CN111774076A - Iron oxychloride-loaded ceramic membrane and preparation method thereof - Google Patents
Iron oxychloride-loaded ceramic membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 239000000919 ceramic Substances 0.000 title claims abstract description 64
- YPLPZEKZDGQOOQ-UHFFFAOYSA-M iron oxychloride Chemical compound [O][Fe]Cl YPLPZEKZDGQOOQ-UHFFFAOYSA-M 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 9
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 14
- 239000003242 anti bacterial agent Substances 0.000 description 10
- 229940088710 antibiotic agent Drugs 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 241000282412 Homo Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005182 global health Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
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Images
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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—
-
- B01J35/59—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The embodiment of the invention provides an iron oxychloride-loaded ceramic membrane, which comprises: the ceramic membrane is prepared from aluminum oxide, titanium dioxide and an iron oxychloride nano catalyst loaded on the surface of the ceramic membrane, wherein the aluminum oxide and the titanium dioxide are used as matrixes. The embodiment of the invention also provides a preparation method of the iron oxychloride-loaded ceramic membrane, which comprises the following steps: s1, ceramic membrane pretreatment; s2, preparing a nano catalyst; s3, loading of a catalyst; and S4, drying and drying. The iron oxychloride-loaded ceramic membrane prepared by the invention has high photo-Fenton catalytic activity, not only has excellent antibiotic removal efficiency, but also has good antifouling property, and is a simple and effective antibiotic removal method with low cost.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to an iron oxychloride-loaded ceramic membrane and a preparation method thereof.
Background
Antibiotics refer to antibacterial drugs that are capable of preventing or treating bacterial infections in humans and animals. Since the discovery of the first antibiotic (penicillin) in 1929, various natural and synthetic antibiotics have been developed and widely used in human medicine and in animal husbandry and agriculture. Antibiotics are ubiquitous in the environment, and after antibiotics are used by humans and animals, about 10% -90% are excreted as parent compounds or bioactive metabolites and then enter receiving water, sediments and soil. From the 90 s of the 20 th century to date, the consumption of antibiotics has increased, with potential negative impacts on human health, livestock husbandry, ecosystems and food safety. Meanwhile, as antibiotic resistance becomes an imminent global health threat, 1000 million people may die by 2050 if the resistance cannot be effectively relieved.
The antibiotic removing method mainly comprises a microbiological method, a physical adsorption method, an advanced oxidation method, a chemical reduction method and the like. The traditional water treatment technology has low degradation efficiency on antibiotics and is easy to generate secondary pollution. The photocatalysis-membrane separation coupling technology not only keeps the advantages of non-selectivity of the photocatalysis technology to high-concentration refractory antibiotics, high reaction rate, complete degradation and the like; meanwhile, the nano-scale catalyst in a reaction liquid system is effectively recovered through the high-efficiency interception and phase-change-free separation characteristics of the membrane separation technology, the separation effect is thorough, the catalyst loss is less, the constancy and the catalysis characteristics of the catalyst in a reactor are maintained, the whole reaction system continuously and effectively operates stably, and the coupling effect is generated: the pollution index of the waste water is reduced, the pollution resistance of the membrane is improved and the service life of the membrane is prolonged by degrading pollutants through a photocatalytic reaction. Therefore, the development of a flat ceramic membrane with a photo-Fenton effect is of great significance for the removal of antibiotics.
Disclosure of Invention
The embodiment of the invention provides an iron oxychloride-loaded ceramic membrane and a preparation method thereof, which aim to overcome the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme.
An iron oxychloride-loaded ceramic membrane, comprising: the ceramic membrane is prepared from aluminum oxide, titanium dioxide and an iron oxychloride nano catalyst loaded on the surface of the ceramic membrane, wherein the aluminum oxide and the titanium dioxide are used as matrixes.
A preparation method of the ceramic membrane loaded with the iron oxychloride comprises the following steps:
s1, ceramic membrane pretreatment: soaking the ceramic membrane in deionized water for 30 minutes, then washing with sodium hydroxide solution for 30 minutes in an alkaline manner, then washing with phosphoric acid solution for 15 minutes in an acid manner, repeatedly washing with distilled water, drying in a vacuum oven, and cooling the ceramic membrane to room temperature for later use;
s2, preparing a nano catalyst: taking ferric trichloride hexahydrate solid, fully grinding the ferric trichloride hexahydrate solid into powder in a mortar, flatly paving the powder of the ferric trichloride hexahydrate at the bottom of a crucible, covering a crucible cover, placing the crucible into a muffle furnace, controlling the temperature rise condition of the muffle furnace to be 5 ℃ per minute, keeping constant temperature after the temperature rises to 250 ℃, reacting for 1 hour, setting the temperature reduction program to be 5 ℃ per minute, turning off a power supply after the temperature is reduced to the normal temperature, taking out a sample after cooling, and repeatedly centrifuging and cleaning to obtain the nano-catalyst ferric oxychloride;
s3, loading of the catalyst: weighing the nano-catalyst iron oxychloride prepared in the step S2, adding 1g of iron oxychloride into every 9mL of the alcohol solution of bis- [3- (triethoxysilyl) propyl ] tetrasulfide, preparing an alcohol suspension of the iron oxychloride, uniformly mixing, and then dripping the mixed solution onto the surface of the ceramic membrane pretreated in the step S1 to form a flat ceramic membrane;
s4, drying and drying: and (4) placing the flat ceramic membrane formed in the step S3 in a vacuum drying oven for high-temperature heating coupling reaction to form the ceramic membrane loaded with the iron oxychloride nano catalyst.
Preferably, in the step S1, 15-20 g.L < -1 > sodium hydroxide solution at 80 ℃ is used for alkali washing, 75% phosphoric acid solution at 50 ℃ is used for acid washing, the drying temperature in a vacuum oven is 90-100 ℃, and the drying time is 1-2 h.
Preferably, in the step S3, the ratio of the volume of the cross-linking agent in the alcoholic solution of bis- [3- (triethoxysilyl) propyl ] tetrasulfide to the total volume of the cross-linking agent in the alcoholic solution is 2 to 3 per thousand.
Preferably, the temperature for the coupling reaction in the step S4 is 90 ℃ and the time is 1 h.
According to the technical scheme provided by the embodiment of the invention, the iron oxychloride-loaded ceramic membrane has high photo-Fenton catalytic activity, excellent antibiotic removal efficiency, good antifouling performance and low cost, can simply and effectively remove antibiotics, and is simple in preparation method and free of secondary pollution.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of the surface of the nano-catalyst iron oxychloride of the invention;
FIG. 2 is a diagram showing the effect of removing nitrobenzene by using the ceramic membrane loaded with iron oxychloride of the present invention;
FIG. 3 is a scanning electron microscope image of the surface of an original ceramic film according to the present invention;
FIG. 4 is a scanning electron microscope image of the ceramic membrane loaded with the iron oxychloride nano-catalyst of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element or intervening elements may also be present. Further, "connected" or "coupled" as used herein may include wirelessly connected or coupled. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
For the convenience of understanding the embodiments of the present invention, the following description will be further explained by taking several specific embodiments as examples in conjunction with the drawings, and the embodiments are not to be construed as limiting the embodiments of the present invention.
The embodiment of the invention provides an iron oxychloride-loaded ceramic membrane, which comprises: the ceramic membrane is prepared from aluminum oxide, titanium dioxide and an iron oxychloride nano catalyst loaded on the surface of the ceramic membrane, wherein the aluminum oxide and the titanium dioxide are used as matrixes.
The embodiment of the invention also provides a preparation method of the iron oxychloride-loaded ceramic membrane, which comprises the following steps:
s1, ceramic membrane pretreatment: soaking the ceramic membrane in deionized water for 30 minutes, then washing the ceramic membrane with sodium hydroxide solution of 15-20 g.L < -1 > at 80 ℃ for 30 minutes in an alkali wash mode, then washing the ceramic membrane with phosphoric acid solution of 75% at 50 ℃ for 15 minutes in an acid wash mode, repeatedly washing the ceramic membrane with distilled water, drying the ceramic membrane in a vacuum oven at 90-100 ℃ for 1-2 hours, and cooling the ceramic membrane to room temperature for later use. In addition, in the pretreatment process of the ceramic membrane, the condition that the membrane surface is damaged due to unclean cleaning or too long time caused by too short washing time is avoided;
s2, preparing a nano catalyst: taking a certain amount of ferric chloride hexahydrate solid, fully grinding the ferric chloride hexahydrate solid into powder in a mortar, spreading the powder of the ferric chloride hexahydrate at the bottom of a crucible, covering a crucible cover, placing the crucible in a muffle furnace, controlling the temperature rise condition of the muffle furnace to be 5 ℃ per minute, keeping constant temperature after the temperature rises to 250 ℃, reacting for 1 hour, cooling, setting the temperature reduction program to be 5 ℃ per minute, turning off a power supply after the temperature is reduced to normal temperature, taking out a sample after cooling, and repeatedly centrifuging and cleaning to obtain the nano-catalyst iron oxychloride;
s3, loading of the catalyst: weighing the nano-catalyst iron oxychloride prepared in the step S2, and preparing an alcohol suspension of the iron oxychloride by adding 1g of the iron oxychloride into every 9mL of the alcohol solution of the bis- [3- (triethoxysilyl) propyl ] tetrasulfide. According to the invention, 10g of iron oxychloride nano catalyst is put into 90mL of an alcohol solution of bis- [3- (triethoxysilyl) propyl ] tetrasulfide, the crosslinking agent for preparing the supported nano catalyst is the alcohol solution of bis- [3- (triethoxysilyl) propyl ] tetrasulfide, the mixture is uniformly mixed, and then the mixed solution is dripped on the surface of the ceramic membrane pretreated in the step S1 to form a flat ceramic membrane, wherein the crosslinking agent is the alcohol solution of bis- [3- (triethoxysilyl) propyl ] tetrasulfide, and the volume ratio of the crosslinking agent to the alcohol solution of the crosslinking agent is 2-3 per thousand (the volume of the crosslinking agent is the total volume of the alcohol solution of the crosslinking agent);
s4, drying and drying: and (4) placing the flat ceramic membrane formed in the step (S3) in a vacuum drying oven to carry out high-temperature heating coupling reaction to form the ceramic membrane loaded with the iron oxychloride nano catalyst, wherein the temperature of the coupling reaction is 90 ℃ and the time is 1 h.
The ceramic membrane loaded with the iron oxychloride nano catalyst obtained in the embodiment of the invention is applied to the degradation of antibiotics in water: the ceramic membrane loaded with the iron oxychloride nano catalyst prepared in the example is added into a water sample containing nitrobenzene, the volume of the water sample is 50mL, the concentration is 10 MuM, the ceramic membrane reacts for 30 minutes at room temperature under the irradiation of 254nm ultraviolet light and in the presence of 8mM hydrogen peroxide, and under the coexistence of 254nm ultraviolet light and 8mM hydrogen peroxide, and the concentrations of nitrobenzene in the water sample are respectively 7.69 MuM, 6.78 MuM, 5.86 MuM and 0 MuM through high performance liquid chromatography detection. It can be seen that the degradation effect of nitrobenzene is much better than that of other 3 conditions in the presence of ultraviolet light and hydrogen peroxide in the ceramic membrane loaded with the iron oxychloride nano catalyst prepared by the invention, so that research results show that the ceramic membrane loaded with the iron oxychloride nano catalyst prepared by the invention has good photo-fenton activity in the degradation process of nitrobenzene.
In order to verify the loss of the catalyst in the loaded iron oxychloride ceramic membrane, the iron oxychloride ceramic membrane is soaked in 10 mu M nitrobenzene solution for 60 minutes, and the content of iron ions in the solution is detected by ion chromatography. The result shows that the leaching amount of the iron ions only accounts for 0.042% of the loading amount, and the extremely small leaching amount of the iron ions indicates that the flat ceramic membrane loaded with the ferric oxychloride is very stable.
In summary, the iron oxychloride-loaded ceramic membrane and the preparation method thereof provided by the invention have the advantages that① As shown in figure 1, the nano catalyst coating prepared by the invention presents a layered distribution with a nano scale (average particle size of 800nm), as shown in figures 3 and 4, the nano catalyst is stably loaded on the surface of the ceramic membrane through the coupling effect of the cross-linking agent, and the ceramic membrane loaded with the iron oxychloride is used for UV and H2O2In the presence of the same, the nitrobenzene can be completely degraded in 10 minutes, but in the presence of UV/FeOCl-coated H2O2② the invention has simple preparation method, no use of noble metal catalyst, wide source of raw materials, low manufacturing cost, high catalytic activity, little loss of catalyst and no secondary pollution.
Those of ordinary skill in the art will understand that: the figures are merely schematic representations of one embodiment, and the blocks or flow diagrams in the figures are not necessarily required to practice the present invention.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for apparatus or system embodiments, since they are substantially similar to method embodiments, they are described in relative terms, as long as they are described in partial descriptions of method embodiments. The above-described embodiments of the apparatus and system are merely illustrative, and the units described as separate parts may or may not be physically separate, and the parts displayed as units may or may not be physical units, may be located in one place, or may be distributed on a plurality of network units. Some or all of the modules may be selected according to actual needs to achieve the purpose of the solution of the present embodiment. One of ordinary skill in the art can understand and implement it without inventive effort.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. An iron oxychloride-loaded ceramic membrane, comprising: the ceramic membrane is prepared from aluminum oxide, titanium dioxide and an iron oxychloride nano catalyst loaded on the surface of the ceramic membrane, wherein the aluminum oxide and the titanium dioxide are used as matrixes.
2. A method for producing an iron oxychloride-loaded ceramic membrane according to claim 1, comprising the steps of:
s1, ceramic membrane pretreatment: soaking the ceramic membrane in deionized water for 30 minutes, then washing with sodium hydroxide solution for 30 minutes in an alkaline manner, then washing with phosphoric acid solution for 15 minutes in an acid manner, repeatedly washing with distilled water, drying in a vacuum oven, and cooling the ceramic membrane to room temperature for later use;
s2, preparing a nano catalyst: taking ferric trichloride hexahydrate solid, fully grinding the ferric trichloride hexahydrate solid into powder in a mortar, flatly paving the powder of the ferric trichloride hexahydrate at the bottom of a crucible, covering a crucible cover, placing the crucible into a muffle furnace, controlling the temperature rise condition of the muffle furnace to be 5 ℃ per minute, keeping constant temperature after the temperature rises to 250 ℃, reacting for 1 hour, setting the temperature reduction program to be 5 ℃ per minute, turning off a power supply after the temperature is reduced to the normal temperature, taking out a sample after cooling, and repeatedly centrifuging and cleaning to obtain the nano-catalyst ferric oxychloride;
s3, loading of the catalyst: weighing the nano-catalyst iron oxychloride prepared in the step S2, adding 1g of iron oxychloride into every 9mL of the alcohol solution of bis- [3- (triethoxysilyl) propyl ] tetrasulfide, preparing an alcohol suspension of the iron oxychloride, uniformly mixing, and then dripping the mixed solution onto the surface of the ceramic membrane pretreated in the step S1 to form a flat ceramic membrane;
s4, drying and drying: and (4) placing the flat ceramic membrane formed in the step S3 in a vacuum drying oven for high-temperature heating coupling reaction to form the ceramic membrane loaded with the iron oxychloride nano catalyst.
3. The method according to claim 2, wherein in step S1, the alkali washing is performed with a sodium hydroxide solution of 80 ℃ 15-20 g.l-1, the acid washing is performed with a phosphoric acid solution of 50 ℃ 75%, the drying temperature in the vacuum oven is 90 ℃ to 100 ℃, and the drying time is 1-2 h.
4. The method according to claim 2, wherein the ratio of the volume of the crosslinking agent in the alcoholic solution of bis- [3- (triethoxysilyl) propyl ] tetrasulfide to the total volume of the alcoholic solution of the crosslinking agent in step S3 is 2 to 3% o.
5. The method according to claim 2, wherein the coupling reaction is carried out at a temperature of 90 ℃ for 1 hour in step S4.
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Application publication date: 20201016 |