CN1234291A - Potassium fluonikelate type inorganic compact oxygen-permeable film material - Google Patents
Potassium fluonikelate type inorganic compact oxygen-permeable film material Download PDFInfo
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- CN1234291A CN1234291A CN 98101692 CN98101692A CN1234291A CN 1234291 A CN1234291 A CN 1234291A CN 98101692 CN98101692 CN 98101692 CN 98101692 A CN98101692 A CN 98101692A CN 1234291 A CN1234291 A CN 1234291A
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Abstract
The present invention provides an inorganic dense oxygen-permeable film material with potassium nickel-fluorate structure. It is characterized by that said material is represented by A2BO4+delta, in which A represents Lanthanide element, and B represents Fe, Co, Ni, Cua nd Zn, and the delta is greater than 0 and less than 0.20. At the same time it provides a doped inorganic dense oxygen-permeable film material with potassium nickel-fluorate structure. It is characterized by that the chemical formula of said material can be represented by A2B1-xCxO4+delta, in which A represents Lanthanide element, B and C are different from each other and independently represent Li, Cr, Mn, Fe, Co, Ni, Cu and Zn, and X is greater than 0 and less than 1, and delta is greater than 0 and less than 0.20. Both the above-mentioned materials can be prepared by means of solid phase reaction method and wet chemical method. Said invention also provides the ion-filled diffusion mass transfer as oxygen-permeating mechanism of main oxygen-transmission path of said inorganic dense oxygen-permeable-film materials.
Description
The present invention relates to as the The Nomenclature Composition and Structure of Complexes of the mixed conductivity material of inorganic oxygen permeation membrane and the oxygen flow mechanism of carrying out the oxygen transmission by the calking oxygen defect.
Membrane separation technique is the new technology that has obtained develop rapidly, extensive application prospect since the sixties.Because this technology is simple to operate, energy consumption is low, treating capacity is big, begins to be used widely many industrial circles from the seventies.The membrane material that is used for isolation technics can be divided into metal (alloy) film, organic high molecular layer, inoranic membrane (comprising ceramic membrane, glass-film, Carbon Molecular Sieve Membrane, zeolite membrane etc.) and composite material film from forming.Up to now, organic high molecular layer is the membrane material that is most widely used and occupies leading position.But organic material is in the inherent shortcoming of aspects such as hear resistance, physical and chemical stability and cleaning, regeneration, makes its separation in some high temperature separation processes and high-tech product, concentrates, the application of aspect such as purifying is restricted.And inoranic membrane is owing to have the advantage of aspects such as good mechanics, chemistry, calorifics stability and easy cleaning regeneration, antimicrobial erosion, and its application just progressively obtains expansion.
The inoranic membrane that is used for the gas separation can be divided into perforated membrane and dense film two big classes on form.Perforated membrane is mainly realized separating by physical processes such as sieving actoion, Knudsen diffusion, surperficial absorption, desorption, diffusion into the surface and capillary condensations, and its permeability is higher, but owing to separate by pore size, thereby selectivity is lower; And dense film realizes selecting to separate by optionally surperficial absorption, desorption and intracell diffusion, has very high selectivity, generally can reach 100%.Compact oxygen permeable film is a class important in the inorganic gas diffusion barrier.
The present existing actual compact oxygen permeable film that uses is a solid electrolyte film, be used in fuel cell, oxygen pump, lambda sensor and the various chemical reaction, its Main Ingredients and Appearance is the zirconia of stabilisation, as the zirconia (YSZ) of stabilized with yttrium oxide, the zirconia (CSZ) of stable calcium oxide, the zirconia (MSZ) and the Bi of stabilized magnesium hydroxide
2O
3-La
2O
3Deng, the zirconia of these stabilisations at room temperature is an insulator, at high temperature then is the fast-ionic conductor of oxygen.It transmits oxygen by the room flooding mechanism.Because its electron conduction is very low, for guaranteeing constantly carrying out of oxygen transmittance process, need add electrode and external circuits, thereby make zirconia oxygen permeation membrane modular construction complicated, reliability decrease, and cause electric energy loss.
Recently, the composite oxides of existing some perovskite structure of bibliographical information are as La
1-xA
xCo
1-yB
yO
3-δ(A=Ba, Sr, Ca; B=Mn, Fe, Ni, Cu, Cr) etc. have mixed conductivity, at high temperature, this class material is the fast conductor of electronics (or electron hole) and oxonium ion, have higher electronic conductance and oxygen conduction, and have good oxygen absorption and desorption, oxygen is also had selectively penetrating equally.Usually after the A position ion of perovskite structure multivariant oxide is replaced by the low price ion,, produced the oxygen room at material internal for keeping electroneutral, but and partial oxygen room sorption of oxygen ion after partial pressure of oxygen increases in gas phase.After partial pressure of oxygen in the gas phase changes, but the oxygen of sorption desorption again in the oxygen room.If the partial pressure of oxygen difference of film both sides, then, be accompanied by higher oxygen-ion conduction and electronic conductance in high oxygen pressure side sorption of oxygen constantly, at low oxygen pressure side desorption oxygen constantly, thereby realize the selectively penetrating of oxygen.The transmission rates of oxygen is relevant with the partial pressure of oxygen and the thickness of oxygen vacancy concentration, film both sides.This class oxygen permeable film material is because higher ionic conductance and electronic conductance, formed the closed-loop path at material internal, thereby do not need additional circuit, some shortcomings of solid electrolyte film have been avoided, make the structure of membrane module very simple, and have simultaneously and separate and catalytic action, thereby become the focus of present compact oxygen permeable film research field.
But the mixed conductivity compact oxygen permeable film material of perovskite structure needs at high temperature, generally will just begin to have oxygen permeability more than 700 ℃, thereby make that the oxygen separation temperature is higher; And present alternative mixed conductivity inorganic compact oxygen permeable film material system is less; The heat endurance of membrane material and mechanical strength are not high yet, and the existence of these problems has all restricted the practical application of such oxygen permeation membrane.
An object of the present invention is to propose and existing Ca-Ti ore type (ABO
3) the different potassium fluoronickelate type (A of compact oxygen permeable film material
2BO
4) the mixed conductivity compact oxygen permeable film material, wherein A, B represent two kinds of different cations respectively, O represents oxonium ion.
Another purpose is that the multicomponent composite oxide that proposes to have the potassium fluoronickelate structure is the inorganic compact oxygen permeable film material.
In the above-mentioned two class oxygen permeable film materials in the mechanism that sees through of oxygen and the Ca-Ti ore type oxygen permeable film material by the oxygen ion vacancy defective carry out the oxygen diffusion, transmit machine-processed different, be that this is the novel concept that oxygen spreads in oxygen permeable film material, transmits with the main path of interstitial site as the oxonium ion transmission.
The present invention is in order to reduce the required temperature of oxygen permeability and separation, improves the oxygen flow flux, and the serviceability temperature scope of expansion oxygen permeation membrane is for high-temperature gas separates and the application of membrane reactor provides how better membrane material system.
The multivariant oxide that the present invention proposes the potassium fluoronickelate structure that the transition elements with I B, II B such as La series elements and Fe, Co, Ni, Cu, zn and VIII forms is an oxygen permeable film material, comprises that these elements and Li, Cr, Mn form the solid solution of potassium fluoronickelate structure and the oxygen permeable film material of this class formation that forms of mixing mutually between them.Its preparation method comprises solid reaction process and wet chemistry method.
The present invention is achieved by the following technical solutions.
Scheme one provides a kind of inorganic compact oxygen permeable film material of potassium fluoronickelate structure, it is characterized in that this material A
2BO
4+ δExpression, wherein A represents that La series elements B represents Fe, Co, Ni, Cu and Zn, 0＜δ＜0.20.
Another program provides a kind of inorganic compact oxygen permeable film material of potassium fluoronickelate structure of doping, it is characterized in that the chemical formula of this material can be expressed as A
2B
1-xC
xO
4+ δ, wherein A represents the La series elements, B, C are different mutually, represent Li, Cr, Mn, Fe, Co, Ni, Cu and Zn independently of one another, 0＜x＜1,0＜δ＜0.20.
Another program of the present invention is by solid reaction process above-mentioned two technical schemes to be implemented.Will be through 6 hours La of 800～900 ℃ of dryings
2O
3, or the corresponding oxide of La series elements be selected from arbitrary oxide among FeO, CoO, NiO, CuO and the ZnO by A
2BO
4Stoichiometric batching, wherein A represents the La series elements, B represents Fe, Co, Ni, Cu and zn; Or press A
2B
1-xC
xO
4Stoichiometric batching, wherein A represents the La series elements, B represents Li, Cr, Mn, Fe, Co, Ni, Cu and zn, 0＜x＜1 respectively independently.Batch is fully ground, mix, in 1000～1300 ℃ temperature range; especially calcination 24～48 hours in air or in the protective atmosphere under 1050～1200 ℃ of temperature; cool to room temperature with the furnace, grind for several times therebetween, to eliminate the inhomogeneities on any composition.After extrusion forming was disk, sintering was 4～24 hours in 1100～1300 ℃ air, cools to room temperature with the furnace with synthetic good powder, and the relative density of material is more than 90% behind the sintering.The material that part is formed is preferably under 400～500 ℃ of oxygen atmospheres and handled 12～24 hours.
Also can prepare the inorganic compact oxygen permeable film material of potassium fluoronickelate structure by wet chemistry method, comprise acetate decomposition method, coprecipitation, citric acid complex one decomposition method.The acetate decomposition method is that acetate with respective metal is by A
2BO
4And A
2B
1-xC
xO
4Stoichiometric be dissolved in a certain amount of distilled water, mixing places 70～90 ℃ of vacuum desiccators dry, carries out thermal decomposition again in 800～1100 ℃ of air, can obtain preparing the powder of inorganic compact oxygen permeation membrane.Coprecipitation is that acetate with respective metal is by A
2BO
4And A
2B
1-xC
xO
4Stoichiometric make mixed aqueous solution, add precipitating reagent, make alkali carbonic acid double salt earlier by co-precipitation, through evaporation, dry, thermal decomposition, obtain mixed-metal oxides, after further mixing, roasting is 4～10 hours in 800～1100 ℃ of air, obtains preparing the powder of membrane material.Citric acid complex-decomposition method is to be raw material with nitrate, presses A
2BO
4And A
2B
1-xC
xO
4Stoichiometric each component solution is added in the citric acid solution, evaporating water behind the mixing is ground, mixing, is heated to 550～650 ℃ and carries out thermal decomposition, obtains preparing the powder of membrane material after the cooling.The powder that will make by wet chemistry method is a disk through extrusion forming, and sintering 4～24 hours in 1100～1300 ℃ air cools to room temperature with the furnace again, and the relative density of material is more than 90% behind the sintering.The material that part is formed is preferably under 400～500 ℃ of oxygen atmospheres and handled 12～24 hours.
The multivariant oxide of potassium fluoronickelate structure has higher ionic conductance and electronic conductance under higher temperature, both numerical value is suitable, at the same order of magnitude, especially ionic conductance is than synthermal high 2～3 orders of magnitude of ionic conductance of Ca-Ti ore type oxygen permeable film material down.This compounds is calcium titanium ore bed (ABO
3) and the lamellar compound alternately arranged of halite layer (AO).The ligancy of A ion is 9, and the ligancy of B ion is 6, forms [BO
6] octahedron.Because not matching of A-O key and B-O key, the A-O layer is subjected to tension, and the B-O layer is subjected to compression, and for keeping stability of structure, the B-O key shrinks, and calcium titanium ore bed is compressed, and causes ion displacement, [BO
6] octahedron is distorted or tilts, thereby stay enough big space to hold extra oxygen in material lattice inside.For keeping stability of structure, the tendency of holding excess oxygen on these positions, space is very strong, and the content of extra stoichiometric oxygen can reach about 0.2 under the normal temperature and pressure, thereby the chemical formula of such material can be written as A
2BO
4+ δ, δ=0～0.2.These calking oxygen have very strong mobility, can be used as the main path that oxonium ion spreads in lattice, moves.
Generally speaking, calking oxygen has lower activation energy and bigger diffusion coefficient compared with room oxygen, thereby can reduce oxygen with calking oxygen as the approach of oxygen transmission and separate temperature required, the serviceability temperature lower limit of oxygen permeation membrane is dropped to below 600 ℃, in this temperature range, existing Ca-Ti ore type oxygen permeation membrane does not reach the effect of separated oxygen, thereby makes potassium fluoronickelate type compact oxygen permeable film can be applicable to membrane catalytic reaction about 500 ℃, and can improve the oxygen flow flux effectively.
Directly measure the oxygen permeability of oxygen permeation membrane with the stable state chromatography, the measurement mechanism of accompanying drawing 1 expression oxygen permeation membrane oxygen permeation flux.Membrane material 1 usefulness vitrified bonding 2 is fixed on Al
2O
3One end of pipe 3 is with Al
2O
3Pipe inserts in the quartz socket tube 4, charges into the mist of air or oxygen and nitrogen in the quartz ampoule, makes the partial pressure of oxygen of film one side adjustable.Other has a stainless steel tube 5 to insert Al
2O
3To the opposite side of membrane material, being used to feed flow is the partial pressure of oxygen of the inert gas of 20～30ml/min with reduction film opposite side in the pipe.Will be by quartz ampoule, the Al of said sequence device
2O
3Pipe, membrane material and stainless steel tube are vertical to be placed in the electric furnace 6, and the temperature of membrane material is accurately measured by the thermocouple 7 that places its side.Under the uniform temperature, because the partial pressure of oxygen difference of film both sides is a motive force with the chemical potential, oxygen just can optionally penetrate into the low oxygen partial pressure side from the high keto sectional pressure side.The oxygen that sees through imports a gas chromatograph 8 that has thermal conductivity detector (TCD) with the inert gas that is blown into and analyzes, and calculates oxygen infiltration rate and oxygen permeation flux.
Accompanying drawing 2 has been represented the La of potassium fluoronickelate structure among the present invention
2NiO
4+ δThe oxygen permeation flux Jo of oxygen permeation membrane (1) under different temperatures
2, and and the La of existing perovskite structure
0.6Sr
0.4Co
0.8Fe
0.2O
3-δThe oxygen permeation flux of oxygen permeation membrane (2) under uniform temp compares.
Describe the present invention in detail with example below.
La
2NiO
4+ δ, prepare with solid reaction process.With La
2O
3(99.99%) and NiO (99.999%) press La
2NiO
4The stoichiometric proportion accurate feed proportioning, calcination 24h in 1120 ℃ of air cools to room temperature with the furnace, synthetic powder is a black.This powder is pressed into the disk that diameter is 13mm, thick 1mm, and sintering 24h in 1220 ℃ of air again obtains relative density greater than 95% compact oxygen permeable film material.The oxygen permeation flux is 4.56 * 10 when obtaining in this material excess oxygen δ=0.10,800 ℃ with thermogravimetric analysis
-8Mol/s cm
2, the oxygen permeation flux is 2.08 * 10 in the time of 700 ℃
-8Mol/s cm
2, the oxygen permeation flux is 0.372 * 10 in the time of 500 ℃
-8Mol/s cm
2Accompanying drawing 2 has compared the La of potassium fluoronickelate structure
2NiO
4+ δ(1) and the La of perovskite structure
0.6Sr
0.4Co
0.8Fe
0.2O
3-δ(2) the oxygen permeation flux under different temperatures.Ordinate is oxygen permeation flux Jo
2(unit is mole/second centimetre
2) logarithm, abscissa is that the inverse of absolute temperature T multiply by 1000.As can be seen from the figure, (right side among the figure) at a lower temperature, the La of potassium fluoronickelate structure
2NiO
4+ δOxygen flux (1) is apparently higher than perovskite structure La
0.6Sr
0.4Co
0.8Fe
0.2O
3-δOxygen flow flux (2).
Embodiment 2
La
2CuO
4+ δ, preparation process is same as example 1.The powder synthesis temperature is 1050 ℃, and the sintering temperature of membrane material is 1150 ℃.In the material during excess oxygen δ=0.06,500 ℃ the oxygen permeation flux greater than 0.1 * 10
-8Mol/scm
2
Embodiment 3
La
2Cu
xNi
1-xO
4+ δ(0＜x＜1), preparation process is same as example 1.The powder synthesis temperature is 1000 ℃, and the sintering temperature of membrane material is 1150 ℃.Excess oxygen δ=0.04～0.10 in the material, the oxygen permeation flux is greater than 0.3 * 10 in the time of 500 ℃
-8Mol/s cm
2
Claims (9)
1. the inorganic compact oxygen permeable film material of a potassium fluoronickelate structure is characterized in that this material A
2BO
4+ δExpression, wherein A represents the La series elements, B represents Fe, Co, Ni, Cu and Zn, 0＜δ＜0.20.
2. the potassium fluonikelate type inorganic compact oxygen-permeable film material of a doping is characterized in that the chemical formula of this material can be expressed as A
2B
1-xC
xO
4+ δ, wherein A represents the La series elements, B, C are different mutually, represent Li, Cr, Mn, Fe, Co, Ni, Cu and Zn independently of one another, 0＜x＜1,0＜δ＜0.20.
3. in above-mentioned arbitrary claim, the transmission of oxonium ion is with the main path of gap digit as the oxygen diffusion mass transfer.
4. in above-mentioned arbitrary claim, the beginning of oxygen sees through temperature and is lower than 600 ℃.
5. in the claim 1 and 2, solid reaction process is adopted in the preparation of potassium fluoronickelate structural film materials.With the corresponding oxide of La series elements be selected from arbitrary oxide among FeO, CoO, NiO, CuO and the ZnO by A
2BO
4Or A
2B
1-xC
xO
4Stoichiometric batching.In 1000～1300 ℃ temperature range, especially calcination 24～48 hours in air or in the protective atmosphere under 1050～1200 ℃ of temperature cools to room temperature with the furnace, grinds for several times therebetween, to promote chemical uniformity.The powder compaction of making is in blocks, and sintering 4～24 hours in 1100～1300 ℃ air is chilled to room temperature again, and the material that part is formed was preferably in 400～500 ℃ of oxygen atmospheres under processing 12～24 hours.
6. in the claim 1 and 2, the preparation of membrane material can be adopted the acetate decomposition method.The acetate of respective metal is pressed A
2BO
4And A
2B
1-xC
xO
4Stoichiometric be dissolved in a certain amount of distilled water, mixing places 70～90 ℃ of vacuum desiccators dry, thermal decomposition in 800～1100 ℃ of air again.The powder compaction of making is in blocks, and sintering 4～24 hours in 1100～1300 ℃ air is chilled to room temperature again, and the material that part is formed was preferably in 400～500 ℃ of oxygen atmospheres under processing 12～24 hours.
7. in the claim 12, the preparation of membrane material can be adopted coprecipitation.The acetate of respective metal is pressed A
2BO
4And A
2B
1-xC
xO
4Stoichiometric make mixed aqueous solution, add precipitating reagent, make alkali carbonic acid double salt earlier by co-precipitation, through evaporation, dry, thermal decomposition, obtain mixed-metal oxides, after further mixing, roasting is 4～10 hours in 800～1100 ℃ of air, obtains preparing the powder of membrane material.The powder compaction of making is in blocks, and sintering 4～24 hours in 1100～1300 ℃ air is chilled to room temperature again, and the material that part is formed was preferably in 400～500 ℃ of oxygen atmospheres under processing 12～24 hours.
8. in the claim 1 and 2, the preparation of membrane material can be adopted citric acid complex-decomposition method.Nitrate with respective metal is raw material, presses A
2BO
4And A
2B
1-xC
xO
4Stoichiometric each component solution is added in the citric acid solution, evaporating water behind the mixing is ground, mixing, is heated to 550～650 ℃ and carries out thermal decomposition, obtains preparing the powder of membrane material after the cooling.With the compacting of the powder that makes in flakes, sintering 4～24 hours in 1100～1300 ℃ air is chilled to room temperature again, and the material that part is formed was preferably in 400～500 ℃ of oxygen atmospheres under processing 12～24 hours.
9. in above-mentioned arbitrary claim, the relative density of membrane material is more than 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98101692 CN1275682C (en) | 1998-05-05 | 1998-05-05 | Potassium nickel fluosilicate type inorganic compact oxygen permeable membrane material |
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|---|---|---|---|
| CN 98101692 CN1275682C (en) | 1998-05-05 | 1998-05-05 | Potassium nickel fluosilicate type inorganic compact oxygen permeable membrane material |
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| Publication Number | Publication Date |
|---|---|
| CN1234291A true CN1234291A (en) | 1999-11-10 |
| CN1275682C CN1275682C (en) | 2006-09-20 |
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ID=5216872
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2868211A1 (en) * | 2004-03-24 | 2005-09-30 | Electricite De France | OXIDE AND ELECTRODE MATERIAL FOR FUEL CELL INCLUDING IT |
| JP2014186941A (en) * | 2013-03-25 | 2014-10-02 | Ngk Insulators Ltd | Air electrode for fuel batteries |
| CN104548957A (en) * | 2014-12-12 | 2015-04-29 | 南京工业大学 | Oxygen permeable membrane material with stable oxygen flux in carbon dioxide-containing atmosphere |
| CN105417494A (en) * | 2016-01-07 | 2016-03-23 | 昆明理工大学 | Device and method for decomposing water through K2NiF4 structure oxygen permeable film material to produce hydrogen |
| CN114538915A (en) * | 2022-01-28 | 2022-05-27 | 华南理工大学 | CO (carbon monoxide)2Stable two-phase mixed conductor oxygen-permeable membrane and preparation method and application thereof |
| CN116571099A (en) * | 2023-06-09 | 2023-08-11 | 中国科学院赣江创新研究院 | Carbon molecular sieve membrane and preparation method and application thereof |
-
1998
- 1998-05-05 CN CN 98101692 patent/CN1275682C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2868211A1 (en) * | 2004-03-24 | 2005-09-30 | Electricite De France | OXIDE AND ELECTRODE MATERIAL FOR FUEL CELL INCLUDING IT |
| WO2005099003A1 (en) * | 2004-03-24 | 2005-10-20 | Electricite De France | Oxide material and a fuel cell electrode containing said material |
| US7572532B2 (en) | 2004-03-24 | 2009-08-11 | Electricite De France | Oxide material and a fuel cell electrode containing said material |
| JP2014186941A (en) * | 2013-03-25 | 2014-10-02 | Ngk Insulators Ltd | Air electrode for fuel batteries |
| CN104548957A (en) * | 2014-12-12 | 2015-04-29 | 南京工业大学 | Oxygen permeable membrane material with stable oxygen flux in carbon dioxide-containing atmosphere |
| CN105417494A (en) * | 2016-01-07 | 2016-03-23 | 昆明理工大学 | Device and method for decomposing water through K2NiF4 structure oxygen permeable film material to produce hydrogen |
| CN105417494B (en) * | 2016-01-07 | 2017-09-22 | 昆明理工大学 | One kind utilizes K2NiF4The apparatus and method of structure oxygen permeable film material hydrogen production by water decomposition |
| CN114538915A (en) * | 2022-01-28 | 2022-05-27 | 华南理工大学 | CO (carbon monoxide)2Stable two-phase mixed conductor oxygen-permeable membrane and preparation method and application thereof |
| CN114538915B (en) * | 2022-01-28 | 2023-10-24 | 华南理工大学 | CO (carbon monoxide) 2 Stable biphase mixed conductor oxygen permeable membrane and preparation method and application thereof |
| CN116571099A (en) * | 2023-06-09 | 2023-08-11 | 中国科学院赣江创新研究院 | Carbon molecular sieve membrane and preparation method and application thereof |
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|---|---|
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