CN103143720B - A kind of preparation method of superfine copper powder - Google Patents
A kind of preparation method of superfine copper powder Download PDFInfo
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- CN103143720B CN103143720B CN201310077160.1A CN201310077160A CN103143720B CN 103143720 B CN103143720 B CN 103143720B CN 201310077160 A CN201310077160 A CN 201310077160A CN 103143720 B CN103143720 B CN 103143720B
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Abstract
A kind of preparation method of superfine copper powder, relate to the preparation method of chemical industry and functional material submicron metal, comprise following process: join in reactor using Cu oxide, mantoquita as raw material, after in reactor, air drains, solvent medium and reducing agent is added in reactor, reactor heating makes reaction temperature reach 60 ~ 280 DEG C, reaction pressure reaches 0.1 ~ 20.0Mpa, and after keeping 0.05 ~ 6.0h reaction to terminate in this condition, reduce reactor pressure to 0 ~ 0.5Mpa, isolate solvent; Stop heating, when temperature is down to room temperature in question response device, isolate pressed powder, namely obtain superfine copper powder through washing, vacuum drying.Preparation method of the present invention has the features such as cheaper starting materials is easy to get, easy to operate, cost is low, and be applicable to large-scale industrial production, products obtained therefrom uniform particles, purity are high.
Description
Technical field
The present invention relates to the preparation method of chemical industry and functional material submicron metal, particularly a kind of preparation method of superfine copper powder.
Background technology
Super-fine material is 20th century new function basic materials that grow up of the mid-80, and the superfine metal material branch that to be one of them important.At present, metal ultra-fine material does not have a strict definition, from several nanometer to the powder of several thousand nanometers, all can be referred to as superfine metal powder material.Because superfine metal material also exists small-size effect, surface-interface effect, quantum size effect and quantum tunneling effect etc., make it have the much character different from identical component conventional material, have many specific performances and great potential using value in fields such as mechanics, electricity, magnetics and chemistry.
Superfine cupper powder has the good conduction of metallic copper, heat conduction, corrosion-resistant, any surface finish and the advantage such as nonmagnetic, be widely used as high performance-price ratio basic functionality powder body material, as for the modern high-tech field such as lube oil additive, the electrically conductive ink in electron trade, the medicine in medical and health industry, mechanical break-in reparation in the catalyst of chemical industry, machinery industry, great exploitation potential for its.
The preparation method of superfine cupper powder is a lot, having of bibliographical information: cryochemistry reducing process (J.Phys.Chem.C, 2007, 111, 14689-14693.), hydro-thermal solvent-thermal method (Cryst.GrowthDes.2006, 6, 2603-2606.), laser radiation method (J.Phys.Chem.B.2002, 106, 9717-9722.), reverse micelle method (Langmuir.2004, 20, 11772-11777.), precursor thermal decomposition (MaterialsLetters.2009, 63, 441-443.), metal evaporation (Chem.Mater.2002, 14, 1183-1186.), vaccum gas phase sedimentation method (Adv.Mater.2003, 15, 303-305.), microemulsion method (Adv.Mater.1999, 11, 1358-1362.).In addition, JoannaP.Cason etc. adopt Supercritical Ethanol reduction Cu (AOT)
2prepare ultra-fine elemental copper (J.Phys.Chem.B.2000,104,1217-1221.), SophieDesmoulins-Krawiec etc. adopt supercritical CO
2-Reduction of methanol Cu (hfac)
2prepare superfine cupper powder (J.Mater.Chem., 2004,14,228-232), Li Yadong etc. adopt solvent-thermal process copper nanoparticle (Chem.Comm, 2011,47,3604-3606.).The patent (CN101264526A, CN101143387A, CN101879606A, CN1803352A, CN1686648A, CN1483540A etc.) of the ultra-fine elemental copper powder of preparation of open report focuses mostly in liquid phase reduction at present.Although these methods achieve the chemical preparation of Nanometer Copper, also existing problems more or less, the copper grain diameter as gained in liquid phase reduction is larger, domain size distribution is wider, and product is easily reunited, and solvent, the reducing agent of use have severe toxicity more, easy contaminated environment, or high cost; Metal evaporation equipment is complicated, cost is high; In solvent-thermal process, requirement for experiment condition is harsh; In the supercritical methanol technology that Cason etc. use, organic copper salt reaction precursor used preparation is difficult, cost is high, there is toxicity.
In sum, design operation is simple, the superfine copper powder synthetic method of suitability for industrialized production can should have good prospects for commercial application.Up to the present, there is not yet and adopt supercritical methanol technology with the oxide of copper for the report of ultra-fine elemental copper powder prepared by raw material.The relatively above-mentioned Cu (AOT) of Cu oxide or mantoquita
2, Cu (hfac)
2deng raw material, cheap, and be easy to obtain.Therefore, the need of production of superfine copper powder a kind ofly overcomes above drawback, simplifies production technology, reduces raw material production cost and can strengthen the new method of adaptability to raw materials.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of superfine copper powder.The present invention prepares elemental copper powder in super (closely) critical fluids system, and the reaction time is short, reaction temperature is low; Strong to the applicability of raw material; Preparation process product is easily separated, and gained elemental copper powder is purer.
The object of the invention is to be achieved through the following technical solutions:
A kind of preparation method of superfine copper powder, described method comprises following process: join in reactor using Cu oxide, mantoquita as raw material, after in reactor, air drains, solvent medium and reducing agent is added in reactor, reactor heating makes reaction temperature reach 60 ~ 280 DEG C, and reaction pressure reaches 0.1 ~ 20.0Mpa, and after keeping 0.05 ~ 6.0h reaction to terminate in this condition, reduce reactor pressure to 0 ~ 0.5Mpa, isolate solvent; Stop heating, when temperature is down to room temperature in question response device, isolate pressed powder, namely obtain superfine copper powder through washing, vacuum drying.
The preparation method of described a kind of superfine copper powder, described Cu oxide and mantoquita comprise one or more mixtures in cupric oxide, cuprous oxide, copper sulphate, basic copper carbonate, copper nitrate.
The preparation method of described a kind of superfine copper powder, described solvent medium comprises methyl alcohol, ethanol, one or more mixtures of low-carbon alcohols.
The preparation method of described a kind of superfine copper powder, described reducing agent comprises one or more mixtures in ammonia, liquefied ammonia, ammonium carbonate, carbonic hydroammonium, urea.
The preparation method of described a kind of superfine copper powder, during described reduction reactor pressure to 0 ~ 0.5Mpa, the time used is 0.1 ~ 2.5h.
The preparation method of described a kind of superfine copper powder, described reaction temperature is 60 ~ 280 DEG C, reaction pressure be 0.1 ~ 20.0Mpa the reaction time is 0.1 ~ 6.0h.
Advantage of the present invention and effect are:
1. the present invention is raw materials used is easy to get, and cost is low; Temperature used low (60 ~ 280 DEG C), decreases energy consumption.
2. the present invention is under reaction temperature and pressure condition, solvent for use medium and reducing agent reach near critical (Near-Critical) state or overcritical (Super-Critical) state, whole reduction reaction is carried out near critical or supercritical medium, thus greatly increase reaction rate, decrease the reaction time.
3. the present invention prepares elemental copper powder in super (closely) critical fluids system, and the reaction time is short, reaction temperature is low; Operation is simple for whole preparation process; The applicability of preparation method to raw material is strong; Raw materials used and reagent is cheap, be easy to get; Preparation process product is easily separated, and gained elemental copper powder is purer.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of obtained elemental copper powder;
Fig. 2 is ESEM (SEM) photo of obtained elemental copper powder.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Operating procedure of the present invention is:
First the oxide of copper or mantoquita are joined in reactor, then in reactor, solvent medium and reducing agent is added, reactor is heated, makes that temperature of reactor reaches 60 ~ 280 DEG C, pressure reaches 0.1 ~ 20.0Mpa, and continue 0.05 ~ 6.0h under this condition, then under the state of maintenance 60 ~ 280 DEG C, in 0.1 ~ 2.5h, releasing reactor pressure to 0 ~ 5.0Mpa, then, reactor is cooled to room temperature, ultra-fine elemental copper powder can be obtained through washing, vacuum drying.
Wherein, preparing needed raw material is one or more mixtures in cupric oxide, cuprous oxide, copper sulphate, basic copper carbonate, copper nitrate; Solvent medium adopts one or more mixtures of the low-carbon alcohols such as methyl alcohol, ethanol; The required reducing agent of reaction is one or more mixtures of ammonia, liquefied ammonia, ammonium carbonate, carbonic hydroammonium, urea; Reaction temperature controls at 60 ~ 280 DEG C; Reaction pressure controls at 0.1 ~ 20.0Mpa; Reaction time controls at 0.05 ~ 6.0h; In releasing reactor, the time controling of pressure is at 0.1 ~ 2.5h.
Embodiment 1:
Take 20.0g copper nitrate and be placed in the reactor that volume is 1L, after adding 144.5g ethanol, after reactor is airtight, be decompressed to 0.04MPa, then by 110.8g ammonia injecting reactor, reactor is heated to 270 DEG C, pressure is 18.8MPa, then reacts 2.4h under this condition, reaction terminate after by Pressure Drop to 0.5MPa, after logical condensed water cooling reactor, isolate solid product, after absolute ethanol washing three times, vacuum drying at 80 DEG C, obtains elemental copper powder 5.8g.
Embodiment 2:
24.0g cupric oxide is placed in the reactor that volume is 1L, add 93g methyl alcohol, reactor is sealed, is evacuated to 0.02MPa with water pump, then in reactor, passes into ammonia 147.8g, reactor pressure is 0.61MPa, reactor is heated to 260 DEG C, pressure is 17.4MPa simultaneously, and after reacting 2.5h under this condition, in 0.5h, reactor pressure is down to 0.3MPa, reactor is naturally cooled to room temperature.Isolate the solid product in reactor, after absolute ethanol washing three times, vacuum drying 1.0h at 80 DEG C, obtains the elemental copper powder of 18.6g.
Embodiment 3:
30.0g cuprous oxide is placed in voltage-resistant reactor, add 60.3g methyl alcohol and 60.0g ethanol, 0.03MPa is decompressed to after reactor is airtight, then 150.0g ammonia is injected, reactor is heated to 165 DEG C, reactor pressure remains 16.8MPa, and after reacting 3.0h under this condition, in 1.6h, reactor pressure is down to 0.2MPa, reactor is naturally cooled to room temperature.Isolate the solid product in reactor, after absolute ethanol washing three times, at 80 DEG C, vacuum drying obtains the elemental copper powder of 24.9g.
Embodiment 4:
Take 43.0g copper nitrate and 30.0g cuprous oxide, be placed in 1L voltage-resistant reactor, after adding 150.0g ethanol and 106.8g carbonic hydroammonium, after reactor is airtight, be decompressed to 0.04MPa, reactor is made to be 250 DEG C in temperature, pressure is keep 1.9h under the condition of 16.8MPa, reaction terminate after by Pressure Drop to 0.2MPa, after cooling reactor, isolate product, with absolute ethanol washing, vacuum drying at 80 DEG C, obtains elemental copper powder 35.5g.
Embodiment 5:
50.0g cupric oxide is placed in voltage-resistant reactor, add 150.0g ethanol and 50.0g ammonium carbonate, after being decompressed to 0.03MPa after reactor is airtight, inject 107.5g ammonia, reactor is heated to 280 DEG C, reactor pressure remains 19.6MPa, and after reacting 1.6h under this condition, in 0.5h, reactor pressure is down to 0.25MPa, reactor is naturally cooled to room temperature.Isolate the solid product in reactor, after absolute ethanol washing three times, vacuum drying obtains elemental copper powder 37.7g.
Embodiment 6:
10.0g cupric oxide and 10.0g copper sulphate are placed in reactor, add 116.3g methyl alcohol and 120.8g ammonium carbonate, reactor is evacuated to 0.03MPa, reactor is heated to 260 DEG C, reactor pressure remains 17.0MPa, and after reacting 1.8h under this condition, in 1.0h, reactor pressure is down to 0.3MPa, reactor is naturally cooled to room temperature.Isolate the solid product in reactor, after absolute ethanol washing three times, vacuum drying 1.0h at 80 DEG C, obtains the elemental copper powder of 11.8g.
Claims (3)
1. a ultra-fine elemental copper raw powder's production technology, it is characterized in that, described method comprises following process: 24.0g cupric oxide is placed in the reactor that volume is 1L, add 93g methyl alcohol, reactor is sealed, 0.02MPa is evacuated to water pump, then in reactor, ammonia 147.8g is passed into, reactor pressure is 0.61MPa, reactor is heated to 260 DEG C, pressure is 17.4MPa simultaneously, and after reacting 2.5h under this condition, in 0.5h, reactor pressure is down to 0.3MPa, reactor is naturally cooled to room temperature;
Isolate the solid product in reactor, after absolute ethanol washing three times, vacuum drying 1.0h at 80 DEG C, obtains the elemental copper powder of 18.6g.
2. a ultra-fine elemental copper raw powder's production technology, it is characterized in that, described method comprises following process: 30.0g cuprous oxide is placed in voltage-resistant reactor, adds 60.3g methyl alcohol and 60.0g ethanol, is decompressed to 0.03MPa after reactor is airtight, then 150.0g ammonia is injected, reactor is heated to 165 DEG C, reactor pressure remains 16.8MPa, and after reacting 3.0h under this condition, in 1.6h, reactor pressure is down to 0.2MPa, reactor is naturally cooled to room temperature;
Isolate the solid product in reactor, after absolute ethanol washing three times, at 80 DEG C, vacuum drying obtains the elemental copper powder of 24.9g.
3. a ultra-fine elemental copper raw powder's production technology, it is characterized in that, described method comprises following process: 50.0g cupric oxide is placed in voltage-resistant reactor, adds 150.0g ethanol and 50.0g ammonium carbonate, after being decompressed to 0.03MPa after reactor is airtight, inject 107.5g ammonia, reactor is heated to 280 DEG C, reactor pressure remains 19.6MPa, and after reacting 1.6h under this condition, in 0.5h, reactor pressure is down to 0.25MPa, reactor is naturally cooled to room temperature;
Isolate the solid product in reactor, after absolute ethanol washing three times, vacuum drying obtains elemental copper powder 37.7g.
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| CN103722180B (en) * | 2014-01-06 | 2016-01-20 | 沈阳化工大学 | A kind of preparation method of superfine simple-substance nickel powder |
| CN103934468B (en) * | 2014-04-02 | 2016-03-30 | 西安交通大学 | The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles |
| CN104556198A (en) * | 2015-01-08 | 2015-04-29 | 沈阳化工大学 | Continuous production method and application of ultrafine cuprous oxide |
| CN112091230A (en) * | 2019-06-18 | 2020-12-18 | 上海沪正实业有限公司 | Nano copper particles and preparation method thereof |
| CN115536057B (en) * | 2022-10-11 | 2023-11-24 | 广西华锡集团股份有限公司 | Method for preparing nano metal oxide by using near supercritical fluid and production equipment |
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| CN101195170A (en) * | 2006-12-06 | 2008-06-11 | 比亚迪股份有限公司 | Method for preparing superfine copper powder |
| EP2206681A2 (en) * | 2009-01-09 | 2010-07-14 | Korea Institute of Science and Technology | Method for preparing metal compound nanoparticles |
| CN102491290A (en) * | 2011-12-12 | 2012-06-13 | 沈阳化工大学 | Method for preparing copper nitride powder |
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| CN101195170A (en) * | 2006-12-06 | 2008-06-11 | 比亚迪股份有限公司 | Method for preparing superfine copper powder |
| EP2206681A2 (en) * | 2009-01-09 | 2010-07-14 | Korea Institute of Science and Technology | Method for preparing metal compound nanoparticles |
| CN102491290A (en) * | 2011-12-12 | 2012-06-13 | 沈阳化工大学 | Method for preparing copper nitride powder |
Non-Patent Citations (3)
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| Metallic copper nanoparticle synthesis in AOT reverse micelles in compressed propane and supercritical ethane solutions;Cason, Joanna P et al.;《The Journal of Physical Chemistry B》;20000125;第104卷(第6期);第1217-1221页 * |
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