KR101526172B1 - Continuous reactor for preparation of metal nano particle using electron beam and Equipment comprising thereof - Google Patents

Abstract

According to the present invention, there is provided a flow path having a predetermined depth and width in a part of an upper plane of a reaction vessel, and the flow path includes an opening portion at least a part of which is open at an upper side of the reaction vessel, A reaction vessel in which the irradiated electron beam is irradiated through the openings of the flow path to convert the reactant into metal nanoparticles; An inlet port provided at one end of the reaction vessel and through which the reactant flows;
A transmissive window made of a polymer material or a metal material having a thickness of 1 μm to 20 μm and connected to the reaction vessel by hermetically sealing the opening portion of the flow passage so as to transmit the electron beam; And an outlet provided at the other end or the other end of the one end of the reaction vessel and through which the mixed solution of the reactant and the product flows out. The continuous reactor for producing metal nanoparticles using the electron beam, And a device for producing metal nanoparticles comprising the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous reactor for manufacturing metal nanoparticles using an electron beam,

The present invention relates to a continuous reactor for producing metal nanoparticles using an electron beam irradiation method and an apparatus for manufacturing metal nanoparticles comprising the same. More particularly, the present invention relates to a reactor capable of producing metal nanoparticles A continuous reactor including a reaction vessel in which a flow path is formed; And a continuous reaction apparatus for the production of metal nanoparticles comprising the continuous reactor and the electron beam irradiator.

Generally, metal nanoparticles that can be used for a fuel cell catalyst or the like are prepared by reducing a metal precursor using a reducing agent to a reaction mixture containing a metal salt, a solvent, a dispersant (stabilizer), etc. used as a metal precursor Chemical methods are mainly used.

As a method for preparing metal nanoparticles other than the above-mentioned chemical methods, an energy irradiation method in which an electron beam (EB), a gamma ray (r-ray), a microwave or an ultraviolet (UV) .

Recently, as one of the energy irradiation methods, a method of manufacturing metal nanoparticles using a method of irradiating a high energy electromagnetic wave such as a gamma ray or an electron beam to a reactant has been developed.

Regarding the production of metal nanoparticles using the gamma irradiation method, the conventional reactor for preparing metal nanoparticles using gamma irradiation is provided with a cylindrical container for accommodating reactants and a stirring device for stirring the reactants. In this case, when the gamma rays are emitted toward the reactor in all directions, the intensity of the gamma rays is inversely proportional to the square of the distance, and gamma rays are not uniformly irradiated to the reactants through the vessel. In order to solve such a problem, Japanese Patent No. 10-0852707 discloses a container for transmitting the energy while receiving a reactant, a stirring member rotatably installed in the container, and a driving member for receiving the power from the power source to operate the stirring member. And the container includes a plane transmission window mainly composed of polyethylene having an opening through which the energy is incident and a polyethylene covering the opening. However, the present invention is applicable to a method for manufacturing nanoparticles using gamma rays only However, in the production of metal nanoparticles by electron beam irradiation, the transmittance of the electron beam is much lower than that of the gamma ray, so that it is difficult for the electron beam to penetrate into the reaction vessel.

The method using irradiation of the electron beam will be described in detail. When a reactant other than a reducing agent is irradiated with an electron beam to generate hydrated electrons and substances of various chemical species, the hydrating electrons function as a reducing agent for reducing the metal precursor, Particles can be generated. As a related art, Japanese Unexamined Patent Application Publication No. 10-2008-0039034 discloses a method for preparing a catalyst for a fuel cell by mixing a catalyst precursor and a solvent and irradiating the mixture with an electron beam having an energy of 1 MeV or less, In the same electron beam irradiation method, since the thickness of the window formed of a polymer material such as polyimide (capton), porous polytetrafluoroethylene or polyurethane is limited to 10 to 100 μm, a considerable number of electron beams can not penetrate into the reaction vessel, There was a falling point.

In addition, all of the above-described prior art techniques correspond to a batch reactor. After the reactants and the solvent are both put into a reaction vessel, the reaction is completed by electron beam, the product is separated, It is necessary to prepare the reactant each time the beam irradiation is performed. Accordingly, the manufacturing time of the metal nanoparticles is increased and mass production is not easy.

Accordingly, there is a need for a continuous reactor for producing metal nanoparticles using an electron beam, in which a reactant is homogeneously mixed, and an energy such as an electron beam is irradiated to the reactant at a uniform intensity .

Korean Patent No. 10-0852707 Korean Patent Publication No. 10-2008-0039034

In order to solve the above problems, the present invention provides a continuous reactor for producing metal nanoparticles, in which energy of an electron beam is irradiated at a uniform intensity and reactants can be uniformly mixed, and metal nanoparticles Thereby providing a manufacturing apparatus.

In order to solve the above-mentioned problems, the present invention provides a reaction vessel having a flow path having a predetermined depth and width on a part of an upper plane of the reaction vessel, wherein the flow path includes an opening A reaction vessel in which an electron beam irradiated through a transmission window is irradiated through an opening portion of the flow path to convert the reactant into metal nanoparticles; An inlet port provided at one end of the reaction vessel and through which the reactant flows; A transmissive window made of a thin metal film having a thickness of 1 to 20 mu m and covering the opening portion of the channel so as to transmit an electron beam so as to be hermetically sealed with the reaction vessel; And an outlet provided at the other end or the other end of the one end of the reaction vessel and through which the mixed solution of the reactant and the product flows out, wherein the opening is not separated along the upper part of the flow path formed on the upper surface of the reaction vessel And the permeable window is integrally formed so as to cover all of the openings in the upper part of the reaction vessel, and the window of the flow passage in the reaction vessel is covered with the permeable window, A gasket including an empty space is provided in an upper portion and a lower portion of the transmission window so as to open a planar portion corresponding to the opening portion of the flow passage, And a plurality of coupling members for coupling the transmission window to be in close contact with the upper surface of the reaction vessel Using an electron beam, to the gong it is characterized by providing the continuous reactor for the production of metal nanoparticles.

In one embodiment, the shape of the channel is selected from a form consisting of one ('-'), 'a', 'c', 'e', or semicircular, semi-elliptical, It can be either.

In one embodiment, the openings may be in the form of a plurality of numbers separated from each other along the upper portion of the flow path formed on the upper surface of the reaction vessel.

In one embodiment, the transmission window and the opening are each formed in a planar shape, and the transmission window is integrally formed so as to cover all the openings in the upper portion of the reaction vessel, or covers only a part of the openings formed in a part of the flow passage. So that a plurality of reaction vessels can be formed in the reaction vessel.

In one embodiment, the width of the flow path is from 1 to 70 mm, and the length of the flow path in the reactor may be from 3 cm to 10 m.

In one embodiment, when the transmission window is made of a polymer material, it is made of any one selected from polyimide, porous polytetrafluoroethylene, polyurethane, polyethylene, and polypropylene, and when the transmission window is made of a metal material, The metal may be a metal selected from the group consisting of a transition metal and an alkaline earth metal, or a metal alloy.

When the transmission window is a metal material thin film, it is made of titanium; beryllium; Porous aluminum foil; And a harvar foil containing a plurality of components selected from cobalt, chromium, nickel, tungsten, molybdenum, manganese, carbon, beryllium and iron.

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In one embodiment, a metal plate is provided on an outer edge of the gasket formed on the upper portion of the transmission window to improve airtightness of the reaction container, the upper and lower gaskets, and the transmission window, and a plurality of second fastening members And the upper and lower gaskets and the permeable window can be brought into close contact with the reaction vessel by the metal plate and the second fastening member.

In one embodiment, the gasket; And a plurality of coupling members for adhering the gasket to the permeable window in such a manner that an opening of the channel in the reaction container is covered with the permeable window so as to be coupled with the reaction vessel to maintain airtightness, A stationary frame capable of covering the rim portion and including an empty space therein so that a flat portion corresponding to the opening portion of the channel is opened; And a coupling member for coupling the fixed frame and the transmission window in close contact with the upper surface of the reaction vessel, wherein the fixing frame includes an O-ring groove and the O-ring is coupled to the fixing frame, And can be closely contacted by the fastening member between the reaction vessels.

 As an embodiment, the gasket; And a plurality of coupling members for adhering the gasket to the permeable window in such a manner that an opening of the channel in the reaction container is covered with the permeable window so as to be coupled with the reaction vessel to maintain airtightness, A stationary frame capable of covering the rim portion and including an empty space therein so that a flat portion corresponding to the opening portion of the channel is opened; And a coupling member for coupling the fixed frame and the transmission window to be in close contact with the upper surface of the reaction vessel, wherein an O-ring groove is provided on an upper surface of the reaction vessel around the opening, And the reaction vessel including the opening portion by the fastening member.

In one embodiment, the outer portion of the reaction vessel not including the flow passage is made of a metal material, and the inner portion including the flow passage is selected from among polyimide, polyethylene (PE), polypropylene (PP), and polyvinyl chloride Or a double-walled structure composed of any one of them.

In one embodiment, the plurality of reaction vessels may be connected to the inlet of another reactor connected to the one reactor by a connection pipe.

In one embodiment, the connection tube may include a static mixer, or may include a reactant intermediate storage device including a stirrer for uniform mixing of reactants.

The present invention also relates to an electron beam irradiator installed in a radiation shielding room; The continuous reactor including a transmission window installed in a radiation shielding room and installed opposite to an electron beam accelerator window of the electron beam irradiator; A reactant storage tank in which a reactant is stored; A pump for transferring the reactants stored in the reactant storage tank to an inlet of the continuous reactor; And a separation device for separating the reacted reaction product from the product through the outlet of the reactor. The continuous reaction device for the production of metal nanoparticles using an electron beam may be provided.

In one embodiment, the continuous reaction apparatus may further include a transfer line for transferring the unreacted material separated in the separation apparatus to the inlet or the reactant storage tank in the continuous reactor.

In one embodiment, the separation device may be a centrifuge device or a filter device.

In one embodiment, the electron beam irradiator has an electron beam accelerator window in the form of a planar ellipse or a rectangle in the form of a plane, the electron beam accelerator window being irradiated with an electron beam so as to face at least a part of the transmissive window provided in the reactor .

In the case of using the continuous reactor for the production of metal nanoparticles of the present invention, the electron beam is uniformly irradiated through the transmission window formed in the upper part of the tubular flow path and transmitted therethrough, so that the metal precursor undergoes a reduction reaction under uniform conditions So that the metal nanoparticles can be uniformly and stably produced.

Further, since the continuous reactor of the present invention uses a transmission window made of a metal material or a polymer material thin film having a thickness of 1 um to 20 um, the transmittance of the electron beam is increased. Even if a low energy electron beam irradiator is used, The metal nanoparticles can be effectively produced.

In addition, since the reaction is continuously performed by the continuous reactor, the present invention does not require a reaction preparation step and a reactor washing step after completion of the reaction due to a batch reaction reactor, and has an advantage of mass production easily.

FIG. 1A is a view showing a continuous reactor having a channel structure of '''according to the present invention, and FIG. 1B is a view showing a continuous reactor having an''shaped channel according to the present invention.
FIG. 2 is a view illustrating a reactor in which openings are integrally formed in a single shape, and a transmission window is integrally formed to cover all the openings in the upper portion of the reaction vessel, according to an embodiment of the present invention.
FIG. 3 is an exploded perspective view of the continuous reactor according to FIG. 2 of the present invention.
FIG. 4 is an exploded perspective view explaining each component of a continuous reactor for producing metal nanoparticles using an electron beam according to another embodiment of the present invention. Referring to FIG.
FIG. 5A illustrates an embodiment in which a transparent window according to the present invention is fixed to a reaction vessel including an opening. FIG.
FIG. 5B is a plan view showing the reaction vessel and the fixed frame according to the case of FIG. 5A, respectively.
FIG. 6A illustrates another embodiment in which the transmission window according to the present invention is fixed to the opening. FIG.
FIG. 6B is a plan view showing only the reaction vessel and the fixed frame according to the case of FIG. 6A, respectively.
7 is a view showing a continuous reaction apparatus for producing metal nanoparticles using an electron beam according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In the accompanying drawings, the dimensions of the structures are enlarged to illustrate the present invention in order to clarify the present invention.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, are intended to specify the presence of stated features, integers, steps, operations, elements, or combinations thereof, , Steps, operations, elements, or combinations thereof, as a matter of principle, without departing from the spirit and scope of the invention.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

FIG. 1 shows a continuous reactor having a ('-') or 'd' -shaped flow path according to the present invention, and FIGS. 2 and 4 show a process for producing metal nanoparticles using an electron beam according to the present invention. And shows an exploded perspective view of the respective components of the continuous reactor in an exploded state.

As shown in FIGS. 1, 2 and 4, the continuous reactor of the present invention includes a reaction vessel 40 including a flow path 30 in which reactants are converted into metal nanoparticles, An outlet port 42 through which the mixed solution of the reactant and the product flows, and an outlet port 42 through which the electron beam is transmitted. The inlet port 41 is formed at the other end of the one end of the reaction vessel, (60).

More specifically, in the continuous reactor of the present invention, the reaction vessel (40) has a channel (30) having a certain depth and width at a part of the upper plane of the reaction vessel (40).

The flow path includes an opening (50) in which at least a part of the upper part of the reaction vessel is opened so that an electron beam can be transmitted through the flow path. do. That is, the flow path corresponds to a path through which a reactant and a solvent that may include a carrier are moved, and the depth, width, and length of the flow path may vary depending on amounts of the reactants, the carrier and the solvent, the reaction rate, have. The depth and width of the channel may each range from 1 mm to 7 cm, and the length of the channel may range from 3 cm to 10 m.

The cross-sectional shape of the reaction vessel of the present invention may be a square, a rectangle, a circle, or an ellipse, but the present invention is not limited thereto.

The flow path in the reaction vessel includes an opening portion 50 in which at least a part of the flow path on the upper side of the reaction vessel is opened so that the electron beam can be transmitted. The electron beam emitted from the transmission window 60 passes through the opening 50 of the flow path and is irradiated to reactants contained in the flow path to cause a chemical reaction.

As shown in FIG. 1, the opening may be formed such that a part of the flow path is exposed to the outside by opening a part of the upper plane of the flow path in the reaction vessel. The continuous reactor of the present invention has a structure in which a transparent window in a planar shape covers the opening portion of the flow path, which is the open space, so that the electron beam can be easily irradiated in the flow path.

The shape of the flow path may be a one ('-') shape, an 'a' shape, a 'c' shape, an 'e' shape, a semicircular shape, a semi-elliptical shape, or a combination thereof. For example, Figs. 1 to 3 show reaction vessels having various channel shapes in the present invention. In the present invention, the flow path may have a structure of '(') ',' C ', and' D 'as shown in FIGS. In addition, the shape of the euros can be classified into 'a', 'semicircle', 'c', semicircle, semicircle and 'd', half ellipse and 'a', half ellipse and ' Quot; and " d " Accordingly, the shape of the opening corresponding to the above-described flow path also has a structure of a '-' shape, or may have a shape of 'a', 'e', 'd', semicircle, semicircle and 'a' It may have various shapes such as' c 'shape, semicircle and' d 'shape, half ellipse and' a 'shape, half ellipse and' c 'shape, half ellipse and' Can have a structure of a day ('-') shape.

For example, as shown in FIG. 3, the flow path may have a plurality of 'e' shaped structures having narrow and thin shapes. In this case, if all of the openings in the channel are covered with one transmission window, all the openings can transmit the same electron beam, thereby increasing the efficiency of the reaction.

As shown in FIG. 1B and FIG. 4, the openings may be formed as a plurality of numbers separated from each other along the upper part of the flow path formed on the upper surface of the reaction vessel, or may be formed integrally May be formed in a single connected form.

In the present invention, the transmission window is made of a material through which an electron beam is transmitted, so that the electron beam can be irradiated as a reactant through the opening space in the flow path. The transmission window may be formed of a thin film of a polymer material or a metal material having a thickness of 1 to 20 μm and may be coupled with the reaction vessel while keeping the airtightness by covering the opening portion of the channel.

In addition, the transmission window and the opening are each formed in a planar shape, and the transmission window is integrally formed so as to cover all the openings in the upper portion of the reaction vessel, so that the electron beam can be transmitted through the upper opening. That is, as shown in FIG. 3, the transmission window may be integrally formed so as to cover all the openings in the upper part of the reaction vessel. In this case, if the area irradiated with the electron beam is made equal to the area of the transmission window, By irradiating the electron beam to all the openings, the efficiency of the reaction can be increased.

Meanwhile, the transmission window may be formed to cover only a part of a plurality of openings formed in the flow path, and a plurality of transmission windows may be in close contact with the reaction vessel. As shown in FIGS. 1B and 4, a plurality of the transmissive windows may be formed in the reaction vessel such that the respective transmissive windows cover a plurality of openings in the reaction vessel formed along the 'C' or 'D' channel.

That is, the transmission window in the present invention includes all of the three portions (the '-a' portion, the middle 'l' portion and the lower '-' portion) formed by the ' And the three portions may be separately formed by two or three transmission windows, and the three portions may be separately bonded to the reaction vessel.

In the present invention, the openings are formed in a single shape integrally connected to one transparent window as shown in FIG. 3, and all the openings in the transparent window are irradiated with an electron beam so that the reaction can be uniformly and efficiently evolved .

The material of the transmissive window may be any material that can transmit the electron beam without being damaged by the electron beam. Generally, a polymer material or a metal material can be used. When the material of the transmission window is a polymer, it is made of any one selected from the group consisting of polyimide, porous polytetrafluoroethylene, polyurethane, polyethylene, and polypropylene, and the polymeric thin film may be a ceramic coating or a non- .

When the material of the transmission window is made of a metal, the metal may be any one metal selected from a transition metal and an alkaline earth metal, or an alloy thereof. Preferably, the metal thin film is made of titanium; beryllium; Porous aluminum foil; And a harvar foil containing a plurality of components selected from among cobalt, chromium, nickel, tungsten, molybdenum, manganese, carbon, beryllium and iron, or an alloy thereof.

In addition, the thickness of the transmission window may be in the range of 1 μm to 10 μm for a polymer material, and 1 μm to 20 μm for a metal material.

In one embodiment, when the transmission window is made of titanium, a thickness of 4 um may be used. In the case of beryllium, 15 um may be used. In the case of harvar foil, 3.8 um may be used.

The height and length of the transmission window may vary depending on the reaction conditions, the size of the reactor, the size and the capacity of the electron beam irradiator, and preferably 2 to 100 cm in width and 0.5 to 10 cm in height, To 40 cm and a height of 1 to 7 cm is suitable, and the transmission window may be used alone or a plurality of transmission windows may be provided.

In the present invention, the permeable window 60 may be in close contact with a flat surface portion of the upper surface other than the opening in the reaction vessel and may be closely contacted by a fastening member or an adhesive so as to maintain airtightness.

The adhesive agent may be sprayed or coated on the upper surface of the transparent window and / or the reaction container so as to form an adhesive layer on a flat portion around the opening in the reaction container, A fixing frame 80 or a gasket 55 may be additionally provided.

The reaction vessel may be made of a metal material such as aluminum and the like, and the inner side including the flow path may be any polymer having acid resistance. However, the reaction vessel may be made of polyimide, polyethylene (PE), polypropylene PP, and polyvinyl chloride (PVC), but the present invention is not limited thereto. Polypropylene, which is a polyolefin material, may be used.

Hereinafter, the case where the transmission window and the reaction vessel are closely contacted by using the fastening member 70 and the gasket 55 will be described.

FIG. 3 shows an embodiment in which the permeation window and the reaction vessel are brought into close contact with each other using the fastening member 70 and the gasket 55.

3, the flow path of the reaction vessel is formed in the reaction vessel by a plurality of times of 'd' shape and / or 'D' shape, and the opening in the reaction vessel is connected to the reaction vessel And the transmission window is integrally formed to cover all of the openings in the upper portion of the reaction vessel.

In this case, in order to keep the airtightness by being connected with the reaction vessel by covering the opening portion of the flow path in the reaction vessel with the transparent window, in the present invention, in the upper and lower portions of the transparent window, A gasket 55 including an empty space may be provided.

The gasket may be made of a metal or a polymer material, and preferably a polymer such as polyimide, polyethylene (PE), polypropylene (PP), or polyvinyl chloride (PVC) having good acid resistance can be used.

The plurality of gaskets provided on the upper and lower portions of the transmission window may have openings (void spaces) that are the same as the shapes of the openings of the flow path, or openings that are larger than the openings .

A plurality of fastening members 70 may be provided on the side of the opening corresponding to the openings in the plurality of gaskets 55, for joining the gasket and the transmission window in close contact with the upper surface of the reaction container.

Here, the fastening member serves to tightly couple the plurality of gaskets 55 and the transmission window to the upper surface of the reaction vessel. The fastening member may be formed of a combination of a common bolt and a nut, and a nut having a thread formed in the reaction vessel may be formed as in the present invention, and a conventional bolt may be used as a fastening member, So that the reaction vessel and the fastening member can be combined.

In order to improve the degree to which the gasket 55 and the permeable window are brought into close contact with the reaction container, in the present invention, the airtightness of the reaction container, the upper and lower gaskets, and the permeable window is improved on the outer edge of the gasket formed on the permeable window And a plurality of second fastening members 72 may be provided in the metal plate. The metal plate protects the transmissive window portion of the continuous reactor from external impact by using an aluminum plate, a SUS plate, a copper plate, a Hastelloy plate or the like having a thickness of 1 mm to 5 mm, The second fastening member 72 of the second fastening member 72 is coupled to the reaction vessel so that the adhesion between the reaction vessel and the upper and lower gaskets and the transmission window can be improved.

The second fastening member 72 has the same function as the fastening member 70 described above. The fastening member may be a combination of a common bolt and a nut, And the reaction vessel and the second fastening member can be joined by using a conventional bolt as a second fastening member and combining it with a nut formed in the reaction vessel.

It is preferable that the second fastening member 72 has a size larger than that of the fastening member 70 coupled to the gasket 55 or can strengthen the fastening member 70.

Further, in the present invention, a fixing frame 80 and a fastening member 70 may be used to closely contact the reaction container and the transmission window. Hereinafter, one embodiment of the present invention in which it is closely contacted by using additional fixing means through the fixed frame 80 will be described with reference to FIG.

FIG. 4 is an exploded perspective view of a continuous reactor having a plurality of openings in a reaction vessel, each of the openings having respective transmission windows, according to another embodiment of the present invention.

Also in this case, the transmission window 60 is made of a metal plate with an open inside, and is provided with a fixing frame 80 having a plurality of holes (non-numbered members) through which the fastening members can pass, The fixing frame 80 may be provided on the outer side of the transmission window and may be fixed to the outer side of the transmission window by a fixing means of the transmission window, And a planar portion corresponding to the opening portion of the flow path is opened so as to include an empty space therein. As described above, the fastening member 70 serves to tightly couple the fixing frame 80 and the transmission window 60 to the upper surface of the reaction vessel. The fastening member may be formed by a combination of a general bolt and a nut, and a fastening member may be joined by forming a nut having a thread formed in the reaction vessel as in the present invention and coupling a conventional bolt thereto.

In addition, in the present invention, in order to maintain hermetic sealing with the reaction vessel, an O-ring groove (groove) which is a groove to which an O-ring is coupled is provided on the fixed frame side, And can be closely contacted by the fastening member between the containers.

Accordingly, as shown in FIG. 4, the fixing frame 80 can be fastened to or detached from the reaction vessel by the fastening member while supporting the rim of the transmission window 60, so that the failure of the reactor or the transmission window There is an advantage that the transmission window can be easily exchanged when a defect occurs.

5A is a cross-sectional view showing that an O-ring groove and an O-ring are provided in the fixed frame 80 used in the present invention and the transmission window 60 is connected to the opening 50 of the reaction vessel through the fastening member 70 Respectively.

As shown in FIG. 5A, it can be seen that an O-ring and an O-ring groove are formed in the fixed frame and the permeable window is tightly attached to the reaction vessel while covering the opening through the fastening member. The reactor is preferably a wall having a double layer of the outer side and the inner side, but a single material may be used.

5B is a plan view showing the reaction vessel of the present invention and the stationary frame only. As shown in the figure, an O-ring groove 51 and an O-ring 52 are provided around the opening 50 of the stationary frame, It is seen that the corresponding opening 50 and the respective grooves for engaging the fastening member are provided.

The upper surface portion of the fixed frame in FIG. 5B is overlapped with the upper surface portion of the reaction vessel of FIG. 5B to be closely contacted.

In addition, the present invention is characterized in that an O-ring groove is not formed in the fixed frame, and an O-ring groove is provided on the upper side of the reaction vessel in the vicinity of the opening, and the O-ring is coupled to the reaction window, As shown in Fig.

This will be described in more detail with reference to FIG. 6A. FIG. 6A is a sectional view of the reaction chamber of FIG. 6A. In FIG. 6A, an O-ring groove is formed on the upper surface of the reaction vessel in the vicinity of the opening, Sectional view showing that the transmission window is covered and tightly contacted through the fastening member 70. As shown in Fig.

That is, in FIG. 6A, an O-ring grooved portion and an O-ring are provided in the vicinity of the upper surface opening portion of the reactor, and the transmission window is closely contacted through the fastening member between the reactor outer side portion and the reactor inner side portion.

In the meantime, in the reaction vessel of the present invention, the outer side portion not including the flow path is made of a metal material, and the inner side portion including the flow path is selected from polyimide, polyethylene (PE), polypropylene (PP), polyvinyl chloride Or a double-walled structure composed of any one of them. Preferably, a polypropylene (PP) may be used for the inner side portion including the flow path.

Illustratively, Figures 5a and 6a illustrate a double wall structure comprising a reactor inner portion made of polypropylene. As shown in FIGS. 5A and 6A, in the double wall structure of the present invention, the outer side portion of the reaction vessel is made of aluminum, and the flow path portion except for the opening portion of the flow path in the anti- A pipe of a half pipe type in which a pipe of a polypropylene having a pupil is vertically cut off in a longitudinal direction is in close contact with the remaining flow path portion except for the opening portion, and the O-ring groove and the O- Or the periphery of the polypropylene layer in the form of a hat pipe formed in the reaction vessel may be extended and the O-ring groove may be provided so as to be closely contacted through the fastening member.

6B is a plan view showing a continuous reactor having the structure shown in FIG. 6A separated from the reaction vessel and the fixed frame, respectively. In the same manner as shown in FIG. 5B, the fixed frame has an empty space corresponding to the opening in the reaction vessel. And a plurality of grooves for engaging the fastening members are provided. On the reaction vessel side, an O-ring groove is provided on the upper surface of the reaction vessel in the vicinity of the opening, O-rings are engaged, A plurality of grooves are provided. In the present invention, the number of the plurality of grooves may be determined in proportion to the size of the opening for fastening each constitution.

Further, the present invention may include a transparent window for viewing the inside of the reactor on the opposite side of the side portion having the transmission window of the reactor.

The material of the window may be transparent or acid resistant, and it may be fastened by using the O-ring and groove or may be fastened by using the gasket, or fastened by a simple combination of bolt nuts .

In the present invention, a plurality of the reaction vessels may be provided, and the plurality of reaction vessels may be connected to the inlet of one of the reactors connected to the one reactor through the connection pipe. That is, one or more reaction vessels of the present invention may be used and they may be coupled in series to prolong the residence time of the reactants and further increase the number of transmission windows, thereby allowing the reactants to have more opportunity to be irradiated with the electron beams. In this case, the connection pipe connecting the reaction vessel and the reaction vessel may include a stirrer or a static mixer for uniform mixing of the reactants, and further includes a reactant intermediate storage device for storing the reactants can do.

Also, the present invention can provide a continuous reaction apparatus for producing metal nanoparticles including the continuous reactor.

FIG. 7 shows the continuous reaction apparatus. In detail, the continuous reaction apparatus for producing metal nanoparticles using an electron beam according to the present invention includes an electron beam irradiator 10 installed in a radioactive shielding room, an electron beam irradiator 10 installed in a radioactive shielding room and facing the electron beam accelerator window of the electron beam irradiator (100) for transferring the reactants, a pump (110) for transferring the reactants stored in the reactant storage tank to the inlet of the continuous reactor, the continuous reactors (20) And a separation device (120) for separating the reacted reaction product from the product through the outlet of the reactor, the continuous reaction device for producing metal nanoparticles using an electron beam.

The present invention relates to a process for preparing a reaction product containing a metal salt, a solvent, and / or a dispersant (stabilizer) and / or a carrier, which are used as a metal precursor through the continuous reaction device, And the hydration electrons function as a reducing agent for reducing the metal precursor, whereby the metal nanoparticles can be produced. The metal nanoparticles have various application ranges such as a fuel cell catalyst.

The reactant storage tank 100 may include a metal precursor and a solvent to be converted into metal nanoparticles by an electron beam. As the metal precursor, a complex comprising a transition metal salt may be used. As the solvent to be used, water, alcohol, acetone, hydrocarbon, and a mixture thereof may be used.

The reactant storage tank 100 may have a single storage tank or a plurality of storage tanks depending on the reaction conditions and the type of reactants. In addition, the reactant storage tank 100 may include a carrier to support the metal nanoparticles together with the metal precursor and the solvent. For example, in order to support platinum nanoparticles on activated carbon, carbon black, etc., the carrier, activated carbon, carbon black, etc., may be contained in the reactant storage tank in the form of slurry and may be transported to the inlet of the continuous reactor of the present invention by a pump.

In the present invention, the separator may be a decanter in which platinum nanoparticles and a carrier can be separated by a static, a centrifugal separator capable of separating a solid component from a liquid component by centrifugation, A filter device capable of separating a component from a liquid component, and the like can be used.

The process for producing the metal nanoparticles using the continuous reaction apparatus will be described in detail. From the reactant storage tank 100 storing the reactants, a transition metal precursor, a solvent and / or a carrier, which is a reactant, 20) and is moved through the flow path. At this time, the transition metal precursor is reduced by the electron beam irradiated through the transmission window to prepare the transition metal nanoparticles. The reactant, which has been reacted through the outlet of the reactor, is separated in the separator 120, Is reused.

Meanwhile, in the present invention, the unreacted material separated from the separator may be reused, and the unreacted material may be further included in a transfer line for transferring the unreacted material to the inlet or the reactant storage tank of the continuous reactor.

On the other hand, the electron beam irradiator may have an electron beam accelerator window in the form of a plane ellipse or a rectangle in the form of a plane.

It is preferable that the accelerator window has a flat surface in correspondence with the opening and the transmission window of the reactor of the present invention, and the shape of the accelerator window has an elliptical shape or a rectangular shape to transmit the electron beam in the opening.

It is preferable that the openings 50 in the continuous reactor of the present invention are formed in a rectangular shape, and the transmission windows correspond to the shapes of the openings. If a rectangular opening is formed on the top surface of the reaction vessel as described above, the intensity of the electron beam irradiated from the electron beam accelerator window in the electron beam irradiator is reduced, and the reaction conditions can be made uniform.

That is, since the electron beam emitted from the electron beam irradiator 10 is horizontally emitted from the irradiation window and the intensity of the electron beam is inversely proportional to the square of the distance, the opening through which the electron beam is incident and the transmission window are formed into a rectangular plane, So that the reactants can be irradiated with a uniform intensity.

The intensity of the electron beam emitted from the electron beam irradiator 10 is not limited, and an electron beam irradiator having various intensities can be used. Preferably, the electron beam irradiator can irradiate an electron beam having an energy of 1 MeV or less and has an energy of 50 to 700 KeV And more preferably has an energy of 100 to 300 keV.

Generally, the reaction at a high energy state is quick and uniform. However, in this case, since the facility of the electron beam generating device must be large, the volume of the entire manufacturing process of the metal nanoparticles is increased so that it is not economical, There is a problem in actual mass production as it generates a lot of regulated X-rays.

On the other hand, when the energy is too low, the reaction does not occur or the reaction rate becomes slow and the productivity of the metal nano-particles deteriorates. Therefore, it is preferable to select the intensity of the electron beam in consideration of process conditions and economical efficiency.

Further, the electron beam preferably has a dose per hour of 1 to 50 kGy / min, more preferably 10 to 40 kGy / min. When irradiated at a dose of less than 1 kGy / min, the energy of the electron beam is too small to cause the reaction time to take too long or to overcome the activation energy and the reaction does not occur. When the electron beam is irradiated at a dose of more than 50 kGy / min It is impossible to manufacture uniform metal nanoparticles due to too high current value and it is not preferable because it causes equipment difficulties.

The reactor 20 is disposed inside the radioactive shielding room 1 so as to face the electron beam irradiator 10. In order to minimize the loss of the electron beam, the electron beam irradiator and the reactor are positioned so as to be as close as possible to each other, The efficiency can be increased. Further, the electron beam accelerator window is irradiated with at least a part of the transmission window provided in the reactor or the entire surface of the transmission window, so that the electron beam is transmitted to the reactant flowing in the flow path of the reactor to induce the chemical reaction.

[0030] The operation of the apparatus for fabricating metal nanoparticles according to the exemplary embodiment of the present invention will be described. First, the continuous reactor of the present invention is disposed inside the radioactive shielding room to face the electron beam irradiator 10, The electron beam irradiator and the reaction vessel are placed so as to be close to each other as close as possible to each other.

Thereafter, the mixed slurry of the solvent, reactant and carrier stored in the reactant storage tank is transferred by the pump to the inlet of the continuous reactor, and then the electron beam irradiator irradiates the electron beam through the transmission window of the reaction vessel.

In this process, the electron beam is irradiated to the reactant through the transmission window, and the opening and the transmission window through which the electron beam is incident and the transmission window are formed in the plane of a quadrangle. The electron beam is uniformly irradiated to the reactant, thereby making it possible to produce metal nanoparticles having a uniform size and shape. Such metal nanoparticles can be used as a conventional catalyst, an electronic material, a printing ink material, a catalyst for a fuel cell, and the like.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, But should be regarded as falling within the scope of the invention.

10. Electron beam irradiator 20. Reactor
30. 40. Reaction vessel
41. Inlet 42. Outlet
50. Openings 51. O-ring grooves
52. O-ring 55. Gasket
60. Transmission window 70. Fastening member
72. Second fastening member 80. Fixing frame
90. Metal plate 100. Reactant storage tank
110. Pump 120. Separation device

Claims (18)

And a flow path having a predetermined depth and width in a part of an upper plane of the reaction vessel, wherein the flow path includes an opening portion at least a part of the upper side of the reaction vessel so that the electron beam can be transmitted, A reaction vessel which is irradiated through the openings of the flow path to convert the reactant into metal nanoparticles;
An inlet port provided at one end of the reaction vessel and through which the reactant flows;
A transmissive window made of a thin metal film having a thickness of 1 to 20 mu m and covering the opening portion of the channel so as to transmit an electron beam so as to be hermetically sealed with the reaction vessel; And
And an outlet through which the mixed solution of the reactant and the product is discharged, the outlet being provided at another end or the other end of the one end of the reaction vessel,
Wherein the opening is formed in a unitary form integrally connected to the upper part of the flow path formed on the upper surface of the reaction vessel without being separated and the transmission window is integrally formed to cover all the openings in the upper part of the reaction vessel,
A gasket including an empty space therein so that a flat portion corresponding to an opening of the flow path is opened at an upper portion and a lower portion of the transmission window in order to keep the airtightness by being coupled with the reaction container by covering the opening portion of the flow path in the reaction container, Respectively,
And a plurality of fastening members for fastening the gasket and the transmission window in close contact with the upper surface of the reaction vessel, on the side of the open portion corresponding to the opening in the gasket. A continuous reactor The method according to claim 1,
It is preferable that the shape of the channel is any one selected from the group consisting of one ('-'), 'a', 'c', 'e', or semicircular, semielliptic, , A continuous reactor The method according to claim 1,
Wherein the openings are formed in a plurality of numbers separated from each other along the upper part of the flow path formed on the upper surface of the reaction vessel. The method according to claim 1,
The transmission window and the opening are respectively in the form of a plane,
Characterized in that the transmission window is integrally formed so as to cover all of the openings in the upper part of the reaction vessel or formed so as to cover only a part of the openings formed in a part of the flow passage, Continuous reactor The method according to claim 1,
Characterized in that the width of the flow path is from 1 to 70 mm and the length of the flow path in the reactor is from 3 cm to 10 m. The method according to claim 1,
Characterized in that the metal thin film of the transmission window is made of a metal selected from the group consisting of a transition metal and an alkaline earth metal or a metal alloy, The method according to claim 6,
The metal thin film may include titanium; beryllium; Porous aluminum foil; And a harvar foil containing a plurality of components selected from cobalt, chromium, nickel, tungsten, molybdenum, manganese, carbon, beryllium and iron. , A continuous reactor delete The method according to claim 1,
A metal plate is provided on an outer edge of the gasket formed on the upper portion of the transmission window to improve airtightness of the reaction container, the upper and lower gaskets, and the transmission window, and a plurality of second fastening members are provided in the metal plate, Characterized in that the reaction vessel and the upper and lower gaskets and the transmission window are in close contact with each other by the second fastening member, The method according to claim 1,
The gasket; And a plurality of coupling members for adhering the gasket to the permeable window in such a manner that an opening of the channel in the reaction container is covered with the permeable window so as to be coupled with the reaction vessel to maintain airtightness, A stationary frame capable of covering the rim portion and including an empty space therein so that a flat portion corresponding to the opening portion of the channel is opened; And a coupling member for coupling the fixed frame and the transmission window in close contact with the upper surface of the reaction vessel, wherein the fixing frame includes an O-ring groove and the O-ring is coupled to the fixing frame, Characterized in that the reaction vessel is closely contacted by the fastening member between the reaction vessels. The method according to claim 1,
The gasket; And a plurality of coupling members for adhering the gasket to the permeable window in such a manner that an opening of the channel in the reaction container is covered with the permeable window so as to be coupled with the reaction vessel to maintain airtightness, A stationary frame capable of covering the rim portion and including an empty space therein so that a flat portion corresponding to the opening portion of the channel is opened; And a coupling member for coupling the fixed frame and the transmission window to be in close contact with the upper surface of the reaction vessel, wherein an O-ring groove is provided on an upper surface of the reaction vessel around the opening, And the reaction vessel including the opening portion is brought into close contact with the fastening member. The method according to claim 1,
Wherein the outer side portion of the reaction vessel not including the flow path is made of a metal material and the inner side portion including the flow path is a double wall made of any one selected from the group consisting of polyimide, polyethylene (PE), polypropylene (PP), and polyvinyl chloride , Characterized in that the continuous reactor The method according to claim 1,
Wherein the plurality of reaction vessels are connected to each other by an inlet pipe of the other reactor to be connected to the one reactor by a connection pipe, 14. The method of claim 13,
Characterized in that the connecting tube comprises a static mixer or comprises a reactant intermediate storage device including a stirrer for uniform mixing of reactants, An electron beam irradiator installed in the radiation shielding room;
The continuous reactor according to any one of claims 1 to 7, 9 to 14, comprising a transmission window installed in a radioactive shielding room and installed opposite to an electron beam accelerator window of the electron beam irradiator.
A reactant storage tank in which a reactant is stored;
A pump for transferring the reactants stored in the reactant storage tank to an inlet of the continuous reactor; And
And a separation device for separating the reacted reaction product from the product through the outlet of the reactor, the continuous reaction device for the production of metal nanoparticles using an electron beam 16. The method of claim 15,
Wherein the continuous reaction apparatus further comprises a transfer line for transferring the unreacted material separated from the separation apparatus to the inlet or the reactant storage tank in the continuous reactor. The continuous reaction apparatus for the production of metal nanoparticles using an electron beam 16. The method of claim 15,
Characterized in that the separation device is a decanter, a centrifugal separator or a filter device. The continuous reaction device for the production of metal nanoparticles using an electron beam The method of claim 15,
Characterized in that the electron beam irradiator has an electron beam accelerator window in the form of a plane ellipse or a rectangle in the form of a plane and the electron beam accelerator window is irradiated with an electron beam so as to face at least a part of the transmission window provided in the reactor Continuous reaction device for the production of metal nanoparticles.

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