CN101456744A - Method for preparing honeycomb type ceramic film - Google Patents
Method for preparing honeycomb type ceramic film Download PDFInfo
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- CN101456744A CN101456744A CNA2008102495361A CN200810249536A CN101456744A CN 101456744 A CN101456744 A CN 101456744A CN A2008102495361 A CNA2008102495361 A CN A2008102495361A CN 200810249536 A CN200810249536 A CN 200810249536A CN 101456744 A CN101456744 A CN 101456744A
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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 film be by metal oxide or mixed metal oxide 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; Physical strength is big, and withstand voltage good wear resistance is good; Pore size distribution is narrow, the separation accuracy height; Advantages such as easy easy cleaning, can be used for gas delivery, liquid separation purification and membrane reactor, in foodstuffs industry (as the clarification removal of impurities of plant extraction liquid, the clarification filtration of garden spgarden stuff, dairy products and concentrated, extract the pectin beverage in the apple residue, soybean, tealeaves deep processing etc.), (as the Sterile Filtration of fermented liquid, thalline concentrates, and albumen, pigment remove for pharmacy and biotechnology; Traditional Chinese medicine extraction substitutes alcohol precipitation process; Liquid glucose removal of impurities, product purification), chemistry and petrochemical complex industry is (as the separating of high temperature, high pressure, solvent system, purifying and make with extra care; The product of uncatalyzed reaction system separates with catalyzer; The production of superfine catalyst and nano-powder) and environment protection (handle and reuse as 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 layer and separating layer, and it at first is to make porous supporting body by forming and sintering, obtains transition layer by membrane pore structure and finishing again, makes effective separating layer by different methods at last.As seen, the complex manufacturing of mineral membrane, the production cycle is long, the cost costliness, furthermore ceramic membrane fragility is big, and these shortcomings have limited its practical application again greatly.Want the large-scale application ceramic membrane, must simplify preparation technology on the one hand, reduce the production cost of ceramic membrane, need to improve effective film area in the unit volume on the other hand, improve the utilising efficiency of mould material.
In the last few years, we have developed inversion of phases/sintering process by means of the technology of preparing of organic hollow tunica fibrosa and have prepared the ceramic hollow fibrous membrane method, and 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 make 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 structure properties 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 separating 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 membrane prepare 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 film-casting liquid of ceramic powder, owing to the exchange of solvent and water makes organic polymer curding out (inversion of phases promptly takes place) form a kind of vesicular structure, will form different pore textures because solvent is different with the exchange velocity of water at the different positions of film.Like this, owing to use water as condensing agent, inversion of phases speed is fast and form dense one deck, at the skeleton and the outside surface of film, because the bigger pore texture of inversion of phases delay formation at the internal surface of film.Can disposablely make like this have porous support layer, the unsymmetric structure ceramic membrane of transition layer and effective separating layer.
The present invention is according to top inversion of phases film forming principle, by a kind of honeycomb type structure mold of particular design, disposable make have porous support layer, the honeycomb type tubular ceramic film of transition layer 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 solved the problem of the easy embrittlement of ceramic hollow fibrous membrane again, thereby easier membrane module and the film separating system of being assembled into.
Specific embodiments of the present invention is as follows:
Develop a kind of preparation method of honeycomb type ceramic film, it is characterized in that preparation process comprises following processing step:
(1) preparation polymers soln
Organic polymer and additive are dissolved in the solvent, make polymers soln;
The weight percent of each component consists of in the described polymers soln:
Organic polymer: solvent: additive=10～25%: 70～90%: 0～10%;
Described organic polymer is polysulfones, polyethersulfone, polyetherimide, poly-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, polymethyl acrylic acid and poly-methyl acrylate, polyethylene arsenic pyrrolidone, ethylene glycol, polyoxyethylene glycol, glycerine or N, N dimethyl-laurylamide;
(2) preparation pottery-polymkeric substance film-casting liquid
In the polymers soln that (1) item makes, adding mean particle size is the ceramic powder of 0.02～5 μ m, fully stirs it is evenly dispersed in the above-mentioned polymers soln fully, obtains pottery-polymkeric substance film-casting liquid; In described pottery-polymkeric substance film-casting liquid by weight, ceramic powder: polymkeric substance=5～15: 1;
(3) preparation honeycomb type tubular ceramic film idiosome
With (a 2) pottery-polymkeric substance film-casting liquid that obtains, vacuum outgas 0.5～2h, the outer pore-forming liquid of pottery after the degassing-polymkeric substance film-casting liquid and core liquid and film, pass 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 organism, 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 solution 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 and outer tube 18 edge covers constitute; Core pipe 16, middle sleeve 17 and the sealing of outer tube 18 1 ends with core liquid import film-casting liquid 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 exit 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, external diameter is set to 1
-3mm.
Advantage of the present invention is:
1. the honeycomb type tubular ceramic film of Huo Deing has unit volume membrane area big (500
-9000m
2/ m
3), intensity height (200
-1200MPa), easy characteristics such as sealing.
2. preparation technology is simple and direct, and once shaped, 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 synoptic diagram;
Fig. 2 is a honeycomb type tubular ceramic membrane structure synoptic diagram;
Fig. 3 is the special stainless steel honeycomb mould structure diagrammatic cross-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.
Embodiment
Among Fig. 1, the pottery-polymkeric substance film-casting liquid after 1 degassing; 2 core liquid; The outer pore-forming liquid of 3 films; 4 film-casting liquid imports; 5 core liquid imports; The outer pore-forming liquid import of 6 films; 7 special-purpose honeycomb type moulds; 8 film-casting liquids enter the film-casting liquid passage; 9 core liquid enter inner core tube---the core liquid passage of needle tubing Shu Zuhe; The outer pore-forming liquid of 10 films enters the outer pore-forming liquid passage of film; 11 layerings come together in the liquid exit 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 layers; 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 film-casting liquid 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
Preparation process comprises following processing step:
(1) preparation polymers soln
Organic polymer and additive are dissolved in the solvent, make polymers soln; The weight of each component consists of in the polymers soln: organic polymer: solvent=10g: 70g; Organic polymer commercial goods N-Methyl pyrrolidone; Solvent commercial goods N-Methyl pyrrolidone.
(2) the ceramic polymkeric substance film-casting liquid of preparation
In the polymers soln that (1) item makes, adding mean particle size is the ceramic powder of 0.02～5 μ m, the ceramic powder alumina powder; Violent stirring 48h is dispersed in the above-mentioned polymers soln it fully, obtains pottery-polymkeric substance film-casting liquid;
In the described film-casting liquid by weight, ceramic powder: polymkeric substance=5～6g: 1g.
(3) preparation honeycomb type ceramic film idiosome
With (a 2) film-casting liquid that obtains, vacuum tightness keeps 0.03MPa, vacuum outgas 0.5～2h, the outer pore-forming liquid (90% the N-Methyl pyrrolidone aqueous solution) of film-casting liquid 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, heat-up rate with 2 ℃/min is heated to 600～800 ℃ of roasting 1～2h to remove organism, then with the heat-up 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 and outer tube 18 edge covers constitute, 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 film-casting liquid 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 exit 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 film-casting liquid 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 once shaped, 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 polymers soln: organic polymer: solvent: additive=25g: 90g: 10g;
Organic polymer commercial goods polyethersulfone, solvent commercial goods N, dinethylformamide, additive commercial goods polyacrylic acid, ceramic powder commercial goods yttrium stable zirconium oxide; Ceramic powder: polymkeric substance=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, and the ceramic membrane idiosome uses 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 commercial goods polyetherimide, solvent commercial goods N, N-dimethyl acetyl ammonia, additive commercial goods polymethyl acrylic acid; Ceramic powder commercial goods La
0.6Sr
0.4Co
0.2Fe
0.8O
3(LSCF); Ceramic powder: polymkeric substance=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 mixing solutions 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, solvent commercial goods dimethyl sulfoxide (DMSO), and additive commercial goods polyethylene arsenic pyrrolidone; Ceramic powder is 8% yttrium stable zirconium oxide, is called for short YSZ, the commercial goods, Tai-Tao porcelain novel material company limited produces in the Yixing City);
Ceramic powder: polymkeric substance=6～8g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 95% N, N-dimethyl acetyl ammonia and 5% alcoholic acid mixing solutions.
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.
Embodiment 5 preparation honeycomb type tubulose LSCF ceramic membranes
In the preparation process, organic polymer: solvent: additive=20g: 85g: 7g; Organic polymer commercial goods cellulose acetate, solvent commercial goods dimethyl sulfoxide (DMSO)+N, dinethylformamide, additive 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: polymkeric substance=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 mixing solutions 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.
This routine organic polymer: solvent=25g: 90g; Organic polymer commercial goods polysulfones, solvent commercial goods dimethyl sulfoxide (DMSO)+N-Methyl pyrrolidone; Ceramic powder is a cerium samarium oxide compound, 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 ceramics powder and polymkeric substance 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 mixing solutions 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 commercial goods polyethersulfone, solvent commercial goods dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive commercial goods polyoxyethylene 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 polymkeric substance 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 mixing solutions of 5% polyethersulfone.
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
This routine organic polymer: solvent: additive=10g: 70g: 10g; Organic polymer commercial goods polyetherimide, solvent commercial goods dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive 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 polymkeric substance is 7: 1; The weight ratio of ceramic powder and polymkeric substance 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 mixing solutions of 5% polyethersulfone 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, solvent commercial goods dimethyl sulfoxide (DMSO) with the commercial goods; Additive commercial goods N, N dimethyl-laurylamide;
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 novel material company limited produces in the Yixing City, and the weight ratio of ceramic powder and polymkeric substance is 8g: 1g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% N, the mixing solutions 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 commercial goods cellulose acetate, solvent commercial goods dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive 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 polymkeric substance is 90g: 10g;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 90% N, the mixing solutions 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 tubular fibre oxygen permeable film
This routine organic polymer is a polyethersulfone; Solvent is N, dinethylformamide; Additive is a polyacrylic acid; The weight composition of each component is during the preparation polymers soln: organic polymer: solvent: additive=250g: 900g: 100g;
During preparation pottery-polymer paste, the ceramic powder of this example use is a cerium samarium oxide compound, 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 polymkeric substance 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 mixing solutions 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 tubular fibre oxygen permeable film
This routine organic polymer is a polyetherimide; Solvent is N, N-dimethyl acetyl ammonia; Additive is a poly-methyl acrylate;
The weight of each component is formed during the preparation polymers soln: 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 polymkeric substance 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 tubular fibre oxygen permeable film
This routine organic polymer is a cellulose acetate; Solvent is N-Methyl pyrrolidone and the dimethyl sulfoxide (DMSO) mixing solutions by any composition; Additive is an ethylene glycol; The weight composition of each component is during the preparation polymers soln: 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 polymkeric substance 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 mixing solutions 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 tubular fibre oxygen permeable film
This routine organic polymer is a polyethersulfone; Solvent is dimethyl sulfoxide (DMSO)+N, dinethylformamide; Additive is a polyoxyethylene glycol;
The weight composition of each component is during the preparation polymers soln: organic polymer: solvent: additive=100g: 700g: 100g;
During preparation pottery-polymer paste, the ceramic powder of this example use is a cerium samarium oxide compound, 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 polymkeric substance is 18: 1;
In the extrusion, core liquid is pure water, and the outer pore-forming liquid of film is 95% N, N-dimethyl acetyl ammonia and 5% alcoholic acid mixing solutions.
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 tubular fibre 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 polymers soln: 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 novel material company limited production in the Yixing City); The weight ratio of ceramic powder and polymkeric substance 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 mixing solutions 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 (5)
1. the preparation method of a honeycomb type ceramic film is characterized in that preparation process comprises following processing step:
(1) preparation polymers soln
Organic polymer and additive are dissolved in the solvent, make polymers soln;
The weight of each component consists of in the described polymers soln:
Organic polymer: solvent: additive=10～25: 70～90: 0～10;
Described organic polymer is polysulfones, polyethersulfone, polyetherimide, poly-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, polymethyl acrylic acid and poly-methyl acrylate, polyethylene arsenic pyrrolidone, ethylene glycol, polyoxyethylene glycol, glycerine or N, N dimethyl-laurylamide;
(2) preparation pottery-polymkeric substance film-casting liquid
In the polymers soln that (1) item makes, adding mean particle size is the ceramic powder of 0.02～5 μ m, fully stirs it is evenly dispersed in the above-mentioned polymers soln fully, obtains pottery-polymkeric substance film-casting liquid; In the described film-casting liquid by weight, ceramic powder: polymkeric substance=5～15: 1;
(3) preparation honeycomb type tubular ceramic film idiosome
With (a 2) film-casting liquid that obtains, vacuum outgas 0.5～2h, the outer pore-forming liquid of film-casting liquid after the degassing and core liquid and film, pass through the different passages of special-purpose honeycomb type mould respectively, in the water coagulation bath that is pressed into synchronously, 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 organism, at 1000～1600 ℃ of following sintering 2～10h, obtains honeycomb type tubular ceramic film at 600～800 ℃ of roasting 1～2h more at last.
2. according to the preparation method of the described a kind of honeycomb type ceramic film of claim 1, it is characterized in that preparing in the honeycomb type ceramic film idiosome process, 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%.
3. according to the preparation method of claim 1 or 2 described a kind of honeycomb type ceramic films, it is characterized in that preparing in the honeycomb type ceramic film idiosome process, the outer pore-forming liquid of described film is the mixed solution of solvent and non-solvents such as water, ethanol, propyl alcohol or ethylene glycol.
4. preparation method according to claim 1 or 2 described a kind of honeycomb type ceramic films 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) and outer tube (18) edge cover constitute; Inner core tube (16), middle sleeve (17) and the sealing of outer tube (18) one ends with core liquid import film-casting liquid 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 exit end opening that the layering of cover, three layers of donut compiles successively to water coagulation bath (20);
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 film-casting liquid 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.
5. according to the preparation method of the described a kind of honeycomb type ceramic film of claim 1, it is characterized in that the internal diameter of the needle tubing of described formation needle tubing bundle (19) is set to 0.5～2mm, external diameter is set to 1～3mm.
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Address after: 201500 No. 285, Lane 5, Tiangong Road, Shanghai, Jinshan District Patentee after: Shanghai Sui Hua Industrial Limited by Share Ltd Address before: 201500 No. 285, Lane 5, Tiangong Road, Shanghai, Jinshan District Patentee before: Shanghai Huishan Industrial Co., Ltd. |