CN108079788A - A kind of preparation method of asymmetric flat ceramic NF membrane - Google Patents
A kind of preparation method of asymmetric flat ceramic NF membrane Download PDFInfo
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- CN108079788A CN108079788A CN201711442268.0A CN201711442268A CN108079788A CN 108079788 A CN108079788 A CN 108079788A CN 201711442268 A CN201711442268 A CN 201711442268A CN 108079788 A CN108079788 A CN 108079788A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 140
- 239000012528 membrane Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004816 latex Substances 0.000 claims abstract description 45
- 229920000126 latex Polymers 0.000 claims abstract description 45
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 49
- 235000015895 biscuits Nutrition 0.000 claims description 24
- 239000002518 antifoaming agent Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 10
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 10
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 10
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229920002774 Maltodextrin Polymers 0.000 claims description 5
- 239000005913 Maltodextrin Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 229910052878 cordierite Inorganic materials 0.000 claims description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920013818 hydroxypropyl guar gum Polymers 0.000 claims description 5
- 229940035034 maltodextrin Drugs 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 235000010981 methylcellulose Nutrition 0.000 claims description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000003854 Surface Print Methods 0.000 claims 1
- 238000010020 roller printing Methods 0.000 abstract description 18
- 238000001914 filtration Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 13
- 230000004907 flux Effects 0.000 abstract description 7
- 238000001728 nano-filtration Methods 0.000 abstract description 7
- 241000256135 Chironomus thummi Species 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000005553 drilling Methods 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 47
- 238000010147 laser engraving Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
Abstract
The invention discloses a kind of preparation methods of asymmetric flat ceramic NF membrane, this method is that the ceramic powder with different chemical compositions and particle size and water base auxiliary agent are mixed ceramic membrane slurry, using special porous latex roller printing on flat ceramic film support, then it is sintered at different temperature, the asymmetric flat ceramic NF membrane with different chemical compositions and pore structure is formed in supporting body surface.Midge hole density, aperture and hole depth on porous latex roller can effectively be adjusted using laser drilling, so as to fulfill the control accurate to ceramic film thickness and uniformity.Ceramic film with different-thickness and surface layer aperture for 5~100nm can be obtained by using the porous latex roller of different hole densities, aperture and hole depth.The asymmetric flat ceramic nanofiltration membrane resistance is small, and filtration flux is high, and service life is long, and manufacturing cost is low, energy conservation and environmental protection.
Description
Technical field
The present invention relates to the technologies of preparing of ceramic membrane, and in particular to a kind of preparation side of asymmetric flat ceramic NF membrane
Method.
Background technology
Ceramic membrane just obtains more and more extensive answer in trade effluent and sanitary wastewater processing, drink water purifying etc.
With playing the effect to become more and more important in environmental protection.But the aperture of ceramic micro filter film is usually between 100~200nm, right
Some fine particles, particularly in water microorganism and organic matter to be separated by filtration effect undesirable, therefore, to some industrial wastewaters
In COD (COD) and BOD (BOD) removal effect it is not notable, it is still difficult after single ceramic micro filter membrane filtration
To reach the discharge of industrial wastewater or reuse requirement.For this purpose, often need to add other chemical agents reduce in waste water COD and
The content of BOD, technological process and processing cost which not only adds wastewater treatment also make chemical composition in waste water more
Complexity is unfavorable for the circulating and recovering of waste water.For fine particle, microorganism and organic matter in waste water is made more effectively to be filtered
Separation, it is necessary to the aperture of ceramic membrane is made to be reduced to below 100nm, and the technique of currently manufactured nanofiltration membrane is asked there are following
Topic：
1. due to nanoparticle activated height, easily there is uneven grow up and makes hole in particle in the sintering process of ceramic membrane
The phenomenon that footpath is uneven, and porosity reduces causes filtering accuracy and filtration flux to reduce.
2. the paint-on technique of existing nanofiltration film layer is mainly realized by silk-screen printing technique, due to wire diameter sizes and aperture
Limitation, the thicknesses of layers printed every time easily lead to film layer thickness usually at 5 μm or more, and when supporter flatness is not good enough
It is thin irregular or even the phenomenon that bite, influence filter efficiency and filtering accuracy.
Therefore, it is to prepare high-performance ceramic to receive how to effectively control the uniform pore diameter and thicknesses of layers of nanofiltration membrane
The key problem in technology of filter membrane.
The content of the invention
It is an object of the invention to provide a kind of preparation method of asymmetric flat ceramic NF membrane, make the hole knot of film layer
Graded is presented in structure from the inside to the outside, so as to effectively improve the bond strength between film layer and supporter, extends nanofiltration membrane
Service life, while high filtration flux can be obtained to greatest extent again.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of asymmetric flat ceramic NF membrane, comprises the following steps：
(1) plastic mud vacuum is extruded as the wet base of hollow type flat ceramic film support, microwave drying obtains flat ceramic
Film support dry body；
(2) according to the material for preparing ceramic film support, flat ceramic film support dry body is burnt at corresponding temperature
Knot, obtains flat ceramic film support biscuit by preferably 1200~1500 DEG C；
(3) laser boring, bore dia 50 are used in the latex roller surface of 300~800mm of length, 200~600mm of diameter
~200 μm, hole depth be 50~150 μm, hole density be 1000~10000/cm2, obtain porous latex roller；
(4) by with it is different composition and grain size ceramic membrane powder with account for powder gross mass 0.2~0.6% dispersant,
0.1~0.5% suspension stabilizer, 0.3~2.0% binding agent, 0.1~0.8% antifoaming agent and 200~800% water
It is mixed with as ceramic membrane slurry；
(5) use porous latex roller printing a layer thickness organic for 1~3 μm on flat ceramic film support biscuit surface
Hole sealing agent；
(6) on the flat ceramic film support biscuit surface for being printed with organic sealing agent, using with different hole densities, hole
The porous latex roller of footpath and hole depth prints the ceramic membrane slurry with identical or different chemical composition and different-grain diameter respectively, pottery
The grain size of porcelain film slurry is sequentially reduced from the inside to the outside, and ceramic film overall thickness is controlled at 5~20 μm；
(7) according to the material for preparing ceramic membrane, the supporter biscuit for being printed with ceramic film is burnt at corresponding temperature
Knot, obtains flat ceramic NF membrane product by preferably 600~1300 DEG C.
The present invention carves different-diameter and the micropore of depth using precise laser engraving technology on latex roller, and rationally adjusts
The spacing between Kong Yukong is controlled, so as to fulfill the accurate control of absorbent ceramic film amount of slurry in latex roller surface hole, Ran Houtong
It crosses certain pressure to squeeze out the ceramic membrane slurry that latex roller surface is adsorbed and be transferred to ceramic film support surface, into one
Step accurately controls the thicknesses of layers for being transferred to ceramic film support surface, uses the party by the regulation and control of ceramic membrane slurry concentration
Method can be by ceramic film thickness control that single prints within 2 μm, and even film layer solves the film layer prepared with spraying process
Thicker and high to the supporter flatness requirement technical barrier of the uniform film layer with silk screen print method preparation of became uneven.Pass through conjunction
Reason regulate and control each membrane layer pulp composition and grain size, it can be achieved that pore structure from supporter to film surface from micron order to nano level
Graded so as to effectively reduce filtration resistance, improves filtration flux.
Further, plastic mud described in step (1) includes one kind in aluminium oxide, carborundum, cordierite or aluminium titanates
It is or a variety of.
Further, the chemical composition of ceramic membrane powder described in step (4) is aluminium oxide, carborundum, cordierite, metatitanic acid
One or more in aluminium, zirconium oxide, silica or titanium oxide, size controlling is between 20~500nm；The ceramic membrane
Powder is subsphaeroidal particle, and particle size distribution range is narrow.
Preferably, dispersant described in step (4) is included in polyvinylpyrrolidone, polyethylene carboxylic acid or ammonium polyacrylate
One or more.
Preferably, suspension stabilizer described in step (4) include hydroxypropyl guar gum, Sodium Polyacrylate, sodium alginate or
One or more in hydroxypropyl methyl cellulose.
Preferably, binding agent described in step (4) includes polyvinyl alcohol, polyethylene glycol, maltodextrin or methylcellulose
In one or more.
Further, antifoaming agent described in step (4) is by organic silicon modified by polyether solution composition.
Further, organic sealing agent described in step (5) includes polyvinyl alcohol, hydroxypropyl methyl cellulose or polyethylene glycol
In one or more, and be modulated into 5~10% solution.
Through asymmetric flat ceramic NF membrane product made from above-mentioned steps, aperture by one lateral outer of supporter according to
Secondary reduction, outermost layer aperture can be adjusted between 5~100nm.
Further explanation is made to the present invention below.
In order to obtain, bond strength is high and the big nanofiltration membrane of filtration flux, it is necessary to try to improve ceramic film support with
Bond strength between membrane material, while reduce the filtration resistance of film layer.In the present invention, the asymmetric apertures structure of film layer is passed through
Design prints the ceramic membrane slurry with identical or different chemical composition and particle size using special porous latex roller by several times
Brush in ceramic membrane supporting body surface, print successively between 2~5 μm by thick by the ceramic film thickness control printed every time
To thin varigrained ceramic membrane slurry 3~5 times.Since porous latex roller surface is using laser accurate engraving, pore size, depth
Degree and density are accurately controlled by computer, are suitable for varigrained ceramic membrane slurry using the latex roller of different hole parameters, together
When can effectively control the thickness of each tunic.Further, since the supporter that latex roller surface is soft, elasticity is good, poor to flatness
Surface can also realize uniform die, and effectively overcome makes film layer uneven or even bite in silk-screen printing due to supporter out-of-flatness
The problem of.Thermal stress between supporter and film layer can effectively be mitigated by the graded of chemical composition, improve supporter and film
The bond strength of interlayer.By the graded of membrane-coating granules size, then the porosity and hole ruler in film layer are effectively had adjusted
It is very little, pore-size is made inwardly gradually to be increased by film surface, and porosity also increased, so as to effectively reduce filtration resistance,
Add filtration flux.
Compared with prior art, advantage of the invention is that：
(1) using laser-engraving technique can accurate control latex roller surface pore size, hole depth and hole density, so as to
Adapt to the ceramic membrane slurry of different-grain diameter, and can by accurately control midge amount number control the thickness of each tunic, and by
The uniformity of thicknesses of layers is ensured in the flexibility and elasticity of latex roller, effectively overcomes conventional spray paint method and silk-screen printing skill
The technical barrier that film layer prepared by art is thicker and screen printing technique is high to supporter flatness requirement.
(2) by adjusting the chemical composition graded of each film layer, the chemical composition of film layer is made by the group close to supporter
It into the surface composition for changing to film successively, can effectively alleviate the thermal stress between supporter and film layer, improve between supporter and film layer
Bond strength.
(3) by adjusting the graded of each membrane layer pulp particle size, the porosity in film layer and hole are effectively had adjusted
Gap size makes pore-size inwardly gradually be increased by film surface, and porosity also increased, and effectively reduce filtration resistance,
Add the filtration flux of nanofiltration membrane.
Specific embodiment
The given examples are served only to explain the present invention below, is not intended to limit the scope of the present invention.
Embodiment 1
A kind of preparation method of asymmetric flat ceramic NF membrane, is as follows：
(1) aluminium oxide of about 5 μm of average grain diameter is prepared as plastic mud, vacuum is extruded as hollow type ceramic membrane branch
The wet base of support body, microwave drying obtain ceramic film support dry body.
(2) ceramic film support dry body at 1350 DEG C is sintered, obtains ceramic film support biscuit.
(3) laser engraving is used in the latex roller surface of length 300mm, diameter 200mm, prepares bore dia 80/ respectively
120/150/180 μm, 60/80/100/120 μm of hole depth, 4444/3086/1975/1370/cm of hole density2Different holes
The porous latex roller in footpath, hole depth and hole density.
(4) on ceramic film support biscuit surface using 4444 80 μm of bore dia, 60 μm of hole depth, hole density/cm2's
The polyvinyl alcohol of porous 2 microns of latex roller printing a layer thickness.
(5) on the ceramic film support biscuit surface for being printed with polyvinyl alcohol, using 180 μm of bore dia, 120 μ of hole depth
M, 1370/cm of hole density2One layer of granularity about 500nm of porous latex roller printing by aluminium oxide and account for aluminium oxide gross mass
0.2% polyvinylpyrrolidone, 0.1% hydroxypropyl guar gum, 0.3% polyvinyl alcohol, 0.1% antifoaming agent and
Ceramic membrane slurry made of 300% water, about 5 μm of thickness；Again using 150 μm of bore dia, 100 μm of hole depth, Kong Mi after drying
Spend 1975/cm2One layer of granularity about 200nm of porous latex roller printing by 50% aluminium oxide and 50% zirconium oxide and account for oxygen
Change the polyvinylpyrrolidone of aluminium and zirconium oxide gross mass 0.2%, 0.1% hydroxypropyl guar gum, 0.3% polyvinyl alcohol,
Ceramic membrane slurry made of 0.1% antifoaming agent and 300% water, about 3 μm of thickness；Finally using 120 μm of bore dia, hole depth
3086 80 μm, hole density/cm2One layer of granularity about 100nm of porous latex roller printing by zirconium oxide and to account for zirconium oxide total
The polyvinylpyrrolidone of quality 0.2%, 0.1% hydroxypropyl guar gum, 0.3% polyvinyl alcohol, 0.1% antifoaming agent and
Ceramic membrane slurry made of 300% water, about 2 μm of thickness.The grain size of ceramic membrane slurry is sequentially reduced from the inside to the outside, ceramics
Film layer overall thickness is controlled at 10 μm or so.
(6) the supporter biscuit for being printed with multi-layer ceramics film slurry at 1100 DEG C is sintered, obtains asymmetric tablet pottery
Porcelain NF membrane product.
It is not less than through asymmetric flat ceramic NF membrane product, the bending strength of supporter made from above-mentioned steps
40MPa, interconnected pore rate about 40%, about 3 μm of average pore size.About 10 μm of ceramic film overall thickness, the porosity of superficial film is about
36%, average pore size about 30nm.
Embodiment 2
A kind of preparation method of asymmetric flat ceramic NF membrane, is as follows：
(1) carborundum (90%) of about 15 μm of average grain diameter is mixed into system with the silicon powder (10%) of average grain diameter 100nm
Standby vacuum is extruded as the wet base of hollow type flat ceramic film support for plastic mud, and microwave drying obtains ceramic film support and does
Base.
(2) ceramic film support dry body at 1450 DEG C is sintered, obtains ceramic film support biscuit.
(3) laser engraving is used in the latex roller surface of length 500mm, diameter 300mm, prepares bore dia 50/ respectively
100/150/200 μm, 50/75/100/125 μm of hole depth, 10000/4000/1975/1089/cm of hole density2Different holes
The porous latex roller in footpath, hole depth and hole density.
(4) on ceramic film support biscuit surface using 4000 100 μm of bore dia, 150 μm of hole depth, hole density/cm2
About 3 μm of porous latex roller printing a layer thickness hydroxypropyl methyl cellulose.
(5) on the ceramic film support biscuit surface for being printed with hydroxypropyl methyl cellulose, using 200 μm of bore dia, hole
1089 125 μm of depth, hole density/cm2About 1 μm of one layer of granularity of porous latex roller printing by carborundum and account for carborundum
The polyethylene carboxylic acid of gross mass 0.3%, 0.2% Sodium Polyacrylate, 0.7% polyethylene glycol, 0.2% antifoaming agent and
Ceramic membrane slurry prepared by 450% water, about 5 μm of thickness；Again using 150 μm of bore dia, 100 μm of hole depth, Kong Mi after drying
Spend 1975/cm2One layer of granularity about 300nm of porous latex roller printing by 50% carborundum and 50% silica and account for
Carborundum and the polyethylene carboxylic acid of silica gross mass 0.3%, 0.2% Sodium Polyacrylate, 0.7% polyethylene glycol,
Ceramic membrane slurry prepared by 0.2% antifoaming agent and 450% water, about 3 μm of thickness；Finally using 50 μm of bore dia, hole depth
10000 50 μm, hole density/cm2One layer of granularity about 50nm of porous latex roller printing silica and account for silica
The polyethylene carboxylic acid of gross mass 0.3%, 0.2% Sodium Polyacrylate, 0.7% polyethylene glycol, 0.2% antifoaming agent and
Ceramic membrane slurry ceramic membrane slurry prepared by 450% water, about 2 μm of thickness.The grain size of ceramic membrane slurry from the inside to the outside according to
Secondary reduction, ceramic film overall thickness are controlled at 10 μm or so.
(6) the supporter biscuit for having printed multi-layer ceramics film slurry at 1000 DEG C is sintered, obtains asymmetric tablet pottery
Porcelain NF membrane product.
It is not less than through asymmetric flat ceramic NF membrane product, the bending strength of supporter made from above-mentioned steps
30MPa, interconnected pore rate about 42%, about 5 μm of average pore size.About 10 μm of ceramic film overall thickness, the porosity of superficial film is about
34%, average pore size about 15nm.
Embodiment 3
A kind of preparation method of asymmetric flat ceramic NF membrane, is as follows：
(1) the cordierite powder of about 10 μm of average grain diameter is prepared as plastic mud, vacuum is extruded as hollow type flat ceramic
The wet base of film support, microwave drying obtain ceramic film support dry body.
(2) ceramic film support dry body at 1300 DEG C is sintered, obtains ceramic film support biscuit.
(3) laser engraving is used in the latex roller surface of length 600mm, diameter 400mm, prepares bore dia 80/ respectively
120/150/180 μm, 60/80/100/120 μm of hole depth, 4444/3086/1975/1370/cm of hole density2Different holes
The porous latex roller in footpath, hole depth and hole density.
(4) on ceramic film support biscuit surface using 4444 80 μm of bore dia, 60 μm of hole depth, hole density/cm2's
The polyethylene glycol of porous about 2 μm of latex roller printing a layer thickness.
(5) on the ceramic film support biscuit surface for being printed with polyethylene glycol, using 180 μm of bore dia, 120 μ of hole depth
M, 1370/cm of hole density2About 1 μm of one layer of granularity of porous latex roller printing by aluminium oxide and account for aluminium oxide gross mass
0.5% ammonium polyacrylate, 0.4% sodium alginate, 1.1% maltodextrin, 0.4% antifoaming agent and 650% water system
Standby ceramic membrane slurry, about 5 μm of thickness；Again using 1975 150 μm of bore dia, 100 μm of hole depth, hole density/cm after drying2
One layer of granularity about 300nm of porous latex roller printing by 50% aluminium oxide and 50% titanium oxide and account for aluminium oxide and titanium oxide
The ammonium polyacrylate of gross mass 0.5%, 0.4% sodium alginate, 1.1% maltodextrin, 0.4% antifoaming agent and 650%
Water prepare ceramic membrane slurry, about 3 μm of thickness；Finally using 120 μm of bore dia, 80 μm of hole depth, hole density 3086/
cm2One layer of granularity about 30nm of porous latex roller printing by titanium oxide and account for the polyacrylic acid of titanium oxide gross mass 0.5%
Ceramic membrane slurry prepared by ammonium, 0.4% sodium alginate, 1.1% maltodextrin, 0.4% antifoaming agent and 650% water,
About 2 μm of thickness.The grain size of ceramic membrane slurry is sequentially reduced from the inside to the outside, and ceramic film overall thickness is controlled at 10 μm or so.
(6) the supporter biscuit for having printed multi-layer ceramics film slurry at 1200 DEG C is sintered, obtains asymmetric nanometer pottery
Porcelain film product.
Through asymmetric nano ceramics film product made from above-mentioned steps, the bending strength of supporter connects not less than 35MPa
Logical porosity about 40%, about 4 μm of average pore size.About 10 μm of ceramic film overall thickness, the porosity about 32% of superficial film are average
Aperture about 10nm.
Embodiment 4
A kind of preparation method of asymmetric flat ceramic NF membrane, is as follows：
(1) aluminium titanates of about 15 μm of average grain diameter is prepared as plastic mud, vacuum is extruded as hollow type ceramic membrane
The wet base of supporter, microwave drying obtain ceramic film support dry body.
(2) ceramic film support dry body at 1200 DEG C is sintered, obtains ceramic film support biscuit.
(3) laser engraving is used in the latex roller surface of length 800mm, diameter 600mm, prepares bore dia 60/ respectively
110/140/200 μm, 70/90/115/140 μm of hole depth, 9000/5000/1735/1121/cm of hole density2Different holes
The porous latex roller in footpath, hole depth and hole density.
(4) on ceramic film support biscuit surface using 9000 60 μm of bore dia, 70 μm of hole depth, hole density/cm2's
The hydroxypropyl methyl cellulose and polyethylene glycol of porous about 1 μm of latex roller printing a layer thickness.
(5) the ceramic film support biscuit surface of hydroxypropyl methyl cellulose and polyethylene glycol is being printed with, using Kong Zhi
1121 200 μm of footpath, 140 μm of hole depth, hole density/cm2About 1 μm of one layer of granularity of porous latex roller printing by aluminium titanates with
And account for the polyvinylpyrrolidone of aluminium titanates gross mass 0.6%, 0.5% hydroxypropyl methyl cellulose, 2.0% Methyl cellulose
Ceramic membrane slurry prepared by element, 0.5% antifoaming agent and 800% water, about 5 μm of thickness；140 μ of bore dia is used after drying again
M, 1735 115 μm of hole depth, hole density/cm2One layer of granularity about 300nm of porous latex roller printing by 50% aluminium titanates with
50% aluminium oxide and to account for the polyvinylpyrrolidone of aluminium titanates and aluminium oxide gross mass 0.6%, 0.5% hydroxypropyl methyl fine
Tie up element, ceramic membrane slurry prepared by 2.0% methylcellulose, 0.5% antifoaming agent and 800% water, about 3 μm of thickness；Most
Afterwards using 5000 110 μm of bore dia, 90 μm of hole depth, hole density/cm2Porous latex roller printing one layer of granularity about 30nm
Aluminium oxide and account for the polyvinylpyrrolidone of aluminium oxide gross mass 0.6%, 0.5% hydroxypropyl methyl cellulose, 2.0%
Ceramic membrane slurry prepared by methylcellulose, 0.5% antifoaming agent and 800% water, about 2 μm of thickness.The grain of ceramic membrane slurry
Footpath size is sequentially reduced from the inside to the outside, and ceramic film overall thickness is controlled at 10 μm or so.
(6) the supporter biscuit for having printed multi-layer ceramics film slurry at 650 DEG C is sintered, obtains asymmetric nano ceramics
Film product.
Through asymmetric nano ceramics film product made from above-mentioned steps, the bending strength of supporter connects not less than 45MPa
Logical porosity about 43%, about 6 μm of average pore size.About 10 μm of ceramic film overall thickness, the porosity about 30% of superficial film are average
Aperture about 20nm.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modifications, equivalent replacements and improvements are made should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of asymmetric flat ceramic NF membrane, which is characterized in that comprise the following steps：
(1) plastic mud vacuum is extruded as the wet base of flat ceramic film support, microwave drying obtains flat ceramic film support and does
Base；
(2) the flat ceramic film support dry body is sintered, obtains flat ceramic film support biscuit；
(3) punched using laser in latex roller surface, obtain porous latex roller, median pore diameter is 50~200 μm, hole depth 50
~150 μm, hole density is 1000~10000/cm2；
(4) by with it is different composition and grain size ceramic membrane powder with account for powder gross mass 0.2~0.6% dispersant, 0.1~
0.5% suspension stabilizer, 0.3~2.0% binding agent, 0.1~0.5% antifoaming agent and 200~800% water mixing system
Standby is ceramic membrane slurry；
(5) use the porous latex roller in described flat ceramic film support biscuit surface printing a layer thickness for 1~3 μm
Organic sealing agent；
(6) on the flat ceramic film support biscuit surface for being printed with organic sealing agent, printed respectively using the porous latex roller
Brush multi-layer ceramics film slurry；The multi-layer ceramics film slurry has identical or different chemical composition；The multi-layer ceramics film slurry
With different-grain diameter, the grain size of ceramic membrane slurry is sequentially reduced from the inside to the outside, and ceramic film overall thickness is controlled in 5~20 μ
m；
(7) the supporter biscuit for being printed with ceramic film is sintered, obtains asymmetric flat ceramic NF membrane.
A kind of 2. preparation method of asymmetric flat ceramic NF membrane according to claim 1, which is characterized in that step
(1) plastic mud described in includes the one or more in aluminium oxide, carborundum, cordierite or aluminium titanates.
A kind of 3. preparation method of asymmetric flat ceramic NF membrane according to claim 1, which is characterized in that step
(3) length of latex roller described in is 300~800mm, a diameter of 200~600mm.
A kind of 4. preparation method of asymmetric flat ceramic NF membrane according to claim 1, which is characterized in that step
(4) chemical composition of ceramic membrane powder described in includes aluminium oxide, carborundum, cordierite, aluminium titanates, zirconium oxide, silica
Or the one or more in titanium oxide, size controlling is in 20~500nm；The ceramic membrane powder is subsphaeroidal particle.
A kind of 5. preparation method of asymmetric flat ceramic NF membrane according to claim 1, which is characterized in that step
(4) dispersant described in includes the one or more in polyvinylpyrrolidone, polyethylene carboxylic acid or ammonium polyacrylate.
A kind of 6. preparation method of asymmetric flat ceramic NF membrane according to claim 1, which is characterized in that step
(4) suspension stabilizer described in is included in hydroxypropyl guar gum, Sodium Polyacrylate, sodium alginate or hydroxypropyl methyl cellulose
It is one or more.
A kind of 7. preparation method of asymmetric flat ceramic NF membrane according to claim 1, which is characterized in that step
(4) binding agent described in includes the one or more in polyvinyl alcohol, polyethylene glycol, maltodextrin or methylcellulose.
A kind of 8. preparation method of asymmetric flat ceramic NF membrane according to claim 1, which is characterized in that step
(4) antifoaming agent described in is by organic silicon modified by polyether solution composition.
A kind of 9. preparation method of asymmetric flat ceramic NF membrane according to claim 1, which is characterized in that step
(5) organic sealing agent described in includes the one or more in polyvinyl alcohol, hydroxypropyl methyl cellulose or polyethylene glycol.
10. according to a kind of preparation method of asymmetric flat ceramic NF membrane of claim 1-9 any one of them, feature exists
In the aperture of gained ceramic membrane is sequentially reduced by one lateral outer of supporter, and outermost layer aperture is 5~100nm.
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