CN107626272B - Device and method for preparing amorphous Ni-B nanoparticles through rapid reaction - Google Patents
Device and method for preparing amorphous Ni-B nanoparticles through rapid reaction Download PDFInfo
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Abstract
The invention provides a device and a method for preparing amorphous Ni-B nano particles by rapid reaction, wherein the device comprises a pressure raw material storage container, an impact reactor and a temperature control reaction container, wherein the impact reactor is positioned at an upper opening of the temperature control reaction container; the impact reactor comprises a central channel positioned in the middle, an even number of symmetrical flow guide channels are arranged around the central channel, the included angle between the symmetrical flow guide channels is 30-150 degrees, at least two pressure raw material storage containers are arranged, one of the pressure raw material storage containers is connected with an inlet of the central channel, and every two symmetrical flow guide channels are respectively connected with the other pressure raw material storage container; the extension lines of the flow guide channel and the central channel are intersected below the impact reactor and positioned in the middle of the cavity of the temperature control reaction container. According to the technical scheme of the invention, the obtained nano material or nano composite material has narrow particle size distribution, uniform appearance, less agglomeration and good stability and consistency.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a device and a method for preparing amorphous Ni-B nano particles through rapid reaction.
Background
The amorphous nano Ni-B has very wide application prospect in the catalysis fields including citral hydrogenation, electrocatalytic water oxidation, benzene hydrogenation and the like, and the corrosion resistance and abrasion resistance fields of metal surfaces. Therefore, the large-scale preparation of the amorphous nano Ni-B also receives extensive attention.
Currently, a reduction method is adopted to prepare Ni-B nanoparticles, and usually a soluble nickel salt is used as a metal precursor, borohydride is used as a reducing agent, and the reaction equation is as follows:
2Ni2++2BH4 -+4H2O—Ni2B+B(OH)4-+9/2H2+3H+
the reaction is extremely fast, and borohydride reacts when in contact with a nickel salt solution, releasing a large amount of heat and hydrogen. If the experimental operation is carried out in the reaction kettle, the stirring mass transfer and heat transfer speed of the reaction kettle is obviously far from the reaction speed of borohydride and nickel salt, so that the product which is firstly reacted is used as a seed and continuously grows up under the continuous supplement of subsequent new products. Meanwhile, new seeds are generated continuously due to uneven stirring mass and heat transfer. Therefore, complex processes such as reduction reaction, growth of existing particles, generation of new seeds, agglomeration of small particles and the like exist in the same reaction kettle, so that the prepared nano particles have the problems of serious size distribution width, serious agglomeration, poor stability and consistency and the like. More particularly, because of the large amount of hydrogen and heat generated by the reaction, there is a significant safety risk if not eliminated in a timely manner.
Therefore, there is a need to develop a device and a method for preparing amorphous Ni-B nanoparticles by using the rapid reaction, so as to solve the problems of the tank reaction, such as wide product size distribution, serious agglomeration, poor stability and consistency, low exhaust and heat dissipation efficiency, and the like, and realize the safe and stable production of Ni-B nanoparticles by using a reduction method on a large scale.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a device and a method for preparing amorphous Ni-B nano particles by rapid reaction, which have the advantages of simple operation, strong controllability and easy amplification, well solve the problems of mismatching of three-pass reaction and reaction speed of rapid reaction and the discharge of heat and gas in the reaction by adopting a liquid flow impact reaction mode and an experimental device with an exhaust heat dissipation hole, and are suitable for continuous and large-scale preparation of the amorphous Ni-B nano particles.
In contrast, the technical scheme adopted by the invention is as follows:
a device for preparing amorphous Ni-B nano-particles by rapid reaction comprises a pressure raw material storage container, an impact reactor and a temperature control reaction container, wherein the impact reactor is positioned at an upper opening of the temperature control reaction container; the impact reactor comprises a central channel positioned in the middle, an even number of symmetrical flow guide channels are arranged around the central channel, the included angle between the symmetrical flow guide channels is 30-150 degrees, the number of the pressure raw material storage containers is at least two, one of the pressure raw material storage containers is connected with an inlet of the central channel, and every two symmetrical flow guide channels are respectively connected with the other pressure raw material storage container; the extension lines of the flow guide channel and the central channel are intersected below the impact reactor and positioned in the middle of the cavity of the temperature control reaction container, and the side wall of the temperature control reaction container is provided with an exhaust hole. Wherein, the flow guide is at least two. One pressure raw material storage container is filled with a mixed aqueous solution of nickel salt and a stabilizing agent, and the other pressure raw material storage container is filled with an aqueous solution of borohydride, wherein the molar ratio of borohydride to nickel salt is not less than 2:1 during feeding.
Wherein, the pressure raw material storage container is used for storing the reaction raw materials and keeping a certain pressure, so that the reaction raw materials can mutually impact at a certain speed. Further, the pressurized raw material storage container may be communicated with a device containing a high-pressure shielding gas to maintain a certain pressure.
The impact reactor is a core component that guides the impact reaction to occur. The central channel is a diversion channel for reaction materials, and an even number of diversion channels are symmetrically distributed on a circle which is at a certain distance from the central channel and are used as diversion channels for another or other various reaction materials. If there are a plurality of reaction materials, the plurality of reaction materials are arranged at intervals. The central channel corresponds to a pressure raw material storage container, every two symmetrical flow guide channels on the edge correspond to the pressure raw material storage container, and the included angle between the symmetrical flow guide channels is 30-150 degrees, so that various reaction materials passing through the flow guide channels are collected below the impact reactor, the liquid flow intersection angle is 30-150 degrees, and the liquid flow intersection and the reaction zone are arranged in the middle of the cavity of the temperature control reaction container and cannot be contacted with the wall of the reactor. The reaction materials are impacted and mixed at high speed in the liquid flow intersection area, and the reaction is completed at the same time. The homogeneous nucleation reaction can be considered as that several liquid streams impact and react in a region far away from the wall, so that the liquid streams are not disturbed by the wall. The continuous reaction mode ensures the continuous and stable reaction, and the large-scale mass production is easy to realize. Moreover, because a liquid flow continuous impact reaction mode is adopted, heat and gas generated by the reaction are relatively stable in unit time, and a relatively open impact reaction area is very favorable for the dissipation of the heat and the gas; in addition, due to the existence of the exhaust holes, the device can be externally connected with an active air exhaust heat dissipation and tail gas treatment device, and the problem that a large amount of gas and heat are released when the nickel salt is reduced by borohydride is well solved.
Furthermore, the product of the rapid impact reaction falls to the bottom of the temperature control reaction container, under the stirring action of the stirring device in the temperature control reaction container, the material which is not completely reacted is completely reacted, and meanwhile, the stirring action also has the function of preventing the product from settling and agglomerating. And (4) allowing the product completely reacted to flow into a product storage container, and performing further aging treatment, namely filtering and washing to obtain the final nano material or nano composite material. Moreover, the temperature control reaction container can properly control the temperature of the reaction area, and the temperature is controlled to be between 15 ℃ and 50 ℃.
The liquid flow impact reaction mode adopted by the technical scheme well solves the problems of three-pass of rapid reaction and unmatched reaction speed on one hand, and solves the problem that reaction products are attached to the wall of the container because the liquid flow impact intersection reaction area is arranged in the middle of the cavity of the container and is not in contact with the wall of the container on the other hand. The reaction device has the advantages of high reaction speed, simple operation, strong controllability, wide application range, easy amplification and the like.
As a further improvement of the invention, the included angle between the symmetrical flow guide channels is 60-120 degrees.
As a further improvement of the invention, a stirring device is arranged at the lower part of the temperature-controlled reaction container. By adopting the technical scheme, the reaction and the dispersion are further mixed and reacted under the stirring of the stirring device, so that reactants are fully reacted and are prevented from agglomerating.
As a further improvement of the invention, the device for preparing amorphous Ni-B nano particles by rapid reaction comprises a product storage container, wherein the bottom of the temperature control reaction container is provided with a discharge hole, and the product storage container is connected with the discharge hole. The temperature control reaction container can properly control the temperature of the reaction area, and the application range of the device is expanded. And (4) allowing the product completely reacted to flow into a product storage container, and performing further aging treatment, namely filtering and washing to obtain the final amorphous nano Ni-B material.
Furthermore, the bottom of the temperature control reaction container is a concave surface, and products can be collected. The bottom of the temperature control reaction container is a plane at the position of a stirring paddle of the stirring device.
As a further improvement of the invention, the device for preparing amorphous Ni-B nanoparticles by rapid reaction comprises a high-pressure protective gas container and raw material storage containers, wherein the high-pressure protective gas container is respectively connected with at least two pressure raw material storage containers through a barometer, the number of the raw material storage containers is not less than that of the pressure raw material storage containers, and the raw material storage containers are respectively connected with the pressure raw material storage containers.
Wherein the high-pressure protective gas container is used for providing gas with certain pressure, and is used for endowing and keeping the pressure in the pressure raw material storage container constant, so that the reaction precursor solution can be impacted at high speed at a certain angle under the guidance of a central channel and a flow guide channel in the impact reactor at a high flow speed, and simultaneously, the mixing and the reaction are completed. The pressure raw material storage container is used for storing reaction raw materials and is communicated with the high-pressure protective gas container to maintain certain pressure, so that the reaction raw materials can mutually impact at a certain speed. Gas pressure gauges are used to monitor and regulate the pressure of the gas.
As a further improvement of the present invention, the raw material storage container includes a first raw material storage container and a second raw material storage container, the pressure raw material storage container includes a first pressure raw material storage container and a second pressure raw material storage container, the first raw material storage container is connected to the first pressure raw material storage container, the second raw material storage container is connected to the second pressure raw material storage container, the first pressure raw material storage container is connected to the central passage, and the second pressure raw material storage container is connected to the symmetrical flow guide channels located around the central passage. The first raw material storage container is filled with an aqueous solution of a nickel salt solution and a stabilizing agent, the second raw material storage container is filled with an aqueous solution of borohydride, and the pH value of the aqueous solution of borohydride is greater than 11.
As a further development of the invention, the raw material storage container is connected to the pressurized raw material storage container by means of a peristaltic pump. Wherein the peristaltic pump is used for realizing the continuous transmission of materials.
As a further improvement of the invention, a stirring device is arranged in the raw material storage container.
The invention also discloses a method for preparing amorphous Ni-B nano particles by adopting the device for preparing amorphous Ni-B nano particles by adopting the rapid reaction, which comprises the following steps:
step S1, adding the mixed aqueous solution of nickel salt and stabilizer into a first raw material storage container; adding a borohydride aqueous solution into a second raw material storage container, and adjusting the pH value to be more than 11 by using alkali; wherein the molar ratio of borohydride to nickel salt is not less than 2: 1;
step S2, starting a temperature control system of the temperature control reaction container to keep the temperature inside the temperature control reaction container between 15 ℃ and 50 ℃;
step S3, the raw materials in the first raw material storage container and the second raw material storage container respectively flow into the first pressure raw material storage container and the second pressure raw material storage container, and simultaneously the high-pressure protective gas container is opened to make the high-pressure protective gas respectively flow into the first pressure raw material storage container and the second pressure raw material storage container;
step S4, the liquid in the first pressure raw material storage container and the liquid in the second pressure raw material storage container enter the impact reactor under the pressure effect, and impact each other and react with each other below the impact reactor at a certain speed through the central channel and the flow guide channel of the impact reactor; after the reaction, the product falls to the bottom of the temperature control reaction container, and finally, after the product is aged, amorphous nano Ni-B powder is obtained after filtration, washing and drying.
Preferably, the liquid of the first pressure feed storage vessel and the second pressure feed storage vessel enter the impingement reactor at equal volumes under pressure.
Further, the liquid pressure in the pressure storage tank is kept at 0.15-2 MPa. By adopting the technical scheme, in the pressure range, the two materials can be ensured to mutually impact at a certain speed below the impact reactor through the central channel and the flow guide channel of the impact reactor, and the amorphous nano Ni-B with small particles can be obtained.
As a further improvement of the invention, the nickel salt is one or a mixture of more of nickel sulfate, nickel nitrate, nickel chloride and nickel acetate, and the concentration is 0.1-2 mol/L; the stabilizer is one or more of PVP (polyvinyl pyrrolidone), CTAB (cetyltrimethylammonium Bromide), CTAC (cetyltrimethylammonium Bromide), sodium citrate, F127, P123, cellullose, fatty acid, oleic acid and the like; wherein, P123 and F127 are triblock polymers, which are all called polyoxyethylene-polyoxypropylene-polyoxyethylene and have a molecular formula of PEO-PPO-PEO.
Compared with the prior art, the invention has the beneficial effects that:
the technical scheme of the invention adopts a continuous production mode, has simple operation, strong controllability and easy amplification, and adopts a liquid flow impact reaction mode to better solve the problems of three-pass of rapid reaction and unmatched reaction speed on one hand, and to better solve the problem that reaction products are attached to the wall of the container because the liquid flow impact intersection reaction zone is arranged in the middle of the cavity of the container and is not contacted with the wall of the container on the other hand. The technical scheme well solves the problems of wide product size distribution, serious agglomeration, poor stability and consistency, low exhaust and heat dissipation efficiency and the like in the kettle type reaction, realizes the safe and stable production of preparing the Ni-B nano particles on a large scale by a reduction method, and obtains the Ni-B nano particle product with narrow size distribution, good stability and consistency and less agglomeration.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for preparing amorphous Ni-B nanoparticles by a rapid reaction according to the present invention.
FIG. 2 is a schematic cross-sectional view of an impact reactor according to the present invention.
Fig. 3 is a schematic top view of an impact reactor according to the present invention, wherein the impact reactor has 3 cells.
Fig. 4 is a schematic view of the pilot hole reaction mass arrangement of the impingement reactor of fig. 3.
Fig. 5 is an SEM image of amorphous Ni-B nanoparticles prepared in example 2.
Fig. 6 is an XRD spectrum of the amorphous Ni-B nanoparticles prepared in example 2.
FIG. 7 is a scanning electron micrograph of Ni-B nanoparticles prepared in comparative example 1 using a 30L reaction vessel.
The reference numerals include: 1-a high-pressure inert gas cylinder, 2-a gas pressure gauge, 3-a first raw material stirring tank, 4-a second raw material stirring tank, 5-a peristaltic pump, 6-a first pressure storage tank, 7-a second pressure storage tank, 8-an impact reactor, 9-an exhaust hole, 10-a temperature control reaction container, 11-a stirrer and 12-a product storage tank; 21-central channel, 22-flow guide channel, 23-intersection impact area.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and with reference to the accompanying drawings. The following examples are merely illustrative of the present invention and should not be construed as limiting thereof.
Example 1
As shown in fig. 1 to 4, a device for preparing amorphous Ni-B nanoparticles by a rapid reaction includes a high-pressure inert gas cylinder 1, a gas pressure gauge 2, a raw material stirring tank, a peristaltic pump 5, a pressure storage tank, an impact reactor 8, a temperature-controlled reaction vessel 10, and a product storage tank 12, wherein the impact reactor 8 is located at an upper opening of the temperature-controlled reaction vessel 10; the impact reactor 8 is equipped with the flow leader 22 of 2 symmetries including the central channel 21 that is located the middle part around lieing in central channel 21, and the contained angle between the symmetrical flow leader 22 is 30~150, the raw materials stirred tank includes first raw materials stirred tank 3 and second raw materials stirred tank 4, the pressure stock chest includes first pressure stock chest 6 and second pressure stock chest 7, first raw materials stirred tank 3 passes through peristaltic pump 5 and is connected with first pressure stock chest 6, second raw materials stirred tank 4 passes through peristaltic pump 5 and is connected with second pressure stock chest 7. And the high-pressure inert gas cylinder 1 is respectively connected with the two pressure storage tanks through a gas pressure gauge 2. The first pressure accumulator 6 is connected with the central channel 21, and the second pressure accumulator 7 is connected with two symmetrical flow guide channels 22 around the central channel 21.
As shown in fig. 1 to 4, the extension lines of the flow guide channel 22 and the central channel 21 intersect below the impact reactor 8 and are located in the middle of the cavity of the temperature-controlled reaction vessel 10 to form an intersection impact region 23. The side wall of the temperature control reaction container 10 is provided with an exhaust hole 9, and the lower part of the temperature control reaction container 10 is provided with a stirrer 11. The bottom of the temperature control reaction vessel 10 is provided with a discharge port, and the discharge port is connected with a product storage tank 12. And a stirring device is arranged in the raw material stirring tank.
The devices are connected together as shown in figure 1 to form a set of production device suitable for preparing nano materials or nano composite materials through rapid reaction.
The method for preparing the amorphous Ni-B nano particles by adopting the device to carry out rapid reaction comprises the following steps:
step S1, starting a temperature control system of the temperature control reaction container 10 to keep the temperature inside the temperature control reaction container 10 between 15 ℃ and 50 ℃;
step S2, adding the mixed aqueous solution of nickel salt and stabilizer into the first raw material stirring tank 3; adding a borohydride aqueous solution into the second raw material stirring tank 4, and adjusting the pH value to be more than 11 by using alkali; wherein the concentration of the nickel salt is 0.1-2mol/L, and the molar ratio of the borohydride to the nickel salt is not less than 2: 1;
step S3, starting the peristaltic pump 5 to make the materials in the first raw material mixing tank 3 and the second raw material mixing tank 4 respectively flow into the first pressure storage tank 6 and the second pressure storage tank 7, and simultaneously starting the high-pressure inert gas cylinder 1 to make the high-pressure protective gas respectively flow into the first pressure storage tank 6 and the second pressure storage tank 7, and make the liquid pressure in the first pressure storage tank 6 and the second pressure storage tank 7 be 0.15-2 MPa.
Step S4, the materials of the first pressure storage tank 6 and the second pressure storage tank 7 enter the impact reactor 8 in equal volume under the action of pressure, and are mutually impacted and reacted in the intersection impact area 23 below the impact reactor 8 at a certain speed through the central channel 21 and the flow guide channel 22 of the impact reactor 8; after the reaction, the product falls to the bottom of the temperature controlled reaction vessel 10. The product of the rapid impact reaction falls to the bottom of the temperature control reaction vessel 10, under the stirring action of the stirrer 11, the material which is not completely reacted is completely reacted, and meanwhile, the stirring action also has the function of preventing the product from settling and agglomerating. The product after complete reaction flows into a product storage tank 12, and amorphous nano Ni-B powder can be obtained by further aging treatment, filtration and washing.
Wherein the nickel salt is one or a mixture of more of nickel sulfate, nickel nitrate, nickel chloride and nickel acetate, and the concentration is 0.1-2 mol/L; the stabilizer is one or more of PVP, CTAB, CTAC, sodium citrate, F127, P123, cell cellulose, fatty acid, oleic acid, etc.; the borohydride is one or a mixture of two of sodium borohydride and potassium borohydride; the alkali is one or a mixture of two of sodium hydroxide and potassium hydroxide.
Example 2
The method and the continuous reaction device provided in example 1 are adopted to prepare amorphous nano Ni-B, and the method comprises the following steps:
adding a certain amount of nickel nitrate and PVP into a first raw material stirring tank 3, and dissolving in pure water to prepare a solution with the nickel salt concentration of 0.5M; the pure water is distilled water or deionized water. Preparing 1M solution from a certain amount of sodium borohydride, adjusting the pH value to be more than 11 by using sodium hydroxide to ensure that no obvious bubbles are generated, and pouring the solution into a second raw material stirring tank 4. And starting the peristaltic pump 5, and enabling the liquid in the first raw material stirring tank 3 and the liquid in the second raw material stirring tank 4 to flow into the first pressure storage tank 6 and the second pressure storage tank 7. And simultaneously opening the high-pressure inert gas cylinder 1 to enable gas to enter the first pressure storage tank 6 and the second pressure storage tank 7, and keeping the liquid pressure in the pressure storage tanks at 0.2 MPa. Before the start of the experiment, the temperature control device of the temperature controlled reaction vessel 10 was turned on to maintain the temperature of the reactor zone at 15 ℃.
The raw materials enter the impact reactor 8 and impact each other and react at a certain speed in a meeting impact zone 23 below the impact reactor 8 through a central channel 21 and a diversion channel 22. After the reaction, the product falls to the bottom of the temperature controlled reaction vessel 10, is stirred by the stirrer 11 to be further mixed, reacted and dispersed, so that the reactants are fully reacted and prevented from agglomerating, and finally flows into the product storage tank 12, and amorphous nano Ni-B particles are obtained. The scanning electron microscope photo and XRD spectrogram of the prepared Ni-B product are shown in figures 5 and 6, so that the prepared Ni-B nano nickel particles are uniform in particle size and regular in morphology, and the XRD spectrogram shows an amorphous structure.
Comparative example 1
For comparison, in a 30L double-layer glass reaction kettle, pure water, nickel nitrate and PVP are firstly added into the reaction kettle according to the same concentration and proportion of reactants, stirred, dissolved and mixed uniformly, and the temperature is kept at 15 ℃. Then, under the condition that the rotating speed of the double-layer three-blade spiral stirring paddle is 450rpm, dropwise adding a mixed aqueous solution of sodium borohydride and sodium hydroxide at 15 ℃ into the reaction kettle, continuing stirring and reacting for 60 minutes after dropwise adding, and finally obtaining a scanning electron microscope photo of a reaction product, wherein the scanning electron microscope photo is shown in figure 7.
As can be seen from comparison of fig. 5 to 7, the particle size of the particles obtained by the technical scheme of embodiment 2 is more uniform and the morphology is more regular.
Example 4
The continuous reaction apparatus and method provided in example 1 were used to prepare amorphous nano Ni-B, which included the following steps:
adding a certain amount of nickel sulfate and CTAB into the first raw material stirring tank 3 to prepare a solution with the concentration of 0.75M, and starting stirring. Preparing a solution with the concentration of 1.5M with a certain amount of sodium borohydride, adjusting the pH value to be more than 11 with potassium hydroxide to ensure that no obvious bubbles are generated, and pouring the solution into a second raw material stirring tank 4.
And starting the peristaltic pump 5, and enabling the liquid in the first raw material stirring tank 3 and the liquid in the second raw material stirring tank 4 to flow into the first pressure storage tank 6 and the second pressure storage tank 7. Meanwhile, the high-pressure inert gas bottle 1 is opened to enable gas to enter the first pressure storage tank 6 and the second pressure storage tank 7, and the liquid pressure in the first pressure storage tank 6 and the second pressure storage tank 7 is kept at 0.35 MPa. Before the experiment, the temperature control device of the temperature controlled reaction vessel 10 was turned on to maintain the temperature of the reactor zone at 20 ℃.
The raw materials enter the impact reactor 8 and impact each other and react at a certain velocity in a converging impact zone 23 below the impact reactor 8 through a central channel 21 and a flow guide 22. After the reaction, the product falls to the bottom of the temperature controlled reaction vessel 10, is stirred by the stirrer 11 for further mixing reaction and dispersion, so that the reactants are fully reacted and prevented from agglomerating, finally flows into the product storage tank 12, and is washed, filtered and dried to obtain the amorphous nano Ni-B particles.
Example 5
The method and the continuous reaction device provided in example 1 are adopted to prepare amorphous nano Ni-B, and the method comprises the following steps:
adding a certain amount of nickel chloride, CTAC and deionized water into the first raw material stirring tank 3 to prepare a solution with the concentration of 1M, and starting stirring. Preparing 3M solution by using a certain amount of potassium borohydride, adjusting the solution by using potassium hydroxide until no obvious bubbles are generated, and pouring the solution into a second raw material stirring tank 4.
And starting the peristaltic pump 5, and enabling the liquid in the first raw material stirring tank 3 and the liquid in the second raw material stirring tank 4 to flow into the first pressure storage tank 6 and the second pressure storage tank 7. Meanwhile, the high-pressure inert gas bottle 1 is opened to enable gas to enter the first pressure storage tank 6 and the second pressure storage tank 7, and the liquid pressure in the first pressure storage tank 6 and the second pressure storage tank 7 is kept at 0.5 MPa. Before the experiment, the temperature control device of the temperature controlled reaction vessel 10 was turned on to maintain the temperature of the reactor zone at 25 ℃.
The raw materials enter the impact reactor 8 and impact each other and react at a certain speed in a meeting impact zone 23 of the impact reactor 8 through a central channel 21 and a diversion channel 22. After the reaction, the product falls to the bottom of the temperature controlled reaction vessel 10, is stirred by the stirrer 11 for further mixing reaction and dispersion, so that the reactants are fully reacted and prevented from agglomerating, finally flows into the product storage tank 12, and is washed, filtered and dried to obtain the amorphous nano Ni-B particles.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (7)
1. A method for continuously preparing amorphous Ni-B nano particles by rapid reaction is characterized in that: which adopts a device for preparing amorphous Ni-B nano particles by rapid reaction,
the device for preparing the amorphous Ni-B nano particles by the rapid reaction comprises a pressure raw material storage container, an impact reactor and a temperature control reaction container, wherein the impact reactor is positioned at an upper opening of the temperature control reaction container; the impact reactor comprises a central channel positioned in the middle, an even number of symmetrical flow guide channels are arranged around the central channel, the included angle between the symmetrical flow guide channels is 30-150 degrees, the number of the pressure raw material storage containers is at least two, one of the pressure raw material storage containers is connected with an inlet of the central channel, and every two symmetrical flow guide channels are respectively connected with the other pressure raw material storage container; the extension lines of the flow guide channel and the central channel are intersected below the impact reactor and positioned in the middle of the cavity of the temperature control reaction container, and the side wall of the temperature control reaction container is provided with an exhaust hole;
wherein, one pressure raw material storage container is filled with a mixed aqueous solution of nickel salt and a stabilizing agent, and the other pressure raw material storage container is filled with a borohydride aqueous solution, and the molar ratio of borohydride to nickel salt is not less than 2:1 during feeding;
the high-pressure protective gas container is connected with at least two pressure raw material storage containers through barometers respectively, the number of the raw material storage containers is not less than that of the pressure raw material storage containers, and the raw material storage containers are connected with the pressure raw material storage containers respectively;
the raw material storage container comprises a first raw material storage container and a second raw material storage container, the pressure raw material storage container comprises a first pressure raw material storage container and a second pressure raw material storage container, the first raw material storage container is connected with the first pressure raw material storage container, the second raw material storage container is connected with the second pressure raw material storage container, the first pressure raw material storage container is connected with the central channel, and the second pressure raw material storage container is connected with symmetrical guide channels positioned around the central channel; the first raw material storage container is filled with an aqueous solution of a nickel salt solution and a stabilizing agent, the second raw material storage container is filled with an aqueous solution of borohydride, and the pH value of the aqueous solution of borohydride is greater than 11;
the preparation method comprises the following steps:
step S1, adding the mixed aqueous solution of nickel salt and stabilizer into a first raw material storage container; adding a borohydride aqueous solution into a second raw material storage container, and adjusting the pH value to be more than 11 by using alkali; wherein the molar ratio of borohydride to nickel salt is not less than 2: 1;
step S2, starting a temperature control system of the temperature control reaction container to keep the temperature inside the temperature control reaction container between 15 ℃ and 50 ℃;
step S3, the raw materials in the first raw material storage container and the second raw material storage container respectively flow into the first pressure raw material storage container and the second pressure raw material storage container, and simultaneously the high-pressure protective gas container is opened, so that the high-pressure protective gas respectively flows into the first pressure raw material storage container and the second pressure raw material storage container, and the liquid pressure in the pressure raw material storage containers is 0.15-2 MPa;
step S4, the liquid in the first pressure raw material storage container and the liquid in the second pressure raw material storage container enter the impact reactor under the pressure effect, and impact each other and react with each other below the impact reactor at a certain speed through the central channel and the flow guide channel of the impact reactor; after the reaction, the product falls to the bottom of the temperature control reaction container; and ageing the finally obtained product, filtering, washing and drying to obtain the amorphous nano Ni-B powder.
2. The rapid reaction continuous preparation method of amorphous Ni-B nanoparticles as claimed in claim 1, characterized in that: the nickel salt is one or a mixture of more of nickel sulfate, nickel nitrate, nickel chloride and nickel acetate, and the concentration is 0.1-2 mol/L; the stabilizer is one or a mixture of PVP, CTAB, CTAC, sodium citrate, F127, P123, cell cellulose, fatty acid and oleic acid;
the borohydride is one or a mixture of two of sodium borohydride and potassium borohydride; the alkali is one or a mixture of two of sodium hydroxide and potassium hydroxide.
3. The rapid reaction continuous preparation method of amorphous Ni-B nanoparticles as claimed in claim 1, characterized in that: the included angle between the symmetrical flow guide channels is 60-120 degrees.
4. The rapid reaction continuous preparation method of amorphous Ni-B nanoparticles as claimed in claim 1, characterized in that: and a stirring device is arranged at the lower part of the temperature control reaction container.
5. The rapid reaction continuous preparation method of amorphous Ni-B nanoparticles as claimed in claim 4, characterized in that: the device comprises a product storage container, wherein a discharge hole is formed in the bottom of the temperature control reaction container, and the product storage container is connected with the discharge hole.
6. The rapid reaction continuous preparation method of amorphous Ni-B nanoparticles as claimed in claim 1, characterized in that: the raw material storage container is connected with the pressure raw material storage container through a peristaltic pump.
7. The rapid reaction continuous preparation method of amorphous Ni-B nanoparticles as claimed in claim 1, characterized in that: and a stirring device is arranged in the raw material storage container.
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| CN104379260A (en) * | 2012-05-10 | 2015-02-25 | 康涅狄格州大学 | Methods and apparatus for making catalyst films |
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| CN1222878A (en) * | 1996-04-01 | 1999-07-14 | 卡伯特公司 | Novel elastomer composites, method and apparatus |
| CN1710137A (en) * | 2005-06-23 | 2005-12-21 | 复旦大学 | Amorphous nickel-boron nuclear-shell, ghost structural material and its preparing material |
| CN101300096A (en) * | 2005-08-10 | 2008-11-05 | 戴雷克塔普拉斯专利及科技有限公司 | Production of nano-scale metal particles |
| CN102560290A (en) * | 2010-12-24 | 2012-07-11 | 国家纳米技术与工程研究院 | Nano nickel boride (NiB) amorphous alloy and preparation method thereof |
| CN102179527A (en) * | 2011-05-10 | 2011-09-14 | 湖南省娄底维亚科技有限公司 | Method for preparing nano nickel powder |
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