CN101456744B - Method for preparing honeycomb type ceramic film - Google Patents
Method for preparing honeycomb type ceramic film Download PDFInfo
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- CN101456744B CN101456744B CN2008102495361A CN200810249536A CN101456744B CN 101456744 B CN101456744 B CN 101456744B CN 2008102495361 A CN2008102495361 A CN 2008102495361A CN 200810249536 A CN200810249536 A CN 200810249536A CN 101456744 B CN101456744 B CN 101456744B
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Abstract
The invention discloses a method for preparing a honeycomb type ceramic membrane. The preparation process comprises the steps of preparing a ceramic-polymer solution, preparing a ceramic-polymer membrane casting solution, preparing a honeycomb type tubular ceramic membrane blank; and preparing a honeycomb type tubular ceramic membrane. A special honeycomb type mold which is formed through bush fitting sequentially by an inner core tube, a middle bushing and an outer bushing from inside to outside is adopted to obtain the honeycomb type tubular ceramic membrane for only one time, and has a nonsymmetrical structure of a porous supporting layer, transition layers and effective separation layers. The honeycomb type tubular ceramic membrane is equivalent to integrating a plurality of ceramic hollow fibrous membranes with nonsymmetrical structures into a bundle, so the honeycomb type tubular ceramic membrane has the advantages of the ceramic hollow fibrous membranes with the nonsymmetrical structures, also successfully solves the problem of easy brittle fracture of the ceramic hollow fibrous membranes, and is easier to assemble into a membrane module and a membrane separation system. The honeycomb type tubular ceramic membrane has the characteristics of large unit volume membrane area (500-9,000m<2>/m<3>), high strength (200-1,200MPa), easy sealing and so on.
Description
Technical field
The invention belongs to the ceramic membrane technical field, be specifically related to a kind of preparation method of honeycomb type ceramic film.
Background technology
Inorganic ceramic membrane be by metal oxide or mixed-metal oxides powder through the high technology ceramics material that high temperature sintering forms with certain Selective Separation performance, have good stability, can be high temperature resistant, acidproof, alkaline-resisting, resistance to oxidation, organic solvent-resistant; Mechanical strength is big, and withstand voltage good wearability is good; Pore-size distribution is narrow, and separation accuracy is high; Be prone to advantages such as cleaning easily; Can be used for that gas separates, fluid separation applications purifies and membrane reactor, food industry (like the clarification removal of impurities of plant extraction liquid, the clarification filtration of Juice, dairy products and concentrating; Extract the pectin beverage in the apple residue; Soybean, tealeaves deep processing etc.), (like the aseptic filtration of zymotic fluid, thalline concentrates, and albumen, pigment remove for pharmacy and bioengineering; Traditional Chinese medicine extraction substitutes alcohol precipitation process; Liquid glucose removal of impurities, product purification), chemistry and petrochemical industry industry is (like the separating of high temperature, high pressure, dicyandiamide solution, purifying and make with extra care; The product of uncatalyzed reaction system separates with catalyst; The production of superfine catalyst and nano-powder) and environmental protection (handle and reuse like oily waste water; The recovery of ultrafine particle in the waste water) etc. the field all is widely used.
Ceramic membrane generally has the unsymmetric structure of porous support layer, transition zone and separating layer, and it at first is to make porous supporting body through forming and sintering, obtains transition zone through membrane pore structure and finishing again, makes effective separating layer through distinct methods at last.It is thus clear that, the complex manufacturing of inoranic membrane, the production cycle is long, cost is expensive, moreover ceramic membrane fragility is big, these shortcomings again big limitations its practical application.Want the large-scale application ceramic membrane, must simplify preparation technology on the one hand, reduce the production cost of ceramic membrane, need improve effective film area in the unit volume on the other hand, improve the utilization ratio of membrane material.
In the last few years, we had developed inversion of phases/sintering process by means of the technology of preparing of organic hollow tunica fibrosa and had prepared the ceramic hollow fibrous membrane method, and had successfully made multiple ceramic hollow fibrous membrane (Xiaoyao Tan; Shaomin Liu; K.Li, Preparation and Characterization of Inorganic Hollow Fibre Membranes, J.MembraneSci.; 188:87-95,2001; Tan Xiaoyao, Meng Bo, Yang Naitao. " asymmetrical solid oxide fuel battery and preparation method thereof ", Chinese invention patent ZL03143242.5,2006; Tan Xiaoyao; Meng Bo; Yang Naitao, " being used for ceramic hollow fibrous membrane reactor and the method for making and the application of making oxygen by air separation ", Chinese invention patent ZL200510042334.6,2007).
The remarkable advantage of this ceramic hollow fibrous membrane is embodied in:
1) porous support layer of film and fine and close thin layer are to process in a step, and technology is simple, does not need expensive device, is suitable for large-scale industrial production;
2) porous layer and fine and close thin layer are commaterials, and structural behaviour is stable;
3) hollow fiber film structure has maximum membrane area/volume ratio, can significantly reduce equipment volume, reduces equipment cost.
Yet therefore the easy fracture because diameter is little of such ceramic hollow fibrous membrane will dress up membrane module and film separation system, could practical application.
The present invention uses a kind of honeycomb type structure mold of particular design; The technology for preparing ceramic hollow fibrous membrane in conjunction with inversion of phases/sintering; Made honeycomb type tubular ceramic film; This invention has successfully solved the expensive of inorganic ceramic film preparation and the big problem of ceramic membrane fragility, for condition has been created in large-scale promotion, the application of ceramic membrane in producing and living.
Summary of the invention
Principle of the present invention is: in containing the casting solution of ceramic powder; Form a kind of loose structure owing to the exchange of solvent and water condenses organic polymer to separate out (inversion of phases promptly takes place), will form different pore structures because solvent is different with the exchange velocity of water at the diverse location of film.Like this, owing to use water as coagulating agent, inversion of phases speed is fast and form dense one deck, at the skeleton and the outer surface of film, because the bigger pore structure of inversion of phases delay formation at the inner surface of film.Can disposablely make like this have porous support layer, the unsymmetric structure ceramic membrane of transition zone and effective separating layer.
The present invention is according to top inversion of phases film forming principle, through a kind of honeycomb type structure mold of particular design, disposable make have porous support layer, the honeycomb type tubular ceramic film of transition zone and effective separating layer unsymmetric structure.This honeycomb type tubular ceramic film is equivalent to the ceramic hollow fibrous membrane of many unsymmetric structures integrated a branch of; Thereby both had an advantage of unsymmetric structure ceramic hollow fibrous membrane; Successfully solve ceramic hollow fibrous membrane again and be prone to the problem of embrittlement, thereby be assembled into membrane module and film separation system more easily.
Specific embodiments of the present invention is following:
Develop a kind of preparation method of honeycomb type ceramic film, it is characterized in that the preparation process comprises following processing step:
(1) preparation polymer solution
Organic polymer and additive are dissolved in the solvent, process polymer solution;
The weight percent of each component consists of in the described polymer solution:
Organic polymer: solvent: additive=10～25%: 70～90%: 0～10%;
Described organic polymer is polysulfones, polyether sulfone, PEI, gather ethyl carbonate or cellulose acetate;
Described solvent is N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethyl acetyl ammonia or dimethyl sulfoxide (DMSO), or two kinds mixture wherein;
Described additive is polyacrylic acid and salt, polymethylacrylic acid and poly-methyl acrylate, polyethylene arsenic pyrrolidone, ethylene glycol, polyethylene glycol, glycerine or N, N dimethyl-lauramide;
(2) preparation pottery-polymer casting solution
In the polymer solution that (1) item makes, adding particle mean size is the ceramic powder of 0.02～5 μ m, fully stirs it is evenly dispersed in the above-mentioned polymer solution fully, obtains pottery-polymer casting solution; In described pottery-polymer casting solution by weight, ceramic powder: polymer=5～15: 1;
(3) preparation honeycomb type tubular ceramic film idiosome
With (a 2) pottery-polymer casting solution that obtains; Vacuum outgas 0.5～2h, the pottery after the degassing-polymer casting solution and core liquid and film be pore-forming liquid outward, passes through the different passages of special-purpose honeycomb type mould respectively; Be pressed into synchronously in the water coagulation bath; The honeycomb type ceramic film idiosome of extruding is retained in 2～48h in the coagulation bath, and it is fully solidified;
(4) preparation honeycomb type tubular ceramic film
(3) ceramic membrane idiosome that obtains is dried, and elder generation to remove organic matter, at 1000～1600 ℃ of following sintering 2～10h, obtains honeycomb type tubular ceramic film at 600～800 ℃ of roasting 1～2h more at last.
The preparation method of above-mentioned honeycomb type ceramic film is characterized in that preparing in the honeycomb type ceramic film idiosome process, and described core liquid is pure water;
The outer pore-forming liquid of described film is N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethyl acetyl ammonia or dimethyl sulfoxide (DMSO) content 90-100wt%, the solution of water content 10～0wt%.
The preparation method of above-mentioned honeycomb type ceramic film is characterized in that preparing in the honeycomb type ceramic film idiosome process, and the outer pore-forming liquid of described film is the mixed liquor of solvent and non-solvents such as water, ethanol, propyl alcohol or ethylene glycol.
The preparation method of above-mentioned a kind of honeycomb type ceramic film is characterized in that:
The structure of described special-purpose honeycomb type mould, from inside to outside successively by inner core tube 16, middle sleeve 17 constitutes with outer tube 18 edge covers; Core pipe 16, middle sleeve 17 and the sealing of outer tube 18 1 ends with core liquid import casting solution import and the outer pore-forming liquid import UNICOM of film, form the liquid-inlet end that layering compiles respectively;
The other end of inner core tube docks with evenly distributed needle tubing bundle, constitutes inner core tube---needle tubing Shu Zuhe; The other end of middle sleeve and outer tube is the taper shape and shrinks, and tapering successively decreases, and forms with needle tubing Shu Weixin, and middle sleeve taper mouth and outer tube taper mouth are inlayed liquid outlet end opening that the layering of cover, three layers of donut compiles successively to water coagulation bath 20;
The preparation method of above-mentioned honeycomb type ceramic film is characterized in that the internal diameter of the needle tubing of described formation needle tubing bundle 19 is set to 0.5-2mm, and external diameter is set to 1-3mm.
Advantage of the present invention is:
1. the honeycomb type tubular ceramic film that obtains has the big (500-9000m of unit volume membrane area
2/ m
3), intensity high (200-1200MPa), the characteristics such as sealing that are prone to.
2. preparation technology is simple and direct, and one-shot forming, sintering prepare graded pore structure, does not need follow-up film modified process promptly to can be used for separating or reaction.
3. production cost is low, is convenient to produce and use.
Description of drawings
Fig. 1 is a honeycomb type tubular ceramic film idiosome extrusion sketch map;
Fig. 2 is a honeycomb type tubular ceramic membrane structure sketch map;
Fig. 3 is the special stainless steel honeycomb mould structure generalized section of preparation honeycomb type tubular ceramic film of the present invention;
Fig. 4 is that the A of Fig. 3 is to structural representation.
The specific embodiment
Among Fig. 1, the pottery-polymer casting solution after 1 degassing; 2 core liquid; The outer pore-forming liquid of 3 films; 4 casting solution imports; 5 core liquid imports; The outer pore-forming liquid import of 6 films; 7 special-purpose honeycomb type moulds; 8 casting solutions get into the casting solution passage; 9 core liquid get into inner core tube---the core liquid passage of needle tubing Shu Zuhe; The outer pore-forming liquid of 10 films gets into the outer pore-forming liquid passage of film; 11 layerings come together in the liquid outlet end of three layers of donut; 12 are pressed in the water coagulation bath synchronously, are frozen into honeycomb type tubular ceramic film idiosome.
Among Fig. 2,13 separating layers; 14 transition zones; 15 porous supporting layers.
Among Fig. 3,16; Inner core tube; 17 middle sleeves; 18 outer tubes; 19 needle tubing bundles; 20 water coagulation baths; 21 core liquid passages; 22 casting solution passages; The outer pore-forming liquid passage of 23 films.
Among Fig. 4, label is identical with Fig. 3.
Embodiment 1: preparation honeycomb type tubulose multiaperture pellumina
The preparation process comprises following processing step:
(1) preparation polymer solution
Organic polymer and additive are dissolved in the solvent, process polymer solution; The weight of each component consists of in the polymer solution: organic polymer: solvent=10g: 70g; Organic polymer is used with commercial goods N-methyl pyrrolidone; Solvent is with commercial goods N-methyl pyrrolidone.
(2) preparation pottery-polymer casting solution
In the polymer solution that (1) item makes, adding particle mean size is the ceramic powder of 0.02～5 μ m, and ceramic powder is used alumina powder; Strong agitation 48h is dispersed in the above-mentioned polymer solution it fully, obtains pottery-polymer casting solution;
In the described casting solution by weight, ceramic powder: polymer=5～6g: 1g.
(3) preparation honeycomb type ceramic film idiosome
With (a 2) casting solution that obtains; Vacuum keeps 0.03MPa, vacuum outgas 0.5～2h, the outer pore-forming liquid (90% the N-methyl pyrrolidone aqueous solution) of casting solution after the degassing and core liquid pure water and film; Pass through the different passages of special-purpose honeycomb type mould respectively, at the N of 0.1atm
2Under the pressure, in the water coagulation bath that is pressed into synchronously; The needle tubing inner/outer diameter that constitutes the needle tubing bundle is 0.5mm/1mm, and the honeycomb type ceramic film idiosome of extruding is retained in 2～8h in the coagulation bath, and it is fully solidified.
(4) preparation ceramic membrane
(3) ceramic membrane idiosome that obtains is dried; Use the electric furnace roasting; Programming rate with 2 ℃/min is heated to 600～800 ℃ of roasting 1～2h to remove organic matter; Then with the programming rate of 3 ℃/min again at 1400～1600 ℃ of following sintering 2～4h, obtain honeycomb type tubulose porous alumina ceramic film at last.
Used special-purpose honeycomb type mould, from inside to outside successively by inner core tube 16, middle sleeve 17 constitutes with outer tube 18 edge covers; Inner core tube, middle sleeve and the sealing of outer tube one end are respectively with the import of core liquid; The outer pore-forming liquid import of casting solution import and film is communicated with, and forms the liquid-inlet end that layering compiles;
The other end of inner core tube docks with evenly distributed needle tubing bundle, constitutes inner core tube---needle tubing Shu Zuhe; The other end of middle sleeve and outer tube is the taper shape and shrinks, and tapering successively decreases, and forms with needle tubing Shu Weixin, and middle sleeve taper mouth and outer tube taper mouth are inlayed the liquid outlet end that the layering of cover, three layers of donut compiles successively;
The needle tubing bundle is set to the outlet of core liquid, and the outer wall of inner core tube---needle tubing Shu Zuhe and middle sleeve inwall gap are set to the casting solution passage, and middle sleeve outer wall and outer sleeve inner wall gap are set to the outer pore-forming liquid passage of film.
The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 0.5mm/1mm.
The honeycomb type tubular ceramic film that obtains, unit volume effective film area can reach 1400m
2/ m
3, intensity can reach 800MPa, and sealing easily.
Preparation technology is simple and direct, and one-shot forming, sintering prepare graded pore structure, does not need follow-up film modified process promptly to can be used for separating or reaction.
Production cost is low, is convenient to produce and use.
Embodiment 2: honeycomb type tubulose porous yttrium stable zirconium oxide film
The weight percent of each component consists of in the polymer solution: organic polymer: solvent: additive=25g: 90g: 10g;
Organic polymer is used the commercial goods polyether sulfone, and solvent is used commercial goods N, and dinethylformamide, additive are used the commercial goods polyacrylic acid, and ceramic powder is used the commercial goods yttrium stable zirconium oxide; Ceramic powder: polymer=14～15g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 98% N, the dinethylformamide aqueous solution; The honeycomb type ceramic film idiosome of extruding is retained in 24～48h in the coagulation bath, and it is fully solidified;
Honeycomb type tubulose yttrium stable zirconium oxide film is taken out, dries, the ceramic membrane idiosome with electric furnace at 1400～1600 ℃ of sintering 5～8h; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 1mm/2mm.The final honeycomb type tubulose porous yttrium stable zirconium oxide film that obtains.All the other are with embodiment 1.
Embodiment 3: honeycomb type tubulose porous La
0.6Sr
0.4Co
0.2Fe
0.8O
3Compact oxygen permeable film
In the preparation process, organic polymer: solvent: additive=17.5g: 80g: 5g; Organic polymer is used the commercial goods PEI, and solvent is used commercial goods N, N-dimethyl acetyl ammonia, and additive is used the commercial goods polymethylacrylic acid; Ceramic powder is used commercial goods La
0.6Sr
0.4Co
0.2Fe
0.8O
3(LSCF); Ceramic powder: polymer=8～10g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% the N-methyl pyrrolidone and the mixed solution of 10% ethylene glycol.
The honeycomb type ceramic film idiosome of extruding is retained in and places 36～48h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose LSCF film is taken out, dries, with 1200～1500 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 1mm/2mm; All the other are with embodiment 1.
In the preparation process, organic polymer: solvent: additive=15g: 75g: 3g; Organic polymer gathers ethyl carbonate with the commercial goods, and solvent is used the commercial goods dimethyl sulfoxide (DMSO), and additive is with commercial goods polyethylene arsenic pyrrolidone; Ceramic powder is 8% yttrium stable zirconium oxide, is called for short YSZ, the commercial goods, Tai-Tao porcelain new material Co., Ltd produces in the Yixing City);
Ceramic powder: polymer=6～8g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 95% N, the mixed solution of N-dimethyl acetyl ammonia and 5% ethanol.
The honeycomb type ceramic film idiosome of extruding is retained in and places 24～36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose YSZ film is taken out, dries, with 1000～1300 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 2mm/3mm; All the other are with embodiment 1.
In the preparation process, organic polymer: solvent: additive=20g: 85g: 7g; Organic polymer is used the commercial goods cellulose acetate, and solvent is with commercial goods dimethyl sulfoxide (DMSO)+N, and dinethylformamide, additive are used commercial goods ethylene glycol; Ceramic powder is a lanthanum strontium cobalt iron oxide, La
0.6Sr
0.4Co
0.2Fe
0.8O
3-α, being called for short LSCF, U.S.'s Praxair (Praxair) company produces; Ceramic powder: polymer=6～8g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% the dimethyl sulfoxide (DMSO) and the mixed solution of 5% propyl alcohol.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 24～36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose LSCF film is taken out, dries, with 1000～1300 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 0.5mm/1mm; All the other are with embodiment 1.
Embodiment 6 preparation honeycomb type tubulose CSO ceramic membranes
This routine organic polymer: solvent=25g: 90g; Organic polymer is used the commercial goods polysulfones, and solvent is with commercial goods dimethyl sulfoxide (DMSO)+N-methyl pyrrolidone; Ceramic powder is a cerium samarium oxide, Ce
0.8Sm
0.2O
2, be called for short CSO, the commercial goods, U.S.'s Praxair (Praxair) company produces; The weight ratio of ceramic powder and polymer is 10～12g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% the dimethyl sulfoxide (DMSO) and the mixed solution of 5% pure water, 5% polysulfones.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 4～36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose CSO ceramic membrane idiosome is taken out, dries, with 1000～1400 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 0.5mm/1mm; All the other are with embodiment 1.
This routine organic polymer: solvent: additive=10g: 70g: 10g; Organic polymer is used the commercial goods polyether sulfone, and solvent is with commercial goods dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive is used the commercial goods polyethylene glycol; The ceramic powder that this example is used is a barium strontium cobalt iron oxide, Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3, being called for short BSCF, U.S.'s Praxair (Praxair) company produces, and the weight ratio of ceramic powder and polymer is 12～13g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% dimethyl sulfoxide (DMSO) and 5% pure water, the mixed solution of 5% polyether sulfone.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 48h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose BSCF ceramic membrane idiosome is taken out, dries, with 1000～1300 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 2mm/3mm; All the other are with embodiment 1
Embodiment 8 preparation honeycomb type tubulose LSGM ceramic membranes
This routine organic polymer: solvent: additive=10g: 70g: 10g; Organic polymer is used the commercial goods PEI, and solvent is with commercial goods dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive is used commercial goods glycerine; The ceramic powder that this example is used is a lanthanum strontium gallium magnesium oxide, La
0.8Sr
0.2Ga
0.8Mg
0.2O
3, being called for short LSGM, U.S.'s Praxair (Praxair) company produces; The weight ratio of ceramic powder and polymer is 7: 1; The weight ratio of ceramic powder and polymer is 13～14g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% N, dinethylformamide and 5% pure water, the mixed solution of 5% polyether sulfone glycerine.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 48h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose LSGM ceramic membrane idiosome is taken out, dries, with 1400～1600 ℃ of roasting 4～6h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 1mm/2mm; All the other are with embodiment 1
This routine organic polymer: solvent: additive=10g: 70g: 3g; Organic polymer gathers ethyl carbonate with the commercial goods, and solvent is used the commercial goods dimethyl sulfoxide (DMSO); Additive is used commercial goods N, N dimethyl-lauramide;
The ceramic powder that this example is used is 8% yttrium stable zirconium oxide, is called for short YSZ, the commercial goods, and Tai-Tao porcelain new material Co., Ltd produces in the Yixing City, and the weight ratio of ceramic powder and polymer is 8g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% N, the mixed solution of dinethylformamide and 10% pure water.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose YSZ ceramic membrane idiosome is taken out, dries, with 1200～1400 ℃ of roasting 5～7h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 0.5mm/1mm; All the other are with embodiment 1
This routine organic polymer: solvent: additive=250g: 900g: 70g; Organic polymer is used the commercial goods cellulose acetate, and solvent is with commercial goods dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive is used commercial goods ethylene glycol;
The ceramic powder that this example is used is a lanthanum strontium cobalt iron oxide, La
0.6Sr
0.4Co
0.2Fe
0.8O
3-α, being called for short LSCF, U.S.'s Praxair (Praxair) company produces; The weight ratio of ceramic powder and polymer is 90g: 10g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% N, the mixed solution of dinethylformamide and 10% pure water.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose LSCF ceramic membrane idiosome is taken out, dries, with 1200～1400 ℃ of roasting 8～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 2mm/3mm; All the other are with embodiment 1.
Preparation honeycomb type tubulose CSO pottery doughnut oxygen permeation membrane
This routine organic polymer is a polyether sulfone; Solvent is N, dinethylformamide; Additive is a polyacrylic acid; The weight composition of each component is during the preparation polymer solution: organic polymer: solvent: additive=250g: 900g: 100g;
During preparation pottery-polymer paste, the ceramic powder of this example use is a cerium samarium oxide, Ce
0.8Sm
0.2O
2, be called for short CSO, the commercial goods, U.S.'s Praxair (Praxair) company produces; The weight ratio of ceramic powder and polymer is 15: 1;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% the N-methyl pyrrolidone and the mixed solution of 10% pure water.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose CSO ceramic membrane idiosome is taken out, dries, with 1400～1600 ℃ of roasting 5～8h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 0.5m/1mm; All the other are with embodiment 1.
Preparation honeycomb type tubulose LSCF pottery doughnut oxygen permeation membrane
This routine organic polymer is a PEI; Solvent is N, N-dimethyl acetyl ammonia; Additive is a poly-methyl acrylate;
The weight of each component is formed during the preparation polymer solution: organic polymer: solvent: additive=175g: 800g: 50g;
During potting porcelain-polymer paste, the ceramic powder that this example is used is a lanthanum strontium cobalt iron oxide, La
0.6Sr
0.4Co
0.2Fe
0.8O
3-α, being called for short LSCF, U.S.'s Praxair (Praxair) company produces; The weight ratio of ceramic powder and polymer is 10: 1;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 98% N, the dinethylformamide aqueous solution;
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 24～36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose LSCF ceramic membrane idiosome is taken out, dries, with 120～1500 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 1m/2mm; All the other are with embodiment 1.
Preparation honeycomb type tubulose LSCF pottery doughnut oxygen permeation membrane
This routine organic polymer is a cellulose acetate; Solvent is N-methyl pyrrolidone and the dimethyl sulfoxide (DMSO) mixed solution by any composition; Additive is an ethylene glycol; The weight composition of each component is during the preparation polymer solution: organic polymer: solvent: additive=250g: 900g: 70g;
During potting porcelain-polymer paste, the ceramic powder that this example is used is a lanthanum strontium cobalt iron oxide, La
0.6Sr
0.4Co
0.2Fe
0.8O
3-α, being called for short LSCF, U.S.'s Praxair (Praxair) company produces; The weight ratio of ceramic powder and polymer is 9: 1;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% the N-methyl pyrrolidone and the mixed solution of 10% ethylene glycol.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 24～36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose LSCF ceramic membrane idiosome is taken out, dries, with 120～1500 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 2mm/3mm; All the other are with embodiment 1.
Preparation honeycomb type tubulose CSO pottery doughnut oxygen permeation membrane
This routine organic polymer is a polyether sulfone; Solvent is dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive is a polyethylene glycol;
The weight composition of each component is during the preparation polymer solution: organic polymer: solvent: additive=100g: 700g: 100g;
During preparation pottery-polymer paste, the ceramic powder of this example use is a cerium samarium oxide, Ce
0.8Sm
0.2O
2, be called for short CSO, the commercial goods, U.S.'s Praxair (Praxair) company produces; The weight ratio of ceramic powder and polymer is 18: 1;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 95% N, the mixed solution of N-dimethyl acetyl ammonia and 5% ethanol.
The honeycomb type ceramic film idiosome of extruding is retained in and places 24～36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose YSZ film is taken out, dries, with 1000～1300 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 2mm/3mm; All the other are with embodiment 1.
Preparation honeycomb type tubulose YSZ pottery doughnut dielectric film
This routine organic polymer is a cellulose acetate; Solvent is dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive is an ethylene glycol;
The weight composition of each component is during the system polymer solution: organic polymer: solvent: additive=250g: 850g: 70g;
During preparation pottery-polymer paste, (ceramic powder that uses of this example is 8% yttrium stable zirconium oxide, is called for short YSZ, commercial goods, Tai-Tao porcelain new material Co., Ltd production in the Yixing City); The weight ratio of ceramic powder and polymer is 81;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% the dimethyl sulfoxide (DMSO) and the mixed solution of 5% propyl alcohol.
The honeycomb type tubular ceramic film idiosome of extruding is retained in and places 24～36h in the coagulation bath to guarantee its Stability Analysis of Structures.Honeycomb type tubulose LSCF film is taken out, dries, with 1000～1300 ℃ of roasting 7～10h of electric furnace; The ratio of the inner/outer diameter of the needle tubing of used needle tubing bundle is set to 0.5mm/1mm; All the other are with embodiment 1.
Claims (1)
1. the preparation method of a honeycomb type ceramic film is characterized in that the preparation process comprises following processing step:
(1) preparation polymer solution
Organic polymer and additive are dissolved in the solvent, process polymer solution;
The weight of each component consists of in the described polymer solution:
Organic polymer: solvent: additive=10～25: 70～90: 0～10;
Described organic polymer is polysulfones, polyether sulfone, PEI, gather ethyl carbonate or cellulose acetate;
Described solvent is N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethylacetylamide or dimethyl sulfoxide (DMSO), or two kinds mixture wherein;
Described additive is polyacrylic acid and salt, polymethylacrylic acid and poly-methyl acrylate, polyvinylpyrrolidone, ethylene glycol, polyethylene glycol, glycerine or N, N dimethyl-lauramide;
(2) preparation pottery-polymer casting solution
In the polymer solution that (1) item makes, adding particle mean size is the ceramic powder of 0.02～5 μ m, fully stirs it is evenly dispersed in the above-mentioned polymer solution fully, obtains pottery-polymer casting solution; In the described casting solution by weight, ceramic powder: polymer=5～15: 1;
(3) preparation honeycomb type tubular ceramic film idiosome
With (a 2) casting solution that obtains, vacuum outgas 0.5～2h, the outer pore-forming liquid of casting solution after the degassing and core liquid and film; Through the different passages of special-purpose honeycomb type mould, be pressed in the water coagulation bath honeycomb type ceramic film idiosome of extruding synchronously respectively; Be retained in 2～48h in the coagulation bath, it is fully solidified;
Described core liquid is pure water;
The outer pore-forming liquid of described film is N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethylacetylamide or dimethyl sulfoxide (DMSO) content 90～100wt%, the solution of water content 10～0wt%;
The structure of described special-purpose honeycomb type mould, from inside to outside successively by inner core tube (16), middle sleeve (17) and outer tube (18) edge cover constitute; Inner core tube (16), middle sleeve (17) and the sealing of outer tube (18) one ends with the outer pore-forming liquid import UNICOM of the import of core liquid, casting solution import and film, form the liquid-inlet end that layering compiles respectively; Needle tubing bundle (19) is set to core liquid outlet (21), inner core tube (16)---and the outer wall and the middle sleeve inwall gap of needle tubing bundle (19) combination are set to casting solution passage (22), and middle sleeve outer wall and outer sleeve inner wall gap are set to the outer pore-forming liquid passage (23) of film;
The other end of inner core tube docks with evenly distributed needle tubing bundle, constitutes inner core tube---needle tubing Shu Zuhe; The other end of middle sleeve and outer tube is the taper shape and shrinks, and tapering successively decreases, and forms with needle tubing Shu Weixin, and middle sleeve taper mouth and outer tube taper mouth are inlayed liquid outlet end opening that the layering of cover, three layers of donut compiles successively to water coagulation bath (20);
(4) preparation honeycomb type tubular ceramic film
(3) ceramic membrane idiosome that obtains is dried, and elder generation to remove organic matter, at 1000～1600 ℃ of following sintering 2～10h, obtains honeycomb type tubular ceramic film at 600～800 ℃ of roasting 1～2h more at last.
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| JP2001027459A (en) * | 1999-07-15 | 2001-01-30 | Zexel Valeo Climate Control Corp | Receiver dryer |
| 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 |
| CN103349918B (en) * | 2013-06-19 | 2015-11-11 | 南京工业大学 | A kind of method preparing multichannel ceramic hollow fibrous membrane |
| DE102013012671A1 (en) | 2013-07-31 | 2015-02-05 | Mann + Hummel Gmbh | Ceramic hollow fiber membranes with improved mechanical properties |
| CN103657436B (en) * | 2013-12-31 | 2016-06-01 | 南京工业大学 | The hollow fiber molecular sieve of a kind of high strength and its preparation method |
| CN104524987A (en) * | 2015-01-16 | 2015-04-22 | 张晓东 | Honeycomb-shaped hollow fiber ceramic ultrafiltration membrane and production method thereof |
| CN104707489A (en) * | 2015-03-25 | 2015-06-17 | 中国科学院城市环境研究所 | Phase conversion pouring preparation process and forming device for inorganic porous ceramic tubular membrane |
| CN105479585B (en) * | 2015-11-25 | 2017-08-25 | 山东理工大学 | The method that 3 D-printing prepares the honeycomb type ceramic film component with stereo channel |
| CN109534843B (en) * | 2017-09-22 | 2021-09-03 | 萍乡市普天高科实业有限公司 | Porous ceramic membrane and preparation mold and method thereof |
| 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 |
| CN111029592B (en) * | 2019-10-28 | 2022-06-24 | 南京工业大学 | Honeycomb high-performance solid oxide reversible battery hydrogen electrode material and preparation method thereof |
| CN111013403B (en) * | 2019-11-15 | 2021-04-23 | 河北工业大学 | Preparation method of hollow flat ceramic membrane |
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