CN108117388A - Ti base two-phase oxygen permeable ceramic film materials - Google Patents
Ti base two-phase oxygen permeable ceramic film materials Download PDFInfo
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- CN108117388A CN108117388A CN201611057524.XA CN201611057524A CN108117388A CN 108117388 A CN108117388 A CN 108117388A CN 201611057524 A CN201611057524 A CN 201611057524A CN 108117388 A CN108117388 A CN 108117388A
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Abstract
Ti base two-phase oxygen permeable ceramic film materials have the structure composition shown in following expression：X wt%Ce1‑yLmyO2‑y/2(100 x) wt% (Ln1‑zBz)1‑aMbTi1‑bO3；20≤x≤80 in formula, 0.05≤y≤0.5,0 ＜ z ＜ 1,0≤a≤0.3,0≤b≤0.5；Wherein Lm and Ln is separately selected from least one of lanthanide series and Y；B is selected from least one of Ca, Ba, Sr, Pb, Bi, and M is selected from least one of Mg, Al, Cr, Fe, Ga, Mn and Sc.The two-phase oxygen permeable ceramic film material of the present invention is prepared into two-phase oxygen permeable ceramic film by coprecipitation one-pot synthesis using it, and preparing high-purity hydrogen, especially water decomposition available for hydrogen separation prepares Hydrogen Separation in hydrogen.Its active element adulterated is base metal, at low cost, has higher Hydrogen Separation performance, and is had good stability, better than hydrogen separation membrane of the prior art.
Description
Technical field
The invention belongs to membrane technology separation fields, are related to a kind of available for the separated two-phase oxygen permeable ceramic film material of hydrogen.
Background technology
With the sustainable development of global economy, the conventional fossil fuel energy increasingly depleted relied on, oil and coal
Burning brings greenhouse effects and acid rain etc. so that there is an urgent need to while fossil fuel is effectively utilized, open in time by the mankind
Hair cleaning, cheap new energy progressively to substitute existing fossil fuel, reach the problem of reducing air pollution.Hydrogen Energy because
Its energy density is high, thermal transition is efficient, to zero environmental is considered as a kind of preferable clear energy sources carrier.And as electricity
The industries such as son, semiconductor, petrochemical industry, metallurgy, fuel cell are required for using high-purity hydrogen.But industrial 90% hydrogen is at present
It is prepared by the steam reforming and water gas shift reaction of fossil feedstock, inevitably containing a small amount of CO, CO2Wait impurity.
The purification process of hydrogen has low-temperature adsorption, pressure swing adsorption method, catalytic purification method, metal hydride separation at present
Method, membrane separation process etc..Various purification process suffer from respective advantage and disadvantage and suitable application area.Low energy consumption for membrane separation process, can be achieved
Continuous separation, easily amplification, production efficiency are high, receive significant attention.Wherein, palladium film or palladium alloy membrane are imitated in hydrogen purification application
Fruit is preferably and application is more.But low stability and Pd resource-expensives and reserves limited (hydrogen embrittlement and and the carbon compound of palladium film
Form PdC0.15Alloy) limit its extensive use.
The new method that hydrogen separation is current purifying hydrogen is carried out using composite conductor oxygen-permeating film reactor.Its principle is mixed
The one side for closing conductor oxygen permeation membrane is passed through vapor, and opposite side is by the use of the hydrogen of low-purity as purge gass.Water resolves at high temperature
Hydrogen and oxonium ion, oxonium ion are directionally migrated to the purging gas side of hypoxemia chemical potential side, then with the low-purity of purging gas side
Hydrogen reaction, while also accelerate film opposite side water decomposition reaction.Hydrogen so is can be obtained by the vapor side of film,
And the hydrogen generated is equal to the hydrogen of equal value of purging gas side consumption, it is achieved thereby that hydrogen separates.Used mixed conductor is saturating
Oxygen ceramic membrane should have high stability and high oxygen permeating amount under reducing atmosphere.The two-phase that fluorite type-Ca-Ti ore type is combined
Oxygen permeable ceramic film stability under reducing atmosphere is high, composition can flexible design, hydrogen separation side is realized in oxygen-permeable membrane reactor
There is very big application prospect in face.
The content of the invention
Low of high cost for stability existing for the separated film of hydrogen in the prior art to solve the problem of, the present invention provides
A kind of Ti bases two-phase oxygen permeable ceramic film material can prepare film forming and be separated for hydrogen, have good separating effect, stability is high, cost
The characteristics of low.
The technical purpose of the present invention is achieved through the following technical solutions：
The technical purpose of first aspect present invention is to provide a kind of Ti bases two-phase oxygen permeable ceramic film material, has and is expressed as below
Structure composition shown in formula：X wt%Ce1-yLmyO2-y/2- (100-x) wt% (Ln1-zBz)1-aMbTi1-bO3；20≤x in formula≤
80,0.05≤y≤0.5,0 ＜ z ＜ 1,0≤a≤0.3,0≤b≤0.5；Wherein Lm and Ln is separately selected from lanthanide series
At least one of with Y；B is selected from least one of Ca, Ba, Sr, Pb, Bi, and M is in Mg, Al, Cr, Fe, Ga, Mn and Sc
At least one.
The technical purpose of second aspect of the present invention is to provide the preparation method of the two-phase oxygen permeable ceramic film material, including with
Lower step：
(A) by composition shown in the structure expression of two-phase oxygen permeable ceramic film material, the amount of ammonium carbonate precipitating reagent needed for calculating,
Sal volatile is made by its excessive 1~3 times；
(B) ethyl alcohol and acetic acid are added in into organic titanium solution, then is slowly added into HNO3In solution, obtain transparent molten
Glue；
(C) composition takes each metal nitrate as shown in the structure expression of two-phase oxygen permeable ceramic film material, mixes in addition to Ti
Other metal nitrates and be dissolved in HNO3In solution；
(D) solution that step (C) obtains is poured into the colloidal sol that step (B) obtains, stirred；
(E) solution that step (D) obtains is poured into the sal volatile of step (A), it is 8~10 to keep solution ph,
Stirring ageing；
(F) precipitation for obtaining step (E) filters or centrifugation, washing, drying roast.
The technical purpose of third aspect present invention is to provide by the two-phase oxygen permeable ceramic film material preparation two-phase oxygen flow
The method of ceramic membrane, including by the powder compression molding of two-phase oxygen permeable ceramic film material, in 1400~1500 DEG C of sintering.
The technical purpose of further aspect of the present invention is to provide to be separated by two-phase oxygen permeable ceramic film prepared by above method in hydrogen
In application.
The Ti base two-phase oxygen permeable ceramic film materials of the present invention have fluorite structure and Ti based perovskite structures simultaneously, the present invention
By adulterating the ratio of element in some element-specifics and each composition of control in its perovskite structure, provide a series of available
It in the material of hydrogen separation membrane, uses it in water decomposition hydrogen production reaction, high-purity hydrogen, the activity member of doping can be isolated
Element is base metal, at low cost, has higher Hydrogen Separation performance, and experiment shows that it is steady in the test of hundreds of hours
It is qualitative good, better than hydrogen separation membrane of the prior art.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of material prepared in embodiment 1,2,3；
Fig. 2 is scanning electron microscope (SEM) figure of film prepared in embodiment 1,2,3；Wherein,
a1、a2For the surface of the film of embodiment 1 and scanning electron microscope (SEM) figure in section；
b1、b2For the surface of the film of embodiment 2 and scanning electron microscope (SEM) figure in section；
c1、c2For the surface of the film of embodiment 3 and scanning electron microscope (SEM) figure in section.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The technical purpose of first aspect present invention is to provide a kind of Ti bases two-phase oxygen permeable ceramic film material, has and is expressed as below
Structure composition shown in formula：X wt%Ce1-yLmyO2-y/2- (100-x) wt% (Ln1-zBz)1-aMbTi1-bO3；20≤x in formula≤
80,0.05≤y≤0.5,0 ＜ z ＜ 1,0≤a≤0.3,0≤b≤0.5；Wherein Lm and Ln is separately selected from lanthanide series
At least one of with Y；B is selected from least one of Ca, Ba, Sr, Pb, Bi, and M is in Mg, Al, Cr, Fe, Ga, Mn and Sc
At least one.
Further, in the structure composition expression formula of above-mentioned two-phase oxygen permeable ceramic film material, 40≤x≤80,0.05≤y
≤ 0.3,0.1≤z≤0.9.As more specific embodiment, 0≤a≤0.2.
Further, in the structure composition expression formula of above-mentioned two-phase oxygen permeable ceramic film material, implement as more specific
Mode, the one kind of B in Sr, Ca and Ba；Lm and Ln separately one kind in Sm, Y, Pr, La and Gd.
In more specifically embodiment, the above-mentioned two-phase oxygen permeable ceramic film material of the present invention, which is selected from, has following formula
One kind in the substance of shown structure composition：
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.1Sr0.9TiO3
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.3Sr0.7TiO3
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.5Sr0.5TiO3。
70wt%Ce0.7Pr0.3O1.85- 30wt% (Sm0.2Sr0.8)0.9TiO3
60wt%Ce0.9Pr0.1O1.95- 40wt% (Pr0.2Sr0.8)0.8Mn0.3Ti0.7O3
60wt%Ce0.7Sm0.3O1.85- 40wt% (Gd0.3Ba0.7)0.85TiO3
80wt%Ce0.7Y0.3O1.85- 20wt% (Gd0.1Ca0.9)0.9Mg0.1Ti0.9O3
80wt%Ce0.7La0.3O1.85- 20wt% (La0.1Ca0.9)0.9Fe0.2Ti0.8O3
The technical purpose of second aspect of the present invention is to provide the preparation method of the two-phase oxygen permeable ceramic film material, including with
Lower step：
(A) by composition shown in the structure expression of two-phase oxygen permeable ceramic film material, the amount of ammonium carbonate precipitating reagent needed for calculating,
Sal volatile is made by its excessive 1~3 times；
(B) ethyl alcohol and acetic acid are added in into organic titanium solution, then is slowly added into HNO3In solution, obtain transparent molten
Glue；
(C) composition takes each metal nitrate as shown in the structure expression of two-phase oxygen permeable ceramic film material, mixes in addition to Ti
Other metal nitrates and be dissolved in HNO3In solution；
(D) solution that step (C) obtains is poured into the colloidal sol that step (B) obtains, stirred；
(E) solution that step (D) obtains is poured into the sal volatile of step (A), it is 8~10 to keep solution ph,
Stirring ageing；
(F) precipitation for obtaining step (E) filters or centrifugation, washing, drying roast.
Further, in above-mentioned preparation method, the concentration of sal volatile is 2~4mol L in step (A)-1。
Further, in above-mentioned preparation method, HNO in step (B) neutralization procedure (C)3The concentration of solution is 0.5~
4.0mol L-1；As further preferably, step (C) and the final HNO of step (B)3Concentration difference<1mol L-1。
Further, in above-mentioned preparation method, organic titanium described in step (B) is butyl titanate and/or metatitanic acid isopropyl
Ester.
Further, in above-mentioned preparation method, the time of stirring ageing is 0.3~5h in step (E).
Further, in above-mentioned preparation method, dry temperature is 60~100 DEG C in step (F), and the temperature of roasting is
300~800 DEG C, the time is 3~6h.
The technical purpose of third aspect present invention is to provide by the two-phase oxygen permeable ceramic film material preparation two-phase oxygen flow
The method of ceramic membrane, including by the powder compression molding of two-phase oxygen permeable ceramic film material, in 1400~1500 DEG C of sintering.
In the method for above-mentioned preparation two-phase oxygen permeable ceramic film, the time of the sintering is preferably 3~5h.
The technical purpose of further aspect of the present invention is to provide as the two-phase oxygen permeable ceramic film prepared by above method in hydrogen point
Application from.
In application of the above-mentioned two-phase oxygen permeable ceramic film in hydrogen separation, it is particularly used for water decomposition and prepares hydrogen in hydrogen
Separation.More specifically operating method is：Water decomposition catalyst is coated in the both sides of the two-phase oxygen permeable ceramic film, is sealed against
In membrane reactor, the one side of film is passed through vapor, and opposite side is by the use of the hydrogen of low-purity as purge gass.The oxygen that water decomposition generates
Ion permeable film is reacted with low-purity hydrogen, promotes the water decomposition reaction of reaction side, and the hydrogen of reaction side is enable to separate,
Obtain high-purity hydrogen.
Describe the specific embodiment of the present invention in detail below in conjunction with technical solution and attached drawing.
In each preparation-obtained two-phase oxygen permeable ceramic film material of embodiment of the invention below, seperation film is made and carries out hydrogen
During separate evaluation, there are water decomposition catalyst in film both sides, are sealed in Ag circles on membrane reactor, film one side is passed through various concentration
Whether vapor contains except hydrogen after outlet side is reacted after cooling liquid, drying with gas chromatographic detection in gained gas
Gas in addition, and measure the flow velocity of hydrogen.The opposite side of film is passed through the hydrogen of various concentration.
Embodiment 1
It is 75wt%Ce with coprecipitation one-pot synthesis chemical expression0.85Sm0.15O1.925- 25wt%Sm0.1Sr0.9TiO3
Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, by excessive 2 times of preparations sal volatile.According to
Above formula each element ratio calculates the amount of each nitrate of Sm, Sr, Ce and butyl titanate, mixes Sm, Sr, Ce metal nitrate and is dissolved in
HNO3In solution.A certain amount of ethyl alcohol and a small amount of glacial acetic acid are added in into butyl titanate；It is then slowly added to HNO3In solution,
Obtain colloidal sol that is transparent and stablizing；Itself and other metal-nitrate solutions are mixed, is stirred evenly, is obtained all metal ions and mix
Close liquid.It is finally poured into sal volatile, solution ph is about 9~10, stirring ageing 3h.Gained is precipitated and is filtered, is washed
It washs, and in 80 DEG C of dryings.Powder is roasted into 5h at 300 DEG C, obtains the presoma of membrane material.
Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, then by the raw cook pressed 1400~1500
DEG C sintering 4h after, be polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film.Its XRD and SEM is respectively such as Fig. 1 and Fig. 2 institutes
Show.
Water decomposition catalyst is coated in film both sides, then hydrogen separation membrane reactor is sealed in Ag circles, in 900 DEG C of hydrogen
The gas rate of departure reaches 3.6mL cm-2min-1, have good stability in the test of about 200h.
Embodiment 2
It is 75wt%Ce with coprecipitation one-pot synthesis chemical expression0.85Sm0.15O1.925- 25wt%Sm0.3Sr0.7TiO3
Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, by excessive 2 times of preparations sal volatile.According to
Above formula each element ratio calculates the amount of each nitrate of Sm, Sr, Ce and butyl titanate, mixes Sm, Sr, Ce metal nitrate and is dissolved in
HNO3In solution.A certain amount of ethyl alcohol and a small amount of glacial acetic acid are added in into butyl titanate；It is then slowly added to HNO3In solution,
Obtain colloidal sol that is transparent and stablizing；Itself and other metal-nitrate solutions are mixed, is stirred evenly, is obtained all metal ions and mix
Close liquid.It is finally poured into sal volatile, solution ph is about 9~10, stirring ageing 3h.Gained is precipitated and is filtered, is washed
It washs, and in 80 DEG C of dryings.Powder is roasted into 5h at 300 DEG C, obtains the presoma of membrane material.
Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, then by the raw cook pressed 1400~1500
DEG C sintering 4h after, be polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film.Its XRD and SEM is respectively such as Fig. 1 and Fig. 2 institutes
Show.
Water decomposition catalyst is coated in film both sides, then hydrogen separation membrane reactor is sealed in Ag circles, in 900 DEG C of hydrogen
The gas rate of departure reaches 3.5mL cm-2min-1, have good stability in the test of about 200h.
Embodiment 3
It is 75wt%Ce with coprecipitation one-pot synthesis chemical expression0.85Sm0.15O1.925- 25wt%Sm0.5Sr0.5TiO3
Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, 3mol L are prepared by excessive 2 times-1Ammonium carbonate
Solution.The amount of each nitrate of Sm, Sr, Ce and butyl titanate is calculated according to above formula each element ratio, mixes Sm, Sr, Ce metal nitre
Hydrochlorate is simultaneously dissolved in HNO3In solution.A certain amount of ethyl alcohol and a small amount of glacial acetic acid are added in into butyl titanate；It is then slowly added to
HNO3In solution, colloidal sol that is transparent and stablizing is obtained；Itself and other metal-nitrate solutions are mixed, stirs evenly, obtains institute
There is metal ion mixed liquor.It is finally poured into sal volatile, solution ph is about 9~10, stirring ageing 3h.By gained
Precipitation filters, washing, and in 80 DEG C of dryings.Powder is roasted into 5h at 300 DEG C, obtains the presoma of membrane material.
Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, then by the raw cook pressed 1400~1500
DEG C sintering 4h after, be polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film.Its XRD and SEM is respectively such as Fig. 1 and Fig. 2 institutes
Show.
Water decomposition catalyst is coated in film both sides, then hydrogen separation membrane reactor is sealed in Ag circles, in 900 DEG C of hydrogen
The gas rate of departure reaches 4.0mL cm-2min-1, have good stability in the test of about 200h.
Embodiment 4
It is 70wt%Ce with coprecipitation one-pot synthesis chemical expression0.7Pr0.3O1.85- 30wt% (Sm0.2Sr0.8)0.9TiO3Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, 3mol L are prepared by excessive 2 times-1's
Sal volatile.Calculate the amount of each nitrate of Sm, Sr, Pr, Ce and butyl titanate according to above formula each element ratio, mixing Sm, Sr,
Pr, Ce metal nitrate are simultaneously dissolved in HNO3In solution.A certain amount of ethyl alcohol and a small amount of glacial acetic acid are added in into butyl titanate；Then
It is slowly added into HNO3In solution, colloidal sol that is transparent and stablizing is obtained；Itself and other metal-nitrate solutions are mixed, stirring is equal
It is even, obtain all metal ions mixed liquor.It is finally poured into sal volatile, solution ph is about 9~10, stirring ageing
3h.Gained is precipitated and is filtered, washing, and in 80 DEG C of dryings.Powder is roasted into 5h at 300 DEG C, obtains the presoma of membrane material.
Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, then by the raw cook pressed 1400~1500
DEG C sintering 4h after, be polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film.
Water decomposition catalyst is coated in film both sides, then hydrogen separation membrane reactor is sealed in Ag circles, in 900 DEG C of hydrogen
The gas rate of departure reaches 3.4mL cm-2min-1, have good stability in the test of about 200h.
Embodiment 5
It is 60wt%Ce with coprecipitation one-pot synthesis chemical expression0.9Pr0.1O1.95- 40wt% (Pr0.2Sr0.8)0.8Mn0.3Ti0.7O3Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, by excessive 2 times of preparations
3mol L-1Sal volatile.The amount of each nitrate of Sr, Pr, Ce, Mn and butyl titanate is calculated according to above formula each element ratio,
Mixing Sr, Pr, Ce, Mn metal nitrate is simultaneously dissolved in HNO3In solution.A certain amount of ethyl alcohol and a small amount of is added in into butyl titanate
Glacial acetic acid；It is then slowly added to HNO3In solution, colloidal sol that is transparent and stablizing is obtained；By itself and other metal-nitrate solutions
Mixing, stirs evenly, obtains all metal ions mixed liquor.Finally be poured into sal volatile, solution ph about 9~
10, stirring ageing 3h.Gained is precipitated and is filtered, washing, and in 80 DEG C of dryings.Powder is roasted into 5h at 300 DEG C, obtains membrane material
Presoma.
Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, then by the raw cook pressed 1400~1500
DEG C sintering 4h after, be polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film.
Water decomposition catalyst is coated in film both sides, then hydrogen separation membrane reactor is sealed in Ag circles, in 900 DEG C of hydrogen
The gas rate of departure reaches 4.5mL cm-2min-1, have good stability in the test of about 200h.
Embodiment 6
It is 60wt%Ce with coprecipitation one-pot synthesis chemical expression0.7Sm0.3O1.85- 40wt% (Gd0.3Ba0.7)0.85TiO3Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, 3mol L are prepared by excessive 2 times-1
Sal volatile.Calculate the amount of each nitrate of Sm, Gd, Ce, Ba and butyl titanate according to above formula each element ratio, mixing Sm,
Gd, Ce, Ba metal nitrate are simultaneously dissolved in HNO3In solution.A certain amount of ethyl alcohol and a small amount of glacial acetic acid are added in into butyl titanate；
It is then slowly added to HNO3In solution, colloidal sol that is transparent and stablizing is obtained；4 mix itself and other metal-nitrate solutions,
It stirs evenly, obtains all metal ions mixed liquor.It is finally poured into sal volatile, solution ph is stirred about 9~10
Mix ageing 3h.Gained is precipitated and is filtered, washing, and in 80 DEG C of dryings.Powder is roasted into 5h at 300 DEG C, before obtaining membrane material
Drive body.
Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, then by the raw cook pressed 1400~1500
DEG C sintering 4h after, be polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film.
Water decomposition catalyst is coated in film both sides, then hydrogen separation membrane reactor is sealed in Ag circles, in 900 DEG C of hydrogen
The gas rate of departure reaches 3.3mL cm-2min-1, have good stability in the test of about 200h.
Embodiment 7
It is 80wt%Ce with coprecipitation one-pot synthesis chemical expression0.7Y0.3O1.85- 40wt% (Gd0.1Ca0.9)0.9Mg0.1Ti0.9O3Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, by excessive 2 times of preparations
3mol L-1Sal volatile.Each nitrate of Y, Mg, Gd, Ce, Ca and butyl titanate are calculated according to above formula each element ratio
Amount mixes Y, Mg, Gd, Ce, Ca metal nitrate and is dissolved in HNO3In solution.Added in into butyl titanate a certain amount of ethyl alcohol and
A small amount of glacial acetic acid；It is then slowly added to HNO3In solution, colloidal sol that is transparent and stablizing is obtained；By itself and other metal nitrates
Solution mixes, and stirs evenly, obtains all metal ions mixed liquor.It is finally poured into sal volatile, solution ph is about
9~10, stirring ageing 3h.Gained is precipitated and is filtered, washing, and in 80 DEG C of dryings.Powder is roasted into 5h at 300 DEG C, is obtained
The presoma of membrane material.
Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, then by the raw cook pressed 1400~1500
DEG C sintering 4h after, be polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film.
Water decomposition catalyst is coated in film both sides, then hydrogen separation membrane reactor is sealed in Ag circles, in 900 DEG C of hydrogen
The gas rate of departure reaches 3.7mL cm-2min-1, have good stability in the test of about 200h.
Embodiment 8
It is 80wt%Ce with coprecipitation one-pot synthesis chemical expression0.7La0.3O1.85- 20wt% (La0.1Ca0.9)0.9Fe0.2Ti0.8O3Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, by excessive 2 times of preparations
3mol L-1Sal volatile.The amount of each nitrate of La, Ce, Ca, Fe and butyl titanate is calculated according to above formula each element ratio,
Mixing La, Ce, Ca, Fe metal nitrate is simultaneously dissolved in HNO3In solution.A certain amount of ethyl alcohol and a small amount of is added in into butyl titanate
Glacial acetic acid；It is then slowly added to HNO3In solution, colloidal sol that is transparent and stablizing is obtained；By itself and other metal-nitrate solutions
Mixing, stirs evenly, obtains all metal ions mixed liquor.Finally be poured into sal volatile, solution ph about 9~
10, stirring ageing 3h.Gained is precipitated and is filtered, washing, and in 80 DEG C of dryings.Powder is roasted into 5h at 300 DEG C, obtains membrane material
Presoma.
Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, then by the raw cook pressed 1400~1500
DEG C sintering 4h after, be polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film.
Water decomposition catalyst is coated in film both sides, then hydrogen separation membrane reactor is sealed in Ag circles, in 900 DEG C of hydrogen
The gas rate of departure reaches 3.2mL cm-2min-1, have good stability in the test of about 200h.
Above-described embodiment can enumerate many, be proved from the substantial amounts of test data of applicant, using technical solution of the present invention
Involved membrane material can obtain good hydrogen separating property.
Claims (11)
1.Ti base two-phase oxygen permeable ceramic film materials, which is characterized in that the two-phase oxygen permeable ceramic film material has following expression
Shown structure composition：X wt%Ce1-yLmyO2-y/2- (100-x) wt% (Ln1-zBz)1-aMbTi1-bO3；20≤x≤80 in formula,
0.05≤y≤0.5,0 ＜ z ＜ 1,0≤a≤0.3,0≤b≤0.5；Wherein Lm and Ln is separately selected from lanthanide series and Y
At least one of；B is selected from least one of Ca, Ba, Sr, Pb, Bi, M in Mg, Al, Cr, Fe, Ga, Mn and Sc extremely
Few one kind.
2. two-phase oxygen permeable ceramic film material according to claim 1, which is characterized in that in its structure composition expression formula,
40≤x≤80,0.05≤y≤0.3,0.1≤z≤0.9.
3. two-phase oxygen permeable ceramic film material according to claim 1, which is characterized in that in its structure composition expression formula, 0
≤a≤0.2。
4. two-phase oxygen permeable ceramic film material according to claim 1, which is characterized in that in its structure composition expression formula, B
One kind in Sr, Ca and Ba.
5. two-phase oxygen permeable ceramic film material according to claim 1, which is characterized in that in its structure composition expression formula,
Lm and Ln separately one kind in Sm, Y, Pr, La and Gd.
6. two-phase oxygen permeable ceramic film material according to claim 1, which is characterized in that it, which is selected from, has following formula institute
One kind in the substance for the structure composition shown：
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.1Sr0.9TiO3
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.3Sr0.7TiO3
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.5Sr0.5TiO3。
70wt%Ce0.7Pr0.3O1.85- 30wt% (Sm0.2Sr0.8)0.9TiO3
60wt%Ce0.9Pr0.1O1.95- 40wt% (Pr0.2Sr0.8)0.8Mn0.3Ti0.7O3
60wt%Ce0.7Sm0.3O1.85- 40wt% (Gd0.3Ba0.7)0.85TiO3
80wt%Ce0.7Y0.3O1.85- 20wt% (Gd0.1Ca0.9)0.9Mg0.1Ti0.9O3
80wt%Ce0.7La0.3O1.85- 20wt% (La0.1Ca0.9)0.9Fe0.2Ti0.8O3。
7. the preparation method of the two-phase oxygen permeable ceramic film material described in claim 1~6 any one, comprises the following steps：
(A) by composition, the amount of ammonium carbonate precipitating reagent needed for calculating, by it shown in the structure expression of two-phase oxygen permeable ceramic film material
Excessive 1~3 times is made into sal volatile；
(B) ethyl alcohol and acetic acid are added in into organic titanium solution, then is slowly added into HNO3In solution, vitreosol is obtained；
(C) composition takes each metal nitrate as shown in the structure expression of two-phase oxygen permeable ceramic film material, mixes its in addition to Ti
His metal nitrate is simultaneously dissolved in HNO3In solution；
(D) solution that step (C) obtains is poured into the colloidal sol that step (B) obtains, stirred；
(E) solution that step (D) obtains is poured into the sal volatile of step (A), it is 8~10 to keep solution ph, stirring
Ageing；
(F) precipitation for obtaining step (E) filters or centrifugation, washing, drying roast.
8. as the method for the two-phase oxygen permeable ceramic film material preparation two-phase oxygen permeable ceramic film described in claim 1~6 any one,
Including by the powder compression molding of two-phase oxygen permeable ceramic film material, in 1400~1500 DEG C of sintering.
9. the application of two-phase oxygen permeable ceramic film prepared by the method described in claim 8 in hydrogen separation.
10. application according to claim 9, which is characterized in that be particularly used for water decomposition and prepare Hydrogen Separation in hydrogen.
11. application according to claim 10, which is characterized in that concrete operation method is：In two-phase oxygen flow ceramics
Water decomposition catalyst is coated in the both sides of film, is sealed against in membrane reactor, and the one side of film is passed through vapor, and opposite side is with low pure
The hydrogen of degree is as purge gass.The oxonium ion that water decomposition generates reacts with low-purity hydrogen through film, promotes the moisture of reaction side
Solution reaction, and the hydrogen of reaction side is enable to separate, obtain high-purity hydrogen.
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