CN110883339B - Method for preparing superfine metal powder - Google Patents
Method for preparing superfine metal powder Download PDFInfo
- Publication number
- CN110883339B CN110883339B CN201811051195.7A CN201811051195A CN110883339B CN 110883339 B CN110883339 B CN 110883339B CN 201811051195 A CN201811051195 A CN 201811051195A CN 110883339 B CN110883339 B CN 110883339B
- Authority
- CN
- China
- Prior art keywords
- micro
- reaction
- metal powder
- solution
- supergravity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- Y02P10/25—Process efficiency
Abstract
The invention discloses a method for preparing superfine metal powder, wherein the metal powder is a nano metal simple substance of Fe, Co, Ni or Cu. The method comprises the following steps: (1) dissolving metal salt, a complexing agent and a surfactant to obtain a metal salt precursor solution A; (2) dissolving a reducing agent and a precipitating agent to obtain a solution B; (3) adding the solution A and the solution B into a supergravity micro-reaction device for reaction; (4) subjecting the solid portion of the product to sonication; (5) and washing and vacuum drying the solid product after ultrasonic treatment to obtain the superfine metal powder. The invention is completed in a supergravity micro-reaction device, which comprises a micro-reaction disc and a filler layer, wherein the micro-reaction disc and the filler layer coaxially and reversely rotate, so that the mass transfer effect is greatly enhanced while the raw materials are rapidly and uniformly mixed, the nucleation size of a product is reduced, the dispersity and uniformity of a metal nano material are improved, the particle size is controllable, and the energy consumption is reduced.
Description
Technical Field
The invention relates to a preparation method of a nano material, in particular to a preparation method of superfine high-dispersion metal powder.
Background
The superfine metal powder has special physical and chemical properties due to the surface effect, volume effect and quantum effect, so that the superfine metal powder has wide application prospect in the fields of catalysis, electromagnetism, metallurgy, aerospace, aviation and the like. At present, the preparation of the superfine metal powder mainly comprises methods such as physical vapor deposition, chemical vapor deposition, liquid phase reduction and the like. The vapor deposition method has the problems of high cost, difficult industrialization and the like, and the traditional liquid phase reduction method has the problems of difficult control of the size and the shape of particles.
The micro-reaction technology is a technology for preparing nano materials by utilizing a miniaturized chemical reaction system with unit reaction interface dimension of micron order, and the technical device has the characteristics of large specific surface area, high transfer rate, short contact time, few byproducts and the like. However, in the process of preparing the nano material, the microchannel reactor is easy to block the channel and difficult to clean. The supergravity field technology is a technology for strengthening mass transfer and micro mixing process by using supergravity environment which is much larger than the gravity acceleration of the earth. The technology enables reactant molecules to generate flowing contact in a supergravity environment, and huge shearing force enables liquid to be broken into nanoscale films, wires and drops, so that huge and rapidly updated new interfaces are generated, the mass transfer process is strengthened, and the size of the obtained metal particles is uniform and controllable.
Disclosure of Invention
The invention provides a method for preparing superfine metal powder, which is carried out in a hypergravity micro-reaction device, can greatly shorten the contact time between raw materials, and strengthen the atomization effect and the mass transfer process.
The object of the invention is achieved in the following technical solutions, however, the invention can be embodied in different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description presented herein is for the purpose of describing particular embodiments and is not intended to be limiting.
In the present invention, the ultrafine metal powder is prepared by the following steps:
(1) dissolving metal salt, complexing agent and surfactant in inorganic and/or organic solvent, and stirring uniformly to obtain metal salt precursor solution A.
(2) Dissolving a reducing agent and a precipitator in an inorganic and/or organic solvent to obtain a solution B.
(3) And introducing protective gas into the supergravity micro-reaction device, and adding the solution A and the solution B into the supergravity micro-reaction device through a metering pump for reaction.
(4) And (4) performing solid-liquid separation on the product in the step (3), washing the solid part to be neutral, adding the solid part into deionized water, adding a dispersing agent, and performing ultrasonic treatment for 30 min.
(5) And (3) carrying out solid-liquid separation on the product after ultrasonic treatment, washing the product for three times by using absolute ethyl alcohol, and finally carrying out vacuum drying at 50-80 ℃ to obtain the superfine metal powder.
Preferably, the inorganic solvent is deionized water, and the organic solvent is one or more of methanol, ethanol, ethylene glycol, isopropanol, glycerol, acetone, n-butane, n-pentane, n-hexane, tetrahydrofuran, dimethyl sulfoxide, cyclohexane, cyclohexanone, benzene, toluene, xylene, dimethyl ether, diethyl ether, ethyl acetate and carbon tetrachloride.
In the invention, the metal powder is a nano simple substance of Fe, Co, Ni or Cu, the metal salt in the step (1) is one or more of chlorides, sulfates, nitrates, phosphates, phosphites, acetates and oxalates of the simple substance, the complexing agent is any one of ammonia water, ethylenediamine, EDTA and sodium tartrate, and the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium oleate, stearic acid, nonylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, lauric glyceride and sodium lauryl sulfate. Wherein the concentration of the metal salt is 0.01-1.5 mol/L, the molar ratio of the complexing agent to the metal salt is (0.01-1): 1, and the concentration of the surfactant is 1-150 g/L.
In the step (2), the precipitant is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate, and the reducing agent is one or more of sodium borohydride, potassium borohydride or hydrazine hydrate, wherein the concentration of the precipitant is 0.8-3.6 mol/L, and the concentration of the reducing agent is 0.2-6 mol/L.
In the step (3), the volume flow ratio of the solution A to the solution B is 1 (0.5-6), the reaction temperature is 30-50 ℃, and the introduced protective gas is one or more of hydrogen, nitrogen, helium and argon.
In the step (4), the dispersing agent is any one of methyl mercaptan, ethanethiol, ethanedithiol, thiophenol and dimercaptopropanol, and the adding amount of the dispersing agent is 0.01-0.5% of the mass of the metal powder.
In the invention, the solid-liquid separation is realized by vacuum filtration or centrifugation and other methods.
The supergravity micro-reaction device used in the invention comprises a shell assembly, a supergravity micro-reaction system, a sample feeding shaft and a power transmission system. The shell assembly comprises a shell, a top plate, a base, a partition plate and a fixing piece for connection and fixation. The supergravity micro-reaction system comprises a rotary drum, a packing layer and a micro-reaction disc, wherein the packing layer and the rotary drum form a sealed cavity, the micro-reaction disc is arranged in the middle of the sealed cavity, and the horizontal distance between the outer edge of the micro-reaction disc and the packing layer is 10-100 mm. The sample injection shaft is fixed with the top plate through a fixing piece, and a sample injection pipe is arranged inside the sample injection shaft.
The power transmission system comprises a transmission shaft, a motor, a bearing and a linkage device, wherein the first transmission shaft is a hollow device, and the first transmission shaft penetrates through a second bearing on the second partition plate and a first bearing on the first partition plate and then is connected with the rotary drum through a No. 1 fixing base; the second transmission shaft passes through a third bearing on the third partition plate, a fourth bearing on the second partition plate and the hollow part of the first transmission shaft in sequence and then is connected with the micro-reaction disk through a No. 2 fixing base. The linkage device comprises an inner gear ring arranged on the inner wall of the first transmission shaft, a 1# gear and a 2# gear set arranged on the second transmission shaft, the relative position of the 2# gear set is fixed through a fixing frame and a fixing shaft, coaxial reverse rotation between the rotary drum and the packing layer and rotation between the rotary drum and the micro-reaction disc are finally realized, and the rotation speed of the micro-reaction disc is 200-4000 rpm. The second rotating shaft is connected with the rotary drum in a sealing mode through a sealing ring, and the sample feeding shaft, the rotary drum, the closed cavity, the micro-reaction disc, the first transmission shaft and the second transmission shaft have a common axial lead.
Preferably, the motor is connected with the third transmission shaft, and drives the second transmission shaft to rotate through a bevel gear linkage device consisting of a 1# bevel gear sleeved on the second rotating shaft and a 2# bevel gear sleeved on the third transmission shaft. The rotation speed ratio between the second rotating shaft and the third rotating shaft can be adjusted by changing the gear ratio between the 1# bevel gear and the 2# bevel gear; the rotation speed ratio between the micro-reaction disk and the rotary drum can be achieved by changing the gear ratio among the 1# gear, the 2# gear and the inner gear ring, wherein the rotation speed ratio between the micro-reaction disk and the packing layer is (1-5): 1.
In the supergravity micro-reaction device adopted in the invention, a sample feeding system and a supergravity micro-reaction system have two different designs.
In one of the devices, the micro-reaction disk consists of an upper disk and a lower disk, the upper disk and the lower disk are fixed through bolts, a mixing cavity and a micro-reaction channel are formed between the upper disk and the lower disk, and the mixing cavity is positioned at the center of the micro-reaction disk and is uniformly divided by a plurality of baffles. The size range of the micro-reaction channels is 0.01-2 mm and are distributed in a linear radial or arc radial mode, the micro-reaction channels are communicated with the material mixing cavity, the size of the micro-reaction channels is reduced along with the extension of the micro-reaction channels to the outer edge of the micro-reaction disk, and the micro-reaction channels are in an expanding structure close to the outer edge of the micro-reaction disk. A round hole is arranged at the axis of the upper disc, and a table top higher than the outer surface of the upper disc is arranged at the outer edge of the round hole; the axis position of the inner side of the lower disc is provided with a columnar groove. An annular feeding cavity is further arranged inside the sample feeding shaft, and the bottom of the annular feeding cavity is connected with the sample feeding pipe. The sample feeding shaft is contracted in size after passing through the round hole of the upper disc to form a conical structure, and a solid columnar bulge is formed at the tail end of the sample feeding shaft and is wedged into a columnar groove of the lower disc. An annular feeding cavity is further formed in the sample feeding shaft, and the sample feeding pipe is communicated with the bottom of the annular feeding cavity and extends to the conical surface of the sample feeding shaft. The sample feeding shaft and the rotary drum, the sample feeding shaft and the circular hole, and the columnar bulge and the columnar groove are connected through sealing rings.
In another device, the sample feeding shaft is connected with the atomizing disc through a No. 3 fixing base, wherein the radius size of the atomizing disc is not more than the radius size of the micro-reaction disc and not less than the radius size of the sample feeding shaft. The sample inlet pipe is connected with the sample inlet and extends to the tail end of the sample inlet shaft, and a Venturi-shaped sample inlet pore passage corresponding to the sample inlet pipe is arranged at the center of the atomizing disc; the distance between the micro-reaction disc and the atomizing disc is 0.01-0.1 mm, and grooves with the size range of 0.01-1 mm are distributed on the top surface of the micro-reaction disc and the bottom surface of the atomizing disc to serve as micro-reaction channels. Wherein the micro reaction channels on the atomizing disk are distributed in a honeycomb shape, the micro reaction channels on the micro reaction disk are distributed in a honeycomb shape, or the micro reaction channels are distributed in a honeycomb shape on the projection part of the atomizing disk and distributed in a linear radial shape or an arc radial shape outside the projection part.
In the method for preparing the superfine metal powder, the controllable particle size of the metal particles can be realized by regulating the rotating speed of the micro-reaction disk and the filler layer and the size of the micro-reaction channel, and the obtained metal powder particles have uniform particle size distribution. Preferably, the rotating speed of the micro-reaction disk is 900-2400 rpm, the rotating speed ratio between the micro-reaction disk and the packing layer is (1-2.5): 1, the size range of the micro-reaction channel is 0.1-1 mm, and the average particle size of the prepared metal particles is 5-25 nm.
Compared with the prior art, the method adopts the supergravity micro-reaction device to prepare the superfine metal powder, and the method can quickly and uniformly mix reaction raw materials by utilizing the micro-reaction channel, and continuously break the raw materials into nano-scale films, wires and drops under the action of supergravity and shearing force to generate a huge and quickly updated new interface, thereby strengthening the mass transfer effect, reducing the nucleation size of a product and improving the dispersion degree and uniformity of the nano-material. The method has the advantages of simple process, wide raw material selection, high production efficiency and low energy consumption, can prepare different superfine metal powder according to different metal salt precursors, and has uniform and controllable particle size of the obtained metal powder and good industrial production value.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic structural diagram of a hypergravity micro-reaction device according to the present invention;
FIG. 2 is another schematic structural diagram of the supergravity micro-reaction device according to the present invention;
FIG. 3 is a schematic view of the linkage arrangement;
FIG. 4 is a top view of the linkage;
FIG. 5 is a schematic illustration of the construction of the bevel gear linkage;
FIG. 6 is a schematic view of the structure of the micro-reaction disk of FIG. 1;
FIG. 7 is an expanded view of FIG. 6;
FIG. 8 is a top view of a portion of the tray of the micro-reaction tray of FIG. 1;
FIG. 9 is a schematic view of the lower plate of the micro-reaction plate of FIG. 1, in which micro-reaction channels are arranged in a straight radial pattern;
FIG. 10 is a schematic view of the lower plate portion of the micro-reaction plate of FIG. 1, wherein the micro-reaction channels are radially arranged in an arc shape;
FIG. 11 is a schematic view of portion A of FIG. 1;
FIG. 12 is a cross-sectional view taken along A '-A' of FIG. 11;
FIG. 13 is a cross-sectional view taken along B '-B' of FIG. 11;
FIG. 14 is a cross-sectional view taken along line C '-C' of FIG. 11;
FIG. 15 is a cross-sectional view taken along line D '-D' of FIG. 11;
FIG. 16 is a schematic view of the sample introduction shaft, atomizing disk and micro-reaction disk in FIG. 2;
FIG. 17 is a distribution diagram of the micro-reaction grooves on the bottom surface of the atomizing disk of FIG. 2;
FIG. 18 is a distribution diagram of micro-reaction grooves on the top surface of the micro-reaction tray of FIG. 2, which are arranged in a honeycomb manner;
FIG. 19 is a diagram showing the distribution of the micro-reaction grooves on the top surface of the micro-reaction disk of FIG. 2, wherein the projection portions of the atomizing disk are in a honeycomb shape and the outer portions of the projection portions are in a linear radial shape;
FIG. 20 is a distribution diagram of micro-reaction grooves on the top surface of the micro-reaction disk in FIG. 2, wherein the projection part of the atomizing disk is in a honeycomb shape and the outer part of the projection part is in an arc-shaped radial distribution.
Description of the reference numerals
11 casing, 12 top plate, 13 base, 14 first clapboard, 15 second clapboard, 16 third clapboard, 17 fixing piece and 18 sample outlet;
21 rotary drum, 22 filler layer, 23 micro reaction disc, 23-1 upper disc, 23-2 lower disc, 23-3 mixing cavity, 23-4 baffle, 23-5 micro reaction channel, 23-6 round hole, 23-7 table surface, 23-8 column groove, 23-9 bolt and 23-10 micro reaction groove;
31 sample injection shaft, 31-1 columnar bulge, 31-2 atomizing disc, 32 sample injection port, 33 annular feed cavity, 34 sample injection pipe and 35 sample injection pore channel;
41 a first transmission shaft, 42 a second transmission shaft, 43 a third transmission shaft, 441 # fixed base, 452 # fixed base, 463 # fixed base and 47 motors;
51 a first bearing, 52 a second bearing, 53 a third bearing, 54 a fourth bearing, 55 a sealing ring;
61 linkage, 61-1 annular gear, 61-21 # gear, 61-32 # gear, 61-4 fixing frame, 61-5 fixing shaft, 62 bevel gear linkage, 62-11 # bevel gear and 62-22 # bevel gear.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below with reference to specific embodiments of the present invention and accompanying drawings. The embodiments described herein are only for illustrating and explaining the present invention and are not to be construed as limiting the present invention, and the scope of the present invention is defined by the disclosure of the claims.
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
dissolving nickel nitrate in deionized water, adding sodium tartrate, uniformly stirring, and adding hexadecyl trimethyl ammonium bromide to prepare a solution A, wherein the concentration of the nickel nitrate is 0.2mol/L, the concentration of the sodium tartrate is 0.04mol/L, and the concentration of the surfactant is 75 g/L; and dissolving sodium hydroxide and sodium borohydride in deionized water to obtain a solution B, wherein the concentration of the sodium hydroxide is 2mol/L, and the concentration of the sodium borohydride is 1.2 mol/L.
Introducing nitrogen into the supergravity micro-reaction device, and then introducing the solution A and the solution B into the supergravity micro-reaction device in a ratio of 1:1 through a metering pump, wherein the reaction temperature is 40 ℃, the rotating speed of a micro-reaction disk is 1800-2200 rpm, the rotating speed ratio between the micro-reaction disk and a filler layer is 1.5:1, and the size range of a micro-reaction channel is 0.5 mm. And (3) centrifuging after the reaction is finished, washing the solid part to be neutral, dispersing the solid part into 500mL of deionized water, adding 2, 3-dimercaptopropanol with the mass being 0.04% of the theoretical mass of the metallic nickel, performing ultrasonic treatment for 30min, centrifuging, washing the obtained black solid part with absolute ethyl alcohol for three times, and performing vacuum drying at 80 ℃ for 2h to obtain the superfine nickel powder, wherein the average particle size of nickel particles is 7 nm.
Example 2:
deionized water and cyclohexane were mixed in a ratio of 2:1 to prepare a mixed solvent. Dissolving ferric sulfate in a mixed solvent, adding stearic acid, uniformly stirring without obvious layering, and adding ammonia water to obtain a solution A, wherein the concentration of the ferric sulfate is 0.8mol/L, the concentration of the ammonia water is 0.01mol/L, and the concentration of a surfactant is 90 g/L; and dissolving sodium hydroxide and hydrazine hydrate in deionized water to obtain a solution B, wherein the concentration of the sodium hydroxide is 1mol/L, and the concentration of the hydrazine hydrate is 0.8 mol/L.
Introducing hydrogen into the supergravity micro-reaction device, and then introducing the solution A and the solution B into the supergravity micro-reaction device in a ratio of 1:1.8 through a metering pump, wherein the reaction temperature is 40 ℃, the rotating speed of a micro-reaction disk is 1800-2200 rpm, the rotating speed ratio between the micro-reaction disk and a filler layer is 1.5:1, and the size range of a micro-reaction channel is 1 mm. And after the reaction is finished, centrifuging, washing the solid part to be neutral, dispersing the solid part into 500mL of deionized water, adding ethanedithiol with the mass of 0.06% of the theoretical mass of the metallic iron, carrying out ultrasonic treatment for 30min, centrifuging, washing the obtained black solid part with absolute ethyl alcohol for three times, and carrying out vacuum drying at 80 ℃ for 2h to obtain the superfine iron powder, wherein the average particle size of the superfine iron powder is 15 nm.
Example 3:
dissolving cobalt chloride in a mixed solvent prepared from deionized water and n-pentane, then adding lauric glyceride, uniformly stirring without obvious layering phenomenon, and then adding EDTA to obtain a solution A, wherein the ratio of the deionized water to the n-pentane in the mixed solvent is 2:1, the concentration of the cobalt chloride is 1mol/L, the concentration of the EDTA is 0.5mol/L, and the concentration of the surfactant is 120 g/L; dissolving sodium carbonate and hydrazine hydrate in a mixed solvent of deionized water and tetrahydrofuran, wherein the ratio of the deionized water to the tetrahydrofuran is 5:1, the concentration of the sodium carbonate is 2mol/L, and the concentration of the hydrazine hydrate is 1 mol/L.
Introducing argon into the supergravity micro-reaction device, and then introducing the solution A and the solution B into the supergravity micro-reaction device in a ratio of 1:1 through a metering pump, wherein the reaction temperature is 40 ℃, the rotating speed of a micro-reaction disk is 1200-1400 rpm, the rotating speed ratio between the micro-reaction disk and a packing layer is 2.5:1, and the size range of a micro-reaction channel is 1 mm. And after the reaction is finished, centrifuging, washing the solid part to be neutral, dispersing the solid part into 500mL of deionized water, adding methyl mercaptan with the mass being 0.06% of the theoretical mass of the metal cobalt, carrying out ultrasonic treatment for 30min, centrifuging, washing the obtained black solid part with absolute ethyl alcohol for three times, and carrying out vacuum drying at 80 ℃ for 2h to obtain the superfine cobalt powder with the average particle size of 22 nm.
Example 4
Dissolving copper sulfate in deionized water, adding sodium dodecyl benzene sulfonate, and adding EDTA to obtain a solution A, wherein the concentration of the copper sulfate is 0.5mol/L, the concentration of the EDTA is 0.1mol/L, and the concentration of the surfactant is 60 g/L; dissolving sodium carbonate and hydrazine hydrate in deionized water, wherein the concentration of the sodium carbonate is 1mol/L, and the concentration of the hydrazine hydrate is 1.2 mol/L.
Introducing argon into the supergravity micro-reaction device, and then introducing the solution A and the solution B into the supergravity micro-reaction device by a metering pump according to the proportion of 1:3.5, wherein the reaction temperature is 40 ℃, the rotating speed of a micro-reaction disk is 1200-1400 rpm, the rotating speed ratio between the micro-reaction disk and a filler layer is 2.5:1, and the size range of a micro-reaction channel is 0.5 mm. And after the reaction is finished, centrifuging, washing the solid part to be neutral, dispersing the solid part into 500mL of deionized water, adding ethanedithiol with the mass of 0.05 percent of the theoretical mass of the metal copper, carrying out ultrasonic treatment for 30min, centrifuging, washing the obtained black solid part with absolute ethyl alcohol for three times, and carrying out vacuum drying at 80 ℃ for 2h to obtain the superfine pain powder, wherein the average particle size of the superfine pain powder is 11 nm.
Claims (9)
1. A method for preparing ultrafine metal powder is characterized by comprising the following steps:
(1) dissolving metal salt, a complexing agent and a surfactant in an inorganic and/or organic solvent, and uniformly stirring to obtain a metal salt precursor solution A;
(2) dissolving a reducing agent and a precipitator in an inorganic and/or organic solvent to obtain a solution B;
(3) introducing protective gas into the supergravity micro-reaction device, and adding the solution A and the solution B into the supergravity micro-reaction device through a metering pump for reaction;
(4) performing solid-liquid separation on the product in the step (3), washing the solid part to be neutral, adding the solid part into deionized water, adding a dispersing agent, and performing ultrasonic treatment for 30 min;
(5) performing solid-liquid separation on the product after ultrasonic treatment, washing the product with absolute ethyl alcohol for three times, and finally performing vacuum drying at 50-80 ℃ to obtain superfine metal powder;
wherein the metal powder is a nano metal simple substance of Fe, Co, Ni or Cu; the hypergravity micro-reaction device comprises a shell assembly, a hypergravity micro-reaction system, a sample feeding shaft and a power transmission system; a sample inlet pipe is arranged in the sample inlet shaft; the supergravity micro-reaction system consists of a rotary drum, a filler layer and a micro-reaction disc, wherein the filler layer and the rotary drum form a closed cavity, and the micro-reaction disc is arranged in the middle of the closed cavity; micro-reaction channels with the size range of 0.01-2 mm are distributed in the micro-reaction disc, and the horizontal distance between the outer edge of the micro-reaction disc and the packing layer is 10-100 mm; the power transmission system comprises a motor, a first transmission shaft, a second transmission shaft and a linkage device, wherein the first transmission shaft is a hollow device and is fixedly connected with the rotary drum, and the second transmission shaft penetrates through the first transmission shaft and is fixedly connected with the micro-reaction disk; the inner wall of the first transmission shaft is provided with an inner gear ring, and the inner gear ring, a 1# gear and a 2# gear set on the second transmission shaft form a linkage device, wherein the relative position of the 2# gear set is fixed through a fixing frame and a fixing shaft; the micro-reaction disk and the packing layer realize coaxial reverse rotation through a linkage device, and the raw materials are continuously crushed into nano-scale films, filaments and drops under the action of supergravity and shearing force; wherein the rotating speed of the micro-reaction disk is 200-4000 rpm, and the rotating speed ratio between the micro-reaction disk and the packing layer is (1-5): 1; the controllable particle size of the metal particles is realized by adjusting the rotating speed of the micro-reaction disk and the filler layer and the size of the micro-reaction channel.
2. The method for preparing ultra fine metal powder as claimed in claim 1, wherein: the inorganic solvent is deionized water, and the organic solvent is one or more of methanol, ethanol, ethylene glycol, isopropanol, glycerol, acetone, n-butane, n-pentane, n-hexane, tetrahydrofuran, dimethyl sulfoxide, cyclohexane, cyclohexanone, benzene, toluene, xylene, dimethyl ether, diethyl ether, ethyl acetate and carbon tetrachloride.
3. The method for preparing ultra fine metal powder as claimed in claim 1, wherein: in the step (1), the metal salt is one or more of chloride, sulfate, nitrate, phosphate, phosphite, acetate or oxalate of any metal simple substance, and the concentration of the metal salt is 0.01-1.5 mol/L; the complexing agent is any one of ammonia water, ethylenediamine, EDTA and sodium tartrate, wherein the molar ratio of the complexing agent to the metal salt is (0.01-1) to 1; the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium oleate, stearic acid, nonylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether and lauric glyceride, and the concentration of the surfactant is 1-150 g/L.
4. The method for preparing ultra fine metal powder as claimed in claim 1, wherein: in the step (2), the precipitant is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate, and the concentration is 0.8-3.6 mol/L; the reducing agent is one or more of sodium borohydride, potassium borohydride or hydrazine hydrate, and the concentration is 0.2-6 mol/L.
5. The method for preparing ultra fine metal powder as claimed in claim 1, wherein: in the step (3), the protective gas is one or more of hydrogen, nitrogen, helium and argon.
6. The method for preparing ultra fine metal powder as claimed in claim 1, wherein: in the step (3), the volume flow ratio of the solution A to the solution B is 1 (0.5-6), and the reaction temperature is 30-50 ℃.
7. The method for preparing ultra fine metal powder as claimed in claim 1, wherein: in the step (4), the dispersing agent is any one of methyl mercaptan, ethanethiol, ethanedithiol, thiophenol and dimercaptopropanol, and the adding amount of the dispersing agent is 0.01-0.5% of the mass of the metal powder.
8. The method for preparing ultra fine metal powder as claimed in claim 1, wherein: the solid-liquid separation is realized by a vacuum filtration or centrifugation method.
9. The method for preparing ultra fine metal powder as claimed in claim 1, wherein: the rotating speed of the micro-reaction disk is 900-2400 rpm, the rotating speed ratio between the micro-reaction disk and the packing layer is (1-2.5): 1, and the size range of the micro-reaction channel is 0.1-1 mm; the prepared superfine metal powder has high dispersibility, no caking phenomenon and a particle size distribution range of 5-25 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811051195.7A CN110883339B (en) | 2018-09-10 | 2018-09-10 | Method for preparing superfine metal powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811051195.7A CN110883339B (en) | 2018-09-10 | 2018-09-10 | Method for preparing superfine metal powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110883339A CN110883339A (en) | 2020-03-17 |
| CN110883339B true CN110883339B (en) | 2022-09-09 |
Family
ID=69745048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811051195.7A Active CN110883339B (en) | 2018-09-10 | 2018-09-10 | Method for preparing superfine metal powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110883339B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112495380A (en) * | 2020-11-03 | 2021-03-16 | 浙江工业大学 | Cu-Fe bimetallic nanosheet and preparation method thereof |
| CN113732279B (en) * | 2021-08-03 | 2024-02-06 | 北京化工大学 | Preparation method of nano gold particles serving as electron microscope developer and obtained nano gold particles |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910367A (en) * | 2013-01-06 | 2014-07-09 | 北京化工大学 | Method for preparing transparent magnesium hydroxide liquid phase dispersion |
| CN104014808A (en) * | 2014-05-29 | 2014-09-03 | 深圳航天科技创新研究院 | Method for preparing monodisperse superfine nickel powder through seeding growth method and micro-reaction system of method |
| CN105127439A (en) * | 2014-05-27 | 2015-12-09 | 北京化工大学 | Preparation method for oil-phase silver nanoparticles |
| CN106943973A (en) * | 2017-04-12 | 2017-07-14 | 福州大学 | The three-dimensional micro- integrated tower of reaction of hypergravity |
| CN107224949A (en) * | 2017-05-19 | 2017-10-03 | 四川大学 | The method that a kind of super gravity field microreactor and liquid-phase precipitation method prepare nano material |
| CN107601574A (en) * | 2017-09-25 | 2018-01-19 | 北京化工大学 | A kind of nanometer α Fe2O3Preparation method |
| CN108247077A (en) * | 2018-01-25 | 2018-07-06 | 深圳市中金岭南科技有限公司 | A kind of method that micro- reaction prepares copper powder |
| CN108339524A (en) * | 2018-02-02 | 2018-07-31 | 中北大学 | A kind of the hypergravity preparation method and device of cellulose base magnetic Nano material |
-
2018
- 2018-09-10 CN CN201811051195.7A patent/CN110883339B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910367A (en) * | 2013-01-06 | 2014-07-09 | 北京化工大学 | Method for preparing transparent magnesium hydroxide liquid phase dispersion |
| CN105127439A (en) * | 2014-05-27 | 2015-12-09 | 北京化工大学 | Preparation method for oil-phase silver nanoparticles |
| CN104014808A (en) * | 2014-05-29 | 2014-09-03 | 深圳航天科技创新研究院 | Method for preparing monodisperse superfine nickel powder through seeding growth method and micro-reaction system of method |
| CN106943973A (en) * | 2017-04-12 | 2017-07-14 | 福州大学 | The three-dimensional micro- integrated tower of reaction of hypergravity |
| CN107224949A (en) * | 2017-05-19 | 2017-10-03 | 四川大学 | The method that a kind of super gravity field microreactor and liquid-phase precipitation method prepare nano material |
| CN107601574A (en) * | 2017-09-25 | 2018-01-19 | 北京化工大学 | A kind of nanometer α Fe2O3Preparation method |
| CN108247077A (en) * | 2018-01-25 | 2018-07-06 | 深圳市中金岭南科技有限公司 | A kind of method that micro- reaction prepares copper powder |
| CN108339524A (en) * | 2018-02-02 | 2018-07-31 | 中北大学 | A kind of the hypergravity preparation method and device of cellulose base magnetic Nano material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110883339A (en) | 2020-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | The design and synthesis of hollow micro‐/nanostructures: present and future trends | |
| Tahir et al. | Synthesis of morphology controlled NiCo-LDH microflowers derived from ZIF-67 using binary additives and their excellent asymmetric supercapacitor properties | |
| Cai et al. | Hollow functional materials derived from metal–organic frameworks: synthetic strategies, conversion mechanisms, and electrochemical applications | |
| Song et al. | Hollow carbon‐based nanoarchitectures based on ZIF: Inward/outward contraction mechanism and beyond | |
| CN103143370B (en) | Preparation method of sulfide/graphene composite nano material | |
| CN110885087B (en) | Method for preparing nano silicon dioxide | |
| CN101710512B (en) | Composite material of graphene and carbon-encapsulated ferromagnetic nano metal and preparation method thereof | |
| CN110883339B (en) | Method for preparing superfine metal powder | |
| Wang et al. | Advanced yolk-shell nanoparticles as nanoreactors for energy conversion | |
| CN101898749B (en) | Method for preparing metal oxide hollow particles or fibers | |
| CN113548932B (en) | Nano composite burning rate catalyst of copper metal complex filled with carbon nano tube | |
| CN102228994A (en) | Method for preparing monodisperse silver core-nickel shell nanoparticles | |
| Wu et al. | High-throughput droplet microfluidic synthesis of hierarchical metal-organic framework nanosheet microcapsules | |
| CN110316696A (en) | A kind of method that can largely prepare binary superlattices lotion ball | |
| Wang et al. | Progress of transition metal sulfides used as the lithium-ion battery anodes | |
| Chen et al. | Synthesis, characterization and catalytic property of manganese dioxide with different structures | |
| CN108855217B (en) | Preparation method and application of copper-based metal organic framework nano sheet | |
| CN110882663B (en) | Hypergravity micro-reaction device | |
| CN111807415B (en) | Fe 2 Mo 3 O 8 Micron-sized hollow sphere and preparation method thereof | |
| CN108356276A (en) | A kind of the hypergravity preparation method and device of cellulose modified nano zero valence iron | |
| ZHANG et al. | Advances on impinging stream intensification mixing mechanism for preparing ultrafine powders | |
| Li et al. | Design strategies for shape-controlled nanocatalysts for efficient dehydrogenation of ammonia borane: A review | |
| Arun Chandru et al. | Initial studies on development of high-performance nano-structured Fe 2 O 3 catalysts for solid rocket propellants | |
| Chen et al. | Controlling crystal growth of MIL-100 (Fe) on Ag nanowire surface for optimizing catalytic performance | |
| Zhao et al. | Convenient hydrothermal treatment combining with “Ship in Bottle” to construct Yolk-Shell N-Carbon@ Ag-void@ mSiO2 for high effective Nano-Catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |