CN105080359B - Preparing method for ceramic hollow fiber oxygen permeating membrane bundle - Google Patents
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Abstract
The invention belongs to the technical field of ion ceramic membranes, and particularly relates to a preparing method for a ceramic hollow fiber oxygen permeating membrane bundle. The adopted technical route for performing, bundling and sintering ceramic hollow fiber membranes includes the steps that precursors of the ceramic hollow fiber membranes are prepared by applying a dry-wet spinning method, and oxygen permeating membranes in a fixed hollow fiber shape and with certain strength are obtained through high-temperature sintering; polymer sol containing a perovskite mixed conductor ceramic powder material is prepared, and the multiple preformed ceramic hollow fiber membranes are bonded into one through a mold, bundled, solidified and formed; the bundled ceramic hollow fiber membranes are sintered at high temperature by adopting programmed temperature rising to obtain the ceramic hollow fiber oxygen permeating membrane bundle finally. The prepared ceramic hollow fiber oxygen permeating membrane bundle is high in strength and can be assembled into a ceramic oxygen permeating membrane assembly conveniently, and the oxygen permeating quantity is remarkably larger than that of a single hollow fiber membrane. The preparing method is simple in technology and convenient for industrial production and dispenses with complex equipment.
Description
Technical field
The invention belongs to cation ceramic technical field of membrane, and in particular to the preparation of perovskite ceramics doughnut oxygen flow perineurium
With integrated intensifying method.
Background technology
Making oxygen by air separation is all of great significance in environmental protection and industrial production, at present mainly by cryogenic rectification come real
It is existing, it is with high costs.Although pressure swing adsorption method or organic embrane method can be used to separate the oxygen and nitrogen in air, but can not be obtained pure
Oxygen.In recent years, the research in terms of inorganic ceramic oxygen permeation membrane makes great progress.This based ceramic film can conduct simultaneously oxygen from
Son and electronics, when the both sides of film have oxygen concentration gradient, under 600 ~ 1100 DEG C of hot conditions, oxygen molecule is in the side of film
Surface dissociation into oxonium ion and electronics, oxonium ion and electronics under the motive force effect of concentration difference jointly through the film after, in film
Another side surface recombinate to form oxygen and discharge, therefore, oxygen can be in the case of no electrode and external circuit from height
Concentration side reaches the side of low concentration through film, forms the oxygen stream of stabilization.Due to this inoranic membrane ceramic electrolyte material
Oxonium ion is only allowed to pass through, thus with 100% oxygen selective penetrated property energy.Compared with organic film, inoranic membrane has much longer making
With the life-span, and more stringent operating environment can be undergone.
The chip or plate type ceramic oxygen permeation membrane used mostly in current laboratory research are not appropriate in actual production should
With, on the one hand, the membrane area very little that it is provided in unit volume, thus oxygen transmission area and surface exchange area are all limited,
On the other hand, chip or plate type ceramic film thickness can not be too thin, and otherwise film-strength does not reach production requirement, additionally, elevated-temperature seal
Connection and ceramic membrane between is also very scabrous problem.Comparatively tubular ceramic membrane is then easier to solve film-strength, height
Temperature sealing and the problem of connection, but the membrane area provided in unit volume is still limited, furthermore tubular membrane is too thick thus can not carry
For enough oxygen penetrations.The hollow fiber ceramic membrane prepared by inversion of phases-sintering technology has a kind of unsymmetric structure, i.e., whole
Body hollow-fibre membrane is made up of dense separation layers and porous support layer.Such a unsymmetric structure is very suitable for oxygen flow
Film, because：（1）Integral membrane can be thicker to provide enough film-strengths；（2）Can be by controlling middle compacted zone
Thickness be effective film and reduce the ion transport resistance of film；（3）Porous layer near film surface can be greatly improved
The area of film surface exchange reaction.Therefore, compared with common ceramic membrane, this asymmetric hollow fiber membrane is expected to be obtained with big
Many oxygen penetrations.Additionally, the membrane structure of doughnut has maximum membrane area/volume ratio, and can effectively overcome elevated-temperature seal
Limitation.
However, ceramic hollow fibrous membrane is because caliber is small, low intensity, and ceramic material is essential frangible, it is difficult to be assembled into
Membrane module, limits its industrial applications.The present invention takes boundling intensifying method for the shortcoming of ceramic hollow fibrous membrane,
Sintered with boundling by the way that ceramic hollow fibrous membrane is preforming, ceramic hollow fibrous membrane beam is obtained.Obtained Ceramic Hollow Fiber
Not only intensity is high for perineurium, is easy to be assembled into ceramic oxygen-permeable membrane component, and oxygen penetration is significantly higher than the saturating of single hollow-fibre membrane
Amount.
The content of the invention
It is an object of the invention to provide a kind of ceramic hollow fibrous membrane intensity and unit area oxygen flow speed of can improving
The preparation method of Ceramic Hollow Fiber oxygen permeation membrane.
The preparation method of the Ceramic Hollow Fiber oxygen permeation membrane that the present invention is provided, using identical with ceramic oxygen-permeable membrane material property
Or excellent catalysis and the sintering character of close oxonium ion-electronics mixed conducting perovskite ceramics electrolyte powder, by single pottery
Porcelain hollow-fibre membrane boundling is combined into hollow fiber membrane bundle, so as to both improve ceramic hollow fibrous membrane intensity, hollow fibre is improved again
Tie up the oxygen flow speed of film unit area.What is prepared concretely comprises the following steps：
（1）Using dry/wet spin processes, ceramic hollow fibrous membrane presoma is prepared；By 800 DEG C ~ 1400 DEG C high temperature sinterings,
Obtain the preforming Ceramic Hollow Fiber oxygen permeation membrane with fixed hollow fibre shape and some strength；
（2）The polymer sol containing perovskite mixing conductor ceramic powder material is prepared, it is preforming by many by mould
Ceramic hollow fibrous membrane be bonded to one, boundling curing molding；Then hollow fiber membrane bundle is taken out and is dried；Here it is so-called many
The quantity of root is decided according to the actual requirements, and generally can be 3-15 roots, preferably 4-10 roots；
（3）Using temperature programming, the ceramic hollow fibrous membrane after boundling is carried out into high temperature sintering, obtain ceramic hollow fine
Dimension oxygen permeation membrane boundling.
Step（1）In, the high temperature sintering temperature is 800 DEG C ~ 1400 DEG C, is made organic in ceramic hollow fibrous membrane presoma
Thing is removed completely, preforming Ceramic Hollow Fiber oxygen permeation membrane is turned into porous or fine and close hollow fiber ceramic membrane, its machinery
Intensity reaches 50 MPa ~ 150 MPa.
Step（2）In, the polymer sol is that to be dispersed in polymer by perovskite mixing conductor ceramic powder molten
It is obtained in liquid, wherein each component share by weight is calculated as：
Ceramics powder body of perovskite：20~50；
Organic polymer：5~30；
Solvent: 35~70.
Wherein, described ceramics powder body of perovskite is that a kind of oxonium ion with perovskite crystal phase structure-electronics mixing is passed
Lead superfine ceramic electrolyte, including A1-xA’xB1-yB’yO3-δ（A=La, Ba, Sm, Pr; A’=Sr, Bi; B=Fe,
Co, Cu, Ca; B’=Fe, Mn, Ga, Ti, Y, Zn Mo, Ta）; ACe1-xM’xO3-δ (A=Sr, Ba; M'= Ti,
Er, Y, Tm, Yb, Tb, Lu, Nd, Sm, Dy, Sr, Hf, Th, Ta, Nb, Pb) etc., wherein x, y is A ',
The element composition of B ' or M ', and 0≤x≤1,0≤y≤1, δ is Lacking oxygen molar fraction in perovskite ceramics material.
Described organic polymer is polysulfones, polyether sulfone, PEI, polyvinyl alcohol or polyvinyl butyral.
Described solvent is 1-METHYLPYRROLIDONE, N,N-dimethylformamide, N, and N- dimethylacetamides ammonia, dimethyl are sub-
Sulfone or ethanol, or two of which mixture.
Step（2）In, the boundling curing molding is that the preforming Ceramic Hollow Fiber oxygen permeation membrane that will need boundling is placed
In mould, keep having certain space between hollow-fibre membrane, then ceramic powder containing perovskite mixing conductor will be prepared
The polymer sol of material is added in mould, colloidal sol is uniformly filled into the gap of hollow-fibre membrane, is finally immersed in water-bath
Make its curing molding.The mould can be circular or square etc..
Step（3）In, the ceramic hollow fibrous membrane after boundling is carried out high temperature sintering by the use temperature programming, be
High temperature sintering is carried out in air or oxygen-enriched air with programmed temperature method in high-temperature electric resistance furnace, specifically with the intensification speed of 2 ~ 5 DEG C/min
Degree is heated slowly to 600 ~ 800 DEG C, sinters 30 ~ 60min to remove organic matter；It is heated to the programming rate of 1 ~ 3 DEG C/min again
1100 ~ 1500 DEG C, sinter 2 ~ 6 hours, room temperature is finally dropped to the cooling rate of 2 ~ 5 DEG C/min, that is, obtain Ceramic Hollow Fiber
Oxygen permeation membrane boundling.
The ceramic hollow fibrous membrane boundling preparation method that the present invention is provided, without complex device, and technological operation is simple, just
In industrialized production.
Brief description of the drawings
Fig. 1 is that embodiment 1 prepares La0.6Sr0.4Co0.2Fe0.8O3-δHollow fiber membrane bundle photo.Wherein, A is apparent figure, B
It is the sectional view of perineurium.
Fig. 2 is integrated 4 La0.6Sr0.4Co0.2Fe0.8O3-δThe oxygen penetration of hollow fiber membrane bundle and the ratio of single membrance permeability amount
Compared with.
Fig. 3 is integrated 10 Ba0.5Sr0.5Co0.4Fe0.6O3-δCeramic Hollow Fiber oxygen flow perineurium photo.Wherein, A is table
Figure is seen, B is the sectional view of hollow fiber bundle.
Specific embodiment
The present invention is further discussed below with reference to embodiment.But embodiments of the present invention not limited to this, it is impossible to be interpreted as
Limiting the scope of the invention.
Embodiment 1：Prepare La0.6Sr0.4Co0.2Fe0.8O3-δHollow fiber membrane bundle
With 1-METHYLPYRROLIDONE solvent (NMP) as solvent, polysulfones（PSf）It is polymeric binder, polyethylene arsenic coughs up alkane
Ketone（PVP）For dispersant prepares La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF) casting solution, prepares LSCF and makes pottery using dry/wet spinning silk method
Porcelain doughnut film precursor, the presoma is sintered under 1280 DEG C of air high temperatures, obtains the preforming LSCF ceramics of densification
Hollow-fibre membrane, it is 126 MPa to determine hollow-fibre membrane mechanical strength using three-point bending method.
Prepare Ba0.5Sr0.5Co0.4Fe0.6O3-δ(BSCF) ceramics polymer colloidal sol：Weigh 5g polyvinyl butyrals（PVB）,
It is dissolved in 40g ethanol, BSCF powder 15g, the h of strong stirring 5 is added until completely dissolved, obtains uniform and stable ceramics and gather
Compound colloidal sol, its weight percent constitutes and is：BSCF：PVB：Ethanol=25：8.33：66.67.
4 preforming LSCF doughnut oxygen permeation membranes are placed in semicircle earthenware, hollow-fibre membrane two twines
Around fine rule, make have certain space between hollow-fibre membrane.The above-mentioned BSCF polymer sols for preparing are poured into mould, is revolved
Turning hollow fiber membrane bundle makes colloidal sol uniformly be filled into the gap of hollow-fibre membrane.Will be filled with the hollow-fibre membrane of polymer sol
Make its curing molding in immersion water-bath.
LSCF hollow fiber membrane bundles after curing molding are taken out and is dried, be then placed in high-temperature electric resistance furnace, by following burning
Knot program carries out high temperature sintering in atmosphere：600 DEG C are heated slowly to the programming rate of 2 DEG C/min, stopping 60min and removing has
Machine thing, then 1250 DEG C are heated to the programming rate of 1 DEG C/min, 6 hours are incubated, finally dropped to the cooling rate of 2 DEG C/min
Room temperature, that is, obtain LSCF doughnut oxygen flow perineuriums, as shown in Figure 1.
Respectively composition film oxygen flow in alundum tube is sealed in by single LSCF doughnuts and containing 4 LSCF hollow fiber membrane bundles
Component, with air as unstripped gas, helium is the oxygen penetration that purge gass determine hollow-fibre membrane and hollow fiber bundle, as a result such as Fig. 2
It is shown.It can be seen that, single hollow-fibre membrane and 4 oxygen permeabilities of LSCF hollow fiber membrane bundles are all raised and increased with temperature
Plus, and in whole temperature range, the oxygen permeability of hollow fiber membrane bundle will be higher than the Oxygen permeation of single hollow-fibre membrane
Rate, such as at 950 DEG C, the oxygen permeability of hollow fiber membrane bundle is 1.57 mL (STP)/cm2Min, and single hollow-fibre membrane
Oxygen permeability there was only 0.88 mL (STP)/cm2·min。
Embodiment 2：Prepare La0.6Sr0.4Co0.2Fe0.8O3-δHollow fiber membrane bundle
The LSCF doughnuts precursor that embodiment 1 is spinned is sintered under 1050 DEG C of air high temperatures, obtains porous
The preforming hollow-fibre membranes of LSCF, its mechanical strength be 55 MPa.
Weigh 10g polyether sulfones（PESf）, it is dissolved in 50g dimethyl sulfoxide solvents, LSCF powder is added until completely dissolved
Body 15g, the h of strong stirring 8 obtain uniform and stable LSCF ceramics polymer colloidal sols.It is with the polymer sol that 6 LSCF are hollow
Fiber oxygen permeation membrane boundling, solidification, are put into high-temperature electric resistance furnace after drying, and high temperature burning is carried out in atmosphere by following sintering procedure
Knot：800 DEG C are heated slowly to the programming rate of 3 DEG C/min, 30min are stopped and is removed organic matter, then with the intensification speed of 3 DEG C/min
Degree is heated to 1350 DEG C, is incubated 4 hours, finally drops to room temperature with the cooling rate of 3 DEG C/min, that is, obtain LSCF doughnuts saturating
Oxygen perineurium.
Operation sequence according to example 1 is applied tests the oxygen permeability of hollow fiber bundle, obtains the hollow fiber membrane bundle at 950 DEG C
Oxygen permeability be 1.79 mL (STP)/cm2·min。
Embodiment 3：Prepare Ba0.5Sr0.5Co0.4Fe0.6O3-δHollow fiber membrane bundle
With 1-METHYLPYRROLIDONE solvent (NMP) as solvent, polyether sulfone（PESf）It is polymeric binder, polyethylene arsenic is coughed up
Alkanone（PVP）For dispersant prepares Ba0.5Sr0.5Co0.4Fe0.6O3-δ(BSCF) casting solution, BSCF is prepared using dry/wet spinning silk method
Ceramic hollow fibrous membrane presoma, the presoma is sintered under 1200 DEG C of air high temperatures, obtains fine and close BSCF ceramic hollows fine
Dimension film, it is 86 MPa to determine hollow-fibre membrane mechanical strength using three-point bending method.
Weigh 5g PEIs（PEI）, it is dissolved in 30g DMF solvents, add until completely dissolved
Enter BSCF powder 12g, the h of strong stirring 5, obtain uniform and stable BSCF ceramics polymer colloidal sols.With the polymer sol by 10
Root BSCF doughnut oxygen permeation membranes boundling, solidification, are put into high-temperature electric resistance furnace after drying, and are entered in atmosphere by following sintering procedure
Row high temperature sintering：600 DEG C are heated slowly to the programming rate of 5 DEG C/min, 30min are stopped and is removed organic matter, then with 2 DEG C/min
Programming rate be heated to 1300 DEG C, be incubated 4 hours, room temperature is finally dropped to the cooling rate of 3 DEG C/min, that is, in obtaining BSCF
Hollow fiber oxygen flow perineurium, as shown in Figure 3.
Test the oxygen permeability of single BSCF doughnuts and 10 BSCF hollow fiber bundles respectively at 900 DEG C, obtain
The oxygen permeability of hollow fiber membrane bundle is 3.34 mL (STP)/cm2Min, and the oxygen permeability of single BSCF hollow-fibre membranes
Only 2.68 mL (STP)/cm2·min。
Embodiment 4 prepares Ba0.5Sr0.5Co0.4Fe0.6O3-δHollow fiber membrane bundle
Preforming Ba used0.5Sr0.5Co0.4Fe0.6O3-δHollow-fibre membrane is that BSCF prepared by above-described embodiment 3 is hollow
Fiber.
With N, N- dimethylacetamides ammonia is solvent, and the process according to embodiment 1 ~ 3 prepares Sm0.5Sr0.5CoO3-δ
（SSC）- polyvinyl alcohol colloidal sol, its weight percent constitutes and is, SSC：Polyvinyl alcohol：N, N- dimethylacetamide ammonia=35：20：45.
With the polymer sol by 8 BSCF doughnut oxygen permeation membranes boundlings, solidification, being put into after drying in high-temperature electric resistance furnace carries out high temperature burning
Knot：700 DEG C are heated to the programming rate of 3 DEG C/min, 45min are stopped and is removed organic matter, then added with the programming rate of 1 DEG C/min
Heat is incubated 3 hours to 1200 DEG C, finally drops to room temperature with the cooling rate of 2 DEG C/min, that is, obtain BSCF doughnut oxygen permeation membranes
Beam.The oxygen permeability of the BSCF hollow fiber membrane bundles at 900 DEG C is 3.51 mL (STP)/cm2·min。
Embodiment 5 prepares La0.4Ca0.6FeO3-δHollow fiber membrane bundle
With N, N- dimethylacetamides ammonia is solvent, polyether sulfone（PESf）It is polymeric binder, polyvinyl pyrrolidone
（PVP）For dispersant prepares La0.4Ca0.6FeO3-δ(LCF) casting solution, LCF Ceramic Hollow Fibers are prepared using dry/wet spinning silk method
Film precursor, the presoma is sintered under 1380 DEG C of air high temperatures, obtains fine and close LCF ceramic hollow fibrous membranes, and its machinery is strong
It is 140 MPa to spend.
With ethanol as solvent, the process according to embodiment 2 prepares BCe0.6Ti0.4O3-δ(BCT)-polyvinyl butyral
(PVB) colloidal sol, its weight percent constitutes and is, BCT：PVB：Ethanol=25：25：50.With the polymer sol by 6 hollow fibres of LCF
Dimension oxygen permeation membrane boundling, solidification, being put into after drying in high-temperature electric resistance furnace carries out high temperature sintering：It is heated to the programming rate of 5 DEG C/min
800 DEG C, stop 60min and remove organic matter, then 1500 DEG C are heated to the programming rate of 2 DEG C/min, 4 hours are incubated, finally with 5
DEG C/cooling rate of min drops to room temperature, that is, obtain LCF doughnut oxygen flow perineuriums.The LCF hollow fiber membrane bundles are at 950 DEG C
Oxygen permeability be 1.89 mL (STP)/cm2Min, and oxygen permeability of the single LCF hollow-fibre membranes at 950 DEG C is
1.31 mL(STP)/cm2·min。
Embodiment 6 prepares La0.4Ca0.6FeO3-δHollow fiber membrane bundle
The LCF doughnuts precursor that above-described embodiment 5 is spinned is sintered under 1100 DEG C of air high temperatures, obtains many
The preforming hollow-fibre membranes of LCF in hole, its mechanical strength is 89 MPa.
With 1-METHYLPYRROLIDONE (NMP) solvent, the process according to embodiment 1 ~ 4 is prepared
Ba0.5Sr0.5Co0.4Fe0.6O3-δ(BSCF)-polyether sulfone (PESf) colloidal sol, its weight percent constitutes and is, BSCF：PESf：NMP=
20：30：50.With the polymer sol by 8 LCF doughnut oxygen permeation membranes boundlings, solidification, it is put into high-temperature electric resistance furnace to enter after drying
Row high temperature sintering：600 DEG C are heated to the programming rate of 2 DEG C/min, 30min are stopped and is removed organic matter, then with the liter of 3 DEG C/min
Warm speed is heated to 1200 DEG C, is incubated 6 hours, finally drops to room temperature with the cooling rate of 3 DEG C/min, that is, obtain the hollow fibres of LCF
Dimension oxygen flow perineurium.The oxygen permeability of the LCF hollow fiber membrane bundles at 950 DEG C is 2.16 mL (STP)/cm2·min。
Embodiment 7 prepares La0.7Sr0.3FeO3-δHollow fiber membrane bundle
With 1-METHYLPYRROLIDONE solvent (NMP) as solvent, polysulfones（PSf）It is polymeric binder, polyethylene arsenic coughs up alkane
Ketone（PVP）For dispersant prepares La0.7Sr0.3FeO3-δ(LSF) casting solution, LSF ceramic hollows fibre is prepared using dry/wet spinning silk method
Dimension film precursor, the presoma is sintered under 1380 DEG C of air high temperatures, obtains the preforming LSF Ceramic Hollow Fibers of densification
Film, its mechanical strength is 113 MPa.
With 1-METHYLPYRROLIDONE (NMP) solvent, the process according to embodiment 1 ~ 4 prepares La0.6Sr0.4CoO3-δ
(LSC)-polyether sulfone (PESf) colloidal sol, its weight percent constitutes and is, LSC：PESf：NMP=20：5：75.Use the polymer sol
By 8 LSF doughnut oxygen permeation membranes boundlings, solidification, being put into after drying in high-temperature electric resistance furnace carries out high temperature sintering：With 2 DEG C/min's
Programming rate is heated to 650 DEG C, stops 45min and removes organic matter, then is heated to 1320 DEG C with the programming rate of 2 DEG C/min, protects
Temperature 5 hours, finally drops to room temperature with the cooling rate of 3 DEG C/min, that is, obtain LSF doughnut oxygen flow perineuriums.The hollow fibres of the LSF
Oxygen permeability of the dimension perineurium at 950 DEG C is 1.13 mL (STP)/cm2·min。
Embodiment 8 prepares La0.7Sr0.3FeO3-δHollow fiber membrane bundle
Preforming La used0.7Sr0.3FeO3-δDoughnut is the LSF hollow-fibre membranes prepared by above-described embodiment 7.
With ethanol as solvent, the process according to embodiment 2 prepares Ba0.7Bi0.3Cu0.8Zn0.2O3-δ(BBCZ)-poly-
Butyral (PVB) colloidal sol, its weight percent constitutes and is, BBCZ：PVB：Ethanol=15：30：55.With the polymer sol by 8
Root LSF doughnut oxygen permeation membranes boundling, solidification, being put into after drying in high-temperature electric resistance furnace carries out high temperature sintering：With the intensification of 2 DEG C/min
Speed is heated to 600 DEG C, stops 60min and removes organic matter, then is heated to 1500 DEG C with the programming rate of 1 DEG C/min, and insulation 4 is small
When, room temperature is finally dropped to the cooling rate of 3 DEG C/min, that is, obtain LSF doughnut oxygen flow perineuriums.The LSF hollow-fibre membranes
Oxygen permeability of the beam at 950 DEG C is 1.99 mL (STP)/cm2·min。
Embodiment 9：Prepare La0.6Sr0.4Co0.2Fe0.8O3-δHollow fiber membrane bundle
Preforming La used0.6Sr0.4Co0.2Fe0.8O3-δDoughnut is the LSF doughnuts prepared by embodiment 1
Film.
With dimethyl sulfoxide (DMSO) as solvent, the process according to embodiment 1 prepares Pr0.6Sr0.4Fe0.3Mn0.7O3-δ
（PSFM）- polyether sulfone（PESf）Colloidal sol, its weight percent constitutes and is, PSFM：PESf：Dimethyl sulfoxide (DMSO)=22：25：53.With this
Be put into high-temperature electric resistance furnace, after drying by following sintering for 6 LSCF doughnut oxygen permeation membranes boundlings, solidification by polymer sol
Program carries out high temperature sintering in atmosphere：600 DEG C are heated slowly to the programming rate of 2 DEG C/min, 30min removings is stopped organic
Thing, then 1400 DEG C are heated to the programming rate of 3 DEG C/min, 4 hours are incubated, room is finally dropped to the cooling rate of 3 DEG C/min
Temperature, obtains LSCF doughnut oxygen flow perineuriums.The oxygen permeability of the LSCF hollow fiber membrane bundles at 950 DEG C is 1.69 mL
(STP)/cm2·min。
Claims (4)
1. the preparation method of Ceramic Hollow Fiber oxygen flow perineurium, it is characterised in that concretely comprise the following steps：
（1）Using dry/wet spin processes, ceramic hollow fibrous membrane presoma is prepared；By 800 DEG C ~ 1400 DEG C high temperature sinterings, obtain
Preforming Ceramic Hollow Fiber oxygen permeation membrane with fixed hollow fibre shape and some strength；
（2）The polymer sol containing perovskite mixing conductor ceramic powder material is prepared, by mould by many preforming potteries
Porcelain hollow-fibre membrane is bonded to one, boundling curing molding；Then hollow fiber membrane bundle is taken out and is dried；
（3）Using temperature programming, the ceramic hollow fibrous membrane after boundling is carried out into high temperature sintering, obtain Ceramic Hollow Fiber oxygen flow
Film boundling；
Step（2）Described in boundling curing molding, be that the preforming Ceramic Hollow Fiber oxygen permeation membrane that will need boundling is placed on mould
In tool, keep having certain space between hollow-fibre membrane, then ceramic powder material containing perovskite mixing conductor will be prepared
Polymer sol add mould, colloidal sol is uniformly filled into the gap of hollow-fibre membrane, being finally immersed in water-bath makes it
Curing molding；
Step（3）Described in using temperature programming, the ceramic hollow fibrous membrane after boundling is carried out into high temperature sintering, be in high-temperature electric
In stove, under air or oxygen-enriched air atmosphere, 600 ~ 800 DEG C are heated slowly to the programming rate of 2 ~ 5 DEG C/min, sintering 30 ~
60min, to remove organic matter；1100 ~ 1500 DEG C are heated to the programming rate of 1 ~ 3 DEG C/min, sinter 2 ~ 6 hours, finally again
Room temperature is dropped to the cooling rate of 2 ~ 5 DEG C/min, that is, obtains Ceramic Hollow Fiber oxygen permeation membrane boundling；
Step（2）In, the polymer sol by perovskite mixing conductor ceramic powder it is dispersed in a polymer solution and
It is obtained, wherein each component share by weight is calculated as：
Ceramics powder body of perovskite：20~50；
Organic polymer：5~30；
Solvent: 35~70.
2. the preparation method of Ceramic Hollow Fiber oxygen flow perineurium according to claim 1, it is characterised in that described calcium titanium
Ore deposit ceramic powder is a kind of oxonium ion with perovskite crystal phase structure-electronics mixed conducting superfine ceramic electrolyte, choosing
From：
A1-xA’xB1-yB’yO3-δ, wherein, A=La, Ba, Sm, Pr； A’=Sr, Bi； B=Fe, Co, Cu, Ca； B’=
Fe, Mn, Ga, Ti, Y, Zn Mo, Ta；
ACe1-xM’xO3-δ, wherein, A=Sr, Ba；M'= Ti, Er, Y, Tm, Yb, Tb, Lu, Nd, Sm, Dy, Sr,
Hf, Th, Ta, Nb, Pb；
Wherein x, y are that the element of A ', B ' or M ' is constituted, and 0≤x≤1, and 0≤y≤1, δ is oxygen in perovskite ceramics material
Room molar fraction.
3. the preparation method of Ceramic Hollow Fiber oxygen flow perineurium according to claim 1, it is characterised in that described is organic
Polymer is polysulfones, polyether sulfone, PEI, polyvinyl alcohol or polyvinyl butyral.
4. the preparation method of Ceramic Hollow Fiber oxygen flow perineurium according to claim 1, it is characterised in that described solvent
It is 1-METHYLPYRROLIDONE, DMF, N, N- dimethylacetamides ammonia, dimethyl sulfoxide (DMSO) or ethanol, or its
In two kinds of mixture.
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| US6139810A (en) * | 1998-06-03 | 2000-10-31 | Praxair Technology, Inc. | Tube and shell reactor with oxygen selective ion transport ceramic reaction tubes |
| CN100361730C (en) * | 2005-01-14 | 2008-01-16 | 山东理工大学 | Ceramic hollow fiber membrane reactor for making oxygen by air separation, and its preparing method and use |
| CN100553751C (en) * | 2007-08-13 | 2009-10-28 | 南京九思高科技有限公司 | A kind of hollow fiber ceramic membrane element and assembly thereof |
| CN101284215B (en) * | 2008-06-03 | 2011-06-15 | 华南理工大学 | Preparation method of perovskite hollow fiber membrane |
| EP2536673A1 (en) * | 2010-02-17 | 2012-12-26 | The University of Queensland | Method of manufacture for hollow fibre ceramic membrane |
| CN102895886B (en) * | 2012-10-22 | 2015-03-04 | 天津工业大学 | Hollow fiber ceramic oxygen permeation membrane with dual composite asymmetric structure and preparation method thereof |
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