CN106669436B - Without the asymmetric mixed conductor hydrogen permeation membrane of support and preparation and application - Google Patents
Without the asymmetric mixed conductor hydrogen permeation membrane of support and preparation and application Download PDFInfo
- Publication number
- CN106669436B CN106669436B CN201710000593.5A CN201710000593A CN106669436B CN 106669436 B CN106669436 B CN 106669436B CN 201710000593 A CN201710000593 A CN 201710000593A CN 106669436 B CN106669436 B CN 106669436B
- Authority
- CN
- China
- Prior art keywords
- permeation membrane
- hydrogen permeation
- mixed conductor
- oxide
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to separation membrane material technical fields, disclose a kind of without the asymmetric mixed conductor hydrogen permeation membrane of support and preparation and application.The preparation method is that: by metal oxide powder grinding, phase is dried and sintered into, dispersion solvent is then added, is dried after grinding, sieving obtains uniform powder；Phase inversion polymer is uniformly mixed with polymer dispersion solvent, phase inversion polymer solution is made；Gained powder is uniformly mixed with phase inversion polymer solution, slurry is made, it is transferred in mold after froth in vacuum, covers template net, added coagulant to carry out phase conversion reaction and be formed by curing diaphragm, gained diaphragm drying, sintering obtain described without the asymmetric mixed conductor hydrogen permeation membrane of support.The through hydrogen capacity of gained mixed conductor hydrogen permeation membrane of the invention is strong, separative efficiency is high, has a good application prospect.
Description
Technical field
The invention belongs to separation membrane material technical fields, and in particular to it is a kind of without support asymmetric mixed conductor hydrogen permeation membrane and
Preparation and application.
Background technique
Basis of the energy as support social development, the existence and activity with the mankind are closely bound up.In rapid economic development
Today, it is convenient that people have enjoyed scientific and technological progress bring；At the same time, the swift and violent growth of population, cause to the energy according to
Rely and intake is also increasing.The energy such as coal, petroleum are still the main body of energy resource structure at this stage, and the unreasonable energy uses band
Serious environmental pollution is carried out, therefore, the exploitation green high-efficient energy is the developing direction of future source of energy structure.
The one kind of Hydrogen Energy as the green high-efficient energy, compared with all first and second fossil energies, possess energy density it is high,
Water is only generated when utilization, is indispensable component part in future source of energy structure the advantages that without carbon or pollutant emission.Though
Right hydrogen is the most abundant element in the world, but natural hydrogen there are few.Therefore it needs through suitable hydrogen source (hydrogenous material)
Carry out hydrogen making.The most abundant hydrogenous material is water (H in the world2It O), is exactly secondly various fossil fuels and various biomass
Deng.In the long run/term most promising method using water as hydrogen source Electrowinning hydrogen, hydrogen manufacturing purity up to 99.7%, because
Enriched for hydrogen source it is inexhaustible, and hydrogen burning release energy after generate water again, be that the recyclable energy of optimal no pollution is raw
Production and Land use systems.But rely on existing electrolysis water technology, hydrogen manufacturing it is relatively inefficient, energy consumption is larger, therefore electrolysis water
Hydrogen manufacturing is only applicable to electric power resource area abundant, can't be widely popularized.Biomass hydrogen preparation is that nowadays process for making hydrogen develops
Forward position, the alcohol reforming hydrogen productions such as methanol have been the technologies of relative maturity, and hydrogen manufacturing purity is very high, but the expense that catalyst is high
Limit the application of alcohol reforming hydrogen production.Because technique is relatively easy, cost is relatively low, and various fossil fuel hydrogen manufacturing are current industry
The main method of hydrogen manufacturing, steam reformation or partial oxidation hydrogen-preparation account for 80% or more in industrial hydrogen production.Industrial hydrogen production tool
The amount of having the characteristics that is big but purity is not high, it is therefore desirable to separating-purifying is carried out to hydrogen using hydrogen isolation technics, once it solves
The problem of hydrogen isolation technics, fossil fuel industrial hydrogen production will be grown rapidly.
Membrane separation technique is the forward position focus of hydrogen separation field in recent years, since membrane separation technique is compared with other industrial separation skills
Art has many advantages, such as that separative efficiency height, less energy-consuming, equipment are simple and low in cost.Therefore develop membrane separation technique to realization petrochemical industry
The large-scale promotion of fuel industry hydrogen manufacturing and Hydrogen Energy is utilized and is played a key effect.Due to Ca-Ti ore type high-temperature proton-conductor ceramics
Material high temperature is hydrogeneous or steam atmosphere in there is good proton conductive, therefore in hydrogen separation, hydrogen-involved reaction device and solid
The fields such as oxide body fuel cell are concerned.But due to conventional High-temperature proton conductor material be by additional power source come
Regulate and control the separation of hydrogen, this just needs to consume a large amount of electric energy, and separative efficiency is not also high, therefore task is to improve material at present
The electron conduction of itself reduces the consumption of electric energy, while improving the permeated hydrogen amount of film again.
Summary of the invention
In order to solve the disadvantage that the above prior art and shortcoming, the primary purpose of the present invention is that providing a kind of no branch
Support the preparation method of asymmetric mixed conductor hydrogen permeation membrane.
It is led by what the above method was prepared without the asymmetric mixing of support another object of the present invention is to provide a kind of
Body hydrogen permeation membrane.
A further object of the present invention is to provide above-mentioned without supporting asymmetric mixed conductor hydrogen permeation membrane answering in hydrogen separation
With.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method without the asymmetric mixed conductor hydrogen permeation membrane of support, including following preparation step:
(1) metal oxide powder ground, dry and sinter into phase, dispersion solvent is then added, is dried after grinding, mistake
Sieve obtains uniform mixed conductor hydrogen permeation membrane material powder；
(2) phase inversion polymer is uniformly mixed with polymer dispersion solvent and phase inversion polymer solution is made；
(3) phase inversion polymer solution obtained by mixed conductor hydrogen permeation membrane material powder obtained by step (1) and step (2) is mixed
Uniformly slurry is made in conjunction, is transferred in mold after froth in vacuum, covers template net, adds coagulant to carry out phase conversion reaction, makes to starch
Material is formed by curing diaphragm, and gained diaphragm drying, sintering obtain described without the asymmetric mixed conductor hydrogen permeation membrane of support.
Preferably, metal oxide described in step (1) is to refer to synthesize while providing proton conduction and electronics biography
Lead and sinter into several in the metal oxide of phase, including but not limited to iron oxide, barium monoxide, strontium oxide strontia, cobalt oxide, oxygen
Change lanthanum, tungsten oxide, molybdenum oxide, neodymia, nickel oxide, copper oxide, gallium oxide, zirconium oxide, yttrium oxide, bismuth oxide, cerium oxide and
At least two mixing in praseodymium oxide.
Dispersion solvent described in step (1) is the solvent for referring to fine dispersion metal-oxide powder, preferably methanol,
At least one of ethyl alcohol, isopropanol, propyl alcohol, acetone, butanone；The additional amount of dispersion solvent make the content 30 of institute's dispersion~
60wt%.
It is ground described in step (1) preferably with ball mill grinding, drum's speed of rotation is 100~600r/min, milling time
For 2~48h.
Drying temperature described in step (1) is preferably 20~80 DEG C；The sintering temperature is preferably 200~1500 DEG C, is burnt
Tie the time be 10~for 24 hours；The sieving is having a size of 100~1000 mesh.
Phase inversion polymer described in step (2) is the polymer that phase conversion reaction can occur, preferably polyacrylonitrile, poly-
At least one of vinylpyrrolidone, Poly-s 179；The polymer dispersion solvent is can be uniform by phase inversion polymer
The solvent of dispersion, preferably N-Methyl pyrrolidone or n-vinyl pyrrolidone；Inversion of phases in the phase inversion polymer solution
The content of polymer is 30~60wt%.
Preferably, the solid content of slurry described in step (3) is 30~80wt%.
The template net is the metal mesh not reacted with slurry, preferably stainless (steel) wire, nickel screen, titanium net or copper mesh.
The coagulant is the substance that phase conversion reaction can occur with phase inversion polymer, preferably N- crassitude
Ketone, methanol, ethyl alcohol, acetone, deionized water or tap water.
The phase conversion reaction time is preferably 1~48h.
Drying described in step (3) is preferably in 60~150 DEG C of 1~48h of drying.
Sintering described in step (3) preferably 500~1300 DEG C be pre-sintered 5~for 24 hours, then in 1000~1700 DEG C of height
Temperature sintering 5~for 24 hours.
It is a kind of to be prepared without asymmetric mixed conductor hydrogen permeation membrane is supported by the above method, it is described asymmetric without supporting
Mixed conductor hydrogen permeation membrane has the unsymmetric structure of the porous side densification in side.
The above-mentioned application without the asymmetric mixed conductor hydrogen permeation membrane of support in hydrogen separation, concrete application process are as follows: will be without branch
It supports asymmetric mixed conductor hydrogen permeation membrane to be sealed in separator, the hydrogen in unstripped gas is made to reach the another of film through film transmission
The separation of hydrogen is realized in side.
The principle of the present invention are as follows: phase inversion polymer solution and mixed conductor hydrogen permeation membrane material powder are mixed to form slurry,
Phase conversion reaction occurs for slurry and coagulant.When phase conversion reaction occurs, phase inversion polymer and coagulant are immiscible, but
Phase inversion polymer dispersion solvent mixes with coagulant.The difference of intermiscibility causes polymer dispersion solvent from phase inversion polymer
Middle precipitation is dissolved in coagulant, and polymer reunion solidification, and forms porous structure, the phase on surface layer under the action of template
Conversion reaction schematic diagram is as shown in Figure 1.Cured slurry is sintered again and is formed a film, polymer removes during the sintering process, obtains one
Side has the asymmetric mixed conductor hydrogen permeation membrane of porous structure other side densification.Mixed conductor hydrogen permeation membrane with compacted zone guarantees
There is theoretic 100% selectivity to hydrogen.On the other hand, which has bigger specific surface
The separative efficiency of hydrogen can be improved in product.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) through hydrogen capacity of asymmetric mixed conductor hydrogen permeation membrane is strong, separative efficiency is high without supporting for present invention gained, and can be with
The relative thickness of porous layer and compacted zone is correspondingly adjusted according to separation demand；
(2) of the invention preparation method is simple, low in cost, strong applicability, can large-scale industrial production.
Detailed description of the invention
Fig. 1 is phase conversion reaction schematic diagram of the present invention；
Fig. 2 is 1 gained of embodiment without the porous layer surface scan electron microscope for supporting asymmetric mixed conductor hydrogen permeation membrane；
Fig. 3 is 1 gained of embodiment without the cross-sectional scans electron microscope for supporting asymmetric mixed conductor hydrogen permeation membrane；
Fig. 4 is the cross-sectional scans electron microscope of 2 gained mixed conductor hydrogen permeation membrane of comparative example.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) lanthana, tungsten oxide, molybdenum oxide are stoichiometrically measured, make the atomic ratio 6:0.5 of La:W:Mo:
0.5, acetone is added, is ground for 24 hours under the revolving speed of 200r/min using ball mill, is dried in air dry oven with 40 DEG C, so
It is sintered for 24 hours under conditions of 800 DEG C afterwards, sinters mixed-metal oxides into single-phase；Third is added into the powder for sinter into phase
Ketone makes powder content 50wt%.12h is ground under the revolving speed of 300r/min using ball mill, with 40 in air dry oven
DEG C drying, cross 400 meshes obtain uniform mixed conductor hydrogen permeation membrane material powder；
(2) Poly-s 179 is mixed with N-Methyl pyrrolidone, it is poly- that the inversion of phases that Poly-s 179 content is 30wt% is made
Polymer solution；
(3) phase inversion polymer solution obtained by mixed conductor hydrogen permeation membrane material powder obtained by step (1) and step (2) is mixed
It closes, is ground for 24 hours under the revolving speed of 200r/min using ball mill, it is 50wt% slurry that solid content, which is made, by ground slurry
De-bubble 2h is vacuumized, is then transferred in mold, nickel screen is covered, adds deionized water to carry out 36h phase conversion reaction, makes slurry curing
It forms diaphragm and shows porous structure；After the completion of phase conversion reaction, diaphragm is transferred to baking oven in 120 DEG C of drying 12h, then
800 DEG C of pre-sintering 12h, finally in 1500 DEG C of high temperature sintering 12h, obtain the present embodiment without supporting the asymmetric saturating hydrogen of mixed conductor
Film.
The porous layer surface and cross-sectional scans electron microscope without the asymmetric mixed conductor hydrogen permeation membrane of support that the present embodiment obtains
It is as shown in Figures 2 and 3 respectively.The present embodiment without supporting asymmetric mixed conductor hydrogen permeation membrane it can be seen from Fig. 2 and Fig. 3
Bore dia is about 30~70 μm, and asymmetric diaphragm integral thickness about 1mm, hole depth is about 800 μm.
The application without the asymmetric mixed conductor hydrogen permeation membrane of support in hydrogen separation of the present embodiment: will be above-mentioned non-right without supporting
Claim mixed conductor hydrogen permeation membrane to be fixed on gas separation to set, through hydrogen capacity 0.15mL/mincm2。
Embodiment 2
(1) lanthana, tungsten oxide, molybdenum oxide are stoichiometrically measured, make the atomic ratio 6:0.5 of La:W:Mo:
0.5, acetone is added, 8h is ground under the revolving speed of 600r/min using ball mill, is dried in air dry oven with 40 DEG C, then
It is sintered 10h under conditions of 1200 DEG C, sinters mixed-metal oxides into single-phase；Third is added into the powder for sinter into phase
Ketone makes powder content 30wt%.12h is ground under the revolving speed of 300r/min using ball mill, with 40 in air dry oven
DEG C drying, cross 400 meshes obtain uniform mixed conductor hydrogen permeation membrane material powder；
(2) Poly-s 179 is mixed with N-Methyl pyrrolidone, it is poly- that the inversion of phases that Poly-s 179 content is 30wt% is made
Polymer solution；
(3) phase inversion polymer solution obtained by mixed conductor hydrogen permeation membrane material powder obtained by step (1) and step (2) is mixed
It closes, 8h is ground under the revolving speed of 600r/min using ball mill, it is 70wt% slurry that solid content, which is made, and ground slurry is taken out
Froth in vacuum 2h, is then transferred in mold, covers stainless (steel) wire, adds ethyl alcohol to carry out 36h phase conversion reaction, makes slurry curing shape
At diaphragm and show porous structure；After the completion of phase conversion reaction, diaphragm is transferred to baking oven in 120 DEG C of drying 12h, then
1300 DEG C of pre-sintering 5h, finally in 1700 DEG C of high temperature sintering 5h, obtain the present embodiment without supporting the asymmetric saturating hydrogen of mixed conductor
Film.
The application without the asymmetric mixed conductor hydrogen permeation membrane of support in hydrogen separation of the present embodiment: will be above-mentioned non-right without supporting
Claim mixed conductor hydrogen permeation membrane to be fixed on gas separation to set, through hydrogen capacity 0.08mL/mincm2。
Embodiment 3
(1) barium monoxide, cerium oxide, iron oxide are stoichiometrically measured, make the atomic ratio 1:0.5 of Ba:Ce:Fe:
0.5, acetone is added, 48h is ground under the revolving speed of 100r/min using ball mill, is dried in air dry oven with 40 DEG C, so
It is sintered for 24 hours under conditions of 500 DEG C afterwards, sinters mixed-metal oxides into single-phase；Third is added into the powder for sinter into phase
Ketone makes powder content 60wt%.It is ground for 24 hours under the revolving speed of 200r/min using ball mill, with 40 in air dry oven
DEG C drying, cross 400 meshes obtain uniform mixed conductor hydrogen permeation membrane material powder；
(2) Poly-s 179 is mixed with N-Methyl pyrrolidone, it is poly- that the inversion of phases that Poly-s 179 content is 30wt% is made
Polymer solution；
(3) phase inversion polymer solution obtained by mixed conductor hydrogen permeation membrane material powder obtained by step (1) and step (2) is mixed
It closes, 48h is ground under the revolving speed of 100r/min using ball mill, it is 50wt% slurry that solid content, which is made, by ground slurry
De-bubble 2h is vacuumized, is then transferred in mold, stainless (steel) wire is covered, adds ethyl alcohol to carry out 36h phase conversion reaction, makes slurry curing
It forms diaphragm and shows porous structure；After the completion of phase conversion reaction, diaphragm is transferred to baking oven in 120 DEG C of drying 12h, then
500 DEG C are pre-sintered for 24 hours, finally 1000 DEG C of high temperature sinterings for 24 hours, obtain the present embodiment without supporting the asymmetric saturating hydrogen of mixed conductor
Film.
The application without the asymmetric mixed conductor hydrogen permeation membrane of support in hydrogen separation of the present embodiment: will be above-mentioned non-right without supporting
Claim mixed conductor hydrogen permeation membrane to be fixed on gas separation to set, through hydrogen capacity 0.12mL/mincm2。
Embodiment 4
(1) lanthana, tungsten oxide, molybdenum oxide are stoichiometrically measured, make the atomic ratio 6:0.5 of La:W:Mo:
0.5, acetone is added, is ground for 24 hours under the revolving speed of 200r/min using ball mill, is dried in air dry oven with 40 DEG C, so
It is sintered for 24 hours under conditions of 800 DEG C afterwards, sinters mixed-metal oxides into single-phase；Second is added into the powder for sinter into phase
Alcohol makes powder content 40wt%.12h is ground under the revolving speed of 300r/min using ball mill, with 40 in air dry oven
DEG C drying, cross 400 meshes obtain uniform mixed conductor hydrogen permeation membrane material powder；
(2) polyvinylpyrrolidone is mixed with n-vinyl pyrrolidone, polyvinyl pyrrolidone content, which is made, is
The phase inversion polymer solution of 30wt%；
(3) phase inversion polymer solution obtained by mixed conductor hydrogen permeation membrane material powder obtained by step (1) and step (2) is mixed
It closes, is ground for 24 hours under the revolving speed of 200r/min using ball mill, it is 30wt% slurry that solid content, which is made, by ground slurry
De-bubble 2h is vacuumized, is then transferred in mold, stainless (steel) wire is covered, N-Methyl pyrrolidone is added to carry out 10h phase conversion reaction,
So that slurry curing is formed diaphragm and shows porous structure；After the completion of phase conversion reaction, diaphragm is transferred to baking oven and is dried at 120 DEG C
Dry 12h, then in 800 DEG C of pre-sintering 12h, finally in 1500 DEG C of high temperature sintering 12h, obtain the asymmetric mixed without supporting of the present embodiment
Close conductor hydrogen permeation membrane.
The application without the asymmetric mixed conductor hydrogen permeation membrane of support in hydrogen separation of the present embodiment: will be above-mentioned non-right without supporting
Claim mixed conductor hydrogen permeation membrane to be fixed on gas separation to set, through hydrogen capacity 0.10mL/mincm2。
Comparative example 1
This comparative example prepares mixed conductor hydrogen permeation membrane using traditional isostatic pressing method, the specific steps are as follows:
Lanthana, tungsten oxide, molybdenum oxide are stoichiometrically measured, the atomic ratio 6:0.5:0.5 of La:W:Mo is made,
Acetone is added, 12h is ground under the revolving speed of 200r/min using ball mill, is dried in air dry oven with 40 DEG C, is then existed
It is sintered under conditions of 800 DEG C for 24 hours, sinters mixed-metal oxides into single-phase；The powder of phase will be sintered under 20MPa pressure
Be pressed into diaphragm, by diaphragm 1500 DEG C of high temperature sinterings for 24 hours, be polishing to obtained with a thickness of 1mm this comparative example mixed conductor it is saturating
Hydrogen film.
The mixed conductor hydrogen permeation membrane of this comparative example is fixed on gas separation to set, through hydrogen capacity 0.01mL/min
cm2。
Comparative example 2
(1) lanthana, tungsten oxide, molybdenum oxide are stoichiometrically measured, make the atomic ratio 6:0.5 of La:W:Mo:
0.5, acetone is added, is ground for 24 hours under the revolving speed of 200r/min using ball mill, is dried in air dry oven with 40 DEG C, so
It is sintered for 24 hours under conditions of 800 DEG C afterwards, sinters mixed-metal oxides into single-phase；Third is added into the powder for sinter into phase
Ketone makes powder content 50wt%.12h is ground under the revolving speed of 300r/min using ball mill, with 40 in air dry oven
DEG C drying, cross 400 meshes obtain uniform mixed conductor hydrogen permeation membrane material powder；
(2) Poly-s 179 is mixed with N-Methyl pyrrolidone, it is poly- that the inversion of phases that Poly-s 179 content is 30wt% is made
Polymer solution；
(3) phase inversion polymer solution obtained by mixed conductor hydrogen permeation membrane material powder obtained by step (1) and step (2) is mixed
It closes, is ground for 24 hours under the revolving speed of 200r/min using ball mill, it is 50wt% slurry that solid content, which is made, by ground slurry
De-bubble 2h is vacuumized, is then transferred in mold, deionized water is added to carry out 36h phase conversion reaction, slurry curing is made to form diaphragm
And show porous structure；After the completion of phase conversion reaction, diaphragm is transferred to baking oven in 120 DEG C of drying 12h, then pre- at 800 DEG C
It is sintered 12h and obtains the mixed conductor hydrogen permeation membrane of this comparative example finally in 1500 DEG C of high temperature sintering 12h.
This comparative example has the mixed conductor hydrogen permeation membrane of porous structure, the difference with embodiment 1 by phase inversion preparation
It is, without covering nickel screen as template during inversion of phases.The cross-sectional scans for the mixed conductor hydrogen permeation membrane that this comparative example obtains
Electron microscope is as shown in figure 4, as seen from Figure 4, porous structure is irregular, diaphragm integral thickness about 1mm, and dense layer thickness is about
400μm。
Application of the saturating hydrogen of the mixed conductor of this comparative example in hydrogen separation: above-mentioned mixed conductor hydrogen permeation membrane is fixed on gas
During separation is set, through hydrogen capacity 0.03mL/mincm2。
The result of embodiment 1, comparative example 1 and the saturating hydrogen of comparative example 2 is compared, the present invention has preferable porous structure
Without supporting asymmetric mixed conductor hydrogen permeation membrane performance to be greatly improved.Under same test condition, permeated hydrogen amount is than symmetrical
Fine and close diaphragm and the irregular asymmetric diaphragm of honeycomb sandwich improve 5 times or more.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of without the preparation method for supporting asymmetric mixed conductor hydrogen permeation membrane, it is characterised in that including following preparation step:
(1) metal oxide powder ground, dry and sinter into phase, dispersion solvent is then added, dries, is sieved after grinding
To uniform mixed conductor hydrogen permeation membrane material powder；
(2) phase inversion polymer is uniformly mixed with polymer dispersion solvent and phase inversion polymer solution is made；
(3) mixed conductor hydrogen permeation membrane material powder obtained by step (1) is mixed with phase inversion polymer solution obtained by step (2)
It is even that slurry is made, it is transferred in mold after froth in vacuum, covers template net, added coagulant to carry out phase conversion reaction, consolidate slurry
Change forms diaphragm, and gained diaphragm drying, sintering obtain described without the asymmetric mixed conductor hydrogen permeation membrane of support；
Template net described in step (3) is stainless (steel) wire, nickel screen, titanium net or copper mesh.
2. according to claim 1 a kind of without the preparation method for supporting asymmetric mixed conductor hydrogen permeation membrane, it is characterised in that:
Metal oxide described in step (1) be iron oxide, barium monoxide, strontium oxide strontia, cobalt oxide, lanthana, tungsten oxide, molybdenum oxide,
In neodymia, nickel oxide, copper oxide, gallium oxide, zirconium oxide, yttrium oxide, bismuth oxide, cerium oxide and praseodymium oxide at least two it is mixed
It closes.
3. according to claim 1 a kind of without the preparation method for supporting asymmetric mixed conductor hydrogen permeation membrane, it is characterised in that:
Dispersion solvent described in step (1) refers at least one of methanol, ethyl alcohol, isopropanol, propyl alcohol, acetone, butanone；Disperse molten
The additional amount of agent makes 30~60wt% of content of institute's dispersion.
4. according to claim 1 a kind of without the preparation method for supporting asymmetric mixed conductor hydrogen permeation membrane, it is characterised in that:
Grinding described in step (1) refers to that with ball mill grinding, drum's speed of rotation is 100~600r/min, and milling time is 2~48h.
5. according to claim 1 a kind of without the preparation method for supporting asymmetric mixed conductor hydrogen permeation membrane, it is characterised in that:
Drying temperature described in step (1) is 20~80 DEG C；The sintering temperature be 200~1500 DEG C, sintering time be 10~for 24 hours；
The sieving is having a size of 100~1000 mesh.
6. according to claim 1 a kind of without the preparation method for supporting asymmetric mixed conductor hydrogen permeation membrane, it is characterised in that:
Phase inversion polymer described in step (2) is at least one of polyacrylonitrile, polyvinylpyrrolidone, Poly-s 179；Institute
The polymer dispersion solvent stated is N-Methyl pyrrolidone or n-vinyl pyrrolidone；Phase in the phase inversion polymer solution
The content for converting polymer is 30~60wt%.
7. according to claim 1 a kind of without the preparation method for supporting asymmetric mixed conductor hydrogen permeation membrane, it is characterised in that:
The solid content of slurry described in step (3) is 30~80wt%；The coagulant be N-Methyl pyrrolidone, methanol, ethyl alcohol,
Acetone, deionized water or tap water.
8. according to claim 1 a kind of without the preparation method for supporting asymmetric mixed conductor hydrogen permeation membrane, it is characterised in that:
The phase conversion reaction time described in step (3) is 1~48h；The drying refers in 60~150 DEG C of 1~48h of drying；It is described
Sintering refer to be pre-sintered 5 at 500~1300 DEG C~for 24 hours, then in 1000~1700 DEG C of high temperature sinterings 5~for 24 hours.
9. a kind of without the asymmetric mixed conductor hydrogen permeation membrane of support, it is characterised in that: by according to any one of claims 1 to 8
Method is prepared, described without the unsymmetric structure for supporting asymmetric mixed conductor hydrogen permeation membrane to have the porous side densification in side.
10. the application as claimed in claim 9 without the asymmetric mixed conductor hydrogen permeation membrane of support in hydrogen separation, it is characterised in that tool
Body application process are as follows: the hydrogen in unstripped gas will be made to penetrate without supporting asymmetric mixed conductor hydrogen permeation membrane to be sealed in separator
Film transmission reaches the other side of film, realizes the separation of hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710000593.5A CN106669436B (en) | 2017-01-03 | 2017-01-03 | Without the asymmetric mixed conductor hydrogen permeation membrane of support and preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710000593.5A CN106669436B (en) | 2017-01-03 | 2017-01-03 | Without the asymmetric mixed conductor hydrogen permeation membrane of support and preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106669436A CN106669436A (en) | 2017-05-17 |
| CN106669436B true CN106669436B (en) | 2019-05-14 |
Family
ID=58850050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710000593.5A Active CN106669436B (en) | 2017-01-03 | 2017-01-03 | Without the asymmetric mixed conductor hydrogen permeation membrane of support and preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106669436B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534818B (en) * | 2017-09-22 | 2021-06-04 | 萍乡市普天高科实业有限公司 | Porous ceramic membrane preparation mold and method |
| JP6691247B1 (en) * | 2019-01-22 | 2020-04-28 | 東京瓦斯株式会社 | Reactor and fuel cell power generation system |
| CN112892228B (en) * | 2019-11-19 | 2022-07-19 | 中国科学院大连化学物理研究所 | Ni-Zr supported by porous Ni tube for hydrogen production1-xMxO2-x/2Film and method for producing same |
| CN114870648B (en) * | 2022-05-17 | 2023-07-18 | 华南理工大学 | Mixed conductor hydrogen permeable membrane material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657501A (en) * | 2005-01-06 | 2005-08-24 | 北京交通大学 | Micronporous ceramic plate and its preparation method |
| CN103638826A (en) * | 2013-12-26 | 2014-03-19 | 中国科学技术大学 | Asymmetrical ceramic separation membrane and preparation method thereof |
-
2017
- 2017-01-03 CN CN201710000593.5A patent/CN106669436B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657501A (en) * | 2005-01-06 | 2005-08-24 | 北京交通大学 | Micronporous ceramic plate and its preparation method |
| CN103638826A (en) * | 2013-12-26 | 2014-03-19 | 中国科学技术大学 | Asymmetrical ceramic separation membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106669436A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106669436B (en) | Without the asymmetric mixed conductor hydrogen permeation membrane of support and preparation and application | |
| KR100648144B1 (en) | High performance anode-supported solide oxide fuel cell | |
| RU2403655C9 (en) | Parent material infiltration and coating process | |
| JP5391391B2 (en) | Method for producing NiO-ceramic composite powder | |
| CA2398711C (en) | Method of fabricating an assembly comprising an anode-supported electrolyte, and ceramic cell comprising such an assembly | |
| CN108461759B (en) | Method for preparing nano composite cathode material of solid oxide fuel cell by impregnation method | |
| CN112436171B (en) | Solid electrolyte support body and preparation method and application thereof | |
| Liu et al. | Fabrication and characterization of a co-fired La0. 6Sr0. 4Co0. 2Fe0. 8O3− δ cathode-supported Ce0. 9Gd0. 1O1. 95 thin-film for IT-SOFCs | |
| CN109888305A (en) | Dipping solution is improved to the method for solid oxide fuel cell porous cathode skeleton wetability | |
| CN109836154A (en) | A kind of method that low-temperature sintering densifies cerium oxide base separation layer in fuel cell | |
| CN101307461B (en) | Method for preparing YSZ-LSM oxygen electrode powder of solid oxidate electrolytic cell | |
| CN114890787A (en) | Oxygen electrode supporting type solid oxide electrolytic cell and preparation method thereof | |
| CN113506905A (en) | Proton conduction type half cell, proton conduction type solid oxide cell, and preparation method and application thereof | |
| CN101222050A (en) | Anti-carbon deposition anode film material and method for producing the same | |
| Xin et al. | Fabrication of dense YSZ electrolyte membranes by a modified dry-pressing using nanocrystalline powders | |
| CN109216740A (en) | A kind of anode support and preparation method thereof of hollow symmetrical SOFC battery | |
| CN115064707B (en) | Multiphase composite anode material based on SFMO nanofiber skeleton and preparation method thereof | |
| CN103253982A (en) | Preparation method of tubular asymmetric oxygen-permeable membrane | |
| CN116178020A (en) | Ceramic connector material of solid oxide fuel cell and preparation method thereof | |
| CN109351134A (en) | Single phase mixed conductor asymmetric oxygen-permeable membrane and preparation method thereof | |
| CN114520356B (en) | Proton conductor type reversible solid oxide battery co-fired at one step at low temperature and preparation method thereof | |
| CN111276705B (en) | Preparation method of metal-supported oxide fuel cell half cell | |
| CN107994234A (en) | Ceramic fuel cell and preparation method thereof | |
| CN101585703B (en) | Preparation method of asymmetrical ceramic hydrogen permeation membrane | |
| KR101335063B1 (en) | Method of large powewr solid oxide fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |