CN113736999A - Method for cooperatively treating arsenic-silver-containing concentrate and waste acid by using sodium sulfide waste residues - Google Patents
Method for cooperatively treating arsenic-silver-containing concentrate and waste acid by using sodium sulfide waste residues Download PDFInfo
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Abstract
The invention relates to a method for cooperatively treating arsenic-silver-containing concentrate and contaminated acid by using sodium sulfide waste residues, which is characterized in that the contaminated acid generated in the flue gas washing process in the roasting smelting process of the arsenic-silver-containing concentrate is taken as a main object, metallurgical engineering and environmental protection engineering are combined, the sodium sulfide waste residues generated in the industrial production of sodium sulfide are used as raw materials, hydrogen sulfide is prepared for treating the contaminated acid, reaction liquid after the hydrogen sulfide is prepared is taken as an additive for the roasting process of the arsenic-silver-containing concentrate, the substance conversion form of silver in the roasting process is changed, silver sulfate easy to cyanide and leach is generated, a new thought and method for cooperatively treating the arsenic-silver-containing concentrate and the contaminated acid by using the sodium sulfide waste residues are provided, and remarkable economic benefits, environmental benefits and social benefits are generated.
Description
Technical Field
The invention belongs to the cross field of metallurgical engineering and environmental engineering, and particularly relates to a method for decomposing and cooperatively treating arsenic-containing silver concentrate and contaminated acid by using sodium sulfide waste residues.
Background
At present, the industrial production methods of sodium sulfide (sodium sulfide) mainly include a pulverized coal reduction mirabilite method, a gas reduction method, a barium sulfate by-product sodium sulfide method and a hydrogen sulfide method. The method for preparing barium sulfate as a byproduct of sodium sulfide is to prepare barium sulfide by reducing barium sulfate with coal, add sodium sulfate solution for treatment to generate sodium sulfide and precipitated barium sulfate, and obtain the barium sulfate by suction filtration, separation, evaporation and concentration. The method discharges a large amount of sodium sulfide waste residues, wherein most of the sodium sulfide waste residues come from carbon contained in coal and sodium sulfide which cannot be separated. The sodium sulfide is 25-30% by detection, and contains a certain amount of sodium carbonate.
It is known that sodium sulfide is very soluble in water, and the aqueous solution is strongly alkaline, has strong irritation and corrosivity when contacting skin and mucous membrane, and can cause burns when contacting skin and hair. Especially, the hydrogen sulfide gas generated by the reaction with water is poisoned to death after being absorbed by human bodies, so the sodium sulfide waste residue can not only cause environmental pollution but also have certain potential safety hazard if not being utilized and treated. Therefore, a resource comprehensive utilization method of the sodium sulfide waste residue needs to be explored, so that the potential value of the sodium sulfide waste residue is effectively excavated, and the environmental pollution and the potential safety hazard are eliminated.
The arsenic-silver-containing concentrate is treated by adopting a two-stage roasting process, a large amount of sulfur dioxide flue gas is generated in the smelting process, flue gas is required to be purified and washed in the sulfuric acid preparation process by using sulfur dioxide, a large amount of polluted acid wastewater is generated in the washing process, the wastewater has the characteristics of high concentration, multiple types, high acidity, complex shape, high treatment difficulty, great harm and the like of heavy metal, main heavy metal ions are arsenic, copper, lead, zinc, cadmium and the like, particularly the arsenic has large concentration fluctuation, the concentration range can be from thousands of mg/L to tens of thousands of mg/L, and the mass concentration of the sulfuric acid can reach 10-200 g/L.
The acid waste water from the smelting flue gas washing is a heavy metal waste water with strong pollution, and can cause great harm even if the concentration is very low. The discharge of the waste acid containing heavy metal causes economic losses in enterprises such as resource loss, equipment corrosion, pollution discharge and charging, pollutes surrounding water environment, and seriously harms ecological environment and human health along with the migration and conversion of heavy metal elements and the enrichment after the heavy metal elements enter a food chain.
Arsenic in the waste acid water is mainly arsenous acid and is the most difficult to treat, so the domestic waste acid water treatment process mainly aims at removing arsenic. At present, the domestic industrial application methods for removing arsenic from waste acid wastewater mainly comprise a neutralization method, a vulcanization-neutralization method, a neutralization-iron salt coprecipitation method and the like. The waste water with high arsenic concentration is dearsenized by sodium sulfide, and then is mixed with other waste water in the factory for neutralization treatment, and the waste water with low arsenic concentration is generally treated by lime-iron salt coprecipitation method. The arsenic removal by adopting a vulcanization method is the main direction of arsenic removal of waste acid water, and the used vulcanizing agents mainly comprise sodium sulfide, barium sulfide, ferrous sulfide and the like, but the current general problem is that the price of the vulcanizing agent is higher, and particularly for the waste acid water containing high arsenic concentration, the treatment cost is higher and reaches more than 100 yuan/m3And (4) waste water.
The scholars in China also do much work on the selection and the optimization of the vulcanizing agent, and the high level, frugal and frugal use of the ferrous sulfide fixed bed to treat the arsenic-containing wastewater achieves better effect; the excellent work is done by preparing ferrous sulfide from pyrite; jiangyuan Ru and the like research the morphological change of arsenic in the treatment of arsenic-containing wastewater by ferrous sulfide; liyalin and the like research the process conditions for recovering arsenic from waste acid wastewater by using ferrous sulfide and obtain better effect. A method and a device (CN201310157992.4) for treating high-concentration arsenic-containing acidic wastewater disclose a method for treating arsenic-containing wastewater by using a ferrous sulfide packed bed. A method (CN201710110032.0) for removing high-concentration As (III) in a water body by ferrous sulfide (FeS) oxidation dissolution provides a method for removing high-concentration As (III) in a water body by FeS oxidation dissolution: firstly, synthesizing amorphous and high-activity FeS in an anaerobic glove box by adopting a simple chemical precipitation method, then removing As (III) in a water body by utilizing the oxidation and dissolution reaction of the FeS, and mainly removing As (III) by utilizing the adsorption performance of Fe (III) iron minerals formed by FeS reaction and forming ferric arsenate to remove arsenic, wherein the removal effect of As (III) is good and no subsequent arsenic release phenomenon exists, which shows that the arsenic removal effect is good and stable. A method and a device (CN201310501529.7) for recycling heavy metal waste acid and wastewater disclose a method and a device for recycling heavy metal waste acid and wastewater, firstly, acid in waste acid can be well separated through selection of an anion membrane and a cation membrane in an electrodialysis process, low-acidity waste liquid containing heavy metal can rapidly recycle valuable heavy metal in the waste liquid by utilizing hydrogen sulfide gas and a jet flow process integration technology, and the recovery rate of heavy metal ions reaches more than 95%.
The existing research data is researched on the preparation and application of ferrous sulfide, the ferrous sulfide is directly added to be applied to waste acid treatment, the recycling of acid in subsequent waste acid is influenced, and the existing documents have the problems of complex preparation process, high application cost and the like of the ferrous sulfide, so that the large-scale industrial application of the ferrous sulfide is restricted. In view of the large treatment difficulty and high treatment cost of the waste acid, the method becomes a main problem in pollution treatment in the colored industry and influences the sustainable development of the colored industry. Therefore, the development of a low-cost and high-efficiency waste acid treatment method is of great significance.
At present, in the roasting and cyaniding process of arsenic-silver-containing concentrate, due to the control of the roasting process and technical conditions, the roasting reaction of the silver mineral is incomplete in the roasting process, and the silver mineral forms a mutual solution state with other metal oxides and gangue minerals in the roasting and conversion process to generate silver silicate and other substances which are difficult to dissolve by cyanide, so that the leaching rate of silver is only about 50%, the cyanide recovery rate of silver is low, and the waste of resources is caused.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for cooperatively treating arsenic-containing silver concentrate and contaminated acid by using sodium sulfide waste residues, so that the comprehensive treatment of the arsenic-containing silver concentrate and the contaminated acid is realized while the treatment of the sodium sulfide waste residues is realized.
In order to achieve the purpose, the invention takes waste acid wastewater generated in the flue gas washing process in the roasting and smelting process of the arsenic-silver-containing concentrate as a main object, combines metallurgical engineering and environmental protection engineering, adopts the waste alkali sulfide residues generated in the industrial production of sodium sulfide as a raw material to prepare hydrogen sulfide for waste acid treatment, takes reaction liquid after preparing the hydrogen sulfide as an additive for the roasting process of the arsenic-silver-containing concentrate, changes the substance conversion form of silver in the roasting process, generates silver sulfate easy to cyanide and leach, and provides a new idea and method for treating the arsenic-silver-containing concentrate and the waste acid cooperatively by using the waste alkali sulfide residues. After the treatment of the invention, the alkaline compounds such as sodium sulfide, sodium carbonate and the like in the sodium sulfide waste residue can be effectively utilized, the main component sodium sulfate solution generated by the decomposition reaction with waste acid returns to the roasting process of the arsenic-containing silver concentrate to generate the silver sulfate compound easy to cyanide leach, the generated hydrogen sulfide gas is directly used for removing heavy metals such as arsenic and the like from the waste acid wastewater, the arsenic-removed residue returns to the roasting production process, the closed cycle production process without waste gas and waste residue discharge is formed, the high-valued utilization of the sodium sulfide waste residue is realized, the high-efficiency and low-cost treatment of the waste acid is created, the silver recovery rate of the arsenic-containing silver concentrate is obviously improved, and the economic benefit, the environmental benefit and the social benefit are obvious.
The adopted specific technical scheme is as follows:
a method for cooperatively treating arsenic-silver-containing concentrate and contaminated acid by using sodium sulfide waste residues comprises the following steps:
1) and (3) producing the sodium sulfide waste residue: obtaining sodium sulfide waste residues by adopting a barium sulfate by-product sodium sulfide method;
2) production of contaminated acid: the arsenic-silver-containing concentrate is treated by a two-stage roasting process, a large amount of sulfur dioxide flue gas is generated in the smelting process, the flue gas is required to be purified and washed in the process of preparing sulfuric acid from sulfur dioxide, and a large amount of waste acid is generated in the washing process;
3) preparing hydrogen sulfide from the sodium sulfide waste residues: grinding and dissolving the sodium sulfide waste residue produced in the step 1) by a ball mill to obtain suspension, and conveying the suspension to an acidification closed stirring tank by a pump; pumping part of the waste acid produced in the step 2) to an acidification closed stirring tank through an acid corrosion resistant pump; hydrogen sulfide gas is produced by the reaction and is conveyed by a fan to enter the next working procedure; after the reaction is finished, the reaction solution after the hydrogen sulfide is prepared enters a two-stage roasting and size mixing process of arsenic-silver-containing concentrate;
4) removing arsenic from hydrogen sulfide: conveying the hydrogen sulfide gas obtained in the step 3) to a waste acid wastewater purification and arsenic precipitation reaction device through a fan, conveying the hydrogen sulfide gas to an efficient concentrator through a pump after reaction, adding polyacrylamide, wherein the supernatant of the concentrator is purified waste acid, the underflow of the concentrator is arsenic sulfide slag, the arsenic slag returns to the two-stage roasting and size mixing process of arsenic-silver-containing concentrate, and arsenic is roasted to generate an arsenic trioxide industrial product;
5) the two-stage roasting process of the arsenic-silver-containing concentrate comprises the following steps: mixing the arsenic-silver-containing concentrate with the reaction liquid obtained after the hydrogen sulfide is prepared in the step 3) and the arsenic sulfide slag in the step 4), pulping, conveying the prepared ore pulp to a primary roasting furnace through a pump, carrying out secondary roasting, and preparing an industrial sulfuric acid product from roasted flue gas through the working procedures of mechanical purification, electric precipitation, cloth bag arsenic collection, wet purification, electric demisting and conversion absorption; the calcine produced after roasting enters the next working procedure;
6) acid leaching and cyaniding of calcine to extract silver: removing impurity metals such as arsenic, iron, copper, zinc and the like which influence the cyaniding and leaching of silver from the calcine obtained in the step 5) through an acid leaching process, adopting cyaniding and leaching and zinc powder replacement processes of ammonia water and sodium cyanide on the acid leaching residue containing silver after acid leaching, wherein the silver leaching rate reaches 92-95%, and smelting and refining silver mud obtained through replacement to obtain a standard silver ingot containing 99.99% of silver.
Further, in the step 1), the sodium sulfide content in the sodium sulfide waste residue is 25-30% by mass, and the sodium carbonate content in the sodium sulfide waste residue is 12-15% by mass.
Further, the concentration of arsenic in the contaminated acid in the step 2) is 5000-15000mg/L, and the mass concentration of sulfuric acid is 100-200 g/L.
Further, the fineness of the suspension in the step 3) is 96-100% of minus 400 meshes, and the conveying flow conveyed to the acidification closed stirring tank is 3-5 m3H; the conveying flow of the waste acid conveyed to the acidification closed stirring tank is 10-20m3H; the reaction temperature is 50-70 ℃, and the reaction time is 4-6 hours; after the reaction is finished, the PH of the reaction solution is 5-6, and the mass percent of sodium sulfateThe content is 20-30%.
Further, the conveying flow of the hydrogen sulfide gas in the step 4) is 10-20m3The reaction time is 2-3 h, the reaction temperature is 30-50 ℃, and the addition amount of the polyacrylamide is 5-10g/m3(ii) a The purified waste acid contains 10-20 mg/L of arsenic, and the mass percentage of the arsenic in the arsenic sulfide slag is 20-50%.
Further, the mass ratio of the arsenic-silver-containing concentrate in the step 5) to the reacted liquid for preparing hydrogen sulfide is 1: 0.1-1: 0.5, and the addition amount of arsenic sulfide slag is 3-5 m3And h, the concentration of the ore pulp is 65-72%.
Further, the roasting temperature in the first-stage roasting furnace in the step 5) is controlled to be 450-600 ℃, and the roasting air quantity is 6000-12000 m3The roasting time is 2-4 h, the roasting temperature of the second-stage roasting is controlled to be 600-700 ℃, and the roasting air quantity is 4000-8000 m3And h, the roasting time is 2-4 h.
Further, the silver content of the acid leaching residue in the step 6) is 5000-10000 g/t.
Compared with the prior art, the invention has the beneficial effects that:
(1) the hydrogen sulfide is prepared by mixing and reacting the sodium sulfide waste residue and a proper amount of the waste acid, so that the low-cost preparation of the vulcanizing agent is realized, the addition amount of alkaline reagents (sodium hydroxide, lime and the like) in the traditional neutralization method is reduced, the high cost of the vulcanizing agents such as industrial sodium sulfide, sodium hydrosulfide and the like in the traditional method is avoided, the economic benefit is remarkable, and the hydrogen sulfide is used for treating waste water of the waste acid and can realize the deep purification of the waste acid.
(2) The high-concentration sodium sulfate solution obtained after the hydrogen sulfide is prepared from the sodium sulfide waste residues is applied to the two-stage roasting process of the arsenic-silver-containing concentrate, the sulfating atmosphere in the roasting process is improved, the conversion rate of silver in minerals to silver sulfate compounds is improved, the silver compounds are easy to cyanide leach, the silver leaching rate of calcine acid leaching cyanidation silver extraction is further improved, and the silver leaching rate reaches 92-95%.
(3) The arsenic slag is returned to the arsenic-silver-containing concentrate two-stage roasting process for harmless treatment, so that the arsenic slag is comprehensively recycled to obtain an arsenic trioxide industrial product, the subsequent treatment cost of hazardous waste is reduced, and the environmental benefit is remarkable.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
1) And (3) producing the sodium sulfide waste residue: converting sodium sulfide mass percentage content of sodium sulfide waste residue obtained by a barium sulfate byproduct sodium sulfide method in a certain plant into 25% and sodium carbonate mass percentage content of 12%;
2) production of contaminated acid: the arsenic-silver-containing concentrate is treated by adopting a two-stage roasting process, a large amount of sulfur dioxide flue gas is generated in the smelting process, the flue gas is required to be purified and washed in the sulfuric acid preparation process by using sulfur dioxide, a large amount of waste acid wastewater is generated in the washing process, the arsenic concentration is 5000mg/L, and the mass concentration of the sulfuric acid can reach 100 g/L;
3) preparing hydrogen sulfide from the sodium sulfide waste residues: grinding and dissolving the sodium sulfide waste residue produced in the step 1) by a ball mill to obtain suspension with the fineness of-400 meshes reaching 96%, conveying the suspension to an acidification closed stirring tank by a pump, wherein the conveying flow is 3m3H; part of the waste acid produced in the step 2) is pumped into an acidification closed stirring tank through an acid corrosion resistant pump, and the conveying flow is 10m3H; the reaction temperature is 50 ℃, the reaction time is 4 hours, and hydrogen sulfide gas is produced; and after the reaction is finished, the PH value is 5, the content of sodium sulfate in the reaction solution after the hydrogen sulfide is prepared reaches 20 percent, and the two-stage roasting and size mixing process of the arsenic-silver-containing concentrate is carried out.
4) Removing arsenic from hydrogen sulfide: conveying the hydrogen sulfide gas obtained in the step 3) to a waste acid wastewater purification and arsenic precipitation reaction device through a fan, wherein the conveying flow of the hydrogen sulfide gas is 10m3H, the reaction time is 2h, the reaction temperature is 30 ℃, the mixture is conveyed to a high-efficiency concentrator through a pump after reaction, and 5g/m of the mixture is added3Polyacrylamide, namely the supernatant fluid of a thickener, namely purified waste acid contains 10mg/L of arsenic, the underflow is arsenic sulfide slag containing 20 percent of arsenic, the arsenic slag returns to the two-stage roasting and size mixing working procedure of arsenic-silver-containing concentrate, and arsenic is roasted to generate an arsenic trioxide industrial product;
5) the two-stage roasting process of the arsenic-silver-containing concentrate comprises the following steps: arsenic-silver-containing concentrate, reaction liquid obtained after preparing hydrogen sulfide in step 3) and sulfuration in step 4)Mixing arsenic slag, mixing the arsenic slag with the solution of arsenic-silver-containing concentrate reacted with the prepared hydrogen sulfide at a ratio of 1:0.1, wherein the addition amount of the arsenic sulfide slag is 3m3H, mixing, adjusting the concentration of the ore pulp to 65%, conveying the ore pulp to a first-stage roasting furnace through a pump, controlling the roasting temperature to be 450 ℃, and controlling the roasting air volume to be 6000m3The roasting time is 2 hours, the temperature of the second-stage roasting is controlled at 600 ℃, and the roasting air quantity is controlled at 4000m3The roasting time is 2 hours, and industrial sulfuric acid products are prepared from roasting flue gas through the working procedures of mechanical purification, electric precipitation, cloth bag arsenic collection, wet purification, electric demisting and conversion absorption;
6) acid leaching and cyaniding of calcine to extract silver: removing impurity metals such as arsenic, iron, copper, zinc and the like which influence the cyaniding and leaching of silver from the calcine obtained in the step 5) through an acid leaching process, carrying out cyaniding and leaching and zinc powder replacement processes on acid leaching slag containing 5000g/t of silver after acid leaching by adopting ammonia water and sodium cyanide, wherein the silver leaching rate reaches 92%, and smelting and refining silver mud obtained through replacement to obtain a standard silver ingot containing 99.99% of silver.
Example 2
1) And (3) producing the sodium sulfide waste residue: converting sodium sulfide waste residue obtained by a barium sulfate byproduct sodium sulfide method in a certain plant into 27.5 percent by mass of sodium sulfide and 13.5 percent by mass of sodium carbonate;
2) production of contaminated acid: the arsenic-silver-containing concentrate is treated by adopting a two-stage roasting process, a large amount of sulfur dioxide flue gas is generated in the smelting process, the flue gas is required to be purified and washed in the sulfuric acid preparation process by using sulfur dioxide, a large amount of waste acid wastewater is generated in the washing process, the arsenic concentration is 10000mg/L, and the mass concentration of the sulfuric acid can reach 150 g/L;
3) preparing hydrogen sulfide from the sodium sulfide waste residues: grinding and dissolving the sodium sulfide waste residue produced in the step 1) by a ball mill to obtain suspension with the fineness of-400 meshes reaching 98%, conveying the suspension to an acidification closed stirring tank by a pump, wherein the conveying flow is 4m3H; part of the waste acid produced in the step 2) is pumped into an acidification closed stirring tank through an acid corrosion resistant pump, and the conveying flow is 15m3H; the reaction temperature is 60 ℃, the reaction time is 5 hours, and hydrogen sulfide gas is produced; the PH value is 5.5 after the reaction is finished, the content of sodium sulfate in reaction liquid after the hydrogen sulfide is prepared reaches 25 percent, and the sodium sulfate enters arsenic-silver-containing concentrateTwo-stage roasting and size mixing process;
4) removing arsenic from hydrogen sulfide: conveying the hydrogen sulfide gas obtained in the step 3) to a waste acid wastewater purification and arsenic precipitation reaction device through a fan, wherein the conveying flow of the hydrogen sulfide gas is 15m3H, the reaction time is 2.5h, the reaction temperature is 40 ℃, the mixture is conveyed to a high-efficiency concentrator through a pump after reaction, and 7.5g/m of the mixture is added3Polyacrylamide, namely the supernatant of a thickener, namely purified waste acid contains 15mg/L of arsenic, the advanced treatment is continued, the bottom flow is arsenic sulfide slag containing 35 percent of arsenic, the arsenic slag returns to the two-stage roasting and size mixing working procedure of arsenic-silver concentrate, and arsenic generates an arsenic trioxide industrial product after roasting;
5) the two-stage roasting process of the arsenic-silver-containing concentrate comprises the following steps: mixing and sizing the arsenic-silver-containing concentrate with the reaction liquid obtained after the hydrogen sulfide is prepared in the step 3) and the arsenic sulfide slag in the step 4), wherein the ratio of the arsenic-silver-containing concentrate to the reaction liquid obtained after the hydrogen sulfide is prepared is 1:0.3, and the addition amount of the arsenic sulfide slag is 4m3H, mixing, adjusting the concentration of the ore pulp to 68.5 percent, conveying the ore pulp to a first-stage roasting furnace through a pump, controlling the roasting temperature to 525 ℃ and the roasting air volume to 9000m3The roasting time is 3 hours, the temperature of the second-stage roasting is controlled at 650 ℃, and the roasting air quantity is controlled at 6000m3The roasting time is 3 hours, and industrial sulfuric acid products are prepared from roasting flue gas through the working procedures of mechanical purification, electric precipitation, cloth bag arsenic collection, wet purification, electric demisting and conversion absorption;
6) acid leaching and cyaniding of calcine to extract silver: removing impurity metals such as arsenic, iron, copper, zinc and the like which influence the silver cyaniding leaching from the calcine obtained in the step 5) through an acid leaching process, adopting cyaniding leaching and zinc powder replacement processes of ammonia water and sodium cyanide to the acid leaching residue containing 7500g/t of silver after acid leaching, wherein the silver leaching rate reaches 93.5%, and smelting and refining silver mud obtained through replacement to obtain a standard silver ingot containing 99.99% of silver.
Example 3
1) And (3) producing the sodium sulfide waste residue: converting sodium sulfide mass percentage content of sodium sulfide in sodium sulfide waste residue obtained by a barium sulfate byproduct sodium sulfide method in a certain plant into 30%, and sodium carbonate mass percentage content of 15%;
2) production of contaminated acid: the arsenic-silver-containing concentrate is treated by adopting a two-stage roasting process, a large amount of sulfur dioxide flue gas is generated in the smelting process, the flue gas is required to be purified and washed in the process of preparing sulfuric acid from sulfur dioxide, a large amount of waste acid wastewater is generated in the washing process, the arsenic concentration is 15000mg/L, and the mass concentration of the sulfuric acid can reach 200 g/L;
3) preparing hydrogen sulfide from the sodium sulfide waste residues: grinding and dissolving the sodium sulfide waste residue produced in the step 1) by a ball mill to obtain suspension with the fineness of-400 meshes reaching 100%, conveying the suspension to an acidification closed stirring tank by a pump, wherein the conveying flow is 5m3H; part of the waste acid produced in the step 2) is pumped into an acidification closed stirring tank through an acid corrosion resistant pump, and the conveying flow is 20m3H; the reaction temperature is 70 ℃, the reaction time is 6h, and hydrogen sulfide gas is produced; and after the reaction is finished, the PH value is 6, the content of sodium sulfate in the reaction solution after the hydrogen sulfide is prepared reaches 30 percent, and the two-stage roasting and size mixing process of the arsenic-silver-containing concentrate is carried out.
4) Removing arsenic from hydrogen sulfide: conveying the hydrogen sulfide gas obtained in the step 3) to a waste acid wastewater purification and arsenic precipitation reaction device through a fan, wherein the conveying flow of the hydrogen sulfide gas is 20m3H, the reaction time is 3h, the reaction temperature is 50 ℃, the mixture is conveyed to a high-efficiency concentrator through a pump after reaction, and 10g/m of the mixture is added3Polyacrylamide, namely the supernatant of a thickener, namely purified waste acid contains 20mg/L of arsenic, the advanced treatment is continued, the bottom flow is arsenic sulfide slag containing 50 percent of arsenic, the arsenic slag returns to the two-stage roasting and size mixing working procedure of arsenic-silver concentrate, and arsenic generates an arsenic trioxide industrial product after roasting; a
5) The two-stage roasting process of the arsenic-silver-containing concentrate comprises the following steps: mixing the arsenic-silver-containing concentrate with the reaction liquid obtained after the hydrogen sulfide is prepared in the step 3) and mixing and sizing the arsenic sulfide slag in the step 4), wherein the ratio of the arsenic-silver-containing concentrate to the reaction liquid obtained after the hydrogen sulfide is prepared is 1:0.5, and the adding amount of the arsenic sulfide slag is 5m3H, mixing, adjusting the concentration of the ore pulp to 72 percent, conveying the ore pulp to a first-stage roasting furnace through a pump, controlling the roasting temperature to be 600 ℃, and controlling the roasting air quantity to be 12000m3The roasting time is 4 hours, the two-stage roasting temperature is controlled to be 700 ℃, and the roasting air quantity is controlled to be 8000m3The roasting time is 4 hours, and industrial sulfuric acid products are prepared from roasting flue gas through the working procedures of mechanical purification, electric precipitation, cloth bag arsenic collection, wet purification, electric demisting and conversion absorption;
6) acid leaching and cyaniding of calcine to extract silver: removing impurity metals such as arsenic, iron, copper, zinc and the like which influence the cyaniding and leaching of silver from the calcine obtained in the step 5) through an acid leaching process, adopting cyaniding and leaching of ammonia water and sodium cyanide and a zinc powder replacement process to the acid leaching residue containing 10000g/t of silver after acid leaching, wherein the silver leaching rate reaches 95%, and smelting and refining silver mud obtained through replacement to obtain a standard silver ingot containing 99.99% of silver.
From the examples 1 to 3, the method disclosed by the invention not only realizes the treatment of the sodium sulfide waste residues, but also synergistically treats the arsenic-silver-containing concentrate, the silver leaching rate reaches 92-95%, and the standard silver ingot containing 99.99% of silver is obtained through smelting and refining.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of the invention is to be construed in all aspects and as broadly as possible, and all changes, equivalents and modifications that fall within the true spirit and scope of the invention are therefore intended to be embraced therein.
Claims (8)
1. A method for cooperatively treating arsenic-silver-containing concentrate and contaminated acid by using sodium sulfide waste residues is characterized by comprising the following steps:
1) and (3) producing the sodium sulfide waste residue: obtaining sodium sulfide waste residues by adopting a barium sulfate by-product sodium sulfide method;
2) production of contaminated acid: the arsenic-silver-containing concentrate is treated by a two-stage roasting process, a large amount of sulfur dioxide flue gas is generated in the smelting process, the flue gas is required to be purified and washed in the process of preparing sulfuric acid from sulfur dioxide, and a large amount of waste acid is generated in the washing process;
3) preparing hydrogen sulfide from the sodium sulfide waste residues: grinding and dissolving the sodium sulfide waste residue produced in the step 1) by a ball mill to obtain suspension, and conveying the suspension to an acidification closed stirring tank by a pump; pumping part of the waste acid produced in the step 2) to an acidification closed stirring tank through an acid corrosion resistant pump; hydrogen sulfide gas is produced by the reaction and is conveyed by a fan to enter the next working procedure; after the reaction is finished, the reaction solution after the hydrogen sulfide is prepared enters a two-stage roasting and size mixing process of arsenic-silver-containing concentrate;
4) removing arsenic from hydrogen sulfide: conveying the hydrogen sulfide gas obtained in the step 3) to a waste acid wastewater purification and arsenic precipitation reaction device through a fan, conveying the hydrogen sulfide gas to an efficient concentrator through a pump after reaction, adding polyacrylamide, wherein the supernatant of the concentrator is purified waste acid, the underflow of the concentrator is arsenic sulfide slag, the arsenic slag returns to the two-stage roasting and size mixing process of arsenic-silver-containing concentrate, and arsenic is roasted to generate an arsenic trioxide industrial product;
5) the two-stage roasting process of the arsenic-silver-containing concentrate comprises the following steps: mixing the arsenic-silver-containing concentrate with the reaction liquid obtained after the hydrogen sulfide is prepared in the step 3) and the arsenic sulfide slag in the step 4), pulping, conveying the prepared ore pulp to a primary roasting furnace through a pump, carrying out secondary roasting, and preparing an industrial sulfuric acid product from roasted flue gas through the working procedures of mechanical purification, electric precipitation, cloth bag arsenic collection, wet purification, electric demisting and conversion absorption; the calcine produced after roasting enters the next working procedure;
6) acid leaching and cyaniding of calcine to extract silver: removing impurity metals such as arsenic, iron, copper, zinc and the like which influence the cyaniding and leaching of silver from the calcine obtained in the step 5) through an acid leaching process, adopting cyaniding and leaching and zinc powder replacement processes of ammonia water and sodium cyanide on the acid leaching residue containing silver after acid leaching, wherein the silver leaching rate reaches 92-95%, and smelting and refining silver mud obtained through replacement to obtain a standard silver ingot containing 99.99% of silver.
2. The method for cooperatively treating the arsenic-silver-containing concentrate and the contaminated acid by using the sodium sulfide waste residue as claimed in claim 1, wherein the sodium sulfide content in the sodium sulfide waste residue in the step 1) is 25-30% by mass, and the sodium carbonate content in the sodium sulfide waste residue in the step 1) is 12-15% by mass.
3. The method as claimed in claim 1, wherein the arsenic concentration in the contaminated acid in step 2) is 5000-15000mg/L, and the mass concentration of sulfuric acid is 100-200 g/L.
4. The method for cooperatively treating the arsenic-silver-containing concentrate and the waste acid by using the sodium sulfide waste residue as claimed in claim 1, wherein the fineness of the suspension in the step 3) is 96-100% of-400 meshes, and the conveying flow rate of the suspension conveyed to the acidification closed stirring tank is 3-5 m3H; the conveying flow of the waste acid conveyed to the acidification closed stirring tank is 10-20m3H; the reaction temperature is 50-70 ℃, and the reaction time is 4-6 hours; after the reaction is finished, the PH of the reaction solution is 5-6, and the mass percent of sodium sulfateThe content is 20-30%.
5. The method for the cooperative treatment of the arsenic-silver-containing concentrate and the waste acid by the sodium sulfide waste residue as claimed in claim 1, wherein the delivery flow rate of the hydrogen sulfide gas in the step 4) is 10-20m3The reaction time is 2-3 h, the reaction temperature is 30-50 ℃, and the addition amount of the polyacrylamide is 5-10g/m3(ii) a The purified waste acid contains 10-20 mg/L of arsenic, and the mass percentage of the arsenic in the arsenic sulfide slag is 20-50%.
6. The method for cooperatively treating arsenic-silver-containing concentrate and contaminated acid by using sodium sulfide waste residues as claimed in claim 1, wherein the mass ratio of the arsenic-silver-containing concentrate in the step 5) to the reaction liquid for preparing hydrogen sulfide is 1: 0.1-1: 0.5, and the addition amount of arsenic sulfide residues is 3-5 m3And h, the concentration of the ore pulp is 65-72%.
7. The method for cooperatively treating arsenic-silver-containing concentrate and contaminated acid by using sodium sulfide waste residues as claimed in claim 1, wherein the roasting temperature in the primary roasting furnace in the step 5) is controlled to be 450-600 ℃, and the roasting air volume is 6000-12000 m3The roasting time is 2-4 h, the roasting temperature of the second-stage roasting is controlled to be 600-700 ℃, and the roasting air quantity is 4000-8000 m3And h, the roasting time is 2-4 h.
8. The method for the synergistic treatment of the arsenic-silver-containing concentrate and the contaminated acid by the sodium sulfide waste residue as claimed in claim 1, wherein the silver content of the acid leaching residue in the step 6) is 5000-10000 g/t.
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