SUPPORTED CATALYST SYNTHESIS DEVICE AND FINE PARTICLE SYNTHESIS DEVICE
20220347669 · 2022-11-03
Assignee
Inventors
Cpc classification
B01J37/0072
PERFORMING OPERATIONS; TRANSPORTING
B22F9/24
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
The supported catalyst synthesis device according to the present disclosure includes a first source for a liquid containing a reducing agent; a second source for a liquid containing elements to constitute single-metal fine particles or solid solution fine particles to be supported; a third source for a liquid containing support particles; a reaction unit that joins flows of these liquids; a liquid feed route connecting between the first source and the reaction unit; a liquid feed route connecting between the second source and the reaction unit; a liquid feed route connecting between the third source and the reaction unit; and a collection unit, connected to the reaction unit via a pipe, to collect a produced reaction product, and further includes a pressure adjustment mechanism connected to the collection unit.
Claims
1. A supported catalyst synthesis device comprising at least: a first source for a liquid containing a reducing agent; a second source for a liquid containing elements to constitute single-metal fine particles or solid solution fine particles to be supported; a third source for a liquid containing support particles; a reaction unit that joins flows of the liquid containing the reducing agent, the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles to be supported, and the liquid containing the support particles; a liquid feed route connecting between the first source and the reaction unit; a liquid feed route connecting between the second source and the reaction unit; a liquid feed route connecting between the third source and the reaction unit; and a collection unit, connected to the reaction unit via a pipe, to collect a produced reaction product, wherein the supported catalyst synthesis device further comprises a pressure adjustment mechanism connected to the collection unit.
2. The supported catalyst synthesis device according to claim 1, further comprising a mechanism that transfers a liquid flowing through either the liquid feed route or the liquid feed route or both, in one direction.
3. The supported catalyst synthesis device according to claim 1 or 2, wherein the liquid feed route includes a stirring mechanism.
4. The supported catalyst synthesis device according to claim 1, further comprising a heating and heat retention mechanism in the liquid feed route.
5. The supported catalyst synthesis device according to claim 1, further comprising a cooling mechanism between the reaction unit and the collection unit.
6. A fine particle synthesis device comprising at least: a first source for a liquid containing a reducing agent; a second source for a liquid containing elements to constitute single-metal fine particles or solid solution fine particles; a reaction unit that joins flows of the liquid containing the reducing agent, and the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles; a liquid feed route connecting between the first source and the reaction unit; a liquid feed route connecting between the second source and the reaction unit; and a collection unit, connected to the reaction unit via a pipe, to collect a produced reaction product, wherein the fine particle synthesis device further comprises a pressure adjustment mechanism connected to the collection unit.
7. The fine particle synthesis device according to claim 6, further comprising a mechanism that transfers a liquid flowing through the liquid feed route in one direction.
8. The fine particle synthesis device according to claim 6, further comprising a heating and heat retention mechanism in the liquid feed route.
9. The fine particle synthesis device according to claim 6, further comprising a cooling mechanism between the reaction unit and the collection unit.
10. The supported catalyst synthesis device according to claim 2, further comprising a heating and heat retention mechanism in the liquid feed route.
11. The supported catalyst synthesis device according to claim 2, further comprising a cooling mechanism between the reaction unit and the collection unit.
12. The supported catalyst synthesis device according to claim 4, further comprising a cooling mechanism between the reaction unit and the collection unit.
13. The supported catalyst synthesis device according to claim 10, further comprising a cooling mechanism between the reaction unit and the collection unit.
14. The fine particle synthesis device according to claim 7, further comprising a heating and heat retention mechanism in the liquid feed route.
15. The fine particle synthesis device according to claim 7, further comprising a cooling mechanism between the reaction unit and the collection unit.
16. The fine particle synthesis device according to claim 8, further comprising a cooling mechanism between the reaction unit and the collection unit.
17. The fine particle synthesis device according to claim 14, further comprising a cooling mechanism between the reaction unit and the collection unit.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0020]
[0021]
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
[0028]
[0029]
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0030] Hereinafter, the present invention will be described in detail by means of embodiments, but the present invention is not construed as being limited to these descriptions. The embodiments may be modified in various ways as long as the effects of the present invention are exhibited.
Supported Catalyst Synthesis Device
[0031] A supported catalyst synthesis device will be described with reference to
[0032] The supported catalyst synthesis device according to the embodiment can reduce the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles to be supported to produce the single-metal fine particles or solid solution fine particles in the reaction unit (D), and cause the single-metal fine particles or solid solution fine particles produced by reduction to be supported on the support particles.
[0033] The first source 3 for the liquid containing the reducing agent is preferably a container for storing the liquid containing the reducing agent. As the reducing agent, a reducible organic solvent may be used such as methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, triethylene glycol, trimethylene glycol, or diethylene glycol, which may be diluted with a solvent such as water, and, furthermore, may contain an alkali, an organic acid or the like added to a solvent such as water to adjust reducing property.
[0034] The second source 1 for the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles to be supported is preferably a container for storing the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles to be supported. Examples of the elements to constitute the single-metal fine particles or solid solution fine particles include palladium, ruthenium, rhodium, silver, osmium, iridium, platinum, gold, molybdenum, rhenium, tungsten, 3d transition element, carbon, and boron. Among these elements, a raw material containing one kind of metal element is used to produce single-metal fine particles. This raw material is dissolved in a liquid such as water to prepare a raw material solution. Among these elements, raw materials containing two or more kinds of metal elements is used to produce solid solution fine particles. These metal materials are dissolved in a liquid such as water to prepare a raw material solution. As a combination of the two or more kinds of metal elements, there are a combination to form a solid solution, a combination not to form a solid solution, and a combination to form an intermetallic compound, in the alloy phase diagram.
[0035] The third source 2 for the liquid containing the support particles is preferably a container for storing the liquid containing the support particles. Examples of the kinds of the support particles include silica, alumina, ceria, zirconia, ceria zirconia, titania, magnesia, tin oxide, activated carbon, carbon black, acetylene black, carbon nanotubes, carbon nanofibers, and carbon nanohorns. The liquid containing the support particles is a liquid in which the support particles are dispersed with a dispersion medium, and the dispersion medium is, for example, water. The dispersion medium may appropriately contain a reducing organic solvent such as methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, triethylene glycol, trimethylene glycol, or diethylene glycol, and an alkali, an organic acid, or the like may be added to the dispersion medium to adjust reducing property as appropriate.
[0036] The liquid feed route (A) connecting between the first source 3 and the reaction unit (D) includes a pipe. As a means for adjusting flow rate of liquid flowing through the pipe, there is a method of placing the first source 3 at a position higher than that of the reaction unit (D) to use the height difference therebetween. In this case, the liquid containing the reducing agent can be carried only by the pipe. In this case, a valve for reducing the flow rate, such as a needle valve or a stop valve, may be placed in the liquid feed route (A).
[0037] The liquid feed route (B) connecting between the second source 1 and the reaction unit (D) includes a pipe. As a means for adjusting flow rate of liquid flowing through the pipe, there is a method of placing the second source 1 at a position higher than that of the reaction unit (D) to use the height difference therebetween. In this case, similarly to the liquid feed route (A), a valve for reducing the flow rate, such as a needle valve or a stop valve, may be placed in the liquid feed route (B).
[0038] The liquid feed route (C) connecting between the third source 2 and the reaction unit (D) includes a pipe. As a means for adjusting flow rate of liquid flowing through the pipe, there is a method of placing the third source 2 at a position higher than that of the reaction unit (D) to use the height difference therebetween. In this case, similarly to the liquid feed route (A), a valve for reducing the flow rate, such as a needle valve or a stop valve, may be placed in the liquid feed route (C).
[0039] The liquid feed route (B) and the liquid feed route (C) may be separately connected to the reaction unit (D). As illustrated in
[0040] The supported catalyst synthesis device according to the embodiment preferably further includes a mechanism (G) that transfers the liquid flowing through either the liquid feed route (B) or the liquid feed route (C) or both, in one direction. In a supported catalyst synthesis device 200 illustrated in
[0041] As illustrated in
[0042] The mechanism (G) is a means for adjusting the flow rate of the liquid flowing through the pipe, such as a plunger, a cylinder, or a regulator, for example.
[0043] As illustrated in
[0044] Next, reference is made to
[0045] In the supported catalyst synthesis device according to the embodiment, the liquid feed route (C) preferably includes a stirring mechanism (H). In the case where the mechanism (G) is provided to transfer the support particles from the liquid feed route (C) to the reaction unit (D), the support particles may sink down at the inside of the mechanism (G). Therefore, by providing the stirring mechanism (H) in the mechanism (G), the support particles can be prevented from sinking down at the inside of the mechanism (G) and the support particles can be uniformly transferred to the reaction unit (D).
[0046] The reaction unit (D) is a reaction container for joining the flows of the liquid containing the reducing agent, the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles to be supported, and the liquid containing the support particles at one place. It is also possible to control the reaction conditions by selecting and adjusting the shape and volume of the reaction container and how to flow the liquid in the container as appropriate. The reaction container also includes a pipe-shaped container. The reaction unit (D) is preferably a pressure container so that the reaction can proceed under pressure. Further, the reaction unit (D) may include a heating means for heating the liquid contained therein, and the heating means may be, for example, a resistance heating element, a far-infrared irradiation device, a microwave irradiation device, direct energization heating, dielectric heating, induction heating, an electric furnace, a heater, or the like.
[0047] The collection unit (E) is a container that is connected to the reaction unit (D) via a pipe to collect a produced reaction product. The collection unit (E) is preferably a pressure container so that the reaction can proceed under pressure in the reaction unit (D).
[0048] The pressure adjustment mechanism (F) is connected to the collection unit (E). The pressure adjustment mechanism (F) may be connected to the collection unit (E) via a pipe. Further, the pressure adjustment mechanism (F) may be connected to the collection unit (E) in an integrated manner. Examples of the pressure adjustment mechanism (F) include a pressurizing and depressurizing means such as a plunger, a cylinder, and a regulator, and the pressure adjustment mechanism (F) is preferably a cylinder that is less likely to cause wear or clogging of the device. The pressure adjustment mechanism (F) adjusts the pressure inside the collection unit (E) and the pressure inside the reaction unit (D) connected to the collection unit (E) via the pipe.
[0049] Since the liquid feed route (A), the liquid feed route (B), and the liquid feed route (C), which are on the upstream side of the reaction unit (D), are also connected to the reaction unit (D), the internal space of the route is under a pressure. However, the liquid is fed toward the reaction unit (D) at a higher pressure. When the liquid containing supports on which single-metal fine particles or solid solution fine particles are supported is collected by the collection unit (E), the pressure in the collection unit (E) is adjusted by the pressure adjustment mechanism (F) so as to adjust the pressure in the reaction unit (D), and as a result, the reduction of the elements to constitute the single-metal fine particles or solid solution fine particles is promoted in the reaction unit (D). In order to make conditions for the promoting reduction, it is preferable to give high energy. In order to make the conditions that can promote reduction, it is preferable to give high energy, and the pressure adjusting mechanism (F) in the collection unit (E) prevents the reducing agent from boiling while raising the temperature in the reaction unit (D). It is possible to adjust the pressure.
[0050] As illustrated in
[0051] As illustrated in
[0052] As an example of producing a supported catalyst using the supported catalyst synthesis device according to the embodiment, a liquid containing an ethanol-containing aqueous solution as a reducing agent is put into the first source 3, heated from room temperature to 450° C. by using a heater of the heating and heat retention mechanism (I) in the liquid feed route (A) via which the reducing agent is transferred, and then transferred to the reaction unit (D). As a liquid containing a single-metal element to be supported, a Pd raw material solution and a Ru raw material solution are put into the second source 1 and transferred to the reaction unit (D) via the liquid feed route (B). A liquid containing alumina as the support to support is put into the third source 2, and the flowing liquid is transferred to the reaction unit (D) while operating the mechanism (G) and the stirring mechanism (H) for transferring the flowing liquid in one direction. After the flows of the ethanol-containing aqueous solution, Pd raw material solution, Ru raw material solution, and alumina are joined at the reaction unit (D), the Pd raw material and Ru raw material are simultaneously reduced on the alumina by the ethanol-containing aqueous solution, while the Pd elements and Ru elements are combined to produce solid solution fine particles, and the solid solution fine particles are supported on alumina to produce a supporting catalyst. The produced supported catalyst is quenched to room temperature using water cooling of the cooling mechanism (J2). The quenching suppresses the sintering of particles. The quenched supported catalyst is collected in the collection unit (E) connected to the pressure adjustment mechanism (F), and the pressure is controlled to 0.1 MPa to 138 MPa to suppress the boiling of the reducing agent. By increasing the pressure, the pressure of the entire device is increased, and the activity of the reaction in the reaction unit (D) is improved.
Fine Particle Synthesis Device
[0053] Next, a fine particle synthesis device will be described, but since the description includes the same contents as that of the supported catalyst synthesis device, the following description will be focused on the differences.
[0054] First, the fine particle synthesis device will be described with reference to
[0055] The fine particle synthesis device according to the embodiment can reduce, in the reaction unit (D), the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles to produce the single-metal fine particles or solid solution fine particles.
[0056] As to the first source 3, the kind of the reducing agent, the second source 1, the liquid feed route (A), the liquid feed route (B), the reaction unit (D), the collection unit (E), and the pressure adjustment mechanism (F), they are the same as those in the case of the supported catalyst synthesis device according to the embodiment. Further, the kind of the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles is the same as “the kind of the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles to be supported” for the supported catalyst synthesis device according to the embodiment.
[0057] The fine particle synthesis device according to the embodiment preferably further includes a mechanism (G) that transfers a liquid flowing through the liquid feed route (B) in one direction. This enables the stable definition of the flow rate and flow velocity of the liquid containing the elements to constitute the single-metal fine particles or solid solution fine particles in the liquid feed route (B), so that stable synthesis of the fine particles can be performed. In a fine particle synthesis device 600 illustrated in
[0058] The specific structure of the mechanism (G) is the same as that of the supported catalyst synthesis device according to the embodiment.
[0059] As illustrated in
[0060] As illustrated in
[0061] As an example of producing fine particles using the fine particle synthesis device according to the embodiment, a liquid containing an ethanol-containing aqueous solution as a reducing agent is put into the first source 3, heated from room temperature to 450° C. by using a heater of the heating and heat retention mechanism (I) in the liquid feed route (A) via which the reducing agent is transferred, and then transferred to the reaction unit (D). As a liquid containing elements to constitute solid solution fine particles, a Pd raw material solution and a Ru raw material solution are put into the second source 1 and transferred to the reaction unit (D) via the liquid feed route (B). After the ethanol-containing aqueous solution, the Pd raw material solution and the Ru raw material solution are joined at the reaction unit (D), the Pd raw material and the Ru raw material are simultaneously reduced by the ethanol-containing aqueous solution, and the Pd element and the Ru element are combined to form solid solution fine particles. The produced solid solution fine particles are quenched to room temperature using water cooling of the cooling mechanism (J2). The quenching suppresses the sintering of particles. The quenched solid solution fine particles are collected in the collection unit (E) connected to the pressure adjustment mechanism (F), and the pressure is controlled to 0.1 MPa to 138 MPa to suppress the boiling of the reducing agent. By increasing the pressure, the pressure of the entire device is increased, and the activity of the reaction in the reaction unit (D) is improved.
REFERENCE SIGNS LIST
[0062] 100, 200, 300, 400 Supported catalyst synthesis device [0063] 500,600,700 Fine particle synthesis device [0064] A Liquid feed route connecting between first source and reaction unit [0065] B Liquid feed route connecting between second source and reaction unit [0066] C Liquid feed route connecting between third source and reaction unit [0067] (B, C) Shared route serving both as liquid feed route (B) and liquid feed route (C) [0068] D Reaction unit [0069] E Collection unit [0070] F Pressure adjustment mechanism [0071] G Mechanism that transfers liquid in one direction [0072] H Stirring mechanism [0073] I Heating and heat retention mechanism [0074] J1, J2 Cooling mechanism [0075] 1 Second source for liquid containing elements to constitute single-metal fine particles or solid solution fine particles [0076] 2 Third source for liquid containing support particles [0077] 3 First source for liquid containing reducing agent [0078] 4 Fourth source for storing mixed liquid of liquid containing elements to constitute single-metal fine particles or solid solution fine particles to be supported and liquid containing support particles [0079] 10a Inhalation side ball [0080] 10b Discharge side ball [0081] 11a Inhalation side pipe [0082] 11bDischarge side pipe [0083] 12 Plunger [0084] 13 Space [0085] 14 Stirring impeller