CN111875129A - Combined treatment process for organophosphorus wastewater with high total phosphorus concentration - Google Patents

Combined treatment process for organophosphorus wastewater with high total phosphorus concentration Download PDF

Info

Publication number
CN111875129A
CN111875129A CN202010695124.1A CN202010695124A CN111875129A CN 111875129 A CN111875129 A CN 111875129A CN 202010695124 A CN202010695124 A CN 202010695124A CN 111875129 A CN111875129 A CN 111875129A
Authority
CN
China
Prior art keywords
wastewater
oxidation
tank
organophosphorus
phosphorus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202010695124.1A
Other languages
Chinese (zh)
Inventor
蔡兰花
王芳
李培则
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongyang Future Industrial Design Co ltd
Original Assignee
Dongyang Future Industrial Design Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongyang Future Industrial Design Co ltd filed Critical Dongyang Future Industrial Design Co ltd
Priority to CN202010695124.1A priority Critical patent/CN111875129A/en
Publication of CN111875129A publication Critical patent/CN111875129A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0254—Nitrogen containing compounds on mineral substrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • 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
    • 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
    • C02F2305/10—Photocatalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention relates to the field of environmental protection, in particular to a combined treatment process of organophosphorus wastewater with high total phosphorus concentration; the method comprises the following steps: pretreatment, a primary chemical phosphorus removal process, a flocculation phosphorus removal process, an oxidation phosphorus removal process and a secondary chemical phosphorus removal process; firstly, preliminarily converting organic phosphorus into inorganic phosphorus salt under the alkaline condition, then adding magnesium salt to perform precipitation reaction to remove part of phosphorus, and then degrading and removing the residual organic phosphorus pollutants by a Fenton-photocatalysis combined oxidation process; the invention adopts the technology of Fenton treatment and photocatalytic oxidation, can reduce the chroma of the wastewater by utilizing the Fenton treatment, can effectively improve the absorption efficiency of a catalyst to light in the subsequent photocatalytic technology, and fully utilizes the residual hydrogen peroxide in the Fenton oxidation process to generate a large amount of active free radicals such as superoxide anions or hydroxyl free radicals, thereby further improving the mineralization removal rate of the organic wastewater subjected to the photocatalytic treatment.

Description

Combined treatment process for organophosphorus wastewater with high total phosphorus concentration
Technical Field
The invention relates to the field of environmental protection, in particular to a combined treatment process of organophosphorus wastewater with high total phosphorus concentration.
Background
The organic phosphorus compounds produced globally have more than 1 ten thousand, and due to the expanded production and wide use of organic phosphorus chemical industry, a large amount of high-concentration toxic organic wastewater produced in the production process can cause serious pollution to water and ecological environment if the toxic organic wastewater is directly discharged.
CN202193674U relates to a treatment facility of waste water, especially relates to a treatment facility of waste water that contains organic phosphorus. Discloses an organophosphorus wastewater treatment device, which comprises a conditioning tank, wherein the conditioning tank is connected with a catalytic oxidation tank, the catalytic oxidation tank is connected with a neutralization aeration tank, the neutralization aeration tank is connected with a sedimentation tank, and the sedimentation tank is connected with a reaction tank. According to the technical scheme of the utility model, equipment structure is simple, can the organic phosphorus in the efficient detach waste water, reduces organic phosphorus waste water to animal and ecological harm.
CN110885158A discloses a method for removing organic phosphorus in tanning wastewater, which comprises the following steps: step one, precipitating the wastewater in a secondary precipitation tank and a high-density tank, then feeding the wastewater into a pre-oxidation tank, and adjusting acid; step two, sequentially feeding the wastewater in the pre-oxidation tank into a multi-stage oxidation tank for Fenton reaction; step three, conveying the wastewater after the Fenton reaction into a multi-stage flocculation tank through a lifting pump, and adding a flocculating agent polyaluminium oxide (PAC) and liquid caustic soda into the flocculation tank; the wastewater after the Fenton reaction is input to a pipeline between the flocculation tanks through a lift pump, a plurality of electromagnetic pulsers are coated on the pipeline, the pipeline in front of each electromagnetic pulser is a venturi tube, and the air inlet of each venturi tube is communicated with the ozone outlet of the ozone generator; and step four, the wastewater from the flocculation tank enters a sedimentation tank for sedimentation. The beneficial effects of the invention are as follows: the method has the advantages of short flow, high treatment efficiency, high total phosphorus removal rate of 90 percent, capability of reducing the total phosphorus content to 0.5mg/L and stable removal efficiency.
CN110526484A provides an organophosphorus pesticide industrial wastewater treatment process, which comprises the following steps: (1) filtering the industrial wastewater of the organophosphorus pesticide by an organic polymer membrane; (2) separating and concentrating the organic phosphorus pesticide industrial wastewater after impurity removal; (3) pumping the concentrated solution obtained in the step (2) into a reactor; (4) directly degrading organophosphorus pesticide; (5) carrying out primary oxidative degradation on organophosphorus pesticide; (6) and (4) carrying out secondary oxidation on the product obtained after the primary oxidation in the step (5). The invention can effectively solve the problems of organophosphorus pesticide wastewater pollution and ecological environment protection.
The methods generally adopted at home and abroad for treating the phosphorus in the wastewater by the invention and the prior art mainly comprise the traditional chemical method, biological method, chemical-assisted biological method, recently developed adsorption method, electrolytic method and the like; in the production of organic phosphorus corrosion inhibitors, a large amount of organic phosphorus compounds such as aminotrimethylene phosphonic Acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC), polyoxyethylene ether glycerol phosphate and the like are contained in the wastewater; the wastewater has the problems of poor biodegradability, complex components and high total phosphorus concentration, and the method cannot achieve good treatment effect.
Disclosure of Invention
In order to solve the problems, the invention provides a combined treatment process of organophosphorus wastewater with high total phosphorus concentration.
A combined treatment process for organophosphorus wastewater with high total phosphorus concentration comprises the following specific preparation scheme:
pretreating, namely filtering the organophosphorus wastewater by using a filter membrane to remove solid impurities, colloidal particles and suspended particles, then feeding the organic wastewater into an adjusting tank, and homogenizing for 5-10 min;
a first-stage chemical phosphorus removal process, namely pumping the homogenized organophosphorus wastewater into a phosphorus removal tank, wherein the phosphorus removal tank is a chemical phosphorus removal tank, firstly adding lime into the tank, adjusting the pH value to 10-13, then standing for 10-15h, and then adding magnesium chloride into the tank, wherein the adding amount of the lime is 800-3The addition amount of magnesium chloride is 200-3(ii) a Precipitating after completion, and overflowing supernatant;
the flocculating and dephosphorizing process comprises the step of adding a flocculating agent into the clear wastewater liquid overflowing in the previous step, wherein the adding amount of the flocculating agent is 300-3Precipitating after finishing, and overflowing supernatant;
an oxidation dephosphorization process, adjusting the pH value of the organic wastewater after the flocculation precipitation treatment to 2-5, adding 50-200g/m3Uniformly mixing the hydrogen peroxide, and further treating organic pollutants by Fenton oxidation to obtain primary oxidation wastewater; the primary oxidation wastewater enters a photoelectrocatalytic oxidation treatment tank to obtain secondary oxidation wastewater; the method is characterized in that the Fenton oxidation adopts a carbon nano tube Fenton catalyst;
the secondary chemical phosphorus removal process comprises the steps of enabling secondary oxidation wastewater to enter a secondary chemical phosphorus removal tank, firstly adding lime into the tank, and then adding a flocculating agent, wherein the adding amount of the lime is 300-800 g/m-3The addition amount of the flocculating agent is 200-300g/m3Then the wastewater flows into an inclined plate sedimentation tank, and the supernatant after sedimentation can be discharged.
The photoelectrocatalysis oxidation catalyst is arranged at the bottom of the reactor and in the center of the polar plate.
The catalyst adopted by the photoelectrocatalysis oxidation is alpha-alumina supported titanium dioxide or silicon dioxide supported manganese oxide or alpha-alumina supported cadmium sulfide.
The photoelectrocatalysis oxidation adopts mercury lamp irradiation to provide a light source.
The flocculant is polyaluminium chloride or polyacrylamide or polyferric sulfate.
The content of the hydrogen peroxide is 10 to 20 percent.
The preparation method of the carbon nanotube Fenton catalyst comprises the following steps:
the method comprises the following steps: adding 10-25 parts by mass of carbon nano tube into 300 parts by mass of 10-30% hydrochloric acid solution at 60-70 ℃, stirring and reacting for 5-10h, washing with water to neutrality, filtering, adding 400 parts by mass of 20-30% ammonia water and 1-4 parts by mass of zinc chloride, controlling the temperature to 10-20 ℃, reacting for 5-10h, filtering, drying to obtain the surface aminated carbon nano tube,
step two: dispersing the carbon nano-tube with aminated surface into 200 parts of sodium hydroxide solution with the mass percent content of 3% -7%, adding 5-10 parts of ferric citrate, 0.01-0.05 part of 1-carboxyethyl-3-methylimidazole nitrate and 5-10 parts of sodium tungstate, controlling the temperature to be 50-70 ℃, stirring for reaction for 2-5h, filtering after the reaction is finished, and then placing the mixture in a drying box with the temperature of 160-200 ℃ for reaction for 20-30h to obtain the carbon nano-tube Fenton catalyst.
The partial reaction equation is schematically shown as follows:
Figure DEST_PATH_IMAGE002
the invention relates to a combined treatment process of organic phosphorus wastewater with high total phosphorus concentration, which comprises the steps of firstly preliminarily converting organic phosphorus into inorganic phosphorus salt under an alkaline condition, then adding magnesium salt to perform a bird dung precipitation reaction to remove part of phosphorus, and then degrading and removing the rest organic phosphorus pollutants through a Fenton-photocatalysis combined oxidation process; according to the invention, the process of Fenton treatment and photocatalytic oxidation is adopted, the Fenton treatment can be utilized to reduce the chromaticity of the wastewater, the absorption efficiency of a catalyst on light in the subsequent photocatalytic process can be effectively improved, the residual hydrogen peroxide in the Fenton oxidation process is fully utilized to generate a large amount of active free radicals such as superoxide anions or hydroxyl free radicals, and the mineralization removal rate of the organic wastewater subjected to photocatalytic treatment is further improved;
the carbon nano tube Fenton catalyst has a microporous structure and strong adsorption capacity, and can adsorb organic phosphorus molecules into the catalyst to accelerate the degradation reaction; the invention solves the limitation of a single phosphorus removal process, and can effectively treat the wastewater with high total phosphorus concentration produced by the organophosphorus water treatment agent.
The carbon nano tube Fenton catalyst can prevent the problem of iron precipitation when the pH value is increased, and 1-carboxyethyl-3-methylimidazole nitrate is added into a reaction system to stabilize iron ions, so that a Fenton reagent can be used under the neutral or near-neutral condition.
Drawings
Fig. 1 is a fourier infrared spectrum of a sample of the carbon nanotube fenton catalyst prepared in example 2.
At 3328cm-1The absorption peak of the nitrogen hydrogen bond is extended and contracted and is 1048cm-1A stretching absorption peak of a carbon-nitrogen single bond exists nearby, so that the surface aminated carbon nanotube participates in the reaction; at 2942/2834cm-1An antisymmetric/symmetric telescopic absorption peak of the hydrocarbon exists nearby, and is 1603/1410cm-1An antisymmetric stretching/symmetric stretching absorption peak of carboxylate ions exists nearby and is 1456cm-1An in-plane bending absorption peak of hydroxyl exists nearby, which indicates that ferric citrate participates in the reaction; at 828cm-1An absorption peak of tungstate ions exists nearby, which indicates that sodium tungstate participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
according to the method in the State environmental protection administration Water and wastewater monitoring and analysis method, the contents of Chemical Oxygen Demand (COD), organic phosphorus (TP) and orthophosphate in wastewater are detected.
In the production process of the organic phosphorus corrosion inhibitor in the experiment, the COD content of the wastewater is 562 mg/L, the TP content of the organic phosphorus is 34.72mg/L, and the orthophosphate content is 6.87 mg/L.
Example 1
A combined treatment process for organophosphorus wastewater with high total phosphorus concentration comprises the following specific preparation scheme:
pretreating, namely filtering the organophosphorus wastewater by using a filter membrane to remove solid impurities, colloidal particles and suspended particles, then feeding the organic phosphorus wastewater into an adjusting tank, and homogenizing for 5 min;
the first-stage chemical phosphorus removal process comprises the steps of pumping organic phosphorus wastewater after homogenization into a phosphorus removal tank, adding lime into the phosphorus removal tank, adjusting the pH value to 10, standing for 10 hours, adding magnesium chloride into the phosphorus removal tank, wherein the adding amount of the lime is 800g/m3The addition amount of magnesium chloride is 200g/m3(ii) a Precipitating after completion, and overflowing supernatant;
the flocculating and dephosphorizing process includes adding flocculating agent in the clear effluent from the previous step in the amount of 300g/m3Precipitating after finishing, and overflowing supernatant;
an oxidation phosphorus removal process, wherein the pH value of the organic wastewater after the flocculation precipitation treatment is adjusted to 2, and 50g/m is added3Uniformly mixing the hydrogen peroxide, and further treating organic pollutants by Fenton oxidation to obtain primary oxidation wastewater; the primary oxidation wastewater enters a photoelectrocatalytic oxidation treatment tank to obtain secondary oxidation wastewater; the method is characterized in that the Fenton oxidation adopts a carbon nano tube Fenton catalyst;
the second-stage chemical phosphorus removal process comprises the steps of feeding the second-stage oxidation wastewater into a second-stage chemical phosphorus removal tank, adding lime into the tank firstly, and then adding a flocculating agent, wherein the adding amount of the lime is 300g/m3FlocculantThe addition amount is 200g/m3Then the wastewater flows into an inclined plate sedimentation tank, and the supernatant after sedimentation can be discharged.
The photoelectrocatalysis oxidation catalyst is arranged at the bottom of the reactor and in the center of the polar plate.
The catalyst adopted by the photoelectrocatalysis oxidation is alpha-alumina loaded titanium dioxide.
The photoelectrocatalysis oxidation adopts mercury lamp irradiation to provide a light source.
The flocculant is polyaluminium chloride.
The content of the hydrogen peroxide is 10 percent.
The preparation method of the carbon nanotube Fenton catalyst comprises the following steps:
the method comprises the following steps: adding 10g of carbon nano tube into 200g of hydrochloric acid solution with the mass percentage content of 10%, stirring and reacting for 5h at the temperature of 60 ℃, washing to be neutral, filtering, adding 300g of ammonia water with the mass percentage content of 20% and 1g of zinc chloride, controlling the temperature to be 10 ℃, reacting for 5h, filtering and drying to obtain the surface aminated carbon nano tube,
step two: dispersing the carbon nano tube with aminated surface into 100g of sodium hydroxide solution with the mass percent content of 3%, adding 5g of ferric citrate, 0.01g of 1-carboxyethyl-3-methylimidazolium nitrate and 5g of sodium tungstate, controlling the temperature to be 50 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, and then placing the mixture in a drying box with the temperature of 160 ℃ for reaction for 20 hours to obtain the carbon nano tube Fenton catalyst.
The wastewater treated by the experiment has the oxygen demand COD content of 42mg/L, the organophosphorus TP content of 0.61mg/L and the orthophosphate content of 0.31 mg/L.
Example 2
A combined treatment process for organophosphorus wastewater with high total phosphorus concentration comprises the following specific preparation scheme:
pretreating, namely filtering the organophosphorus wastewater by using a filter membrane to remove solid impurities, colloidal particles and suspended particles, then feeding the organic wastewater into an adjusting tank, and homogenizing for 8 min;
a first-stage chemical phosphorus removal process, namely pumping the homogenized organic phosphorus wastewater into a phosphorus removal tank, wherein the phosphorus removal tank is chemicalA dephosphorization pool, lime is added into the pool firstly, the pH value is adjusted to 11, then the pool is kept stand for 13 hours, and then magnesium chloride is added into the pool, wherein the adding amount of the lime is 1000g/m3The addition amount of magnesium chloride is 350g/m3(ii) a Precipitating after completion, and overflowing supernatant;
the flocculating and dephosphorizing process includes adding flocculating agent in the clear effluent from the previous step in the amount of 400g/m3Precipitating after finishing, and overflowing supernatant;
an oxidation phosphorus removal process, wherein the pH value of the organic wastewater after the flocculation precipitation treatment is adjusted to 3, and 120g/m is added3Uniformly mixing the hydrogen peroxide, and further treating organic pollutants by Fenton oxidation to obtain primary oxidation wastewater; the primary oxidation wastewater enters a photoelectrocatalytic oxidation treatment tank to obtain secondary oxidation wastewater; the method is characterized in that the Fenton oxidation adopts a carbon nano tube Fenton catalyst;
the second-stage chemical phosphorus removal process comprises the steps of feeding second-stage oxidation wastewater into a second-stage chemical phosphorus removal tank, adding lime into the tank firstly, and then adding a flocculating agent, wherein the adding amount of the lime is 600g/m3The addition amount of the flocculating agent is 240g/m3Then the wastewater flows into an inclined plate sedimentation tank, and the supernatant after sedimentation can be discharged.
The photoelectrocatalysis oxidation catalyst is arranged at the bottom of the reactor and in the center of the polar plate.
The catalyst adopted by the photoelectrocatalysis oxidation is silicon dioxide loaded manganese oxide.
The photoelectrocatalysis oxidation adopts mercury lamp irradiation to provide a light source.
The flocculant is polyacrylamide.
The content of the hydrogen peroxide is 15%.
The preparation method of the carbon nanotube Fenton catalyst comprises the following steps:
the method comprises the following steps: adding 16g of carbon nano tube into 220g of hydrochloric acid solution with the mass percentage content of 15%, stirring and reacting for 7h at 65 ℃, washing with water to be neutral, filtering, adding 330g of ammonia water with the mass percentage content of 20% and 1g of zinc chloride, controlling the temperature to be 10 ℃, reacting for 5h, filtering and drying to obtain the surface aminated carbon nano tube,
step two: dispersing the carbon nano tube with aminated surface into 100g of sodium hydroxide solution with the mass percent content of 3%, adding 5g of ferric citrate, 0.01g of 1-carboxyethyl-3-methylimidazolium nitrate and 5g of sodium tungstate, controlling the temperature to be 50 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, and then placing the mixture in a drying box with the temperature of 160 ℃ for reaction for 20 hours to obtain the carbon nano tube Fenton catalyst.
The wastewater treated by the experiment has the oxygen demand COD content of 37 mg/L, the organophosphorus TP content of 0.57mg/L and the orthophosphate content of 0.28 mg/L.
Example 3
A combined treatment process for organophosphorus wastewater with high total phosphorus concentration comprises the following specific preparation scheme:
pretreating, namely filtering the organophosphorus wastewater by using a filter membrane to remove solid impurities, colloidal particles and suspended particles, then feeding the organic wastewater into an adjusting tank, and homogenizing for 10 min;
the first-stage chemical phosphorus removal process comprises the steps of pumping the homogenized organophosphorus wastewater into a phosphorus removal tank, adding lime into the phosphorus removal tank, adjusting the pH value to 13, standing for 15 hours, adding magnesium chloride into the phosphorus removal tank, wherein the adding amount of the lime is 1500g/m3The addition amount of magnesium chloride is 500g/m3(ii) a Precipitating after completion, and overflowing supernatant;
the flocculating and dephosphorizing process includes adding flocculating agent in the clear effluent from the previous step in the amount of 600g/m3Precipitating after finishing, and overflowing supernatant;
an oxidation phosphorus removal process, namely adjusting the pH value of the organic wastewater after the flocculation precipitation treatment to be 7, and adding 200g/m3Uniformly mixing the hydrogen peroxide, and further treating organic pollutants by Fenton oxidation to obtain primary oxidation wastewater; the primary oxidation wastewater enters a photoelectrocatalytic oxidation treatment tank to obtain secondary oxidation wastewater; the method is characterized in that the Fenton oxidation adopts a carbon nano tube Fenton catalyst;
the second-stage chemical phosphorus removal process comprises the steps of feeding the second-stage oxidation wastewater into a second-stage chemical phosphorus removal tank, adding lime into the tank, and then adding a flocculating agent into the tank, wherein the lime is addedThe addition amount is 800g/m3The addition amount of the flocculating agent is 300g/m3Then the wastewater flows into an inclined plate sedimentation tank, and the supernatant after sedimentation can be discharged.
The photoelectrocatalysis oxidation catalyst is arranged at the bottom of the reactor and in the center of the polar plate.
The catalyst adopted by the photoelectrocatalysis oxidation is alpha-alumina loaded cadmium sulfide.
The photoelectrocatalysis oxidation adopts mercury lamp irradiation to provide a light source.
The flocculating agent is polymeric ferric sulfate.
The content of the hydrogen peroxide is 20%.
The preparation method of the carbon nanotube Fenton catalyst comprises the following steps:
the method comprises the following steps: adding 25g of carbon nano tube into 300g of hydrochloric acid solution with the mass percent content of 30%, stirring and reacting for 10h at 70 ℃, washing with water to be neutral, filtering, adding 400g of ammonia water with the mass percent content of 30% and 4g of zinc chloride, controlling the temperature to be 20 ℃, reacting for 10h, filtering and drying to obtain the surface aminated carbon nano tube,
step two: dispersing the carbon nano tube with aminated surface into 200g of sodium hydroxide solution with the mass percent content of 7%, adding 10g of ferric citrate, 0.05g of 1-carboxyethyl-3-methylimidazolium nitrate and 10g of sodium tungstate, controlling the temperature to be 70 ℃, stirring for reaction for 5 hours, filtering after the reaction is finished, and then placing the mixture in a drying box with the temperature of 200 ℃ for reaction for 30 hours to obtain the carbon nano tube Fenton catalyst.
The wastewater treated by the experiment has the oxygen demand COD content of 34mg/L, the organophosphorus TP content of 0.54mg/L and the orthophosphate content of 0.26 mg/L.
Comparative example 1
The preparation method of the carbon nanotube Fenton catalyst comprises the following steps:
dispersing carbon nanotubes in 100g of sodium hydroxide solution with the mass percentage content of 3%, adding 5g of ferric citrate, 0.01g of 1-carboxyethyl-3-methylimidazolium nitrate and 5g of sodium tungstate, controlling the temperature to be 50 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, and then placing the mixture in a drying box with the temperature of 160 ℃ for reaction for 20 hours to obtain the carbon nanotube Fenton catalyst.
The rest of the process is the same as that of the embodiment 1,
the wastewater treated by the experiment has the oxygen demand COD content of 102 mg/L, the organophosphorus TP content of 3.8mg/L and the orthophosphate content of 2.7 mg/L.
Comparative example 2
A combined treatment process for organophosphorus wastewater with high total phosphorus concentration comprises the following specific preparation scheme:
pretreating, namely filtering the organophosphorus wastewater by using a filter membrane to remove solid impurities, colloidal particles and suspended particles, then feeding the organic phosphorus wastewater into an adjusting tank, and homogenizing for 5 min;
the first-stage chemical phosphorus removal process comprises the steps of pumping organic phosphorus wastewater after homogenization into a phosphorus removal tank, adding lime into the phosphorus removal tank, adjusting the pH value to 10, standing for 10 hours, adding magnesium chloride into the phosphorus removal tank, wherein the adding amount of the lime is 800g/m3The addition amount of magnesium chloride is 200g/m3(ii) a Precipitating after completion, and overflowing supernatant;
the flocculating and dephosphorizing process includes adding flocculating agent in the clear effluent from the previous step in the amount of 300g/m3Precipitating after finishing, and overflowing supernatant;
the second-stage chemical phosphorus removal process comprises the steps of feeding the second-stage oxidation wastewater into a second-stage chemical phosphorus removal tank, adding lime into the tank firstly, and then adding a flocculating agent, wherein the adding amount of the lime is 300g/m3The addition amount of the flocculating agent is 200g/m3Then the wastewater flows into an inclined plate sedimentation tank, and the supernatant after sedimentation can be discharged.
The flocculant is polyaluminium chloride.
The wastewater treated by the experiment has the oxygen demand COD content of 397mg/L, the organophosphorus TP content of 21.42mg/L and the orthophosphate content of 3.71 mg/L.
Comparative example 3
The preparation method of the carbon nanotube Fenton catalyst comprises the following steps:
the method comprises the following steps: adding 10g of carbon nano tube into 200g of hydrochloric acid solution with the mass percentage content of 10%, stirring and reacting for 5h at the temperature of 60 ℃, washing to be neutral, filtering, adding 300g of ammonia water with the mass percentage content of 20% and 1g of zinc chloride, controlling the temperature to be 10 ℃, reacting for 5h, filtering and drying to obtain the surface aminated carbon nano tube,
step two: dispersing the carbon nano tube with aminated surface into 100g of sodium hydroxide solution with the mass percent content of 3%, adding 5g of ferric citrate and 5g of sodium tungstate, controlling the temperature to be 50 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, and then placing the mixture in a drying oven with the temperature of 160 ℃ for reaction for 20 hours to obtain the carbon nano tube Fenton catalyst.
The rest of the process is the same as that of the embodiment 1,
the wastewater treated by the experiment has the oxygen demand COD content of 71mg/L, the organophosphorus TP content of 1.14mg/L and the orthophosphate content of 2.17 mg/L.

Claims (7)

1. A combined treatment process for organophosphorus wastewater with high total phosphorus concentration comprises the following specific preparation scheme:
pretreating, namely filtering the organophosphorus wastewater by using a filter membrane to remove solid impurities, colloidal particles and suspended particles, then feeding the organic wastewater into an adjusting tank, and homogenizing for 5-10 min;
a first-stage chemical phosphorus removal process, namely pumping the homogenized organophosphorus wastewater into a phosphorus removal tank, wherein the phosphorus removal tank is a chemical phosphorus removal tank, firstly adding lime into the tank, adjusting the pH value to 10-13, then standing for 10-15h, and then adding magnesium chloride into the tank, wherein the adding amount of the lime is 800-3The addition amount of magnesium chloride is 200-3(ii) a Precipitating after completion, and overflowing supernatant;
the flocculating and dephosphorizing process comprises the step of adding a flocculating agent into the clear wastewater liquid overflowing in the previous step, wherein the adding amount of the flocculating agent is 300-3Precipitating after finishing, and overflowing supernatant;
an oxidation dephosphorization process, adjusting the pH value of the organic wastewater after the flocculation precipitation treatment to 2-7, adding 50-200g/m3Uniformly mixing the hydrogen peroxide, and further treating organic pollutants by Fenton oxidation to obtain primary oxidation wastewater; the primary oxidation wastewater enters a photoelectrocatalytic oxidation treatment tank to obtain secondary oxidation wastewater; it is characterized in thatA carbon nano tube Fenton catalyst is adopted in the Fenton oxidation;
the secondary chemical phosphorus removal process comprises the steps of enabling secondary oxidation wastewater to enter a secondary chemical phosphorus removal tank, firstly adding lime into the tank, and then adding a flocculating agent, wherein the adding amount of the lime is 300-800 g/m-3The addition amount of the flocculating agent is 200-300g/m3Then the wastewater flows into an inclined plate sedimentation tank, and the supernatant after sedimentation can be discharged.
2. The combined treatment process of the organophosphorus wastewater with high total phosphorus concentration according to claim 1, wherein: the photoelectrocatalysis oxidation catalyst is arranged at the bottom of the reactor and in the center of the polar plate.
3. The combined treatment process of the organophosphorus wastewater with high total phosphorus concentration according to claim 1, wherein: the catalyst adopted by the photoelectrocatalysis oxidation is alpha-alumina supported titanium dioxide or silicon dioxide supported manganese oxide or alpha-alumina supported cadmium sulfide.
4. The combined treatment process of the organophosphorus wastewater with high total phosphorus concentration according to claim 1, wherein: the photoelectrocatalysis oxidation adopts mercury lamp irradiation to provide a light source.
5. The combined treatment process of the organophosphorus wastewater with high total phosphorus concentration according to claim 1, wherein: the flocculant is polyaluminium chloride or polyacrylamide or polyferric sulfate.
6. The combined treatment process of the organophosphorus wastewater with high total phosphorus concentration according to claim 1, wherein: the content of the hydrogen peroxide is 10 to 20 percent.
7. The combined treatment process of the organophosphorus wastewater with high total phosphorus concentration according to claim 1, wherein: the preparation method of the carbon nanotube Fenton catalyst comprises the following steps:
the method comprises the following steps: adding 10-25 parts by mass of carbon nano tube into 300 parts by mass of 10-30% hydrochloric acid solution at 60-70 ℃, stirring and reacting for 5-10h, washing with water to neutrality, filtering, adding 400 parts by mass of 20-30% ammonia water and 1-4 parts by mass of zinc chloride, controlling the temperature to 10-20 ℃, reacting for 5-10h, filtering, drying to obtain the surface aminated carbon nano tube,
step two: dispersing the carbon nano-tube with aminated surface into 200 parts of sodium hydroxide solution with the mass percent content of 3% -7%, adding 5-10 parts of ferric citrate, 0.01-0.05 part of 1-carboxyethyl-3-methylimidazole nitrate and 5-10 parts of sodium tungstate, controlling the temperature to be 50-70 ℃, stirring for reaction for 2-5h, filtering after the reaction is finished, and then placing the mixture in a drying box with the temperature of 160-200 ℃ for reaction for 20-30h to obtain the carbon nano-tube Fenton catalyst.
CN202010695124.1A 2020-07-19 2020-07-19 Combined treatment process for organophosphorus wastewater with high total phosphorus concentration Withdrawn CN111875129A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010695124.1A CN111875129A (en) 2020-07-19 2020-07-19 Combined treatment process for organophosphorus wastewater with high total phosphorus concentration

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010695124.1A CN111875129A (en) 2020-07-19 2020-07-19 Combined treatment process for organophosphorus wastewater with high total phosphorus concentration

Publications (1)

Publication Number Publication Date
CN111875129A true CN111875129A (en) 2020-11-03

Family

ID=73154887

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010695124.1A Withdrawn CN111875129A (en) 2020-07-19 2020-07-19 Combined treatment process for organophosphorus wastewater with high total phosphorus concentration

Country Status (1)

Country Link
CN (1) CN111875129A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113149344A (en) * 2021-03-29 2021-07-23 昆明理工大学 Processing method of vegetable juice stock solution
CN116891328A (en) * 2023-09-07 2023-10-17 北京惠宇乐邦环保科技有限公司 Recycling treatment method of acephate production wastewater

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113149344A (en) * 2021-03-29 2021-07-23 昆明理工大学 Processing method of vegetable juice stock solution
CN116891328A (en) * 2023-09-07 2023-10-17 北京惠宇乐邦环保科技有限公司 Recycling treatment method of acephate production wastewater

Similar Documents

Publication Publication Date Title
CN103991987B (en) A kind of pretreatment high phosphorus waste water removes technique and the process system thereof of total phosphorus
CN105906142B (en) A kind of landfill leachate advanced treatment system and processing method
WO2010133151A1 (en) Organic wastewater recycling treatment method
CN104961304A (en) High-concentration fluorine chemical wastewater treatment technology
CN104591449A (en) Method for removing bromine from disperse dye wastewater
CN112607963A (en) System and method for reducing percolate concentrated solution of waste incineration plant
CN111875129A (en) Combined treatment process for organophosphorus wastewater with high total phosphorus concentration
CN102976537B (en) Comprehensive physical and chemical treatment device and method of organic silicon wastewater
CN112794555A (en) Novel method for treating wastewater by reinforced coagulation
CN106396191A (en) Emergency treatment process and device of waste water with high COD and high NH3-N
CN216998076U (en) Industrial wastewater treatment system
CN208762301U (en) A kind of depth removes the device of cyanide in coking wastewater
CN211595265U (en) Advanced treatment system for cyanogen-fluorine combined pollution wastewater
CN210711151U (en) Device of high difficult waste water is handled to fragrant MBR of combining of iron carbon
CN112551744A (en) Method for treating wastewater by utilizing acidic coagulated Fenton oxidation
CN106630312B (en) Treatment system, treatment method and application of coking phenol-cyanogen wastewater
CN102642901A (en) Three-level polyaluminium chloride coagulation treatment method for electro-polishing wastewater
CN212174735U (en) System for be used for handling rubber auxiliary agent CBS waste water
CN114349268A (en) Method for treating industrial wastewater
CN115536206A (en) Advanced treatment combined process for chemical degradation-resistant sewage
CN111039376A (en) Composite efficient phosphorus removal agent applied to sewage treatment field and preparation method thereof
CN211770805U (en) Sewage treatment device for oily waste alkali liquor
CN205803237U (en) Electroplating sewerage processing system
CN108128974B (en) Device and process for enhancing adsorption of industrial wastewater by utilizing domestic sewage excess sludge
CN112299668B (en) high-COD lead-zinc industrial beneficiation wastewater treatment system and method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20201103

WW01 Invention patent application withdrawn after publication