CN111549228B - Dearsenification method in high acidity system and arsenic recovery method in high acidity system - Google Patents
Dearsenification method in high acidity system and arsenic recovery method in high acidity system Download PDFInfo
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
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- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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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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Abstract
The application relates to a dearsenification method in a high acidity system and a recovery method of arsenic in the high acidity system, belonging to the technical field of hydrometallurgy. A method for arsenic removal in a high acidity system comprising: in a system with acid concentration more than 1mol/L, mixing a tin-containing dearsenization agent and an arsenic-containing solution for reaction to obtain arsenic-tin precipitate. The tin-containing dearsenization agent is mixed with the arsenic-containing solution, and tin and arsenic precipitates which can be difficultly dissolved in a high-acidity system are generated through the reaction of tin and arsenic, so that the arsenic is removed in the high-acidity system. The method for recovering arsenic in a high-acidity system is used for alkaline leaching of arsenic-removed slag (washing slag), arsenic is dissolved into a solution by controlling the pH value of a reaction end point, tin is remained in the leaching slag in the form of hydrated tin dioxide, and the hydrated tin dioxide has strong activity, can be dissolved in an alkali solution (including a sodium carbonate solution) and a concentrated acid, can be used for removing arsenic in an arsenic-removed solution, and realizes the reutilization of resources.
Description
Technical Field
The application relates to the technical field of hydrometallurgy, and particularly relates to a dearsenification method in a high acidity system and a recovery method of arsenic in the high acidity system.
Background
As arsenic-containing solution is generated in the industrial production and treatment process, under the environment-friendly requirement, the problem of how to safely and environmentally treat high-arsenic materials is faced by most of factory enterprises at present because of the high toxicity of arsenic.
The arsenic removal in the prior art is relatively difficult in technology under a low-acid system, and can be realized by precipitation of various arsenates, such as ferric arsenate, cuprous arsenate, calcium arsenate and the like. And the arsenic removal in the high-acidity system is relatively difficult, and the waste acid generated by preparing acid from high-arsenic copper electrolyte and metallurgical flue gas is taken as a typical representative. The most prominent of the high-arsenic copper electrolyte is that several methods for purifying and removing arsenic are available at present, including electrodeposition, organic solvent extraction, ion exchange, chemical precipitation, adsorption, etc. The main industrial application of the method is the electrodeposition method, the electrodeposition method has high energy consumption and high treatment cost relative to the treatment process, potential environmental risks also exist, the arsenic-removing slag still needs to recover copper and separate arsenic, the method is not a proper terminal treatment process, and the treatment process flow is quite long for arsenic.
The waste acid generated in acid preparation from metallurgical flue gas is mostly treated by a arsenate (ferric arsenate or calcium arsenate) precipitation method after neutralization, and a vulcanization precipitation method is also adopted, but the vulcanization precipitation method relates to preparation and use of hydrogen sulfide, so that the production safety problem is more prominent, various heavy metals can be precipitated together in the vulcanization precipitation process, and the subsequent treatment process is more troublesome.
Disclosure of Invention
In view of the defects of the prior art, an object of the embodiments of the present application includes providing a method for removing arsenic in a high acidity system and a method for recovering arsenic in a high acidity system, so as to solve the technical problem of difficulty in removing arsenic in a high acidity system.
In a first aspect, the present application provides a method for arsenic removal in a high acidity system, including: in a system with acid concentration not less than 1mol/L, mixing a tin-containing dearsenization agent and an arsenic-containing solution for reaction to obtain arsenic-tin precipitate.
According to the embodiment of the application, the tin-containing dearsenization agent is mixed with the arsenic-containing solution, and tin and arsenic precipitates which can be dissolved difficultly in a high-acidity system are generated through the reaction of tin and arsenic, so that arsenic is removed in the high-acidity system.
In some embodiments of the present disclosure, the mass ratio of tin in the dearsenization agent to arsenic in the arsenic-containing solution is 0.2-2.0, and optionally, the dearsenization agent is added in small amounts for multiple times to perform the dearsenization reaction.
In some embodiments of the present application, the mixed solution obtained by mixing the dearsenic agent with the arsenic-containing solution has a four-valent tin ion. In the application, the tin which reacts with arsenic to realize dearsenification is tetravalent tin, so in order to improve the dearsenification effect of tin, tin ions in the mixed solution are in a four-valence state.
In some embodiments of the present application, the dearsenic agent includes metallic tin, tin-containing alloys, soluble stannous salts, soluble high tin salts, soluble stannates, and hydrated tin dioxide. The dearsenization agent can be dissolved in a solution and can perform dearsenization.
In some embodiments of the present application, where the dearsenic agent includes at least one of metallic tin, a tin-containing alloy, and a soluble stannous salt, the dearsenic agent is mixed with the arsenic-containing solution and an oxidizing agent is added to the mixed solution to convert tin ions in the mixed solution to a tetravalent state.
When the dearsenization agent comprises at least one of metallic tin, tin-containing alloy and soluble stannous salt, after the dearsenization agent is mixed with the arsenic-containing solution for reaction, the tin in the solution is mainly in a divalent state, and part of divalent tin can be oxidized by arsenate or oxidized by oxygen in the air during the stirring reaction to obtain tetravalent tin. However, the oxidation effect is poor, the oxidation amount is limited, and the dearsenification effect of tin is affected, so when the dearsenification agent comprises at least one of metallic tin, tin-containing alloy and soluble stannous salt, an oxidant is added into the mixed solution to convert tin ions in the mixed solution into a four-valence state.
In some embodiments of the present application, the dearsenic agent is mixed with the arsenic-containing solution for a reaction time greater than 30 minutes. The reaction time enables the dearsenic agent to fully react with the arsenic-containing solution.
In a second aspect, the present application provides a method for recovering arsenic in a high acidity system, including: the arsenic removal method in the high acidity system is adopted to remove arsenic from the arsenic-containing solution, so as to obtain arsenic removal slag and arsenic removal liquid. And washing the arsenic-removed slag to obtain water washing liquid and water washing slag. And (3) carrying out alkaline leaching on the washing slag to obtain leaching slag and leaching liquid. Wherein, the pH value of the solution is controlled in the leaching process, so that the pH value of the solution at the end point of the reaction is not more than 10.
The method for recovering arsenic in the high-acidity system can adopt sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide and the like to carry out alkaline leaching on arsenic-removed slag (water washing slag), and enables tin to exist in the leached slag in the form of hydrated tin dioxide by controlling the pH value of a reaction end point.
In some embodiments of the present application, the end-point pH adjuster comprises at least one of an acid, an acidic oxide, or an acid salt during leaching, optionally at least one of de-arsenic slag, carbon dioxide, or sodium bicarbonate.
When the alkalinity is too high, the de-arsenic slag is added to enable the de-arsenic slag to react with the alkali in the system so as to reduce the content of the alkali and further reduce the pH value; and adding carbon dioxide, dissolving the carbon dioxide in the solution to obtain carbonic acid, reacting the carbonic acid with alkali to reduce the alkali content and further reduce the pH value, or reacting bicarbonate radical with sodium stannate to promote the hydrolysis of tin to generate hydrated tin dioxide, promoting the tin dissolved into the solution in the leaching process to be hydrolyzed and separated out again, and realizing the separation of arsenic and tin.
In some examples of the present application, the leaching temperature is greater than 60 ℃.
The leaching temperature mainly affects the reaction speed, and too low temperature leads to slow reaction speed. In order to shorten the process time, the leaching temperature is more than 60 ℃, and the reaction speed is proper at the temperature.
In some embodiments of the present application, the leaching residue is used as a dearsenization agent to mix with the arsenic-containing solution for reaction so as to remove arsenic from the arsenic-containing solution. The leaching slag obtained by the method mainly comprises hydrated tin dioxide, and can be used as a de-arsenic agent to remove arsenic from an arsenic-containing solution, so that the cyclic utilization of resources is realized, and the cost is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a schematic flow chart of a method for recovering arsenic in a high acidity system according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following describes a method for removing arsenic in a high acidity system and a method for recovering arsenic in a high acidity system in embodiments of the present application.
The embodiment of the application provides a dearsenification method in a high acidity system, which comprises the following steps: in a system with acid concentration not less than 1mol/L, mixing a tin-containing dearsenization agent and an arsenic-containing solution for reaction to obtain arsenic-tin precipitate.
The high acidity system in this application is a system in which the acid concentration is not less than 1mol/L, and the high acidity system is relative to the low acid system. The low-acid system can realize arsenic removal through precipitation of various arsenates, such as ferric arsenate, cuprous arsenate, calcium arsenate and the like. At a pH of >0, tetravalent tin is hydrolyzed, and it is reported that impurities such as arsenic are removed by hydrolytic adsorption of tin in a high pH system, but in a high acidity system, tetravalent tin is also increased in solubility and is difficult to hydrolyze. The inventor of the application finds that arsenic and tin can generate quite complex chemical coprecipitation reaction in a high-acidity system, and the obtained arsenic and tin precipitate is difficult to dissolve in the high-acidity system, so that arsenic removal is realized.
The dearsenization agent in the application is a tin-containing substance, and comprises metallic tin, tin-containing alloy, soluble stannous salt, soluble high-tin salt, soluble stannate and hydrated tin dioxide. After the tin-containing dearsenization agent is mixed with the arsenic-containing solution, the dearsenization agent can be dissolved in the solution, and the arsenic and the tin can react as follows:
formula 1, Sn4++H2O+AsO4 3-＝Sn(OH)AsO4↓+H+(precipitation reaction);
formula 2, 3Sn4++4AsO4 3-＝Sn3(AsO4)4↓ (precipitation reaction);
formula 3, 2Sn4++H2O+2AsO4 3-＝Sn2O(AsO4)2↓+2H+(precipitation reaction);
formula 4, Sn4++2H++2AsO4 3-+aH2O＝SnH2(AsO4)2·aH2O ↓ (precipitation reaction);
formula 5, Sn4++(2+x)H2O＝SnO2·xH2O+4H+(precipitation reaction);
formula 6, 2SnO2·xH2O+6H++2AsO4 3-＝Sn2O(AsO4)2↓+(3+2x)H2O (precipitation reaction);
formula 7 SnO2·xH2O+6H++2AsO4 3-+(a-2-x)H2O＝SnH2(AsO4)2·aH2O↓。
From the above formula, in the mixed solution obtained by mixing the dearsenic agent and the arsenic-containing solution, the tetravalent tin and arsenic are subjected to a precipitation reaction. When the dearsenization agent comprises at least one of metallic tin, tin-containing alloy and soluble stannous salt, after the dearsenization agent is mixed with the arsenic-containing solution, the tin in the solution is mainly in a divalent state, and part of divalent tin can be oxidized by arsenate or oxidized by oxygen in the air during stirring reaction to obtain tetravalent tin. However, such an oxidation effect is poor, and thus the arsenic removal effect of tin is affected, and therefore, when the arsenic removal agent includes at least one of metallic tin, a tin-containing alloy, and a soluble stannous salt, an oxidizing agent is added to the mixed solution to convert tin ions in the mixed solution into a tetravalent state.
In some embodiments of the present application, the oxidizing agent may be oxygen or hydrogen peroxide, for example, air is introduced for oxidation, and the specific oxidation mode is determined according to the actual situation, so that other impurities are not introduced.
In order to ensure that tin and arsenic fully react and achieve a good arsenic removal effect, the mass ratio of the addition amount of tin in the arsenic removal agent to arsenic in the arsenic-containing solution is 0.2-2.0. In some embodiments of the present application, the dearsenic agent is mixed with the arsenic-containing solution in small, multiple additions. Through a large amount of experimental researches, the inventor of the application finds that the mode can improve the total reaction amount of the tin and the arsenic so as to improve the full reaction of the tin and the arsenic.
In the embodiment of the present invention, the reaction temperature of tin and arsenic may be room temperature (e.g., 0 ℃ to 40 ℃), or may be under heating. In some embodiments of the present application, the reaction temperature of tin with arsenic is no less than 70 ℃. Under the temperature condition, the tin arsenic precipitate obtained by the reaction of tin and arsenic has low viscosity, is easy for solid-liquid separation and washing, and is beneficial to production operation.
In order to ensure that the dearsenic agent and the arsenic-containing solution fully react, the time for mixing the dearsenic agent and the arsenic-containing solution for reaction in the embodiment of the application is more than 30 min. The reaction time may be 30min, 40min, 60min or 120 min. It should be noted that the reaction time is not necessarily too long, and the reaction is completed, and too long time may reduce the production efficiency.
The method adopts the tin-containing dearsenization agent, and tin arsenic precipitates which can be difficultly dissolved in a high-acidity system are generated through the reaction of tetravalent tin ions and arsenic (arsenate ions or arsenic ions), so that the arsenic is removed in the high-acidity system.
The existing tin and arsenic separation methods mainly comprise the following steps:
1. and (3) separating arsenic and tin by high-temperature oxidizing roasting-acid leaching. After high-temperature roasting, the arsenic-tin coprecipitation structure is dissociated, tin becomes relatively inert tin dioxide, and the inert tin dioxide cannot be leached by acid in the subsequent acid leaching process so as to realize leaching separation with arsenic.
2. High-temperature alkaline roasting-leaching to separate arsenic and tin. After high-temperature alkaline roasting, sodium carbonate roasting is mainly adopted, and an alkalescent roasting process is utilized to dissociate an arsenic-tin coprecipitation structure, so that tin becomes relatively inert tin dioxide, and arsenic forms sodium arsenate which is easily leached and separated in the subsequent leaching process.
3. And (4) alkaline leaching of sulfide. The arsenic-tin mixture is leached in a combined solution of sodium sulfide and sodium hydroxide so that the tin is not leached in the form converted to tin sulfide and the arsenic is separated in the form of sodium arsenate.
Although the three processes can realize the separation of arsenic and tin, tin finally forms inert tin dioxide or tin sulfide, which is difficult to utilize for the dearsenification process of the application. Through experimental research, the inventor of the application can obtain hydrated tin dioxide which can be used as a de-arsenic agent by adopting different tin-arsenic separation processes so as to realize the recycling of tin.
In a second aspect, referring to fig. 1, an embodiment of the present application provides a method for recovering arsenic in a high acidity system, including:
the arsenic removal method in the high acidity system is adopted to remove arsenic from the arsenic-containing solution, so as to obtain arsenic removal slag and arsenic removal liquid. The arsenic-removed slag in the application is mainly tin arsenic precipitate, and then tin arsenic in the arsenic-removed slag is separated.
And washing the arsenic-removed slag to obtain water washing liquid and water washing slag. The purpose of this step is to remove the entrained impurities from the arsenic-removed slag. The water scrubbing solution can be mixed with the arsenic removal solution for subsequent treatment.
Performing alkaline leaching on the washing slag by adopting a countercurrent leaching or conventional leaching process, wherein Na is controlled in the leaching process2CO3The mol ratio of the NaOH to the As is 0.5-2.0, or the mol ratio of the NaOH to the As is 1.0-3.0, the solid-to-liquid ratio (g/mL) in the leaching process is 1/3-1/8, the pH value of the solution is controlled in the leaching process, and the solution is enabled to react at the endAnd (4) when the pH value is not more than 10, obtaining leaching slag and leaching liquid. Preferably, the solution has a pH at the end of the reaction of not more than 9. If the alkalinity in the leaching system is too strong, part of tin and arsenic are leached and dissolved together, and the recovery rate of tin and the recovery of arsenic-containing solution are influenced, namely the separation effect of arsenic and tin is influenced. In some examples of the present application, arsenic removal residue, carbon dioxide or sodium bicarbonate is used as a pH adjusting agent for the solution during leaching. When the alkalinity is too high, the de-arsenic slag is added to enable the de-arsenic slag to react with the alkali in the system so as to reduce the content of the alkali and further reduce the pH value; and adding carbon dioxide, dissolving the carbon dioxide in the solution to obtain carbonic acid, reacting the carbonic acid with alkali to reduce the alkali content and further reduce the pH value, or reacting bicarbonate radical with sodium stannate to promote the hydrolysis of tin to generate hydrated tin dioxide, and reducing the leaching loss of tin.
In some embodiments of the present application, the water washing residue is subjected to alkaline leaching with sodium carbonate or sodium hydroxide, and alkaline leaching with potassium carbonate, potassium hydroxide, or the like may also be performed. The alkaline leaching with sodium carbonate mainly involves the following reactions:
2Sn(OH)AsO4+(x-1)H2O+3CO3 2-＝2SnO2·xH2O+2AsO4 3-+3CO2↑；
Sn3(AsO4)4+3xH2O+6CO3 2-＝3SnO2·xH2O+4AsO4 3-+6CO2↑；
Sn2O(AsO4)2+2xH2O+3CO3 2-＝2SnO2·xH2O+2AsO4 3-+3CO2↑；
SnH2(AsO4)2·aH2O+3CO3 2-＝SnO2·xH2O+2AsO4 3-+(a+1-x)H2O+3CO2↑。
the alkaline leaching with sodium hydroxide mainly involves the following reactions:
Sn(OH)AsO4+(x-2)H2O+6OH-＝SnO2·xH2O+AsO4 3-；
Sn3(AsO4)4+(3x-6)H2O+12OH-＝3SnO2·xH2O+4AsO4 3；
Sn2O(AsO4)2+(2x-3)H2O+6OH-＝2SnO2·xH2O+2AsO4 3-；
SnH2(AsO4)2·aH2O+6OH-＝SnO2·xH2O+2AsO4 3-+(a+4-x)H2O。
preferably, the water washed slag is subjected to alkaline leaching with sodium carbonate. On one hand, the pH value of the solution at the reaction end point cannot be more than 10, and the sodium carbonate is weak in alkalinity relative to sodium hydroxide, so that the reaction is easier to control. On the other hand, sodium carbonate is low in cost.
In the examples of the present application, the leaching temperature mainly affects the reaction speed, and too low temperature leads to slow reaction speed. In order to shorten the process time, the leaching temperature is more than 60 ℃, and the reaction speed is proper at the temperature. Optionally, the leaching temperature is 60 ℃, 70 ℃, 80 ℃ or 90 ℃.
And (3) heating the solution to 80-100 ℃ after the alkaline leaching reaction is complete, and promoting the hydrolysis of tin, so that a small amount of tin leached from the solution is further hydrolyzed at high temperature. The holding time is at least 10min in order to promote the hydrolysis and precipitation of tin. Stirring and cooling to obtain a precipitated product; or carbon segregation. The obtained leaching slag is mainly hydrated tin dioxide and can be used as a dearsenization agent.
Wherein, the carbon precipitation when a small amount of tin exists in the solution mainly involves the following reaction (the carbon agent can be sodium bicarbonate or carbon dioxide):
SnO2·xH2O+2OH-＝Sn(OH)6 2-+(x-2)H2o (when the leaching pH value is too high, a small amount of converted hydrated tin dioxide is dissolved);
Sn(OH)6 2-+xH2O+2HCO3 -＝SnO2·xH2O+4H2O+2CO3 2-；
Sn(OH)6 2-+xH2O+CO2＝SnO2·xH2O↓+3H2O+CO3 2-；
Sn(OH)6 2-+xH2O+2CO2＝SnO2·xH2O↓+2H2O+2HCO3 -。
the method for recovering arsenic in the high-acidity system provided by the embodiment of the application carries out alkaline leaching on arsenic-removed slag (washing slag), arsenic is dissolved into a solution by controlling the pH value of a reaction end point, and tin is remained in the leached slag in the form of hydrated tin dioxide, so that the hydrated tin dioxide has strong activity, can be dissolved in alkali liquor (including sodium carbonate solution) and concentrated acid, can be used for removing arsenic in arsenic-removed liquid, and realizes the reutilization of resources.
The features and properties of the present application are further described in detail below with reference to examples (mainly copper electrolyte is taken as an example).
Example 1
The embodiment provides a dearsenification method in a high acidity system, which comprises the following steps:
under the condition of 25 ℃, adding stannous sulfate into 150ml of arsenic-containing peracid solution, then adding hydrogen peroxide for oxidation, and reacting for 2 hours to obtain tin-arsenic precipitates, namely arsenic-removing residues. Wherein the mass ratio of the added tin to the arsenic in the high-acid solution is 0.4. The compositions of the arsenious acid solution are as follows:
TABLE 1 arsenic-containing peracid solution composition/(g/L)
| H2SO4 | As | Cu | Fe | Ni | Sb | Sn | Bi |
| 185 | 16.54 | 48.14 | 0.673 | 12.51 | 0.097 | 0.047 | 0.044 |
Examples 2 to 5
Examples 2 to 5 differ from example 1 only in that the reaction temperatures were: 40 ℃, 60 ℃, 80 ℃ and 90 ℃.
Example 6
The embodiment provides a dearsenification method in a high acidity system, which comprises the following steps:
sodium stannate was added to 150ml of the arsenic-containing peracid crystallization mother liquor having the composition shown in Table 2 at 80 ℃ and reacted for 2 hours. Wherein the mass ratio of the added tin to the arsenic in the solution is 0.26.
TABLE 2 arsenic-containing peracid crystallization mother liquor composition (g/L)
| H2SO4 | As | Sb | Ni | Cu | Sn |
| About 350 | 22.5 | 0.68 | 20.5 | 30.2 | 0.07 |
Example 7
This example provides a method for arsenic removal in a high acidity system, which differs from example 6 only in that: the mass ratio of the added amount of tin to arsenic in the solution was 0.48.
Example 8
This example provides a dearsenification method in a high acidity system, which is different from example 7 in that dearsenification is performed in two steps, the mass ratio of the amount of tin added to arsenic in the solution is 0.48 in total, the first step is 0.26, the second step is 0.22, and the dearsenification reaction temperature and time are the same.
Example 9
The embodiment provides a method for recovering arsenic in a high acidity system, which comprises the following steps:
washing the arsenic-removed slag obtained in the example 1 with water to obtain washing slag; leaching the washing slag by adopting sodium carbonate to obtain Na2CO3The mol ratio of As/As is 2.0, the solid-to-liquid ratio is 1:5, the leaching temperature is 60 ℃, and the pH value of the solution at the end point of the reaction is controlledLess than or equal to 10. After reacting for 2h, boiling the solution for 30min, then stirring and cooling, and carrying out solid-liquid separation to obtain the hydrated tin dioxide.
Example 10
The embodiment provides a method for recovering arsenic in a high acidity system, which comprises the following steps:
washing the arsenic-removed slag obtained in the example 1 with water to obtain washing slag; leaching the washing slag by adopting sodium carbonate to obtain Na2CO3The mol ratio of As/As is 2.0, the solid-to-liquid ratio is 1:5, the leaching temperature is 80 ℃, and the pH value of the solution at the end of the reaction is controlled to be less than or equal to 10. After reacting for 2h, boiling the solution for more than 10min, stirring and cooling the solution until the leaching is complete to obtain the hydrated tin dioxide.
Example 11
This example provides a method for recovering arsenic in a high acidity system, which is different from example 8 only in that: the leaching temperature was 30 ℃.
Comparative example 1
The comparative example provides a dearsenification method in a high acidity system, and the difference from the example 4 is that no hydrogen peroxide is added for oxidation after stannous sulfate is added.
Comparative example 2
This comparative example provides a method for arsenic removal in a high acidity system comprising: adopting a parallel continuous circulation method to carry out electrodeposition dearsenification.
Comparative example 3
This comparative example provides a method for recovering arsenic in a high acidity system, which differs from example 10 only in that: the pH value of the solution is not controlled, and the pH value of the solution at the end of the reaction is 11.
Test example 1
The compositions of the solutions and arsenic-removed slag obtained by arsenic removal in examples 1 to 8 and comparative examples 1 to 2 were analyzed, and the arsenic removal effect and the proportion of arsenic and tin reaction during precipitation were calculated, and the results are shown in tables 3 and 4.
The composition analysis of the alkaline leaching solution of arsenic-removed slag and the alkaline leaching slag of examples 9 to 11 and comparative example 3 was performed, and the separation effect of arsenic and tin in the alkaline leaching process of arsenic-removed slag was calculated, and the results are shown in table 5.
TABLE 3 evaluation of the effects of the examples and comparative examples for arsenic removal in high acidity system
Table 4 evaluation of the effect of comparative example 2
As can be seen from examples 1 to 8, both the tetravalent tin ions and the stannate radicals have arsenic removal effects in a high-acid system, wherein the reaction temperature has little influence on the arsenic removal effect of tin, but influences the filtration performance of arsenic removal slag in examples 1 to 5. As can be seen from comparison of examples 6-7, the addition of a small amount of arsenic removal process for multiple times is beneficial to improving the arsenic removal efficiency of tin (namely the arsenic removal capability of tin per unit mass).
Compared with the comparative example 2, the embodiments 1-8 have the advantages of simple process, low energy consumption, safe technical process and less potential risk.
TABLE 5 evaluation of the effect of alkaline separation of arsenic-removed slag
| As leaching rate/%) | Leaching rate of Sn/%) | Evaluation of arsenic-tin separation Effect | |
| Example 9 | 72.45 | ＜2 | Good separation effect and high separation efficiency |
| Example 10 | 85.34 | ＜2 | Good separation effect and high separation efficiency |
| Example 11 | 32.14 | ＜2 | Good separation effect and low separation efficiency |
| Comparative example 3 | 65.51 | 60.87 | Cannot realize separation |
From examples 9 to 11, it can be seen that the arsenic-tin removing slag can realize good arsenic-tin separation by alkaline leaching with pH value controlled, and the separation efficiency thereof is improved along with the increase of the reaction temperature, and the comparative example 3 shows that tin can be leached along with the alkaline leaching without pH value controlled in the alkaline leaching process, so that the separation cannot be realized, but the re-precipitation of tin can be realized by secondary pH value control, and finally, the effective separation of arsenic-tin and the recycling of tin are realized.
Test example 2
The hydrated tin dioxide obtained in example 8 is used as a dearsenization agent and added into the arsenic-containing peracid solution provided in example 1 to react for 2 hours, so that tin-arsenic precipitate can be obtained, which indicates that the hydrated tin dioxide can be obtained by the recovery process provided in example 8, and can be coprecipitated with arsenic, and the mass ratio of arsenic to tin in the precipitate reaches 1.256.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (11)
1. A method for removing arsenic in a high acidity system, wherein the acid concentration in the high acidity system is not less than 1mol/L, the method comprising:
in a system with acid concentration not less than 1mol/L, mixing a tin-containing dearsenization agent and an arsenic-containing solution for reaction to obtain arsenic-tin precipitate;
in the mixed solution obtained after the dearsenic agent is mixed with the arsenic-containing solution, tin ions are in a four-valence state.
2. The method according to claim 1, wherein the mass ratio of tin in the dearsenifying agent to arsenic in the arsenic-containing solution is 0.2 to 2.0.
3. The method of claim 2, wherein the dearsenification reaction is performed by adding the dearsenification agent in a small amount and a plurality of times.
4. The method of claim 1, wherein the dearsenifying agent comprises metallic tin, tin-containing alloys, soluble stannous salts, soluble high tin salts, soluble stannates, and hydrated tin dioxide.
5. The method according to claim 1 or 4, wherein when the dearsenic agent comprises at least one of metallic tin, a tin-containing alloy and a soluble stannous salt, the dearsenic agent is mixed with the arsenic-containing solution, and then an oxidizing agent is added to the mixed solution to convert tin ions in the mixed solution into a tetravalent state.
6. The method of claim 1, wherein the dearsenifying agent is mixed with the arsenic-containing solution for a reaction time of greater than 30 min.
7. A method for recovering arsenic in a high acidity system is characterized by comprising the following steps:
performing dearsenification on the arsenic-containing solution by adopting the dearsenification method in the high acidity system according to any one of claims 1 to 6 to obtain dearsenification slag and dearsenification solution;
washing the arsenic-removed slag to obtain washing liquid and washing slag;
carrying out alkaline leaching on the washing slag to obtain leaching slag and leaching liquid; wherein the pH value of the solution is controlled in the leaching process, so that the pH value of the solution at the end point of the reaction is not more than 10.
8. The method of claim 7, wherein the end-point pH adjuster comprises at least one of an acid, an acidic oxide, or an acid salt during leaching.
9. The method of claim 8, wherein the end-point pH adjuster is at least one of de-arsenic slag, carbon dioxide, or sodium bicarbonate.
10. The method of claim 7, wherein the leaching temperature is greater than 60 ℃.
11. The method according to claim 7, wherein the leaching residue is mixed with an arsenic-containing solution as the dearsenizing agent and reacted to remove arsenic from the arsenic-containing solution.
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| RU1810823C (en) * | 1990-12-21 | 1993-04-23 | Днепропетровский государственный университет им.300-летия воссоединения Украины с Россией | Method of iron assay in arsenic salts |
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| CN109777963A (en) * | 2019-03-14 | 2019-05-21 | 王柯娜 | A kind of recycling processing method of copper smelter cigarette ash |
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| JP3999805B1 (en) * | 2006-04-28 | 2007-10-31 | Ｄｏｗａメタルマイン株式会社 | Arsenic-containing solution processing method |
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| CN105274359A (en) * | 2015-10-21 | 2016-01-27 | 北京矿冶研究总院 | Method for extracting and separating valuable metals from secondary lead smelting slag |
| CN105948104A (en) * | 2016-04-28 | 2016-09-21 | 中南大学 | Method for preparing sodium stannate by using tin anode slime oxygen pressure alkaline leaching |
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