CN102671552B - Method for preparing tubular asymmetrical mixed conductor compact film - Google Patents
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- CN102671552B CN102671552B CN201210137396.5A CN201210137396A CN102671552B CN 102671552 B CN102671552 B CN 102671552B CN 201210137396 A CN201210137396 A CN 201210137396A CN 102671552 B CN102671552 B CN 102671552B
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- 239000011533 mixed conductor Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 25
- 239000000463 material Substances 0.000 claims abstract description 67
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 238000005507 spraying Methods 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000007921 spray Substances 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 230000007547 defect Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 235000021323 fish oil Nutrition 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000000462 isostatic pressing Methods 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
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- 238000010438 heat treatment Methods 0.000 abstract description 11
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 53
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- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
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- 238000012512 characterization method Methods 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 3
- 235000012489 doughnuts Nutrition 0.000 description 3
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- 238000005245 sintering Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 101150058765 BACE1 gene Proteins 0.000 description 1
- 229910002136 La0.6Sr0.4Co0.8Fe0.2O3−δ Inorganic materials 0.000 description 1
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Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a tubular asymmetrical mixed conductor compact film and a preparation method thereof. The preparation method comprises the following steps: rotating a tubular support body along an axis; spraying a mixed conductor material on the surface of the support body along the axis of the support body; and performing joint heat treatment to obtain the tubular asymmetrical mixed conductor compact film. The preparation method is simple, high in repeatability and suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of tubular type inoranic membrane, particularly relate to the preparation method of the asymmetric mixed conductor dense film of a kind of tubular type.
Background technology
Mixed conductor dense film, owing to having huge application prospect in gas separaion and petrochemical industry, has become the study hotspot in the fields such as current material and chemical industry.For mixed conductor dense film material, the key realizing industrial applications is to improve permeation flux, solve the problem such as the stability of film, the elevated-temperature seal of assembly.Scholars unanimously thinks that reduction thicknesses of layers not only can improve the permeation flux of film, effectively can also solve the stability problem of material simultaneously.But along with the reduction of thickness, the mechanical strength of film decreases, the commercial Application of film also becomes difficulty.Generally believe if the thickness of film is less than 150 μm, film just needs to support, to ensure its enough mechanical strength.Tubular membrane has larger membrane area compared with chip film simultaneously, and membrane module is easy to sealing, and therefore, the non-exploitation to type mixed conductor dense film of tubular type is the focus that scholars pays close attention to always.
The mainly dip-coating method of the asymmetric mixed conductor dense film of current tubular type, (Kawahara et al., Ind.Eng.Chem.Res., 2010 such as Kawahara, 49,5511) adopt dip-coating method on tubular type supporter, prepared the thick La of one deck 60 μm
0.6sr
0.4ti
0.3fe
0.7o
3dense film.Patent CN200810225603 discloses a kind of preparation method of tubular support dense oxide film, the mode of lift plated film is adopted to prepare one deck dense oxide film on perforated tubular ceramic supporting body, although obtain good penetrability and the high tubular type support membrane reaction tube of mechanical performance, but prepared rete is thicker, and not easily prepare the long-tube support membrane of uniform film thickness.
Adopt dip-coating method to prepare tubular type anisotropic membrane, the longer wall cling phenomenon occurred in the process of masking of supporter is more serious, thus causes the uneven thickness of film, and upper terminal membrane is thin, lower end thickness.It is easy that this technique prepares short tubular type anisotropic membrane, but if the long membrane module of preparation industrialization can run into a lot of problem, as thickness is uneven, existing defects, is difficult to densification, repeatability etc.And the asymmetric mixed conductor dense film preparation method of tubular type is the rete applying mixed conductor material on the supporter sintered at present, but because the sintering shrinkage performance between rete and supporter is not mated, cause the interface cohesion place between rete and supporter to be easily peeling the problem such as not fine and close with separation membrane layer.The present invention proposes the preparation method of the asymmetric mixed conductor dense film of a kind of new tubular type.
Summary of the invention
The object of the invention is the preparation method providing the asymmetric mixed conductor dense film of a kind of tubular type in order to improve the deficiencies in the prior art, the method by spraying rete on the tubular type supporter green compact of spinning, then by supporter and the common heat treatment of rete, prepare and there is fine and close zero defect and the asymmetric mixed conductor dense film of tubular type of the ultra-thin film layers of uniform film thickness (<50 μm).
Technical scheme of the present invention is: the preparation method of the asymmetric mixed conductor dense film of a kind of tubular type, and concrete steps are as follows:
A prepares mixed conductor material powder;
Mixed conductor material powder obtained in step a mixes with pore-creating additive by b, and wherein pore-creating additive quality accounts for 0 ~ 30% of mixed powder gross mass; Then mixed powder is made tubular type supporter green compact;
C is mixed with spraying suspension by mixed conductor material, solvent and dispersant, wherein suspension composition and ratio to be mass concentration be 55 ~ 98.5% solvent, mass concentration be 0.5 ~ 30% mixed conductor material and mass concentration be the dispersant of 1 ~ 15%; Above-mentioned mass concentration obtains for benchmark with the quality of suspension total amount;
D will be placed under environment temperature is 50 ~ 300 ° of C environment with the tubular type supporter of the rotating speed automatic rotation of 60 ~ 300r/min, prolong supporter axial direction with spray gun with 6 ~ 300cm/min speed to move, the tubular type supporter green surface that the suspension spray prepared by above-mentioned steps c is prepared to step b;
E is dry by spray coated supporter, roasting, cooling, the obtained asymmetric mixed conductor dense film of tubular type.
The average grain diameter of the mixed conductor material powder granule described in preferred steps a is 0.2 ~ 100 μm; The internal diameter of the tubular type supporter green compact described in step b is 1 ~ 30mm, and thickness is 0.5 ~ 5mm.
Preferably above-mentioned mixed conductor material is ion-electron mixed conductor material or proton-electron mixed conductor material; Wherein preferably described ion-electron mixed conductor material is Ca-Ti ore type, K
2niF
4type or Brownmillerite type; Preferred proton-electron mixed conductor material is Ca-Ti ore type; Wherein the general formula of Ca-Ti ore type mixed conductor material is A
1-xa '
xb
1-y-zb '
yb "
zo
3-δwherein: A, A ' be any one element in La, Nd, Sm, Ca, Sr, Ba or Na, B, B ', B " be any one element in Co, Fe, Mn, Cr, Ni, Cu, Ga, Mg, Ce, Al, Zr, Y, Pr, Th, In or V; 0≤x≤1; 0≤y≤1; 0≤z≤1, δ is oxygen lattice defect number.
In preferred above-mentioned steps a the preparation method of mixed conductor material be high-temperature solid phase reaction method, citric acid method, improvement citric acid method or improve citric acid and combine one in complexometry with EDTA.Concrete preparation method is see document (Tan et al., J.Membr.Sci., 2003,212,157; Tsai et al., J.Am.Ceram.Soc., 1998,81,1437).
Wherein in step b, the preparation method of tubular type supporter is the one in wire-cut process, isostatic pressing method or phase inversion.
Mixed conductor material wherein in step b and step c in supporter and suspension can be same material or non-same material, and preparation method can be identical or different.
Adding pore-creating additive in preferred steps b tubular type supporter preparation process is one or more in starch, graphite, methylcellulose, active carbon or polypropylene; Solvent in preferred steps c is the mixture of one or more of water, ethanol, ethylene glycol, isopropyl alcohol, n-butanol or normal octane; Dispersant is the mixture of one or more in glycerine, Tween-80, fish oil, neopelex or tristerin.
In preferred steps c, hybrid mode is mechanical ball milling or ultrasonic dispersion.; In preferred steps d, supporter environment temperature reaches requirement by the heating of Resistant heating case or infrared heating lamp.
In preferred steps d, the distance of shower nozzle and supporter is 5 ~ 20cm.The natural drying in atmosphere of supporter in preferred steps e, or under 50 ~ 70 ° of C dry 1 ~ 2h; 2 ~ 5h is incubated, then with programming rate to 1100 ~ 1400 of 0.5 ~ 5 ° of C/min ° C roasting 1 ~ 5h with programming rate to 400 ~ 600 of 1 ~ 5 ° of C/min ° C; Again with the cooling rate of 0.5 ~ 5 ° of C/min to room temperature.
According to rete requirement to be prepared, suspension spray can be repeated spraying to tubular type supporter green surface, spraying number of times is generally 2 ~ 100 times, and general obtained thicknesses of layers is 5 ~ 50 μm.
The support body layer pore structure of the asymmetric mixed conductor dense film of the tubular type that the present invention prepares is homogeneous pore structure, graded pore structure or doughnut structure.
Beneficial effect:
1, the present invention only can prepare thicknesses of layers by spraying method and is less than 50 μm and the asymmetric mixed conductor dense film of the uniform tubular type of thickness.
2, the present invention by directly preparing mixed conductor rete on the tubular type supporter green compact for sintering, obtaining the asymmetric dense film of tubular type, solve a rete compactness difficult problem through common heat treatment process.
3, preparation method of the present invention is simple, reproducible, is applicable to prepare mixed conductor dense film on the tubular type supporter of Different Pore Structures, different size, is convenient to scale and amplifies.
4, prepare the applicable scope of the asymmetric mixed conductor dense film of the tubular type with Different Pore Structures in the present invention wide, practical value is remarkable.
Accompanying drawing explanation
Fig. 1 is SrCo
0.4fe
0.5zr
0.1o
3-δthe Electronic Speculum figure of the asymmetric dense film section of tubular type.
Fig. 2 is SrCo
0.4fe
0.5zr
0.1o
3-δthe Electronic Speculum figure on compact film surface.
Fig. 3 is SrCo
0.4fe
0.5zr
0.1o
3-δthe Electronic Speculum figure of open support surface.
Detailed description of the invention
Embodiment 1
Supporter and rete are all Ca-Ti ore type SrCo
0.4fe
0.5zr
0.1o
3-δion-electron mixed conductor material.Support body material adopts high temperature solid-state method synthesis, and its grain diameter is 80 μm, adopts wire-cut process to be prepared into the tubular type supporter green compact that internal diameter is 1mm, thickness is 0.75mm, wherein containing pore creating material active carbon 15wt%; Film material employing improvement citric acid is combined complexometry and is prepared with EDTA, its grain diameter is 10 μm, is then moved in 31.57g ethanol by 3.96g film material, then adds 0.17g Tween-80 and 0.30g glycerine as dispersant, be uniformly dispersed under ultrasound condition, obtain suspension; Supporter green compact being positioned over environment temperature is in 150 ° of C Resistant heating casees, allow it rotate with the rotating speed of 200r/min, spray gun, apart from supporter 20cm, prolongs supporter axial direction with 300cm/min speed and moves, and by suspension spray supporting body surface, spray 10 times; Supporter after spraying is taken out and is placed in still air natural drying 2h, 2.5h is incubated again with the programming rate to 400 of 2 ° of C/min ° C, then with the programming rate to 1250 of 0.5 ° of C/min ° C roasting 2h, again with the cooling rate of 2 ° of C/min to room temperature, obtain the tubular type asymmetric Ca-Ti ore type ion-electron mixed conductor membrane that supporter and rete are same material.The microstructure of tubular type anisotropic membrane is characterized by SEM (SEM), result shows, interface cohesion between supporter and rete is good, thickness 20 μm, uniform film thickness, supporter presents homogeneous pore structure (as shown in Figure 1), and the fine and close zero defect (as shown in Figure 2) of film surface, supporter has loose structure (as shown in Figure 3).
Embodiment 2
Supporter is Brownmillerite type Ca
2feAlO
5ion-electron mixed conductor material, rete is all Ca-Ti ore type La
0.6sr
0.4co
0.8fe
0.2o
3-δion-electron mixed conductor material.Support body material adopts and improves citric acid method synthesis, its grain diameter is 60 μm, adopt wire-cut process to be prepared into the tubular type supporter green compact that internal diameter is 30mm, thickness is 5mm, wherein containing pore creating material 30wt%, pore creating material is mixed according to mass ratio 1:1 by graphite and methylcellulose; Film material adopts equally and improves citric acid method preparation, its grain diameter is 20 μm, is then moved into by 14g film material in the mixed solution of 18.60g isopropyl alcohol and 7.20g ethylene glycol, then adds 6.862g fish oil as dispersant, be uniformly dispersed with mechanical ball milling, obtain suspension; Under supporter green compact are positioned over infrared heating lamp, environment temperature is 200 ° of C, allows it rotate with the rotating speed of 300r/min, spray gun is apart from supporter 12cm, prolong supporter axial direction with 60cm/min speed to move, and by suspension spray supporting body surface, spray 25 times; Supporter after spraying is taken out and is placed in dry 1.5h under 50 ° of C, 2h is incubated again with the programming rate to 450 of 1.5 ° of C/min ° C, then with the programming rate to 1300 of 1.5 ° of C/min ° C roasting 4h, again with the cooling rate of 5 ° of C/min to room temperature, obtain the tubular type asymmetric Ca-Ti ore type ion-electron mixed conductor membrane that supporter and rete are not same material.Show through Microstructure characterization, the interface cohesion between supporter and rete is good, thickness 40 μm, uniform film thickness, and supporter presents graded pore structure, and the fine and close zero defect of film surface, supporter has loose structure.
Embodiment 3
Supporter is Ca-Ti ore type La
0.6sr
0.4ga
0.3fe
0.65al
0.05o
3-δion-electron mixed conductor material, rete is all K
2niF
4type La
2niO
4+ δion-electron mixed conductor material.Support body material adopts high-temperature solid phase reaction method synthesis, its grain diameter is 100 μm, adopt isostatic pressing method to be prepared into the tubular type supporter green compact that internal diameter is 18mm, thickness is 2.5mm, wherein containing pore creating material 20wt%, pore creating material is mixed according to mass ratio 1:2 by starch and polypropylene; Film material adopts citric acid method preparation, and its grain diameter is 5 μm, is then moved in 28.7g normal octane by 4.2g film material, then adds 2.1g tristerin as dispersant, is uniformly dispersed, obtains suspension with mechanical ball milling; Supporter green compact being positioned over environment temperature is in 300 ° of C Resistant heating casees, allow it rotate with the rotating speed of 170r/min, spray gun, apart from supporter 5cm, prolongs supporter axial direction with 200cm/min speed and moves, and by suspension spray supporting body surface, spray 2 times; Supporter after spraying is taken out and is placed in dry 2h under 65 ° of C, 4h is incubated again with the programming rate to 500 of 5 ° of C/min ° C, then with the programming rate to 1100 of 3 ° of C/min ° C roasting 5h, again with the cooling rate of 3 ° of C/min to room temperature, obtain the tubular type asymmetric Ca-Ti ore type ion-electron mixed conductor membrane that supporter and rete are not same material.Show through Microstructure characterization, the interface cohesion between supporter and rete is good, thickness 35 μm, uniform film thickness, and supporter presents graded pore structure, and the fine and close zero defect of film surface, supporter has loose structure.
Embodiment 4
Supporter and rete are all Ca-Ti ore type SrCe
0.95y
0.05o
3-δproton-electron mixed conductor material.Support body material adopts citric acid method synthesis, and its grain diameter is 1.5 μm, adopts phase inversion to be prepared into the tubular type supporter green compact that internal diameter is 1mm, thickness is 0.8mm, wherein containing pore creating material polypropylene 5wt%; Film material improvement citric acid is combined complexometry and is prepared with EDTA, its grain diameter is 0.2 μm, then 0.5g film material is moved in 46.8g isopropyl alcohol and 35.5g n-butanol mixed solution, add 0.8g neopelex again as dispersant, be uniformly dispersed with mechanical ball milling, obtain suspension; Under supporter green compact are positioned over infrared heating lamp, environment temperature is 50 ° of C, allows it rotate with the rotating speed of 100r/min, and spray gun, apart from supporter 8cm, prolongs supporter axial direction with 6cm/min speed and moves, and by suspension spray supporting body surface, spray 50 times; Supporter after spraying is taken out and is placed in dry 1h under 70 ° of C, 3h is incubated again with the programming rate to 600 of 2 ° of C/min ° C, then with the programming rate to 1400 of 5 ° of C/min ° C roasting 1h, again with the cooling rate of 2 ° of C/min to room temperature, obtain the tubular type asymmetric Ca-Ti ore type proton-electron mixed conductor membrane that supporter and rete are same material.Show through Microstructure characterization, the interface cohesion between supporter and rete is good, thickness 10 μm, uniform film thickness, and supporter presents doughnut pore structure, and the fine and close zero defect of film surface, supporter has loose structure.
Embodiment 5
Supporter is Ca-Ti ore type La
0.9ca
0.1crO
3-δproton-electron mixed conductor material, rete is all Ca-Ti ore type BaCe
0.7zr
0.2y
0.1o
3-δproton-electron mixed conductor material.Support body material adopts citric acid method synthesis, and its grain diameter is 20 μm, adopts phase inversion to be prepared into the tubular type supporter green compact that internal diameter is 1.6mm, thickness is 0.5mm, wherein not containing pore creating material; It is 5 μm that film material adopts citric acid method to prepare its grain diameter equally, is then moved in 41.17g water by 0.22g film material, then adds 3.6g fish oil as dispersant, adopts ultrasonic dispersion to mix, obtains suspension; Supporter green compact being positioned over environment temperature is in 160 ° of C Resistant heating casees, allow it rotate with the rotating speed of 60r/min, spray gun, apart from supporter 15cm, prolongs supporter axial direction with 60cm/min speed and moves, and by suspension spray supporting body surface, spray 100 times; Supporter after spraying is taken out and is placed in still air natural drying 2h, 2.5h is incubated again with the programming rate to 500 of 1 ° of C/min ° C, then with the programming rate to 1250 of 2 ° of C/min ° C roasting 4h, again with the cooling rate of 0.5 ° of C/min to room temperature, obtain the tubular type asymmetric Ca-Ti ore type proton-electron mixed conductor membrane that supporter and rete are not same material.Show through Microstructure characterization, the interface cohesion between supporter and rete is good, thickness 25 μm, uniform film thickness, and supporter presents doughnut pore structure, and the fine and close zero defect of film surface, supporter has loose structure.
Claims (8)
1. a preparation method for the asymmetric mixed conductor dense film of tubular type, its concrete steps are as follows:
A prepares mixed conductor material powder;
Mixed conductor material powder obtained in step a mixes with pore-creating additive by b, and wherein pore-creating additive quality accounts for 0 ~ 30% of mixed powder gross mass; Then mixed powder is made tubular type supporter green compact;
C is mixed with spraying suspension by mixed conductor material, solvent and dispersant, wherein suspension composition and ratio to be mass concentration be 55 ~ 98.5% solvent, mass concentration be 0.5 ~ 30% mixed conductor material and mass concentration be the dispersant of 1 ~ 15%; Above-mentioned mass concentration obtains for benchmark with the quality of suspension total amount;
D will be placed under environment temperature is 50 ~ 300 DEG C of environment with the tubular type supporter of the rotating speed automatic rotation of 60 ~ 300r/min, prolong supporter axial direction with spray gun with 6 ~ 300cm/min speed to move, the tubular type supporter green surface that the suspension spray prepared by above-mentioned steps c is prepared to step b;
E is dry by spray coated supporter, roasting, cooling, the obtained asymmetric mixed conductor dense film of tubular type; Wherein said roasting is with programming rate to 400 ~ 600 of 1 ~ 5 DEG C/min DEG C insulation 2 ~ 5h, then with programming rate to 1100 ~ 1400 of 0.5 ~ 5 DEG C/min DEG C roasting 1 ~ 5h; Described being cooled to is lowered the temperature with the cooling rate of 0.5 ~ 5 DEG C/min.
2. preparation method according to claim 1, is characterized in that the average grain diameter of the mixed conductor material powder granule described in step a is 0.2 ~ 100 μm; The internal diameter of the tubular type supporter green compact described in step b is 1 ~ 30mm, and thickness is 0.5 ~ 5mm.
3. preparation method according to claim 1, is characterized in that mixed conductor material is ion-electron mixed conductor material or proton-electron mixed conductor material; Wherein said ion-electron mixed conductor material is Ca-Ti ore type, K
2niF
4type, Brownmillerite type; Proton-electron mixed conductor material is Ca-Ti ore type; Wherein the general formula of Ca-Ti ore type mixed conductor material is A
1-xa '
xb
1-y-zb '
yb "
zo
3-δwherein: A, A ' be any one element in La, Nd, Sm, Ca, Sr, Ba or Na, B, B ', B " be any one element in Co, Fe, Mn, Cr, Ni, Cu, Ga, Mg, Ce, Al, Zr, Y, Pr, Th, In or V; 0≤x≤1; 0≤y≤1; 0≤z≤1, δ is oxygen lattice defect number.
4. preparation method according to claim 1, is characterized in that the preparation method of mixed conductor material in step a is high-temperature solid phase reaction method, citric acid method, improvement citric acid method or improve citric acid and combine one in complexometry with EDTA; In step b, the preparation method of tubular type supporter is the one in wire-cut process, isostatic pressing method or phase inversion.
5. preparation method according to claim 1, is characterized in that the additive described in step b is one or more in starch, graphite, methylcellulose, active carbon or polypropylene.
6. preparation method according to claim 1, the solvent that it is characterized in that in step c is the mixture of one or more of water, ethanol, ethylene glycol, isopropyl alcohol, n-butanol or normal octane; Dispersant is the mixture of one or more in glycerine, Tween-80, fish oil, neopelex or tristerin.
7. preparation method according to claim 1, is characterized in that the distance of shower nozzle and supporter in steps d is 5 ~ 20cm.
8. preparation method according to claim 1, is characterized in that the drying described in step e is supporter natural drying in atmosphere, or at 50 ~ 70 DEG C dry 1 ~ 2h.
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| CN103253982A (en) * | 2013-05-23 | 2013-08-21 | 上海大学 | Preparation method of tubular asymmetric oxygen-permeable membrane |
| CN103768965B (en) * | 2014-01-09 | 2015-12-30 | 南京工业大学 | A kind of preparation method of multichannel mixed conductor hollow-fibre membrane |
| CN109351134A (en) * | 2018-09-07 | 2019-02-19 | 上海大学 | Single phase mixed conductor asymmetric oxygen-permeable membrane and preparation method thereof |
| CN109487299B (en) * | 2018-12-03 | 2020-12-25 | 山西大学 | High-temperature electrolysis of CO2Cathode material of electrolytic cell and preparation method thereof |
| CN110128125A (en) * | 2019-06-27 | 2019-08-16 | 南京工业大学 | A kind of preparation method of anisotropic membrane |
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2012
- 2012-05-04 CN CN201210137396.5A patent/CN102671552B/en active Active
Non-Patent Citations (1)
| Title |
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| Fabrication of SrCo0.4Fe0.5Zr0.1O3-δ asymmetric tubular membrane by a spin-spraying technique;Liu, Zhengkun等;《AIChE Annual Meeting, Conference Proceedings》;20101231;a232/1-a232/5 * |
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