CN112933997B - Preparation method and application of inorganic modified membrane based on in-situ reduction - Google Patents

Preparation method and application of inorganic modified membrane based on in-situ reduction Download PDF

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CN112933997B
CN112933997B CN202110114380.1A CN202110114380A CN112933997B CN 112933997 B CN112933997 B CN 112933997B CN 202110114380 A CN202110114380 A CN 202110114380A CN 112933997 B CN112933997 B CN 112933997B
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inorganic
membrane
mixture
modified
situ reduction
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CN112933997A (en
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马军
张逸萱
甄宇菲
孙志强
刘晴靓
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WATER RESOURCES NATIONAL ENGINEERING RESEARCH CENTER HARBIN INSTITUTE OF TECHNOLOGY
Harbin Institute of Technology
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Harbin Institute of Technology
National Engineering Research Center for Water Resources of Harbin Institute of Technology Co Ltd
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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
    • B01D67/0039—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
    • B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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

Abstract

A preparation method and application of an inorganic modified membrane based on in-situ reduction relate to a preparation method and application of a modified inorganic membrane. The invention aims to solve the problems that the existing commercial membrane is easy to cause pollution in the using process, the cost is increased by cleaning and removing the pollution, secondary pollution is caused, and small molecular organic matters cannot be removed. The method comprises the following steps: firstly, preparing a catalyst loading layer; secondly, loading a load layer on the surface of the inorganic membrane to obtain the inorganic membrane loaded with the load layer, and then calcining to obtain a modified inorganic membrane; thirdly, preparing a catalyst seed solution; and fourthly, immersing the modified inorganic membrane into the catalyst seed solution. An inorganic modified membrane based on in-situ reduction is used in combination with an oxidant for treating micropollutants in drinking water, treating pollutants in water after secondary treatment in a sewage treatment plant, treating nondegradable pollutants in industrial wastewater, and treating turbidity and algae in lake and reservoir water. The invention can obtain the inorganic modified membrane based on in-situ reduction.

Description

Preparation method and application of inorganic modified membrane based on in-situ reduction
Technical Field
The invention relates to a preparation method and application of a modified inorganic membrane.
Background
The generation of the membrane technology plays an important role in solving the problems of algae pollution and two insects. The membrane has a sieving function, and the pollutant can be separated from the water body by selecting the membrane with a proper pore size and a physical effect according to the size of the pollutant. While this method of physical separation is simple and does not introduce new contaminants, it also has significant limitations. Firstly, the membrane can cause serious membrane pollution in the using process, pollutants with the pore size being much larger than that of the membrane are deposited on the surface of the membrane and form a filter cake layer, the membrane flux and the pollutant removal rate are obviously influenced along with the compaction and thickening of the filter cake layer, the pollution can be relieved by cleaning, but the cleaning not only generates cost, but also causes secondary pollution. Secondly, pollutants similar to the pore diameter of the membrane are likely to be attached to the inner wall of the pore of the membrane in the removal process and are difficult to remove by cleaning. Finally, small organic molecules such as antibiotics, algal toxins, and personal care products may pass through the pores of the membrane. It is therefore necessary to modify commercial membranes based on physical sieving to remove contaminants, which are common in the market.
Disclosure of Invention
The invention aims to solve the problems that the existing commercial membrane is easy to cause pollution in the using process, the pollution is removed by cleaning, the cost is increased, secondary pollution is caused, and small molecular organic matters cannot be removed, and provides a preparation method of an inorganic modified membrane based on in-situ reduction and application thereof.
A preparation method of an inorganic modified membrane based on in-situ reduction is completed according to the following steps:
firstly, preparing a catalyst supporting layer:
adding an organic matter with a loading function into the buffer solution to obtain a loading layer solution;
the buffer solution in the step one is obtained by dissolving a buffer into water, wherein the concentration of the buffer is 0.1 mmol/L-25 mmol/L;
the organic matter with the loading function in the step one is one or a mixture of more of trimesic acid, chitin, chitosan, cellulose, glucose, fructose, galactose and glutamic acid;
secondly, loading a loading layer on the surface of the inorganic membrane by adopting the first method, the second method or the third method to obtain the inorganic membrane loaded with the loading layer, and then calcining to obtain a modified inorganic membrane;
the calcination temperature in the step two is 600-1200 ℃, the calcination time is 6-12 h, the temperature rise rate of the calcination is 3-15 ℃/min, and the airflow during the calcination is 150-250 mL/min;
dispersing a transition metal compound into a solvent, and stirring to obtain a catalyst seed solution;
the transition metal compound in the third step is one or a mixture of more of titanium tetrachloride, potassium permanganate, ferric chloride, ferric nitrate, cobalt chloride, copper sulfate and zinc chloride;
the concentration of the transition metal compound in the catalyst seed solution in the third step is 1 mmol/L-200 mmol/L;
and fourthly, immersing the modified inorganic membrane into the catalyst seed solution for 5 to 18 hours to obtain the inorganic modified membrane based on in-situ reduction.
The principle of the invention is as follows:
the invention loads the catalyst on the surface of the inorganic membrane in an in-situ reduction mode, adds a small amount of oxidant into the water body to be treated, when water flows through the membrane surface, the catalyst can quickly catalyze the oxidant and pollutants to react, thereby converting the pollutants into non-toxic and harmless micromolecules, simultaneously reducing the content of the pollutants deposited on the membrane surface or attached in membrane pores, relieving and even removing membrane pollution, fixing the catalyst on the membrane in the in-situ reduction mode without independently introducing other reducing agents, generating no reduction by-products, saving reduction agents, and being a green and environment-friendly membrane modification mode.
The invention has the beneficial effects that:
the invention reduces and fixes the catalyst in oxidation state on the membrane based on the principle of in-situ reduction, and prepares a modified inorganic membrane, which has the following advantages:
the catalyst is reduced and stably loaded on the membrane based on the principle of in-situ reduction, so that the reducing agent is saved, secondary pollution is not generated, and the preparation method is green and efficient;
secondly, the catalyst on the membrane can rapidly catalyze the degradation of pollutants and plays an important role in thoroughly removing the pollutants;
thirdly, the catalyst on the membrane can rapidly catalyze the degradation of pollutants, has obvious effect on relieving or even eliminating membrane pollution, saves the medicament and cost for cleaning the membrane, and prolongs the service time of the membrane;
fourthly, the construction of the loading layer provides wider loading sites for the catalyst, and the catalytic efficiency of the membrane is improved;
fifthly, the catalyst on the membrane can rapidly catalyze the degradation of pollutants, so that the using amount of a chemical oxidant can be saved, and the cost for removing the pollutants is reduced;
sixthly, removing the pollutants without a pure physical screening effect, and removing the pollutants with the sizes smaller than the membrane pore diameter;
and seventhly, the inorganic modified membrane based on in-situ reduction prepared by the method has rapid and efficient degradation capability, and the removal rate of pollutants can reach 90% within 5 min.
The method is based on the in-situ reduction technology, the catalyst in an oxidation state in the solution is reduced and fixed on the surface of the membrane, the membrane preparation process does not need to introduce a reducing agent, the method is efficient and environment-friendly, the prepared modified membrane not only has the function of pollutant interception, but also can thoroughly degrade pollutants under the condition of low addition of an oxidant, and the modified membrane has very positive effects on removing pollutants in water and relieving membrane pollution and has good practical application prospect.
The invention can obtain the inorganic modified membrane based on in-situ reduction.
Drawings
FIG. 1 is a diagram showing the results of a modified inorganic membrane obtained in step two of the example, in which 1 is a hollow fiber membrane and 2 is a support layer;
FIG. 2 is a schematic cross-sectional view of an in-situ reduction-based inorganic modified membrane obtained in step four of the example, in which 1 is a hollow fiber membrane, 2 is a support layer chitin, and 3 is MnO2；
FIG. 3 is a graph showing the effect of the in-situ reduction-based inorganic modified membrane prepared in example one on the degradation of sulfamethoxazole in pharmaceutical wastewater in combination with an oxidizing agent in example five;
FIG. 4 is a graph showing the effect of the in-situ reduction-based inorganic modified membrane prepared in example two in combination with an oxidizing agent on the degradation of sulfamethoxazole in pharmaceutical wastewater in example five;
FIG. 5 is a graph showing the effect of the combination of the inorganic modified membrane based on in-situ reduction prepared in example III and an oxidizing agent on the degradation of sulfamethoxazole in pharmaceutical wastewater in example V;
FIG. 6 is a graph showing the effect of the combination of the inorganic modified membrane based on in-situ reduction prepared in example four and an oxidizing agent on the degradation of sulfamethoxazole in pharmaceutical wastewater in example five.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment is a preparation method of an inorganic modified membrane based on in-situ reduction, which is completed by the following steps:
firstly, preparing a catalyst supporting layer:
adding an organic matter with a loading function into the buffer solution to obtain a loading layer solution;
the buffer solution in the step one is obtained by dissolving a buffer into water, wherein the concentration of the buffer is 0.1 mmol/L-25 mmol/L;
the organic matter with the loading function in the step one is one or a mixture of more of trimesic acid, chitin, chitosan, cellulose, glucose, fructose, galactose and glutamic acid;
secondly, loading a loading layer on the surface of the inorganic membrane by adopting the first method, the second method or the third method to obtain the inorganic membrane loaded with the loading layer, and then calcining to obtain a modified inorganic membrane;
the calcination temperature in the step two is 600-1200 ℃, the calcination time is 6-12 h, the temperature rise rate of the calcination is 3-15 ℃/min, and the airflow during the calcination is 150-250 mL/min;
dispersing a transition metal compound into a solvent, and stirring to obtain a catalyst seed solution;
the transition metal compound in the third step is one or a mixture of more of titanium tetrachloride, potassium permanganate, ferric chloride, ferric nitrate, cobalt chloride, copper sulfate and zinc chloride;
the concentration of the transition metal compound in the catalyst seed solution in the third step is 1 mmol/L-200 mmol/L;
and fourthly, immersing the modified inorganic membrane into the catalyst seed solution for 5 to 18 hours to obtain the inorganic modified membrane based on in-situ reduction.
The beneficial effects of the embodiment are as follows:
the embodiment reduces and fixes the catalyst in an oxidation state on the membrane based on the principle of in-situ reduction to prepare the modified inorganic membrane, and has the following advantages:
the catalyst is reduced and stably loaded on the membrane based on the principle of in-situ reduction, so that the reduction agent is saved, secondary pollution is not generated, and the preparation method is green and efficient;
secondly, the catalyst on the membrane can rapidly catalyze the degradation of pollutants and plays an important role in thoroughly removing the pollutants;
thirdly, the catalyst on the membrane can rapidly catalyze the degradation of pollutants, has obvious effect on relieving or even eliminating membrane pollution, saves the medicament and cost for cleaning the membrane, and prolongs the service time of the membrane;
fourthly, the construction of the loading layer provides wider loading sites for the catalyst, and the catalytic efficiency of the membrane is improved;
fifthly, the catalyst on the membrane can rapidly catalyze the degradation of pollutants, so that the using amount of a chemical oxidant can be saved, and the cost for removing the pollutants is reduced;
sixthly, removing the pollutants without a pure physical screening effect, and removing the pollutants with the sizes smaller than the membrane pore diameter;
and seventhly, the inorganic modified membrane prepared by the embodiment based on in-situ reduction has rapid and efficient degradation capability, and the removal rate of pollutants can reach 90% within 5 min.
This embodiment can obtain an inorganic modified film based on in-situ reduction.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the buffering agent in the step one is a mixture of boric acid and borax, a mixture of citric acid and sodium citrate, a mixture of acetic acid-sodium acetate, a mixture of sodium dihydrogen phosphate and disodium hydrogen phosphate, tris (hydroxymethyl) aminomethane hydrochloride or a mixture of borax and sodium hydroxide. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the molar ratio of the boric acid to the borax in the mixture of the boric acid and the borax is 1 (1-70); the molar ratio of citric acid to sodium citrate in the mixture of citric acid and sodium citrate is (1-20) to (1-20); the molar ratio of acetic acid to sodium acetate in the acetic acid-sodium acetate mixture is (1-10) to (1-20); the molar ratio of the sodium dihydrogen phosphate to the disodium hydrogen phosphate in the mixture of the sodium dihydrogen phosphate and the disodium hydrogen phosphate is (1-15) to (1-20); the molar ratio of the borax to the sodium hydroxide in the mixture of the borax and the sodium hydroxide is (1-5) to 1. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the concentration of the organic matter with the loading function in the loading layer solution in the step one is 0.2 g/L-25 g/L. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the inorganic film in the step two is a commercial inorganic film, and the commercial inorganic film is Al2O3、TiO2、ZrO2、SiO2A composite of one or more of zeolite and glass. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the first method in the second step is as follows: uniformly coating the solution of the load layer on the surface of an inorganic membrane, and drying; secondly, repeating the step I for 3 to 50 times to obtain the inorganic membrane loaded with the load layer; the second method in the second step is as follows: immersing the inorganic membrane into the solution of the load layer for 0.5 h-1 h, taking out and drying to obtain the inorganic membrane loaded with the load layer; the third method in the second step is as follows: firstly, immersing an inorganic film into a load layer solution, then pulling up the coated film, and finally drying; secondly, repeating the step I for 3 to 50 times to obtain the inorganic membrane loaded with the load layer; the drying in the step two is freeze drying, natural ventilation drying and drying by using an oven, wherein the drying temperature is less than 40 ℃, and the drying time is 3-10 h. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and the calcining atmosphere in the second step is helium atmosphere, nitrogen atmosphere, xenon atmosphere or vacuum atmosphere. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the stirring speed in the third step is 500 r/min-1000 r/min, and the stirring time is 1 h-2 h; the solvent in the third step is water, glycol, dimethylformamide or dimethyl sulfoxide. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the embodiment is that an inorganic modified membrane based on in-situ reduction is combined with an oxidant for use, and is used for treating micro-pollutants in drinking water, treating pollutants in secondary treatment water of a sewage treatment plant, treating pollutants difficult to degrade in industrial wastewater, and treating turbidity and algae in lake water and reservoir water.
The detailed implementation mode is ten: the present embodiment differs from the ninth embodiment in that: the oxidant is one or a mixture of several of persulfate, ozone, ferrate, hydrogen peroxide and perchlorate. The other steps are the same as in the ninth embodiment.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the preparation method of the inorganic modified membrane based on in-situ reduction is completed according to the following steps:
firstly, preparing a catalyst supporting layer:
adding chitin into the buffer solution to obtain a chitin solution;
the buffer solution in the step one is obtained by dissolving a buffer into water, wherein the concentration of the buffer is 10 mmol/L; the buffering agent is a mixture of boric acid and borax, wherein the molar ratio of the boric acid to the borax is 1: 35;
the concentration of chitin in the chitin solution in the step one is 1 g/L;
secondly, evenly coating the chitin solution on the surface of the inorganic membrane, and drying for 10 hours at 25 ℃; secondly, repeating the step for 50 times to obtain the inorganic membrane loaded with the chitin; putting the inorganic membrane loaded with the chitin into a tubular furnace, introducing nitrogen into the tubular furnace at the air flow rate of 220mL/min, heating the tubular furnace from room temperature to 900 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and calcining for 2 hours at 900 ℃ to obtain a modified inorganic membrane;
the inorganic film substrate in the step two is a commodity inorganic film which is made of TiO2The hollow fiber membrane is prepared;
thirdly, mixing KMnO4Disperse to deionizeStirring the mixture in water for 1 hour at the stirring speed of 500r/min to obtain a catalyst seed solution;
KMnO in the catalyst seed solution in step three4The concentration of (A) is 10 mmol/L;
and fourthly, immersing the modified inorganic membrane into the catalyst seed solution for 10 hours to obtain the inorganic modified membrane based on in-situ reduction.
FIG. 1 is a diagram showing the results of a modified inorganic membrane obtained in step two of the example, in which 1 is a hollow fiber membrane and 2 is a support layer;
FIG. 2 is a schematic cross-sectional view of an in-situ reduction-based inorganic modified membrane obtained in step four of the example, in which 1 is a hollow fiber membrane, 2 is a support layer chitin, and 3 is MnO2；
Example two: the preparation method of the inorganic modified membrane based on in-situ reduction is completed according to the following steps:
firstly, preparing a catalyst supporting layer:
adding chitin into the buffer solution to obtain a chitin solution;
the buffer solution in the step one is obtained by dissolving a buffer into water, wherein the concentration of the buffer is 10 mmol/L; the buffering agent is a mixture of boric acid and borax, wherein the molar ratio of the boric acid to the borax is 1: 35;
the concentration of chitin in the chitin solution in the step one is 1 g/L;
secondly, evenly coating the chitin solution on the surface of the inorganic membrane, and drying for 10 hours at 25 ℃; secondly, repeating the step for 50 times to obtain the inorganic membrane loaded with the chitin; putting the inorganic membrane loaded with the chitin into a tubular furnace, introducing nitrogen into the tubular furnace at the air flow rate of 220mL/min, heating the tubular furnace from room temperature to 900 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and calcining for 2 hours at 900 ℃ to obtain a modified inorganic membrane;
the inorganic film substrate in the step two is a commodity inorganic film which is made of TiO2The hollow fiber membrane is prepared;
thirdly, mixing Fe (NO)3)3·9H2O and KMnO4Dispersing into deionized water, and stirring at a stirring speed of 500r/min for 1h to obtain a catalyst seed solution;
fe (NO) in the catalyst seed solution described in step three3)3·9H2The concentration of O is 10mmol/L, KMnO4The concentration of (A) is 10 mmol/L;
and fourthly, immersing the modified inorganic membrane into the catalyst seed solution for 15 hours to obtain the inorganic modified membrane based on in-situ reduction.
Example three: the preparation method of the inorganic modified membrane based on in-situ reduction is completed according to the following steps:
firstly, preparing a catalyst supporting layer:
adding trimesic acid into the buffer solution to obtain a trimesic acid solution;
the buffer solution in the step one is obtained by dissolving a buffer into water, wherein the concentration of the buffer is 10 mmol/L; the buffering agent is a mixture of boric acid and borax, wherein the molar ratio of the boric acid to the borax is 1: 35;
the concentration of trimesic acid in the trimesic acid solution in the step one is 0.5 g/L;
uniformly coating a trimesic acid solution on the surface of an inorganic membrane, and drying at-50 ℃ for 10 hours; ②, repeating the step for 20 times to obtain an inorganic membrane of trimesic acid; putting the inorganic membrane loaded with trimesic acid into a tubular furnace, introducing nitrogen into the tubular furnace, wherein the air flow rate is 220mL/min, heating the tubular furnace from room temperature to 900 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and calcining for 2h at 900 ℃ to obtain the modified inorganic membrane;
the inorganic film substrate in the step two is a commodity inorganic film which is made of TiO2The hollow fiber membrane is prepared;
thirdly, mixing Fe (NO)3)3·9H2Dispersing O into deionized water, and stirring at the stirring speed of 500r/min for 1h to obtain a catalyst seed solution;
fe (NO) in the catalyst seed solution described in step three3)3·9H2The concentration of O is 10 mmol/L;
and fourthly, immersing the modified inorganic membrane into the catalyst seed solution for 10 hours to obtain the inorganic modified membrane based on in-situ reduction.
Example four: the preparation method of the inorganic modified membrane based on in-situ reduction is completed according to the following steps:
firstly, preparing a catalyst supporting layer:
adding chitin into the buffer solution to obtain a chitin solution;
the buffer solution in the step one is obtained by dissolving a buffer into water, wherein the concentration of the buffer is 10 mmol/L; the buffering agent is a mixture of boric acid and borax, wherein the molar ratio of the boric acid to the borax is 1: 35;
the concentration of chitin in the chitin solution in the step one is 1 g/L;
secondly, evenly coating the chitin solution on the surface of the inorganic membrane, and drying for 10 hours at 25 ℃; secondly, repeating the step I for 20 times to obtain the inorganic membrane loaded with the chitin; putting the inorganic membrane loaded with the chitin into a tubular furnace, introducing nitrogen into the tubular furnace at the air flow rate of 220mL/min, heating the tubular furnace from room temperature to 900 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and calcining for 2 hours at 900 ℃ to obtain a modified inorganic membrane;
the inorganic film substrate in the step two is a commercial inorganic film, and the commercial inorganic film is Al2O3A film;
thirdly, mixing Fe (NO)3)3·9H2Dispersing O into deionized water, and stirring at the stirring speed of 500r/min for 1h to obtain a catalyst seed solution;
fe (NO) in the catalyst seed solution described in step three3)3·9H2The concentration of O is 10 mmol/L;
and fourthly, immersing the modified inorganic membrane into the catalyst seed solution for 10 hours to obtain the inorganic modified membrane based on in-situ reduction.
Example five: the in-situ reduction-based inorganic modified membranes prepared in examples one, two, three and four were used to treat sulfamethoxazole-containing pharmaceutical wastewater in combination with peroxymonosulfate, respectively, according to the following steps:
adding an oxidant per-sulfate (PMS) into the pharmaceutical factory wastewater containing sulfamethoxazole, enabling the wastewater to respectively pass through the inorganic modified membranes based on in-situ reduction prepared in the first, second, third and fourth embodiments in a cross-flow filtration mode, wherein the driving force is the pressure formed by a water column of 100cm, carrying out an experiment for 25min, sampling once every 5min, and measuring the concentration of sulfamethoxazole by using a high performance liquid chromatography, wherein the degradation condition of the sulfamethoxazole is shown in figures 3-6;
the initial concentration of sulfamethoxazole in the pharmaceutical factory wastewater containing sulfamethoxazole is 10 mg/L;
the concentration of the oxidant PMS in the pharmaceutical factory wastewater containing sulfamethoxazole is 1 mmol/L.
The effect of the combination of the inorganic modified film based on in-situ reduction prepared in the first, second, third and fourth examples and the oxidant on the degradation of sulfamethoxazole in pharmaceutical wastewater is shown in fig. 3 to 6;
FIG. 3 is a graph showing the effect of the in-situ reduction-based inorganic modified membrane prepared in example one on the degradation of sulfamethoxazole in pharmaceutical wastewater in combination with an oxidizing agent in example five;
FIG. 4 is a graph showing the effect of the in-situ reduction-based inorganic modified membrane prepared in example two in combination with an oxidizing agent on the degradation of sulfamethoxazole in pharmaceutical wastewater in example five;
FIG. 5 is a graph showing the effect of the combination of the inorganic modified membrane based on in-situ reduction prepared in example III and an oxidizing agent on the degradation of sulfamethoxazole in pharmaceutical wastewater in example V;
FIG. 6 is a graph showing the effect of the combination of the inorganic modified membrane based on in-situ reduction prepared in example four and an oxidizing agent on the degradation of sulfamethoxazole in pharmaceutical wastewater in example five.
As can be seen from fig. 3 to 6, the inorganic modified films based on in-situ reduction prepared in examples one, two, three and four have fast and efficient degradation capability, and the removal rate of the pollutants within 5min is about 90%.

Claims (9)

1. The preparation method of the inorganic modified membrane based on in-situ reduction is characterized by comprising the following steps of:
firstly, preparing a catalyst supporting layer:
adding an organic matter with a loading function into the buffer solution to obtain a loading layer solution;
the buffer solution in the step one is obtained by dissolving a buffer into water, wherein the concentration of the buffer is 0.1 mmol/L-25 mmol/L;
the organic matter with the loading function in the step one is one or a mixture of more of trimesic acid, chitin, chitosan, cellulose, glucose, fructose, galactose and glutamic acid;
secondly, loading a loading layer on the surface of the inorganic membrane by adopting the first method, the second method or the third method to obtain the inorganic membrane loaded with the loading layer, and then calcining to obtain a modified inorganic membrane;
the calcining atmosphere in the second step is helium atmosphere, nitrogen atmosphere, xenon atmosphere or vacuum atmosphere; the calcination temperature in the step two is 600-1200 ℃, the calcination time is 6-12 h, the temperature rise rate of the calcination is 3-15 ℃/min, and the airflow during the calcination is 150-250 mL/min;
dispersing a transition metal compound into a solvent, and stirring to obtain a catalyst seed solution;
the transition metal compound in the third step is one or a mixture of more of potassium permanganate, ferric chloride, ferric nitrate, cobalt chloride and copper sulfate;
the concentration of the transition metal compound in the catalyst seed solution in the third step is 1 mmol/L-200 mmol/L;
and fourthly, immersing the modified inorganic membrane into the catalyst seed solution for 5 to 18 hours to obtain the inorganic modified membrane based on in-situ reduction.
2. The method of claim 1, wherein the buffer in step one is a mixture of boric acid and borax, a mixture of citric acid and sodium citrate, a mixture of acetic acid-sodium acetate, a mixture of sodium dihydrogen phosphate-disodium hydrogen phosphate, tris hydrochloride, or a mixture of borax and sodium hydroxide.
3. The method for preparing the inorganic modified film based on in-situ reduction according to claim 2, wherein the molar ratio of the boric acid to the borax in the mixture of the boric acid and the borax is 1 (1-70); the molar ratio of citric acid to sodium citrate in the mixture of citric acid and sodium citrate is (1-20) to (1-20); the molar ratio of acetic acid to sodium acetate in the acetic acid-sodium acetate mixture is (1-10) to (1-20); the molar ratio of the sodium dihydrogen phosphate to the disodium hydrogen phosphate in the mixture of the sodium dihydrogen phosphate and the disodium hydrogen phosphate is (1-15) to (1-20); the molar ratio of the borax to the sodium hydroxide in the mixture of the borax and the sodium hydroxide is (1-5) to 1.
4. The method according to claim 1, wherein the concentration of the organic material having a supporting function in the supporting layer solution in the first step is 0.2 g/L-25 g/L.
5. The method according to claim 1, wherein the inorganic film in step two is a commercial inorganic film, and the commercial inorganic film is Al2O3、TiO2、ZrO2、SiO2A composite of one or more of zeolite and glass.
6. The method for preparing an inorganic modified membrane based on in-situ reduction according to claim 1, wherein the first method in the second step is: uniformly coating the solution of the load layer on the surface of an inorganic membrane, and drying; secondly, repeating the step I for 3 to 50 times to obtain the inorganic membrane loaded with the load layer; the second method in the second step is as follows: immersing the inorganic membrane into the solution of the load layer for 0.5 h-1 h, taking out and drying to obtain the inorganic membrane loaded with the load layer; the third method in the second step is as follows: firstly, immersing an inorganic film into a load layer solution, then pulling up the coated film, and finally drying; secondly, repeating the step I for 3 to 50 times to obtain the inorganic membrane loaded with the load layer; the drying in the step two is freeze drying, natural ventilation drying and drying by using an oven, wherein the drying temperature is less than 40 ℃, and the drying time is 3-10 h.
7. The method for preparing an inorganic modified film based on in-situ reduction according to claim 1, wherein the stirring speed in the third step is 500r/min to 1000r/min, and the stirring time is 1h to 2 h; the solvent in the third step is water, glycol, dimethylformamide or dimethyl sulfoxide.
8. Use of an in-situ reduction-based inorganic modified membrane prepared by the preparation method of claim 1, wherein an in-situ reduction-based inorganic modified membrane is used in combination with an oxidizing agent for treating micropollutants in drinking water, treating pollutants present in water after secondary treatment in sewage treatment plants, treating nondegradable pollutants in industrial wastewater, treating turbidity and algae in lake and reservoir water.
9. The use of an in-situ reduction-based inorganic modified membrane according to claim 8, wherein the oxidant is one or a mixture of persulfate, ozone, ferrate, hydrogen peroxide and perchlorate.
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