CN111197171A - Wet copper extraction process - Google Patents
Wet copper extraction process Download PDFInfo
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- CN111197171A CN111197171A CN202010099775.4A CN202010099775A CN111197171A CN 111197171 A CN111197171 A CN 111197171A CN 202010099775 A CN202010099775 A CN 202010099775A CN 111197171 A CN111197171 A CN 111197171A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a wet copper extraction process, which comprises the following steps of S1: selecting copper oxide ore, crushing and grinding to obtain mineral powder; s2: adding acid liquor into the mineral powder obtained in the step S1 for acid leaching treatment, then stirring for 3-5 hours, adding certain water for dilution after stirring is finished, and standing for precipitation after dilution; s3, filtering the particles precipitated in the step S2 to obtain filter residues, and obtaining filtrate with the PH of 2-4; s4: and (4) producing electrodeposited copper by electrodepositing the filtrate obtained in the step S3. According to the wet copper extraction process, the Co ions are added into the copper electrolyte, so that the anode corrosion speed is favorably slowed down, the anode potential is reduced, and the proper concentration of the Co ions in the electrolyte is 100 mg/L; the addition of the guar gum to the electric accumulated liquid is beneficial to the generation of cathode copper with smooth and flat surface, the dosage of the guar gum is 50g per ton of copper, the effect of thiourea is obvious when the current density of the copper electrolysis process is higher (300A/square meter), and the thiourea can be used as an additive.
Description
Technical Field
The invention relates to a copper extraction process, in particular to a wet copper extraction process.
Background
The wet-method copper extraction has general attention on the aspects of low-grade refractory copper ore resources, utilization of copper-containing gold concentrate and the like, and particularly the successful application of a high-selectivity copper extractant and a matched extraction process thereof in production promotes the development of the wet-method copper extraction industry.
The traditional wet copper extraction classical process consists of three main procedures of leaching, solvent extraction and electrodeposition, and the quality of cathode copper and the process energy consumption can be directly influenced by the type and the dosage of an electrodeposition additive in the electrodeposition process. Therefore, we improve the technology and propose a wet copper extraction process.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a wet copper extraction process.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention relates to a wet copper extraction process, which comprises the following steps:
s1: selecting copper oxide ore, crushing the copper oxide ore by a crusher, grinding the crushed copper oxide ore by a grinder, and grinding the crushed copper oxide ore to 0.088-0.14 mm to obtain ore powder;
s2: adding acid liquor into the mineral powder obtained in the step S1 for acid leaching treatment, enabling the liquid-solid ratio to reach 3:1, then stirring for 3-5 hours, adding a certain amount of water for dilution after stirring is finished, and standing and precipitating after dilution;
s3, filtering the particles precipitated in the step S2 to obtain filter residues, and then washing the filter residues with water by water spraying to obtain filtrate with the PH of the filtrate being 2-4;
s4: and (4) producing electrodeposited copper by electrodepositing the filtrate obtained in the step S3.
In a preferred embodiment of the present invention, the electrodeposition in step S4 includes a rectifier, a peristaltic pump, an anode material, a cathode material, and an electrolyte.
As a preferred technical scheme of the invention, the rectifier is a YJ-2060 type rectifier and is used for controlling the current density in the electrowinning process, and the peristaltic pump is an BTl 00-1L type pump and is used for controlling the circulation speed of the electrowinning liquid.
In a preferred embodiment of the present invention, the anode material is Pb-1.2% Sn-O.03% Ca alloy having a specification of 90mm × 55mm × 5mm, and the cathode material is 316 stainless steel having a specification of 100mm × 60mm × 5 mm.
As a preferable technical scheme of the invention, the polar distance between the anode material and the cathode material is 80-100 mm.
As a preferable technical scheme of the invention, the components of the electrolyte are Cu ions, sulfuric acid and Cl ions, and the contents of the Cu ions, the sulfuric acid and the Cl ions are 45g/L, 170g/L and 35g/L respectively.
As a preferable technical scheme of the invention, the electrolyte further comprises cobalt sulfate, guar gum and thiourea, wherein the content of the cobalt sulfate is 80-200mg/L, the content of each ton of guar gum is 20-80g, and 20-40g of thiourea is added to each ton of copper.
As a preferable technical scheme of the invention, the temperature of the electro-deposition liquid is 42 +/-0.5 ℃.
As a preferred technical scheme of the invention, the anode material is pretreated, dried and weighed before use, and is subjected to constant-current polarization in a self-made electrodeposition system, wherein the polarization time is 120h, and the working condition is that the current density is 200A/m 2.
As a preferable technical scheme of the invention, the anode and cathode materials are heated and boiled for 30-50min by sugar alkali solution after being used, the sugar alkali solution is glucose and sodium hydroxide, and the contents of the glucose and the sodium hydroxide solution are 20g/L and 100g/L respectively.
The invention has the beneficial effects that: according to the wet copper extraction process, the Co ions are added into the copper electrolyte, so that the anode corrosion speed is favorably slowed down, the anode potential is reduced, and the proper concentration of the Co ions in the electrolyte is 100 mg/L; the addition of the guar gum to the electric accumulated liquid is beneficial to the generation of cathode copper with smooth and flat surface, the dosage of the guar gum is 50g per ton of copper, the effect of thiourea is obvious when the current density of the copper electrolysis process is higher (300A/square meter), and the thiourea can be used as an additive.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram showing the effect of Co ion concentration on anodic corrosion rate and anodic potential in a wet copper extraction process of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example (b): the invention relates to a wet copper extraction process, which comprises the following steps:
s1: selecting copper oxide ore, crushing the copper oxide ore by a crusher, grinding the crushed copper oxide ore by a grinder, and grinding the crushed copper oxide ore to 0.088-0.14 mm to obtain ore powder;
s2: adding acid liquor into the mineral powder obtained in the step S1 for acid leaching treatment, enabling the liquid-solid ratio to reach 3:1, then stirring for 3-5 hours, adding a certain amount of water for dilution after stirring is finished, and standing and precipitating after dilution;
s3, filtering the particles precipitated in the step S2 to obtain filter residues, and then washing the filter residues with water by water spraying to obtain filtrate with the PH of the filtrate being 2-4;
s4: and (4) producing electrodeposited copper by electrodepositing the filtrate obtained in the step S3.
The electrodeposition in the step S4 includes a rectifier, a peristaltic pump, an anode material, a cathode material and an electrolyte, the rectifier is a YJ-2060 type rectifier for controlling the current density in the electrodeposition process, the peristaltic pump is a BTl 00-1L type pump for controlling the circulation speed of the electrodeposition liquid, the anode material is Pb-1.2% Sn-O.03% Ca alloy with the specification of 90mm × 55mm × 5mm, the cathode material is 316 stainless steel with the specification of 100mm × 60mm × 5mm, the polar distance between the anode material and the cathode material is 80-100mm, the electrolyte comprises Cu ions, sulfuric acid and Cl ions, the contents of the Cu ions, the sulfuric acid and the Cl ions are 45g/L, 170g/L and 35g/L respectively, the electrolyte further includes cobalt sulfate, gule gum and thiourea, the contents of the cobalt sulfate are 80-200mg/L respectively, the content of the ton gule gum is 20-80g, adding 20-40g of thiourea into each ton of copper, controlling the temperature of the electrodeposition solution to be 42 +/-0.5 ℃, pretreating, drying and weighing the anode material before use, carrying out constant current polarization in a self-made electrodeposition system for 120h under the working condition that the current density is 200A/m2, heating and boiling the anode material and the cathode material for 30-50min by using a sugar-alkali solution after use, wherein the sugar-alkali solution is glucose and sodium hydroxide, and the contents of the glucose solution and the sodium hydroxide solution are respectively 20g/L and 100g/L
Example 1:
the electrolyte comprises 45g/L of Cu ions, 170g/L of sulfuric acid, 80-200mg/L of cobalt sulfate, 20-80g of Gule gum per ton, 20-40g of thiourea per ton and 42 +/-0.5 ℃ of electro-deposition liquid.
The embodiment is used for researching the influence of Co ions on the anode corrosion rate, the electrolyte is not added with Cl ions, the Co ions have good electrocatalysis effect on the anode oxygen evolution reaction, the oxygen evolution overpotential and the anode potential can be reduced, thereby reducing the bath voltage, simultaneously slowing down the corrosion speed of the lead-based anode, not only protecting the anode, but also reducing the lead content in cathode copper, wherein the adding amount of Co ions is usually 80-200mg/L in industrial practice, as can be seen from figure 1, the concentration of Co ions has the same corrosion rate to the lead anode, the influence of the anode potential is obvious, the anode corrosion rate and the anode potential are both reduced along with the increase of the concentration of Co ions, when the concentration of Co ions is increased to 80mg/L, the influence of continuously increasing the concentration of Co ions on the corrosion rate of the anode is small, therefore, the amount of Co ions added for reducing the anodic corrosion rate is preferably 80 mg/L. When the addition amount of Co ions is increased from 0 to 100mg/L, the anode potential is reduced by 110mV, namely the anode oxygen evolution overpotential is reduced by 110 mV. The action mechanism of the Co ions is that the Co ions and the lead oxide form an activation center, so that the overpotential of oxygen precipitation is favorably reduced, firm lead oxide is favorably formed, and the release of lead-containing particles to the electrolyte is reduced. The concentration of Co ions in the electrolyte solution is continuously increased, and the reduction speed of the anode potential is slowed, so that when the Co ions are used for reducing the anode potential, the proper addition amount is 100 mg/L. Comprehensively considering the influence of Co ions on the corrosion rate and oxygen evolution potential of the copper electrodeposition anode, the concentration of C02+ in the copper electrodeposition liquid is selected to be 100 mg/L.
Example 2:
the electrolyte comprises 45g/L of Cu ions, 170g/L of sulfuric acid, 80-200mg/L of cobalt sulfate, 20-80g of ton of guar gum and 42 +/-0.5 ℃ of electro-deposition liquid.
This embodiment is used for studying the influence of Guler to the negative pole copper appearance, current density is 200A/square meter when studying the influence of Guler to the negative pole appearance, thiourea and Cl ion are not added, Guler is one of the most important additive of copper electrodeposition process, it can increase the negative pole polarization potential to add Guler, change crystal nucleus formation and growth rate, control electrochemistry crystallization process, avoid point discharge, make the smooth level and smooth in negative pole copper surface, the ton copper Guler quantity of present copper electrodeposition factory is 20 ~ 80 g. As seen from a macroscopic view obtained by an experiment, the appearance of the cathode copper gradually becomes smooth and compact as the addition amount of the guar gum is increased from 20g/t to 150g/t, and the stripe shape completely disappears. Considering that the wet copper extraction generally adopts an extraction-electrodeposition process, the electrowinning barren liquor is commonly used as a back extractant for copper extraction in industry, and the overdosed Guerban can enter the extraction process to influence the performance of the extractant, so that the addition of the Guerban is not too high, and the dosage of the copper Guerban per ton is 50 g.
Example 3: the electrolyte comprises 45g/L of Cu ions, 170g/L of sulfuric acid and 80-200mg/L of cobalt sulfate, the content of thiourea per ton is 20-40g, and the temperature of the electro-deposition solution is 42 +/-0.5 ℃.
The embodiment is used for researching the influence of thiourea on the appearance of the cathode copper, the current density is 200A/square meter and 300A/square meter when the influence of the thiourea on the appearance of the cathode is researched, no Gule adhesive and Cl ions are added, and the influence mechanism of the addition of the thiourea on the copper electrodeposition is mainly 2: firstly, thiourea dissolved in the electrolyte solution forms a glue film with poor conductivity to be adsorbed on the surface of a cathode, so that cathode polarization is increased, copper ions are difficult to discharge at the cathode, the copper electrodeposition speed is reduced, and cathode copper compact deposition is realized; secondly, thiourea dissolved in the electrolyte solution can generate cuprous sulfide particles on the cathode, can be used as new active crystal nuclei, is beneficial to refining crystallization of the cathode, has compact and flat crystal faces, and has more obvious effect at high current density, and experimental data shows that the appearance of the cathode is hardly influenced by adding thiourea when the current density is 200A/square meter, which indicates that the effect of generating new crystal nuclei by adding thiourea at the current density is not obvious, and the effect of adding thiourea is obvious when the current density is 300A/square meter, which indicates that the thiourea plays an important role at the high current density. Therefore, the method can be preliminarily considered that the prior copper electrodeposition process in China can not add thiourea as an additive due to the low current density (200 +/-20A/square meter); the copper electrolysis process has high current density (300A/square meter), obvious thiourea effect and capacity of using thiourea as additive.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A wet copper extraction process comprises the following steps:
s1: selecting copper oxide ore, crushing the copper oxide ore by a crusher, grinding the crushed copper oxide ore by a grinder, and grinding the crushed copper oxide ore to 0.088-0.14 mm to obtain ore powder;
s2: adding acid liquor into the mineral powder obtained in the step S1 for acid leaching treatment, enabling the liquid-solid ratio to reach 3:1, then stirring for 3-5 hours, adding a certain amount of water for dilution after stirring is finished, and standing and precipitating after dilution;
s3, filtering the particles precipitated in the step S2 to obtain filter residues, and then washing the filter residues with water by water spraying to obtain filtrate with the PH of the filtrate being 2-4;
s4: and (4) producing electrodeposited copper by electrodepositing the filtrate obtained in the step S3.
2. The wet copper extraction process of claim 1, wherein the electrodeposition in step S4 comprises a rectifier, a peristaltic pump, an anode material, a cathode material and an electrolyte.
3. The wet copper extraction process according to claim 2, wherein the rectifier is a YJ-2060 type rectifier for controlling the current density during the electrodeposition process, and the peristaltic pump is an BTl 00-1L type pump for controlling the circulation rate of the electrodeposition liquid.
4. The wet copper extraction process of claim 2, wherein the anode material is 90mm x 55mm x 5mm Pb-1.2% Sn — o.03% Ca alloy, and the cathode material is 100mm x 60mm x 5mm 316 stainless steel.
5. The wet copper extraction process according to claim 2, wherein the polar distance between the anode material and the cathode material is 80-100 mm.
6. The wet copper extraction process according to claim 2, wherein the electrolyte components are Cu ions, sulfuric acid and Cl ions, and the contents of the Cu ions, the sulfuric acid and the Cl ions are 45g/L, 170g/L and 35g/L respectively.
7. The wet copper extraction process according to claim 2, wherein the electrolyte further comprises cobalt sulfate, guar gum and thiourea, the content of the cobalt sulfate is 80-200mg/L, the content of the guar gum per ton is 20-80g, and 20-40g of thiourea per ton of copper is added.
8. The wet copper extraction process according to claim 1, wherein the electrodeposition temperature is 42 ± 0.5 ℃.
9. The wet copper extraction process according to claim 1, wherein the anode material is pretreated, dried and weighed before use, and is subjected to constant current polarization in a self-made electrodeposition system for 120 hours under the working condition of current density of 200A/square meter.
10. The wet copper extraction process according to claim 1, wherein the anode and cathode materials are heated and boiled for 30-50min after use by sugar alkali solution, the sugar alkali solution is glucose and sodium hydroxide, and the content of the glucose and the sodium hydroxide solution is 20g/L and 100g/L respectively.
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| CN202010099775.4A CN111197171A (en) | 2020-02-18 | 2020-02-18 | Wet copper extraction process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113096884A (en) * | 2021-04-01 | 2021-07-09 | 江西中晟金属有限公司 | Preparation method of high-purity copper bar |
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| CN104195592A (en) * | 2014-09-25 | 2014-12-10 | 江苏鑫成铜业有限公司 | Waste scrap copper recovery process method |
| CN106834699A (en) * | 2017-01-20 | 2017-06-13 | 湖南埃格环保科技有限公司 | A kind of copper-contained sludge harmless treatment and the method for higher value application |
| CN108505065A (en) * | 2018-05-11 | 2018-09-07 | 云南驰宏锌锗股份有限公司 | A kind of method that difficulty selects glutenite copper mine production tough cathode |
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2020
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084585A (en) * | 1993-08-10 | 1994-03-30 | 李学刚 | Process for one-stage electrolytic extraction of copper |
| US20070125659A1 (en) * | 2005-11-14 | 2007-06-07 | Hecker Cartes Christian H D | Process for optimizing the process of copper electro-winning and electro-refining by superimposing a sinussoidal current over a continuous current |
| JP2009074140A (en) * | 2007-09-21 | 2009-04-09 | Sumitomo Metal Mining Co Ltd | Wet copper refining method for copper raw material comprising copper sulfide mineral |
| CN101451195A (en) * | 2007-12-03 | 2009-06-10 | 孙华信 | Technology process of extracting copper from copper oxide ore |
| CN102586600A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Process for recycling valuable metal from lead copper matte |
| CN103374655A (en) * | 2012-04-24 | 2013-10-30 | 中国瑞林工程技术有限公司 | Wet-method copper extraction process |
| CN103422119A (en) * | 2013-07-19 | 2013-12-04 | 紫金矿业集团股份有限公司 | Method for producing tough cathode with cupric sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113096884A (en) * | 2021-04-01 | 2021-07-09 | 江西中晟金属有限公司 | Preparation method of high-purity copper bar |
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