CN103752186A - Preparation method for ceramic ultra-filtration membrane - Google Patents
Preparation method for ceramic ultra-filtration membrane Download PDFInfo
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- CN103752186A CN103752186A CN201410036726.0A CN201410036726A CN103752186A CN 103752186 A CN103752186 A CN 103752186A CN 201410036726 A CN201410036726 A CN 201410036726A CN 103752186 A CN103752186 A CN 103752186A
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Abstract
The invention relates to a preparation method for a ceramic ultra-filtration membrane. Particularly, a selective laser sintering molding technology is used for rapidly molding porous ceramic particles obtained by sol-gel treatment, sintering and grinding to prepare the ceramic ultra-filtration membranes with different shapes, three-dimensional structures and thicknesses. The preparation method is simple, short in molding cycle and practical, and has high application value, the shape diversity is ensured, the obtained ceramic ultra-filtration membranes are high in retention rate, and have an aperture distribution range of 10 to 100 nm, and the water flux of the ceramic ultra-filtration membranes under the operation condition of 0.1Mpa is 100 to 200 L/m<3>.h.
Description
Technical field
The present invention relates to a kind of film separation field, be specifically related to a kind of preparation method of ceramic super-filtering film.
Background technology
Milipore filter is a kind of for take differential static pressure as motive force, according to the difference of relative molecular mass, carries out separated membrane technology.The distinctive micropore of milipore filter is detention bacterium, most of virus, colloid and mud effectively, reaches separation, classification, purifying, concentrated object.Nowadays in industry and sphere of life, obtained extensive use, for separating of, concentrated, purifying biological goods, in pharmaceutical products and food industry, also for the terminal processes of blood processing, desalinization, wastewater treatment, drink water purifying and ultra-pure water preparation.
Inorganic Ultrafiltration Membrane particularly inorganic ceramic ultra-filtering film owing to having, the advantage such as anti-mechanicalness is strong, high temperature resistant, corrosion-resistant, chemical-resistant reagent is widely used at film separation field.The large multiplex particles sintering legal system of ceramic super-filtering film is for basement membrane at present, and with sol-gel process preparation feedback layer, in preparing Ceramic excessive filtration membrane process, all to use the supporter of porous as carrier, and the shape of carrier is all unified fixing, can not be along with needs of production arbitrarily changes, complicated planform also cannot moulding, thereby has limited the scope of application of ceramic super-filtering film.
China Patent Publication No. CN102743979A discloses a kind of preparation method of zirconia ceramics milipore filter, the present invention prepares Zirconium oxalate sol by chemical coprecipitation, adopt low temperature calcination method to prepare the Zirconium powder of easy dispersion, then carry out grinding distribution, add subsequently coalescents, drying control agent, defoamer to make coating liquid, this coating liquid is applied on porous ceramic film support, through super-dry, sintering, obtain zirconia ceramics milipore filter rete, reduce energy consumption, improved the cost performance of milipore filter.
China Patent Publication No. CN101791524A discloses a kind of unsymmetric structure ceramic super-filtering film and preparation method thereof, the present invention by one dimension fibre shape dispersion of materials in colloidal sol, fully mix, add dispersant, thickener, defoamer to be mixed with preparation liquid, on porous supporting body, film, after drying, form transition zone, at transition zone surface coating colloidal sol preparation liquid, wet film is dried, dried, roasting, naturally lower the temperature and obtain unsymmetric structure ceramic super-filtering film, this ceramic super-filtering film has water flux advantage greatly.
China Patent Publication No. CN1686920A discloses a kind of preparation method of ceramic micro filter film, this method is scattered in nano-scale oxide in dispersant, thickener, defoamer and anticorrisive agent mixed aqueous solution, evenly form coating liquid, add again template, with prepared coating liquid, on porous metals or porous ceramic support, film, and after drying, dry at wet film, process and remove polymer template agent, finally carry out roasting moulding, obtain ceramic microfiltration membrane.
Above-mentioned patent is all the preparation method of ceramic super-filtering film, different formulas and preparation method have been adopted, made the ceramic super-filtering film of excellent performance, but all used the carrier of porous supporting body as film, thereby the milipore filter of preparation has, and shape is single, molding cycle is grown, the defect of milipore filter forming method backwardness, be unfavorable for the needs of ceramic super-filtering film in actual production process, limited the application and development of ceramic super-filtering film.
Summary of the invention
, difficult forming single for current ceramic super-filtering film shape, the long defect of molding cycle, a kind of preparation method of ceramic super-filtering film has been proposed, for achieving the above object, the present invention carries out rapid shaping processing by the porous ceramics particulate making through sol-gel, sintering, grinding with selective laser sintering and moulding technology, be prepared into the ceramic super-filtering film of various space structures, forming method is simple, practical, and water flux is large etc.
The preparation method's of a kind of ceramic super-filtering film of the present invention concrete preparation process is as follows:
1) colloidal solid of 10-20 weight portion is dissolved at normal temperatures while stirring by 70-80 parts by weight solvent, mixing speed 50-80r/min, allows colloidal solid form in solvent to disperse homogeneous, stable colloidal sol;
2) together with the pore creating material of colloidal sol step 1) being obtained and 2-5 weight portion, join in planetary ball mill, under the speed conditions of 300-350r/min, fully grind, disperse, mix 20-30min after discharging, carry out suction filtration and obtain mixture;
3) by step 2) mixture that obtains puts into high temperature sintering furnace, sintering 1-2h at the temperature of 600-800 ℃, the cooling rear discharging of normal temperature, then grind with planetary ball mill, then sieve, obtain porous ceramics particulate;
4) according to the needs of practical condition, the requirement to ceramic super-filtering film on thickness, shape, space structure is analyzed, and utilizes computer to set up mathematical model, writes performing a programme and the order of three-dimensional fast shaping;
5) porous ceramics particulate step 3) being obtained joins in the hopper of powder sintered laser fast shaping machine, with computer, import performing a programme and the order that step 4) writes, powder sintered laser fast shaping machine carries out three-dimensional fast shaping under the automatic control of computer, makes the ceramic super-filtering film of difformity, stereochemical structure, thickness.
The concrete preparation process 1 of above-mentioned a kind of ceramic super-filtering film), in, described colloidal solid is one or more in aluminium oxide, titanium oxide, zirconia, silica sol; Described solvent is deionized water; Described pore creating material is that diameter is the nano-calcium carbonate of 10-100nm, one or both in nano-calcium carbonate magnesium.
The concrete preparation process 2 of above-mentioned a kind of ceramic super-filtering film), in, described sieving was 2000-5000 object sieve.
The concrete preparation process 3 of above-mentioned a kind of ceramic super-filtering film) in, described powder sintered laser fast shaping machine adopts selective laser sintering and moulding technology, adopt CO2 laser instrument by the 3-D graphic designing on computer, under the control of computer, the principle that is coated in the printing dusty material sinter molding of the one deck on workbench, a kind of in the main former of three-dimensional fast shaping technology, mainly by scanning system, laser control system, heating element heater, moulding cylinder, feeding system, moving component, cooling system, kinetic control system, software systems form.
The present invention utilizes the principle of selective laser sintering and moulding technology in rapid shaping, the porous ceramics particulate making through sol-gel, sintering, grinding is carried out to forming processes with selective laser sintering and moulding technology, make the ceramic super-filtering film of various space structures, forming method is simple, molding cycle is short, practical, the rejection of this ceramic super-filtering film is large, pore size distribution range 10-100nm, under the operating condition of 0.1Mpa, water flux is 100-200L/m
3h.
The outstanding feature of the present invention is:
1, the present invention adopts three-dimensional fast shaping technology, makes ceramic super-filtering film convenient formation, molding cycle is short, shape is diversified, meets the demand to the various shapes of ceramic super-filtering film and structure.
2, the present invention does not need mould, has greatly improved the production efficiency of ceramic super-filtering film, has widened range of application.
3, production process of the present invention is simple, easy to operate, and production cost is low, is easy to suitability for industrialized production, and range of application is more extensive.
The technological process of production of the present invention is shown in Figure of description 1.
The specific embodiment
Below by the specific embodiment, the present invention is described in further detail, but this should be interpreted as to scope of the present invention only limits to following example.In the situation that not departing from said method thought of the present invention, various replacements or the change according to ordinary skill knowledge and customary means, made, all should be within the scope of the present invention.
embodiment 1
1) the alumina gel particle of 10 weight portions is dissolved at normal temperatures while stirring by 70 parts by weight of deionized water, mixing speed 50r/min, allows colloidal solid form in solvent to disperse homogeneous, stable colloidal sol;
2) together with the nano-calcium carbonate of colloidal sol step 1) being obtained and 2 weight portions, join in planetary ball mill, under the speed conditions of 300r/min, fully grind, disperse, mix 20min after discharging, carry out suction filtration and obtain mixture;
3) by step 2) mixture that obtains puts into high temperature sintering furnace, sintering 1h at the temperature of 600 ℃, the cooling rear discharging of normal temperature, then grind with planetary ball mill, then cross 2000 mesh sieves, obtain porous ceramics particulate;
4) according to the needs of practical condition, the requirement to ceramic super-filtering film on thickness, shape, space structure is analyzed, and utilizes computer to set up mathematical model, writes performing a programme and the order of three-dimensional fast shaping;
5) porous ceramics particulate step 3) being obtained joins in the hopper of powder sintered laser fast shaping machine, with computer, import performing a programme and the order that step 4) writes, powder sintered laser fast shaping machine carries out three-dimensional fast shaping under the automatic control of computer, makes the ceramic super-filtering film of difformity, stereochemical structure, thickness.
embodiment 2
1) the alumina gel particle of 15 weight portions is dissolved at normal temperatures while stirring by 80 parts by weight of deionized water, mixing speed 60r/min, allows colloidal solid form in solvent to disperse homogeneous, stable colloidal sol;
2) together with the nano-calcium carbonate magnesium of colloidal sol step 1) being obtained and 3 weight portions, join in planetary ball mill, under the speed conditions of 300r/min, fully grind, disperse, mix 20min after discharging, carry out suction filtration and obtain mixture;
3) by step 2) mixture that obtains puts into high temperature sintering furnace, sintering 1h at the temperature of 700 ℃, the cooling rear discharging of normal temperature, then grind with planetary ball mill, then cross 2000 mesh sieves, obtain porous ceramics particulate;
4) according to the needs of practical condition, the requirement to ceramic super-filtering film on thickness, shape, space structure is analyzed, and utilizes computer to set up mathematical model, writes performing a programme and the order of three-dimensional fast shaping;
5) porous ceramics particulate step 3) being obtained joins in the hopper of powder sintered laser fast shaping machine, with computer, import performing a programme and the order that step 4) writes, powder sintered laser fast shaping machine carries out three-dimensional fast shaping under the automatic control of computer, makes the ceramic super-filtering film of difformity, stereochemical structure, thickness.
embodiment 3
1) the alumina gel particle of 10 weight portions is dissolved at normal temperatures while stirring by 80 parts by weight of deionized water, mixing speed 70r/min, allows colloidal solid form in solvent to disperse homogeneous, stable colloidal sol;
2) together with the nano-calcium carbonate of colloidal sol step 1) being obtained and 4 weight portions, join in planetary ball mill, under the speed conditions of 350r/min, fully grind, disperse, mix 30min after discharging, carry out suction filtration and obtain mixture;
3) by step 2) mixture that obtains puts into high temperature sintering furnace, sintering 1.5h at the temperature of 800 ℃, the cooling rear discharging of normal temperature, then grind with planetary ball mill, then cross 3000 mesh sieves, obtain porous ceramics particulate;
4) according to the needs of practical condition, the requirement to ceramic super-filtering film on thickness, shape, space structure is analyzed, and utilizes computer to set up mathematical model, writes performing a programme and the order of three-dimensional fast shaping;
5) porous ceramics particulate step 3) being obtained joins in the hopper of powder sintered laser fast shaping machine, with computer, import performing a programme and the order that step 4) writes, powder sintered laser fast shaping machine carries out three-dimensional fast shaping under the automatic control of computer, makes the ceramic super-filtering film of difformity, stereochemical structure, thickness.
embodiment 4
1) the alumina gel particle of 20 weight portions is dissolved at normal temperatures while stirring by 80 parts by weight of deionized water, mixing speed 80r/min, allows colloidal solid form in solvent to disperse homogeneous, stable colloidal sol;
2) together with the nano-calcium carbonate magnesium of colloidal sol step 1) being obtained and 5 weight portions, join in planetary ball mill, under the speed conditions of 350r/min, fully grind, disperse, mix 30min after discharging, carry out suction filtration and obtain mixture;
3) by step 2) mixture that obtains puts into high temperature sintering furnace, sintering 2h at the temperature of 700 ℃, the cooling rear discharging of normal temperature, then grind with planetary ball mill, then cross 5000 mesh sieves, obtain porous ceramics particulate;
4) according to the needs of practical condition, the requirement to ceramic super-filtering film on thickness, shape, space structure is analyzed, and utilizes computer to set up mathematical model, writes performing a programme and the order of three-dimensional fast shaping;
5) porous ceramics particulate step 3) being obtained joins in the hopper of powder sintered laser fast shaping machine, with computer, import performing a programme and the order that step 4) writes, powder sintered laser fast shaping machine carries out three-dimensional fast shaping under the automatic control of computer, makes the ceramic super-filtering film of difformity, stereochemical structure, thickness.
embodiment 5
1) the alumina gel particle of 15 weight portions is dissolved at normal temperatures while stirring by 75 parts by weight of deionized water, mixing speed 70r/min, allows colloidal solid form in solvent to disperse homogeneous, stable colloidal sol;
2) together with the nano-calcium carbonate of colloidal sol step 1) being obtained and 4 weight portions, join in planetary ball mill, under the speed conditions of 300r/min, fully grind, disperse, mix 25min after discharging, carry out suction filtration and obtain mixture;
3) by step 2) mixture that obtains puts into high temperature sintering furnace, sintering 2h at the temperature of 700 ℃, the cooling rear discharging of normal temperature, then grind with planetary ball mill, then cross 4000 mesh sieves, obtain porous ceramics particulate;
4) according to the needs of practical condition, the requirement to ceramic super-filtering film on thickness, shape, space structure is analyzed, and utilizes computer to set up mathematical model, writes performing a programme and the order of three-dimensional fast shaping;
5) porous ceramics particulate step 3) being obtained joins in the hopper of powder sintered laser fast shaping machine, with computer, import performing a programme and the order that step 4) writes, powder sintered laser fast shaping machine carries out three-dimensional fast shaping under the automatic control of computer, makes the ceramic super-filtering film of difformity, stereochemical structure, thickness.
Claims (4)
1. a preparation method for ceramic super-filtering film, is characterized in that concrete preparation method is as follows:
1) colloidal solid of 10-20 weight portion is dissolved at normal temperatures while stirring by 70-80 parts by weight solvent, mixing speed 50-80r/min, allows colloidal solid form in solvent to disperse homogeneous, stable colloidal sol;
2) together with the pore creating material of colloidal sol step 1) being obtained and 2-5 weight portion, join in planetary ball mill, under the speed conditions of 300-350r/min, fully grind, disperse, mix 20-30min after discharging, carry out suction filtration and obtain mixture;
3) by step 2) mixture that obtains puts into high temperature sintering furnace, sintering 1-2h at the temperature of 600-800 ℃, the cooling rear discharging of normal temperature, then grind with planetary ball mill, then sieve, obtain porous ceramics particulate;
4) according to the needs of practical condition, the requirement to ceramic super-filtering film on thickness, shape, space structure is analyzed, and utilizes computer to set up mathematical model, writes performing a programme and the order of three-dimensional fast shaping;
5) porous ceramics particulate step 3) being obtained joins in the hopper of powder sintered laser fast shaping machine, with computer, import performing a programme and the order that step 4) writes, powder sintered laser fast shaping machine carries out three-dimensional fast shaping under the automatic control of computer, makes the ceramic super-filtering film of difformity, stereochemical structure, thickness.
2. according to the preparation method of a kind of ceramic super-filtering film of preparation described in claim 1, it is characterized in that described pore creating material is that diameter is the nano-calcium carbonate of 10-100nm, one or both in nano-calcium carbonate magnesium.
3. according to the preparation method of a kind of ceramic super-filtering film of preparation described in claim 1, it is characterized in that described sieving was 2000-5000 object sieve.
4. according to the preparation method of a kind of ceramic super-filtering film of preparation described in claim 1, it is characterized in that described powder sintered laser fast shaping machine adopts selective laser sintering and moulding technology, adopt CO2 laser instrument by the 3-D graphic designing on computer, under the control of computer, the principle that is coated in the printing dusty material sinter molding of the one deck on workbench, a kind of in the main former of three-dimensional fast shaping technology, mainly by scanning system, laser control system, heating element heater, moulding cylinder, feeding system, moving component, cooling system, kinetic control system, software systems form.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109626979A (en) * | 2019-02-15 | 2019-04-16 | 中国计量大学 | A kind of preparation method of the adjustable calcium silicates porous ceramic film of hole shape |
| CN110559872A (en) * | 2019-08-14 | 2019-12-13 | 浙江理工大学 | Preparation method of shaft disc type rotating ceramic membrane |
| US10525417B2 (en) | 2018-01-04 | 2020-01-07 | University Of Washington | Nanoporous ceramic membranes, membrane structures, and related methods |
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| CN101333115A (en) * | 2007-06-29 | 2008-12-31 | 哈尔滨工业大学 | Laminate preparation method of ceramic pieces of complex shape |
| CN102806018A (en) * | 2012-07-12 | 2012-12-05 | 三达膜环境技术股份有限公司 | Method for lower-temperature sintering to prepare acid and alkali-resistant titanium dioxide ceramic ultrafiltration membrane |
| CN103013196A (en) * | 2012-12-18 | 2013-04-03 | 上海迪道科技有限公司 | Method for manufacturing ultrathin nano-coating used for surface modification of inorganic nonmetallic material |
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Patent Citations (4)
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| WO1991012879A1 (en) * | 1990-02-21 | 1991-09-05 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Inorganic membranes and a process for making inorganic membranes |
| CN101333115A (en) * | 2007-06-29 | 2008-12-31 | 哈尔滨工业大学 | Laminate preparation method of ceramic pieces of complex shape |
| CN102806018A (en) * | 2012-07-12 | 2012-12-05 | 三达膜环境技术股份有限公司 | Method for lower-temperature sintering to prepare acid and alkali-resistant titanium dioxide ceramic ultrafiltration membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10525417B2 (en) | 2018-01-04 | 2020-01-07 | University Of Washington | Nanoporous ceramic membranes, membrane structures, and related methods |
| CN109626979A (en) * | 2019-02-15 | 2019-04-16 | 中国计量大学 | A kind of preparation method of the adjustable calcium silicates porous ceramic film of hole shape |
| CN110559872A (en) * | 2019-08-14 | 2019-12-13 | 浙江理工大学 | Preparation method of shaft disc type rotating ceramic membrane |
| CN110559872B (en) * | 2019-08-14 | 2022-03-01 | 浙江理工大学 | Preparation method of shaft disc type rotating ceramic membrane |
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