CN116314873A - Continuous mass production system for fuel cell catalyst and preparation method for fuel cell catalyst - Google Patents
Continuous mass production system for fuel cell catalyst and preparation method for fuel cell catalyst Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
- B01F33/8362—Mixing plants; Combinations of mixers combining mixing with other treatments with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- General Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a continuous batch production system of a fuel cell catalyst and a preparation method of the fuel cell catalyst. The continuous batch production system of the fuel cell catalyst and the preparation method of the fuel cell catalyst can avoid possible amplification effects of the intermittent kettle type microwave reactor and the solid single-mode continuous flow microwave chemical reactor, ensure the performance of the Pt-based catalyst and the consistency among batches, realize the integrated batch production from feeding to discharging, and realize the large-scale mass production of the catalyst.
Description
Technical Field
The invention relates to the field of fuel cell catalysts, in particular to a continuous batch production system of a fuel cell catalyst and a preparation method of the fuel cell catalyst.
Background
At present, the proton exchange membrane fuel cell technology of China is rapidly developed, and the localization of the fuel cell is primarily realized. But its large-scale commercial application still faces serious challenges such as high cost, short lifetime, etc. The major cost of PEMFCs comes from Pt-based catalysts. As key materials of PEMFCs, enterprises for producing PEMFCs catalysts exist in China, but the daily output of many enterprises is only hundred grams, and the phenomenon of batch supply exists. For the user side, the cost, time, reliability and consistency of purchasing the catalyst in kilogram grade at one time are certainly more advantageous than purchasing the catalyst in gram grade in batches.
There are many methods for preparing fuel cell Pt-based catalysts, such as polyol method, oleylamine method, impregnation reduction method and NaBH method 4 Etc. The polyol method is a simple and green preparation method, mainly uses ethylene glycol as a solvent and also as a reducing agent and a stabilizing agent, and does not need to additionally use other reducing agents and surfactants. In the process of preparing the catalyst by using the polyol method, microwave-assisted acceleration reaction can be used, and the technology of using microwave-assisted glycol has the advantages of both microwave radiation heating and the technology of using the polyol, and can prepare various metal nano particles rapidly and efficiently. In the process of preparing the metal nano-particles by adopting the ethylene glycol, the ethylene glycol is heated to generate glyoxal, glycollic acid and the like, so that the metal nano-particles have reducibility, can negatively charge metal particles generated by reaction, effectively prevent agglomeration and growth among the metal particles, and have the function of stabilizing the metal particles. In addition, compared with the prior artCompared with the heating mode, the microwave radiation heating mode has the characteristics of high heating speed, uniform heating and the like, can promote the nano particles to be quickly reduced and nucleated, and finally has the advantages of good dispersity, small particle size and narrow distribution range of the prepared metal nano particles. The microwave-assisted ethylene glycol method not only ensures the reliability of the product, but also can effectively shorten the reaction time to improve the production efficiency of the catalyst.
The traditional microwave-assisted ethylene glycol method uses a batch kettle type multimode microwave reactor, all reactants are generally added into a unit kettle at the beginning, and the reaction temperature of the reactants is determined by adjusting the microwave heating time. Because of the load traction effect of the microwave resonant cavity heating and the association with the microwave source excitation position setting, all modes can occur, or can occur partially, and the occurrence frequency is irregular. Therefore, in the actual working process of the resonant cavity, unpredictable multiple modes coexist, the heating effect of strong and weak superposition is achieved, the microwave electric field is totally distributed in a certain range, but the electric field distribution intensity law cannot be accurately found, so that when the intermittent kettle type multimode microwave reactor is used for preparing the Pt-based catalyst, the reacted solution is heated unevenly, the reaction solution is heated for the same time in batches, and the reactant temperatures are different. Therefore, the metal particle size of the Pt-based catalyst prepared using the batch-type multi-mode microwave reactor is not uniform and the performance repeatability of the catalyst between batches is poor. The production efficiency of such batch mode is relatively low from the point of view of producing the product.
Because of the problems existing in the preparation of the Pt-based catalyst by the intermittent kettle type multi-mode microwave reactor, the solid single-mode continuous flow microwave chemical reactor can be used as a microwave source for preparing the Pt-based catalyst, so that the defects of the kettle type reactor can be avoided, the reactor has two advantages of the solid source and the single-mode microwave technology, the chemical process requirements of preparing the Pt-based catalyst by a microwave-assisted polyol method can be met, continuous flow preparation can be realized, and two flow preparation modes of normal pressure and pressure are supported. The conventional solid single-mode continuous flow microwave chemical reactor is mainly used as a reactor for full liquid phase chemical reaction, the cavity of the reactor is arranged in a vertical mode, and the spiral coil is arranged in the cavity of the solid single-mode continuous flow microwave chemical reactor. The reaction solution adopts continuous pump or pressure pump to feed, and the feed inlet sets up in spiral coil upper portion, after the reaction solution gets into the spiral coil in the cavity, gradually by the pump body propulsion spiral coil bottom, after the reaction solution in the cavity rapid heating, upwards discharge by spiral coil bottom. Although the conventional solid single-mode continuous flow microwave chemical reactor can avoid the problems of the batch kettle type multimode microwave reactor, the reduced Pt-based catalyst falls back and is mixed with unreacted solution due to the problem of Pt-based catalyst accumulation caused by the vertical structural cavity of the reactor, so that the catalyst performance is affected. When the conventional solid single-mode continuous flow microwave chemical reactor with the vertical cavity is used for preparing the Pt-based catalyst, the problems of accumulation and mixing of the Pt-based catalyst exist, and the performance and batch-to-batch consistency of the Pt-based catalyst are further affected. In addition, at present, when a conventional solid single-mode continuous flow microwave chemical reactor is adopted to prepare the Pt-based catalyst, only the chemical reaction process and the dispersion chemical reaction solution can be completed, and the product washing step is completed in a segmented way. The complete equipment for batch production of the integrated proton exchange membrane fuel cell catalyst can meet the whole set of process flow of preparing the catalyst by using the microwave-assisted polyol method, and one process from feeding to finished product production is not available.
Disclosure of Invention
The invention mainly solves the technical problems of providing a continuous batch production system of a fuel cell catalyst and a preparation method of the fuel cell catalyst, which can avoid possible amplification effects of an intermittent kettle type microwave reactor and a solid single-mode continuous flow microwave chemical reactor, ensure the performance and the consistency among batches of Pt-based catalysts, realize integrated batch production from feeding to discharging and realize large-scale mass production of the catalyst.
In order to solve the technical problems, the invention adopts a technical scheme that: the continuous batch production system of the fuel cell catalyst comprises a feeding unit, a production unit and a discharging unit which are sequentially connected through pipelines; the feeding unit comprises a mixing tank, a stirring device and ultrasonic dispersing equipment are arranged on the mixing tank, raw materials in the mixing tank are processed by the ultrasonic dispersing equipment and the stirring device to generate a reaction solution, and the reaction solution flows through a pipeline to enter the production unit; the production unit comprises a continuous microwave reactor and a storage tank group, wherein the continuous microwave reactor comprises at least two single-mode microwave cavities which are connected in series, a spiral coil pipe which is horizontally arranged is arranged in the single-mode microwave cavity, the reaction solution flows through the spiral coil pipe in a horizontal spiral mode and enters the storage tank group after being heated by a microwave radiation source, the storage tank group comprises at least two storage tanks which are arranged in parallel, and the storage tanks stir and react the reaction solution in the storage tank to obtain a reaction product and flow into the discharge unit through a pipeline; the discharging unit comprises a vacuum filtration washing device, the vacuum filtration washing device comprises a container kettle, a filtrate kettle and a vacuumizing device which are sequentially arranged from top to bottom, and the reaction product is subjected to suction filtration to obtain a catalyst.
In a preferred embodiment of the invention, the mixing tank is provided with a feeding port for feeding raw materials, the mixing tank is also provided with a temperature sensor and a pH meter for detecting the temperature and the pH of the reaction solution, and the outer side of the mixing tank is provided with a jacket for filling cooling water.
In a preferred embodiment of the invention, a speed-regulating screw pump is sequentially arranged between the mixing tank and the continuous microwave reactor, and the reaction solution is continuously fed into the continuous microwave reactor through the speed-regulating screw pump.
In a preferred embodiment of the invention, a control valve is arranged between the speed-regulating screw pump and the mixing tank, and a magnetic filter and a temperature sensor are also arranged between the speed-regulating screw pump and the continuous microwave reactor.
In a preferred embodiment of the present invention, the single-mode microwave cavity is horizontally arranged, and the spiral coil is a glass tube or a polytetrafluoroethylene tube.
In a preferred embodiment of the invention, a temperature sensor and a pressure regulating valve are arranged between the inlet of the storage tank and the outlet of the continuous microwave reactor.
In a preferred embodiment of the invention, the stirring device, the temperature sensor, the pH meter and the liquid level sensor are arranged on the storage tank, and the reaction product in the storage tank flows into the container kettle after being sucked into the pipeline through the negative pressure of the vacuumizing device.
In a preferred embodiment of the invention, a filter plate is arranged between the container kettle and the filtrate kettle, and a washing liquid supply device is also connected above the container kettle.
In order to solve the technical problems, the invention adopts another technical scheme that: there is provided a method for preparing a fuel cell catalyst by the continuous mass production system of a fuel cell catalyst as described above, comprising the steps of: a. adding quantitative carbon black powder, isopropanol or ultrapure water and ethylene glycol into a mixing tank from a feed port, filling cooling water into a jacket of the mixing tank, starting ultrasonic dispersion equipment above the mixing tank, after ultrasonic dispersion of carbon black slurry for a certain time, starting a stirring device to form uniform carbon black slurry, adding ethylene chloroplatinic acid glycol solution with a metal loading of 10-70 mass% in a metering ratio, continuously stirring, and adding sodium hydroxide glycol solution to adjust the pH value of the reaction solution to 9-13 until the pH value of the reaction solution is stable; b. opening a control valve, enabling the reaction solution to pass through an electromagnetic speed-regulating screw pump, adjusting the flow speed and the flow rotation direction, absorbing the magnetic materials carried by the screw pump through a magnetic filter, enabling the reaction solution to flow into a continuous microwave reactor in the horizontal spiral flow direction, heating by a microwave radiation source, leaving the microwave reactor in a horizontal spiral mode, and conveying the reaction solution to a storage tank arranged in parallel after the pressure of the reaction solution is adjusted by a pressure adjusting valve; c. feeding a storage tank, wherein a liquid level sensor in the storage tank senses the liquid level, a stirring device is started, the reaction solution starts to be stirred until the liquid level in the storage tank reaches a high liquid level, the storage tank pauses feeding, then the other storage tank repeats the feeding step until the feeding is completed, the reaction product in the storage tank is cooled to room temperature, dilute nitric acid solution is fed into the storage tank, when the pH value of the reaction product is 1-3, the storage tank starts to discharge, and the reaction product enters a container kettle by virtue of the negative pressure of a vacuumizing device;
d. the reaction product is pumped out in the container kettle sequentially through the filter membrane on the filter plate and the vacuumizing device, the solid matter is left on the filter membrane to form a filter cake, meanwhile, the washing liquid is sent into the container kettle through the spray pipe by the washing liquid supply device, the residual solid matter is washed for a plurality of times until the solid matter is filtered into the filter cake for the last time, the filter cake is washed and discharged, the discharge valve is opened to discharge the solution, the filter membrane is taken out after the washing is finished, and the black product on the filter membrane is the Pt-based catalyst.
In a preferred embodiment of the present invention, the temperature of the carbon black slurry in the step a is below 25 ℃, after the carbon black slurry is ultrasonically dispersed for 0.5 to 1.5 hours, stirring slurry is started, and the carbon black slurry is stirred for 1 to 4 hours to form uniform carbon black slurry; and (c) in the step (b), the discharging temperature of the reaction solution is 130-150 ℃, the time for the reaction solution to flow through the continuous microwave reactor is 50-80 s, and the pressure of a pipeline system is 0-0.25 MPa.
The beneficial effects of the invention are as follows: according to the continuous batch production system of the fuel cell catalyst and the preparation method of the fuel cell catalyst, the microwave continuous reactor with the cavity arranged horizontally is adopted to prepare the Pt-based catalyst, and the reaction solution passes through the coil pipe of the continuous microwave reactor in a horizontal spiral mode, so that the problems of accumulation and mixing of the Pt-based catalyst caused by the cavity of the vertical structure are solved, and the performance of the catalyst and the consistency among batches are ensured.
The continuous batch production system of the fuel cell catalyst and the preparation method of the fuel cell catalyst can meet the whole set of process flow of preparing the catalyst by a microwave-assisted polyol method, realize integrated continuous batch production from feeding to discharging, have simple operation and high production efficiency, avoid possible amplification effects of an intermittent kettle type microwave reactor and a solid single-mode continuous flow microwave chemical reactor, and ensure the performance of the Pt-based catalyst and consistency among batches.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the description below are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art, wherein:
FIG. 1 is a schematic view of a continuous mass production system for fuel cell catalysts according to a preferred embodiment of the present invention;
FIG. 2 is a partial schematic view of FIG. 1;
FIG. 3 is a partial schematic view of FIG. 1;
FIG. 4 is a TEM image of a catalyst prepared according to the present application and a comparative example, and a comparative image of particle size distribution;
the components in the drawings are marked as follows: 1. mixing tank, 11, agitating unit, 12, ultrasonic dispersion equipment, 13, the feed inlet, 14, control valve, 2, continuous microwave reactor, 21, single mode microwave cavity, 22, spiral coil, 3, storage tank group, 31, storage tank, 4, vacuum filtration washing device, 41, container cauldron, 42, filtrate cauldron, 43, evacuating device, 44, filter plate, 45, washing liquid supply device, 5, speed governing screw pump, 6, magnetic filter, 7, air-vent valve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. The structures, proportions, sizes, etc. shown in the drawings are shown only in connection with the present disclosure, and are not intended to limit the scope of the invention, since any modification, variation in proportions, or adjustment of the size, etc. of the structures, proportions, etc. should be considered as falling within the spirit and scope of the invention, without affecting the effect or achievement of the objective. Also, the terms "upper", "lower", "left", "right", "middle", and the like are used herein for descriptive purposes only and are not intended to limit the scope of the invention for modification or adjustment of the relative relationships thereof, as they are also considered within the scope of the invention without substantial modification to the technical context.
Referring to fig. 1, a continuous mass production system of fuel cell catalysts comprises a feeding unit, a production unit and a discharging unit which are sequentially connected through pipelines, wherein the pipelines are made of stainless steel and provided with bushings made of polytetrafluoroethylene.
The feeding unit comprises a jacketed mixing tank 1. The mixing tank 1 is provided with a feeding port 13 for feeding raw materials, and the mixing tank 1 is also provided with a temperature sensor and a pH meter for detecting the temperature and the pH of the reaction solution. The outer side of the mixing tank 1 is provided with a jacket for filling cooling water. The mixing tank 1 is provided with a stirring device 11 and an ultrasonic dispersing device 12, raw materials in the mixing tank 1 are processed by the ultrasonic dispersing device 12 and the stirring device 11 to generate a reaction solution, and the reaction solution flows through a pipeline to enter a production unit.
All stirring devices 11 are vertical cylinders, the height-diameter ratio size of which is determined according to the height-diameter ratio and the loading coefficient of the container according to the operation, and the stirring devices are composed of stirring driving devices and stirring paddles, and belong to conventional stirring devices, and are not repeated here.
The ultrasonic dispersing device 12 (prior art device) is composed of an ultrasonic transducer, a horn and a tool head. The ultrasonic transducer can perform telescopic motion in the longitudinal direction, and can realize micro amplitude and accuracy to the micron level. If the amplitude needs to be regulated and controlled to be larger, the amplitude is amplified through the amplitude transformer, and meanwhile, the reaction solution and the ultrasonic transducer can be isolated. Ultrasonic energy is transmitted to the tool head through the horn and the tool head emits ultrasonic energy into the reaction solution. The ultrasonic dispersing apparatus 12 is provided with a temperature sensor for monitoring the temperature of the reaction solution at the time of ultrasonic dispersion, and the temperature of the reaction solution is controlled by adjusting the flow rate and the temperature of the cooling water in the jacket.
The production unit comprises a continuous microwave reactor 2 and a storage tank group 3, wherein the continuous microwave reactor 2 comprises at least two single-mode microwave cavities 21 which are connected in series. The single-mode microwave cavity 21 is arranged horizontally. A spiral coil 22 is horizontally arranged in the single-mode microwave cavity 21, and the spiral coil 22 is a glass tube or a polytetrafluoroethylene tube. The reaction solution flows through the spiral coil 22 in a horizontal spiral manner and is heated by a microwave radiation source to enter the storage tank group 3. The solid single-mode continuous microwave reactor 2 is formed by connecting two single-mode microwave cavities 21 in series, wherein the cavities are of stainless steel integrated welding forming, micro-positive pressure full-sealing and side-opening type inner cavity structures, polytetrafluoroethylene anti-corrosion coatings are arranged on the inner surfaces of the cavities, the cavities are of horizontal structures, glass spiral coils 22 or polytetrafluoroethylene tubes are arranged in the cavities, and an infrared or optical fiber thermometer is arranged at an inlet and an outlet of the solid single-mode continuous reactor to realize accurate temperature control. The power of a single microwave source is 0-1000W, and the microwave frequency is 2450MHz.
The storage tank group 3 includes at least two storage tanks 31 arranged in parallel. A pressure regulating valve 7 is arranged between the storage tank 31 and the continuous microwave reactor 2. The reaction solution in the storage tank 31 is stirred and reacted to obtain a reaction product and flows into the discharge unit through a pipe. The storage tank 31 is made of stainless steel, a feed inlet 13 and an exhaust port are arranged above the storage tank 31, and the stirring device, the temperature sensor, the industrial online pH meter, the liquid level height sensor and the electromagnetic valve are arranged. The reaction product in the storage tank 31 is sucked into the pipe by the negative pressure of the vacuum suction device 43 and flows into the vessel tank 41.
A speed-regulating screw pump 5 is arranged between the mixing tank 1 and the continuous microwave reactor 2 in sequence. The electromagnetic speed-regulating screw pump 5 (thick slurry pump, prior art equipment) is made of high-quality acid-alkali-resistant stainless steel for all metal parts contacting materials, the lining is made of nontoxic and odorless rubber, the working temperature range can reach 0-120 ℃, and the slurry viscosity can be less than 10000Pa.s and the slurry containing particles can be conveyed. The pump body can realize stable conveying of slurry with higher concentration, and has no phenomena of overflow, pulsation, stirring, slurry shearing and the like. The rotation direction of the pump can change the flow direction of liquid, so that the forward flushing of the pipeline direction is realized. The reaction solution was continuously fed into the continuous microwave reactor 2 by means of a speed-adjusting screw pump. A magnetic filter 6 and a temperature sensor are also arranged between the speed regulating screw pump 5 and the continuous microwave reactor 2. The magnetic filter 6 (prior art device) is made of food grade 304 stainless steel, has strong corrosion resistance and is easy to clean. The stainless steel strong magnetic rod is made of 316 stainless steel, and the filter can be disassembled and assembled through a rapid clamp seal design. A control valve 14 is arranged between the speed-regulating screw pump 5 and the mixing tank 1.
The discharging unit comprises a vacuum filtration washing device 4, the vacuum filtration washing device 4 comprises a container kettle 41, a filtrate kettle 42 and a vacuum pumping device 43 which are sequentially arranged from top to bottom, and the catalyst is obtained after the reaction product is subjected to suction filtration. A filter plate 44 is arranged between the container kettle 41 and the filtrate kettle 42, and a washing liquid supply device is also connected above the container kettle 41. The container kettle 41 and the filtrate kettle 42 are made of high borosilicate glass, and a filter plate 44 made of polytetrafluoroethylene is arranged between the container kettle 41 and the filtrate kettle 42. A feed inlet and a flushing liquid spray pipe are arranged above the reaction product accommodating kettle body, and the flushing liquid spray pipe is connected with an automatic valve and a washing liquid supply device 45. A discharge valve is arranged in the center of the lower part of the filtrate accommodating kettle body, and a vacuumizing tube is arranged on the upper part of the filtrate accommodating kettle body. The container kettle 41, the filtrate kettle 42 and the filter plate 44 can be accurately disassembled and assembled through a quick clamp seal design.
The preparation method of the fuel cell catalyst is carried out by the continuous mass production system of the fuel cell catalyst and comprises the following steps:
a. and (3) taking a certain amount of carbon black powder, isopropanol or ultrapure water and ethylene glycol, putting the carbon black powder, the isopropanol or the ultrapure water and the ethylene glycol into a mixing tank from a feed port, filling cooling water into a jacket of the mixing tank, starting ultrasonic dispersion equipment at two sides above the mixing tank, and immersing an ultrasonic tool head into carbon black slurry by adjusting the length of an ultrasonic amplitude transformer. And simultaneously, adjusting proper ultrasonic dispersion frequency and power, monitoring the temperature of the carbon black slurry through a temperature sensor, and keeping the temperature of the carbon black slurry below 25 ℃. After the carbon black slurry is ultrasonically dispersed for 0.5-1.5h, starting a stirring device, stirring the carbon black slurry for 1-4 h to form uniform carbon black slurry, then adding a chloroplatinic acid glycol solution with a metal loading of 10-70% in a metering ratio, continuously stirring for 1-3h, and then adding a sodium hydroxide glycol solution to adjust the pH value of the reaction solution to 9-13 until the pH value of the reaction solution is stable.
b. After the flow speed and the flow rotation direction of the reaction solution are regulated through an electromagnetic speed regulating screw pump and the magnetic materials carried by the screw pump are absorbed through a magnetic filter, the reaction solution flows into the continuous microwave reactor in the horizontal spiral flow direction, is heated by a microwave radiation source and leaves the microwave reactor in a horizontal spiral mode, the reaction solution flows through a pressure regulating valve to regulate the pressure, the problems of boiling phenomenon and pipeline blockage caused by substances with lower boiling points in the reaction solution are avoided, the electromagnetic speed regulating screw pump is set to regulate the flow rate of the reaction solution, and the power, the material heating temperature and the discharging temperature of the solid single-mode continuous microwave reactor are set to determine the heating temperature of the reaction solution. The temperature sensor at the discharge port of the microwave reactor monitors the temperature of the solution after reaction, the discharge temperature of the reaction solution is generally controlled to be 130-150 ℃, the time for the reaction solution to flow through the microwave reactor is 50-80 s, and the pressure of a reaction pipeline system is 0-0.25 MPa. By feeding into storage tanks arranged in parallel.
c. The material storage tank is fed, the exhaust port valve of the material storage tank is in a normally open state, and electromagnetic valves are arranged at each feeding end and each discharging end of the material storage tank. When the electromagnetic valve at the feeding end of the storage tank A is opened, the electromagnetic valve at the discharging end is closed, and the product is conveyed to the storage tank A. When the reaction product is pumped into the storage tank body, the stirring driver drives the stirring paddle when the liquid level sensor reaches a low liquid level. When the liquid level in the storage tank A reaches a high liquid level, the electromagnetic valve at the feeding end of the storage tank A is closed through the sensing of the liquid level height sensor, the electromagnetic valve at the feeding end of the storage tank B is opened at the moment, the electromagnetic valve at the discharging end is closed, and reaction products are conveyed into the storage tank B to finish the storage switching. After cooling reaction products in the storage tank A to room temperature, feeding dilute nitric acid solution into the storage tank, and when the pH value of the reaction products is 1-3, starting discharging the storage tank, and entering the container kettle by means of negative pressure of a vacuumizing device;
d. the reaction product is pumped out in the container kettle sequentially through the filter membrane on the filter plate and the vacuumizing device, the solid matters are left on the filter membrane to form a filter cake, meanwhile, the washing liquid supply device sends washing liquid into the container kettle through the spray pipe, the residual solid matters are washed for a plurality of times, and the vacuumizing pipe is used for carrying out suction filtration until the solid matters are finally subjected to suction filtration to form the filter cake, then the filter cake is washed and discharged, the discharge valve is opened to discharge the solution, the filter membrane is taken out after the washing is finished, and the black product on the filter membrane is the Pt-based catalyst.
As can be seen from fig. 4, pt nanoparticles of the catalyst prepared according to the present invention are uniformly dispersed on a carbon support. As can be seen from the particle size distribution, the particle size distribution of the Pt nanoparticles prepared by the method is relatively narrow, and the particle size of the Pt nanoparticles is about 3.08nm. Comparative example 1 is a catalyst prepared by a tank type microwave reactor, pt nanoparticles were significantly agglomerated, and the particle size distribution was relatively broad, with the Pt nanoparticles having a particle size of about 3.29nm. Comparative example 2 a catalyst prepared by a single vertical structure solid single mode continuous microwave reactor, pt nanoparticles had a slight agglomeration phenomenon, and the particle size distribution was also relatively narrow, with the Pt nanoparticles having a particle size of about 3.20nm.
Compared with the prior art, the method adopts the solid single-mode microwave continuous reactor with the horizontal cavity to prepare the Pt-based catalyst, the reaction solution is heated uniformly, and meanwhile, the problems of catalyst accumulation, material mixing and the like can be avoided by being provided with the pressure valve, so that the performance of the catalyst and the consistency among batches are ensured. The equipment not only can meet the whole set of process flow for preparing the catalyst by a microwave-assisted polyol method, realizes integrated batch production from feeding to product discharge, improves the production efficiency (the capacity scale of the produced catalyst reaches 0.2-3 kg/day), but also avoids the possible amplification effect of an intermittent kettle type microwave reactor and a solid single-mode continuous flow microwave chemical reactor, and ensures the performance of the Pt-based catalyst and the consistency among batches.
The invention and its embodiments have been described above by way of illustration and not limitation, and the invention is illustrated in the accompanying drawings and described in the drawings in which the actual structure is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.
Claims (10)
1. A continuous batch production system of fuel cell catalyst is characterized by comprising a feeding unit, a production unit and a discharging unit which are sequentially connected through a pipeline;
the feeding unit comprises a mixing tank, a stirring device and ultrasonic dispersing equipment are arranged on the mixing tank, raw materials in the mixing tank are processed by the ultrasonic dispersing equipment and the stirring device to generate a reaction solution, and the reaction solution flows through a pipeline to enter the production unit;
the production unit comprises a continuous microwave reactor and a storage tank group, wherein the continuous microwave reactor comprises at least two single-mode microwave cavities which are connected in series, a spiral coil pipe which is horizontally arranged is arranged in the single-mode microwave cavity, the reaction solution flows through the spiral coil pipe in a horizontal spiral mode and enters the storage tank group after being heated by a microwave radiation source, the storage tank group comprises at least two storage tanks which are arranged in parallel, and the storage tanks stir and react the reaction solution in the storage tank to obtain a reaction product and flow into the discharge unit through a pipeline;
the discharging unit comprises a vacuum filtration washing device, the vacuum filtration washing device comprises a container kettle, a filtrate kettle and a vacuumizing device which are sequentially arranged from top to bottom, and the reaction product is subjected to suction filtration to obtain a catalyst.
2. The continuous mass production system of fuel cell catalysts according to claim 1, wherein the mixing tank is provided with a feed port for feeding raw materials, the mixing tank is further provided with a temperature sensor and a pH meter for detecting the temperature and pH of the reaction solution, and a jacket for filling cooling water is provided outside the mixing tank.
3. The continuous mass production system of fuel cell catalysts according to claim 1, wherein a speed-regulating screw pump is sequentially provided between the mixing tank and the continuous microwave reactor, and the reaction solution is continuously fed into the continuous microwave reactor through the speed-regulating screw pump.
4. The continuous mass production system of fuel cell catalyst according to claim 3, wherein a control valve is provided between the speed-adjusting screw pump and the mixing tank, and a magnetic filter and a temperature sensor are further provided between the speed-adjusting screw pump and the continuous microwave reactor.
5. The continuous mass production system of fuel cell catalyst according to claim 1, wherein the single-mode microwave cavity is arranged horizontally, and the spiral coil is a glass tube or a polytetrafluoroethylene tube.
6. The continuous mass production system of fuel cell catalyst according to claim 5, wherein a temperature sensor and a pressure regulating valve are provided between the inlet of the tank and the outlet of the continuous microwave reactor.
7. The continuous mass production system of fuel cell catalyst according to claim 1, wherein the stirring device, the temperature sensor, the pH meter and the liquid level sensor are provided on the storage tank, and the reaction product in the storage tank flows into the vessel tank after being sucked into the pipe by the negative pressure of the vacuumizing device.
8. The continuous mass production system of fuel cell catalysts according to claim 6, wherein a filter plate is provided between the vessel tank and the filtrate tank, and a washing liquid supply device is further connected above the vessel tank.
9. A method for preparing a fuel cell catalyst, characterized by being prepared by the continuous mass production system of a fuel cell catalyst according to claim 1, comprising the steps of:
a. adding quantitative carbon black powder, isopropanol or ultrapure water and ethylene glycol into a mixing tank from a feed port, filling cooling water into a jacket of the mixing tank, starting ultrasonic dispersion equipment above the mixing tank, after ultrasonic dispersion of carbon black slurry for a certain time, starting a stirring device to form uniform carbon black slurry, adding ethylene chloroplatinic acid glycol solution with a metal loading of 10-70 mass% in a metering ratio, continuously stirring, and adding sodium hydroxide glycol solution to adjust the pH value of the reaction solution to 9-13 until the pH value of the reaction solution is stable;
b. opening a control valve, enabling the reaction solution to pass through an electromagnetic speed-regulating screw pump, adjusting the flow speed and the flow rotation direction, absorbing the magnetic materials carried by the screw pump through a magnetic filter, enabling the reaction solution to flow into a continuous microwave reactor in the horizontal spiral flow direction, heating by a microwave radiation source, leaving the microwave reactor in a horizontal spiral mode, and conveying the reaction solution to a storage tank arranged in parallel after the pressure of the reaction solution is adjusted by a pressure adjusting valve;
c. feeding a storage tank, wherein a liquid level sensor in the storage tank senses the liquid level, a stirring device is started, the reaction solution starts to be stirred until the liquid level in the storage tank reaches a high liquid level, the storage tank pauses feeding, then the other storage tank repeats the feeding step until the feeding is completed, the reaction product in the storage tank is cooled to room temperature, dilute nitric acid solution is fed into the storage tank, when the pH value of the reaction product is 1-3, the storage tank starts to discharge, and the reaction product enters a container kettle by virtue of the negative pressure of a vacuumizing device;
d. the reaction product is pumped out in the container kettle sequentially through the filter membrane on the filter plate and the vacuumizing device, the solid matter is left on the filter membrane to form a filter cake, meanwhile, the washing liquid is sent into the container kettle through the spray pipe by the washing liquid supply device, the residual solid matter is washed for a plurality of times until the solid matter is filtered into the filter cake for the last time, the filter cake is washed and discharged, the discharge valve is opened to discharge the solution, the filter membrane is taken out after the washing is finished, and the black product on the filter membrane is the Pt-based catalyst.
10. The method for preparing the fuel cell catalyst according to claim 9, wherein the temperature of the carbon black slurry in the step a is below 25 ℃, after the carbon black slurry is ultrasonically dispersed for 0.5-1.5h, stirring the slurry, and stirring the carbon black slurry for 1-4 h to form uniform carbon black slurry; and (c) in the step (b), the discharging temperature of the reaction solution is 130-150 ℃, the time for the reaction solution to flow through the continuous microwave reactor is 50-80 s, and the pressure of a reaction pipeline system is 0-0.25 MPa.
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| CN104667849A (en) * | 2015-02-06 | 2015-06-03 | 南京博炫生物科技有限公司 | High-power microwave reactor and microwave continuous pressure reaction system |
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| CN114177858A (en) * | 2021-12-13 | 2022-03-15 | 清氢(北京)科技有限公司 | Large-scale preparation method and large-scale preparation device of electrocatalyst |
| CN114247402A (en) * | 2021-12-16 | 2022-03-29 | 浙江锋源氢能科技有限公司 | Continuous microwave reaction device and preparation method of hydrogen fuel cell catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104667849A (en) * | 2015-02-06 | 2015-06-03 | 南京博炫生物科技有限公司 | High-power microwave reactor and microwave continuous pressure reaction system |
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Application publication date: 20230623 |