CN114573087A - Method for degrading phenol wastewater by using copper pyrophosphate as catalyst - Google Patents

Method for degrading phenol wastewater by using copper pyrophosphate as catalyst Download PDF

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Publication number
CN114573087A
CN114573087A CN202210268064.4A CN202210268064A CN114573087A CN 114573087 A CN114573087 A CN 114573087A CN 202210268064 A CN202210268064 A CN 202210268064A CN 114573087 A CN114573087 A CN 114573087A
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Prior art keywords
phenol
catalyst
wastewater
copper pyrophosphate
phenol wastewater
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Chinese (zh)
Inventor
邓苗
丁明刚
邓建雄
刘朋
谢宇风
黎晓海
刘向彬
颜浩然
熊维威
郇彩娟
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Chengdu Univeristy of Technology
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Chengdu Univeristy of Technology
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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
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Removal Of Specific Substances (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a method for degrading phenol wastewater by taking copper pyrophosphate as a catalyst, which is applied to the treatment of phenol wastewater for the first time. Copper pyrophosphate catalyzes hydrogen peroxide to degrade phenol wastewater, belongs to a Fenton-like system, has the advantages of mild use condition, wide pH range, high phenol removal rate, low cost, small secondary pollution, easy recycling of a catalyst and the like, and has great application value in organic wastewater treatment. According to the invention, copper pyrophosphate is innovatively used as a Fenton-like catalyst and used for treating phenol wastewater, so that the phenol removal rate is high, and the method has innovativeness and high practical application value.

Description

Method for degrading phenol wastewater by using copper pyrophosphate as catalyst
Technology neighborhood
The invention belongs to the technical field of phenol wastewater treatment, and particularly relates to copper pyrophosphate (Cu)2P2O7) With hydrogen peroxide (H)2O2) A method for degrading phenol wastewater by using a Fenton-like system.
Background
Phenol is a common chemical raw material, is widely applied to the fields of food, pharmacy, fine chemical industry, petrochemical industry and preparation and synthesis of medicines, has wide sources, and mainly comprises petrifaction, hospital pharmacy, cigarettes, papermaking, dye and paint and the like. The phenolic compounds are various, such as phenol, cresol, chlorophenol, and the like, and the pollution is most prominent with phenol and cresol. Phenol has good stability and solubility in water, is toxic and is not easily biodegradable, and the international environmental protection organization sets a permissible limit of phenol emission to the environment of about a few micrograms per liter, because phenol is extremely toxic even at low concentrations in water and phenol is accumulated in the environment, which causes serious environmental and ecological problems. Therefore, it is necessary to find a simple and efficient phenol removal method.
The main methods for treating the phenol-containing wastewater at present comprise: physical and chemical methods (extraction, adsorption, membrane separation, etc.), biological methods (enzyme treatment, activated sludge, immobilized microorganisms, etc.), and advanced oxidation methods (electrochemical oxidation, Fenton and Fenton-like, ozone oxidation, photocatalysis, etc.). The advanced oxidation technology can degrade most organic pollutants indiscriminately, has the advantages of mild reaction conditions, simple equipment, high treatment efficiency and the like, is widely applied to the treatment process of high-concentration organic wastewater, particularly the Fenton-like technology is mature gradually in recent years, overcomes the defects of low effective utilization rate of hydrogen peroxide, large catalyst adding amount, generation of iron mud, severe secondary pollution and catalytic conditions caused by the fact that the conventional Fenton technology is low in hydrogen peroxide, and is favored in the treatment of phenol wastewater.
Most of the existing Fenton-like catalysts are metal simple substances and oxides thereof, and hardly soluble salt-like catalysts exist.The invention patent CN102951723A discloses a method for degrading phenol wastewater by mineral catalytic hydrogen peroxide, wherein the removal rate of phenol can reach more than 99%; the invention patent CN105776494B discloses a method for degrading phenol wastewater by using CuO/ZSM-5 to catalyze persulfate, wherein the removal rate of phenol can reach more than 99%; the invention patent CN109529841A discloses a ferrite (CuFe)2O4) The method for treating phenol wastewater by using the Fenton-like catalyst has the advantages that the removal rate of phenol can reach more than 90%; the invention patent CN110092505A discloses a method for degrading phenol wastewater by using attapulgite clay to catalyze hydrogen peroxide, which mainly plays a role in Fe in the attapulgite2+And Fe3+Similar to the traditional Fenton technology, the removal rate of phenol can reach more than 95%.
Cu2P2O7Is a slightly soluble salt, is commonly used as an analytical reagent, an electroplating additive, a phosphate pigment preparation and is used for providing Cu in cyanide-free electroplating2+The anti-carburizing coating is used as a catalyst and is only reported, particularly, the anti-carburizing coating is not used as a Fenton-like catalyst at home and abroad, is insoluble in water, is easy to recover, has a wide pH application range (3-10), and has strong innovation and application value when being used in a Fenton-like technology for degrading phenol wastewater.
Disclosure of Invention
The invention aims to provide a Cu-based alloy2P2O7Method for degrading phenol wastewater by using catalyst, Cu2P2O7Is an insoluble salt, belongs to a novel Fenton-like catalyst, and expands the Cu content2P2O7The application way of the method provides a new method for treating the phenol wastewater quickly, efficiently and at low cost.
The treatment method comprises the steps of adding a certain amount of copper pyrophosphate catalyst and hydrogen peroxide into the wastewater containing the phenols, adjusting the catalytic reaction temperature and the initial pH, and standing for a period of time for catalytic degradation.
The treatment target in the treatment method includes, but is not limited to, phenol-based wastewater such as phenol, cresol, and chlorophenol.
In the treatment method, the phenol concentration of the phenol wastewater is 50-500 mg/L.
The adding amount of the copper pyrophosphate in the treatment method is 1-5 g/L.
In the treatment method, the concentration of the hydrogen peroxide is 30%, and the adding amount is 2-10 ml/L.
The reaction temperature in the treatment method is 20-50 ℃.
The initial pH in the treatment method is 3-10.
The reaction time in the treatment method is 0.5-5 h.
And (3) testing and processing results:
after the reaction is finished, manganese dioxide (MnO) is added2) Stopping the reaction, filtering and collecting filtrate by using a 0.22 mu m microporous filter membrane, diluting the filtrate by 50 times, testing and calculating the phenol concentration by adopting a 4-aminoantipyrine direct photometry method, and converting the phenol removal rate.
In the existing report, Cu2P2O7The Fenton-like system formed by the phosphate pigment and hydrogen peroxide is used in the field of wastewater treatment, has no relevant report, belongs to a new application in the treatment of phenol wastewater, and has strong innovation.
Compared with the prior art, the method for degrading phenol has the advantages of mild reaction conditions, wide pH range of 3-10, controllable degradation rate, low cost, high efficiency and Cu2P2O7The catalyst is insoluble in water, is easy to recycle, causes little secondary pollution, has the highest phenol removal rate of 99.9 percent, has high environmental value and economic benefit, and is easy for industrial application.
Drawings
FIG. 1 is a process flow of copper pyrophosphate catalytic degradation of phenol wastewater.
Detailed description of the invention
The invention is further described below with reference to specific treatment methods, but the scope of the invention is not limited thereto.
Example one
The specific treatment method of the phenol wastewater comprises the following steps:
50mL of simulated phenol wastewater with a phenol concentration of 100mg/L was taken, and 0.15g of Cu was added2P2O7(3g/L), followed by the addition of 0.5mL of H2O2(10ml/L) and pH 7.5, standing in a constant temperature water bath at 30 deg.C for catalytic reaction, and adding manganese dioxide (MnO) after 4 hr2) Terminating the reaction, filtering by using a 0.22 mu m microporous filter membrane, collecting filtrate, diluting by 50 times, and then adopting a 4-aminoantipyrine direct photometry method to test and calculate the phenol concentration, and converting the phenol removal rate, wherein the phenol removal rate is shown in table 1.
Example two-example nineteen
The phenol wastewater treatment method is the same as the first embodiment, and Cu is changed2P2O7The dosage of the catalyst, the dosage of hydrogen peroxide, the initial pH and the reaction temperature are different, and are shown in table 1 specifically, other steps are the same as those in the first embodiment, and the phenol removal rate after the reaction is finished is shown in table 1.
TABLE 1
Figure BDA0003553174010000031
Figure BDA0003553174010000041

Claims (9)

1. A method for degrading phenol wastewater by taking copper pyrophosphate as a catalyst is characterized in that the treatment method comprises the steps of adding a certain amount of copper pyrophosphate catalyst and hydrogen peroxide into the phenol wastewater, adjusting the reaction temperature and the initial pH value, and standing for a period of time for catalytic degradation.
2. The method of claim 1, wherein the catalyst is homemade copper pyrophosphate.
3. The method according to claim 1, wherein the treatment object includes, but is not limited to, phenol-based wastewater such as phenol, cresol, chlorophenol, and the like.
4. The method according to claim 1, wherein the concentration of phenol in the phenol wastewater is 50-500 mg/L.
5. The method according to claim 1, wherein the amount of copper pyrophosphate added is 1 to 5 g/L.
6. The method according to claim 1, wherein the amount of hydrogen peroxide added is 2-10 ml/L.
7. The method according to claim 1, wherein the reaction temperature is 20 to 50 ℃.
8. The method of claim 1, wherein the initial pH is 3 to 10.
9. The method of claim 1, wherein the catalytic time is 0.5 to 5 hours.
CN202210268064.4A 2022-03-18 2022-03-18 Method for degrading phenol wastewater by using copper pyrophosphate as catalyst Pending CN114573087A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120110751A1 (en) * 2009-07-02 2012-05-10 University Of Leeds Catalysed Dye Systems
CN109529841A (en) * 2018-12-20 2019-03-29 南京工业大学 A kind of preparation method handling the heterogeneous effective catalyst of phenolic waste water Fenton-like
CN113680313A (en) * 2021-09-15 2021-11-23 成都理工大学 Preparation method of easily-regenerated methylene blue adsorbent
US20220041477A1 (en) * 2020-08-07 2022-02-10 Geomatrix, LLC INCREASED WASTEWATER FLOW WITH FENTON's REAGENT

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120110751A1 (en) * 2009-07-02 2012-05-10 University Of Leeds Catalysed Dye Systems
CN109529841A (en) * 2018-12-20 2019-03-29 南京工业大学 A kind of preparation method handling the heterogeneous effective catalyst of phenolic waste water Fenton-like
US20220041477A1 (en) * 2020-08-07 2022-02-10 Geomatrix, LLC INCREASED WASTEWATER FLOW WITH FENTON's REAGENT
CN113680313A (en) * 2021-09-15 2021-11-23 成都理工大学 Preparation method of easily-regenerated methylene blue adsorbent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. LI, ET AL.: "Recent advances in Cu-Fenton systems for the treatment of industrial wastewaters: Role of Cu complexes and Cu composites", 《JOURNAL OF HAZARDOUS MATERIALS》 *

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