CN114378092A - Method for oxidation stabilization treatment of arsenic sulfide slag and application thereof - Google Patents
Method for oxidation stabilization treatment of arsenic sulfide slag and application thereof Download PDFInfo
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Abstract
The invention discloses a method for treating arsenic sulfide slag through oxidation stabilization and application thereof, wherein the method comprises the steps of continuously and slowly adding excessive oxidant into the arsenic sulfide slag to be treated, continuously stirring under normal pressure, adding alkaline metal oxide at intervals after the oxidant is dropwise added, controlling the molar ratio of alkaline metal ions to arsenic ions to be more than 2, reacting for 1-2.5h, and standing for natural maintenance. The method provided by the invention can avoid introducing new impurities, continuously dropwise adding hydrogen peroxide to oxidize heat generated by arsenic sulfide slag so as to provide initial temperature for follow-up, is favorable for stabilizing reaction, and has the advantages of low price and easy obtainment of curing agents, convenient process operation and mild conditions; the reaction process of the method provided by the invention does not need high-temperature high-pressure treatment, the energy consumption is low, the operation is safe, highly stable arsenic-containing solid precipitates can be formed after the treatment, the leaching toxicity of the arsenic slag is stably lower than 0.5mg/l after maintenance, and the arsenic slag can be directly filled in a field for landfill.
Description
Technical Field
The invention relates to the technical field of heavy metal pollutant treatment, and particularly relates to a method for treating arsenic sulfide slag through oxidation stabilization and application thereof.
Background
Arsenic is usually associated in non-ferrous metal minerals, non-ferrous smelting mostly adopts pyrometallurgy, and 40-50 wt% of arsenic enters smelting flue gas in the smelting process; when the smelting flue gas is used as a raw material to produce sulfuric acid, the smelting flue gas is generally washed and purified, and the process can generate polluted acid with the arsenic concentration of 2000-20000 mg/L. According to the relevant standards, the arsenic emission concentration in industrial wastewater should be lower than 0.5mg/L, and the sulfide precipitation method is taken as a typical representative of wastewater treatment technology by adding H to arsenic-containing wastewater2S、Na2The method achieves the aim of removing heavy metals by using the mode that vulcanizing agents such as S, CaS and the like generate insoluble vulcanization precipitates, has the advantages of high treatment rate, high precipitation efficiency, effective recovery of valuable metals and the like, and is most widely applied to the treatment of arsenic-containing wastewater, particularly high-concentration arsenic-containing heavy metal wastewater.
However, at the same time, the industrial application of the sulfidation precipitation method is accompanied by the generation of a large amount of arsenic sulfide slag, and therefore, the safe disposal of the arsenic sulfide slag has been reluctant.
Arsenic sulfide slag is a dangerous waste with strong corrosiveness, and particularly, the arsenic content in the arsenic sulfide slag is about 10-60 percent, and the main component of the arsenic sulfide slag is amorphous As2S3The part of the arsenic-containing material contains elemental sulfur, is insoluble in hydrochloric acid and sulfuric acid, is soluble in concentrated nitric acid and is easy to dissolve in alkali, the arsenic of the arsenic-containing material has high activity, mostly exists in an oxidizable state and an acid extractable state, and is easy to migrate and convert under the influence of factors such as light, temperature, pH value and other coexisting substances. Arsenic migrates to the surface or underground water to cause water body pollution or is adsorbed by soil to affect the growth of crops and directly or indirectly harm the cropsThe human body is healthy. In addition, the arsenic sulfide slag also contains other toxic heavy metals such as Pb, Cd and Cr, and the leaching toxicity of the arsenic sulfide slag is usually higher than the identification standard of hazardous wastes.
In conclusion, the arsenic sulfide slag has the characteristics of fine particles, high water content, strong corrosivity, high arsenic activity, complex components and the like; how to realize the stabilization, reduction and resource treatment of the arsenic sulfide slag is an urgent problem faced by the current nonferrous smelting enterprises.
At present, the resource treatment of arsenic sulfide slag mainly generates arsenic oxide, arsenate or simple substance arsenic, and pyrogenic treatment such as redox roasting and wet method arsenic extraction are generally adopted. Wherein: the pyrogenic process is to perform oxidation roasting, reduction roasting or vacuum roasting on the arsenic sulfide slag to obtain arsenic-containing steam separated from other materials, and the arsenic steam is secondarily oxidized and collected to obtain As2O3But the pyrogenic process has the defects of serious environmental pollution, large investment, small raw material application range and the like; the wet arsenic extraction is to separate arsenic from arsenic sulfide slag in the form of arsenate by acid leaching, alkali leaching or salt leaching, and further refine to obtain As2O3The wet arsenic extraction process has low energy consumption, less pollution and high efficiency, but has complex process and high treatment cost. In a word, the resource utilization method relieves the pollution and harm of the arsenic sulfide slag to the environment to a certain extent, realizes resource utilization of the arsenic sulfide slag, but also has the problems of low recovery efficiency, relative limitation of arsenic product market and the like; meanwhile, due to the continuous refinement of the smelting technology, the content of valuable metals in the high-arsenic contaminated acid and the high-arsenic electrolyte is gradually reduced, the recovery value of the valuable metals in the arsenic sulfide slag obtained after the sulfuration precipitation is not high, and the safe disposal of the arsenic sulfide slag is still the current environmental protection problem.
The stabilization is mainly to reduce the solubility, the mobility and the toxicity of toxic substances such as heavy metals and the like by adding medicaments to change the permeability, the compressibility and the like of wastes so as to reduce the pollution of the toxic substances to the environment.
The existing research shows that the stabilization solidification technology can realize the harmless disposal of the arsenic sulfide slag. Zhoushui et al found that the leaching concentration of arsenic was greatly reduced from 1780.00mg/L to 1.37mg/L under the optimum experimental conditions where the mass ratio of sludge, lime, magnesia, cement and arsenic slag was 2.0: 1.0: 0.1: 0.3: 1.0 by mixing arsenic sulfide slag with sludge, lime, magnesia and cement; however, the technology has the defects of large dosage of medicament, large weight gain and capacity increase ratio of the final product and the like.
The arsenic sulfide slag is solidified by utilizing industrial manganese slag through calcination, the leaching concentration of arsenic in a solidified product is up to 4.4mg/L under the optimal process condition (the water-cement ratio is 1.67, and the maintenance is carried out for 28 days), and meanwhile, the calcination causes the volatilization of arsenic, thereby causing secondary pollution.
Qiong Lu et al solidified arsenic sulfide slag by calcining calcium oxide at medium temperature, and calcined for 2h under the optimal reaction conditions (As/Ca molar ratio of 1: 8, 550 ℃), with the As leaching concentration of 4.08mg/L (much higher than 1.2mg/L of the relevant standard).
Therefore, how to provide a stabilizing treatment method for arsenic sulfide slag, which has simple process, stable effect and low cost, is still a problem to be solved by technical personnel in the field of hazardous waste harmless treatment and disposal.
In view of this, the invention is particularly proposed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for treating arsenic sulfide slag through oxidation stabilization and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for oxidation stabilization treatment of arsenic sulfide slag comprises the following steps:
continuously and slowly adding excessive oxidant into the arsenic sulfide slag to be treated, continuously stirring under normal pressure, adding alkaline metal oxide at intervals after the oxidant is dropwise added, wherein the adding amount of the alkaline metal oxide is that the molar ratio of alkaline metal ions to arsenic ions is controlled to be more than 2, reacting for 1-2.5h, and standing for natural curing.
In the technical scheme, the oxidant is at least one of sodium hypochlorite, potassium permanganate, hydrogen peroxide, ferric chloride hexahydrate and ferric sulfate.
In a preferred embodiment of the present invention, the oxidizing agent is hydrogen peroxide.
In the above technical solution, the basic metal oxide is at least one of magnesium oxide, calcium oxide, iron oxide, and manganese oxide.
In a preferred embodiment of the present invention, the basic metal oxide is calcium oxide.
In the technical scheme, the reaction temperature of the mixture of the arsenic sulfide slag and the oxidant is controlled to be 30-75 ℃.
In a preferred embodiment of the invention, the reaction temperature of the mixture of the arsenic sulfide slag and the oxidant is controlled to be 35-60 ℃.
Further, in the above technical solution, the rotation speed of the stirring is 200-.
In one embodiment of the invention, the method for oxidation stabilization treatment of arsenic sulfide slag specifically comprises the following steps:
s1, continuously dropwise adding hydrogen peroxide into the arsenic sulfide slag to be treated by a peristaltic pump under the condition of normal pressure, wherein the adding amount of the hydrogen peroxide is controlled in such a way that the liquid-solid ratio of the hydrogen peroxide to the arsenic sulfide slag is 0.85-1.20: 1, the temperature of a reaction system is controlled to be 40-85 ℃, and continuously stirring strongly;
s2, adding calcium oxide with the mass 0.35-0.55 times of that of the arsenic sulfide slag into the reaction system of the step S1 at intervals of 4 times, and continuously stirring at 800rpm of 300-;
and S3, cooling the mixed slag obtained after the reaction in the step S2 to room temperature, standing for natural curing, and filling and processing.
In detail, in the above technical solution, in step S1, the dropping speed of the hydrogen peroxide solution is 0.35-0.7ml/min for every 30g of arsenic sulfide slag.
In detail, in the technical scheme, in step S2, calcium oxide is uniformly added at intervals for 3-4 times within 20-50min after hydrogen peroxide is added to the arsenic sulfide slag to be treated.
Further, in the above technical scheme, the reaction time is 30-60 min.
In detail, in the above technical solution, in step S3, the standing natural curing time is 1-7 d.
Still further, in the above technical scheme, the content of trivalent arsenic in the arsenic sulfide slag to be treated is 280-600mg/g in terms of arsenic.
The invention also provides application of the method for treating arsenic sulfide slag through oxidation stabilization in treatment of arsenic sulfide-containing waste slag.
Compared with the prior art, the invention has the following advantages:
(1) the method for oxidation stabilization treatment of arsenic sulfide slag uses hydrogen peroxide as an oxidant, avoids introducing new impurities in the treatment process, has no secondary pollution, continuously dropwise adds heat generated by oxidation of arsenic sulfide slag by hydrogen peroxide to provide initial temperature for the next reaction, is favorable for stabilization reaction, uses calcium oxide as a curing agent, is cheap and easy to obtain, is convenient to operate in the process, and has mild reaction conditions;
(2) according to the method for treating arsenic sulfide slag through oxidation stabilization, provided by the invention, high-temperature and high-pressure treatment is not needed in the reaction process, the energy consumption is low, the operation is safe, highly stable arsenic-containing solid precipitates can be formed after treatment, the leaching toxicity of the arsenic slag is stably lower than 0.5mg/L after maintenance, the leaching toxicity of the arsenic is far lower than 5mg/L specified in GB5085.3-2007 hazardous waste identification standard leaching toxicity identification, the arsenic slag stably reaches the latest landfill standard GB18598-2019 landfill pollutant control standard, and the arsenic slag can be directly filled into a field;
(3) the method for oxidation stabilization treatment of arsenic sulfide slag provided by the invention is mainly carried out through two stages, in the oxidation stage, an oxidant oxidizes arsenic from +3 to +5, sulfur from-2 to sulfur with 0 or higher valence, in the stabilization stage, arsenic is subjected to arsenate precipitation and crystallization mineralization reaction, arsenate radicals are combined with metal ions to form arsenic-containing minerals with small solubility product, and XRD and SEM analysis show that low-solubility calcium arsenate Ca salt4(OH)2(AsO4)2·4H2O and Ca5(AsO4)3(OH) and the likeMeanwhile, the arsenic-containing mineral can be coordinated and adsorbed with a coordination group in a medicament to form various stabilizing acting forces, particle size analysis shows that the grain size of the mineralized slag obtained after oxidation stabilization treatment is obviously increased, and meanwhile, the formed calcium sulfate physically wraps arsenic and reduces the leaching concentration of the arsenic, so that the treatment effect is good, and the arsenic toxicity leaching concentration reaches 0.27 mg/L;
(4) the method for treating arsenic sulfide slag through oxidation stabilization provided by the invention is wide in arsenic content range, has the advantages of economy, environmental protection, short process flow and the like, has wide actual industrial application prospect, and has important practical significance in the field of hazardous waste treatment and disposal.
Drawings
FIG. 1 is a graph showing a comparison of toxic leaching concentrations of solid products obtained by treating arsenic sulfide slag at different amounts of oxidant added in example 1 of the present invention;
FIG. 2 is an XRD spectrum of a solid product obtained by treating arsenic sulfide slag under different oxidant adding amounts in example 1 of the present invention;
FIG. 3 is an XPS fine spectrum of S of a solid product obtained by treating arsenic sulfide slag under conditions of 6ml (a) and 30ml (b) respectively in the case of example 1 of the present invention;
FIG. 4 is a graph showing the comparison of the toxic leaching concentrations of solid products obtained by treating arsenic sulfide slag at different calcium oxide dosages in example 2 of the present invention;
FIG. 5 is a graph showing the comparison of the toxic leaching concentrations of solid products obtained by treating arsenic sulfide slag under different water bath temperatures in example 3 of the present invention;
FIG. 6 is an SEM photograph of a solid product obtained by treating arsenic sulfide slag under optimum process conditions in example 4 of the present invention;
FIG. 7 is a graph showing a distribution of the particle size of arsenic sulfide slag used in example 4 of the present invention;
FIG. 8 is a graph showing the particle size distribution of the solid product obtained by treating arsenic sulfide slag under the optimum process conditions in example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the means used are conventional in the art unless otherwise specified.
The terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The starting materials used in the present invention are all commercially available conventional products unless otherwise specified.
Example 1
In this example 1, the influence of different amounts of the oxidant on the leaching toxicity of As in the stabilized arsenic sulfide slag in the oxidation stabilization process of the arsenic sulfide slag is compared, and the specific process is As follows:
weighing 30.00g of arsenic sulfide slag in a 250mL beaker, placing the beaker in a water bath kettle at the temperature of 20 ℃ (controlling the initial temperature of the reaction to be 20 ℃, and ensuring the temperature of a reaction system to be 30-75 ℃ along with the heat release of the reaction), fully and uniformly stirring and mixing by using a powerful stirrer, wherein the stirring speed of the stirrer is constant at 600r/min, the dosage of an oxidant (30% hydrogen peroxide) is respectively 0, 6, 12, 18, 24, 30, 36 and 42mL, continuously and dropwise adding the hydrogen peroxide at the speed of (0.6mL/min) by using a peristaltic pump, after the dropwise adding of the oxidant is finished, uniformly and intermittently adding 13.5g of CaO for three times in 30min, taking out the beaker after the reaction is finished, sealing by using a preservative film and naturally maintaining for two days, and freeze-drying the obtained solidified slag by using a freeze dryer.
According to the standard of sulfuric acid-nitric acid method for leaching toxicity of solid wastes (HJ/T299-2007), an As toxicity leaching test is carried out by adopting a turnover type oscillator, the As ion concentration is analyzed by ICP-OES, and the specific result is shown in figure 1; as can be seen from FIG. 1, the concentrations of arsenic ions in the leachate were 2311.5, 254, 10.17, 6.975, 0.47, 0.51, 0.33 and 0.36mg/L, respectively.
The XRD of the precipitated solid slag obtained after the arsenic sulfide slag is treated is compared with that of a standard card, and a graph is shown in figure 2; as can be seen from FIG. 2, the arsenic sulfide slag was treated with Ca at the oxidant addition levels of 30, 36 and 42ml4(OH)2(AsO4)2·4H2O and Cas(AsO4)3(OH) and the like. In the absence of oxidant, arsenic sulfide slag can stably exist under acidic condition, and when hydrogen peroxide is added, As3+Is oxidized to H3AsO4And H2AsO4 -Etc. while sulfur is oxidized to higher sulfur, As is increased with the addition of an oxidizing agent5+The content is increased.
As shown in FIG. 3, XPS fine spectrum of S of solid product obtained by treating arsenic sulfide slag with an oxidant (30% hydrogen peroxide) in an amount of 6ml (a) and 30m1(b), respectively. As can be seen from FIG. 3, the XPS fine spectrum comparing the amount of oxidant with 6ml S, S when 30ml of oxidant was added2-The content is obviously reduced, and more SO is generated by oxidation3 2-And SO4 2-Calcium sulfate is easily formed; research shows that under proper conditions, the solution containing arsenate anions reacts with calcium sulfate to form calcium arsenate minerals such as arsenite, and the formation of the minerals absorbing arsenate anions depends on Ca2+Under the conditions of relative concentration of ions, pH value, temperature and the like, the arsenolite is preferentially formed on the surface of the calcium sulfate salt, the arsenolite and other calcium arsenate minerals have higher solubility products, the formation of the arsenite and the arsenate minerals is favorable for the stability of arsenic slag, and meanwhile, excessive calcium sulfate can wrap the calcium arsenate salt, so that the leaching toxicity of the arsenic after the stabilizing treatment is further reduced.
Example 2
In this example 2, the influence of different amounts of CaO on the leaching toxicity of As in the stabilized arsenic sulfide slag in the oxidation stabilization process of the arsenic sulfide slag is compared, and the specific process is As follows:
weighing 30.00g of arsenic sulfide slag in a 250mL beaker, placing the beaker in a water bath kettle at the temperature of 20 ℃ (the initial temperature of the reaction is controlled to be 20 ℃, the temperature of a reaction system is ensured to be 30-75 ℃ along with the heat release of the reaction), fully and uniformly stirring and mixing by using a powerful stirrer, wherein the stirring speed of the stirrer is constant to be 600r/min, the using amount of an oxidant (30% hydrogen peroxide) is fixed to be 24mL, continuously dropwise adding hydrogen peroxide at the speed of (0.6mL/min) by using a peristaltic pump, after the dropwise addition of the oxidant, 6 g, 7.5 g, 9 g, 10.5 g, 12 g, 13.5g and 15g of CaO (the mass ratio of calcium oxide to arsenic sulfide slag is 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1, 0.4: 1, 0.45: 1 and 0.5: 1 respectively) are added at uniform intervals for three times in 30min, after the reaction is finished, the beaker is taken out, the beaker is sealed by using a preservative film and naturally maintained for two days, and the obtained solidified slag is freeze-dried by using a freeze dryer.
According to the standard of sulfuric acid-nitric acid method for leaching toxicity of solid wastes (HJ/T299-2007), a toxicity leaching test of As is carried out by using a turnover type oscillator, and the As ion concentration is analyzed by using ICP-OES, and specific results are shown in FIG. 4. As can be seen from FIG. 4, the concentrations of arsenic ions in the leachate were 37.575, 3.895, 2.84, 2.43, 2.355, 0.575 and 0.40mg/L, respectively; along with the increase of the amount of CaO, the pH value of the reaction system is continuously increased, which is beneficial to leaching arsenic sulfide, and meanwhile, more calcium arsenate minerals are formed by rich calcium ions and arsenate ions.
Example 3
In this example 3, the influence of different water bath temperatures on the leaching toxicity of As in the stabilized arsenic sulfide slag in the oxidation stabilization process of the arsenic sulfide slag is compared, and the specific process is As follows:
weighing 30.00g of arsenic sulfide slag in a 250mL beaker, respectively placing the beaker in a water bath kettle at the temperature of 20 ℃, 40 ℃, 60 and 80 ℃, fully and uniformly stirring and mixing the arsenic sulfide slag by using a powerful stirrer, wherein the stirring speed of the stirrer is constant at 600r/min, the dosage of an oxidant (30% hydrogen peroxide) is fixed at 30mL, continuously dropwise adding the hydrogen peroxide at the speed of 0.6mL/min by using a peristaltic pump, uniformly and alternately adding 13.5g of CaO for three times in 30min after the dropwise adding of the oxidant is finished, taking out the beaker after the reaction is finished, sealing the beaker by using a preservative film, naturally maintaining the beaker for two days, and freeze-drying the obtained solidified slag by using a freeze dryer.
According to the standard of sulfuric acid-nitric acid method for leaching toxicity of solid wastes (HJ/T299-2007), a toxicity leaching test of As is carried out by using a turnover type oscillator, and the As ion concentration is analyzed by using ICP-OES, and specific results are shown in FIG. 5. As can be seen from FIG. 5, the concentrations of arsenic ions in the leachate were 0.5, 0.27, 0.42 and 0.48mg/L, respectively; the analysis result shows that the oxidation process is a continuous exothermic reaction, the reaction in the previous stage provides an initial temperature for the surface reaction, and the water bath temperature has little influence on the leaching toxicity of As in the oxidation stabilization process of the arsenic sulfide slag.
Example 4
In this example 4, arsenic sulfide slag is treated under the optimal process conditions (arsenic sulfide slag: hydrogen peroxide is 1 g: 1mL, the sampling rate of oxidant is 0.6mL/min, the amount of CaO is 13.5g, the adding time and adding mode are 30min and the arsenic sulfide slag is added evenly at intervals in three times, the temperature of water bath is 40 ℃, and the stirring rate is 600r/min), and the leaching toxicity test is performed on the obtained solidified slag according to the standard, and the specific process is as follows:
weighing 30.00g of arsenic sulfide slag in a 250mL beaker, placing the beaker in a water bath kettle at the temperature of 40 ℃, fully and uniformly stirring and mixing the arsenic sulfide slag by using a powerful stirrer, wherein the stirring speed of the stirrer is constant at 600r/min, the using amount of an oxidant (30% hydrogen peroxide) is fixed at 30mL, continuously dropwise adding the hydrogen peroxide at the speed of 0.6mL/min by using a peristaltic pump, after the dropwise adding of the oxidant is finished, uniformly and alternately adding 13.5g of CaO for three times in 30min, taking out the beaker after the reaction is finished, sealing the beaker by using a preservative film, naturally maintaining the beaker for two days, and freeze-drying the obtained solidified slag by using a freeze dryer.
According to the standard of ' solid waste leaching toxicity leaching sulfuric acid-nitric acid method ' (HJ/T299-2007 '), a turnover type oscillator is adopted to carry out As toxicity leaching tests, ICP-OES is used for analyzing As ion concentrations, the arsenic ion concentrations in leachate are respectively 0.27mg/L, the arsenic leaching concentrations are far lower than the limit value (5mg/L) of the GB5085.3-2007 (solid waste identification standard-leaching toxicity identification) standard, and the requirement of the limit value (1.2mg/L) of the ' hazardous waste landfill pollution control standard ' (GB18598-2019) can be stably met.
FIG. 6 shows the results of example 4 of the present inventionSEM image of solidified slag obtained under optimal process conditions, wherein the SEM image shows characteristic needle-like morphology, and combined with corresponding XRD image (shown in figure 2) under the optimal process conditions, the generation of Bothe reported mineral Ca in the solidified slag can be inferred5(AsO4)3(OH), the arsenate has low solubility and can keep stable in a wide pH range, meanwhile, a large amount of calcium sulfate dihydrate crystals are generated, the particle size of a stabilized product is analyzed (the result is shown in figure 8), compared with the original slag (the result is shown in figure 7), the particle size of the product is increased by nearly two times, the calcium sulfate and the generated calcium arsenate are probably wrapped mutually, and the reason why the treatment effect is excellent is also one of the reasons.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention.
It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for oxidation stabilization treatment of arsenic sulfide slag is characterized in that,
the method comprises the following steps:
continuously and slowly adding excessive oxidant into the arsenic sulfide slag to be treated, continuously stirring under normal pressure, adding alkaline metal oxide at intervals after the oxidant is dropwise added, wherein the adding amount of the alkaline metal oxide is that the molar ratio of alkaline metal ions to arsenic ions is controlled to be more than 2, reacting for 1-2.5h, and standing for natural curing.
2. The method for oxidation-stabilization treatment of arsenic sulfide slag according to claim 1,
the oxidant is at least one of sodium hypochlorite, potassium permanganate, hydrogen peroxide, ferric chloride hexahydrate and ferric sulfate, and hydrogen peroxide is preferred;
and/or the alkaline metal oxide is at least one of magnesium oxide, calcium oxide, iron oxide and manganese oxide, and is preferably calcium oxide.
3. The method for oxidation-stabilization treatment of arsenic sulfide slag according to claim 1,
the reaction temperature of the mixture of the arsenic sulfide slag and the oxidant is controlled to be 30-75 ℃, and preferably 35-60 ℃.
4. The method for oxidation-stabilization treatment of arsenic sulfide slag according to any one of claims 1 to 3,
the stirring rotation number is 200-.
5. The method for oxidation-stabilization treatment of arsenic sulfide slag according to any one of claims 1 to 4,
the method specifically comprises the following steps:
s1, continuously dropwise adding hydrogen peroxide into the arsenic sulfide slag to be treated by a peristaltic pump under the condition of normal pressure, wherein the adding amount of the hydrogen peroxide is controlled in such a way that the liquid-solid ratio of the hydrogen peroxide to the arsenic sulfide slag is 0.85-1.20: 1, the temperature of a reaction system is controlled to be 40-85 ℃, and continuously stirring strongly;
s2, adding calcium oxide with the mass 0.35-0.55 times of that of the arsenic sulfide slag into the reaction system of the step S1 at intervals of 4 times, and continuously stirring at 800rpm of 300-;
and S3, cooling the mixed slag obtained after the reaction in the step S2 to room temperature, standing for natural curing, and filling and processing.
6. The method for oxidation-stabilization treatment of arsenic sulfide slag according to claim 5,
in the step S1, the dropping speed of the hydrogen peroxide is 0.35-0.7mL/min corresponding to every 30g of arsenic sulfide slag;
and/or in step S2, adding calcium oxide uniformly at intervals for 3-4 times within 20-50min after adding hydrogen peroxide dropwise into the arsenic sulfide slag to be treated.
7. The method for oxidation-stabilization treatment of arsenic sulfide slag according to claim 5 or 6,
the reaction time is 30-60 min.
8. The method for oxidation-stabilization treatment of arsenic sulfide slag according to claim 5,
in step S3, the standing natural curing time is 1-7 d.
9. The method for oxidation-stabilization treatment of arsenic sulfide slag according to any one of claims 1 to 8,
the content of trivalent arsenic in the arsenic sulfide slag to be treated is 280-600mg/g in terms of arsenic.
10. Use of a method according to any one of claims 1 to 9 in the treatment of arsenic sulphide containing waste residues.
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| CN102151690A (en) * | 2011-01-20 | 2011-08-17 | 杭州大地环保有限公司 | Method for treating arsenic sulfide residue |
| CN105963902A (en) * | 2016-05-03 | 2016-09-28 | 云南大地丰源环保有限公司 | Method for innocent treatment of arsenic sulfide residues |
| CN113351630A (en) * | 2021-07-01 | 2021-09-07 | 中城华宇（北京）矿业技术有限公司 | Harmless treatment method for arsenic sulfide slag |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116140325A (en) * | 2023-01-03 | 2023-05-23 | 重庆交通大学 | Formula, treatment method and finished product of stable solidified electrolytic manganese slag |
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