CN111359450B - Ceramic ultrafiltration membrane with efficient photocatalytic function and preparation method thereof - Google Patents
Ceramic ultrafiltration membrane with efficient photocatalytic function and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 88
- 239000000919 ceramic Substances 0.000 title claims abstract description 85
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 56
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 85
- 239000011248 coating agent Substances 0.000 claims abstract description 67
- 238000000576 coating method Methods 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 40
- 239000010936 titanium Substances 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 230000007704 transition Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000007598 dipping method Methods 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- -1 salt ion Chemical class 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- 235000010981 methylcellulose Nutrition 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 31
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 9
- 239000000149 chemical water pollutant Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- 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
- B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
Abstract
The invention discloses a ceramic ultrafiltration membrane with a high-efficiency photocatalytic function and a preparation method thereof, wherein the preparation method comprises the following steps: s1, uniformly stirring 100 parts of coarse-grain-size ceramic matrix powder, 10-30 parts of fine-grain-size ceramic matrix powder, 2-6 parts of binder, 1-3 parts of lubricant and 15-30 parts of water according to parts by weight, forming, preparing a green body and drying; s2, sintering the green body into a porous support body; s3, dipping and coating the coating liquid on the inner surface or the outer surface of the porous support body, drying and sintering to form a transition coating; s4, respectively dipping and coating the outer surface of the transition coating of the porous support body and the surface without the transition coating with the nano titanium sol coating solution and the nano titanium sol coating solution diluted by 1-5 times, and drying to obtain a ceramic membrane substrate; s5, placing the ceramic membrane substrate into a reaction kettle for hydrothermal reaction, and soaking and washing the ceramic membrane substrate with an alkaline solution after the hydrothermal reaction is finished to obtain the ceramic ultrafiltration membrane with the efficient photocatalytic function. The ceramic ultrafiltration membrane prepared by the method has good catalytic effect.
Description
Technical Field
The invention belongs to the technical field of ceramic membrane separation, and particularly relates to a ceramic ultrafiltration membrane with a high-efficiency photocatalytic function and a preparation method thereof.
Background
Ceramic membrane separation has been widely used in the fields of separation of special sewage containing oil, organic solvent, acid and alkali and complex organic matters, MBR water treatment, high-temperature dust removal, tail gas catalysis and other air purification fields. The ceramic membrane has the characteristics of acid and alkali resistance, organic solvent resistance, long service life and stable water outlet.
However, the ceramic membrane applied in the field of sewage treatment has the defect that the interception rate of COD except oil is not high, usually only 10-30%, and the interception rate of ammonia nitrogen is basically not high. In air purification, it does not have the interception or degradation capability of VOCS or organic waste gases. The nano titanium oxide has the characteristic of photocatalytic degradation of organic matters, is already used for VOCS treatment and sewage treatment, and has certain degradation capability on COD and ammonia nitrogen in sewage. However, the nano titanium oxide loses catalytic activity after being sintered again at high temperature. Therefore, the waste water is usually added directly into the sewage to be treated in a powder form and is easy to lose. Or the nano titanium oxide is bonded in substances such as a filter screen, diatom ooze and the like by using an organic binder, the catalytic capability of the nano titanium oxide is blocked by the organic binder, the catalytic capability is reduced, and the organic binder is firstly catalyzed and degraded along with the photocatalysis process, so that the nano titanium oxide falls off. Meanwhile, the catalytic ability of the nano titanium oxide needs high-frequency ultraviolet light, and the wavelength is usually required to be below 385nm, which limits the catalytic effect of the nano titanium oxide in practical application, because the high-frequency ultraviolet light has poor penetrating power and is easy to absorb.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a ceramic ultrafiltration membrane with high efficiency photocatalytic function and a preparation method thereof, wherein the prepared ceramic membrane can greatly improve the catalytic time of the filtration process and improve the catalytic effect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a ceramic ultrafiltration membrane with a high-efficiency photocatalytic function comprises the following steps:
s1, uniformly stirring 100 parts of coarse-grain-size ceramic matrix powder, 10-30 parts of fine-grain-size ceramic matrix powder, 2-6 parts of binder, 1-3 parts of lubricant and 15-30 parts of water according to parts by weight, forming, preparing a tubular or flat green body, and drying.
S2, putting the green body dried in the step S1 into a kiln to sinter into a porous support body.
And S3, dipping and coating the coating liquid on the inner surface or the outer surface of the porous support body, drying and sintering to obtain the porous support body with the porous transition coating on one surface.
And S4, respectively dipping and coating the nano titanium sol coating solution and the nano titanium sol coating solution diluted by 1-5 times by water on the outer surface of the porous support body transition coating prepared in the step S3 and the surface without the transition coating, and drying to prepare the ceramic membrane substrate.
And S5, placing the ceramic membrane substrate into a high-pressure reaction kettle, adding purified water into the reaction kettle to completely submerge the ceramic membrane substrate, sealing the reaction kettle and carrying out hydrothermal reaction, taking out the ceramic membrane substrate after the reaction is finished, and soaking and washing the ceramic membrane substrate with an alkaline solution to remove organic matters, thereby preparing the ceramic ultrafiltration membrane with the efficient photocatalytic function.
Further, the grain size of the coarse-grain ceramic matrix powder is 20-100 um, and the grain size of the fine-grain ceramic matrix powder is 0.3-3 um.
Further, the ceramic matrix powder is high-purity quartz powder with the purity higher than 99.5% or high-purity alumina powder with the purity higher than 99.9%.
Further, the coating solution in step S3 includes the following raw materials in parts by mass: 5-30 parts of ceramic matrix powder with the particle size of 0.1-1 um, 1-5 parts of binder, 1-5 parts of film forming agent and 100 parts of water.
Further, in step S4, the preparation of the nano titanium sol coating solution includes the following steps:
p1, adding nitrate into 5-20% titanyl sulfate solution to make the concentration of salt ion be 0.0005-0.2% of titanium ion concentration.
P2, adding 5-10% ammonia water solution into the solution prepared in the step P1, and stirring to react until the pH value of the solution is 8-9.
P3 washing the solution obtained in step P2 with water and suction-filtering the precipitate until the sulfate ion concentration in the precipitate is less than 10 ppm.
P4, adding water into the solution prepared in the step P3, and stirring until the concentration of titanium ions is 0.8-8% of the total mass of the solution.
And P5, adding a 4-20% nitric acid aqueous solution until the pH of the solution is reduced to 0.5-1.5, and stirring the solution for 4-12 hours at the temperature of 60-85 ℃ to prepare the titanium solution.
And P6, adding 1-10 parts of water into the prepared titanium solution, uniformly stirring, adding a film-forming agent accounting for 1-8% of the total mass of the solution and a binder accounting for 0.3-4% of the total mass of the solution, and uniformly stirring to obtain the nano titanium sol coating solution.
The nitrate is one or more of manganese nitrate, gadolinium nitrate and vanadium nitrate, and the sum of the concentrations of one or more of manganese ions, gadolinium ions and vanadium ions is 0.0005-0.2% of the concentration of titanium ions.
The plasticizer is one or two of glycerol and polyethylene glycol, the addition amount of the glycerol is 2-5% of the total mass of the solution, and the addition amount of the polyethylene glycol is 1-3% of the total mass of the solution.
The binder is one or two of methyl cellulose and polyvinyl alcohol, the addition amount of the methyl cellulose is 0.3-1% of the total mass of the solution, and the addition form is dry powder or aqueous solution; the addition amount of the polyvinyl alcohol is 0.5-3% of the total mass of the solution, and the addition form is 10-30% of aqueous solution.
Further, the dipping time in the step S3 and the step S4 is 30-300S.
Further, the drying temperature in the step S1, the step S3 and the step S4 is 50-120 ℃, and the drying time is 8-60 hours.
Further, the sintering temperature of the porous support body is 1400-1750 ℃, the sintering time is 30-80 hours, the sintering temperature of the transition coating is 1200-1500 ℃, and the sintering time is 10-50 hours.
Further, in the step S5, the temperature of the hydrothermal reaction is 180-235 ℃, and the hydrothermal heat preservation time is 6-24 hours.
Preferably, the alkaline solution used in step S5 is an aqueous sodium hydroxide solution.
The invention also discloses a ceramic ultrafiltration membrane with high-efficiency photocatalysis function, which is prepared by adopting the method.
The invention has the following beneficial effects:
1. the diluted nanometer titanium oxide particles are impregnated in the support body and hydrothermally synthesized, and due to the dilute impregnation concentration, an ultrafiltration coating with small pore diameter is not formed but is dispersed in the large pores of the support body. Therefore, the catalytic stroke and time of the filtering process are greatly improved, and the catalytic effect is improved.
2. The sol-hydrothermal method is adopted to directly form firm bonding on the support body, so that the inactivation problem caused by high-temperature sintering is avoided, and the nano titanium oxide ultrafiltration membrane layer with high catalytic efficiency is obtained, and the catalytic activity of the nano titanium oxide ultrafiltration membrane layer is 4-10 times higher than that of the nano titanium oxide ultrafiltration membrane layer sintered at high temperature.
3. High-purity quartz powder is used as a support body and a transition layer material, or high-purity alumina is used as the support body and the transition layer material. The two materials have high permeability to ultraviolet light, so that the ultraviolet light can penetrate through the support body and be absorbed by the titanium oxide inside, and a photocatalytic function is obtained. The common support has high shielding performance on ultraviolet light, and the nano titanium oxide is difficult to obtain enough ultraviolet light for catalysis.
4. The lattice distortion of the nano titanium oxide crystal can be formed by adding micro manganese and vanadium plasma, so that the ultraviolet absorption wavelength of the nano titanium oxide crystal is improved, and the ultraviolet absorption wavelength can be generally improved from 385nm to 420-450nm, so that the catalytic efficiency of the nano titanium oxide crystal is improved.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example one
A preparation method of a ceramic ultrafiltration membrane with a high-efficiency photocatalytic function comprises the following steps:
the method comprises the following steps of firstly, uniformly stirring 100 parts by mass of high-purity quartz powder with the particle size of 20 microns and the purity higher than 99.5%, 15 parts by mass of high-purity quartz powder with the particle size of 0.3 micron and the purity higher than 99.5%, 5 parts by mass of a binder, 2 parts by mass of a lubricant and 20 parts by mass of water, extruding or compression molding to form a tubular or flat green body, and drying.
And secondly, putting the dried green body into a kiln to sinter the green body into a high-purity quartz porous support body with certain strength, wherein the sintering temperature is 1600 ℃, and the sintering time is 50 hours.
And step three, uniformly mixing 15 parts of high-purity quartz powder with the particle size of 0.1um and the purity of more than 99.5 percent, 2 parts of binder, 3 parts of film-forming agent and 100 parts of water to form the film coating liquid.
And fourthly, dipping and coating the coating liquid on one surface of the inner surface or the outer surface of the porous support body, drying and sintering, wherein the dipping time is 100s, the drying temperature is 120 ℃, the drying time is 8h, the sintering temperature is 1200 ℃, and the sintering time is 25h, so that one surface of the support body is provided with a porous transition coating with a certain thickness and a finer pore diameter.
Fifthly, adding manganese nitrate into the titanyl sulfate solution with the concentration of 10% to ensure that the concentration of manganese ions is 0.0005-0.2% of that of titanium ions; dropwise adding 5% ammonia water solution, and stirring for reaction until the pH value of the solution is 8-9; filtering the solution with precision filter paper to obtain precipitate, and continuously adding water for filtering until the concentration of sulfate ions in the precipitate is lower than 10 ppm; adding a certain amount of water and stirring to ensure that the concentration of titanium ions is 0.8-8% of the total mass of the solution; continuously adding 4% nitric acid aqueous solution into the solution until the pH value of the solution is reduced to 0.5-1.5, and stirring for 8h at 60 ℃ to obtain a titanium solution; adding 10 parts of water into the prepared titanium solution, uniformly stirring, adding glycerol accounting for 2% of the total mass of the solution and a methyl cellulose aqueous solution accounting for 0.3% of the total mass of the solution, and uniformly stirring to form the nano titanium sol coating solution.
And sixthly, dipping and coating the nano titanium sol coating liquid on the surface of the transition coating for 120s, and then drying for 15h at the temperature of 90 ℃.
And seventhly, diluting the nano titanium sol coating solution by 2 times, dipping and coating the surface of the support body without the transition coating for 50s, and drying for 24h at 75 ℃.
And eighthly, placing the dried support body into a high-pressure reaction kettle, adding purified water into the reaction kettle, completely submerging the ceramic membrane substrate, sealing the reaction kettle, heating to 200 ℃, keeping the temperature for 10 hours to carry out hydrothermal reaction, taking out the ceramic membrane substrate after the reaction is finished, soaking and washing the ceramic membrane substrate by using a sodium hydroxide aqueous solution with the concentration of 1% to remove organic matters, and obtaining the ceramic ultrafiltration membrane with the photocatalytic function, wherein one surface of the ceramic ultrafiltration membrane has a complete nano titanium oxide membrane layer, and the whole support body is dispersedly sintered with nano titanium oxide particles.
The ceramic ultrafiltration membrane with the high-efficiency photocatalytic function prepared in the embodiment is tested, 2 ultraviolet light with 10 watts is adopted, the ceramic ultrafiltration membrane is irradiated left and right in a natural light source, and the MBR process is carried out on the biochemical landfill leachate. Water inlet conditions are as follows: COD was 793mg/L and ammonia nitrogen was 109mg/L, and the influent water was passed through the ceramic ultrafiltration membrane at a flow rate of 4 m/s under a filtration pressure of 0.2MPa, and the test results are shown in Table 1.
Example two
A preparation method of a ceramic ultrafiltration membrane with a high-efficiency photocatalytic function comprises the following steps:
the method comprises the following steps of firstly, uniformly stirring 100 parts by mass of high-purity alumina powder with the particle size of 50 microns and the purity higher than 99.9%, 30 parts by mass of high-purity alumina powder with the particle size of 1.5 microns and the purity higher than 99.5%, 6 parts by mass of a binder, 3 parts by mass of a lubricant and 20 parts by mass of water, extruding or compression molding to form a tubular or flat green body, and drying.
And secondly, putting the dried green body into a kiln to sinter the green body into a high-purity quartz porous support body with certain strength, wherein the sintering temperature is 1600 ℃, and the sintering time is 80 hours.
And thirdly, uniformly mixing 10 parts of high-purity aluminum oxide powder with the particle size of 0.5um and the purity of more than 99.5 percent, 3 parts of a binder, 3 parts of a film forming agent and 100 parts of water to form the film coating liquid.
And fourthly, dipping and coating the coating liquid on one surface of the inner surface or the outer surface of the porous support body, drying and sintering, wherein the dipping time is 150s, the drying temperature is 90 ℃, the drying time is 30h, the sintering temperature is 1350 ℃, and the sintering time is 15h, so that one surface of the support body is provided with a porous transition coating with a certain thickness and a thinner pore diameter.
Fifthly, adding manganese nitrate into a 15% titanyl sulfate solution to enable the concentration of manganese ions to be 0.0005-0.2% of that of titanium ions; dropwise adding 8% ammonia water solution, and stirring for reaction until the pH value of the solution is 8-9; filtering the solution with precision filter paper to obtain precipitate, and continuously adding water for filtering until the concentration of sulfate ions in the precipitate is lower than 10 ppm; adding a certain amount of water and stirring to ensure that the concentration of titanium ions is 0.8-8% of the total mass of the solution; continuously adding 10% nitric acid aqueous solution into the solution until the pH value of the solution is reduced to 0.5-1.5, and stirring for 6h at 75 ℃ to obtain a titanium solution; adding 5 parts of water into the prepared titanium solution, uniformly stirring, adding polyethylene glycol accounting for 1% of the total mass of the solution and polyvinyl alcohol aqueous solution accounting for 0.5% of the total mass of the solution and having a concentration of 20%, and uniformly stirring to form the nano titanium sol coating solution.
And sixthly, dipping and coating the nano titanium sol coating liquid on the surface of the transition coating for 200s, and then drying for 8h at the temperature of 120 ℃.
And seventhly, diluting the nano titanium sol coating solution by 3 times, dipping and coating the surface of the support body without the transition coating for 100s, and drying for 18h at the temperature of 100 ℃.
And eighthly, placing the dried support body into a high-pressure reaction kettle, adding purified water into the reaction kettle, completely submerging the ceramic membrane substrate, sealing the reaction kettle, heating to 180 ℃, keeping the temperature for 14 hours to carry out hydrothermal reaction, taking out the ceramic membrane substrate after the reaction is finished, soaking and washing the ceramic membrane substrate by using a sodium hydroxide aqueous solution with the concentration of 2% to remove organic matters, and obtaining the ceramic ultrafiltration membrane with the photocatalytic function, wherein one surface of the ceramic ultrafiltration membrane has a complete nano titanium oxide membrane layer, and the whole support body is dispersedly sintered with nano titanium oxide particles.
The ceramic ultrafiltration membrane with the high-efficiency photocatalytic function prepared in the embodiment is tested, 2 ultraviolet light with 10 watts is adopted, the ceramic ultrafiltration membrane is irradiated left and right in a natural light source, and the MBR process is carried out on the biochemical landfill leachate. Water inlet conditions are as follows: COD was 793mg/L and ammonia nitrogen was 109mg/L, and the influent water was passed through the ceramic ultrafiltration membrane at a flow rate of 4 m/s under a filtration pressure of 0.2MPa, and the test results are shown in Table 1.
EXAMPLE III
A preparation method of a ceramic ultrafiltration membrane with a high-efficiency photocatalytic function comprises the following steps:
the method comprises the following steps of firstly, uniformly stirring 100 parts by mass of high-purity quartz powder with the particle size of 100 microns and the purity higher than 99.5%, 20 parts by mass of high-purity quartz powder with the particle size of 3 microns and the purity higher than 99.5%, 8 parts by mass of a binder, 2 parts by mass of a lubricant and 22 parts by mass of water, extruding or compression molding to form a tubular or flat green body, and drying.
And secondly, putting the dried green body into a kiln to sinter the green body into a high-purity quartz porous support body with certain strength, wherein the sintering temperature is 1750 ℃ and the sintering time is 55 h.
And step three, uniformly mixing 12 parts of high-purity quartz powder with the particle size of 1um and the purity higher than 99.5%, 2 parts of a binder, 4 parts of a film forming agent and 100 parts of water to form a coating liquid.
And fourthly, dipping and coating the coating liquid on one surface of the inner surface or the outer surface of the porous support body, drying and sintering, wherein the dipping time is 300s, the drying temperature is 120 ℃, the drying time is 15h, the sintering temperature is 1500 ℃, and the sintering time is 25h, so that one surface of the support body is provided with a porous transition coating with a certain thickness and a thinner pore diameter.
Fifthly, adding manganese nitrate into a 12% titanyl sulfate solution to enable the concentration of manganese ions to be 0.0005-0.2% of that of titanium ions; dripping 10% ammonia water solution and stirring for reaction until the pH value of the solution is 8-9; filtering the solution with precision filter paper to obtain precipitate, and continuously adding water for filtering until the concentration of sulfate ions in the precipitate is lower than 10 ppm; adding a certain amount of water and stirring to ensure that the concentration of titanium ions is 0.8-8% of the total mass of the solution; continuously adding 20% nitric acid aqueous solution into the solution until the pH value of the solution is reduced to 0.5-1.5, and stirring for 10 hours at 85 ℃ to obtain a titanium solution; adding 5 parts of water into the prepared titanium solution, uniformly stirring, respectively adding 2% of glycerol, 1% of polyethylene glycol, 0.5% of methyl cellulose and 10% of polyvinyl alcohol, and uniformly stirring to obtain the nano titanium sol coating solution.
And sixthly, dipping and coating the nano titanium sol coating liquid on the surface of the transition coating for 200s, and then drying for 20h at the temperature of 100 ℃.
And seventhly, diluting the nano titanium sol coating solution by 5 times, dipping and coating the surface of the support body without the transition coating for 150s, and drying for 15h at the temperature of 110 ℃.
And eighthly, placing the dried support body into a high-pressure reaction kettle, adding purified water into the reaction kettle, completely submerging the ceramic membrane substrate, sealing the reaction kettle, heating to 230 ℃, keeping the temperature for 12 hours to carry out hydrothermal reaction, taking out the ceramic membrane substrate after the reaction is finished, soaking and washing the ceramic membrane substrate by using a 3% sodium hydroxide aqueous solution to remove organic matters, and obtaining the ceramic ultrafiltration membrane with the photocatalytic function, wherein one surface of the ceramic ultrafiltration membrane has a complete nano titanium oxide membrane layer, and the whole support body is dispersedly sintered with nano titanium oxide particles.
The ceramic ultrafiltration membrane with the high-efficiency photocatalytic function prepared in the embodiment is tested, 2 ultraviolet light with 10 watts is adopted, the ceramic ultrafiltration membrane is irradiated left and right in a natural light source, and the MBR process is carried out on the biochemical landfill leachate. Water inlet conditions are as follows: COD was 793mg/L and ammonia nitrogen was 109mg/L, and the influent water was passed through the ceramic ultrafiltration membrane at a flow rate of 4 m/s under a filtration pressure of 0.2MPa, and the test results are shown in Table 1.
Comparative example 1
A common ceramic membrane support body and a high-temperature sintered nano titanium oxide ultrafiltration membrane are adopted for carrying out comparison test, 2 10-watt ultraviolet light is adopted to irradiate the ceramic ultrafiltration membrane from left to right in a natural light source, and MBR process is carried out on the biochemical landfill leachate. Water inlet conditions are as follows: COD was 793mg/L and ammonia nitrogen was 109mg/L, and the influent water was passed through the ceramic ultrafiltration membrane at a flow rate of 4 m/s under a filtration pressure of 0.2MPa, and the test results are shown in Table 1.
Comparative example No. two
A common ceramic membrane support body and a sol-hydrothermal nano titanium oxide ultrafiltration membrane are adopted for comparison test, 2 10W ultraviolet light is adopted, the ceramic ultrafiltration membrane is irradiated left and right in a natural light source, and the MBR process is carried out on the biochemical landfill leachate. Water inlet conditions are as follows: COD was 793mg/L and ammonia nitrogen was 109mg/L, and the influent water was passed through the ceramic ultrafiltration membrane at a flow rate of 4 m/s under a filtration pressure of 0.2MPa, and the test results are shown in Table 1.
Comparative example No. three
The method is characterized in that a high-purity quartz or high-purity alumina ceramic membrane matrix with high ultraviolet light transmittance and a sol-hydrothermal titanium oxide ultrafiltration membrane are adopted for comparison test, 2 10W ultraviolet lights are adopted to irradiate the ceramic ultrafiltration membrane from left to right in a natural light source, and the biochemical landfill leachate is subjected to MBR process. Water inlet conditions are as follows: COD was 793mg/L and ammonia nitrogen was 109mg/L, and the influent water was passed through the ceramic ultrafiltration membrane at a flow rate of 4 m/s under a filtration pressure of 0.2MPa, and the test results are shown in Table 1.
Analysis of results
The traditional method only coats the nano titanium sol coating liquid on the transition coating to form the titanium oxide ultrafiltration membrane, and the aperture of the ultrafiltration membrane is very small and is usually only 10-50nm, so the thickness of the ultrafiltration membrane can only be maintained at 0.5-20 microns, and the excessive thickness can cause lower permeation flux of water and gas, therefore, the sewage or VOCS gas is filtered at the thickness of 0.5-20 microns, the catalysis time is too short, and the catalysis effect is insufficient. The invention additionally impregnates the inside of the support body and hydrothermally synthesizes thinner nano titanium oxide particles, and because of the dilute impregnation concentration, an ultrafiltration coating with small aperture can not be formed, but is dispersed in the large aperture of the support body. Therefore, the catalytic stroke and time of the filtering process are greatly improved, and the catalytic effect is improved. Meanwhile, the nano titanium oxide loses catalytic activity by adopting high-temperature sintering, and the catalytic activity is reduced by 80-90 percent generally. And the sol-hydrothermal method directly forms firm bonding on the support body, so that the inactivation problem caused by high-temperature sintering is avoided, and the nano titanium oxide ultrafiltration membrane layer with high catalytic efficiency is obtained, and the catalytic activity of the nano titanium oxide ultrafiltration membrane layer is 4-10 times higher than that of the nano titanium oxide ultrafiltration membrane layer sintered at high temperature.
The test results of example one, example two, example three, comparative example one, comparative example two, and comparative example three are summarized as shown in table 1.
Table 1: test results of COD content and ammonia nitrogen content of filtered water
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of a ceramic ultrafiltration membrane with a high-efficiency photocatalytic function is characterized by comprising the following steps:
s1, uniformly stirring 100 parts of coarse-grain-size ceramic matrix powder, 10-30 parts of fine-grain-size ceramic matrix powder, 2-6 parts of binder, 1-3 parts of lubricant and 15-30 parts of water according to parts by weight, forming, preparing a tubular or flat green body and drying; the grain size of the coarse-grain ceramic matrix powder is 20-100 um, and the grain size of the fine-grain ceramic matrix powder is 0.3-3 um; the ceramic matrix powder is high-purity quartz powder with the purity higher than 99.5 percent or high-purity alumina powder with the purity higher than 99.9 percent;
s2, putting the green body dried in the step S1 into a kiln, and sintering into a porous support body;
s3, dipping and coating the coating liquid on the inner surface or the outer surface of the porous support body, drying and sintering to obtain the porous support body with a porous transition coating on one surface;
s4, respectively dipping and coating the nano titanium sol coating solution and the nano titanium sol coating solution diluted by 1-5 times by water on the outer surface of the transition coating of the porous support body prepared in the step S3 and the surface without the transition coating, and drying to prepare a ceramic membrane substrate; the preparation of the nano titanium sol coating solution comprises the following steps:
p1, adding nitrate into 5-20% titanyl sulfate solution to make the concentration of salt ion be 0.0005-0.2% of titanium ion concentration;
p2, dripping 5-10% ammonia water solution into the solution prepared in the step P1, and stirring for reaction until the pH value of the solution is 8-9;
p3, washing the solution prepared in the step P2 with water and filtering out precipitates until the sulfate ion concentration in the precipitates is lower than 10 ppm;
p4, adding water into the solution prepared in the step P3, and stirring until the concentration of titanium ions is 0.8-8% of the total mass of the solution;
p5, adding a nitric acid water solution with the concentration of 4-20% until the pH value of the solution is reduced to 0.5-1.5, and stirring the solution for 4-12 hours at the temperature of 60-85 ℃ to prepare a titanium solution;
p6, adding 1-10 parts of water into the prepared titanium solution, uniformly stirring, adding a film-forming agent accounting for 1-8% of the total mass of the solution and a binder accounting for 0.3-4% of the total mass of the solution, and uniformly stirring to obtain a nano titanium sol coating solution;
and S5, placing the ceramic membrane substrate into a high-pressure reaction kettle, adding purified water into the reaction kettle to completely submerge the ceramic membrane substrate, sealing the reaction kettle and carrying out hydrothermal reaction, taking out the ceramic membrane substrate after the reaction is finished, and soaking and washing the ceramic membrane substrate with an alkaline solution to remove organic matters, thereby preparing the ceramic ultrafiltration membrane with the efficient photocatalytic function.
2. The method for preparing a ceramic ultrafiltration membrane with a high-efficiency photocatalytic function according to claim 1, wherein the membrane coating solution in the step S3 comprises the following raw materials in parts by mass: 5-30 parts of ceramic matrix powder with the particle size of 0.1-1 um, 1-5 parts of binder, 1-5 parts of film forming agent and 100 parts of water.
3. The method for preparing the ceramic ultrafiltration membrane with the high-efficiency photocatalysis function according to claim 1, which is characterized in that: the nitrate is one or more of manganese nitrate, gadolinium nitrate and vanadium nitrate, and the sum of the concentrations of one or more of manganese ions, gadolinium ions and vanadium ions is 0.0005-0.2% of the concentration of titanium ions.
4. The method for preparing the ceramic ultrafiltration membrane with the high-efficiency photocatalysis function according to claim 1, which is characterized in that: the film forming agent is one or two of glycerol and polyethylene glycol, the addition amount of the glycerol is 2-5% of the total mass of the solution, and the addition amount of the polyethylene glycol is 1-3% of the total mass of the solution.
5. The method for preparing the ceramic ultrafiltration membrane with the high-efficiency photocatalysis function according to claim 1, which is characterized in that: the binder is one or two of methyl cellulose and polyvinyl alcohol, the addition amount of the methyl cellulose is 0.3-1% of the total mass of the solution, and the addition form is dry powder or aqueous solution; the addition amount of the polyvinyl alcohol is 0.5-3% of the total mass of the solution, and the addition form is 10-30% of aqueous solution.
6. The method for preparing the ceramic ultrafiltration membrane with the high-efficiency photocatalysis function according to claim 1, which is characterized in that: the dipping time in the step S3 and the step S4 is 30-300S, the drying temperature in the step S1, the drying time in the step S3 and the drying time in the step S4 are 50-120 ℃, the drying time is 8-60 h, the sintering temperature of the porous support body is 1400-1750 ℃, the sintering time is 30-80 h, the sintering temperature of the transition coating is 1200-1500 ℃, the sintering time is 10-50 h, the hydrothermal reaction temperature in the step S5 is 180-235 ℃, the hydrothermal heat preservation time is 6-24 h, and the alkaline solution adopted in the step S5 is a sodium hydroxide aqueous solution.
7. A ceramic ultrafiltration membrane with high efficiency photocatalytic function prepared by the method of any one of claims 1 to 6.
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