CN114606400B - Treatment method of high-iron arsenic-zinc-containing leaching residues - Google Patents
Treatment method of high-iron arsenic-zinc-containing leaching residues Download PDFInfo
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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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- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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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
- C22B41/00—Obtaining germanium
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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
- C22B58/00—Obtaining gallium or indium
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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
- C22B7/007—Wet processes by acid leaching
Abstract
The invention discloses a treatment method of high-iron arsenic-zinc-containing leaching residues, which comprises the following steps: (1) Mixing Gao Tiehan arsenic zinc leaching slag with copper slag and zinc hydrometallurgy zinc electrodeposition waste liquid; (2) Sulfur dioxide is introduced into the slurry to react so as to obtain lead-silver slag and reducing leaching liquid; (3) Mixing iron powder with the reducing leaching solution for reaction; (4) Mixing a part of the copper-precipitating and arsenic-removing liquid with the cuprous arsenide underflow, and simultaneously introducing oxygen; (5) mixing zinc powder with the arsenic-immobilized liquid for reaction; (6) Mixing the copper-deposited liquid with another part of the copper-deposited arsenic-removed liquid; (7) carrying out zinc hydrometallurgy and iron precipitation on the recovered liquid. Therefore, the method has the advantages of short flow, environmental protection and high recovery rate of valuable metals, and simultaneously realizes concentrated solidification of the element arsenic to open a way, thereby having good safety and environmental protection benefits and economic benefits.
Description
Technical Field
The invention relates to the field of metallurgy, in particular to a treatment method of high-iron arsenic-containing zinc leaching residues.
Background
Arsenic is a harmful impurity element in the zinc smelting process, and mainly has the following effects: firstly, arsenic impurities in the new liquid exceed standard, so that electrolysis burning plate is easy to cause, the electric efficiency is reduced, and the electrolysis process cannot be performed when serious; secondly, arsine toxic gas is easy to generate in the replacement reaction process of the arsine-containing acid solution, and serious threat is brought to the life safety of staff; thirdly, the arsenic content is an important index for measuring part of product quality, such as hematite, gypsum and the like, and the quality of the product is affected by the exceeding of arsenic content, so that the economic benefit is affected; fourthly, the arsenic-containing wastewater and the arsenic-containing waste residue have great influence on the ecological environment. Thus, the open circuit of arsenic is an important task for zinc smelting enterprises. In the traditional zinc smelting process, arsenic is generally dispersed in materials such as gypsum slag, jarosite slag, needle iron slag, lead silver slag, smoke dust and the like, so that the arsenic is dispersed, and is difficult to intensively solidify and open a circuit.
Scorodite crystals are a very stable crystalline form of ferric arsenate hydrate (FeAsO) 4 ·2H 2 O), the solubility in aqueous solution is much smaller than that of amorphous ferric arsenate, no secondary pollution is caused by long-term storage, and the method is considered to be the most suitable arsenic-containing solid waste for storage. The stability of scorodite is mainly influenced by the crystallization strength and the particle size, and the scorodite with large particles has small specific surface area, low leaching toxicity and high stability. Thus, scorodite arsenic fixing methodIs the most ideal arsenic open circuit method at present. Common methods for synthesizing scorodite are a hydrothermal method and a modified atmospheric method. In the process of preparing scorodite by a hydrothermal method, the supersaturation degree in the reaction system is low, so that crystal nuclei can grow stably, and scorodite crystals with large particles and high crystallinity can be obtained. In 2008, FUJITA et al proposed the synthesis of scorodite crystals using a modified atmospheric process, but this process is prone to the formation of amorphous ferric arsenate during the preparation process.
Along with development and utilization of high-quality zinc resources, the zinc smelting raw material increasingly presents the characteristic of high impurity polymetallic, mainly shows high iron and high arsenic, and is rich in valuable metal elements such as copper, indium, lead, tin, silver and the like. The existing zinc smelting technology cannot efficiently clean and treat the minerals, so that the development of a zinc smelting method for efficiently recovering valuable metals such as zinc, indium, copper, iron and the like and realizing arsenic centralized solidification open circuit is of great significance aiming at high-iron arsenic-containing zinc leaching residues.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, one object of the invention is to provide a method for treating high-iron arsenic-zinc-containing leaching residues. The method has the advantages of short flow, environmental friendliness and high recovery rate of valuable metals, and simultaneously realizes centralized solidification of the element arsenic, thereby having good safety and environmental protection benefits and economic benefits.
In one aspect of the invention, the invention provides a method for treating high-iron arsenic-zinc-containing leaching slag, wherein the Gao Tiehan arsenic-zinc leaching slag comprises iron, arsenic and indium. According to an embodiment of the invention, the method comprises:
(1) Mixing Gao Tiehan arsenic zinc leaching slag with copper slag and zinc hydrometallurgy zinc electrodeposit waste liquid so as to obtain slurry;
(2) Sulfur dioxide is introduced into the slurry to react so as to obtain lead-silver slag and reducing leaching liquid;
(3) Mixing iron powder with the reducing leaching solution for reaction so as to obtain cuprous arsenide underflow and copper precipitation and dearsenification liquid;
(4) Mixing a part of the copper-precipitating and arsenic-removing liquid with the cuprous arsenide bottom flow, and simultaneously introducing oxygen so as to obtain ferric arsenate precipitation and arsenic-fixing liquid;
(5) Mixing zinc powder with the arsenic-immobilized liquid for reaction so as to obtain copper concentrate and copper-precipitated liquid;
(6) Mixing the copper-precipitated liquid with another part of the copper-precipitated dearsenified liquid so as to obtain metal slag and recovered liquid;
(7) And carrying out zinc hydrometallurgy and iron precipitation on the recovered liquid so as to obtain iron slag and iron precipitation liquid.
According to the treatment method of the high-iron arsenic-zinc-containing leaching slag, the high-iron arsenic-zinc-containing leaching slag is mixed with copper slag and zinc hydrometallurgy zinc electrowinning waste liquid to obtain slurry containing zinc ions, iron ions, indium ions, silver ions, copper ions and lead ions, and then sulfur dioxide and SO are introduced 2 The strong reducibility of Fe (III) is reduced to Fe (II), and simultaneously the reduction of elements such As lead, silver and the like is carried out, lead silver slag and a reducing leaching solution containing Cu (II), as (III) and Fe (II) are obtained, iron powder is added into the reducing leaching solution for reaction, and the iron powder can react with Cu (II) and As (III) in the reducing leaching solution according to 6Cu 2+ +2As 3+ +9Fe＝9Fe 2+ +2Cu 3 Reacting As ∈ to obtain cuprous arsenide bottom flow and copper-precipitating and arsenic-removing liquid, mixing part of the copper-precipitating and arsenic-removing liquid with the cuprous arsenide bottom flow, and introducing oxygen and Cu 3 As is leached and decomposed into free Cu (I) and As (III), and then the Cu (I) is oxidized to form Cu (II), the reaction formula is Cu + +O 2 +H + ＝Cu 2+ +HO 2 As (III) is oxidized to form As (V), and the presence of Cu (II) accelerates the oxidation of Fe (II) to Fe (III), with the reaction formula Cu 2+ +Fe 2+ ＝Cu + +Fe 3+ Thereby the Fe (III) reaches a supersaturation state, and further the Fe and the As in the system are promoted to be Fe 3+ +H 3 AsO 4 +2H 2 O＝FeAsO4·2H 2 O↓+3H + And (3) carrying out a main reaction to generate ferric arsenate precipitate, wherein the residual liquid is arsenic-fixing liquid. Then zinc powder is added into the arsenic-fixing liquid, copper concentrate and copper-precipitating liquid are obtained through displacement reaction, and the obtained copper-precipitating liquid and the other part of copper-precipitating liquidAnd mixing the separated copper-precipitation dearsenifying liquid, then feeding the mixed liquid into a scattered metal recovery system to obtain various metal slag and recovered liquid, and finally, carrying out zinc hydrometallurgy on the recovered liquid to obtain iron slag and iron-precipitation liquid. Therefore, the method has the advantages of short flow, environmental protection and high recovery rate of valuable metals, and simultaneously realizes concentrated solidification of the element arsenic to open a way, thereby having good safety and environmental protection benefits and economic benefits.
In addition, the treatment method of the high-iron arsenic-zinc leaching slag according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, in step (1), the Gao Tiehan arsenic zinc leaching slag is mixed with the copper slag at a total Cu to total As molar ratio of (3.0 to 5.0): 1. Thus, it is ensured that As (III) generates Cu As completely As possible when the subsequent Cu (II) and As (III) react together 3 As precipitates.
In some embodiments of the invention, the liquid to solid ratio of the zinc leach slag and the copper slag to the zinc hydrometallurgy zinc electrodeposit waste stream is (6 to 8) g:1mL.
In some embodiments of the invention, in step (2), the sulfur dioxide is introduced at a rate of 1000 to 2000m 3 /h。
In some embodiments of the invention, in step (2), the reaction satisfies at least one of the following conditions: the initial acidity is 100-130 g/L; the temperature is 110-120 ℃; the pressure is 0.2-0.3 MPa; the time is 1.5-3.0 h. Therefore, the method can realize better copper precipitation and arsenic removal effects, ensure that the iron powder and As (III) do not react basically, and greatly reduce AsH 3 Is generated.
In some embodiments of the invention, in step (3), the iron powder has an excess factor of 1.5 to 1.6. Thereby, the valuable elements in the reducing leaching liquid can be ensured to be fully reduced.
In some embodiments of the invention, in step (3), the reaction is carried out at a temperature of 80 to 90 ℃ for a time of 0.5 to 2.0 hours.
In some embodiments of the invention, in step (3), the pH of the reaction is from 2.0 to 4.0.
In some embodiments of the invention, in step (4), the oxygen gas is introduced at a rate of 500 to 1500m 3 /h。
In some embodiments of the invention, in step (4), the initial acidity of the system is 50-100 g/L. Thereby, ferric arsenate precipitation may be facilitated.
In some embodiments of the present invention, in step (4), the cuprous arsenide underflow and a portion of the copper-precipitating de-arsenic liquor have a total Fe to total As molar ratio of (1.5-2.0): 1, mixing. Thereby, fe (III) can be brought into a supersaturation state, and ferric arsenate (FeAsO) is produced 4 ·2H 2 O) precipitation.
In some embodiments of the invention, in step (4), the system satisfies at least one of the following conditions: the pH value is 1.0-2.0; the temperature is 160-200 ℃; the pressure is 1.0-2.0 MPa; the time is 2.5-3.5 h.
In some embodiments of the invention, in step (5), the zinc dust has an excess factor of 1.2 to 1.5. Thereby, complete replacement of copper can be ensured.
In some embodiments of the invention, in step (5), the pH of the reaction is from 2.0 to 4.0. Thus, the metal slag containing germanium and/or gallium and/or indium can be obtained by facilitating the replacement reaction or neutralization precipitation of the subsequent metal slag.
In some embodiments of the invention, step (6) further comprises: the slag is subjected to a displacement reaction or a neutralization precipitation in order to obtain a slag containing germanium and/or gallium and/or indium.
In some embodiments of the invention, further comprising: and (3) neutral leaching the iron-precipitating solution to obtain the metallic zinc.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow diagram of a method for treating high-iron arsenic-zinc leaching residues according to one embodiment of the invention;
FIG. 2 is a schematic flow chart of a method for treating high-iron arsenic-zinc leaching residues according to still another embodiment of the invention;
FIG. 3 is a schematic flow chart of a method for treating high-iron arsenic-zinc leaching residues according to yet another embodiment of the invention;
FIG. 4 is a flow chart of a process for treating high-iron arsenic-zinc leaching residue according to one embodiment of the invention;
fig. 5 is a flow chart of a treatment process of the high-iron arsenic-zinc leaching residue according to an embodiment of the invention.
Detailed Description
The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In one aspect of the invention, the invention provides a method for treating zinc leaching residues. According to an embodiment of the invention, the method comprises:
s100: mixing Gao Tiehan arsenic zinc leaching slag with copper slag and zinc hydrometallurgy zinc electro-deposition waste liquid
In the step, gao Tiehan arsenic zinc leaching slag is mixed with copper slag and zinc hydrometallurgy zinc electrodeposit waste liquid to obtain slurry.
Further, the high-iron arsenic-containing zinc leaching slag and the copper slag are mixed according to the molar ratio of total Cu to total As of (3.0-5.0): 1. The inventor finds that if the molar ratio of total Cu to total As is too high, unnecessary consumption of energy materials is caused in the copper slag leaching process, and if the molar ratio of total Cu to total As is too low, incomplete As precipitation is caused, and the arsenic removal effect is poor. In the high-iron arsenic-zinc-containing leaching residue, if the molar ratio of Cu to As is 1 (3.0 to 5.0), the addition of copper residue is not required.
Further, the liquid-solid ratio of the zinc leaching slag and the copper slag to the zinc hydrometallurgy zinc electro-deposition waste liquid is (6-8) g:1mL. The inventor discovers that if the addition amount of the zinc electrowinning waste liquid of the wet zinc hydrometallurgy is excessive, the pH value of the reduction leaching liquid is higher, which is unfavorable for ferric arsenate (FeAsO) in the copper precipitation and dearsenization process 4 ·2H 2 O) formation of a precipitate. If the addition amount of the zinc hydrometallurgy zinc electrowinning waste liquid is too small, the leaching rate of Cu and As is low, and the reduction leaching effect is not ideal.
S200: sulfur dioxide is introduced into the slurry for reaction
In the step, sulfur dioxide is introduced into the slurry obtained in the step S100, and the sulfur dioxide can reduce and leach valuable elements in the zinc leaching slag to obtain lead-silver slag and a reducing leaching liquid. Specifically, the sulfur dioxide is introduced at a rate of 1000-2000 m 3 /h。
Further, the above reaction satisfies at least one of the following conditions: the initial acidity is 100-130 g/L; the temperature is 110-120 ℃; the pressure is 0.2-0.3 MPa; the time is 1.5-3.0 h. The inventor finds that if the initial acidity is too high, the pH of the reducing leaching solution is too high, which is unfavorable for ferric arsenate (FeAsO) in the copper precipitation and dearsenization process 4 ·2H 2 O) generating sediment, if the initial acid degree is too low, the leaching rate of Cu and As is low, and the reduction leaching effect is not ideal; meanwhile, if the temperature is too high, energy waste is caused, and if the temperature is too low, the leaching rate of Cu and As is low; if the pressure is too high, the energy waste, the process control risk and the cost are high, and if the pressure is too low, the leaching rate of Cu and As is low, and the reaction rate is slow; in addition, if the reaction time is too long, energy waste and low production efficiency are caused, and if the reaction time is too short, the leaching rate of Cu and As is low, and the reaction rate is slow.
S300: mixing iron powder with the reducing leaching solution for reaction
In the step, iron powder is mixed with the reducing leaching solution for reaction, and the iron powder can jointly react with Cu (II) and As (III) in the reducing leaching solution to generate Cu 3 As is precipitated, the effect of copper precipitation and dearsenification is realized, and cuprous arsenide underflow and copper precipitation and dearsenification liquid are obtained.
Further, the excess coefficient of the iron powder is 1.5 to 1.6. The inventor finds that if the addition amount of the iron powder is insufficient, the precipitation rate of Cu and As is low, and if the addition amount of the iron powder is excessive, the Fe content of the solution after copper precipitation and arsenic removal is excessive, so that the effect of the subsequent iron precipitation process is poor.
Further, the temperature of the reaction is 80-90 ℃ and the time is 0.5-2.0 h. The inventor finds that if the reaction temperature is too high, the energy waste and the process control risk are high, and if the reaction temperature is too low, the reaction rate is slow; if the reaction time is too long, the As content in the solution after copper precipitation and arsenic removal is high.
Further, the pH of the reaction is 2.0 to 4.0. The inventors found that if the pH of the reaction is too high, in solution 3+ Hydrolysis precipitation causes loss of In, and if the pH of the reaction is too low, the consumption of the reducing agent or neutralizing agent required In the subsequent metal slag replacement reaction or neutralization precipitation is too great.
S400: mixing a part of the copper-precipitating dearsenified solution with cuprous arsenide bottom flow, and introducing oxygen
In the step, part of the solution after copper precipitation and arsenic removal is mixed with the bottom flow of cuprous arsenide, and oxygen and Cu are introduced simultaneously 3 As is decomposed into Cu (I) and As (III), cu (I) is oxidized to form Cu (II), as (III) is oxidized to form As (V), and the existence of Cu (II) accelerates the oxidization of Fe (II) to Fe (III), so that Fe (III) reaches a supersaturation state, and Fe and As in the system are promoted to be in accordance with Fe 3+ +H 3 AsO 4 +2H 2 O＝FeAsO 4 ·2H 2 O↓+3H + The main reaction of the method is to generate ferric arsenate precipitate, and the residual liquid is arsenic-fixing liquid, wherein the ferric arsenate precipitate is commonly called scorodite, and the crystal form of the ferric arsenate precipitate is mainly a stable regular octahedron, which is favorable for stacking treatment, thereby realizing centralized solidification open circuit of arsenic. Specifically, the oxygen gas is introduced at a rate of 500-1500 m 3 /h。
Further, the initial acidity of the system is 50-100 g/L. The inventors found that if the initial acidity is too high or too low, it is detrimental to the iron arsenate (FeAsO) during the copper precipitation and dearsenization 4 ·2H 2 O) formation of a precipitate.
Further, the molar ratio of the cuprous arsenide bottom flow to the total As in the copper precipitation and arsenic removal liquid is (1.5-2.0): 1, mixing. The inventor finds that if the molar ratio of total Fe to total As is too high, the solution after copper precipitation and arsenic removal contains too high Fe, the effect of the subsequent iron precipitation process is poor, and if the molar ratio of total Fe to total As is too low, the precipitation rate of Cu and As is low, and the solution after copper precipitation and arsenic removal contains high As.
Further, the system satisfies at least one of the following conditions: the pH value is 1.0-2.0; the temperature is 160-200 ℃; the pressure is 1.0-2.0 MPa; the time is 2.5-3.5 h. The inventors found that at a pH of 1 to 2, the formation of ferric arsenate (FeAsO) is favored 4 ·2H 2 O) precipitation).
S500: zinc powder and arsenic-fixing liquid are mixed for reaction
In the step, zinc powder and the arsenic-fixing post-liquid are mixed for reaction, and after displacement reaction, copper concentrate and copper-precipitating post-liquid are obtained.
Further, the zinc powder has an excess factor of 1.2 to 1.5. The inventor discovers that if the addition amount of zinc powder is too large, the consumption of auxiliary materials is large, the cost is high, if the addition amount of zinc powder is too small, copper precipitation is incomplete, and the copper-precipitated liquid contains Cu 2+ High.
Further, the pH of the reaction is 2.0 to 4.0. The inventors found that if the pH of the reaction is too high or too low, the substitution reaction or neutralization precipitation of the metal slag is not favored.
S600: mixing the solution after copper deposition with another part of the solution after copper deposition and arsenic removal
In the step, the solution after copper deposition is mixed with the other part of the solution after copper deposition and arsenic removal, and then the mixture enters a system for comprehensively recycling scattered metals to obtain metal slag and the solution after the recovery.
Further, referring to fig. 2, step S600 further includes: and carrying out displacement reaction or neutralization precipitation on the metal slag to obtain the metal slag containing germanium and/or gallium and/or indium.
S700: wet zinc smelting and iron depositing are carried out on the recovered liquid
In the step, the recovered solution obtained in the step S600 is subjected to zinc hydrometallurgy and iron precipitation, and conditions required by iron precipitation are controlled to obtain iron slag and iron precipitation solution. It should be noted that, the conditions required for iron deposition are conventional processes, and are not described herein.
Further, referring to fig. 3 and 4, the above-mentioned zinc leaching residue treatment method further includes step S800: and (5) neutral leaching is carried out on the solution after iron precipitation.
In the step, the neutral leaching of the solution after iron deposition can be performed to recover the metallic zinc in the solution after iron deposition.
Mixing the high-iron arsenic-containing zinc leaching slag with copper slag and zinc hydrometallurgy zinc electrodeposition waste liquid to obtain slurry containing zinc ions, iron ions, indium ions, silver ions, copper ions and lead ions, and then introducing sulfur dioxide and SO 2 The strong reducibility of Fe (III) is reduced to Fe (II), and simultaneously the reduction of elements such As lead, silver and the like is carried out, lead silver slag and a reducing leaching solution containing Cu (II), as (III) and Fe (II) are obtained, iron powder is added into the reducing leaching solution for reaction, and the iron powder can react with Cu (II) and As (III) in the reducing leaching solution according to 6Cu 2+ +2As 3+ +9Fe＝9Fe 2+ +2Cu 3 Reacting As ∈ to obtain cuprous arsenide bottom flow and copper-precipitating and arsenic-removing liquid, mixing part of the copper-precipitating and arsenic-removing liquid with the cuprous arsenide bottom flow, and introducing oxygen and Cu 3 As is leached and decomposed into free Cu (I) and As (III), and then the Cu (I) is oxidized to form Cu (II), the reaction formula is Cu + +O 2 +H + ＝Cu 2+ +HO 2 As (III) is oxidized to form As (V), and the presence of Cu (II) accelerates the oxidation of Fe (II) to Fe (III), with the reaction formula Cu 2+ +Fe 2+ ＝Cu + +Fe 3+ Thereby the Fe (III) reaches a supersaturation state, and further the Fe and the As in the system are promoted to be Fe 3+ +H 3 AsO 4 +2H 2 O＝FeAsO4·2H 2 O↓+3H + And (3) carrying out a main reaction to generate ferric arsenate precipitate, wherein the residual liquid is arsenic-fixing liquid. And then zinc powder is added into the solid arsenic post-liquid, copper concentrate and copper post-precipitation liquid are obtained through displacement reaction, the obtained copper post-precipitation liquid is mixed with another part of copper post-precipitation dearsenification liquid and then enters a scattered metal recovery system to obtain various metal slag and recovered post-liquid, and finally, the recovered post-liquid is subjected to zinc hydrometallurgy and iron precipitation to obtain iron slag and iron post-precipitation liquid. Therefore, the method has the advantages of short flow, environmental protection and high recovery rate of valuable metals, and simultaneously realizes concentrated solidification of the element arsenic to open a way, thereby having good safety and environmental protection benefits and economic benefits.
The following detailed description of embodiments of the invention is provided for the purpose of illustration only and is not to be construed as limiting the invention. In addition, all reagents employed in the examples below are commercially available or may be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Examples
Raw materials: the high-iron arsenic-zinc-containing leaching slag contains copper, indium, lead, tin, silver, iron, arsenic and other elements, and the main components and the contents thereof are as follows after determination: the alloy contains 11.46% of Fe, 0.32% of As and 330g/t of In; 45.92% of Cu in the copper slag.
Reduction leaching: the molar ratio of the high-iron arsenic-containing zinc leaching slag to the copper slag is 4:1, mixing the zinc leaching slag, the copper slag and the zinc hydrometallurgy zinc electrodeposition waste liquid according to the solid-to-liquid ratio of 7g:1mL is mixed and pulped and then enters a reduction autoclave, the initial acidity is controlled to be 120g/L, the temperature is controlled to be 110 ℃, and then the mixture is subjected to 1200m 3 Rate of/h of SO 2 Controlling the kettle pressure to be 0.3MPa, and carrying out reduction leaching reaction for 2.5h;
under the conditions of high temperature and high acid, valuable metals such as zinc, iron, indium, copper and the like in the high-iron arsenic-zinc leaching slag are leached into solution, and SO is utilized 2 Reducing Fe (III) into Fe (II) to promote zinc ferrite decomposition (the process also comprises indium ferrite decomposition), and simultaneously carrying out reduction of elements such as lead, silver and the like to obtain lead silver slag and a reduction leaching solution;
wherein the main components and the content of the reducing leaching liquid are as follows: 42g/L, fe (III) Fe (II) 0.3g/L, cu 3.2.2 g/L, as 0.87g/L, in mg/L, wherein the reduction rate of Fe (III) is 99.0%, and the enrichment ratio of lead and silver is more than 12.
Copper precipitation and arsenic removal: adding the reducing leaching solution into a copper precipitation dearsenification reaction tank, then adding iron powder, controlling the excess coefficient of the iron powder to be 1.5, controlling the reaction temperature to be 85 ℃, and reacting for 0.5h;
arsenic in the reducing leaching solution mainly exists in the form of As (III), and under the condition of adding iron powder, as (III) in the solution is precipitated according to 6Cu 2+ +2As 3+ +9Fe＝9Fe 2+ +2Cu 3 As ∈ reaction proceeds to obtain cuprous arsenideUnderflow and copper-precipitating dearsenifying liquid; meanwhile, under the acidic condition, the metallic iron and As (III) are basically not reacted, thereby greatly reducing AsH 3 Is beneficial to the safety of site operation and the occupational health of staff;
the main components and the content of the cuprous arsenide underflow are as follows: 39.4% of Cu and 14.3% of As; the main components of the copper-precipitating and arsenic-removing liquid are as follows: fe 48.1g/L, cu 10.3.3 mg/L, as 3.1.1 mg/L; the precipitation rate of copper and arsenic in the process is more than 98 percent.
Fixing arsenic: part of the cuprous arsenide underflow and the solution after copper precipitation and arsenic removal is mixed according to the mole ratio of total Fe to total As of 1.5:1, mixing, and feeding into an autoclave for fixing arsenic, controlling pH to 1.2, pressure to 2.0MPa, temperature to 180deg.C, and mixing at 850m 3 Oxygen was introduced at a rate of/h and reacted for 3h.
Zn-Cu-Fe-As-H under high temperature, pressurized and oxidizing atmosphere 2 SO 4 In the system, cu 3 Leaching and decomposing As into free Cu (I) and As (III), and oxidizing Cu (I) to form Cu (II) and oxidizing As (III) to form As (V); the presence of Cu (II) accelerates the oxidation of Fe (II) to Fe (III) (Cu under an oxygen atmosphere) 2+ +Fe 2+ ＝Cu + +Fe 3+ ，Cu + +O 2 +H + ＝Cu 2+ +HO 2 ) Thereby the Fe (III) reaches a supersaturation state, and the Fe and the As in the system are promoted to be Fe 3+ +H 3 AsO 4 +2H 2 O＝FeAsO4·2H 2 O↓+3H + The main reaction is carried out, the coprecipitation is ferric arsenate precipitation (which contains basic ferric sulfate, iron vitriol and zinc polymer) mainly containing ferric arsenate particles, and the residual liquid is arsenic-fixing liquid. The ferric arsenate sediment is commonly called scorodite, and the crystal form of the ferric arsenate sediment is mainly a stable regular octahedron, which is beneficial to stacking treatment, thereby realizing centralized solidification open circuit of arsenic.
Wherein the ferric arsenate sediment mainly comprises the following components in percentage by weight: fe32.4%, as24.7%; the arsenic-fixing liquid comprises the following main components in percentage by weight: cu31.7g/L, fe < 1g/L, as < 0.3g/L; the arsenic precipitation rate in the process is more than 96 percent, and the iron precipitation rate is more than 92 percent.
Copper deposition: and (3) feeding the arsenic-fixed liquid into a copper-precipitating reaction tank, adding zinc powder with the zinc powder excess coefficient of 1.5, and carrying out displacement reaction to obtain copper concentrate and copper-precipitating liquid. Copper concentrate is sold, and valuable metals are recycled.
Wherein the main components and the content of the copper concentrate are as follows: cu58.7%, zn < 2%; the Cu content of the copper-precipitating solution is less than 1g/L.
Comprehensively recovering the scattered metal: mixing the copper-precipitating solution with the rest copper-precipitating dearsenifying solution, and feeding into a system for comprehensively recovering rare metal, wherein Fe (III) in the reducing leaching solution is introduced with SO 2 After the reaction, almost all the Fe (II) is reduced to generate, and various metal slag rich in germanium and/or gallium and/or indium and comprehensively recovered liquid can be obtained by adopting a zinc powder replacement or neutralization precipitation method.
And (3) iron deposition: placing the comprehensively recovered solution into a ferric precipitation reaction kettle, controlling the temperature to 175 ℃ and controlling the temperature to 900m 3 And (3) introducing oxygen, controlling the kettle pressure to be 1.5MPa, and reacting for 3 hours to obtain iron slag and iron-precipitating liquid.
Wherein the content of Fe in the iron slag is 55.32 percent, and the Fe content of the solution after iron precipitation is less than 5g/L.
In summary, according to the treatment method of the high-iron arsenic-zinc-containing leaching residues, SO is utilized first 2 The valuable elements in Gao Tiehan arsenic-zinc leaching slag are fully leached in the strong reducing atmosphere, and the leaching rate of zinc, copper, iron, arsenic and indium is more than 96 percent; and then part of iron in the leaching solution reacts with arsenic to generate stable ferric arsenate precipitate, so that concentrated solidification open circuit of impurity arsenic is realized by more than 85%, the problem of arsenic dispersion and difficult open circuit in the zinc hydrometallurgy process is solved, and the potential hazard of arsenic to the environment is avoided; meanwhile, copper in the zinc material is recovered in the form of copper concentrate, the recovery rate is more than 90%, and the rest iron is produced into high-quality iron slag through a zinc hydrometallurgy iron precipitation process.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (16)
1. A method for treating high-iron arsenic-zinc-containing leaching slag, wherein the Gao Tiehan arsenic-zinc leaching slag comprises iron, arsenic and indium, and is characterized by comprising the following steps:
(1) Mixing Gao Tiehan arsenic zinc leaching slag with copper slag and zinc hydrometallurgy zinc electrodeposit waste liquid so as to obtain slurry;
(2) Sulfur dioxide is introduced into the slurry to react so as to obtain lead-silver slag and reducing leaching liquid;
(3) Mixing iron powder with the reducing leaching solution for reaction so as to obtain cuprous arsenide underflow and copper precipitation and dearsenification liquid;
(4) Mixing a part of the copper-precipitating and arsenic-removing liquid with the cuprous arsenide bottom flow, and simultaneously introducing oxygen so as to obtain ferric arsenate precipitation and arsenic-fixing liquid;
(5) Mixing zinc powder with the arsenic-immobilized liquid for reaction so as to obtain copper concentrate and copper-precipitated liquid;
(6) Mixing the copper-precipitated liquid with another part of the copper-precipitated dearsenified liquid so as to obtain metal slag and recovered liquid;
(7) And carrying out zinc hydrometallurgy and iron precipitation on the recovered liquid so as to obtain iron slag and iron precipitation liquid.
2. The method according to claim 1, wherein in the step (1), the Gao Tiehan arsenic zinc leaching residue and the copper residue are mixed in a molar ratio of total Cu to total As of (3.0 to 5.0): 1.
3. The method according to claim 1, wherein in the step (1), the solid-to-liquid ratio of the zinc leaching residue and the copper slag to the zinc hydrometallurgy electro-deposition waste liquid is (6 to 8) g:1mL.
4. The process according to claim 1, wherein in step (2), the sulfur dioxide is introduced at a rate of 1000 to 2000m 3 /h。
5. The process of claim 1, wherein in step (2), the reaction satisfies at least one of the following conditions:
the initial acidity is 100-130 g/L;
the temperature is 110-120 ℃;
the pressure is 0.2-0.3 MPa;
the time is 1.5-3.0 h.
6. The method according to claim 1, wherein in the step (3), the iron powder has an excess factor of 1.5 to 1.6.
7. The process according to claim 1, wherein in step (3), the reaction is carried out at a temperature of 80 to 90 ℃ for a time of 0.5 to 2.0 hours.
8. The process according to claim 1, wherein in step (3), the pH of the reaction is 2.0 to 4.0.
9. The process according to claim 1, wherein in the step (4), the oxygen gas is introduced at a rate of 500 to 1500m 3 /h。
10. The process according to claim 1, wherein in step (4), the initial acidity of the system is 50 to 100g/L.
11. The process according to claim 1, wherein in step (4), the cuprous arsenide underflow and a part of the copper-precipitating de-arsenic liquor are mixed according to a total Fe to total As molar ratio of (1.5-2.0): 1, mixing.
12. The process of claim 1, wherein in step (4), the system satisfies at least one of the following conditions:
the pH value is 1.0-2.0;
the temperature is 160-200 ℃;
the pressure is 1.0-2.0 MPa;
the time is 2.5-3.5 h.
13. The process of claim 1, wherein in step (5), said zinc dust has an excess factor of 1.2 to 1.5.
14. The process according to claim 1, wherein in step (5), the pH of the reaction is 2.0 to 4.0.
15. The process of claim 1, wherein step (6) further comprises: the slag is subjected to a displacement reaction or a neutralization precipitation in order to obtain a slag containing germanium and/or gallium and/or indium.
16. The method of processing according to claim 1, further comprising: and (3) neutral leaching the iron-precipitating solution to obtain the metallic zinc.
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| CN115109920B (en) * | 2022-06-20 | 2023-09-22 | 云锡文山锌铟冶炼有限公司 | Method for reducing zinc and sulfur in hematite by zinc hydrometallurgy system |
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