CN114134332A - Method for selectively leaching valuable metals in zinc kiln slag - Google Patents

Method for selectively leaching valuable metals in zinc kiln slag Download PDF

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Publication number
CN114134332A
CN114134332A CN202111438800.8A CN202111438800A CN114134332A CN 114134332 A CN114134332 A CN 114134332A CN 202111438800 A CN202111438800 A CN 202111438800A CN 114134332 A CN114134332 A CN 114134332A
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China
Prior art keywords
slag
leaching
zinc
solution
indium
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Pending
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CN202111438800.8A
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Chinese (zh)
Inventor
张帆
卢佳佳
张艳琼
黄巍巍
张思瑞
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Yunnan Minzu University
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Yunnan Minzu University
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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
    • C22B7/04—Working-up slag
    • 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
    • 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
    • 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
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • 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
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • 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
    • 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 invention discloses a method for selectively leaching valuable metals in zinc kiln slag, and belongs to the technical field of comprehensive utilization of resources. The invention takes zinc hydrometallurgy kiln slag as a raw material, a sulfuric acid aqueous solution as a leaching agent, the zinc kiln slag is selectively leached through oxygen pressure, valuable metals such as zinc, copper, indium and the like enter a leaching solution, and iron is hydrolyzed and converted into hematite under a high-temperature oxygen atmosphere and is retained in the leaching slag. And adding metal iron powder into the leaching solution for replacing and recovering copper, adding zinc oxide powder into the solution after copper precipitation for neutralizing and precipitating indium to obtain zinc sulfate solution and indium slag. The invention realizes the selective leaching of copper, zinc and indium in the zinc kiln slag and reduces the recovery cost of valuable metals in the zinc kiln slag. The method has the advantages of simple process and economy, and can treat materials with low content of valuable metals.

Description

Method for selectively leaching valuable metals in zinc kiln slag
Technical Field
The invention relates to a method for selectively leaching valuable metals in zinc kiln slag, belonging to the technical field of comprehensive utilization of resources.
Background
The conventional zinc hydrometallurgy process is adopted, and about 0.8 ton of zinc kiln slag is produced when 1 ton of metal zinc is produced. Every year, ChinaThe zinc smelting enterprise produces about 400 million tons of zinc kiln slag. Although most of Cu, Ag and Fe in the raw materials for smelting the zinc remain in the zinc kiln slag, the contents of Cu, Ag and Fe in the zinc kiln slag are still low. For the smelting slag with lower valuable metal content, some smelting enterprises select a method for producing copper matte by mixing zinc kiln slag and pyrite at high temperature to recover copper and silver in the zinc kiln slag. Because the contents of Cu and Ag in the zinc kiln slag are low, the method has poor economic benefit and low-concentration SO2The waste gas is difficult to treat. And part of smelting enterprises adopt flotation-magnetic separation and other beneficiation methods to treat the zinc kiln slag to respectively produce iron ore concentrate, carbon powder, tailings and other minerals. However, the separation of Cu and Ag in the zinc kiln slag in iron ore concentrate and tailings is low, and the recovery rate of valuable metals is low. In conclusion, the zinc kiln slag produced by zinc smelting enterprises in China is large in quantity and contains a certain amount of valuable metals every year, and the zinc kiln slag is a metal resource worth of recycling. However, at present, no efficient and clean treatment method can effectively recover valuable metals in the zinc kiln. Under the background, the invention provides a method for treating zinc kiln slag by oxygen pressure selective leaching.
Disclosure of Invention
The invention provides a method for selectively leaching valuable metals in zinc kiln slag, aiming at the problems of the existing wet-process zinc smelting kiln slag treatment technology. The invention can realize the economic and high-efficiency recovery of valuable metals such as copper, zinc, indium and the like in the zinc kiln slag.
The invention relates to a method for selectively leaching valuable metals in zinc kiln slag, which comprises the following steps:
the method comprises the following steps: and mixing the zinc kiln slag and a sulfuric acid solution, and then performing a leaching link. The leaching link consists of pre-neutralization and oxygen pressure leaching. The zinc kiln slag is firstly mixed with oxygen pressure leaching liquid obtained in the last leaching link for pre-neutralization, and the mixture is reacted for 10 to 30min at the temperature of between 40 and 80 ℃, and the pH value at the end point of the reaction is controlled to be between 1.0 and 1.5. And then, obtaining pre-neutralization liquid and pre-neutralization slag through solid-liquid separation. The preneutralized slag and the sulfuric acid solution are mixed and then added into a high-pressure reaction kettle for oxygen pressure leaching, and the reaction is carried out for 2 to 4 hours under the conditions that the temperature is 120 to 180 ℃ and the oxygen partial pressure is 0.1 to 1.2 MPa. The copper, indium and zinc in the zinc kiln slag are leached into the solution, and the iron in the zinc kiln slag is converted into hematite to enter the slag. And then, carrying out solid-liquid separation to obtain an oxygen pressure leaching solution and oxygen pressure leaching slag.
Step two: adding iron powder into the pre-neutralization solution, performing liquid-solid separation after a displacement reaction to obtain copper slag and a displaced solution; the adding amount of the iron powder is 1.1 to 1.4 times of the theoretical amount of the simple substance iron needed for replacing the copper ions in the leaching solution.
Step three: adding zinc oxide powder into the solution after replacement to regulate and control the pH value of the end point to be 3.5-4.0, and hydrolyzing and precipitating indium in the solution to obtain indium precipitation slag and indium precipitation night. And the indium precipitation slag is used as a raw material for extracting indium, and the liquid after indium precipitation is sent to a zinc hydrometallurgy main system.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: in this embodiment, the wet zinc smelting kiln slag mainly comprises the following components by mass percent: fe 34.14%, Cu 1.34%, Zn 2.65%, As 0.53%, S5.27%, In 104.3 g/t.
A method for comprehensively utilizing kiln slag and waste acid in zinc hydrometallurgy comprises the following specific steps:
(1) under the condition that the temperature is 50 ℃, 100g of wet-process zinc smelting kiln slag is added into 1.0L of dilute sulfuric acid solution A for pre-neutralization until the pH value of the solution is 1.2, so that a neutralization solution and neutralization slag are obtained; wherein the concentration of sulfuric acid in the dilute sulfuric acid solution A is 20 g/L;
(2) mixing the neutralized slag obtained in the step (1) with 1.0L of dilute sulfuric acid solution B, pulping, performing oxygen pressure leaching to obtain oxidized leached slag and oxidized leached liquid, and returning the oxidized leached liquid to the step (1) to replace the dilute sulfuric acid solution A for pre-neutralization under the conditions that the temperature is 140 ℃ and the oxygen partial pressure is 0.8 Mpa; wherein the concentration of the dilute sulfuric acid solution B is 80 g/L;
(3) adding iron powder into the preneutralized solution obtained in the step (1) at the temperature of 80 ℃ for displacement copper precipitation treatment, and obtaining copper precipitation slag and a copper precipitation solution after 20 min; wherein the adding amount of the iron powder is 1.4 times of the stoichiometric theoretical value of the chemical reaction; in the embodiment, the precipitation rate of copper is 98.6%, and the obtained copper precipitation slag contains Cu47.43%;
(4) adding zinc oxide powder into the copper precipitation solution obtained in the step (3) at the temperature of 50 ℃ to perform neutralization indium precipitation treatment, controlling the pH value of the reaction end point to be 3.8, and obtaining indium precipitation slag and indium precipitation solution after 30 min; the precipitation rate of indium in this example was 95.3%.
Example 2: in this embodiment, the wet zinc smelting kiln slag mainly comprises the following components by mass percent: fe 29.73%, Cu 1.62%, Zn 2.43%, As 0.49%, S5.68%, and In 116.5 g/t.
A method for comprehensively utilizing kiln slag and waste acid in zinc hydrometallurgy comprises the following specific steps:
(1) under the condition that the temperature is 60 ℃, 100g of wet-process zinc smelting kiln slag is added into 1.2L of dilute sulfuric acid solution A for pre-neutralization until the pH value of the solution is 1.4, so as to obtain a neutralization solution and neutralization slag; wherein the concentration of sulfuric acid in the dilute sulfuric acid solution A is 15 g/L;
(2) mixing the neutralized slag obtained in the step (1) with 1.2L of dilute sulfuric acid solution B under the conditions of the temperature of 160 ℃ and the oxygen partial pressure of 1.0Mpa, carrying out oxygen pressure leaching to obtain oxidized leached slag and oxidized leached liquid, and returning the oxidized leached liquid to the step (1) to replace the dilute sulfuric acid solution A for pre-neutralization; wherein the concentration of the dilute sulfuric acid solution B is 70 g/L;
(3) adding iron powder into the preneutralized solution obtained in the step (1) at the temperature of 70 ℃ for displacement copper precipitation treatment, and obtaining copper precipitation slag and a copper precipitation solution after 20 min; wherein the adding amount of the iron powder is 1.3 times of the stoichiometric theoretical value of the chemical reaction; in the embodiment, the precipitation rate of copper is 96.4%, and the obtained copper precipitation slag contains Cu52.46%;
(4) adding zinc oxide powder into the copper precipitation solution obtained in the step (3) at the temperature of 50 ℃ to perform neutralization indium precipitation treatment, controlling the pH value of the reaction end point to be 3.5, and obtaining indium precipitation slag and indium precipitation solution after 30 min; the precipitation rate of indium in this example was 93.7%.
Example 3: in this embodiment, the wet zinc smelting kiln slag mainly comprises the following components by mass percent: 25.43 percent of Fe, 1.03 percent of Cu, 2.02 percent of Zn, 0.42 percent of As, 5.04 percent of S and 90.6g/t of In.
A method for comprehensively utilizing kiln slag and waste acid in zinc hydrometallurgy comprises the following specific steps:
(1) under the condition that the temperature is 50 ℃, 100g of zinc hydrometallurgy kiln slag is added into 0.8L of dilute sulfuric acid solution A for pre-neutralization until the pH value of the solution is 1.0, so as to obtain a neutralization solution and neutralized slag, wherein the sulfuric acid concentration in the dilute sulfuric acid solution A is 25 g/L;
(2) mixing the neutralized slag obtained in the step (1) with 0.8L of dilute sulfuric acid solution B under the conditions of the temperature of 150 ℃ and the oxygen partial pressure of 1.0Mpa, carrying out oxygen pressure leaching to obtain oxidized leached slag and oxidized leached liquid, and returning the oxidized leached liquid to the step (1) to replace the dilute sulfuric acid solution A for pre-neutralization; wherein the concentration of the dilute sulfuric acid solution B is 80 g/L;
(3) adding iron powder into the preneutralized solution obtained in the step (1) at the temperature of 80 ℃ for displacement copper precipitation treatment, and obtaining copper precipitation slag and a copper precipitation solution after 20 min; wherein the adding amount of the iron powder is 1.4 times of the stoichiometric theoretical value of the chemical reaction; in the embodiment, the precipitation rate of copper is 98.8%, and the obtained copper precipitation slag contains Cu48.79%;
(4) adding zinc oxide powder into the copper precipitation solution obtained in the step (3) at the temperature of 60 ℃ to perform neutralization indium precipitation treatment, controlling the pH value of the reaction end point to be 3.7, and obtaining indium precipitation slag and indium precipitation solution after 30 min; the precipitation rate of indium in this example was 94.9%.

Claims (3)

1. A method for selectively leaching valuable metals in zinc kiln slag is characterized by comprising the following steps:
the method comprises the following steps: and mixing the zinc kiln slag and a sulfuric acid solution, and then performing a leaching link. The leaching link consists of pre-neutralization and oxygen pressure leaching. The zinc kiln slag is firstly mixed with oxygen pressure leaching liquid obtained in the last leaching link for 'preneutralization', and then preneutralization liquid and preneutralization slag are obtained through solid-liquid separation. And mixing the preneutralized slag and a sulfuric acid solution, adding the mixture into a high-pressure reaction kettle for oxygen pressure leaching, leaching copper, indium and zinc in zinc kiln slag into the solution, and converting iron in the zinc kiln slag into hematite into slag. And then, carrying out solid-liquid separation to obtain an oxygen pressure leaching solution and oxygen pressure leaching slag.
Step two: and adding iron powder into the pre-neutralization solution, performing displacement reaction and then performing liquid-solid separation to obtain copper slag and a solution after copper precipitation.
Step three: and adding zinc oxide powder into the copper precipitation solution, and hydrolyzing and precipitating indium in the copper precipitation solution to obtain indium precipitation slag and indium precipitation solution. And the indium precipitation slag is used as a raw material for extracting indium, and the liquid after indium precipitation is sent to a zinc hydrometallurgy main system.
2. The method for selectively leaching valuable metals from zinc kiln slag according to claim 1, wherein the leaching link in the first step is composed of pre-neutralization and oxygen pressure leaching, the zinc kiln slag is firstly mixed with the oxygen pressure leaching solution obtained in the last leaching link for pre-neutralization, the reaction is carried out for 10-30min at the temperature of 40-80 ℃, and the pH at the end point of the reaction is controlled to be 1.0-1.5.
3. The method for selectively leaching valuable metals from zinc kiln slag according to claim 1, wherein the preneutralized slag in the first step is mixed with sulfuric acid solution and then added into a high-pressure reaction kettle for oxygen pressure leaching, and the mixture is reacted for 2 to 4 hours at the temperature of 120 ℃ to 180 ℃ and under the oxygen partial pressure of 0.1MPa to 1.2 MPa.
CN202111438800.8A 2021-11-26 2021-11-26 Method for selectively leaching valuable metals in zinc kiln slag Pending CN114134332A (en)

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