CN107857301A - A kind of calcium swage Ca2Fe2O5Method for preparing catalyst - Google Patents
A kind of calcium swage Ca2Fe2O5Method for preparing catalyst Download PDFInfo
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- CN107857301A CN107857301A CN201711101380.8A CN201711101380A CN107857301A CN 107857301 A CN107857301 A CN 107857301A CN 201711101380 A CN201711101380 A CN 201711101380A CN 107857301 A CN107857301 A CN 107857301A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Abstract
The invention discloses a kind of calcium swage Ca2Fe2O5Method for preparing catalyst, this method, as predecessor, are configured to solution after adding a certain amount of water, are stirred 30 minutes at 40 DEG C, solution is uniformly dispersed using ferric nitrate, calcium nitrate and citric acid.Wherein, as foaming agent, foamed the citric acid of addition 12h at 180 DEG C, and obtained foaming substance is ground and sieved, 4h is calcined at 650 DEG C in Muffle furnace, finally gives the Ca of high-purity2Fe2O5Catalyst.The Ca prepared with this method2Fe2O5Specific surface area of catalyst is big, has stable skeleton structure, extremely strong stability is still kept after the oxidation and reduction of multiple oxidant and reducing agent, available in the fields such as burning chemistry chains, hydrogen production of chemical chain and photocatalysis.
Description
Technical field
The present invention relates to a kind of calcium swage Ca2Fe2O5Method for preparing catalyst, belong to burning chemical industry and field of material technology.
Background technology
A2B2O5There is type oxide good crystal structure, unique electrochemical properties and specific catalytic action to make
It is attracted widespread attention in directions such as solid fuel cell new material, specific catalytic reactions.And Ca2Fe2O5As calcium iron
One kind of stone-type structure oxide, it possesses the features such as wide material sources, cost are cheap, chemical property is stable and the coefficient of expansion is low
With many advantages, therefore brownmillerite type oxide Ca2Fe2O5It is increasingly becoming the focus of people's research and the new material of focus development.
Because such brownmillerite type oxide has specific skeleton structure and pore size distribution feature, make it in functional material such as catalysis, magnetic
Property the aspect of performance such as material, pressure sensitive, high-temperature superconductor there is excellent performance, and available for oxygen sensitive components, magnetic member
Device, battery cathode material etc., prospect is extensive.
Ca2Fe2O5Equally there is larger application prospect in terms of photocatalysis technology, work as Ca2Fe2O5Particle size is small to receiving
During meter level, specific surface area will also increase, and photocatalysis performance will greatly improve.Its structure has the Lacking oxygen of high concentration, is advantageous to
Activation of catalyst adsorbs oxygen molecule, while the Fe of iron ion one in its structure3+With Fe4+Form is present, and easily obtains the Fe of electronics4 +The zwitterion in water can be effectively promoted to separate, so as to improve its photocatalysis performance.Ca in the same circumstances2Fe2O5Light
Catalytic performance and catalytic activity are substantially better than ABO3.In recent years, Ca2Fe2O5Due to excellent oxidation and reduction characteristic, people
Be try to use it for the directions, such as gasification of biomass, hydrogen production of chemical chain such as heat catalysis conversion, have a extensive future.
However, the research and application currently for such catalyst are less, the research especially in terms of preparation is fresher for report
Road.Traditional preparation Ca2Fe2O5Method mainly includes solid phase reaction, high-energy ball milling combination solid phase reaction, citric acid-infra-red radiation
The methods of method, hydro-thermal and sol-gel.Traditional solid reaction process prepares Ca2Fe2O5, it is contacting with each other using material,
Occur to chemically react and constantly spread in the contact interface of solid material, it is only necessary to by preparing raw material mechanical mixture, by high temperature
Corresponding catalyst can be prepared in calcining.Although solid reaction process equipment is simple, technological process is convenient, such technique energy
Consumption is quite big, is scattered in that uniformity is relatively poor due to mechanical mixture, therefore the usual purity of product synthesized is not high, is only applicable
In the situation relatively low to Quality and property requirement.And hydro-thermal method, sol-gal process and ammonium salt decomposition method etc. are adopted, its change synthesized
Product constituent is accurate, purity is high, good dispersion but processing step are relatively complicated, synthesis cycle is long, is not suitable for a large amount of systems
Standby and industrialized production.For above-mentioned preparation method, more reaction temperature high energy consumption, preparation and generated time more or less be present
The long, dispersiveness in mixed process and lack of homogeneity, flow Complicated Periodic are long, are not suitable for a large amount of the problems such as preparing, serious limit
Calcium swage Ca is made2Fe2O5The extensive use of powder.Develop a kind of operating process it is simple, easily prepared, economical and practical with it is high
The Ca of performance2Fe2O5Material it is promoted with using most important.
The content of the invention
Technical problem：The present invention provides a kind of calcium swage Ca2Fe2O5Method for preparing catalyst, using citric acid in middle low temperature
So as to be modified preparation to it, this method operating process is simple, it is cheap to prepare cost and can effectively improve catalyst for foaming
Specific surface area, micropore and mesoporous area's pore volume, catalytic performance and cyclical stability.
Technical scheme：The calcium swage Ca of the present invention2Fe2O5Method for preparing catalyst, comprise the following steps：
1) ferric nitrate, calcium nitrate and citric acid are mixed, wherein ferric nitrate and calcium nitrate are according to Ca: Fe mol ratio (0.9-
1.1): 1 is added；
2) deionized water is added, is configured to solution, iron nitrate solution concentration is 0.08-0.12mol/L, calcium nitrate solution
Concentration is 0.072-0.132mol/L；
3) solution that configuration obtains is stirred at 30-50 DEG C；
4) solution that the step 3) obtains is placed in drying box, is foamed in 180-190 DEG C of temperature range and dry 12-
24 hours, and obtained solid sample is crushed and ground；
5) sample after being ground in the step 4) is put into Muffle furnace, 3-4 hours is calcined at 650-850 DEG C, risen
Warm rate guarantee is ground to the solid powder after calcining, finally gives calcium swage Ca in 3-5 DEG C/min2Fe2O5Catalyst.
In the preferred scheme of preparation method of the present invention, mole addition is 1-3 times of calcium iron integral molar quantity in step 1).
In the preferred scheme of preparation method of the present invention, the mixing time of solution is 20-40 minutes in step 3).
In the preferred scheme of preparation method of the present invention, the particle diameter of the high temperature foamed in step 4) after broken and grind
Less than 0.3mm.
In the preferred scheme of preparation method of the present invention, the Muffle furnace high-temperature calcination in step 5) is under oxygen or air atmosphere
Carry out.
In the preferred scheme of preparation method of the present invention, the sample particle diameter after being ground in step 5) is controlled in 0.10-0.25mm
Between.
Beneficial effect：The present invention compared with prior art, has advantages below：
The present invention proposes prepares calcium swage Ca using citric acid foaming2Fe2O5Catalyst.With existing preparation method phase
Than not only having that equipment operation is convenient, technological process is simple, catalyst can be used for a large amount of systems concurrently using low-temp foaming method in citric acid
The advantage such as standby, be also integrated with energy consumption is low, catalyst dispersity can it is excellent, specific surface area is big, has specific skeleton structure etc. all
More advantages.
The Ca prepared using low-temp foaming method in citric acid2Fe2O5Catalyst, that is, possess such as sol-gel process, hydro-thermal
The liquid phase methods such as method, ammonium salt decomposition method prepare the uniformity of catalyst, and greatly shorten catalyst in whole preparation flow
In the cycle, laid a good foundation for its industrialization development.This method can be according to Ca2Fe2O5The different requirements of powder and purposes, are used
The addition of different citric acids, with the Ca of performance needed for acquisition2Fe2O5Catalyst.
In the present invention, the predecessor in after low-temp foaming at 650 DEG C after calcining, you can forms stabilization
Ca2Fe2O5Catalyst, compared with the solid phase reaction at traditional 1000 DEG C, there is obvious advantage.Catalyst cyclical stability is more
It is good, to Ca2Fe2O5Catalyst, by 50 synthesis gas reduction and CO2After gas oxidation, still with fairly good stable circulation
Performance, the activity of catalyst do not reduce substantially.
The inventive method compares traditional citric acid sol-gel method preparation method, simple and easy, easy to operate, suitable for industry
Change preparation and application, obtained catalyst performance stabilised is excellent, considerably beyond within technical staff institute energy intended scope.
Brief description of the drawings
Fig. 1 calcium swages Ca2Fe2O5Method for preparing catalyst flow chart
Ca under Fig. 2 difference citric acid additions2Fe2O5The XRD picture of catalyst
Fig. 3 difference citric acid additions are to Ca2Fe2O5The influence of specific surface area of catalyst and pore volume
Fig. 4 difference citric acid additions are to Ca2Fe2O5The influence of catalyst pores volume distribution
Fig. 5 difference citric acid additions are to Ca2Fe2O5The influence of catalyst pores area distributions
Fig. 6 difference calcining heats are to Ca2Fe2O5The influence of catalyst component
Fig. 7 difference calcining heats are to Ca2Fe2O5The influence of specific surface area of catalyst and pore volume
Fig. 8 difference calcining heats are to Ca2Fe2O5The influence of catalyst pores volume distribution
Fig. 9 difference calcining heats are to Ca2Fe2O5The influence of catalyst pores area distributions
Figure 10 Ca2Fe2O5Catalyst photoelectron intensity can modified-image-XPS with combination
Figure 11 Ca2Fe2O5Catalyst Ca-2p photoelectrons intensity can modified-image with combination
Figure 12 Ca2Fe2O5Catalyst Fe -2p photoelectrons intensity can modified-image with combination
Figure 13 Ca2Fe2O5Catalyst C-1s photoelectrons intensity can modified-image with combination
Figure 14 Fe2O350 redox reaction procedure quality changes of catalyst
Figure 15 Ca2Fe2O550 redox reaction procedure quality changes of catalyst
Embodiment
With reference to embodiment and Figure of description, the present invention is further illustrated.
Embodiment 1：
Comprise the following steps：
1) ferric nitrate, calcium nitrate are mixed according to a certain percentage with citric acid, according to Ca: Fe mol ratio 0.9: 1, citric acid
: (Fe+Ca)=3: 1 are added；
2) mixed solution containing three kinds of ferric nitrate, calcium nitrate and citric acid predecessors is configured, makes the concentration of iron nitrate solution
For 0.08mol/L, the concentration of calcium nitrate solution is 0.072mol/L；
3) solution that configuration obtains is stirred into 20min at 50 DEG C；
4) solution after stirring is placed in drying box, after 180 DEG C of temperature ranges foam and dry 24 hours, will obtained
Foamed crushing and screening to particle diameter 0.25mm；
5) the above-mentioned broken solid powder with after screening is put into Muffle furnace, it is small with calcining 4 under air atmosphere at 650 DEG C
When, heating rate ensures in 3 DEG C/min.Sample after calcining is sieved according to different-grain diameter, it is compound to finally give calcium iron
Type Ca2Fe2O5Catalyst.
Embodiment 2：
1) ferric nitrate, calcium nitrate are mixed according to a certain percentage with citric acid, according to Ca: Fe mol ratio 1.1: 1, citric acid
: (Fe+Ca)=2: 1 are added；
2) mixed solution containing three kinds of ferric nitrate, calcium nitrate and citric acid predecessors is configured, makes the concentration of iron nitrate solution
For 0.12mol/L, the concentration of calcium nitrate solution is 0.132mol/L；
3) solution that configuration obtains is stirred into 30min at 40 DEG C；
4) solution after stirring is placed in drying box, after 185 DEG C of temperature ranges foam and dry 15 hours, will obtained
Foamed crushing and screening to particle diameter 0.25mm；
5) the above-mentioned broken solid powder with after screening is put into Muffle furnace, at 750 DEG C with calcining 3.5 under air atmosphere
Hour, heating rate ensures in 4 DEG C/min.Sample after calcining is sieved according to different-grain diameter, calcium iron is finally given and answers
Mould assembly Ca2Fe2O5Catalyst.
Embodiment 3：
1) ferric nitrate, calcium nitrate are mixed according to a certain percentage with citric acid, according to Ca: Fe mol ratio 1: 1, citric acid:
(Fe+Ca)=1: 1 it is added；
2) mixed solution containing three kinds of ferric nitrate, calcium nitrate and citric acid predecessors is configured, makes the concentration of iron nitrate solution
For 0.10mol/L, the concentration of calcium nitrate solution is 0.10mol/L；
3) solution that configuration obtains is stirred into 40min at 30 DEG C；
4) solution after stirring is placed in drying box, after 190 DEG C of temperature ranges foam and dry 12 hours, will obtained
Foamed crushing and screening to particle diameter 0.25mm；
5) the above-mentioned broken solid powder with after screening is put into Muffle furnace, it is small with calcining 3 under air atmosphere at 850 DEG C
When, heating rate ensures in 5 DEG C/min.Sample after calcining is sieved according to different-grain diameter, it is compound to finally give calcium iron
Type Ca2Fe2O5Catalyst.
Embodiment 4：
1) ferric nitrate, calcium nitrate are mixed according to a certain percentage with citric acid, according to Ca: Fe mol ratio 1: 1, citric acid:
(Fe+Ca)=2: 1 it is added；
2) mixed solution containing three kinds of ferric nitrate, calcium nitrate and citric acid predecessors is configured, makes the concentration of iron nitrate solution
For 0.11mol/L, the concentration of calcium nitrate solution is 0.11mol/L；
3) solution that configuration obtains is stirred into 30min at 35 DEG C；
4) solution after stirring is placed in drying box, after 180 DEG C of temperature ranges foam and dry 24 hours, will obtained
Foamed crushing and screening to particle diameter 0.25mm；
5) the above-mentioned broken solid powder with after screening is put into Muffle furnace, it is small with calcining 4 under air atmosphere at 850 DEG C
When, heating rate ensures in 3 DEG C/min.Sample after calcining is sieved according to different-grain diameter, it is compound to finally give calcium iron
Type Ca2Fe2O5Catalyst.
The present invention proposes prepares calcium swage Ca using citric acid foaming2Fe2O5Catalyst.Existing preparation Ca2Fe2O5's
Although solid reaction process equipment is simple, technological process is convenient, and such process energy consumption is quite big, due to being scattered in for mechanical mixture
Uniformity is relatively poor, therefore the usual purity of product synthesized is not high, is only applicable to the situation relatively low to Quality and property requirement.
And hydro-thermal method, sol-gal process and ammonium salt decomposition method etc. are adopted, the chemical product constituent that it is synthesized is accurate, purity is high, divides
Scattered property is good but processing step is relatively complicated, synthesis cycle is long, is not suitable for a large amount of preparations and industrialized production.With above-mentioned existing preparation
Method is compared, and not only has that equipment operation is convenient, technological process is simple, catalyst can be used for concurrently using low-temp foaming method in citric acid
It is a large amount of the advantage such as to prepare, be also integrated with energy consumption is low, catalyst dispersity can it is excellent, specific surface area is big, has specific skeleton knot
The many advantages such as structure.
The Ca prepared using low-temp foaming method in citric acid2Fe2O5Catalyst, that is, possess such as sol-gel process, hydro-thermal
The liquid phase methods such as method, ammonium salt decomposition method prepare the uniformity of catalyst, and greatly shorten catalyst in whole preparation flow
In the cycle, laid a good foundation for its industrialization development.In low-temp foaming method according to citric acid boiling point at 175 DEG C, when temperature height
Will gradually it be decomposed when 175 DEG C, there is provided hydroxyl and carboxyl functional group, and then promote solution crosslinking and foam, it is efficiently formed
There is the distribution of specific pore volume and the Ca of skeleton structure2Fe2O5Catalyst.As shown in figure 1, it is Ca2Fe2O5Method for preparing catalyst
Basic procedure.Presoma after foaming is after the preparation flows such as simple grinding, dry and calcining, you can obtains final
High-performance Ca2Fe2O5Product.The shadow that different citric acid additions are distributed to catalyst XRD results, BET surface area and pore volume
Ring as Figure 2-Figure 5.It can be found that using the addition of citric acid foaming to Ca2Fe2O5The formation of powder influences smaller, lemon
The mol ratio of lemon acid and (Ca+Fe) can form Ca in 1-4 sections2Fe2O5Catalyst.And Ca2Fe2O5The ratio surface of catalyst
Product reduces again as the amount increase of citric acid first raises, but is held in 50m2/ more than g.Increase with the addition of citric acid,
It will also be seen that the pore volume of particle increased less than 10nm sections, in 10-100nm mesoporous and macropore section,
Its pore volume has the trend for reducing or leveling off to 0.It can be seen that the raising of citric acid amount can promote catalyst pore structure distribution more
Uniformly, and this method is in addition to above-mentioned advantage, also can be according to Ca2Fe2O5The different requirements of powder and purposes, using different lemons
The addition of acid, with the Ca of performance needed for acquisition2Fe2O5Catalyst.
For calcining heat to Ca2Fe2O5The influence that catalyst is formed does not have as shown in fig. 6, when temperature is 550 DEG C
Form Ca2Fe2O5Crystal, only some Ca is understood according to XRD result2Fe2O5Formed, also partial crystals are calcium carbonate,
Its main cause be 550 DEG C at, due to citric acid foaming can produce a certain amount of carbon distribution, at a suitable temperature can with air
Oxygen react to form CO2, and then react to form calcium carbonate with CaO.So as to hinder Ca2Fe2O5Catalyst enters
One step is formed.When temperature is higher than 650 DEG C, Ca can be formed2Fe2O5, and calcining heat is higher, the Ca of formation2Fe2O5Peak intensity
Degree is higher, represents calcium swage Ca2Fe2O5Catalyst is more stable.Contrast understands that the predecessor in after low-temp foaming passes through
After being calcined at 650 DEG C, you can form stable Ca2Fe2O5Catalyst, compared with the solid phase reaction at traditional 1000 DEG C, have bright
Aobvious advantage.Fig. 6-Fig. 8 is respectively that different calcining heats are distributed to specific surface area of catalyst, pore volume distribution and hole area
Influence.It can be seen from result, temperature gets over the specific surface area of high catalyst and pore volume has reduction, especially from 550 DEG C to 650 DEG C
Temperature-rise period, due to lattice variations be present, BET specific surface area, pore volume and hole area change are more obvious, work as temperature
After 650 DEG C, its variable quantity is relatively reduced, and the structure of catalyst also gradually tends towards stability.Figure 14-Figure 15 is respectively Fe2O3With
Ca2Fe2O5Catalyst carries out 50 synthesis gas reduction and CO as oxygen carrier2Oxidation experiment, new preparation side is used with checking
Catalyst cyclical stability under method.Compare and understand, iron oxide carries out redox reaction experiment as oxygen carrier, in the first seven time
In circular response, catalyst performance significantly declines, and as reaction continues, is basically stable at the redox model of a very little
Enclose；And to Ca2Fe2O5Catalyst, by 50 synthesis gas reduction and CO2It is still steady with fairly good circulation after gas oxidation
Qualitative energy, the activity of catalyst do not reduce substantially.
Analyzed for more than, it can be seen that low temperature is sent out in being carried out using citric acid as foaming agent to ferric nitrate and calcium nitrate
Bubble, the predecessor after being foamed can the excellent Ca of processability by high-temperature calcination2Fe2O5Catalyst.This method is with passing
The preparation method change of system citric acid sol-gel method is compared, simple and easy, easy to operate, suitable for preparation of industrialization and application, is obtained
The catalyst performance stabilised arrived is excellent, considerably beyond within technical staff institute energy intended scope.
Above-described embodiment is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill of the art
For personnel, under the premise without departing from the principles of the invention, some improvement and equivalent substitution can also be made, these are to the present invention
Claim be improved with the technical scheme after equivalent substitution, each fall within protection scope of the present invention.
Claims (6)
- A kind of 1. calcium swage Ca2Fe2O5Method for preparing catalyst, it is characterised in that this method comprises the following steps：1) ferric nitrate, calcium nitrate and citric acid are mixed, wherein ferric nitrate and calcium nitrate are according to Ca: Fe mol ratio (0.9-1.1): 1 is added；2) deionized water is added, is configured to solution, iron nitrate solution concentration is 0.08-0.12mol/L, the concentration of calcium nitrate solution For 0.072-0.132mol/L；3) solution that configuration obtains is stirred at 30-50 DEG C；4) solution that the step 3) obtains is placed in drying box, is foamed in 180-190 DEG C of temperature range and to dry 12-24 small When, and obtained solid sample is crushed and ground；5) sample after being ground in the step 4) is put into Muffle furnace, calcined at 650-850 DEG C 3-4 hours, heating speed Rate ensures, in 3-5 DEG C/min, to be ground the solid powder after calcining, finally gives calcium swage Ca2Fe2O5Catalyst.
- A kind of 2. calcium swage Ca according to claim 12Fe2O5Method for preparing catalyst, it is characterised in that the step 1) mole addition of citric acid is 1-3 times of calcium iron integral molar quantity in.
- A kind of 3. calcium swage Ca according to claim 12Fe2O5Method for preparing catalyst, it is characterised in that the step 3) time of stirring is 20-40 minutes in.
- A kind of 4. calcium swage Ca according to claim 1,2 or 32Fe2O5Method for preparing catalyst, it is characterised in that described The particle diameter of high temperature foamed in step 4) after broken and grind is less than 0.3mm.
- A kind of 5. calcium swage Ca according to claim 1,2 or 32Fe2O5Method for preparing catalyst, it is characterised in that described Muffle furnace calcining in step 5) is carried out under oxygen or air atmosphere.
- A kind of 6. calcium swage Ca according to claim 1,2 or 32Fe2O5Method for preparing catalyst, it is characterised in that described Sample particle diameter after being ground in step 5) is controlled between 0.10-0.25mm.
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| CN111298827A (en) * | 2020-02-03 | 2020-06-19 | 天津大学 | Mesoporous molecular sieve loaded copper-doped calcium ferrite type strontium cobaltate ultrafiltration membrane filler for water purification and preparation method thereof |
| CN112275290A (en) * | 2019-10-23 | 2021-01-29 | 中南大学 | Copper-based oxygen carrier with lattice oxygen participating in methanol autothermal reforming hydrogen production and preparation and application thereof |
| CN112811476A (en) * | 2020-12-31 | 2021-05-18 | 华中科技大学 | Nickel-doped brownmillerite type oxygen carrier and preparation method and application thereof |
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