CN108117044A - A kind of method for preparing high-purity hydrogen - Google Patents
A kind of method for preparing high-purity hydrogen Download PDFInfo
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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Abstract
A kind of method for preparing high-purity hydrogen, is separated with membrane reactor, the material preparation of the structure and composition as shown in following expression of the film in the membrane reactor：X wt%Ce1‑yLnyO2‑y/2(100 x) wt% (Lm1‑zBz)1‑aMO3；20≤x≤80 in formula, 0.05≤y≤0.5,0 ＜ z ＜ 1,0≤a≤0.3；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；M is selected from least one of Al, Cr, Mg, Mn, Ni, Fe, Ga and Ti.Film in the membrane reactor is by being provided simultaneously with the material preparation of fluorite structure and perovskite structure, by the ratio that element in some element-specifics and each composition of control is adulterated in its fluorite and perovskite structure, film prepared therefrom is in hydrogen separation, with at low cost, the characteristics of Hydrogen Separation performance is high, and membrane stability is good.
Description
Technical field
The invention belongs to membrane technology separation fields, and in particular to one kind carries out separation preparation using two-phase oxygen flow ceramic material
The method of high-purity 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
To solve low separation efficiency existing for the purification process of hydrogen in the prior art, seperation film is of high cost, and stability is poor
The problem of, the present invention provides a kind of method for preparing high-purity hydrogen, and good separating effect, stability is high, at low cost.
The technical purpose of the present invention is achieved through the following technical solutions：
The technical purpose of the present invention is to provide a kind of method for preparing high-purity hydrogen, is separated with membrane reactor, described
The material preparation of film structure and composition as shown in following expression in membrane reactor：X wt%Ce1-yLnyO2-y/2-
(100-x) wt% (Lm1-zBz)1-aMO3；20≤x≤80 in formula, 0.05≤y≤0.5,0 ＜ z ＜ 1,0≤a≤0.3；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；M is selected from
At least one of Al, Cr, Mg, Mn, Ni, Fe, Ga and Ti.
Method using the present invention carries out hydrogen separation and prepares high-purity hydrogen, and the film in the membrane reactor is by being provided simultaneously with
The material preparation of fluorite structure and perovskite structure, by adulterating some element-specifics and control in its fluorite and perovskite structure
The ratio of each element in its composition is made, film prepared therefrom is at low cost in hydrogen separation, having, and Hydrogen Separation performance is high, film
High-purity hydrogen can be prepared in the characteristics of stability is good.
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；
Fig. 3 is X-ray diffraction (XRD) spectrogram of material prepared in embodiment 9；
Fig. 4 is scanning electron microscope (SEM) figure of film prepared in embodiment 9；Wherein, d1、d2For the table of the film of embodiment 4
The scanning electron microscope in face and section (SEM) figure；
Fig. 5 is hydrogen separated performance and stability of the film prepared in embodiment 9 at 900 DEG C.
Fig. 6 is X-ray diffraction (XRD) spectrogram of material prepared in embodiment 12.
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 the present invention is to provide a kind of method for preparing high-purity hydrogen, is separated with membrane reactor, described
The material preparation of film structure and composition as shown in following expression in membrane reactor：X wt%Ce1-yLnyO2-y/2-
(100-x) wt% (Lm1-zBz)1-aMO3；20≤x≤80 in formula, 0.05≤y≤0.5,0 ＜ z ＜ 1,0≤a≤0.3；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；M is selected from
At least one of Al, Cr, Mg, Mn, Ni, Fe, Ga and Ti.
In the above-mentioned methods, as one of preferred embodiment, in the structure and composition expression formula of membrane material, 40≤x
≤ 80,0.05≤y≤0.3,0.1≤z≤0.9,0≤a≤0.2.
In the above-mentioned methods, one of preferred embodiment is：In the structure and composition expression formula of membrane material, B is preferred
From at least one of Ba, Ca and Sr.M is selected from least one of Al, Cr, Mg, Mn, Fe, Ga and Ti.Lm and Ln are independently
The one kind of ground in Sm, Y, Pr, La and Gd.
In the above-mentioned methods, as more specific embodiment, the membrane material of preparation includes at least one in following substance
Kind：
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
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.6Sr0.4Cr0.3Fe0.7O3
60wt%Ce0.9Y0.1O1.95- 40wt%Pr0.7Ca0.3Cr0.3Fe0.7O3
40wt%Ce0.75Gd0.25O1.87- 60wt%La0.5Sr0.5Cr0.5Fe0.5O3
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.6Sr0.4Al0.3Fe0.7O3
80wt%Ce0.8Sm0.2O1.9- 20wt%La0.5Sr0.5Ga0.3Fe0.7O3
60wt%Ce0.95Sm0.05O1.97- 40wt%Nb0.3Sr0.7Ga0.3Fe0.7O3
70wt%Ce0.8Y0.2O1.9- 30wt%Sm0.5Sr0.5Ti0.3Fe0.7O3
60wt%Ce0.85Gd0.15O1.925- 40wt%Sm0.7Ba0.3Mn0.4Fe0.6O3
65wt%Ce0.85Sm0.15O1.925- 35wt%Sm0.4Sr0.6Ga0.1Cr0.3Fe0.6O3
60wt%Ce0.85Gd0.15O1.925- 40wt%Sm0.6Sr0.4Ti0.1Cr0.3Fe0.6O3。
In the above-mentioned methods, the high-purity hydrogen for preparing refers to obtain height with the product of oxygen-permeable membrane reactor processing water decomposition
Purity hydrogen.More specifically embodiment is：Material with the expression formula structure and composition is prepared into through tabletting, sintering
Film is coated water decomposition catalyst in the both sides of film, is sealed against in membrane reactor, and the one side of film is passed through vapor, opposite side
By the use of the hydrogen of low-purity as purge gass, the oxonium ion that water decomposition generates reacts with low-purity hydrogen through film, promotes reaction side
Water decomposition reaction, and the hydrogen of reaction side is enable to separate, obtains high-purity hydrogen.
Further, in the above-mentioned methods the involved material with the expression formula structure and composition using solid
Phase method or coprecipitation one-pot synthesis,
The concrete operation step of wherein solid phase method is：It forms and takes as shown in the structure expression of two-phase oxygen permeable ceramic film material
Oxide or the carbonate powder mixing of each metal, add in ethyl alcohol, and 4~12h of ball milling is dry, calcine 4 in 800~1200 DEG C~
5h。
The concrete operation step of coprecipitation is：
(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.
In above-mentioned coprecipitation, as more specific embodiment, in step (A) concentration of sal volatile for 2~
4mol L-1；HNO in step (B) neutralization procedure (C)3The concentration of solution is 0.5~4.0mol L-1；As further excellent
Choosing, step (C) and the final HNO of step (B)3Concentration difference<1mol L-1。
In above-mentioned coprecipitation, organic titanium described in step (B) is butyl titanate and/or isopropyl titanate；Step (E)
The time of middle stirring ageing is 0.3~5h.
In above-mentioned coprecipitation, 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.
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, film is made and carries out hydrogen separation
When, there are water decomposition catalyst in film both sides, are sealed in Ag circles on membrane reactor, and film one side is passed through the vapor of various concentration,
Whether containing gas in addition to hydrogen in gained gas after outlet side is reacted after cooling liquid, drying with gas chromatographic detection
Body, and measure the flow velocity of hydrogen.The opposite side of film is passed through the hydrogen of various concentration.
Embodiment 1
(1) preparation of membrane material：It is 75wt%Ce with coprecipitation one-pot synthesis chemical expression0.85Sm0.15O1.925-
25wt%Sm0.1Sr0.9TiO3Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, by 2 times excessive
Prepare sal volatile.Calculate the amount of each nitrate of Sm, Sr, Ce and butyl titanate according to above formula each element ratio, mixing Sm,
Sr, 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.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 4h.Its XRD and
SEM difference is as depicted in figs. 1 and 2.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 3.6mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 2
(1) preparation of membrane material：It is 75wt%Ce with coprecipitation one-pot synthesis chemical expression0.85Sm0.15O1.925-
25wt%Sm0.3Sr0.7TiO3Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, by 2 times excessive
Prepare sal volatile.Calculate the amount of each nitrate of Sm, Sr, Ce and butyl titanate according to above formula each element ratio, mixing Sm,
Sr, 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.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 4h.Its XRD and
SEM difference is as depicted in figs. 1 and 2.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 3.5mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 3
(1) preparation of membrane material：It is 75wt%Ce with coprecipitation one-pot synthesis chemical expression0.85Sm0.15O1.925-
25wt%Sm0.5Sr0.5TiO3Membrane material, specific method is：The amount of precipitating reagent ammonium carbonate is calculated according to above formula, by 2 times excessive
Prepare 3mol L-1Sal volatile.The amount of each nitrate of Sm, Sr, Ce and butyl titanate is calculated according to above formula each element ratio,
Mixing Sm, Sr, Ce metal nitrate is simultaneously dissolved in HNO3In solution.A certain amount of ethyl alcohol and a small amount of ice second are added in into butyl titanate
Acid；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
It closes, stirs evenly, obtain 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.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 4h.Its XRD and
SEM difference is as depicted in figs. 1 and 2.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 4.0mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 4
(1) preparation of membrane material：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, by excess
2 times are prepared 3mol L-1Sal volatile.Each nitrate of Sm, Sr, Pr, Ce and metatitanic acid fourth are calculated according to above formula each element ratio
The amount of ester mixes Sm, Sr, Pr, Ce metal nitrate and is dissolved in HNO3In solution.A certain amount of ethyl alcohol is added in into butyl titanate
With 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
Salting liquid mixes, and stirs evenly, obtains all metal ions mixed liquor.It is finally 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, is obtained
To the presoma of membrane material.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 4h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 3.4mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 5
(1) preparation of membrane material：It is 60wt%Ce with coprecipitation one-pot synthesis chemical expression0.7Pr0.3O1.85-
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,
3mol L are prepared by excessive 2 times-1Sal volatile.According to above formula each element ratio calculate each nitrate of Sr, Pr, Ce, Mn and
The amount of butyl titanate mixes Sr, Pr, Ce, Mn metal nitrate and is dissolved in HNO3In solution.It is 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 gold
Genus nitrobacter solution mixes, and stirs evenly, obtains all metal ions mixed liquor.Finally it is poured into sal volatile, it is molten
Liquid pH value is about 9~10, stirring ageing 3h.Gained is precipitated and is filtered, washing, and in 80 DEG C of dryings.By powder in 300 DEG C of roastings
5h obtains the presoma of membrane material.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 4h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 4.5mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 6
(1) preparation of membrane material：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, by excess
2 times are prepared 3mol L-1Sal volatile.Each nitrate of Sm, Gd, Ce, Ba and metatitanic acid fourth are calculated according to above formula each element ratio
The amount of ester mixes Sm, Gd, Ce, Ba metal nitrate and is dissolved in HNO3In solution.A certain amount of ethyl alcohol is added in into butyl titanate
With 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
Salting liquid mixes, and stirs evenly, obtains all metal ions mixed liquor.It is finally 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, is obtained
To the presoma of membrane material.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 4h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 3.3mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 7
(1) preparation of membrane material：It is 80wt%Ce with coprecipitation one-pot synthesis chemical expression0.7Y0.3O1.85-
20wt% (Gd0.1Ca0.9)0.9Mg0.1Ti0.9O3Membrane 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-1Sal volatile.Each nitrate of Y, Mg, Gd, Ce, Ca is calculated according to above formula each element ratio
And the amount of butyl titanate, it mixes Y, Mg, Gd, Ce, Ca metal nitrate and is dissolved in HNO3In solution.One is added in into butyl titanate
Quantitative 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 its
He mixes metal-nitrate solutions, stirs evenly, obtains all metal ions mixed liquor.Finally it is poured into sal volatile
In, solution ph is about 9~10, stirring ageing 3h.Gained is precipitated and is filtered, washing, and in 80 DEG C of dryings.By powder 300
DEG C roasting 5h, obtain the presoma of membrane material.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 4h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 3.7mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 8
(1) preparation of membrane material：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,
3mol L are prepared by excessive 2 times-1Sal volatile.According to above formula each element ratio calculate each nitrate of La, Ce, Ca, Fe and
The amount of butyl titanate mixes La, Ce, Ca, Fe metal nitrate and is dissolved in HNO3In solution.It is 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 gold
Genus nitrobacter solution mixes, and stirs evenly, obtains all metal ions mixed liquor.Finally it is poured into sal volatile, it is molten
Liquid pH value is about 9~10, stirring ageing 3h.Gained is precipitated and is filtered, washing, and in 80 DEG C of dryings.By powder in 300 DEG C of roastings
5h obtains the presoma of membrane material.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired oxygen permeable ceramic film after 1400~1500 DEG C are sintered 4h.
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.
Embodiment 9
(1) preparation of membrane material：It is 75wt%Ce with solid phase method one-pot synthesis chemical expression085Sm0.15O1.925-
25wt%Sm0.6Sr0.4Cr0.3Fe0.7O3Membrane material, specific method is：In the ratio mixed phase shown in more than chemical expression
Answer CeO2、Sm2O3、Cr2O3、SrCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add in ethanol in proper amount,
It becomes flowable thick.By slurry ball milling 10h；Then slurry is dried, two-phase is obtained then at 1200 DEG C of calcining 5h
Oxide powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.Its XRD and
SEM difference is as shown in Figure 3 and Figure 4.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 6.2mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 360h
Good, the results are shown in Figure 5 for hydrogen separating property and stability test.
Embodiment 10
(1) preparation of membrane material：It is 60wt%Ce with solid phase method one-pot synthesis chemical expression0.9Y0.1O1.95- 40wt%
Pr0.7Ca0.3Cr0.3Fe0.7O3Membrane material, specific method is：CeO is answered in the ratio mixed phase shown in more than chemical expression2、
Y2O3、Cr2O3、PrO2、CaCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add in ethanol in proper amount, make
It becomes flowable thick.By slurry ball milling 10h；Then slurry is dried, two-phase oxygen is obtained then at 1100 DEG C of calcining 5h
Compound powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 6.4mL cm in 900 DEG C of Hydrogen Separation rates-2min-1。
Embodiment 11
(1) preparation of membrane material：It is 40wt%Ce with solid phase method one-pot synthesis chemical expression0.75Gd0.25O1.87-
60wt%La0.5Sr0.5Cr0.5Fe0.5O3Membrane material, specific method is：In the ratio mixed phase shown in more than chemical expression
Answer CeO2、Gd2O3、La2O3、Cr2O3、SrCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add in suitable
Ethyl alcohol is measured, is become flowable thick.By slurry ball milling 10h；Then slurry is dried, is obtained then at 1200 DEG C of calcining 5h
To two-phase oxide powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 2.5mL cm in 900 DEG C of Hydrogen Separation rates-2min-1。
Embodiment 12
(1) preparation of membrane material：It is 75wt%Ce with solid phase method one-pot synthesis chemical expression0.85Sm0.15O1.925-
25wt%Sm0.6Sr0.4Al0.3Fe0.7O3Membrane material, specific method is：In the ratio mixed phase shown in more than chemical expression
Answer CeO2、Sm2O3、Al2O3、SrCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add in ethanol in proper amount,
It becomes flowable thick.By slurry ball milling 10h；Then slurry is dried, two-phase is obtained then at 1000 DEG C of calcining 5h
Oxide powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.Its XRD is tied
Fruit is as shown in Figure 6.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 4.0mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 13
(1) preparation of membrane material：It is 80wt%Ce with solid phase method one-pot synthesis chemical expression0.8Sm0.2O1.9- 20wt%
La0.5Sr0.5Ga0.3Fe0.7O3Membrane material, specific method is：CeO is answered in the ratio mixed phase shown in more than chemical expression2、
Sm2O3、La2O3、Ga2O3、SrCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add in ethanol in proper amount,
It becomes flowable thick.By slurry ball milling 10h；Then slurry is dried, two-phase is obtained then at 1100 DEG C of calcining 5h
Oxide powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 4.8mL cm in 900 DEG C of Hydrogen Separation rates-2min-1。
Embodiment 14
(1) preparation of membrane material：It is 60wt%Ce with solid phase method one-pot synthesis chemical expression0.95Sm0.05O1.97-
40wt%Nb0.3Sr0.7Ga0.3Fe0.7O3Membrane material, specific method is：In the ratio mixed phase shown in more than chemical expression
Answer CeO2、Sm2O3、Ga2O3、SrCO3、Nb2O3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add in suitable
Ethyl alcohol is measured, is become flowable thick.By slurry ball milling 10h；Then slurry is dried, is obtained then at 1200 DEG C of calcining 5h
To two-phase oxide powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 5.0mL cm in 900 DEG C of Hydrogen Separation rates-2min-1。
Embodiment 15
(1) preparation of membrane material：It is 70wt%Ce with solid phase method one-pot synthesis chemical expression0.8Y0.2O1.9- 30wt%
Sm0.5Sr0.5Ti0.3Fe0.7O3Membrane material, specific method is：CeO is answered in the ratio mixed phase shown in more than chemical expression2、
Y2O3、Sm2O3、TiO2、SrCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add in ethanol in proper amount, make
It becomes flowable thick.By slurry ball milling 10h；Then slurry is dried, two-phase oxygen is obtained then at 1200 DEG C of calcining 5h
Compound powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 5.8mL cm in 900 DEG C of Hydrogen Separation rates-2min-1, stability is good in the test of about 200h
It is good.
Embodiment 16
(1) preparation of membrane material：It is 60wt%Ce with solid phase method one-pot synthesis chemical expression0.85Gd0.15O1.925-
40wt%Sm0.7Ba0.3Mn0.4Fe0.6O3Membrane material, specific method is：In the ratio mixed phase shown in more than chemical expression
Answer CeO2、Gd2O3、Sm2O3、TiO2、Mn2O3、BaCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add
Enter ethanol in proper amount, become flowable thick.By slurry ball milling 10h；Then slurry is dried, then at 1200 DEG C of calcinings
5h obtains two-phase oxide powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 5.0mL cm in 900 DEG C of Hydrogen Separation rates-2min-1。
Embodiment 17
(1) preparation of membrane material：It is 65wt%Ce with solid phase method one-pot synthesis chemical expression0.85Sm0.15O1.925-
35wt%Sm0.4Sr0.6Ga0.1Cr0.3Fe0.6O3Membrane material, specific method is：It is mixed in the ratio shown in more than chemical expression
Close corresponding CeO2、Sm2O3、Ga2O3、Cr2O3、SrCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder, and add
Enter ethanol in proper amount, become flowable thick.By slurry ball milling 10h；Then slurry is dried, then at 1200 DEG C of calcinings
5h obtains two-phase oxide powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 7.2mL cm in 900 DEG C of Hydrogen Separation rates-2min-1。
Embodiment 18
(1) preparation of membrane material：It is 60wt%Ce with solid phase method one-pot synthesis chemical expression0.85Gd0.15O1.925-
40wt%Sm0.6Sr0.4Ti0.1Cr0.3Fe0.6O3Membrane material, specific method is：It is mixed in the ratio shown in more than chemical expression
Close corresponding CeO2、Gd2O3、Sm2O3、TiO2、Cr2O3、SrCO3、Fe2O3, obtain mixed powder.Then put it into ball grinder,
And ethanol in proper amount is added in, it becomes flowable thick.By slurry ball milling 10h；Then slurry is dried, then at 1200 DEG C
Calcining 5h obtains two-phase oxide powder.
(2) film is prepared by above-mentioned material：Pressure of the gained powder in 200~400MPa is pushed into sheetmolding, it then will pressure
Good raw cook is polished into the film of 0.5mm thickness to get desired biphase ceramics film after 1400~1500 DEG C are sintered 5h.
(3) water decomposition prepares high-purity hydrogen：Water decomposition catalyst is coated in film both sides, being then sealed in hydrogen with Ag circles separates
Membrane reactor reaches 4.2mL cm in 900 DEG C of Hydrogen Separation rates-2min-1。
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 (10)
1. a kind of method for preparing high-purity hydrogen, is separated with membrane reactor, which is characterized in that the film in the membrane reactor
The material preparation of structure and composition as shown in following expression：X wt%Ce1-yLnyO2-y/2- (100-x) wt% (Lm1- zBz)1-aMO3；20≤x≤80 in formula, 0.05≤y≤0.5,0 ＜ z ＜ 1,0≤a≤0.3；Wherein Lm and Ln are separately selected
From at least one of lanthanide series and Y；B is selected from least one of Ca, Ba, Sr, Pb, Bi；M be selected from Al, Cr, Mg, Mn,
At least one of Ni, Fe, Ga and Ti.
2. according to the method described in claim 1, it is characterized in that, in the structure and composition expression formula of separation membrane material, 40
≤ x≤80,0.05≤y≤0.3,0.1≤z≤0.9.
3. according to the method described in claim 2, it is characterized in that, in the structure and composition expression formula of separation membrane material, 0≤
a≤0.2。
4. according to the method described in claim 1, it is characterized in that, in the structure and composition expression formula of separation membrane material, B is selected
From at least one of Ba, Sr and Ca.
5. according to the method described in claim 1, it is characterized in that, in the structure and composition expression formula of separation membrane material, M is selected
From at least one of Al, Cr, Mg, Mn, Fe, Ga and Ti.
6. according to the method described in claim 1, it is characterized in that, in the structure and composition expression formula of separation membrane material, Lm
With Ln separately one kind in Sm, Y, Pr, La and Gd.
7. according to the method described in claim 1, it is characterized in that, the membrane material prepared includes at least one in following substance
Kind：
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
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.6Sr0.4Cr0.3Fe0.7O3
60wt%Ce0.9Y0.1O1.95- 40wt%Pr0.7Ca0.3Cr0.3Fe0.7O3
40wt%Ce0.75Gd0.25O1.87- 60wt%La0.5Sr0.5Cr0.5Fe0.5O3
75wt%Ce0.85Sm0.15O1.925- 25wt%Sm0.6Sr0.4Al0.3Fe0.7O3
80wt%Ce0.8Sm0.2O1.9- 20wt%La0.5Sr0.5Ga0.3Fe0.7O3
60wt%Ce0.95Sm0.05O1.97- 40wt%Nb0.3Sr0.7Ga0.3Fe0.7O3
70wt%Ce0.8Y0.2O1.9- 30wt%Sm0.5Sr0.5Ti0.3Fe0.7O3
60wt%Ce0.85Gd0.15O1.925- 40wt%Sm0.7Ba0.3Mn0.4Fe0.6O3
65wt%Ce0.85Sm0.15O1.925- 35wt%Sm0.4Sr0.6Ga0.1Cr0.3Fe0.6O3
60wt%Ce0.85Gd0.15O1.925- 40wt%Sm0.6Sr0.4Ti0.1Cr0.3Fe0.6O3。
8. according to the method described in claim 1, it is characterized in that, the high-purity hydrogen for preparing refers to at oxygen-permeable membrane reactor
The product of reason water decomposition obtains high-purity hydrogen.
9. according to the method described in claim 8, it is characterized in that, concrete operation step is：There to be the expression formula structure
Film forming is prepared through tabletting, sintering with the material of composition, water decomposition catalyst is coated in the both sides of film, is sealed against in membrane reactor
In, the one side of film is passed through vapor, and opposite side by the use of the hydrogen of low-purity as purge gass, decompose the oxonium ion generated and penetrate by water side
Film, the low-purity hydrogen with purging gas side react, and promote the water decomposition reaction of reaction side, and enable the hydrogen point of reaction side
From acquisition high-purity hydrogen.
10. according to the method described in claim 9, it is characterized in that, the material with the expression formula structure and composition uses
Coprecipitation or solid phase method one-pot synthesis.
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