CN115261625A - Method for recovering copper and arsenic step by step in combined leaching of black copper mud and arsenic filter cake - Google Patents
Method for recovering copper and arsenic step by step in combined leaching of black copper mud and arsenic filter cake Download PDFInfo
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- 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
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- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
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- C22B15/00—Obtaining copper
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- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
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Abstract
The invention discloses a method for recovering copper and arsenic step by step in combined leaching of black copper mud and an arsenic filter cake. Firstly, pulping black copper mud and dilute sulfuric acid or a reduced liquid, carrying out oxygen pressure acid leaching reaction on the obtained slurried liquid to obtain a leached liquid, carrying out pressure filtration on the leached liquid to obtain a copper-rich liquid and lead-bismuth slag, and recycling the lead-bismuth slag; sequentially carrying out evaporation concentration, cooling crystallization and filtration on the copper-rich liquid to obtain copper sulfate crystals and a crystallized liquid; slurrying the crystallized solution and a sulfuric acid solution or a reduced solution and an arsenic filter cake, carrying out oxygen pressure acid leaching reaction on the obtained slurry to obtain a leached solution, and filtering to obtain an arsenic-rich solution and sulfur slag; and (4) carrying out reduction reaction on the arsenic-rich solution to obtain an arsenic trioxide product and a reduced solution, and recycling the reduced solution. The invention can comprehensively and efficiently treat the black copper sludge and the arsenic filter cake.
Description
1. The technical field is as follows:
the invention relates to the technical field of secondary utilization of hazardous waste containing copper and arsenic, in particular to a method for recovering copper and arsenic step by step in combined leaching of black copper mud and an arsenic filter cake.
2. Background art:
in the copper electrolysis process, besides copper, as, sb and Bi with the electric potential close to that of Cu enter the electrolyte in the electrolysis process, so that impurity elements in the copper electrolyte are increased, and the product quality is influenced by continuous enrichment. Therefore, the electrolyte needs to be purified. The electrolyte is purified by adopting an electrodeposition process, as, sb and Bi are removed by electrodeposition, but a large amount of corresponding Cu is electrodeposited, and black copper mud is formed. At present, the method for treating the black copper sludge mainly comprises furnace returning treatment, arsenic circulation in a system is caused by the furnace returning treatment, the quality of copper matte is influenced, and impurity elements of Sb, bi and the like to a copper smelting system are introduced again. Therefore, a new process for treating the black copper sludge needs to be found. The existing methods for treating the black copper sludge are divided into a wet method and a fire method. The wet treatment of the black copper sludge mostly adopts methods such as oxygen-pressure acid leaching and oxygen-pressure alkali leaching. The invention patent application CN 103288133A discloses a method for preparing arsenic trioxide by using black copper mud. In the method, sodium hydroxide is used As a leaching agent, wherein As enters a solution in a pentavalent form, sb, bi, cu and the like are mainly left in slag, then sulfuric acid is used for adjusting the pH, and sulfur dioxide is introduced to obtain As2O3. The invention patent application CN 103290221A discloses a method for recovering copper, arsenic and antimony from black copper sludge. In the method, sulfuric acid is used for leaching Cu and As in black copper sludge, and then alkali is used for adjusting the pH value in a leaching solution to prepare copper arsenate. For the two existing treatment processes, the problems of long process and difficult treatment of waste brine exist, and the leachate obtained after direct oxygen pressure acid leaching has high copper and arsenic content and is difficult to separate copper and arsenic.
The arsenic filter cake acid-contaminated station treats waste residues generated by other heavy metals such as arsenic, copper and the like through a vulcanization process, the arsenic filter cake treatment method has solidification landfill, certain risks may exist in the solidification landfill, the national landfill policy on hazardous wastes is more severe, and the solidification landfill is the next strategy; oxidizing roasting, wherein the oxidizing roasting process generates arsenic trioxide, the field environment is severe, the purity of the recovered arsenic trioxide is not high, and fewer manufacturers for treating arsenic filter cakes by using a pyrogenic process are provided in China; a wet process comprising: 1) Copper powder is replaced, oxidized and reduced to obtain arsenic trioxide; the wet process has the problems of safe production and reliable process, but has long normal pressure displacement flow, high cost and low arsenic yield. 2) Acid leaching under oxygen pressure: the arsenic filter cake is treated by acid leaching under oxygen pressure, and the method has the advantages of short process, high efficiency and high recovery rate.
3. The invention content is as follows:
the technical problem to be solved by the invention is as follows: according to the current conditions of the existing treatment processes of the black copper mud and the arsenic filter cake, in order to comprehensively and efficiently treat the black copper mud and the arsenic filter cake, the invention provides a method for treating the black copper mud and the arsenic filter cake by using oxygen pressure acid leaching, namely the invention provides a method for recovering copper and arsenic step by step in the combined leaching of the black copper mud and the arsenic filter cake.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a method for recovering copper and arsenic step by step in combined leaching of black copper mud and arsenic filter cakes, which comprises the following steps:
a. g, pulping the black copper mud and dilute sulfuric acid or the black copper mud and the reduced liquid obtained in the step g in a matching manner to obtain a pulping liquid;
b. b, putting the slurry liquid obtained in the step a into a reactor, introducing steam for heating, introducing industrial pure oxygen for carrying out oxygen pressure acid leaching reaction after heating to the reaction temperature, and obtaining a leached liquid after reaction; carrying out filter pressing on the obtained leached liquid to obtain copper-rich liquid and lead-bismuth slag, wherein the obtained lead-bismuth slag is used for treating a lead smelting system;
c. c, introducing the copper-rich liquid obtained in the step b into the evaporator for evaporation and concentration, wherein the specific gravity of the evaporated liquid is 1.39-1.42;
d. introducing the evaporated liquid into a crystallization tank for cooling crystallization, and filtering by using a belt filter after cooling crystallization to obtain copper sulfate crystals and a crystallized liquid;
e. slurrying the obtained crystallized liquid, sulfuric acid solution and arsenic filter cake, or slurrying the obtained crystallized liquid, the reduced liquid in the step g and the arsenic filter cake to obtain arsenic filter cake slurry;
f. e, introducing the arsenic filter cake slurry liquid obtained in the step e into a reactor, introducing steam for heating, introducing oxygen for carrying out oxygen pressure acid leaching reaction, and obtaining a leached liquid after the reaction; carrying out filter pressing on the obtained leached liquid to obtain arsenic-rich liquid and sulfur slag;
g. guiding the arsenic-rich liquid obtained in the step f into a reduction reaction kettle, introducing sulfur dioxide gas for reduction reaction, and obtaining arsenic trioxide and a reduced liquid after the reaction; centrifuging and drying the obtained arsenic trioxide to obtain an arsenic trioxide product (sold or used as a raw material for preparing metal arsenic), and returning the reduced liquid to the step e or the step a for slurrying.
According to the method for recovering copper and arsenic step by step in the combined leaching of the black copper sludge and the arsenic filter cake, the concentration of the dilute sulfuric acid in the step a is 80-120 g/L; the volume-mass ratio of the dilute sulfuric acid to the black copper sludge is 6-8 mL:1g of a compound; the volume mass ratio of the reduced liquid to the black copper mud is 6-8 mL:1g of the total weight of the composition.
According to the method for recovering copper and arsenic step by step in the combined leaching of the black copper mud and the arsenic filter cake, in the step b, the reaction pressure is 0.7-1.1 Mpa, the reaction temperature is 110-120 ℃, and the reaction time is 1.5-3 hours in the oxygen pressure acid leaching process; the flow rate of the industrial pure oxygen is 300-400 m3/h。
According to the method for recycling copper and arsenic step by step in the combined leaching of the black copper mud and the arsenic filter cake, the evaporation and concentration in the step c is vacuum evaporation or direct evaporation by adopting an enamel evaporator.
According to the method for recovering copper and arsenic step by step in the combined leaching of the black copper mud and the arsenic filter cake, the cooling crystallization temperature in the step d is 20-25 ℃ (preferably 20-22 ℃); the cooling mode is cooling by circulating water or adding a refrigerator device for cooling;
the obtained copper sulfate crystal is reused as a raw material of a smelting system, or a copper sulfate product is obtained by methods of re-dissolving, impurity removal and re-crystallization for sale.
According to the method for recovering copper and arsenic step by step in the combined leaching of the black copper sludge and the arsenic filter cake, the acidity of the sulfuric acid solution in the step e is 60-80 g/l;
when the crystallized solution, the sulfuric acid solution and the arsenic filter cake are slurried, the ratio of the sum of the volumes of the crystallized solution and the sulfuric acid solution to the mass of the arsenic filter cake is 10-12 mL:1g of a compound; and G, when the liquid after crystallization, the liquid after reduction in the step g and the arsenic filter cake are pulped, the ratio of the sum of the volumes of the liquid after crystallization and the liquid after reduction to the mass of the arsenic filter cake is 10-12 mL:1g.
According to the method for recovering copper and arsenic step by step in the combined leaching of the black copper mud and the arsenic filter cake, in the oxygen pressure acid leaching process in the step f, the reaction pressure is 1.0-1.3 MPa, the reaction temperature is 105-120 ℃, and the reaction time is 2.5-4 hours; the flow rate of the oxygen is 200-300 m3/h；
The obtained sulfur slag directly enters a smelting system to provide heat, and sulfur dioxide flue gas is generated to prepare acid; or obtaining a sulfur product by flotation.
According to the method for recovering copper and arsenic step by step in the combined leaching of the black copper mud and the arsenic filter cake, in the reduction reaction process in the step g, the concentration of sulfur dioxide gas is 5-8% (sulfur dioxide is introduced into a reduction reaction kettle through the bottom of the reaction kettle or is introduced into the reduction reaction kettle in a Venturi circulation mode), and the introduction amount of the sulfur dioxide gas is 200-300 m3/h。
According to the method for recovering copper and arsenic step by step in the combined leaching of the black copper mud and the arsenic filter cake, in the reduction reaction process in the step g, the reaction temperature is controlled to be 25-30 ℃, and the reaction time is 8-12 hours.
The technical principle adopted by the technical scheme of the invention is as follows:
the main component of the black copper mud is copper-arsenic alloy, the black copper mud is leached by using an oxygen pressure acid leaching method, copper and arsenic are rapidly leached under the conditions of high temperature and high pressure, and copper sulfate solubility curves are used for evaporation concentration and cooling crystallization to obtain copper sulfate crystals; the arsenic filter cake is stable in a normal state, and a certain amount of copper ions are supplemented for oxygen pressure acid leaching by adopting an oxygen pressure acid leaching method, so that the arsenic acid solution is obtained by efficient leaching and oxidation, and arsenic acid is reduced by sulfur dioxide to obtain arsenic trioxide. The relevant reaction equation is as follows:
4Cu3As+9O2+12H2SO4＝12CuSO4+4HAsO2+10H2O
2HAsO2+O2+2H2O＝2H3AsO4
2As2S3+3O2+2H2O＝4HAsO2+6S
2HAsO2+O2+2H2O＝2H3AsO4
2H3AsO4+2SO2+2H2O＝As2O3·3H2O+2H2SO4
the invention has the following positive beneficial effects:
1. the black copper mud and the arsenic filter cake are jointly treated by the oxygen pressure acid leaching method, and the leaching efficiency of the black copper mud and the arsenic filter cake is greatly improved by adopting the oxygen pressure acid leaching method.
2. The invention provides a method for leaching arsenic filter cakes by using a liquid obtained after black copper mud crystallization, which not only opens a circuit for the high-copper high-arsenic liquid, but also promotes the oxygen pressure acid leaching reaction of the arsenic filter cakes; the leachate obtained by leaching the arsenic filter cake through the acid pressing is an arsenic acid solution, the reaction of the arsenic acid solution for generating the arsenious acid through reduction of sulfur dioxide is an acid production process, the leaching process of the black copper mud is an acid consumption process, and the black copper mud is leached by using the reduced leachate, so that 20% of acid in the system can be balanced, the system can run more stably, and the external liquid discharge capacity is reduced.
3. According to the technical scheme, black copper mud and arsenic filter cakes are treated by oxygen pressure acid leaching, harmful elements are extracted, and obtained leaching slag can be used as a raw material of a smelting system, so that arsenic circulation of the smelting system is reduced, and the treatment capacity of the smelting system is improved; the black copper sludge leachate is evaporated, concentrated, cooled and crystallized to obtain copper sulfate crystals, the copper content of the obtained copper sulfate crystals is more than 33%, the copper recovery rate is more than 71%, the arsenic trioxide is obtained by reducing, centrifuging, washing and drying the arsenic filter cake leachate through sulfur dioxide, the purity of the arsenic trioxide can reach 99.3%, the direct yield of the arsenic trioxide reaches 90%, and therefore the purpose of recovering copper and arsenic is achieved.
4. Description of the drawings:
FIG. 1 is a schematic diagram of a process flow of the method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes.
5. The specific implementation mode is as follows:
the invention is further illustrated by the following examples, which do not limit the scope of the invention.
Example 1:
the invention relates to a method for recovering copper and arsenic step by step in combined leaching of black copper mud and arsenic filter cakes, which comprises the following detailed steps:
a. proportioning and pulping black copper mud (the chemical components of main metal elements are Cu 40.1% and As 25.37%) and dilute sulfuric acid, wherein the concentration of the dilute sulfuric acid is 120g/L; the volume-mass ratio of the dilute sulfuric acid to the black copper sludge is 6mL:1g of a compound; obtaining slurrying liquid after slurrying;
b. putting the slurry liquid obtained in the step a into a reactor, introducing steam for heating, introducing industrial pure oxygen for oxygen pressure acid leaching reaction after heating to the reaction temperature, wherein the flow of the industrial pure oxygen is 350m3Reaction pressure of 0.9Mpa, reaction temperature of 120 ℃ and reaction time of 2.5h, and leaching solution is obtained after reaction; filter-pressing the obtained leached liquid to obtain copper-rich liquid (Cu)2+：70.21g/l、As5+:40.25 g/l) and lead bismuth slag (Pb: 21.35%, bi:23.13 percent) and the obtained lead bismuth slag is used for the treatment of a lead smelting system;
c. c, introducing the copper-rich liquid obtained in the step b into an evaporator, and concentrating by evaporation to obtain an evaporated liquid with the specific gravity of 1.42;
d. introducing the evaporated solution into a crystallization tank for cooling crystallization at 20 deg.C, filtering with a belt filter to obtain copper sulfate crystal (Cu: 33.17%; reused As raw material for smelting system) and crystallized solution (Cu: 39.23g/l, as)5+：90.53g/l)；
e. Preparing a solution from the obtained crystallized solution and a sulfuric acid solution, adding an arsenic filter cake into the prepared solution to perform arsenic filter cake slurrying (As 39.19% in the arsenic filter cake), and obtaining an arsenic filter cake slurrying solution;
the acidity of the sulfuric acid solution is 80g/l; when the crystallized solution, the sulfuric acid solution and the arsenic filter cake are slurried, the proportion between the sum of the volumes of the crystallized solution and the sulfuric acid solution and the mass of the arsenic filter cake is 10mL:1g of a compound;
f. introducing the arsenic filter cake slurry liquid obtained in the step e into a reactor, introducing steam for heating, and introducing oxygen for carrying out oxygen pressure acid leaching reaction, wherein the reaction pressure is 1.2MPa, the reaction temperature is 115 ℃, the reaction time is 3h, and the flow of the oxygen is 260m3H; obtaining leached liquid after reaction; filter pressing the obtained leached liquid to obtain arsenic-rich liquid (As)3+：10.38g/l，As5+:35.26 g/l) and sulfur slag (S: 72.35 percent, directly feeding the obtained sulfur slag into a smelting system to provide heat, and generating sulfur dioxide flue gas for acid preparation);
g. f, guiding the arsenic-rich liquid obtained in the step f into a reduction reaction kettle, and introducing sulfur dioxide gas for reduction reaction, wherein the concentration of the sulfur dioxide gas is 6%, and the introduction amount of the sulfur dioxide gas is 220m3The reaction temperature is 30 ℃, the reaction time is 10 hours, and arsenic trioxide and reduced liquid are obtained after the reaction; centrifuging and drying the obtained arsenic trioxide to obtain an arsenic trioxide product (As)2O3:99.2 percent of arsenic sold or made As raw material for preparing metal arsenic), returning the reduced liquid to the step e or the step a for pulping (As in the reduced liquid)3+：13.7g/l，As5+：1.32g/l)。
Example 2:
the invention relates to a method for recovering copper and arsenic step by step in combined leaching of black copper mud and arsenic filter cakes, which comprises the following detailed steps:
a. proportioning and pulping black copper mud (the chemical components of main metal elements are Cu 40.1 percent and As 25.37 percent) and dilute sulfuric acid, wherein the concentration of the dilute sulfuric acid is 100g/L; the volume-mass ratio of the dilute sulfuric acid to the black copper sludge is 7mL:1g of a compound; obtaining slurrying liquid after slurrying;
b. putting the slurry liquid obtained in the step a into a reactor, introducing steam for heating, introducing industrial pure oxygen for carrying out acid leaching reaction at the reaction temperature, wherein the flow of the industrial pure oxygen is 320m3Reaction pressure of 0.9Mpa, reaction temperature of 120 ℃ and reaction time of 3h, and leaching solution is obtained after reaction; carrying out filter pressing on the obtained leached liquid to obtain copper-rich liquid (Cu)2+：69.58g/l，As5+:51.42 g/l) and lead bismuth slag (Pb: 22.14%, bi:24.15 percent) and the obtained lead-bismuth slag is used for the treatment of a lead smelting system;
c. c, introducing the copper-rich liquid obtained in the step b into an evaporator, and concentrating by evaporation to obtain an evaporated liquid with the specific gravity of 1.41;
d. introducing the evaporated solution into a crystallization tank for cooling crystallization at 20 deg.C, filtering with a belt filter to obtain copper sulfate crystal (Cu: 32.83%, reused As raw material of smelting system) and crystallized solution (Cu: 38.13g/l, as)5+：94.70g/l)；
e. Preparing a solution from the obtained crystallized solution and a sulfuric acid solution, adding an arsenic filter cake into the prepared solution to perform arsenic filter cake slurrying (As 39.19% in the arsenic filter cake), and obtaining an arsenic filter cake slurrying solution;
the acidity of the sulfuric acid solution is 70g/l; when the crystallized solution, the sulfuric acid solution and the arsenic filter cake are slurried, the ratio of the sum of the volumes of the crystallized solution and the sulfuric acid solution to the mass of the arsenic filter cake is 11mL:1g of a compound;
f. introducing the arsenic filter cake slurry liquid obtained in the step e into a reactor, introducing steam for heating, and introducing oxygen for carrying out oxygen pressure acid leaching reaction, wherein the reaction pressure is 1.2MPa, the reaction time is 3.5h, the reaction temperature is 115 ℃, and the flow of the oxygen is 220m3H; obtaining leached liquid after reaction; filter pressing the obtained leached liquid to obtain arsenic-rich liquid (As)3+：15.38g/l，As5+:40.12 g/l) and sulphur slag (S: 75.23%, directly feeding the obtained sulfur slag into a smelting system to provide heat, and generating sulfur dioxide flue gas to prepare acid);
g. f enriching the obtained productIntroducing the arsenic liquid into a reduction reaction kettle, introducing sulfur dioxide gas for reduction reaction, wherein the concentration of the sulfur dioxide gas is 5%, and the introduction amount of the sulfur dioxide gas is 280m3The reaction temperature is 30 ℃, the reaction time is 10 hours, and arsenic trioxide and reduced liquid are obtained after the reaction; centrifuging and drying the obtained arsenic trioxide to obtain an arsenic trioxide product (As)2O3:99.28% of raw material sold or prepared by metallic arsenic), returning the reduced liquid to the step e or the step a for pulping (As in the reduced liquid)3+：12.6g/l，As5+：1.12g/l)。
Example 3:
the invention relates to a method for recovering copper and arsenic step by step in combined leaching of black copper mud and arsenic filter cakes, which comprises the following detailed steps:
a. proportioning and pulping black copper mud (the chemical components of main metal elements are Cu 40.1 percent and As 25.37 percent) and dilute sulfuric acid, wherein the concentration of the dilute sulfuric acid is 80g/L; the volume-mass ratio of the dilute sulfuric acid to the black copper sludge is 8mL:1g; obtaining slurry liquid after the slurry is prepared;
b. putting the slurry liquid obtained in the step a into a reactor, introducing steam for heating, introducing industrial pure oxygen for carrying out acid leaching reaction at the reaction temperature, wherein the flow of the industrial pure oxygen is 380m3H, the reaction pressure is 1.0Mpa, the reaction temperature is 110 ℃, the reaction time is 2h, and the leached liquid is obtained after the reaction; carrying out filter pressing on the obtained leached liquid to obtain copper-rich liquid (Cu)2+：73.15g/l，As5+:52.34 g/l) and lead bismuth slag (Pb: 21.23%, bi:22.14 percent) and the obtained lead bismuth slag is used for the treatment of a lead smelting system;
c. c, introducing the copper-rich liquid obtained in the step b into an evaporator, and concentrating by evaporation to obtain an evaporated liquid with the specific gravity of 1.40;
d. introducing the evaporated solution into a crystallization tank for cooling crystallization at 22 deg.C, filtering (with belt filter) to obtain copper sulfate crystal (Cu: 32.9%, reused As raw material of smelting system) and crystallized solution (Cu: 40.13g/l, as)5+：89.37g/l)；
e. Preparing a solution from the crystallized solution and the reduced solution obtained in the step g, and adding an arsenic filter cake (As 39.19% in the arsenic filter cake) into the prepared solution to perform arsenic filter cake slurrying to obtain an arsenic filter cake slurrying solution;
when the crystallized solution, the reduced solution and the arsenic filter cake are slurried, the ratio of the sum of the volumes of the crystallized solution and the reduced solution to the mass of the arsenic filter cake is 11mL:1g;
f. e, introducing the arsenic filter cake slurry liquid obtained in the step e into a reactor, introducing steam for heating, introducing oxygen for carrying out oxygen pressure acid leaching reaction, wherein the reaction pressure is 1.2MPa, the reaction time is 2.5h, the reaction temperature is 110 ℃, and the flow of the oxygen is 280m3H; obtaining a leached liquid after reaction; filter pressing the obtained leached liquid to obtain arsenic-rich liquid (As)3+：14.42g/l，As5+:50.37 g/l) and sulphur slag (S: 73.35%, directly feeding the obtained sulfur slag into a smelting system to provide heat, and generating sulfur dioxide flue gas for acid preparation);
g. f, guiding the arsenic-rich liquid obtained in the step f into a reduction reaction kettle, and introducing sulfur dioxide gas for reduction reaction, wherein the concentration of the sulfur dioxide gas is 8%, and the introduction amount of the sulfur dioxide gas is 220m3The reaction temperature is 30 ℃, the reaction time is 10 hours, and arsenic trioxide and reduced liquid are obtained after the reaction; centrifuging and drying the obtained arsenic trioxide to obtain an arsenic trioxide product (As)2O3:99.3 percent of arsenic sold or made As raw material for preparing metal arsenic), returning the reduced liquid to the step e or the step a for slurrying (As in the reduced liquid)3+：11.8g/l，As5+：1.26g/l)。
Claims (9)
1. A method for recovering copper and arsenic step by step in combined leaching of black copper mud and arsenic filter cakes is characterized by comprising the following steps:
a. g, pulping the black copper mud and dilute sulfuric acid or the black copper mud and the reduced liquid obtained in the step g in a matching manner to obtain a pulping liquid;
b. b, putting the slurry liquid obtained in the step a into a reactor, introducing steam for heating, introducing industrial pure oxygen for carrying out oxygen pressure acid leaching reaction after heating to the reaction temperature, and obtaining a leached liquid after reaction; carrying out filter pressing on the obtained leached liquid to obtain copper-rich liquid and lead-bismuth slag, wherein the obtained lead-bismuth slag is used for treating a lead smelting system;
c. c, introducing the copper-rich liquid obtained in the step b into an evaporator for evaporation and concentration, wherein the specific gravity of the evaporated liquid is 1.39-1.42;
d. introducing the evaporated liquid into a crystallization tank for cooling crystallization, and filtering by using a belt filter after cooling crystallization to obtain copper sulfate crystals and a crystallized liquid;
e. slurrying the obtained crystallized liquid, sulfuric acid solution and arsenic filter cake, or slurrying the obtained crystallized liquid, the reduced liquid in the step g and the arsenic filter cake to obtain arsenic filter cake slurry;
f. e, introducing the arsenic filter cake slurry liquid obtained in the step e into a reactor, introducing steam for heating, introducing oxygen for carrying out oxygen pressure acid leaching reaction, and obtaining a leached liquid after the reaction; carrying out filter pressing on the obtained leached liquid to obtain arsenic-rich liquid and sulfur slag;
g. guiding the arsenic-rich liquid obtained in the step f into a reduction reaction kettle, introducing sulfur dioxide gas for reduction reaction, and obtaining arsenic trioxide and a reduced liquid after the reaction; centrifuging and drying the obtained arsenic trioxide to obtain an arsenic trioxide product, and returning the reduced solution to the step e or the step a for pulping.
2. The method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes according to claim 1, wherein the method comprises the following steps: the concentration of the dilute sulfuric acid in the step a is 80-120 g/L; the volume-mass ratio of the dilute sulfuric acid to the black copper sludge is 6-8 mL:1g of a compound; the volume-mass ratio of the reduced liquid to the black copper mud is 6-8 mL:1g of the total weight of the composition.
3. The method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes according to claim 1, characterized by comprising the following steps: in the step b, the reaction pressure in the oxygen pressure acid leaching process is 0.7-1.1 Mpa, the reaction temperature is 110-120 ℃, and the reaction time is 1.5-3 h; the flow of the industrial pure oxygen is 300-400 m3/h。
4. The method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes according to claim 1, characterized by comprising the following steps: and c, evaporating and concentrating to vacuum evaporation or directly evaporating by using an enamel evaporator.
5. The method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes according to claim 1, wherein the method comprises the following steps: the cooling crystallization temperature in the step d is 20-25 ℃; the cooling mode is cooling by circulating water or adding a refrigerator device for cooling;
the obtained copper sulfate crystal is reused as a raw material of a smelting system, or a copper sulfate product is obtained by methods of re-dissolving, impurity removal and re-crystallization for sale.
6. The method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes according to claim 1, characterized by comprising the following steps: the acidity of the sulfuric acid solution in the step e is 60-80 g/l;
when the solution after crystallization, the sulfuric acid solution and the arsenic filter cake are pulped, the ratio of the sum of the volumes of the solution after crystallization and the sulfuric acid solution to the mass of the arsenic filter cake is 10-12 mL:1g of a compound; and G, when the post-crystallization liquid, the reduced liquid in the step g and the arsenic filter cake are pulped, the ratio of the sum of the volumes of the post-crystallization liquid and the reduced liquid to the mass of the arsenic filter cake is 10-12 mL:1g.
7. The method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes according to claim 1, characterized by comprising the following steps: in the oxygen pressure acid leaching process in the step f, the reaction pressure is 1.0-1.3 MPa, the reaction temperature is 105-120 ℃, and the reaction time is 2.5-4 h; the flow rate of the oxygen is 200-300 m3/h；
The obtained sulfur slag directly enters a smelting system to provide heat, and sulfur dioxide flue gas is generated to prepare acid; or obtaining a sulfur product by flotation.
8. The method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes according to claim 1, characterized by comprising the following steps: g, in the reduction reaction process, the concentration of the sulfur dioxide gas is 5-8%, and the introduction amount of the sulfur dioxide gas is 200-300 m3/h。
9. The method for recovering copper and arsenic step by step in combined leaching of black copper sludge and arsenic filter cakes according to claim 1, characterized by comprising the following steps: and g, in the reduction reaction process in the step g, controlling the reaction temperature to be 25-30 ℃ and the reaction time to be 8-12 h.
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| CN115821065A (en) * | 2022-12-21 | 2023-03-21 | 黑龙江紫金铜业有限公司 | Recycling method for recycling arsenic and leaching residues from black copper mud and arsenic filter cake |
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