CN112624486A - Oxidation treatment process for arsenic-containing waste acid wastewater - Google Patents
Oxidation treatment process for arsenic-containing waste acid wastewater Download PDFInfo
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- CN112624486A CN112624486A CN202011500742.2A CN202011500742A CN112624486A CN 112624486 A CN112624486 A CN 112624486A CN 202011500742 A CN202011500742 A CN 202011500742A CN 112624486 A CN112624486 A CN 112624486A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
Abstract
The invention relates to an oxidation treatment process of arsenic-containing waste acid water, which comprises the steps of fixing arsenic by conventional ferric salt, precise filtration pretreatment and diaphragm electrochemical oxidation, namely, precise filtration is carried out on the waste acid water by precise filtration equipment, and filtrate enters a regulating tank; passing through a diaphragm electrolytic cell, wherein the electrolytic cell is divided into an anode chamber and a cathode chamber by a diaphragm, a soluble salt solution is contained in the cathode chamber, and the filtrate of an adjusting tank is pumped into the anode chamber; controlling certain current and liquid level of a diaphragm electrolytic cell through electrochemical oxidation to perform electrochemical oxidation of arsenic; neutralizing ferric salt to fix arsenic, neutralizing acid in the oxidized liquid with alkali, and fixing arsenic with ferric salt. The method has the advantages of capability of converting trivalent arsenic in the waste acid into pentavalent arsenic, simple and economic process flow, no introduction of other ions, great reduction of later-stage arsenic solidification cost, simple equipment structure, less investment, strong universality and the like, and is suitable for application in the metallurgical and chemical industry.
Description
Technical Field
The invention relates to an oxidation treatment process of arsenic-containing waste acid wastewater, which is suitable for application in the metallurgical and chemical industries.
Background
Arsenic is an element with high abundance on the earth, is a main associated pollutant in the smelting process of nonferrous and rare noble metals, and is one of main waste water harmful elements in modern chemical engineering. The existing arsenic-containing wastewater treatment technology is mainly a ferric salt solidification method, so that arsenic is converted into the most stable ferric arsenate form, and the release to the environment is reduced. The trivalent arsenic (III) needs to be oxidized to pentavalent arsenic (V) before it reacts with the iron salt. At present, common oxidants of trivalent arsenic mainly comprise air, oxygen, ozone, hydrogen peroxide and other chemical reagents, and obviously, the adopted chemical reagents have the defects of high cost, low oxidation efficiency, unstable indexes and the like.
In order to solve the problems, some adopt a chemical oxidation method to oxidize low-valence arsenic, for example, Chinese patent CN105417767B discloses a method for removing arsenic from sulfuric acid waste acid wastewater, the method adopts lime milk suspension to precipitate and directly remove arsenic, no effective oxidation is carried out on arsenic, and the generated calcium arsenate has poor stability and great harm to the environment; for another example, chinese patent CN102992505B discloses a "method for treating high-arsenic waste acid wastewater", in which sodium sulfide is used to precipitate arsenic in the wastewater in the form of arsenic sulfide, which has low secondary utilization value and is hazardous waste, and even if secondary reprocessing is performed, the problems of increased cost and risk are also present; for example, Chinese patent CN105347544A discloses a method for precipitating and separating arsenic from waste acid wastewater, which adopts hot air to oxidize arsenic, and has the problems of low oxidation efficiency and poor feasibility of implementation; for another example, chinese patent CN111018229A discloses "a method for utilizing sulfuric acid waste acid wastewater resources from copper smelting and obtaining arsenic-containing products", in which trivalent arsenic is oxidized by air and hydrogen peroxide respectively, and the chemical oxidation method has high efficiency but high oxidation cost.
Therefore, the research and development of the oxidation treatment process of the arsenic-containing waste acid wastewater is very urgent and has great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an oxidation treatment process of arsenic-containing waste acid wastewater, can effectively solve the problem of high cost of oxidation treatment of arsenic in arsenic-containing waste acid in the production process of non-ferrous metal smelting industry, and also provides an oxidation technology of arsenic which is more environment-friendly and has high cost performance.
The task of the invention is completed by the following technical scheme:
the oxidation treatment process of arsenic-containing waste acid wastewater comprises the steps of fixing arsenic by conventional ferric salt, precise filtration pretreatment and diaphragm electrochemical oxidation, and comprises the following specific process steps and conditions:
A. performing precision filtration, namely performing precision filtration on the waste acid and wastewater through precision filtration equipment, and enabling filtrate to enter an adjusting tank;
B. the electrolytic cell is divided into an anode chamber and a cathode chamber by a diaphragm, a soluble salt solution is contained in the cathode chamber, and the filtrate of the regulating tank is pumped into the anode chamber;
C. electrochemical oxidation, namely controlling certain current and liquid level of the diaphragm electrolytic cell to perform electrochemical oxidation of arsenic;
D. neutralizing iron salt to fix arsenic, neutralizing acid in the oxidized liquid with alkali, and fixing arsenic with iron salt.
The percentages referred to in the description are percentages by mass, PVDF means polyvinylidene fluoride and SS means suspended matter.
The invention has the following advantages or effects:
(1) the green and efficient conversion of trivalent arsenic in the waste acid into pentavalent arsenic is realized.
(2) The process flow is simple and economic, other ions are not introduced, and the curing cost of the arsenic in the later period is greatly reduced.
(3) The equipment has simple structure, less investment and strong applicability.
(4) The universality is strong, and the method is also applicable to the safe solidification containing trivalent arsenic generated in the industries such as chemical engineering and the like besides the treatment of waste acid generated in the smelting process of copper, lead and zinc metals.
Drawings
FIG. 1 is a process flow diagram of an oxidation treatment process of arsenic-containing waste acid wastewater according to the invention.
FIG. 2 is a schematic diagram of an electrolytic bath structure of an oxidation treatment process of arsenic-containing waste acid wastewater according to the invention.
The description is described in further detail below with reference to the accompanying drawings.
Detailed Description
As shown in figures 1 and 2, the oxidation treatment process of arsenic-containing waste acid wastewater comprises the steps of conventional iron salt arsenic fixation, and is characterized by further comprising the steps of precise filtration pretreatment and membrane electrochemical oxidation, wherein the specific process steps and conditions are as follows:
A. performing precision filtration, namely performing precision filtration on the waste acid and wastewater through precision filtration equipment, and enabling filtrate to enter an adjusting tank;
B. the electrolytic cell is divided into an anode chamber and a cathode chamber by a diaphragm, a soluble salt solution is contained in the cathode chamber, and the filtrate of the regulating tank is pumped into the anode chamber;
C. electrochemical oxidation, namely controlling certain current and liquid level of the diaphragm electrolytic cell to perform electrochemical oxidation of arsenic;
D. neutralizing iron salt to fix arsenic, neutralizing acid in the oxidized liquid with alkali, and fixing arsenic with iron salt.
The process of the invention may further be:
and the aperture of the micropores of the precision filtering equipment in the step A is 0.1-0.5 mu m.
The step A of the precision filtration equipment comprises any one of a ceramic membrane, a PVDF ultrafiltration membrane and a disc tube membrane.
The SS content in the filtrate obtained in the step A is less than 10 mg/L.
The diaphragm of the electrolytic cell in the step B is any one of an anion diaphragm, an asbestos diaphragm and a PP microporous membrane.
And the anode and the cathode of the electrolytic cell in the step B are plate-shaped or porous reticular electrodes.
The step B is characterized in that the anode coating of the electrolytic cell is a mixture of titanium suboxide, graphene, ruthenium and iridium, and the coating comprises 75.0-85.0% of titanium suboxide, 5.0-10.0% of graphene and ruthenium: 1.0-5.0%, iridium: 1.0 to 5.0 percent.
The anode material of the electrolytic cell in the step B is a titanium-based anode, and the thickness of the coating is 1.5-10.0 mu m; the cathode is a titanium cathode or a stainless steel cathode.
And the soluble salt in the step B is any one or more of sodium chloride, sodium sulfate and sodium nitrate, and the mass concentration is 100-300 g/L.
The working current density of the anode in the step B is 50-500A/m2。
And the temperature of the electrolytic system in the step B is 40-80 ℃.
And the step B electrolytic tank adopts mechanical stirring or gas-filled stirring, and a high-level tank or forced circulation mode to mix the electrolyte.
And B, the liquid level of the cathode of the diaphragm electrolytic cell is 0.5-3.0 cm higher than that of the anode.
And B, the electrolytic retention time of the filtrate in the anode chamber in the step B is 0.5-10 h.
And C, the oxidation rate of the arsenic of the anode in the step C is 95-99%.
And D, the pH value of the acid neutralization end point in the step D is 2.0-2.5.
And D, the neutralizing agent in the step D is any one of calcium oxide, calcium hydroxide and limestone, the neutralizing slag is gypsum, and the gypsum can be sold after being washed.
And D, the iron salt in the step D is various iron salts sold in the market or iron-containing tailings and iron-containing solid waste residues generated in the selection and smelting process.
The following further describes embodiments of the present invention with reference to specific examples and comparative examples.
Example 1
The arsenic content in copper concentrate in a certain copper smelting plant in northern China is 0.45 percent, and in waste acid generated in the smelting process, the content of sulfuric acid is 108g/L, the total arsenic is 10.2g/L, the content of trivalent arsenic is 8.6g/L, the content of SS is 50.6mg/L, and the conductivity is 126.5ms/cm. The water is filtered by a PVDF precise filter membrane and then is introduced into an anode chamber of an anion diaphragm electrolytic cell, and a cathode chamber of the electrolytic cell is 150g/L of sodium chloride solution; the current density of the cathode liquid level is 250A/m higher than that of the anode liquid level by 1.0cm2And the retention time is controlled to be 2.5 h. After the anodic oxidation, the solution is neutralized by limestone and then enters the traditional ferric salt solidification process. The arsenic concentration in the solidified solid waste residue toxic leaching solution is 0.2mg/L, which is lower than 5mg/L required by national hazardous waste identification standard.
Example 2
Arsenic content in copper gold ore in Fujian copper smelting plant is 0.68%, and in waste acid generated in the smelting process, sulfuric acid: 95g/L, total arsenic 12.2g/L, trivalent arsenic 9.3g/L, SS120.6mg/L, conductivity 136.5 ms/cm. After the water is precisely filtered by a ceramic membrane, introducing the water into an anode chamber of a PP diaphragm electrolytic cell, wherein a cathode chamber of the electrolytic cell is 180g/L of sodium sulfate solution; the current density of the cathode liquid level is 350A/m and is 2.5cm higher than that of the anode liquid level2And the retention time is controlled to be 3.5 h. After the anodic oxidation, the solution is neutralized by calcium oxide and then enters the traditional iron salt curing process. The arsenic concentration in the solidified solid waste residue toxic leaching solution is 1.5mg/L, which is lower than 5mg/L required by national hazardous waste identification standard.
Example 3
Arsenic content in a lead-zinc ore smelting plant of Guangdong is 0.3%, and in waste acid generated in the smelting process, sulfuric acid: 98g/L, 9.2g/L of total arsenic, 7.1g/L of trivalent arsenic, SS150.6mg/L and 106.5ms/cm of conductivity. After the water is subjected to precise filtration by a ceramic membrane, introducing the water into an anode chamber of an anion diaphragm electrolytic cell, wherein the cathode chamber of the electrolytic cell is 200g/L of sodium nitrate solution; the current density of the cathode liquid level is 250A/m when the cathode liquid level is 2.0cm higher than the anode liquid level2The retention time is controlled to be 1.5 h. After the anodic oxidation, the solution is neutralized by limestone and then enters the traditional ferric salt solidification process. The arsenic concentration in the solidified solid waste residue toxic leaching solution is 1.5mg/L, which is lower than 5mg/L required by national hazardous waste identification standard.
Comparative example
The trivalent arsenic content in the wastewater from Henan enterprises is 15.5g/L, and compared with the conventional oxidation treatment process by using hydrogen peroxide or calcium hypochlorite, the respective technical and economic indexes are shown in Table 1.
Table 1: comparison of different treatment process indexes
As can be seen from the above examples and comparative examples, the present invention has the advantages of low labor intensity, low treatment cost, no slag and no introduction of impurity ions.
As described above, the present invention can be preferably realized. The above embodiments are only preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Claims (18)
1. The oxidation treatment process of arsenic-containing waste acid wastewater comprises conventional ferric salt for fixing arsenic, and is characterized by further comprising precise filtration pretreatment and diaphragm electrochemical oxidation, wherein the specific process steps and conditions are as follows:
A. performing precision filtration, namely performing precision filtration on the waste acid and wastewater through precision filtration equipment, and enabling filtrate to enter an adjusting tank;
B. the electrolytic cell is divided into an anode chamber and a cathode chamber by a diaphragm, a soluble salt solution is contained in the cathode chamber, and the filtrate of the regulating tank is pumped into the anode chamber;
C. electrochemical oxidation, namely controlling certain current and liquid level of the diaphragm electrolytic cell to perform electrochemical oxidation of arsenic;
D. neutralizing iron salt to fix arsenic, neutralizing acid in the oxidized liquid with alkali, and fixing arsenic with iron salt.
2. The process as claimed in claim 1, wherein the fine filtering device of step A has a pore size of 0.1-0.5 μm.
3. The process as claimed in claim 1 or 2, wherein the step a microfiltration apparatus comprises any one of a ceramic membrane, a PVDF ultrafiltration membrane, and a disc tube membrane.
4. The process as set forth in claim 1, characterized in that the SS content of the filtrate from step A is less than 10 mg/L.
5. The process as set forth in claim 1, wherein the step B electrolytic bath diaphragm is any one of anion diaphragm, asbestos diaphragm and PP microporous membrane.
6. The process as claimed in claim 1, wherein the anodes and cathodes of the electrolytic cells in step B are plate-shaped or porous reticular electrodes.
7. The process as claimed in claim 1 or 6, wherein the anode coating of the electrolytic cell in the step B is a mixture of titanium suboxide, graphene, ruthenium and iridium, and the coating comprises 75.0-85.0% of titanium suboxide, 5.0-10.0% of graphene, ruthenium: 1.0-5.0%, iridium: 1.0 to 5.0 percent.
8. The process as claimed in claim 1 or 6, wherein the anode material of the electrolytic cell in the step B is a titanium-based anode, and the thickness of the coating is 1.5-10.0 μm; the cathode is a titanium cathode or a stainless steel cathode.
9. The process as claimed in claim 1, wherein the soluble salt in step B is one or more of sodium chloride, sodium sulfate and sodium nitrate, and the mass concentration is 100-300 g/L.
10. The process as claimed in claim 1, wherein the working current density of the anode in step B is 50-500A/m2。
11. The process as claimed in claim 1, wherein the temperature of the electrolysis system in step B is 40-80 ℃.
12. The process as claimed in claim 1, wherein the step B electrolytic bath is mixed by mechanical stirring or pneumatic stirring, an elevated tank or forced circulation.
13. The process as claimed in claim 1, wherein the cathode liquid level of the diaphragm electrolyzer in the step B is 0.5-3.0 cm higher than the anode liquid level.
14. The process as claimed in claim 1, wherein the electrolytic residence time of the filtrate in the anode chamber in the step B is 0.5-10 h.
15. The process as claimed in claim 1 or 14, wherein the arsenic oxidation rate of the anode in step C is 95-99%.
16. The process as set forth in claim 1, characterized in that the step D acid neutralization end point pH is 2.0 to 2.5.
17. The process as set forth in claim 1, wherein the neutralizing agent in the step D is any one of calcium oxide, calcium hydroxide and limestone, and the neutralized slag is gypsum which can be sold after washing.
18. The process as claimed in claim 1, wherein the iron salt in step D is various iron salts sold in the market or iron-containing tailings and iron-containing solid waste residues produced in the dressing and smelting process.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114059077A (en) * | 2021-10-27 | 2022-02-18 | 湖南有色金属研究院有限责任公司 | Arsenic filter cake treatment method |
| CN115069747A (en) * | 2022-06-07 | 2022-09-20 | 湖北中和联信环保股份有限公司 | Treatment process of arsenic-containing waste salt |
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Cited By (3)
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