CN113122718B

CN113122718B - Two-stage leaching process of black copper mud

Info

Publication number: CN113122718B
Application number: CN201911390482.5A
Authority: CN
Inventors: 尚鹤; 温建康; 武彪; 杨鑫龙; 刘爽; 刘学
Original assignee: GRIMN Engineering Technology Research Institute Co Ltd; GRINM Resources and Environment Technology Co Ltd
Current assignee: GRIMN Engineering Technology Research Institute Co Ltd; GRINM Resources and Environment Technology Co Ltd
Priority date: 2019-12-30
Filing date: 2019-12-30
Publication date: 2023-02-07
Anticipated expiration: 2039-12-30
Also published as: CN113122718A

Abstract

The invention relates to a two-stage leaching process of black copper mud, which is realized by the following steps: 1) Crushing and grinding the black copper mud to-0.125 mm; 2) First-stage leaching: mixing the crushed and ground black copper sludge powder and a dilute sulfuric acid solution in proportion, and stirring and leaching; 3) Washing and filtering the first-stage leaching residue; 4) Secondary leaching: mixing the first-stage leaching residue with a dilute sulfuric acid solution added with a chemical leaching aid according to a certain proportion, and then stirring and leaching. The method disclosed by the invention is used for leaching copper and arsenic in black copper mud by adopting a two-stage leaching method, and has the characteristics of mild conditions, simplicity in operation, high leaching rates of copper and arsenic and the like.

Description

Two-stage leaching process of black copper mud

Technical Field

The invention belongs to the field of metallurgy, and relates to a two-stage leaching process of black copper mud.

Background

In the process of copper electrolytic refining, the components of the electrolyte are changed continuously, the concentration of copper ions is increased continuously, impurities are accumulated continuously, and the concentration of sulfuric acid is reduced gradually. In order to maintain the copper, acid content and impurity concentration in the electrolyte within specified ranges, the electrolyte must be purified and adjusted to ensure proper operation of the electrolysis process and the quality of the cathode copper. In the process of removing As, sb and Bi in the two-stage electrodeposition decoppering process of purifying the copper electrolyte, cu, as, sb and Bi in the electrolyte are precipitated and separated on a cathode together to form black copper mud.

From the process of producing the black copper sludge, it is known that the main components of the black copper sludge are Cu and As, and other elements such As Sb, bi, pb, and the like exist due to the difference in the components of the blister copper anode. If the black copper sludge is used As a copper-containing raw material and returned to a smelting system for batching, due to the fact that the content of other elements such As As, sb, bi, pb and the like is high, the harmful elements are circulated in a closed circuit in the copper smelting system, influence on process conditions, operation and product quality of each smelting process can be brought to different degrees, equipment production capacity can be reduced, energy consumption is increased, health of operators is harmed, and finally, the harmful elements can be enriched in intermediate materials such As smoke dust, acid sludge and the like to form high-risk solid wastes, most of the wastes are not effectively utilized, so that not only is the waste of resources caused, but also the environmental hazard is large. Therefore, the black copper mud is comprehensively utilized and valuable metals are recovered, the discharge of high-risk solid wastes is reduced, and the virtuous cycle of the production process is one of the hot spots of copper smelting research.

Disclosure of Invention

The invention aims to provide a two-stage leaching process of black copper mud, which is different from roasting, pressure leaching and other processes and is characterized by mild operation conditions, strong controllability, high leaching rates of copper and arsenic and high resource utilization rate.

In order to achieve the purpose, the invention provides a two-stage leaching process of black copper mud, which comprises the following steps:

(1) Crushing and grinding the black copper mud to-0.125 mm;

(2) First-stage leaching: mixing the crushed and ground black copper sludge powder and a dilute sulfuric acid solution in proportion in a stirring tank for stirring and leaching to obtain a first-stage leaching residue and a copper-arsenic-containing solution;

(3) Washing and filtering the first-stage leaching residue;

(4) Secondary leaching: mixing the first-stage leaching residue and a dilute sulfuric acid solution added with a chemical auxiliary leaching agent according to a certain proportion, and then stirring and leaching in a stirring tank.

Furthermore, the black copper mud in the step (1) is an arsenic-containing and copper-containing material generated in the process of copper electrolytic refining technology during the induced copper removal and impurity removal, wherein the arsenic content is 5% -20%, and the copper content is 20% -50%.

Furthermore, the solid-to-liquid ratio g/mL of the black copper sludge powder to the dilute sulfuric acid solution in the first-stage leaching in the step (2) is 15-5, the sulfuric acid content in the dilute sulfuric acid solution is 50-100 g/L, the leaching temperature is 50-100 ℃, and the leaching time is 2-6 h.

Furthermore, the first-stage leaching residue washing and filtering in the step (3) is to wash the leaching residue in the step (2) with clean water for 1-3 times and then filter.

Furthermore, the solid-to-solid ratio g/mL of the secondary leaching solution in the step (4) is 10-5.

Furthermore, the chemical leaching aid in the step (4) is ferric sulfate, and the concentration of the chemical leaching aid is 1-200 g/L.

The invention has the beneficial effects that:

the invention provides a two-stage leaching process of black copper mud, which is different from the processes of roasting, pressure leaching and the like and is characterized by mild conditions, simple operation and high leaching rate of copper and arsenic, and the leaching rate can reach more than 90 percent.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

As shown in figure 1, the invention is characterized in that black copper mud is crushed and ground, black copper mud powder, water and sulfuric acid are mixed according to a certain proportion and then subjected to primary leaching to extract copper and arsenic in the black copper mud, and leaching residues are filtered and washed after the primary leaching is finished and then subjected to secondary leaching with sulfuric acid, water and an auxiliary leaching agent according to a certain proportion to further extract copper and arsenic in the black copper mud.

The present invention will be further illustrated by the following examples

Example 1

The process is used for black copper sludge of a smelting plant in Shandong province, the black copper sludge contains 21.37 percent of copper, 6.93 percent of arsenic and other elements mainly including Pb and S, and the main element content of the sample is shown in Table 1

TABLE 1 chemical multielement analysis of a black copper sludge

The leaching process of the black copper mud comprises the following steps:

(1) Crushing and grinding sample of black copper mud

The black copper mud is crushed and ground to obtain black copper mud powder with the granularity of-0.125 mm.

(2) Leaching for the first time;

and carrying out primary agitation leaching in an agitation tank, wherein the liquid-solid ratio (g/ml) is 10, the sulfuric acid concentration is 100g/L, the leaching temperature is 90 ℃, and the leaching time is 4h.

(3) Washing and filtering the first-stage leaching residue;

washing the first-stage leaching residue obtained in the previous step with water for 2 times, and filtering;

(4) And (4) secondary leaching.

And (3) placing the washed first-stage leaching residue in a stirring tank for second-stage stirring leaching, wherein the liquid-solid ratio (g/ml) is 10, the sulfuric acid concentration is 50g/L, the leaching temperature is 30 ℃, and the leaching time is 6h.

Through calculation, when the two-stage leaching process for the black copper mud is used for treating the black copper mud, the copper leaching rate can reach 98.39%, and the arsenic leaching rate can reach 91.13%.

From the embodiments, the two-stage leaching process for the black copper mud provided by the invention has the advantages of mild operation conditions, strong controllability, high leaching rates of copper and arsenic and high resource utilization rate.

Claims

1. A two-stage leaching process of black copper mud is characterized in that: the method comprises the following steps:

(1) Crushing and grinding the black copper mud to-0.125 mm;

(3) Washing and filtering the first-stage leaching residue;

(4) Secondary leaching: mixing the first-stage leaching residue and a dilute sulfuric acid solution added with a chemical auxiliary leaching agent according to a certain proportion, and then stirring and leaching in a stirring tank;

wherein the black copper mud in the step (1) is an arsenic-containing and copper-containing material generated in the process of copper electrolytic refining technology during the induced copper removal and impurity removal, the arsenic content is 5-20%, and the copper content is 20-50%;

the solid-liquid ratio g/mL of the black copper sludge powder to the dilute sulfuric acid solution in the first-stage leaching in the step (2) is 15-5, the sulfuric acid content in the dilute sulfuric acid solution is 50-100 g/L, the leaching temperature is 50-100 ℃, and the leaching time is 2-6 h;

the step (3) of washing and filtering the first-stage leaching residue is to wash the leaching residue in the step (2) for 1 to 3 times by using clear water and then filter the washing and filtering;

the solid ratio g/mL of the second-stage leaching solution in the step (4) is 10-5, the content of sulfuric acid in a dilute sulfuric acid solution is 20-200 g/L, the leaching temperature is 20-90 ℃, and the leaching time is 2-6 h;

the chemical leaching aid in the step (4) is ferric sulfate, and the concentration of the chemical leaching aid is 1-200 g/L.