CN104174298B - A kind of preparation method of water purification gradient silicon carbide ceramic membrane - Google Patents
A kind of preparation method of water purification gradient silicon carbide ceramic membrane Download PDFInfo
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- CN104174298B CN104174298B CN201410412804.2A CN201410412804A CN104174298B CN 104174298 B CN104174298 B CN 104174298B CN 201410412804 A CN201410412804 A CN 201410412804A CN 104174298 B CN104174298 B CN 104174298B
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Abstract
The invention belongs to Materials Science and Engineering field, be specifically related to a kind of preparation method of water purification gradient silicon carbide ceramic membrane, include following steps: 1) silicon carbide ceramics supporter preparation; 2) preparation in carborundum intermediate layer; 3) preparation of silicon carbide film layer, final obtained water purification gradient silicon carbide ceramic membrane materials.Beneficial effect of the present invention is: obtained silicon carbide ceramics membrane material, and interconnected pore rate is high, and in gradient, intensity is high, pure water flux is high, strong acid-base resistance, and different levels interface binding intensity is high for gas cell distribution, easy and simple to handle, yield rate is high.Prepared water purification gradient silicon carbide ceramic membrane materials, rupture strength > 30MPa, pure water flux is greater than 5m
3/ (m
2h), pH value tolerance range 0-14.
Description
Technical field
The invention belongs to Materials Science and Engineering field, be specifically related to a kind of preparation method of water purification gradient silicon carbide ceramic membrane.
Background technology
Along with China's rapid development of economy, the water treatment amount in industrial production and daily life constantly increases.Only for water pollutions, the sewage of China 77% is unprocessed directly to be discharged, and the river of 46.7% is polluted, and brings great harm to the healthy of people.In water treatment field, membrane material has become the key component realizing the technical process such as fluid is separated, concentrated and purifying.Compared with organic film, inorganic ceramic membrane has that mechanical strength is high, organic solvent-resistant, wear-resistant, the many advantages such as antimicrobial erosion, chemical resistance medicament corrodes, fenestra is indeformable, contamination resistance is strong, easy and simple to handle, easy cleaning, represent the developing direction of water technology.
First inorganic ceramic membrane obtains industrial applications in the dairy husbandry of France and Grape Wine Industry, after expand to the fields such as food industry, environmental project, biomedicine, chemical petroleum gradually.The research and development of inoranic membrane receive in major industrial country to be paid attention to widely, and the domestic research to ceramic membrane starts from the later stage nineties in last century, mainly concentrates on alumina film material, and in sewage disposal, carried out application, achieves good benefit.
But in industrial wastewater, its waste water often exists that discharge capacity is large, high temperature, high alkalinity, highly acidity, containing features such as heavy metals, the strainability of inorganic ceramic membrane is had higher requirement, now widely used alumina film material, be difficult to resist strong acid, strong alkali environment, shorten the service life of alumina film material, accelerate the replacement cycle of film material, improve cost of sewage disposal greatly.In addition, alumina film material hydrophilicity is general, causes the flux of punishing water low, makes sewage treating efficiency low, also improve pollution treatment cost to a certain extent.
Carborundum chemistry excellent stability, resistance to strong acid, alkali, can use, and hydrophilicity is good in the scope of pH value 0-14, and its performance characteristics makes silicon carbide ceramic membrane in sewage disposal, have natural advantage, is the important directions of inorganic ceramic membrane development from now on.But realize the suitability for industrialized production of silicon carbide ceramic membrane, also need to form in the structure of silicon carbide ceramic membrane, the coating of hole characteristic, moulding process, film, carry out design optimization in firing process etc., make silicon carbide ceramics membrane material have good mechanical strength, chemical stability and strainability.Exploitation has that good chemical is stablized, the silicon carbide film material of heat endurance, high purity water flux is for promoting that the development of Environmental Protection in China cause has positive effect, remarkable economic and social benefits.
Summary of the invention
Technical problem to be solved by this invention is the preparation method providing a kind of water purification gradient silicon carbide ceramic membrane for above-mentioned prior art, the method can prepare resistance to strong acid, alkali, full pH scope is general, and maximum allowable operating temperature (M.A.O.T.) reaches 800 DEG C, and maximum pure water flux is greater than 10m
3/ (m
2h) silicon carbide ceramics membrane product.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of water purification gradient silicon carbide ceramic membrane, includes following steps:
1) silicon carbide ceramics supporter preparation
A1, raw material are chosen: carborundum powder, organosilicon polymer, pitch, kerosene in mass ratio 100:8-14:6-10:3-5 are chosen for subsequent use;
B1, raw material mix: first carborundum powder and organosilicon polymer are mixed formation mixture, then pitch and kerosene are mixed formation mixture, finally again mixed by the mixture obtained respectively;
C1, silicon carbide ceramics support the shaping of voxel embryo: the mixture of step B1 gained is put into extrusion shaping machine, are shaped to multichannel tubulose element embryo;
Firing of D1, silicon carbide ceramics supporter: silicon carbide ceramics is supported voxel embryo and put into tube furnace, be warming up to 400 DEG C by the speed of 6 DEG C/min, then be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtained silicon carbide ceramics supporter;
2) preparation in carborundum intermediate layer
Prepared by A2, starch-hydrocolloid: by water, starch, cellulose ether in mass ratio 100:40-50:0.1-0.5 mix, obtained starch-hydrocolloid;
The pretreatment of B2, silicon carbide ceramics supporter: by step 1) the silicon carbide ceramics supporter of gained is placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of C2, carborundum intermediate layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:50-60:5-6:0.1-0.5 mix, obtained carborundum intermediate layer slurries;
D2, carborundum intervening layers: inject carborundum intermediate layer slurries by the passage of the pretreated silicon carbide ceramics supporter of step B2, make carborundum intermediate layer slurries flow in the passage of silicon carbide ceramics supporter 20-30s;
E2, the firing of carborundum intermediate layer: by by the silicon carbide ceramics supporter after the coating of step D2 method, put into tube furnace, be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtain the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
3) preparation of silicon carbide film layer
The pretreatment of the silicon carbide ceramics supporter in A3, surperficial sintered silicon carbon intermediate layer: by step 2) the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer of gained is again placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of B3, silicon carbide film layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:50-60:5-6:0.1-0.5 mix, obtained silicon carbide film layer slurries;
C3, silicon carbide film layer apply: silicon carbide film layer slurries are injected the passage of silicon carbide ceramics supporter by the pretreated surperficial sintered silicon carbon intermediate layer of steps A 3, and silicon carbide film layer slurries are flowed 20-30s in the passage of the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
Firing of D3, silicon carbide film layer: by the silicon carbide ceramics supporter in the surperficial sintered silicon carbon intermediate layer by step C3 method coating silicon carbide rete slurries, put into tube furnace, 1400-1500 DEG C is warming up to by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, silicon carbide film layer is sintered to carborundum interlayer surfaces, final obtained water purification gradient silicon carbide ceramic membrane materials.
By such scheme, step 1) described in carborundum powder average grain diameter be 80-100 μm, purity 98%; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane, molecular weight 1000; Pitch is No. 90 asphalt or No. 110 asphalt.
By such scheme, step 2) described in carborundum powder average grain diameter be 10-60 μm, purity 98%; Starch average grain diameter is 0.1-1 μm; Cellulose ether is CMC ether or hydroxyethyl ether cellulose, and molecular weight is 20000; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane.
By such scheme, step 3) described in carborundum powder average grain diameter be 1-10 μm, purity 98%.
The water purification gradient silicon carbide ceramic membrane of gained of the present invention comprises supporter, intermediate layer, rete three parts, and three parts are carborundum and fire and form.
Adopt carborundum powder and the organosilicon polymer of certain particle diameter, the mixing such as pitch by extruded be multichannel tubular silicon carbide support voxel embryo, carborundum supporter is become again by high-temperature firing, its medium pitch a kind ofly has good toughness and the organic matter of adhesive property, the effect of bonded silicon carbide powder can be played, and in extruded process, make carborundum support voxel embryo and there is certain intensity and toughness, carborundum is avoided to support voxel embryo spontaneous bending, cracking etc., simultaneously pitch at high temperature can burn release, carborundum supporter is made to have higher interconnected pore rate, organosilicon polymer plays the effect of bonded silicon carbide after firing, makes carborundum supporter have good mechanical strength, chemical stability.
Intermediate layer is the carbofrax material of particle diameter between supporter and rete, and because between rete and support, particle diameter difference is comparatively large, if be directly coated in support by rete, in use easily cause interface stress to concentrate, rete is disengaging under the washing away of water; The design marginal intermediate layer of one deck particle diameter, can alleviate the interfacial stress in use procedure, improves serviceability.Silicon carbide film layer adheres on intermediate layer, plays the effect of impurity in separating liquid.
In preparation technology, its order, for after supporter fired, applies intermediate and also fires, apply rete again and fire after completing, final formation water purification gradient silicon carbide ceramic membrane materials, because the particle diameter of intermediate layer silicon carbide powder is less than supporter, the particle diameter of rete silicon carbide powder is less than intermediate, in each coating procedure, intermediate silicon carbide powder easily infiltrates supporter, rete silicon carbide powder easily infiltrates intermediate, causes pore plugging, reduces the strainability of silicon carbide film material.Therefore when applying intermediate layer, first supporter is immersed in starch-hydrocolloid, starch is made to block the hole of supporter, apply intermediate layer carborundum again, the object that the intermediate layer granulate preventing particle diameter less enters supporter can be reached, coating for rete is also adopted and is used the same method, and reaches same effect.
Beneficial effect of the present invention is: obtained silicon carbide ceramics membrane material, and interconnected pore rate is high, and in gradient, intensity is high, pure water flux is high, strong acid-base resistance, and different levels interface binding intensity is high for gas cell distribution, easy and simple to handle, yield rate is high.Prepared water purification gradient silicon carbide ceramic membrane materials, rupture strength > 30MPa, pure water flux is greater than 5m
3/ (m
2h), pH value tolerance range 0-14.
Accompanying drawing explanation
Fig. 1 is the microscopic appearance figure of embodiments of the invention 1 gained silicon carbide ceramics membrane material.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme of the present invention is further described in detail, but this explanation can not be construed as limiting the invention.
Embodiment 1:
1) silicon carbide ceramics supporter preparation
A1, raw material are chosen: carborundum powder, organosilicon polymer, pitch, kerosene in mass ratio 100:8:7:3 are chosen for subsequent use;
B1, raw material mix: first carborundum powder and organosilicon polymer are mixed formation mixture, then pitch and kerosene are mixed formation mixture, finally again mixed by the mixture obtained respectively;
C1, silicon carbide ceramics support the shaping of voxel embryo: the mixture of step B1 gained is put into extrusion shaping machine, are shaped to multichannel tubulose element embryo;
Firing of D1, silicon carbide ceramics supporter: silicon carbide ceramics is supported voxel embryo and put into tube furnace, be warming up to 400 DEG C by the speed of 6 DEG C/min, then be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtained silicon carbide ceramics supporter;
2) preparation in carborundum intermediate layer
Prepared by A2, starch-hydrocolloid: by water, starch, cellulose ether in mass ratio 100:42:0.2 mix, obtained starch-hydrocolloid;
The pretreatment of B2, silicon carbide ceramics supporter: by step 1) the silicon carbide ceramics supporter of gained is placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of C2, carborundum intermediate layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:53:5:0.2 mix, obtained carborundum intermediate layer slurries;
D2, carborundum intervening layers: inject carborundum intermediate layer slurries by the passage of the pretreated silicon carbide ceramics supporter of step B2, make carborundum intermediate layer slurries flow in the passage of silicon carbide ceramics supporter 20-30s;
E2, the firing of carborundum intermediate layer: by by the silicon carbide ceramics supporter after the coating of step D2 method, put into tube furnace, be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtain the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
3) preparation of silicon carbide film layer
The pretreatment of the silicon carbide ceramics supporter in A3, surperficial sintered silicon carbon intermediate layer: by step 2) the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer of gained is again placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of B3, silicon carbide film layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:50:5:0.1 mix, obtained silicon carbide film layer slurries;
C3, silicon carbide film layer apply: silicon carbide film layer slurries are injected the passage of silicon carbide ceramics supporter by the pretreated surperficial sintered silicon carbon intermediate layer of steps A 3, and silicon carbide film layer slurries are flowed 20-30s in the passage of the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
Firing of D3, silicon carbide film layer: by the silicon carbide ceramics supporter in the surperficial sintered silicon carbon intermediate layer by step C3 method coating silicon carbide rete slurries, put into tube furnace, 1400-1500 DEG C is warming up to by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, silicon carbide film layer is sintered to carborundum interlayer surfaces, final obtained water purification gradient silicon carbide ceramic membrane materials.
Carborundum powder average grain diameter described in step (1) is 80 μm, purity 98%; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane, molecular weight 1000; Pitch is No. 90 asphalt or No. 110 asphalt.
Carborundum powder average grain diameter described in step (2) is 10 μm, purity 98%; Starch average grain diameter is 0.1 μm; Cellulose ether is CMC ether or hydroxyethyl ether cellulose, and molecular weight is 20000; The same step of organosilicon polymer (1).
Carborundum powder average grain diameter described in step (3) is 1 μm, purity 98%, the same step of other materials (2).
Water purification gradient silicon carbide ceramic membrane materials prepared by the present invention, rupture strength 32MPa, pure water flux 6m
3/ (m
2h), pH value tolerance range 0-14.
From accompanying drawing 1, water purification gradient silicon carbide ceramic membrane prepared by the present invention is respectively supporter, intermediate layer, rete from the bottom to top; Three layers of carborundum particle diameter, aperture reduce successively, and interlayer contact is good, does not occur interpenetrative phenomenon, defines good gradient-structure.
Embodiment 2:
1) silicon carbide ceramics supporter preparation
A1, raw material are chosen: carborundum powder, organosilicon polymer, pitch, kerosene in mass ratio 100:9:7:4 are chosen for subsequent use;
B1, raw material mix: first carborundum powder and organosilicon polymer are mixed formation mixture, then pitch and kerosene are mixed formation mixture, finally again mixed by the mixture obtained respectively;
C1, silicon carbide ceramics support the shaping of voxel embryo: the mixture of step B1 gained is put into extrusion shaping machine, are shaped to multichannel tubulose element embryo;
Firing of D1, silicon carbide ceramics supporter: silicon carbide ceramics is supported voxel embryo and put into tube furnace, be warming up to 400 DEG C by the speed of 6 DEG C/min, then be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtained silicon carbide ceramics supporter;
2) preparation in carborundum intermediate layer
Prepared by A2, starch-hydrocolloid: by water, starch, cellulose ether in mass ratio 100:43:0.3 mix, obtained starch-hydrocolloid;
The pretreatment of B2, silicon carbide ceramics supporter: by step 1) the silicon carbide ceramics supporter of gained is placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of C2, carborundum intermediate layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:54:5:0.3 mix, obtained carborundum intermediate layer slurries;
D2, carborundum intervening layers: inject carborundum intermediate layer slurries by the passage of the pretreated silicon carbide ceramics supporter of step B2, make carborundum intermediate layer slurries flow in the passage of silicon carbide ceramics supporter 20-30s;
E2, the firing of carborundum intermediate layer: by by the silicon carbide ceramics supporter after the coating of step D2 method, put into tube furnace, be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtain the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
3) preparation of silicon carbide film layer
The pretreatment of the silicon carbide ceramics supporter in A3, surperficial sintered silicon carbon intermediate layer: by step 2) the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer of gained is again placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of B3, silicon carbide film layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:52:5.4:0.2 mix, obtained silicon carbide film layer slurries;
C3, silicon carbide film layer apply: silicon carbide film layer slurries are injected the passage of silicon carbide ceramics supporter by the pretreated surperficial sintered silicon carbon intermediate layer of steps A 3, and silicon carbide film layer slurries are flowed 20-30s in the passage of the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
Firing of D3, silicon carbide film layer: by the silicon carbide ceramics supporter in the surperficial sintered silicon carbon intermediate layer by step C3 method coating silicon carbide rete slurries, put into tube furnace, 1400-1500 DEG C is warming up to by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, silicon carbide film layer is sintered to carborundum interlayer surfaces, final obtained water purification gradient silicon carbide ceramic membrane materials.
Carborundum powder average grain diameter described in step (1) is 90 μm, purity 98%; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane, molecular weight 1000; Pitch is No. 90 asphalt or No. 110 asphalt.
Carborundum powder average grain diameter described in step (2) is 20 μm, purity 98%; Starch average grain diameter is 0.5 μm; Cellulose ether is CMC ether or hydroxyethyl ether cellulose, and molecular weight is 20000; The same step of organosilicon polymer (1).
Carborundum powder average grain diameter described in step (3) is 5 μm, purity 98%, the same step of other materials (2).
Water purification gradient silicon carbide ceramic membrane materials prepared by the present invention, rupture strength 36MPa, pure water flux 7m
3/ (m
2h), pH value tolerance range 0-14.
Embodiment 3:
1) silicon carbide ceramics supporter preparation
A1, raw material are chosen: carborundum powder, organosilicon polymer, pitch, kerosene in mass ratio 100:10:8:4 are chosen for subsequent use;
B1, raw material mix: first carborundum powder and organosilicon polymer are mixed formation mixture, then pitch and kerosene are mixed formation mixture, finally again mixed by the mixture obtained respectively;
C1, silicon carbide ceramics support the shaping of voxel embryo: the mixture of step B1 gained is put into extrusion shaping machine, are shaped to multichannel tubulose element embryo;
Firing of D1, silicon carbide ceramics supporter: silicon carbide ceramics is supported voxel embryo and put into tube furnace, be warming up to 400 DEG C by the speed of 6 DEG C/min, then be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtained silicon carbide ceramics supporter;
2) preparation in carborundum intermediate layer
Prepared by A2, starch-hydrocolloid: by water, starch, cellulose ether in mass ratio 100:43:0.2 mix, obtained starch-hydrocolloid;
The pretreatment of B2, silicon carbide ceramics supporter: by step 1) the silicon carbide ceramics supporter of gained is placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of C2, carborundum intermediate layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:54:6:0.2 mix, obtained carborundum intermediate layer slurries;
D2, carborundum intervening layers: inject carborundum intermediate layer slurries by the passage of the pretreated silicon carbide ceramics supporter of step B2, make carborundum intermediate layer slurries flow in the passage of silicon carbide ceramics supporter 20-30s;
E2, the firing of carborundum intermediate layer: by by the silicon carbide ceramics supporter after the coating of step D2 method, put into tube furnace, be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtain the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
3) preparation of silicon carbide film layer
The pretreatment of the silicon carbide ceramics supporter in A3, surperficial sintered silicon carbon intermediate layer: by step 2) the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer of gained is again placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of B3, silicon carbide film layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:60:6:0.4 mix, obtained silicon carbide film layer slurries;
C3, silicon carbide film layer apply: silicon carbide film layer slurries are injected the passage of silicon carbide ceramics supporter by the pretreated surperficial sintered silicon carbon intermediate layer of steps A 3, and silicon carbide film layer slurries are flowed 20-30s in the passage of the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
Firing of D3, silicon carbide film layer: by the silicon carbide ceramics supporter in the surperficial sintered silicon carbon intermediate layer by step C3 method coating silicon carbide rete slurries, put into tube furnace, 1400-1500 DEG C is warming up to by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, silicon carbide film layer is sintered to carborundum interlayer surfaces, final obtained water purification gradient silicon carbide ceramic membrane materials.
Carborundum powder average grain diameter described in step (1) is 90 μm, purity 98%; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane, molecular weight 1000; Pitch is No. 90 asphalt or No. 110 asphalt.
Carborundum powder average grain diameter described in step (2) is 36 μm, purity 98%; Starch average grain diameter is 0.5 μm; Cellulose ether is CMC ether or hydroxyethyl ether cellulose, and molecular weight is 20000; The same step of organosilicon polymer (1).
Carborundum powder average grain diameter described in step (3) is 7 μm, purity 98%, the same step of other materials (2).
Water purification gradient silicon carbide ceramic membrane materials prepared by the present invention, rupture strength 39MPa, pure water flux 9m
3/ (m
2h), pH value tolerance range 0-14.
Embodiment 4:
1) silicon carbide ceramics supporter preparation
A1, raw material are chosen: carborundum powder, organosilicon polymer, pitch, kerosene in mass ratio 100:11:8:5 are chosen for subsequent use;
B1, raw material mix: first carborundum powder and organosilicon polymer are mixed formation mixture, then pitch and kerosene are mixed formation mixture, finally again mixed by the mixture obtained respectively;
C1, silicon carbide ceramics support the shaping of voxel embryo: the mixture of step B1 gained is put into extrusion shaping machine, are shaped to multichannel tubulose element embryo;
Firing of D1, silicon carbide ceramics supporter: silicon carbide ceramics is supported voxel embryo and put into tube furnace, be warming up to 400 DEG C by the speed of 6 DEG C/min, then be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtained silicon carbide ceramics supporter;
2) preparation in carborundum intermediate layer
Prepared by A2, starch-hydrocolloid: by water, starch, cellulose ether in mass ratio 100:45:0.4 mix, obtained starch-hydrocolloid;
The pretreatment of B2, silicon carbide ceramics supporter: by step 1) the silicon carbide ceramics supporter of gained is placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of C2, carborundum intermediate layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:53:6:0.4 mix, obtained carborundum intermediate layer slurries;
D2, carborundum intervening layers: inject carborundum intermediate layer slurries by the passage of the pretreated silicon carbide ceramics supporter of step B2, make carborundum intermediate layer slurries flow in the passage of silicon carbide ceramics supporter 20-30s;
E2, the firing of carborundum intermediate layer: by by the silicon carbide ceramics supporter after the coating of step D2 method, put into tube furnace, be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtain the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
3) preparation of silicon carbide film layer
The pretreatment of the silicon carbide ceramics supporter in A3, surperficial sintered silicon carbon intermediate layer: by step 2) the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer of gained is again placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of B3, silicon carbide film layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:60:6:0.5 mix, obtained silicon carbide film layer slurries;
C3, silicon carbide film layer apply: silicon carbide film layer slurries are injected the passage of silicon carbide ceramics supporter by the pretreated surperficial sintered silicon carbon intermediate layer of steps A 3, and silicon carbide film layer slurries are flowed 20-30s in the passage of the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
Firing of D3, silicon carbide film layer: by the silicon carbide ceramics supporter in the surperficial sintered silicon carbon intermediate layer by step C3 method coating silicon carbide rete slurries, put into tube furnace, 1400-1500 DEG C is warming up to by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, silicon carbide film layer is sintered to carborundum interlayer surfaces, final obtained water purification gradient silicon carbide ceramic membrane materials.
Carborundum powder average grain diameter described in step (1) is 92 μm, purity 98%; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane, molecular weight 1000; Pitch is No. 90 asphalt or No. 110 asphalt.
Carborundum powder average grain diameter described in step (2) is 51 μm, purity 98%; Starch average grain diameter is 0.6 μm; Cellulose ether is CMC ether or hydroxyethyl ether cellulose, and molecular weight is 20000; The same step of organosilicon polymer (1).
Carborundum powder average grain diameter described in step (3) is 8.1 μm, purity 98%, the same step of other materials (2).
Water purification gradient silicon carbide ceramic membrane materials prepared by the present invention, rupture strength 41MPa, pure water flux 11m
3/ (m
2h), pH value tolerance range 0-14.
Embodiment 5:
1) silicon carbide ceramics supporter preparation
A1, raw material are chosen: carborundum powder, organosilicon polymer, pitch, kerosene in mass ratio 100:13:8:4 are chosen for subsequent use;
B1, raw material mix: first carborundum powder and organosilicon polymer are mixed formation mixture, then pitch and kerosene are mixed formation mixture, finally again mixed by the mixture obtained respectively;
C1, silicon carbide ceramics support the shaping of voxel embryo: the mixture of step B1 gained is put into extrusion shaping machine, are shaped to multichannel tubulose element embryo;
Firing of D1, silicon carbide ceramics supporter: silicon carbide ceramics is supported voxel embryo and put into tube furnace, be warming up to 400 DEG C by the speed of 6 DEG C/min, then be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtained silicon carbide ceramics supporter;
2) preparation in carborundum intermediate layer
Prepared by A2, starch-hydrocolloid: by water, starch, cellulose ether in mass ratio 100:46:0.3 mix, obtained starch-hydrocolloid;
The pretreatment of B2, silicon carbide ceramics supporter: by step 1) the silicon carbide ceramics supporter of gained is placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of C2, carborundum intermediate layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:55:6:0.3 mix, obtained carborundum intermediate layer slurries;
D2, carborundum intervening layers: inject carborundum intermediate layer slurries by the passage of the pretreated silicon carbide ceramics supporter of step B2, make carborundum intermediate layer slurries flow in the passage of silicon carbide ceramics supporter 20-30s;
E2, the firing of carborundum intermediate layer: by by the silicon carbide ceramics supporter after the coating of step D2 method, put into tube furnace, be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtain the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
3) preparation of silicon carbide film layer
The pretreatment of the silicon carbide ceramics supporter in A3, surperficial sintered silicon carbon intermediate layer: by step 2) the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer of gained is again placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of B3, silicon carbide film layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:58:5.8:0.45 mix, obtained silicon carbide film layer slurries;
C3, silicon carbide film layer apply: silicon carbide film layer slurries are injected the passage of silicon carbide ceramics supporter by the pretreated surperficial sintered silicon carbon intermediate layer of steps A 3, and silicon carbide film layer slurries are flowed 20-30s in the passage of the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
Firing of D3, silicon carbide film layer: by the silicon carbide ceramics supporter in the surperficial sintered silicon carbon intermediate layer by step C3 method coating silicon carbide rete slurries, put into tube furnace, 1400-1500 DEG C is warming up to by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, silicon carbide film layer is sintered to carborundum interlayer surfaces, final obtained water purification gradient silicon carbide ceramic membrane materials.
Carborundum powder average grain diameter described in step (1) is 100 μm, purity 98%; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane, molecular weight 1000; Pitch is No. 90 asphalt or No. 110 asphalt.
Carborundum powder average grain diameter described in step (2) is 60 μm, purity 98%; Starch average grain diameter is 1 μm; Cellulose ether is CMC ether or hydroxyethyl ether cellulose, and molecular weight is 20000; The same step of organosilicon polymer (1).
Carborundum powder average grain diameter described in step (3) is 10 μm, purity 98%, the same step of other materials (2).Water purification gradient silicon carbide ceramic membrane materials prepared by the present invention, rupture strength 45MPa, pure water flux 13m
3/ (m
2h), pH value tolerance range 0-14.
Claims (1)
1. a water purification preparation method for gradient silicon carbide ceramic membrane, includes following steps:
1) silicon carbide ceramics supporter preparation
A1, raw material are chosen: carborundum powder, organosilicon polymer, pitch, kerosene in mass ratio 100:8-14:6-10:3-5 are chosen for subsequent use; Described carborundum powder average grain diameter is 80-100 μm, purity 98%; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane, molecular weight 1000; Pitch is No. 90 asphalt or No. 110 asphalt;
B1, raw material mix: first carborundum powder and organosilicon polymer are mixed formation mixture, then pitch and kerosene are mixed formation mixture, finally again mixed by the mixture obtained respectively;
C1, silicon carbide ceramics support the shaping of voxel embryo: the mixture of step B1 gained is put into extrusion shaping machine, are shaped to multichannel tubulose element embryo;
Firing of D1, silicon carbide ceramics supporter: silicon carbide ceramics is supported voxel embryo and put into tube furnace, be warming up to 400 DEG C by the speed of 6 DEG C/min, then be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtained silicon carbide ceramics supporter;
2) preparation in carborundum intermediate layer
Prepared by A2, starch-hydrocolloid: by water, starch, cellulose ether in mass ratio 100:40-50:0.1-0.5 mix, obtained starch-hydrocolloid;
The pretreatment of B2, silicon carbide ceramics supporter: by step 1) the silicon carbide ceramics supporter of gained is placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of C2, carborundum intermediate layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:50-60:5-6:0.1-0.5 mix, obtained carborundum intermediate layer slurries; Described carborundum powder average grain diameter is 10-60 μm, purity 98%; Starch average grain diameter is 0.1-1 μm; Cellulose ether is CMC ether or hydroxyethyl ether cellulose, and molecular weight is 20000; Organosilicon polymer is Polycarbosilane or poly-borosilicate alkane;
D2, carborundum intervening layers: inject carborundum intermediate layer slurries by the passage of the pretreated silicon carbide ceramics supporter of step B2, make carborundum intermediate layer slurries flow in the passage of silicon carbide ceramics supporter 20-30s;
E2, the firing of carborundum intermediate layer: by by the silicon carbide ceramics supporter after the coating of step D2 method, put into tube furnace, be warming up to 1400-1500 DEG C by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, obtain the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
3) preparation of silicon carbide film layer
The pretreatment of the silicon carbide ceramics supporter in A3, surperficial sintered silicon carbon intermediate layer: by step 2) the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer of gained is again placed in starch-hydrocolloid and floods 2min, drier in an oven;
The preparation of B3, silicon carbide film layer slurries: by water, carborundum powder, organosilicon polymer, cellulose ether in mass ratio 100:50-60:5-6:0.1-0.5 mix, obtained silicon carbide film layer slurries; Described carborundum powder average grain diameter is 1-10 μm, purity 98%;
C3, silicon carbide film layer apply: silicon carbide film layer slurries are injected the passage of silicon carbide ceramics supporter by the pretreated surperficial sintered silicon carbon intermediate layer of steps A 3, and silicon carbide film layer slurries are flowed 20-30s in the passage of the silicon carbide ceramics supporter in surperficial sintered silicon carbon intermediate layer;
Firing of D3, silicon carbide film layer: by the silicon carbide ceramics supporter in the surperficial sintered silicon carbon intermediate layer by step C3 method coating silicon carbide rete slurries, put into tube furnace, 1400-1500 DEG C is warming up to by the speed of 9 DEG C/min, and be incubated 1h, cool to room temperature with the furnace, silicon carbide film layer is sintered to carborundum interlayer surfaces, final obtained water purification gradient silicon carbide ceramic membrane materials.
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