CN110640162A - Method for preparing, pretreating and dispersing superfine copper powder - Google Patents
Method for preparing, pretreating and dispersing superfine copper powder Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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Abstract
The invention relates to a method for preparing, pretreating and dispersing superfine copper powder, which comprises the steps of pretreating, dispersing and reducing copper ore, wherein the method for dispersing pretreated copper concentrate comprises the following steps: adding a dispersion medium into the mixing kettle, removing oxygen, mixing and dispersing, and heating and mixing. The method can obviously improve the dispersion effect of the copper ore raw material, so that the superfine copper powder obtained by reduction has more uniform granularity.
Description
Technical Field
The invention belongs to the field of copper powder preparation, and particularly relates to a method for preparing, pretreating and dispersing superfine copper powder.
Background
The superfine copper powder is an indispensable basic raw material of the nano copper material with good conductivity and high strength. Due to the excellent electrical properties, the conductive coating is widely applied to conductive adhesives, conductive coatings and electrode materials, and researches in recent years find that the conductive coating can be used for preparing catalysts and lubricating oil additives, and can be used for treating osteoporosis, fracture and the like.
The ultrafine particle material is powder with the particle size of 1-100 nm, and is also called nano particle material (in application, the ultrafine particle material is expanded to several microns). Nanoparticles have small size effects, large specific surface and macroscopic quantum tunneling effects, and thus nanopowders exhibit many superior properties not found in micron-sized powders.
The nano copper powder has large specific surface and more surface active centers, and is an excellent catalyst in metallurgy and petrochemical industry. The nanometer copper powder catalyst has very high activity and selectivity in the hydrogenation and dehydrogenation reaction of high molecular polymer, and is very effective in the process of acetylene polymerization reaction for preparing conductive fiber.
In the process of purifying and treating the automobile exhaust, the nanometer copper powder as a catalyst can be used for partially replacing noble metals of platinum and ruthenium, so that toxic carbon monoxide is converted into carbon dioxide, and nitrogen monoxide is converted into nitrogen dioxide.
The superfine copper powder obtained by the preparation method in the prior art has uneven granularity, so that the technical problem in the field is to develop a preparation method of the superfine copper powder which has higher purity, smaller granularity and good dispersibility and has simple process.
Disclosure of Invention
The invention aims to solve the defect of uneven dispersion in the prior art, and provides a method for preparing, pretreating and dispersing superfine copper powder.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a method for preparing, pretreating and dispersing superfine copper powder comprises the steps of pretreating, dispersing and reducing copper ore pulp, wherein the dispersing method comprises the following steps:
s1, adding a dispersion medium into the mixing kettle;
s2, removing oxygen: vacuumizing the mixing kettle to ensure that the vacuum degree is less than or equal to-0.05 Mpa, then filling inert gas into the mixing kettle to ensure that the pressure value in the mixing kettle is more than or equal to 1.55Mpa, and measuring the oxygen concentration in the mixing kettle to be less than or equal to 0.01 percent;
s3, mixing and dispersing: adding the pretreated copper ore pulp into the dispersion medium, wherein the mixing weight ratio is as follows: mixing the dispersion medium =1 (8-12), wherein ultrasonic wave is adopted for auxiliary mixing in the mixing process, the ultrasonic frequency is 18KHz-40KHz, and the power is 320 mW/cm;
s4, heating and mixing: and heating and mixing the mixing kettle, keeping the temperature at 40-55 ℃, and performing centrifugal stirring at the centrifugal speed of 2000-2500rpm to finish the dispersed copper ore pulp.
Preferably, the dispersion medium is PVP or PVA or gelatin or a combination thereof.
Further preferably, the weight ratio of the PVP, the PVA and the gelatin is 1:1: 2. After the three materials are mixed in the proportion, the performance is stronger, and the effect on the copper ore pulp is larger.
Preferably, the pretreatment of the copper ore pulp comprises the following steps:
1) sequentially adding water, NaCl and dilute hydrochloric acid into powdery copper concentrate with the copper content of 20-30 wt% and the particle size of 15-246 mu m and the distribution amount of more than 90% to stir and ball-mill;
2) and activating and removing the chemical from the copper concentrate along with the continuous stirring and ball milling, and filtering by a 200-mesh sieve to obtain the pretreated copper ore pulp.
Further preferably, the water of step 1) is added in an amount of 2.9 to 3.1 times the weight of the powdered copper concentrate, and NaCl is added in a proportion of 480-500kg of NaCl per ton of powdered copper concentrate, the dilute hydrochloric acid is an aqueous hydrochloric acid solution having a concentration of 9.8 to 10.2wt%, and the pH of the dilute hydrochloric acid is adjusted to 4 to 5. Can make the copper concentrate activating and pesticide removing effect better.
Preferably, the reduction process comprises the steps of adding the dispersed copper ore pulp into a reducing agent, aging, filtering, carrying out solid-liquid separation, carrying out wet grinding, drying and screening to obtain the superfine copper powder.
Further preferably, the reducing agent comprises ethanol, sodium triethylborohydride, potassium borohydride, stannous chloride, sodium hypophosphite, formaldehyde, hydrazine hydrate, L-ascorbic acid, lithium aluminum hydride or polyethyleneimine or a combination thereof.
Preferably, in the step S2, the inert gas is a mixed gas of nitrogen and helium, and the volume ratio of the nitrogen to the helium is (1.5-2.5): 1. The mixed gas has good performance and low cost.
The invention has the following beneficial effects:
the method adopts the following processes to disperse the copper ore, and a dispersion medium is added into a mixing kettle; removing oxygen; mixing and dispersing: adding the pretreated copper ore pulp into the dispersion medium, mixing according to the weight ratio of the copper ore pulp to the dispersion medium =1:8-12, and performing ultrasonic-assisted mixing in the mixing process, wherein the ultrasonic frequency is 18KHz-40KHz, and the power is 320 mW/cm; heating and mixing: the mixing kettle is heated and mixed, the temperature is maintained at 40-55 ℃, and centrifugal stirring is adopted, the centrifugal speed is 2000-2500 rpm. The method can obviously improve the dispersion effect of the copper ore raw material, so that the superfine copper powder obtained by reduction has more uniform granularity.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited to the scope of the examples. These examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
A method for preparing, pretreating and dispersing superfine copper powder comprises the steps of pretreating, dispersing and reducing copper ore pulp, wherein the method for dispersing pretreated copper concentrate comprises the following steps:
s1, adding a dispersion medium into the mixing kettle;
s2, removing oxygen: vacuumizing the mixing kettle to ensure that the vacuum degree is less than or equal to-0.05 Mpa, then filling inert gas into the mixing kettle, wherein the inert gas is the mixed gas of nitrogen and helium, the volume ratio of the nitrogen to the helium is 2:1, so that the pressure value in the mixing kettle is more than or equal to 1.55Mpa, and determining that the oxygen concentration in the mixing kettle is less than or equal to 0.01%;
s3, mixing and dispersing: adding the pretreated copper ore pulp into the dispersion medium, mixing according to the weight ratio of the copper ore pulp to the dispersion medium =1:8, and adopting ultrasonic wave for auxiliary mixing in the mixing process, wherein the frequency of the ultrasonic wave is 18KHz, and the power is 320 mW/cm;
s4, heating and mixing: the mixing kettle was heated and mixed with the temperature maintained at 40 ℃ and with centrifugal stirring at a centrifugal speed of 2000 rpm.
The dispersion medium is a mixture of PVP, PVA and gelatin.
The addition ratio of PVP, PVA and gelatin is 1:1: 2.
The pretreatment of the copper ore comprises the following steps: putting powdery copper concentrate with the copper content of 25wt% and the particle size of 15-246 mu m and the distribution amount of more than 90% into a high-energy stirring ball mill, adding a proper amount of water during stirring, adding a proper amount of NaCl and dilute hydrochloric acid for stirring and ball milling, wherein the adding amount of the water is 3 times of the weight of the powdery copper concentrate, adding 498kg of NaCl into each ton of the powdery copper concentrate, adding the dilute hydrochloric acid which is an HCL aqueous solution with the concentration of 9.9wt%, and enabling the pH to be 4-5; and activating and removing the chemical from the copper concentrate along with the continuous stirring and ball milling, and filtering by a 200-mesh sieve to obtain the pretreated copper concentrate pulp.
The electrolytic reduction process is to add the dispersed copper ore solution into a reducing agent, age after reacting for a certain time, then carry out solid-liquid separation by filtration, and obtain the superfine copper powder after wet grinding, drying and screening.
The reducing agent comprises a mixture of ethanol, sodium triethylborohydride, potassium borohydride, stannous chloride, sodium hypophosphite, formaldehyde, hydrazine hydrate, L-ascorbic acid, lithium aluminum hydride and polyethyleneimine, wherein the molar concentration of the reducing agent is 1 mol/L.
The conversion rate of the copper powder in this example was 90% or more, the particle size distribution was 100 ~ 500nm, and the oxygen content did not change much when the copper powder was left in the air for 60 days.
Example 2
A method for preparing, pretreating and dispersing superfine copper powder comprises the steps of copper ore pretreatment, dispersion and reduction, and the method for dispersing pretreated copper concentrate comprises the following steps:
s1, adding a dispersion medium into the mixing kettle;
s2, removing oxygen: vacuumizing the mixing kettle to ensure that the vacuum degree is less than or equal to-0.05 Mpa, then filling inert gas into the mixing kettle, wherein the inert gas is the mixed gas of nitrogen and helium, the volume ratio of the nitrogen to the helium is 2:1, so that the pressure value in the mixing kettle is more than or equal to 1.55Mpa, and determining that the oxygen concentration in the mixing kettle is less than or equal to 0.01%;
s3, mixing and dispersing: adding the pretreated copper ore pulp into the dispersion medium, mixing according to the weight ratio of the copper ore pulp to the dispersion medium =1:9, and adopting ultrasonic wave for auxiliary mixing in the mixing process, wherein the ultrasonic frequency is 20KHz, and the power is 320 mW/cm;
s4, heating and mixing: the mixing kettle was heated and mixed with maintaining a temperature of 42 ℃ and with centrifugal stirring at a centrifugal rate of 2100 rpm.
The dispersion medium is a mixture of PVP, PVA and gelatin.
The addition ratio of PVP, PVA and gelatin is 1:1: 2.
The pretreatment of the copper ore comprises the following steps: putting powdery copper concentrate with 20-30 wt% of copper content and more than 90% of particle size between 15-246 mu m into a high-energy stirring ball mill, adding a proper amount of water during stirring, and then adding a proper amount of NaCl and dilute hydrochloric acid for stirring and ball milling, wherein the addition amount of the water is 3 times of the weight of the powdery copper concentrate, the NaCl is added according to the proportion that 495kg of NaCl is added into each ton of the powdery copper concentrate, the dilute hydrochloric acid is HCL aqueous solution with the concentration of 10.1wt%, and the addition amount of the dilute hydrochloric acid ensures that the pH is 4-5; and activating and removing the chemical from the copper concentrate along with the continuous stirring and ball milling, and filtering by a 200-mesh sieve to obtain the pretreated copper concentrate pulp.
The electrolytic reduction process is to add the dispersed copper ore solution into a reducing agent, age after reacting for a certain time, then carry out solid-liquid separation by filtration, and obtain the superfine copper powder after wet grinding, drying and screening.
The reducing agent comprises a mixture of ethanol, sodium triethylborohydride, potassium borohydride, stannous chloride, sodium hypophosphite, formaldehyde, hydrazine hydrate, L-ascorbic acid, lithium aluminum hydride and polyethyleneimine, wherein the molar concentration of the reducing agent is 2 mol/L.
The conversion rate of the copper powder in this example was 91% or more, the particle size distribution was 90 ~ 500nm, and the oxygen content did not change much when the copper powder was left in the air for 60 days.
Example 3
A method for preparing, pretreating and dispersing superfine copper powder comprises the steps of copper ore pretreatment, dispersion and reduction, and the method for dispersing pretreated copper concentrate comprises the following steps:
s1, adding a dispersion medium into the mixing kettle;
s2, removing oxygen: vacuumizing the mixing kettle to ensure that the vacuum degree is less than or equal to-0.05 Mpa, then filling inert gas into the mixing kettle, wherein the inert gas is the mixed gas of nitrogen and helium, the volume ratio of the nitrogen to the helium is 2:1, so that the pressure value in the mixing kettle is more than or equal to 1.55Mpa, and determining that the oxygen concentration in the mixing kettle is less than or equal to 0.01%;
s3, mixing and dispersing: adding the pretreated copper ore pulp into the dispersion medium, mixing according to the weight ratio of the copper ore pulp to the dispersion medium =1:10, and adopting ultrasonic wave for auxiliary mixing in the mixing process, wherein the frequency of the ultrasonic wave is 25KHz, and the power is 320 mW/cm;
s4, heating and mixing: the mixing kettle was heated and mixed at 45 ℃ with centrifugal stirring at a speed of 2200 rpm.
The dispersion medium is a mixture of PVP, PVA and gelatin.
The addition ratio of PVP, PVA and gelatin is 1:1: 2.
The pretreatment of the copper ore comprises the following steps: putting powdery copper concentrate with 20-30 wt% of copper content and more than 90% of particle size of 15-246 mu m into a high-energy stirring ball mill, adding a proper amount of water during stirring, and then adding a proper amount of NaCl and dilute hydrochloric acid for stirring and ball milling, wherein the addition amount of the water is 3 times of the weight of the powdery copper concentrate, the NaCl is added according to the proportion that 490kg of NaCl is added into each ton of the powdery copper concentrate, the dilute hydrochloric acid is HCL aqueous solution with the concentration of 9.9wt%, and the addition amount of the dilute hydrochloric acid ensures that the pH is 4-5; and activating and removing the chemical from the copper concentrate along with the continuous stirring and ball milling, and filtering by a 200-mesh sieve to obtain the pretreated copper concentrate pulp.
The electrolytic reduction process is to add the dispersed copper ore solution into a reducing agent, age after reacting for a certain time, then carry out solid-liquid separation by filtration, and obtain the superfine copper powder after wet grinding, drying and screening.
The reducing agent comprises a mixture of ethanol, sodium triethylborohydride, potassium borohydride, stannous chloride, sodium hypophosphite, formaldehyde, hydrazine hydrate, L-ascorbic acid, lithium aluminum hydride and polyethyleneimine, wherein the molar concentration of the reducing agent is 4 mol/L.
The conversion rate of the copper powder in this example was 92% or more, the particle size distribution was 80 ~ 500nm, and the oxygen content did not change much when the copper powder was left in the air for 60 days.
Example 4
A method for preparing, pretreating and dispersing superfine copper powder comprises the steps of copper ore pretreatment, dispersion and reduction, and the method for dispersing pretreated copper concentrate comprises the following steps:
s1, adding a dispersion medium into the mixing kettle;
s2, removing oxygen: vacuumizing the mixing kettle to ensure that the vacuum degree is less than or equal to-0.05 Mpa, then filling inert gas into the mixing kettle, wherein the inert gas is the mixed gas of nitrogen and helium, the volume ratio of the nitrogen to the helium is 2:1, so that the pressure value in the mixing kettle is more than or equal to 1.55Mpa, and determining that the oxygen concentration in the mixing kettle is less than or equal to 0.01%;
s3, mixing and dispersing: adding the pretreated copper ore pulp into the dispersion medium, mixing according to the weight ratio of the copper ore pulp to the dispersion medium =1:11, and adopting ultrasonic wave for auxiliary mixing in the mixing process, wherein the frequency of the ultrasonic wave is 35KHz, and the power is 320 mW/cm;
s4, heating and mixing: the mixing kettle was heated and mixed, the temperature was maintained at 50 ℃ and centrifugal stirring was used, the centrifugal rate being 2400 rpm.
The dispersion medium is a mixture of PVP, PVA and gelatin.
The addition ratio of PVP, PVA and gelatin is 1:1: 2.
The pretreatment of the copper ore comprises the following steps: putting powdery copper concentrate with 20-30 wt% of copper content and more than 90% of particle size of 15-246 mu m into a high-energy stirring ball mill, adding a proper amount of water during stirring, and then adding a proper amount of NaCl and dilute hydrochloric acid for stirring and ball milling, wherein the addition amount of the water is 2.9 times of the weight of the powdery copper concentrate, the NaCl is added according to the proportion that 480kg of NaCl is added into each ton of the powdery copper concentrate, the dilute hydrochloric acid is HCL aqueous solution with the concentration of 9.8wt%, and the addition amount of the dilute hydrochloric acid ensures that the pH is 4-5; and activating and removing the chemical from the copper concentrate along with the continuous stirring and ball milling, and filtering by a 200-mesh sieve to obtain the pretreated copper concentrate pulp.
The electrolytic reduction process is to add the dispersed copper ore solution into a reducing agent, age after reacting for a certain time, then carry out solid-liquid separation by filtration, and obtain the superfine copper powder after wet grinding, drying and screening.
The reducing agent comprises sodium triethylborohydride, wherein the molar concentration of the reducing agent is 6 mol/L.
The conversion rate of the copper powder in this example was 93% or more, the particle size distribution was 70 ~ 500nm, and the oxygen content did not change much when the copper powder was left in the air for 60 days.
Example 5
A method for preparing, pretreating and dispersing superfine copper powder comprises the steps of copper ore pretreatment, dispersion and reduction, and the method for dispersing pretreated copper concentrate comprises the following steps:
s1, adding a dispersion medium into the mixing kettle;
s2, removing oxygen: vacuumizing the mixing kettle to ensure that the vacuum degree is less than or equal to-0.05 Mpa, then filling inert gas into the mixing kettle, wherein the inert gas is the mixed gas of nitrogen and helium, the volume ratio of the nitrogen to the helium is 2:1, so that the pressure value in the mixing kettle is more than or equal to 1.55Mpa, and determining that the oxygen concentration in the mixing kettle is less than or equal to 0.01%;
s3, mixing and dispersing: adding the pretreated copper ore pulp into the dispersion medium, mixing according to the weight ratio of the copper ore pulp to the dispersion medium =1:12, and adopting ultrasonic wave for auxiliary mixing in the mixing process, wherein the frequency of the ultrasonic wave is 40KHz, and the power is 320 mW/cm;
s4, heating and mixing: the mixing kettle was heated and mixed at 55 ℃ with centrifugal stirring at a rate of 2500 rpm.
The dispersion medium is a mixture of PVP, PVA and gelatin.
The addition ratio of PVP, PVA and gelatin is 1:1: 2.
The pretreatment of the copper ore comprises the following steps: putting powdery copper concentrate with 20-30 wt% of copper content and more than 90% of particle size of 15-246 mu m into a high-energy stirring ball mill, adding a proper amount of water during stirring, and then adding a proper amount of NaCl and dilute hydrochloric acid for stirring and ball milling, wherein the addition amount of the water is 3.1 times of the weight of the powdery copper concentrate, the NaCl is added according to the proportion that 500kg of NaCl is added into each ton of the powdery copper concentrate, the dilute hydrochloric acid is HCL aqueous solution with the concentration of 10.2wt%, and the addition amount of the dilute hydrochloric acid ensures that the pH is 4-5; and activating and removing the chemical from the copper concentrate along with the continuous stirring and ball milling, and filtering by a 200-mesh sieve to obtain the pretreated copper concentrate pulp.
The electrolytic reduction process is to add the dispersed copper ore solution into a reducing agent, age after reacting for a certain time, then carry out solid-liquid separation by filtration, and obtain the superfine copper powder after wet grinding, drying and screening.
The reducing agent comprises a mixture of sodium hypophosphite, wherein the molar concentration of the reducing agent is 8 mol/L.
The conversion rate of the copper powder in this example was 94% or more, the particle size distribution was 60 ~ 500nm, and the oxygen content did not change greatly when the copper powder was left in the air for 60 days.
Claims (8)
1. A method for preparing, pretreating and dispersing superfine copper powder comprises the steps of pretreating, dispersing and reducing copper ore pulp, and is characterized in that the dispersing method comprises the following steps:
s1, adding a dispersion medium into the mixing kettle;
s2, removing oxygen: vacuumizing the mixing kettle to ensure that the vacuum degree is less than or equal to-0.05 Mpa, then filling inert gas into the mixing kettle to ensure that the pressure value in the mixing kettle is more than or equal to 1.55Mpa, and measuring the oxygen concentration in the mixing kettle to be less than or equal to 0.01 percent;
s3, mixing and dispersing: adding the pretreated copper ore pulp into the dispersion medium, wherein the mixing weight ratio is as follows: mixing the dispersion medium =1 (8-12), wherein ultrasonic wave is adopted for auxiliary mixing in the mixing process, the ultrasonic frequency is 18KHz-40KHz, and the power is 320 mW/cm;
s4, heating and mixing: and heating and mixing the mixing kettle, keeping the temperature at 40-55 ℃, and performing centrifugal stirring at the centrifugal speed of 2000-2500rpm to finish the dispersed copper ore pulp.
2. The method of claim 1, wherein: the dispersion medium is PVP or PVA or gelatin or a combination thereof.
3. The method of claim 2, wherein: the addition weight ratio of the PVP, the PVA and the gelatin is 1:1: 2.
4. The method of claim 1, wherein: the pretreatment of the copper ore pulp comprises the following steps:
1) sequentially adding water, NaCl and dilute hydrochloric acid into powdery copper concentrate with the copper content of 20-30 wt% and the particle size of 15-246 mu m and the distribution amount of more than 90% to stir and ball-mill;
2) and activating and removing the chemical from the copper concentrate along with the continuous stirring and ball milling, and filtering by a 200-mesh sieve to obtain the pretreated copper ore pulp.
5. The method of claim 4, wherein: the adding amount of the water in the step 1) is 2.9-3.1 times of the weight of the powdery copper concentrate, the NaCl is added according to the proportion that 480-500kg of NaCl is added into each ton of the powdery copper concentrate, the dilute hydrochloric acid is a hydrochloric acid aqueous solution with the concentration of 9.8-10.2wt%, and the pH value of the dilute hydrochloric acid is adjusted to be 4-5.
6. The method of claim 1, wherein: the reduction process comprises the steps of adding the dispersed copper ore pulp into a reducing agent, aging, filtering, carrying out solid-liquid separation, and carrying out wet grinding, drying and screening to obtain the superfine copper powder.
7. The method of claim 6, wherein: the reducing agent comprises ethanol, sodium triethylborohydride, potassium borohydride, stannous chloride, sodium hypophosphite, formaldehyde, hydrazine hydrate, L-ascorbic acid, lithium aluminum hydride or polyethyleneimine or a combination thereof.
8. The method of claim 1, wherein: in the step S2, the inert gas is a mixed gas of nitrogen and helium, and the volume ratio of the nitrogen to the helium is (1.5-2.5): 1.
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| US1679337A (en) * | 1924-10-29 | 1928-07-31 | Metals Production Company Of N | Heat treatment and concentration of copper ores |
| GB791916A (en) * | 1954-09-14 | 1958-03-12 | Sherritt Gordon Mines Ltd | Improved method of extracting copper values from material containing copper |
| EP0041841A1 (en) * | 1980-06-11 | 1981-12-16 | Cato Research Corporation | Process for the recovery of metals from their ores |
| CN101007354A (en) * | 2007-02-01 | 2007-08-01 | 江苏技术师范学院 | Method for preparing ultra-fine copper powder from copper concentrate ore directly and ultrasonic membrane electrolysis |
| CN101524763A (en) * | 2009-04-23 | 2009-09-09 | 金川集团有限公司 | Method for preparing submicron spherical copper powder |
| CN101890505A (en) * | 2010-07-21 | 2010-11-24 | 株洲冶炼集团股份有限公司 | Superfine cupper powder and preparation method thereof |
| CN101942679A (en) * | 2010-10-25 | 2011-01-12 | 江苏技术师范学院 | Method for preparing, pre-treating and dispersing superfine copper powder |
| CN105297078A (en) * | 2014-06-17 | 2016-02-03 | 中山大学 | Ultrasonic-assisted pulp electrolysis method for tailing sand |
| CN108941605A (en) * | 2018-08-02 | 2018-12-07 | 西安雷晶新材料科技有限公司 | A kind of preparation method of superfine cupper powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1679337A (en) * | 1924-10-29 | 1928-07-31 | Metals Production Company Of N | Heat treatment and concentration of copper ores |
| GB791916A (en) * | 1954-09-14 | 1958-03-12 | Sherritt Gordon Mines Ltd | Improved method of extracting copper values from material containing copper |
| EP0041841A1 (en) * | 1980-06-11 | 1981-12-16 | Cato Research Corporation | Process for the recovery of metals from their ores |
| CN101007354A (en) * | 2007-02-01 | 2007-08-01 | 江苏技术师范学院 | Method for preparing ultra-fine copper powder from copper concentrate ore directly and ultrasonic membrane electrolysis |
| CN101524763A (en) * | 2009-04-23 | 2009-09-09 | 金川集团有限公司 | Method for preparing submicron spherical copper powder |
| CN101890505A (en) * | 2010-07-21 | 2010-11-24 | 株洲冶炼集团股份有限公司 | Superfine cupper powder and preparation method thereof |
| CN101942679A (en) * | 2010-10-25 | 2011-01-12 | 江苏技术师范学院 | Method for preparing, pre-treating and dispersing superfine copper powder |
| CN105297078A (en) * | 2014-06-17 | 2016-02-03 | 中山大学 | Ultrasonic-assisted pulp electrolysis method for tailing sand |
| CN108941605A (en) * | 2018-08-02 | 2018-12-07 | 西安雷晶新材料科技有限公司 | A kind of preparation method of superfine cupper powder |
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Application publication date: 20200103 |