WO2025097577A1 - Flow-type preparation method and device for nano material - Google Patents
Flow-type preparation method and device for nano material Download PDFInfo
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- WO2025097577A1 WO2025097577A1 PCT/CN2023/142681 CN2023142681W WO2025097577A1 WO 2025097577 A1 WO2025097577 A1 WO 2025097577A1 CN 2023142681 W CN2023142681 W CN 2023142681W WO 2025097577 A1 WO2025097577 A1 WO 2025097577A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1856—Stationary reactors having moving elements inside placed in parallel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- the present invention relates to the field of nano material technology preparation, and in particular to a flow-type preparation method and device for nano material.
- micro-nano materials is a new system constructed or created according to certain rules based on nanoscale material units, including nano-array systems, mesoporous assembly systems, and thin film mosaic systems.
- nanoscale material units including nano-array systems, mesoporous assembly systems, and thin film mosaic systems.
- micro-nano materials generally refer to materials with sizes at the micron and nanometer levels, which have unique physical, chemical and biological properties.
- micro-nano materials can be single crystals, polycrystalline or amorphous structures.
- micro-nano materials include nanoparticles, nanowires, nanosheets, nanotubes, etc., and their size will not only affect the electronic, optical, thermal and other properties of micro-nano materials, but also their oxidation and reduction reactions.
- the core-shell structure of core-shell materials is an ordered assembly structure formed by one micro-nano material encapsulating another material through chemical bonds or other forces.
- the surface properties of the core particles can be tailored, the surface charge, functional groups and reaction characteristics of the core can be changed, and the stability and dispersibility of the core can be improved. Its unique structural characteristics can give the material different properties. It plays an important role in catalysis, photocatalysis, batteries, gas storage and separation.
- the commonly used preparation methods of existing nanometal particles include chemical reduction, vapor deposition, hydrothermal synthesis, sol-gel method, photochemical method, microemulsion method, template method, phase transfer method, ultrasonic method, etc.
- the methods such as the radiation method are easily affected by the reaction conditions during the preparation process, and the reaction process is difficult to accurately control.
- its morphology is usually restricted by the raw material container or the template during synthesis, and there are problems such as difficulty in continuous and large-scale preparation. These problems have hindered the mass production of nanomaterials.
- the present invention provides a flow-type preparation method and device for nanomaterials.
- an embodiment of the present invention provides a continuous preparation method of nanomaterials, which comprises:
- Step S4 drawing the unreacted complete solution from the solution collector through a reflux pipe and returning it to the reactant container;
- the micro-nano metal solution comprises micro-nano metal particles and a solvent.
- the micro-nano metal particles are bidirectional metal particles.
- the solvent includes deionized water and an organic solvent
- the organic solvent is an alcohol organic solvent or a ketone organic solvent.
- the flow rate of the metal ion solution and the micro-nano metal solution flowing into the reaction channel is 4:1 or 1:1 or 2:1.
- the reaction channel is controlled by applying any one of ultrasound, ultraviolet rays and high temperature to the metal ion solution and the micro-nano metal solution, so that the metal ion solution and the micro-nano metal solution are fully contacted and undergo a displacement reaction to form a reaction mixed solution.
- An embodiment of the present invention also provides a continuous preparation device for nanomaterials, including a reactant container, a particle collector arranged relative to the reactant container, a reaction channel connected to both the reactant container and the particle collector, a solution collector connected to the particle collector, and a reflux mechanism connected to both the solution collector and the reactant container.
- the reactant container includes a first reaction container, a first replenishing channel and a first reflux port arranged on two opposite sides of the first reaction container, a second reaction container spaced apart from the first reaction container, a second replenishing channel and a second reflux port arranged on two opposite sides of the second reaction container, and a connecting pipe connected to the bottom of both the first reaction container and the second reaction container.
- the reaction channel comprises a water bath ultrasonic container located between the connecting pipe and the particle collector and a hollow pipe located in the water bath ultrasonic container, one end of the hollow pipe is connected to the connecting pipe, and the other end of the hollow pipe is connected to the particle collector; the shape of the hollow pipe is linear or spiral.
- the particle collector includes a processing mechanism connected to one end of the hollow pipe away from the connecting pipe and a particle collecting mechanism detachably connected to the processing mechanism, the solution collector is connected to the particle collecting mechanism, and the reflux mechanism is simultaneously connected to the solution collector, the first reflux port and the second reflux port; the processing mechanism is a filter and/or a centrifuge.
- the metal ion solution and the micro-nano metal solution undergo a replacement reaction in the reaction channel under the setting of the communicating vessel principle to form a reaction mixture solution, and the reaction mixture solution includes a completely reacted solution and an unreacted solution.
- the reaction mixture solution then flows into a particle collector, and the completely reacted solution forms the required nanomaterial particles to be adsorbed in the particle collector; the unreacted solution flows into the solution collector, and the reflux mechanism extracts the unreacted solution in the solution collector, and the micro-nano metal solution and the metal ion solution in the unreacted solution are correspondingly refluxed into the corresponding reactant containers, and then the nanomaterial particles in the particle collector are collected.
- the flow-type preparation method and device of nanomaterials provided by the present invention realize large-scale flow-type continuous production of nanomaterial particles, and can directly collect the completely reacted particles, effectively improving production efficiency and output, and is particularly suitable for the industrial field. It has good industrialization prospects.
- FIG1 is a schematic flow diagram of a flow-type preparation method of a nanomaterial according to the present invention.
- FIG2 is a schematic structural diagram of a flow-type preparation device for nanomaterials according to the present invention.
- FIG3 is a schematic structural diagram of another embodiment of a flow-type preparation device for nanomaterials according to the present invention.
- the present invention provides a flow-type preparation method of nanomaterials, comprising:
- Step S1 placing one or more metal ion solutions and micro-nano metal solutions in a reactant container;
- Step S2 respectively controlling the metal ion solution and the micro-nano metal solution to flow into the reaction channel at a specific flow rate at the same time, so that the metal ion solution and the micro-nano metal solution are fully in contact and undergo a replacement reaction to form a reaction mixed solution, wherein the reaction mixed solution includes a completely reacted solution and an unreacted completely solution;
- Step S3 controlling the completely reacted solution and the unreacted completely reacted solution to flow into a particle collector and a solution collector respectively;
- Step S4 drawing the unreacted complete solution from the solution collector through a reflux pipe and returning it to the reactant container;
- Step S5 looping the process from step S1 to step S4.
- the micro-nano metal solution includes micro-nano metal particles and a solvent, wherein the micro-nano metal particles are bidirectional metal particles, such as copper particles, antimony particles, zinc particles and nickel particles.
- the solvent includes deionized water and an organic solvent, and the organic solvent is an alcohol organic solvent or a ketone organic solvent.
- the flow rate of the metal ion solution and the micro-nano metal solution flowing into the reaction channel is 4:1 or 1:1 or 2:1.
- the specific flow rate is set according to different reaction solutions. Different flow rate ratios, for example, the reactant containers are used to hold the solution containing copper salt after pretreatment and the reducing agent ascorbic acid and the protective agent polyvinyl pyrrolidone K30 to form a reduction system. Through the principle of communicating vessels, it can generally be determined according to specific experimental requirements and reaction conditions. The flow rate ratio can be selected as 1:1 or 2:1. If the reactant containers are used to hold silver ammonia solution and nano copper particles containing ethanol solution, the flow rates on both sides are controlled to 4:1 through the principle of communicating vessels.
- the reaction channel is controlled by applying any one of ultrasound, ultraviolet rays and high temperature to the metal ion solution and the micro-nano metal solution, so that the metal ion solution and the micro-nano metal solution can fully contact each other to undergo a replacement reaction.
- a flow-type preparation device 100 of nanomaterials includes a reactant container 1, a particle collector 2 arranged relatively to the reactant container 1, a reaction channel 3 connected to both the reactant container 1 and the particle collector 2, a solution collector 4 connected to the particle collector 2, and a reflux mechanism 5 connected to both the solution collector 4 and the reactant container 1.
- the reactant container 1 can contain liquid or solid-liquid mixture.
- the reactant container 1 is connected to the reaction channel 3, and the solution stored in the reactant container 1 will flow into the reaction channel 3 at the same time or enter the reaction channel 3 in sequence according to the set sequence.
- the end of the reaction channel 3 is connected to the particle collector 2.
- the reactant container 1 includes a first reaction container 11, a first replenishing channel 12 and a first reflux port 13 arranged on two opposite sides of the first reaction container 11, a second reaction container 14 spaced apart from the first reaction container 11, a second replenishing channel 15 and a second reflux port 16 arranged on two opposite sides of the second reaction container 14, and a connecting pipe 17 connected to the bottom of both the first reaction container 11 and the second reaction container 14.
- the reaction container is provided with two, namely a first reaction container 11 and a second reaction container 12.
- the reaction container 14 is not limited thereto, and its specific number can be adjusted according to actual conditions, and the reaction container can contain liquid or solid-liquid mixture.
- the temperature of the reaction solution can be controlled in the reaction container and stirring can be applied to make the reaction solution uniform; at the same time, the first reaction container 11 and the second reaction container 1 are respectively provided with a first supplementary channel 12 and a second supplementary channel 15 on the periphery thereof, so that the reactants can be supplemented in time and quickly to avoid the phenomenon of insufficient reactants.
- the reaction channel 3 includes a water bath ultrasonic container 31 located between the connecting pipe 17 and the particle collector 4 and a hollow pipe 32 located in the water bath ultrasonic container 31, one end of the hollow pipe 32 is connected to the connecting pipe 17, and the other end of the hollow pipe 32 is connected to the particle collector 4.
- the shape of the hollow pipe 32 is linear or spiral, and in order to more conveniently control the flow rate of the reaction solution in the hollow pipe 32, a flow rate control valve can be added to the hollow pipe 32.
- the water bath ultrasonic container 31 contains an aqueous solution, and the hollow pipe 32 is partially immersed in the aqueous solution contained in the water bath ultrasonic container 31, and the water bath ultrasonic container 31 can apply ultrasound or temperature control to the hollow pipe 32 to promote the metal ion solution to fully contact with the micro-nano metal solution to cause a replacement reaction.
- the particle collector 2 includes a processing mechanism 21 connected to one end of the hollow pipe 32 away from the connecting pipe 17 and a particle collecting mechanism 22 that is detachably connected to the processing mechanism 21, the solution collector 4 is connected to the particle collecting mechanism 22, and the reflux mechanism 5 is simultaneously connected to the solution collector 4, the first reflux port 13 and the second reflux port 16.
- the number of the particle collecting mechanism 22 can be one or more, and is not limited thereto.
- the processing mechanism 21 is a suction filter and/or a centrifuge. If the processing mechanism 21 is a suction filter, the nano material particles are deposited in the particle collecting mechanism 22, thereby achieving collection; if the processing mechanism 21 is a centrifuge, the nano material particles are deposited in the inner side wall of the particle collecting mechanism 22, thereby achieving collection.
- the particle collection mechanism 22 and the processing mechanism 21 form a detachable connection, which is convenient for changing different collection modes to meet different collection needs.
- the collected particles can also be removed by disassembly, which reduces time cost and improves production efficiency.
- the flow-type preparation device 100 of nanomaterials provided by the present invention can also disassemble the solution collector 4 and the reflux mechanism 5, and can still realize the large-scale flow-type continuous production of the above-mentioned nanomaterial particles.
- the metal ion solution and the micro-nano metal solution undergo a replacement reaction in the reaction channel under the setting of the communicating vessel principle to form a reaction mixed solution
- the reaction mixed solution includes a reaction complete solution and an unreacted complete solution
- the reaction mixed solution flows into the particle collector, and the reaction complete solution forms the required nanomaterial particles to be adsorbed in the particle collector;
- the unreacted solution flows into the solution collector, the reflux mechanism extracts the unreacted solution in the solution collector, and the micro-nano metal solution and the metal ion solution in the unreacted solution are correspondingly refluxed into the corresponding reactant container, and then the nanomaterial particles in the particle collector are collected.
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Abstract
Description
相关申请的交叉引用CROSS-REFERENCE TO RELATED APPLICATIONS
本申请要求于2023年11月08日提交中国专利局的申请号为202311488007.8、名称为《一种纳米材料的流动式制备方法及装置》的中国专利申请的优先权,其全部内容通过引用结合在本申请中。This application claims the priority of Chinese patent application No. 202311488007.8, filed with the Chinese Patent Office on November 8, 2023, and entitled "A Flowing Preparation Method and Device for Nanomaterials", the entire contents of which are incorporated by reference in this application.
本发明设计纳米材料技术制备领域，尤其涉及到一种纳米材料的流动式制备方法及装置。The present invention relates to the field of nano material technology preparation, and in particular to a flow-type preparation method and device for nano material.
微纳米材料的纳米结构是以纳米尺度的物质单元为基础按一定规律构筑或营造的一种新体系，其中包括纳米阵列体系、介孔组装体系、薄膜嵌镶体系。从而导致了纳米微粒的热、磁、光、敏感特性和表面稳定性等不同于正常粒子，使其应用前景使用广泛；微纳米材料一般是指尺寸在微米和纳米级别的材料，具有独特的物理、化学和生物学性质，其中，微纳米材料可以是单一晶体、多晶体或非晶体结构。常见的微纳米材料包括纳米颗粒、纳米线、纳米片、纳米管等，其尺寸的大小不仅会影响微纳米材料的电子、光学、热学等性质还会影响其氧化和还原的反应。例如，核壳材料的核壳结构是由一种微纳米材料通过化学键或其它作用力将另一种材料包覆起来形成的有序组装结构。通过包覆技术能对内核微粒表面性质进行剪裁，改变内核表面电荷、官能团和反应特性，提高内核的稳定性与分散性，其独特的结构特性能够赋予材料不同的性质。在催化、光催化、电池、气体存储及分离等方面发挥着重要作用。The nanostructure of micro-nano materials is a new system constructed or created according to certain rules based on nanoscale material units, including nano-array systems, mesoporous assembly systems, and thin film mosaic systems. As a result, the thermal, magnetic, optical, sensitive properties and surface stability of nanoparticles are different from normal particles, making their application prospects widely used; micro-nano materials generally refer to materials with sizes at the micron and nanometer levels, which have unique physical, chemical and biological properties. Among them, micro-nano materials can be single crystals, polycrystalline or amorphous structures. Common micro-nano materials include nanoparticles, nanowires, nanosheets, nanotubes, etc., and their size will not only affect the electronic, optical, thermal and other properties of micro-nano materials, but also their oxidation and reduction reactions. For example, the core-shell structure of core-shell materials is an ordered assembly structure formed by one micro-nano material encapsulating another material through chemical bonds or other forces. Through the coating technology, the surface properties of the core particles can be tailored, the surface charge, functional groups and reaction characteristics of the core can be changed, and the stability and dispersibility of the core can be improved. Its unique structural characteristics can give the material different properties. It plays an important role in catalysis, photocatalysis, batteries, gas storage and separation.
然而，现有的纳米金属颗粒常用的制备方法有化学还原法、气相沉积法、水热合成法、溶胶凝胶法、光化学法、微乳液法、模板法、相转移法、超声法 和辐射法等方法，由于在制备过程中，容易受到反应条件的影响，反应过程难以精确控制，同时其形貌通常受制于原料容器或合成时的模板，存在着难以连续、大规模制备等问题。这些问题对纳米材料的量产化造成了阻碍。However, the commonly used preparation methods of existing nanometal particles include chemical reduction, vapor deposition, hydrothermal synthesis, sol-gel method, photochemical method, microemulsion method, template method, phase transfer method, ultrasonic method, etc. The methods such as the radiation method are easily affected by the reaction conditions during the preparation process, and the reaction process is difficult to accurately control. At the same time, its morphology is usually restricted by the raw material container or the template during synthesis, and there are problems such as difficulty in continuous and large-scale preparation. These problems have hindered the mass production of nanomaterials.
因此，亟需提供一种纳米材料的流动式制备方法及装置解决上述问题。Therefore, there is an urgent need to provide a flow-type preparation method and device for nanomaterials to solve the above problems.
发明内容Summary of the invention
针对相关技术的不足，本发明提出一种纳米材料的流动式制备方法及装置。In view of the deficiencies in the related art, the present invention provides a flow-type preparation method and device for nanomaterials.
为了解决上述技术问题，本发明实施例提供了一种纳米材料的连续制备方法，其包括：In order to solve the above technical problems, an embodiment of the present invention provides a continuous preparation method of nanomaterials, which comprises:
步骤S1，在反应物容器内盛放一种或多种金属离子溶液与微纳级金属溶液；Step S1, placing one or more metal ion solutions and micro-nano metal solutions in a reactant container;
步骤S2，分别控制所述金属离子溶液与所述微纳级金属溶液按照特定的流速同时流入反应通道内，使得所述金属离子溶液和所述微纳级金属溶液进行充分接触并发生置换发应形成反应混合溶液，所述反应混合溶液包括反应完全溶液和未反应完全溶液；Step S2, respectively controlling the metal ion solution and the micro-nano metal solution to flow into the reaction channel at a specific flow rate at the same time, so that the metal ion solution and the micro-nano metal solution are fully in contact and undergo a replacement reaction to form a reaction mixed solution, wherein the reaction mixed solution includes a completely reacted solution and an unreacted completely solution;
步骤S3，控制所述反应完全溶液和所述未反应完全溶液分别流入颗粒收集器和溶液收集器中；Step S3, controlling the completely reacted solution and the unreacted completely reacted solution to flow into a particle collector and a solution collector respectively;
步骤S4，通过回流管从所述溶液收集器中汲取所述未反应完全溶液回流至所述反应物容器内；Step S4, drawing the unreacted complete solution from the solution collector through a reflux pipe and returning it to the reactant container;
步骤S5，循环所述步骤S1至步骤S4过程。Step S5, looping the process from step S1 to step S4.
优选的，所述微纳级金属溶液包括微纳级金属颗粒和溶剂。Preferably, the micro-nano metal solution comprises micro-nano metal particles and a solvent.
优选的，所述微纳级金属颗粒为双向金属颗粒。Preferably, the micro-nano metal particles are bidirectional metal particles.
优选的，所述溶剂为包括自去离子水和有机溶剂，所述有机溶剂为醇类有机溶剂或酮类有机溶剂。Preferably, the solvent includes deionized water and an organic solvent, and the organic solvent is an alcohol organic solvent or a ketone organic solvent.
优选的，所述金属离子溶液与所述微纳级金属溶液流入所述反应通道内的流速为4：1或1:1或2:1。Preferably, the flow rate of the metal ion solution and the micro-nano metal solution flowing into the reaction channel is 4:1 or 1:1 or 2:1.
优选的，所述反应通道通过对所述金属离子溶液和所述微纳级金属溶液施加超声、紫外线以及高温中的任意一种方式控制，以使得所述金属离子溶液和所述微纳级金属溶液进行充分接触并发生置换发应形成反应混合溶液。 Preferably, the reaction channel is controlled by applying any one of ultrasound, ultraviolet rays and high temperature to the metal ion solution and the micro-nano metal solution, so that the metal ion solution and the micro-nano metal solution are fully contacted and undergo a displacement reaction to form a reaction mixed solution.
本发明实施例还提供了一种纳米材料的连续制备装置，包括反应物容器、与所述反应物容器相对间隔设置的颗粒收集器、同时与所述反应物容器和所述颗粒收集器相连通的反应通道、与所述颗粒收集器连通的溶液收集器以及与同时与所述溶液收集器和反应物容器相连接的回流机构。An embodiment of the present invention also provides a continuous preparation device for nanomaterials, including a reactant container, a particle collector arranged relative to the reactant container, a reaction channel connected to both the reactant container and the particle collector, a solution collector connected to the particle collector, and a reflux mechanism connected to both the solution collector and the reactant container.
优选的，所述反应物容器包括第一反应容器、相对设置在所述第一反应容器相对两周侧的第一补充通道和第一回流口、与所述第一反应容器间隔设置的第二反应容器、相对设置在所述第二反应容器相对两周侧的第二补充通道和第二回流口以及同时与所述第一反应容器和所述第二反应容器底部相连通的连通管。Preferably, the reactant container includes a first reaction container, a first replenishing channel and a first reflux port arranged on two opposite sides of the first reaction container, a second reaction container spaced apart from the first reaction container, a second replenishing channel and a second reflux port arranged on two opposite sides of the second reaction container, and a connecting pipe connected to the bottom of both the first reaction container and the second reaction container.
优选的，所述反应通道包括位于所述连通管与所述颗粒收集器之间的水浴超声容器和位于水浴超声容器内的空心管道，所述空心管道一端与所述连通管连接，所述空心管道的另一端与所述颗粒收集器连接；所述空心管道的形状为直线型或螺旋型。Preferably, the reaction channel comprises a water bath ultrasonic container located between the connecting pipe and the particle collector and a hollow pipe located in the water bath ultrasonic container, one end of the hollow pipe is connected to the connecting pipe, and the other end of the hollow pipe is connected to the particle collector; the shape of the hollow pipe is linear or spiral.
优选的，所述颗粒收集器包括与所述空心管道远离所述连通管一端连接的处理机构和与所述处理机构形成可拆卸连接的颗粒收集机构，所述溶液收集器与颗粒收集机构相连接，所述回流机构同时与所述溶液收集器、所述第一回流口以及所述第二回流口相连接；所述处理机构为抽滤机和/或离心机。Preferably, the particle collector includes a processing mechanism connected to one end of the hollow pipe away from the connecting pipe and a particle collecting mechanism detachably connected to the processing mechanism, the solution collector is connected to the particle collecting mechanism, and the reflux mechanism is simultaneously connected to the solution collector, the first reflux port and the second reflux port; the processing mechanism is a filter and/or a centrifuge.
与相关技术相比，本发明提供的一种纳米材料的流动式制备方法及装置中，通过所述金属离子溶液与所述微纳级金属溶液在连通器原理的设定下，在反应通道中发生置换反应形成反应混合溶液，反应混合溶液包括反应完全溶液和未反应完全溶液，随后反应混合溶液流入颗粒收集器中，反应完全溶液形成所需要的纳米材料颗粒将吸附在颗粒收集器中；未反应完全的溶液流入溶液收集器中，回流机构抽取溶液收集器中的未反应完全的溶液，并将未反应完全溶液中的微纳级金属溶液与金属离子溶液对应回流入至对应的反应物容器中，随后对颗粒收集器中的纳米材料颗粒进行收集。通过本发明提供的一种纳米材料的流动式制备方法及装置，实现了纳米材料颗粒大批量流动式连续生产，同时能够直接收集反应完全的颗粒，有效提高生产效率与产量，尤其适用于工业领域， 有较好的产业化前景。Compared with the related art, in the flow-type preparation method and device of nanomaterials provided by the present invention, the metal ion solution and the micro-nano metal solution undergo a replacement reaction in the reaction channel under the setting of the communicating vessel principle to form a reaction mixture solution, and the reaction mixture solution includes a completely reacted solution and an unreacted solution. The reaction mixture solution then flows into a particle collector, and the completely reacted solution forms the required nanomaterial particles to be adsorbed in the particle collector; the unreacted solution flows into the solution collector, and the reflux mechanism extracts the unreacted solution in the solution collector, and the micro-nano metal solution and the metal ion solution in the unreacted solution are correspondingly refluxed into the corresponding reactant containers, and then the nanomaterial particles in the particle collector are collected. The flow-type preparation method and device of nanomaterials provided by the present invention realize large-scale flow-type continuous production of nanomaterial particles, and can directly collect the completely reacted particles, effectively improving production efficiency and output, and is particularly suitable for the industrial field. It has good industrialization prospects.
下面结合附图详细说明本发明。通过结合以下附图所作的详细描述，本发明的上述或其他方面的内容将变得更清楚和更容易理解。附图中：The present invention will be described in detail below in conjunction with the accompanying drawings. The above and other aspects of the present invention will become clearer and easier to understand through the detailed description made in conjunction with the following drawings. In the accompanying drawings:
图1为本发明一种纳米材料的流动式制备方法的流程示意图；FIG1 is a schematic flow diagram of a flow-type preparation method of a nanomaterial according to the present invention;
图2为本发明一种纳米材料的流动式制备装置的结构示意图；FIG2 is a schematic structural diagram of a flow-type preparation device for nanomaterials according to the present invention;
图3为本发明一种纳米材料的流动式制备装置另一实施方式的结构示意图。FIG3 is a schematic structural diagram of another embodiment of a flow-type preparation device for nanomaterials according to the present invention.
在此记载的具体实施方式\实施例为本发明的特定的具体实施方式，用于说明本发明的构思，均是解释性和示例性的，不应解释为对本发明实施方式及本发明范围的限制。除在此记载的实施例外，本领域技术人员还能够基于本申请权利要求书和说明书所公开的内容采用显而易见的其它技术方案，这些技术方案包括采用对在此记载的实施例的做出任何显而易见的替换和修改的技术方案，都在本发明的保护范围之内。The specific embodiments and examples described herein are specific embodiments of the present invention, which are used to illustrate the concept of the present invention, are explanatory and exemplary, and should not be interpreted as limiting the embodiments of the present invention and the scope of the present invention. In addition to the examples described herein, those skilled in the art can also adopt other obvious technical solutions based on the claims and the contents disclosed in the specification of this application, and these technical solutions include any obvious replacement and modification of the embodiments described herein, which are within the scope of protection of the present invention.
请参考图1所示，本发明提供的一种纳米材料的流动式制备方法，包括：Referring to FIG. 1 , the present invention provides a flow-type preparation method of nanomaterials, comprising:
步骤S1，在反应物容器内盛放一种或多种金属离子溶液与微纳级金属溶液；Step S1, placing one or more metal ion solutions and micro-nano metal solutions in a reactant container;
步骤S2，分别控制所述金属离子溶液与所述微纳级金属溶液按照特定的流速同时流入反应通道内，使得所述金属离子溶液和所述微纳级金属溶液进行充分接触并发生置换发应形成反应混合溶液，所述反应混合溶液包括反应完全溶液和未反应完全溶液；Step S2, respectively controlling the metal ion solution and the micro-nano metal solution to flow into the reaction channel at a specific flow rate at the same time, so that the metal ion solution and the micro-nano metal solution are fully in contact and undergo a replacement reaction to form a reaction mixed solution, wherein the reaction mixed solution includes a completely reacted solution and an unreacted completely solution;
步骤S3，控制所述反应完全溶液和所述未反应完全溶液分别流入颗粒收集器和溶液收集器中；Step S3, controlling the completely reacted solution and the unreacted completely reacted solution to flow into a particle collector and a solution collector respectively;
步骤S4，通过回流管从所述溶液收集器中汲取所述未反应完全溶液回流至所述反应物容器内；Step S4, drawing the unreacted complete solution from the solution collector through a reflux pipe and returning it to the reactant container;
步骤S5，循环所述步骤S1至步骤S4过程。Step S5, looping the process from step S1 to step S4.
在本实施例中，所述微纳级金属溶液包括微纳级金属颗粒和溶剂，所述微纳级金属颗粒为双向金属颗粒，如铜颗粒、锑颗粒、锌颗粒和镍颗粒中的一种 或多种。所述溶剂为包括自去离子水和有机溶剂，所述有机溶剂为醇类有机溶剂或酮类有机溶剂。In this embodiment, the micro-nano metal solution includes micro-nano metal particles and a solvent, wherein the micro-nano metal particles are bidirectional metal particles, such as copper particles, antimony particles, zinc particles and nickel particles. The solvent includes deionized water and an organic solvent, and the organic solvent is an alcohol organic solvent or a ketone organic solvent.
具体的，所述金属离子溶液与所述微纳级金属溶液流入所述反应通道内的流速为4：1或1:1或2:1，具体流速是根据不同的反应溶液设定不同的流速比例，例如，反应物容器分别用于盛放经过预处理后含有铜盐的溶液以及盛放还原剂抗坏血酸与保护剂聚乙烯吡咯烷酮K30组成还原体系，通过连通器原理，一般可根据具体实验要求和反应条件而定的，可选取流速比为1:1或2:1。若反应物容器分别用于盛放银氨溶液与含有乙醇溶液的纳米铜颗粒，通过连通器原理将两边流速控制为4:1。Specifically, the flow rate of the metal ion solution and the micro-nano metal solution flowing into the reaction channel is 4:1 or 1:1 or 2:1. The specific flow rate is set according to different reaction solutions. Different flow rate ratios, for example, the reactant containers are used to hold the solution containing copper salt after pretreatment and the reducing agent ascorbic acid and the protective agent polyvinyl pyrrolidone K30 to form a reduction system. Through the principle of communicating vessels, it can generally be determined according to specific experimental requirements and reaction conditions. The flow rate ratio can be selected as 1:1 or 2:1. If the reactant containers are used to hold silver ammonia solution and nano copper particles containing ethanol solution, the flow rates on both sides are controlled to 4:1 through the principle of communicating vessels.
在本实施例中，所述反应通道通过对所述金属离子溶液和所述微纳级金属溶液施加超声、紫外线以及高温中的任意一种方式控制，以使得所述金属离子溶液与所述微纳级金属溶液可以充分接触发生置换反应。In this embodiment, the reaction channel is controlled by applying any one of ultrasound, ultraviolet rays and high temperature to the metal ion solution and the micro-nano metal solution, so that the metal ion solution and the micro-nano metal solution can fully contact each other to undergo a replacement reaction.
请参考图2所示，本发明提供的一种纳米材料的流动式制备装置100，包括反应物容器1、与所述反应物容器1相对间隔设置的颗粒收集器2、同时与所述反应物容器1和所述颗粒收集器2相连通的反应通道3、与所述颗粒收集器2连通的溶液收集器4以及与同时与所述溶液收集器4和反应物容器1相连接的回流机构5。Please refer to Figure 2, a flow-type preparation device 100 of nanomaterials provided by the present invention includes a reactant container 1, a particle collector 2 arranged relatively to the reactant container 1, a reaction channel 3 connected to both the reactant container 1 and the particle collector 2, a solution collector 4 connected to the particle collector 2, and a reflux mechanism 5 connected to both the solution collector 4 and the reactant container 1.
上述结构中，所述反应物容器1内可以盛放液体，也可以是固液混合物。反应物容器1与反应通道3连接，反应物容器1内存放的溶液将同时汇入反应通道3内或根据所设置的先后顺序，依次进入反应通道3。所述反应通道3末端接入颗粒收集器2。In the above structure, the reactant container 1 can contain liquid or solid-liquid mixture. The reactant container 1 is connected to the reaction channel 3, and the solution stored in the reactant container 1 will flow into the reaction channel 3 at the same time or enter the reaction channel 3 in sequence according to the set sequence. The end of the reaction channel 3 is connected to the particle collector 2.
具体的，所述反应物容器1包括第一反应容器11、相对设置在所述第一反应容器11相对两周侧的第一补充通道12和第一回流口13、与所述第一反应容器11间隔设置的第二反应容器14、相对设置在所述第二反应容器14相对两周侧的第二补充通道15和第二回流口16以及同时与所述第一反应容器11和所述第二反应容器14底部相连通的连通管17。Specifically, the reactant container 1 includes a first reaction container 11, a first replenishing channel 12 and a first reflux port 13 arranged on two opposite sides of the first reaction container 11, a second reaction container 14 spaced apart from the first reaction container 11, a second replenishing channel 15 and a second reflux port 16 arranged on two opposite sides of the second reaction container 14, and a connecting pipe 17 connected to the bottom of both the first reaction container 11 and the second reaction container 14.
在本实施例中，所述反应容器设置为两个，分别为第一反应容器11和第二 反应容器14，但不限于此，其具体数量可以根据实际情况进行调整，且反应容器内可以盛放液体，也可以是固液混合物。另外，在反应容器内可以控制反应溶液温度并且可以施加搅拌，使反应溶液均匀；于此同时，所述第一反应容器11和所述第二反应容器1的周侧分别设置了第一补充通道12和第二补充通道15，可以及时、迅速对反应物进行补充，避免出现反应物出现不足的现象。In this embodiment, the reaction container is provided with two, namely a first reaction container 11 and a second reaction container 12. The reaction container 14 is not limited thereto, and its specific number can be adjusted according to actual conditions, and the reaction container can contain liquid or solid-liquid mixture. In addition, the temperature of the reaction solution can be controlled in the reaction container and stirring can be applied to make the reaction solution uniform; at the same time, the first reaction container 11 and the second reaction container 1 are respectively provided with a first supplementary channel 12 and a second supplementary channel 15 on the periphery thereof, so that the reactants can be supplemented in time and quickly to avoid the phenomenon of insufficient reactants.
进一步的，所述反应通道3包括位于所述连通管17与所述颗粒收集器4之间的水浴超声容器31和位于水浴超声容器31内的空心管道32，所述空心管道32一端与所述连通管17连接，所述空心管道32的另一端与所述颗粒收集器4连接。Furthermore, the reaction channel 3 includes a water bath ultrasonic container 31 located between the connecting pipe 17 and the particle collector 4 and a hollow pipe 32 located in the water bath ultrasonic container 31, one end of the hollow pipe 32 is connected to the connecting pipe 17, and the other end of the hollow pipe 32 is connected to the particle collector 4.
在本实施例中，所述空心管道32的形状为直线型或螺旋型，且为了更方便的控制所述空心管道32中反应溶液的流速，还可以在所述空心管道32上增加流速控制阀。此外，所述水浴超声容器31盛放有水溶液，所述空心管道32部分浸没于所述水浴超声容器31内盛放的水溶液当中，且所述水浴超声容器31可以对所述空心管道32施加超声或温度控制，以促使金属离子溶液与微纳级金属溶液充分接触发生置换反应。In this embodiment, the shape of the hollow pipe 32 is linear or spiral, and in order to more conveniently control the flow rate of the reaction solution in the hollow pipe 32, a flow rate control valve can be added to the hollow pipe 32. In addition, the water bath ultrasonic container 31 contains an aqueous solution, and the hollow pipe 32 is partially immersed in the aqueous solution contained in the water bath ultrasonic container 31, and the water bath ultrasonic container 31 can apply ultrasound or temperature control to the hollow pipe 32 to promote the metal ion solution to fully contact with the micro-nano metal solution to cause a replacement reaction.
更进一步的，所述颗粒收集器2包括与所述空心管道32远离所述连通管17一端连接的处理机构21和与所述处理机构21形成可拆卸连接的颗粒收集机构22，所述溶液收集器4与颗粒收集机构22相连接，所述回流机构5同时与所述溶液收集器4、所述第一回流口13以及所述第二回流口16相连接。Furthermore, the particle collector 2 includes a processing mechanism 21 connected to one end of the hollow pipe 32 away from the connecting pipe 17 and a particle collecting mechanism 22 that is detachably connected to the processing mechanism 21, the solution collector 4 is connected to the particle collecting mechanism 22, and the reflux mechanism 5 is simultaneously connected to the solution collector 4, the first reflux port 13 and the second reflux port 16.
在本实施例中，所述颗粒收集机构22的数量可以为一个或多个，且不限于此。另外，所述处理机构21为抽滤机和/或离心机，若所述处理机构21为抽滤机，则将纳米材料颗粒沉积在颗粒收集机构22中，从而实现收集；所述处理机构21为离心机，则将纳米材料颗粒沉积在颗粒收集机构22的内侧壁中，从而实现收集。In this embodiment, the number of the particle collecting mechanism 22 can be one or more, and is not limited thereto. In addition, the processing mechanism 21 is a suction filter and/or a centrifuge. If the processing mechanism 21 is a suction filter, the nano material particles are deposited in the particle collecting mechanism 22, thereby achieving collection; if the processing mechanism 21 is a centrifuge, the nano material particles are deposited in the inner side wall of the particle collecting mechanism 22, thereby achieving collection.
值得一提的是，所述颗粒收集机构22与所述处理机构21形成可拆卸连接，方便更换不同的收集模式以满足不同的收集需求，同时也可通过拆卸取出收集的颗粒，降低了时间成本，提高了生产效率。 It is worth mentioning that the particle collection mechanism 22 and the processing mechanism 21 form a detachable connection, which is convenient for changing different collection modes to meet different collection needs. At the same time, the collected particles can also be removed by disassembly, which reduces time cost and improves production efficiency.
需要说明的是，请参考图3所示，在另一实施方式中，本发明的提供的一种纳米材料的流动式制备装置100还可以将所述溶液收集器4和回流机构5拆卸，依旧可以实现上述纳米材料颗粒大批量流动式连续生产。It should be noted that, referring to FIG. 3 , in another embodiment, the flow-type preparation device 100 of nanomaterials provided by the present invention can also disassemble the solution collector 4 and the reflux mechanism 5, and can still realize the large-scale flow-type continuous production of the above-mentioned nanomaterial particles.
与相关技术相比，本发明提供的一种纳米材料的流动式制备方法及装置中，通过所述金属离子溶液与所述微纳级金属溶液在连通器原理的设定下，在反应通道中发生置换反应形成反应混合溶液，反应混合溶液包括反应完全溶液和未反应完全溶液，随后反应混合溶液流入颗粒收集器中，反应完全溶液形成所需要的纳米材料颗粒将吸附在颗粒收集器中；未反应完全的溶液流入溶液收集器中，回流机构抽取溶液收集器中的未反应完全的溶液，并将未反应完全溶液中的微纳级金属溶液与金属离子溶液对应回流入至对应的反应物容器中，随后对颗粒收集器中的纳米材料颗粒进行收集。通过本发明提供的一种纳米材料的流动式制备方法及装置，实现了纳米材料颗粒大批量流动式连续生产，同时能够直接收集反应完全的颗粒，有效提高生产效率与产量，尤其适用于工业领域，有较好的产业化前景。Compared with the related art, in the flow-type preparation method and device of nanomaterials provided by the present invention, the metal ion solution and the micro-nano metal solution undergo a replacement reaction in the reaction channel under the setting of the communicating vessel principle to form a reaction mixed solution, the reaction mixed solution includes a reaction complete solution and an unreacted complete solution, and then the reaction mixed solution flows into the particle collector, and the reaction complete solution forms the required nanomaterial particles to be adsorbed in the particle collector; the unreacted solution flows into the solution collector, the reflux mechanism extracts the unreacted solution in the solution collector, and the micro-nano metal solution and the metal ion solution in the unreacted solution are correspondingly refluxed into the corresponding reactant container, and then the nanomaterial particles in the particle collector are collected. Through the flow-type preparation method and device of nanomaterials provided by the present invention, large-scale flow-type continuous production of nanomaterial particles is realized, and at the same time, the particles that have reacted completely can be directly collected, which effectively improves production efficiency and output, and is particularly suitable for the industrial field, with good industrialization prospects.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何纂改、等同替换、改进等，均应包含在本发明的权利要求范围之内。 The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention shall be included in the scope of the claims of the present invention.
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