CN108046788A - A kind of preparation method of self-cleaning ceramic film - Google Patents
A kind of preparation method of self-cleaning ceramic film Download PDFInfo
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- CN108046788A CN108046788A CN201711291802.2A CN201711291802A CN108046788A CN 108046788 A CN108046788 A CN 108046788A CN 201711291802 A CN201711291802 A CN 201711291802A CN 108046788 A CN108046788 A CN 108046788A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 63
- 238000004140 cleaning Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 22
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000003643 water by type Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 7
- 229920002261 Corn starch Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000008120 corn starch Substances 0.000 claims description 6
- 229940099112 cornstarch Drugs 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 6
- 150000002171 ethylene diamines Chemical class 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 6
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229940037003 alum Drugs 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 44
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000004907 flux Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract description 2
- 230000000802 nitrating effect Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010017577 Gait disturbance Diseases 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/34—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by radiation
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a kind of preparation methods of self-cleaning ceramic film, belong to water-treatment technology field.This method is using mullite low cost feedstock gangue and bauxite as raw material, by adding auxiliary agent, inexpensive ceramic film support is prepared, then silica and TiO 2 sol are coated in supporting body surface with dipping cladding process, by high-temperature process up to a kind of inexpensive self-cleaning ceramic film.The obtained ceramic membrane of the present invention has self-cleaning function, and manufacturing cost is cheap, has a clear superiority compared with traditional ceramics film.Ceramic membrane produced by the present invention, low cost of raw materials, and containing the nitrating silica with photocatalysis, voluntarily fouling membrane is handled under photocatalysis, the membrane flux and film process efficiency of itself are improved, duration is effectively used with longer compared to conventional ceramic film.
Description
Technical field
The present invention relates to a kind of preparation methods of the self-cleaning ceramic film of low cost, belong to water-treatment technology field.
Background technology
UF membrane has obtained extensively as an efficient isolation technics in the numerous areas such as petrochemical industry and environmental protection
Using.However, its function is single, fouling membrane phenomenon is serious, film surface leads to the absorption of organic matter and fenestra in membrane separating process
The blockage problem of pollutant in road directly results in the attenuation of membrane flux, reduces film process efficiency, and membrane pollution problem becomes UF membrane
Technology stumbling-block preventing the development.In order to solve membrane pollution problem, fouling membrane is handled usually using Physical Chemical Cleaning, still
This process can increase expense so that process complications are unfavorable for producing.Photocatalysis can effectively degradation of dye, phenols, halide,
Its final mineralising is the innocuous substances such as water, carbon dioxide by the organic matters such as hydro carbons, pesticide；Optically catalytic TiO 2 oxidation technology
The new water pollution treatment technology environmental-friendly as one oneself through be widely used for water removal in hardly degraded organic substance, Ke Yihe
Membrane separation technique is combined, and slows down the fouling membrane phenomenon in membrane separating process.However, smaller powdered form titanium dioxide fine particles are deposited
Recycling rate of waterused is low, recycling is difficult the shortcomings of.By the way that titanium dioxide optical catalyst is supported on ceramic membrane surface, preparation is provided
There is the multifunctional ceramic film of photocatalytic activity, while solving photochemical catalyst hardly possible recycling, enhance fouling membrane resistance.
Inorganic ceramic membrane has many advantages, such as high temperature resistant, antiacid alkali and high mechanical strength, has been applied to environmental protection, energy at present
Source, food, chemical industry, medicine and other fields.But inorganic ceramic membrane is in the application there are the problems such as manufacturing cost is high, performance is single,
So how to reduce the manufacturing cost of inorganic ceramic membrane becomes current research hot spot.
The content of the invention
Present invention mainly solves the technical issues of：For absorption of the film surface to organic matter during current ceramic membrane separation
And in fenestra passage pollutant blockage problem, directly result in the attenuation of membrane flux, reduce film process efficiency, and ceramic membrane is should
There are the problems such as manufacturing cost is high, performance is single, provide a kind of preparation method of inexpensive self-cleaning ceramic film, the party in
Method is using mullite low cost feedstock gangue and bauxite as raw material, by adding auxiliary agent, prepares inexpensive ceramic membrane branch
Support body, then silica and TiO 2 sol are coated in supporting body surface with dipping cladding process, by high-temperature process to obtain the final product
A kind of low cost self-cleaning ceramic film.The obtained ceramic membrane of the present invention has self-cleaning function, and manufacturing cost is cheap, makes pottery with tradition
Porcelain film is compared and had a clear superiority.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
(1) formed according to mullite raw material, be in mass ratio 3:2 weigh gross mass be 5~10kg gangue and
Bauxite is put into polyurethane ball-milling pot, adds in zirconia ball mill and in horizontal planetary batch mixer with 500~600r/min
Rotating speed 8~10h of ball milling mixing, obtain the mixed-powder of gangue and bauxite；
(2) the above-mentioned obtained mixed-powders of 1~2kg is taken to be put into aluminium oxide mortar, add in 20~30g cornstarch and 2~
3L mass concentrations are 15% poly-vinyl alcohol solution, are placed on magnetic stirrer, are stirred with the rotating speed of 400~500r/min afterwards
It mixes uniformly, is sufficiently mixed dispensing and generates bubble, mixture is poured on mould for tabletting press afterwards, 190~200MPa's
A diameter of 10~15mm sheets supporter is pressed under high pressure；
(3) sheet supporter obtained above is put into high temperature sintering furnace, temperature programming is to 200 DEG C, heating rate 5
DEG C/min, and 30~40min of isothermal holding is warming up to remove moisture therein, then with the rate of 3 DEG C/min at 200 DEG C
1300 DEG C, and 2~3h of heat preservation sintering at 1300 DEG C, up to inexpensive mullite porous ceramic film support after being cooled to room temperature
Body, it is spare；
(4) measure 15~20mL silester and 10~15mL absolute ethyl alcohols are poured into 200mL beakers, stirred with glass bar
Uniformly, it is placed on afterwards on magnetic stirrer, setting rotating speed is 200~300r/min, sequentially it is slowly added dropwise 10 while stirring~
The hydrochloric acid that ethanol solution, 15~20mL deionized waters and the 1~2mL mass concentrations that 15mL mass concentrations are 80% are 30% is molten
Liquid continues 30~40min of stirring and obtains silicon dioxide gel；
(5) measure 15~20mL absolute ethyl alcohols to be put into 500mL beakers, with magnetic stirrer with 800~900r/min's
Rotating speed is vigorously stirred, and 15~20mL butyl titanates and 6~8mL glacial acetic acid are slowly added dropwise in whipping process, is put into afterwards super
Sonic oscillator continues 1~2mL of addition ethylenediamines as nitrogen dopant, carries out 30~40min of sonic oscillation obtained solutions 1；
(6) 2~3mL deionized waters are measured again to be added in 10~15mL absolute ethyl alcohols, stirred evenly with glass bar obtained
Solution 2, is placed on magnetic stirrer afterwards, is stirred with the rotating speed of 200~300r/min, solution 2 is instilled dropwise molten
In liquid 1, faint yellow TiO 2 sol is made；
(7) it is inexpensive mullite porous ceramic film support obtained above is molten with immersion coating silica respectively
Glue and TiO 2 sol, the material coated stand 24~30h, put it into Muffle furnace afterwards at room temperature, be passed through nitrogen into
Row protection is warming up to 450 DEG C with the rate program of 2 DEG C/min, and constant temperature takes out after keeping 2~3h, and cooled to room temperature to obtain the final product
A kind of low cost self-cleaning ceramic film.
The concrete application method of the present invention：Inexpensive self-cleaning ceramic film produced by the present invention is taken to be arranged on treatment tank
In, layer of ceramic film is set every 50~80cm, 5~8 layers is set altogether, treatment sewage is allowed to flow through ceramic membrane, pollution therein
Substance is by ceramic membrane interception or absorption, and due to the photocatalysis of titanium dioxide, ceramic membrane of the invention has automatic cleaning action,
Compared to conventional ceramic film, membrane flux and film process efficiency all have a clear superiority, effectively using duration extend 30% with
On.
The beneficial effects of the invention are as follows：Ceramic membrane produced by the present invention, low cost of raw materials, and contain and urged with light
Change effect nitrating silica, voluntarily fouling membrane is handled under photocatalysis, improve the membrane flux of itself and
Film process efficiency effectively uses duration compared to conventional ceramic film with longer.
Specific embodiment
It is formed according to mullite raw material, is in mass ratio 3:2 weigh gross mass as the gangue of 5~10kg and aluminium alum
Soil is put into polyurethane ball-milling pot, is added in zirconia ball mill and is turned in horizontal planetary batch mixer with 500~600r/min
Fast 8~10h of ball milling mixing, obtains the mixed-powder of gangue and bauxite；The above-mentioned obtained mixed-powders of 1~2kg is taken to be put into oxygen
Change in aluminium mortar, add in 20~30g cornstarch and 2~3L mass concentrations as 15% poly-vinyl alcohol solution, be placed on afterwards
It on magnetic stirrer, is stirred evenly with the rotating speed of 400~500r/min, be sufficiently mixed dispensing and generate bubble, it afterwards will be mixed
It closes object to be poured on mould for tabletting press, a diameter of 10~15mm sheets supporter is pressed under the high pressure of 190~200MPa；It will be upper
It states sheet supporter obtained and is put into high temperature sintering furnace, to 200 DEG C, heating rate is 5 DEG C/min for temperature programming, and at 200 DEG C
30~40min of lower isothermal holding is warming up to 1300 DEG C to remove moisture therein, then with the rate of 3 DEG C/min, and at 1300 DEG C
2~3h of lower heat preservation sintering, it is spare up to inexpensive mullite porous ceramic film support after being cooled to room temperature；Measurement 15~
20mL silester and 10~15mL absolute ethyl alcohols are poured into 200mL beakers, are stirred evenly with glass bar, are placed on magnetic force afterwards
On mixer, setting rotating speed is 200~300r/min, and it is 80% that 10~15mL mass concentrations are sequentially slowly added dropwise while stirring
Ethanol solution, 15~20mL deionized waters and 1~2mL mass concentrations are 30% hydrochloric acid solution, continue 30~40min of stirring and obtain
To silicon dioxide gel；It measures 15~20mL absolute ethyl alcohols to be put into 500mL beakers, with magnetic stirrer with 800~900r/
The rotating speed of min is vigorously stirred, and 15~20mL butyl titanates and 6~8mL glacial acetic acid, Zhi Houfang are slowly added dropwise in whipping process
Enter ultrasonator, continue 1~2mL of addition ethylenediamines as nitrogen dopant, carry out 30~40min of sonic oscillation obtained solutions 1；
2~3mL deionized waters are measured again to be added in 10~15mL absolute ethyl alcohols, and obtained solution 2, Zhi Houfang is stirred evenly with glass bar
It puts on magnetic stirrer, is stirred with the rotating speed of 200~300r/min, solution 2 is instilled in solution 1 dropwise, be made light
Yellow TiO 2 sol；Inexpensive mullite porous ceramic film support obtained above is used into immersion coating dioxy respectively
SiClx colloidal sol and TiO 2 sol, the material coated stand 24~30h, put it into Muffle furnace afterwards, be passed through at room temperature
Nitrogen is protected, and is warming up to 450 DEG C with the rate program of 2 DEG C/min, constant temperature takes out after keeping 2~3h, naturally cools to room
Temperature is up to a kind of inexpensive self-cleaning ceramic film.
Example 1
It is formed according to mullite raw material, is in mass ratio 3:2 weigh gross mass puts for the gangue and bauxite of 5kg
Into in polyurethane ball-milling pot, zirconia ball mill is added in and in horizontal planetary batch mixer with the rotating speed ball milling mixing of 500r/min
8h obtains the mixed-powder of gangue and bauxite；The above-mentioned obtained mixed-powders of 1kg is taken to be put into aluminium oxide mortar, add in 20g
Cornstarch and the poly-vinyl alcohol solution that 2L mass concentrations are 15%, are placed on magnetic stirrer, afterwards with 400r/min's
Rotating speed stirs evenly, and is sufficiently mixed dispensing and generates bubble, mixture is poured on mould for tabletting press afterwards, 190MPa's
A diameter of 10mm sheets supporter is pressed under high pressure；Sheet supporter obtained above is put into high temperature sintering furnace, program liter
For temperature to 200 DEG C, heating rate is 5 DEG C/min, and at 200 DEG C isothermal holding 30min to remove moisture therein, then with 3 DEG C/
The rate of min is warming up to 1300 DEG C, and the heat preservation sintering 2h at 1300 DEG C, more up to inexpensive mullite after being cooled to room temperature
Hole ceramic film support, it is spare；It measures 15mL silester and 10mL absolute ethyl alcohols is poured into 200mL beakers, stirred with glass bar
It mixes uniformly, is placed on afterwards on magnetic stirrer, setting rotating speed is 200r/min, and 10mL mass is sequentially slowly added dropwise while stirring
The hydrochloric acid solution that ethanol solution, 15mL deionized waters and the 1mL mass concentrations that concentration is 80% are 30% continues to stir 30min
Obtain silicon dioxide gel；It measures 15mL absolute ethyl alcohols to be put into 500mL beakers, with magnetic stirrer with the rotating speed of 800r/min
It is vigorously stirred, 15mL butyl titanates and 6mL glacial acetic acid is slowly added dropwise in whipping process, is put into ultrasonator afterwards, after
Continuous addition 1mL ethylenediamines carry out sonic oscillation 30min obtained solutions 1 as nitrogen dopant；The addition of 2mL deionized waters is measured again
Into 10mL absolute ethyl alcohols, obtained solution 2 is stirred evenly with glass bar, is placed on afterwards on magnetic stirrer, with 200r/min
Rotating speed be stirred, solution 2 is instilled in solution 1 dropwise, be made faint yellow TiO 2 sol；By it is obtained above it is low into
This mullite porous ceramic film support is respectively with immersion coating silicon dioxide gel and TiO 2 sol, the material coated
Material is stood for 24 hours at room temperature, is put it into Muffle furnace afterwards, is passed through nitrogen and is protected, is warming up to the rate program of 2 DEG C/min
450 DEG C, constant temperature takes out after keeping 2h, and cooled to room temperature is up to a kind of inexpensive self-cleaning ceramic film.
The concrete application method of the present invention：Inexpensive self-cleaning ceramic film produced by the present invention is taken to be arranged on treatment tank
In, layer of ceramic film is set every 50cm, 5 layers is set altogether, treatment sewage is allowed to flow through ceramic membrane, polluter therein is made pottery
Porcelain film retains or absorption, and due to the photocatalysis of titanium dioxide, ceramic membrane of the invention has automatic cleaning action, compared to general
Logical ceramic membrane, membrane flux and film process efficiency all have a clear superiority, and effectively extend 33% using duration.
Example 2
It is formed according to mullite raw material, is in mass ratio 3:2 weigh gross mass puts for the gangue and bauxite of 8kg
Into in polyurethane ball-milling pot, zirconia ball mill is added in and in horizontal planetary batch mixer with the rotating speed ball milling mixing of 550r/min
9h obtains the mixed-powder of gangue and bauxite；The above-mentioned obtained mixed-powders of 1kg is taken to be put into aluminium oxide mortar, add in 25g
Cornstarch and the poly-vinyl alcohol solution that 2L mass concentrations are 15%, are placed on magnetic stirrer, afterwards with 450r/min's
Rotating speed stirs evenly, and is sufficiently mixed dispensing and generates bubble, mixture is poured on mould for tabletting press afterwards, 195MPa's
A diameter of 13mm sheets supporter is pressed under high pressure；Sheet supporter obtained above is put into high temperature sintering furnace, program liter
For temperature to 200 DEG C, heating rate is 5 DEG C/min, and at 200 DEG C isothermal holding 35min to remove moisture therein, then with 3 DEG C/
The rate of min is warming up to 1300 DEG C, and the heat preservation sintering 2h at 1300 DEG C, more up to inexpensive mullite after being cooled to room temperature
Hole ceramic film support, it is spare；It measures 18mL silester and 13mL absolute ethyl alcohols is poured into 200mL beakers, stirred with glass bar
It mixes uniformly, is placed on afterwards on magnetic stirrer, setting rotating speed is 250r/min, and 13mL mass is sequentially slowly added dropwise while stirring
The hydrochloric acid solution that ethanol solution, 18mL deionized waters and the 1mL mass concentrations that concentration is 80% are 30% continues to stir 35min
Obtain silicon dioxide gel；It measures 18mL absolute ethyl alcohols to be put into 500mL beakers, with magnetic stirrer with the rotating speed of 850r/min
It is vigorously stirred, 18mL butyl titanates and 7mL glacial acetic acid is slowly added dropwise in whipping process, is put into ultrasonator afterwards, after
Continuous addition 1mL ethylenediamines carry out sonic oscillation 35min obtained solutions 1 as nitrogen dopant；The addition of 2mL deionized waters is measured again
Into 13mL absolute ethyl alcohols, obtained solution 2 is stirred evenly with glass bar, is placed on afterwards on magnetic stirrer, with 250r/min
Rotating speed be stirred, solution 2 is instilled in solution 1 dropwise, be made faint yellow TiO 2 sol；By it is obtained above it is low into
This mullite porous ceramic film support is respectively with immersion coating silicon dioxide gel and TiO 2 sol, the material coated
Material stands 26h at room temperature, puts it into Muffle furnace afterwards, is passed through nitrogen and is protected, is warming up to the rate program of 2 DEG C/min
450 DEG C, constant temperature takes out after keeping 2h, and cooled to room temperature is up to a kind of inexpensive self-cleaning ceramic film.
The concrete application method of the present invention：Inexpensive self-cleaning ceramic film produced by the present invention is taken to be arranged on treatment tank
In, layer of ceramic film is set every 65cm, 7 layers is set altogether, treatment sewage is allowed to flow through ceramic membrane, polluter therein is made pottery
Porcelain film retains or absorption, and due to the photocatalysis of titanium dioxide, ceramic membrane of the invention has automatic cleaning action, compared to general
Logical ceramic membrane, membrane flux and film process efficiency all have a clear superiority, and effectively extend 35% using duration.
Example 3
It is formed according to mullite raw material, is in mass ratio 3:2 weigh the gangue and bauxite that gross mass is 10kg
It puts into polyurethane ball-milling pot, add in zirconia ball mill and is mixed in horizontal planetary batch mixer with the rotating speed ball milling of 600r/min
10h is closed, obtains the mixed-powder of gangue and bauxite；The above-mentioned obtained mixed-powders of 2kg is taken to be put into aluminium oxide mortar, are added in
30g cornstarch and the poly-vinyl alcohol solution that 3L mass concentrations are 15%, are placed on magnetic stirrer, afterwards with 500r/min
Rotating speed stir evenly, be sufficiently mixed dispensing and generate bubble, mixture is poured on mould for tabletting press afterwards, in 200MPa
High pressure under be pressed into a diameter of 15mm sheets supporter；Sheet supporter obtained above is put into high temperature sintering furnace, program
It is warming up to 200 DEG C, heating rate is 5 DEG C/min, and isothermal holding 40min is to remove moisture therein at 200 DEG C, then with 3
DEG C/rate of min is warming up to 1300 DEG C, and the heat preservation sintering 3h at 1300 DEG C, up to inexpensive mullite after being cooled to room temperature
Base porous ceramic film support, it is spare；It measures 20mL silester and 15mL absolute ethyl alcohols is poured into 200mL beakers, use glass
Stick stirs evenly, and is placed on afterwards on magnetic stirrer, and setting rotating speed is 300r/min, and 15mL is sequentially slowly added dropwise while stirring
The hydrochloric acid solution that ethanol solution, 20mL deionized waters and the 2mL mass concentrations that mass concentration is 80% are 30%, continues to stir
40min obtains silicon dioxide gel；It measures 20mL absolute ethyl alcohols to be put into 500mL beakers, with magnetic stirrer with 900r/min
Rotating speed be vigorously stirred, 20mL butyl titanates and 8mL glacial acetic acid are slowly added dropwise in whipping process, is put into sonic oscillation afterwards
Device continues to add 2mL ethylenediamines as nitrogen dopant, carries out sonic oscillation 40min obtained solutions 1；3mL deionized waters are measured again
It is added in 15mL absolute ethyl alcohols, stirs evenly obtained solution 2 with glass bar, be placed on afterwards on magnetic stirrer, with 300r/
The rotating speed of min is stirred, and solution 2 is instilled in solution 1 dropwise, and faint yellow TiO 2 sol is made；It will be obtained above
Inexpensive mullite porous ceramic film support with immersion coating silicon dioxide gel and TiO 2 sol, has coated respectively
Material stand 30h at room temperature, put it into Muffle furnace afterwards, be passed through nitrogen and protected, with the rate program liter of 2 DEG C/min
To 450 DEG C, constant temperature takes out temperature after keeping 3h, and cooled to room temperature is up to a kind of inexpensive self-cleaning ceramic film.
The concrete application method of the present invention：Inexpensive self-cleaning ceramic film produced by the present invention is taken to be arranged on treatment tank
In, layer of ceramic film is set every 80cm, 8 layers is set altogether, treatment sewage is allowed to flow through ceramic membrane, polluter therein is made pottery
Porcelain film retains or absorption, and due to the photocatalysis of titanium dioxide, ceramic membrane of the invention has automatic cleaning action, compared to general
Logical ceramic membrane, membrane flux and film process efficiency all have a clear superiority, and effectively extend 38% using duration.
Claims (1)
- A kind of 1. preparation method of self-cleaning ceramic film, it is characterised in that specific preparation process：(1) formed according to mullite raw material, be in mass ratio 3:2 weigh gross mass as the gangue of 5~10kg and aluminium alum Soil is put into polyurethane ball-milling pot, is added in zirconia ball mill and is turned in horizontal planetary batch mixer with 500~600r/min Fast 8~10h of ball milling mixing, obtains the mixed-powder of gangue and bauxite；(2) the above-mentioned obtained mixed-powders of 1~2kg is taken to be put into aluminium oxide mortar, add in 20~30g cornstarch and 2~3L matter The poly-vinyl alcohol solution that concentration is 15% is measured, is placed on afterwards on magnetic stirrer, it is equal with the rotating speed stirring of 400~500r/min It is even, it is sufficiently mixed dispensing and generates bubble, mixture is poured on mould for tabletting press afterwards, in the high pressure of 190~200MPa Under be pressed into a diameter of 10~15mm sheets supporter；(3) sheet supporter obtained above is put into high temperature sintering furnace, temperature programming to 200 DEG C, heating rate for 5 DEG C/ Min, and 30~40min of isothermal holding is warming up to 1300 to remove moisture therein, then with the rate of 3 DEG C/min at 200 DEG C DEG C, and 2~3h of heat preservation sintering at 1300 DEG C, rear to obtain the final product inexpensive mullite porous ceramic film support is cooled to room temperature, It is spare；(4) measure 15~20mL silester and 10~15mL absolute ethyl alcohols are poured into 200mL beakers, stirred with glass bar equal It is even, it is placed on afterwards on magnetic stirrer, setting rotating speed is 200~300r/min, sequentially it is slowly added dropwise 10 while stirring~ The hydrochloric acid that ethanol solution, 15~20mL deionized waters and the 1~2mL mass concentrations that 15mL mass concentrations are 80% are 30% is molten Liquid continues 30~40min of stirring and obtains silicon dioxide gel；(5) measure 15~20mL absolute ethyl alcohols to be put into 500mL beakers, with magnetic stirrer with the rotating speed of 800~900r/min It is vigorously stirred, 15~20mL butyl titanates and 6~8mL glacial acetic acid is slowly added dropwise in whipping process, be put into ultrasound afterwards and shake Device is swung, continues 1~2mL of addition ethylenediamines as nitrogen dopant, carries out 30~40min of sonic oscillation obtained solutions 1；(6) 2~3mL deionized waters are measured again to be added in 10~15mL absolute ethyl alcohols, obtained solution is stirred evenly with glass bar 2, it is placed on magnetic stirrer, is stirred with the rotating speed of 200~300r/min afterwards, solution 2 is instilled into solution 1 dropwise In, faint yellow TiO 2 sol is made；(7) by inexpensive mullite porous ceramic film support obtained above respectively with immersion coating silicon dioxide gel and TiO 2 sol, the material coated stand 24~30h, put it into Muffle furnace afterwards at room temperature, are passed through nitrogen and are protected Shield is warming up to 450 DEG C with the rate program of 2 DEG C/min, and constant temperature takes out after keeping 2~3h, and cooled to room temperature is up to a kind of Self-cleaning ceramic film.
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| CN109665818A (en) * | 2018-12-03 | 2019-04-23 | 浙江昕明环境科技有限公司 | A kind of firing double-direction control technology of aluminum oxide porous material |
| CN110479111A (en) * | 2019-08-21 | 2019-11-22 | 深圳市盘古环保科技有限公司 | A kind of preparation method of photocatalysis composite ceramic film |
| CN113926441A (en) * | 2021-10-12 | 2022-01-14 | 北京林业大学 | A kind of Si-doped TiO2 nanorod grafting photocatalytic coupling self-cleaning modified ceramic membrane and preparation method thereof |
| CN114230317A (en) * | 2022-01-13 | 2022-03-25 | 罗剑 | Preparation process of rice hull-based bauxite ceramic membrane |
| CN116675554A (en) * | 2023-07-31 | 2023-09-01 | 广东四通建材股份有限公司 | High-strength stone-like ceramic water permeable brick and preparation method thereof |
| CN117065581A (en) * | 2023-09-05 | 2023-11-17 | 山东水发优膜科技有限公司 | Ceramic composite membrane for degreasing wastewater and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665818A (en) * | 2018-12-03 | 2019-04-23 | 浙江昕明环境科技有限公司 | A kind of firing double-direction control technology of aluminum oxide porous material |
| CN109665818B (en) * | 2018-12-03 | 2019-11-26 | 浙江昕明环境科技有限公司 | A kind of firing preparation process of aluminum oxide porous material |
| CN110479111A (en) * | 2019-08-21 | 2019-11-22 | 深圳市盘古环保科技有限公司 | A kind of preparation method of photocatalysis composite ceramic film |
| CN113926441A (en) * | 2021-10-12 | 2022-01-14 | 北京林业大学 | A kind of Si-doped TiO2 nanorod grafting photocatalytic coupling self-cleaning modified ceramic membrane and preparation method thereof |
| CN113926441B (en) * | 2021-10-12 | 2023-11-21 | 北京林业大学 | A Si-doped TiO2 nanorod grafted photocatalytic coupling self-cleaning modified ceramic membrane and its preparation method |
| CN114230317A (en) * | 2022-01-13 | 2022-03-25 | 罗剑 | Preparation process of rice hull-based bauxite ceramic membrane |
| CN116675554A (en) * | 2023-07-31 | 2023-09-01 | 广东四通建材股份有限公司 | High-strength stone-like ceramic water permeable brick and preparation method thereof |
| CN116675554B (en) * | 2023-07-31 | 2023-10-17 | 广东四通建材股份有限公司 | High-strength stone-like ceramic water permeable brick and preparation method thereof |
| CN117065581A (en) * | 2023-09-05 | 2023-11-17 | 山东水发优膜科技有限公司 | Ceramic composite membrane for degreasing wastewater and preparation method thereof |
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