CN108941605A - A kind of preparation method of superfine cupper powder - Google Patents
A kind of preparation method of superfine cupper powder Download PDFInfo
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- CN108941605A CN108941605A CN201810872053.0A CN201810872053A CN108941605A CN 108941605 A CN108941605 A CN 108941605A CN 201810872053 A CN201810872053 A CN 201810872053A CN 108941605 A CN108941605 A CN 108941605A
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- cupper powder
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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
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Abstract
The invention discloses a kind of preparation methods of superfine cupper powder, are related to technical field of metal material.The preparation method uses under the collective effect of sinusoidal state ultrasonic wave and variable-frequency ultrasonic, solution A is added in solution B under certain temperature, reacts aging after a certain period of time, then after filtering is separated by solid-liquid separation, after wet grinding, drying, screening, superfine cupper powder can be obtained.Preparation method of the present invention is simple, the superfine cupper powder of preparation not only even particle size distribution, but also purity is not less than 99.98%.
Description
Technical field
The present invention relates to technical field of metal material, and in particular to a kind of preparation method of superfine cupper powder.
Background technique
Superfine cupper powder has extensive use in civilian, industrial and national defence.Superfine cupper powder, which is that conductivity is good, intensity is high, to be received
The rice indispensable basic material of copper material.Due to its excellent electric property, it is widely used in conducting resinl, conductive coating and electrode
Material.The specific surface of superfine cupper powder is big, Active sites number is more, is excellent catalyst in metallurgy and petrochemical industry,
During the hydrogenation and dehydrogenation reaction and the acetylene polymerization reaction production conductive fiber that are widely used in high molecular polymer.In vapour
In tail gas decontamination process, superfine cupper powder can be used to partially replace noble metal platinum and ruthenium as catalyst, make toxic
Carbon monoxide be converted into carbon dioxide, so that nitric oxide is changed into nitrogen dioxide.Superfine cupper powder adds as lube oil additive
It is added in automobile engine lubricating oil, engine start electric current can be reduced and increases cylinder pressure, it can also be in cylinder liner-piston group
Upper formation protective film ensures that automobile can also drive safely for a long time, there is important Military Application when lubricating system breaks down
Value.Superfine cupper powder is also applied to the drug for the treatment of osteoporosis and fracture.Traditional electrolytic copper powder is since particle is larger, mist
Change method is not suitable for preparing superfine cupper powder since the copper powder of production is oxidizable.The production method of superfine cupper powder can divide at present
Are as follows: physical method and solution phase chemical reduction.Physical method includes ball-milling method, gas phase steam method, plasma method, gamma-ray irradiation-water
Thermal crystalline combination method and freeze-drying etc., since at high cost, equipment is expensive, due to complex process etc., is not suitable for extensive raw
Produce superfine cupper powder.Research hotspot concentrates on solution phase chemical reduction at present.The ultra-fine copper of existing solution phase chemical reduction preparation
Powder Particle Size is distributed more widely, and purity is not high, and about 99.7%.
Summary of the invention
In order to solve the problems in the existing technology, the present invention provides a kind of preparation method of superfine cupper powder, the systems
Preparation Method is simple, and reaction condition milder, since reaction temperature is low, therefore energy consumption is very low, and the superfine cupper powder not only granularity prepared
It is evenly distributed, and purity is not less than 99.98%.
In order to achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of preparation method of superfine cupper powder, comprising the following steps:
Under the collective effect of sinusoidal state ultrasonic wave and variable-frequency ultrasonic, copper salt solution A is added under certain temperature
In reducing agent solution B, aging after a certain period of time is reacted, then after filtering is separated by solid-liquid separation, after wet grinding, drying, screening,
Superfine cupper powder can be obtained.
Further, the mantoquita include copper chloride, stannous chloride, copper sulphate, cuprous sulfate, copper nitrate, cuprous nitrate,
The one or more of copper acetate and thio copper cyanider, wherein the molar concentration of solute is 0.5mol/L-4mol/L in solution A.
Further, the reducing agent includes ethyl alcohol, sodium triethylborohydride, potassium borohydride, stannous chloride, ortho phosphorous acid
One or more of sodium, formaldehyde, hydrazine hydrate, L-AA, lithium aluminium hydride reduction and polyethyleneimine wherein restore in solution B
The molar concentration of agent is 1mol/L-8mol/L.
Further, in the solution A on the basis of copper, the mol ratio of solution A and solution B is 1:0.75-1:3.
Further, in the solution A on the basis of copper, the mol ratio of solution A and solution B is 1:2, the solution A
The molar concentration of middle solute is 1mol/L-3.6mol/L；The molar concentration of reducing agent is 1.5mol/L-5.5mol/L in solution B.
Further, the frequency of the sinusoidal state ultrasonic wave is 18KHz-40KHz, power 320mW/cm2；Variable-frequency ultrasound
The frequency of wave is 25KHz-45KHz, power 300mW/cm2。
Further, the frequency of the sinusoidal state ultrasonic wave is 25KHz-35KHz, power 320mW/cm2；Variable-frequency ultrasound
The frequency of wave is 28KHz-40KHz, power 300mW/cm2。
Further, reaction temperature is 30-100 DEG C, reaction time 10-300mins, ageing time 10-
300mins。
Further, reaction temperature is 50 DEG C, reaction time 30mins, ageing time 60mins.
Further, the superfine cupper powder purity of the preparation method preparation is not less than 99.98%, average grain diameter 1400-
1800 mesh.
The utility model has the advantages that compared with prior art, the present invention in the preparation method of superfine cupper powder by 18-40KHz,
320mW/cm2Sinusoidal state ultrasonic wave and 25-45KHz, 300mW/cm2Mantoquita is promoted to be reduced under the collective effect of variable-frequency ultrasonic
The reaction process of copper, accelerates reaction process, increases mass transfer, improves product yield height, and product purity is high；Institute of the present invention
The preparation method for stating superfine cupper powder is simple, and reaction condition milder, low energy consumption, and the superfine cupper powder purity of preparation is not less than
99.98%, average volume particle diameter is 1400-1800 mesh, even particle size distribution and purity is high.
Detailed description of the invention
Fig. 1 is the SEM scanning electron microscope (SEM) photograph of superfine cupper powder in the prior art；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of superfine cupper powder manufactured in the present embodiment.
Specific embodiment
A kind of preparation method of superfine cupper powder disclosed by the invention, comprising the following steps:
A kind of preparation method of superfine cupper powder, comprising the following steps:
Under the collective effect of sinusoidal state ultrasonic wave and variable-frequency ultrasonic, copper salt solution A is added under certain temperature
In reducing agent solution B, aging after a certain period of time is reacted, then after filtering is separated by solid-liquid separation, after wet grinding, drying, screening,
Superfine cupper powder can be obtained.
Further, the mantoquita include copper chloride, stannous chloride, copper sulphate, cuprous sulfate, copper nitrate, cuprous nitrate,
The one or more of copper acetate and thio copper cyanider, wherein the molar concentration of solute is 0.5mol/L-4mol/L in solution A.
Further, the reducing agent includes ethyl alcohol, sodium triethylborohydride, potassium borohydride, stannous chloride, ortho phosphorous acid
One or more of sodium, formaldehyde, hydrazine hydrate, L-AA, lithium aluminium hydride reduction and polyethyleneimine wherein restore in solution B
The molar concentration of agent is 1mol/L-8mol/L.
Further, in the solution A on the basis of copper, the mol ratio of solution A and solution B is 1:0.75-1:3.
Further, in the solution A on the basis of copper, the mol ratio of solution A and solution B is 1:2, the solution A
The molar concentration of middle solute is 1mol/L-3.6mol/L；The molar concentration of reducing agent is 1.5mol/L-5.5mol/L in solution B.
Further, the frequency of the sinusoidal state ultrasonic wave is 18KHz-40KHz, power 320mW/cm2；Variable-frequency ultrasound
The frequency of wave is 25KHz-45KHz, power 300mW/cm2。
Further, the frequency of the sinusoidal state ultrasonic wave is 25KHz-35KHz, power 320mW/cm2；Variable-frequency ultrasound
The frequency of wave is 28KHz-40KHz, power 300mW/cm2。
Further, reaction temperature is 30-100 DEG C, reaction time 10-300mins, ageing time 10-
300mins。
Further, reaction temperature is 50 DEG C, reaction time 30mins, ageing time 60mins.
Further, the superfine cupper powder purity of the preparation method preparation is not less than 99.98%, average grain diameter 1400-
1800 mesh.It should be noted that it is 1400-1600 mesh that screen sizes are selected in screening described in the present embodiment, to reach preferable grain
Diameter distribution.
The present invention is further elaborated with reference to the accompanying drawings and examples.
Embodiment 1
33.61g copper chloride is taken, is configured to the copper chloride solution that molar concentration is 1mol/L with deionized water；Take 16.12g
Sodium hypophosphite is made into sodium hypophosphite/sodium hydroxide solution of 1.5mol/L in 125mL 6mol/L sodium hydroxide solution；
The copper chloride solution of preparation is added in sodium hypophosphite/sodium hydroxide solution of above-mentioned preparation, microwave reactor is placed in.Anti-
80 DEG C of temperature are answered, sinusoidal state ultrasonic frequency 25KHz, power 320mW/cm2With variable-frequency ultrasound wave frequency rate 28KHz, power
300mW/cm2Aging 30mins allows particle maturation after common lower reaction 40mins.It filters, grinds after reaction, done at 100 DEG C
It is dry, 1400 meshes point.It is tested through inductively coupled plasma spectrum generator, the purity of superfine cupper powder is 99.985%.
Embodiment 2
140.67g copper nitrate is taken, the copper nitrate solution of 3mol/L is configured to deionized water；Take 281.59g commercially available 40%
Hydrazine hydrate solution is made into hydrazine hydrate/potassium hydroxide solution of 4.2mol/L in 250mL 6mol/L potassium hydroxide solution；It will
The copper nitrate solution of preparation is added in hydrazine hydrate/potassium hydroxide solution of above-mentioned preparation, is placed in microwave reactor.In reaction temperature
50 DEG C, sinusoidal state ultrasonic frequency 28KHz, power 320mW/cm2With variable-frequency ultrasound wave frequency rate 30KHz, power 300mW/cm2Altogether
Aging 60mins allows particle maturation after same-action reaction 30mins.It filters, grinds after reaction, dry at 100 DEG C, 1500 mesh
Screening.It is tested through inductively coupled plasma spectrum generator, the purity of superfine cupper powder is 99.989%.
Embodiment 3
59.85g copper sulphate is taken, the copper-bath of 1.5mol/L is configured to deionized water；Take 59.27g commercially available 38%
Formalin is made into formaldehyde/sodium hydroxide solution of 4mol/L in 125mL 6mol/L sodium hydroxide solution；By preparation
Copper-bath is added in formaldehyde/sodium hydroxide solution of above-mentioned preparation, is placed in microwave reactor.At 60 DEG C of reaction temperature, just
String state ultrasonic frequency 35KHz, power 320mW/cm2With variable-frequency ultrasound wave frequency rate 32KHz, power 300mW/cm2Under collective effect
Reaction 50mins followed by aging 90mins allows particle maturation.It filters, grinds after reaction, dry at 100 DEG C, 1600 meshes
Point.It is tested through inductively coupled plasma spectrum generator, the purity of superfine cupper powder is 99.982%.
Embodiment 4
45.41g copper acetate is taken, copper acetate/tetrahydrofuran solution of 1mol/L is configured to tetrahydrofuran；Take 13.49g boron
Hydrofining is configured to 2mol/L potassium borohydride/tetrahydrofuran solution as solvent with tetrahydrofuran；The acetic acid copper solution of preparation is added
Enter in potassium borohydride/tetrahydrofuran solution of above-mentioned preparation, is placed in microwave reactor.At 90 DEG C of reaction temperature, sinusoidal state ultrasound
Wave frequency rate 30KHz, power 320mW/cm2With variable-frequency ultrasound wave frequency rate 40KHz, power 300mW/cm2It is reacted under collective effect
200mins followed by aging 100mins allows particle maturation.It filters, grinds after reaction, dry at 100 DEG C, 1500 meshes
Point.It is tested through inductively coupled plasma spectrum generator, the purity of superfine cupper powder is 99.987%.
It should be noted that the electron microscope of the superfine cupper powder of the preparation of preparation method described in the present embodiment is more existing with reference to Fig. 2
The more edge of dispersion and chondritic of superfine cupper powder (as shown in Figure 1) in technology is relatively sharp, and particle diameter distribution is relatively narrow, and
And purity is high, preparation method is simple, and reaction condition milder, low energy consumption, and described Fig. 1 and Fig. 2 are all made of identical Electronic Speculum multiplying power
It is shot.
It is the preferred embodiment of the present invention above, it is noted that for those skilled in the art,
Various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as this hair
Bright protection scope.
Claims (10)
1. a kind of preparation method of superfine cupper powder, it is characterised in that: the following steps are included:
Under the collective effect of sinusoidal state ultrasonic wave and variable-frequency ultrasonic, copper salt solution A is added to reduction under certain temperature
In agent solution B, aging after a certain period of time is reacted, then after filtering is separated by solid-liquid separation, after wet grinding, drying, screening
Obtain superfine cupper powder.
2. a kind of preparation method of superfine cupper powder according to claim 1, it is characterised in that: the mantoquita includes chlorination
The one or more of copper, stannous chloride, copper sulphate, cuprous sulfate, copper nitrate, cuprous nitrate, copper acetate and thio copper cyanider,
The molar concentration of solute is 0.5mol/L-4mol/L in middle solution A.
3. a kind of preparation method of superfine cupper powder according to claim 1, it is characterised in that: the reducing agent includes second
Alcohol, sodium triethylborohydride, potassium borohydride, stannous chloride, sodium hypophosphite, formaldehyde, hydrazine hydrate, L-AA, aluminum hydride
One or more of lithium and polyethyleneimine, wherein the molar concentration of reducing agent is 1mol/L-8mol/L in solution B.
4. a kind of preparation method of superfine cupper powder according to claim 1, it is characterised in that: be with copper in the solution A
The mol ratio of benchmark, solution A and solution B is 1:0.75-1:3.
5. a kind of preparation method of superfine cupper powder according to claim 1 or 4, it is characterised in that: with copper in the solution A
On the basis of, the mol ratio of solution A and solution B is 1:2, and the molar concentration of solute is 1mol/L-3.6mol/ in the solution A
L；The molar concentration of reducing agent is 1.5mol/L-5.5mol/L in solution B.
6. a kind of preparation method of superfine cupper powder according to claim 1, it is characterised in that: the sine state ultrasonic wave
Frequency is 18KHz-40KHz, power 320mW/cm2；The frequency of variable-frequency ultrasonic is 25KHz-45KHz, power 300mW/
cm2。
7. a kind of preparation method of superfine cupper powder according to claim 6, it is characterised in that: the sine state ultrasonic wave
Frequency is 25KHz-35KHz, power 320mW/cm2；The frequency of variable-frequency ultrasonic is 28KHz-40KHz, power 300mW/
cm2。
8. a kind of preparation method of superfine cupper powder according to claim 1 or 6, it is characterised in that: reaction temperature 30-
100 DEG C, reaction time 10-300mins, ageing time 10-300mins.
9. a kind of preparation method of superfine cupper powder according to claim 8, it is characterised in that: reaction temperature is 50 DEG C, instead
It is 30mins, ageing time 60mins between seasonable.
10. a kind of preparation method of superfine cupper powder according to claim 10, it is characterised in that: the preparation method preparation
Superfine cupper powder purity be not less than 99.98%, average grain diameter 1400-1800 mesh.
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| CN110640162A (en) * | 2019-10-08 | 2020-01-03 | 三峡大学 | Method for preparing, pretreating and dispersing superfine copper powder |
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