CN114406280B - Method for preparing nanometer copper powder by taking chalcopyrite as raw material - Google Patents
Method for preparing nanometer copper powder by taking chalcopyrite as raw material Download PDFInfo
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- CN114406280B CN114406280B CN202210069885.5A CN202210069885A CN114406280B CN 114406280 B CN114406280 B CN 114406280B CN 202210069885 A CN202210069885 A CN 202210069885A CN 114406280 B CN114406280 B CN 114406280B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052951 chalcopyrite Inorganic materials 0.000 title claims abstract description 35
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002994 raw material Substances 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 230000005496 eutectics Effects 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000011010 flushing procedure Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 5
- 235000019743 Choline chloride Nutrition 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 5
- 229960003178 choline chloride Drugs 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910001369 Brass Inorganic materials 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 6
- 239000010951 brass Substances 0.000 description 6
- 229910001779 copper mineral Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1658—Leaching with acyclic or carbocyclic agents of different types in admixture, e.g. with organic acids added to oximes
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing nanometer copper powder by taking chalcopyrite as a raw material, which comprises the following steps: s1, fully grinding chalcopyrite and an additive M, transferring to an electric furnace at 400-450 ℃ for roasting for 3-5 hours, cooling to room temperature along with the furnace, and taking out a roasting product to obtain a roasting product A; s2, adding the roasting product A into a eutectic solvent at 80-120 ℃ for stirring leaching to obtain a leaching solution B; adding a reducing agent into the leaching solution B, and stirring and dissolving to obtain a solution C; adding potassium hydroxide or sodium hydroxide into the solution C, stirring and dissolving to obtain a solution D; s3, transferring the solution D to a reaction vessel with the temperature of 95-120 ℃ for stirring reaction for 1-12 h, separating out a product after the reaction is finished, washing and drying to obtain the nanometer copper powder. The method directly produces the high-value nanometer copper powder by taking the middle-low-grade chalcopyrite as the raw material, has short flow, is easy to operate, fully utilizes the middle-low-grade chalcopyrite and improves the added value of copper products.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a method for preparing nano copper powder by taking chalcopyrite as a raw material.
Background
The crust has less copper content and the relative abundance is only 7×10 -5 Far lower than metals such as aluminum, iron and magnesium, and even lower than titanium. At present, more than 240 copper-bearing minerals exist in nature, about 30-40 copper minerals are common, and only more than 10 copper minerals with industrial exploitation value exist. Copper mine resources in China find out that reserves are large in base number, but economic recoverable reserves are relatively small, and only account for 3.5% of the world, so that huge amounts of copper concentrate are imported each year. On the one hand, the copper ores in China are characterized by more medium-low grade ores and less rich ores, the average copper-containing grade is 0.71%, and most of copper resources which are not mined and utilized nationally are medium-low grade copper ores; on the other hand, the added value of copper ore smelting products in China is low. Copper minerals can be classified into three types of pyrite, sulphide ores and oxide ores. Pyritum is rarely found in nature, mainly in sulphide ores and oxide ores. In particular, sulphide ores are most widely distributed and are the main raw material for copper smelting at present. The minimum grade of copper ore mined in industry at present is 0.4% -0.5%. The mined low-grade ore is beneficiated and enriched, so that the grade of copper is improved to 10% -30%. The main phases of the copper sulfide ore are usually chalcopyrite, pyrite, sphalerite, gangue and the like, and the chalcopyrite is the main copper mineral in the middle-low grade copper sulfide ore and is one of the copper minerals which are most difficult to leach out from the copper sulfide.
Currently, chalcopyrite fire copper smelting is still dominant, and about 70-80% of copper in the world is produced by the traditional fire smelting process of matte smelting-matte blowing-fire refining-electrorefining. However, as the high-grade copper ores are continuously consumed, the copper ores are lower in grade, the medium-low grade ores are more and more, the smelting cost is increased continuously, and meanwhile, the problems of energy consumption, environmental protection and the like are increasingly outstanding; the other main copper extraction method of chalcopyrite is a wet process, and the typical process is leaching-extraction-electrodeposition, and the leaching process mainly comprises roasting leaching, pressure leaching, chloridizing leaching, ammonia leaching, bacterial leaching and the like, and faces the problems of more process steps, long leaching period, high reagent consumption, large sewage quantity and the like. Meanwhile, the product finally obtained by the traditional pyrogenic or wet copper smelting process mainly comprises electrolytic copper powder/plates, and has the advantages of low added value, long process flow, high energy consumption, complex operation and high reagent consumption.
The nano copper powder has a plurality of properties different from those of common copper powder due to the characteristics of small size, large specific surface area, low resistivity, small size effect, surface interface effect, quantum scale effect, quantum tunneling effect and the like, and becomes an important base material which is widely applied to various fields, so that the preparation technology of the nano copper powder which is simpler and more convenient to research and cheaper in research has important significance for promoting the development of related industries.
If the high-value nanometer copper powder can be directly produced by taking the medium-low grade copper ore as the raw material, the situation that the high-quality copper ore resources in China are increasingly stressed can be relieved, and the added value of the product can be improved. In the prior art, no method for directly preparing nano copper powder by taking chalcopyrite as a raw material is reported.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the method for preparing the nano copper powder by taking the chalcopyrite as the raw material.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing nanometer copper powder by taking chalcopyrite as a raw material comprises the following steps:
s1, grinding chalcopyrite and an additive M to 200-500 meshes, sieving, transferring to an electric furnace at 400-450 ℃ for roasting for 3-5 hours, cooling to room temperature along with the furnace, taking out a roasting product to obtain a roasting product A, and sealing and preserving the roasting product A for later use;
s2, adding the roasting product A into a eutectic solvent at 80-120 ℃ for stirring leaching to obtain a leaching solution B; adding a reducing agent into the leaching solution B, and stirring and dissolving to obtain a solution C; adding potassium hydroxide or sodium hydroxide into the solution C, stirring and dissolving to obtain a solution D;
s3, transferring the solution D to a reaction vessel with the temperature of 95-120 ℃ for stirring reaction for 1-12 hours, separating out a product after the reaction is finished, flushing with absolute ethyl alcohol for 3 times, then flushing with diluted hydrochloric acid with the concentration of 1-5% vol for 2 times, finally flushing with pure water for 3-5 times, and drying the washed product in vacuum to obtain the nano copper powder with the purity of more than 99.9%.
In step S1, the additive M is ammonium sulfate.
Further, the eutectic solvent is an organic solvent obtained by mixing quaternary ammonium salt and polyol according to a molar ratio of 1 (2-4) at 50-80 ℃.
Preferably, the quaternary ammonium salt is choline chloride, tetramethyl ammonium chloride or benzyl triethyl ammonium chloride; the polyalcohol is ethylene glycol, propylene glycol, glycerol, butanediol, n-butanol or xylitol.
Preferably, the chalcopyrite is anhydrous powder, the granularity range is 1-80 mu m, and the grade is 0.1-70% of Cu.
In the step S2, the addition amount of A in the eutectic solvent is 1-20 g/L, the stirring speed is 300-600 r/min, and the leaching time is 6-12 h. The reducing agent is at least one of sodium hypophosphite, potassium hypophosphite, hydrazine hydrate and sodium ascorbate; the mol ratio of the addition of the reducing agent to the total copper content in the leaching solution B is (2-3): 1. the molar ratio of the addition amount of potassium hydroxide or sodium hydroxide to the total copper content in the leaching solution C is (2-3): 1.
preferably, the stirring speed in step S2 is 300 to 600r/min, and the stirring speed in step S3 is 300 to 500r/min.
Compared with the prior art, the invention has the following advantages:
1. the preparation method provided by the invention can directly prepare the nanometer copper powder by taking the middle-low grade chalcopyrite as the raw material, the leaching rate of the chalcopyrite copper is more than 90%, and a new way is opened up for comprehensively utilizing the middle-low grade chalcopyrite. And compared with a synthesis system of an aqueous solution, the unique physical and chemical properties of the eutectic solvent system enable the eutectic solvent system to become a good multifunctional integrated green solvent such as a dissolving agent, a reaction medium, a dispersing agent, a surfactant, a template agent, a morphology control agent and the like, so that nanoparticle synthesis is facilitated, and nanoparticle aggregation and nano powder oxidation in the preparation process can be effectively inhibited. In addition, dispersing agents, surfactants, antioxidants, protective agents and the like are not needed to be added in the reaction process, and no pH interference exists, so that the purity of the prepared nanometer copper powder is high.
2. The method provided by the invention has the advantages of short flow, simple operation, mild process conditions, low-cost and easily-obtained raw materials, suitability for industrial production and wide application prospect.
3. The nanometer copper powder prepared by the method is reddish brown, has uniform particle size, controllable product granularity, narrow granularity distribution range, high copper powder purity and high product added value, and can control the granularity in the range of 50-110 nm according to the needs.
Drawings
Fig. 1 is an XRD pattern of the nano copper powder prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the nano copper powder prepared in example 1 of the present invention.
Detailed Description
The embodiment of the invention provides a method for preparing nanometer copper powder by taking chalcopyrite as a raw material, which directly takes medium-low grade chalcopyrite as the raw material to prepare the nanometer copper powder, wherein the leaching rate of the chalcopyrite copper is more than 90 percent, and the prepared nanometer copper powder has high purity, uniform granularity and difficult agglomeration. The method comprises the following steps:
s1, fully grinding chalcopyrite and an additive M to 200-500 meshes, sieving, transferring to an electric furnace at 400-450 ℃ for roasting for 3-5 hours, cooling to room temperature along with the furnace, taking out a roasting product to obtain a roasting product A, and sealing and preserving the roasting product A for later use;
s2, adding the roasting product A into a eutectic solvent at 80-120 ℃ for stirring leaching to obtain a leaching solution B; adding a reducing agent into the leaching solution B, and stirring and dissolving to obtain a solution C; adding potassium hydroxide or sodium hydroxide into the solution C, stirring and dissolving to obtain a solution D;
s3, transferring the solution D to a reaction vessel with the temperature of 95-120 ℃ for stirring reaction for 1-12 hours, separating out a product after the reaction is finished, flushing with absolute ethyl alcohol for 3 times, then flushing with 1-5% vol diluted hydrochloric acid for 2 times, finally flushing with pure water for 3-5 times, and drying the washed product in vacuum to obtain the high-purity nanometer copper powder.
Example 1
A method for preparing nanometer copper powder by taking chalcopyrite as a raw material comprises the following steps:
s1, taking 2g of brass mineral powder with the granularity of 45 mu m and the copper content of 14%, fully grinding the brass mineral powder and 0.2g of additive ammonium sulfate to 300 meshes, sieving the mixture, then moving the mixture into a resistance furnace with the temperature of 430 ℃ for roasting for 4 hours, cooling the mixture to room temperature along with the furnace, taking out a roasted product to obtain a roasted product A, and sealing and storing the roasted product A for standby.
S2, mixing choline chloride and ethylene glycol at the temperature of 60 ℃ according to the molar ratio of 1:2 to obtain the eutectic solvent. 0.55g of A was added to 50mL of a eutectic solvent at 100℃and stirred to leach, thereby obtaining leachate B. 1.8g of sodium ascorbate was added to 50mL of the leachate B, and the mixture was dissolved with stirring to obtain a solution C. 0.8g of potassium hydroxide was added to the solution C and dissolved by stirring to obtain a solution D.
S3, transferring the solution D into a reaction vessel at 100 ℃ for liquid phase reduction, wherein the reaction time is 8 hours, and the stirring speed is 500r/min. Separating out the product after the reaction is finished, washing 3 times by absolute ethyl alcohol and 2 times by 5% vol diluted hydrochloric acid, washing 3 times by pure water, and vacuum drying the washed product to obtain the high-purity nanometer copper powder. The nano copper powder prepared in the example is subjected to X-ray diffraction, and the diffraction pattern is shown in figure 1. As can be seen by comparing with the standard pattern of Cu, the nano copper powder prepared by the invention has no other impurity diffraction peaks, which indicates that the nano copper powder prepared by the invention has high purity. The purity of the nanometer copper powder prepared in the embodiment is more than 99.9 percent through detection. The scanning electron microscope image of the nano copper powder prepared in the embodiment is shown in fig. 2, and the nano copper powder particles are uniform in size and are dispersed and not agglomerated. The particle size of the nanometer copper powder prepared by the implementation rate is 65nm.
Example 2
A method for preparing nanometer copper powder by taking chalcopyrite as a raw material comprises the following steps:
s1, taking 5g of brass mineral powder with the granularity of 35 mu m and the copper content of 5%, fully grinding the brass mineral powder and 2g of additive ammonium sulfate to 300 meshes, sieving the mixture, then moving the mixture into a resistance furnace with the temperature of 420 ℃ for roasting for 4 hours, cooling the mixture with the furnace to room temperature, taking out a roasted product, obtaining a roasted product A, and sealing and storing the roasted product A for standby.
S2, mixing choline chloride and ethylene glycol at the temperature of 80 ℃ according to the molar ratio of 1:2 to obtain the eutectic solvent. 1.0g of A was added to 100mL of a eutectic solvent at 105℃and stirred to leach to obtain leachate B. 3.2g of sodium hypophosphite was added to 50mL of the leachate B, and the mixture was dissolved with stirring to obtain solution C. 1.8g of sodium hydroxide was added to the solution C and dissolved by stirring to obtain a solution D.
S3, transferring the solution D into a reaction vessel at 105 ℃ for liquid phase reduction, wherein the reaction time is 6h, and the stirring speed is 400r/min. Separating out the product after the reaction is finished, flushing 3 times by absolute ethyl alcohol and 2 times by 3 percent vol diluted hydrochloric acid, flushing 3 times by pure water, and vacuum drying the washed product to obtain the high-purity nanometer copper powder. The detection shows that the purity of the nano copper powder prepared in the embodiment is more than 99.9%, and the granularity is 76nm.
Example 3
A method for preparing nanometer copper powder by taking chalcopyrite as a raw material comprises the following steps:
s1, taking 1g of brass mineral powder with the granularity of 60 mu m and the copper content of 10%, fully grinding the brass mineral powder and 0.2g of additive ammonium sulfate to 300 meshes, sieving the mixture, then moving the mixture into a resistance furnace with the temperature of 450 ℃ for roasting for 3 hours, cooling the mixture to room temperature along with the furnace, taking out a roasting product to obtain a roasting product A, and sealing and storing the roasting product A for standby.
S2, mixing choline chloride and ethylene glycol at the temperature of 50 ℃ according to the molar ratio of 1:2 to obtain the eutectic solvent. 0.6g of A was added to 60mL of a eutectic solvent at 110℃and stirred to leach to obtain leachate B. 1.7g of sodium ascorbate was added to 50mL of the leaching solution B, and the solution C was obtained by stirring and dissolving. 0.6g of sodium hydroxide was added to the solution C and dissolved by stirring to obtain a solution D.
S3, transferring the solution D into a reaction vessel at 110 ℃ for liquid phase reduction, wherein the reaction time is 2h, and the stirring speed is 400r/min. Separating out the product after the reaction is finished, washing 3 times by absolute ethyl alcohol and 2 times by 2 percent vol diluted hydrochloric acid, washing 3 times by pure water, and vacuum drying the washed product to obtain the high-purity nanometer copper powder. The detection shows that the purity of the nano copper powder prepared in the embodiment is more than 99.9%, and the granularity is-101 nm.
Therefore, the nano copper powder prepared by the invention has brown color, high copper powder purity, uniform particle size, controllable product granularity, controllable granularity in the range of 50-110 nm as required and narrow granularity distribution range.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The method for preparing the nanometer copper powder by taking chalcopyrite as a raw material is characterized by comprising the following steps of:
s1, grinding chalcopyrite and an additive M to 200-500 meshes, sieving, transferring to an electric furnace at 400-450 ℃ for roasting for 3-5 hours, cooling to room temperature along with the furnace, taking out a roasting product to obtain a roasting product A, and sealing and storing the roasting product A for later use;
s2, adding the roasting product A into a eutectic solvent at 80-120 ℃ for stirring leaching to obtain a leaching solution B; adding a reducing agent into the leaching solution B, and stirring and dissolving to obtain a solution C; adding potassium hydroxide or sodium hydroxide into the solution C, stirring and dissolving to obtain a solution D;
s3, transferring the solution D to a reaction container with the temperature of 95-120 ℃ for stirring reaction for 1-12 hours, separating out a product after the reaction is finished, flushing with absolute ethyl alcohol for 3 times, then flushing with 1-5% vol diluted hydrochloric acid for 2 times, finally flushing with pure water for 3-5 times, and vacuum drying the washed product to obtain nano copper powder with the purity of more than 99.9%;
wherein the additive M is ammonium sulfate;
the chalcopyrite is anhydrous powder, the granularity range is 1-80 mu m, and the grade is 0.1-70% of Cu.
2. The method for preparing nano copper powder by using chalcopyrite as a raw material according to claim 1, wherein in the step S1, the eutectic solvent is an organic solvent obtained by mixing quaternary ammonium salt and polyalcohol according to a molar ratio of 1 (2-4) at 50-80 ℃.
3. The method for preparing nano copper powder by taking chalcopyrite as a raw material according to claim 2, wherein the quaternary ammonium salt is choline chloride, tetramethyl ammonium chloride or benzyl triethyl ammonium chloride; the polyalcohol is ethylene glycol, propylene glycol, glycerol, butanediol, n-butanol or xylitol.
4. The method for preparing nano copper powder by taking chalcopyrite as a raw material according to claim 1, wherein in the step S2, the addition amount of A in the eutectic solvent is 1-50 g/L, the stirring speed is 300-600 r/min, and the leaching time is 6-12 h.
5. The method for preparing nano copper powder by using chalcopyrite as a raw material according to claim 1, wherein in the step S2, the reducing agent is at least one of sodium hypophosphite, potassium hypophosphite, hydrazine hydrate and sodium ascorbate; the molar ratio of the addition of the reducing agent to the total copper content in the leaching solution B is (2-3): 1.
6. the method for preparing nano copper powder by using chalcopyrite as a raw material according to claim 1, wherein in the step S2, the molar ratio of the addition amount of potassium hydroxide or sodium hydroxide to the total copper content in the leaching solution C is (2-3): 1.
7. the method for preparing nano copper powder by using chalcopyrite as a raw material according to claim 1, wherein the stirring speed in the step S2 is 300-600 r/min, and the stirring speed in the step S3 is 300-500 r/min.
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