NaOH, ammonia water, urea and other precipitants, and then add the surfactant, The general choice of surfactants: cetyltrimethylammonium bromide, AOT, etc. The ratio of surfactant to metal ion is 0:1-5:1

Wherein the molar ratio of surfactant to metal ion is 0:1-5:1, the solution is centrifuged, dried, and calcined at 800-900°C for 4-10h;

Selective solution combustion method: Weigh the metal salt, A(NO ₃ ) _x , B(NO ₃ ) _y of the inert oxide carrier according to the required ratio, and calculate the amount of fuel according to the molar number of metal ions. The fuel is usually selected as: Glycine and urea, the molar ratio of fuel to metal ions is 2:1-4:1, dissolved in deionized water, the solution is placed in a muffle furnace preheated to 500 ° C, burned, and then heated at 800-900 ℃ roasting 4-10h.

One or more of Pt, Pd, Rh, and Ir can be selected as co-catalysts to be loaded on the perovskite active material. The loading methods include impregnation method and combustion method; specifically:

a): Immersion method Weigh a certain amount of loaded perovskite active material, add it to deionized water, stir vigorously to form a suspension, and weigh it according to the stated ratio (generally, the cocatalyst is 0-5wt% of the active material). Take a certain amount of promoter metal salt (usually nitrate or chlorate) and dissolve it in the suspension. The suspension was evaporated to dryness in a water bath at 80°C, dried, and calcined at 500°C for 2h.

b): The combustion method weighs a certain amount of metal salts of inert carriers, metal salts of perovskite compounds, and metal salts of cocatalysts according to the required ratio, calculates and weighs the combustion agent (usually urea) according to the content of the metal salts or glycine), add deionized water to dissolve, place the solution in a muffle furnace preheated to 500°C, burn it, and then bake it at 800-900°C for 4-10h.

The supported perovskite compound can be used to decompose CO ₂ in a two-step thermochemical cycle, and the reaction consists of the following two steps:

a: Perovskite ABO _3-δ (δ=0-1) supported by an inert carrier is reduced to release oxygen in a high-temperature Ar atmosphere, and the reaction temperature is 1100-1300°C;

b: Active materials containing a large number of oxygen vacancies react with CO to generate _CO at a reaction temperature of 800–1200 °C.

The reaction is carried out in a fixed bed reactor,

The structure of the fixed bed reactor is as follows: comprising a corundum tube, a corundum crucible with an upper end opening and a hole in the bottom is provided in the corundum tube, a supporting corundum tube is provided below the corundum crucible, and the corundum crucible is placed in the corundum tube through the supporting corundum tube below it For positioning, quartz wool is arranged above the inner bottom hole of the corundum crucible, and active materials are filled in the corundum crucible on the quartz wool.

Compared with the known technology, the present invention has the following characteristics:

1. In the present invention, the perovskite ABO _3-δ (δ=0-1) supported by an inert carrier is used as the active material for the first time, and a two-step CO ₂ decomposition reaction is carried out.

2. The active material provided by the present invention can give a larger amount of oxygen at a lower reduction temperature (1200-1300° C.).

3. The perovskite ABO _3-δ (δ=0-1) supported by the inert carrier provided by the present invention can use the high-temperature heat generated by solar energy concentration as an energy source, and use _CO as a reaction raw material to produce CO without other Sustainable and clean without any by-products.

Description of drawings

Fig. ₁ LaFeO Oxygen production curve spectrogram;

_Fig . 2LaFeO Hydrogen production curve spectrogram;

Fig. 3 Schematic diagram of the structure of the fixed bed reactor.

Fig. 4 XRD pattern of active material ABO _3-δ .

Fig. 5 Raman diagram of active material ABO _3-δ .

Detailed ways

The present invention will be further described through examples below, but the embodiments of the present invention are not limited thereto, and should not be construed as limiting the protection scope of the present invention.

The following reaction is carried out in a fixed bed reactor. The fixed bed reactor includes a corundum tube. A corundum crucible with an upper end opening and a hole in the bottom is arranged in the corundum tube. A supporting corundum tube is provided below the corundum crucible, and the corundum crucible passes through The supporting corundum tube is positioned in the corundum tube, quartz wool is arranged above the inner bottom hole of the corundum crucible, and active materials are filled in the corundum crucible on the quartz wool.

During application, take 0.4g of active material and place it in a corundum crucible, supported by quartz wool, the material of the reactor is also a corundum tube, the inner diameter of the reaction tube (corundum tube) is 14mm, and the reaction product is directly analyzed by gas chromatography.

Example 1

a: Weigh 4.33g of lanthanum nitrate (10mmol), 4.04g of ferric nitrate (10mmol), and 7.6856g of citric acid and dissolve them in 100ml of deionized water, stir at room temperature for 30min, stir in an 80-degree water bath until evaporated, and place in Dry it in an oven at 120°C until it foams, grind it, and bake it at 700°C for 4 hours to prepare the LaFeO ₃ sample.

b: Mechanical mixed load. The inert high temperature resistant oxide carrier SiO ₂ and the perovskite material LaFeO ₃ were weighed according to a mass ratio of 3:1, ball milled for 8 hours, mixed evenly and then calcined at 900° C. for 10 hours.

Example 2

a: Weigh 4.33g of lanthanum nitrate (10mmol), 2.5101g of manganese nitrate (10mmol), and 7.6856g of citric acid and dissolve them in 100ml of deionized water, stir at room temperature for 30min, stir in an 80-degree water bath until evaporated, and place in Dry in an oven at 120°C until foaming, grind, and bake at 700°C for 4 hours to prepare LaMnO ₃ samples.

b: Mechanical mixed load. The inert high temperature resistant oxide carrier SiO ₂ and the perovskite material LaMnO ₃ were weighed according to a mass ratio of 3:1, ball milled for 8 hours, mixed evenly and then roasted at 900° C. for 10 hours.

Example 3

a: Weigh 4.33g of lanthanum nitrate (10mmol), 2.9105g of cobalt nitrate (10mmol), and 7.6856g of citric acid and dissolve them in 100ml of deionized water, stir at room temperature for 30min, stir in a water bath at 80°C until evaporated, and place in LaCoO ₃ samples were prepared by drying in an oven at 120°C until foaming, grinding, and calcination at 700°C for 4 hours.

b: Mechanical mixed load. The inert high temperature resistant oxide carrier SiO ₂ and the perovskite material LaCoO ₃ were weighed according to a mass ratio of 3:1, ball milled for 8 hours, mixed evenly and then roasted at 900° C. for 10 hours.

Example 4

a: Weigh 4.33g of lanthanum nitrate (10mmol), 2.9081g of nickel nitrate (10mmol), and 7.6856g of citric acid and dissolve them in 100ml of deionized water, stir at room temperature for 30min, stir in a water bath at 80°C until evaporated, and place in Dried in an oven at 120°C until foaming, milled, and fired at 700°C for 4 hours to prepare LaNiO ₃ samples.

b: Mechanical mixed load. The inert high temperature resistant oxide carrier SiO ₂ and the perovskite material LaNiO ₃ were weighed according to a mass ratio of 3:1, ball milled for 8 hours, mixed evenly and then calcined at 900° C. for 10 hours.

Example 5

a: Weigh 4.33g of lanthanum nitrate (10mmol), 2.3803g of chromium nitrate (10mmol), and 7.6856g of citric acid and dissolve them in 100ml of deionized water, stir at room temperature for 30min, stir in a water bath at 80°C until evaporated, and place in Dry it in an oven at 120°C until it foams, grind it, and bake it at 700°C for 4 hours to prepare a LaCrO ₃ sample.

b: Mechanical mixed load. The inert high temperature resistant oxide carrier SiO ₂ and the perovskite material LaCrO ₃ were weighed according to a mass ratio of 3:1, ball milled for 8 hours, mixed evenly and then calcined at 900° C. for 10 hours.

Example 6

a: Dissolve 2.1163g of strontium nitrate (10mmol), 4.04g of ferric nitrate (10mmol), and 7.6856g of citric acid in 100ml of deionized water, stir at room temperature for 30min, and stir in an 80-degree water bath until it evaporates to dryness. Dried in an oven at 120°C until foaming, milled, and calcined at 700°C for 4 hours to prepare a SrFeO ₃ sample.

b: Mechanical mixed load. The inert high temperature resistant oxide carrier SiO ₂ and the perovskite material SrFeO ₃ were weighed according to a mass ratio of 3:1, ball milled for 8 hours, mixed evenly and then roasted at 900° C. for 10 hours.

Example 7

a: Weigh 3.031g of lanthanum nitrate, 0.6349g of strontium nitrate (10mmol), 4.04g of ferric nitrate (10mmol), and 7.6856g of citric acid dissolved in 100ml of deionized water, stir at room temperature for 30min, and stir in an 80-degree water bath until Evaporate to dryness, dry in an oven at 120°C until foaming, grind, and bake at 700°C for 4 hours to prepare La _0.7 Sr _0.3 FeO ₃ samples.

b: Mechanical mixed load. The inert high temperature resistant oxide carrier SiO ₂ and the perovskite material La _0.7 Sr _0.3 FeO ₃ were weighed according to a mass ratio of 3:1, ball milled for 8 hours, mixed evenly and then calcined at 900°C for 10 hours.

Example 8

a: Weigh 3.031g of lanthanum nitrate, 1.3028g of cerium nitrate (10mmol), 4.04g of ferric nitrate (10mmol), and 7.6856g of citric acid dissolved in 100ml of deionized water, stir at room temperature for 30min, and stir in an 80-degree water bath until Evaporate to dryness, dry in an oven at 120°C until foaming, grind, and bake at 700°C for 4 hours to prepare La _0.7 Ce _0.3 FeO ₃ samples.

b: Mechanical mixed load. According to the mass ratio of 3:1, the inert high temperature resistant oxide carrier SiO ₂ and the perovskite material La _0.7 Ce _0.3 FeO ₃ were weighed, ball milled for 8 hours, mixed evenly and baked at 900°C for 10 hours.

Example 9

a: Weigh 4.33g of lanthanum nitrate, 2.828g of ferric nitrate (10mmol), 0.7530g of manganese nitrate, and 7.6856g of citric acid and dissolve them in 100ml of deionized water, stir at room temperature for 30min, and stir in a water bath at 80°C until evaporated to dryness. Dry it in an oven at 120°C until it foams, grind it, and bake it at 700°C for 4 hours to prepare the LaFe _0.7 Mn _0..3 O ₃ sample.

b: Mechanical mixed load. According to the mass ratio of 3:1, the inert high temperature resistant oxide carrier SiO ₂ and the perovskite material LaFe _0.7 Mn _0..3 O ₃ were weighed, ball milled for 8 hours, mixed evenly and roasted at 900°C for 10 hours.

Example 10

a: Weigh 4.33g of lanthanum nitrate, 2.828g of ferric nitrate (10mmol), 0.8732g of cobalt nitrate, and 7.6856g of citric acid and dissolve them in 100ml of deionized water, stir at room temperature for 30min, and stir in an 80-degree water bath until evaporated to dryness. Dry it in an oven at 120°C until it foams, grind it, and bake it at 700°C for 4 hours to prepare the LaFe _0.7 Co _0..3 O ₃ sample.

b: Mechanical mixed load. According to the mass ratio of 3:1, the inert high temperature resistant oxide carrier SiO ₂ and the perovskite material LaFe _0.7 Co _0..3 O ₃ were weighed, ball milled for 8 hours, mixed evenly and roasted at 900°C for 10 hours.

Example 11

Preparation of LaFe _0.95 Pt _0.05 O ₃ by combustion method. Weigh 4.33g of lanthanum nitrate (10mmol), 3.838g of ferric nitrate (9.5mmol), 0.5mmolH ₂ PtCl ₆ , and 40mmol of glycine and dissolve them in deionized water, stir at room temperature for 30min, and stir in a water bath at 80°C until evaporated to dryness. Burn in an oven at 500°C and bake at 700°C for 4h. According to the mass ratio of 3:1, the inert high temperature resistant oxide carrier SiO ₂ and the supported perovskite material LaFe _0.95 Pt _0.05 O ₃ were weighed, ball milled for 8 hours, mixed evenly and roasted at 900°C for 10 hours.

Example 12

Weigh 0.4g of 25wt% LaFeO ₃ /SiO ₂ sample and place it in a reaction tube. The deoxidation temperature is selected at 1300°C. After a period of constant temperature treatment, the temperature is lowered, and CO ₂ is introduced. The reaction temperature is selected at 1100-1200°C, and the reaction is completed after 2 hours. _O2 production and CO production are listed in Table 1.

Example 13

Same as Example 12, except that the sample is 0.4g 25wt% LaMnO ₃ /SiO ₂ .

Example 14

Same as Example 12, except that the sample is 0.4g 25wt% LaCoO ₃ /SiO ₂ .

Example 15

Same as Example 12, except that the sample is 0.4g 25wt% LaFe _0.7 Co _0.3 O ₃ /SiO ₂ .

Example 16

Same as Example 12, except that the sample is 0.4g 25wt% LaFe _0.7 Mn _0.3 O ₃ /SiO ₂ .

Example 17

Same as Example 12, except that the sample is 0.4 g of 2wt% Pt/LaFeO ₃ loaded on SiO ₂ with a mass fraction of 25%.

According to the treatment conditions described in the above examples, the amounts of O ₂ and CO obtained are listed in Table 1 in detail.

Table 1 CO/O ₂ production of active material ABO _3-δ (δ=0-1) (ml/gABO _3-δ (δ=0-1)

In summary, the present invention has synthesized a series of perovskite (ABO ₃ ) compounds loaded on inert high-temperature-resistant oxide carriers (SiO ₂ , Al ₂ O ₃ , ZrO ₂ , YSZ, etc.), and these materials can all be passed A two-step reaction that splits _CO2 into CO. The main steps are: (1) the active material first releases oxygen at a higher temperature (1100-1300°C); (2) the active material containing a large number of oxygen vacancies reacts with _CO2 at a lower temperature (900-1100°C), release CO. The patent of the present invention uses perovskite as an active material for the decomposition reaction of _CO2 for the first time. Compared with other active materials, perovskite-based active materials can release a large amount of oxygen at a lower temperature and produce a larger amount of CO. The active material and method for decomposing _CO2 provided by the present invention can use the high-temperature heat generated by solar energy focusing as an energy source, and use _CO2 as a reaction raw material to produce CO without other by-products, clean and pollution-free, and is expected to become a CO ₂ , an efficient technology for the production of chemical fuels.

Claims (7)

1. an application for support type perovskite compound, with inertia refractory oxide SiO ₂, Al ₂o ₃, ZrO ₂or YSZ is carrier, the perovskite compound of load is as active material, and the chemical formula of described active material is ABO _3-δ, δ=0-1, wherein A is a kind of or two or more in rare earth ion or alkaline earth ion, and B is a kind of or two or more in transition metal ions, and the load capacity of active material is the 20-50wt% of support type perovskite compound, it is characterized in that:

Described support type perovskite compound can be used for two step thermochemical cycle decomposition CO ₂, this reaction is made up of following two steps:

A: the perovskite ABO of inert carrier load _3-δ, δ=0-1, in high temperature Ar atmosphere, oxygen is deviate from reduction, and reaction temperature is 1100-1300 DEG C;

B: the active material containing a large amount of Lacking oxygen and CO ₂reaction generates CO, and reaction temperature is 800-1200 DEG C.

2. according to the application of support type perovskite compound described in claim 1, it is characterized in that: for improving reaction rate, select Pt, Pd, Rh, Ir and NiO, MoO, a kind of or be two or morely carried on perovskite active material as co-catalyst in CoO transition metal oxide, the load capacity of co-catalyst is the 0-5wt% of support type perovskite compound.

3., according to the application of support type perovskite compound described in claim 1, it is characterized in that:

Wherein A is a kind of or two or more in La, Ce, Sr, Ca, Ba, Bi; B is a kind of or two or more in Fe, Mn, Cu, Co, Ni, Cr.

4. according to the application of support type perovskite compound described in claim 1, it is characterized in that: the compound loaded way selection of described support type perovskite is: the mode of direct mechanical mixing, chemical precipitation load, surfactants' templating or solution combustion method;

Select the mode of mechanical mixture: take active material and oxide carrier according to required ratio, fully mix in stone roller alms bowl, 800-900 DEG C of roasting 4-10h in Muffle furnace;

Select the mode of chemical precipitation load: take oxide carrier according to required ratio, be suspended in the deionized water of deoxygenation, after the nitrogen of logical 2h, in proportion by A (NO ₃) _x, B (NO ₃) _ybe dissolved in this suspension, add NaOH solution, the concentration of NaOH solution is 1-3mol/L, until pH is adjusted to 8.5, solution is heated to 65 DEG C, passes into air simultaneously, and solution centrifugal is dry, 900 DEG C of roasting 10h;

Select surfactants' templating: the slaine, the A (NO that take oxide carrier according to required ratio ₃) _x, B (NO ₃) _y, add precipitating reagent NaOH, ammoniacal liquor or urea, then add surfactant, surfactant is softex kw or AOT; Wherein the mol ratio of surfactant and metal ion is 0:1-5:1, by solution centrifugal, dry, 800-900 DEG C of roasting 4-10h;

Select solution combustion method: the slaine, the A (NO that take indifferent oxide carrier according to required ratio ₃) _x, B (NO ₃) _ythe consumption of fuel is calculated according to the molar basis of metal ion, fuel is chosen as: glycine and/or urea, the molar ratio of fuel and metal ion is 2:1-4:1, add in deionized water and dissolve, be placed in by this solution in the Muffle furnace being preheating to 500 DEG C in advance, burning, afterwards at 800-900 DEG C of roasting 4-10h;

Described X=2 or 3, y=2 or 3.

5. according to the application of support type perovskite compound described in claim 4, it is characterized in that: select a kind of in Pt, Pd, Rh, Ir or be two or morely carried on perovskite active material as co-catalyst, carrying method has infusion process and combustion method; Be specially:

A): infusion process takes the perovskite active material of support type, adds in deionized water, strong agitation, form suspension, take the slaine of co-catalyst according to required ratio, be dissolved in suspension; By this suspension evaporate to dryness in 80 DEG C of water-baths, dry, 500 DEG C of roasting 2h;

B): combustion method takes slaine, the slaine of perovskite compound, the slaine of co-catalyst of a certain amount of inert carrier according to required ratio, take incendiary agent according to the cubage of slaine, add in deionized water and dissolve, this solution is placed in the Muffle furnace being preheating to 500 DEG C in advance, burning, afterwards at 800-900 DEG C of roasting 4-10h.

6. according to the application of support type perovskite compound described in claim 4 or 5, it is characterized in that: in roasting afterproduct, co-catalyst is the 0-5wt% of active material; The slaine of co-catalyst is nitrate or chlorate; Incendiary agent is urea or glycine.

7., according to the application of support type perovskite compound described in claim 1, it is characterized in that:

Reaction is carried out in fixed bed reactors,

The structure of described fixed bed reactors is: comprise an alundum tube, the corundum crucible of a upper end open, bottom of which has holes is provided with in alundum tube, a support alundum tube is provided with below corundum crucible, corundum crucible by the support alundum tube below it in alundum tube inner position, the top of the inner bottom stomidium of corundum crucible is provided with silica wool, on silica wool, be filled with active material in corundum crucible.