CN118222845A - Method for recovering copper by high-iron low-arsenic matte through synergistic oxygen pressure leaching of high-arsenic matte - Google Patents
Method for recovering copper by high-iron low-arsenic matte through synergistic oxygen pressure leaching of high-arsenic matte Download PDFInfo
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 220
- 238000002386 leaching Methods 0.000 title claims abstract description 148
- 239000010949 copper Substances 0.000 title claims abstract description 116
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 98
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 69
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 69
- 239000001301 oxygen Substances 0.000 title claims abstract description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 19
- 239000002893 slag Substances 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 93
- 239000007788 liquid Substances 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000011133 lead Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000009853 pyrometallurgy Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 229910017251 AsO4 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses a method for recycling copper by high-iron low-arsenic matte through synergistic oxygen pressure leaching, which comprises the steps of mixing high-iron low-arsenic matte and high-arsenic matte, adding the mixture into sulfuric acid-copper sulfate solution for oxygen pressure leaching, and carrying out liquid-solid separation to obtain copper sulfate solution and leached residues, wherein the mass ratio of the high-iron low-arsenic matte to the high-arsenic matte is 1:2-5. According to the invention, industrial solid waste high-iron low-arsenic matte is used as an arsenic fixing agent, so that iron in high-iron low-arsenic matte slag enters a solution in a form of Fe 3+ in an oxygen pressure acidic leaching process, arsenic in high-arsenic matte enters the solution in a form of AsO 4 3+, fe 3+ and AsO 4 3+ generate an acidic insoluble substance FeAsO 4 to enter leaching slag, and copper in high-arsenic matte and high-iron low-arsenic matte enters leaching liquid in a form of copper sulfate, thereby realizing separation of copper and arsenic, and further realizing recycling of copper and low-cost solidification of arsenic.
Description
Technical Field
The invention belongs to the technical field of resource recovery, and particularly relates to a method for recovering copper by high-iron low-arsenic matte synergistic oxygen pressure leaching.
Background
Copper removal treatment is often required before lead electrolysis is carried out on the lead-cast anode plate, and the current common methods are copper removal by sulfuration and copper removal by liquation. The copper-removed dross is subjected to reduction smelting in a reverberatory furnace and the like to obtain a byproduct lead matte, and the lead matte with high arsenic content is often named As arsenic matte, and the components of the lead matte comprise 45-60% of Cu, 10-20% of As, 0-2% of Fe, 0.1-1% of S, 5-20% of Pb, 1-10% of Sb, 2000-4000 g/t of Ag and 1-5 g/t of Au. The arsenic matte has high content of valuable metals, but the arsenic is dispersed and difficult to be intensively recovered or treated harmlessly in the process of recovering the copper and other valuable metals due to high content of arsenic and complex components, so that the environmental risk is high. The arsenic matte treatment process mainly comprises two processes, namely a pyrogenic process and a wet process.
The arsenic matte pyrogenic process mainly comprises volatilizing arsenic into flue gas at high temperature or adding arsenic fixing agent to make arsenic enter slag phase, and then treating and recovering arsenic from flue gas or slag phase. The patent document with the application number 202111140210.7 discloses a method for volatilizing arsenic into smoke by roasting arsenic matte by low-temperature weak oxidation, wherein the arsenic-containing smoke is subjected to alkali washing by lime and hydrogen peroxide to fix the arsenic, and the arsenic-removing roasting slag is subjected to reduction copper-making electrolysis to recover copper, so that copper-arsenic separation is realized. Patent document with publication number of CN 113528852A discloses that high-arsenic lead matte is mixed with lead-containing materials for oxidation smelting, arsenic enters smoke for arsenic trioxide recovery, copper is formed into matte for oxidation converting to form blister copper for recovery, and lead is formed into high-lead slag for reduction smelting to recover lead. However, arsenic in flue gas generated by the pyrogenic process is difficult to be dispersed and intensively treated, and the pyrogenic process has high investment cost and high energy consumption.
At present, wet treatment of arsenic matte is a mainstream process, and mainly comprises the processes of normal-pressure acid leaching, oxygen pressure alkaline leaching and arsenic removal and the like. The patent document with 201610446668.8 discloses a method for separating arsenic and recovering copper by low-temperature acid leaching, high Wen Chenshen and cyclone electrolytic copper. Patent document with publication number of CN107557592A discloses a method for leaching high-arsenic lead matte and pyrite by oxygen pressure sulfuric acid, which comprises the steps of obtaining copper-containing leaching liquid and arsenic-containing leaching slag, carrying out cyclone electrodeposition on the copper-containing leaching liquid to obtain cathode copper, thereby realizing copper recovery and arsenic solidification, but the process can generate sulfur in the oxygen pressure leaching process to cause poor copper leaching effect. Patent document with publication number CN107385209A discloses an oxygen pressure leaching arsenic matte, SO 2 reduction is carried out on the leaching solution to prepare As 2O3, cyclone electrolysis is carried out on copper in the reduced solution to prepare cathode copper, and separation and recovery of copper and arsenic in the arsenic matte are realized. Patent document 201110191860.4 discloses a method for oxygen pressure leaching of arsenic matte by adopting an NH 3-(NH4)2SO4 weak alkaline composite system at 110-200 ℃, wherein copper and NH 3 undergo a coordination chemical reaction to enter a solution for separating copper. Patent document with publication number CN103255289A discloses a method for oxygen pressure alkaline leaching of arsenic matte to obtain copper-containing leaching residues and arsenic-containing leaching solution, and cooling and crystallizing the arsenic-containing leaching solution to recover arsenic, thereby realizing copper-arsenic separation. The leaching solution has high arsenic content, incomplete separation of copper and arsenic, and poor quality of cathode copper is easily caused. The wet treatment of arsenic matte adopts normal pressure acid leaching to easily cause arsenic leaching to cause high arsenic content in leaching liquid and difficult treatment, and adopts oxygen pressure alkali leaching to cause low leaching rate of arsenic or copper, so that the high arsenic content in solution still can influence the quality of copper in the copper recovery process, and the arsenic is not easy to treat. The process of solidifying arsenic in slag by oxygen pressure acid leaching can effectively realize the short-process separation of copper and arsenic, but the existing arsenic fixing agents of pyrite and ferric salt have high cost and can influence the leaching rate of copper. Therefore, there is a need to find more suitable arsenic fixing agent so as to develop a more efficient and short-process technology to realize copper and arsenic separation and achieve the purpose of recovering valuable metals such as copper.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides a method for recovering copper by high-iron low-arsenic matte through synergistic oxygen pressure leaching.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
A method for recovering copper by high-iron low-arsenic matte synergistic oxygen pressure leaching of high-arsenic matte comprises the steps of mixing high-iron low-arsenic matte and high-arsenic matte, adding the mixture into sulfuric acid-copper sulfate solution for oxygen pressure leaching, and carrying out liquid-solid separation to obtain copper sulfate solution and leached slag, wherein the mass ratio of the high-iron low-arsenic matte to the high-arsenic matte is 1:2-5.
In the method for recovering copper by the high-iron low-arsenic matte synergistic oxygen pressure leaching of the high-arsenic matte, preferably, the concentration of Cu 2+ ions in the sulfuric acid-copper sulfate solution is 1-3 g/L, and the concentration of H 2SO4 is 80-180 g/L.
In the method for recovering copper by the high-iron low-arsenic matte synergistic oxygen pressure leaching of the high-arsenic matte, preferably, the oxygen partial pressure in the oxygen pressure leaching is 1.3-1.6 MPa, and the liquid-solid ratio in the leaching process is 8-10 mL/g.
In the method for recovering copper by the high-iron low-arsenic matte synergistic oxygen pressure leaching of the high-arsenic matte, preferably, the oxygen pressure leaching temperature is 150-200 ℃, the leaching time is 2-4 h, and the stirring speed in the leaching process is 300-500 r/min.
In the method for recovering copper by the high-iron low-arsenic matte through the synergistic oxygen pressure leaching, preferably, the components of the high-iron low-arsenic matte comprise: 1 to 5 percent of Cu, 0 to 1 percent of As, 40 to 55 percent of Fe, 5 to 10 percent of S, 1 to 5 percent of Pb and 50 to 300g/t of Ag.
The method for recycling copper by the high-iron low-arsenic matte through the combined oxygen pressure leaching of the high-arsenic matte preferably comprises the following components: 45-60% of Cu, 10-20% of As, 0-2% of Fe, 0.1-1% of S, 5-20% of Pb, 1-10% of Sb and 2000-4000 g/t of Ag.
In the method for recovering copper by the high-iron low-arsenic matte and the oxygen pressure leaching of the high-arsenic matte, preferably, the granularity of the high-iron low-arsenic matte and the granularity of the Gao Shen matte are both above 150 meshes.
In the method for recovering copper by the high-iron low-arsenic matte synergistic oxygen pressure leaching of the high-arsenic matte, preferably, the copper sulfate solution is subjected to cyclone electrodeposition to obtain high-purity cathode copper.
In the method for recycling copper by the high-iron low-arsenic matte and the oxygen pressure leaching of the high-arsenic matte, preferably, the leached slag is returned to a pyrometallurgical system to recycle other valuable metals.
According to the technical scheme, under the condition of oxygen pressure, copper in the high-arsenic matte and the high-iron low-arsenic matte enters the solution in the form of copper sulfate in the sulfuric acid solution leaching process, arsenic is solidified in leaching slag in the form of ferric arsenate, and the whole process realizes selective leaching of copper and solidification of arsenic, and specifically comprises the following steps:
CuxAsy+H2SO4+O2＝xCu2++yH3AsO4+H2O (1-1);
CuS+O2+4H+＝Cu2++H2O+S↓ (1-2)；
Cu+Cu2+＝2Cu+ (1-3)；
4Cu++O2+4H+＝4Cu2++2H2O (1-4)；
4Fe+3O2+12H+＝4Fe3++6H2O (1-5)；
4FeS+3O2+12H+＝4Fe3++6H2O+4S↓ (1-6)；
Fe3++AsO4 3+＝FeAsO4↓ (1-7)。
compared with the prior art, the invention has the advantages that:
(1) According to the invention, industrial solid waste high-iron low-arsenic matte is used as an arsenic fixing agent, so that iron in high-iron low-arsenic matte slag enters a solution in a form of Fe 3+ in an oxygen pressure acidic leaching process, arsenic in high-arsenic matte enters the solution in a form of AsO 4 3+, fe 3+ and AsO 4 3+ generate acidic insoluble substances FeAsO 4 to enter leaching slag, and copper in high-arsenic matte and high-iron low-arsenic matte enters leaching liquid in a form of copper sulfate, thereby realizing separation of copper and arsenic, and further realizing recycling of copper and low-cost solidification of arsenic.
(2) In the oxygen pressure leaching process, because the reaction of oxygen and arsenic matte is a gas-solid reaction, the gas-solid reaction efficiency is generally low, and the reaction time is relatively long, the Cu 2+ is introduced into the reaction liquid, so that the elementary substance copper in the arsenic matte and Cu 2+ undergo disproportionation reaction to generate Cu +,Cu+, and then the Cu +,Cu+ is oxidized by the oxygen to generate Cu 2+ which exists stably, the gas-solid reaction is changed into a liquid-solid reaction and a gas-liquid reaction, the reaction efficiency is remarkably improved, and the introduced Cu 2+ serves as an oxidized intermediate medium.
(3) The invention converts arsenic and iron into arsenic-iron alloy through a pyrometallurgy reduction smelting process, and changes the arsenic and iron into products with high added value for sale, and simultaneously other valuable metals such as lead, silver and the like are enriched into crude lead to be comprehensively recovered.
(4) In the process, the recovery rate of copper reaches over 96 percent, and over 99 percent of arsenic is solidified in leaching slag in the oxygen pressure acid leaching process, so that the high-efficiency separation of copper and arsenic is realized, further, the comprehensive recovery of copper, lead, silver and other valuable metals in high-arsenic matte and high-iron low-arsenic matte is realized, the arsenic can be used for preparing an arsenic-iron alloy through reduction smelting, the resource utilization of arsenic is realized, the valuable metals such as lead, antimony, gold, silver and the like are enriched in crude lead, the resource utilization of solid waste is realized, and the effect of changing waste into valuables is realized.
In conclusion, the method can realize thorough separation of copper and arsenic and recycling of copper by adopting the high-iron low-arsenic matte to cooperate with oxygen pressure leaching of the high-arsenic matte in one step, the industrial solid waste high-iron low-arsenic matte is fully recycled, the whole process is simple to operate, the method is suitable for large-scale continuous production of the arsenic matte, and a new thought is provided for recycling of the high-arsenic matte and separation of copper and arsenic.
Drawings
FIG. 1 is a flow chart of the process for recovering copper by the high-iron low-arsenic matte synergistic oxygen pressure leaching of the high-arsenic matte.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the invention, but the scope of the invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The compositions of the high iron low arsenic matte and the high arsenic matte used in the following examples and comparative examples are shown in table 1.
TABLE 1 high iron low arsenic matte and high arsenic matte composition
Example 1:
In this embodiment, the method for recovering copper by high-iron low-arsenic matte co-oxygen pressure leaching of high-arsenic matte is shown in fig. 1, and comprises the following steps:
(1) Respectively crushing high-iron low-arsenic matte and high-arsenic matte to 200 meshes;
(2) Weighing 30g of crushed high-iron low-arsenic matte and 120g of crushed high-arsenic matte in the step (1), mixing and adding the crushed high-iron low-arsenic matte and the crushed high-arsenic matte into an autoclave, and adding 1.5L of sulfuric acid-copper sulfate solution according to a liquid-solid ratio of 10mL/g, wherein the concentration of Cu 2+ in the sulfuric acid-copper sulfate solution is 2g/L, H 2SO4 and the concentration of Cu 2+ in the sulfuric acid-copper sulfate solution is 120g/L;
(3) Starting an autoclave power supply, setting the stirring speed to be 500r/min, starting a stirrer and a heater at the reaction temperature of 180 ℃, simultaneously introducing oxygen, controlling the oxygen partial pressure to be 1.6MPa, reacting for 3.5h after the temperature reaches the reaction temperature, and cooling to room temperature after the reaction is completed;
(4) Carrying out liquid-solid separation on the reaction liquid obtained in the step (3) to obtain a copper sulfate solution and leaching slag, washing the leaching slag with pure water for a plurality of times, drying and weighing the leaching slag, testing Cu, as, fe, sb, H 2SO4 acidity of the leaching liquid, and testing Cu and As of the leaching slag, wherein the result is shown in a table 2;
(5) And (3) carrying out cyclone electrodeposition on the leaching solution obtained in the step (4) to obtain high-purity cathode copper, and returning leaching slag to a pyrometallurgy system to recycle other valuable metals.
Table 2 technical index of each step in example 1
Therefore, in the embodiment, the copper leaching rate reaches 98.87%, which indicates that the copper leaching effect is good, meanwhile, arsenic is not leached basically, and indicates that the high-iron low-arsenic matte and the high-arsenic matte cooperate with oxygen pressure leaching to inhibit the leaching of arsenic, so that the arsenic concentration in the leaching solution is not high, the cyclone electrolysis can be directly carried out to recycle copper, and the electrodeposited solution can be returned to a leaching system for recycling.
Therefore, the embodiment adopts the high-iron low-arsenic matte to cooperatively leach the high-arsenic matte by oxygen pressure, so that the high-efficiency leaching of copper and the inhibition effect of arsenic can be achieved.
Example 2:
In this embodiment, the method for recovering copper by high-iron low-arsenic matte co-oxygen pressure leaching of high-arsenic matte is shown in fig. 1, and comprises the following steps:
(1) Respectively crushing high-iron low-arsenic matte and high-arsenic matte to 200 meshes;
(2) Weighing 40g of crushed high-iron low-arsenic matte and 110g of crushed high-arsenic matte in the step (1), mixing and adding into an autoclave, and adding 1.5L of sulfuric acid-copper sulfate solution according to a liquid-solid ratio of 10mL/g, wherein the concentration of Cu 2+ in the sulfuric acid-copper sulfate solution is 2g/L, H 2SO4 and the concentration is 100g/L;
(3) Starting an autoclave power supply, setting the stirring speed to be 500r/min, starting a stirrer and a heater at the reaction temperature of 180 ℃, simultaneously introducing oxygen, controlling the oxygen partial pressure to be 1.5MPa, reacting for 3.5h after the temperature reaches the reaction temperature, and cooling to room temperature after the reaction is completed;
(4) Carrying out liquid-solid separation on the reaction liquid obtained in the step (3) to obtain a copper sulfate solution and leaching slag, washing the leaching slag with pure water for a plurality of times, drying and weighing the leaching slag, testing Cu, as, fe, sb, H 2SO4 acidity of the leaching liquid, and testing Cu and As of the leaching slag, wherein the result is shown in a table 3;
(5) And (3) carrying out cyclone electrodeposition on the leaching solution obtained in the step (4) to obtain high-purity cathode copper, and returning leaching slag to a pyrometallurgy system to recycle other valuable metals.
Table 3 technical indices of the respective steps in example 2
Therefore, in the embodiment, the copper leaching rate reaches 97.64%, which shows that the copper leaching effect is good, and meanwhile, after the high-iron low-arsenic matte is increased, arsenic is basically not leached, which shows that the high-iron low-arsenic matte and the high-arsenic matte cooperate with oxygen pressure leaching to well inhibit arsenic leaching, so that the arsenic concentration in the leaching solution is very low, and the copper can be directly recycled by cyclone electrolysis after the oxidizing agent is added for iron removal, and the liquid can be returned to a leaching system for recycling after electrodeposition.
Therefore, the embodiment adopts the high-iron low-arsenic matte to cooperatively leach the high-arsenic matte by oxygen pressure, so that the high-efficiency leaching of copper and the inhibition effect of arsenic can be achieved.
Example 3:
In this embodiment, the method for recovering copper by high-iron low-arsenic matte co-oxygen pressure leaching of high-arsenic matte is shown in fig. 1, and comprises the following steps:
(1) Respectively crushing high-iron low-arsenic matte and high-arsenic matte to 200 meshes;
(2) Weighing 40g of crushed high-iron low-arsenic matte and 110g of crushed high-arsenic matte in the step (1), mixing and adding into an autoclave, and adding 1.5L of sulfuric acid-copper sulfate solution according to a liquid-solid ratio of 10mL/g, wherein the concentration of Cu 2+ in the sulfuric acid-copper sulfate solution is 2g/L, H 2SO4 and 150g/L;
(3) Starting an autoclave power supply, setting the stirring speed to be 500r/min, starting a stirrer and a heater at the reaction temperature of 180 ℃, simultaneously introducing oxygen, controlling the oxygen partial pressure to be 1.6MPa, reacting for 3.5h after the temperature reaches the reaction temperature, and cooling to room temperature after the reaction is completed;
(4) Carrying out liquid-solid separation on the reaction liquid obtained in the step (3) to obtain a copper sulfate solution and leaching slag, washing the leaching slag with pure water for a plurality of times, drying and weighing the leaching slag, testing Cu, as, fe, sb, H 2SO4 acidity of the leaching liquid, and testing Cu and As of the leaching slag, wherein the result is shown in a table 4;
(5) And (3) carrying out cyclone electrodeposition on the leaching solution obtained in the step (4) to obtain high-purity cathode copper, and returning leaching slag to a pyrometallurgy system to recycle other valuable metals.
Table 4 technical index of each step in example 3
In the embodiment, the copper leaching rate reaches 98.77%, which shows that the copper leaching effect is relatively good, meanwhile, arsenic is not leached basically, which shows that the high-iron low-arsenic matte and the high-arsenic matte cooperate with oxygen pressure leaching to well inhibit the leaching of arsenic, so that the arsenic concentration in the leaching solution is very low, the leaching solution can be directly subjected to cyclone electrolysis to recycle copper, and the electrodeposited solution can be returned to a leaching system for recycling.
Therefore, the embodiment adopts the high-iron low-arsenic matte to cooperatively leach the high-arsenic matte by oxygen pressure, so that the high-efficiency leaching of copper and the inhibition effect of arsenic can be achieved.
Comparative example 1:
In the comparative example, the copper is recovered by leaching the high-arsenic matte at normal pressure, and the method comprises the following steps:
(1) Crushing high-arsenic matte to 200 meshes respectively, and adding 200g into a 2L beaker; adding 1.6L of sulfuric acid-copper sulfate solution according to the liquid-solid ratio of 8mL/g, wherein the concentration of Cu 2+ in the sulfuric acid-copper sulfate solution is 2g/L, H 2SO4 and the concentration is 120g/L;
(2) Placing the beaker filled with the reaction materials in the step (1) into a water bath kettle, setting the stirring speed to be 500r/min, setting the temperature of the water bath kettle to be 80 ℃, starting a stirrer and a water bath kettle heater, simultaneously adding 300mL of hydrogen peroxide, reacting for 3.5h after the temperature reaches the reaction temperature, and cooling to the room temperature after the reaction is completed;
(3) And (3) carrying out liquid-solid separation on the reaction liquid obtained in the step (2) to obtain a copper sulfate solution and leaching slag, washing the leaching slag with pure water for multiple times, drying and weighing the leaching slag, testing the acidity of the leaching liquid by Cu, as, fe, sb, H 2SO4, and testing Cu and As of the leaching slag, wherein the result is shown in Table 5.
Table 5 technical index of each process in comparative example
The comparative example carries out oxidation leaching of high-arsenic matte under normal pressure, the copper leaching rate reaches 70.81%, which shows that the copper leaching effect is general, but the leaching rate of arsenic reaches 80.07%, so that most of arsenic is leached, and the leaching solution has great arsenic precipitation difficulty.
Comparative example 2:
in this comparative example, the high arsenic matte was recovered using oxygen pressure leaching, comprising the steps of:
(1) Crushing high-arsenic matte to 200 meshes respectively, and adding 150g into a 2L beaker; adding 1.5L of sulfuric acid-copper sulfate solution according to the liquid-solid ratio of 10mL/g, wherein the concentration of Cu 2+ in the sulfuric acid-copper sulfate solution is 2g/L, H 2SO4 and the concentration is 120g/L;
(2) Starting an autoclave power supply, setting the stirring speed to be 500r/min, starting a stirrer and a heater at the reaction temperature of 180 ℃, simultaneously introducing oxygen, controlling the oxygen partial pressure to be 1.6MPa, reacting for 3.5h after the temperature reaches the reaction temperature, and cooling to room temperature after the reaction is completed;
(3) Carrying out liquid-solid separation on the reaction liquid obtained in the step (2) to obtain a copper sulfate solution and leaching slag, washing the leaching slag with pure water for a plurality of times, drying and weighing the leaching slag, testing Cu, as, fe, sb, H 2SO4 acidity of the leaching liquid, and testing Cu and As of the leaching slag, wherein the result is shown in a table 6;
(4) And (3) carrying out cyclone electrodeposition on the leaching solution obtained in the step (3) to obtain high-purity cathode copper, and returning leaching slag to a pyrometallurgy system to recycle other valuable metals.
Table 6 Process specifications in comparative examples
As is clear from the test data in Table 6, the leaching rate of copper in the comparative example reaches 97.68%, but the leaching rate of arsenic also reaches 91.05%, the arsenic content in the leaching solution reaches more than 15g/L, the leaching solution can only obtain low-grade cathode copper through cyclone electrodeposition, and the arsenic content in the solution after electrodeposition is high and needs further treatment.
In conclusion, the high-iron low-arsenic matte is adopted as an arsenic fixing agent, the high-arsenic matte and the high-iron low-arsenic matte are matched and mixed for oxygen pressure sulfuric acid leaching, the leaching rate of copper is more than 98%, the solidification rate of arsenic is more than 99%, copper and arsenic are thoroughly separated in the oxygen pressure acid leaching process, meanwhile, copper-containing leaching liquid can be subjected to cyclone electrodeposition to obtain high-purity cathode copper for sale, arsenic-containing leaching residues are returned to a pyrometallurgy system for reduction smelting and recovery of valuable metals such as lead and silver, and meanwhile, arsenic and iron are combined to form arsenic-iron alloy for sale, so that the recycling of arsenic is realized.
Finally, it should be noted that: the foregoing is merely a preferred example of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for recycling copper by high-iron low-arsenic matte through synergistic oxygen pressure leaching of high-arsenic matte is characterized in that high-iron low-arsenic matte and high-arsenic matte are mixed, added into sulfuric acid-copper sulfate solution for oxygen pressure leaching, and subjected to liquid-solid separation to obtain copper sulfate solution and leached residues, wherein the mass ratio of the high-iron low-arsenic matte to the high-arsenic matte is 1:2-5.
2. The method for recycling copper by high-iron low-arsenic matte synergistic oxygen pressure leaching of high-arsenic matte according to claim 1, wherein the concentration of Cu 2+ ions in the sulfuric acid-copper sulfate solution is 1-3 g/L, and the concentration of H 2SO4 is 80-180 g/L.
3. The method for recovering copper by high-iron low-arsenic matte synergistic oxygen pressure leaching of high-arsenic matte according to claim 1, wherein the oxygen partial pressure in the oxygen pressure leaching process is 1.3-1.6 MPa, and the liquid-solid ratio in the leaching process is 8-10 mL/g.
4. The method for recovering copper by high-iron low-arsenic matte synergistic oxygen pressure leaching of high-arsenic matte according to claim 1, wherein the oxygen pressure leaching temperature is 150-200 ℃, the leaching time is 2-4 h, and the stirring speed in the leaching process is 300-500 r/min.
5. The method for recovering copper by high-iron low-arsenic matte synergistic oxygen pressure leaching of high-arsenic matte according to claim 1, wherein the components of the high-iron low-arsenic matte comprise: 1 to 5 percent of Cu, 0 to 1 percent of As, 40 to 55 percent of Fe, 5 to 10 percent of S, 1 to 5 percent of Pb and 50 to 300g/t of Ag.
6. The method for recovering copper by high-iron low-arsenic matte synergistic oxygen pressure leaching of high-arsenic matte according to claim 1, wherein the Gao Shen matte comprises the following components: 45-60% of Cu, 10-20% of As, 0-2% of Fe, 0.1-1% of S, 5-20% of Pb, 1-10% of Sb and 2000-4000 g/t of Ag.
7. The method for recovering copper by high-iron low-arsenic matte synergistic oxygen pressure leaching of high-arsenic matte according to claim 1, wherein the particle size of the high-iron low-arsenic matte and Gao Shen matte is above 150 meshes.
8. The method for recovering copper by combining high-iron low-arsenic matte with oxygen pressure leaching of high-arsenic matte according to any one of claims 1 to 7, wherein the copper sulfate solution is subjected to cyclone electrodeposition to obtain high-purity cathode copper.
9. The method for recovering copper by combining high-iron low-arsenic matte with oxygen pressure leaching of high-arsenic matte according to any one of claims 1to 7, wherein the leached slag is returned to a pyrometallurgical system for recovering other valuable metals.
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| Publication Number | Publication Date |
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| CN118222845A true CN118222845A (en) | 2024-06-21 |
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