A method for treating acid high-salt tungsten residue wastewater and recovering heavy metals and organic matters

Abstract

The application provides a method for treating acid high-salt tungsten residue wastewater and recycling heavy metals and organic matters, which comprises four steps of precipitation, primary adsorption, secondary adsorption and oxidative deamination. First, ammonium oxalate is added into the tungsten residue wastewater to obtain intermediate effluent I and iron oxalate precipitate; then the intermediate effluent I is passed through a silver-copper exchange resin column to remove silver and copper in the wastewater, and intermediate effluent II is obtained; then the intermediate effluent II is passed through an organic matter exchange resin column to remove organic matters in the wastewater, and intermediate effluent III is obtained; finally, alkali is added into the intermediate effluent III to adjust the pH value to alkaline, an ammonia nitrogen remover is added, and aeration reaction is carried out; after the reaction is completed, PAM coagulant aid is added, and the mixture is statically deposited to obtain sludge and final effluent, and ammonia nitrogen in the wastewater is effectively removed. The method effectively removes heavy metals, ammonia nitrogen, COD and other pollutants in the acid high-salt tungsten residue wastewater, realizes recycling of iron, silver, copper and organic extractant, saves resources and protects the environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of wastewater treatment, in particular, to a method for treating acidic high-salt tungsten slag wastewater and recovering heavy metals and organic matter. BACKGROUND

[0002] Tungsten slag wastewater is produced by further smelting slag produced after tungsten smelting to further extract useful metals. Tungsten slag smelting generally adopts pretreatment, acidolysis, silver extraction, tungsten extraction, scandium extraction, iron and manganese extraction and other treatment processes to recover tungsten and other useful metals. The produced wastewater still contains high concentrations of various useful metal substances, mainly including calcium, iron, silver, copper, nickel, manganese, extractant organic matter and the like. The metal substances contained therein still have important recycling value. The extractant contained therein is a reagent required in the tungsten slag smelting process and can be recycled and reused. Direct discharge of tungsten slag production wastewater will inevitably pollute the ecological environment and does not meet the discharge requirements. Therefore, the tungsten slag wastewater is treated to extract and recover heavy metals and extractant organic matter, which can realize resource recycling and effective treatment of wastewater and has important economic value and environmental protection value.

[0003] Tungsten slag wastewater is a strong acid wastewater containing high salt and ammonia nitrogen and is difficult to be directly treated by conventional biological methods. The present application optimizes the design according to the characteristics of various substances in the wastewater and provides an innovative and scientific tungsten slag wastewater treatment method, which provides a new idea for the treatment of tungsten slag wastewater. SUMMARY

[0004] The present application aims to provide a method for treating acidic high-salt tungsten slag wastewater and recovering heavy metals and organic matter to solve the technical problem that direct discharge of existing tungsten slag production wastewater will inevitably pollute the ecological environment and does not meet the discharge requirements. The present application treats tungsten slag wastewater to extract and recover heavy metals and extractant organic matter, which can realize resource recycling and effective treatment of wastewater.

[0005] To achieve the above-mentioned purpose, the present application provides a method for treating acidic high-salt tungsten slag wastewater and recovering heavy metals and organic matter, comprising the following steps:

[0006] S1: ammonium oxalate is added to the tungsten slag wastewater, stirred and reacted, and then settled and precipitated to obtain intermediate effluent one and iron oxalate precipitate;

[0007] S2: the intermediate effluent one obtained in step S1 is passed through a silver-copper exchange resin column to remove silver and copper in the wastewater, thereby obtaining intermediate effluent two;

[0008] S3: the intermediate effluent two obtained in step S2 is passed through an organic matter exchange resin column to remove organic matter in the wastewater, thereby obtaining intermediate effluent three;

[0009] S4: adding alkali to the intermediate effluent water obtained in step S3 to adjust the pH value, then adding an ammonia-nitrogen removal agent, and mixing and reacting by air aeration to remove ammonia-nitrogen in the wastewater; after the reaction is completed, adding a coagulant aid, uniformly stirring slowly, and then standing and precipitating to obtain final effluent water and sludge.

[0010] Further, in step S1, the mass ratio of the ammonium oxalate to the iron in the tungsten residue wastewater is 3-4:1, the stirring reaction time is 0.5-1.0 h, and the standing and precipitating time is 0.5-2.0 h.

[0011] Further, in step S2, the silver-copper exchange resin column is filled with gel-type strong acid cation exchange resin, the total exchange capacity is 1.0-3.0 mmol / mL of wet resin, the wet true density is 1.05-1.15 g / mL, the height-diameter ratio of the silver-copper exchange resin column is 3-6:1, and the running flow rate is 2-10 BV / h.

[0012] Further, after step S2, step S5 is further included: after the silver-copper exchange resin column is saturated with adsorption, a silver-copper eluent is injected into the silver-copper exchange resin column to regenerate the silver-copper exchange resin, the silver and copper ions adsorbed by the silver-copper exchange resin are transferred to the silver-copper eluent and discharged, and the regenerated silver-copper exchange resin is reused; elemental copper powder is added to the silver-copper eluent, stirred and reacted to obtain elemental silver and a copper-containing eluent, and the copper-containing eluent is electrolyzed to obtain elemental copper.

[0013] Further, in step S5, the silver-copper eluent is one or more of nitric acid, sulfuric acid, hydrofluoric acid and hydrochloric acid, and the concentration is 4%-15%; and the regeneration flow rate of the silver-copper exchange resin column is 1-4 BV / h.

[0014] Further, in step S3, the organic matter exchange resin column is filled with cross-linked polystyrene macroporous adsorption resin, the specific surface area is 200-1200 m2 / g, the porosity is 20%-50%, the average pore size is 10-50 nm, the wet true density is 1.05-1.15 g / mL, the height-diameter ratio of the organic matter exchange resin column is 3-6:1, and the running flow rate is 2-10 BV / h.

[0015] Further, after step S3, step S6 is further included: after the organic matter exchange resin column is saturated with adsorption, an organic matter eluent is injected into the organic matter exchange resin column to regenerate the organic matter exchange resin, the regeneration flow rate is 1-4 BV / h, the organic matter adsorbed by the organic matter exchange resin is transferred to the organic matter eluent and discharged, and the regenerated organic matter exchange resin is reused; the organic matter eluent is heated for rectification, the organic matter eluent is separated in the form of gas, collected and reused for the regeneration of the organic matter exchange resin, and the produced organic matter is recycled.

[0016] Further, in step S6, the organic matter desorption agent is methanol, and the distillation temperature is 70 DEG C.

[0017] Further, in step S4, the ammonia nitrogen removal agent is a powder formed by uniformly mixing 10% to 40% of an adsorbent, 30% to 60% of an oxidant and 20% to 45% of a coagulant, the dosing amount is 1 to 10 g / L, the adsorbent is one or more of struvite, diatomite, molecular sieve, activated carbon, activated alumina and zeolite, the coagulant is one or more of polyaluminum chloride, aluminum sulfate, ferric sulfate, ferric chloride, polyferric sulfate and polyacrylamide, and the oxidant is one or more of bleaching powder, sodium hypochlorite, calcium hypochlorite, potassium permanganate, potassium perchlorate, potassium chlorate, potassium ferrate, sodium persulfate and benzoyl peroxide; the aeration mixing reaction time is 1.0 to 4.0 h, and the standing precipitation time is 0.5 to 2.0 h.

[0018] Further, in step S4, the alkali is one or more of sodium hydroxide, ammonia water and lime, and the pH value is adjusted to a range of 9.0 to 12.0; the coagulant aid is polyacrylamide, and the dosing amount is 1 to 20 mg / L.

[0019] The method has the following beneficial effects:

[0020] 1. The method realizes the recovery of iron, silver, copper and organic matter in tungsten slag production wastewater and the effective treatment of the wastewater through the series connection of multiple processes.

[0021] 2. The tungsten slag production wastewater is an acidic high-salt wastewater, which is difficult to treat by conventional biological treatment methods, the method combines physical and chemical methods to achieve simple and effective treatment of the wastewater, the front process section does not need to adjust the pH value to realize the treatment and recovery of heavy metals and organic matter, the process flow is simple, and cost is saved.

[0022] 3. The method uses an ammonia nitrogen removal agent to remove ammonia nitrogen in the wastewater by oxidation and deamination, compared with the biological ammonia oxidation method, the method is suitable for high-salt wastewater treatment, reduces sludge production and saves electric energy.

[0023] In addition to the objects, features and advantages described above, the present application has other objects, features and advantages. The present application will be further described in detail below with reference to the drawings. BRIEF DESCRIPTION OF DRAWINGS

[0024] The accompanying drawings, which form a part of this application, are included to provide a further understanding of the application, and are incorporated in and constitute a part of this application. The embodiments illustrated in the drawings are provided to explain the present application and, do not limit the present application. In the drawings:

[0025] Figure 1 A flow chart of the overall process of the method for treating acid high-salinity tungsten slag wastewater and recovering heavy metals and organic matter according to the present application;

[0026] Figure 2 A flow chart of step S1 in the present application;

[0027] Figure 3 A flow chart of step S4 in the present application;

[0028] Figure 4 A flow chart of step S5 in the present application;

[0029] Figure 5 A flow chart of step S6 in the present application;

[0030] S1 - precipitation method; S2 - first-stage adsorption; S3 - second-stage adsorption; S4 - oxidative deamination; S5 - silver-copper exchange resin regeneration; S6 - organic matter exchange resin regeneration. DETAILED DESCRIPTION

[0031] The embodiments of the present application will be described in detail below with reference to the accompanying drawings, but the present application can be implemented in various different ways as defined and covered by the claims. In the embodiments, the specific techniques or conditions not mentioned are performed according to the techniques or conditions described in the literature in the art or according to the product manual. The reagents or instruments not mentioned by the manufacturer are all conventional products that can be obtained commercially.

[0032] Tungsten slag is a by-product generated in the process of smelting tungsten ore. After smelting, the discarded tungsten slag still contains a large amount of useful metals such as tungsten, copper, nickel, silver, manganese, iron, scandium, calcium, etc., and has recycling value. After recycling, the amount of waste can be reduced, the secondary pollution of solid waste and the environmental pollution problem of heavy metals can be reduced. In a typical tungsten slag smelting process, after the metal substances are refined by "acid leaching → pressure filtration → iron powder replacement of silver → N235 extraction of tungsten → P204 + TBP extraction of scandium → precipitation of manganese iron → removal of calcium chloride", production wastewater is generated. The wastewater is acidic, high-salinity, contains iron, manganese, silver, copper, nickel, calcium and other useful metal substances, contains ammonia nitrogen and extractant organic matter, and generally has a pH of 1-3, a salinity of 15%-18%, iron of 15000-20000 mg / L, silver of 10-50 mg / L, copper of 500-800 mg / L, ammonia nitrogen of 800-1000 mg / L, and TOC of 600-1000 mg / L.

[0033] Tungsten slag wastewater is a kind of wastewater with high salinity, poor biodegradability and high heavy metal content, which is difficult to be treated by ordinary biochemical treatment process, and the wastewater has the value of recovering heavy metals, the present application provides a tungsten slag wastewater treatment method, which combines physical method with chemical method, first removes iron in the wastewater by using precipitation method, then removes silver, copper and other valuable heavy metals and extractant organic matter in the wastewater by using multi-stage ion exchange method, and recovers the heavy metals and organic matter by resin regeneration, and removes ammonia nitrogen in the wastewater by oxidation and ammonia removal. The tungsten slag wastewater treated by the method can not only realize effective treatment of the wastewater, but also realize resource recovery of heavy metals and organic matter, and provides a new idea for tungsten slag wastewater treatment.

[0034] As shown in Figures 1 to 5 An acid high-salt tungsten slag wastewater treatment and heavy metal and organic matter recovery method, sequentially comprising four steps of precipitation method S1, primary adsorption S2, secondary adsorption S3 and oxidation and ammonia removal S4, and specifically as follows:

[0035] S1 precipitation method: ammonium oxalate is added to the tungsten slag wastewater, stirred and reacted, and after the reaction is completed, the intermediate effluent I and iron oxalate precipitate are obtained by standing and precipitating, the iron oxalate precipitate is discharged and recovered, and the iron in the wastewater is removed and recovered;

[0036] The reaction equation of iron ion Fe(III) in tungsten slag wastewater and ammonium oxalate is as follows:

[0037] 2Fe 3+ +3(NH4)2C2O4→6NH4 + +Fe2(C2O4)3(s)

[0038] Iron oxalate is difficult to dissolve in water and decomposes when heated to 100 DEG C, and the iron oxalate can be directly utilized or further treated to obtain elemental iron.

[0039] S2 primary adsorption: the intermediate effluent I is subjected to primary adsorption, after flowing through a silver-copper exchange resin column, silver and copper in the wastewater are removed by ion exchange and adsorbed to the silver-copper exchange resin column, and the intermediate effluent II is obtained. After the silver-copper exchange resin column is saturated, S5 silver-copper exchange resin column regeneration is performed.

[0040] S3 secondary adsorption: the intermediate effluent II is subjected to secondary adsorption, after flowing through an organic matter exchange resin column, organic matter in the wastewater is removed by being adsorbed to the organic matter exchange resin column, and the intermediate effluent III is obtained; after the organic matter exchange resin column is saturated, S6 organic matter exchange resin column regeneration is performed.

[0041] S4 Oxidative deamination: first add base to adjust the pH value of the intermediate effluent, then add ammonia nitrogen removal agent, and mix the reaction by aeration with air to remove ammonia nitrogen in the wastewater. After the reaction is completed, add a certain amount of polyacrylamide, slowly stir and mix evenly, strengthen coagulation, then stand and precipitate to obtain the final effluent and sludge.

[0042] S5 Silver-copper exchange resin regeneration: after the silver-copper exchange resin column is saturated with adsorption, silver-copper eluent is injected into the silver-copper exchange resin column to regenerate the silver-copper exchange resin. The silver and copper ions adsorbed by the silver-copper exchange resin are transferred to the silver-copper eluent and discharged. The regenerated silver-copper exchange resin is reused. Elemental copper powder is added to the silver-copper eluent, and the mixture is stirred to react. A displacement reaction occurs, and elemental silver and copper-containing eluent are obtained after the silver ions are displaced. The copper-containing eluent is then electrolyzed to obtain elemental copper, which is recycled. The silver-copper eluent is one or more of nitric acid, sulfuric acid, hydrofluoric acid, and hydrochloric acid, with a concentration of 4% to 15%. The regeneration flow rate of the silver-copper exchange resin column is 1 to 4 BV / h.

[0043] The reaction of copper displacing silver is as follows:

[0044] Cu(s) + Ag + → Cu 2+ + Ag(s)

[0045] S6 Organic matter exchange resin regeneration: after the organic matter exchange resin column is saturated with adsorption, organic matter eluent is injected into the organic matter exchange resin column to regenerate the organic matter exchange resin. The regeneration flow rate is 1 to 4 BV / h. The organic matter adsorbed by the organic matter exchange resin is transferred to the organic matter eluent and discharged. The regenerated organic matter exchange resin is reused. The organic matter eluent is heated to a certain temperature for rectification. The organic matter eluent is separated in the form of gas and collected for reuse in the regeneration of the organic matter exchange resin. The produced organic matter is recycled. The organic matter eluent is methanol. The rectification temperature is 70°C.

[0046] Further, in step S1, the mass ratio of ammonium oxalate to iron in the tungsten slag wastewater is 3 to 4:1, the stirring reaction time is 0.5 to 1.0 h, and the standing and precipitating time is 0.5 to 2.0 h.

[0047] Further, in step S2, the silver-copper exchange resin column is filled with gel-type strong acid cation exchange resin. The total exchange capacity is 1.0 to 3.0 mmol / mL of wet resin, and the wet true density is 1.05 to 1.15 g / mL. The height-to-diameter ratio of the silver-copper exchange resin column is 3 to 6:1, and the operating flow rate is 2 to 10 BV / h.

[0048] Further, in the step S3, the organic exchange resin column is filled with cross-linked polystyrene macroporous adsorption resin, with a specific surface area of 200-1200 m 2 / g, a porosity of 20-50%, an average pore size of 10-50 nm, a wet true density of 1.05-1.15 g / mL, a height-diameter ratio of the organic exchange resin column of 3-6:1, and a running flow rate of 2-10 BV / h.

[0049] Further, in the step S4, the base is one or more of sodium hydroxide, ammonia water, and lime, with a pH adjustment range of 9.0-12.0; the ammonia-nitrogen removal agent is a powder uniformly mixed from 10%-40% adsorbent, 30%-60% oxidant, and 20%-45% coagulant, with a dosage of 1-10 g / L; the adsorbent is one or more of struvite, diatomite, molecular sieve, activated carbon, activated alumina, and zeolite; the coagulant is one or more of polyaluminum chloride, aluminum sulfate, ferric sulfate, ferric chloride, polyferric sulfate, and polyacrylamide; the oxidant is one or more of bleaching powder, sodium hypochlorite, calcium hypochlorite, potassium permanganate, potassium perchlorate, potassium chlorate, potassium ferrate, sodium persulfate, and benzoyl peroxide; the aeration mixing reaction time is 1.0-4.0 h, and the standing precipitation time is 0.5-2.0 h; and the coagulant aid is polyacrylamide, with a dosage of 1-20 mg / L.

[0050] Example 1

[0051] Take 2 L of tungsten slag wastewater, add 120 g of ammonium oxalate, stir for 1 h, and stand for 30 min to obtain intermediate effluent one and iron oxalate precipitate.

[0052] Take 1 L of intermediate effluent one, slowly flow from top to bottom through the silver-copper exchange resin column to obtain intermediate effluent two, the silver-copper exchange resin column is filled with gel-type strong acid cation exchange resin, and the silver-copper exchange resin column is pretreated by acid washing, alkali washing, and water washing before initial use, with a diameter of 80 mm and a height of 240 mm.

[0053] Slowly flow the intermediate effluent two from top to bottom through the organic exchange resin column to obtain intermediate effluent three, the organic exchange resin column is filled with cross-linked polystyrene macroporous adsorption resin, and the organic exchange resin column is pretreated by acid washing, alkali washing, and water washing before initial use, with a diameter of 80 mm and a height of 240 mm.

[0054] Take 500 mL of intermediate effluent three, add 50% sodium hydroxide solution to adjust the pH to 10.0, add 2.0 g of ammonia-nitrogen removal agent, stir for 2 h, then add 0.5 mL of 1% polyacrylamide solution, slowly stir to mix uniformly, stand for 30 min, and take the supernatant to detect water quality.

[0055] The water quality of the example test is as follows:

[0056] Table 1 Test data of Example 1

[0057]

[0058]

[0059] The TOC of the raw water of the tungsten residue wastewater test of this example is 645 mg / L, the ammonia nitrogen is 836 mg / L, the organic matter (extractant) is 42 mg / L, the total iron is 17,000 mg / L, the total silver is 12.50 mg / L, the total copper is 473.75 mg / L, and the salinity is 15% to 18%. The salinity of the raw water is high, and it is difficult to treat high-salinity wastewater by conventional biological methods.

[0060] After being treated by the process, the organic matter concentration of the final effluent is <1 mg / L, the TOC is 98.2 mg / L, the total iron is 12 mg / L, the total silver is 0.19 mg / L, the total copper is 8.50 mg / L, and the ammonia nitrogen is 13 mg / L. One ton of wastewater can recover 17.0 kg of iron, 12.31 g of silver, 465.25 g of copper, and 546.8 g of organic matter (extractant).

[0061] Example 2

[0062] Take 1 L of tungsten residue wastewater, a total of 4 portions, and add 17 g, 34 g, 51 g, and 68 g of ammonium oxalate, respectively. Stir for 1 h, and let stand for 30 min to obtain intermediate effluent one and iron oxalate precipitate. Dry the iron oxalate precipitate at 80°C to constant weight. The measured data are as follows.

[0063] Table 2 Test data of Example 2

[0064]

[0065] This example shows that ammonium oxalate can effectively remove iron ions in tungsten residue wastewater, and the removal rate of iron ions can reach 99.57%. Iron oxalate is produced, which has recycling value.

[0066] Example 3

[0067] Take 2,500 mL of intermediate effluent three, and add 50% sodium hydroxide solution to adjust the pH to 10.0. Divide into 5 portions, each 500 mL, and add 0 g, 0.5 g, 1.0 g, 2.0 g, and 3.0 g of ammonia nitrogen removal agent, respectively. The ammonia nitrogen removal agent dosages are 0 g / L, 1.0 g / L, 2.0 g / L, 4.0 g / L, and 6.0 g / L, respectively. Stir for 2 h, then add 0.5 mL of 1% polyacrylamide solution, respectively, mix uniformly at a slow stirring speed, let stand for 30 min, and take the supernatant to detect the water quality.

[0068] Table 3 Test data of Example 3

[0069]

[0070] The embodiment shows that the ammonia nitrogen remover can effectively remove the ammonia nitrogen in the tungsten residue wastewater, and when the dosage of the ammonia nitrogen remover is 4.0 g / L, the removal rate of the ammonia nitrogen can reach 98.61%.

[0071] In summary, the application provides a method for treating acid high-salt tungsten residue wastewater and recycling heavy metals and organic matters, which comprises four steps of precipitation, primary adsorption, secondary adsorption and oxidative ammonia removal. Specifically, ammonium oxalate is added into the tungsten residue wastewater to obtain intermediate effluent I and iron oxalate precipitate; the intermediate effluent I is passed through a silver-copper exchange resin column to remove silver and copper in the wastewater and obtain intermediate effluent II; the intermediate effluent II is passed through an organic matter exchange resin column to remove organic matters in the wastewater and obtain intermediate effluent III; the intermediate effluent III is first added with alkali to adjust the pH value to alkaline, and then added with an ammonia nitrogen remover, and aerated and reacted, and after the reaction is completed, PAM coagulant aid is added, and the mixture is statically deposited to obtain sludge and final effluent, and the ammonia nitrogen in the wastewater is effectively removed. The application combines physical method and chemical method to effectively remove heavy metals, ammonia nitrogen, COD and other pollutants in the acid high-salt tungsten residue wastewater, realizes the recycling of iron, silver, copper and organic extractant, saves resources and protects the environment; at the same time, the wastewater is simply and effectively treated, the heavy metals and organic matters can be treated and recycled without adjusting the pH value in the front part of the process, the process flow is simple, and the cost is saved.

[0072] The above only describes the preferred embodiments of the application and is not used to limit the application. For those skilled in the art, the application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the application shall be included in the protection scope of the application.

Claims

1. A method for treating acidic high-salt tungsten residue wastewater and recovering heavy metals and organic matter, characterized in that, Includes the following steps: S1: Add ammonium oxalate to tungsten slag wastewater, stir to react, let stand to precipitate, and obtain intermediate effluent and ferric oxalate precipitate. S2: Pass the intermediate effluent obtained in step S1 through a silver-copper exchange resin column to remove silver and copper from the wastewater, and obtain intermediate effluent II. S3: Pass the intermediate effluent 2 obtained in step S2 through an organic matter exchange resin column to remove organic matter from the wastewater, and obtain intermediate effluent 3. S4: First, add alkali to the intermediate effluent obtained in step S3 to adjust the pH value, then add ammonia nitrogen removal agent, and introduce air to aerate and react to remove ammonia nitrogen from the wastewater; after the reaction is completed, add coagulant aid, stir slowly and evenly, and then let it stand to settle to obtain the final effluent and sludge. The tungsten slag wastewater is an acidic, high-salinity wastewater with a pH of 1-3, salinity of 15%-18%, iron content of 15000-20000 mg / L, silver content of 10-50 mg / L, copper content of 500-800 mg / L, ammonia nitrogen content of 800-1000 mg / L, TOC content of 600-1000 mg / L, and organic extractant. In step S1, the mass ratio of ammonium oxalate to iron in the tungsten slag wastewater is 3-4:1, the stirring reaction time is 0.5-1.0 h, and the settling time is 0.5-2.0 h, generating ferric oxalate precipitate; the iron ion removal rate is as high as 99.57%; In step S2, the silver-copper exchange resin column is filled with gel-type strong acid cation exchange resin; in step S3, the organic exchange resin column is filled with cross-linked polystyrene macroporous adsorption resin. In step S4, the ammonia nitrogen removal agent is a powder uniformly mixed with 10%~40% adsorbent, 30%~60% oxidant, and 20%~45% coagulant, with a dosage of 1~10 g / L. The adsorbent is one or more of struvite, diatomaceous earth, molecular sieve, activated carbon, activated alumina, and zeolite. The coagulant is one or more of polyaluminum chloride, aluminum sulfate, ferric sulfate, ferric chloride, polyferric sulfate, and polyacrylamide. The oxidant is one or more of bleaching powder, sodium hypochlorite, calcium hypochlorite, potassium permanganate, potassium perchlorate, potassium perchlorate, potassium perferrate, sodium persulfate, and benzoyl peroxide. The aeration and mixing reaction time is 1.0~4.0 h, and the settling time is 0.5~2.0 h. The ammonia nitrogen removal rate is as high as 98.61%. Following step S2, step S5 is further included: after the silver-copper exchange resin column becomes saturated with adsorption, a silver-copper desorbent is injected into the column to regenerate the resin. The silver and copper ions adsorbed by the resin are transferred to a silver-copper desorption solution and discharged. The regenerated resin is then reused. Elemental copper powder is added to the desorption solution, and the mixture is stirred to obtain elemental silver and a copper-containing desorption solution. The copper-containing desorption solution is then electrolyzed to obtain elemental copper. The removal rate of silver ions is as high as 98.48%, and the removal rate of copper ions is as high as 98.21%. After step S3, step S6 is further included: after the organic matter exchange resin column is saturated, an organic matter desorption agent is injected into the organic matter exchange resin column to regenerate the organic matter exchange resin, the regeneration flow rate is 1-4 BV / h, the organic matter adsorbed by the organic matter exchange resin is transferred to the organic matter desorption liquid and discharged, and the organic matter exchange resin column is reused after regeneration; the organic matter desorption liquid is heated for rectification, the organic matter desorption agent is separated in the form of gas, and is collected and reused for regeneration of the organic matter exchange resin, and the generated organic matter is recycled; the removal rate of the organic matter is 97.62% or more.

2. The method for treating and recovering heavy metals and organic matters from acid high-salt tungsten residue wastewater according to claim 1, characterized in that, In step S2, the gel-type strong acid cation exchange resin has a full exchange capacity of 1.0-3.0 mmol / mL of wet resin and a wet true density of 1.05-1.15 g / mL, the silver-copper exchange resin column has a height-diameter ratio of 3-6:1, and the operation flow rate is 2-10 BV / h.

3. The method for treating and recovering heavy metals and organic matters from acid high-salt tungsten residue wastewater according to claim 1, characterized in that, In step S5, the silver-copper desorption agent uses one or more of nitric acid, sulfuric acid, hydrofluoric acid and hydrochloric acid, and the concentration is 4%-15%; the regeneration flow rate of the silver-copper exchange resin column is 1-4 BV / h.

4. The method for treating and recovering heavy metals and organic matters from acid high-salt tungsten residue wastewater according to claim 1, characterized in that, In step S3, the cross-linked polystyrene macroporous adsorption resin has a specific surface area of 200-1200 m 2 / g, a porosity of 20%-50%, an average pore size of 10-50 nm, a wet true density of 1.05-1.15 g / mL, the organic matter exchange resin column has a height-diameter ratio of 3-6:1, and an operating flow rate of 2-10 BV / h.

5. The method for treating and recovering heavy metals and organic matters from acid high-salt tungsten residue wastewater according to claim 1, characterized in that, In step S6, the organic matter desorption agent is methanol, and the rectification temperature is 70°C.

6. The method for treating and recovering heavy metals and organic matters from acid high-salt tungsten residue wastewater according to claim 1, characterized in that, In step S4, the alkali is one or more of sodium hydroxide, ammonia water and lime, and the pH value is adjusted to a range of 9.0-12.0; the coagulant aid is polyacrylamide, and the dosage is 1-20 mg / L.

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