CN100413568C - Mixed conductorial oxygen penetrated membrane in perovskite type in cerium series, prepartion and application - Google Patents
Mixed conductorial oxygen penetrated membrane in perovskite type in cerium series, prepartion and application Download PDFInfo
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- CN100413568C CN100413568C CNB2004101004557A CN200410100455A CN100413568C CN 100413568 C CN100413568 C CN 100413568C CN B2004101004557 A CNB2004101004557 A CN B2004101004557A CN 200410100455 A CN200410100455 A CN 200410100455A CN 100413568 C CN100413568 C CN 100413568C
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Abstract
The present invention relates to a perovskite type cerium-containing series mixed conductor oxygen-penetrating film which is characterized in that the chemical formula of the oxygen-permeating film is BaCe<x>B<1-x>O<3-delta>; B is selected from one or a plurality of Cr, Mn, Fe, Zn, Ga, Al, Zr, Mg and Y; 0 <x<0.6, and delta=0 to 0.5. The novel dense ceramic oxygen-permeating film material is a perovskite oxide with no cobalt doped. The oxygen-permeating film material has high oxygen permeability and high stability in a reducing atmosphere.
Description
Technical field:
The present invention relates to the high oxygen permeability of no cobalt and under reducing atmosphere the composite conductor oxygen-permeating film of high stability design, preparation, structure and be used for particularly selecting oxygen separation from air from containing oxygen gas mixture.
Background technology:
Composite conductor oxygen-permeating film refers to a new ceramics film that has oxygen conduction and electron conduction roughly the same the time.This material is (especially when temperature greater than 700 ℃ time) at high temperature, when there is oxygen concentration gradient in the film both sides, oxygen can be conducted to the hypoxemia nip by the hyperoxia nip by body with the form of oxonium ion, and electronics can conduct in the opposite direction simultaneously, thereby makes material keep electroneutral.This material does not resemble needs external circuits to come conduction electron the SOFC.And because oxygen is to conduct with the form of oxonium ion, the permselective property of oxygen is 100% in theory.One of them potential application direction of composite conductor oxygen-permeating film is to select separated oxygen as membrane separator from mix oxygen-containing gas, and business accounting shows with composite conductor oxygen-permeating film system oxygen might reduce expense nearly 50% than sky branch legal system oxygen.People generally believe if can develop and have enough many fields that the composite conductor oxygen-permeating film of oxygen permeating amount and thermo-chemical stability greatly can satisfy present aerobic market, for example from small-scale application the oxygen pump in the medical science aspect to large-scale combustion reaction etc.Be listed as the fifth-largest industrial chemicals at U.S.'s oxygen and nitrogen, thereby, will have very large application prospect if can develop suitable oxygen flow material.The Air Products of air separation company of U.S.'s maximum and Praxiar have dropped into a huge sum of money and have carried out this research.The Another application field of composite conductor oxygen-permeating film is in chemical reaction process, and wherein the most potential industrial large-scale application is used for methane portion oxidation synthesis gas exactly.There is abundant natural gas in occurring in nature, is the problem that basic organic chemical industry's product is a 21 century people growing interest with conversion of natural gas how.Along with the continuous increase of China's natural gas proved reserves and the enforcement of strategy to develop western regions, efficiently utilize new technology, the new technology of research and development natural gas have crucial meaning for the efficient of improving energy structure in China, the western gas utilization of raising, the western expanding economy of promotion.Natural gas via synthesis gas synthetic liquid fuel is called for short GTL (Gas to Liquid) process, and its technical development has obtained showing great attention to of various countries' scientific research and industrial quarters in recent years.
Perovskite structure is a version the most common in the oxygen permeable film material, and many oxygen permeable film materials with good oxygen permeability all have perovskite structure.Teraoka is the earliest to La
1-xSr
xCo
1-yFe
yO
3-δThe oxygen permeating amount of series perovskite oxygen permeable film material has carried out the mensuration of system.Later many research workers redeterminate and study, La the oxygen permeating amount of this series material
1-xSr
xCoO
3-δ, La
1-xSr
xFeO
3-δ, La
1-xA
xCo
1-yFe
yO
3-δ(A=Sr, Ca), SrCo
0.8Fe
0.2O
3-δ, SrCo
1-xB
xO
3-δ(B=Cr, Mn, Fe, Ni, Cu, Ti x=0.5) find that the data that Teraoka reported are higher, but have also proved La (Ba, Ca, Sr) CoFeO simultaneously
3-δSeries is the good oxygen permeable film material that a class has high oxygen flow ability really.
Though this class material has higher oxygen permeability, its chemical stability and structural stability in reducing atmosphere is all very poor.This is owing to all come the B position of adulterated with Ca and Ti ore in this class material with Co.Because cobalt easily is reduced into than lower valency (as 2+ or 0), has caused this class material to have high thermal coefficient of expansion and low structural stability and chemical stability.Owing to these reasons, the compact oxygen permeable film material that this class contains cobalt is difficult to industrial extensive oxygen separation and transforms the natural gas preparing synthetic gas.
U.S. Eltron research team has developed the oxygen permeable film material La of a kind of high chemical stability and high structural stability
xSr
1-xGa
yFe
1-yO
3-δThis class material has brownmillerite type structure.Yet because its low oxygen permeability and expensive manufacture of materials cost have finally hindered it in industrial extensive use.
Summary of the invention:
Purpose of the present invention just is to prepare a kind of novel oxygen permeable film material with high oxygen permeability and high stability.
Particularly, the invention provides a kind of perovskite type oxygen pervious membrane of mixed conductor in cerium contained series, it is characterized in that: the chemical formula of described oxygen permeation membrane is BaCe
xB
1-xO
3-δ
Wherein B is selected from one or more among Cr, Mn, Fe, Zn, Ga, Al, Zr, Mg, the Y;
0＜x＜0.6，δ＝0～0.5。
In the perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of the present invention, preferably, B is one or more among Fe, Zn, Mg, the Y.
In the perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of the present invention, most preferably, the chemical formula of oxygen permeation membrane is BaCe
xFe
1-xO
3-δ
In the perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of the present invention, best 0.1＜x＜0.2.
The present invention also provides the preparation method of above-mentioned perovskite type oxygen pervious membrane of mixed conductor in cerium contained series, with the nitrate that contains barium, cerium and B is raw material, adopt citric acid and ethylenediamine tetra-acetic acid associating complexometry, it is characterized in that: will synthesize good powder ball milling 5～40 hours, sintering is carried out in compression moulding under 40～160 atmospheric pressure at last under 1100～1250 ℃.
Perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of the present invention can be used for selecting separated oxygen from containing oxygen gas mixture, also can be used to make solid-fuelled electrode.
Perovskite type oxygen pervious membrane of mixed conductor in cerium contained series provided by the invention has high oxygen permeability, and high chemical stability that has under reducing atmosphere and high structural stability.
Description of drawings:
Fig. 1 is BaCe
xFe
1-xO
3-δThe XRD figure of series composite oxides;
Fig. 2 is BaCe
0.15Fe
0.85O
3-δUnder different temperatures, use 5%H
21 hour XRD figure of+Ar reduction;
Fig. 3 is BaCe
xFe
1-xO
3-δOxygen infiltration capacity under the series different temperatures;
Fig. 4 is the SEM figure of the diaphragm of x=0.15.
The specific embodiment:
Embodiment 1
Adopt complexometry to prepare BaCe
xFe
1-xO
3-δ(x=0.15-0.85) powder.Get stoichiometric Ba (NO
3)
2, Ce (NO
3)
3, Fe (NO
3)
3Solution adds EDTA acid and citric acid.Wherein EDTA acid, the ratio of the amount of substance of citric acid and total metal ion is: 1: 1: 1.This mixed liquor at 80 ℃ of heating evaporations, is got a transparent hot melt aubergine colloid at last, this colloidal sol is removed organic matter at 400 ℃ of following heating flames.At last the gained powder was promptly got the ceramic powder of homogeneous in 5 hours 950 ℃ of roastings.With the BaCe that obtains after 950 ℃ of roastings
xFe
1-xO
3-δThe series composite oxide powder carries out material phase analysis, and the result as shown in Figure 1.The result shows that the composite oxides that have only x=0.15 and 0.85 are the pure phase cubic perovskite structure, and the composite oxides of other compositions are made up of two kinds of different perovskite oxides.From XRD result as can be known, these two kinds of different perovskite oxides are respectively BaCe
0.15Fe
0.85O
3-δAnd BaCe
0.85Fe
0.15O
3-δIn these a series of composite oxide materials, remove BaCe
0.85Fe
0.15O
3-δDo not have outside the detectable oxygen permeating amount that arrives, the oxygen permeating amount of other material as shown in Figure 3.
Embodiment 2
Measure BaCe
0.15Fe
0.85O
3-δStability in reducing atmosphere.This powder compressing tablet is sieved into 20～40 purpose particles, get 1 this particle of gram, use 5%H then
2-Ar gaseous mixture is respectively 800,850, and 900 ℃ were respectively reduced 1 hour.The gained particle grinds thin the sign with XRD later.As shown in Figure 2, this material can be good at keeping perovskite structure, and this illustrates BaCe
0.15Fe
0.85O
3-δIn reducing atmosphere, have extraordinary stability, be suitable for making up membrane reactor and carry out the hydro carbons portion oxidation synthesis gas.
Embodiment 3
The composite oxide powder that embodiment 1 is synthetic grinds in agate mortar, then with sieve sieve out not in the stove under still air 1140-1200 ℃ sintering 5-15 hour.The relative density of the diaphragm behind all sintering is all greater than 93%.Fig. 4 is the SEM figure of the diaphragm of x=0.15.As can be seen from this figure, membrane surface is made of the big crystal grain of about 10 μ m, does not have tangible hole and slight crack to exist; And from the cross section, this diaphragm is very fine and close.
Embodiment 4
BaCe
0.15Fe
0.85O
3-δThe mensuration of the oxygen infiltration capacity of oxygen permeation membrane.Diaphragm thickness is: 1mm, adopt the gold sealing.Air velocity is 100ml/min, and the helium flow velocity is 30ml/min.Between 800-950 ℃, carry out the oxygen penetration testing.850 ℃ of oxygen infiltration capacities are 0.32ml/mincm
2, 950 ℃ of oxygen infiltration capacities are up to 0.52ml/mincm
2
Embodiment 5
Measure BaCe
0.2Fe
0.8O
3-δThe oxygen infiltration capacity and the relation between the diaphragm thickness.The ceramic membrane that two thickness are respectively 1mm and 1.5mm is sealed in and carries out the oxygen penetration testing in the oxygen permeator respectively, and all test conditions are the same.(b, c) the oxygen infiltration capacity that has provided the oxygen permeation membrane of two different-thickness concerns with variation of temperature Fig. 3.Therefore the infiltration capacity of 1mm diaphragm can obtain high oxygen infiltration capacity by the thickness that reduces film obviously greater than the 1.5mm diaphragm as can be seen.
Embodiment 6
Test b aCe
0.14Fe
0.8M
0.06O
3-δ(M=Zn, Mg, oxygen permeability behavior Y).Powder preparation method is identical with embodiment 1.Characterizing as can be known through XRD, three kinds of materials are perovskite structure.Diaphragm in Muffle furnace under still air 1100-1350 ℃ of sintering 3～5 hours.The relative density of the diaphragm behind all sintering is all greater than 93%.At diaphragm thickness is 1mm, and air velocity is 100ml/min, and the helium flow velocity is under the condition of 30ml/min, carries out the oxygen penetration testing between 800-950 ℃.Test result shows that the material of Zn doping and the material that Mg mixes have oxygen permeating amount much at one, are about 0.6ml/mincm at 950 ℃
2, the oxygen permeating amount of the material that Y mixes is then less.
The oxygen permeating amount of assorted material is then less.
Claims (7)
1. perovskite type oxygen pervious membrane of mixed conductor in cerium contained series, it is characterized in that: the chemical formula of described oxygen permeation membrane is BaCe
xB
1-xO
3-δ
Wherein B is selected from one or more among Cr, Mn, Fe, Zn, Ga, Al, Zr, Mg, the Y;
0＜x＜0.6，δ＝0～0.5。
2. according to the described perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of claim 1, it is characterized in that: wherein B is selected from one or more among Fe, Zn, Mg, the Y.
3. according to the described perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of claim 2, it is characterized in that: the chemical formula of described oxygen permeation membrane is BaCe
xFe
1-xO
3-δ
4. according to claim 1,2 or 3 described perovskite type oxygen pervious membrane of mixed conductor in cerium contained series, it is characterized in that: 0.1＜x＜0.2 wherein.
5. the preparation method of the described perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of claim 1, with the nitrate that contains barium, cerium and B is raw material, adopt citric acid and ethylenediamine tetra-acetic acid associating complexometry, synthetic composite granule, it is characterized in that: will synthesize good composite granule ball milling 5～40 hours, sintering is carried out in compression moulding under 0～160 atmospheric pressure at last under 1100～1250 ℃.
6. the described perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of one of claim 1～4 is used for selecting separated oxygen from containing oxygen gas mixture.
7. the described perovskite type oxygen pervious membrane of mixed conductor in cerium contained series of one of claim 1～4 is used to make solid-fuelled electrode.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008074181A1 (en) * | 2006-12-18 | 2008-06-26 | Bp P.L.C. | Oxygen separation membrane |
| CN101295791B (en) * | 2007-04-24 | 2011-01-26 | 中国科学院大连化学物理研究所 | Ternary complex cathode material of intermediate/low temperature solid-oxide fuel battery |
| CN101450861B (en) * | 2007-12-06 | 2011-12-14 | 中国科学院大连化学物理研究所 | Method for preparing unsymmetrical biphase composite oxygen permeable membrane |
| CN101306330B (en) * | 2008-02-01 | 2011-11-02 | 中国科学技术大学 | Production method of mixed conductor oxygen permeable membrane and oxygen/carbon monoxide mixed gas |
| CN101265080B (en) * | 2008-04-18 | 2010-12-08 | 华南理工大学 | Zinc-containing series perovskite mixing conductor oxygen-penetrating film and its preparation method and application |
| CN102895886B (en) * | 2012-10-22 | 2015-03-04 | 天津工业大学 | Hollow fiber ceramic oxygen permeation membrane with dual composite asymmetric structure and preparation method thereof |
| CN108114609B (en) * | 2016-11-26 | 2021-01-22 | 中国科学院大连化学物理研究所 | Preparation method of single-phase ceramic oxygen permeable membrane repair material |
| CN106925136B (en) * | 2017-03-31 | 2019-11-15 | 华南理工大学 | A kind of anion doped Ca-Ti ore type mixed conductor hydrogen permeation membrane material and the preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258557A (en) * | 1998-12-25 | 2000-07-05 | 中国科学院大连化学物理研究所 | Preparation and application of perovskite Bi-containing mixed oxygen-penetrating conductor film |
| US6488739B1 (en) * | 1987-03-13 | 2002-12-03 | Bp Corporation North America Inc. | Oxygen production process |
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2004
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6488739B1 (en) * | 1987-03-13 | 2002-12-03 | Bp Corporation North America Inc. | Oxygen production process |
| CN1258557A (en) * | 1998-12-25 | 2000-07-05 | 中国科学院大连化学物理研究所 | Preparation and application of perovskite Bi-containing mixed oxygen-penetrating conductor film |
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