CN109847256B - Ferric arsenate @ polymer arsenic fixation material, preparation method thereof and arsenic fixation method of arsenic-containing solution - Google Patents
Ferric arsenate @ polymer arsenic fixation material, preparation method thereof and arsenic fixation method of arsenic-containing solution Download PDFInfo
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Abstract
The invention belongs to the technical field of harmful waste treatment, and particularly discloses an iron arsenate @ polymer arsenic fixing material which comprises a core and a polymer coating the core, wherein the core is iron arsenate; the core is further preferably ferric arsenate coated with ferrous sulfide. The invention also provides a preparation method of the ferric arsenate @ polymer solid arsenic material and a method for preparing the ferric arsenate @ polymer solid arsenic material by adopting arsenic-containing wastewater. The invention discovers that the ferric arsenate @ polymer solid arsenic material with the core-shell structure has good stability, particularly stability under alkaline conditions, and is beneficial to reducing leaching toxicity.
Description
Technical Field
The invention belongs to the field of environmental management, and particularly relates to a method for treating an arsenic-containing solution.
Background
Arsenic is a toxic element, and is stably present in rock strata and soil mainly in the form of low-toxicity insoluble arsenates such as calcium, iron, manganese, aluminum and the like and sulfides such as realgar, orpiment, arsenopyrite and the like in crust. In the process of developing and utilizing mineral resources, the natural stable form of arsenic is damaged to release high-toxicity water-soluble arsenic, and particularly high-concentration arsenic-containing wastewater generated in the process of smelting non-ferrous metals becomes one of the main ways of releasing high-toxicity arsenic. In recent years, many regional arsenic poisoning events occur in areas with dense colored smelting industries such as Hunan, Guangxi, Guizhou, Yunnan and the like in China, and arsenic pollution becomes a sensitive problem of wide social attention. For the high-arsenic metallurgical wastewater, the treatment methods reported in the literature include a chemical precipitation method, an ion exchange method, an adsorption method, an extraction method, a biochemical method [ and the like ], but only the chemical precipitation method can be applied on an industrial scale at present. The basic principle of the chemical precipitation method is to convert high-toxicity arsenic in solution into low-toxicity insoluble arsenate, and return the low-toxicity insoluble arsenate to the nature through safe landfill. The chemical precipitation method requires that the insoluble arsenate precipitate has high arsenic removal efficiency, good arsenic fixation safety and the lower the cost, the better. According to national standards, the residual arsenic concentration in the water solution after arsenic removal is required to be reduced to 50 micrograms per liter in the aspect of arsenic removal efficiency, and the arsenic fixing safety is evaluated by a toxicity leaching experiment (TCLP), and the arsenic concentration in the leaching solution is required to be less than 5 milligrams per liter.
At present, only two types of insoluble arsenates, namely calcium arsenate and ferric arsenate, can better meet the requirements. The arsenic removing process of calcium arsenate and ferric arsenate is basically similar, and by adding a ferric salt precipitator such As lime or ferric sulfate according to a certain Ca/As ratio or Fe/As ratio, and adding a neutralizing agent to adjust the pH value, the insoluble calcium arsenate and ferric arsenate precipitates can be obtained. As for arsenic-containing wastewater with high acid concentration, lime is used as a neutralizing agent, and the generated calcium arsenate is used for fixing arsenic, which is a commonly used method for enterprises at present, but the CaS0 in the water solution after arsenic removal4The content is high, and the subsequent treatment is very troublesome. Generally, the comprehensive operation cost of removing arsenic by calcium arsenate is lower than that of ferric arsenate, but the ferric arsenate has obvious advantages in the aspects of high efficiency of removing arsenic and safety of fixing arsenic. Solubility of ferric arsenate in Water (AB type insoluble electrolyte, solubility product 10)-21～10-24About 10 solubility-nmol.L-4 ratio of calcium arsenate (A2B3 type insoluble electrolyte with solubility product of 10)—18～10—21Solubility about 10—5The mol.L < - > is smaller than 100 ten thousand times, and simultaneously calcium arsenate is contacted with carbon dioxide in the air to form calcium carbonate and water-soluble arsenic acid, so that the 'anti-dissolution phenomenon' of the arsenic is caused, and the problem of potential safety hazard exists. Because the popularization and application of ferric arsenate have cost obstacles, domestic metallurgical enterprises mostly prefer to select calcium arsenate with potential safety hazards for arsenic removal. While the ferric arsenate is removed to formThis is greatly reduced to a level equivalent to calcium arsenate, and it is necessary to reduce the consumption of the iron salt precipitant by at least half, that is, to reduce the Fe/As ratio from about 4 to within 2 from the technical viewpoint. Ferric arsenate has poor alkali resistance, and is easy to hydrolyze under alkaline conditions to generate ferrite hydrate, thereby causing arsenic 'redissolution' and influencing arsenic fixing effect.
Disclosure of Invention
Aiming at the defects of high arsenic fixation cost, poor arsenic fixation effect and the like of the existing arsenic fixation technology, the invention provides an iron arsenate @ polymer arsenic fixation material and aims to reduce the leaching toxicity of the arsenic fixation material.
The second objective of the invention is to provide a preparation method of the ferric arsenate @ polymer solid arsenic material for arsenic fixation with low cost and high efficiency, which can prepare the ferric arsenate @ polymer solid arsenic material with a core-shell structure with particularly good stability from arsenic in an arsenic-containing solution through a simple and low-cost process, so as to realize a method for arsenic fixation through one-step molding and realize permanent fixation of arsenic.
The third purpose of the invention is to provide an arsenic fixing method for converting arsenic in arsenic-containing wastewater into the ferric arsenate @ polymer arsenic fixing material by using the preparation method.
The ferric arsenate @ polymer solid arsenic material comprises a core and a polymer coating the core, wherein the core is ferric arsenate.
The invention discovers that the ferric arsenate @ polymer solid arsenic material with the core-shell structure has good stability, particularly stability under alkaline conditions, and is beneficial to reducing leaching toxicity.
Preferably, the core is ferric arsenate with a ferrous sulfide layer coated on the surface. The preferable material of the invention comprises ferric arsenate, a ferrous sulfide layer coated on the surface of the ferric arsenate and a polymer coated on the surface of the ferrous sulfide layer. The preferred material has been found to be less toxic to leaching and more stable.
Preferably, the ferric arsenate @ polymer solid arsenic material comprises a polymer substrate and a core embedded in the polymer substrate.
Preferably, the polymer is a hydrophilic polymer, and more preferably is polyvinyl alcohol; the molecular weight is preferably 1000 to 10000.
Preferably, the amount of the polymer is 1 to 10 percent by mass of ferric arsenate.
The invention also provides a preparation method of the ferric arsenate @ polymer solid arsenic material, which comprises the steps of dispersing the nuclear material in a polymer solution, and removing a solvent to obtain the ferric arsenate @ polymer solid arsenic material.
Preferably, the core is ferric arsenate, and ferric arsenate precipitate is obtained by arsenic fixation treatment of arsenic-containing solution.
Preferably, the arsenic fixing treatment step comprises: pre-adjusting the pH value of the arsenic-containing solution to be acidic, then adding ferrous salt and introducing oxygen-containing gas, stirring and reacting under a heating condition, and carrying out solid-liquid separation to obtain ferric arsenate precipitate.
Arsenic in the arsenic-containing solution is pentavalent arsenic; can be arsenic-containing waste water produced by metallurgical industry, or arsenic-containing leachate of arsenic-containing smoke dust and/or slag.
The method is generally suitable for various arsenic-containing smelting waste liquids, or arsenic-containing leachate of high-arsenic smoke dust generated in the smelting process of lead, zinc, antimony, copper, tin and the like and metallurgical waste materials such as high-arsenic anode mud generated in the electrolytic process of lead bullion, silver, copper and the like.
The method of the invention has no requirement on the arsenic content in the arsenic-containing solution. The arsenic content in the arsenic-containing solution is, for example, 5 to 50 g/l.
The key point of the technical scheme of the invention is that arsenic is converted into ferric arsenate with better stability, and a polymer layer is further generated on the surface of the ferric arsenate to protect the ferric arsenate, so that a special core-shell structure material is formed, the permanent fixation of arsenic in the arsenic-containing waste liquid or the arsenic-containing leachate can be effectively realized, and the secondary pollution caused by the dissolution of the fixed arsenic is prevented.
In the invention, arsenic in the arsenic-containing solution is converted into ferric arsenate by arsenic fixing means, thereby facilitating subsequent polymer coating.
Preferably, the arsenic fixing treatment step comprises: pre-adjusting the pH value of the arsenic-containing solution to be acidic, then adding ferrous salt and introducing oxygen-containing gas, stirring and reacting under a heating condition, and carrying out solid-liquid separation to obtain ferric arsenate precipitate. Research shows that the ferric arsenate obtained by the arsenic fixing method has good octahedral crystal form, and can form a compact ferrous sulfide coating layer by unexpectedly utilizing subsequent surface etching.
Preferably, the pH value of the arsenic-containing solution is adjusted to 1-3; more preferably 1 to 2. The pH is adjusted with sulfuric acid solution and/or sodium hydroxide solution.
Preferably, the ferrous salt is Fe2+Water-soluble salts of (a); more preferably at least one of ferrous sulfate, ferrous chloride and ferrous nitrate.
Preferably, the addition amount of the ferrous salt in the arsenic-containing solution is 1.2-5 times of the molar amount of arsenic in the arsenic-containing solution; more preferably 1.5 to 3 times.
Preferably, the oxygen-containing gas is oxygen and/or air.
Preferably, the flow rate of the oxygen-containing gas is 0.1 to 5 liters per minute.
Preferably, the temperature in the arsenic fixation treatment process is 70-95 ℃; the arsenic fixing treatment time is preferably 6-12 hours. Namely, adding ferrous salt and introducing oxygen-containing gas into the arsenic-containing solution, heating to 70-95 ℃, stirring for reaction for 6-12 hours, and carrying out solid-liquid separation to obtain ferric arsenate solid.
Preferably, the core is ferric arsenate with a ferrous sulfide layer coated on the surface, and the preparation process comprises the following steps: and (3) placing the ferric arsenate precipitate into a sulfide solution with the concentration of 0.001-0.2 moL/L, carrying out surface etching at the temperature of 5-40 ℃, and depositing ferrous sulfide on the ferric arsenate to obtain the nuclear material.
In the invention, a ferrous sulfide coating layer is innovatively formed on the surface of the obtained ferric arsenate in situ by a surface etching method; in the process of forming the coating, the problems of ferric arsenate corrosion and poor coating compactness in the surface etching process need to be solved. In order to solve the problem, the research of the invention finds that the concentration and the temperature of the sulfide salt in the etching process can be controlled in the required range, so that the ferrous sulfide coating with good compactness can be successfully obtained; the stability of the arsenic fixing material can be further improved by matching the action of the polymer outer layer.
Preferably, the concentration of the sulfide salt is 0.001 to 0.1 moL/L. Controlling in this preferred range can further improve the compactness of the coated ferrous sulfide, further improve its leaching safety under alkaline conditions.
Preferably, the sulfide solution is ionizable S2-An aqueous solution of a water-soluble salt of (a); the ionizable compound can emit S2-The water-soluble salt of (3) is more preferably at least one of sodium sulfide, potassium sulfide, sodium hydrogen sulfide and potassium hydrogen sulfide.
Preferably, the temperature in the surface etching process is 10-20 ℃; more preferably 10 to 15 ℃. It has been found that controlling the temperature at the preferred temperature can further improve the compactness of the coated ferrous sulfide and further improve the leaching safety under alkaline conditions.
The surface etching time is preferably 1-24 hours.
The nuclear material is placed in a polymer solution, the polymer solution is placed in a mold, and then the solvent is removed, so that the ferric arsenate @ polymer solid arsenic material is obtained.
Preferably, the polymer is polyvinyl alcohol; the preferable amount of polyvinyl alcohol is 1 to 10% by mass of the core.
Preferably, the core is immersed into the polyvinyl alcohol aqueous solution at the temperature of 95-100 ℃ and stirred for 0.5-2 hours.
Preferably, the material of the mold is a metal, iron, or the like.
The technical scheme of the invention has the following beneficial effects:
1. the invention innovatively provides an iron arsenate @ polymer arsenic fixing material, and the compound and the material with the coating appearance are found to have good leaching safety;
2. the invention also discovers that a layer of ferric sulfide is etched on the surface of ferric arsenate in advance, and a layer of polymer is further coated, so that the leaching safety of the solid arsenic material is further improved;
3. the toxicity leaching experiment (TCLP) is carried out according to the regulation of a solid waste leaching toxicity leaching method horizontal oscillation method HJ557-2010, and the result shows that the arsenic concentration in the leachate is lower than 5 mg/L specified in hazardous waste identification standard leaching toxicity identification GB5085.3-2007, and the standard of safe arsenic-fixing compounds is met.
4. The technical scheme of the invention realizes the fixation of arsenic by a two-step method, the reaction condition is mild, and the steps are simple; the adopted solid arsenic raw materials are ferrous salt, air or oxygen and the like, so that the price is low, and the popularization and the application are facilitated; the prepared ferric arsenate/polyvinyl alcohol material with the core-shell structure is safe and reliable through a toxicity leaching test, can be used as an ideal arsenic fixing material, and solves the problem of arsenic pollution of the current metallurgical enterprises.
Drawings
FIG. 1 is a detailed flow chart of the present invention;
FIG. 2 is an X-ray powder diffraction pattern of the solid arsenic material with a core-shell structure in example 1 of the present invention;
fig. 3 is a scanning electron microscope image of the arsenic-fixing material with a core-shell structure in example 1 of the present invention.
Detailed Description
The following examples are intended to illustrate the invention without further limiting its scope. The raw material arsenic-containing aqueous solution adopted by the invention is taken from a high-arsenic smoke dust leachate produced by a certain tellurium smeltery in Hunan, and the leachate preparation method is prepared according to the patent 'a high-arsenic metallurgical waste gradient dearsenification method' (patent number 201110379510). The arsenic content of the solution was determined by ICP and the concentration of arsenic in the solution was adjusted by evaporation or dilution with water.
In a toxicity leaching experiment (TCLP), according to the regulation of a solid waste leaching toxicity leaching method HJ557-2010, the prepared ferric arsenate/polyvinyl alcohol core-shell structure material is added into distilled water, the solid-to-liquid ratio is 1 to 10, the core-shell structure material is horizontally vibrated for 8 hours, the core-shell structure material is kept stand for 16 hours, then the leaching solution is filtered and collected, and a plasma direct-reading spectrometer (ICP) is used for testing the concentration of arsenic in the leaching solution.
Example 1
1 l of a 30 g/l arsenic-containing solution was prepared as described above, and the pH of the solution was adjusted to 1 using concentrated sulfuric acid. 166.83 g of ferrous sulfate heptahydrate were weighed out in a molar ratio of iron to arsenic of 1.5 and added to the solution while keeping the solution stirred. Oxygen was passed through the solution at a flow rate of 0.5 l/min. The solution was heated to 90 ℃ and kept stirring for reaction with oxygen for 7 hours. And (3) filtering after the solution is cooled, washing the precipitate with deionized water, and drying to obtain a light green powder solid. And measuring the arsenic content in the solution after reaction by using a plasma direct-reading spectrometer (ICP), and obtaining the arsenic precipitation rate of 99.6% by calculation. Soaking the obtained solid powder in a 95 ℃ polyvinyl alcohol aqueous solution with the mass of 10 percent of that of ferric arsenate, stirring for 0.5 hour, pouring the polyvinyl alcohol aqueous solution into a cuboid iron mold, heating and evaporating to remove water, and then pouring out to obtain a green brick solid which is a target product. Finally, the product is subjected to X-ray powder diffraction and field emission scanning electron microscope tests, and FIG. 2 is an X-ray powder diffraction pattern of the solid arsenic material with the core-shell structure, so that the prepared material is really a compound of ferric arsenate dihydrate and polyvinyl alcohol; FIG. 3 is a scanning electron microscope image of the solid arsenic material with the core-shell structure, from which it can be clearly seen that a layer of shell composed of particles is formed on the surface of the material, indicating that the material is the core-shell structure material.
Example 2
1 l of a 10 g/l arsenic-containing solution was prepared as described above, and the pH of the solution was adjusted to 1 using concentrated sulfuric acid. 74.15 grams of ferrous sulfate heptahydrate were weighed out in a molar ratio of iron to arsenic of 2 and added to the solution while keeping the solution stirred. Oxygen was introduced into the solution at a flow rate of 2 liters/min. The solution was heated to 80 ℃ and kept stirring for reaction with oxygen for 9 hours. And (3) filtering after the solution is cooled, washing the precipitate with deionized water, and drying to obtain light green powder solid (ferric arsenate solid). And measuring the arsenic content in the solution after reaction by using a plasma direct-reading spectrometer (ICP), and obtaining the arsenic precipitation rate of 99.4% by calculation. Soaking the obtained solid powder in a 95 ℃ polyvinyl alcohol aqueous solution with the mass of 5 percent of that of ferric arsenate, stirring for 1 hour, pouring the polyvinyl alcohol aqueous solution into a cylindrical wax mold, heating and evaporating to remove water, and pouring out to obtain a green cylindrical solid which is a target product.
Example 3
1 l of a 50 g/l arsenic-containing solution was prepared as described above, and the pH of the solution was adjusted to 2 using concentrated sulfuric acid. 397.62 g of ferrous chloride tetrahydrate are weighed out in the iron arsenic molar ratio 3 and added to the solution while keeping the solution stirred. Air was blown into the solution at a flow rate of 5 liters/min. The solution was heated to 70 ℃ and kept stirring to react with oxygen for 12 hours. And (3) filtering after the solution is cooled, washing the precipitate with deionized water, and drying to obtain a light green powder solid. And measuring the arsenic content in the solution after reaction by using a plasma direct-reading spectrometer (ICP), and obtaining the arsenic precipitation rate of 99.5% by calculation. Soaking the obtained solid powder in a 95 ℃ polyvinyl alcohol aqueous solution with the mass of 1 percent of that of ferric arsenate, stirring for 2 hours, pouring the polyvinyl alcohol aqueous solution into a square polytetrafluoroethylene mold, heating to evaporate water, and pouring out to obtain a green brick solid which is a target product.
Example 4
Compared with example 1, the difference is that a layer of ferrous sulfide is etched on the surface of the prepared ferric sulfide precipitate.
Soaking the obtained ferric arsenate solid powder in a sodium sulfide solution with the temperature of 5 ℃ and the molar concentration of 0.003 mol per liter for 20 hours, filtering, washing and drying to obtain red powder which is a target product (ferric arsenate @ ferrous sulfide material; crystal form and octahedral coating structure with the particle size of 10-50 micrometers);
the obtained ferric arsenate @ ferrous sulfide material is soaked in a polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 5% of the ferric arsenate @ ferrous sulfide material) at 95 ℃ and stirred for 1 hour, the polyvinyl alcohol aqueous solution is poured into a cylindrical waxy mould, and the cylindrical solid is obtained after the polyvinyl alcohol aqueous solution is heated and evaporated to dryness and poured out, so that the green cylindrical solid is obtained, and the green cylindrical solid is the target product.
Example 5
Compared with example 1, the difference is that a layer of ferrous sulfide is etched on the surface of the prepared ferric sulfide precipitate.
Soaking the obtained ferric arsenate solid powder in a sodium sulfide solution with the temperature of 40 ℃ and the molar concentration of 0.2mol per liter for 1 hour, filtering, washing and drying to obtain red powder which is a target product (ferric arsenate @ ferrous sulfide material; crystal form and octahedral coating structure with the particle size of 10-50 micrometers);
the obtained ferric arsenate @ ferrous sulfide material is soaked in a polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 5% of the ferric arsenate @ ferrous sulfide material) at 95 ℃ and stirred for 1 hour, the polyvinyl alcohol aqueous solution is poured into a cylindrical waxy mould, and the cylindrical solid is obtained after the polyvinyl alcohol aqueous solution is heated and evaporated to dryness and poured out, so that the green cylindrical solid is obtained, and the green cylindrical solid is the target product.
Example 6
Compared with example 1, the difference is that a layer of ferrous sulfide is etched on the surface of the prepared ferric sulfide precipitate.
Soaking the obtained ferric arsenate solid powder in a sodium sulfide solution with the temperature of 15 ℃ and the molar concentration of 0.1mol per liter for 3 hours, filtering, washing and drying to obtain red powder which is a target product (ferric arsenate @ ferrous sulfide material; crystal form and octahedral coating structure with the particle size of 10-50 micrometers);
the obtained ferric arsenate @ ferrous sulfide material is soaked in a polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 5% of the ferric arsenate @ ferrous sulfide material) at 95 ℃ and stirred for 1 hour, the polyvinyl alcohol aqueous solution is poured into a cylindrical waxy mould, and the cylindrical solid is obtained after the polyvinyl alcohol aqueous solution is heated and evaporated to dryness and poured out, so that the green cylindrical solid is obtained, and the green cylindrical solid is the target product.
Example 7
Compared with example 6, the difference is that a layer of ferrous sulfide is etched on the surface of the prepared ferric sulfide precipitate, and the temperature of the etching process is 60 ℃.
The temperature in the etching process is high, the ferric arsenate material with the surface coated with ferrous sulfide is not obtained, and the material coated with the polymer is similar to the materials in the embodiments 1-3.
Example 8
Compared with example 6, the difference is that a layer of ferrous sulfide is etched on the surface of the prepared ferric sulfide precipitate, and the concentration of the sulfide solution in the etching process is 0.5 moL/L.
The temperature in the etching process is high, the ferric arsenate material with the surface coated with ferrous sulfide is not obtained, and the material coated with the polymer is similar to the materials in the embodiments 1-3.
Comparative example 1
The only difference compared to example 1 is that no polymer coating was performed.
The products of the above examples 1-8 and comparative examples were subjected to toxicity leaching tests according to the regulations of "solid waste leaching toxicity leaching method horizontal oscillation method HJ 557-2010", and the results show that the arsenic concentration in the leachate is lower than 5 mg/l, which is obviously better than the relevant standards.
| Case(s) | Arsenic concentration of alkaline leaching solution |
| Example 1 | 1.6 mg per liter |
| Example 2 | 1.9 mg per liter |
| Example 3 | 2.1 mg per liter |
| Example 4 | 0.6 mg per liter |
| Example 5 | 1.1 mg per liter |
| Example 6 | 0.1 mg per liter |
| Example 7 | 1.8 mg per liter |
| Example 8 | 2.3 mg per liter |
| Comparative example 1 | 40 mg per liter |
Through an alkaline leaching experiment, the uncoated ferric arsenate material can be dissolved in an alkaline solution, and the arsenic concentration in the leaching solution is far greater than 5 mg/L; the arsenic concentration in the coated material leachate is lower than 5 mg/L, and the coated material leachate is safe solid waste and is a safe arsenic-fixing material.
Through comparison between examples 4 to 6 and examples 1 to 3 and examples 7 and 8, it is found that the leaching stability can be further remarkably improved by forming ferrous sulfide on the surface of ferric arsenate by in-situ etching in advance and then coating the ferrous sulfide with a polymer. Particularly, in the preferable range of example 6, a dense ferrous sulfide layer can be formed, which contributes to further improvement of the alkaline leaching stability.
Claims (14)
1. A method for fixing arsenic of arsenic-containing solution is characterized in that after the pH of the arsenic-containing solution is adjusted to acidity in advance, ferrous salt and oxygen-containing gas are added, stirring reaction is carried out under heating condition, and solid-liquid separation is carried out to obtain ferric arsenate precipitate; the ferric arsenate has an octahedral crystal form;
dispersing the ferric arsenate in a polyvinyl alcohol solution at the temperature of 95-100 ℃, stirring for 0.5-2 hours, and removing a solvent to obtain a core-shell structure material; wherein, the core is ferric arsenate, and the shell is polyvinyl alcohol coated with ferric arsenate;
the amount of the polyvinyl alcohol is 1 to 10 percent of the weight of the ferric arsenate.
2. The method of claim 1, wherein the core is ferric arsenate coated with a ferrous sulfide layer;
the preparation process comprises the following steps: placing the ferric arsenate precipitate into a sulfide solution with the concentration of 0.001-0.2 moL/L, carrying out surface etching at the temperature of 5-40 ℃, and depositing ferrous sulfide on the ferric arsenate to prepare the nuclear material;
in the polyvinyl alcohol solution, the content of polyvinyl alcohol is 5% of the ferric arsenate @ ferrous sulfide material.
3. The method of claim 1, wherein the pH of the arsenic-containing solution is adjusted to 1 to 3 during the arsenic fixation treatment.
4. The method of claim 1, wherein the ferrous salt is Fe2+Water-soluble salts of (a).
5. The method of claim 1, wherein the ferrous salt is at least one of ferrous sulfate, ferrous chloride, and ferrous nitrate.
6. The method of claim 1, wherein the amount of the ferrous salt added to the arsenic-containing solution is 1.2 to 5 times the molar amount of arsenic in the arsenic-containing solution.
7. The method of claim 1, wherein the oxygen-containing gas is oxygen and/or air.
8. The method of claim 1, wherein the flow rate of the oxygen-containing gas is 0.1 to 5 liters per minute.
9. The method of claim 1, wherein the temperature of the arsenic fixing treatment process is 70-95 ℃.
10. The method of claim 1, wherein the arsenic fixing treatment time is 6 to 12 hours.
11. The method of claim 1, wherein the arsenic-bearing solution is an arsenic-bearing wastewater produced by the metallurgical industry, or an arsenic-bearing leachate comprising arsenic-bearing flue dust and/or slag.
12. The method of claim 1, wherein the arsenic content of the arsenic-containing aqueous solution is 5 to 50 g/l.
13. The method of arsenic sequestration of an arsenic-containing solution of claim 2, wherein the sulfide solution is ionizable to form S2-An aqueous solution of a water-soluble salt of (a).
14. The method of claim 13, wherein the ionizable species is ionized to form S2-The water-soluble salt of (A) is at least one of sodium sulfide, potassium sulfide, sodium hydrogen sulfide and potassium hydrogen sulfide;
the concentration of the sulfide solution is 0.001-0.1 moL/L;
the temperature of the surface etching process is 10-20 ℃;
the surface etching time is 1-24 hours.
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| Synthesis and characterization of iron-PVA hydrogel microspheres and their use in the arsenic (V) removal from aqueous solution;Armindo Santos 等;《Chemical Engineering Journal》;Elsevier B.V.;20120913;第210卷;文章第422页第1节，第433页第2节，第434页第3节，第442页第4节 * |
| 生物纳米FeS强化灰岩去除酸矿废水中砷的研究;王艳香 等;《岩石矿物学杂质》;科学出版社;20160925;第35卷(第5期);参见文章第894页，第895页第2节，第896页第3节，表1，图2，表3 * |
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