CN107363268B - Device and method for continuously preparing high-solid-content nano silver - Google Patents
Device and method for continuously preparing high-solid-content nano silver Download PDFInfo
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Abstract
The invention provides a device and a method for continuously preparing high-solid-content nano silver, wherein the device comprises a raw material container, an impinging stream mixer, a microwave reactor, an ultrasonic growth combination device and an ultrasonic stirring growth device, the raw material container comprises an alcohol raw material container and a plurality of silver salt mixed solution raw material containers, the alcohol raw material container and one silver salt mixed solution raw material container are respectively connected with a feed inlet of the impinging stream mixer, a discharge outlet of the impinging stream mixer is connected with the microwave reactor, an outlet of the microwave reactor is connected with an inlet of the ultrasonic growth combination device, and an outlet of the ultrasonic growth combination device is connected with the ultrasonic stirring growth device. The technical scheme of the invention has the advantages of continuity, divisible nucleation and growth processes, high concentration of the precursor, high production efficiency, good stability, strong controllability, easy amplification and the like, and is particularly suitable for industrial large-scale preparation of silver nanoparticles with good consistency and stability.
Description
Technical Field
The invention belongs to the technical field of metal nano material preparation, and particularly relates to a device and a method for continuously preparing high-solid-content nano silver.
Background
Due to the unique physical and chemical properties of the silver nanoparticles, the silver nanoparticles have wide application prospects in a plurality of fields including electric conduction, heat conduction, sterilization, surface enhanced Raman, metal enhanced fluorescence scattering, sensing, imaging and the like. Based on the statistics published by Project on embedding Nanotechnologies 2013, 622 companies in 32 countries have a total of 1814 commodities containing nanomaterials on sale, with 435 products containing silver nanomaterials accounting for 24% of the total. In recent years, with the application and development of nano silver in new fields such as sensing, imaging and flexible electronic devices, and with the nanocrystallization of silver materials used in the fields of electric conduction and heat conduction, the market prospect of nano silver materials will be wider as one of the most mature commercialized nano materials.
The premise and material basis of large-scale commercial application of nano-silver materials is necessarily the large-scale preparation of high-solid-content nano-silver particles. The existing preparation method of silver nanoparticles can be divided into a physical method and a chemical method, wherein the physical method has the advantages of no solvent and less product impurities, but has the disadvantages of difficulty in obtaining a large amount of nanoparticles with uniform size, high energy consumption and raw material waste in the preparation process, and complex and expensive equipment. The chemical method is more energy-saving, the experimental conditions are more easily controlled, and the size and the shape of the prepared nano material are more effectively controlled, so that the method is the most widely applied method for preparing various nano materials at present.
The common chemical methods for preparing the nano silver particles mainly comprise a reduction method, a hydrothermal synthesis method, a polyol method, a photochemical method and the like, wherein the methods usually adopt a discontinuous mode, nucleation and growth are carried out in the same reaction vessel to prepare the nano silver particles, the nucleation and growth processes for preparing the nano silver cannot be separated, and the prepared nano silver particles have wide size distribution and poor consistency and stability among batches. In addition, the methods have a common problem that in order to make the final product have uniform shape and size, the concentration of the precursor is generally not more than 0.1mol/L, so that the solid content of the prepared nano silver sol is very low and is far from the requirement of commercial application. Therefore, the discontinuous methods which can not be divided into nucleation and growth processes and have low precursor concentration do not have the condition for industrially producing the nano silver, and a device and a method which can continuously prepare the high-solid-content silver nano particles on a large scale are needed to be developed.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a device and a method for continuously preparing high-solid-content nano silver, which have the advantages of continuity, capability of forming nuclei and growing processes in a segmenting manner, high precursor concentration, high production efficiency, good stability, strong controllability, easiness in amplification and the like, and are particularly suitable for industrial large-scale preparation of silver nano particles with good consistency and stability.
In contrast, the technical scheme adopted by the invention is as follows:
a device for continuously preparing high-solid-content nano silver comprises a raw material container, an impinging stream mixer, a microwave reactor, an ultrasonic growth combination device and an ultrasonic stirring growth device, wherein the raw material container comprises an alcohol raw material container and a plurality of silver salt mixed solution raw material containers, the alcohol raw material container and one silver salt mixed solution raw material container are respectively connected with a feed inlet of the impinging stream mixer, a discharge outlet of the impinging stream mixer is connected with the microwave reactor, an outlet of the microwave reactor is connected with an inlet of the ultrasonic growth combination device, and an outlet of the ultrasonic growth combination device is connected with the ultrasonic stirring growth device; the ultrasonic growth combination device comprises at least two ultrasonic growth units which are connected in series, each ultrasonic growth unit comprises an ultrasonic reactor and a silver salt mixed liquid raw material container, in each ultrasonic growth unit, an outlet of the silver salt mixed liquid raw material container is connected with an inlet of the ultrasonic reactor, and the ultrasonic reactors of two adjacent ultrasonic growth units are connected with each other;
pumping the raw materials in the alcohol raw material container and the silver salt mixed solution raw material container into an impinging stream mixer for mixing, then entering a microwave reactor for microwave heating reaction to obtain silver seed sol, entering the microwave-heated silver seed sol into an ultrasonic reactor of an ultrasonic growth combination device, simultaneously entering the silver salt mixed solution in the silver salt mixed solution raw material container of the ultrasonic growth unit into the ultrasonic reactor for further growing the silver seeds, in the ultrasonic growth combination device, after the silver seeds grow to the required particle size in multiple stages, flowing into an ultrasonic stirring growth device, further reacting under the double actions of ultrasound and stirring, and completely consuming the silver salt raw material; the silver salt mixed solution is a mixed solution of silver salt, a surfactant and water.
The impinging stream mixer integrates the advantages of the impinging stream mixer and the static mixer, can realize rapid mixing of two liquids with volume flow rates which are not much different by adopting opposite high-speed impinging, and further realizes more uniform mass transfer mixing of the liquids after impinging and mixing through the static mixer. The mass transfer requirements of different liquid materials, such as mixing effect, mixing time, mixing flow and the like, can be simply realized by means of improving the flow velocity of liquid flow, increasing the pipe diameter size, prolonging the length of a pipeline and the like, so that the impinging stream mixer has the advantages of high mass transfer mixing speed, high mixing efficiency, large flow, easiness in amplification, continuity, stability, strong controllability and the like. In particular, no power element is arranged in the whole mixer, so that the energy-saving effect is remarkable.
The ultrasonic growth combination device is composed of ultrasonic growth units, and can be connected in series with a plurality of ultrasonic growth units as required, so that the silver particle seeds are subjected to multistage growth to obtain nano silver particles with required sizes. The ultrasonic reactor can carry out ultrasonic treatment on the liquid flowing through the tank, and the high temperature and high pressure generated by the acoustic cavitation phenomenon are utilized to accelerate the reaction, so that the seeds are further reacted to generate nano particles with larger sizes. The ultrasonic reactor is preferably a probe type ultrasonic reactor.
The ultrasonic stirring growth device can be an ultrasonic stirring growth groove, namely an ultrasonic stirring container or an ultrasonic stirring groove, and is used for growing the nano silver particles; the device can make the raw materials flowing into the device fully react under the dual action of ultrasound and stirring on one hand, and on the other hand, has good dispersion effect on the nano silver particles.
Furthermore, a corundum glass spiral tube is arranged in the microwave reactor. In the microwave reactor, liquid flows through the spiral pipe and is rapidly heated by microwaves, and the heating temperature and the heat preservation time of the liquid flow can be conveniently controlled by adjusting the microwave power, the pipe diameter and the length of the spiral pipe and the flow velocity of the liquid flow, so that the liquid flow is rapidly, efficiently and uniformly heated. The silver salt reacts with the alcohol in the device under the action of the microwave, and uniform and stable small-size silver sol is generated under the protection of the surfactant and is used as a seed for the next growth.
The preparation of the nano-particles usually has two stages of nucleation and growth, if the nucleation and the growth are carried out in the same reaction system, the nucleation and the growth are mutually competitive and mutually influenced, the nano-particles are prepared in one reaction vessel, the nucleation and the growth processes are mixed together, and meanwhile, the complex processes of the chemical reaction, the generation of new crystal nuclei, the growth of the existing crystal nuclei, the agglomeration of small particles and the like exist, so that the problems of wide particle size distribution, uneven appearance, poor performance stability and consistency and the like of a final product are caused. For example, in the prior art, the methods for preparing nano silver, such as a reduction method, a hydrothermal synthesis method, a polyol method, a photochemical method and the like, silver salt, a reducing agent, a solvent and a surfactant are uniformly mixed in a certain proportion in a single reaction vessel, and then the silver salt is reduced by heating, illumination and reflux treatment to obtain nano silver particles. Therefore, the methods all adopt an intermittent production mode, the nucleation and growth processes cannot be divided in the same reaction vessel, and the prepared nano silver particles have wide size distribution and poor consistency and stability among batches. More importantly, the concentration of silver salt used is low, not exceeding 0.1M, in order to provide a uniform morphology and size of the final product. The nano silver sol prepared in the way has the problems of very low solid content, wide particle size distribution of products, uneven appearance, poor performance stability and consistency and the like.
By adopting the technical scheme of the invention, the advantages of rapid microwave heating, ultrasonic acoustic cavitation effect and selective desalination of a reverse osmosis membrane are comprehensively utilized, and the continuous and stable preparation of the high-solid-content nano silver is realized by applying the high-concentration silver salt precursor and performing division nucleation and growth processes. By adopting the preparation device, a large amount of stable silver nano seeds can be prepared in a microwave reactor by virtue of the characteristics of high microwave heating speed and uniform heating, the silver seeds grow under the action of ultrasonic acoustic cavitation in a subsequent probe type ultrasonic reactor, and the silver nano particles with required size are obtained by connecting a plurality of ultrasonic growth units in series.
As a further improvement of the invention, the ultrasonic growth combination device comprises 2-10 ultrasonic growth units.
As a further improvement of the invention, in the ultrasonic growth unit, the silver salt mixed liquid raw material container is connected with the inlet of the ultrasonic reactor through a peristaltic pump.
As a further improvement of the invention, the device for continuously preparing the high-solid-content nano silver further comprises a reverse osmosis membrane desalting device, a concentration device, a waste liquid tank and a silver sol storage container, wherein an outlet of the ultrasonic stirring growth device is connected with an inlet of the reverse osmosis membrane desalting device, an outlet of the reverse osmosis membrane desalting device is connected with an inlet of the concentration device and the waste liquid tank, and an outlet of the concentration device is connected with the silver sol storage container. The reverse osmosis membrane desalting device is a desalting device composed of reverse osmosis membranes, and can selectively remove inorganic salts in the nano silver sol to realize product purification. By adopting the technical scheme, the obtained silver nanoparticle solution is subjected to impurity removal by a reverse osmosis membrane desalting device, and the nano silver sol with higher solid content is obtained by a concentration device; the purified nano silver sol is subjected to concentration by a concentration device to remove redundant solvent, so that the high-solid-content nano silver sol with the mass fraction of 30-80% of silver can be prepared and stored in a silver sol storage tank, and waste liquid and impurities are collected in a waste material tank.
As a further improvement of the invention, the concentration device is a reduced pressure distillation device, a filtering device or other concentration devices.
As a further improvement of the invention, the alcohol raw material container and the silver salt mixed solution raw material container are respectively connected with the feed inlet of the impinging stream mixer through peristaltic pumps.
As a further improvement of the invention, a stirring device is arranged in the raw material container.
The device for continuously preparing the high-solid-content nano silver in the technical scheme is a set of reaction system suitable for industrial production and used for continuously and rapidly preparing the nano silver. The reaction system has the outstanding advantages of fast mixing, fast heating and temperature rising speed, continuity, stability, strong controllability, easy amplification, good energy-saving effect and the like, and is a set of reaction system suitable for industrial production of nano silver. Particularly, the reaction system has strong universality and can be suitable for industrial production of a plurality of chemical liquid phase reactions with high reaction speed and high requirements on three-pass.
The invention also discloses a method for continuously preparing the high-solid-content nano silver, which adopts the device for continuously preparing the high-solid-content nano silver to prepare the high-solid-content nano silver and comprises the following steps:
step S1, pouring a mixed solution of silver salt, a surfactant and water into a silver salt mixed solution raw material container, and stirring;
s2, pumping the raw materials in the alcohol raw material container and one silver salt mixed solution raw material container into an impinging stream mixer for mixing; preferably, the raw materials in the alcohol raw material container and one silver salt mixed liquid raw material container are mixed by flowing into the impinging stream mixer at a constant flow rate.
S3, when liquid flows out of the microwave reactor, starting microwaves for heating for 0.5-30min at the heating temperature of 50-100 ℃;
s4, when the silver seed sol in the microwave reactor flows into the ultrasonic reactor of the ultrasonic growth combination device, starting ultrasonic waves, and introducing the silver salt mixed solution raw material in the silver salt mixed solution raw material container of the ultrasonic growth unit into the ultrasonic reactor for reaction to grow the silver seeds;
s5, in the ultrasonic growth combination device, after the silver seeds grow to the required particle size in multiple stages, the silver seeds flow into an ultrasonic stirring growth container, and further react under the double actions of ultrasonic and stirring to completely consume the silver salt raw material;
and S6, allowing the product generated in the step S5 to flow into a reverse osmosis membrane desalting device, removing reaction impurities, allowing the product to flow into a concentrating device, concentrating to obtain silver sol with the solid content of 30-80%, and allowing the concentrated silver sol to flow into a silver sol storage container to obtain the high-solid-content nano silver.
As a further improvement of the invention, the silver salt is at least one of silver nitrate and silver acetate.
As a further improvement of the invention, the concentration of the silver salt in the silver salt mixed solution is 0.1mol/L-5mol/L.
As a further improvement of the invention, the alcohol is a mixture of one or more of methanol, ethanol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol, polyethylene glycol.
As a further improvement of the invention, the surfactant is one or a mixture of more of fatty acid, sodium polyacrylate, polyacrylic acid, polyvinylpyrrolidone, lauric acid, cellulose, citric acid, sodium citrate, oleylamine, hydroxyethyl cellulose, cetyltrimethylammonium chloride;
as a further improvement of the present invention, the water is distilled water or ultrapure water.
As a further improvement of the invention, in the step S2, the flow rate of the raw materials of the alcohol raw material container and the silver salt mixed liquid raw material container flowing into the impinging stream mixer is 0.1-50L/min.
As a further improvement of the invention, in step S5, in the ultrasonic growth combined device, the flow rate of the raw material of the silver salt mixed liquid raw material container in each ultrasonic growth unit flowing into the ultrasonic reactor is 0.1-30L/min.
Compared with the prior art, the invention has the following beneficial effects:
firstly, by adopting the technical scheme of the invention, the advantages of rapid microwave heating temperature rise, ultrasonic acoustic cavitation effect and the like are comprehensively utilized, the continuous and stable preparation of the high-solid-content nano silver is realized by adopting a high-concentration silver salt precursor through a continuous production mode and through the processes of segmentation nucleation and growth, and the preparation method has the advantages of continuity, divisible nucleation and growth, high precursor concentration, high production efficiency, good stability, strong controllability, easiness in amplification and the like, and is particularly suitable for industrial large-scale preparation of silver nano particles with good consistency and stability.
Secondly, the technical scheme of the invention has the advantages of simple process, strong operation controllability, narrow size distribution of nano silver particles, stable product performance, easy mass production, low energy consumption and the like, and has strong industrialization conditions and prospects.
Thirdly, the reaction system and the preparation method of the technical scheme of the invention have strong universality and are also suitable for preparation of other similar nano materials which can be prepared by wet chemical reaction, including but not limited to nano metal gold, nickel, copper and other nano particles. The silver nanoparticles prepared by the device and the method have the characteristics of uniform size, uniform appearance, adjustable size, high solid content and less impurities.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for continuously preparing high-solid-content nano silver according to example 1 of the present invention.
Fig. 2 is a schematic structural diagram of an ultrasonic growth unit in embodiment 1 of the present invention.
Fig. 3 is a TEM image of silver nanoparticles prepared in example 2 of the present invention.
Fig. 4 is a TEM image of silver nanoparticles prepared in example 3 of the present invention.
Fig. 5 is a TEM image of silver nanoparticles prepared in example 4 of the present invention.
The reference numerals include:
the method comprises the following steps of 1-alcohol raw material dissolving tank, 2-first peristaltic pump, 3-impinging stream mixer, 4-second peristaltic pump, 5-microwave reactor, 6-first silver salt mixed solution raw material dissolving tank, 7-probe type ultrasonic reactor, 8-third peristaltic pump, 9-second silver salt mixed solution raw material dissolving tank, 10-ultrasonic growth combination device, 11-ultrasonic stirring growth tank, 12-reverse osmosis membrane desalting device, 13-concentration device, 14-waste tank and 15-silver sol storage tank.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Example 1
As shown in fig. 1 and fig. 2, an apparatus for continuously preparing high solid content nano silver comprises a raw material container, an impinging stream mixer 3, a microwave reactor 5, an ultrasonic growth combination device 10, an ultrasonic agitation growth tank 11, a reverse osmosis membrane desalination device 12, a concentration device 13, a waste liquid tank 14 and a silver sol storage tank 15, wherein the raw material container comprises an alcohol raw material dissolution tank 1 and a plurality of silver salt mixed liquid raw material containers, and the silver salt mixed liquid raw material containers at least comprise a first silver salt mixed liquid raw material dissolution tank 6 and a second silver salt mixed liquid raw material dissolution tank 9; the alcohol raw material dissolving tank 1 is connected with a feed inlet of an impinging stream mixer 3 through a first peristaltic pump 2, the first silver salt mixed solution raw material tank is connected with a feed inlet of the impinging stream mixer 3 through a second peristaltic pump 4, a discharge port of the impinging stream mixer 3 is connected with a microwave reactor 5, an outlet of the microwave reactor 5 is connected with an inlet of an ultrasonic growth combination device 10, and an outlet of the ultrasonic growth combination device 10 is connected with an ultrasonic stirring growth groove 11. The outlet of the ultrasonic stirring growth tank 11 is connected with the inlet of a reverse osmosis membrane desalting device 12, the outlet of the reverse osmosis membrane desalting device 12 is connected with the inlet of a concentration device 13 and a waste liquid tank 14, and the outlet of the concentration device 13 is connected with a silver sol storage tank 15.
As shown in fig. 1 and fig. 2, the ultrasonic growth combination apparatus 10 includes at least two ultrasonic growth units connected in series, each ultrasonic growth unit is composed of a probe-type ultrasonic reactor 7 and a silver salt mixed solution raw material container, i.e., a second silver salt mixed solution raw material dissolving tank 9, in each ultrasonic growth unit, an outlet of the second silver salt mixed solution raw material dissolving tank 9 is connected to an inlet of the probe-type ultrasonic reactor 7 through a third peristaltic pump 8, and the probe-type ultrasonic reactors 7 of two adjacent ultrasonic growth units are connected to each other. A stirring device is arranged in the raw material container, and a corundum glass spiral pipe is arranged in the microwave reactor 5; the concentration device 13 is a reduced pressure distillation device, a filtering device or other concentration devices.
Preferably, the ultrasonic growth combination device 10 comprises 2 to 10 ultrasonic growth units. In the ultrasonic growth unit, each second silver salt mixed solution raw material dissolving tank 9 is connected with an inlet of a probe type ultrasonic reactor 7 through a peristaltic pump.
The devices are connected together as shown in figure 1 to form a set of reaction system for continuously and rapidly preparing nano silver, which is suitable for industrial production.
The invention also discloses a method for continuously preparing the high-solid-content nano silver, which adopts the device for continuously preparing the high-solid-content nano silver to prepare the high-solid-content nano silver and comprises the following steps:
and S1, pouring a mixed solution of silver salt, a surfactant and water into the first silver salt mixed solution raw material dissolving tank 6 and the second silver salt mixed solution raw material dissolving tank 9, and starting a stirrer to fully stir and mix. The silver salt is one of silver nitrate and silver acetate, and the concentration range of the silver salt is between 0.1mol/L and 5mol/L. The alcohol is one or more of methanol, ethanol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol and polyethylene glycol; the surfactant is one or more of fatty acid, sodium polyacrylate, polyacrylic acid, polyvinylpyrrolidone, lauric acid, cellulose, citric acid, sodium citrate, oleylamine, hydroxyethyl cellulose and hexadecyl trimethyl ammonium chloride, and the water is distilled water or ultrapure water;
and S2, starting the first peristaltic pump 2 and the second peristaltic pump 4 to introduce the raw materials in the alcohol raw material dissolving tank 1 and the first silver salt mixed liquid raw material dissolving tank 6 into the impinging stream mixer 3 for mixing, so as to realize the rapid and uniform mixing of the materials. The flow control range of the liquid in the alcohol raw material dissolving tank 1 and the first silver salt mixed solution raw material dissolving tank 6 is 0.1-50L/min;
s3, when liquid flows out of the microwave reactor 5, starting microwaves for heating for 0.5-30min at the heating temperature of 50-100 ℃;
s4, when the silver seed sol in the microwave reactor 5 flows into a probe type ultrasonic reactor 7 of the ultrasonic growth combination device 10, starting ultrasonic waves, and starting a third peristaltic pump 8 to introduce silver salt mixed liquid raw materials (silver salt concentration is 0.1-5 mol/L) in a second silver salt mixed liquid raw material dissolving tank 9 of the ultrasonic growth unit into the probe type ultrasonic reactor 7 for reaction so as to grow silver seeds;
s5, in the ultrasonic growth combination device 10, after the silver seeds grow to the required particle size in multiple stages, the silver seeds flow into an ultrasonic stirring growth container, and further react under the double actions of ultrasonic and stirring to completely consume silver salt raw materials;
and S6, enabling the product generated in the step S5 to flow into a reverse osmosis membrane desalting device 12, removing reaction impurities, then flowing into a concentration device 13, concentrating to enable the solid content of the silver sol to reach 30% -80%, and enabling the concentrated silver sol to flow into a silver sol storage tank 15 to obtain the high-solid-content nano silver.
Example 2
The continuous reaction system and method provided in example 1 were used to prepare nano-silver, comprising the following steps:
putting a certain amount of glycol into an alcohol raw material dissolving tank 1, adding a certain amount of silver nitrate, ultrapure water and polyvinylpyrrolidone into a first silver salt mixed solution raw material dissolving tank 6 and a second silver salt mixed solution raw material dissolving tank 9 of each ultrasonic growth unit in an ultrasonic growth combined device 10 according to a certain proportion, and stirring for 30min to fully dissolve and mix; wherein the concentration of silver nitrate in the first silver salt mixed solution raw material dissolving tank 6 is 0.5mol/L. The concentration of silver nitrate in the second silver salt mixed solution raw material dissolving tank 9 of each ultrasonic growth unit in the ultrasonic growth combination device 10 is 0.1mol/L.
And starting the first peristaltic pump 2 and the second peristaltic pump 4, setting the flow rate to be 1L/min, and enabling the mixed liquid in the alcohol raw material dissolving tank 1 and the first silver salt mixed liquid raw material dissolving tank 6 to flow into the impinging stream mixer 3 in equal volume so as to quickly and uniformly mix the materials.
When liquid flows out of the microwave reactor 5, the microwave heating is started immediately, the heating time of the materials in the microwave reactor 5 is set to be 10min, and the temperature is controlled to be 60 ℃.
When the silver seed sol in the microwave reactor 5 flows into the probe type ultrasonic reactor 7, the ultrasonic and third peristaltic pump 8 is started, and the silver nitrate (0.1 mol/L) solution in the second silver salt mixed solution raw material dissolving tank 9 is introduced at 0.5L/min to grow the silver seeds. The silver sol growing in the probe type ultrasonic reactor 7 enters the probe type ultrasonic reactor 7 of the next ultrasonic growth unit, ultrasonic waves and a peristaltic pump are started, and the silver nitrate solution (0.1 mol/L) in the second silver salt mixed solution raw material dissolving tank 9 is introduced at the same flow rate of 0.5L/min, so that the silver seeds grow further. In this way, in the ultrasonic growth combination device 10, the silver seeds grow to the required particle size through 3 ultrasonic growth units connected in series, and then flow into the ultrasonic stirring growth tank, and the silver nitrate is consumed in further reaction under the double actions of ultrasonic and stirring. The finally produced product flows into a reverse osmosis membrane desalination device 12, and flows into a concentration device 13 after reaction impurities are removed. After concentration, the silver sol flows into a silver sol storage tank 15 to obtain the final silver sol, the silver particle size is about 20nm, and the solid content is 30%. Fig. 3 is a TEM image of the silver nanoparticles prepared in this example, from which it can be seen that the obtained silver nanoparticles have a uniform particle size.
Example 3
The continuous reaction system and method provided in example 1 were used to prepare nano-silver, including the following steps:
a certain amount of glycol and ethanol are placed in an alcohol raw material dissolving tank 1, a certain amount of silver acetate, ultrapure water and trisodium citrate are added into a first silver salt mixed solution raw material dissolving tank 6 and a second silver salt mixed solution raw material dissolving tank 9 of each ultrasonic growth unit in an ultrasonic growth combined device 10 according to a certain proportion, and the mixture is stirred for 30min to be fully dissolved and mixed. Wherein, the concentration of the silver acetate in the first silver salt mixed liquid raw material dissolving tank 6 is 2mol/L. The concentration of silver acetate in the second silver salt mixed liquid raw material dissolving tank 9 of each ultrasonic growth unit in the ultrasonic growth combination device 10 is 1mol/L.
And starting the first peristaltic pump 2 and the second peristaltic pump 4, setting the flow rate to be 6L/min, and enabling the mixed liquid in the alcohol raw material dissolving tank 1 and the first silver salt mixed liquid raw material dissolving tank 6 to flow into the impinging stream mixer 3 in equal volume so as to quickly and uniformly mix the materials.
When liquid flows out of the microwave reactor 5, the microwave heating is started immediately, the heating time of the materials in the microwave reactor 5 is set to be 10min, and the temperature is controlled to be 70 ℃.
When the silver seed sol in the microwave reactor 5 flows into the probe type ultrasonic reactor 7, the ultrasonic waves and the third peristaltic pump 8 are started, and the silver acetate (1 mol/L) solution in the second silver salt mixed solution raw material dissolving tank 9 is introduced at 2L/min to grow the silver seeds. The silver sol growing in the probe type ultrasonic reactor 7 enters the probe type ultrasonic reactor 7 of the next ultrasonic growth unit, ultrasonic waves and a peristaltic pump are started, and the silver acetate solution (1 mol/L) in the second silver salt mixed solution raw material dissolving tank 9 is introduced at the same flow rate of 2L/min, so that the silver seeds grow further. In this example, the ultrasonic growth assembly 10 includes 5 ultrasonic growth units. In the ultrasonic growth combination device 10, after the silver seeds grow to the required particle size through 5 grades, the silver seeds flow into the ultrasonic stirring growth tank, and the silver acetate is further completely consumed through the further reaction under the double actions of the ultrasonic and the stirring. The finally produced product flows into a reverse osmosis membrane desalting device 12, reaction impurities are removed, and the product flows into a concentration device 13. After concentration, the silver sol flows into a silver sol storage tank 1518 to obtain the final silver sol, the silver particle size is about 40nm, and the solid content is 50%. Fig. 4 is a TEM image of the silver nanoparticles prepared in this example, from which it can be seen that the obtained silver nanoparticles have a uniform particle size.
Example 4
The continuous reaction system and method provided in example 1 were used to prepare nano-silver, including the following steps:
a certain amount of glycerol is placed in the alcohol raw material dissolving tank 1, a certain amount of silver nitrate, ultrapure water and hydroxyethyl cellulose are added into the first silver salt mixed solution raw material dissolving tank 6 and the second silver salt mixed solution raw material dissolving tank 9 of each ultrasonic growth unit in the ultrasonic growth combined device 10 according to a certain proportion, and the mixture is stirred for 30min to be fully dissolved and mixed. Wherein the concentration of silver nitrate in the first silver salt mixed solution raw material dissolving tank 6 is 3mol/L. The concentration of silver nitrate in the second silver salt mixed liquid raw material dissolving tank 9 of each ultrasonic growth unit in the ultrasonic growth combination device 10 is 1.5mol/L.
And starting the first peristaltic pump 2 and the second peristaltic pump 4, setting the flow rate to be 30L/min, and enabling mixed liquid in the alcohol raw material dissolving tank 1 and the first silver salt mixed liquid raw material dissolving tank 6 to flow into the impinging stream mixer 3 in equal volume so as to quickly and uniformly mix the materials.
When liquid flows out of the microwave reactor 5, starting microwave heating immediately, setting the heating time of the material in the microwave reactor 5 to be 10min, and controlling the temperature to be 80 ℃;
when the silver seed sol in the microwave reactor 5 flows into the probe type ultrasonic reactor 7, the ultrasonic wave and the third peristaltic pump 8 are started, and the silver nitrate solution (1.5 mol/L) in the second silver salt mixed solution raw material dissolving tank 9 is introduced at 10L/min to grow the silver seeds. The silver sol growing in the probe type ultrasonic reactor 7 enters the probe type ultrasonic reactor 7 of the next ultrasonic growth unit, ultrasonic waves and a peristaltic pump are started, and silver nitrate solution (1.5 mol/L) in a second silver salt mixed solution raw material dissolving tank 9 is introduced at the same flow rate of 10L/min, so that silver seeds grow further. The ultrasonic growth assembly 10 comprises 6 ultrasonic growth units. In the ultrasonic growth combination device 10, the silver seeds grow to the required particle size through 6 grades, then flow into the ultrasonic stirring growth tank, and further react under the double actions of ultrasonic and stirring to consume the silver acetate. The finally produced product flows into a reverse osmosis membrane desalination device 12, and flows into a concentration device 13 after reaction impurities are removed. After concentration, the silver sol flows into a stirring storage tank to obtain the final silver sol, the silver particle size is about 110nm, and the solid content is 70%. Fig. 5 is a TEM image of the silver nanoparticles prepared in this example, and it can be seen from fig. 5 that the silver nanoparticles obtained by the technical solution of the present invention have uniform particle size.
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 (10)
1. The device for continuously preparing the high-solid-content nano silver is characterized in that: the device comprises a raw material container, an impinging stream mixer, a microwave reactor, an ultrasonic growth combination device and an ultrasonic stirring growth device, wherein the raw material container comprises an alcohol raw material container and a plurality of silver salt mixed solution raw material containers; the ultrasonic growth combination device comprises at least two ultrasonic growth units which are connected in series, each ultrasonic growth unit comprises an ultrasonic reactor and a silver salt mixed liquid raw material container, in each ultrasonic growth unit, an outlet of the silver salt mixed liquid raw material container is connected with an inlet of the ultrasonic reactor, and the ultrasonic reactors of two adjacent ultrasonic growth units are connected with each other;
pumping the raw materials in the alcohol raw material container and the silver salt mixed solution raw material container into an impinging stream mixer for mixing, then entering a microwave reactor for microwave heating reaction to obtain silver seed sol, entering the silver seed sol heated by the microwave into an ultrasonic reactor of an ultrasonic growth combination device, simultaneously entering the silver salt mixed solution of the silver salt mixed solution raw material container of the ultrasonic growth unit into the ultrasonic reactor for further growing the silver seeds, in the ultrasonic growth combination device, after the silver seeds are grown to the required particle size in a multistage manner, flowing into an ultrasonic stirring growth device, further reacting under the dual action of ultrasound and stirring, and completely consuming the silver salt raw material; the silver salt mixed solution is a mixed solution of silver salt, a surfactant and water.
2. The apparatus for continuously preparing high solid content nano silver according to claim 1, wherein: the ultrasonic growth combined device comprises 2-10 ultrasonic growth units.
3. The apparatus for continuously preparing high solid content nano silver according to claim 1, wherein: in the ultrasonic growth unit, a silver salt mixed solution raw material container is connected with an inlet of an ultrasonic reactor through a peristaltic pump.
4. The apparatus for continuously preparing high solid content nano silver according to any one of claims 1~3 wherein: the ultrasonic stirring growth device comprises an ultrasonic stirring growth device, a reverse osmosis membrane desalting device, a concentration device, a waste liquid tank and a silver sol storage container, wherein an outlet of the ultrasonic stirring growth device is connected with an inlet of the reverse osmosis membrane desalting device, an outlet of the reverse osmosis membrane desalting device is connected with an inlet of the concentration device and the waste liquid tank, and an outlet of the concentration device is connected with the silver sol storage container.
5. The apparatus for continuously preparing high solid content nano silver according to claim 4, wherein: the alcohol raw material container and the silver salt mixed solution raw material container are respectively connected with a feed inlet of the impinging stream mixer through peristaltic pumps.
6. The apparatus for continuously preparing high solid content nano silver according to claim 4, wherein: a stirring device is arranged in the raw material container, and a corundum glass spiral tube is arranged in the microwave reactor; the concentration device is a reduced pressure distillation device, a filtering device or other concentration devices.
7. A method for continuously preparing high-solid-content nano silver is characterized by comprising the following steps: the device for continuously preparing high-solid-content nano silver, which is prepared by the method as claimed in claim 4, comprises the following steps:
step S1, pouring a mixed solution of silver salt, a surfactant and water into a silver salt mixed solution raw material container, and stirring;
s2, introducing the raw materials in the alcohol raw material container and one of the silver salt mixed solution raw material containers into an impinging stream mixer for mixing;
s3, when liquid flows out of the microwave reactor, starting microwaves for heating for 0.5-30min at the heating temperature of 50-100 ℃;
s4, when the silver seed sol in the microwave reactor flows into the ultrasonic reactor of the ultrasonic growth combination device, starting ultrasonic waves, and introducing the silver salt mixed solution raw material in the silver salt mixed solution raw material container of the ultrasonic growth unit into the ultrasonic reactor for reaction to grow the silver seeds;
s5, in the ultrasonic growth combination device, after the silver seeds grow to the required particle size in multiple stages, the silver seeds flow into an ultrasonic stirring growth container, and further react under the double actions of ultrasonic and stirring to completely consume silver salt raw materials;
and S6, enabling the product generated in the step S5 to flow into a reverse osmosis membrane desalting device, removing reaction impurities, then flowing into a concentration device, concentrating to enable the solid content of the silver sol to reach 30% -80%, and enabling the concentrated silver sol to flow into a silver sol storage container to obtain the high-solid-content nano silver.
8. The method for continuously preparing high-solid-content nano silver according to claim 7, which is characterized in that: the silver salt is at least one of silver nitrate and silver acetate, and the concentration of the silver salt in the silver salt mixed solution is 0.1-5 mol/L.
9. The method for continuously preparing high-solid-content nano silver according to claim 8, characterized by comprising the following steps: the alcohol is one or more of methanol, ethanol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol, and polyethylene glycol; the surfactant is one or more of fatty acid, sodium polyacrylate, polyacrylic acid, polyvinylpyrrolidone, lauric acid, cellulose, citric acid, sodium citrate, oleylamine, hydroxyethyl cellulose and hexadecyl trimethyl ammonium chloride, and the water is distilled water or ultrapure water.
10. The method for continuously preparing high-solid-content nano silver according to claim 8, characterized by comprising the following steps: in the step S2, the flow rate of the raw materials of the alcohol raw material container and the silver salt mixed solution raw material container flowing into the impinging stream mixer is 0.1-50L/min; in the step S5, in the ultrasonic growth combination device, the flow rate of the raw material of the silver salt mixed solution raw material container in each ultrasonic growth unit flowing into the ultrasonic reactor is 0.1-30L/min.
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