CN111039327A - Method for converting arsenic slag into scorodite in one step - Google Patents
Method for converting arsenic slag into scorodite in one step Download PDFInfo
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- CN111039327A CN111039327A CN201911410278.5A CN201911410278A CN111039327A CN 111039327 A CN111039327 A CN 111039327A CN 201911410278 A CN201911410278 A CN 201911410278A CN 111039327 A CN111039327 A CN 111039327A
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a method for converting arsenic slag into scorodite in one step, which mainly adopts a hydrothermal method, introduces ferric sulfate solution as a mineralizer, quickly converts the arsenic slag into scorodite with large particle size in a certain oxidation environment, optimizes the conversion condition and evaluates the stability of the scorodite. Preferred experimental conditions were determined: the hydrothermal product of lime green scorodite is obtained after hydrothermal time of 6 hours under the conditions that the temperature is 160 ℃, the pH =2 and the Fe/As molar ratio is 1.2:1, the particle size of the scorodite is 10-30 mu m, the toxic leaching concentration of arsenic is less than 2mg/L, the regulation of solid waste identification standard-leaching toxicity identification (GB5085.3-2007) is met, if arsenic slag is arsenic sulfide slag, the method can be used for stabilizing the arsenic slag and recovering elemental sulfur, and the method shows that the technology is economical and effective for stabilizing treatment of the arsenic slag.
Description
Technical Field
The invention belongs to the field of non-ferrous metal smelting technology and environmental protection, and particularly relates to a method for converting arsenic slag into scorodite in one step.
Background
Arsenic often coexists in minerals containing precious metals or non-ferrous metals, and thus a large amount of acidic high-concentration arsenic-containing wastewater is produced during metal smelting, ore dressing and sulfuric acid preparation. The treatment of the arsenic-containing waste water mainly adopts a precipitation process, however, a large amount of arsenic-containing waste residues such as calcium arsenate residues, ferric arsenate residues, arsenic sulfide residues and the like are generated in the treatment process, and the method is widely used due to the simple sulfide precipitation process and good treatment effect. Arsenic slag belongs to hazardous waste, is easy to cause cancer, is mostly in an amorphous state, is easy to dissolve in alkali metal hydroxide and carbonate, and is also easy to be oxidized into arsenic acid by peroxide or concentrated nitric acid to be dissolved, so that arsenic is released into the environment again in the form of arsenate, and great influence is generated on human beings and the environment, and therefore, the stabilizing treatment of the arsenic slag is particularly important.
At present, the stabilizing technology of arsenic-containing waste residue can be mainly divided into two main types, one type is physical solidification, including cement solidification, polymer encapsulation, glass solidification and the like; for example, the arsenic sulfide slag reacts with sodium sulfide, then oxidant is added for oxidation, then ferric salt or aluminum salt is added, finally cement solidification is adopted, and the leaching toxicity of arsenic is reduced (a method for harmless treatment of arsenic sulfide slag [ Z ]]CN 105963902A), but this method greatly increases the volume of solids, putting some pressure on the landfill, but still risks the release of arsenate to the environment by re-dissolution; the other is to fix arsenic in chemical bond form in the compound by chemical or biological method, thereby achieving the purpose of stabilizing treatment. For example, Wangyun, et al, dry and dehydrate arsenic sulfide slag, then add sulfur powder, stir it evenly, press it into blocks, sinter it under hot pressure, fix the arsenic sulfide slag, the leaching toxicity of arsenic can be reduced by more than 90% (a method for hot-pressing sintering and solidifying arsenic sulfide slag [ Z ]]CN 108580513A), the method not only does not recover sulfur resources, but also adds a certain amount of sulfur powder, the experimental cost is higher, and the risk of secondary pollution is caused; regulating sulfur by small waves or the likeThe liquid-solid ratio, pH and oxidation-reduction potential of the arsenic-removing slag are fed into a high-temperature high-pressure hydrothermal reaction kettle for curing reaction to realize the hydrothermal stable curing of the arsenic sulfide slag (Minwavelet, firewood, Nihon, etc.. a processing method for the hydrothermal stable curing of the arsenic sulfide slag [ Z]CN 106823238A), although the method can realize the stabilization of arsenic sulfide slag in a short period, arsenic in the final product still exists in an amorphous form of arsenic sulfide, and the risk of secondary pollution exists; zhang SHOU CHUN, et al, first oxidation leaching arsenic alkali residue to obtain leachate containing sodium carbonate and sodium arsenate, concentrating the leachate, and introducing CO2Dealkalizing, filtering to obtain dealkalized leachate and sodium bicarbonate crystals, adding acid into the leachate to control the pH value to be 1.0-2.5 to obtain an arsenic-rich solution, and adding ferrous salt and H into the obtained arsenic-containing solution2O2The mixed solution is reacted at the temperature of 75-95 ℃ to obtain scorodite crystals. (arsenic fixation method for preparing scorodite by stabilizing arsenic alkali residue [ Z ]]CN 109809494A); the method adopts a multistage alkaline leaching method, mechanically stirs the waste residue containing arsenic with low concentration for 10 to 12 hours at the temperature of 60 to 80 ℃, sequentially leaches the waste residue in three stages, and adds acid to neutralize and precipitate alkaline leaching solution containing arsenic to recover As2O3And adding ferric sulfate into the filtered leachate to generate scorodite precipitate. (method for harmless treatment of low-concentration arsenic-containing waste residue and arsenic recovery [ Z ]]CN 106011475A). The above-mentioned methods for producing scorodite involve the steps of leaching-oxidation-reprecipitation of arsenic residues, and therefore the process is complicated.
In order to simplify the treatment process, researches have been made to improve the treatment process of arsenic slag from leaching-reprecipitation (two-step method) to direct conversion of arsenic slag into scorodite (one-step method), such as zhangweifang et al, in which arsenic sulfide slag is mixed with a solution containing iron ions and nitrate ions and then subjected to hydrothermal treatment, and finally the arsenic sulfide slag is converted into stable scorodite (a method for further detoxifying and recovering sulfur from arsenic sulfide slag) [ Z ]. CN110240112A ], but after treatment by the method, a large amount of toxic gases of nitric oxide and nitrogen dioxide are generated, so that the atmospheric environment is seriously polluted, and the generation of gases has certain explosion risk for the hydrothermal process; in addition, the method is only applied to the treatment of the arsenic sulfide slag.
Disclosure of Invention
Aiming at the current research situation of the stabilization treatment of arsenic slag, the invention provides a method for converting arsenic slag into scorodite in one step, taking arsenic sulfide slag as an example, and mixing the arsenic sulfide slag with ferric sulfate (Fe) with a certain concentration2(SO4)3) The solutions are mixed, a small amount of hydrogen peroxide is added to provide an oxidation environment for hydrothermal treatment, dissolved sulfur ions and trivalent arsenic in the arsenic slag are respectively oxidized into elemental sulfur and pentavalent arsenic in the oxidation environment, and then arsenate radicals and trivalent iron ions react to generate scorodite with large particle size, so that the stabilization of arsenate radicals is realized.
In order to achieve the purpose, the technical scheme of the invention is as follows;
a method for converting arsenic slag into scorodite in one step is characterized in that: the method comprises the following steps:
(1) preparing a mixed solution of a ferric sulfate solution and a hydrogen peroxide solution, adjusting the pH value with sulfuric acid, and uniformly stirring;
(2) adding arsenic slag into the mixed solution obtained in the step (1), and stirring and mixing uniformly;
(3) and (3) transferring the solid-liquid mixture obtained in the step (2) to a high-pressure reaction kettle for hydrothermal reaction, naturally cooling to room temperature, and drying after solid-liquid separation to obtain a lime-green precipitate scorodite.
Further, in the step (1), the concentration of the ferric sulfate solution is 0.027-0.054 mol/L, the concentration of the hydrogen peroxide solution is 5-10 wt%, and the pH value of the mixed solution is 1-3.
Further, the arsenic slag is arsenic sulfide slag or calcium arsenate slag, the arsenic sulfide slag comprises arsenic trisulfide and arsenic pentasulfide, and the calcium arsenate slag comprises CaHAsO4And Ca3(AsO4)2(ii) a When the arsenic slag is arsenic sulfide slag, gray green precipitated scorodite and yellow floating solid (elemental sulfur) can be obtained after reaction, wherein the recovery rate of the elemental sulfur is 60-90%, the precipitation conversion rate of the arsenic can reach more than 90%, the particle size of the scorodite is about 30 mu m, and the toxic leaching of the scorodite completely meets the identification standard of dangerous wastes after being tested; when the arsenic slag is calcium arsenate slag, gray green can be obtained after reactionThe scorodite is colored and precipitated, the precipitation conversion rate of arsenic can reach more than 90%, the particle size of scorodite is about 10 mu m, and the toxic leaching of scorodite completely meets the identification standard of dangerous waste.
Further, the solid-liquid ratio of the arsenic slag to the mixed liquid in the solid-liquid mixture in the step (2) is 1: 150-1: 80 g/ml.
Further, in the step (3), the hydrothermal reaction temperature is 100-160 ℃, the hydrothermal reaction time is 4-10 hours, and the filling rate of the reaction in the reaction kettle is 50% -80%.
The reaction equation involved in the invention is as follows (taking arsenic sulfide slag existing in large quantity as an example):
As2S3+5H2O2+2Fe3++ 2H2O=2FeAsO4•2H2O+3S↓ +6H+。
the invention has the beneficial effects that:
the method provided by the invention is simple to operate, the generated scorodite has large particles, is easy to precipitate, has small volume and high stability, and the leaching result is far smaller than the toxic identification standard (the leaching method is shown in HJT 299-2007) standard limit value (5 mg/L) of the hazardous waste, thereby indicating that the technology is economic and effective in stabilizing treatment of arsenic slag.
Drawings
FIG. 1 is an XRD pattern of arsenic sulfide slag before treatment in example 1;
FIG. 2 is an SEM image of arsenic sulfide slag from example 1 before treatment;
FIG. 3 is an XRD pattern of scorodite produced under different hydrothermal temperature conditions in example 1;
FIG. 4 is a SEM image of scorodite produced at different hydrothermal temperatures in example 1;
FIG. 5 is an XRD pattern of scorodite produced under different iron to arsenic molar ratios in example 2;
FIG. 6 is a SEM image corresponding to scorodite produced by different iron to arsenic molar ratios in example 2;
FIG. 7 is an XRD pattern of calcium arsenate slag before treatment in example 5;
FIG. 8 is the XRD pattern of scorodite, a product of the treatment of example 5;
figure 9 is an SEM image of the product scorodite after treatment of example 5.
Detailed Description
The present invention will be further described with reference to the following examples, but the embodiments of the present invention are not limited thereto.
Example 1
Adding 0.1 g of arsenic sulfide slag into a reaction kettle, adding 10mL of 10wt% hydrogen peroxide and 5 mL of 0.08 mol/L ferric sulfate solution to enable the solid-to-liquid ratio to be 1:150 g/mL, adjusting the pH value to be =2 by adopting sulfuric acid, uniformly stirring, then respectively placing the reaction kettle into a reaction kettle to react for 10 hours at 100 ℃, 120 ℃, 140 ℃ and 160 ℃, and naturally cooling to room temperature. Through cleaning and flotation, the yellow caking sulfur simple substance and the gray green scorodite solid are finally obtained through separation, the particle size of the scorodite is increased along with the rise of the temperature, and the stability is improved. The toxicity leaching experiment shows that the toxicity leaching of arsenic is less than 1.2 mg/L.
Example 2
Adding 0.1 g of arsenic sulfide slag into a reaction kettle, adding 10mL of 10wt% hydrogen peroxide and 5 mL of 0.08-0.16 mol/L (Fe/As = 1-2) ferric sulfate solution to enable the solid-to-liquid ratio to be 1:150 g/mL, adjusting the pH =2 by adopting sulfuric acid, uniformly stirring, placing the reaction kettle at 160 ℃ for reacting for 10h, and naturally cooling to room temperature. And finally separating by cleaning and flotation to obtain yellow agglomerated sulfur simple substance and gray green scorodite solid. The arsenic fixation rate increases from 82% to 92% with increasing iron concentration and the particle size becomes smaller. When the iron to arsenic molar ratio reaches 1.6:1, the product is a mixed phase of scorodite and iron oxides. The toxic leaching of arsenic in scorodite generated under the condition is less than 1.5 mg/L.
Example 3
Adding 0.1 g of arsenic sulfide slag into a reaction kettle, adding 10mL of 10wt% hydrogen peroxide and 5 mL of 0.1mol/L ferric sulfate solution to enable the solid-to-liquid ratio to be 1:150 g/mL, respectively adjusting the pH to be 1, 2 or 3 by using sulfuric acid, uniformly stirring, placing the reaction kettle at 160 ℃ for reaction for 10 hours, and naturally cooling to room temperature. And finally separating by cleaning and flotation to obtain yellow agglomerated sulfur simple substance and gray green scorodite solid. Experimental results show that arsenic in the arsenic sulfide slag can be fixed within the pH value range of 1-3, the arsenic fixing rate can reach 91% at the highest when the pH value is 2, and the leaching toxicity concentration of the arsenic is less than 1.0 mg/L.
Example 4
Adding 0.1 g of arsenic sulfide slag into a reaction kettle, adding 10mL of 10wt% hydrogen peroxide and 5 mL of 0.08 mol/L ferric sulfate solution to enable the solid-to-liquid ratio to be 1:150 g/mL, adjusting the pH to be =2, after uniformly stirring, putting the reaction kettle into 160 ℃ to respectively react for 6, 8 or 10 hours, and naturally cooling to room temperature. And finally separating by cleaning and flotation to obtain yellow agglomerated sulfur simple substance and gray green scorodite solid. Under the condition, toxic leaching results of scorodite are less than 1.2 mg/L.
Example 5
Adding 0.15g of calcium arsenate into a reaction kettle, adding 10mL of 10wt% hydrogen peroxide and 5 mL of 0.1mol/L ferric sulfate solution to enable the solid-to-liquid ratio to be 1:150 g/mL, adjusting the pH to be =2, stirring uniformly, then placing the reaction kettle at 150 ℃ for reaction for 5h, and naturally cooling to room temperature. And centrifugally drying to obtain the lime-green scorodite.
Similarly, a plurality of embodiments can be provided according to the protection scope defined by the claims and the technical solution provided by the present specification. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles and spirit of the invention, and these are intended to be within the scope of the invention.
Claims (5)
1. A method for converting arsenic slag into scorodite in one step is characterized in that: the method comprises the following steps:
(1) preparing a mixed solution of ferric sulfate and hydrogen peroxide, adjusting the pH value with sulfuric acid, and uniformly stirring;
(2) adding arsenic slag into the mixed solution obtained in the step (1), and stirring and mixing uniformly;
(3) and (3) transferring the solid-liquid mixture obtained in the step (2) to a high-pressure reaction kettle for hydrothermal reaction, naturally cooling to room temperature, and drying after solid-liquid separation to obtain a lime-green precipitate scorodite.
2. The method of claim 1, wherein: in the step (1), the concentration of the ferric sulfate solution is 0.027-0.054 mol/L, the concentration of the hydrogen peroxide solution is 5-10 wt%, and the pH value of the mixed solution is 1-3.
3. The method of claim 1, wherein: the arsenic slag is arsenic sulfide slag or calcium arsenate slag, the arsenic sulfide slag comprises arsenic trisulfide and arsenic pentasulfide, and the calcium arsenate slag comprises CaHAsO4And Ca3(AsO4)2。
4. The method of claim 1, wherein: and (3) in the step (2), the solid-liquid ratio of the arsenic slag to the mixed liquid is 1: 150-1: 80 g/ml.
5. The method of claim 1, wherein: in the step (3), the hydrothermal reaction temperature is 100-160 ℃, the hydrothermal reaction time is 4-10 h, and the filling rate of the reaction in the reaction kettle is 50-80%.
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Cited By (2)
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| CN115304105A (en) * | 2022-09-14 | 2022-11-08 | 中南大学 | Method for hydrothermally solidifying arsenic-rich crystal |
| CN115448372A (en) * | 2022-09-14 | 2022-12-09 | 中南大学 | Method for hydrothermal oxygen pressure solidification of high-arsenic crystal by composite ferric salt |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304105A (en) * | 2022-09-14 | 2022-11-08 | 中南大学 | Method for hydrothermally solidifying arsenic-rich crystal |
| CN115448372A (en) * | 2022-09-14 | 2022-12-09 | 中南大学 | Method for hydrothermal oxygen pressure solidification of high-arsenic crystal by composite ferric salt |
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| CN115448372B (en) * | 2022-09-14 | 2023-09-22 | 中南大学 | Method for solidifying high-arsenic crystal by using composite iron salt through hydrothermal oxygen pressure |
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Application publication date: 20200421 |