CN115425241A - Reduction treatment device and method for carbon-supported platinum catalyst - Google Patents
Reduction treatment device and method for carbon-supported platinum catalyst Download PDFInfo
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- CN115425241A CN115425241A CN202211122481.4A CN202211122481A CN115425241A CN 115425241 A CN115425241 A CN 115425241A CN 202211122481 A CN202211122481 A CN 202211122481A CN 115425241 A CN115425241 A CN 115425241A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 230000009467 reduction Effects 0.000 title claims abstract description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 53
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- 238000006722 reduction reaction Methods 0.000 claims abstract description 71
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- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000011261 inert gas Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
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- 239000002253 acid Substances 0.000 description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
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- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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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
-
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a reduction treatment device for a carbon-supported platinum catalyst, wherein a reaction tube is provided with a sand core for containing a catalyst pile layer; the reducing gas input unit and the purging unit are both communicated with the input end of the mixing tank, the output end of the mixing tank is communicated with the upper flange of the reaction tube, and the lower flange of the reaction tube is communicated with the tail gas treatment unit; the heating furnace surrounds the periphery of the reaction tube; and the reducing gas enters the reaction tube from the upper flange after passing through the mixing tank, moves downwards and performs reduction reaction with the catalyst stack layer, the reduction product falls onto the lower flange through the gap of the sand core, and finally the reduction product is treated by the tail gas treatment unit. The invention also discloses a reduction treatment method for the carbon-supported platinum catalyst. According to the invention, the vertical reaction tube made of quartz is adopted, the catalyst is flatly laid on the sand core in the reaction tube, and the reducing gas can be fully contacted with the catalytic substance after entering the reaction tube from the upper flange, so that the problem of insufficient reduction of the catalyst is avoided.
Description
Technical Field
The invention relates to the technical field of hydrogen fuel cells, in particular to a reduction treatment device and method for a carbon-supported platinum catalyst.
Background
The proton exchange membrane fuel cell is a device for directly converting chemical energy into electric energy through electrochemical reaction, wherein the hydrogen fuel cell taking hydrogen as fuel has better application prospect in the fields of new energy automobiles, national defense war industry and the like due to the advantages of environmental friendliness, high energy density, high conversion efficiency and the like. It has the advantages of zero emission, no pollution, high fuel efficiency and the like. The basic reaction principle of the hydrogen fuel cell is that fuel gas hydrogen generates hydrogen oxidation reaction at an anode to lose electrons and change the electrons into protons, the protons are combined with water and then migrate to a cathode through a proton exchange membrane to generate oxygen reduction reaction with oxygen and the electrons from an external circuit to generate water, and the electrons form current through the external circuit to do work outwards. The ORR reaction at the cathode is very slow in kinetics and usually requires the use of a catalyst containing the noble metal platinum (Pt) to accelerate the reaction rate.
In order to save cost, through the development of over twenty years, the catalyst of the hydrogen fuel cell is developed from a catalyst containing pure Pt nano particles to a catalyst containing Pt nano particles loaded by carbon nano tubes (carbon-loaded platinum catalyst for short), and the Pt loading capacity is reduced. One typical preparation procedure for the carbon-supported platinum catalyst is: immersing the carbon nano tube particles in an aqueous solution containing chloroplatinic acid for a period of time, and filtering and collecting to obtain a catalyst primary product. The primary product is treated by the drying equipment to remove free water on the surface of the catalyst, and then transferred to the reduction treatment device. On the reduction treatment device, the chemical substance' chloroplatinic acid aqueous compound (Cl) 6 H 2 Pt.xH 2 O) "is reduced to a simple substance of platinum at a certain temperature in an atmosphere containing hydrogen, and then" a carbon nanotube-supported Pt nanoparticle catalyst "is obtained.
In this step of the above-mentioned atmosphere reduction process, HCl and H as by-products are produced simultaneously while obtaining the platinum simple substance 2 And O. If the by-product cannot leave the catalyst surface in time, it will lead to the reduction of platinum atomsInsufficient original condition or slow chemical reduction speed. For particles located at different positions of the catalyst stack, uneven gas diffusion will result in uneven reduction of the platinum atoms.
By-products of the reduction reaction, HCl and H 2 O is weak in corrosivity in a gas state, but is strong in acid hydrochloric acid when condensed into a liquid state, and has strong chemical corrosion performance on metals except gold and zirconium alloy. Gold and zirconium alloys are extremely expensive, and quartz pipelines are mostly selected as reactors of the device at present. However, quartz is not a plastic material, but a brittle material, and the brittle material has a property of breaking fracture when undergoing a small deformation. At present, the upper limit of the safe pressure in the quartz tube is generally considered to be 0.02MPa (gauge pressure) by industry suppliers and customers. When the pressure of the gas in the pipe exceeds the upper limit, the gas in the pipe can be leaked, so that the safety risk is high.
At present, a horizontal reaction tube containing a gas circuit and a heating device is adopted in a reduction device, and catalyst particles to be treated are directly placed in the horizontal reaction tube, or the catalyst particles to be treated are placed in a carrying container firstly, and then the carrying container is placed in the horizontal reaction tube. Gas enters from one side of the horizontal reaction tube, passes through the catalyst stack layer and is discharged from the other side. Since the catalyst layer generally does not block the entire cross section of the quartz tube, the gas diffuses into the layer at least in part and mostly sweeps over the top of the layer, so that the resistance to gas flow created by the catalyst layer is low and the operating pressure of such devices is near atmospheric. And as the flow rate of the reducing gas increases, most of the gas is still blown over the upper portion or the shallow surface of the catalyst stack layer, and the middle-lower layer of the catalyst stack layer still cannot contact with the fresh reducing gas.
The existing reduction device of a horizontal reaction tube with a gas circuit and a heating device has the following defects: 1. because the catalyst particles are in microscopic scale, the carrier of the catalyst particles is carbon nanotubes with a diameter of 2-50 nm and an average length of about 10000 nm. The number of the stacked particles with the thickness of 1cm is not less than 10000. The dense pile layer causes the reducing gas containing hydrogen to blow mainly the outer surface or shallow layer of the pile layer and the middle and lower layers of the pile layerThe particles are primarily diffused by the gas, resulting in catalyst particles located at different depths, with insufficient reduction, or slow reduction rates. 2. The pile layer of the horizontal reaction device is uneven in heating, so that particles at different depths of the pile layer are not reduced uniformly, the treatment effect of the catalyst among different batches is inconsistent, and the application of the catalyst to civil large-batch fuel cells is influenced. 3. The existing upper flange, lower flange and downstream pipeline of the reaction tube do not solve the problem of HCl and H 2 And O corrosion. The safety problem of corrosion leakage can be avoided only by frequent detection and frequent replacement of equipment. 4. The technological operation and safety of the existing catalytic reduction equipment of the platinum-carbon catalyst are interlocked, and unmanned guard and interlocking cannot be met. Can only be judged by people, has low efficiency and is easy to have safety accidents.
The invention patent application with publication number CN114572971A discloses a method for preparing graphene on the surface of copper powder, which mixes the copper powder and a substance only containing carbon, hydrogen, oxygen and copper elements according to a certain proportion, puts the substance into a heating zone of a tubular furnace, and calcines under the combined action of a mixed atmosphere of high-purity hydrogen and high-purity argon introduced under atmospheric pressure. However, the reaction vessel of this application is a horizontal type apparatus, and the above-mentioned problems cannot be solved.
Disclosure of Invention
The invention aims to provide a reduction treatment device and a reduction treatment method for a carbon-supported platinum catalyst, and the technical problems to be solved by the invention are as follows: the platinum-carbon-containing catalyst particles for the hydrogen fuel cell have the problems of insufficient reduction, slow reduction speed or uneven reduction in an atmosphere containing hydrogen; reduction products of chloroplatinic acid aqueous Compounds (HCl and H) 2 O) corrosion of equipment parts leading to the risk of flammable and explosive hydrogen leaks; the manual attendance of platinum carbon catalyst particles for fuel cells during the reduction operation is inefficient and erroneous.
In order to solve the technical problems, the invention provides the following technical scheme:
a reduction treatment device for a carbon-supported platinum catalyst comprises a reducing gas input unit, a purging unit, a mixing tank, a reaction tube, a heating furnace and a tail gas treatment unit;
the reaction tube is of a vertical structure and comprises a quartz tube, an upper flange and a lower flange; the upper flange is arranged at the upper end of the quartz tube, and the lower flange is arranged at the lower end of the quartz tube; a sand core used for containing the catalyst pile layer is arranged in the quartz tube, and the sand core is provided with a plurality of pores;
the reducing gas input unit and the purging unit are both communicated with the input end of the mixing tank, the output end of the mixing tank is communicated with the upper flange of the reaction tube, and the lower flange of the reaction tube is communicated with the tail gas treatment unit; the heating furnace surrounds the periphery of the reaction tube;
and the reducing gas enters the reaction tube from the upper flange after passing through the mixing tank, moves downwards and performs reduction reaction with the catalyst stack layer, the reduction product falls onto the lower flange through the gap of the sand core, and finally the reduction product is treated by the tail gas treatment unit.
The advantages are that: according to the invention, the vertical reaction tube made of quartz is adopted, the catalyst is flatly laid on the sand core in the reaction tube, and the reducing gas can fully contact with the catalytic substance after entering the reaction tube from the upper flange, so that the problem of insufficient reduction of the catalyst is avoided. Meanwhile, the reaction tube with the vertical structure and the sand core with the small holes in the reaction tube can reduce HCl and H serving as reduction products 2 O can flow into the lower end of the reaction tube in time, so that the situation that part of the catalyst cannot react with reducing gas due to the fact that reducing products are accumulated in the catalyst is avoided, and the problems of slow reducing speed and uneven reducing are solved.
Preferably, the reducing gas input unit includes a reducing gas pipe, a first solenoid valve, a first flow controller, and a first check valve;
the input end of the reducing gas pipe is communicated with the input end of the mixing tank through a pipeline, the first electromagnetic valve, the first flow controller and the first one-way valve are sequentially installed on the pipeline between the reducing gas pipe and the mixing tank respectively, and the circulation direction of the first one-way valve is from the reducing gas pipe to the mixing tank.
Preferably, the purge unit includes an inert gas pipe, a second solenoid valve, a second flow controller, and a second check valve;
the input end of the inert gas pipe is communicated with the input end of the mixing tank through a pipeline, the second electromagnetic valve, the second flow controller and the second one-way valve are sequentially installed on the pipeline between the reducing gas pipe and the mixing tank respectively, and the circulation direction of the second one-way valve is from the inert gas pipe to the mixing tank.
Preferably, the tail gas treatment unit comprises an alkali liquor neutralization tank, an adsorption tank and a vacuum pump;
the input end of the alkali liquor neutralization tank is communicated with the lower flange of the reaction tube, the output end of the alkali liquor neutralization tank is communicated with the input end of the adsorption tank, and the output end of the adsorption tank is communicated with the atmosphere after passing through a vacuum pump.
Preferably, the hydrogen sensor further comprises a control system, wherein the control system comprises a PLC processor, a touch screen, a first pressure gauge, a second pressure gauge, a first pressure sensor, a second pressure sensor, a first temperature sensor, a second temperature sensor, a third temperature sensor, a fourth temperature sensor, a fifth temperature sensor, a sixth temperature sensor and a hydrogen detector.
The input end of the PLC processor is respectively connected with the touch screen, the first pressure gauge, the second pressure gauge, the first pressure sensor, the second pressure sensor, the first temperature sensor, the second temperature sensor, the third temperature sensor, the fourth temperature sensor, the fifth temperature sensor, the sixth temperature sensor and the hydrogen detector;
the first pressure meter and the first pressure sensor are both arranged on a pipeline between the mixing tank and the reaction tube; the second pressure meter and the second pressure sensor are both arranged on a pipeline between the adsorption tank and the vacuum pump;
the first temperature sensor, the second temperature sensor and the third temperature sensor are respectively inserted into the reaction tube through three openings of the upper flange, and are respectively sleeved in the sleeve made of ceramic materials and are respectively inserted into catalyst stack layers with different depths;
the fourth temperature sensor, the fifth temperature sensor and the sixth temperature sensor are respectively and sequentially arranged on three independent hearths of the heating furnace from top to bottom;
the hydrogen detector is positioned on the outer side of the device;
the output end of the PLC processor is connected with the first electromagnetic valve, the first flow controller, the second electromagnetic valve, the second flow controller, the heating furnace, the vacuum pump and the touch screen.
Preferably, the upper flange is provided with four openings, one of the openings is communicated with the output end of the mixing tank through an air inlet, and the other three openings can be respectively inserted into the temperature sensors;
the lower flange is provided with a gas outlet which is communicated with the tail gas treatment unit; the inner bottom surface of the lower flange is conical, and the gradient of the conical shape is less than 170 degrees.
Preferably, the heating furnace adopts three sections of independent temperature control hearths, and the length of a heating zone in the middle of the heating furnace is set to be 3-6 times of the height of a catalyst bed layer in the reaction tube.
Preferably, polytetrafluoroethylene is sprayed on the surfaces of the inner cavities of the upper flange, the lower flange, the mixing tank and the alkali liquor neutralizing tank.
The invention also discloses a method for adopting the reduction treatment device for the carbon-supported platinum catalyst, which is characterized by comprising the following steps: the method comprises the following steps:
s1, cleaning the inner wall and the sand core in the reduction reaction tube by using deionized water, and drying by using an oven to remove water molecules;
s2, pouring a catalyst into the upper part of the sand core of the reaction tube, and enabling the pile layer to be cylindrical in the reaction tube, wherein the pile layer is tightly attached to the inner wall of the reaction tube;
s3, mounting the upper flange and the lower flange at the top and the bottom of the reaction tube, and fixing a sealing gasket and an O-shaped ring; vertically inserting ceramic sleeves of the three thermocouples into the reaction tube from the tube openings of the upper flange, immersing the reaction tube in the bed layer, and then placing the thermocouples into the ceramic sleeves;
s4, opening an air inlet valve of the inert gas, setting the flow rate of the inert gas, wherein the flow rate is determined based on the loading amount of the catalyst, and the space velocity range is 300-3000 h -1 Purging 5After purging is finished, closing an air inlet valve of inert gas, opening a vacuum pump, sucking for 3-5min, and then closing the vacuum pump;
s5, opening an air inlet valve of the reducing gas, setting the flow rate of the reducing gas, wherein the flow rate is determined based on the loading amount of the catalyst, and the space velocity range is 300-3000 h -1 (ii) a Setting the temperature of the heating furnace at 200-1000 deg.c and heating rate of 3-12 deg.c/min, and stopping heating after the fourth, fifth and sixth temperature sensors reach set temperature; when the temperature difference of the first temperature sensor, the second temperature sensor and the third temperature sensor which are positioned at different radius positions of the catalyst stack layer is +/-2 ℃, and the temperature is kept for more than 10mins, the temperature of the catalyst stack layer is considered to be stable and uniform, and the temperature is kept for 1-5 hours;
s6, after the catalyst is reduced at the temperature and the pressure for a certain time, setting the cooling rate of the heating furnace at 1-5 ℃/min, cooling to a temperature detected by the first temperature sensor to be below 50 ℃, and closing an air inlet valve of the reducing gas; according to the step S4, performing inert gas purging again to discharge flammable and explosive reducing gas;
and S7, after the reaction is finished, opening the upper flange, taking out the catalyst bed layer to liquid, and carrying out liquid seal.
Preferably, when the measured value of the first pressure sensor exceeds 0.02mpa by 80%, the PLC processor starts the vacuum pump, and the pressure of the equipment and the pipeline of the whole device is rapidly and integrally reduced; and (3) maintaining the vacuum pump to continuously operate, and if the flow of the air flow at the upstream of the upper flange is overlarge, so that the measured value of the first pressure sensor exceeds 0.02Mpa by 80%, the PLC processor can lower the set flow of the first flow controller and the set flow of the second flow controller.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention ensures that the pressure of the internal reducing gas does not exceed the upper limit of the safe pressure of the quartz tube in the reduction treatment process through the process flow and PLC control. Under the premise, a vertical reaction tube made of quartz is adopted, a catalyst is flatly laid on a sand core in the reaction tube, and reducing gas enters the reaction tube from an upper flangeThe catalyst can be fully contacted with a catalytic substance, so that the problem of insufficient reduction of the catalyst is avoided. Meanwhile, the reaction tube with a vertical structure and the sand core with small holes in the reaction tube can ensure that the reduction products HCl and H 2 O can flow into the lower end of the reaction tube in time, so that the situation that part of the catalyst can not react with the reducing gas due to the fact that the reducing product is accumulated in the catalyst is avoided, and the problems of slow reducing speed and uneven reducing are solved.
(2) The invention solves the problem of corrosivity of the reduction product by the design of a sealing structure of an upper flange, a lower flange, a mixing tank and an alkali liquor neutralization tank of the reaction tube, the surface spraying of an inner cavity and the material selection of a contact atmosphere.
(3) The PLC processor is connected with the sensors, receives temperature and pressure signals when the whole device runs, can control the start and stop of equipment such as the first electromagnetic valve, the second electromagnetic valve, the first flow controller, the second flow controller, the vacuum pump and the like to adjust the temperature and pressure in the device, and realizes unmanned duty and safety interlocking of the platinum-carbon catalyst particles for the fuel cell in the reduction operation through the interlocking control. Meanwhile, the hydrogen sensor arranged on the outer side of the device can monitor the content of hydrogen outside the device in real time, and can timely process the leakage of flammable and explosive hydrogen caused by overpressure or accidents.
(4) The invention can keep the airspeed range of the catalyst within 300-3000 h -1 The reduction efficiency of the catalyst is improved while the safety of the reaction tube is ensured. If the upper space velocity is exceeded, this will lead to excessive pressure in the upper part of the bed and may lead to rupture of the reactor tubes. If the space velocity is lower than the lower limit space velocity, the reduction rate is low, and the catalyst may be insufficiently reduced.
Drawings
FIG. 1 is a schematic connection diagram of an embodiment of the present invention;
FIG. 2 is a schematic diagram of a reaction tube structure according to an embodiment of the present invention;
FIG. 3 is an enlarged view of a portion A of FIG. 2;
FIG. 4 is a partial enlarged view of B of FIG. 2;
FIG. 5 is an enlarged view of portion C of FIG. 2;
FIG. 6 is an enlarged view of a portion D of FIG. 2;
FIG. 7 is a top view of an upper flange of a reaction tube according to an embodiment of the present invention;
in the figure: 1. a reducing gas input unit; 11. a reducing gas pipe; 12. a first solenoid valve; 13. a first flow controller; 14. a first check valve; 2. a purging unit; 21. an inert gas pipe; 22. a second solenoid valve; 23. a second flow controller; 24. a second one-way valve; 3. a mixing tank; 4. a reaction tube; 41. a quartz tube; 42. an upper flange; 43. a lower flange; 44. a sand core; 45. clamping a hoop; 46. opening a hole; 47. a support; 48. an air outlet; 49. a sealing gasket; 410. an O-shaped sealing ring; 411. a sleeve; 5. a heating furnace; 6. a tail gas treatment unit; 61. an alkali liquor neutralization tank; 62. an adsorption tank; 63. a vacuum pump; 7. a control system; 71. a first pressure gauge; 72. a first pressure sensor; 73. a second pressure gauge; 74. a second pressure sensor; 75. a first temperature sensor; 76. a second temperature sensor; 77. a third temperature sensor; 78. a fourth temperature sensor; 79. a fifth temperature sensor; 710. a sixth temperature sensor; 711. a hydrogen gas detector; 8. polytetrafluoroethylene.
Detailed Description
In order to facilitate the understanding of the technical solutions of the present invention for those skilled in the art, the technical solutions of the present invention will be further described with reference to the drawings attached to the specification.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
Referring to fig. 1, the embodiment discloses a reduction treatment device for a carbon-supported platinum catalyst, which comprises a reducing gas input unit 1, a purging unit 2, a mixing tank 3, a reaction tube 4, a heating furnace 5 and a tail gas treatment unit 6;
the reducing gas input unit 1 includes a reducing gas pipe 11, a first electromagnetic valve 12, a first flow controller 13, and a first check valve 14; the input end of the reducing gas pipe 11 is communicated with the input end of the mixing tank 3 after passing through the first electromagnetic valve 12, the first flow controller 13 and the first check valve 14 in sequence. The reducing gas pipe 11 has pure hydrogen gas or a mixed gas containing hydrogen gas and an inert gas therein, the first electromagnetic valve 12 can control the communication or closing of the reducing gas pipe 11 and the mixing tank 3, the first flow controller 13 can control the flow rate therebetween, and the first check valve 14 can prevent the gas from flowing back into the reducing gas pipe 11 to contaminate the internal gas.
The purge unit 2 includes an inert gas pipe 21, a second electromagnetic valve 22, a second flow controller 23, and a second check valve 24; the input end of the inert gas pipe 21 is communicated with the input end of the mixing tank 3 after passing through the second electromagnetic valve 22, the second flow controller 23 and the second one-way valve 24 in sequence. The inert gas pipe 21 has pure nitrogen gas or pure argon gas or a mixture of the two gas therein, the second electromagnetic valve 22 can control the connection or the disconnection between the inert gas pipe 21 and the mixing tank 3, the second flow controller 23 can control the flow rate therebetween, and the second check valve 24 can prevent the gas from flowing back into the inert gas pipe 21 to contaminate the internal gas.
Referring to fig. 2 to 7, the reaction tube 4 has a vertical structure, and includes a quartz tube 41, an upper flange 42, and a lower flange 43; the upper flange 42 is arranged at the upper end of the quartz tube 41 and is fixed with the quartz tube 41 through the hoop 45, the lower flange 43 is arranged at the lower end of the quartz tube 41 and is fixed with the quartz tube 41 through the hoop 45, and the upper flange 42 and the lower flange 43 are fixed with the quartz tube 41 through the detachable hoop 45 structure, so that the disassembly is convenient.
The middle part of the quartz tube 41 is also provided with a sand core 44 for containing a catalyst. The sand core 44 of this embodiment has a pore size void ranging from 10 to 30 μm and the quartz tube 41 has an inner diameter ranging from 30 to 160mm. When the reactor is used, the catalyst is poured into the upper part of the sand core 44 of the reaction tube 4, the pile layer is cylindrical in the reaction tube 4, and the pile layer is tightly attached to the inner wall of the reaction tube 4, so that the catalyst is fully reduced.
The upper flange 42 is provided with four openings 46, wherein one opening 46 is an air inlet and is used for being communicated with the output end of the mixing tank 3. Three other openings 46 may be inserted into the temperature sensors, respectively.
The lower flange 43 is provided with an air outlet 48, and the air outlet 48 is communicated with the tail gas treatment unit 6. The bottom surface of the interior of the lower flange 43 is tapered with a slope of less than 170 ° to facilitate collection of the reduction product after the reduction reaction of the catalyst and output from the gas outlet 48.
The bottom of the reaction tube 4 is also provided with a support 47 for supporting the reaction tube 4.
Meanwhile, in order to ensure the sealing performance inside the quartz tube 41, O-ring seals 410 and sealing gaskets 49 are disposed between the upper flange 42 and the quartz tube 41, and between the lower flange 43 and the quartz tube 41. The O-ring 410 and the gasket 49 are made of fluororubber or perfluororubber.
The quartz tube 41 of the present embodiment has the characteristic of resisting corrosion of acid and alkali, and the inner cavity surfaces of the upper flange 42 and the lower flange 43 are both sprayed with polytetrafluoroethylene 8 or modified materials thereof, so as to ensure that the upper flange 42 and the lower flange 43 can resist corrosion of acid and alkali. The overall apparatus of the reaction tube 4 can thus avoid the problem of corrosion of the equipment by the reduction products HCl and H2O of the chloroplatinic acid hydrate (cl6h2pt.xh2o), and the reaction can be carried out safely without frequent replacement of the equipment.
The heating furnace 5 is surrounded on the periphery of the reaction tube 4, the heating furnace 5 adopts three sections of hearths with independent temperature control, the three sections of independent temperature control can reach a longer constant temperature area, and the temperature uniformity of a catalyst bed layer is facilitated. The length of the heating zone in the middle of the heating furnace 5 is set to be 3-6 times of the height of the catalyst bed in the reaction tube 4. The heating and controlling temperature range of the heating furnace 5 is from room temperature to 1000 ℃.
The tail gas treatment unit 6 comprises an alkali liquor neutralization tank 61, an adsorption tank 62 and a vacuum pump 63; the input end of the alkali liquor neutralization tank 61 is communicated with the gas outlet 48 of the reaction tube 4, the output end is communicated with the input end of the adsorption tank 62, and the output end of the adsorption tank 62 is communicated with the atmosphere after passing through a vacuum pump 63 for discharging tail gas.
The alkali liquor neutralizing tank 61 is made of 316L stainless steel, and the inner cavity surface of the alkali liquor neutralizing tank 61 is sprayed with polytetrafluoroethylene 8 or modified materials thereof, so that the alkali liquor neutralizing tank can resist corrosion of acid and alkali. The inside contains an alkaline solution for neutralizing HCl generated in the reaction tube 4.
The adsorption tank 62 is made of polycarbonate, quartz glass, or the like. An adsorbent is arranged in the adsorption tank 62, and the adsorbent of the quartz inside is active carbon or allochroic silica gel.
The vacuum pump 63 is a corrosion-resistant diaphragm pump, the vacuum degree limit is 200mbar, and the aeration rate is not lower than 120L/min.
It should be noted that the pipelines connecting the devices are made of polytetrafluoroethylene 8 or modified materials thereof, and can resist corrosion of acid and alkali.
The control system 7 includes a PLC processor (not shown), a touch panel (not shown), a first pressure gauge 71, a first pressure sensor 72, a second pressure gauge 73, a second pressure sensor 74, a first temperature sensor 75, a second temperature sensor 76, a third temperature sensor 77, a fourth temperature sensor 78, a fifth temperature sensor 79, a sixth temperature sensor 710, and a hydrogen gas detector 711.
The PLC processor is respectively connected with the touch screen, the first pressure gauge 71, the second pressure gauge 73, the first pressure sensor 72, the second pressure sensor 74, the first temperature sensor 75, the second temperature sensor 76, the third temperature sensor 77, the fourth temperature sensor 78, the fifth temperature sensor 79, the sixth temperature sensor 710 and the hydrogen detector 711.
The first pressure gauge 71 and the first pressure sensor 72 are arranged on the pipeline between the mixing tank 3 and the reaction tube 4 and used for monitoring the pressure value at the upper flange 42; a second pressure gauge 73 and a second pressure sensor 74 are provided on the pipe between the canister 62 and the vacuum pump 63 for monitoring the pressure value at the lower flange 43. Since the gas flow is from the upper flange 42 through the dense stack to the lower flange 43, a pressure differential is created across the stack, and the pressure measurement from the first pressure sensor 72 is generally not lower than the pressure measurement from the second pressure sensor 74. The upper flange 42 is more likely to exceed 0.02Mpa (gauge pressure) than the lower flange 43, and the upper flange 42 of the reaction tube 4 tends to cause gas leakage exceeding 0.02 Mpa. When the first pressure sensor 72 measures more than 0.02mpa by 80%, the PLC processor activates the vacuum pump 63. The pressure of the equipment and the pipeline of the whole device is rapidly reduced integrally. The vacuum pump 63 is maintained in continuous operation, and if the flow rate of the gas flow upstream of the upper flange 42 is too high, which results in the measurement value of the second pressure sensor 74 exceeding 0.02mpa by 80%, the PLC processor will lower the set flow rates of the first flow controller 13 and the second flow controller 23, so as to reduce the flow rates and further reduce the pressure.
The first temperature sensor 75, the second temperature sensor 76 and the third temperature sensor 77 are installed in the reaction tube 4, inserted through the three openings 46 of the upper flange 42, respectively, and the first temperature sensor 75, the second temperature sensor 76 and the third temperature sensor 77 measure the temperature of the catalyst stack at different depths, respectively. Specifically, the first temperature sensor 75, the second temperature sensor 76, and the third temperature sensor 77 are all K-type thermocouples, and the outer surface is stainless steel 316L or hastelloy C-276. The thermocouple is placed in a ceramic sleeve 411, and the ceramic sleeve 411 is inserted into the stack to prevent the temperature sensor from contacting corrosive materials.
The fourth temperature sensor 78, the fifth temperature sensor 79 and the sixth temperature sensor 710 are sequentially and respectively installed on three independent hearths of the heating furnace 5 from top to bottom, and are used for monitoring the temperature of the heating furnace 5.
The hydrogen gas detector 711 is located above the device, and the hydrogen gas detector 711 is exposed to the air for detecting the concentration of hydrogen gas that may leak out, thereby confirming whether the device leaks.
The PLC processor is also connected with the first electromagnetic valve 12, the first flow controller 13, the second electromagnetic valve 22, the second flow controller 23, the heating furnace 5, the vacuum pump 63 and the touch screen.
The operation flow of the catalytic reduction apparatus of the present example is as follows:
s1, cleaning the inner wall and the sand core 44 in the reduction reaction tube 4 by using deionized water, and drying by using an oven to remove water molecules.
S2, pouring the catalyst into the upper part of the sand core 44 of the reaction tube 4, and enabling the pile layer to be cylindrical in the reaction tube 4, wherein the pile layer is required to be tightly attached to the inner wall of the reaction tube 4.
And S3, installing the upper flange 42 and the lower flange 43 at the top and the bottom of the reaction tube 4, and fixing the sealing washer 49 and the O-shaped ring. The ceramic bushings 411 of the three thermocouples are vertically inserted into the reaction tube 4 from the nozzle of the upper flange 42 and immersed inside the bed, and then the thermocouples are put into the ceramic bushings 411 again.
S4, opening an air inlet valve of the inert gas, setting the flow of the inert gas, wherein the flow is determined based on the loading amount of the catalyst, the air space velocity range of the gas is 300-3000 h < -1 >, purging is carried out for 5-20min, when the measured value of the first pressure sensor 72 exceeds 0.02Mpa by 80%, the PLC processor starts the vacuum pump 63, and the pressure of the equipment and the pipeline of the whole device is rapidly reduced integrally. The vacuum pump 63 is maintained in operation and if the flow rate of the gas stream upstream of the upper flange 42 is too high, resulting in the measurement value of the first pressure sensor 72 exceeding 0.02mpa by 80%, the PLC processor will adjust the set flow rates of the first flow controller 13 and the second flow controller 23 downward. And after the purging is finished, closing the gas inlet valve of the inert gas, maintaining or opening the vacuum pump 63, pumping for 3-5min, and then closing the vacuum pump 63.
S5, opening an air inlet valve of the reducing gas, setting the flow rate of the reducing gas, wherein the flow rate is determined based on the loading amount of the catalyst, and the space velocity of the gas in the embodiment ranges from 300 h-1 to 3000h-1. Setting the temperature of the heating furnace 5 within the range of 200-1000 ℃, wherein the heating rate is 3-12 ℃/min, and stopping heating after the fourth temperature sensor 78, the fifth temperature sensor 79 and the sixth temperature sensor 710 reach the set temperature. When the temperature difference between the first temperature sensor 75, the second temperature sensor 76 and the third temperature sensor 77 which are positioned at different radius positions of the catalyst stack is +/-2 ℃, and is kept for more than 10mins, the temperature of the catalyst stack can be considered to be stable and uniform, and is kept for 1-5 hours. In the above process, when the measurement value of the first pressure sensor 72 exceeds 0.02mpa by 80%, the PLC processor starts the vacuum pump 63. The pressure of the equipment and the pipeline of the whole device is quickly reduced as a whole. If the flow rate of the upstream gas flow is too high, which causes the measurement value of the first pressure sensor 72 to exceed 0.02mpa by 80%, the PLC processor will adjust the set flow rates of the first flow controller 13 and the second flow controller 23 downward.
S6, after the catalyst is reduced at the temperature and the pressure for a certain time, setting the cooling rate of the heating furnace 5 at 1-5 ℃/min, cooling to a temperature detected by the first temperature sensor 75 to be below 50 ℃, and closing an air inlet valve of the reducing gas. And (5) according to the step S4, carrying out inert gas purging again to discharge flammable and explosive reducing gas.
And S7, after the reaction is finished, opening the upper flange 42, taking out the catalyst bed layer to liquid, and carrying out liquid seal to prevent the influence of oxygen in the air on the catalyst.
In this embodiment, the vertical reaction tube 4 made of quartz is adopted, and the catalyst is laid on the sand core 44 in the reaction tube 4, so that the reducing gas can fully contact with the catalytic material after entering the reaction tube 4 from the upper flange 42, thereby avoiding the problem of insufficient reduction of the catalyst. Meanwhile, the reaction tube 4 with the vertical structure and the sand core 44 with the small holes arranged inside can enable the reduction products HCl and H2O to flow into the lower end of the reaction tube 4 in time, so that the phenomenon that part of the catalyst cannot react with the reduction gas due to the accumulation of the reduction products in the catalyst is avoided, and the problems of slow reduction speed and uneven reduction are solved.
The space velocity of the catalyst can be kept within the range of 300-3000 h in the embodiment -1 The reduction efficiency of the catalyst is improved while the safety of the reaction tube 4 is ensured. If the upper space velocity is exceeded, this will lead to an excessive pressure in the upper part of the bed and possibly to a rupture of the reaction tubes 4. If the space velocity is lower than the lower limit, the reduction rate is low, and the catalyst may be insufficiently reduced.
The problem of corrosivity of the reduction product is solved by spraying polytetrafluoroethylene 8 or modified materials thereof on the surfaces of the upper flange 42 of the reaction tube 4, the lower flange 43, the mixing tank 3 and the inner cavity of the alkali liquor neutralization tank 61.
The first temperature sensor 75, the second temperature sensor 76 and the third temperature sensor 77 monitor the temperatures of the catalyst at different depths and send data to the PLC processor, the fourth temperature sensor 78, the fifth temperature sensor 79 and the sixth temperature sensor 710 monitor the temperatures of three independent hearths of the heating furnace 5 and send data to the PLC processor, and the PLC controller can automatically adjust the temperature range of the catalyst during reduction reaction.
The first pressure sensor 72 and the second pressure sensor 74 monitor the pressure at the upper flange 42 and the flange respectively and send data to the PLC controller, and the PLC controller can control the start and stop of the first electromagnetic valve 12, the second electromagnetic valve 22, the first flow controller 13, the second flow controller 23 and the vacuum pump 63 to adjust the pressure according to whether the first pressure sensor 72 and the second pressure sensor 74 exceed 0.02 Mpa. Through linkage control, the unattended operation and safety linkage of the platinum-carbon catalyst particles for the fuel cell in the reduction operation are realized, and the leakage of flammable and explosive hydrogen caused by overpressure or accidents is prevented.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference signs in the claims are not intended to be construed as limiting the claim concerned.
The above-mentioned embodiments only represent embodiments of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the concept of the present invention, and these embodiments are all within the protection scope of the present invention.
Claims (10)
1. A reduction treatment device for a carbon-supported platinum catalyst is characterized in that: comprises a reducing gas input unit (1), a purging unit (2), a mixing tank (3), a reaction tube (4), a heating furnace (5) and a tail gas treatment unit (6);
the reaction tube (4) is of a vertical structure and comprises a quartz tube (41), an upper flange (42) and a lower flange (43); the upper flange (42) is arranged at the upper end of the quartz tube (41), and the lower flange (43) is arranged at the lower end of the quartz tube (41); a sand core (44) for containing a catalyst stack layer is arranged in the quartz tube (41), and the sand core (44) is provided with a plurality of pores;
the reducing gas input unit (1) and the purging unit (2) are both communicated with the input end of the mixing tank (3), the output end of the mixing tank (3) is communicated with the upper flange (42) of the reaction pipe (4), and the lower flange (43) of the reaction pipe (4) is communicated with the tail gas treatment unit (6); the heating furnace (5) is surrounded on the periphery of the reaction tube (4);
reducing gas enters the reaction tube (4) through the upper flange (42) after passing through the mixing tank (3), the reducing gas moves downwards and performs reduction reaction with the catalyst stack layer, a reduction product falls onto the lower flange (43) through a gap of the sand core (44), and finally the reduction product is treated through the tail gas treatment unit (6).
2. The reduction treatment apparatus for a carbon-supported platinum catalyst according to claim 1, characterized in that: the reducing gas input unit (1) comprises a reducing gas pipe (11), a first electromagnetic valve (12), a first flow controller (13) and a first one-way valve (14);
the input end of the reducing gas pipe (11) is communicated with the input end of the mixing tank (3) through a pipeline, the first electromagnetic valve (12), the first flow controller (13) and the first one-way valve (14) are sequentially installed on the pipeline between the reducing gas pipe (11) and the mixing tank (3) respectively, and the flow direction of the first one-way valve (14) is from the reducing gas pipe (11) to the mixing tank (3).
3. The reduction treatment apparatus for a platinum-on-carbon catalyst according to claim 1, characterized in that: the purging unit (2) comprises an inert gas pipe (21), a second electromagnetic valve (22), a second flow controller (23) and a second one-way valve (24);
the input of inert gas pipe (21) passes through the input intercommunication of pipeline and blending tank (3), second solenoid valve (22), second flow controller (23) and second check valve (24) are installed respectively in proper order on the pipeline between reducing gas pipe (11) and blending tank (3), the circulation direction of second check valve (24) is from inert gas pipe (21) to blending tank (3).
4. The reduction treatment apparatus for a carbon-supported platinum catalyst according to claim 1, characterized in that: the tail gas treatment unit (6) comprises an alkali liquor neutralization tank (61), an adsorption tank (62) and a vacuum pump (63);
the input end of the alkali liquor neutralization tank (61) is communicated with the lower flange (43) of the reaction tube (4), the output end of the alkali liquor neutralization tank is communicated with the input end of the adsorption tank (62), and the output end of the adsorption tank (62) is communicated with the atmosphere after passing through a vacuum pump (63).
5. The reduction treatment apparatus for a carbon-supported platinum catalyst according to claim 1, characterized in that: the hydrogen gas sensor is characterized by further comprising a control system (7), wherein the control system (7) comprises a PLC processor, a touch screen, a first pressure gauge (71), a second pressure gauge (73), a first pressure sensor (72), a second pressure sensor (74), a first temperature sensor (75), a second temperature sensor (76), a third temperature sensor (77), a fourth temperature sensor (78), a fifth temperature sensor (79), a sixth temperature sensor (710) and a hydrogen gas detector (711).
The input end of the PLC processor is respectively connected with the touch screen, the first pressure gauge (71), the second pressure gauge (73), the first pressure sensor (72), the second pressure sensor (74), the first temperature sensor (75), the second temperature sensor (76), the third temperature sensor (77), the fourth temperature sensor (78), the fifth temperature sensor (79), the sixth temperature sensor (710) and the hydrogen detector (711);
the first pressure gauge (71) and the first pressure sensor (72) are arranged on a pipeline between the mixing tank (3) and the reaction tube (4); the second pressure gauge (73) and the second pressure sensor (74) are arranged on a pipeline between the adsorption tank (62) and the vacuum pump (63);
the first temperature sensor (75), the second temperature sensor (76) and the third temperature sensor (77) are respectively inserted into the reaction tube (4) through three open holes (46) of the upper flange (42), and the first temperature sensor (75), the second temperature sensor (76) and the third temperature sensor (77) are respectively sleeved in a sleeve (411) made of ceramic materials and are respectively inserted into catalyst reactor layers with different depths;
the fourth temperature sensor (78), the fifth temperature sensor (79) and the sixth temperature sensor (710) are respectively and sequentially arranged on three independent hearths of the heating furnace (5) from top to bottom;
the hydrogen detector (711) is positioned outside the device;
the output end of the PLC processor is connected with the first electromagnetic valve (12), the first flow controller (13), the second electromagnetic valve (22), the second flow controller (23), the heating furnace (5), the vacuum pump (63) and the touch screen.
6. The reduction treatment apparatus for a platinum-on-carbon catalyst according to claim 1, characterized in that: the upper flange (42) is provided with four openings (46), one opening (46) is communicated with the output end of the mixing tank (3) through an air inlet, and the other three openings (46) can be respectively inserted into a temperature sensor;
the lower flange (43) is provided with a gas outlet (48), and the gas outlet (48) is communicated with the tail gas treatment unit (6); the inner bottom surface of the lower flange (43) is conical, and the gradient of the conical shape is less than 170 degrees.
7. The reduction treatment apparatus for a carbon-supported platinum catalyst according to claim 1, characterized in that: the heating furnace (5) adopts three sections of hearths with independent temperature control, and the length of a heating zone in the middle of the heating furnace (5) is set to be 3-6 times of the height of a catalyst bed layer in the reaction tube (4).
8. The reduction treatment apparatus for a platinum-on-carbon catalyst according to claim 1, characterized in that: the inner cavity surfaces of the upper flange (42), the lower flange (43), the mixing tank (3) and the alkali liquor neutralizing tank (61) are all sprayed with polytetrafluoroethylene (8).
9. A method of using the reduction treatment apparatus for a platinum-on-carbon catalyst according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
s1, cleaning the inner wall and the sand core (44) in the reduction reaction tube (4) by using deionized water, and drying by using an oven to remove water molecules;
s2, pouring a catalyst into the upper part of the sand core (44) of the reaction tube (4), and enabling the pile layer to be cylindrical in the reaction tube (4), wherein the pile layer is tightly attached to the inner wall of the reaction tube (4);
s3, mounting the upper flange (42) and the lower flange (43) on the top and the bottom of the reaction tube (4), and fixing a sealing gasket (49) and an O-shaped ring; vertically inserting ceramic sleeves (411) of three thermocouples into the reaction tube (4) from the tube openings of the upper flange (42), immersing the reaction tube in the bed layer, and then placing the thermocouples into the ceramic sleeves (411);
s4, opening an air inlet valve of the inert gas, setting the flow of the inert gas, wherein the flow is determined based on the loading amount of the catalyst, the space velocity range is 300-3000 h < -1 >, purging is carried out for 5-20min, after the purging is finished, the air inlet valve of the inert gas is closed, a vacuum pump (63) is opened, suction is carried out for 3-5min, and then the vacuum pump (63) is closed;
s5, opening an air inlet valve of the reducing gas, setting the flow of the reducing gas, wherein the flow is determined based on the loading amount of the catalyst, and the airspeed range is 300-3000 h < -1 >; meanwhile, the temperature of the heating furnace (5) is set, the temperature range is 200-1000 ℃, the heating rate is 3-12 ℃/min, and the temperature is stopped after the fourth temperature sensor (78), the fifth temperature sensor (79) and the sixth temperature sensor (710) reach the set temperature; when the temperature difference of a first temperature sensor (75), a second temperature sensor (76) and a third temperature sensor (77) which are positioned at different radius positions of the catalyst stack layer is +/-2 ℃, and the temperature is kept for more than 10mins, the temperature of the catalyst stack layer is considered to be stable and uniform, and then the temperature is kept for 1-5 hours;
s6, after the catalyst is reduced at the temperature and the pressure for a certain time, setting the cooling rate of the heating furnace (5) at 1-5 ℃/min, cooling to the temperature detected by the first temperature sensor (75) to be below 50 ℃, and closing an air inlet valve of the reducing gas; according to the step S4, performing inert gas purging again to discharge flammable and explosive reducing gas;
and S7, after the reaction is finished, opening the upper flange (42), taking out the catalyst bed layer to liquid, and carrying out liquid seal.
10. The reduction treatment method for a carbon-supported platinum catalyst according to claim 9, characterized in that: when the measured value of the first pressure sensor (72) exceeds 0.02Mpa by 80%, the PLC processor starts the vacuum pump (63), and the pressure of the equipment and the pipeline of the whole device is rapidly and integrally reduced; and maintaining the vacuum pump (63) to continuously operate, and if the flow rate of the gas flow at the upstream of the upper flange (42) is overlarge, so that the measured value of the first pressure sensor (72) exceeds 0.02Mpa by 80%, the PLC processor downwards adjusts the set flow rates of the first flow controller (13) and the second flow controller (23).
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