KR20190063291A - Catalyst production device and system - Google Patents

Abstract

The present invention relates to a core-shell catalyst production device with improved durability and electrochemical performance of a catalyst by including a nitrogen element in a core in a liquid phase, and a system for the same. A catalyst production device comprises: a reaction chamber (30) having a predetermined size with a circular or prismatic shape and including a raw material injection port (80); two or more reaction chambers (20) positioned inside the reaction chamber (30), having a cylindrical shape, and connected to each other by a fluid flow pipe (70); and a cavitation generation device (10) having a protrusion part to be inserted into the reaction chamber (20). A catalyst production system comprises: the catalyst production device; a pump (40) connected to the fluid flow pipe (70) to allow a fluid to flow; a filter (50) for filtering particulate matters flowing inside the fluid flow pipe (70); and a drying device for drying the catalyst filtered by the filter (50).

Description

[0001] Catalyst production device and system [0002]

The present invention relates to an apparatus and a system for producing a catalyst, and more particularly to an apparatus and a system for producing a core-shell catalyst having improved durability and electrochemical performance of a catalyst by including a nitrogen element in a core in a liquid phase .

Fuel cell, which is generally regarded as a next generation energy source, is a device that directly converts chemical energy generated by oxidation / reduction of fuel into electric energy. Recently, fuel cell (fuel cell) It is expected to be the future electric power for the future. The electrode reaction in the fuel cell consists of the hydrogen oxidation reaction in the anode and the oxygen reduction reaction in the anode. In a fuel cell system driven at low temperature, such as a polymer electrolyte membrane fuel cell, The reaction rate must be effectively increased in order to occur smoothly.

For the above reasons, platinum (Pt), which is a noble metal catalyst, has been inevitably used in the conventional fuel cell system. However, although the platinum catalyst exhibits excellent energy conversion efficiency, the fuel cell is problematic because it is very expensive and has a limited amount of reserves. In particular, the need for a new, high-efficiency, yet low-cost, electrical catalyst has been among the most urgent issues associated with PEMFC (Polymer electrolyte membrane fuel cell). In order to solve the above-mentioned failure factors and to promote the commercialization of fuel cells, in order to replace the platinum electrode supported on the present carbon support in recent years, it has been proposed to use nano-particles including a plurality of components such as alloy nanoparticles and core- Particles (multi-component nanoparticles) have been studied. This method has the disadvantage that synthesis is cumbersome and not economical, inevitably increases the particle size, and disappears of the surface area having catalytic activity. In particular, a technology has been developed that minimizes the deterioration of the catalyst performance compared with the platinum catalyst, which is composed of a transition metal-based core and a platinum-based shell. However, in this case, the durability of the catalyst is limited, . In order to solve such a problem, a technique of injecting nitrogen into the core has been developed. However, after the core is manufactured, nitrogen is added to the core and the shell is coated in order to manufacture the apparatus. There have been disadvantages. In addition, since the production of the core and the shell is not continuously performed, there is a limit to the mass production of the low-platinum core-shell catalyst having improved durability.

Korean Patent No. 1468113 Korean Patent Publication No. 2013-0039456 U.S. Published Patent Application No. 2015-0147682

Accordingly, in order to solve the above problems, the present invention provides a manufacturing apparatus and system that can easily and efficiently manufacture a core-shell catalyst composed of an unbleached core and a platinum shell and having improved durability of the catalyst, It is aimed to present a method.

It is an object of the present invention to provide a core-shell catalyst device, a system, and a method of operating the same, in which a catalyst manufacturing step of forming a core and a shell and a nitriding step of including nitrogen in the core are simultaneously performed.

The apparatus for producing a catalyst according to the present invention comprises: a reaction chamber having a predetermined size having a circular or rectangular shape; A reaction chamber which is located inside the reaction chamber and has one or more cylinders and is interconnected by a fluid flow pipe; And a cavitation generating device having a protrusion for insertion into the reaction chamber.

Here, the empty space between the reaction chambers in the reaction chamber is filled with a heat insulating material. In addition to the cavitation generator, each of the reaction chambers has an ultrasonic generator capable of resonating with the natural frequency of the solvent in the reaction chamber .

The catalyst production system according to the present invention comprises the above catalyst production apparatus according to the present invention; A pump connected to the fluid flow pipe to flow the fluid; A filter for filtering particulate matter flowing inside the fluid flow pipe; And a drying device for drying the filtered catalyst on the filter.

The method for operating the catalyst production system according to the present invention may further comprise the steps of: (1) introducing a raw material containing a predetermined amount of a reducing solvent, a liquid nitrogen source, a noble metal precursor, a transition metal precursor, and a carbon support through the raw material inlet; A second step of operating the cavitation generator; Moving the fluid in the fluid flow pipe by operating the pump; Filtering the produced catalyst through a filter; And drying the filtered catalyst on the filter.

Here, the method includes the step of activating an ultrasonic wave generator that resonates with the natural frequency of the solvent between steps 1 and 2.

The apparatus for producing a catalyst according to the present invention can produce a core-shell catalyst under a liquid phase condition and, at the same time, can carry out a nitriding treatment for containing nitrogen in a core in a single process, and has an effect specific to the mass production of a core- .

In addition, the apparatus for producing a catalyst according to the present invention has a plurality of reaction chambers in one reaction chamber, and the reaction chambers are constituted by a continuous reaction connected to each other through a fluid flow pipe, which is advantageous for mass production of a core-shell catalyst .

1 shows the construction of a catalyst production system according to the present invention.
2 shows a configuration of a reaction chamber according to the present invention.

The present invention relates to an apparatus and a system for producing a core-shell catalyst having improved durability and electrochemical performance of a catalyst by incorporating a nitrogen element in the core in a liquid phase.

It is to be understood that the terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings with respect to the specific details for carrying out the present invention, It should be interpreted in the meaning and concept consistent with the technical idea of the present invention based on the principle that the concept of the term can be appropriately defined in order to explain it. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, It should be understood that there may be various equivalents and variations thereof.

Hereinafter, an apparatus, a system, and a method for operating the catalyst according to the present invention will be described in detail with reference to FIG. The main components of the apparatus for producing a catalyst according to the present invention are a reaction chamber 30 having a raw material inlet port 80, a reaction chamber 20, a cavitation generator 10, an ultrasonic generator 60, The cavitation generating device 10, the ultrasonic generator 60 and the heat insulating material are located in the reaction chamber 30 and the ultrasonic wave generating device 10 is installed in the reaction chamber 20, And the cavitation generator 10 is configured to be inserted into the reaction chamber 20. In the reaction chamber 30, two or more reaction chambers 20 are spaced apart from each other. Each of the reaction chambers 20 is interconnected by a fluid flow pipe 70, The heat insulating material is located in the spaced-apart space.

The apparatus for producing a catalyst according to the present invention is basically a device suitable for producing a catalyst by inducing a reaction of a raw material composed of a liquid phase or a gaseous phase by heat and pressure supply based on cavitation and more specifically to a catalyst composed of a core and a shell using cavitation Is a device specialized for improving the durability of the core-shell catalyst by containing nitrogen in the core portion. Specifically, in the apparatus for producing a catalyst according to the present invention, the raw material may be a liquid nitrogen source, a reducing solvent, a precious metal precursor, a solution containing a transition metal precursor having a relatively higher vapor pressure than the precious metal precursor, and a carbon support, Cavitation is generated by irradiating the raw material with a high output ultrasonic wave by using the cavitation generator 10. The high frequency oscillation of the ultrasonic waves generated by the cavitation generator 10 generates bubbles in the cavity which causes oscillatory growth and finally the cavitation It explodes. This series of processes caused by ultrasonic irradiation is also called 'acoustics cavitation mechanism'. The joint explosion occurring in the last stage of the acoustic cavitation mechanism can cause a huge heat energy reaching about 5000K, and its extinction is achieved within a very short time of about 10 ^-6 seconds. When two or more reactants in a chemical reaction to which ultrasonic irradiation is applied are two or more substances having different vapor pressures, the speed at which the two or more reactants are evaporated into bubbles due to the high frequency vibration of ultrasonic waves are different, The structural and electrochemical characteristics of the result can be controlled. For example, when two or more metal precursors are used as a reactant and ultrasound is irradiated to produce nanoparticles containing two or more metals, the two or more metal precursors may have a difference in vapor pressure, The distribution of the metal element can be controlled. In the apparatus for producing a catalyst according to the present invention, the metal precursor having a low vapor pressure in the nanoparticle is positioned in a shell portion and the metal precursor having a high vapor pressure is positioned in a core portion, Can be obtained.

In the apparatus for producing a catalyst according to the present invention, the cavitation generator 10 is configured to be coupled with each reaction chamber 20 and has a stick-like protrusion so that it can be inserted downward from the upper part of the reaction chamber 20. The cavitation generator 10 may be an output capable of generating ultrasonic waves to the extent that cavitation can be generated in the reducing solvent used in the present invention by irradiating ultrasonic waves. The reducing solvent of the present invention is generally used in the art and can be a solvent having a reducing power at a temperature of 70 ° C or higher. Specifically, it has a reducing power at a temperature of 70 ° C to 400 ° C. Examples thereof include di- - ethylene glycol and poly-ethylene glycol. The reducing solvent serves to reduce the metal precursor as a reactant in the cavity formed by the ultrasonic treatment.

Referring to FIG. 2, the reaction chamber 20 of the present invention includes a cavitation generator (not shown), which can be inserted into the reaction chamber 20, for dispersing and increasing the reaction volume due to vertical rise of the jet flow generated upon occurrence of cavitation 10, and more specifically, it is more preferably a cylindrical shape extending from the upper portion to the lower portion. In the reaction chamber 20, a plurality of two or more reaction chambers 30 having a predetermined shape having a circular or rectangular shape are disposed, and the reaction chamber 20 is provided with an ultrasonic generator 60 . The two or more reaction chambers 20 are connected to each other by a fluid flow pipe 70, and a space between the reaction chambers 20 is filled with a heat insulating material. As described above, the chemical reaction of the raw material takes place in the reaction chamber 20 of the present invention, and the catalyst is produced through this reaction. The cavitation generator 10 is inserted into the reaction chamber 20 from the upper part to the lower part of each reaction chamber 20 to induce the cavitation in the solvent. In this process, even distribution of the raw material in the solvent before cavitation occurs may affect the uniformity of the catalyst and the quality of production, and in particular, the rate of occurrence of microbubbles affects the overall catalyst production efficiency. Accordingly, in the present invention, the ultrasonic wave generator 60 is attached to each of the reaction chambers 20 located in two or more reaction chambers 30 to disperse the raw material through ultrasonic vibration before cavitation occurs, Cavitation is generated by the cavitation generator 10 in the state where bubbles are generated. In the apparatus for producing a catalyst according to the present invention, the ultrasonic generator 60 may be installed on a side surface or a bottom surface of the reaction chamber 20, and when the ultrasonic wave is generated, And is configured to resonate the reductive solvent by vibrating at the same frequency.

Another important feature of the apparatus for producing a catalyst according to the present invention is that the reaction can be performed continuously, not in the conventional batch type reactor configuration. To this end, the reaction chamber 20 is configured in such a manner that two or more reaction chambers 20 are interconnected by a fluid flow pipe 70, as described above. The inlet of the fluid flow pipe 70 in each reaction chamber 20 is located at the top of the reaction chamber 20 and the outlet of the fluid flow pipe 70 may be at the bottom of the reaction chamber 20. The outflow portion of the fluid flow pipe 70 formed in the reaction chamber 30 in the apparatus for producing a catalyst of the present invention is connected to and driven by the pump 40 and the fluid flow pipe 70, And is connected to the chamber 30 so as to circulate. In addition, in the apparatus for producing a catalyst according to the present invention, the two or more reaction chambers 20 are spaced apart from each other by vibration such as cavitation, and the heat insulating material is located in the spacing space, The temperature change of the tube 70 can be minimized.

In order for the catalyst to be manufactured using the apparatus for producing a catalyst according to the present invention, it is necessary to perform the continuous flow catalyst production process, the flow of the fluid by the pump 40 and the filtration and drying by the filter 50, Do. In this regard, the catalyst production system using the apparatus for producing a catalyst according to the present invention includes a pump 40 for connecting a fluid flow pipe 70 to flow a fluid, a filter for filtering particulate matter flowing in the fluid flow pipe 70, (50), and a drying device for drying the filtered catalyst in the filter (50). In the present invention, it is preferable that the pump 40 is a device capable of pumping the fluid, and the pump 40 is capable of transferring the liquid material so that the organic solvent can be transferred. In the catalyst production system according to the present invention, the filter 50 preferably has a pore size of 100 μm or less composed of cellulose and a polymer, and a filter 50 having an inactive characteristic such as Teflon or PE is suitable.

In order to operate the catalyst production system according to the present invention, a raw material containing a predetermined amount of a reducing solvent, a liquid nitrogen source, a noble metal precursor, a transition metal precursor, and a carbon support is introduced through the raw material inlet 80, Three steps of activating the generator 10, three steps of operating the pump 40 to flow the fluid in the fluid flow pipe 70, four steps of filtering the generated catalyst through the filter 50, , And drying the filtered catalyst. A step of washing the filter 50 using water in the filtering process of the four steps may be added. In this case, a washing water supply line may be configured to supply the washing water to the filter 50 portion. As shown in the above operation method, the catalyst production apparatus according to the present invention can produce catalysts having a shape of core and shell through reaction of raw materials including a reducing solvent, a liquid nitrogen source, a noble metal precursor, a transition metal precursor, The nitrogen source of the liquid phase used in the present invention is not particularly limited as it is generally used in the art, and for example, urea may be used. The noble metal precursor may have a vapor pressure lower than the vapor pressure of the transition metal precursor. Specifically, the noble metal precursor is not particularly limited, and is generally used in the art. However, the noble metal precursor is not limited to the precursor of the noble metal such as an acetylacetonate precursor, a noble metal hexafluoroacetylacetonate precursor, and a noble metal pentafluoroacetylacetonate precursor It may be at least one selected. The transition metal precursor may be at least one selected from the group consisting of precursors of nickel, cobalt, iron and manganese, although the transition metal precursor is generally used in the art and is not particularly limited. The transition metal precursor may be at least one selected from the group consisting of an acetyl acetonate precursor of a transition metal and a hexafluoroacetylacetonate precursor of a transition metal. Such transition metal precursors are rapidly volatilized by high vapor pressures and are quickly trapped in cavities by ultrasonic waves, so that in the core-shell structure of the reaction product, the transition metal can be located in the core portion. The carbon support may be a porous carbon support. When a porous carbon support is used, a large amount of core / shell structure nanoparticles can be efficiently supported by a large surface area.

In the method of operating the catalyst production system according to the present invention, it may include the step of activating the ultrasonic generator 60 that resonates with the natural frequency of the solvent between the first stage and the second stage.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. The scope of protection of the present invention should be construed under the following claims, and all technical ideas within the scope of equivalents thereof should be construed as being included in the scope of the present invention.

10: cavitation generator 20: reaction chamber
30: reaction chamber 40: pump
50: filter 60: ultrasonic generator
70: fluid flow pipe 80: material inlet

Claims (6)

A reaction chamber having a predetermined size with a circular or rectangular shape and including a raw material inlet;
A reaction chamber located inside the reaction chamber, the reaction chamber having at least one cylinder shape and including a fluid flow pipe;
And a cavitation generating device having a protrusion for insertion into the reaction chamber.
The catalyst manufacturing apparatus according to claim 1, wherein the empty space between the reaction chambers in the reaction chamber is filled with a heat insulating material.
The apparatus of claim 1, wherein an ultrasonic generator capable of resonating with the natural frequency of the solvent in the reaction chamber is attached to each reaction chamber separately from the cavitation generator.
A catalyst manufacturing apparatus according to any one of claims 1 to 3;
A pump connected to the fluid flow pipe of claim 1 to flow the fluid;
A filter for filtering particulate matter flowing inside the fluid flow pipe;
And a drying device for drying the filtered catalyst on the filter,
A method for operating the catalyst production system of claim 4,
Introducing a raw material containing a predetermined amount of a reducing solvent, a liquid nitrogen source, a noble metal precursor, a transition metal precursor, and a carbon support through the raw material inlet;
A second step of operating the cavitation generator;
Moving the fluid in the fluid flow pipe by operating the pump;
Filtering the produced catalyst through a filter;
And a step of drying the filtered catalyst on the filter.
The method for operating a catalyst production system according to claim 5, comprising operating the ultrasonic generator for resonating with the natural frequency of the solvent between steps 1 and 2

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