CN116200595A - Method for comprehensively recovering valuable metals from high-sulfur copper-containing material - Google Patents

Abstract

The invention relates to the technical field of hydrometallurgy, and discloses a method for comprehensively recovering valuable metals from high-sulfur copper-containing materials, including the following steps: S1 carries out oxygen-enriched leaching of high-sulfur copper-containing materials to obtain a stage of leaching slag and a stage of Leaching solution; S2 ball-mills the first-stage leaching slag in S1, and performs second-stage leaching in the first-stage leaching solution to obtain the second-stage leaching residue and second-stage leaching solution; S3 extracts the second-stage leaching solution in S2 and obtains cathode copper through an electrowinning process, The raffinate is neutralized for zinc precipitation to obtain zinc precipitation slag and zinc precipitation solution, and the zinc precipitation solution is returned to S1 for leaching; S4 recovers lead from the second-stage leaching residue in S2. The present invention uses high-sulfur copper-containing materials as raw materials, adopts a graded leaching treatment method to process the raw materials, can effectively separate copper and produce cathode copper, and recover other valuable metals in the materials at the same time, so as to realize efficient comprehensive utilization of resources.

Description

A method for comprehensive recovery of valuable metals from high-sulfur copper-containing materials

technical field

The invention relates to the technical field of hydrometallurgy, in particular to a method for comprehensively recovering valuable metals from high-sulfur copper-containing materials.

Background technique

Copper is an important basic raw material of the national economy. Because of its good comprehensive performance, it is widely used in electrical, electronic, transportation, metallurgy, construction, art, energy petrochemical, marine industry and high-tech fields. It is used in non-ferrous metal materials It is second only to aluminum in consumption ranking. As the world's largest copper producer, trading country and consumer country, my country occupies an important position in the global copper industry.

Copper is mainly sulfide ore in nature, and oxide ore is formed by the slow oxidation and metamorphism of sulfide ore. There are two processes for extracting copper from copper materials: fire method and wet method. Which method to use depends on factors such as the chemical composition and mineral composition of the ore. However, the existing methods for extracting copper have the problems of low recovery rate of copper and the impact of sulfur emission on environmental pollution.

Contents of the invention

<Technical Problems Solved by the Invention>

The method is used to solve the problems of low recovery rate of copper and the influence of sulfur discharge on environmental pollution in the existing method for extracting copper.

<Technical solution adopted in the present invention>

In view of the above-mentioned technical problems, the object of the present invention is to provide a method for comprehensively recovering valuable metals from high-sulfur copper-containing materials.

The present invention uses high-sulfur copper-containing materials as raw materials, adopts a graded leaching treatment method to process the raw materials, can effectively separate copper and produce cathode copper, and recover other valuable metals in the materials at the same time, so as to realize efficient comprehensive utilization of resources.

The specific content is as follows:

The invention provides a method for comprehensively recovering valuable metals from high-sulfur copper-containing materials, comprising the following steps:

S1 performs oxygen-enriched leaching of high-sulfur copper-containing materials to obtain a leaching slag and a leaching solution;

S2 ball mills the first-stage leaching slag in S1, and performs second-stage leaching in the first-stage leaching solution to obtain the second-stage leaching residue and the second-stage leaching solution;

S3 extracts the second-stage leaching solution in S2 through extraction and electrowinning process to obtain cathode copper, and neutralizes the zinc precipitation with the raffinate to obtain zinc precipitation slag and zinc precipitation solution, and returns the zinc precipitation solution to S1 for leaching;

S4 recovers lead from the second-stage leaching residue in S2.

<Beneficial effects achieved by the present invention>

(1) The present invention adopts the all-wet method to process high-sulfur and copper-containing complex materials, which has higher efficiency, lower energy consumption, no acid gas generation, and saves roasting, tail gas treatment and other processes compared with pyroprocessing.

(2) The processing method provided by the present invention can process the raw materials in an indiscriminate manner. No matter the composition of the raw materials changes, the method can quickly and efficiently process complex ore by changing the corresponding leaching conditions in its steps.

(3) The treatment method provided by the present invention has a more efficient way in terms of zinc-copper separation and zinc precipitation, quickly separates zinc-copper, and solves the difficult problem of zinc-copper separation. The total copper recovery rate is as high as 95%, the zinc recovery rate is higher than 96%, and the purity of the output cathode copper can reach more than 99%.

Description of drawings

Fig. 1 is a flow chart of a method for comprehensively recovering valuable metals from high-sulfur copper-containing materials.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

<Technical solution>

The invention provides a method for comprehensively recovering valuable elements from high-sulfur copper-containing materials, the raw material used is high-sulfur copper-containing materials, comprising the following steps:

S1. Carry out high-temperature oxygen-enriched leaching of complex high-sulfur copper-containing materials to obtain a section of leaching residue and leaching solution;

S2 performs second-stage leaching on the first-stage leaching slag obtained in S1 after ball milling, and the first-stage leaching solution is continued to be used in the second-stage leaching to obtain the second-stage leaching residue and the second-stage leaching solution;

S3 processes the second-stage leaching solution obtained in S2, obtains cathode copper through extraction and electrowinning processes, and neutralizes the zinc precipitation with the raffinate to obtain zinc precipitation slag and zinc precipitation liquid, and returns the zinc precipitation liquid to S1 for leaching;

In S4, lead recovery and harmless treatment are performed on the leached slag obtained in S2 by sending fire.

Further, in step S1, configure a certain amount of sulfuric acid solution, add a certain amount of high-sulfur copper-containing material, use a stirrer to stir the mixed solution at a certain speed, continue heating during the stirring process, and feed pure oxygen at a certain rate.

Wherein, the concentration of sulfuric acid in the configured sulfuric acid solution is 100-300g/l, and the amount of minerals added is, according to the liquid-solid ratio, the liquid-solid ratio is 4-10:1; preferably, the liquid-solid ratio is 5 :1, the initial acidity is 160g/l.

Further, the prepared mixed solution is heated up, and stirred, and oxygen is introduced while stirring, and the conditions are that the stirring speed is 100-500rpm; the heating temperature is 50-100°C; the oxygen partial pressure is 0.1-0.5Mp, The ventilation volume is 1~100L/min. Preferably, the stirring speed is 300 rpm, the temperature is 85-90° C., the oxygen partial pressure is 0.2 Mp, and the ventilation flow rate is 10 L/min.

Further, solid-liquid separation is performed on the leaching mixture in step S2, and the obtained leach residue is subjected to ball milling, under the conditions that the ball milling speed is 100-500 rpm, the ball milling time is 10-100 min, and the ball milling liquid-solid ratio is 0.5-1:1. Preferably, the ball milling speed is 300rpm, the time is 30min, and the ball milling liquid-solid ratio is 0.5:1.

Further, the filtrate after leaching in the S1 step is mixed with the S2 ball milling slag, and stirring and heating are applied. The specific conditions are that the stirring speed is 100-500 rpm; the heating temperature is 50-100°C; the oxygen partial pressure is 0.1-0.5 Mp, ventilation volume 1-100L/min. Preferably, the stirring speed is 300 rpm, the temperature is 85-90° C., the oxygen partial pressure is 0.2 Mp, and the ventilation flow rate is 10 L/min.

Further, in step S3, the leaching solution of step S2 is subjected to solid-liquid separation, and the obtained leaching solution of S2 is subjected to extraction and separation of zinc and copper. The specific conditions are that Lix984 is used for separation and extraction of zinc and copper, and the extraction ratio is 1-5:1, and the extraction agent The concentration is 10-30%, and the number of extraction stages is 3-10. Preferably, the O/A ratio is 3:1, the concentration of the extractant is 15%, and the number of extraction stages is 3-5.

Further, the raffinate obtained in step S3 is neutralized and zinc-precipitated, and the specific conditions are that sodium carbonate, sodium bicarbonate or other alkaline precipitating agents are added to the solution, and the precipitation pH value is 7-9, and the preferred precipitation pH value is 8.0～8.5.

Further, solid-liquid separation is performed after zinc precipitation, and the separated liquid is returned to step S1 for repeated use.

Further, after the extraction in step S3, the copper sulfate solution is electrolyzed to obtain cathode copper.

Further, in S4, lead is recovered by fire method, which is one of rotary kiln, blast furnace reduction smelting, oxygen-enriched bottom blowing lead smelting, and oxygen-enriched side blowing reduction.

The present invention uses high-sulfur and copper-containing complex materials as raw materials. After simple wet treatment, copper and zinc can be efficiently separated, and alkali salts are used for zinc precipitation, which can efficiently separate copper and zinc and zinc precipitation, and achieve a greater limit. The comprehensive utilization of resources is in line with the national overall policy of energy conservation and consumption reduction. Aiming at the comprehensive utilization of complex copper mines, it effectively improves the recovery level, supplements the shortcomings of insufficient resources, and greatly improves the processing capacity of complex minerals.

<Example>

Example 1

This embodiment provides a method for comprehensively recovering valuable elements from high-sulfur copper-containing materials, comprising the following steps:

S1 conducts high-temperature oxygen-enriched leaching of complex high-sulfur copper-containing materials to obtain a section of leaching residue and leaching solution;

Configure a sulfuric acid solution, the concentration of sulfuric acid is 100g/l, and the mass ratio of the solution to the high-sulfur copper-containing complex material is 5:1. The material is put into the solution for reaction. The reaction temperature is 80°C, the reaction time is 2h, and the stirring speed is 300rpm. Oxygen partial pressure 0.2Mp, oxygen flow rate 10L/min.

S2 performs solid-liquid separation on the leaching step of step S1, performs ball milling on the leached slag, the ball milling intensity is 300 rpm, the liquid-solid ratio of the ball milling is 0.5:1, and the ball milling time is 10 min; after the ball milling is completed, the step S1 leachate is mixed with the solid sample after ball milling, Continue the reaction, the reaction temperature is 90°C, the stirring intensity is 300rpm, and the time is 3h; after the reaction is completed, the solid-liquid separation is carried out to obtain the leaching solution and leaching residue;

S3 conducts separation and extraction of zinc and copper on the leaching solution in step S2, configures an extraction agent with a concentration of 15%, and performs extraction according to the ratio O/A ratio of 2:1, and the number of extraction stages is 3. The raffinate contains 0.83g/l copper and 21.5g/l zinc. The raffinate was adjusted to a pH value of 8.0 with soda ash to obtain a white precipitate, which was a zinc hydrolysis precipitation product. The extract was back-extracted with sulfuric acid to obtain a copper sulfate solution with a concentration of 41.2 g/l, and the back-extracted copper sulfate solution was electrolyzed to obtain cathode copper.

S4 returns the zinc-precipitated liquid obtained in step S3 to step S1 for repeated use, and performs fire or wet treatment on the leached slag obtained in step S2 to obtain lead products.

Example 2

This embodiment provides a method for comprehensively recovering valuable elements from high-sulfur copper-containing materials, comprising the following steps:

S1 conducts high-temperature oxygen-enriched leaching of complex high-sulfur copper-containing materials to obtain a section of leaching residue and leaching solution;

Configure sulfuric acid solution, the concentration of sulfuric acid is 160g/l, the mass ratio of the solution to the high-sulfur copper-containing complex material is 5:1, weigh the material and put it into the solution for reaction, the reaction temperature is 80°C, the reaction time is 2h, the stirring speed is 300rpm, and the oxygen partial pressure 0.2Mp, oxygen flow rate 15L/min.

S2 performs solid-liquid separation on the leaching step of step S1, and performs ball milling on the leach slag, the ball milling intensity is 300rpm, the ball milling liquid-solid ratio is 0.5; 1, the ball milling time is 10min; after the ball milling is completed, the step S1 leachate is mixed with the ball milled solid sample, Continue the reaction, the reaction temperature is 90°C, the stirring intensity is 300rpm, and the time is 4h; after the reaction is completed, the solid-liquid separation is carried out to obtain the leaching liquid and leaching residue;

S3 conducts separation and extraction of zinc and copper on the leaching solution in step S2, configures an extraction agent with a concentration of 20%, and performs extraction according to the ratio O/A ratio of 1:1, and the number of extraction stages is 3. The raffinate contains 123g/l copper and 22.1g/l zinc. The raffinate was adjusted to a pH value of 8.0 with soda ash to obtain a white precipitate, which was a zinc hydrolysis precipitation product. The extract was back-extracted with sulfuric acid to obtain a copper sulfate solution with a concentration of 37.6 g/l, and the back-extracted copper sulfate solution was electrolyzed to obtain cathode copper.

S4 returns the zinc-precipitated liquid obtained in step S3 to step S1 for repeated use, and performs fire or wet treatment on the leached slag obtained in step S2 to obtain lead products.

Example 3

This embodiment provides a method for comprehensively recovering valuable elements from high-sulfur copper-containing materials, comprising the following steps:

S1 conducts high-temperature oxygen-enriched leaching of complex high-sulfur copper-containing materials to obtain a section of leaching residue and leaching solution;

Configure sulfuric acid solution, the concentration of sulfuric acid is 160g/l, the mass ratio of the solution to the high-sulfur and copper-containing complex material is 10:1, weigh the material and put it into the solution for reaction, the reaction temperature is 80°C, the reaction time is 2h, the stirring speed is 300rpm, the oxygen content Pressure 0.2Mp, oxygen flow rate 15L/min.

S2 performs solid-liquid separation on the leaching step of step S1, conducts ball milling on the leached slag, the ball milling intensity is 300rpm, the ball milling liquid-solid ratio is 0.5:1, and the ball milling time is 20min; after the ball milling is completed, the leachate of step S1 is mixed with the solid sample after ball milling , continue the reaction, the reaction temperature is 90°C, the stirring intensity is 300rpm, and the time is 4h; after the reaction is completed, the solid-liquid separation is carried out to obtain the leaching liquid and leaching residue;

S3 conducts separation and extraction of zinc and copper on the leaching solution in step S2, configures an extraction agent with a concentration of 15%, and performs extraction according to the ratio O/A ratio of 2:1, and the number of extraction stages is 3. The raffinate contains copper 12g/l and zinc concentration 11.1g/l. The raffinate was adjusted to pH 8.0 with soda ash, and a white precipitate was obtained, which was the product of zinc hydrolysis precipitation. The extract was back-extracted with sulfuric acid to obtain a copper sulfate solution with a concentration of 31.6 g/l, and the back-extracted copper sulfate solution was electrolyzed to obtain cathode copper.

S4 returns the zinc-precipitated liquid obtained in step S3 to step S1 for repeated use, and performs fire or wet treatment on the leached slag obtained in step S2 to obtain lead products.

Example 3

This embodiment provides a method for comprehensively recovering valuable elements from high-sulfur copper-containing materials, comprising the following steps:

S1 conducts high-temperature oxygen-enriched leaching of complex high-sulfur copper-containing materials to obtain a section of leaching residue and leaching solution;

Configure a sulfuric acid solution, the concentration of sulfuric acid is 160g/l, the mass ratio of the solution to the high-sulfur copper-containing complex material is 5:1, weigh the material and put it into the solution for reaction, the reaction temperature is 90°C, the reaction time is 2h, the stirring speed is 300rpm, and the oxygen content Pressure 0.2Mp, oxygen flow rate 20L/min.

S2 performs solid-liquid separation on the leaching step of step S1, and performs ball milling on the leach slag, the ball milling intensity is 300rpm, the ball milling liquid-solid ratio is 0.5; 1, the ball milling time is 20min; after the ball milling is completed, the step S1 leachate is mixed with the ball milled solid sample, Continue the reaction, the reaction temperature is 90°C, the stirring intensity is 300rpm, and the time is 4h; after the reaction is completed, the solid-liquid separation is carried out to obtain the leaching liquid and leaching residue;

S3 conducts separation and extraction of zinc and copper on the leaching solution in step S2, configures an extraction agent with a concentration of 15%, and performs extraction according to the ratio O/A ratio of 3:1, and the number of extraction stages is 3. The extract contains 24.1g/l copper and 23.8g/l zinc. The raffinate was adjusted to a pH value of 8.0 with soda ash to obtain a white precipitate, which was a zinc hydrolysis precipitation product. The extract was back-extracted with sulfuric acid to obtain a copper sulfate solution with a concentration of 41.6 g/l, and the back-extracted copper sulfate solution was electrolyzed to obtain cathode copper.

S4 returns the zinc-precipitated liquid obtained in step S3 to step S1 for repeated use, and performs fire or wet treatment on the leached slag obtained in step S2 to obtain lead products.

Example 4

This embodiment provides a method for comprehensively recovering valuable elements from high-sulfur copper-containing materials, comprising the following steps:

S1 conducts high-temperature oxygen-enriched leaching of complex high-sulfur copper-containing materials to obtain a section of leaching residue and leaching solution;

Configure sulfuric acid solution, the concentration of sulfuric acid is 200g/l, the mass ratio of the solution to the high-sulfur copper-containing complex material is 5:1, weigh the material and put it into the solution for reaction, the reaction temperature is 90°C, the reaction time is 2h, the stirring speed is 300rpm, and the oxygen content Pressure 0.2Mp, oxygen flow rate 20L/min.

S2 performs solid-liquid separation on the leaching step of step S1, and performs ball milling on the leach slag, the ball milling intensity is 300rpm, the ball milling liquid-solid ratio is 0.5; 1, the ball milling time is 20min; after the ball milling is completed, the step S1 leachate is mixed with the ball milled solid sample, Continue the reaction, the reaction temperature is 90°C, the stirring intensity is 300rpm, and the time is 4h; after the reaction is completed, the solid-liquid separation is carried out to obtain the leaching liquid and leaching residue;

S3 conducts separation and extraction of zinc and copper on the leaching solution in step S2, configures an extraction agent with a concentration of 15%, and performs extraction according to the ratio O/A ratio of 3:1, and the number of extraction stages is 3. The extract contains 24.6g/l copper and 24.2g/l zinc. The raffinate was adjusted to a pH value of 8.0 with soda ash to obtain a white precipitate, which was a zinc hydrolysis precipitation product. The extract was back-extracted with sulfuric acid to obtain a copper sulfate solution with a concentration of 42.1 g/l, and the back-extracted copper sulfate solution was electrolyzed to obtain cathode copper.

S4 returns the zinc-precipitated liquid obtained in step S3 to step S1 for repeated use, and performs fire or wet treatment on the leached slag obtained in step S2 to obtain lead products.

<Test example>

The cathode copper obtained in Examples 1-4 was subjected to typical component analysis, and the results are shown in Table 1.

Table 1 Typical composition analysis test results of cathode copper (%)

Element Example 1 Example 2 Example 3 Example 4 Cu 99.9 99.9 99.9 99.9 Pb 0.0006 0.0006 0.0005 0.0006 Zn 0.001 0.0005 0.001 0.006 Cd 0.003 0.004 0.003 0.004 Fe 0.002 0.002 0.003 0.002 Sb 0.0002 0.0003 0.0002 0.0002 S 0.002 0.001 0.002 0.002 Si 0.006 0.005 0.005 0.005

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A method for comprehensively recovering valuable metals from high-sulfur copper-containing materials, characterized in that, comprising the steps: S1 performs oxygen-enriched leaching of high-sulfur copper-containing materials to obtain a leaching slag and a leaching solution; S2 ball mills the first-stage leaching slag in S1, and performs second-stage leaching in the first-stage leaching solution to obtain the second-stage leaching residue and the second-stage leaching solution; S3 extracts the second-stage leaching solution in S2 through extraction and electrowinning process to obtain cathode copper, and neutralizes the zinc precipitation with the raffinate to obtain zinc precipitation slag and zinc precipitation solution, and returns the zinc precipitation solution to S1 for leaching; S4 recovers lead from the second-stage leaching residue in S2. 2. the method for comprehensive recovery of valuable metals from high-sulfur copper-containing materials according to claim 1, characterized in that, In S1, the operation method of oxygen-enriched leaching is that the high-sulfur copper-containing material is added to the sulfuric acid solution, and pure oxygen is introduced during the stirring and heating process. 3. The method for comprehensively recovering valuable metals from high-sulfur copper-containing materials according to claim 2, characterized in that the concentration of the sulfuric acid solution is 100 to 300g/l; Add in a ratio of 4 to 10:1. 4. The method for comprehensively recovering valuable metals from high-sulfur copper-containing materials according to claim 2 or 3, characterized in that, in S1, the stirring speed is 100-500rpm; the heating temperature is 50-100°C; The partial pressure is 0.1~0.5Mp, the ventilation volume is 1~100L/min, and the reaction time is 2~5h. 5. The method for comprehensively recovering valuable metals from high-sulfur copper-containing materials according to claim 1, characterized in that, in S2, the ball milling speed is 100-500 rpm, and the ball milling time is 10-100 min. 6. the method for comprehensive recovery of valuable metals from high-sulfur copper-containing materials according to claim 1, characterized in that, in S2, the operation method of the second-stage leaching is that one-stage leachate is blended with ball milling slag after ball milling, And apply stirring and heating. 7. The method for comprehensively recovering valuable metals from high-sulfur copper-containing materials according to claim 6, characterized in that, in S2, the process parameters of the second-stage leaching are, the stirring speed is 100～500rpm; the heating temperature is 50 ~100°C; oxygen partial pressure 0.1~0.5Mp, ventilation volume 1~100L/min. 8. The method for comprehensively recovering valuable metals from high-sulfur copper-containing materials according to any one of claims 1 to 3, 5 to 7, characterized in that, in S3, the second-stage leachate is separated and extracted with Lix984. 9. The method for comprehensively recovering valuable metals from high-sulfur copper-containing materials according to claim 8, characterized in that the extraction ratio is 1-5:1, the concentration of the extractant is 10-30%, and the extraction stages are 3-5:1. 10 levels. 10. the method for comprehensive recovery of valuable metals from high-sulfur copper-containing materials according to claim 8, characterized in that, in S3, the raffinate is neutralized and the alkaline precipitant used for zinc precipitation is sodium carbonate or Sodium bicarbonate, the precipitation pH value is 7-9.

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