CN112811728A - Method for standard treatment of mother liquor for producing superfine spherical silver powder and recycling valuable components - Google Patents
Method for standard treatment of mother liquor for producing superfine spherical silver powder and recycling valuable components Download PDFInfo
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Abstract
The invention discloses a method for treating mother liquor of superfine spherical silver powder production and recovering valuable components up to the standard, which comprises the steps of removing nitric acid in the mother liquor of superfine spherical silver powder production through solvent extraction and recovering the nitric acid in a pure nitrate product form; then extracting polyvinylpyrrolidone or polyvinyl alcohol in raffinate by adopting a membrane separation method, and recycling the recovered polymeric dispersant; the low molecular weight dehydroascorbic acid and ammonia are left in the clear liquid separated by the membrane, and are respectively degraded by a chemical oxidation method and separated and recovered by an air stripping method or a gas stripping method; finally, the clear liquid enters a biochemical tank for advanced treatment to remove residual COD and NH in the clear liquid3And (4) pollutants such as-N and the like are discharged or recycled after reaching the standard. The method greatly reduces the treatment difficulty and treatment cost of the waste liquid from the production of the superfine spherical silver powder, reduces the generation of waste liquid and waste materials, fully recycles valuable components in the mother liquid, reduces the production cost of the silver powder, and also reduces the resource waste.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment and secondary resource recovery, and particularly relates to a method for treating mother liquor produced by superfine spherical silver powder and recovering valuable components after reaching standards.
Background
The method is characterized in that a liquid phase chemical reduction method is adopted to synthesize a 0.1-10 micron superfine spherical silver powder material, particularly to synthesize the superfine spherical silver powder for the silver paste of the solar cell, silver nitrate is generally used as a silver source, ascorbic acid is used as a reducing agent, and an organic macromolecular substance polyvinyl pyrrolidone (PVP) or polyvinyl alcohol (PVA) is used as a dispersing agent. The large amount of silver powder mother liquor discharged in the synthesis process is acidic waste liquor with high chroma and pH value less than 1.0, which is composed of high-concentration nitrate radicals (10-30 g/L), high-concentration polyvinylpyrrolidone (10-25 g/L) or polyvinyl alcohol dispersant, high-concentration dehydroascorbic acid, excessive reducing agent ascorbic acid (20-40 g/L) and a small amount of inorganic ammonium salt, and the index ranges of the pollution factors are respectively as follows: 30000-60000 mg/L of COD and NO3 -15000～25000mg/L，NH3the-N is 1000-5000 mg/L, the pH value is 0.6-0.9, and the-N belongs to acid waste liquid which is high in salt, nitrogen and COD and is difficult to treat.
For the acid waste liquid with high salt, high nitrogen and high COD, the existing treatment process is to add alkali to the waste liquid for neutralization, directly evaporate and separate out the mixture solid of organic matters and nitrates, or evaporate and concentrate to separate out the nitrates after oxidizing and degrading the COD, and evaporate the condensed water as the raw water for biochemical pond treatment, but because the concentration of pollution factors of the evaporated condensed water exceeds the upper limit requirement of the biochemical pond treatment on the quality of the raw water, the evaporated liquid needs to be subjected to pre-denitration, deaminization and COD degradation, and the like, so that the treatment cost is high, and the stable standard reaching treatment effect is difficult to obtain. In addition, the nitrate and the organic matters are separated out in the form of mixed solid waste, and the solid waste has certain risk of explosion and spontaneous combustion during production, transportation and further treatment. The method also comprises a process route of oxidizing and degrading COD by a Fenton method, evaporating and salting out, and evaporating condensed water to enter biochemical treatment for deep degradation of COD, ammonia nitrogen and total nitrogen; according to the process route, because raw water contains a large amount of nitrate radicals and COD, a large amount of chemical raw materials such as hydrogen peroxide are consumed for Fenton oxidative degradation of COD, the amount of produced iron slag is large, high-value chemical products such as PVP (polyvinyl pyrrolidone) cannot be effectively recycled, and meanwhile, sodium nitrate crystals precipitated by evaporation have low purity and high content of organic impurities, so that valuable utilization is difficult to obtain.
Therefore, the relative lag of the superfine spherical silver powder wastewater treatment technology becomes one of the key technical problems restricting the development of the domestic silver powder production industry.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for processing the superfine spherical silver powder to produce mother liquor and recycling valuable components after reaching the standard.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for treating mother liquor produced by superfine spherical silver powder and recycling valuable components after reaching standards comprises the following steps:
(1) removing nitric acid in the mother liquor of the superfine spherical silver powder production by adopting an extraction method, and recovering the nitrate by back extraction;
(2) separating polyvinylpyrrolidone or polyvinyl alcohol in the raffinate obtained in the step (1) by adopting a membrane separation method, and purifying and recovering the separated polyvinylpyrrolidone or polyvinyl alcohol;
(3) degrading organic matters in the clear liquid separated by the membrane in the step (2) by adopting a chemical oxidation method;
(4) removing ammonia in the clear liquid treated in the step (3) by adopting a stripping method or a gas stripping method, and recovering the ammonia in the form of ammonia water;
(5) and (4) deeply treating the pollutants remained in the clear liquid treated in the step (4) by using a biochemical pool to ensure that the water quality reaches the discharge standard.
Preferably, in the step (1), the extraction agent used for extraction comprises a main extraction agent, a phase modifier and a solvent.
Preferably, the main extractant is at least one of an organic amine extractant and a neutral extractant.
The organic amine extractant may be selected from at least one of primary, secondary, tertiary or quaternary amines, including at least one of secondary primary (N1923), 1- (3-ethylheptyl) 4-ethyloctylamine (Alamine 21F81), multi-branched hexadecyl tertiary primary (Primene JMT), N-dodecyl (dialkylmethyl) amine (Alamine 9D-178), N-laurylamine (Amberlite LA-2), trialkylamine (N235), trilaurylamine (Alamine 304), trioctylamine (Alamine 336), Triisooctylamine (TIOA), triheptylamine (N208), trioctylmethylammonium chloride, (Aliquat 336), trioctylmethylammonium methylcarbonate (HBNC 38), tribasic alkylmethylammonium chloride (N263), tribasic alkylmethylammonium methylcarbonate (HBNC35), tribasic alkylmethylammonium methosulfate (HBNS 35).
The neutral extractant comprises: neutral oxygen-containing extractant, neutral phosphorus-containing extractant, neutral sulfur-containing extractant, and amide extractant. Wherein the neutral oxygen-containing extracting agent comprises at least one of sec-octanol, methyl isobutyl ketone (MIBK) and ethyl acetate. The neutral sulfur-containing extractant comprises dioctyl sulfoxide (DOSO). The neutral phosphorus-containing extractant comprises at least one of diisoamyl methyl phosphonate (DAMP), dibutyl butyl phosphonate (DBBP), diisomixed methyl phosphonate (P311) and tributyl phosphate (TBP). The amide extractant includes N, N-bis (1-methylheptyl) hexanamide (N503).
The phase modifier serves to increase the compatibility of the components and allow the extractant to form a homogeneous single organic phase. The phase modifier is C8 straight-chain alcohol and comprises at least one of n-octanol, isooctanol and sec-octanol.
The solvent is used for adjusting the viscosity and density of the organic phase, is a low-viscosity solvent which is difficult to dissolve in the water phase, such as straight-chain hydrocarbon or aromatic hydrocarbon with the distillation point of above 120 ℃, and comprises at least one of No. 120 solvent oil, No. 160 solvent oil and No. 260 solvent oil.
Preferably, the extractant comprises the following components in percentage by weight: 5-40% vol of main extractant, 0.5-20% vol of phase modifier and 40-80% vol of solvent.
Preferably, the extraction denitration process of the step (1) is carried out in a box-type mixer-settler or in a tower-type extraction device; the extraction process comprises the mixing of a mother liquor water phase and an extraction organic phase, and the clarification and separation process after the mixing, wherein nitrate radicals are transferred from the mother liquor to the organic phase, so that the separation of the nitrate radicals from other components of the mother liquor is realized. The nitrate-loaded organic phase is then back-extracted with an alkaline solution to bring nitrate ions into the aqueous phase to obtain a pure nitrate solution. The organic phase after the back extraction is mixed and washed by pure water until the washing water is neutral, thereby realizing the regeneration and being continuously recycled as an extracting agent. The nitrate solution can be directly used as fertilizer by evaporating crystallization or freezing crystallization to obtain high-purity nitrate product. The back extraction mother liquor after the nitrate is separated out can be regenerated by adding alkali liquor and can be continuously recycled as a back extraction agent.
Preferably, the alkali liquor used for the back extraction comprises at least one of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and ammonia water; the concentration of the alkali liquor is 0.1-10 mol/L.
Preferably, the step (2) further comprises deoiling the raffinate before the membrane separation.
Preferably, the separation membrane used in the membrane separation in the step (2) is an ultrafiltration membrane, and the pore diameter of the ultrafiltration membrane is 1 KD-25 KD.
Because the pH value of the raffinate after removing the nitric acid and deoiling is improved, the raffinate can be directly separated by using an ultrafiltration membrane, the high molecular weight dispersant polyvinylpyrrolidone or polyvinyl alcohol in the raffinate is retained in concentrated solution, and then pure water is used for multiple dilution and ultrafiltration separation to obtain pure polyvinylpyrrolidone or polyvinyl alcohol concentrated solution. The concentrated solution can be evaporated and concentrated to separate out pure polyvinylpyrrolidone or polyvinyl alcohol solid products, or further evaporated and concentrated to a concentrated solution with a certain concentration and then directly reused in the synthesis production of silver powder.
The membrane-permeated liquid (i.e., clear liquid) discharged after the membrane separation is a dilute solution containing organic substances such as dehydroascorbic acid and ascorbic acid, and a small amount of free ammonia or ammonium salt, and is treated by a chemical oxidation method, whereby the organic substances such as dehydroascorbic acid in the dilute solution can be oxidatively decomposed to finally generate carbon dioxide and water. After the treatment of extraction separation, membrane separation and chemical oxidation degradation, the liquid ammonia in the waste liquid mainly exists in a free ammonia state, so that the ammonia can be removed and separated by adopting a blow-off method or a gas stripping method, and the low-concentration ammonia water is recycled.
The nitric acid is removed through extraction, the polyvinylpyrrolidone or polyvinyl alcohol is separated through a membrane, and only trace COD, ammonia nitrogen, total nitrogen and other pollutants remain in the waste liquid after ammonia nitrogen and organic pollutant degradation are removed, so that the waste liquid can enter a biochemical tank for deep degradation and removal treatment, and the water can be directly discharged or recycled after reaching the discharge standard.
Preferably, the chemical oxidation method of step (3) is a wet chemical oxidation method or an electrochemical oxidation method; the chemical oxidant used in the wet chemical oxidation method may be one or more of peroxide, hypochlorite, chlorate, perchlorate, permanganate, manganese dioxide, etc.
Compared with the prior art, the invention has the beneficial effects that: the invention optimizes the processing process route of the mother liquid for producing the superfine spherical silver powder, adopts the process combination of specific types and specific sequences, realizes the standard-reaching treatment of the mother liquid for producing the superfine spherical silver powder and the full recycling of valuable components, and comprises the following steps: firstly, the extraction deacidification is utilized to recover the waste liquidHigh content nitric acid in the waste liquid and producing high purity nitrate product, raising the pH value of the waste liquid, ultrafiltering to intercept and recover high molecular weight polyvinyl pyrrolidone or polyvinyl alcohol, purifying and reusing the polyvinyl pyrrolidone or polyvinyl alcohol in silver powder production, degrading easily degradable organic matter in the waste liquid by chemical oxidation, separating and recovering ammonia in the waste liquid by air stripping method, and finally deeply treating trace amount of COD and NH in the waste liquid by biochemical pond3N and the like, so that the water quality reaches the discharge standard. The method greatly reduces the treatment difficulty and treatment cost of the waste liquid from the production of the superfine spherical silver powder, reduces the generation of waste liquid and waste materials, fully recycles valuable components in the mother liquid, reduces the production cost of the silver powder, and also reduces the resource waste. The invention solves the problems of high treatment cost and large equipment investment of the mother solution for producing the superfine spherical silver powder, and also avoids the generation of dangerous solid wastes such as nitrate, organic matters and the like.
Drawings
FIG. 1 is a process route of the method for treating the superfine spherical silver powder to reach the standard to produce the mother liquor and recycling the valuable components.
Detailed Description
The technical solutions of the present invention will be further described with reference to the following embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
The invention relates to a method for treating mother liquor produced by superfine spherical silver powder and recovering valuable components after reaching the standard, which comprises the following steps:
(1) removing nitric acid in the mother liquor of the superfine spherical silver powder production by adopting an extraction method, and recovering the nitrate by back extraction;
(2) separating polyvinylpyrrolidone or polyvinyl alcohol in the raffinate obtained in the step (1) by adopting a membrane separation method, and purifying and recovering the separated polyvinylpyrrolidone or polyvinyl alcohol;
(3) degrading organic matters in the clear liquid separated by the membrane in the step (2) by adopting a chemical oxidation method;
(4) removing ammonia in the clear liquid treated in the step (3) by adopting a stripping method or a gas stripping method, and recovering the ammonia in the form of ammonia water;
(5) and (4) deeply treating the pollutants remained in the clear liquid treated in the step (4) by using a biochemical pool to ensure that the water quality reaches the discharge standard.
In the step (1), the extracting agent used for extraction comprises the following components in percentage by weight: 5-40% vol of main extractant, 0.5-20% vol of phase modifier and 40-80% vol of solvent. The main extractant is at least one of organic amine extractant and neutral extractant. The organic amine extractant may be selected from at least one of primary, secondary, tertiary or quaternary amines, including at least one of primary secondary (N1923), 1- (3-ethylheptyl) 4-ethyloctylamine (Alamine 21F81), primary multi-branched hexadecyl tertiary-carbonate (Primene JMT), N-dodecyl (dialkylmethyl) amine (Alamine 9D-178), N-laurylamine (Amberlite LA-2), trialkylamine (N235), trilaurylamine (Alamine 304), trioctylamine (Alamine 336), Triisooctylamine (TIOA), triheptylamine (N208), trioctylmethylammonium chloride, (Aliquat 336), trioctylmethylammonium (HBNC 38), tribasic alkylmethylammonium chloride (N263), tribasic alkylmethylammonium carbonate (HBNC35), tribasic alkylmethylammonium sulfate (HBNS 35). The neutral extractant can be selected from at least one of neutral oxygen-containing extractant, neutral phosphorus-containing extractant, neutral sulfur-containing extractant, and amide extractant. Wherein the neutral oxygen-containing extractant can be at least one selected from secondary octanol, methyl isobutyl ketone (MIBK) and ethyl acetate. The neutral sulfur-containing extractant may be selected from dioctyl sulfoxide (DOSO). The neutral phosphorus-containing extractant may be selected from at least one of diisoamyl methyl phosphonate (DAMP), dibutyl butyl phosphonate (DBBP), diisomixed methyl phosphonate (P311), and tributyl phosphate (TBP). The amide extractant may be selected from N, N-bis (1-methylheptyl) hexanamide (N503). The phase modifier is C8 linear chain alcohol, and can be selected from at least one of n-octanol, isooctanol, and sec-octanol. The solvent is low viscosity solvent with a boiling point above 120 deg.C and difficult to dissolve in water phase, such as straight chain hydrocarbon or aromatic hydrocarbon, and can be selected from at least one of No. 120 solvent oil, No. 160 solvent oil, and No. 260 solvent oil.
In addition, the extraction denitration process of the step (1) is carried out in a box-type mixing and clarifying tank or a tower-type extraction device, and the extraction process comprises the processes of mixing the mother liquor aqueous phase with the extraction organic phase and clarifying and separating after mixing.
And after extraction, performing back extraction on the extraction liquid by using an alkali liquor with the concentration of 0.1-10 mol/L to enable nitrate ions to enter a water phase, thereby obtaining a pure nitrate solution. The nitrate solution can be used as a high-purity nitrate product by an evaporative crystallization or freezing crystallization method, or can be directly used as a fertilizer in a solution mode. The alkali solution is at least one selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, and ammonia water.
In the step (2), before the membrane separation, the raffinate is subjected to oil removal treatment. The membrane separation adopts an ultrafiltration membrane with the aperture of 1 KD-25 KD. The membrane separation can retain the high molecular weight dispersant polyvinylpyrrolidone or polyvinyl alcohol in the raffinate in the concentrated solution, and the pure concentrated solution of polyvinylpyrrolidone or polyvinyl alcohol can be obtained by further diluting the concentrated solution for many times with pure water and performing ultrafiltration separation. And (3) evaporating and concentrating the obtained concentrated solution to separate out a pure polyvinylpyrrolidone or polyvinyl alcohol solid product, or further evaporating and concentrating the concentrated solution to a certain concentration and then directly recycling the concentrated solution to the synthesis production of the silver powder.
In the step (3), organic substances such as dehydroascorbic acid in the clear liquid discharged from the membrane separation can be oxidatively decomposed by a chemical oxidation method to finally generate carbon dioxide and water. The chemical oxidation method is a wet chemical oxidation method or an electrochemical oxidation method, wherein the chemical oxidant adopted by the wet chemical oxidation method can be one or more of peroxide, hypochlorite, chlorate, perchlorate, permanganate, manganese dioxide and the like.
After the chemical oxidation treatment, the liquid ammonia in the waste liquid mainly exists in a free ammonia state, and the ammonia can be removed and separated by adopting a stripping method or a gas stripping method, and the low-concentration ammonia water is recycled.
After the treatment of the steps (1) to (4), only trace pollutants such as COD, ammonia nitrogen and total nitrogen remain in the waste liquid, so that the waste liquid can enter a biochemical pool for deep degradation and removal treatment, and the water can be directly discharged or recycled after reaching the discharge standard.
Application example:
firstly, recovering nitric acid in mother liquor for producing silver powder
The extraction agent is selected to be composed of: n235 (trioctyl/decyl tertiary amine) is used as a main extracting agent, tributyl phosphate (TBP) is used as a co-extracting agent, N-octanol is used as a phase modifier, and sulfonated kerosene is used as a solvent. Mixing the main extractant, the co-extractant, the phase modifier and the solvent according to a certain proportion to prepare an extraction organic phase, extracting the silver powder production mother liquor, and then carrying out back extraction on the extraction liquor by adopting alkali liquor; the extraction and stripping conditions are shown in Table 1.
The silver powder production mother liquor comprises the following components:
test groups 1-3: NO3- 23g/L+PVP 18g/L+C6H6O6(dehydroascorbic acid) 39g/L + C6H8O6(ascorbic acid) 1.95 g/L; the pH value is 0.75;
test groups 4-5: NO3- 19g/L+PVA 15g/L+C6H6O6(dehydroascorbic acid) 36g/L + C6H8O6(ascorbic acid) 0.95 g/L; the pH value is 0.80;
test group 6: NO3- 25g/L+PVA 18g/L+C6H6O6(dehydroascorbic acid) 34g/L + C6H8O6(ascorbic acid) 0.95 g/L; the pH was 0.80.
Organic phase regeneration: the organic phase after the back extraction is mixed and washed by pure water until the washing water is neutral, and then the organic phase can be continuously recycled as an extracting agent. The water phase after back extraction is nearly saturated nitrate solution, the nitrate solution is cooled to a lower temperature to precipitate solid nitrate crystals, the mother liquor after the nitrate crystals are precipitated is the saturated nitrate solution at the crystallization temperature, the nitrate solution is heated to 30 ℃, and then alkali liquor is added to dissolve the nitrate solution to prepare the alkali liquor concentration required by back extraction, and the nitrate solution can be used as back extraction agent to be continuously recycled.
TABLE 1
Note: in Table 1, the extraction process is 3-stage extraction, and 10min/3 times in the table means 10min per extraction, and 3 times of extraction.
Second, the PVP in the raffinate of the test group 1-3 is recovered
Raffinate obtained by extraction of the test groups 1-3 is respectively pumped into a membrane separation device, the model of a membrane is TW30-1812-50HR, the material is PES10, and the cut-off molecular weight is 10000D. The specification parameters of the ultrafiltration membrane are as follows: the length of the rolled membrane is 239mm, and the membrane area is 0.32m2The pore diameter is 30 nm. As shown in FIG. 1, clear solution 3 of the membrane device was mixed uniformly, and then a sample was taken, and the concentrate 3 was sampled, and PVP and dehydroascorbic acid (C) were analyzed6H6O6) And ascorbic acid (C)6H8O6) The content of (a). The contents of ascorbic acid, dehydroascorbic acid, and PVP in the clear solution 3 and the concentrated solution 3 were measured by a high performance liquid chromatograph, and the results are shown in table 2.
In Table 2, the raffinate recovered from run 1 was from run A and B, the raffinate recovered from run 2 was from run C and D, and the raffinate recovered from run 3 was from run E and F.
The raffinate of test groups 1-3 consists of the following components:
test group 1: NO3- 0.0015g/L+PVP 17.8g/L+C6H6O6(dehydroascorbic acid) 38.5g/L + C6H8O6(ascorbic acid) 1.89 g/L; the pH value is 3.2;
test group 2: NO3- 0.0021g/L+PVP 15.6g/L+C6H6O6(dehydroascorbic acid) 36.8g/L + C6H8O6(ascorbic acid) 1.03 g/L; the pH value is 3.5;
test group 3: NO3- 0.0021g/L+PVP 12.6g/L+C6H6O6(dehydroascorbic acid) 32.5g/L + C6H8O6(ascorbic acid) 0.86 g/L; the pH was 3.3.
TABLE 2
As can be seen from Table 2, after passing through the 3-stage membrane separation, the majority of dehydroascorbic acid (C) in the feed was6H6O6) And ascorbic acid (C)6H8O6) The concentrated solution discharged from the grade-3 membrane is enriched with PVP, the separation of high molecular weight PVP from low molecular weight dehydroascorbic acid and ascorbic acid is realized, and the concentrated solution 3 is further concentrated to obtain solid PVP with PVP purity of more than 94% or a concentrated solution which can be directly applied to the synthesis of the superfine spherical silver powder.
Third, recycling PVP concentrated solution by membrane separation
The PVP concentrated solution recovered in the above membrane separation test was reused for silver powder synthesis (see use examples 1 to 3), while the comparative examples 1 to 3 used commercially available PVP solid. Dissolving PVP concentrated solution or solid material, ascorbic acid crystal and 25% ammonia water in pure water according to a proportion, and uniformly mixing to prepare reducing solution; dissolving silver nitrate crystal in pure water, and adding ammonia water to adjust pH value. Taking 1000mL of silver nitrate solution and 1000mL of reducing agent solution respectively, firstly pouring the reducing agent solution into a flask with the volume of 3000mL and a stirring device, adding the prepared silver nitrate solution into the flask at the stirring speed of 250rpm and at the temperature of 40 ℃, directly adding the silver nitrate solution, adding stearic acid emulsion, stirring for 30min after adding the silver nitrate solution, then washing with water until the conductivity is below 100 mu s/cm, filtering and separating, drying the silver powder filter cake in a vacuum oven at the temperature of 60 ℃ for 5h, taking out, crushing and depolymerizing the silver powder filter cake by using a high-speed crusher at 20000rpm, and sending samples to analyze the particle size distribution, the specific surface, the tap density and the morphology of an electron microscope SEM (scanning electron microscope), wherein the results are shown in Table 3.
TABLE 3
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for treating mother liquor produced by superfine spherical silver powder and recycling valuable components after reaching standards is characterized by comprising the following steps:
(1) removing nitric acid in the mother liquor of the superfine spherical silver powder production by adopting an extraction method, and recovering the nitrate by back extraction;
(2) separating polyvinylpyrrolidone or polyvinyl alcohol in the raffinate obtained in the step (1) by adopting a membrane separation method, and purifying and recovering the separated polyvinylpyrrolidone or polyvinyl alcohol;
(3) degrading organic matters in the clear liquid separated by the membrane in the step (2) by adopting a chemical oxidation method;
(4) removing ammonia in the clear liquid treated in the step (3) by adopting a stripping method or a gas stripping method, and recovering the ammonia in the form of ammonia water;
(5) and (4) deeply treating the pollutants remained in the clear liquid treated in the step (4) by using a biochemical pool to ensure that the water quality reaches the discharge standard.
2. The method of claim 1, wherein in step (1), the extractant used in the extraction is an organic amine extractant and/or a neutral extractant as the main extractant.
3. The method of claim 2, wherein the organic amine extractant is selected from at least one of a primary amine, a secondary amine, a tertiary amine, or a quaternary amine; the neutral extractant is selected from at least one of neutral oxygen-containing extractant, neutral phosphorus-containing extractant, neutral sulfur-containing extractant and amide extractant.
4. The method of claim 2, wherein the extractant further comprises a phase modifier, and the phase modifier is a C8 linear alcohol.
5. The method of claim 2, wherein the extractant further comprises a solvent, and the solvent comprises at least one of mineral spirits No. 120, mineral spirits No. 160, and mineral spirits No. 260.
6. The method of claim 2, wherein the extractant comprises the following components: 5-40% vol of main extractant, 0.5-20% vol of phase modifier and 40-80% vol of solvent.
7. The method according to claim 1, wherein the step (1) is a back extraction with an alkali solution; preferably, the alkali liquor comprises at least one of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and ammonia water; preferably, the concentration of the alkali liquor is 0.1-10 mol/L.
8. The method of claim 1, wherein step (2) further comprises subjecting the raffinate to a deoiling treatment prior to the membrane separation.
9. The method according to claim 1, wherein the separation membrane used in the membrane separation in step (2) is an ultrafiltration membrane having a pore size of 1KD to 25 KD.
10. The method of claim 1, wherein the chemical oxidation process of step (3) is a wet chemical oxidation process or an electrochemical oxidation process.
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