CN111790399A - Catalyst for treating wastewater by cooperating with low-temperature plasma technology, preparation and application thereof, and method for treating phenol wastewater - Google Patents
Catalyst for treating wastewater by cooperating with low-temperature plasma technology, preparation and application thereof, and method for treating phenol wastewater Download PDFInfo
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- CN111790399A CN111790399A CN202010793738.3A CN202010793738A CN111790399A CN 111790399 A CN111790399 A CN 111790399A CN 202010793738 A CN202010793738 A CN 202010793738A CN 111790399 A CN111790399 A CN 111790399A
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C02F2101/345—Phenols
Abstract
The invention provides a catalyst for treating wastewater by cooperating with a low-temperature plasma technology, preparation and application thereof, and a method for treating phenol wastewater, and belongs to the technical field of wastewater treatment catalysts. In the catalyst provided by the invention, Mn in the active component can efficiently utilize high-energy particles and activated O3(ii) a Ce can effectively transfer active oxygen; m can effectively utilize ultraviolet light to extra energy such as high energy electron, ozone and ultraviolet light that can make full use of low temperature plasma technology produced can effectively match plasma technology, solves the not enough shortcoming of energy utilization that individual plasma technology exists. Under the same reaction conditions, the method of the inventionThe catalyst and the low-temperature plasma technology are matched with each other, so that the degradation efficiency of phenol can be effectively improved, and in addition, the catalyst and the plasma technology can effectively treat high-concentration phenol wastewater (the concentration is more than 200 mg/L).
Description
Technical Field
The invention relates to the technical field of wastewater treatment catalysts, in particular to a catalyst for treating wastewater by cooperating with a low-temperature plasma technology, preparation and application thereof, and a method for treating phenol wastewater.
Background
Phenol is an important chemical raw material and a production intermediate, is widely applied to the industries of petrochemical industry, leather, plastics, spices and the like, and can generate a large amount of phenol-containing wastewater in the production and application processes. The phenol wastewater can not only harm human health, but also destroy ecological environment. At present, the biological method is the most widely used wastewater treatment method in industry, but phenol has biological toxicity, and the biological method is difficult to effectively treat the wastewater.
The low-temperature plasma technology is a novel advanced oxidation technology, is widely applied to the field of wastewater treatment, and can generate ultraviolet light, OH and O through discharge3And a large amount of strong oxidizing substances, thereby realizing the harmless treatment of the organic pollutants. Research shows that the degradation mechanism of dielectric barrier discharge on pollutants mainly has the effects of high-energy electrons, ozone oxidation and ultraviolet light. Although the low temperature plasma technology alone has a certain degradation effect on the pollutants, it has a great limitation and defect, mainly represented by the generation of high energy particles, ultraviolet light and O3And the like cannot be fully utilized, thereby causing energy waste.
Utilizing the adsorption capacity of the catalyst to pollutants, O3The decomposition effect and the photocatalysis effect are combined, and the defect of insufficient energy utilization existing in a single plasma technology can be solved by combining a catalyst and the plasma technology. However, despite a series of research efforts on catalysts, the existing catalysts have difficulty in effectively utilizing high-energy particles, ultraviolet light and O3And it is difficult to match the plasma effectively.
Disclosure of Invention
The invention aims to provide a catalyst for treating wastewater by cooperating with a low-temperature plasma technology, and preparation and application thereof, and a method for treating phenol wastewater.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a catalyst for treating wastewater by cooperating with low-temperature plasma technology, which comprises a carrier and a catalyst supportAn active component carried on the carrier, the carrier being a carbon material, the active component being a composite metal oxide comprising MnO2、CeO2And MO, wherein M is at least one of Fe, Co, Ni or Zn.
Preferably, the carbon material is activated carbon, carbon nanotubes or N-doped carbon nanotubes.
Preferably, in the catalyst, the mass percentage of the composite metal oxide is 1-40%, and the balance is a carrier.
Preferably, in the catalyst, the MnO is2、CeO2The mass ratio of the total mass of the MnO to the MO is 1: 10-10: 1, and the MnO is2And CeO2The mass ratio of (A) to (B) is 1: 10-10: 1.
The invention provides a preparation method of a catalyst for treating wastewater by cooperating with a low-temperature plasma technology, which comprises the following steps:
mixing an aqueous solution of metal oxide precursor salt, a complexing agent, a carbon material and a precipitator, and carrying out precipitation reaction to obtain a precursor;
roasting the precursor to obtain a catalyst for treating wastewater by cooperating with a low-temperature plasma technology;
the metal oxide precursor salt is manganese salt, cerium salt and M salt, wherein M is at least one of Fe, Co, Ni or Zn.
Preferably, the complexing agent is one or more of citric acid, ethylenediamine, acetylacetone and disodium ethylene diamine tetraacetate; the molar ratio of the complexing agent to the metal oxide precursor salt is (1.2-5): 1.
Preferably, the precipitant is at least one of sodium hydroxide, urea, ammonium chloride, ammonia water, ammonium bicarbonate, ammonium carbonate, ammonium nitrate and ammonium sulfate; the molar ratio of the precipitant to the metal ions in the metal oxide precursor salt is (1.2-3): 1.
preferably, the roasting temperature is 200-700 ℃, and the roasting time is 2-12 h.
The invention provides application of the catalyst in the technical scheme or the catalyst prepared by the preparation method in the technical scheme in the treatment of phenol wastewater by cooperating with a low-temperature plasma technology.
The invention provides a method for treating phenol wastewater by cooperating with low-temperature plasma, which comprises the following steps:
pretreating the catalyst for wastewater treatment by using hydrogen in cooperation with a low-temperature plasma technology to obtain a pretreated catalyst;
carrying out phenol wastewater treatment in a coaxial dielectric barrier discharge low-temperature plasma reactor by using the pretreated catalyst;
the catalyst for treating wastewater by cooperating with the low-temperature plasma technology is the catalyst in the technical scheme or the catalyst prepared by the preparation method in the technical scheme.
The invention provides a catalyst for treating wastewater by cooperating with a low-temperature plasma technology, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is a carbon material, the active component is a composite metal oxide, and the composite metal oxide comprises MnO2、CeO2And MO, wherein M is at least one of Fe, Co, Ni or Zn.
In the catalyst, Mn has multiple valence states, so that the utilization of high-energy particles and the activation of ozone can be realized by utilizing the conversion of different valence states; CeO (CeO)2The oxygen transfer performance is good, so that active oxygen can be effectively transferred; m is a semiconductor which promotes the transfer and conversion of photons and electrons, and M is effective in the use of ultraviolet light2、CeO2And MO, thereby being capable of fully utilizing extra energy such as high-energy electrons, ozone, ultraviolet light and the like generated by the low-temperature plasma technology, being capable of effectively matching the plasma technology and solving the defect of insufficient energy utilization existing in the single plasma technology.
Under the same reaction condition, the catalyst provided by the invention is matched with a low-temperature plasma technology to effectively improve the phenol degradation efficiency (more than 90%), and in addition, the catalyst provided by the invention is matched with the plasma technology to effectively treat high-concentration phenol wastewater (the concentration is more than 200mg/L), while the single low-temperature plasma technology can only treat low-concentration wastewater.
Detailed Description
The invention provides a catalyst for treating wastewater by cooperating with a low-temperature plasma technology, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is a carbon material, the active component is a composite metal oxide, and the composite metal oxide comprises MnO2、CeO2And MO, wherein M is at least one of Fe, Co, Ni or Zn.
In the present invention, the required raw materials are all commercially available products well known to those skilled in the art, unless otherwise specified.
The catalyst for treating wastewater by cooperating with the low-temperature plasma technology provided by the invention comprises a carrier, wherein the carrier is a carbon material, and the carbon material is preferably activated carbon, carbon nano tubes or N-doped carbon nano tubes. The specification of the carbon material is not particularly limited in the present invention, and any commercially available material known in the art may be used.
The catalyst for treating wastewater by cooperating with the low-temperature plasma technology comprises an active component loaded on the carrier. In the present invention, the active component is a composite metal oxide including MnO2、CeO2And MO, wherein M is at least one of Fe, Co, Ni or Zn.
In the catalyst, the mass percentage of the composite metal oxide is preferably 1 to 40%, more preferably 5 to 30%, and even more preferably 10 to 20%, with the balance being a carrier. In the present invention, the MnO in the catalyst2、CeO2The mass ratio of the total mass of (A) to MO is preferably 1: 10-10: 1, preferably 1: 8-8: 1, and more preferably 1: 5-5: 1; the MnO2And CeO2The mass ratio of (a) to (b) is preferably 1:10 to 10:1, preferably 1:8 to 8:1, and more preferably 1:5 to 5: 1.
In the catalyst, Mn in the active component can efficiently utilize high-energy particles and activate O3(ii) a Ce can effectively transfer active oxygen; m can effectively utilize ultraviolet light, can effectively match with a plasma technology,the defect of insufficient energy utilization existing in a single plasma technology is overcome.
The invention provides a preparation method of a catalyst for treating wastewater by cooperating with a low-temperature plasma technology, which comprises the following steps:
mixing an aqueous solution of metal oxide precursor salt, a complexing agent, a carbon material and a precipitator, and carrying out precipitation reaction to obtain a precursor;
roasting the precursor to obtain a catalyst for treating wastewater by cooperating with a low-temperature plasma technology;
the metal oxide precursor salt is manganese salt, cerium salt and M salt, wherein M is at least one of Fe, Co, Ni or Zn.
The method comprises the steps of mixing an aqueous solution of metal oxide precursor salt, a complexing agent, a carbon material and a precipitator, and carrying out precipitation reaction to obtain a precursor. In the invention, the metal oxide precursor salt is manganese salt, cerium salt and M salt, and M is at least one of Fe, Co, Ni or Zn. When M is a plurality of metals, the proportion of different metals is not particularly limited and can be any. The invention has no special limitation on the specific types of the metal oxide precursor salts, and soluble metal salts well known to those skilled in the art can be adopted; in an embodiment of the present invention, the metal oxide precursor salt is specifically manganese nitrate tetrahydrate, cerium nitrate hexahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, ferrous nitrate hexahydrate, or copper nitrate hexahydrate. The preparation process of the aqueous solution of the metal oxide precursor salt is not particularly limited, and different types of metal oxide precursor salts can be directly dissolved in water.
In the present invention, the molar ratio of the metal oxide precursor salt to the carbon material is preferably (1 to 54): 800, more preferably (10 to 50): 800, more preferably (20 to 35): 800. in the present invention, the concentration of total metal ions in the aqueous solution of the metal oxide precursor salt is preferably 14 to 571.4mg/mL, more preferably 50 to 400mg/mL, and even more preferably 100 to 300 mg/mL.
In the invention, the complexing agent is preferably one or more of citric acid, ethylenediamine, acetylacetone and ethylene diamine tetraacetic acid; when the complexing agents are several of the above types, the proportion of the complexing agents of different types is not particularly limited, and the complexing agents can be mixed at any proportion. In the present invention, the molar ratio of the complexing agent to the metal oxide precursor salt is preferably (1.2 to 5):1, more preferably (1.5 to 4.0):1, and still more preferably (2.0 to 3.0): 1.
In the present invention, the precipitant is preferably at least one of sodium hydroxide, urea, ammonium chloride, aqueous ammonia, ammonium bicarbonate, ammonium carbonate, ammonium nitrate, and ammonium sulfate; when the precipitating agents are several of the above types, the proportion of the precipitating agents of different types is not specially limited, and the precipitating agents can be mixed at any proportion. In the present invention, the molar ratio of the precipitant to the metal ion in the metal oxide precursor salt is preferably (1.2 to 3): 1, more preferably (1.5 to 2.5): 1, more preferably 2.0: 1.
in the invention, the process of mixing the aqueous solution of the metal oxide precursor salt, the complexing agent, the carbon material and the precipitant is preferably to add the complexing agent into the aqueous solution of the metal oxide precursor salt, stir for 1h, add the carbon material into the obtained mixed solution, stir for 2-12 h, and add the precipitant into the obtained mixture. The stirring conditions are not particularly limited in the present invention, and the materials can be uniformly mixed according to the procedures well known in the art. The invention ensures that the carbon material and other materials are fully and uniformly dispersed by stirring.
In the invention, the precipitation reaction is preferably carried out under ultrasonic conditions, the temperature of the precipitation reaction is preferably room temperature, i.e. no additional heating or cooling is carried out, and the time of the precipitation reaction is preferably 2-12 h, more preferably 5-10 h, and further preferably 6-8 h. The ultrasonic conditions are not particularly limited in the present invention, and the precipitation reaction can be sufficiently performed according to a process well known in the art. The invention promotes the full reaction of materials in the precipitation reaction process through ultrasonic conditions. In the precipitation reaction process, metal ions in the metal oxide precursor salt generate metal hydroxide under the action of a complexing agent and a precipitator.
After the precipitation reaction is completed, the reaction material obtained is preferably filtered, and the solid obtained by filtering is washed and dried to obtain the precursor. The filtration, washing and drying processes are not particularly limited in the present invention and may be performed according to processes well known in the art.
After the precursor is obtained, the precursor is roasted to obtain the catalyst for treating the wastewater by cooperating with the low-temperature plasma technology.
In the present invention, the calcination is preferably performed under an inert atmosphere, which is not particularly limited in the present invention, and may be an inert atmosphere known in the art, specifically nitrogen; the roasting temperature is preferably 200-700 ℃, and more preferably 300-600 ℃; the time is preferably 2 to 12 hours, more preferably 5 to 10 hours, and further preferably 6 to 8 hours.
In the roasting process, the metal hydroxide is converted into a composite metal oxide which is used as an active component of the catalyst and is loaded on a carbon material carrier.
The invention provides application of the catalyst in the technical scheme or the catalyst prepared by the preparation method in the technical scheme in the treatment of phenol wastewater by cooperating with a low-temperature plasma technology. The method of the present invention is not particularly limited, and the method may be applied according to a procedure well known in the art.
The invention provides a method for treating phenol wastewater by cooperating with low-temperature plasma, which comprises the following steps:
pretreating the catalyst for wastewater treatment by using hydrogen in cooperation with a low-temperature plasma technology to obtain a pretreated catalyst;
carrying out phenol wastewater treatment in a coaxial dielectric barrier discharge low-temperature plasma reactor by using the pretreated catalyst;
the catalyst for treating wastewater by cooperating with the low-temperature plasma technology is the catalyst in the technical scheme or the catalyst prepared by the preparation method in the technical scheme.
The invention adopts hydrogen pair to cooperate with low-temperature plasmaAnd (3) pretreating the catalyst for wastewater treatment by using the daughter technology to obtain a pretreated catalyst. In the invention, the temperature of the pretreatment is preferably 50-200 ℃, more preferably 80-160 ℃, further preferably 100-120 ℃, and the reduction time is preferably 1-6 hours, more preferably 2-5 hours, further preferably 3-4 hours. The invention reduces the catalyst through hydrogen pretreatment, increases the amount of the low-valence oxide in the catalyst, and activates and transfers active oxygen (high-energy particles and O)3) Thereby improving the catalytic effect of the catalyst.
After the pretreated catalyst is obtained, the invention utilizes the pretreated catalyst to carry out phenol wastewater treatment in a coaxial dielectric barrier discharge low-temperature plasma reactor. In the invention, the concentration of the phenol pollutant in the phenol wastewater is preferably 100-1000 mg/L, more preferably 200-800 mg/L, and even more preferably 400-600 mg/L, the reaction temperature for treating the phenol wastewater is preferably normal temperature, and the reaction pressure is preferably normal pressure. In the examples of the present invention, the treatment amount of phenol wastewater was 100mL (concentration: 500mg/L), the amount of the catalyst was 10g, and the air flow rate was 120 mL/min. The coaxial dielectric barrier discharge low-temperature plasma reactor is not particularly limited, and equipment well known in the field can be selected.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dissolving 2.31g (0.0092mol) of manganese nitrate tetrahydrate, 1.51g (0.0035mol) of cerium nitrate hexahydrate and 3.11g (0.011mol) of cobalt nitrate hexahydrate in a conical flask filled with 100mL of deionized water, stirring and dissolving to obtain an aqueous solution of a metal oxide precursor salt, adding 5.93mL (0.09mol) of ethylenediamine, continuing stirring for 1h, adding 10g (0.833mol) of activated carbon carrier (AC) while stirring, continuing stirring for 120 min, and then adding 1.2g of sodium hydroxide (0).03mol) and 1.2g of urea (0.02mol), carrying out ultrasonic treatment for 120 minutes, then carrying out suction filtration on the obtained product, washing the product with deionized water for three times, drying the obtained solid powder at 100 ℃ for 8 hours, and then roasting the dried solid powder at 400 ℃ for 4 hours in a nitrogen atmosphere to obtain a catalyst, which is recorded as MnO2-CeO2-CoO/AC, wherein the mass percentage of each metal oxide is respectively 8% MnO2、6％CeO2、8％CoO。
Example 2
This example differs from example 1 only in that: the support was Carbon Nanotubes (CN), the rest of the conditions were the same as in example 1, and the catalyst thus prepared was denoted MnO2-CeO2-CoO/CN, wherein the mass percent of each metal oxide is respectively 8% MnO2、6％CeO2、8％CoO。
Example 3
This example differs from example 1 only in that: the support is nitrogen modified carbon nanotube (N-CN), the rest conditions are the same as example 1, and the prepared catalyst is marked as MnO2-CeO2-CoO/N-CN, wherein the mass percent of each metal oxide is respectively 8% MnO2、6％CeO2、8％CoO。
Example 4
Catalyst preparation example 3 was followed with the exception that 3.11g of cobalt nitrate hexahydrate was replaced by 3.11g of nickel nitrate hexahydrate in example 3, and the conditions were otherwise the same as in example 3, and the catalyst obtained was characterized as MnO2-CeO2-NiO/N-CN, wherein the mass percent of each metal oxide is respectively 8% MnO2、6％CeO2、8％NiO。
Example 5
Catalyst preparation example 3 was followed with the exception that 3.11g of cobalt nitrate hexahydrate in example 3 was replaced with 3.27g of zinc nitrate hexahydrate (297.49), and the conditions were otherwise the same as in example 3, and the catalyst prepared was characterized as MnO2-CeO2-ZnO/N-CN, wherein the mass percent of each metal oxide is respectively 8% MnO2、6％CeO2、8％ZnO。
Example 6
Preparation of the catalystThe procedure is as in example 3, except that in example 3, 3.11g of cobalt nitrate hexahydrate are replaced by 3.17g of ferrous nitrate hexahydrate (287.859), the conditions are as in example 3, and the catalyst obtained is denoted MnO2-6％CeO28 percent of FeO/N-CN, wherein the mass percent of each metal oxide is respectively 8 percent of MnO2、6％CeO2、8％FeO。
Example 7
Catalyst preparation referring to example 3, except that 3.11g of cobalt nitrate hexahydrate was replaced with 3.25g of copper nitrate hexahydrate (295.56) in example 3, the conditions were the same as in example 3, and the catalyst obtained was recorded as 8% MnO2-6％CeO28 percent of CuO/N-CN, wherein the mass percent of each metal oxide is respectively 8 percent of MnO2、6％CeO2、8％CuO。
Application example 1
The catalyst prepared in the embodiment 1-3 is used for treating phenol wastewater, and the specific steps are as follows: the catalysts prepared in examples 1 to 3 were pre-reduced with hydrogen for 1 hour at 100 ℃ to obtain pre-treated catalysts, and then the phenol wastewater was treated in a coaxial dielectric barrier discharge low-temperature plasma reactor using the pre-treated catalysts, wherein the phenol wastewater was 100mL (concentration 500mg/L), the catalyst amount was 10g, the air flow was 120mL/min, the reaction temperature was room temperature, the reaction pressure was normal pressure, and the specific evaluation results are shown in table 1.
TABLE 1 performances of harmlessly treating phenol wastewater by using different supported catalysts prepared in examples 1-3 in cooperation with low-temperature plasma
As can be seen from Table 1, the catalyst of the present invention can be well combined with a synergistic low temperature plasma technology to achieve a high TOC degradation rate of phenol wastewater.
Application example 2
The catalysts prepared in examples 4 to 7 were subjected to wastewater treatment performance tests in accordance with the method of application example 1, and the results are shown in Table 2.
TABLE 2 performances of harmless phenol wastewater treatment by using different oxide component catalysts in cooperation with low-temperature plasma
As can be seen from Table 2, the catalysts prepared according to the present invention without using the metal oxide component can achieve effective treatment of phenol wastewater.
Application example 3
The catalyst prepared in example 5 was subjected to a performance test in accordance with the method of application example 1 except that the phenol concentration was 100mg/L, and the results are shown in Table 3.
Application example 4
The catalyst prepared in example 5 was subjected to a performance test in accordance with the method of application example 1 except that the phenol concentration was 300mg/L, and the results are shown in Table 3.
Application example 5
The catalyst prepared in example 5 was subjected to a performance test in accordance with the method of application example 1 except that the phenol concentration was 800mg/L, and the results are shown in Table 3.
TABLE 3 phenol concentration vs. MnO2-CeO2Effect of the catalytic Performance of the-ZnO/N-CN catalysts
As can be seen from Table 3, the catalyst prepared by the invention can also realize high TOC degradation rate under different phenol concentrations, and the catalyst prepared by the invention can be effectively matched with a low-temperature plasma technology to improve the treatment effect of wastewater on the basis of realizing full utilization of energy.
Comparative example 1
The comparative example does not prepare a catalyst, i.e., does not add any catalyst when used for harmlessly treating phenol wastewater in cooperation with low-temperature plasma.
Comparative example 2
This comparative example differs from example 5 in that only 6.35g of manganese nitrate tetrahydrate was dissolved in a conical flask containing 100mL of deionized water, the procedure was the same as example 5, and the catalyst obtained was characterized as MnO2N-CN, wherein MnO2The mass percentage of (B) is 22%.
Comparative example 3
This comparative example differs from example 5 in that only 5.55g of cerium nitrate hexahydrate was dissolved in a conical flask containing 100mL of deionized water, the procedure was the same as in example 5, and the catalyst obtained was designated CeO2N-CN, of which CeO2The mass percentage of (B) is 22%.
Comparative example 4
This comparative example differs from example 5 in that only 8.04g of zinc nitrate hexahydrate was dissolved in a conical flask containing 100mL of deionized water, the procedure was the same as example 5, and the catalyst obtained was designated as ZnO/N-CN, where the ZnO content was 22% by mass.
According to the scheme of application example 1, the catalysts prepared in comparative examples 1-4 are used for harmlessly treating phenol wastewater in cooperation with low-temperature plasma, and the results are shown in table 4.
TABLE 4 Performance of catalysts prepared in comparative examples 1 to 4 for harmlessly treating phenol wastewater in cooperation with low-temperature plasma
As can be seen from table 4, when no catalyst was added, the degradation rate of phenol wastewater by the single synergistic low-temperature plasma harmless treatment was extremely low, and effective treatment of wastewater could not be achieved. The degradation rate of the prepared single metal oxide catalyst to TOC is obviously lower than that of the composite metal oxide prepared in the embodiments 1-7 of the invention, and the prepared catalyst can effectively cooperate with a low-temperature plasma technology to treat phenol wastewater, so that the treatment effect is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The catalyst for treating wastewater by cooperating with the low-temperature plasma technology is characterized by comprising a carrier and an active component loaded on the carrier, wherein the carrier is a carbon material, the active component is a composite metal oxide, and the composite metal oxide comprises MnO2、CeO2And MO, wherein M is at least one of Fe, Co, Ni or Zn.
2. The catalyst of claim 1, wherein the carbon material is activated carbon, carbon nanotubes, or N-doped carbon nanotubes.
3. The catalyst according to claim 1, wherein the mass percentage of the composite metal oxide in the catalyst is 1 to 40%, and the balance is a carrier.
4. The catalyst of claim 1, wherein said MnO is present in said catalyst2、CeO2The mass ratio of the total mass of the MnO to the MO is 1: 10-10: 1, and the MnO is2And CeO2The mass ratio of (A) to (B) is 1: 10-10: 1.
5. The preparation method of the catalyst for treating wastewater by cooperating with the low-temperature plasma technology as claimed in any one of claims 1 to 4, comprising the following steps:
mixing an aqueous solution of metal oxide precursor salt, a complexing agent, a carbon material and a precipitator, and carrying out precipitation reaction to obtain a precursor;
roasting the precursor to obtain a catalyst for treating wastewater by cooperating with a low-temperature plasma technology;
the metal oxide precursor salt is manganese salt, cerium salt and M salt, wherein M is at least one of Fe, Co, Ni or Zn.
6. The preparation method of claim 5, wherein the complexing agent is one or more of citric acid, ethylenediamine, acetylacetone and disodium ethylenediamine tetraacetate; the molar ratio of the complexing agent to the metal oxide precursor salt is (1.2-5): 1.
7. The production method according to claim 5, wherein the precipitant is at least one of sodium hydroxide, urea, ammonium chloride, aqueous ammonia, ammonium bicarbonate, ammonium carbonate, ammonium nitrate, and ammonium sulfate; the molar ratio of the precipitant to the metal ions in the metal oxide precursor salt is (1.2-3): 1.
8. the preparation method according to claim 5, wherein the roasting temperature is 200-700 ℃ and the roasting time is 2-12 h.
9. The catalyst of any one of claims 1 to 4 or the catalyst prepared by the preparation method of any one of claims 5 to 8 is applied to the treatment of phenol wastewater by cooperating with a low-temperature plasma technology.
10. A method for treating phenol wastewater by cooperating with low-temperature plasma is characterized by comprising the following steps:
pretreating the catalyst for wastewater treatment by using hydrogen in cooperation with a low-temperature plasma technology to obtain a pretreated catalyst;
carrying out phenol wastewater treatment in a coaxial dielectric barrier discharge low-temperature plasma reactor by using the pretreated catalyst;
the catalyst for treating wastewater by cooperating with the low-temperature plasma technology is the catalyst as claimed in any one of claims 1 to 4 or the catalyst prepared by the preparation method as claimed in any one of claims 5 to 8.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279343A (en) * | 2020-10-21 | 2021-01-29 | 西北农林科技大学 | Plasma device of biomass carbon material and sewage-nitrogen fertilizer irrigation recycling method thereof |
| CN112551556A (en) * | 2020-12-22 | 2021-03-26 | 山西永东化工股份有限公司 | Method for preparing sodium carbonate by plasma oxidation deposition of coal chemical industry phenol wastewater |
| CN112892548A (en) * | 2021-01-25 | 2021-06-04 | 天津大学 | Preparation method of manganese-based catalyst for sewage treatment and manganese-based catalyst |
| CN113457658A (en) * | 2021-08-06 | 2021-10-01 | 南昌航空大学 | Surface modification method of biomass carbon material |
| CN113751013A (en) * | 2021-10-18 | 2021-12-07 | 重庆大学 | Low-temperature plasma heterogeneous catalyst and preparation method and application thereof |
| RU2797665C1 (en) * | 2022-12-19 | 2023-06-07 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" | Method for purifying water from phenol |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1809413A (en) * | 2003-06-17 | 2006-07-26 | 日铁矿业株式会社 | Gas processing method and gas processing apparatus utilizing oxidation catalyst and low-temperature plasma |
| US20090223806A1 (en) * | 2005-11-07 | 2009-09-10 | Frederic Thevenet | Combined treatment of gaseous effluents by cold plasma and photocatalysts |
| CN101780412A (en) * | 2010-02-12 | 2010-07-21 | 新奥科技发展有限公司 | Catalyst for treating industrial waste water under normal temperature and normal pressure and preparation method thereof |
| CN104307534A (en) * | 2014-10-31 | 2015-01-28 | 天津市联合环保工程设计有限公司 | Preparation method for MnO2-CeO2-CoO/AC ternary supported catalyst for treatment of phenolic wastewater |
| CN105126613A (en) * | 2015-10-08 | 2015-12-09 | 张哲夫 | Low-temperature plasma catalytic oxidation gas deodorization method |
| CN105289651A (en) * | 2015-10-21 | 2016-02-03 | 中国科学院过程工程研究所 | Bimetallic catalyst for catalytic oxidation of VOCs and preparation method and application of bimetallic catalyst |
| CN110339707A (en) * | 2019-06-21 | 2019-10-18 | 厦门大学 | A kind of method of low temperature plasma catalysis oxidation VOCs |
-
2020
- 2020-08-10 CN CN202010793738.3A patent/CN111790399B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1809413A (en) * | 2003-06-17 | 2006-07-26 | 日铁矿业株式会社 | Gas processing method and gas processing apparatus utilizing oxidation catalyst and low-temperature plasma |
| US20090223806A1 (en) * | 2005-11-07 | 2009-09-10 | Frederic Thevenet | Combined treatment of gaseous effluents by cold plasma and photocatalysts |
| CN101780412A (en) * | 2010-02-12 | 2010-07-21 | 新奥科技发展有限公司 | Catalyst for treating industrial waste water under normal temperature and normal pressure and preparation method thereof |
| CN104307534A (en) * | 2014-10-31 | 2015-01-28 | 天津市联合环保工程设计有限公司 | Preparation method for MnO2-CeO2-CoO/AC ternary supported catalyst for treatment of phenolic wastewater |
| CN105126613A (en) * | 2015-10-08 | 2015-12-09 | 张哲夫 | Low-temperature plasma catalytic oxidation gas deodorization method |
| CN105289651A (en) * | 2015-10-21 | 2016-02-03 | 中国科学院过程工程研究所 | Bimetallic catalyst for catalytic oxidation of VOCs and preparation method and application of bimetallic catalyst |
| CN110339707A (en) * | 2019-06-21 | 2019-10-18 | 厦门大学 | A kind of method of low temperature plasma catalysis oxidation VOCs |
Non-Patent Citations (2)
| Title |
|---|
| PATHPIREDDY MANOJ KUMAR REDDY等: "Mineralization of Phenol in Water by CatalyticNon-Thermal Plasma Reactor–An Eco-FriendlyApproach for Wastewater Treatment", 《PLASMA PROCESS. POLYM.》 * |
| 邹仁鋘: "《基本有机化工反应工程》", 30 September 1981, 化学工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279343A (en) * | 2020-10-21 | 2021-01-29 | 西北农林科技大学 | Plasma device of biomass carbon material and sewage-nitrogen fertilizer irrigation recycling method thereof |
| CN112551556A (en) * | 2020-12-22 | 2021-03-26 | 山西永东化工股份有限公司 | Method for preparing sodium carbonate by plasma oxidation deposition of coal chemical industry phenol wastewater |
| CN112892548A (en) * | 2021-01-25 | 2021-06-04 | 天津大学 | Preparation method of manganese-based catalyst for sewage treatment and manganese-based catalyst |
| CN113457658A (en) * | 2021-08-06 | 2021-10-01 | 南昌航空大学 | Surface modification method of biomass carbon material |
| CN113751013A (en) * | 2021-10-18 | 2021-12-07 | 重庆大学 | Low-temperature plasma heterogeneous catalyst and preparation method and application thereof |
| RU2797665C1 (en) * | 2022-12-19 | 2023-06-07 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" | Method for purifying water from phenol |
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