CN104857911A - High-performance oxygen adsorbent and preparation method thereof - Google Patents
High-performance oxygen adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-performance oxygen adsorbent and a preparation method thereof, wherein the oxygen adsorbent material is a mixed conductor ceramic material having oxygen selectivity, and provides extremely high oxygen selectivity by using lattice oxygen vacancy to carry out chemical adsorption and desorption on oxygen when the temperature is increased or decreased. The production method comprises: uniformly mixing raw materials according to a ratio, calcining for a certain time at a high temperature to prepare large-particle oxide powder, and carrying out double ball milling to refine the particles so as to prepare the multi-metal composite oxide powder. The novel oxygen adsorbent of the present invention can be used for temperature changing oxygen adsorbing and has high oxygen adsorption.
Description
Technical field
The invention belongs to Application in Chemical Engineering technical field, be specifically related to a kind of high-performance oxygen absorbent and preparation method thereof.
Background technology
Oxygen is the active gas of a kind of chemical property, and along with the development of society, oxygen is in petrochemical industry, and metallurgy industry, national defense industry, there has been increasing extensive use in the fields such as health care.At present, the main method of oxygen has traditional cryogenic rectification method, membrane separation process and pressure swing adsorption method.Low temperature process is comparatively traditional method for producing oxygen through, by through air compressing, cools, the saturated liquefaction of humid air, and the boiling-point difference of recycling oxygen nitrogen component, is separated oxygen nitrogen with rectificating method, thus obtains highly purified oxygen and nitrogen.Low temperature process technology maturation, is applicable to large-scale production high purity oxygen gas and nitrogen, is the air separating method be most widely used at present.Membrane separation process and pressure swing adsorption method are the emerging technologies of current oxygen, and membrane separation technique forms gas concentration gradient to be separated by gas with various in film, is characterized in, operating means is simple, easy to operate, be not suitable for maximizing and produce, the oxygen purity of production is 40% ~ 50%; And pressure-variable adsorption is the adsorption tower allowing air pass through containing adsorbent, be separated by the selective absorption of adsorbent and obtain oxygen, its feature is: flow process is simple, and equipment is easy, middle-size and small-size production scale, and the oxygen-nitrogen purity of producing gained is 90% ~ 99%.Along with the propelling of time, PSA Technology obtains researches and develops more and more widely, particularly in the development and related process technologies of adsorbent, obtains greater advance.But, the adsorbance of the performance of the adsorbent that pressure-variable adsorption uses such as adsorbent, adsorbing separation coefficient, and the aspect such as adsorbent intensity need further raising, these all have very large impact to the fast development of omnibus control system technology.
Mixed conductor material be one roughly the same time there is the new ceramic material of oxonium ion and electronic conductivity, to oxygen, there is adsorptive selectivity.When partial pressure of oxygen declines or temperature raises, or when the simultaneous temperature that declines of partial pressure of oxygen raises, this material just can oxygen loss, when partial pressure of oxygen raises or temperature reduces or when temperature reduces and partial pressure of oxygen raises, the oxygen in environment can enter into material again.And in order to keep the electroneutral of material, while material oxygen uptake and oxygen loss, electronics also conducts in material.As the mixed conductor ceramic material of Novel oxygen adsorbent and the oxygen flow mechanism of compact oxygen permeable film similar, namely absorption and the desorption of oxygen is carried out by Lacking oxygen and oxygen generation chemical reaction, and oxygen conducts in material conductor under the effect of driving force, so be 100% in theory to the permselective property of oxygen, be far longer than the oxygen nitrogen separation of molecular sieve.Although Chinese scholars is used as composite conductor oxygen-permeating film to ceramic material carried out large quantifier elimination, but this technology is achieved large-scale industrialization and is also faced with a lot of problem, such as, membrane material will possess high oxygen flow ability, there are enough thermo-chemical stabilities, membrane material also should match with the thermal coefficient of expansion of reactor assemblies, and to realize good sealing, these are all difficult to realize on a membrane material simultaneously.And similar mixed conductor ceramic material is used as Novel oxygen adsorbent through granulation, when practical operation, just there is not elevated-temperature seal difficulty or lose the problems such as ability to take oxygen because of Expansion And Fracture.Therefore, Novel oxygen adsorbent is adopted to carry out oxygen separating and remove the prospect of having a very wide range of applications.
Ca-Ti ore type mixed conductor ceramic material has high electron conduction and oxygen conduction.For the saturating ceramic material of Ca-Ti ore type mixed conductor, the performance indications such as its oxygen desorption amount, chemical stability and structural stability and its element form closely related.Desirable perovskite structure has cubic symmetry, and molecular formula can be expressed as ABO
3-δ, A position is occupied by the metal ion that some ionic radius such as alkali metal, alkaline-earth metal, rare earth metal are larger, and B position is occupied by the transition metal ions that ionic radius is less.In perovskite structure, the oxygen absorbed of material is generally determined jointly by oxygen ionic conductivity and electronic conductivity.Generally, oxygen ionic conductivity is the key of oxygen absorbed.In Ca-Ti ore type mixed conductor, the charge compensation form that the concentration of increase A position low price doped metal ion and minimizing B position ion rise valency can make oxygen vacancy concentration increase.But after oxygen vacancy concentration reaches certain value, Lacking oxygen can occur to associate or ordered arrangement, makes ionic conductivity reduce on the contrary.For mixed conductor ceramic material, the selection of doped chemical should follow following strategy: 1) select low-valent metal carry out doping and improve its doping content as much as possible in A position, the transition metal that ability of appraising at the current rate is suitable is selected in B position, while keeping certain electronic conductivity, reduce the charge compensation form that ion rises valency, thus make in perovskite structure, there is higher oxygen vacancy concentration (or oxygen nonstochiometry ratio); 2) select the element of heavy ion radius to adulterate, structure cell free volume is increased, is conducive to the migration of oxonium ion; 3) select the metallic element that the Average bond energy of metal-oxygen is lower, reduce structure cell to the binding force of oxygen, the migration activation energy of oxygen is reduced; 4) the tolerance factor is as far as possible close to 1, makes material keep perovskite structure so that the structural stability had.Teraoka etc. are the earliest to La
1-xsr
xco
1-yfe
yo
3-δoxygen flow ceramic material system is studied [TeraokaY.et al., Chem.Lett., 11 (1985) 1743-1746], finds that the oxygen desorption amount of this system increases along with the increase of Co and Sr content.Have studied again with LaCoO subsequently
3for the perovskite composite oxides of parent, find the La for adulterating in A position
0.6a
0.4co
0.8fe
0.2o
3-δmaterial, the order of its oxygen desorption amount size is Ba > Ca > Sr > Na, for the above-mentioned material of B position doping, the order of its oxygen desorption amount size is Cu > Ni > Co > Fe > Cr > Mn, wherein SrCo
0.8fe
0.2o
3-δthere is the highest oxygen desorption amount.But SrCo
0.8fe
0.2o
3-δphase structure is stable not.In order to improve the stability of this material, make cubic perovskite structure can lower in temperature (<800 DEG C), partial pressure of oxygen lower (10kPa) condition under stable existence, researcher adulterate in A position other metallic element replace part Sr, as Sr
1-xa
xco
0.8fe
0.2o
3-δ(A=La, Ba).Prado have studied La
xsr
1-xco
0.8fe
0.2o
3-δthe stability [Prado F.et al., Solid State Ionics, 152/153 (2002) 647-655] of structure.Find that A position certain La that adulterates can improve SrCo
0.8fe
0.2o
3-δstability.But when the content of La increases, the electrical conductivity of oxonium ion but reduces.Shao etc. find the A position Ba replacement Sr of 50%, make Ba
0.5sr
0.5co
0.8fe
0.2o
3-δtime, not only improve the stability of material, and oxygen desorption amount can also be made to increase [Shao Z.et al., J.Membr.Sci., 172 (2000) 177-188].Shao have studied again the Ba of A position doping different content to SrCo
0.8fe
0.2o
3-δthe impact [Shao Z.etal., Separ.Purif.Technol., 25 (2001) 419-429] of stability and oxygen desorption amount, finds that its optimum mix amount is 0.2≤x≤0.5.Within the scope of this doping, perovskite structure can stable existence always, and oxygen desorption amount compares SrCo
0.8fe
0.2o
3-δalso high.Except the doping of A position, the metal ion that also can have a high stable valence state by the doping of B position improves the stability of oxygen flow ceramic material.It has been generally acknowledged that the mixed conductor containing Co has high oxygen desorption amount, but the structural instability containing Co material limits its practical application.Ishihara has the LaGaO of high ionic conductivity and low thermal coefficient of expansion
3mix Fe, Ni [Ishihara T.et al., Catal.Surveys from Japan, 4 (2001) 175-176] in the oxide of base, successfully develop La
0.8sr
0.2ga
0.6fe
0.4o
3-δoxygen impermeable material, has good structural stability.
Summary of the invention
The object of this invention is to provide a kind of high-performance oxygen absorbent and preparation method thereof, this oxygen adsorbent material is the mixed conductor ceramic material with oxygen selective, when temperature raises or reduce, it utilizes Lattice Oxygen room to carry out chemisorbed and the desorption of oxygen, only absorbs the oxygen composition in air-flow.
The invention provides a kind of oxygen absorbent, this sorbent material is ABO
3-δtype Ca-Ti ore type mixed conductor material, described ABO
3-δca-Ti ore type mixed conductor is deficiency perovskite material, and its chemical formula is A
1-xa '
xb
1-yb '
yo
3-δ, wherein, the span of x is 0≤x≤0.3, and the span of y is 0≤y≤0.3, and δ is non-stoichiometric, 0< δ <0.5; A is rare-earth metal La system, alkaline-earth metal Mg, at least one (in A preferred La, Sr, Ba at least one) in Ca, Sr, Ba; B is transition metal Co, at least one (in B preferred Co, Al, Fe, Nb, Ti at least one) in Al, Fe, Nb, Cu, Zr, Mn, Cr, Ti.
Present invention also offers a kind of preparation method of oxygen absorbent, chemical molecular formula according to target oxygen adsorbent forms, by ball milling 5-15h after metallic element mol ratio correct amount raw material, mix, adopt solid-phase synthesis, by roasting at high temperature 900 DEG C-1400 DEG C after the raw material that mix, prepare the perofskite type oxide powder that particle is larger, then re-start ball milling 5-15h, obtain polymetallic composite oxide powder, be oxygen absorbent;
Concrete steps are as follows:
1) a certain amount of BaCO is got
3, SrCO
3, Al
2o
3and Fe
2o
3powder by proportioning mixing, and adds ethanol in proper amount and is together placed in ball grinder, after ball milling 5-15h, takes out and dries, obtain the tiny powder mixed;
2) by 1) gained powder puts into corundum crucible, and put into Muffle furnace high-temperature roasting 5-10h after compacting, make fully to react between reactant, obtain the perovskite oxide powder that particle is larger;
3) by 2) the bulky grain oxide powder ball milling again of gained, obtain evenly tiny perovskite oxide powder Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ;
4) Co is adopted respectively
2o
3, TiO
2and Nb
2o
5replacement step 1 successively) in Al
2o
3, repeat above-mentioned steps 1-3), namely can obtain adsorbent B a
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δand Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δoxide powder;
5) dry pressing is adopted, by step 1-4) the oxide powder Manual tablet pressing machine that obtains is pressed into bar shaped and circle element embryo for sintering;
6) by 5) gained element embryo puts into high temperature box furnace and at high temperature sinters 5-10h and obtain Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δand Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δbar shaped ceramic block and round ceramic sheet, to test the electrical conductivity of oxide and to investigate its sintering situation.
The preparation method of oxygen absorbent provided by the invention, reactant materials powder BaCO in described step 1)
3, SrCO
3, Al
2o
3, Fe
2o
3in molar ratio for 3:17:1.5:8.5 is for mixing, Ball-milling Time is 10h first.
The preparation method of oxygen absorbent provided by the invention, described step 2) in the powder temperature that is placed in Muffle furnace roasting be 1050 DEG C, obtain the perovskite oxide powder that particle is larger after roasting 10h.
The preparation method of oxygen absorbent provided by the invention, in described step 3), the time of secondary ball milling is 5h, obtains complete reaction, the fine particle powder mixed.
The preparation method of oxygen absorbent provided by the invention, in described step 5), for testing the electrical conductivity of oxide powder and investigating its sintering situation, the process of suppressing plain embryo is, gets 2g powder and is placed in tablet press machine, under the pressure of 4MP, pressurize obtains bar morph embryo in 30 seconds afterwards, idiosome length is about 25mm, and width is about 5mm, and thickness is about 3mm; Get 1g powder and be placed in tablet press machine, under the pressure of 10MP, pressurize obtains circular plain embryo in 30 seconds afterwards, and plain embryo diameter is about 17mm, and thickness is about 1mm.
The preparation method of oxygen absorbent provided by the invention, in described step 6), the plain embryo obtained by obsession is put into high temperature box furnace and is sintered, and sintering temperature 1400 DEG C, obtains Ba after 5h during sintering
0.15sr
0.85al
0.15fe
0.85o
3-δbar shaped and round ceramic, corresponding Ba
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δand Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δthe sintering temperature of bar shaped and round ceramic is respectively: 1350 DEG C, 1400 DEG C and 1450 DEG C.
Oxygen absorbent provided by the invention is used for variable-temperature oxygen absorption, thus carries out air separation or oxygen removal of impurities, and hydrogen-storing material.
For achieving the above object, high-performance oxygen absorbent provided by the invention and preparation method thereof is mainly: (1) is at Ba
xsr
1-xco
yfe
1-yo
3-δon the basis of series oxygen permeable film material, difference doping is carried out to B position, obtain higher stability to make material.Except the doping of common low price ion receptor, also add the doping of high price stabilizing ion acceptor.(2) ratio between each element in material composition is changed, to obtain higher oxygen desorption amount.(3) by the adjustment to not homoatomic embryo sintering temperature, its sintering situation is investigated.
The present invention is at Ba
xsr
1-xco
yfe
1-yo
3-δon the basis of Series oxides, by the different element that adulterates to B position, except common low price element al, be more doped with higher price element ti, obtain higher stability to make oxide.Then, redistribution has been carried out, to obtain higher oxygen desorption amount to the content of composition each in raw material.The present invention adopted solid-phase synthesis before this, after being mixed by proportioning by raw material after at high temperature roasting a period of time, prepare the perofskite type oxide powder that particle is larger, then secondary ball milling micronized particles, obtain particle tiny, the oxygen adsorbent material powder that absorption property is high.Then adopt dry pressing, under a certain pressure fine powder be pressed into plain embryo, then by plain embryo through high temperature sintering to study its sintering character and electrical conductivity.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the perovskite oxide powder adopting Solid phase synthesis,
(a) Ba
0.15sr
0.85co
0.15fe
0.85o
3-δ, (b) Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ, (c) Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δ(d) Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δoxide powder;
Fig. 2 is (a) Ba
0.15sr
0.85co
0.15fe
0.85o
3-δ, (b) Ba
0.15sr
0.85feO
3-δ, (c) Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ(d) Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δelectrical conductivity;
Fig. 3 is Ba
0.15sr
0.85al
0.15fe
0.85o
3-δthe variable-temperature oxygen absorption of oxide powder and desorption process.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
1) a certain amount of BaCO is got
3, SrCO
3, Al
2o
3and Fe
2o
3powder by proportioning mixing, and adds ethanol in proper amount and is together placed in ball grinder, after ball milling 5-15h, takes out and dries, obtain the tiny powder mixed;
2) by 1) gained powder puts into corundum crucible, and put into Muffle furnace high-temperature roasting 10-15h after compacting, make fully to react between reactant, obtain the perovskite oxide powder that particle is larger;
3) by 2) the bulky grain oxide powder ball milling again of gained, obtain evenly tiny perovskite oxide powder Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ;
4) Co is adopted respectively
2o
3, TiO
2and Nb
2o
5replacement step 1 successively) in Al
2o
3, repeat above-mentioned steps 1-3), namely can obtain adsorbent B a
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δand Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δoxide powder;
5) dry pressing is adopted, by step 1-4) the oxide powder Manual tablet pressing machine that obtains is pressed into bar shaped and circle element embryo for sintering;
6) by 5) gained element embryo puts into high temperature box furnace and at high temperature sinters 5-10h and obtain Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δand Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δbar shaped ceramic block and round ceramic sheet, to test the electrical conductivity of oxide and to investigate its sintering situation.
Embodiment 1
Get a certain amount of BaCO
3, SrCO
3, Al
2o
3and Fe
2o
3material powder, 3:17:3:17 mixing in molar ratio, adds ball milling after ethanol in proper amount, and dried by the material mixed after ball milling, compacting, puts into Muffle furnace high-temperature roasting, obtains the perovskite oxide powder Ba that particle is larger
0.15sr
0.85al
0.15fe
0.85o
3-δ.
Adopt Co respectively
2o
3, TiO
2and Nb
2o
5replace the Al in previous step successively
2o
3, repeat operation, the Ba that obtained particle is larger
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δand Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δoxide powder;
Embodiment 2
Oarse-grained oxide powder embodiment 1 obtained carries out secondary ball milling post-drying, and the powder that takes a morsel respectively carries out XRD sign, result as shown in Figure 1, Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85co
0.15fe
0.85o
3-δand Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δoxide powder is the perovskite structure of pure phase, Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δoxide powder is non-pure phase perovskite.Carried out high temperature HT-XRD to each oxide powder further to test, after oxide powder being heated to 1000 DEG C, its perovskite structure is still destroyed.Meanwhile, also entered stability test, by each oxide powder in the air of 800 DEG C after roasting 100h, XRD result shows, Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85co
0.15fe
0.85o
3-δand Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δoxide powder is still pure phase perovskite structure, and description architecture has good stability.
Embodiment 3
The each perovskite oxide material powder obtained by embodiment 1, adopts dry pressing, at the pressure of 4MP, after being pressed into bar shaped element embryo when pressurize 30-60 second, then by Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δand Ba
0.15sr
0.85feO
3-δbar morph embryo, is placed in Muffle furnace, and at 1300-1450 DEG C, sintering obtains bar shaped ceramic block respectively, and (in figure, a, b, c, d represent Ba to the electrical conductivity of mensuration respectively as shown in Figure 2
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85feO
3-δ, Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δ).
Embodiment 4
To Ba
0.15sr
0.85al
0.15fe
0.85o
3-δoxide powder investigates its oxygen desorption and desorption process by heating up and lowering the temperature, and result as shown in Figure 3.Sample powder is carried out heating and cooling operation between 300-925 DEG C, and temperature rate is ± 15 DEG C/min, and air velocity is 100mL/min, and its weight change is 2.60%, and corresponding oxygen desorption capacity is 18.2mL/ (g oxide).
Comparative example 1
For SrCo
xfe
1-xo
3-δseries oxides material, researcher finds, in A position, doping Ba can increase oxygen desorption amount, and research also finds, the doping of Ba inhibits the oxidation of B position metal ion, namely makes Co
4+, Fe
4+easier with Co
3+, Fe
3+exist, the ratio of B position low price state ion is increased, and the tolerance factor is increased, and this may be its constitutionally stable reason; The increase of B position low price state ion concentration, also will improve the concentration of Lacking oxygen, increase the electrical conductivity of oxonium ion simultaneously.So in the present invention, wish that the stability being increased oxide material by the Ba of doping 0.15 improves its oxygen desorption amount simultaneously.
Comparative example 2
Except the doping of A position, there is in the doping of B position the metal ion of high stable valence state, the stability of mixed conductor material can be improved.In the present invention, except doping at a low price ion receptor doping, the doping of high price stabilizing ion acceptor is also added.In addition, although have higher oxygen desorption amount containing the mixed conductor material of Co, the structural instability containing Co material limits its practical application.Thus in the present invention, give several not containing the B position doping oxide of Co, to improve the stability of oxide material.
Claims (8)
1. an oxygen absorbent, is characterized in that: the material of this adsorbent is deficiency Ca-Ti ore type mixed conductor material, and its chemical formula is A
1-xa '
xb
1-yb '
yo
3-δ;
Wherein, the span of x is 0≤x≤0.3, and the span of y is 0≤y≤0.3,0< δ <0.5;
A is rare-earth metal La system, alkaline-earth metal Mg, at least one or multiple in Ca, Sr, Ba;
B is transition metal Co, at least one or multiple in Al, Fe, Nb, Cu, Zr, Mn, Cr, Ti.
2. according to oxygen absorbent described in claim 1, it is characterized in that: described A is at least one in La, Sr, Ba.
3. according to oxygen absorbent described in claim 1, it is characterized in that: described B is at least one in Co, Fe, Nb, Ti.
4. according to oxygen absorbent described in claim 1, it is characterized in that: this adsorbent is Ba
0.15sr
0.85al
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85co
0.15fe
0.85o
3-δ, Ba
0.15sr
0.85ti
0.15fe
0.85o
3-δand Ba
0.15sr
0.85nb
0.15fe
0.85o
3-δin one.
5. a preparation method for oxygen absorbent described in claim 1, is characterized in that:
Chemical molecular formula according to target oxygen adsorbent forms, mix by ball milling after metallic element mol ratio correct amount raw material, then at high temperature repeatedly roasting, prepare the perofskite type oxide powder that particle is larger, then ball milling is re-started, obtain polymetallic composite oxide powder, be oxygen absorbent.
6. according to the preparation method of oxygen absorbent described in claim 5, it is characterized in that: described raw-material sintering temperature is 900 DEG C-1400 DEG C, the time is 5-10h.
7. according to the preparation method of oxygen absorbent described in claim 5, it is characterized in that: described Ball-milling Time is 5-15h.
8. oxygen absorbent described in claim 1 is used for variable-temperature oxygen absorption, thus carries out air separation or oxygen concentration, and hydrogen-storing material.
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| CN108114688A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of oxygen absorbent for oxygen coalescence |
| CN108117086A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of oxygen absorbent |
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| CN109759077A (en) * | 2019-01-08 | 2019-05-17 | 南京航空航天大学 | A kind of perovskite oxide catalyst and its preparation method and application |
| CN110589772A (en) * | 2019-08-28 | 2019-12-20 | 南京工业大学 | Oxygen separation device and process |
| CN111410515A (en) * | 2020-05-07 | 2020-07-14 | 信阳学院 | Cobalt-containing and doped high-performance oxygen adsorbent |
| CN112794374A (en) * | 2020-12-31 | 2021-05-14 | 大连海事大学 | Co-based perovskite oxide, preparation method thereof and application thereof in air separation |
| CN113652206A (en) * | 2021-08-20 | 2021-11-16 | 郑州轻工业大学 | Calcium-magnesium-based thermochemical adsorption heat storage material and preparation method thereof |
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| CN106861602A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of oxygen absorbent |
| CN108114688A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of oxygen absorbent for oxygen coalescence |
| CN108117086A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of oxygen absorbent |
| CN106976916A (en) * | 2017-04-17 | 2017-07-25 | 东南大学 | A kind of preparation method of high stability from carrier hydrogen-storing material |
| 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 |
| CN109759077A (en) * | 2019-01-08 | 2019-05-17 | 南京航空航天大学 | A kind of perovskite oxide catalyst and its preparation method and application |
| CN109759077B (en) * | 2019-01-08 | 2021-12-07 | 南京航空航天大学 | Perovskite oxide catalyst and preparation method and application thereof |
| CN110589772A (en) * | 2019-08-28 | 2019-12-20 | 南京工业大学 | Oxygen separation device and process |
| CN111410515A (en) * | 2020-05-07 | 2020-07-14 | 信阳学院 | Cobalt-containing and doped high-performance oxygen adsorbent |
| CN112794374A (en) * | 2020-12-31 | 2021-05-14 | 大连海事大学 | Co-based perovskite oxide, preparation method thereof and application thereof in air separation |
| CN113652206A (en) * | 2021-08-20 | 2021-11-16 | 郑州轻工业大学 | Calcium-magnesium-based thermochemical adsorption heat storage material and preparation method thereof |
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