CN113101930A - Preparation of copper ferrite Fenton catalyst with coralline morphology and application of copper ferrite Fenton catalyst in Fenton catalytic oxidation of landfill leachate - Google Patents
Preparation of copper ferrite Fenton catalyst with coralline morphology and application of copper ferrite Fenton catalyst in Fenton catalytic oxidation of landfill leachate Download PDFInfo
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- CN113101930A CN113101930A CN202110268739.0A CN202110268739A CN113101930A CN 113101930 A CN113101930 A CN 113101930A CN 202110268739 A CN202110268739 A CN 202110268739A CN 113101930 A CN113101930 A CN 113101930A
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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
- B01J23/70—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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本发明属于废水处理领域，具体公开了一种珊瑚状形貌的铁酸铜类芬顿催化剂的制备方法，向溶解有Fe2+、Cu2+的原料溶液中连续地滴加碱溶液，进行共沉淀反应；共沉淀反应过程中，碱溶液的滴加速度为3～4mL/min；pH为10～11；共沉淀反应结束后再在50～70℃的温度下陈化，随后经固液分离，即得所述的铁酸铜类芬顿催化剂。本发明还包括将所述的催化剂用于垃圾渗滤液的非均相类芬顿降解。本发明人研究发现，采用本发明的方法可显著提高类芬顿催化氧化膜滤浓缩液的性能，可使膜滤浓缩液中CODCr、UV254、色度去除率分别达到88～95％、90～96％、96～99％。The invention belongs to the field of wastewater treatment, and specifically discloses a preparation method of a copper ferrite -based Fenton catalyst with coral-like morphology. Co-precipitation reaction; during the co-precipitation reaction, the dropping rate of the alkaline solution is 3-4 mL/min; the pH is 10-11; after the co-precipitation reaction is over, it is aged at a temperature of 50-70 ° C, and then subjected to solid-liquid separation , that is, the copper ferrite-based Fenton catalyst is obtained. The present invention also includes the use of the catalyst for heterogeneous Fenton-like degradation of landfill leachate. The inventors have found that the method of the present invention can significantly improve the performance of the Fenton-like catalytic oxidation membrane filtration concentrate, and the removal rates of COD Cr , UV 254 and chromaticity in the membrane filtration concentrate can reach 88-95%, respectively. 90～96%, 96～99%.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a method for improving membrane filtration concentrated solution (membrane filtration concentrated solution for short) of Fenton-like catalytic oxidation garbage percolate.
Technical Field
The sanitary landfill is the most commonly adopted garbage treatment method at home and abroad at present, and the factors of the degradation of garbage piles, the inflow of underground water, surface runoff and the like in the landfill process of garbage can cause the generation of a large amount of garbage percolate. The biochemical treatment method is widely applied to the treatment of the sanitary landfill leachate due to low operation cost, but the COD of biochemical effluent waterCrAnd the chromaticity can not meet the discharge requirement of the pollution control standard of the domestic garbage landfill (GB 16889-2008). Therefore, in the current main treatment process of the landfill leachate, membrane separation methods such as nanofiltration and reverse osmosis are usually adopted to further concentrate the biochemical effluent, the effluent after membrane filtration can reach the discharge standard, and the produced membrane filtration concentrate with higher pollutant concentration is generally re-filled into a landfill. However, the long-term recharging of the membrane filtration concentrate can cause the accumulation of salt and pollutants, which not only causes the great reduction of the water yield of membrane treatment, but also causes the deterioration of biochemical treatment of landfill leachate, and even causes the breakdown of the whole sanitary landfill leachate treatment system. If the membrane filtration concentrated solution can be subjected to biochemical treatment again after being simply treated by other treatment processes and discharged up to the standard, recharging is not needed, so that the treatment effect of the whole sanitary landfill leachate treatment system is greatly improved, and the treatment cost is reduced.
The advanced oxidation method is a technology widely applied to sewage treatment, and has the advantages of high pollutant removal rate, capability of improving biodegradability of refractory organic matters and the like. The commonly used advanced oxidation processes are mainly homogeneous fenton and heterogeneous fenton technologies using hydrogen peroxide as the oxidant. However, under high salt conditions, the homogeneous fenton-like technique is not ideal for removing organic substances. For example, Peng et al (Peng S, Zhang W, He J, et al, Enhancement of Fenton oxidation for moving organic matter from hydrosaline solution by using a hydrated acrylamide hydroxide and benzoquinone [ J ]. Environmental sciences,2016,41(3):16-23) treated high-salt wastewater with a chloride ion concentration of 5mol/L by using the homogeneous Fenton method, the TOC removal rate was only 40%. On the other hand, although some heterogeneous fenton technologies can partially remove organic substances under high salt conditions, there is a problem that the removal rate of organic substances is not high, compared to the homogeneous fenton technology. For example, chinese patent CN111151290A discloses a method for treating high-salt dye wastewater by heterogeneous fenton-like technology, wherein when the sintering temperature of the catalyst is 500 ℃, the degradation efficiency of the catalyst on the high-salt dye wastewater is only 70%, and the catalyst has many preparation processes, high energy consumption, and is not economical and efficient enough.
Therefore, for high CODCrLandfill leachate with high chroma and high salt content, particularly membrane filtration concentrated solution, needs to find out a method for effectively removing COD (chemical oxygen demand) at low cost under the condition of high salt contentCrAnd chroma method, and researching its action mechanism to implement high CODCrAnd chroma removal rate.
Disclosure of Invention
In view of the problems of the prior art, the present invention aims to provide a copper ferrite-based fenton catalyst (also referred to as a fenton-like catalyst, a heterogeneous catalyst or simply a catalyst) with a special coral-like morphology and excellent fenton-like catalytic activity.
The second purpose of the invention is to provide a method for catalyzing landfill leachate based on the special catalyst, which aims to improve the oxidation degradation effect of the landfill leachate and realize the COD of the landfill leachateCrColor and UV254The synchronous and efficient removal is realized.
The landfill leachate contains high concentrationHigh concentration of refractory organic pollutants such as aromatic-like protein, humic-like acid, microbial metabolite, fulvic acid, etc., and has high chroma, high salinity, and difficult realization of CODCrChroma, UV254Synchronous high-efficiency processing; in addition, the membrane concentrated solution for the landfill leachate has more complex pollutant components, higher concentration and greater degradation difficulty, and is more difficult to realize COD (chemical oxygen demand)CrChroma, UV254Synchronously removing; aiming at the technical problem, the invention provides the following solutions through research:
a preparation method of copper ferrite Fenton catalyst with coralline shape comprises dissolving Fe2+、Cu2+Continuously dropwise adding an alkali solution into the raw material solution to perform coprecipitation reaction; in the coprecipitation reaction process, the dropping speed of the alkali solution is 3-4 mL/min, and the pH value is 10-11;
and after the coprecipitation reaction is finished, aging at the temperature of 50-70 ℃, and then carrying out solid-liquid separation to obtain the copper ferrite Fenton catalyst.
Aiming at the problems of great difficulty in Fenton degradation of landfill leachate, and particularly difficult realization of COD (chemical oxygen demand)CrChroma, UV254The industrial problem of synchronous treatment, the inventor surprisingly found through research that the alkali solution is innovatively and continuously dripped to contain Fe2+、Cu2+The catalyst with special coralliform high surface roughness (rich surface projections) can be obtained unexpectedly based on the dropping speed of alkali in the coprecipitation stage, the pH value in the reaction stage and the subsequent combined control of an aging process and an aging temperature parameter. More surprisingly, the catalyst with a special structure obtained by the special method has excellent degradation effect on the Fenton-like oxidation of the landfill leachate, and can realize the COD (chemical oxygen demand) of the landfill leachateCrChroma, UV254The synchronization and the high-efficiency processing are realized.
In the invention, the combined control of the coprecipitation-aging process and the conditions of alkali dropping rate, pH and temperature in the coprecipitation stage is the key for constructing the special coralliform rich thorn-convex structure and improving the Fenton degradation of the landfill leachate.
In the present invention, the raw material solution is a solution in which Fe is dissolved2+、Cu2+An aqueous solution of (a).
In the present invention, Fe2+Provided by a water soluble ferrous salt.
Preferably, the water-soluble ferrous iron is at least one of ferrous sulfate and ferrous chloride.
In the present invention, Cu2+Provided by a water soluble copper salt.
Preferably, the water-soluble copper salt is at least one of copper sulfate, copper nitrate and copper chloride.
In the present invention, Fe is contained in the raw material solution2+、Cu2+The molar ratio of (A) to (B) is 2-3: 1.
in the invention, the alkali solution is alkali aqueous solution.
The base is preferably NH3.H2At least one of O, NaOH and KOH.
The molar concentration of alkali in the alkali solution is 2-4M; more preferably 3 to 3.5M.
In the invention, the temperature of the coprecipitation reaction process is 80-90 ℃.
In the invention, the time of the coprecipitation reaction process is 1-2 h.
According to the invention, the coprecipitation reaction system is aged, and further the crystallization behavior of the material can be controlled unexpectedly through the combined control of the aging conditions, so that the material with high crystal phase purity, coral-shaped and rich thorn-convex structures can be obtained; more importantly, the material with the special structure can show unexpected effect on Fenton-like catalysis of the landfill leachate.
In the invention, the temperature of the aging stage is preferably 50-60 ℃.
In the invention, the time of the aging stage is 20-48 h; further preferably 24 to 48; further preferably 30 to 48 hours.
In the invention, after aging, solid-liquid separation is carried out, and the obtained solid is washed (for example, washed by water until the pH of the filtrate is close to neutral) and dried to obtain the heterogeneous catalyst.
The invention also provides application of the Fenton-like catalyst in Fenton-like catalytic oxidation of landfill leachate (namely a Fenton-like catalytic oxidation method of the landfill leachate), and the copper ferrite Fenton-like catalyst prepared by the preparation method, an oxidant and the landfill leachate are mixed to carry out Fenton-like catalytic oxidation reaction, so that treated effluent is obtained.
The research of the invention finds that the co-precipitation-aging process is benefited, and the combined cooperative control of the conditions is further matched, so that the degradation effect of the landfill leachate can be unexpectedly improved, and the realization of the COD of the landfill leachate is facilitatedCrChroma, UV254The synchronization and the high-efficiency processing are realized.
Preferably, the landfill leachate is polluted wastewater containing at least one pollutant of humoid, fulvic acid and microbial metabolic byproducts;
preferably, the COD of the landfill leachateCr2500-20000 mg/L, chroma of 500-2000 times and Cl-The content is 10000-20000 mg/L;
preferably, the landfill leachate is membrane filtration concentrated solution of the landfill leachate.
In the invention: the oxidant can be an oxidant well known in the field of Fenton-like, and is preferably hydrogen peroxide;
preferably, in the Fenton-like catalytic oxidation reaction process, the concentration of the oxidant is 100-250 mmol/L; more preferably 200 to 250 mmol/L.
Preferably, the pH value in the Fenton-like catalytic oxidation reaction process is 2-5; further preferably 2 to 4; more preferably 3 to 3.5.
The use amounts of the heterogeneous Fenton-like catalyst and the oxidant are not particularly required, and can be adjusted according to the use requirements. Preferably, in the Fenton-like catalytic oxidation reaction process, the dosage of the copper ferrite Fenton-like catalyst is 1-5 g/L; further preferably 1 to 2.5; more preferably 1.5 to 2.5.
The preferable Fenton-like catalytic oxidation method of the landfill leachate comprises the following steps of:
(a) to dissolve Fe2+、Cu2+Continuously dropwise adding an alkali solution into the raw material solution to perform coprecipitation reaction; in the coprecipitation reaction, the dropping speed of the alkali solution is 3-4 mL/min; the pH value is 10-11; the reaction temperature is 80-90 ℃; the reaction time is 1-2 h;
(b) after the coprecipitation reaction is finished, aging for 20-48 h at the temperature of 50-70 ℃, and then carrying out solid-liquid separation to obtain a heterogeneous catalyst;
(c) and (c) contacting the heterogeneous catalyst obtained in the step (b) with landfill leachate, and carrying out Fenton-like catalytic oxidation reaction under an oxidant to obtain treated effluent.
For example, the preferable Fenton-like catalytic oxidation method of landfill leachate in the invention is to filter the membrane filtration concentrate through a 0.45 μm membrane, measure the membrane filtration concentrate into a flask and adjust the pH, add the catalyst and the solution prepared in the invention into the flask to perform Fenton-like oxidation reaction, after the reaction is finished, separate the oxide from the membrane filtration concentrate by using a magnet, filter the membrane filtration concentrate before and after degradation through a 0.45 μm membrane, take part of the filtrate, and measure the membrane filtration concentrate before and after degradation according to HJ/T399 COD-like 2007 and GB 11903-89CrAnd chroma, measuring UVA before and after membrane filtration concentrated solution degradation by using an ultraviolet visible spectrophotometer254Calculating the CODCrChroma and UVA254The removal rate of (3).
Specific embodiments are, for example: after filtering the landfill leachate through a 0.45-micron membrane, measuring a membrane filtration concentrated solution into a flask, adjusting the pH to 3-3.5, adding 0.1-0.2 g/0.1L of the catalyst prepared by the invention and 100-250 mmol/L of 30% H2O2The solution is put into a flask and is shaken for 2 to 4 hours in a constant-temperature water bath at the temperature of between 25 and 35 ℃. After the reaction is finished, separating the catalyst from the membrane filtration concentrated solution by using a magnet, filtering the membrane filtration concentrated solution before and after degradation by using a 0.45 mu m membrane, taking part of filtrate, and measuring COD (chemical oxygen demand) in the membrane filtration concentrated solutionCr、UV254The chroma removal rate is respectively 88-95%, 90-96% and 96-99%.
The Fenton-like catalyst prepared by the method has a special coral shape and a rich protruding structure, and can catalyze and decompose hydrogen peroxide to generate hydroxyl radicals with strong oxidizing property to oxidize and degrade membrane filtration concentrated solution. And analyzing the change condition of the soluble organic matters in the membrane filtration concentrated solution by methods such as ultraviolet-visible spectrum, three-dimensional fluorescence spectrum, fluorescence area integration and the like.
Aiming at the heterogeneous Fenton-like oxidation reaction of the heterogeneous Fenton-like catalyst applied to the membrane filtration concentrated solution, the membrane filtration concentrated solution before and after degradation is filtered by a 0.45-micrometer membrane, part of filtrate is taken to carry out ultraviolet visible spectrum and three-dimensional fluorescence detection, and five areas divided in the three-dimensional fluorescence spectrum are subjected to fluorescence area integration, and the result is shown in attached figures 5 and 6 and an attached table 1. The result shows that in the heterogeneous Fenton-like reaction process of the copper ferrite composite oxide catalytic membrane filtration concentrated solution prepared by the invention, part of organic matters in the membrane filtration concentrated solution are directly mineralized into CO2And H2The other part of O is decomposed into micromolecular organic matters such as formic acid, acetic acid and the like which are easy to be biochemically generated, thereby leading the COD of the membrane filtration concentrated solutionCrAnd the chroma is greatly reduced, and the biodegradability is greatly improved.
The invention has the advantages and positive effects that:
(1) innovatively provides the Fe under alkaline solution2+And Cu2+The co-precipitation-aging combined process is carried out, and further, the accurate control of the alkali dropping rate in the co-precipitation process, the pH value in the reaction stage and the pH condition in the aging process is found to generate a synergistic effect, so that the heterogeneous catalyst which has a special coral shape and rich and convex appearance can be obtained unexpectedly. The catalyst with the special morphology has an excellent catalytic degradation effect in the aspect of Fenton-like catalysis. In addition, the heterogeneous catalyst provided by the invention has good crystal phase purity, excellent structural stability and excellent catalytic performance and cycle stability.
(2) The heterogeneous catalyst obtained by the process has unexpected effect on Fenton-like catalytic degradation of landfill leachate, and can realize CODCr、UV254And the chroma is synchronously and efficiently removed.
Research finds that the COD is aimed atCr2500-20000 mg/L, chroma of 500-2000 times and Cl-The content of the liquid membrane filtration concentrated solution of the landfill leachate of the sanitary landfill is 10000-20000 mg/L, which can ensure that COD (chemical oxygen demand) in the membrane filtration concentrated solutionCr、UV254The chroma removal rate is respectively 88-95%, 90-96% and 96-99%.
(3) The Fenton-like catalyst provided by the invention can be obtained without high-temperature roasting, and has the advantages of rich raw material sources, simple process, low requirement on equipment, no raw material loss, high yield, low energy consumption and the like.
(4) The Fenton-like catalyst provided by the invention has the advantages of strong magnetic force, high magnetic separation recovery rate and good recycling performance.
Drawings
FIG. 1 is an SEM photograph of Fenton-like catalysts obtained in examples 1, 3 and 9. As can be seen from the figure, the Fenton-like catalyst prepared by jointly controlling the key conditions of catalyst synthesis has rich thorns and bulges on the surface and has the brand-new appearance of a coral-shaped surface, so that the active sites of the catalyst are greatly increased, and the efficiency of the Fenton-like catalytic oxidation membrane filtration concentrate of the catalyst is further improved to a great extent.
FIG. 2 is an SEM photograph of Fenton-like catalysts obtained in comparative examples 6, 7, 11 and 12. As can be seen from the figure, the catalyst prepared by the method does not have special morphology under the condition required by the invention, so that the Fenton-like catalytic performance of the catalyst is poor.
FIG. 3 is an XRD spectrum of the Fenton-like catalyst obtained in example 3. Researches show that the diffraction peak of the sample prepared by the method is narrow and high, which indicates that the sample has good crystallinity, and the diffraction peak completely accords with the characteristic peak of eight-phase copper ferrite (JCPDS 25-0283).
FIG. 4 is a graph showing the effect of heterogeneous Fenton-like catalytic oxidation of the membrane filtration concentrate of landfill leachate in example 3. As can be seen from the figure, the membrane filtration concentrated solution water body after Fenton-like catalytic oxidation is nearly colorless, and the catalyst prepared by the preparation method disclosed by the invention has stronger magnetism and high magnetic separation recovery rate.
FIG. 5 is a UV-Vis spectrum of the heterogeneous Fenton-like catalytic oxidation of the liquid membrane filtration concentrate of landfill leachate in example 3. In a heterogeneous Fenton reaction system, the absorbance of the membrane filtration concentrate in an ultraviolet-visible light region is reduced obviously along with the prolonging of the reaction time, and the result shows that the organic matters in the membrane filtration concentrate are oxidized by hydroxyl radicals, the concentration of the organic matters is reduced, and the aromaticity and the conjugation degree are greatly reduced.
FIG. 6 is a three-dimensional fluorescence spectrum of a liquid membrane filtration concentrate of refuse leachate of a sanitary landfill before and after heterogeneous Fenton-like catalytic oxidation in example 3, and it can be seen from the three-dimensional fluorescence spectrum that most of fulvic acid-like substances and humic acid-like substances are removed significantly during the reaction process, and part of metabolic byproducts of microorganisms are removed.
Table 1 is a fluorescence area integral table of the divided areas in the three-dimensional fluorescence spectrum of FIG. 6. As can be seen from the table, the relative content of humic-like acid substances and fulvic-like acid substances in the membrane filtration concentrate is greatly reduced, while the relative content of microbial metabolic byproducts is greatly increased.
TABLE 1 integral percentage of fluorescence area of each substance before and after degradation of membrane filtration concentrate
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the claims of the present invention.
Examples 1 to 9
Preparation of copper ferrite composite oxide
(1) According to the molar ratio of Fe/Cu elements of 2: 1 weighing a certain amount of FeSO4·7H2O and CuSO4·5H2Dissolving the O solid in deionized water, and uniformly stirring to obtain a mixed raw material solution.
(2) Continuously dropwise adding 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1) to perform coprecipitation reaction, wherein the dropwise adding speed of the sodium hydroxide solution is 3-4 mL/min; the reaction temperature is 80-90 ℃, and the pH value in the coprecipitation process is controlled to be 10-11; the reaction time was 1.5 h.
(3) Cooling the reaction system obtained in the step (2) to 50-70 ℃, standing and aging for 20-48 h. Magnetic separation is adopted to obtain solid matter, the solid matter is washed by deionized water until the pH value is neutral, air-blast drying is carried out for 4 hours at the temperature of 80 ℃, and the solid matter is ground into powder and stored for standby.
Secondly, aiming at the membrane filtration concentrated solution, investigating the catalytic effect of the copper ferrite composite oxide in the heterogeneous Fenton-like oxidation reaction
Membrane filtration Concentrate (COD)Cr2500mg/L, a color of 500 times and Cl-10000mg/L) is filtered by a 0.45 mu m membrane, 100mL of membrane filtration concentrated solution is measured and put into a flask, the pH is adjusted to 3.0, 2g/L (2 g is added in each L of membrane filtration concentrated solution) of the catalyst prepared by the invention and 250mmol/L of 30% H are added2O2The solution was shaken in a flask in a 30 ℃ thermostatic water bath for 3 h. After the reaction is finished, separating the oxide from the membrane filtration concentrated solution by using a magnet, filtering the membrane filtration concentrated solution before and after degradation by using a 0.45 mu m membrane, taking part of filtrate, and determining COD (chemical oxygen demand) of the membrane filtration concentrated solution before and after degradation according to HJ/T399-CrAnd chroma, measuring UVA before and after membrane filtration concentrated solution degradation by using an ultraviolet visible spectrophotometer254Calculating the CODCrChroma and UVA254The removal rate of (c) was determined (see table 2).
Table 2 shows the catalytic degradation effect of the copper ferrite catalyst in the heterogeneous Fenton-like oxidation reaction
As shown in Table 2, in the catalyst synthesis process, the Fenton-like catalyst prepared under the conditions that the dropping speed of the alkali liquor is 3-4 mL/min, the reaction pH is 10-11, the aging temperature is 50-70 ℃, and the aging time is 24-48 h has rich stabbing and convex surfaces and has a brand new appearance of a coral-shaped surface. Researches show that the catalyst with coral-shaped morphology has unexpected effect on Fenton-like catalysis of membrane filtration concentrate, and canRealize COD and UV254The chroma removal rate is respectively 88-95%, 90-96% and 96-99%.
Examples 10 to 11
Using the heterogeneous Fenton-like catalyst prepared in example 3 (dropping speed of alkali solution: 4mL/min, reaction pH: 11, aging temperature: 60 ℃ C., aging time: 48 hours), various aqueous membrane filtration Concentrates (COD)Cr1000-20000 mg/L, 1000-2000 times of chroma and Cl-15000-20000 mg/L) (Table 3), and the degradation conditions are the same as those in example 3.
Table 3 shows the catalytic degradation effect of the copper ferrite catalyst on the heterogeneous Fenton-like oxidation reaction of the membrane filtration concentrate with different water qualities
Examples 12 to 17
Using the heterogeneous Fenton-like catalyst prepared in example 3 (dropping speed of alkali solution: 4mL/min, reaction pH: 11, aging temperature: 60 ℃ C., aging time: 48 hours), membrane filtration concentrates (same as example 3; COD)Cr2500mg/L, a color of 500 times and Cl-10000mg/L) (Table 4).
Table 4 examines the catalytic degradation effect of different degradation conditions on the heterogeneous Fenton-like oxidation reaction of the membrane filtration concentrate
Examples 18 to 20
Using the heterogeneous Fenton-like catalyst of example 3 (dropping speed of alkali solution: 4mL/min, reaction pH: 11, aging temperature: 60 ℃ C., aging time: 48 hours), circulation was carried outRing use performance test (degradation conditions same as example 3) and investigation of the cycle number of heterogeneous Fenton-like catalysts and the membrane filtration concentrate (same as example 3; COD)Cr2500mg/L, a color of 500 times and Cl-10000mg/L) degradation effect of Fenton-like oxidation (see Table 5).
TABLE 5 relationship between the number of times of recycling of non-stoichiometric copper ferrite composite oxide and the degradation effect of Fenton-like oxidation reaction of membrane filtration concentrate
Therefore, the catalyst prepared by the preparation method has good stability.
Comparative examples 1 to 2
This comparative example was identical to the membrane filtration Concentrates (COD) used in examples 10 to 11Cr10000-20000 mg/L, 1000-2000 times of chroma and Cl-15000-20000 mg/L), filtering with 0.45 μm membrane, measuring 100mL membrane filtration concentrate into flask, adjusting pH to 3.0, performing conventional homogeneous Fenton reaction, and adding H2O2：Fe2+The molar ratio is 10: 1 adding 30% of H2O2Solution and 20% FeSO4The solution was shaken in a flask in a 30 ℃ thermostatic water bath for 3 h. After the reaction is finished, filtering the membrane filtration concentrated solution before and after degradation by a 0.45 mu m membrane, taking part of filtrate, and determining COD (chemical oxygen demand) of the membrane filtration concentrated solution before and after degradation according to HJ/T399-CrAnd chroma, measuring UVA before and after membrane filtration concentrated solution degradation by using an ultraviolet visible spectrophotometer254Calculating the CODCrChroma and UVA254The removal rate of (c) was as shown in Table 6.
TABLE 6 degradation Effect of conventional homogeneous Fenton reaction on Membrane filtration concentrate
Comparative example 3
Membrane filtration Concentrate (COD)Cr2500mg/L, a color of 500 times and Cl-Content of 10000mg/L) is filtered by a 0.45 μm membrane, 100mL of membrane filtration concentrated solution is measured and put into a flask, pH is adjusted to 3.0, 2g/LFe is added3O4And 250 mmol/L30% H2O2The solution was shaken in a flask in a 30 ℃ thermostatic water bath for 3 h. After the reaction is finished, separating the catalyst from the membrane filtration concentrate by using a magnet, filtering the membrane filtration concentrate before and after degradation by using a 0.45 mu m membrane, taking part of filtrate, and determining COD (chemical oxygen demand) of the membrane filtration concentrate before and after degradation according to HJ/T399-CrAnd chroma, measuring UVA before and after membrane filtration concentrated solution degradation by using an ultraviolet visible spectrophotometer254Calculating the CODCrChroma and UVA254The removal rate of (c) was determined (see table 7).
TABLE 7 Fe3O4Catalytic effect of Fenton-like oxidation reaction on membrane filtration concentrated solution
Comparative example 4
Membrane filtration Concentrate (COD)Cr2500mg/L, a color of 500 times and Cl-Content of 10000mg/L) was filtered through a 0.45 μm membrane, 100mL of the membrane-filtered concentrate was measured into a flask and pH was adjusted to 3.0, 2g/LFeOOH and 250mmol/L of 30% H were added2O2The solution was shaken in a flask in a 30 ℃ thermostatic water bath for 3 h. After the reaction is finished, separating the catalyst from the membrane filtration concentrate by using a magnet, filtering the membrane filtration concentrate before and after degradation by using a 0.45 mu m membrane, taking part of filtrate, and determining COD (chemical oxygen demand) of the membrane filtration concentrate before and after degradation according to HJ/T399-CrAnd chroma, measuring UVA before and after membrane filtration concentrated solution degradation by using an ultraviolet visible spectrophotometer254Calculating the CODCrChroma and UVA254The removal rate of (c) was determined (see table 8).
TABLE 8 Fe3O4Catalytic effect of Fenton-like oxidation reaction on membrane filtration concentrated solution
Comparative example 5
Membrane filtration concentrate (same as example 3, COD)Cr2500mg/L, a color of 500 times and Cl-Content of 10000mg/L) was filtered through a 0.45 μm membrane, 100mL of the membrane filtration concentrate was measured into a flask and the pH was adjusted to 3.0 with H2O2：Fe2+The molar ratio is 10: 1 FeSO addition4-CuSO4Mixed solution (Fe: Cu molar ratio 2: 1) and 30% H2O2The solution was shaken in a flask in a 30 ℃ thermostatic water bath for 3 h. After the reaction is finished, separating the catalyst from the membrane filtration concentrate by using a magnet, filtering the membrane filtration concentrate before and after degradation by using a 0.45 mu m membrane, taking part of filtrate, and determining COD (chemical oxygen demand) of the membrane filtration concentrate before and after degradation according to HJ/T399-CrAnd chroma, measuring UVA before and after membrane filtration concentrated solution degradation by using an ultraviolet visible spectrophotometer254Calculating the CODCrChroma and UVA254The removal rate of (c) was as shown in Table 9.
TABLE 9 FeSO4-CuSO4Fenton-like oxidation reaction catalytic effect of mixed solution on membrane filtration concentrated solution
Comparative examples 6 to 13
Compared with the embodiment 3, the single key innovation point of the preparation method is changed, the catalyst is prepared, and the catalytic effect of the Fenton-like oxidation reaction of the membrane filtration concentrated solution is examined.
Membrane filtration concentrate (same as example 3; COD)Cr2500mg/L, a color of 500 times and Cl-10000mg/L) was filtered through a 0.45 μm membrane, 100mL of membrane filtration concentrate was measured into a flask and the pH was adjusted to 3.0, 2g/L (2 g per L of membrane filtration concentrate) of the catalyst prepared in the following table and 250mmol/L of 30% H were added2O2The solution was shaken in a flask in a 30 ℃ thermostatic water bath for 3 h. After the reaction is finished, separating the oxide from the membrane filtration concentrated solution by using a magnet, filtering the membrane filtration concentrated solution before and after degradation by using a 0.45 mu m membrane, taking part of filtrate, and determining COD (chemical oxygen demand) of the membrane filtration concentrated solution before and after degradation according to HJ/T399-CrAnd chroma, measuring UVA before and after membrane filtration concentrated solution degradation by using an ultraviolet visible spectrophotometer254Calculating the CODCrChroma and UVA254The removal rate of (c) was as shown in Table 10.
TABLE 10 Fenton-like catalytic oxidation effect of catalysts prepared with modified key innovation points on membrane filtration concentrates
Researches show that the catalyst prepared by changing a single key innovation point of the preparation method has certain catalytic capability on Fenton-like oxidation reaction of the membrane filtration concentrated solution, but the effect is not as good as that of the catalyst with unique coral-shaped surface appearance prepared under the precise control preparation condition.
Comparative example 14
Compared with example 3, the key degradation conditions were changed, and the membrane filtration Concentrate (COD) was examinedCr2500mg/L, a color of 500 times and Cl-Content of 10000mg/L) of the catalytic effect of the Fenton-like oxidation reaction.
TABLE 11 Finton-like catalytic Oxidation Effect on Membrane filtration concentrates by varying Key degradation conditions
In summary, based on the above embodiments and comparative examples: the preparation conditions of the invention are precisely controlled, and the prepared catalyst with abnormally rough surface and unique coral-shaped appearance is used for treating COD (chemical oxygen demand) of membrane filtration concentrated solutionCrAnd chroma, UV254Has obvious removing effect, good Fenton-like catalytic oxidation performance and good recycling performance.
Claims (10)
1. A preparation method of copper ferrite Fenton catalyst with coral-shaped appearance is characterized by comprising the following steps: to dissolve Fe2+、Cu2+Continuously dropwise adding an alkali solution into the raw material solution to perform coprecipitation reaction; in the coprecipitation reaction process, the dropping speed of the alkali solution is 3-4 mL/min; the pH value is 10-11;
and after the coprecipitation reaction is finished, aging at the temperature of 50-70 ℃, and then carrying out solid-liquid separation to obtain the copper ferrite Fenton catalyst.
2. The method of claim 1, wherein: fe2+Provided by water soluble ferrous salt;
the water-soluble ferrous is preferably at least one of ferrous sulfate and ferrous chloride;
preferably, Cu2+Provided by a water-soluble copper salt;
the water-soluble copper salt is preferably at least one of copper sulfate, copper nitrate and copper chloride.
3. The method of claim 1, wherein: fe in the raw material solution2+、Cu2+The molar ratio of (A) to (B) is 2-3: 1.
4. the method of claim 1, wherein: the alkali solution is an alkali aqueous solution;
the base is preferably NH3.H2At least one of O, NaOH and KOH;
the molar concentration of alkali in the alkali solution is 2-4M.
5. The method of claim 1, wherein: the temperature in the coprecipitation reaction process is 80-90 ℃;
preferably, the time of the coprecipitation reaction process is 1-2 h.
6. The method of claim 1, wherein: the time of the aging stage is 20-48 h; further preferably 24 to 48; further preferably 30 to 48 hours.
7. A Fenton-like catalytic oxidation method of landfill leachate, which is characterized in that a copper ferrite Fenton-like catalyst prepared by the preparation method of any one of claims 1 to 6, an oxidant and the landfill leachate are mixed to perform a Fenton-like catalytic oxidation reaction, so as to obtain treated effluent.
8. The Fenton-like catalytic oxidation method for landfill leachate of claim 7, wherein,
the landfill leachate is polluted wastewater containing at least one pollutant of humoid, fulvic acid and microbial metabolic byproducts;
preferably, the COD of the landfill leachateCr2500-20000 mg/L, chroma of 500-2000 times and Cl-The content is 10000-20000 mg/L.
9. The Fenton-like catalytic oxidation method of landfill leachate of claim 8, wherein,
the landfill leachate is membrane filtration concentrated solution of the landfill leachate.
10. The Fenton-like catalytic oxidation method of landfill leachate according to any one of claims 7 to 9, wherein: the oxidant is hydrogen peroxide;
preferably, in the Fenton-like catalytic oxidation reaction process, the concentration of the oxidant is 100-250 mmol/L; preferably 200 to 250 mmol/L;
preferably, the pH value in the Fenton-like catalytic oxidation reaction process is 2-5; further preferably 3 to 3.5;
preferably, in the Fenton-like catalytic oxidation reaction process, the dosage of the copper ferrite Fenton-like catalyst is 1-5 g/L; further preferably 1 to 2.5; more preferably 1.5 to 2.5.
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