CN110627186B - Wastewater treatment method for generating singlet oxygen by catalyzing persulfate through modified cobalt oxide - Google Patents
Wastewater treatment method for generating singlet oxygen by catalyzing persulfate through modified cobalt oxide Download PDFInfo
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Abstract
The invention provides a method for treating wastewater by catalyzing persulfate to generate singlet oxygen by regulating and controlling the performance of cobalt oxide. The method has the following characteristics: cobalt metal salt, extra added metal salt and organic ligand react in a reaction solvent, the obtained solid is calcined in the air at a certain heating rate to obtain modified cobalt oxide, and the modified cobalt oxide is mixed with persulfate and added into wastewater, so that singlet oxygen can be generated to remove organic pollutants in water. The method described by the invention is simple, does not need expensive equipment and medicines, and has low cost; the modification of the cobalt oxide changes the property of the cobalt oxide, so that the cobalt oxide can catalyze persulfate to generate singlet oxygen in a heterogeneous mode, and the problem of carbon dissolution of the traditional carbon-containing heterogeneous catalyst is solved.
Description
Technical Field
The invention relates to the field of advanced oxidation water treatment, in particular to a method for efficiently removing organic pollutants in water by enabling cobalt oxide to generate singlet oxygen when catalyzing persulfate through oxygen vacancy regulation.
Background
The advanced oxidation technology for degrading pollutants in water by utilizing strong oxidizing groups attracts extensive research and certain-scale application in the field of water treatment, and becomes an important component of the current water treatment technology and one of the main development directions in the future.
The earliest advanced oxidation technology utilized the catalytic reaction between hydrogen peroxide and ferrous iron to generate hydroxyl radicals, which degraded pollutants. However, the technology has the defects of narrow pH value application range, large amount of iron mud generated by reaction and the like, which are not overcome so far.
The heterogeneous persulfate system with recoverable catalyst and wide pH application range is a promising advanced oxidation technology at present as the development continuation of the traditional technology. The system can generate a plurality of oxidizing radicals such as sulfate radicals, hydroxyl radicals, singlet oxygen and the like, wherein the singlet oxygen is molecular oxygen in an excited state, has the characteristics of high reaction activity, long survival time, no generation of toxic and harmful byproducts after oxidation and the like, belongs to a green and environment-friendly oxidant, has the advantage of high selective degradation of specific pollutants, and has important significance in the field of organic pollutant control in water.
However, as far as we know, the heterogeneous catalyst capable of activating persulfate to generate singlet oxygen is mainly a carbon-containing catalyst, and the carbon element of the heterogeneous catalyst is oxidized into an organic matter, so that the risk of secondary pollution is introduced. In view of the application prospect of the heterogeneous persulfate system and the important significance of singlet oxygen in the water treatment process, the development of a novel carbon-free heterogeneous catalyst capable of catalyzing persulfate to generate singlet oxygen is significant.
Cobalt oxide is a commonly used heterogeneous persulfate catalyst that has proven to be excellent, but this process does not produce singlet oxygen. The cobalt oxide which has excellent performance, widely exists, is easy to commercialize and does not contain carbon is modified by a technical means, so that the cobalt oxide has the capacity of generating singlet oxygen in the process of catalyzing persulfate, a novel water treatment technology capable of avoiding secondary pollution is developed, and the method has important significance.
Disclosure of Invention
The invention aims to provide a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide, which is characterized by comprising the following steps of:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
1-50 parts by weight of non-cobalt metal salt
10-1000 parts by weight of organic ligand
The solid-liquid ratio of the solid raw material to the reaction solvent is 1: 10-1: 200
After the reaction is finished, separating to obtain a solid product;
heating the solid product in the step 2 to a fixed temperature, and then carrying out heat preservation and calcination;
putting the solid product treated in the step 3 and persulfate into wastewater to be treated, wherein the adding concentration of the persulfate is as follows: 0.05 g/L-5 g/L;
the mixture ratio is as follows:
1 to 200 parts by weight of persulfate
And 5, stirring to finish the treatment of the wastewater.
Similar to the above method, the present invention also provides a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide in the case of using a catalyst carrier, which is characterized by comprising the following steps:
1, adding cobalt metal salt, non-cobalt metal salt, organic ligand and catalyst carrier into a reaction solvent together;
the mixture ratio of the raw materials is as follows:
the solid-liquid ratio of the solid raw material to the reaction solvent is 1: 1-1: 2000
Separating the loaded catalyst carrier after the reaction is finished;
heating the separated catalyst carrier in the step 2 to a fixed temperature, and then carrying out heat preservation and calcination;
placing the catalyst carrier subjected to heating treatment in wastewater to be treated, and adding persulfate into the wastewater, wherein the persulfate adding concentration is as follows: 0.05 g/L-5 g/L;
the mixture ratio is as follows:
catalyst carrier 1 part by weight
0.01 to 2 parts by weight of persulfate
And 5, allowing the wastewater to flow through a catalyst carrier to finish the treatment of the wastewater.
Further, in step 1), the cobalt metal salt is selected from: one or more of cobalt nitrate, cobalt sulfate and cobalt chloride; the non-cobalt metal salt is selected from: one or more of non-cobalt metal nitrate, non-cobalt metal sulfate and non-cobalt metal chloride are mixed; the organic ligand is selected from: one or more of methylimidazole, terephthalic acid, trimesic acid, 2-methylimidazole or 1, 4-terephthalic acid; the reaction solvent is selected from: one or more of methanol, dimethyl sulfoxide and high purity water.
Further, the cobalt metal salt is selected from: cobalt nitrate, cobalt nitrite, sodium cobalt nitrite, cobalt nitrate hexahydrate, cobalt sulfate, cobalt sulfite, cobalt sulfate heptahydrate, cobalt chloride. The non-cobalt metal salt is selected from: metal nitrates, sulfates or chlorides which can decompose metal oxides at high temperatures.
Further, the metal nitrate that can decompose the metal oxide at high temperature is selected from: zinc nitrate, copper nitrate, ferric nitrate, nickel nitrate, manganese nitrate, cadmium nitrate and chromium nitrate.
The metal sulfate that decomposes at high temperature to form metal oxides is selected from: one or more of zinc sulfate, copper sulfate, ferric sulfate, nickel sulfate, manganese sulfate, cadmium sulfate and chromium sulfate.
The metal chloride salt which decomposes at elevated temperature to form a metal oxide is selected from: zinc chloride, copper chloride, ferric chloride, nickel chloride, manganese chloride, cadmium chloride and/or chromium chloride.
Further, in the heating process of the step 3), the temperature of the solid sample is raised to 500 ℃ at the rate of 1-2 ℃ per minute in the air, and after the solid sample is subjected to heat preservation and calcination at 500 ℃ for 30 minutes to 4 hours at 300-.
Further, the persulfate is peroxymonosulfate.
Further, the salt of peroxymonosulfate is selected from the group consisting of: potassium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxymonosulfate, and sodium peroxymonosulfate.
Further, the catalyst carrier is active carbon particles, aluminum oxide particles, a steel wire mesh or plastic filler.
It is worth to be noted that the basic concept of the present invention is to add one or more additional metal salts, mix them with cobalt salts in a reaction solvent and add an organic ligand to generate a cobalt-based polymetallic organic framework material, and calcine the cobalt-based polymetallic organic framework material in air at a certain temperature and a certain temperature rise rate to obtain a modified cobalt oxide; the modified cobalt oxide and the peroxymonosulfate are added into a water sample to be treated at the same time according to a certain proportion, and the organic matters in the water sample can be removed after stirring for a period of time. By controlling the heating rate and the additionally added metal salt, the oxygen vacancy content of the surface of the modified cobalt oxide is changed, and the generation of singlet oxygen during the catalysis of persulfate is realized.
The invention has the beneficial effects that: the invention provides a novel heterogeneous catalyst based on cobalt oxide, which realizes the generation of singlet oxygen in the persulfate catalyzing process, avoids the risk of secondary pollution caused by the traditional carbon-containing catalyst, and realizes the high-efficiency removal of organic pollutants cleanly. The method is simple, does not need expensive equipment and medicines, and has low cost.
Drawings
FIG. 1 TEM and energy spectrum of Zn doped modified cobalt oxide;
FIG. 2, the modified cobalt oxide catalyzes peroxymonosulfate to treat rhodamine B wastewater;
FIG. 3 shows capture agent experiments for degrading rhodamine B;
FIG. 4. Capture agent experiments for degradation of carbamazepine.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide is characterized by comprising the following steps:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
1-50 parts by weight of non-cobalt metal salt
10-1000 parts by weight of organic ligand
The solid-liquid ratio of the solid raw material to the reaction solvent is 1: 10-1: 200
The cobalt metal salt is selected from: one or more of cobalt nitrate, cobalt sulfate and cobalt chloride; preferably, the cobalt metal salt is selected from: cobalt nitrate, cobalt nitrite, sodium cobalt nitrite, cobalt nitrate hexahydrate, cobalt sulfate, cobalt sulfite, cobalt sulfate heptahydrate, cobalt chloride.
The non-cobalt metal salt is selected from: one or more of non-cobalt metal nitrate, non-cobalt metal sulfate and non-cobalt metal chloride are mixed; preferably, the metal salt other than cobalt is selected from: metal nitrates, sulfates or chlorides which can decompose metal oxides at high temperatures. More preferably, the metal nitrate that can decompose to a metal oxide at high temperature is selected from: zinc nitrate, copper nitrate, ferric nitrate, nickel nitrate, manganese nitrate, cadmium nitrate and chromium nitrate. The metal sulfate that decomposes at high temperature to form metal oxides is selected from: one or more of zinc sulfate, copper sulfate, ferric sulfate, nickel sulfate, manganese sulfate, cadmium sulfate and chromium sulfate. The metal chloride salt which decomposes at elevated temperature to form a metal oxide is selected from: zinc chloride, copper chloride, ferric chloride, nickel chloride, manganese chloride, cadmium chloride and/or chromium chloride.
The organic ligand is selected from: one or more of methylimidazole, terephthalic acid, trimesic acid, 2-methylimidazole or 1, 4-terephthalic acid;
the reaction solvent is selected from: one or more of methanol, dimethyl sulfoxide and high purity water.
After the reaction is finished, separating to obtain a solid product;
heating the solid product in the step 2);
in the heating process, after the solid sample is heated to 300-500 ℃ in the air at the heating rate of 1-2 ℃ per minute and is kept for 30 minutes to 4 hours, the newly obtained product is recovered, cleaned and dried.
Putting the solid product treated in the step 3 and persulfate into wastewater to be treated;
the mixture ratio is as follows:
1 to 200 parts by weight of persulfate
Preferably, the persulfate is a peroxymonosulfate. More preferably, the salt of peroxymonosulfate is selected from the group consisting of: the peroxymonosulfate is selected from the group consisting of: potassium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxymonosulfate, and sodium peroxymonosulfate.
And 5, stirring to finish the treatment of the wastewater.
Example 2:
a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide is characterized by comprising the following steps:
1, adding cobalt metal salt, non-cobalt metal salt, organic ligand and catalyst carrier into a reaction solvent together;
the mixture ratio of the raw materials is as follows:
the solid-liquid ratio of the solid raw material to the reaction solvent is 1: 1-1: 2000
The cobalt metal salt is selected from: one or more of cobalt nitrate, cobalt sulfate and cobalt chloride; preferably, the cobalt metal salt is selected from: cobalt nitrate, cobalt nitrite, sodium cobalt nitrite, cobalt nitrate hexahydrate, cobalt sulfate, cobalt sulfite, cobalt sulfate heptahydrate, cobalt chloride.
The non-cobalt metal salt is selected from: one or more of non-cobalt metal nitrate, non-cobalt metal sulfate and non-cobalt metal chloride are mixed; preferably, the metal salt other than cobalt is selected from: metal nitrates, sulfates or chlorides which can decompose metal oxides at high temperatures. More preferably, the metal nitrate that can decompose to a metal oxide at high temperature is selected from: zinc nitrate, copper nitrate, ferric nitrate, nickel nitrate, manganese nitrate, cadmium nitrate and chromium nitrate. The metal sulfate that decomposes at high temperature to form metal oxides is selected from: one or more of zinc sulfate, copper sulfate, ferric sulfate, nickel sulfate, manganese sulfate, cadmium sulfate and chromium sulfate. The metal chloride salt which decomposes at elevated temperature to form a metal oxide is selected from: zinc chloride, copper chloride, ferric chloride, nickel chloride, manganese chloride, cadmium chloride and/or chromium chloride.
The organic ligand is selected from: one or more of methylimidazole, terephthalic acid, trimesic acid, 2-methylimidazole or 1, 4-terephthalic acid;
the reaction solvent is selected from: one or more of methanol, dimethyl sulfoxide and high purity water.
The catalyst carrier is active carbon particles, aluminum oxide particles, a steel wire mesh and plastic fillers.
Separating the loaded catalyst carrier after the reaction is finished;
heating the separated catalyst carrier in the step 2); in the thermal process, after the solid sample is heated to 300-500 ℃ in the air at the heating rate of 1-2 ℃ per minute and is kept for 30 minutes to 4 hours, the newly obtained product is recovered, cleaned and dried.
Placing the catalyst carrier subjected to heating treatment in wastewater to be treated, and adding peroxymonosulfate into the wastewater, wherein the adding concentration of the peroxymonosulfate is as follows: 0.05 g/L-5 g/L;
and 5, allowing the wastewater to flow through a catalyst carrier to finish the treatment of the wastewater.
Example 3:
the main steps of this example are the same as example 1, specifically:
a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide is characterized by comprising the following steps:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
cobalt nitrate 1 part by weight
1 part by weight of zinc nitrate
2-methylimidazole 4 parts by weight
The solid-liquid ratio of the solid raw material to the reaction solvent is 1:20
The reaction solvent is methanol
And 2, standing the mixed system in the step 1 at room temperature for 24 hours, and then performing suction filtration and separation to obtain a solid.
And 3, placing the solid in the step 2) into an open tubular furnace, raising the temperature of a solid sample to 400 ℃ in air at a heating rate of 2 ℃ per minute, keeping the temperature for 2 hours, recovering, cleaning and drying a new product.
The modified cobalt oxide was characterized by transmission electron microscopy and X-ray energy scattering spectroscopy by X-ray diffraction, the results are shown in fig. 1. The spectrum shows that zinc is uniformly doped into cobalt oxide.
Putting the solid product treated in the step 3 and potassium hydrogen peroxymonosulfate into wastewater to be treated;
the mixture ratio is as follows:
solid product 1 part by weight
1 part by weight of potassium hydrogen peroxymonosulfate
The pollutant in the wastewater (water sample) to be treated is dye rhodamine B, and the concentration is 50 mg/L. The adding concentration of the solid product is 200 mg/L, and the adding concentration of potassium peroxymonosulfate is 200 mg/L.
And 5, after stirring and reacting for 10 min, the rhodamine B decolorization rate can reach 100 percent.
The pollutant removal effect was measured by uv-vis spectroscopy, and the control group was measured, and the results are shown in fig. 2. The degradation rate of the modified cobalt oxide is greatly improved. The active group types mainly acting in the reaction are confirmed by utilizing a trapping agent experiment, and the result is shown in figure 3, ethanol cannot obviously inhibit the degradation effect, and L-histidine completely inhibits the reaction effect, so that singlet oxygen is a main active group in the reaction, and the modified cobalt oxide is proved to generate singlet oxygen in the process of catalyzing persulfate.
Example 4:
the main steps of this example are the same as example 1, specifically:
a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide is characterized by comprising the following steps:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
cobalt nitrate 1 part by weight
1 part by weight of zinc nitrate
2 parts by weight of 2-methylimidazole
The solid-to-liquid ratio of the solid starting material to the reaction solvent (high purity water) was 1: 25.
And 2, standing the mixed system in the step 1 at room temperature for 12 hours, and then performing suction filtration and separation to obtain a solid.
And 3, placing the solid in the step 2) into an open tubular furnace, heating the solid sample from room temperature to 400 ℃ in the air at the heating rate of 2 ℃ per minute, preserving the temperature for 2 hours, and then naturally cooling to obtain the modified cobalt oxide.
Putting the solid product treated in the step 3 and potassium hydrogen peroxymonosulfate into wastewater to be treated;
the mixture ratio is as follows:
modified cobalt oxide 1 part by weight
1.5 parts by weight of potassium hydrogen peroxymonosulfate
The pollutant in the wastewater (water sample) to be treated is a drug carbamazepine with the concentration of 5mg/L, the adding concentration of the modified cobalt oxide is 50 mg/L, and the adding concentration of potassium hydrogen peroxymonosulfate is 75 mg/L.
And 5, after stirring and reacting for 5 min, the removal rate of the carbamazepine can reach 100 percent.
The concentration of carbamazepine before and after the reaction was measured by high performance liquid chromatography, and a trapping agent experiment was performed, and the results are shown in fig. 4. The modified cobalt oxide can catalyze the peroxymonosulfate system to generate singlet oxygen and efficiently degrade carbamazepine.
Claims (8)
1. The wastewater treatment method for generating singlet oxygen by catalyzing persulfate through modified cobalt oxide is characterized by comprising the following steps:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
cobalt metal salt 10 parts by weight
1-50 parts by weight of non-cobalt metal salt
10-1000 parts by weight of organic ligand
The cobalt metal salt is selected from: one or more of cobalt nitrate, cobalt sulfate and cobalt chloride;
the non-cobalt metal salt is selected from: one or more of non-cobalt metal nitrate, non-cobalt metal sulfate and non-cobalt metal chloride are mixed;
the organic ligand is selected from: one or more of methylimidazole, terephthalic acid, trimesic acid, 2-methylimidazole or 1, 4-terephthalic acid;
the reaction solvent is selected from: one or more of methanol, dimethyl sulfoxide and high-purity water;
after the reaction is finished, separating to obtain a solid product;
3, raising the temperature of the solid product in the step 2) to 300-500 ℃ at the temperature rise rate of 1-2 ℃ per minute in the air, and preserving the temperature for 30 minutes to 4 hours;
putting the solid product treated in the step 3 and persulfate into wastewater to be treated, wherein the adding concentration of the persulfate is as follows: 0.05 g/L-5 g/L;
the mixture ratio is as follows:
solid product 10 parts by weight
1 to 200 parts by weight of persulfate
And 5, stirring to finish the treatment of the wastewater.
2. The wastewater treatment method for generating singlet oxygen by catalyzing persulfate through modified cobalt oxide is characterized by comprising the following steps:
1, adding cobalt metal salt, non-cobalt metal salt, organic ligand and catalyst carrier into a reaction solvent together;
the mixture ratio of the raw materials is as follows:
cobalt metal salt 10 parts by weight
1-50 parts by weight of non-cobalt metal salt
10-1000 parts by weight of organic ligand
100 to 100000 parts by weight of a catalyst carrier
Separating the loaded catalyst carrier after the reaction is finished;
3, raising the temperature of the separated catalyst carrier in the step 2) to 300-500 ℃ in the air at the temperature rise rate of 1-2 ℃ per minute, and preserving the temperature for 30 minutes to 4 hours;
placing the catalyst carrier subjected to heating treatment in wastewater to be treated, and adding persulfate into the wastewater, wherein the persulfate adding concentration is as follows: 0.05 g/L-5 g/L;
the mixture ratio is as follows:
catalyst carrier 1 part by weight
0.01 to 2 parts by weight of persulfate
And 5, allowing the wastewater to flow through a catalyst carrier to finish the treatment of the wastewater.
3. The method for treating wastewater by using modified cobalt oxide to catalyze persulfate to generate singlet oxygen according to claim 1 or 2, which comprises the following steps:
the cobalt metal salt is selected from: cobalt nitrate, cobalt nitrite, sodium cobalt nitrite, cobalt nitrate hexahydrate, cobalt sulfate, cobalt sulfite, cobalt sulfate heptahydrate, cobalt chloride;
the non-cobalt metal salt is selected from: metal nitrates, sulfates or chlorides which can decompose metal oxides at high temperatures.
4. The method for treating wastewater by using modified cobalt oxide to catalyze persulfate to generate singlet oxygen according to claim 3, wherein the method comprises the following steps:
the metal nitrate that can decompose to a metal oxide at high temperature is selected from: one or more of zinc nitrate, copper nitrate, ferric nitrate, nickel nitrate, manganese nitrate, cadmium nitrate and chromium nitrate;
the metal sulfate that decomposes at high temperature to form metal oxides is selected from: one or more of zinc sulfate, copper sulfate, ferric sulfate, nickel sulfate, manganese sulfate, cadmium sulfate and chromium sulfate;
the metal chloride salt which decomposes at elevated temperature to form a metal oxide is selected from: zinc chloride, copper chloride, ferric chloride, nickel chloride, manganese chloride, cadmium chloride and/or chromium chloride.
5. The method for treating wastewater by using modified cobalt oxide to catalyze persulfate to generate singlet oxygen according to claim 1 or 2, which comprises the following steps:
in the heating process of the step 3), after the solid sample is subjected to heat preservation and calcination in the air, a new product is recovered, cleaned and dried.
6. The method for treating wastewater by using modified cobalt oxide to catalyze persulfate to generate singlet oxygen according to claim 1 or 2, which comprises the following steps: the persulfate is peroxymonosulfate.
7. The method for treating wastewater by using modified cobalt oxide to catalyze persulfate to generate singlet oxygen according to claim 6, wherein the method comprises the following steps: the peroxymonosulfate is selected from the group consisting of: potassium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxymonosulfate, and sodium peroxymonosulfate.
8. The method for treating wastewater by using modified cobalt oxide to catalyze persulfate to generate singlet oxygen according to claim 2, wherein the method comprises the following steps: the catalyst carrier is active carbon particles, aluminum oxide particles, a steel wire mesh or plastic fillers.
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| CN113101940A (en) * | 2021-04-25 | 2021-07-13 | 山西中科国蕴环保科技有限公司 | Catalyst for activating persulfate and method for treating sewage by using catalyst |
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