CN110777260B - Wet processing technology for preparing simple substance arsenic - Google Patents
Wet processing technology for preparing simple substance arsenic Download PDFInfo
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- CN110777260B CN110777260B CN201911247884.XA CN201911247884A CN110777260B CN 110777260 B CN110777260 B CN 110777260B CN 201911247884 A CN201911247884 A CN 201911247884A CN 110777260 B CN110777260 B CN 110777260B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application discloses a wet treatment process for preparing simple substance arsenic, which belongs to the technical field of metallurgy and environmental protection and comprises arsenic (As)5+) The solution or the smelting waste acid is used as a raw material, arsenic in arsenic-containing waste water in the nonferrous industry can be directly reduced into simple substance arsenic, the amount of arsenic-containing solid waste can be reduced, the arsenic is recycled, and a new way is opened up for the industrial treatment of the arsenic-containing waste water in the nonferrous smelting industry. Reduces the dosage of vulcanizing agent and greatly relieves the problem of sodium salt enrichment of smelting enterprises. The method adopts common reducing agents such as aluminum powder and cadmium powder to rapidly treat harmful element arsenic which restricts the development scale of smelting enterprises, has wide social and economic benefits, and is worth popularizing in the non-ferrous smelting industry.
Description
Technical Field
The invention belongs to the field of metallurgical technology and environmental protection, and particularly relates to a wet treatment process for preparing elemental arsenic.
Background
The raw materials of the nonferrous smelting industry are mainly sulfide concentrates, the sulfide concentrates have higher and higher impurities along with the shortage of the raw material market, particularly the arsenic content is more and more, the arsenic mainly exists in the sulfide concentrates in the form of sulfides and oxides, and in the pyrometallurgical process, the arsenic mainly volatilizes into smelting flue gas in the form of oxides, and part of the arsenic enters into a slag phase. In the dust collection process of the flue gas, part of arsenic can be directly condensed to produce arsenic trioxide, the rest arsenic is washed in the acid preparation process and enters waste acid, and the waste acid is vulcanized to produce arsenic sulfide slag which is then treated by a unit with treatment quality.
With the continuous expansion of nonferrous smelting scale, arsenic-containing solid waste in China is more and more at present, and the treatment of the arsenic-containing solid waste can be divided into the traditional pyrogenic treatment and wet treatment processes. The pyrogenic process treatment process is characterized in that arsenic is separated and recovered in the form of white arsenic by utilizing the characteristic that arsenide is volatile at high temperature, but the process has serious environmental pollution and severe production environment; the wet treatment process generally comprises the steps of selectively leaching arsenic-containing solid waste to remove arsenic, and then recycling or harmlessly treating the arsenic, wherein the process can generate a large amount of solid waste, is high in treatment cost and is not beneficial to environmental protection. With the increasing environmental protection situation, the nonferrous smelting industry explores to convert arsenic in arsenic-containing solid waste into white arsenic and further convert the white arsenic into simple substance arsenic so as to realize reduction and harmlessness, which is a necessary way for the development of the industry in the future.
Chinese patent 201310310187.0 discloses a method for recovering simple substance arsenic from arsenic sulfide slag, which comprises dissolving arsenic in arsenic sulfide by alkaline oxidation, adding concentrated hydrochloric acid and stannous chloride powder, reacting for 8h, separating solid and liquid to obtain black solid simple substance arsenic, and recovering stannous chloride from the solution by electrolysis. The process has long flow and high cost. Chinese patent 201810798135.5 discloses a process for obtaining simple substance arsenic by reduction of arsenic trioxide, which comprises mixing arsenic trioxide, low-melting-point substance, reducing agent and soda ash uniformly, placing into a crucible for heat preservation reaction to obtain low-melting-point and difficult-to-volatilize arsenic alloy, and recovering arsenic alloy in vacuum to obtain metallic arsenic. The invention provides a wet processing technology for rapidly preparing simple substance arsenic aiming at arsenic-containing liquid in the nonferrous smelting industry.
Disclosure of Invention
Aiming at the current situations of great environmental pollution and high cost of reducing white arsenic into elemental arsenic by pyrogenic process in the nonferrous industry, the invention provides a simple and convenient wet-process treatment process for the elemental arsenic with high recovery rate and good environmental benefit5+) The solution is used as raw material, and one is waste smelting acid.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a wet processing technology for preparing simple substance arsenic by taking arsenic-containing solution as raw material comprises the following steps:
the method comprises the following steps: taking an arsenic-containing solution (containing As0.2-60 g/L) as a raw material, detecting and analyzing the content of pentavalent arsenic, adding a reducing agent A into the solution for reduction, wherein the using amount of the reducing agent A is 1.5-3 times of the molar theoretical consumption of the pentavalent arsenic in the solution, and after 0.5-6 h of reduction, finishing the reaction and realizing the reaction principle:
As5++2e→As3+；
step two: adjusting the acidity of the liquid obtained in the step one by using sulfuric acid, and controlling the concentration of the sulfuric acid in the solution to be 10-250 g/L;
step three: heating the solution obtained in the second step to 40-95 ℃, adding a reducing agent B according to the molar ratio 1 (1.5-4) of arsenic to the reducing agent B in the liquid, and continuing to react for 1-5 h after the addition, wherein the reaction principle is as follows:
2AsO3 3-+3Cd+12H+→2As+3Cd2++6H2O；
AsO3 3-+Al+6H+→As+Al3++3H2O；
step four: and D, carrying out solid-liquid separation on the reacted liquid obtained in the step three to obtain filtered solution and solid, drying and dehydrating the solid to obtain simple substance arsenic, and feeding the filtered liquid into a subsequent wastewater treatment process to recover other elements.
The reducing agent A in the step one is one or a mixture of more than two of sulfur dioxide, sodium sulfite, sodium metabisulfite and sodium thiosulfate in any proportion.
The reducing agent B in the third step is one or a mixture of more than two of aluminum powder and cadmium powder in any proportion.
Preferably, the arsenic-containing solution in the first step contains 1-30 g/L of arsenic, the concentration of sulfuric acid in the second step is 50-150 g/L, and the heating temperature in the third step is not less than 60 ℃.
A wet treatment process for preparing simple substance arsenic by taking smelting waste acid as a raw material comprises the following steps:
(1) copper deposition by vulcanization; taking smelting waste acid (the content of sulfuric acid in the waste acid is 30-150 g/L) as a raw material, adding arsenic sulfide into the solution, wherein the using amount of the arsenic sulfide is 0.4-1.5 times of the molar amount of copper ions in the solution, heating to 50-100 ℃, reacting for 1-4 hours, carrying out solid-liquid separation to obtain copper precipitation liquid and copper sulfide slag, and taking the copper sulfide slag as copper concentrate to be added into a pyrometallurgical copper smelting system; step (1) is not essential, when Cu is contained in the waste acid2+Step (1) is only required when the concentration is more than 0.5g/L, if Cu in waste acid2+The concentration is less than or equal to 0.5g/L, and the reduction and arsenic precipitation in the step (2) are directly carried out;
(2) reduction and arsenic precipitation: placing the copper-deposited solution obtained in the step (1) at 40-95 ℃ for heat preservation, adding a reducing agent according to the dosage of 0.9-1.8 times of the molar weight of arsenic, continuing to react for 1-5 h after the addition is finished, and performing solid-liquid separation to obtain a reduced solution and simple substance arsenic;
(3) and (4) sulfurizing and depositing arsenic: adding a vulcanizing agent into the reduced liquid obtained in the step (2), wherein the consumption of the vulcanizing agent is 1.1-1.8 times of the theoretical consumption of arsenic in the waste acid, the reaction time is 10-120 min, and performing solid-liquid separation to obtain arsenic sulfide and an arsenic precipitation liquid; and (3) returning the arsenic sulfide to the step (1) for copper sulfide precipitation, and allowing the arsenic-precipitated liquid to enter a water treatment process.
Further, the reducing agent in the step (2) is one or a mixture of more than two of aluminum powder, iron powder and zinc powder in any proportion.
Further, the vulcanizing agent in the step (3) is one or a mixture of more than two of sodium sulfide, sodium hydrosulfide and ferrous sulfide in any proportion.
The invention has the beneficial effects that: the wet treatment process for preparing the elemental arsenic can directly reduce the arsenic in the arsenic-containing wastewater in the nonferrous industry into the elemental arsenic, can reduce the amount of arsenic-containing solid waste, recycles the arsenic, and opens up a new way for the industrialized treatment of the arsenic-containing wastewater in the nonferrous smelting industry. Reduces the dosage of vulcanizing agent and greatly relieves the problem of sodium salt enrichment of smelting enterprises.
The method adopts common reducing agents such as aluminum powder and cadmium powder to rapidly treat harmful element arsenic which restricts the development scale of smelting enterprises, has wide social and economic benefits, and is worth popularizing in the non-ferrous smelting industry.
Drawings
FIG. 1 is a flow diagram of the process of the present invention using an arsenic-containing solution as a feedstock;
FIG. 2 is a process flow diagram of the invention using waste smelting acid as raw material.
Detailed Description
In order to make the production process and technical effects of the present invention known in detail to those skilled in the art, the technical solutions and technical effects of the present invention are further described below with specific examples.
Example 1
A wet treatment process for preparing simple substance arsenic by taking an arsenic-containing solution as a raw material is shown in figure 1, and comprises the following steps of taking a liquid containing 17g/L of arsenic (wherein the pentavalent arsenic is 16 g/L) and 40g/L of sulfuric acid (the liquid is an arsenic-containing waste liquid of an acid smelting and making system, and the same is true below) as a raw material:
taking 4m of arsenic-containing liquid for carrying out upward slope cultivation, placing the liquid in a reaction kettle, adding 114kg of sodium sulfite solid, and reacting for 3 h; adding 120kg of commercially available 98% concentrated sulfuric acid with mass fraction to enable the sulfuric acid concentration of the solution to reach 60g/L, heating to 70 ℃, slowly adding 37kg of aluminum powder within 1h, continuing to react for 3h after the addition is finished, and filtering to obtain 67.7kg of solid simple substance arsenic with arsenic content of 99.6%, wherein the filtrate contains 50mg/L of arsenic, the sulfuric acid concentration is 35g/L, and the arsenic recovery rate is more than 99.5%.
Example 2
A wet treatment process for preparing elemental arsenic by taking an arsenic-containing solution as a raw material is shown in figure 1, and comprises the following steps of taking a liquid containing 29g/L of arsenic (26 g/L of pentavalent arsenic) and 100g/L of sulfuric acid as raw materials:
taking 4m of arsenic-containing liquid for carrying out labor-saving cultivation, placing the arsenic-containing liquid in a reaction kettle, and introducing sulfur dioxide gas with the purity of 20-30% (the introduced sulfur dioxide is purified flue gas generated in the smelting process, and is not a product with higher purity; the addition amount is larger because the mass transfer effect of the sulfur dioxide gas and the liquid is poor), wherein the gas flow is 40m for carrying out labor/h, and the reaction is carried out for 2 h; and then heating to 85 ℃, slowly adding 520kg of cadmium powder, continuing to react for 2h after the addition is finished, and filtering to obtain 115.6kg of solid simple substance arsenic with 99.8% of arsenic, wherein the filtrate contains 20mg/L of arsenic and 72g/L of sulfuric acid, and the recovery rate of arsenic is more than 99.9%.
Example 3
A wet treatment process for preparing elemental arsenic by taking an arsenic-containing solution as a raw material is shown in figure 1, and comprises the following steps of taking liquid containing 60g/L of arsenic (53 g/L of pentavalent arsenic) and 150g/L of sulfuric acid as raw materials:
taking 4m of arsenic-containing liquid for carrying out the ethanol distillation, placing the arsenic-containing liquid in a reaction kettle, adding 500kg of sodium metabisulfite solid, and reacting for 4 h; and then heating to 85 ℃, slowly adding 132kg of aluminum powder, continuing to react for 4h after the addition is finished, and filtering to obtain 239.2kg of solid simple substance arsenic with 99.8% of arsenic, wherein the filtrate contains 40mg/L of arsenic and 124g/L of sulfuric acid, and the arsenic recovery rate is more than 99.9%.
Example 4
A wet treatment process for preparing elemental arsenic by using smelting waste acid as a raw material is shown in figure 2, and comprises the following specific processes:
taking (containing Cu)2+ 2g/L、As3+15g/L and sulfuric acid 150 g/L) waste acid 5m high-speed plantationPlacing the obtained product in a reaction kettle, adding 8.4kg of arsenic sulfide (containing 50wt% of arsenic), heating to 90 ℃, reacting for 2 hours, and filtering to obtain 5.3 m of copper precipitation liquid for carrying out heavy labor (containing 15g/L of arsenic) and 16kg of copper sulfide slag (containing 60.5% of copper); adding 90kg of iron powder serving as a reducing agent into the copper-precipitated solution, reacting for 4 hours, and filtering to obtain reduced solution 5.2m (containing 0.9g/L of arsenic) and 75kg of simple substance arsenic (containing 98.6 percent of arsenic); adding 12kg of sodium sulfide (containing 30wt% of sulfur) as a vulcanizing agent into the reduced solution, reacting for 30min, and filtering to obtain 9.4kg of arsenic sulfide and 5.4m of liquid after arsenic precipitation for carrying out thin film plantation (containing 2mg/L of arsenic); the arsenic-precipitated liquid enters a lime neutralization water treatment process, the recovery rate of arsenic is 100%, the direct recovery rate is more than 94%, and the recovery rate of copper is 96%.
Claims (4)
1. A wet processing technology for preparing simple substance arsenic by taking arsenic-containing solution as raw material is characterized by comprising the following steps:
the method comprises the following steps: taking an arsenic-containing solution containing 0.2-60 g/L of arsenic as a raw material, detecting and analyzing the content of pentavalent arsenic, adding a reducing agent A into the solution for reduction, wherein the using amount of the reducing agent A is 1.5-3 times of the molar theoretical consumption of the pentavalent arsenic in the solution, and after reducing for 0.5-6 hours, finishing the reaction; the reducing agent A is one or a mixture of more than two of sulfur dioxide, sodium sulfite, sodium metabisulfite and sodium thiosulfate in any proportion;
step two: adjusting the acidity of the liquid obtained in the step one by using sulfuric acid, and controlling the concentration of the sulfuric acid in the solution to be 10-250 g/L;
step three: heating the solution obtained in the step two to 40-95 ℃, adding a reducing agent B according to the molar ratio of arsenic to the reducing agent B of 1 (1.5-4) in the liquid, and continuing to react for 1-5 h after the addition is finished; the reducing agent B is one or a mixture of more than two of aluminum powder and cadmium powder in any proportion;
step four: and D, carrying out solid-liquid separation on the reacted liquid obtained in the step three to obtain filtered solution and solid, drying and dehydrating the solid to obtain simple substance arsenic, and feeding the filtered liquid into a subsequent wastewater treatment process to recover other elements.
2. The wet processing process for preparing elemental arsenic from an arsenic-containing solution as claimed in claim 1, wherein the arsenic-containing solution in the first step contains 1-30 g/L arsenic.
3. The wet processing process for preparing elemental arsenic from an arsenic-containing solution as claimed in claim 1, wherein the concentration of sulfuric acid in the second step is 50-150 g/L.
4. The wet processing process for preparing elemental arsenic from an arsenic-containing solution as claimed in claim 1, wherein the heating temperature in step three is 60 ℃ to 95 ℃.
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