CN103372446B - A kind of support type perovskite compound and Synthesis and applications thereof - Google Patents
A kind of support type perovskite compound and Synthesis and applications thereof Download PDFInfo
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- CN103372446B CN103372446B CN201210108926.3A CN201210108926A CN103372446B CN 103372446 B CN103372446 B CN 103372446B CN 201210108926 A CN201210108926 A CN 201210108926A CN 103372446 B CN103372446 B CN 103372446B
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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
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Abstract
The present invention relates to a kind of with indifferent oxide carrier (SiO
2, Al
2o
3, ZrO
2, YSZ etc.) perovskite (ABO of load
3-δ; δ=0-1) compound as active material, by two step thermochemical cycle decomposition CO
2, produce the method for CO.Key step is: (1) active material first at high temperature releases oxygen; (2) active material containing a large amount of Lacking oxygen at a lower temperature with CO
2reaction, releases CO.Patent of the present invention utilizes perovskite to carry out CO as active material first
2decomposition reaction, perovskite active material, compared with other active materials, can release a large amount of oxygen (under 1300 DEG C of conditions 16-25ml/g) at a lower temperature, produces the CO(20-30ml/g of appreciable amount).The heat of high temperature that the present invention can utilize solar focusing to produce as energy source, with CO
2as reaction raw materials, produce CO, cleanliness without any pollution.
Description
Technical field
The present invention relates to two step thermochemical cycles and decompose CO
2, relate to more specifically with inertia refractory oxide support (SiO
2, Al
2o
3, ZrO
2, YSZ etc.) the perovskite ABO of load
3-δ(δ=0-1) compound decomposes CO as active material
2, preparation CO, this type of material can provide the CO of appreciable amount at a lower temperature, has boundless application prospect in energy-saving and emission-reduction.
Background technology
Due to the unsustainable property of fossil energy, and it utilizes the problem such as greenhouse effects, environmental pollution produced, and makes research that is clean, eco-friendly regenerative resource system extremely urgent.China is current is CO
2discharge the second big country, CO
2discharge capacity, in the very fast situation increased, is subject to increasing international community pressure.Solar energy has the advantages such as inexhaustible, cleaning is pollution-free, renewable, utilizes solar energy by greenhouse gases CO
2be converted into the chemical fuel being convenient to store, be day by day subject to the extensive concern of international community.
Metal oxide two step thermochemical cycle decomposition H
2o/CO
2technology collects solar energy deposit exactly and chemical fuel is prepared in one, is one of the focus in current new forms of energy research and development field.The key step of this reaction is: reduce in the inert atmosphere of (1) active material first under high temperature (higher than in 1400 DEG C), releases oxygen.(2) active material containing a large amount of Lacking oxygen is (lower than 1200 DEG C) and H at a lower temperature
2o/CO
2reaction, releases H
2/ CO.Expression is as follows:
The thermodynamics calculation results shows to only have the metal oxide of minority can complete this circulation.The many system of current research has ferriferous oxide, ZnO, CeO
2, V
2o
5, SnO
2deng.
The people such as Nakamura (SolarEnergy, 1977,19:467-475) propose Fe the earliest
3o
4/ FeO Thermochemical water decomposition cyle for hydrogen production system, (the SolarEnergy such as Steinfeld on this basis, 1999,65 (1): 43-53) design principle of solar heat chemical reactor is given, and (Energy & Fuels2008,22,3544-3550) calculate Fe
3o
4/ FeO and ZnO/Zn decomposes CO
2possibility.Too high for ferrite decomposition temperature, the problems such as causing sintering of becoming different mutually in decomposable process, the ferriferous oxide MFe of compound
2o
4(common vector carrier is ZrO to the ferriferous oxide of (M=Mg, Cu, Mn, Ni, Co, Zn) and load
2, YZS) be in succession developed.The Co that JamesE.Miller etc. (JournalofMaterialScience, 2008,43:4714-4728) develop
0.67fe
2.33o
4the product hydrogen activity of 8ml/g still can be kept after the circulation of 30 ,/YSZ sample.United States Patent (USP) (application number 20080089834) describes the preparation method of the ferriferous oxide of YZS load and the actual conditions of decomposition water reaction thereof in detail.The topmost problem that ferrite exists is that reaction rate is excessively slow, and the active material hydrogen output of unit mass is too low, about CO
2the experiment of decomposing also does not launch.
Steinfeld etc. (SolarEnergy, 1999,65 (1): 59-69) utilize solar energy to complete the cyclic process of ZnO/Zn first.The subject matter that this process exists is that under high temperature, Zn steam can not be separated in time with oxygen, Zn is again oxidized, and in the process of water decomposition, Zn and water react the ZnO layer generated and can be wrapped in Zn surface and prevent the contact of Zn and water, thus inhibit hydrogen production reaction.V
2o
5, SnO
2and GeO
2same problem is all there is etc. volatile oxide.United States Patent (USP) (application number 20110059009) describes V in detail
2o
5reaction unit and reaction condition.Equally, about CO
2the experiment of decomposing also does not launch.
Abanades etc. (SolarEnergy, 2006,80:1611-1623) complete CeO first
2/ Ce
2o
3the reaction of two step thermochemical cycle decomposition water.What WilliamC.Chueh etc. (Science, 2010,330:1797-1800) were detailed have studied CeO
2the cycle performance of system, after experimental result shows 500 circulations, CeO
2it is better that the hydrogen output of system and hydrogen generation rate all keep.They also utilize solar energy reactor to be 325gCeO
2amplification test, repeatedly circulation after, CeO
2still keep stable activity.CeO
2system is non-volatile, and anti-caking power is strong, H
2it is fast that/CO produces speed, and good cycle, has industrial prospect, obtains everybody extensive concern.CeO
2the subject matter that system exists has reduction temperature too high; CeO
2there is higher molal weight, cause unit mass hydrogen output lower; The thermograde of two-step reaction is too large, and the recycling of heat is more difficult.
Also do not have about two step thermochemical cycle decomposition H in China's document and patent
2o/CO
2the report of hydrogen manufacturing work.
Be not difficult to find from the work of having been reported, two step thermochemical cycle decomposition H
2o/CO
2work be also in elementary phase of basic research, the subject matter that current existing active material exists is: (1) metal oxide back temperature is high; (2) the Lacking oxygen amount of reusable edible is less; (3) cycle performance is poor.Therefore, be necessary very much to develop and can provide more available Lacking oxygen at a lower temperature, and metastable metal oxide active material under hot conditions.
The reduction temperature of this active material lower than most of bibliographical information active material put oxygen temperature, relatively large oxygen can be released between 1200 DEG C-1300 DEG C.
Summary of the invention
The present invention aims to provide inertia refractory oxide support (SiO
2, Al
2o
3, ZrO
2, YSZ etc.) perovskite (ABO of load
3) compound is at two step thermochemical cycle decomposition CO
2in application, with perovskite (ABO
3) compound as active material, by two step thermochemical cycle decomposition CO
2, prepare the method for CO.
Another object of the present invention is to provide perovskite ABO
3-δ(δ=0-1) compound decomposition CO
2the optimal condition parameter of reaction.
For achieving the above object, the invention provides following aspect:
A kind of 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, such as Fe, Mn, Cu, Co, Ni, Cr etc.
The load capacity of active material is the 20-50wt% of support type perovskite compound.
For improving reaction rate, Pt, Pd, Rh, Ir and NiO can be selected, a kind of or be two or morely carried on perovskite active material as co-catalyst in the transition metal oxides such as MoO, CoO, the load capacity of co-catalyst is the 0-5wt% of support type perovskite compound;
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.
The preparation method of described support type perovskite compound: the compound loaded mode of described support type perovskite can be chosen as: 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 NaOH, ammoniacal liquor, the precipitating reagents such as urea, then add surfactant, surfactant is generally selected: softex kw, AOT etc.The ratio of surfactant and metal ion is 0: 1-5: 1
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 usually: glycine and 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.
Can to select in Pt, Pd, Rh, Ir a kind of or to 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 a certain amount of support type, add in deionized water, strong agitation, form suspension, take the slaine (normally nitrate or chlorate) of a certain amount of co-catalyst according to described ratio (general co-catalyst is the 0-5wt% of active material), 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 (being generally urea or glycine) 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.
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) reduces and deviates from oxygen in high temperature Ar atmosphere, 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.
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.
The present invention, compared with known technology, has following characteristics:
1. the present invention is first with the perovskite ABO of inert carrier load
3-δ(δ=0-1), as active material, has carried out two steps and has decomposed CO
2reaction.
2. active material provided by the invention (1200-1300 DEG C) can provide relatively large oxygen under lower reduction temperature.
3. the perovskite ABO of inert carrier load provided by the invention
3-δ(δ=0-1), can utilize heat of high temperature that solar energy collecting produces as energy source, with CO
2as reaction raw materials, produce CO, without other any accessory substances, sustainable and cleanliness without any pollution.
Accompanying drawing explanation
Fig. 1 LaFeO
3produce oxygen curve spectrogram;
Fig. 2 LaFeO
3produce hydrogen curve spectrogram;
The structural representation of Fig. 3 fixed bed reactors.
Fig. 4 active material ABO
3-δxRD figure.
Fig. 5 active material ABO
3-δraman figure.
Detailed description of the invention
Below by embodiment, the present invention will be further described, but embodiments of the present invention are not limited thereto, and can not be interpreted as limiting the scope of the invention.
Following reaction is carried out in fixed bed reactors, described fixed bed reactors 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.
During application, get 0.4g active material and be placed in corundum crucible, support with silica wool, reactor material is equally also alundum tube, and reaction tube (alundum tube) internal diameter is 14mm, and product is directly analyzed by gas chromatography.
Embodiment 1
A: take 4.33g lanthanum nitrate (10mmol), 4.04g ferric nitrate (10mmol), 7.6856g citric acid be dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the LaFeO of system
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material LaFeO
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 2
A: take 4.33g lanthanum nitrate (10mmol), 2.5101g manganese nitrate (10mmol), 7.6856g citric acid be dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the LaMnO of system
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material LaMnO
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 3
A: take 4.33g lanthanum nitrate (10mmol), 2.9105g cobalt nitrate (10mmol), 7.6856g citric acid be dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the LaCoO of system
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material LaCoO
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 4
A: take 4.33g lanthanum nitrate (10mmol), 2.9081g nickel nitrate (10mmol), 7.6856g citric acid be dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the LaNiO of system
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material LaNiO
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 5
A: take 4.33g lanthanum nitrate (10mmol), 2.3803g chromic nitrate (10mmol), 7.6856g citric acid be dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the LaCrO of system
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material LaCrO
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 6
A: take 2.1163g strontium nitrate (10mmol), 4.04g ferric nitrate (10mmol), 7.6856g citric acid be dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the SrFeO of system
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material SrFeO
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 7
A: take 3.031g lanthanum nitrate, 0.6349g strontium nitrate (10mmol), 4.04g ferric nitrate (10mmol), 7.6856g citric acid are dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the La of system
0.7sr
0.3feO
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material La
0.7sr
0.3feO
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 8
A: take 3.031g lanthanum nitrate, 1.3028g cerous nitrate (10mmol), 4.04g ferric nitrate (10mmol), 7.6856g citric acid are dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the La of system
0.7ce
0.3feO
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material La
0.7ce
0.3feO
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 9
A: take 4.33g lanthanum nitrate, 2.828g ferric nitrate (10mmol), 0.7530g manganese nitrate, 7.6856g citric acid be dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the LaFe of system
0.7mn
0..3o
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material LaFe
0.7mn
0..3o
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 10
A: take 4.33g lanthanum nitrate, 2.828g ferric nitrate (10mmol), 0.8732g cobalt nitrate, 7.6856g citric acid be dissolved in the deionized water of 100ml, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 120 DEG C of baking oven inner dryings until foaming, mill, 700 DEG C of roasting 4h, the LaFe of system
0.7co
0..3o
3sample.
B: mechanical mixture load.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, perovskite material LaFe
0.7co
0..3o
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 11
Combustion method prepares LaFe
0.95pt
0.05o
3.Take 4.33g lanthanum nitrate (10mmol), 3.838g ferric nitrate (9.5mmol), 0.5mmolH
2ptCl
6, 40mmol glycine is dissolved in deionized water, stirring at room temperature 30min, stir until evaporate to dryness as in the water-baths of 80 degree, be put in 500 DEG C of baking oven combustion, 700 DEG C of roasting 4h.Mass ratio according to 3: 1 takes inertia refractory oxide support SiO
2, support type perovskite material LaFe
0.95pt
0.05o
3, ball milling 8h, at 900 DEG C of roasting 10h after mixing.
Embodiment 12
Take 0.4g25wt%LaFeO
3/ SiO
2sample, is placed in reaction tube, and the thermal creep stress of deoxidation 1300 DEG C, lowers the temperature after constant temperature process a period of time, pass into CO
2, reaction temperature selects 1100-1200 DEG C, and reaction 2h terminates.O
2output and CO output list in table 1.
Embodiment 13
With embodiment 12, just sample is 0.4g25wt%LaMnO
3/ SiO
2.
Embodiment 14
With embodiment 12, just sample is 0.4g25wt%LaCoO
3/ SiO
2.
Embodiment 15
With embodiment 12, just sample is 0.4g25wt%LaFe
0.7co
0.3o
3/ SiO
2.
Embodiment 16
With embodiment 12, just sample is 0.4g25wt%LaFe
0.7mn
0.3o
3/ SiO
2.
Embodiment 17
With embodiment 12, just sample is that 0.4g is carried on SiO
2mass fraction is the 2wt%Pt/LaFeO of 25%
3.
According to the treatment conditions described in above embodiment, the O obtained
2, the amount of CO lists in table 1 in detail.
Table 1 active material ABO
3-δthe CO/O of (δ=0-1)
2output (ml/gABO
3-δ(δ=0-1)
In sum, the present invention has synthesized a series of inertia refractory oxide support (SiO
2, Al
2o
3, ZrO
2, YSZ etc.) perovskite (ABO of load
3) compound, this kind of material all can pass through two-step reaction, by CO
2be decomposed into CO.Key step is: first (1) active material releases oxygen under higher temperature (1100-1300 DEG C); (2) active material containing a large amount of Lacking oxygen is (900-1100 DEG C) and CO at a lower temperature
2reaction, releases CO.Patent of the present invention utilizes perovskite to carry out CO as active material first
2decomposition reaction, perovskite active material, relative to other active materials, can be released a large amount of oxygen at a lower temperature, produce relatively large CO.Active material provided by the invention and decomposition CO
2method, heat of high temperature that solar focusing produces can be utilized as energy source, with CO
2as reaction raw materials, produce CO, there is no other accessory substances, cleanliness without any pollution, be expected to become and reduce CO by solar energy
2, the effective technology of preparative chemistry fuel.
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.
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| US10800665B1 (en) * | 2014-09-05 | 2020-10-13 | National Technology & Engineering Solutions Of Sandia, Llc | Redox-active oxide materials for thermal energy storage |
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| CN109745987A (en) * | 2018-12-13 | 2019-05-14 | 大连海事大学 | The preparation method and application of strontium cobalt-based properties of perovskite mixed-oxide oxygen carrier |
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| ES2926393B2 (en) * | 2021-03-08 | 2023-06-22 | Univ Rey Juan Carlos | METHOD FOR OBTAINING H2, CO AND/OR SYNTHESIS GAS USING PEROVSKITE TYPE MATERIALS AND USE OF THESE MATERIALS |
| CN113003611A (en) * | 2021-04-07 | 2021-06-22 | 昆明理工大学 | Preparation method and application of lanthanum manganate |
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