CN115921887A - Preparation method and preparation device of micro-nano copper powder - Google Patents
Preparation method and preparation device of micro-nano copper powder Download PDFInfo
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- CN115921887A CN115921887A CN202211466071.1A CN202211466071A CN115921887A CN 115921887 A CN115921887 A CN 115921887A CN 202211466071 A CN202211466071 A CN 202211466071A CN 115921887 A CN115921887 A CN 115921887A
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- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 4
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
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Abstract
The invention discloses a preparation method and a preparation device of micro-nano copper powder. The preparation method of the micro-nano copper powder comprises the following steps: 1) Adding the reducing solution and the copper salt solution into a micro mixer to obtain a mixed solution; 2) Adding the mixed solution into a microreactor for reaction to obtain reaction solution; 3) And concentrating, cleaning and drying the reaction solution to obtain the micro-nano copper powder. The micro-nano copper powder is prepared by the preparation method. The preparation device of the micro-nano copper powder is used in the preparation method and comprises the following steps: the device comprises a first storage tank, a second storage tank, a first pump instrument, a second pump instrument, a micro mixer, a micro reactor and a product container. The preparation method of the micro-nano copper powder provided by the invention belongs to a wet chemical method and can realize continuous preparation.
Description
Technical Field
The invention relates to the field of metal powder preparation processes, in particular to a preparation method and a preparation device of micro-nano copper powder.
Background
The micro-nano copper powder has excellent physicochemical properties, particularly good conductive, lubricating, antibacterial and catalytic properties, can be used as a main material or an important component in typical application scenes of conductive slurry metal powder, solid lubricants and additives, high-molecular polymer antibacterial agents and the like, and has important market value. At present, the wet chemical reduction method can realize the precise preparation of the micro-nano copper powder, and the method also has the characteristics of less equipment investment, short process flow, low industrial production cost and the like.
However, the traditional wet chemical method belongs to batch reaction, and micro-nano copper powder cannot be continuously synthesized.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a preparation method and a preparation device of micro-nano copper powder, and aims to solve the problem that the micro-nano copper powder cannot be continuously synthesized by a wet chemical method.
In order to achieve the purpose, the invention provides a preparation method of micro-nano copper powder, which comprises the following steps: 1) Adding the reducing solution and the copper salt solution into a micro mixer to obtain a mixed solution; 2) Adding the mixed solution into a microreactor for reaction to obtain reaction liquid; 3) And concentrating, cleaning and drying the reaction solution to obtain the micro-nano copper powder.
Optionally, in the step 2), the reaction temperature is 25-120 ℃; and/or the drying temperature is 25-90 ℃.
Optionally, in step 2), the reaction time is greater than 5 minutes.
Alternatively, in step 1), the reducing solution comprises a reducing agent, a polymeric dispersant and a solvent; and/or the copper salt solution comprises a copper salt, a polymer dispersant and a solvent.
Optionally, in step 1), the reducing solution comprises a reducing agent, a polymer dispersant and a solvent, the reducing agent comprises at least one of ascorbic acid, sodium ascorbate, isoascorbic acid and sodium erythorbate, and the mass ratio of the reducing agent, the polymer dispersant and the solvent is (0.1-10):
(0.1～5):(50～200)。
optionally, in step 1), the copper salt solution includes a copper salt, a polymer dispersant and a solvent, the copper salt includes at least one of divalent copper salts, and the mass ratio of the copper salt, the polymer dispersant and the solvent is (0.01-8): 0.1-10): 50-200.
Optionally, the reducing solution comprises a reducing agent, a polymer dispersant and a solvent, wherein the polymer dispersant comprises at least one of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and polyether; and/or the reducing solution comprises a reducing agent, a polymer dispersing agent and a solvent, wherein the solvent comprises at least one of alcohol and water.
In order to achieve the above object, the present invention further provides a device for preparing micro-nano copper powder, which is used in the above preparation method, and comprises: the first liquid storage tank and the second liquid storage tank are respectively and correspondingly used for storing the reduction solution and the copper salt solution; the micro mixer is arranged at the downstream of the first liquid storage tank and the second liquid storage tank, is respectively communicated with the first liquid storage tank and the second liquid storage tank, and is used for mixing the entering reducing solution and the copper salt solution; the micro-reactor is arranged at the downstream of the micro-mixer, is communicated with the micro-mixer and is used for reacting the mixed liquid in the micro-mixer; and the product container is arranged at the downstream of the microreactor, is communicated with the microreactor and is used for collecting the product generated in the microreactor.
Optionally, the cross-sectional area of the microreactor is 0.005-1 cm 2 。
Optionally, a first pump instrument is arranged between the first liquid storage tank and the micro mixer, so that the reducing solution in the first liquid storage tank is pumped into the micro mixer; and/or a second pump instrument is arranged between the micro mixer and the second liquid storage tank so as to pump the copper salt solution in the second liquid storage tank into the micro mixer.
The invention has the beneficial effects that: the invention aims to provide a preparation method capable of continuously and stably preparing micro-nano copper powder, which can realize the preparation of the micro-nano copper powder with specific morphology or specific particle size distribution and the rapid amplification of gram-level to kilogram-level products, obtains more accurate reaction temperature control because the mixing process of continuous reaction is more uniform and rapid, can realize the particle size control of the nano copper in a certain range by regulating and controlling various parameters of a micro mixer and a micro reactor, and ensures that the whole preparation process has good reproducibility.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a diagram of a production apparatus of the present invention, and the meanings of the reference numerals are shown in Table 1.
FIG. 2 is a scanning electron microscope photograph of example 1.
FIG. 3 is an X-ray diffraction chart of example 1.
TABLE 1. Micro-nano copper powder preparing device
| Reference numerals | Name(s) | Reference numerals | Name(s) |
| 1 | The |
5 | Micro |
| 2 | First |
6 | Micro-reactor |
| 3 | Second pump type apparatus | 7 | |
| 4 | Second storage tank |
The implementation, functional features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the following embodiments are only used for explaining the present invention and are not used for limiting the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood in the art to which the claimed subject matter belongs.
At present, the wet chemical reduction method of the micro-nano copper powder can realize the accurate preparation of the micro-nano copper powder, and has the characteristics of less equipment investment, short process flow, low industrial production cost and the like.
However, the wet chemical method belongs to batch reaction, and micro-nano copper powder cannot be continuously synthesized.
In order to solve the problems, the invention provides a preparation method of micro-nano copper powder, which comprises the following steps:
1) Adding the reducing solution and the copper salt solution into a micro mixer to obtain a mixed solution;
specifically, the reducing agent and the copper ions form seed crystals in the mixing process inside the micro mixer, so that the micro-nano copper powder can grow in the subsequent steps. The micromixer has good tolerance to the reaction solvent, raw materials and the like, and comprises at least one of an active micromixer (such as a microfluid ultrasonic mixer, a magnetic stirring micromixer, a pressure disturbance mixer and the like) or a passive micromixer (such as a T-shaped micromixer, a shunt micromixer, an injection micromixer, a chaotic micromixer and the like).
2) Adding the mixed solution into a microreactor for reaction to obtain reaction liquid;
specifically, the mixed solution continuously flows in the microchannel, the reducing agent and copper ions finish the growth process in the microreactor, and the sectional area of the microreactor is 0.005-1 cm 2 The number of the flow channels is 1 to 50, the cross section of each flow channel is square or circular, and the length of each flow channel is 0.1 to 100 meters. The micro-reactor has good tolerance to the raw materials and solvents adopted by the reaction, and meets the requirements of substance mixing, heat exchange, flow control and the like required by the reaction. The material of the micro-reactor can be metal (such as stainless steel or titanium alloy), plastic (such as polytetrafluoroethylene), rubber (such as silicon rubber) and the like. It should be noted that there are many ways to obtain a microreactor, such as by direct winding of commercially available tubules, or by machining and assembling plates. In contrast, the former is structurally simple and low in cost, but may face the situation where the product blocks the pipeline. The latter can be processed into a microstructure in the flow channel, and the mass transfer is strengthened by repeatedly changing the flow state of the fluid, which is beneficial to the forward reaction, but the cost is relatively high.
3) Concentrating, cleaning and drying the reaction solution to obtain micro-nano copper powder;
the concentration is at least one of centrifugation, rotary evaporation, reduced pressure distillation and cross flow filtration; the solvent adopted for cleaning is at least one of methanol, ethanol and water; the drying is at least one of an electric heating air blast drying oven, a vacuum oven and freeze drying. Specifically, the solution containing the product at the microreactor outlet was collected in its entirety and transferred in portions to centrifuge tubes and centrifuged with a high-speed centrifuge at 12000 rpm for 5 minutes. After centrifugation was complete, the supernatant was discarded. Adding a proper amount of ethanol, dispersing the product by using ultrasonic waves, and centrifuging again. The above process is repeated 3-5 times. And putting the obtained product into a vacuum oven, vacuumizing to-0.1 MPa, setting the temperature to be 60 ℃, and drying.
Preferably, in the step 2), the reaction temperature of the microreactor is 25-120 ℃, and the drying temperature is 25-90 ℃. More preferably, the reaction temperature is controlled to be 60-90 ℃ by water bath heating, the reaction is favorably and rapidly carried out, and the drying temperature is 50-70 ℃.
Preferably, in step 2), the reaction time of the mixed solution in the microreactor is longer than 5 minutes, so that sufficient reaction can be realized, and the reducing agent can completely reduce the divalent copper ions in the copper salt solution into elemental copper.
Preferably, in step 1), the reducing solution includes a reducing agent, a polymer dispersant and a solvent; and/or the copper salt solution comprises a copper salt, a polymer dispersant and a solvent, wherein the copper salt comprises or does not comprise crystallization water. The polymer dispersant can improve the dispersibility of the system and prevent the nanometer copper from growing too fast and further causing the uneven particle size of the nanometer copper.
Preferably, in the step 1), the reducing agent comprises at least one of ascorbic acid, sodium ascorbate, isoascorbic acid and sodium erythorbate, and the mass ratio of the reducing agent, the polymer dispersant and the solvent is (0.1-10): (0.1-5): (50-200).
Preferably, in the step 1), the copper salt solution comprises a copper salt, a polymer dispersant and a solvent, wherein the copper salt comprises at least one of divalent copper salts, and the mass ratio of the copper salt, the polymer dispersant and the solvent is (0.01-8): (0.1-10): 50-200).
Preferably, the reducing solution comprises a reducing agent, a polymer dispersant and a solvent, wherein the polymer dispersant is a surfactant and has a molecular weight ranging from 2000 to 55000, and the polymer dispersant comprises at least one of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and polyether; and/or the reducing solution comprises a reducing agent, a polymer dispersant and a solvent, wherein the solvent comprises at least one of alcohol and water.
In order to solve the above problems, the present invention further provides a device for preparing micro-nano copper powder, which is used in the above preparation method, and comprises: in order to achieve the above object, the present invention further provides a device for preparing micro-nano copper powder, which is used in the above preparation method, and comprises: the first liquid storage tank and the second liquid storage tank are respectively and correspondingly used for storing a reducing solution and a copper salt solution; the micro mixer is arranged at the downstream of the first liquid storage tank and the second liquid storage tank, is respectively communicated with the first liquid storage tank and the second liquid storage tank, and is used for mixing the entering reducing solution and the copper salt solution; the micro-reactor is arranged at the downstream of the micro-mixer, is communicated with the micro-mixer and is used for reacting the mixed liquid in the micro-mixer; and the product container is arranged at the downstream of the microreactor, is communicated with the microreactor and is used for collecting the product generated in the microreactor.
Preferably, the cross-sectional area of the micro-reactor is 0.005-1 cm 2 . In this embodiment, the micro-reactor is formed by winding a silicone rubber tube, and a water bath device and a temperature control device are provided for the micro-reactor, so as to realize accurate control of the reaction temperature. For example, a silicone tube with an inner diameter of 1.6 mm and a length of 10 m is used and wound into a coil with a diameter of 10 cm to save volume. Obviously, the adjustment of the sectional area of the micro-reactor can be realized by changing the inner diameter of the silicone tube, or adopting a plurality of silicone tubes with the same sectional area to be connected in parallel and the combination of the silicone tubes and the silicone tubes, so as to obtain the target reaction flux.
Preferably, a first pump instrument is arranged between the first liquid storage tank and the micro mixer so as to pump the reducing solution in the first liquid storage tank into the micro mixer; and/or a second pump instrument is arranged between the micro mixer and the second liquid storage tank so as to pump the copper salt solution in the second liquid storage tank into the micro mixer. Wherein the pump type devices comprise peristaltic pumps, plunger pumps and the like. In the specific operation, a reducing solution is stored in the first storage tank 1, the reducing solution enters the micro mixer through the first pump type instrument 2, correspondingly, a copper salt solution is stored in the second storage tank 4, the copper salt solution enters the micro mixer 5 through the second pump type instrument 3, the uniformly mixed solution immediately enters the microreactor 6 for reaction, the reaction time is longer than 5 minutes, the reaction temperature is preferably 75 ℃, the reaction is fully completed to obtain a reaction solution, and the reaction solution flows into the product container 7, wherein the whole microchannel keeps going in an upper-in and a lower-out state to avoid blockage caused by the generated copper powder. It should be noted that the whole reaction process is carried out continuously, and the continuous synthesis of the monodisperse nano copper powder is realized by continuously supplementing reaction raw materials into the first storage tank 1 and the second storage tank 4.
The technical solution of the present invention will be further described in detail with reference to the following specific examples.
Example 1:
preparation of reducing solution: 5.0g of ascorbic acid and 1.2g of polyvinylpyrrolidone (average molecular weight 55000) are weighed into a beaker, 100mL of ethanol is added, the beaker is placed on a flat heating table and stirred at the rotation speed of 550 rpm until all raw materials are dissolved to obtain a solution reduction solution, and the solution reduction solution is transferred into the first storage tank 1.
Preparation of copper salt solution: 1.8g of copper acetate monohydrate and 1.2g of polyvinylpyrrolidone (average molecular weight of 55000) are weighed into a beaker, 100mL of ethanol is added, and the mixture is stirred and dissolved at room temperature and the rotation speed of 550 r/min until all the raw materials are dissolved to obtain a copper salt solution, and the copper salt solution is transferred into a second storage tank 4.
Preparing micro-nano copper powder: extracting the solution in the first storage tank 1 and the solution in the second storage tank 4 by adopting two small peristaltic pumps, fully mixing the solution in the first storage tank 1 and the solution in the second storage tank 4 by adopting a passive T-shaped micro mixer to obtain mixed solution, immediately introducing the mixed solution into a micro reactor, wherein the sectional area of the micro reactor is 0.008cm 2 The reaction temperature was 65 ℃. The total time of the reaction of the mixed solution in the microreactor is controlled to be 5 minutes by adjusting the pump speed. The solution containing the product at the microreactor outlet was collected in its entirety and transferred in portions to centrifuge tubes and centrifuged in a high-speed centrifuge at 12000 rpm for 5 minutes. After the centrifugation was completed, the supernatant was discarded. Adding a proper amount of ethanol, dispersing the product by using ultrasonic waves, and centrifuging again. Repeating the above process for 3-5 times. Putting the obtained product intoAnd (4) vacuumizing the vacuum oven to-0.1 MPa, and drying at the temperature of 60 ℃ to obtain the micro-nano copper powder.
Example 2:
preparation of reducing solution: weighing 4.0g of isoascorbic acid and 1.0g of polyvinylpyrrolidone (average molecular weight of 10000) into a beaker, adding 100mL of ethanol, placing the beaker on a flat heating table, heating while stirring at the rotation speed of 550 r/min until all raw materials are dissolved to obtain a solution reduction solution, and transferring the solution reduction solution into a first storage tank 1.
Preparation of copper salt solution: 1.2g of copper acetate and 1.0g of polyvinylpyrrolidone (average molecular weight 10000) are weighed into a beaker, 100mL of ethanol is added, stirring and dissolving are carried out at room temperature, the rotating speed is 550 r/min, until all raw materials are dissolved completely, copper salt solution is obtained, and the obtained solution is transferred into a second storage tank 4.
Preparing micro-nano copper powder: extracting the solution in the first storage tank 1 and the solution in the second storage tank 4 by using two small peristaltic pumps, fully mixing the solution in the first storage tank and the solution in the second storage tank by using a passive T-shaped micro mixer to obtain mixed solution, immediately introducing the mixed solution into a micro reactor, wherein the sectional area of the micro reactor is 0.02cm 2 The reaction temperature was 65 ℃. The total time of the reaction of the mixed solution in the microreactor is controlled to be 10 minutes by adjusting the pump speed. The solution containing the product at the microreactor outlet was collected in its entirety and transferred in portions to centrifuge tubes and centrifuged in a high-speed centrifuge at 12000 rpm for 5 minutes. After the centrifugation was completed, the supernatant was discarded. Adding a proper amount of ethanol, dispersing the product by using ultrasonic waves, and centrifuging again. Repeating the above process for 3-5 times. And putting the obtained product into a vacuum oven, vacuumizing to-0.1 MPa, and drying at the temperature of 60 ℃ to obtain the micro-nano copper powder.
Example 3:
preparation of reducing solution: 10g of sodium ascorbate and 2.0g of polyethylene glycol (average molecular weight 5000) are weighed into a beaker, 100mL of water are added, and the mixture is dissolved by stirring at room temperature at the rotation speed of 550 rpm until all the raw materials are dissolved completely to obtain a reducing solution, and the reducing solution is transferred into a first storage tank 1.
Preparation of copper salt solution: 3.2g of copper acetate and 2.0g of polyethylene glycol (average molecular weight 5000) are weighed into a beaker, 100mL of water is added, the mixture is stirred and dissolved at room temperature at the rotation speed of 550 r/min until all the raw materials are dissolved to obtain a copper salt solution, and the copper salt solution is transferred into a second storage tank 4.
Preparing micro-nano copper powder: extracting the solution in the first storage tank 1 and the solution in the second storage tank 4 by using two small peristaltic pumps, fully mixing the solution in the first storage tank and the solution in the second storage tank by using a passive T-shaped micro-mixer to obtain a mixed solution, immediately introducing the mixed solution into a micro-reactor, wherein the cross section of the micro-reactor is 0.031cm 2 The reaction temperature was 75 ℃. The total time of the mixed solution in the micro-reactor is controlled to be 60 minutes by adjusting the pump speed. The solution containing the product at the microreactor outlet was collected completely and transferred in portions to centrifuge tubes and centrifuged with a high speed centrifuge at 12000 rpm for 5 minutes. After the centrifugation was completed, the supernatant was discarded. Adding a proper amount of ethanol, dispersing the product by using ultrasonic waves, and centrifuging again. Repeating the above process for 3-5 times. And putting the obtained product into a vacuum oven, vacuumizing to-0.1 MPa, and drying at the temperature of 60 ℃ to obtain the micro-nano copper powder.
Example 4:
preparation of reducing solution: 9.0g of sodium ascorbate and 1.0g of polyvinylpyrrolidone (average molecular weight 20000) were weighed into a beaker, 100mL of ethanol was added, the beaker was placed on a flat plate heating table and heated while stirring at a rotation speed of 550 rpm until all the raw materials were dissolved to obtain a solution reducing solution, and the solution reducing solution was transferred to the first storage tank 1.
Preparation of copper salt solution: weighing 2.5g copper sulfate and 1.0g polyvinylpyrrolidone (average molecular weight 20000) into a beaker, adding 100mL ethanol, stirring at room temperature for dissolving at 550 r/min until all raw materials are dissolved to obtain a copper salt solution, and transferring to a second storage tank 4.
Preparing micro-nano copper powder: extracting the solution in the first storage tank 1 and the solution in the second storage tank 4 by using two small peristaltic pumps, fully mixing the solution in the first storage tank and the solution in the second storage tank by using a passive T-shaped micro-mixer to obtain a mixed solution, immediately introducing the mixed solution into a micro-reactor, wherein the cross section of the micro-reactor is 0.031cm 2 On the contraryThe temperature should be 80 ℃. The total time of the reaction of the mixed solution in the microreactor is controlled to be 30 minutes by adjusting the pump speed. The solution containing the product at the microreactor outlet was collected completely and transferred in portions to centrifuge tubes and centrifuged with a high speed centrifuge at 12000 rpm for 5 minutes. After the centrifugation was completed, the supernatant was discarded. Adding appropriate amount of ethanol, dispersing the product with ultrasound, and centrifuging again. Repeating the above process for 3-5 times. And putting the obtained product into a vacuum oven, vacuumizing to-0.1 MPa, and drying at the temperature of 60 ℃ to obtain the micro-nano copper powder.
Example 5:
preparation of reducing solution: 9.0g of sodium erythorbate and 1.0g of polyvinylpyrrolidone (average molecular weight 55000) are weighed into a beaker, 100mL of a mixed solution of water and methanol 1:1 is added, the beaker is placed on a flat heating table and heated while stirring at the rotation speed of 550 revolutions per minute until all raw materials are dissolved completely to obtain a solution reduction solution, and the solution reduction solution is transferred into the first storage tank 1.
Preparation of copper salt solution: weighing 2.5g copper sulfate and 1.0g polyvinylpyrrolidone (average molecular weight 55000) into a beaker, adding 100mL mixed solution of water and methanol 1:1, stirring at room temperature for dissolving at the rotation speed of 550 rpm until all raw materials are dissolved to obtain copper salt solution, and transferring into a second storage tank 4.
Preparing micro-nano copper powder: extracting the solution in the first storage tank 1 and the second storage tank 4 by two small peristaltic pumps, fully mixing the solution in the first storage tank and the solution in the second storage tank by a passive T-shaped micro-mixer to obtain a mixed solution, immediately introducing the mixed solution into a micro-reactor, wherein the cross section of the micro-reactor is 0.080cm 2 The reaction temperature was 85 ℃. The total time of the reaction of the mixed solution in the microreactor is controlled to be 30 minutes by adjusting the pump speed. The solution containing the product at the microreactor outlet was collected completely and transferred in portions to centrifuge tubes and centrifuged with a high speed centrifuge at 12000 rpm for 5 minutes. After the centrifugation was completed, the supernatant was discarded. Adding a proper amount of ethanol, dispersing the product by using ultrasonic waves, and centrifuging again. Repeating the above process for 3-5 times. Putting the obtained product into a vacuum oven, vacuumizing to-0.1 MPa, and setting the temperature to be 6And (5) drying at 0 ℃ to obtain the micro-nano copper powder.
Example 6:
preparation of reducing solution: 7.0g of ascorbic acid and 0.5g of polyethylene oxide (average molecular weight 100000) are weighed into a beaker, 100mL of water is added, the beaker is placed on a flat heating table and stirred at the rotation speed of 550 rpm until all raw materials are dissolved to obtain a reducing solution, and the reducing solution is transferred into the first storage tank 1.
Preparation of copper salt solution: 2.5g of copper sulfate and 0.5g of polyethylene oxide (average molecular weight 100000) are weighed into a beaker, 100mL of water is added, and the mixture is stirred and dissolved at room temperature at the rotation speed of 550 r/min until all raw materials are dissolved to obtain a copper salt solution, and the copper salt solution is transferred into a second storage tank 4.
Preparing micro-nano copper powder: extracting the solution in the first storage tank 1 and the solution in the second storage tank 4 by using two small peristaltic pumps, fully mixing the solution in the first storage tank and the solution in the second storage tank by using a passive T-shaped micro-mixer to obtain a mixed solution, immediately introducing the mixed solution into a micro-reactor, wherein the cross section of the micro-reactor is 0.32cm 2 The reaction temperature was 90 ℃. The total time of the reaction of the mixed solution in the microreactor is controlled to be 30 minutes by adjusting the pump speed. The solution containing the product at the microreactor outlet was collected completely and transferred in portions to centrifuge tubes and centrifuged with a high speed centrifuge at 12000 rpm for 5 minutes. After the centrifugation was completed, the supernatant was discarded. Adding appropriate amount of ethanol, dispersing the product with ultrasound, and centrifuging again. The above process is repeated 3-5 times. And putting the obtained product into a vacuum oven, vacuumizing to-0.1 MPa, and drying at the temperature of 75 ℃ to obtain the micro-nano copper powder.
Further, an appropriate amount of the product of example 1 was subjected to phase analysis by X-ray powder diffraction method, and the test results were compared with a standard material card. It was confirmed that the copper powder obtained in this example matched the characteristic peaks of the standard copper PDF card (No. 04-0836), and it was shown to be a nanocopper crystal with good crystallinity as seen from the results shown in fig. two of the drawings.
The invention realizes a preparation method capable of continuously and stably preparing the micro-nano copper powder, the preparation method can realize the preparation of the micro-nano copper powder with specific morphology or specific particle size distribution, and can also realize the rapid amplification of gram-level to kilogram-level products, and because the mixing process of continuous reaction is more uniform and rapid, more accurate reaction temperature control is obtained, the whole preparation process has good reproducibility, and the preparation method has wide application prospect.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the micro-nano copper powder is characterized by comprising the following steps:
1) Adding the reducing solution and the copper salt solution into a micro mixer to obtain a mixed solution;
2) Adding the mixed solution into a microreactor for reaction to obtain reaction liquid;
3) And concentrating, cleaning and drying the reaction solution to obtain the micro-nano copper powder.
2. The method for preparing micro-nano copper powder according to claim 1, wherein, in the step 2),
the reaction temperature is 25-120 ℃; and/or the presence of a gas in the atmosphere,
the drying temperature is 25-90 ℃.
3. The method for preparing micro-nano copper powder according to claim 1, wherein in the step 2), the reaction time is 5-60 minutes.
4. The method for preparing micro-nano copper powder according to claim 1, wherein in step 1), the reducing solution comprises a reducing agent, a polymer dispersant and a solvent; and/or the presence of a gas in the gas,
the copper salt solution comprises a copper salt, a polymeric dispersant and a solvent.
5. The method for preparing micro-nano copper powder according to claim 1, wherein in the step 1), the reducing solution comprises a reducing agent, a polymer dispersant and a solvent, the reducing agent comprises at least one of ascorbic acid, sodium ascorbate, isoascorbic acid and sodium isoascorbate, and the mass ratio of the reducing agent, the polymer dispersant and the solvent is (0.1-10): (0.1-5): 50-200).
6. The method for preparing micro-nano copper powder according to claim 1, wherein in the step 1), the copper salt solution comprises copper salt, polymer dispersant and solvent, the copper salt comprises at least one of divalent copper salts, and the mass ratio of the copper salt, the polymer dispersant and the solvent is (0.01-8): (0.1-10): 50-200).
7. The method for preparing micro-nano copper powder according to claim 1, wherein,
the reducing solution comprises a reducing agent, a polymer dispersant and a solvent, wherein the polymer dispersant comprises at least one of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and polyether; and/or the presence of a gas in the atmosphere,
the reducing solution comprises a reducing agent, a polymer dispersing agent and a solvent, wherein the solvent comprises at least one of alcohol and water.
8. A micro-nano copper powder preparation device, which is used in the preparation method according to any one of claims 1 to 7, and comprises:
the first liquid storage tank and the second liquid storage tank are respectively and correspondingly used for storing the reduction solution and the copper salt solution;
the micro mixer is arranged at the downstream of the first liquid storage tank and the second liquid storage tank, is respectively communicated with the first liquid storage tank and the second liquid storage tank, and is used for mixing the entering reducing solution and the copper salt solution;
the micro-reactor is arranged at the downstream of the micro-mixer, is communicated with the micro-mixer and is used for reacting the mixed liquid in the micro-mixer; and the number of the first and second groups,
and the product container is arranged at the downstream of the microreactor, is communicated with the microreactor and is used for collecting the product generated in the microreactor.
9. The apparatus for preparing micro-nano copper powder according to claim 8, wherein the cross-sectional area of the micro-reactor is 0.005-1 cm 2 。
10. The apparatus for preparing micro-nano copper powder according to claim 8,
a first pump instrument is arranged between the first liquid storage tank and the micro mixer so as to pump the reducing solution in the first liquid storage tank into the micro mixer; and/or the presence of a gas in the gas,
and a second pump instrument is arranged between the micro mixer and the second liquid storage tank so as to pump the copper salt solution in the second liquid storage tank into the micro mixer.
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