CN112391530A - Method for recovering copper in copper sludge - Google Patents

Method for recovering copper in copper sludge Download PDF

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CN112391530A
CN112391530A CN202011190844.9A CN202011190844A CN112391530A CN 112391530 A CN112391530 A CN 112391530A CN 202011190844 A CN202011190844 A CN 202011190844A CN 112391530 A CN112391530 A CN 112391530A
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copper
alcohol
solution
alkali
sludge
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CN112391530B (en
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陈小平
付嘉琦
席细平
陈泊宏
范敏
石金明
罗成龙
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ENERGY RESEARCH INSTITUTE OF JIANGXI ACADEMY OF SCIENCES
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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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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
    • C22B15/008—Leaching or slurrying with non-acid solutions containing salts of alkali or alkaline earth metals
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a method for recovering copper in copper sludge, which comprises the following steps: mixing copper sludge, alkali and an organic solvent for thermal reaction, and filtering, washing and drying a reaction product to obtain copper powder; the organic solvent is alcohol, an alcohol aqueous solution or an alcohol-containing organic solution. The method has the advantages of low recovery cost, simple and convenient operation of the recovery method, realization of nearly complete recovery of copper in the copper sludge generated in the copper material processing process, good economic benefit and contribution to realization of industrialized popularization.

Description

Method for recovering copper in copper sludge
Technical Field
The invention belongs to the technical field of precious metal recovery, and particularly relates to a method for recovering copper in copper sludge.
Background
During the copper material processing, a large amount of copper mud is easily generated, the main components of the copper mud are copper and oil stains, such as wire drawing oil, emulsified oil and the like, the copper mud belongs to dangerous waste products, but the copper mud contains 20-50 wt% of copper, so that considerable economic benefits are obtained, and the existing copper mud recovery method mainly comprises an oxidation leaching method and a roasting method.
The Chinese invention patent (application number CN201910836739.9) provides a method for recycling and harmlessly treating black copper mud, which adopts an acid oxidation leaching method to leach copper in the copper mud into Cu2+Then obtaining copper by an electrodeposition method. The method uses a large amount of hydrogen peroxide and sulfuric acid, generates a large amount of waste water, and has the problems of high recovery cost, serious environmental pollution, incomplete copper leaching, incomplete copper recovery and the like.
The roasting method needs the procedures of drying, grinding, roasting, acid leaching, electrodeposition and the like on the copper sludge, has high recovery cost, is easy to cause air pollution, and has high tail gas treatment cost.
Therefore, in view of the problems in the prior art, it is desirable to develop a method for recovering copper from copper sludge generated during copper wire processing at low cost and in an environmentally friendly manner.
Disclosure of Invention
In order to solve the problems in the prior art, the invention discloses a low-cost and environment-friendly method for recovering copper in copper sludge, and provides the following technical scheme:
a method for recovering copper in copper sludge comprises the following steps:
mixing copper sludge, alkali and an organic solvent for thermal reaction, and filtering, washing and drying a reaction product to obtain copper powder;
the organic solvent is alcohol, an alcohol aqueous solution or an alcohol-containing organic solution.
Furthermore, the alcohol content in the alcohol aqueous solution is 5 vol% to 30 vol%.
Further, the alcohol-containing organic solution is an alcohol-containing acetone solution, and the alcohol content in the alcohol-containing acetone solution is 5 vol% to 30 vol%.
Further, the alcohol is a liquid alcohol at normal temperature.
Further, the alcohol is methanol, ethanol or propanol.
Further, the alkali is one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
Further, the alkali is solid alkali or alkali solution, and the concentration of the alkali solution is 0.01-5 mol/L.
Further, the ratio of the mass of the copper mud to the volume of the alkali solution is 1: 5-50, wherein the mass unit is g, and the volume unit is ml.
Further, the reaction temperature of the thermal reaction is 100-400 ℃, and the reaction time is 1-48 h.
Further, the drying method is vacuum drying.
The invention has the beneficial effects that:
the reagents used in the recovery process are conventional chemical reagents, are cheap and easy to obtain, and have low recovery cost; the recovery method is simple and convenient to operate, and the waste liquid generated in the process can be recycled, so that the method is green and environment-friendly; the method can realize nearly complete recovery of copper in the copper sludge generated in the copper wire processing process, has good economic benefit, and is beneficial to realizing industrialized popularization.
Drawings
Fig. 1 is a flow chart of the recovery of copper from copper sludge according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the process of processing copper wires, a large amount of copper mud is generated, a large amount of copper is contained in the copper mud, and if the copper mud can be recycled, considerable economic benefits can be generated. From the aspects of reducing the recovery cost, reducing the environmental pollution and the like, the invention discloses a method for recovering copper from copper sludge, which comprises the following steps:
mixing copper sludge, alkali and an organic solvent for thermal reaction, and filtering, washing and drying a reaction product to obtain copper powder; the organic solvent is alcohol, alcohol water solution or alcohol-containing organic solution.
The method comprises the steps of mixing the copper sludge with alkali, reducing the oxidized copper oxide and cuprous oxide into copper under hydrothermal or organic thermal reaction, and simultaneously separating the copper from organic solvents used in the experimental process and oil stains and other components in the copper sludge, so that the nearly complete recovery of the copper in the copper sludge can be realized.
In one embodiment, the alcohol content in the alcohol aqueous solution is 5 vol% to 30 vol%, and may be 5 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%; wherein vol% refers to volume percent;
in another embodiment, the alcoholic organic solution is an alcoholic acetone solution, wherein the alcohol content in the alcoholic acetone solution is 5 vol% to 30 vol%, and may be 5 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%;
in one embodiment, the alcohol is a liquid alcohol at ambient temperature.
In one embodiment, the alcohol is a linear monohydric alcohol containing 1-5 carbons, preferably methanol, ethanol, or propanol;
in one embodiment, the base may be one or more of sodium hydroxide, potassium hydroxide and sodium carbonate;
in one embodiment, the thermal reaction is preferably a solvothermal reaction, the base added is a solid base, and the ratio of the mass of the copper sludge (in grams) to the amount of the solid base (in moles) is preferably 1:5.00 × 10-50.250, can be 1: 5.00X 10-5、1：0.050、1:0.100、1:0.150、1:0.200、 1:0.250, in the solvent thermal reaction, the added organic solvent is alcohol or an organic solution containing alcohol;
in another embodiment, the thermal reaction is preferably a hydrothermal reaction, the added base is an alkali solution, the concentration of the alkali solution is preferably 0.01mol/L to 5mol/L, and may be 0.01mol/L, 0.50mol/L, 1.5mol/L, 2.5mol/L, 4.0mol/L, 5mol/L, and the ratio of the mass of the copper sludge (in grams) to the volume of the alkali solution (in milliliters) is 1: 5-50, which can be 1:5, 1:10, 1:25, 1:40, 1: 50;
the methanol, ethanol, propanol, acetone and alkali reagents used in the recovery process of the invention are all conventional commercial chemical reagents.
In one embodiment, the reaction temperature of the hydrothermal reaction is preferably 100 ℃ to 400 ℃, such as 100 ℃, 150 ℃, 250 ℃, 300 ℃, 350 ℃ and 400 ℃, and the reaction time can be 1-48 h, such as 1h, 8h, 16h, 24h, 36h and 48 h;
in one embodiment, the above drying method is vacuum drying;
the steps of thermal reaction, filtration, washing, drying and the like related to the recovery method are all conventional chemical operations, the process is simple, and the waste liquid generated in the process can be recycled.
It should be noted that organic solvents such as methanol, ethanol, propanol, acetone, and the like, and alkaline reagents such as sodium hydroxide, potassium hydroxide, sodium carbonate, and the like, which are related to the present invention, are commercially available common reagents, and may be premium grade pure, analytical pure, chemical pure, and the like, and the purity level is not particularly limited.
Example 1
Stirring 30g of copper mud and 150ml of 5mol/L potassium hydroxide solution, then adding 65ml of methanol, stirring to obtain mixed slurry, transferring the mixed slurry obtained above into a hydrothermal kettle, carrying out hydrothermal reaction at 100 ℃ for 36 hours to obtain a precipitate and a solution, carrying out solid-liquid separation, washing the solid with water, carrying out vacuum drying at 50 ℃ for 24 hours to obtain copper powder, and returning the solution and a precipitate water cleaning solution to be used for preparing the mixed slurry.
Example 2
And (2) stirring 30g of copper sludge and 750ml of 2.5mol/L potassium hydroxide solution, then adding 250ml of propanol, stirring to obtain mixed slurry, transferring the mixed slurry obtained above into a hydrothermal kettle, carrying out hydrothermal reaction at 300 ℃ for 48 hours to obtain a precipitate and a solution, carrying out solid-liquid separation, washing the solid with water, carrying out vacuum drying at 50 ℃ for 24 hours to obtain copper powder, and returning the solution and a precipitate water cleaning solution to be used for preparing the mixed slurry.
Example 3
Stirring 30g of copper sludge and 1.5L of 0.01mol/L sodium hydroxide solution, then adding 80ml of ethanol, stirring to obtain mixed slurry, transferring the mixed slurry obtained above into a hydrothermal kettle, carrying out hydrothermal reaction at 400 ℃ for 16h to obtain a precipitate and a solution, carrying out solid-liquid separation, washing the solid with water, carrying out vacuum drying at 50 ℃ for 24h to obtain copper powder, and returning the solution and a precipitate water cleaning solution to be used for preparing the mixed slurry.
Example 4
Taking 100g of copper mud and 5 multiplied by 10-3Stirring the mol sodium hydroxide solid, adding 500ml ethanol, stirring to obtain mixed slurry, transferring the mixed slurry obtained above into a hydrothermal kettle, carrying out hydrothermal reaction for 8h at 150 ℃ to obtain a precipitate and a solution, carrying out solid-liquid separation, washing the solid with water, and carrying out vacuum drying for 24h at 50 ℃ to obtain copper powder, wherein the solution and the precipitate water cleaning solution are returned for preparation of the mixed slurry.
Example 5
Taking 100g of copper mud and 15mol of potassium hydroxide solid, stirring, adding 800ml of propanol, stirring to obtain mixed slurry, transferring the mixed slurry obtained above into a hydrothermal kettle, carrying out hydrothermal reaction at 250 ℃ for 24 hours to obtain precipitate and solution, carrying out solid-liquid separation, washing the solid with water, carrying out vacuum drying at 50 ℃ for 24 hours to obtain copper powder, and returning the solution and the precipitate water cleaning solution to the preparation of the mixed slurry.
Example 6
Taking 100g of copper sludge, 5mol of sodium carbonate and 20mol of sodium hydroxide solid, stirring, adding 300ml of methanol and 700ml of acetone, stirring to obtain mixed slurry, transferring the mixed slurry obtained above into a hydrothermal kettle, carrying out hydrothermal reaction at 350 ℃ for 1h to obtain a precipitate and a solution, carrying out solid-liquid separation, washing the solid with water, carrying out vacuum drying at 50 ℃ for 24h to obtain copper powder, and returning the solution and a precipitate water cleaning solution to be used for preparing the mixed slurry.
The copper recovery for the 6 examples above is shown in the following table:
Figure RE-GDA0002883944450000061
wherein: the mass of copper in the copper sludge before recovery was measured by an inductively coupled plasma mass spectrometer.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art may still modify the technical solutions described in the foregoing embodiments, or may equally substitute some or all of the technical features; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.

Claims (10)

1. A method for recovering copper in copper sludge is characterized by comprising the following steps:
mixing copper sludge, alkali and an organic solvent for thermal reaction, and filtering, washing and drying a reaction product to obtain copper powder;
the organic solvent is alcohol, an alcohol aqueous solution or an alcohol-containing organic solution.
2. The recycling method according to claim 1, characterized in that: in the alcohol aqueous solution, the content of the alcohol is 5 vol% -30 vol%.
3. The recycling method according to claim 1, characterized in that: the alcoholic organic solution is alcoholic acetone solution, and the content of alcohol in the alcoholic acetone solution is 5-30 vol%.
4. A recovery process according to any one of claims 1 to 3, characterized in that: the alcohol is liquid alcohol at normal temperature.
5. A recovery process according to any one of claims 1 to 3, characterized in that: the alcohol is methanol, ethanol or propanol.
6. The recycling method according to claim 1, characterized in that: the alkali is one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
7. The recycling method according to claim 6, characterized in that: the alkali is solid alkali or alkali solution, and the concentration of the alkali solution is 0.01-5 mol/L.
8. The recycling method according to claim 7, characterized in that: the ratio of the mass of the copper sludge to the volume of the organic solvent is 1: 5-50, wherein the mass unit is g, and the volume unit is ml.
9. The recycling method according to claim 1, characterized in that: the reaction temperature of the thermal reaction is 100-400 ℃, and the reaction time is 1-48 h.
10. The recycling method according to claim 1, characterized in that: the drying method is vacuum drying.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113403134A (en) * 2021-06-23 2021-09-17 江西省科学院能源研究所 Copper wire drawing oil waste liquid treatment method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033505A (en) * 2007-04-20 2007-09-12 中南大学 Method of leaching valuable metal from anode sludge with high content of antimony, bismuth and copper
KR20080018302A (en) * 2006-08-24 2008-02-28 서안켐텍 주식회사 Process for preparing cuprous chloride with high quality from cupric chloride containing waste
CN107745133A (en) * 2017-10-07 2018-03-02 江西省科学院能源研究所 A kind of inexpensive environment-friendly preparation method thereof of Nanometer Copper

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080018302A (en) * 2006-08-24 2008-02-28 서안켐텍 주식회사 Process for preparing cuprous chloride with high quality from cupric chloride containing waste
CN101033505A (en) * 2007-04-20 2007-09-12 中南大学 Method of leaching valuable metal from anode sludge with high content of antimony, bismuth and copper
CN107745133A (en) * 2017-10-07 2018-03-02 江西省科学院能源研究所 A kind of inexpensive environment-friendly preparation method thereof of Nanometer Copper

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113403134A (en) * 2021-06-23 2021-09-17 江西省科学院能源研究所 Copper wire drawing oil waste liquid treatment method
CN113403134B (en) * 2021-06-23 2022-05-20 江西省科学院能源研究所 Copper wire drawing oil waste liquid treatment method

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