CN106861602A - A kind of oxygen absorbent - Google Patents
A kind of oxygen absorbent Download PDFInfo
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- CN106861602A CN106861602A CN201510927399.2A CN201510927399A CN106861602A CN 106861602 A CN106861602 A CN 106861602A CN 201510927399 A CN201510927399 A CN 201510927399A CN 106861602 A CN106861602 A CN 106861602A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
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- C01B13/0259—Physical processing only by adsorption on solids
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0259—Physical processing only by adsorption on solids
- C01B13/0277—Temperature swing adsorption
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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Abstract
The present invention discloses a kind of oxygen absorbent, with A1±xB1±yO3-δChemical formula, wherein, A is at least one of rare earth or alkali earth metal La, Sr, Ba and Pr；B is transition metal Fe, at least one of Co, Ti and Zr；δ is non-stoichiometric.The oxygen absorbent is the composite oxide material with mixed oxygen ion-electronic conductivity matter, and when temperature is raised and lowered, oxide material can be desorbed and be adsorbed to oxygen, there is high oxygen adsorptive selectivity.Preparation method is that high temperature is repeatedly calcined after raw material is mixed by metering proportion, then through ball milling micronized particles, prepares ultra-fine high-performance composite oxide powder.This new oxygen absorbent is used for variable-temperature oxygen and adsorbs and be desorbed, and with oxygen adsorption capacity higher.
Description
Technical field
The invention belongs to Application in Chemical Engineering technical field, more particularly to a kind of high-performance oxygen absorbent and preparation method thereof.
Background technology
Traditional method for producing oxygen through mainly has cryogenic freezing partition method, membrane separation process and absorption method.Low temperature process utilizes oxygen
Nitrogen boiling point is different, and oxygen is directly prepared from air, and the law technology is ripe, it is adaptable to mass produce pure oxygen high
Gas and nitrogen, are to be most widely used method for producing oxygen through at present.Membrane separation process and absorption method are emerging oxygenerating technologies,
Membrane separation technique in film forms gas concentration gradient to separate by gas with various, is characterized in simple to operate
It is convenient, but be not suitable for maximization production；And absorption method is to allow air by the adsorption tower containing adsorbent, then lead to
Cross the selective absorption of adsorbent to separate oxygen processed, its feature is：Flow is simple, and equipment is easy, middle-size and small-size
Production scale, the oxygen purity obtained by production is high.Propulsion over time, adsorption separation technology is got over
Come on more exploitations and concern, the particularly development to adsorbent and related process technologies to achieve it is larger enter
Exhibition.But the performances such as the adsorbance of the adsorbent for absorption method, adsorbing separation coefficient, adsorbent intensity also have
Further raising is treated, these fast developments all to adsorption oxygen-preparation technology have significant impact.
Mixed conductor material is that, while having the new ceramic material of oxonium ion and electron conduction, have to oxygen
Adsorptive selectivity.When oxygen drops or temperature are raised, or temperature is raised while oxygen drops,
This material will oxygen loss；When partial pressure of oxygen is raised or temperature reduction, or temperature drop while partial pressure of oxygen rising
Low, the oxygen in environment can be entered into material lattice again.And in order to keep electroneutral, in material oxygen uptake and mistake
While oxygen, electronics also conducts in material.Mixed conductor ceramic material is used as oxygen absorbent, its adsorption machine
Reason is similar with the oxygen flow mechanism of compact oxygen permeable film, occurs to chemically react with Lacking oxygen by oxygen to adsorb and take off
Attached oxygen, is conducted in the presence of oxygen chemical gesture driving force in material conductor, therefore in theory to oxygen
Permselective property is 100%, much larger than the oxygen nitrogen separation that common molecular is sieved.Ceramic material is used as mixing
Conductor oxygen permeation membrane is difficult to realize heavy industrialization, and same type of material is used as new oxygen absorbent and is used as thoroughly
Oxygen film is compared, in practical operation, in the absence of the problems such as elevated-temperature seal is difficult or fracture loses oxygen uptake ability.Therefore,
It is made that new oxygen absorbent carries out oxygen separating and removing has a very wide range of applications prospect of mixed conductor material.
Ca-Ti ore type mixed conductor oxygen permeable ceramic material has electronics and oxygen conduction high, oxygen adsorbance
And the performance indications such as stability of material constitute closely related with its element.The molecular formula of preferable perovskite structure
It is represented by ABO3, with cubic symmetry, A is occupied by the larger metal ion of some ionic radius,
Such as alkali metal, alkaline-earth metal, rare earth metal；B is occupied by the less transition metal ions of ionic radius.
In the structure, the oxygen absorbed of material is typically together decided on by oxygen ionic conductivity and electronic conductivity.Generally, oxygen
Ionic conductivity plays decisive action to oxygen absorbed, the concentration of A low price doped metal ion of increase and subtracts
The charge compensation form that few B ion rises valency can increase oxygen vacancy concentration.But, when oxygen vacancy concentration reaches
After certain value, Lacking oxygen can associate or carry out ordered arrangement, on the contrary reduce ionic conductivity.Teraoka
Etc. have studied with LaCoO3Be the perovskite composite oxides of parent, find for A adulterate
La0.6A0.4Co0.8Fe0.2O3-δMaterial, the order of its oxygen adsorbance size is Ba ＞ Ca ＞ Sr ＞ Na, for B
The above-mentioned material of doping, the order of its oxygen adsorbance size is Cu ＞ Ni ＞ Co ＞ Fe ＞ Cr ＞ Mn, wherein
SrCo0.8Fe0.2O3-δWith highest oxygen adsorbance, but its phase structure is not sufficiently stable [Teraoka Y.et al., Chem.
Lett., 3 (1988), 503-506].In order to improve the stability of the material, researcher adulterates other at A
Metallic element substitution part Sr, such as Sr1-xAxCo0.8Fe0.2O3-δ(A=La, Ba).Prado have studied LaxSr1- xCo0.8Fe0.2O3-δStability [Prado F.et al., the SolidState Ionics, 152/153 (2002) 647- of structure
655].It was found that the A certain La of doping can improve SrCo0.8Fe0.2O3-δStability, but with La
The increase oxygen ionic conductivity of content is but reduced.Shao et al. has found that A replaces Sr with 50% Ba,
It is made Ba0.5Sr0.5Co0.8Fe0.2O3-δWhen, the stability of material can not only be improved, can also increase oxygen adsorbance [Shao
Z.et al.,J.Membr.Sci.,172(2000)177-188].Shao et al. have studied A doping difference and contains again
The Ba of amount is to SrCo0.8Fe0.2O3-δInfluence [Shao the Z.et al., Separ.Purif. of stability and oxygen adsorbance
Technol., 25 (2001) 419-429], it is found that its optimum mix amount is 0.3≤x≤0.5.Herein in the range of doping,
Perovskite structure can stable existence always, and oxygen adsorbance compares SrCo0.8Fe0.2O3-δIt is also high.Except A
Doping is outer, it is also possible to improve oxygen flow ceramics material by the B metal ion for being doped with stable valence state high
The stability of material.It has been generally acknowledged that the mixed conductor containing Co has oxygen adsorbance high, but containing the knot of Co materials
Structure instability limit its practical application.
The content of the invention
Present invention aim at a kind of high performance oxygen absorbent of offer, and provide its preparation method.The oxygen is adsorbed
Agent material is the mixed conductor ceramic material with oxygen selective, in intensification or cooling, material use Lattice Oxygen
Room carries out desorption and the absorption of oxygen, the oxygen gas component for only adsorbing or being desorbed in air-flow.
One aspect of the present invention provides a kind of oxygen absorbent, and it has A1±xB1±yO3-δChemical formula,
Described A is at least one of rare earth or alkali earth metal La, Sr, Ba and Pr；
Described B is transition metal Fe, at least one of Co, Ti and Zr；
Wherein, δ is non-stoichiometric.
On the other hand, the present invention provides the preparation method of above-mentioned oxygen absorbent：Methods described is by A or B
Metal oxide or metal carbonate uniformly mix in proportion, and gained mixture is in 800 DEG C≤T≤1300 DEG C bar
The oxide powder that bulky grain is obtained is calcined under part, then micronized particles, obtain superfine composite oxide powder.
Another further aspect, the present invention provides application of the above-mentioned oxygen absorbent in variable-temperature oxygen absorption.
For SrCoxFe1-xO3-δSeries oxides material, research finds that the Ba that adulterated at A can increase
Oxygen adsorbance, meanwhile, research has further been found that the doping of Ba inhibits the B oxidation of metal ion,
Increase the B ratio of low price state ion, this is probably BaxSr1-xCoyFe1-yO3-δConstitutionally stable one
Individual reason；The B increase of low price ion ratio simultaneously, will also improve the concentration of Lacking oxygen, increase oxonium ion
Electrical conductivity.So in the present invention, it is desirable to which oxide material is increased by composite mixed Ba and Ti
Stability, while improving its oxygen adsorbance.
It has been generally acknowledged that the mixed conductor material containing Co has oxygen adsorbance high, but material structure containing Co is not
Stability limits its practical application.Thus in the present invention, the Co elements that adulterated at B are abandoned, is wished
Prestige improves the stability of oxide material with this.
In addition to A is adulterated, the metal ion of stable valence state higher, Ke Yigai are doped with B
The stability of kind mixed conductor material.Thus in the present invention, when being doped to B, using higher
Valency stabilizing ion Ti4+B doping is carried out, to reach the purpose of reinforcing material stability.
Brief description of the drawings
The width of accompanying drawing of the present invention 3, wherein：
Fig. 1 is Ba0.15Sr0.85Ti0.15Fe0.85O3-δOxide powder is in the high temperature being warming up to during 1000 DEG C
XRD diffracting spectrums；
Fig. 2 is Ba0.15Sr0.85Ti0.15Fe0.85O3-δThe variable-temperature oxygen absorption of oxide powder and desorption process；
Fig. 3 is Ba0.15Sr0.85Ti0.15Fe0.85O3-δGained is ceramic after oxide powder sinters 5h at 1350 DEG C
The surface of piece and section SEM scheme, wherein (a, b) is surface, (c, d) is section.
Specific embodiment
Oxygen absorbent provided by the present invention, specially ABO3-δDeficiency perovskite material, its chemical formula
It is A1±xB1±yO3-δ, wherein, described A is rare earth or alkaline-earth metal La, at least one in Sr, Ba and Pr
Kind；Described B is transition-metal Fe, at least one of Co, Ti and Zr；Wherein, δ is non-stoichiometry
Than.
The oxygen absorbent A that the present invention is provided1±xB1±yO3-δSpecific embodiment in, described 0≤x≤0.2,
0≤y≤0.2。
In one of concrete mode of above-mentioned technical proposal, described B is at least one of Fe, Ti and Co；
More preferably B is Fe and/or Ti.For the materials A1±xB1±yO3-δ, adulterate TiO2A can be improved1±xB1±yO3- δThe absorption property and stability of adsorbent, therefore in the technical scheme being more highly preferred to, B is Fe and Ti.
In another specific embodiment, described A is at least one of La, Sr and Ba；It is preferred that A is
Sr and/or Ba；Most preferably Sr and Ba.
Oxygen absorbent provided by the present invention, it is further preferable that having BaxSr1-xTiyFe1-yO3-δChemical formula,
Wherein 0≤x≤0.2,0≤y≤0.2.Most preferably scheme is Ba0.15Sr0.85Ti0.15Fe0.85O3-δ。
Another aspect of the present invention provides the preparation method of the oxygen absorbent, is prepared using synthesis by solid state reaction,
The metal oxide or metal carbonate of A or B are uniformly mixed in proportion, gained mixture is at 800 DEG C
The oxide powder that bulky grain is obtained is calcined under the conditions of≤T≤1300 DEG C, then micronized particles, obtain ultra-fine multiple
Close oxide powder.
In the specific embodiment of above-mentioned preparation method, raw material mixing and refinement are carried out using the method for ball milling.
Ball milling is carried out after ethanol submergence raw material is added in raw material blend step, in mixed material, Ball-milling Time is
5h≤t≤10h.The refinement of bulky grain product is carried out by secondary ball milling, and Ball-milling Time is 5h≤t≤10h.
More specifically describe, described preparation method is used to prepare has BaxSr1-xTiyFe1-yO3-δChemistry
The oxygen absorbent of formula, methods described comprises the following steps：
(1) by raw material BaCO3、SrCO3、TiO2And Fe2O3Powder mixes in ball grinder, adds ethanol
After ball milling 5~10 hours, drying is taken out, obtain well mixed tiny powder；Wherein, the rate of charge of raw material
Example is according to meeting 0≤x≤0.2, the criterion calculation of 0≤y≤0.2；
(2) 800~1300 DEG C of step (1) gained powder is calcined 10~15 hours, obtains the oxide of larger particles
Powder；It is calcined 10 hours under the conditions of being preferable over 1050 DEG C；
(3) bulky grain powder obtained by step (2) is obtained the oxygen absorbent powder of homogenous superfine through 5~10h of ball milling.
The implementation method being more highly preferred to, described preparation method is used to prepare Ba0.15Sr0.85Ti0.15Fe0.85O3-δ
(BSTiF) oxygen absorbent, the rate of charge of raw material is in described step (1)：BaCO3:SrCO3：
TiO2:Fe2O3According to mol ratio 3:17:3:8.5 mixing.
In the preparation method of above-mentioned any oxygen absorbent, can also comprise the steps：
A. dry pressing is used, gained oxide powder is suppressed into circular plain embryo with tablet press machine；
It is preferred that the method using comprising the following steps：Take 1g powders to be placed in tablet press machine, in the pressure of 10MP
Under, pressurize is obtained circular element embryo after 30~120 seconds, plain embryo diameter is about 17mm, and thickness is about 1mm.
B. the plain embryo of step (a) gained is put into high temperature box furnace, sintering obtains oxygen in 5~10 hours at high temperature
The round ceramic piece of compound split, so that the sintering situation to oxide powder is investigated；
It is preferred that the method using comprising the following steps：Plain embryo obtained by step (a) compacting is put into high temperature box furnace
Middle sintering, 1350 DEG C of sintering temperature, sintering obtains Ba after 5 hours0.15Sr0.85Ti0.15Fe0.85O3-δRound ceramic
Piece.
The present invention is in BaxSr1-xCoyFe1-yO3-δOn the basis of serial oxygen permeable film material, carry out difference to B and mix
It is miscellaneous, it is different with the past common low price ion receptor doping, add the doping of higher price stabilizing ion acceptor；
And the ratio of each element is designed in being constituted to material, oxygen adsorbance higher is obtained.It is of the present invention
Oxygen absorbent has a good application prospect in variable-temperature oxygen absorption, can be applied to include that air is separated or oxygen
The numerous areas of removal of impurities, can also realize the application of broad range as hydrogen-storing material.
Following embodiments will be further described to the present invention, but not answer this and limit the present invention.
Embodiment 1
(1) present invention first takes BaCO3、SrCO3、TiO2And Fe2O3Material powder, in molar ratio 3：17：
3：8.5 mixing, add ball milling after ethanol in proper amount, the material drying that will be well mixed after ball milling, insert corundum earthenware
Repeatedly it is calcined 10 hours under the conditions of 1000~1200 DEG C after being compacted in crucible, obtains the larger Ca-Ti ore type oxygen of particle
Compound powder.
(2) oxide powder of the bulky grain obtained by step (1) is carried out into secondary ball milling, is then dried,
The oxygen absorbent powder of homogenous superfine is obtained.Taking a small amount of powder carries out XRD signs, as a result shows
Ba0.15Sr0.85Ti0.15Fe0.85O3-δOxide powder is the perovskite structure of pure phase.Further to oxidate powder
Body carries out in-situ high temperature XRD tests, as a result as shown in Figure 1.From figure 1 it appears that by oxide
Powder is heated to only being occurred in that during 1000 DEG C the characteristic diffraction peak of perovskite structure from room temperature.Meanwhile,
Stability test also is entered to oxide powder, oxide powder has been calcined 100 in 800 DEG C of still air
After hour, the diffraction maximum of perovskite structure is still can only see in its XRD, illustrate that its structural stability is good
It is good.
(3) to the Ba prepared by step (2)0.15Sr0.85Ti0.15Fe0.85O3-δ, oxide powder is by rising gently
Lower the temperature to investigate the absorption of its oxygen and desorption process, as a result as shown in Figure 2.By sample powder 300-900 DEG C it
Between carry out heating and cooling operation, temperature rate is ± 15 DEG C/min, and air velocity is 100mL/min.
(4) by Ca-Ti ore type Ba obtained in step (2)0.15Sr0.85Ti0.15Fe0.85O3-δOxide material powder,
Using dry pressing, in the pressure of 10MP, circular proembryo is suppressed in pressurize in the case of 30 seconds, then by plain embryo
It is placed in high temperature Muffle furnace, 5h is sintered at 1350 DEG C and obtains round ceramic piece, its table is observed by SEM
Face and the sintering situation in section, as a result as shown in Figure 3.
Claims (9)
1. a kind of oxygen absorbent, with A1±xB1±yO3-δChemical formula,
Described A is at least one of rare earth or alkali earth metal La, Sr, Ba and Pr；
Described B is transition metal Fe, at least one of Co, Ti and Zr；
Wherein, δ is non-stoichiometric.
2. according to the oxygen absorbent described in claim 1, it is characterised in that：Described B is Fe and/or Ti.
3. according to the oxygen absorbent described in claim 1, it is characterised in that：Described A is Sr and/or Ba.
4. according to the oxygen absorbent described in claim 1, it is characterised in that chemical formula A1±xB1±yO3-δIn,
0≤x≤0.2,0≤y≤0.2.
5. according to the oxygen absorbent described in claim 1, it is characterised in that：Described oxygen absorbent has
BaxSr1-xTiyFe1-yO3-δChemical formula.
6. the preparation method of the oxygen absorbent described in claim 1, it is characterised in that：By the metal of A or B
Oxide or metal carbonate uniformly mix in proportion, and gained mixture is under the conditions of 800 DEG C≤T≤1300 DEG C
Roasting is obtained the oxide powder of bulky grain, and then micronized particles, obtain superfine composite oxide powder.
7. in accordance with the method for claim 6, comprise the following steps：
(1) by raw material BaCO3、SrCO3、TiO2And Fe2O3Powder mixes in ball grinder, adds ethanol ball
Mill takes out drying after 5~10 hours, obtains well mixed tiny powder；
(2) 800~1300 DEG C of step (1) gained powder is calcined 10~15 hours, obtains the oxidate powder of larger particles
Body；
(3) bulky grain powder obtained by step (2) is obtained the oxygen absorbent powder of homogenous superfine through 5~10h of ball milling.
8. in accordance with the method for claim 7, it is characterised in that BaCO in described step (1)3:SrCO3：
TiO2:Fe2O3According to mol ratio 3:17:3:8.5 mixing.
9. application of the oxygen absorbent described in claim 1 in variable-temperature oxygen adsorption process.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114302861A (en) * | 2019-08-30 | 2022-04-08 | 三菱化学株式会社 | Metal oxide, oxygen adsorption/desorption device, oxygen concentration device, and method for producing metal oxide |
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| CN1315920A (en) * | 1998-07-16 | 2001-10-03 | 拉瓦勒大学 | Process for synthesizing metal oxides and metal oxide having perovskite or perovskite-like crystal structure |
| CN101837278A (en) * | 2009-03-18 | 2010-09-22 | 中国科学院大连化学物理研究所 | Oxygen adsorbent, preparation method and application thereof |
| CN104857911A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | High-performance oxygen adsorbent and preparation method thereof |
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| CN114302861B (en) * | 2019-08-30 | 2023-09-29 | 三菱化学株式会社 | Metal oxide, oxygen adsorption/desorption device, oxygen concentration device, and method for producing metal oxide |
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