CN1077449C - Mixed conductive compact oxygen permeable membrane material - Google Patents
Mixed conductive compact oxygen permeable membrane material Download PDFInfo
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- CN1077449C CN1077449C CN 98111285 CN98111285A CN1077449C CN 1077449 C CN1077449 C CN 1077449C CN 98111285 CN98111285 CN 98111285 CN 98111285 A CN98111285 A CN 98111285A CN 1077449 C CN1077449 C CN 1077449C
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Abstract
The present invention relates to a mixed conductive compact oxygen permeable film material which is used for oxygen permeation, the film material is prepared from a composition of a perovskite crystal type composite oxide and zirconia, and the general formula of the composite oxide is C<1-x>C'<x>D<1-y>D'<Y>O<3-5>. Delta is the number of the defects of oxygen lattices; C and C' are either element in Ld, Sm, Nd, Pr, Ba, Ca, Sr, Na and La; D and D' are either element in Mn, Cr, Fe, Co, Ni and Cu; 0<=x<=1, and 0<=y<=1; the content of zirconia is from 1 to 40% (weight). The present invention has favorable stability under a high-temperature oxygen-lack atmosphere. The oxygen permeation performance is close to that of the original perovskite crystal type oxide, and longtime operation can be realized.
Description
The present invention relates to a kind of mixed conductive compact oxygen permeable membrane material that is used for the oxygen infiltration.
In recent years, film reaction technology is expected to obtain commercial Application in some field, for example, be developed into a kind of Ca-Ti ore type compact oxygen permeable film abroad with oxonium ion electronics mixed conducting ability, this kind film can be used for oxygen separation and methane conversion becomes in the industrialization film reaction processes such as methyl alcohol, formaldehyde, ethene, synthesis gas (to see United States Patent (USP) U.S.Pat.No.5,160,713, Nov.3,1992).This membrane material (as the La-Sr-Co-Fe oxide) is and mineral CaTiO
3The based composite oxide that crystal formation is identical, its general formula are CDO
3, can form C with other metal substitute in C position and D position
1-XC '
XD
1-YD '
YO
3-δ, wherein C is Ld, Sm, Nd, Pr, Ba, Ca, Sr, Na, La, and D is Mn, Cr, Fe, Co, Ni, Cu etc., and δ is an oxygen lattice defect number.This membrane material has the oxygen ion conduction ability because of containing certain oxygen lattice defect, is thought one of optimal material that carries out at present the oxygen separation by the scientist of states such as Europe, the U.S., Japan.Result of study shows that the permeability of perofskite type oxide when low temperature is minimum, along with temperature raises and rising rapidly, the cellular glass film of infiltration capacity in the time of 600 ℃ and 4nm is suitable, when temperature reached more than 1200 ℃, high two orders of magnitude of the permeability ratio cellular glass of oxygen reached 1-5m
3(stp)/m
2Hr, visible perovskite crystal formation oxygen permeation membrane at high temperature more has practical value.Yet the deficiency of perovskite crystal formation oxygen permeation membrane is: after stablizing certain hour under the high temperature oxygen deficient atmospheres, crystalline structure can change, and directly causes the fracture of film, and effect is restricted.
The purpose of this invention is to provide a kind of mixed conductive compact oxygen permeable membrane material, it not only has high oxonium ion and electronic conduction ability, and still has good chemistry and structural stability under high temperature anoxic atmosphere, is suitable for long period of operation.
Material of the present invention is that general formula is C
1-XC '
XD
1-YD '
YO
3-δPerovskite crystal formation composite oxides and zirconic composition, wherein δ is the lattice defect number, and C, C ' are any one element among Ld, Sm, Nd, Pr, Ba, Ca, Sr, Na, the La, and D, D ' are any one element among Mn, Cr, Fe, Co, Ni, the Cu, 0≤x≤1,0≤y≤1; Zirconic content is 1～40% (weight) of above-mentioned perovskite crystal formation composite oxides.
Membrane material of the present invention can adopt conventional method preparations such as solid reaction process, sol-gel process or organic acid complexometry.
Solid reaction process is after the oxide of required each element of this material or nitrate, carbonate are mixed in proportion, and takes out after at high temperature reacting a period of time, grinds, sieves certain particle size and promptly get membrane material.
Sol-gel process is that the hydrolyzable predecessor with required each element of this material is prepared into stable, transparent colloidal sol, and drying promptly gets membrane material after the heat treatment.
The organic acid complexometry claims " liquid hybrid technology " again, it is in the organic acid that the cationic salt of the required element of this material or oxide are dissolved in function groups, is made into the solution of finite concentration and pH value, decomposes through elevated temperature heat, heat treatment, the powder that obtains certain particle size after milling promptly gets membrane material.
Above-mentioned membrane material can be made film by conventional forming techniques such as isostatic pressing method, plasticity extrusions.According to the difference of film component, rise to 950-1300 ℃ with the heating rate of 2 ℃/min, be incubated after 5 hours speed cooling back and take out with 2 ℃/min, promptly get film.
The zirconia that mixes among the present invention has improved the fracture strength of former perovskite crystal formation material, even under hot conditions, the local stress that thermal expansion produces can not make its fracture yet, because zirconia itself also is a kind of mixed conducting type oxide, has higher oxygen ion conduction ability, a spot of doping has not only improved the microstructure of original perovskite oxide, and little to its permeance property influence.Thereby material of the present invention not only has high oxygen transmission rate, and under high temperature anoxic atmosphere, still have good chemistry and structural stability, but continued operation is not broken, be applicable to oxygen separation from air, oxygen mixture, the oxidative coupling of methane and the industrial applications in film reaction fields such as partial oxidation and fuel cell.
Below in conjunction with oxygen transmission rate and chemistry under high temperature oxygen deficient atmospheres and structural stability and the oxygen permeability of accompanying drawing to material of the present invention.
Fig. 1 is existing perovskite-type material SrFe
0.6Co
0.4O
3-δX-ray diffraction curve map in air under the different temperatures.
Fig. 2 is existing perovskite-type material SrFe
0.6Co
0.4O
3-δX-ray diffraction curve map in the helium atmosphere under the different temperatures.
Fig. 3 is the SrFe that 10% zirconia of one of membrane material of the present invention mixes
0.6Co
0.4O
3-δX-ray diffraction curve map in air under the different temperatures.
Fig. 4 is the SrFe that 10% zirconia of one of membrane material of the present invention mixes
0.6Co
0.4O
3-δX-ray diffraction curve map in the helium atmosphere under the different temperatures.
Fig. 5 is the 10% zirconic SrFe that mixes
0.6Co
0.4O
3-δFilm and existingly do not mix zirconic La
0.2Sr
0.8Fe
0.8Co
0.6O
3-δThe comparison of film oxygen transmission rate under different temperatures.
Fig. 6 represents SrFe
0.6Co
0.4O
3-δIn, the zirconia doping is respectively the comparison of three kinds of films of the present invention oxygen transmission rate under different temperatures of 1%, 10%, 40%.
Fig. 7 is the membrane reactor structural representation.
Fig. 1 is illustrated in the air atmosphere, the SrFe of existing oxygen-freeization zirconium0.6Co
0.4O
3－δFilm rises to 950 ℃ from 400 ℃, be cooled to again each temperature section X-ray diffraction (XRD) result in 30 ℃ of processes, as seen from Figure 1, baseline and characteristic peak are all very stable, the SrFe of namely existing oxygen-freeization zirconium0.6Co
0.4O
3－δFilm is in air atmosphere the time, and its structure is stable. Fig. 2 represents, In the helium atmosphere, the SrFe of oxygen-freeization zirconium0.6Co
0.4O
3－δFilm rises to 950 ℃ from 30 ℃, and is colder But each temperature section X-ray diffraction (XRD) result to 30 ℃ of processes shows diffraction among Fig. 2 The baseline at peak is all unstable, characteristic peak division during since 400 ℃, during to 650 ℃ corresponding to 68 ℃, 78 ℃ diffractive features peak is not obvious, and other small peak occurs, even from High-temperature cooling to 30 ℃ The time, its baseline and characteristic peak are still not obvious. The SrFe of oxygen-freeization zirconium is described0.6Co
0.4O
3－δMaterial is under the anoxic atmosphere, and its structure is unsettled. From Fig. 1, Fig. 2 curve as can be known, existing The perovskite crystal formation membrane material of oxygen-freeization zirconium can only use containing under the oxygen atmosphere, can not be applied to anoxic In the film reaction process under the atmosphere.
Fig. 3 represents that the present invention is mixed with 10% zirconic SrFe0.6Co
0.4O
3－δFilm is at air In the atmosphere, rise to 1350 ℃ of X-ray diffractions that are cooled to again each temperature section 30 ℃ of processes from 30 ℃ (XRD) result. Among Fig. 3, base line and characteristic peak below 1150 ℃ are all very stable, illustrate In this temperature model, the aerial structure of membrane material of the present invention is stable. Fig. 4 represents that the present invention mixes 10% zirconic SrFe is arranged0.6Co
0.4O
3－δFilm X under the various temperature in argon atmosphere penetrates Line diffraction (XRD) result, as seen from Figure 4, below 950 ℃ the time, baseline and characteristic peak are all Very stable, characteristic peak does not divide yet, and only more than 1050 ℃ the time, two times of angles of diffraction go out near 62 degree Existing one little new peak, and the baseline characteristic peak is all unchanged, shows that this moment, membrane structure took place by slight the variation. According to Fig. 4 as can be known, when membrane material of the present invention is worked under the anoxic atmosphere below 950 ℃, its structure Stable, can not rupture. Because the film reaction temperature is generally below 950 ℃, so membrane material of the present invention Can satisfy commercial Application.
Fig. 5 represents that the present invention is mixed with 10% zirconic SrFe0.6Co
0.4O
3－δFilm and existingly do not mix zirconic La0.2Sr
0.8Fe
0.8Co
0.2O
3－δThe two oxygen transmission rate of film all increases with the rising of temperature, when 850 ℃ (1123K), mixes zirconic SrFe0.6Co
0.4O
3－δThe oxygen infiltration rate of film is 0.355cm3(STP)/cm
2And La .min,0.2Sr
0.8Fe
0.8Co
0.2O
3－δThe oxygen infiltration rate of film is 0.325cm3(STP)/cm
2.min, add oxidation in the visible membrane material of the present invention Oxygen permeability impact to perovskite-type material behind the zirconium is little.
Fig. 6 represent in the membrane material of the present invention the zirconia incorporation not simultaneously, the comparison of its oxygen transmission rate. As shown in Figure 6, the oxygen transmission rate of each film all increases with the rising of temperature, in the time of 850 ℃, contains 1% zirconic SrFe0.6Co
0.4O
3－δThe oxygen transmission rate of film is 0.453cm3(STP)/cm
2.min, contain 10% zirconic SrFe0.6Co
0.4O
3－δThe oxygen transmission rate of film is 0.355cm3(STP)/cm
2.min, contain 40% zirconic SrFe0.6Co
0.4O
3－δThe oxygen transmission rate of film is 0.231cm3(STP)
/cm
2.min. As seen, the oxygen transmission rate of membrane material of the present invention descends with the increase of zirconia content, Be suitable for the zirconia content of membrane material of the present invention of commercial Application in 1-40% (weight) scope Be advisable.
Fig. 7 represents the membrane reactor structure, among the figure, and the 8th, quartz outer tube, the 7th, quartz inner pipe, quartz Inner tube 7 is divided into two sections up and down, is provided with oxygen permeable membrane 3 and sealing ring 4 between the upper-lower section. Spring 9 to On be tight against inner tube 7, guarantee the sealing between film 3 and the inner tube 7. Air is passed into by lower end inlet tube 6 The hypomere of quartz inner pipe 7, airborne oxygen-permeable film 3 enters the epimere of quartz inner pipe 7, and from upper The helium mix that end inlet tube 1 passes into is discharged collection from top outlet 2. Separate the air behind the oxygen Discharge from lower part outlet 6.
Preparation, film forming and the film-strength of membrane material of the present invention are described below by embodiment.
Embodiment one: adopt solid reaction process to prepare the 10%ZrO that contains of one of membrane material of the present invention
2SrFe
0.6Co
0.4O
3-δ
Take by weighing ZrO
2(5%Y
2O
3Partially stabilized) 10 the gram, SrCO
3(analyzing pure) 68.94 grams, Fe
2O
3(analyzing pure) 22.37 grams, Co (NO
3)
2.6H
2O (analyzing pure) 54.09 grams, add the liquid isopropyl alcohol that does not dissolve above-mentioned material, putting into the ball mill wet-milling took out after 10 hours, in drying box, fully pack into after dry (baking temperature is lower than 100 ℃) in the resistant to elevated temperatures crucible, be warming up to 850 ℃ with the speed of 2 ℃/min, and temperature 5 hours, it is fully reacted takes out after back speed with 2 ℃/min is cooled to room temperature, grind, add isopropyl alcohol again, ball milling promptly gets after 24 hours and contains 10%ZrO
2SrFe
0.6Co
0.4O
3-δMembrane material.
Embodiment two: adopt the organic acid complexometry to prepare the 10%ZrO that contains of one of membrane material of the present invention
2SrFe
0.6Co
0.4O
3-δ
Take by weighing ZrOCl
2.8H
2O (5%Y
2O
3Partially stabilized 1.3078 grams, Sr (NO
3)
2(analyzing pure) 6.7966 grams are dissolved in 10 milliliter of 65%～68% red fuming nitric acid (RFNA), add citric acid (analyzing pure) 20.4802 gram (citric acid molal quantitys: metal cation molal quantity summation=2: 1) then, with concentration is that 30% ammoniacal liquor is regulated pH value to 3～3.5, stirs 12 hours.Solution is poured in the beaker of 3L, put into 200 ℃ of evaporations of baking oven, have a large amount of bubbles to overflow, solution tails off, swollen, the spontaneous combustion in back about 10 seconds, material is puffy, the taking-up back of milling moves into crucible, is calcined to 1030 ℃, constant temperature 5 hours with the heating rate of 2 ℃/min, be cooled to room temperature, the taking-up grinding promptly makes the present invention and contains 10%ZrO
2SrFe
0.6Co
0.4O
3-δ5 gram membrane materials.
Embodiment three: the film forming procedure of quiet methods such as employing
The present invention is contained ZrO
2The perovskite powder fine ground, sieve less than 360 purpose powders, add about 1～3% the distilled water back that stirs and placed one day, the powder that takes by weighing 1.5g is poured mould into, vibration simultaneously makes it to be full of mould, is forced into 12MPa with tablet press machine, leaves standstill to take out mold releasability after the release in 5 minutes and promptly get film.
Embodiment four: the strength ratio during the film of different materials reacts under the anoxic atmosphere
Present embodiment adopts following three kinds of materials to carry out the film-strength test: the SrFe of (1) oxygen-free zirconium
0.6Co
0.4O
3-δFilm;
(2) La of oxygen-free zirconium
0.2Sr
0.8Fe
0.8Co
0.2O
3-δFilm;
(3) one of the present invention contains 10% zirconic SrFe
0.6Co
0.4O
3-δFilm;
With the thickness of making of above three kinds of materials is the 2mm film, is respectively charged in the membrane reactor shown in Figure 7, from import 6 bubbling airs, and makes the partial pressure of oxygen of oxygen permeation membrane 3 downsides keep 0.21atm, and airborne oxygen-permeable film 3 enters the upside of quartz inner pipe linchpin 7.Feed helium from import 1, and make the partial pressure of oxygen of film upside keep 2.1 * 10
-3Atm, the mist of oxygen and helium is discharged by outlet 2.The air that has removed oxygen is discharged by outlet 5.Test shows that film (1) promptly broke in the moment that feeds helium, can't realize the oxygen process of osmosis.Film (2) can not break in the moment that feeds helium, but in the oxygen flow process, when after temperature raises, dropping to room temperature again, and film rupture, so it can realize the oxygen flow process, but can not be long in the high temperature anoxic following working time of atmosphere, not a kind of good membrane material.Film (3) all can not break in the above conditions, illustrates that to be mixed with the stability of zirconic perovskite-type material under high temperature anoxic atmosphere fabulous.Because film (1) can't be measured its oxygen transmission rate, so the oxygen transmission rate curve of only can draw among Fig. 5 film (2) and film (3).
Claims (2)
1. mixed conductive compact oxygen permeable membrane material is characterized in that this material is is C by general formula
1-xC ｀
xD
1-yD ｀
y, O
3-δBrilliant composite oxides of perovskite and zirconic composition, wherein δ is an oxygen lattice defect number, C, C ｀ are any one element among Ld, Sm, Nd, Pr, Ba, Ca, Sr, Na, the La, D, D ｀ are any one element among Mn, Cr, Fe, Co, Ni, the Cu, 0≤x≤1,0≤y≤1, wherein zirconic content are 1～40% (weight).
2. according to the mixed conductive compact oxygen flow material of claim 1, it is characterized in that said zirconia content is 10～20% (weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98111285 CN1077449C (en) | 1998-05-06 | 1998-05-06 | Mixed conductive compact oxygen permeable membrane material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98111285 CN1077449C (en) | 1998-05-06 | 1998-05-06 | Mixed conductive compact oxygen permeable membrane material |
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|---|---|
| CN1203831A CN1203831A (en) | 1999-01-06 |
| CN1077449C true CN1077449C (en) | 2002-01-09 |
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|---|---|---|---|
| CN 98111285 Expired - Lifetime CN1077449C (en) | 1998-05-06 | 1998-05-06 | Mixed conductive compact oxygen permeable membrane material |
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|---|---|---|---|---|
| CN1325149C (en) * | 2005-04-06 | 2007-07-11 | 南京工业大学 | Alumina doped mixed conductive dense oxygen penetrating membrane material |
| CN100354033C (en) * | 2005-09-12 | 2007-12-12 | 南京工业大学 | Supported mixed conductor dense film and its preparation method |
| JP4791872B2 (en) * | 2006-03-30 | 2011-10-12 | 株式会社ノリタケカンパニーリミテド | Conductive paste |
| WO2008074181A1 (en) * | 2006-12-18 | 2008-06-26 | Bp P.L.C. | Oxygen separation membrane |
| CN101274224B (en) * | 2008-05-12 | 2010-12-01 | 南京工业大学 | Highly stable molybdenum-contained mixed conducting compact oxygen permeable membrane material, and 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 |
| CN107198973B (en) * | 2017-06-12 | 2020-04-03 | 上海大学 | Can increase CO2Preparation method of iron-based ceramic oxygen permeable membrane with oxygen permeation stability under atmosphere |
| CN111389242B (en) * | 2020-03-19 | 2022-08-05 | 上海大学 | Cobalt-free anti-CO 2 Poisoned high oxygen-permeable biphase oxygen-permeable membrane material, its preparation method and application |
| CN112794374B (en) * | 2020-12-31 | 2022-10-14 | 大连海事大学 | Co-based perovskite oxide, preparation method thereof and application thereof in air separation |
| CN113209842B (en) * | 2021-04-02 | 2022-08-23 | 浙江师范大学 | Composite separation membrane with electric field sensitivity during Congo red filtration |
| CN114149068B (en) * | 2021-11-23 | 2023-08-29 | 武汉理工大学 | High-valence iron-containing Fe (IV) perovskite type composite oxide and low-temperature roasting synthesis method and application thereof |
| CN114988875B (en) * | 2022-06-16 | 2023-03-24 | 中山大学 | Copper-containing two-phase mixed conductor oxygen-permeable membrane material with high oxygen flux and preparation method thereof |
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1998
- 1998-05-06 CN CN 98111285 patent/CN1077449C/en not_active Expired - Lifetime
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