CN111072206A - Method for treating acidic sewage - Google Patents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/62—Heavy metal compounds
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- 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
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
The invention discloses a method for treating acidic sewage, which specifically comprises the following steps: (1) preparing raw materials, adding the neutralized solution into acidic sewage, mixing to obtain a mixed solution, and controlling the pH of the mixed solution to be 2-2.5, wherein the neutralized solution is prepared from arsenic alkali residues; (2) adding an oxidant into the mixed solution for reaction, adding ferric sulfate until the mixture is completely reacted, and filtering to obtain an arsenic removal solution and filter residue A; (3) adding a vulcanizing agent into the arsenic removal solution to react completely, and filtering to obtain a sulfate solution and filter residue B; (4) adding ferric sulfate or ferrous sulfate into the sulfate solution, controlling the pH value of the solution to be 8-10, reacting till the solution is complete, and filtering to obtain sulfate filtrate and filter residue C. The method utilizes the arsenic-alkali residue to treat the acid-containing wastewater, simultaneously enriches valuable heavy metals, has low material cost, realizes the arsenic removal rate in the acid wastewater of more than 99 percent, realizes the utilization rate of the leaching solution of the arsenic-alkali residue of more than 99 percent, and realizes the recovery rate of the valuable heavy metals of more than 99 percent.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a method for treating acidic sewage.
Background
During pyrometallurgy of nonferrous metals, the acidic sewage generated by leaching has complex components, mainly comprises arsenic, mercury, cadmium, copper, zinc and other toxic and harmful ions and elements such as fluorine, chlorine, sulfur and the like, and because a large amount of acidic gas is dissolved into the acidic sewage, the sulfuric acid content in the acidic sewage reaches 100 g/L.
At present, the existing acidic sewage treatment at home and abroad mainly comprises a lime method, a lime and iron salt method, a vulcanization method, a pyrolusite method, ion exchange, electrodialysis, a permeable membrane treatment method, an iron oxide coating sand treatment method and the like. However, the method mainly aims at the standard-reaching discharge of the acidic sewage, and the sulfuric acid and valuable metals in the acidic sewage cannot be effectively recovered.
Meanwhile, antimony resources in China are very rich, a large amount of arsenic alkali slag is often generated in the industrial production of antimony smelting, the arsenic alkali slag is a product of adding alkali to remove arsenic in the refining process of crude antimony, wherein the mass percentages of antimony and arsenic are respectively 20% -40% and 3% -9%, and the total alkalinity is 20% -30%. Arsenic in the arsenic alkali residue exists in the form of soluble sodium arsenate, and is extremely toxic, and the arsenic alkali residue is also rich in a large amount of residual alkali, so that the arsenic alkali residue has serious pollution to the environment and is harmful to the survival safety of human beings.
At present, the treatment methods of arsenic alkali slag include a solidification landfill method, a pyrogenic process treatment and a wet process treatment. The wet method for treating the arsenic alkali residue is the most extensive field researched at present, and has the advantages of low cost, good effect, no secondary pollution and cyclic utilization of resources. At present, the harmless treatment of arsenic alkali slag in industry has the phenomenon of incomplete separation of sodium arsenate and sodium carbonate, and the sodium arsenate product which is subsequently recovered is difficult to sell and needs to be stabilized and solidified again. Therefore, the efficient and safe recovery of valuable antimony and arsenic stabilization from arsenic alkali residue are problems to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for treating acidic sewage, which can simultaneously realize the stabilization process of arsenic element in acid-containing wastewater and arsenic alkali residue and the enrichment process of valuable heavy metal in the acid-containing wastewater, achieve the excellent effect of treating waste by waste and obviously reduce the cost.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for treating acidic sewage specifically comprises the following steps:
(1) preparing raw materials, adding a neutralization solution into acidic sewage, mixing to obtain a mixed solution, controlling the pH of the mixed solution to be 2-2.5, and treating the neutralization solution with arsenic alkali residue;
(2) adding an oxidant into the mixed solution for reaction, adding ferric sulfate until the mixture is completely reacted, and filtering to obtain an arsenic removal solution and filter residue A;
(3) adding a vulcanizing agent into the arsenic removal solution to react completely, and filtering to obtain a sulfate solution and filter residue B;
(4) and adding ferric sulfate or ferrous sulfate into the sulfate solution, controlling the pH of the solution to be 8-10, reacting completely, and filtering to obtain sulfate filtrate and filter residue C.
The idea of the technical scheme is that the acid-containing wastewater can be treated by utilizing the hazardous waste generated by an antimony smelting plant by selecting the neutralization solution obtained by treating the arsenic alkali residue, so that the purpose of treating waste by waste is achieved, the material cost is low, the arsenic removal and stabilization rate in the acid wastewater and the arsenic alkali residue reaches more than 99%, the enrichment degree of valuable metals is high, a sulfate solution capable of being continuously utilized can be obtained, the zero emission of the wastewater is realized, the method is simple to operate, the treatment cost is low, and the method is suitable for large-scale sewage treatment.
Preferably, the method for preparing the neutralized solution in step (1) comprises the following steps:
(1) preparing raw materials, leaching the arsenic alkali residue with water, and filtering to obtain a leaching solution and filter residue D;
(2) adding an antimony removal agent into the leachate to react completely, and filtering to obtain a neutralized solution and filter residue E.
The design idea is that residual antimony metal in the arsenic alkaline residue can be enriched by leaching the arsenic alkaline residue, an alkaline leachate mainly containing sodium arsenate is obtained, and a product obtained after leaching can be directly used in the treatment process of acidic sewage, so that the utilization rate of the arsenic alkaline residue leachate reaches over 99 percent, and the purpose of treating waste by waste is realized.
Preferably, the leaching temperature is controlled to be 30-60 ℃. The design idea is that the leaching temperature is controlled to be 30-60 ℃, so that the dissolving speed of metal salts and residual alkali in the arsenic alkali residue can be increased, and the leaching efficiency is increased.
Preferably, in the technical scheme, the volume ratio of the water to the arsenic alkali residue is (3-6): 1. the design idea is that according to the content proportion of various substances in the arsenic alkali residue, the metal salts and residual alkali in the arsenic alkali residue can be completely dissolved by selecting a proper volume ratio of water to the arsenic alkali residue, so that the utilization rate of the leaching solution and the recovery rate of subsequent valuable metals are improved.
Preferably, the antimony removal agent is a hydrogen peroxide solution with the mass portion of 1.2% -2.0%. The idea of the design is that the hydrogen peroxide solution with the mass part of 1.2-2.0% is used for removing antimony, so that the antimony element has a good oxidation effect, and new impurity elements cannot be introduced into the system, thereby facilitating subsequent treatment.
Preferably, the method for treating acidic sewage further comprises a step of recovering the filter residue B, the filter residue D and the filter residue E. The idea of the design is that metal recovery treatment is carried out on the filter residue B, the filter residue D and the filter residue E, so that enriched metal antimony and valuable metals can be recovered, the recovery rate of the valuable heavy metals reaches over 99%, the enrichment rate of the valuable heavy metals is improved by over 6 times compared with that of the traditional acid sewage process, and the resource recycling is completed while the wastewater is treated.
Preferably, in the above technical scheme, the method for treating acidic wastewater further comprises a step of treating filter residue, wherein the step of treating filter residue comprises the following operations: and (3) dissolving the filter residue A and the filter residue C in the acidic sewage, controlling the pH value to be 1-1.5, adding ferric sulfate to react completely, filtering to obtain filtrate and scorodite, and returning the filtrate to the acidic sewage of the step (1) for continuous reaction.
Preferably, in the above technical solution, the method for treating acidic wastewater further comprises a sulfate filtrate treatment step, wherein the sulfate filtrate treatment step comprises the following operations: and (3) adjusting the pH value of the sulfate solution to 7 by using a sulfuric acid solution, evaporating and crystallizing to obtain sodium sulfate decahydrate and mother liquor, and returning the mother liquor to the arsenic removal solution obtained in the step (3) for continuous reaction. The idea of the design is that sodium sulfate decahydrate with certain market value can be obtained after the sulfate solution is subjected to evaporative crystallization treatment, and mother liquor obtained by evaporative crystallization is returned to the step (3) for continuous reaction, so that no wastewater discharge in the whole process can be realized, and the method is environment-friendly.
Preferably, in the step (2), the oxidant is hydrogen peroxide, and the molar ratio of the oxidant to the arsenic element in the mixed solution is (1.2-1.5): 1. the idea of the design is that hydrogen peroxide is used as an oxidant, so that the mixed solution is good in oxidation effect, no new impurity element is introduced, and the subsequent treatment is facilitated.
Preferably, in the step (2), the molar ratio of the ferric sulfate to the arsenic element in the solution is (1-2): 1. the design idea is that when the pH value is 2-2.5, trivalent iron reacts with arsenate radical to generate amorphous ferric arsenate, and the molar ratio of iron to arsenic is 1: 1, considering that ferric iron can generate a small amount of hydrous ferric oxide precipitate under the condition, the iron-arsenic ratio in the solution needs to be more than 1, otherwise, the arsenic precipitation is not complete; if the ratio of iron to arsenic is too large, iron salt is wasted, and consumption of a subsequent vulcanizing agent is increased. By limiting the molar ratio of ferric sulfate to arsenic to be (1-2): 1, the deposition effect on arsenic metal can be improved, and the recovery rate of arsenic metal is improved.
Preferably, in the step (3), the vulcanizing agent is sodium sulfide, the amount of the sodium sulfide is 1-1.2 times of the theoretical amount, and the vulcanization reaction time is 60-90 min.
Preferably, in the step (4), the molar ratio of the ferric sulfate or the ferrous sulfate to the arsenic element is (4-8): 1.
compared with the prior art, the invention has the advantages that: the process of the invention utilizes the hazardous waste arsenic-alkali slag generated by an antimony smelting plant to treat the acid-containing wastewater, has low material cost, simultaneously realizes the stabilization process of arsenic element in the acid-containing wastewater and the arsenic-alkali slag and the enrichment process of valuable heavy metal in the acid-containing wastewater, achieves the excellent effect of treating waste by waste, realizes zero discharge of wastewater, has high stability of scorodite waste residue of a final product, and has arsenic leaching toxicity lower than the leaching threshold value specified in the hazardous waste identification standard leaching toxicity identification (GB5085.3-2007)(5mg·L-1) And the stabilizing and curing treatment cost is saved. The process disclosed by the invention is used for treating the arsenic-containing waste residue and the acidic waste water, so that the removal and stabilization rate of arsenic in the acidic waste water and the arsenic-alkali residue reaches more than 99%, the utilization rate of the arsenic-alkali residue leachate reaches more than 99%, the recovery rate of valuable heavy metals reaches more than 99%, the enrichment rate of the valuable heavy metals is improved by more than 6 times compared with that of the traditional treatment process of the acidic waste water, the subsequent recovery of the valuable heavy metals is facilitated, and the comprehensive treatment cost is reduced by more than 50% compared with that of the prior treatment process.
Drawings
FIG. 1 is a flow chart of a method for treating acidic wastewater according to example 1.
Detailed Description
Example 1
The invention is described in further detail below with reference to the figures and specific examples.
As shown in fig. 1, in the method for treating acidic wastewater of this embodiment, the target to be treated is arsenic caustic sludge from an antimony smelting plant and acidic wastewater from a lead-zinc smelting plant, the main chemical components of the arsenic caustic sludge and the acidic wastewater are shown in tables 1 and 2, wherein the phase analysis of the arsenic caustic sludge is shown in table 3, and the method specifically includes the following steps:
(1) crushing arsenic alkali slag of an antimony smelting plant, adding hot water, stirring, leaching and filtering to obtain a leaching solution and a filter residue 1, wherein the leaching temperature is 40 ℃, and the solid-to-liquid ratio of the arsenic alkali slag to the hot water is 6: 1, leaching time is 40 min.
(2) Putting the leachate into a container, adding hydrogen peroxide under stirring, controlling the adding time of the hydrogen peroxide to be 20min and the oxidation reaction time to be 60min, and filtering to obtain a neutralized solution and filter residue 2.
(3) The acidic wastewater is put into a stirring tank and the neutralized solution is added until the pH value is 2. At this time, the arsenic content in the solution was measured to be 4.63 g/L. Adding hydrogen peroxide into the stirring tank for oxidation, wherein H2O2：As3+In a molar ratio of 1.2:1, reacting for 60min, adding ferric sulfate after oxidation to precipitate arsenic, wherein the molar ratio of ferric sulfate to arsenic is 1.2:1, the reaction time is 60min, and filtering to obtain an arsenic removal solution and filter residue 3. At this time, the arsenic content of the arsenic removing solution was measured to be 220mgAnd L, the combination of the table 3 shows that the removal rate of arsenic in the arsenic removal solution is 95%, compared with the traditional sulfuration-lime-iron salt process, the amount of the sulfuration slag in the process is reduced by more than 90%, the content of valuable heavy metals in the sulfuration slag is greatly increased, and the investment cost of subsequent valuable metal recovery equipment is reduced.
(4) And (4) adding sodium sulfide into the arsenic removal solution obtained in the step (3) at normal temperature, keeping stirring and reacting for 60min, and removing heavy metals and residual arsenic, wherein the use amount of the sodium sulfide is 1.1 times of the theoretical value. Filtering to obtain filter residue 4 rich in valuable heavy metals and a sodium sulfate solution. And recycling the filter residue 1, the filter residue 2 and the filter residue 4 to obtain the metal antimony and other valuable metals.
(5) Adding ferric sulfate into the sodium sulfate solution, wherein the molar ratio of the ferric sulfate to the arsenic is 7: 1, adjusting the pH value to 8 by using lime milk, sodium bicarbonate, sodium carbonate or sodium hydroxide, stirring for reacting for 60min to remove residual arsenic, and filtering to obtain filter residue 5 and sodium sulfate filtrate. At this time, the main impurity element components in the sodium sulfate filtrate are shown in table 4, it can be seen that the content of heavy metal impurities in the sodium sulfate filtrate obtained in this embodiment is low, and the produced anhydrous sodium sulfate product meets the standard requirements of GB/T6009-2014 industrial anhydrous sodium sulfate.
(6) And adding sulfuric acid into the sodium sulfate filtrate to adjust the pH value to 7, and evaporating and crystallizing to prepare sodium sulfate decahydrate. Drying the sodium sulfate decahydrate to obtain anhydrous sodium sulfate, recycling the evaporation condensate water, returning the evaporation mother liquor to the evaporation crystallization process, and periodically extracting part of the mother liquor to return to the vulcanization process in the step (4).
(7) Pouring the filter residue 3 and the filter residue 5 into a high-temperature reactor, adding a certain amount of acidic sewage, adjusting the pH value to 1.2 by using sulfuric acid, heating, stirring and dissolving, adding ferric sulfate, and controlling the molar ratio of iron to arsenic in the solution to be 1.2:1, heating to 95 ℃, and keeping the temperature for 12 hours. Filtering to obtain filtrate and scorodite after the reaction is finished, and returning the filtrate to the step (3); the leaching toxicity of scorodite was detected by a leaching toxicity identification method (TCLP), and the results are shown in table 5, which indicates that the arsenic residue (scorodite) produced in this example has good stability of arsenic, and the leaching toxicity of arsenic is lower than the leaching threshold (5 mg. L) specified in "hazardous waste identification standard leaching toxicity identification" (GB5085.3-2007)-1)。
TABLE 1 composition and content of main elements of acidic wastewater in example 1
TABLE 2 composition and content of main elements of As-soda residue in example 1
TABLE 3 arsenic caustic sludge phase analysis in example 1
| Physical phase | Arsenic oxide | Elemental arsenic | Arsenic sulfide | Arsenate salt |
| Arsenic content (%) | 4.19 | 0.0017 | 0.11 | 0.132 |
TABLE 4 composition and content of main impurity elements in sodium sulfate filtrate in step (5) of example 1
TABLE 5 leach toxicity test results for scorodite of example 1
| The concentration of the leaching solution is mg.L-1 | Standard value mg.L for leaching-1 |
| 1.42 | 5 |
Example 2
In the method for simultaneously treating arsenic-alkali slag and acidic sewage of this embodiment, the treated objects are arsenic-alkali slag of a certain antimony smelting plant and acidic sewage of a certain lead-zinc smelting plant, and the main chemical components of the arsenic-alkali slag and the acidic sewage are shown in tables 6 and 7, and the method specifically includes the following steps:
(1) crushing arsenic alkali slag of an antimony smelting plant, adding hot water, stirring, leaching and filtering to obtain a leaching solution and a filter residue 1, wherein the leaching temperature is 80 ℃, and the solid-to-liquid ratio is 4: 1, the leaching time is 2 hours.
(2) Putting the leachate into a container, adding hydrogen peroxide under stirring, controlling the adding time of the hydrogen peroxide to be 30min and the whole oxidation reaction time to be 90min, and filtering to obtain a neutralized solution and filter residue 2.
(3) The acidic wastewater is put into a stirring tank and the neutralized solution is added until the pH value is 2.5. Adding hydrogen peroxide into a stirring tank for oxidation, H2O2：As3+In a molar ratio of 1.4: 1, reacting for 90min, adding ferric sulfate after oxidation to precipitate arsenic, wherein the molar ratio of ferric sulfate to arsenic is 1.3: 1. The reaction time is 60min, and the arsenic removal solution and the filter residue 3 are obtained by filtration.
(4) And (4) adding sodium sulfide into the arsenic removal solution obtained in the step (3) at normal temperature, keeping stirring and reacting for 60min, and removing heavy metals and residual arsenic, wherein the use amount of the sodium sulfide is 1.2 times of the theoretical value. Filtering to obtain filter residue 4 rich in valuable heavy metals and a sodium sulfate solution. And recycling the filter residue 1, the filter residue 2 and the filter residue 4 to obtain the metal antimony and other valuable metals.
(5) Adding ferric sulfate into the sodium sulfate solution, wherein the molar ratio of the ferric sulfate to the arsenic is 8: 1, adjusting the pH value to 9 by using lime milk, sodium bicarbonate, sodium carbonate or sodium hydroxide, stirring for reacting for 60min to remove residual arsenic, and filtering to obtain filter residue 5 and sodium sulfate filtrate. At this time, the main impurity element components in the sodium sulfate filtrate are shown in table 8, it can be seen that the content of heavy metal impurities in the sodium sulfate filtrate obtained in this embodiment is low, and the produced anhydrous sodium sulfate product meets the standard requirements of GB/T6009-2014 industrial anhydrous sodium sulfate.
(6) And adding sulfuric acid into the sodium sulfate filtrate to adjust the pH value to 7, and evaporating and crystallizing to prepare sodium sulfate decahydrate. Drying the sodium sulfate decahydrate to obtain anhydrous sodium sulfate, recycling the evaporation condensate water, returning the evaporation mother liquor to the evaporation crystallization process, and periodically extracting part of the mother liquor to return to the vulcanization process in the step (4).
(7) Pouring the filter residue 3 and the filter residue 5 into a high-temperature reactor, adding a certain amount of acidic sewage, adjusting the pH value to 1.5 by using sulfuric acid, heating, stirring and dissolving, adding ferric sulfate, and controlling the molar ratio of iron to arsenic in the solution to be 1: 1, heating to 95 ℃, and preserving heat for 10 hours. Filtering to obtain filtrate and scorodite after the reaction is finished, and returning the filtrate to the step (3); the leaching toxicity of scorodite was detected by a leaching toxicity identification method (TCLP), and the results are shown in table 5, which indicates that the arsenic residue (scorodite) produced in this example has good stability of arsenic, and the leaching toxicity of arsenic is lower than the leaching threshold (5 mg. L) specified in "hazardous waste identification standard leaching toxicity identification" (GB5085.3-2007)-1)。
TABLE 6 composition and content of main elements of acidic wastewater in example 2
TABLE 7 composition and content of main elements of As-soda residue in example 2
TABLE 8 leach toxicity test results for scorodite of example 2
| The concentration of the leaching solution is mg.L-1 | Standard value mg.L for leaching-1 |
| 1.38 | 5 |
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. The method for treating the acidic sewage is characterized by comprising the following steps:
(1) preparing raw materials, adding the neutralized solution into acidic sewage, mixing to obtain a mixed solution, and controlling the pH of the mixed solution to be 2-2.5; the neutralization solution is obtained by treating arsenic alkali residue;
(2) adding an oxidant and ferric sulfate into the mixed solution to react completely, and filtering to obtain an arsenic removal solution and filter residue A;
(3) adding a vulcanizing agent into the arsenic removal solution to react completely, and filtering to obtain a sulfate solution and filter residue B;
(4) and adding ferric sulfate or ferrous sulfate into the sulfate solution, controlling the pH of the solution to be 8-10, reacting completely, and filtering to obtain sulfate filtrate and filter residue C.
2. The method for treating acidic sewage according to claim 1, wherein the method for preparing the neutralized solution in step (1) comprises the steps of:
(1) preparing raw materials, leaching the arsenic alkali residue with water and filtering to obtain leachate and filter residue D;
(2) adding an antimony removal agent into the leachate to react completely, and filtering to obtain a neutralized solution and filter residue E.
3. The method for treating acidic wastewater according to claim 2, wherein the leaching temperature of the arsenic-alkali residue is 30 to 60 ℃.
4. The method for treating acidic wastewater according to claim 2, wherein the volume ratio of the water to the arsenic alkali residue is (3-6): 1.
5. the method for treating acidic sewage according to claim 2, wherein the antimony removing agent is a hydrogen peroxide solution with a mass fraction of 1.2-2.0%.
6. The method for treating acidic sewage according to claim 2, further comprising the step of recovering residue B, residue D and residue E.
7. The method for treating acidic sewage according to claim 1, further comprising the step of treating filter residue, wherein the step of treating filter residue comprises: and (3) dissolving the filter residue A and the filter residue C in the acidic sewage, controlling the pH value to be 1-1.5, adding ferric sulfate to react completely, filtering to obtain filtrate and scorodite, and returning the filtrate to the acidic sewage in the step (1) for continuous reaction.
8. The method of treating acidic wastewater according to claim 1, further comprising the step of treating a sulfate filtrate, wherein the step of treating the sulfate filtrate comprises the operations of: and (4) adjusting the pH of the sulfate filtrate to 7 by using a sulfuric acid solution, evaporating and crystallizing to obtain sodium sulfate decahydrate and mother liquor, and returning the mother liquor to the arsenic removal solution obtained in the step (3) for continuous reaction.
9. The method for treating acidic sewage according to claims 1 to 8, wherein an oxidant in the step (2) is hydrogen peroxide, and the molar ratio of the oxidant to arsenic in the mixed solution is (1.2-1.5): 1.
10. the method for treating acidic wastewater according to claim 1-8, wherein the molar ratio of ferric sulfate to arsenic in the solution in the step (2) is (1-2): 1.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014208338A (en) * | 2013-03-29 | 2014-11-06 | 三菱マテリアル株式会社 | Method for separating and immobilizing arsenic |
| CN104818387A (en) * | 2015-04-22 | 2015-08-05 | 南昌航空大学 | Method for separating and purifying sodium salts in arsenic alkali residue |
| CN105858958A (en) * | 2016-04-28 | 2016-08-17 | 湖南浩美安全环保科技有限公司 | Arsenic-antimony-cyanogen-containing mine wastewater treatment method |
| CN106865827A (en) * | 2017-03-31 | 2017-06-20 | 湖南求是检测科技有限公司 | Sewage water treatment method and processing system |
| CN107459166A (en) * | 2017-08-15 | 2017-12-12 | 昆明理工大学 | The curing of sour recycling and arsenic in a kind of waste acid |
| CN108441642A (en) * | 2018-04-08 | 2018-08-24 | 郴州钖涛环保科技有限公司 | The wet method recycling and harmless treatment process of antimony smelting arsenic alkali slag |
| CN108588428A (en) * | 2018-05-16 | 2018-09-28 | 中南大学 | The electrochemical method of arsenic and alkali in a kind of separation arsenic alkaline slag |
| US20190023585A1 (en) * | 2015-12-28 | 2019-01-24 | Central South University | Method and apparatus for the recovery and deep treatment of polluted acid |
| CN109913659A (en) * | 2019-02-27 | 2019-06-21 | 郴州钖涛环保科技有限公司 | A kind of method of antimony smelting arsenic alkali slag and flue gas during smelting comprehensive treatment |
-
2019
- 2019-12-16 CN CN201911295166.XA patent/CN111072206B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014208338A (en) * | 2013-03-29 | 2014-11-06 | 三菱マテリアル株式会社 | Method for separating and immobilizing arsenic |
| CN104818387A (en) * | 2015-04-22 | 2015-08-05 | 南昌航空大学 | Method for separating and purifying sodium salts in arsenic alkali residue |
| US20190023585A1 (en) * | 2015-12-28 | 2019-01-24 | Central South University | Method and apparatus for the recovery and deep treatment of polluted acid |
| CN105858958A (en) * | 2016-04-28 | 2016-08-17 | 湖南浩美安全环保科技有限公司 | Arsenic-antimony-cyanogen-containing mine wastewater treatment method |
| CN106865827A (en) * | 2017-03-31 | 2017-06-20 | 湖南求是检测科技有限公司 | Sewage water treatment method and processing system |
| CN107459166A (en) * | 2017-08-15 | 2017-12-12 | 昆明理工大学 | The curing of sour recycling and arsenic in a kind of waste acid |
| CN108441642A (en) * | 2018-04-08 | 2018-08-24 | 郴州钖涛环保科技有限公司 | The wet method recycling and harmless treatment process of antimony smelting arsenic alkali slag |
| CN108588428A (en) * | 2018-05-16 | 2018-09-28 | 中南大学 | The electrochemical method of arsenic and alkali in a kind of separation arsenic alkaline slag |
| CN109913659A (en) * | 2019-02-27 | 2019-06-21 | 郴州钖涛环保科技有限公司 | A kind of method of antimony smelting arsenic alkali slag and flue gas during smelting comprehensive treatment |
Non-Patent Citations (1)
| Title |
|---|
| 曾桂生等: "《砷碱渣中物质的结晶与分离》", 31 May 2016, 冶金工业出版社 * |
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