CN104058744A - Preparation method of oxygen permeating membrane with high oxygen permeating rate and oxygen permeating stability - Google Patents
Preparation method of oxygen permeating membrane with high oxygen permeating rate and oxygen permeating stability Download PDFInfo
- Publication number
- CN104058744A CN104058744A CN201410274688.2A CN201410274688A CN104058744A CN 104058744 A CN104058744 A CN 104058744A CN 201410274688 A CN201410274688 A CN 201410274688A CN 104058744 A CN104058744 A CN 104058744A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- preparation
- oxygen permeating
- powder
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of an oxygen permeating membrane with high oxygen permeating rate and oxygen permeating stability, and belongs to the technical field of functional ceramic materials. The preparation method comprises the following steps of (1), preparing Ba0.5Sr0.5Co0.9Nb0.1O(3-x) powder by a solid-phase synthetic method; (2), preparing a membrane sheet: uniformly mixing the Ba0.5Sr0.5Co0.9Nb0.1O(3-x) powder, a dispersing agent and a binder in a proportion (proportion by mass) of 100:(0.25-0.45):(0.25-0.45), pressing the mixed mixture into circular sheet biscuits with thickness of 2-4 mm by utilizing a steel mould, wherein forming pressure is 100-130MPa; and firing the biscuits at 1060-1140 DEG C to obtain Ba0.5Sr0.5Co0.9Nb0.1O(3-x) oxygen permeating membrane. The oxygen permeating membrane prepared by the preparation method disclosed by the invention works for a long time at 850 DEG C in the Ba0.5Sr0.5Co0.9Nb0.1O(3-x) membrane, so that oxygen permeating amount is high and can be kept stable.
Description
Technical field
The present invention relates to a kind of preparation method with the oxygen permeable film of high oxygen transmission rate and oxygen flow stability, belong to ceramic material preparing technical field.
Background technology
Composite conductor oxygen-permeating film material is a kind of ceramic material of perovskite structure, there is the dual conductivity of oxonium ion and electronics, in theory oxygen there is is 100% selection perviousness, in fields such as pure oxygen preparation, fuel cell and membrane reactors, have broad application prospects.Oxygen permeable film material for oxygen separation not only needs to possess higher oxygen flow ability, also should have the feature that keeps structural stability in long-time oxygen permeation simultaneously.In all mould materials, the mould material of Co based perovskite structure possesses relatively high oxygen flow ability, is therefore paid close attention to widely.But the mould material of Co based perovskite structure structural stability in the process of long-time oxygen flow is poor.
BaCo
0.9nb
0.1o
3-x(BCN) oxygen permeating amount of mould material is higher, and through test, the oxygen permeating amount of BCN diaphragm can reach 2.3mLcm at 850 ℃
2min
1, but along with the prolongation oxygen permeating amount of time there will be relaxation phenomenon, at 850 ℃, after the experiment of 150h oxygen flow, oxygen permeating amount has declined 64%, therefore need to be optimized to improve its oxygen flow stability to BCN mould material.Doping is a kind of conventional optimization method, and different doped elements is not quite similar on the impact of the impact of material oxygen permeating amount and oxygen flow stability, so doped element, doping and adulterating method are most important.
Summary of the invention
For BaCo
0.9nb
0.1o
3-x(BCN) the high oxygen transmission rate of oxygen permeable film, low stability feature, the object of this invention is to provide a kind of oxygen permeable film Ba with high oxygen transmission rate and oxygen flow stability
0.5sr
0.5co
0.9nb
0.1o
3-xpreparation method, Ba
0.5sr
0.5co
0.9nb
0.1o
3-xoxygen permeable film is a kind ofly to have higher oxygen permeating amount, and has the oxygen permeable film material of long-time oxygen flow stability simultaneously.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method with the oxygen permeable film of high oxygen transmission rate and oxygen flow stability, has following steps:
1) by solid-phase synthesis, prepare Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder, wherein x represents oxygen room: first purity is all greater than to 99% BaCO
3, SrCO
3, Co
3o
4and Nb
2o
5powder in molar ratio for 1:1:0.6:0.1 is dry mixed ball milling 48h, then by mixture isostatic cool pressing under 75MPa, afterwards solid phase synthesis at 920 ℃, after fragmentation, mistake 40 mesh sieves, carry out again the alcohol wet-milling of 24h, make powder median size reach 1 ~ 3 μ m, after being dried, obtain Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder;
2) preparation of diaphragm: by Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder, dispersion agent, binding agent are in 100:(0.25～0.45): the ratio of (0.25～0.45) (mass ratio) is evenly mixed, utilize steel die that the mixture mixing is pressed into the disk biscuit that thickness is 2～4mm, forming pressure is 100～130MPa; Biscuit is fired to 8～12h at 1060～1140 ℃, obtain Ba
0.5sr
0.5co
0.9nb
0.1o
3-xoxygen flow diaphragm.
Described step 2) in, dispersion agent is oleic acid.
Described step 2) in, binding agent is Xylo-Mucine.
Compare with existing permeable membrane sheet, the present invention has following outstanding substantive distinguishing features and advantage significantly:
Ba in the present invention
0.5sr
0.5co
0.9nb
0.1o
3-xthe relative BaCo of oxygen permeating amount of diaphragm
0.9nb
0.1o
3-x(BCN) there is certain decline, but all higher than the oxygen permeating amount of other mould material, as BaCo
0.7fe
0.2nb
0.1o
3-x(BCFN), Ba
0.5sr
0.5co
0.8fe
0.2o
3-x(BSCF).And at 850 ℃, Ba
0.5sr
0.5co
0.9nb
0.1o
3-xdiaphragm can keep stable at the middle oxygen permeating amount that works long hours.
Accompanying drawing explanation
Fig. 1 is oxygen flow experimental installation schematic diagram of the present invention.
Fig. 2 is the Ba of sintering at 1060～1100 ℃
0.5sr
0.5co
0.9nb
0.1o
3-xthe microscopic appearance of diaphragm.
Fig. 3 is the Ba that utilizes the oxygen flow experimental installation shown in Fig. 1 to measure
0.5sr
0.5co
0.9nb
0.1o
3-xthe oxygen permeating amount of diaphragm under differing temps, wherein oxygen permeating amount is by O in helium one side
2the measurement and calculation of concentration value and obtaining.
Fig. 4 is the Ba that utilizes the oxygen flow experimental installation shown in Fig. 1 to measure
0.5sr
0.5co
0.9nb
0.1o
3-xthe oxygen permeating amount of diaphragm at 850 ℃ schemed over time.
Embodiment
Below in conjunction with accompanying drawing, the embodiment of the present invention is elaborated:
embodiment 1
1) by solid-phase synthesis, prepare Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder: first purity is all greater than to 99% BaCO
3, SrCO
3, Co
3o
4and Nb
2o
5powder in molar ratio for 1:1:0.6:0.1 is dry mixed ball milling 48h, then by mixture isostatic cool pressing under 75MPa, afterwards at 920 ℃ of solid phase synthesis, pass through broken, mistake 40 mesh sieves, after carry out again the wet-milling of 24h alcohol, make powder median size reach 1 ~ 3 μ m, obtain Ba after dry
0.5sr
0.5co
0.9nb
0.1o
3-xpowder;
2) preparation of diaphragm: by Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder, dispersion agent, binding agent utilize steel die that the mixture mixing is pressed into the disk biscuit that thickness is 2～4mm after evenly mixing in the ratio of 100:0.25:0.25 (mass ratio), and forming pressure is 130MPa.Biscuit is fired to 10h at 1140 ℃ and obtain Ba
0.5sr
0.5co
0.9nb
0.1o
3-xoxygen flow diaphragm.
3) as shown in Figure 1, oxygen permeating amount is characterized: utilize sand paper by Ba
0.5sr
0.5co
0.9nb
0.1o
3-xoxygen flow diaphragm is polished thick to 1mm, utilizes at 945 ℃ silver ring that oxygen flow diaphragm is packaged between Glass tubing and alundum tube, and the useful area of oxygen flow diaphragm is 1.3cm
2, then the side at oxygen flow diaphragm passes into 110mLmin
-1air, opposite side passes into 80mLmin
-1helium, with 1 ℃ of min
-1speed be cooled to probe temperature point, after temperature-stable 1h, to passing into a side of helium, carry out O
2the mensuration of concentration value and record.
embodiment 2
The present embodiment step 1) and step 3) are identical with embodiment 1, and difference is,
2) preparation of diaphragm: by Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder, dispersion agent, binding agent evenly mix in the ratio of 100:0.35:0.35 (mass ratio), utilize steel die that the mixture mixing is pressed into the disk biscuit that thickness is 2～4mm, and forming pressure is 110MPa.Biscuit is fired to 8h at 1100 ℃ and obtain Ba
0.5sr
0.5co
0.9nb
0.1o
3-xoxygen flow diaphragm.
embodiment 3
The present embodiment step 1) and step 3) are identical with embodiment 1, and difference is,
2) preparation of diaphragm: by Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder, dispersion agent, binding agent evenly mix in the ratio of 100:0.45:0.45 (mass ratio), utilize steel die that the mixture mixing is pressed into the disk biscuit that thickness is 2～4mm, and forming pressure is 100MPa.Biscuit is fired to 12h at 1060 ℃ and obtain Ba
0.5sr
0.5co
0.9nb
0.1o
3-xoxygen flow diaphragm.
As shown in Figure 2, the Ba of sintering at 1060～1140 ℃
0.5sr
0.5co
0.9nb
0.1o
3-xmembrane surface crystal grain is all grown up, and diaphragm is fine and close.Along with the rising of sintering temperature, grain-size is increasing.Grain size does not have too much influence to the oxygen permeating amount of diaphragm.Utilization oxygen flow device is as shown in Figure 1 to Ba
0.5sr
0.5co
0.9nb
0.1o
3-xthe oxygen permeating amount of diaphragm is measured.Fig. 3 is the Ba of sintering at 1060～1140 ℃
0.5sr
0.5co
0.9nb
0.1o
3-xthe oxygen permeating amount of diaphragm is with the variation diagram of probe temperature.Along with the rising of temperature, oxygen permeating amount increases gradually, and when temperature is 900 ℃, oxygen permeating amount reaches 2.3mLcm
2min
1, this numeric ratio is with the BaCo under test condition
0.7fe
0.2nb
0.1o
3-xand Ba (BCFN)
0.5sr
0.5co
0.8fe
0.2o
3-x(BSCF) diaphragm all wants high.Fig. 4 is Ba
0.5sr
0.5co
0.9nb
0.1o
3-xdiaphragm is the variation diagram along with the time at the oxygen permeating amount of 850 ℃, and after the oxygen flow experiment of 150h, it is stable that oxygen permeating amount can keep.And BaCo
0.9nb
0.1o
3-x(BCN) diaphragm is in the oxygen permeating amount of the 850 ℃ decay serious along with time lengthening there will be, under identical test condition, and BaCo
0.9nb
0.1o
3-x(BCN) oxygen permeating amount of diaphragm can be down to 1.0 mLcm in 150h
2min
1below, rate of descent reaches 64%.Therefore, Ba
0.5sr
0.5co
0.9nb
0.1o
3-xmould material is a kind of mould material simultaneously with high oxygen transmission rate and long-time oxygen flow stability.
Claims (3)
1. a preparation method with the oxygen permeable film of high oxygen transmission rate and oxygen flow stability, is characterized in that having following steps:
1) by solid-phase synthesis, prepare Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder, wherein x represents oxygen room: first purity is all greater than to 99% BaCO
3, SrCO
3, Co
3o
4and Nb
2o
5powder in molar ratio for 1:1:0.6:0.1 is dry mixed ball milling 48h, then by mixture isostatic cool pressing under 75MPa, afterwards at 920 ℃ of solid phase synthesis, pass through broken, mistake 40 mesh sieves, after carry out again the wet-milling of 24h alcohol, make powder median size reach 1 ~ 3 μ m, obtain Ba after dry
0.5sr
0.5co
0.9nb
0.1o
3-xpowder;
2) preparation of diaphragm: by Ba
0.5sr
0.5co
0.9nb
0.1o
3-xpowder, dispersion agent, binding agent are 100:(0.25～0.45 in mass ratio): evenly mix (0.25～0.45), utilizes steel die that the mixture mixing is pressed into the disk biscuit that thickness is 2～4mm, and forming pressure is 100～130MPa; Biscuit is fired to 8～12h at 1060～1140 ℃, obtain Ba
0.5sr
0.5co
0.9nb
0.1o
3-xoxygen flow diaphragm.
2. the preparation method with the oxygen permeable film of high oxygen transmission rate and oxygen flow stability according to claim 1, is characterized in that described step 2) in dispersion agent be oleic acid.
3. the preparation method with the oxygen permeable film of high oxygen transmission rate and oxygen flow stability according to claim 1, is characterized in that described step 2) in binding agent be Xylo-Mucine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410274688.2A CN104058744A (en) | 2014-06-19 | 2014-06-19 | Preparation method of oxygen permeating membrane with high oxygen permeating rate and oxygen permeating stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410274688.2A CN104058744A (en) | 2014-06-19 | 2014-06-19 | Preparation method of oxygen permeating membrane with high oxygen permeating rate and oxygen permeating stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104058744A true CN104058744A (en) | 2014-09-24 |
Family
ID=51546719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410274688.2A Pending CN104058744A (en) | 2014-06-19 | 2014-06-19 | Preparation method of oxygen permeating membrane with high oxygen permeating rate and oxygen permeating stability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104058744A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829231A (en) * | 2015-04-14 | 2015-08-12 | 上海大学 | Fluorite-perovskite type double-phase mixing conductor oxygen-permeation membrane material and preparation method thereof |
| CN105016714A (en) * | 2015-07-09 | 2015-11-04 | 上海大学 | CO2-resistant perovskite type oxygen-permeable membrane material and preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6361584B1 (en) * | 1999-11-02 | 2002-03-26 | Advanced Technology Materials, Inc. | High temperature pressure swing adsorption system for separation of oxygen-containing gas mixtures |
| CN101575210A (en) * | 2009-06-22 | 2009-11-11 | 北京科技大学 | Method for improving structural stability of BaCo0.7Fe0.2Nb0.1O3-Delta oxygen permeation membrane material |
| CN102367209A (en) * | 2011-07-11 | 2012-03-07 | 南京工业大学 | Oxide-doped medium-low temperature mixed conducting oxygen-permeable membrane material and its preparation method |
-
2014
- 2014-06-19 CN CN201410274688.2A patent/CN104058744A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6361584B1 (en) * | 1999-11-02 | 2002-03-26 | Advanced Technology Materials, Inc. | High temperature pressure swing adsorption system for separation of oxygen-containing gas mixtures |
| CN101575210A (en) * | 2009-06-22 | 2009-11-11 | 北京科技大学 | Method for improving structural stability of BaCo0.7Fe0.2Nb0.1O3-Delta oxygen permeation membrane material |
| CN102367209A (en) * | 2011-07-11 | 2012-03-07 | 南京工业大学 | Oxide-doped medium-low temperature mixed conducting oxygen-permeable membrane material and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| JING ZHAO ET AL.: "Optimization of BaxSr1−xCo0.9Nb0.1O3−δ perovskite as oxygen semi-permeable membranes by compositional tailoring", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
| JING ZHAO ET AL.: "Optimization of BaxSr1−xCo0.9Nb0.1O3−δ perovskite as oxygen semi-permeable membranes by compositional tailoring", 《SEPARATION AND PURIFICATION TECHNOLOGY》, vol. 71, 11 November 2009 (2009-11-11) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829231A (en) * | 2015-04-14 | 2015-08-12 | 上海大学 | Fluorite-perovskite type double-phase mixing conductor oxygen-permeation membrane material and preparation method thereof |
| CN105016714A (en) * | 2015-07-09 | 2015-11-04 | 上海大学 | CO2-resistant perovskite type oxygen-permeable membrane material and preparation method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zeng et al. | Re-evaluation of Ba0. 5Sr0. 5Co0. 8Fe0. 2O3− δ perovskite as oxygen semi-permeable membrane | |
| US10727493B2 (en) | Oriented apatite-type doped rare earth silicate and/or germanate ion conductor and method for manufacturing same | |
| CN102875145B (en) | Layered perovskite structural ceramic and preparation method thereof | |
| Pan et al. | Improvement of oxygen permeation in perovskite hollow fibre membranes by the enhanced surface exchange kinetics | |
| Chen et al. | Effect of Zr4+ doping on the oxygen stoichiometry and phase stability of SrCo0. 8Fe0. 2O3− δ oxygen separation membrane | |
| CN101613199B (en) | High-performance zinc oxide composite ceramic voltage dependent resistor material and preparation method | |
| CN104446468A (en) | X9R ceramic capacitor dielectric material and preparation method thereof | |
| CN104150903B (en) | Low-temperature mixed conductor oxygen permeable film and preparation method thereof in one | |
| Armstrong et al. | Role of Perovskite Phase on the Oxygen Permeation Properties of the Sr4Fe6− x Co x O 13+ δ System | |
| CN101973764A (en) | Textured calcium bismuth niobate ceramic material and preparation method thereof | |
| CN104058744A (en) | Preparation method of oxygen permeating membrane with high oxygen permeating rate and oxygen permeating stability | |
| CN101948303B (en) | A-site Ba, Sr, Ca ions-doped SrCo0.8Fe0.2O3-delta-base perovskite oxygen permeable membrane material and application thereof | |
| Choi et al. | Oxygen permeation properties of BSCF5582 tubular membrane fabricated by the slip casting method | |
| CN104817322B (en) | A kind of temperature-stable capacitor ceramic material Sr4euTiNb9o30and preparation method thereof | |
| CN103449815A (en) | Codoped apatite structure ceramic material and preparation method thereof | |
| CN107892570B (en) | Barium titanate doped modified lanthanum zirconate ceramic material and preparation method thereof | |
| Pippardt et al. | Co‐firing technology for the preparation of asymmetric oxygen transporting membranes based on BSCF and Zr‐doped BSCF | |
| CN104817323B (en) | Temperature-stable ceramic capacitor dielectric material Sr4gdTiNb9o30and preparation method thereof | |
| CN105884352A (en) | Novel ceramic capacitor material Ba4RFe0.5Nb9.5O30(R=La, Eu, Gd) and preparation method thereof | |
| CN103113108B (en) | A kind of preparation method of boron carbide ceramics | |
| Wang et al. | Effects of surface modification with Co3O4 nanoparticles on the oxygen permeability of Ba0. 5Sr0. 5Co0. 8Fe0. 2O3-δ membranes | |
| CN104692800A (en) | Temperature-stable lead-free giant dielectric constant ceramic material | |
| CN103253982A (en) | Preparation method of tubular asymmetric oxygen-permeable membrane | |
| CN101274224B (en) | Highly stable molybdenum-contained mixed conducting compact oxygen permeable membrane material, and preparation method and application thereof | |
| Choi et al. | Preparation of asymmetric tubular oxygen separation membrane with oxygen permeable Pr2Ni0. 75Cu0. 25Ga0. 05O4+ δ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140924 |