CN115245751A - Preparation method of catalytic self-cleaning ceramic membrane - Google Patents
Preparation method of catalytic self-cleaning ceramic membrane Download PDFInfo
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- CN115245751A CN115245751A CN202111573982.XA CN202111573982A CN115245751A CN 115245751 A CN115245751 A CN 115245751A CN 202111573982 A CN202111573982 A CN 202111573982A CN 115245751 A CN115245751 A CN 115245751A
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- 239000012528 membrane Substances 0.000 title claims abstract description 138
- 239000000919 ceramic Substances 0.000 title claims abstract description 90
- 238000004140 cleaning Methods 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000004907 flux Effects 0.000 claims abstract description 16
- -1 iron ions Chemical class 0.000 claims abstract description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims description 20
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 19
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 8
- 239000002569 water oil cream Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
-
- 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
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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Abstract
The invention relates to the technical field of separation membrane materials, in particular to a preparation method of a catalytic self-cleaning ceramic membrane. The method grafts the p-acyl chloride pyridine on the surface of the ceramic membrane and the pore wall through a covalent bond, coordinates iron ions through N element on the pyridine ring, reduces the iron ions into nano iron atoms through hydrazine hydrate, and finally oxidizes the iron atoms into nano iron oxide particles in the air. The nano ferric oxide on the surface and the pores of the catalytic self-cleaning ceramic membrane prepared by the method is uniformly distributed, high-temperature calcination is not needed, the permeation flux and the pollution resistance of the membrane are improved, and most importantly, the catalytic self-cleaning capability of the ceramic membrane is also endowed.
Description
Technical Field
The invention relates to the technical field of separation membrane materials, in particular to a preparation method of a catalytic self-cleaning ceramic membrane.
Background
As an advanced separation membrane material, the inorganic ceramic membrane is widely applied to the fields of chemical production, food processing, bio-pharmaceuticals, wastewater treatment, sewage recycling, deep purification of drinking water and the like. Compared with a polymer organic membrane, the ceramic membrane has the characteristics of high mechanical strength, acid and alkali resistance, high temperature resistance, resistance to various organic solvents and oxidants, good pollution resistance, high filtration precision, long service life and the like. In recent years, flat plate-shaped ceramic membranes are widely applied to a domestic sewage membrane bioreactor process, and the ceramic membranes show high water production flux and excellent service life and are indispensably favored by people.
However, as the use time is prolonged, inevitable membrane contamination is increased and the water yield of the membrane is decreased, thereby failing to meet the demand for real production. Conventional backwashing and sodium hypochlorite soaking are also insufficient to return the membrane flux to the original level. The chemical cleaning by soaking in acid-base aqueous solution is the most effective and direct solution, but the acid-base cleaning causes damages to membrane materials, membrane assemblies and membrane separation performance, and mainly causes secondary pollution to the environment.
Therefore, the development of a ceramic membrane with catalytic self-cleaning function has been the focus of attention. Conventionally, transition metal oxides with catalytic activity are doped into a membrane substrate or a membrane transition layer and a separation layer, but the melting substances formed by high-temperature firing are inevitable, so that a large number of pockmark-shaped defects are formed on the surface of the membrane material, and the filtration performance is seriously influenced. Alternatively, the fired ceramic membrane is impregnated with an aqueous solution of transition metal nitrate, and then calcined at high temperature for crystallization. The porous ceramic membrane adsorbs nitrate aqueous solution by means of capillary action force, so that the distribution is uneven, and after high-temperature calcination and crystallization, metal oxide crystals grow up, the pore blockage of the ceramic membrane is easy to occur, the water permeation resistance is increased, and the membrane permeation flux is very low.
The invention relates to a method for preparing nano iron oxide by using a ceramic membrane, which is characterized in that abundant hydroxyl functional groups on the surface and the pore wall of the ceramic membrane are used as active sites, p-acyl chloride pyridine is grafted, then iron ions are coordinated, hydrazine hydrate is used for reducing the iron ions into a nano iron simple substance, and finally the nano iron oxide is oxidized into the nano iron oxide in the air. The method does not need high-temperature calcination, namely the nano iron oxide can be uniformly distributed on the surface of the ceramic membrane and the pore wall, and the risk that metal ions are calcined into oxides at high temperature and crystals grow to block the pores of the membrane can be avoided. The surface and the pore wall of the ceramic membrane are grafted with nano iron oxide with the function of catalytically activating hydrogen peroxide, when the membrane is polluted and blocked, the membrane seriously polluted is soaked in hydrogen peroxide solution for a period of time, and the nano iron oxide activates the hydrogen peroxide to generate hydroxyl radicals with the oxidation potential of 2.80 eV. The hydroxyl free radicals can degrade pollutants adsorbed or deposited on the surface or in pores of the membrane into small molecular acid without selectivity, and even mineralize into carbon dioxide and water, so that the aim of catalyzing the self-cleaning membrane is fulfilled.
Disclosure of Invention
The invention provides a method for uniformly preparing a layer of nano iron oxide particles on the surface and the pore wall of a ceramic membrane by grafting, coordination, reduction and weak oxidation, aiming at the inevitable membrane pollution problem of the current ceramic membrane in the use process and the defects and problems of the catalytic self-cleaning ceramic membrane prepared by various iron oxidation doping modifications or thermal deposition modifications, and the method does not influence the permeation flux of the ceramic membrane and also endows the ceramic membrane with the catalytic self-cleaning capability.
The technical scheme for realizing the aim of the invention is a preparation method of a catalytic self-cleaning ceramic membrane, which comprises the following steps:
step 1, ceramic membrane surface pretreatment: ultrasonically cleaning a flat ceramic membrane for 20min in ultrasonic waves, and then soaking the flat ceramic membrane in an ethanol solution for 1h to remove impurities on the surface and in pores of the flat ceramic membrane;
step 2, grafting p-acyl chloride pyridine on the ceramic membrane: soaking the ceramic membrane pretreated in the step 1 in a dichloromethane solution containing p-acyl chloride pyridine with a certain concentration for 1h, repeatedly washing the surface of the ceramic membrane with dichloromethane, and drying the ceramic membrane in vacuum at the temperature of 40 ℃ to obtain the ceramic membrane grafted with pyridine, wherein the reaction process is as follows:
step 3, coordination of iron ions: soaking the ceramic membrane grafted with pyridine obtained in the step 2 in an acetone solution containing iron acetate with a certain concentration, reacting for 12 hours at the temperature of 30 ℃, repeatedly washing with acetone for a plurality of times, and drying in vacuum at the temperature of 40 ℃ to obtain the ceramic membrane coordinated with iron ions, wherein the reaction process is as follows:
step 4, reducing iron ions into a nano iron simple substance: soaking the ceramic membrane coordinated with iron ions obtained in the step 3 in an aqueous solution containing hydrazine hydrate with a certain concentration, reacting for 1h at room temperature, repeatedly washing with water for a plurality of times, and vacuum drying at 60 ℃ to obtain the ceramic membrane grafted with the nano iron simple substance, wherein the reaction process is as follows:
step 5, preparing nano iron oxide: and (4) placing the ceramic membrane grafted with the nano iron simple substance obtained in the step (4) into an oven, and preserving the temperature for 3 hours at 80 ℃ to obtain the ceramic membrane grafted with the nano iron oxide, wherein the reaction process is as follows:
step 6, catalyzing the self-cleaning process: and (3) filtering the oil-water emulsion compounded in a laboratory by using the ceramic membrane grafted with the nano iron oxide obtained in the step (5), and soaking the membrane in hydrogen peroxide solution with a certain concentration for a period of time when the membrane is seriously polluted and blocked, so that pollutants on the surface of the membrane or in pores of the membrane can be degraded, and the permeation flux of the membrane is recovered.
Preferably, in step 1 of the above production method, the ceramic film is a composite ceramic film of one or more of alumina, titania, zirconia, silica, and silicon carbide.
Further preferably, in step 1 of the above production method, the ceramic film is alumina or silicon carbide.
Preferably, in step 2 of the above production method, the concentration of the p-acylchloropyridine is 0.1 to 1g/L.
Preferably, in step 3 of the above production method, the concentration of the iron acetate is 0.5 to 5g/L.
Preferably, in step 4 of the above preparation method, the concentration of hydrazine hydrate is 0.1 to 1g/L.
Preferably, in step 6 of the preparation method, the concentration of the hydrogen peroxide is 0.01 to 0.05mol/L, and the soaking time is 1 to 180min.
The invention has the following beneficial effects:
(1) According to the method, the hydroxyl functional groups rich on the surface of the ceramic membrane and the wall of the pore channel are used as active sites, and uniformly distributed nano iron oxide particles can be prepared on the surface of the ceramic membrane and the wall of the pore channel;
(2) According to the method, the nano iron oxide particles are prepared on the surface and the pore wall of the ceramic membrane by a grafting-coordination-reduction-weak oxidation method, high-temperature calcination treatment is not needed, iron oxide crystals cannot grow, the pores of the membrane are blocked, and the permeation flux of the ceramic membrane is reduced;
(3) The ceramic membrane prepared by the method has large permeation flux and can be a 'boundary slip' fluid theory formed by nano iron oxide particles on the surface and the pore wall of the membrane;
(4) The ceramic prepared by the method has a catalytic self-cleaning function, and when the membrane is polluted and blocked, the polluted ceramic membrane is soaked in hydrogen peroxide solution with a certain concentration for a period of time, the nano iron oxide activates the hydrogen peroxide to generate hydroxyl radicals, so that pollutants adsorbed or deposited on the surface or in pores of the membrane are degraded into small molecular acid without selectivity and even mineralized into carbon dioxide and water, and the aim of catalyzing the self-cleaning membrane is fulfilled.
Drawings
FIG. 1 is a schematic cross-sectional view of a ceramic membrane according to the present invention
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the present disclosure in any way.
Example 1
Ultrasonically cleaning a flat silicon carbide ceramic membrane in ultrasonic waves for 20min, and then soaking the membrane in an ethanol solution for 1h to remove impurities on the surface and in pores of the membrane;
example 2
Step 1, ultrasonically cleaning a flat silicon carbide ceramic membrane in ultrasonic waves for 20min, and then soaking the flat silicon carbide ceramic membrane in an ethanol solution for 1h to remove impurities on the surface and in pores of the flat silicon carbide ceramic membrane;
step 2, soaking the flat silicon carbide ceramic membrane pretreated in the step 1 in a dichloromethane solution containing p-acyl chloride pyridine with the concentration of 0.5g/L for 1 hour, then repeatedly washing the surface of the flat silicon carbide ceramic membrane with dichloromethane, and carrying out vacuum drying at 40 ℃ to obtain the flat silicon carbide ceramic membrane grafted with pyridine;
step 3, soaking the flat silicon carbide ceramic membrane grafted with pyridine obtained in the step 2 in an acetone solution of ferric acetate with the concentration of 1g/L, reacting for 12 hours at the temperature of 30 ℃, repeatedly washing with acetone for a plurality of times, and performing vacuum drying at the temperature of 40 ℃ to obtain the flat silicon carbide ceramic membrane coordinated with iron ions;
step 4, soaking the flat silicon carbide ceramic membrane coordinated with the iron ions obtained in the step 3 in a hydrazine hydrate aqueous solution with the concentration of 0.2g/L, reacting for 1 hour at room temperature, then repeatedly washing with water for a plurality of times, and drying in vacuum at 60 ℃ to obtain the flat silicon carbide ceramic membrane grafted with the nano iron simple substance;
step 5, placing the flat silicon carbide ceramic membrane grafted with the nano iron simple substance obtained in the step 4 into an oven, and preserving the temperature for 3 hours at 80 ℃ to obtain a flat silicon carbide ceramic membrane grafted with nano iron oxide;
and 6, filtering the flat silicon carbide ceramic membrane of the nano iron oxide obtained in the step 5 into oil-water emulsion compounded in a laboratory, and soaking the membrane into 0.02mol/L hydrogen peroxide solution for 90min when the membrane is seriously polluted and blocked, so that pollutants on the surface of the membrane or in pores of the membrane can be degraded, and the permeation flux of the membrane is recovered.
Example 3
And (3) other conditions are unchanged, the concentration of the iron acetate is 2g/L, the catalytic self-cleaning type flat silicon carbide ceramic membrane is prepared, and the anti-pollution and catalytic self-cleaning performance of the membrane is inspected.
Example 4
And (3) preparing the catalytic self-cleaning ceramic membrane under the conditions that other conditions are unchanged and the concentration of the iron acetate is 3g/L, and inspecting the pollution resistance and the catalytic self-cleaning performance of the membrane.
Example 5
And (3) other conditions are unchanged, the concentration of the iron acetate is 4g/L, the catalytic self-cleaning ceramic membrane is prepared, and the pollution resistance and the catalytic self-cleaning performance of the membrane are inspected.
The catalytic self-cleaning ceramic membrane prepared by the invention is used for filtering oil-water emulsion compounded in a laboratory, and the test conditions and the process of the separation performance, the pollution resistance and the catalytic self-cleaning function are as follows: the invention adopts an immersion type constant negative pressure suction dead-end filtration mode, filters deionized water under-0.02 MPa, and tests the pure water flux (J) of the membrane W1 ) (ii) a Then filtering 0.5g/L edible soybean oil simulated oil-water emulsion (J) under-0.02 MPa p ) Testing the oil-water separation performance and the catalytic self-cleaning capacity of the membrane; the membrane was back-rinsed with 2 times the flow of deionized water for 1min, the deionized water was filtered at-0.02 MPa, and the membrane pure water flux (J) was tested W2 ) Recovery Rate (FRR) 1 ) (ii) a Then soaking the membrane in 0.02mol/L hydrogen peroxide for 60min, filtering deionized water under-0.02 MPa, and testing the pure water flux (J) of the membrane W3 ) Recovery Rate (FRR) 2 )。
The ceramic membrane prepared by the invention has the following evaluation on separation performance, pollution resistance and catalytic self-cleaning function:
water flux (J) is defined as: under certain operating conditions, unit time(t) the volume (V) of water per membrane area (A) permeated in L/m 2 H, the specific calculation formula is as follows:
the calculation formula of the retention rate (R) of the ceramic membrane to the oil-water emulsion is as follows:
TOC P and TOC P The concentrations of the oils in the permeate and feed were measured using a total organic carbon meter.
The specific calculation formula of the water Flux Recovery Rate (FRR) is as follows:
examples 1 to 5 comparative separation performance, anti-contamination performance and catalytic self-cleaning ability of the ceramic membrane separation oil-water emulsion are as follows:
| examples | J W1 | J P | J W2 | J W3 | FRR 1 | FRR 2 | R |
| Example 1 | 1056 | 82 | 458 | 487 | 43.37 | 46.12 | 93.1 |
| Example 2 | 1114 | 86 | 590 | 862 | 52.96 | 77.38 | 95.2 |
| Example 3 | 1127 | 87 | 613 | 974 | 54.39 | 86.42 | 97.8 |
| Example 4 | 1135 | 96 | 635 | 1042 | 55.94 | 91.80 | 98.6 |
| Example 5 | 1132 | 94 | 639 | 1057 | 56.44 | 93.37 | 99.3 |
Experimental results show that the catalytic self-cleaning type flat silicon carbide ceramic membrane prepared by the method has the advantages of improved permeation flux, excellent anti-pollution performance and catalytic self-cleaning capability.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the invention, that is, all equivalent variations and modifications within the scope of the present invention and the specification should be included in the scope of the present invention.
Claims (6)
1. A preparation method of a catalytic self-cleaning ceramic membrane is characterized by comprising the following steps:
step 1, ultrasonically cleaning a ceramic membrane for 20min in ultrasonic waves, and then soaking the ceramic membrane in an ethanol solution for 1h to remove impurities on the surface and in pores of the ceramic membrane;
step 2, soaking the ceramic membrane pretreated in the step 1 in dichloromethane solution containing p-acyl chloride pyridine with a certain concentration for 1 hour, then repeatedly washing the surface of the ceramic membrane with dichloromethane, and carrying out vacuum drying at 40 ℃ to obtain the ceramic membrane grafted with pyridine;
step 3, soaking the ceramic membrane grafted with pyridine obtained in the step 2 in an acetone solution containing iron acetate with a certain concentration, reacting for 12 hours at the temperature of 30 ℃, repeatedly washing with acetone for a plurality of times, and drying in vacuum at the temperature of 40 ℃ to obtain the ceramic membrane coordinated with iron ions;
step 4, soaking the ceramic membrane coordinated with iron ions obtained in the step 3 in a hydrazine hydrate aqueous solution with a certain concentration, reacting for 1h at room temperature, then repeatedly washing with water for a plurality of times, and carrying out vacuum drying at 60 ℃ to obtain a ceramic membrane grafted with the nano iron simple substance;
step 5, placing the ceramic membrane grafted with the nano iron simple substance obtained in the step 4 into an oven, and keeping the temperature for 3 hours at 80 ℃ to obtain a ceramic membrane grafted with nano iron oxide;
and 6, filtering the oil-water emulsion compounded in a laboratory by the ceramic membrane of the nano iron oxide obtained in the step 5, and soaking the membrane into hydrogen peroxide solution with a certain concentration for a period of time when the membrane is seriously polluted and blocked, so that pollutants on the surface of the membrane or in pores of the membrane can be degraded, and the permeation flux of the membrane is recovered.
2. The method according to claim 1, wherein the ceramic film is a composite ceramic film of one or more of alumina, titania, zirconia, silica, and silicon carbide.
3. The method according to claim 1, wherein the concentration of the p-acylchloropyridine is 0.1 to 1g/L.
4. The method according to claim 1, wherein the concentration of the iron acetate is 0.5 to 5g/L.
5. The method according to claim 1, wherein the concentration of hydrazine hydrate is 0.1 to 1g/L.
6. The preparation method according to claim 1, wherein the concentration of hydrogen peroxide is 0.01-0.05 mol/L, and the dipping time is 1-180 min.
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