CN108993475B - Ternary composite material heterogeneous light Fenton catalyst and preparation and application thereof - Google Patents

Ternary composite material heterogeneous light Fenton catalyst and preparation and application thereof Download PDF

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CN108993475B
CN108993475B CN201810936719.4A CN201810936719A CN108993475B CN 108993475 B CN108993475 B CN 108993475B CN 201810936719 A CN201810936719 A CN 201810936719A CN 108993475 B CN108993475 B CN 108993475B
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sludge
catalyst
temperature
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roasting
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CN108993475A (en
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张立慧
安世林
张思濡
于杨
黄菲
黄和
乔纳森贝尔
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Nanjing Tech University
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/18—Arsenic, antimony or bismuth
    • 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
    • B01J23/843—Arsenic, antimony or bismuth
    • B01J23/8437—Bismuth
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C02F2101/36—Organic compounds containing halogen

Abstract

The invention relates to a preparation method for preparing a supported catalyst by taking roasted municipal sludge residues as a carrier and three high-activity metals as active components. The invention obtains the sludge catalyst carrier with high specific surface area and high porosity by roasting the municipal domestic sludge at high temperature and uses TiO2、AgNO3、MnO2、Fe(NO3)3·9H2O、InN3O9·xH2O(X＝2)、Sr(NO3)2、Bi(NO3)3And mixing any three metal components in the metal compounds according to a certain element molar ratio to prepare a ternary metal compound precursor, loading the ternary metal compound precursor on a sludge carrier, and roasting at high temperature again to obtain the sludge catalyst with high catalytic activity and high stability. The catalyst is applied to a heterogeneous light Fenton system to treat refractory high-concentration industrial organic wastewater, and belongs to the field of water treatment technology and environmental functional materials.

Description

Ternary composite material heterogeneous light Fenton catalyst and preparation and application thereof
Technical Field
The invention relates to a ternary composite metal supported catalyst prepared by taking municipal sludge as a carrier and three stable metals which are not easy to lose as active components, which is applied to a heterogeneous light Fenton system for treating high-concentration industrial organic wastewater which is difficult to degrade, and belongs to the field of water treatment technology and environmental functional materials.
Technical Field
The municipal sludge is a necessary product in the sewage treatment process, and the annual sewage treatment capacity of China can reach 550 hundred million m at present3Above that, 3500 million tons or more of sludge with a water content of 80% and 700 million tons or more of dry sludge are expected to be produced all year round, and as the urban sewage treatment amount increases year by year, the sludge accumulation amount is also increasing. According to research and analysis, the sludge in a general urban sewage treatment plant is rich in organic matters, nitrogen and phosphorus elements, and also contains a small amount of metal elements such as magnesium, calcium, manganese, iron and the like, the sludge contains a lot of harmful substances such as bacterial thalli, organic pollutants, inorganic particles and toxic heavy metals such as arsenic, copper, mercury, chromium and the like, and if the sludge is not treated in time, secondary pollution is caused, and great harm is caused to human activities and ecological environment. At present, the incineration process is considered as one of the best practical techniques in sludge treatment by countries around the world. The process has grown in maturity in europe, the united states, japan, and the like, and is known for its outstanding features of high processing speed, high reduction degree, energy reuse, and the like. In China, the treatment technology of the sludge is not perfect at the present stage, and the most common methods are land landfill, incineration treatment, water body consumption and landscaping composting. Besides, the sludge particles obtained by dewatering and pretreating sludge can be used for preparing high-quality catalysts in the field of sewage purification, and the attempt to introduce sludge into the field of catalysis has become a great trend of sludge research at present.
The rapid development of social economy promotes the industrialization and the urbanization process to be accelerated continuously, the discharge amount of industrial wastewater and urban sewage is increased continuously, the organic industrial wastewater contains organic pollutants which are high in concentration, high in toxicity and difficult to degrade, the problem of water pollution is serious day by day, the organic matters which are difficult to degrade form great threats to the natural environment and the human health, and the effective treatment of the organic matters becomes a research hotspot in the field of environment. Although the traditional water treatment methods such as physical adsorption, chemical oxidation, biological treatment, flocculation precipitation and the like are generally applied, the treatment has certain limitations. Therefore, the treatment of organic wastewater is urgent, and the finding of an economic and effective water pollution treatment method is of great significance.
The advanced oxidation technology is a high-efficiency oxidation technologyIn the channel for decomposing organic pollutants, hydroxyl free radicals (. OH) with strong oxidizing capability are generated by a chemical or physical-chemical method, and macromolecular refractory organic matters are oxidized and decomposed into CO which does not pollute the environment under the reaction conditions of high temperature, high pressure, electricity, light, catalysts and the like2And H2And O. The Fenton oxidation method is an effective method for removing refractory organic matters, the Fenton reaction has excellent oxidizability compared with general chemical reactions, equipment is simple and easy to operate, reaction conditions are mild, the Fenton oxidation method is widely used for treating refractory organic wastewater, and the Fenton reaction has many defects, such as narrow pH window, easy generation of dangerous waste iron mud, incapability of recycling of a catalyst and the like. However, heterogeneous Fenton catalysis is an environment-friendly advanced oxidation technology, but the catalytic efficiency of the heterogeneous catalyst is lower than that of the homogeneous Fenton reaction, so as to further improve H2O2The oxidation efficiency of (1) introducing ultraviolet light or visible light into a heterogeneous Fenton reaction system, which is beneficial to accelerating H decomposition2O2The OH-forming heterogeneous light Fenton technology not only improves H2O2The utilization rate of the catalyst is improved, various defects of the traditional Fenton technology are overcome, the problem that the catalyst is difficult to recycle is solved, the cost of wastewater treatment is greatly reduced, and the catalyst has great prospects in the field of catalytic oxidation of organic pollutants.
Photocatalytic research is a green project with promise on a global scale, but is challenging to apply in practice due to the limitations of photocatalytic technology. In order to make up for the technical defects, the research selects to dope and modify the catalyst, and metal components such as Ti, Ag, Mn, Fe, In, Sr, Bi and the like with high activity are loaded on the surface of the catalyst, so that the absorption of the catalyst to light is enhanced, the hole-electron separation efficiency is improved, and the catalytic activity of the catalyst is further improved. Therefore, finding a suitable catalyst as a metal active group carrier is the first requirement for efficient degradation treatment of organic industrial wastewater.
The sludge contains a large amount of organic matters, sludge residues obtained by roasting at a certain high temperature under the condition of introducing air have the structural characteristics of high specific surface area and good pores, and can adsorb wasteOrganic pollutants and heavy metals in water and as a catalyst for degrading high-concentration organic industrial wastewater. The sludge residue is used as the catalyst in the catalytic oxidation reaction, and the method has the advantages of simple preparation, high catalytic activity, less impregnation amount of active components, easy recovery of the catalyst, low cost and the like. Adding TiO into the mixture2、AgNO3、MnO2、Fe(NO3)3·9H2O、InN3O9·xH2O、Sr(NO3)2、Bi(NO3)3Any three of the metals are taken as metal active components, are mixed according to a certain metal element molar ratio, obtain a ternary composite metal precursor solution through ultrasound, and then are loaded on the peat to be roasted to prepare the ternary composite metal precursor sludge catalyst with good catalytic performance, low cost and stability.
Disclosure of Invention
The invention aims to provide a preparation method and application of a catalyst with stable structure and high activity for treating refractory industrial organic wastewater in a heterogeneous light Fenton reaction system. The invention takes sludge residue after high-temperature roasting as a carrier and TiO2、AgNO3、MnO2、Fe(NO3)3·9H2O、InN3O9·xH2O(X＝2)、Sr(NO3)2、Bi(NO3)3Any three of metal compounds are taken as metal active components, are mixed according to a certain metal element molar ratio, are subjected to ultrasonic treatment to obtain a ternary composite metal precursor solution, are loaded on sludge residues to be roasted to prepare a ternary composite metal sludge catalyst with good catalytic performance, low cost and stability, a novel efficient heterogeneous light Fenton catalyst is prepared, and H is added2O2And under the condition of introducing ultraviolet light, the high-concentration industrial organic wastewater is degraded by catalytic oxidation. The invention uses the sludge residue loaded with metal as the catalyst to treat high-concentration organic industrial wastewater, realizes the resource utilization of sludge, achieves the effect of treating wastes with processes of wastes against one another, and the catalyst can be widely applied to the field of treatment of high-concentration organic industrial wastewaterIs widely applied to the industry.
In order to achieve the aim, the sludge catalyst with high catalytic activity is prepared by controlling sludge modification conditions, drying temperature, roasting temperature, metal loading capacity, metal loading proportion and loading time. By changing the illumination intensity of ultraviolet light, the dosage of the sludge catalyst and H2O2The conditions such as dosage and the like further verify that the ternary composite metal sludge catalyst provided by the invention can efficiently degrade organic pollutants in water, and is a heterogeneous photo-Fenton catalyst with excellent catalytic performance. The method for preparing the ternary composite metal precursor catalyst provided by the invention comprises the following steps:
1. a method for preparing a photo-Fenton catalyst by using sludge loaded with ternary active metals is characterized by comprising the following steps:
the preparation method of the sludge catalyst carrier comprises the following steps:
(1) drying a small amount of sludge of the urban domestic sewage plant under the condition of 100-125 ℃ (preferably 110 ℃) until the weight is unchanged;
(2) heating the obtained sludge under the condition of introducing air, raising the temperature to 300-800 ℃ (the optimal temperature is 400-600 ℃) at the rate of 3-6 ℃/min, calcining for 2-8 h (preferably 3-6 h), cooling to 15-35 ℃ (the optimal temperature is 25-30 ℃), and mechanically crushing to obtain the sludge catalyst carrier with high specific surface area and high porosity.
2. Taking TiO as a carrier by using the sludge catalyst prepared by the method of claim 1 as a carrier2、AgNO3、MnO2、Fe(NO3)3·9H2O、InN3O9·xH2O(X＝2)、Sr(NO3)2、Bi(NO3)3Mixing three metal components according to a certain element molar ratio, adding 50-100 mL of distilled water, placing the metal mixed solution into an ultrasonic reactor for ultrasonic treatment for 4-18 h (preferably 4-12 h), and at 10-90 ℃ (preferably 20-60 ℃) to prepare a composite metal precursor solution, and placing the solution into an oven for 100-150 ℃ (preferably 20-60 ℃)And (3) drying at the constant temperature of 120 ℃ for 12-24 h (preferably 12-18 h) until the weight is unchanged, thereby obtaining the composite metal precursor solid particles. The loading amount of the salt is 0.1-5.0 wt% (preferably 3.0-5.0 wt%), calculated by the mass of the metal in the salt, the two are fully ground and mixed under the temperature condition of 400-900 ℃ (preferably 500-700 ℃), and the mixture is roasted for 0.5-8 h (preferably 2-5 h) to prepare the ternary composite metal sludge catalyst.
3. A novel catalyst obtained by the preparation of the claims 1 and 2 is used for catalyzing, oxidizing and degrading high-concentration industrial organic wastewater in a heterogeneous light Fenton system, wherein the catalyst is a sludge catalyst carrier obtained by the preparation of the claim 1 and a ternary metal composite sludge catalyst obtained by the preparation of the claim 2.
4. Use of the sludge residue catalyst according to claim 4:
the catalyst catalyzes H by light2O2OH is generated, high-concentration organic industrial wastewater is efficiently treated and degraded, and the intermittent reaction is as follows: simulating the initial pH of industrial o-chlorophenol wastewater: 2 to 7 (preferably pH 3 to 5), reaction temperature 10 to 70 ℃ (preferably 20 to 50 ℃), H2O2(mg/L): COD (mg/L) is 0.3-3.0 (preferably H)2O2(mg/L): COD (mg/L) is 0.5-1.5, light intensity is 100-2000W (preferably 500-1000W), and the amount of catalyst added is 0.05-3.0 g/L (preferably 0.5-2.0 g/L).
The light is ultraviolet light or visible light.
The ternary composite metal catalyst has the following advantages:
the sludge catalyst has very high catalytic activity on high-concentration and difficult-to-degrade organic industrial wastewater, and ultraviolet light and H are introduced by using o-chlorophenol to simulate the industrial organic wastewater2O2Under the condition, the organic waste can be efficiently degraded, and the reaction has a wider pH window, is an excellent sludge catalyst and has good market prospect.
Secondly, the sludge catalyst has a stable structure, metal components are not easy to lose, and the recovery efficiency is very high;
thirdly, the inventionThe sludge catalyst raw material (Industrial H)2O2Urban domestic sludge), low cost, low active metal loading, simple catalyst preparation operation flow and easy control of the reaction process.
Drawings
FIG. 1 is a graph showing the o-chlorophenol removal rate versus reaction time in example 1.
The blank group is implemented under the conditions of ultraviolet light intensity of 1000W, reaction time of 150min and H2O2(mg/L)：COD(mg/L)＝1.2；
② the sludge group with 500 ℃ is implemented under the conditions of 1000W ultraviolet light intensity, 150min reaction time and H2O2(mg/L): COD (mg/L) ═ 1.2, 0.20g of sludge residue was added to the solution;
thirdly, the implementation conditions of the ternary composite material group are that the ultraviolet light intensity is 1000W, the reaction time is 150min, H2O2(mg/L): COD (mg/L) ═ 1.2, 0.20g of the composite catalyst was added to the solution.
Detailed Description
The ternary composite metal sludge catalyst provided by the invention can be used for treating high-concentration organic wastewater difficult to degrade, and improving the removal rate of organic matters, so that the wide application of a heterogeneous photo-Fenton technology is promoted. The specific embodiment is as follows:
example 1:
drying the urban domestic sludge at 105 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at 500 ℃ for 4h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③Fe(NO3)3·9H2O、InN3O9·xH2O(X＝2)、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor to perform ultrasonic treatment for 8 hours at the temperature of 50 ℃ to prepare a composite metal precursor solution, and drying the composite metal precursor solution at the constant temperature of 120 ℃ for 18 hours until the weight of the composite metal precursor solution is constant to obtain the composite material solid particles, wherein the loading capacity of the salt is 5.0 wt% in the three metal mass meters. Ball milling and mixing the two, and collectingThe same roasting method is used for roasting for 3 hours at the temperature of 500 ℃ to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.20g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 1.2, the UV intensity was 1000W, and after 150min of reaction, the conversion of o-chlorophenol was 96.5% and the TOC removal was 90.1%.
Example 2:
drying the urban domestic sludge at the temperature of 110 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at 400 ℃ for 2h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③InN3O9·xH2O(X＝2)、Sr(NO3)2、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor for ultrasonic treatment for 6 hours at the temperature of 40 ℃ to prepare a composite metal precursor solution, and drying the composite metal precursor solution for 18 hours at the constant temperature of 110 ℃ to constant weight to obtain the composite material solid particles, wherein the loading capacity of the salt is 4.0 wt% respectively. Ball milling and mixing the two, and roasting the mixture for 3 hours at the temperature of 400 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.2g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) is 1, the ultraviolet light intensity is 700W, and after the reaction is carried out for 150min, the conversion rate of o-chlorophenol is 93.8 percent, and the TOC removal rate is 88.6 percent.
Example 3:
drying the urban domestic sludge at the temperature of 100 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at the temperature of 600 ℃ for 3h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③MnO2、Fe(NO3)3·9H2O、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor to perform ultrasonic treatment for 8 hours at the temperature of 60 ℃ to prepare a composite metal precursor solution, and drying for 16 hours at the constant temperature of 140 ℃ to constant weight to obtain the composite material solid particles, wherein the loading capacity of the salt is 3.0 wt% in the three metal mass meters. Ball milling and mixing the two, and roasting the mixture for 3 hours at the temperature of 600 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.15g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 1.5, the ultraviolet light intensity was 700W, and after 150min of reaction, the conversion of o-chlorophenol was 88.4% and the TOC removal was 79.6%.
Example 4:
drying the urban domestic sludge at the temperature of 110 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at 400 ℃ for 5h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③TiO2、AgNO3、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor for ultrasonic treatment for 10 hours at the temperature of 60 ℃ to prepare a composite metal precursor solution, and drying for 16 hours at the constant temperature of 120 ℃ to constant weight to obtain the composite material solid particles, wherein the loading capacity of the salt is 3.0 wt.% in the mass of the three metals. Ball milling and mixing the two, and roasting the mixture for 5 hours at the temperature of 400 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.2g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 1, the ultraviolet light intensity was 500W, and after 150min of the reaction, the conversion of o-chlorophenol was 77.8% and the TOC removal was 68.4%.
Example 5:
drying the urban domestic sludge at the temperature of 110 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at 500 ℃ for 5h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③TiO2、AgNO3、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor to be subjected to ultrasonic treatment for 10 hours at the temperature of 60 ℃ to prepare a composite metal precursor solution, and drying the composite metal precursor solution at the constant temperature of 120 ℃ for 18 hours until the weight of the composite metal precursor solution is constant to obtain the composite material solid particles, wherein the loading capacity of the salt is 4.5 wt% in the three metal mass meters. Ball milling and mixing the two, and roasting for 4 hours at 500 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.25g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 0.5, the UV intensity was 300W, and after 150min of reaction, the conversion of o-chlorophenol was 78.4% and the TOC removal was 68.6%.
Example 6:
drying the urban domestic sludge at 105 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at the temperature of 600 ℃ for 6h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③TiO2、Fe(NO3)3·9H2O、InN3O9·xH2And (3) respectively measuring the salt loading capacity of three metals of O (X ═ 2) by mass, placing the metal mixed solution into an ultrasonic reactor, carrying out ultrasonic treatment for 12 hours at the temperature of 40 ℃ to prepare a composite metal precursor solution, and drying the composite metal precursor solution at the constant temperature of 120 ℃ for 20 hours until the weight is constant to obtain the composite material solid particles. Ball milling and mixing the two, and roasting for 6 hours at 600 ℃ by adopting the same roasting method to prepare the sludge catalyst.
(iv) heterogeneous light Fenton reaction experimental conditions: the dosage of the sludge catalyst is 0.25g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 1.5, the UV intensity was 500W, and after 150min of reaction, the conversion of o-chlorophenol was 88.1% and the TOC removal was 70.2%.
Comparative example 1:
drying the urban domestic sludge at the temperature of 90 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at 900 ℃ for 6h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③Fe(NO3)3·9H2O、InN3O9·xH2O(X＝2)、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor for ultrasonic treatment for 1h at the temperature of 60 ℃ to prepare a composite metal precursor solution, and drying the composite metal precursor solution for 10h at the constant temperature of 80 ℃ to constant weight to obtain the composite material solid particles, wherein the loading capacity of the salt is 5.0 wt% respectively in the three metal mass meters. Ball milling and mixing the two, roasting for 4 hours at 900 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.15g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 0.2, the UV intensity was 2500W, and after 150min of reaction, the conversion of o-chlorophenol was 78.1% and the TOC removal was 50.2%.
Comparative example 2:
drying the urban domestic sludge at the temperature of 90 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at 800 ℃ for 6h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③InN3O9·xH2O(X＝2)、Sr(NO3)2、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor for ultrasonic treatment for 2h at the temperature of 60 ℃ to prepare a composite metal precursor solution, and drying the composite metal precursor solution for 18h at the constant temperature of 90 ℃ to constant weight to obtain the composite material solid particles, wherein the loading capacity of the salt is 0.05 wt% respectively in the three metal mass meters. Ball milling and mixing the two, and roasting the mixture for 10 hours at 1000 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.1g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 3.5, the UV intensity was 2000W, and after 150min of reaction, the conversion of o-chlorophenol was 70.4% and the TOC removal was 48.3%.
Comparative example 3:
drying the urban domestic sludge at the temperature of 125 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at 1000 ℃ for 6h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③MnO2、Fe(NO3)3·9H2O、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor to perform ultrasonic treatment for 20 hours at the temperature of 40 ℃ to prepare a composite metal precursor solution, and drying the composite metal precursor solution for 8 hours at the constant temperature of 90 ℃ to constant weight to obtain the composite material solid particles, wherein the loading capacity of the salt is 0.5 wt% respectively in the three metal mass meters. Ball milling and mixing the two, roasting for 4 hours at 900 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.05g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 4.0, the UV intensity was 80W, and after 150min of reaction, the conversion of o-chlorophenol was 58.3% and the TOC removal was 30.2%.
Comparative example 4:
drying the urban domestic sludge at 120 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at 800 ℃ for 5h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③TiO2、AgNO3、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor for ultrasonic treatment for 36h at the temperature of 60 ℃ to prepare a composite metal precursor solution, and drying for 6h at the constant temperature of 160 ℃ to constant weight to obtain the composite material solid particles, wherein the loading capacity of the salt is 0.05 wt% in the three metal mass meters. Ball milling and mixing the two, and roasting the mixture for 10 hours at 800 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.1g/L, the initial concentration of the o-chlorophenol is 1000mg/L, and Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 4.5, the ultraviolet light intensity was 200W, and after 150min of the reaction, the conversion of o-chlorophenol was 62.1% and the TOC removal was 43.8%.
Comparative example 5:
drying the urban domestic sludge at 135 ℃.
② putting the sludge into a muffle furnace, using N2Heating at a heating rate of 3 ℃/min as protective gas, roasting at the temperature of 300 ℃ for 6h, cooling to room temperature, and mechanically crushing to obtain the sludge residue carrier.
③TiO2、AgNO3、Bi(NO3)3And (3) putting the metal mixed solution into an ultrasonic reactor to perform ultrasonic treatment for 1.5h at the temperature of 60 ℃ to prepare a composite metal precursor solution, and drying the composite metal precursor solution at the constant temperature of 70 ℃ for 10h to constant weight to obtain the composite material solid particles, wherein the loading capacity of the salt is 0.03 wt% in the mass meter of the three metals. Ball milling and mixing the two, and roasting the mixture for 2 hours at 1000 ℃ by adopting the same roasting method to prepare the sludge catalyst.
Fourthly, heterogeneous phase light Fenton reaction experiment conditions: the dosage of the sludge catalyst is 0.05g/L, and the initial concentration of the o-chlorophenol is 1000mg/L，Na2SO4The content is 5g/L, H2O2(mg/L): the COD (mg/L) was 0.1, the ultraviolet intensity was 100W, and after 150min of reaction, the conversion of o-chlorophenol was 49.8% and the TOC removal was 35.4%.

Claims (7)

1. A preparation method of a sludge-loaded ternary active metal photo-Fenton catalyst is characterized by comprising the following steps:
the preparation method of the sludge catalyst carrier comprises the following steps:
(1) drying sludge of an urban domestic sewage plant at 100-125 ℃ until the weight is unchanged;
(2) heating the obtained sludge under the condition of introducing air, raising the temperature from room temperature to 300-800 ℃ at the rate of 3-6 ℃/min, calcining for 2-8 h, cooling to 15-35 ℃, and mechanically crushing to obtain a sludge residue catalyst carrier with high specific surface area and high porosity;
taking TiO2、AgNO3、MnO2、Fe(NO3)3·9H2O、InN3O9·xH2O、Sr(NO3)2、Bi(NO3)3Any three of the metal compounds, wherein InN3O9·xH2Mixing three metal compounds according to a certain element molar ratio, wherein the molar number of any one metal compound is not less than 30% by taking the total molar weight of the three metal compounds as 100%, adding distilled water, placing the obtained metal mixed solution into an ultrasonic reactor to perform ultrasonic treatment for 4-18 h at the temperature of 10-90 ℃ to prepare a composite metal precursor solution, and placing the precursor solution into an oven to perform constant temperature drying for 12-24 h at the temperature of 100-150 ℃ until the weight of the precursor solution is unchanged to obtain composite metal precursor solid particles; and (2) fully grinding and mixing the catalyst carrier and the composite metal precursor solid particles, and roasting at the temperature of 400-900 ℃ for 0.5-8 h to prepare the ternary composite metal sludge catalyst, wherein the loading amount of each metal compound is 0.1-5.0 wt% based on the mass of the metal in the metal compound.
2. The method of claim 1, wherein:
drying sludge of the urban domestic sewage plant at 110 ℃ until the weight of the sludge is unchanged;
in the step (2), the temperature is increased from 15-35 ℃ to 400-600 ℃ at the heating rate of 3-6 ℃/min, the calcination time is 3-6 h, the mixture is cooled to 25-30 ℃,
in the step (2), putting the metal mixed solution into an ultrasonic reactor, performing ultrasonic treatment for 4-12 h at the temperature of 20-60 ℃ to obtain a composite metal precursor solution, putting the precursor solution into an oven, and drying at the constant temperature of 120 ℃ for 12-18 h until the weight is unchanged to obtain composite metal precursor solid particles; and (2) fully grinding and mixing the catalyst carrier and the composite metal precursor solid particles, and roasting at the temperature of 500-700 ℃ for 2-5 h to prepare the ternary composite metal sludge catalyst, wherein the loading amount of each metal compound is 3.0-5.0 wt% based on the mass of the metal in the metal compound.
3. A catalyst prepared by the method of claim 1.
4. The use of the catalyst of claim 3 in a process of catalytic oxidative degradation of industrial organic wastewater in a heterogeneous photo-Fenton system.
5. Use according to claim 4, wherein the catalyst catalyzes H by light2O2Generating OH, treating and degrading organic industrial wastewater, wherein the intermittent reaction conditions are as follows: initial pH of wastewater: 2 to 7, the reaction temperature is 10 to 70 ℃, the unit of mg/L is H2O2: COD = 0.3-3.0, light intensity is 100-2000W, and the adding amount of the catalyst is 0.05-3.0 g/L.
6. The use according to claim 4, wherein the catalyst catalyzes H by light2O2Generating OH, treating and degrading organic industrial wastewater, wherein the intermittent reaction conditions are as follows: initial pH of wastewater: 3 to 5 ℃, the reaction temperature is 20 to 50 ℃, and the concentration is expressed in mgL is a unit, H2O2: COD = 0.5-1.5, light intensity is 500-1000W, and the adding amount of the catalyst is 0.5-2.0 g/L.
7. The application of claim 4, wherein the industrial organic wastewater is one or more than two of printing, electroplating, chemical industry and pharmaceutical phenolic wastewater.
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