CN117144146B - Copper smelting leaching liquid treating agent and copper smelting leaching liquid treating method - Google Patents

Copper smelting leaching liquid treating agent and copper smelting leaching liquid treating method Download PDF

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CN117144146B
CN117144146B CN202311414457.2A CN202311414457A CN117144146B CN 117144146 B CN117144146 B CN 117144146B CN 202311414457 A CN202311414457 A CN 202311414457A CN 117144146 B CN117144146 B CN 117144146B
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copper smelting
sodium hydroxide
barium nitrate
treating agent
sulfuric acid
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CN117144146A (en
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廖元杭
林鸿汉
王瑞鹏
孟云
陈杭
葛素志
王宇宁
蒋国民
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Science Environmental Co ltd
Central South University
Zijin Copper Co Ltd
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Science Environmental Co ltd
Central South University
Zijin Copper Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0084Treating solutions
    • C22B15/0089Treating solutions by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention provides a copper smelting leaching solution treating agent and a copper smelting leaching solution treating method. The copper smelting leaching liquid treating agent comprises the following raw materials of barium nitrate, sodium hydroxide and sulfuric acid. The copper smelting leaching liquid treating agent is used for treating copper smelting leaching liquid, and can simplify the treatment process flow of the leaching liquid, improve the removal rate of arsenic, antimony and bismuth and reduce the treatment cost. The invention also provides a treatment method of the copper smelting leaching solution.

Description

Copper smelting leaching liquid treating agent and copper smelting leaching liquid treating method
Technical Field
The invention belongs to the technical field of copper smelting, and particularly relates to a copper smelting leaching solution treating agent and a copper smelting leaching solution treating method.
Background
Copper smelting is a complex process involving a number of links and process steps, from the extraction of metallic copper from copper ores to the production of high purity copper metal, the major links including beneficiation, smelting, refining and copper-smelting waste residue treatment.
Copper ores often contain both accompanying elements, impurities and other metals. Beneficiation is the first step in copper smelting, and the useful minerals in the ore are separated from waste rocks and impurities by physical and chemical methods. In the beneficiation process, the content of accompanying elements such as arsenic, antimony, bismuth and the like and the influence of the accompanying elements on the subsequent process are considered. Ores with high accompanying element content may also require a reduction in content by pretreatment. In copper smelting, ore Leaching (Leaching) is one of the key links in producing Leaching solutions. Ore leaching is the process of dissolving metal or useful components from an ore by chemical reaction into a liquid phase, commonly referred to as leaching, which generally occurs in a pre-treatment stage of extracting the metal, which is a method of separating the metal from the raw ore. Metallic copper in copper ores is typically leached by an acidic solution (e.g., sulfuric acid) to dissolve the copper into a liquid phase to form a leachate. This leachate contains ions of the extracted metal, such as copper ions. The leachate may then need to be subjected to a series of subsequent processing steps including solid-liquid separation, purification of the leachate, precipitation or extraction of metals, etc., to finally obtain the target metal product. In summary, the ore leaching step in copper smelting is the main stage of producing leaching solution, which creates conditions for the subsequent extraction and processing steps by dissolving metals from the raw ore into the liquid phase.
Therefore, a new leachate treatment agent needs to be developed to realize efficient separation of copper, arsenic, antimony and bismuth in the leachate.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides a copper smelting leaching solution treating agent.
The invention also provides a preparation method of the copper smelting leaching liquid treating agent.
The invention also provides a treatment method of the copper smelting leaching solution.
The invention provides a copper smelting leaching solution treating agent, which is prepared from raw materials including barium nitrate, sodium hydroxide and sulfuric acid, wherein the mass ratio of the barium nitrate to the sodium hydroxide is 8-15:1, and the concentration of the sulfuric acid is 100-600 g/L;
the preparation method of the copper smelting leaching liquid treating agent comprises the following steps: mixing the barium nitrate and the sodium hydroxide in a wet environment, roasting, and soaking the roasting product in sulfuric acid.
The copper smelting leaching solution of the invention is leaching solution obtained after solid-liquid separation in hydrometallurgical treatment.
The invention relates to one of the technical schemes of copper smelting leaching liquid treating agent, which has at least the following beneficial effects:
the copper smelting leaching liquid treating agent is used for treating copper smelting leaching liquid, and can simplify the treatment process flow of the leaching liquid, improve the removal rate of arsenic, antimony and bismuth and reduce the treatment cost.
The copper smelting leaching liquid treating agent has the advantages of easily available raw materials and low cost.
The barium nitrate has the function of synthesizing insoluble inducer, providing a similar way of seed crystal, reducing the solubility of double salt of arsenic, antimony and bismuth and realizing co-precipitation of arsenic, antimony and bismuth.
The sodium hydroxide is used as a barium nitrate modifier, and reacts with barium nitrate to form barium salt with a special structure. Barium salt with special structure refers to the generation of active barium hydroxide Ba (OH) 2 ·xH 2 O。
The sulfuric acid acts as an auxiliary agent for forming double salts. "double salt" refers to a mixture of barium salts of a particular crystal form containing barium nitrate, barium sulfite, and the like.
The mass ratio of the barium nitrate to the sodium hydroxide is less than 8-15:1, so that the impurity removal effect of the product is poor, and the cost is increased; the mass ratio of the barium nitrate to the sodium hydroxide is larger than 8-15:1, which leads to poor impurity removal effect and increased cost, so that the mass ratio of the barium nitrate to the sodium hydroxide is 8-15:1, which is a proper proportion range.
The concentration of sulfuric acid is lower than 100g/L, no double salt is generated, and the product has no impurity removal effect; the concentration of sulfuric acid is higher than 600g/L, which leads to the rise of cost and great operation difficulty, so that the concentration of sulfuric acid is 100 g/L-600 g/L, which is a proper concentration range.
According to some embodiments of the invention, the mass ratio of the barium nitrate to the sodium hydroxide is 10-15:1.
According to some embodiments of the invention, the concentration of sulfuric acid is 300 g/L-600 g/L.
In a second aspect, the invention provides a method for preparing the copper smelting leaching agent, which comprises the following steps: mixing the barium nitrate and sodium hydroxide, roasting, and soaking the roasting product in sulfuric acid.
The invention relates to a technical scheme in a preparation method of a copper smelting leaching agent treatment agent, which at least has the following beneficial effects:
the preparation method of the invention does not need expensive equipment and complex process control, has low reaction conditions, easily obtained raw materials, low production cost and easy industrial production.
Mixing the barium nitrate and sodium hydroxide, and roasting, wherein the reaction is as follows:
Ba(NO 3 ) 2 +2NaOH+xH 2 O→Ba(OH) 2 ·xH 2 O+2NaNO 3 the purpose is to form barium salts of specific structures.
In the process of mixing the barium nitrate and the sodium hydroxide, in order to convert the anhydrous barium hydroxide into the hydrate, it is necessary to provide a moist environment, that is, sufficient water molecules, and therefore, a small amount of water needs to be added for further mixing.
The roasting product is soaked in sulfuric acid to form barium salt with special structure.
Mixing barium nitrate and sodium hydroxide according to a certain proportion, roasting at constant temperature, and placing the barium nitrate in an activated state, wherein the barium nitrate has a special structure in granularity and crystal form. Then soaking in concentrated sulfuric acid solution to generate barium double salt. Enhancing the capability of capturing arsenic, antimony and bismuth ions and promoting the co-precipitation of the arsenic, the antimony and the bismuth.
The double salt is in an activated state, namely the double salt is in a fine-grain porous shape, has strong activity and can induce the efficient precipitation of arsenic in the leaching solution.
According to some embodiments of the invention, barium nitrate is mixed with sodium hydroxide in powder form and calcined.
In the process of mixing barium nitrate and sodium hydroxide, in order to convert anhydrous barium hydroxide into hydrate, the mixing may be performed by adding an appropriate amount of water during the mixing of barium nitrate and sodium hydroxide or stirring in a high humidity environment.
According to some embodiments of the invention, the firing temperature is 200 ℃ to 400 ℃.
According to some embodiments of the invention, the roasting time is 0.5 h-2 h.
According to some embodiments of the invention, the firing is performed under a protective atmosphere.
According to some embodiments of the invention, the protective atmosphere comprises nitrogen or argon.
According to some embodiments of the invention, the soaking treatment time is 0.5 h-2 h.
According to some embodiments of the invention, the method further comprises grinding the calcined product to a particle size of 200 mesh to 600 mesh prior to soaking.
Grinding to a certain mesh number can increase the contact area of barium salt and solution and increase the coprecipitation rate.
The third aspect of the invention provides a method for treating a copper smelting leaching solution, which comprises the following steps: and adding the copper smelting leaching agent into the copper smelting leaching agent to carry out coprecipitation reaction.
The invention relates to a technical scheme in a treatment method of copper smelting leaching liquid, which at least has the following beneficial effects:
the treatment method of the copper smelting leaching solution has simple process flow, can efficiently separate copper from arsenic, antimony and bismuth in the leaching solution, improves the removal rate of the arsenic, the antimony and the bismuth, and reduces the treatment cost.
According to some embodiments of the invention, the solid-to-liquid ratio of the copper smelting leaching agent to the copper smelting leaching agent is 1:10-15.
According to some embodiments of the invention, the coprecipitation reaction time is 1h to 4h.
According to some embodiments of the invention, during the coprecipitation reaction, a stirring treatment is performed.
According to some embodiments of the invention, the stirring process is performed at a rate of 100rpm to 300rpm.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
In some embodiments of the invention, the invention provides a copper smelting leaching solution treating agent, which is prepared from raw materials including barium nitrate, sodium hydroxide and sulfuric acid, wherein the mass ratio of the barium nitrate to the sodium hydroxide is 8-15:1, and the concentration of the sulfuric acid is 100-600 g/L;
the preparation method of the copper smelting leaching liquid treating agent comprises the following steps: mixing barium nitrate and sodium hydroxide in a moist environment, roasting, and soaking the roasted product in sulfuric acid.
It can be understood that the copper smelting leaching solution treating agent can simplify the treatment process flow of the leaching solution, improve the removal rate of arsenic, antimony and bismuth and reduce the treatment cost when being used for treating the copper smelting leaching solution.
It can also be understood that the copper smelting leaching liquid treating agent has the advantages of easily available raw materials and low cost.
The barium nitrate is used as a indissolvable inducer, provides a similar seed crystal mode, reduces the solubility of the arsenic-antimony-bismuth double salt and realizes the coprecipitation of arsenic-antimony-bismuth.
The sodium hydroxide is used as a barium nitrate modifier, and reacts with barium nitrate to form barium salt with a special structure. Barium salt with special structure refers to the generation of active barium hydroxide Ba (OH) 2 ·xH 2 O。
The sulfuric acid is used as an auxiliary agent for forming double salts, and the double salts refer to a mixture of special crystal barium salts containing barium nitrate, barium sulfite and the like.
It is noted that the mass ratio of barium nitrate to sodium hydroxide is less than 8-15:1, which results in poor impurity removal effect and increased cost; the mass ratio of the barium nitrate to the sodium hydroxide is larger than 8-15:1, which leads to poor impurity removal effect and increased cost, so that the mass ratio of the barium nitrate to the sodium hydroxide is 8-15:1, which is a proper proportion range.
It should also be noted that the concentration of sulfuric acid is lower than 100g/L, which results in no double salt generation and no impurity removal effect of the product; the concentration of sulfuric acid is higher than 600g/L, which leads to the rise of cost and great operation difficulty, so that the concentration of sulfuric acid is 100 g/L-600 g/L, which is a proper concentration range.
In some embodiments of the invention, the mass ratio of barium nitrate to sodium hydroxide is 10-15:1.
In some embodiments of the invention, the concentration of sulfuric acid is 300g/L to 600g/L.
In still other embodiments of the present invention, the present invention provides a method of preparing a copper smelting leach solution treatment agent, comprising the steps of: mixing barium nitrate and sodium hydroxide, roasting, and soaking the roasted product in sulfuric acid.
It can be understood that the preparation method of the invention does not need expensive equipment and complex process control, has harsh reaction conditions, easily obtained raw materials, low production cost and easy industrial production.
Mixing the barium nitrate and sodium hydroxide, and roasting, wherein the reaction is as follows:
Ba(NO 3 ) 2 +2NaOH+xH 2 O→Ba(OH) 2 ·xH 2 O+2NaNO 3 the purpose is to form barium salts of specific structures.
In the process of mixing barium nitrate and sodium hydroxide, in order to convert anhydrous barium hydroxide into hydrate, it is necessary to provide a moist environment, that is, sufficient water molecules, and therefore, a small amount of water needs to be added for further mixing.
Since commercially available barium hydroxide does not have a specific structure and is not a hydrate, commercially available barium hydroxide cannot be used as it is.
The roasting product is soaked in sulfuric acid to form barium salt with special structure.
Mixing barium nitrate and sodium hydroxide according to a certain proportion, roasting at constant temperature, and placing the barium nitrate in an activated state, wherein the barium nitrate has a special structure in granularity and crystal form. Then soaking in concentrated sulfuric acid solution to generate barium double salt. Enhancing the capability of capturing arsenic, antimony and bismuth ions and promoting the co-precipitation of the arsenic, the antimony and the bismuth.
The double salt is in an activated state, namely the double salt is in a fine-grain porous shape, has strong activity and can induce the efficient precipitation of arsenic in the leaching solution.
In some embodiments of the invention, barium nitrate is mixed with sodium hydroxide in powder form and calcined.
In the process of mixing barium nitrate and sodium hydroxide, in order to convert anhydrous barium hydroxide into hydrate, the mixing may be performed by adding an appropriate amount of water during the mixing of barium nitrate and sodium hydroxide or stirring in a high humidity environment.
In some embodiments of the invention, the firing temperature is 200 ℃ to 400 ℃.
In some embodiments of the invention, the firing time is 0.5h to 2h.
In some embodiments of the invention, the firing is performed under a protective atmosphere.
In some embodiments of the invention, the protective atmosphere comprises nitrogen or argon.
In some embodiments of the invention, the soaking time is 0.5h to 2h.
In some embodiments of the invention, the method of preparing the copper smelting leach liquor treatment agent further includes grinding the roasted product to a particle size of 200 mesh to 600 mesh prior to soaking.
Grinding to a certain mesh number can increase the contact area of barium salt and solution and increase the coprecipitation rate.
In other embodiments of the present invention, the present invention provides a method for treating a copper smelting leach solution, the method comprising: the copper smelting leaching agent is added into copper smelting leaching liquid to carry out coprecipitation reaction.
It can be understood that the treatment method of the copper smelting leaching solution has simple process flow, can efficiently separate copper from arsenic, antimony and bismuth in the leaching solution, improves the removal rate of the arsenic, antimony and bismuth, and reduces the treatment cost.
In some embodiments of the invention, the solid-to-liquid ratio of the copper smelting leach liquor treatment agent to the copper smelting leach liquor is 1:10-15.
In some embodiments of the invention, the time of the coprecipitation reaction is 1 to 4 hours.
In some embodiments of the invention, the stirring process is performed during the coprecipitation reaction.
In some embodiments of the invention, the stirring process is at a rate of 100rpm to 300rpm.
The technical solution of the present invention will be better understood in conjunction with the following specific examples.
Example 1
The copper smelting leaching solution treating agent is prepared in the embodiment, and the preparation raw materials comprise 100g of barium nitrate powder, 10g of sodium hydroxide powder and 500mL of sulfuric acid with the concentration of 100 g/L.
The preparation method comprises the following steps: mixing barium nitrate and sodium hydroxide, roasting, and soaking the roasted product in sulfuric acid.
During the mixing of barium nitrate and sodium hydroxide, a small amount of water is added.
The temperature of calcination was 300 ℃.
The roasting time is 0.5h.
The roasting atmosphere is nitrogen.
The soaking treatment time is 0.5h.
After the soaking treatment, the product is washed and ground to below 400 meshes.
Example 2
The copper smelting leaching solution treating agent is prepared in the embodiment, and the preparation raw materials comprise 100g of barium nitrate powder, 10g of sodium hydroxide powder and 500mL of sulfuric acid with the concentration of 100 g/L.
The preparation method comprises the following steps: mixing barium nitrate and sodium hydroxide, roasting, and soaking the roasted product in sulfuric acid.
During the mixing of barium nitrate and sodium hydroxide, a small amount of water is added.
The temperature of calcination was 300 ℃.
The roasting time is 0.5h.
The roasting atmosphere is argon.
The soaking treatment time is 1h.
After the soaking treatment, the product is washed and ground to below 400 meshes.
Example 3
The copper smelting leaching solution treating agent is prepared in the embodiment, and the preparation raw materials comprise 100g of barium nitrate powder, 10g of sodium hydroxide powder and 500mL of sulfuric acid with the concentration of 100 g/L.
The preparation method comprises the following steps: mixing barium nitrate and sodium hydroxide, roasting, and soaking the roasted product in sulfuric acid.
During the mixing of barium nitrate and sodium hydroxide, a small amount of water is added.
The temperature of calcination was 300 ℃.
The roasting time is 1h.
The roasting atmosphere is argon.
The soaking treatment time is 1h.
After the soaking treatment, the product is washed and ground to below 400 meshes.
Comparative example 1
This comparative example produced a copper smelting leach solution treating agent, which was different from example 1 in that barium nitrate and sodium hydroxide were not mixed and then calcined, but were directly subjected to a soaking treatment in sulfuric acid using commercially available barium hydroxide.
Performance testing
A certain copper smelting leach solution was treated with the copper smelting leach solution treating agents of examples 1 to 3 and comparative example 1, respectively.
The treatment method comprises the following steps:
1000mL of sulfuric acid solution containing copper, arsenic, antimony and bismuth is measured, wherein the contents of the copper, the arsenic, the antimony and the bismuth are 31.32g/L, 19.30g/L, 8.72g/L and 21.15g/L respectively;
heating to 60 ℃ in a constant-temperature water bath kettle;
adding activated barium nitrate according to a liquid-solid ratio of 12:1, and coprecipitating for 2 hours under the condition of stirring speed of 150 r/min. And detecting the removal rate of arsenic, antimony and bismuth. The results are shown in Table 1.
TABLE 1
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (9)

1. The copper smelting leaching liquid treating agent is characterized in that the preparation raw materials comprise barium nitrate, sodium hydroxide and sulfuric acid, wherein the mass ratio of the barium nitrate to the sodium hydroxide is 8-15:1, and the concentration of the sulfuric acid is 100-600 g/L;
the preparation method of the copper smelting leaching liquid treating agent comprises the following steps: mixing the barium nitrate and the sodium hydroxide in a wet environment, roasting, and soaking the roasting product in sulfuric acid.
2. The copper smelting leaching solution treating agent according to claim 1, wherein the mass ratio of the barium nitrate to the sodium hydroxide is 10-15:1.
3. The copper smelting leach solution treatment agent of claim 1, wherein the sulfuric acid concentration is 300g/L to 600g/L.
4. The copper smelting leach solution treatment agent of claim 1, wherein the roasting temperature is 200 ℃ to 400 ℃; and/or roasting for 0.5-2 hours.
5. The copper smelting leaching solution treating agent according to claim 1, wherein the soaking treatment time is 0.5-2 hours.
6. The copper smelting leach solution treating agent according to claim 1, wherein the method for producing the copper smelting leach solution treating agent further comprises grinding the roasted product to a particle size of 200 mesh to 600 mesh before the soaking treatment.
7. The treatment method of the copper smelting leaching solution is characterized by comprising the following steps of: adding the copper smelting leaching agent according to any one of claims 1 to 6 to copper smelting leaching solution for coprecipitation reaction.
8. The treatment method according to claim 7, wherein the solid-to-liquid ratio of the copper smelting leach solution treatment agent to the copper smelting leach solution is 1:10-15.
9. The method according to claim 7, wherein the coprecipitation reaction time is 1 to 4 hours.
CN202311414457.2A 2023-10-30 2023-10-30 Copper smelting leaching liquid treating agent and copper smelting leaching liquid treating method Active CN117144146B (en)

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