CN115425241B - 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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- CN115425241B CN115425241B CN202211122481.4A CN202211122481A CN115425241B CN 115425241 B CN115425241 B CN 115425241B CN 202211122481 A CN202211122481 A CN 202211122481A CN 115425241 B CN115425241 B CN 115425241B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 230000009467 reduction Effects 0.000 title claims abstract description 60
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- 238000006722 reduction reaction Methods 0.000 claims abstract description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 239000010453 quartz Substances 0.000 claims abstract description 28
- 238000010926 purge Methods 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims description 87
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 239000011261 inert gas Substances 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 20
- 238000006386 neutralization reaction Methods 0.000 claims description 16
- 238000001179 sorption measurement Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000002360 explosive Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000000446 fuel Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- 229910001093 Zr alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009530 blood pressure measurement Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
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- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 229910009111 xH2 O Inorganic materials 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 stack 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; 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 reducing product falls onto the lower flange through the gap of the sand core, and finally the reducing 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 quartz reaction tube is adopted, the catalyst is flatly paved on the sand core in the reaction tube, and the reducing gas can fully contact with the catalyst 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 and military 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, etc. The basic reaction principle of the hydrogen fuel cell is that the hydrogen of the fuel gas is subjected to hydrogen oxidation reaction at the anode to lose electrons and become protons, the protons are combined with water and then migrate to the cathode through the proton exchange membrane, oxygen reduction reaction is carried out between the protons and oxygen and electrons from an external circuit to generate water, and the electrons form current through the external circuit to do work. The cathodic ORR reaction is very slow in kinetics and it is often necessary to use a catalyst containing the noble metal platinum (Pt) to accelerate the reaction rate.
In order to save the cost, the catalyst of the hydrogen fuel cell is developed from pure Pt-containing nano particles to a Pt-containing nano particle catalyst (carbon-supported platinum catalyst for short) supported by carbon nano tubes through the development of more than twenty years, and the Pt load is reduced. One typical preparation scheme for a 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 the carbon nano tube particles to obtain a catalyst primary product. The initial product is treated with free water in the free state on the surface of the catalyst by a 'drying device', and then transferred to a 'reduction treatment device'. In the reduction treatment device, when a chemical substance "chloroplatinic acid hydrate (Cl 6H2Pt.xH2 O)" on the catalyst is reduced into a platinum simple substance under the atmosphere containing hydrogen at a certain temperature, the Pt nano-particle catalyst supported by the carbon nano-tube is further obtained.
In this step of the above atmosphere reduction process, HCl and H 2 O, which are byproducts, will be simultaneously produced while elemental platinum is obtained. If the byproducts cannot timely leave the catalyst surface, insufficient reduction of platinum atoms or slow chemical reduction speed can be caused. For particles located at different positions of the catalyst stack, uneven gas diffusion will result in uneven reduction of platinum atoms.
The byproducts of the reduction reaction, namely HCl and H 2 O, have weaker corrosiveness in a gas state, but are strong acid hydrochloric acid when condensed into a liquid state, and have strong chemical corrosion performance on metals except gold and zirconium alloy. Gold and zirconium alloys are extremely expensive, and quartz pipes are currently used as reactors of devices. However, quartz is not a plastic material, but a brittle material, which breaks the fracture properties with little deformation. Currently, industry suppliers and customers generally consider that the upper safety pressure limit in quartz tubes is 0.02MPa (gauge pressure). When the pressure of the gas in the pipe exceeds the upper limit, the gas in the pipe may leak, and a high safety risk is caused.
At present, a reduction device adopts a horizontal reaction tube containing a gas circuit and a heating device, catalyst particles to be treated are directly placed in the horizontal reaction tube, or the catalyst particles to be treated are placed in a containing container, and then the containing container is placed in the horizontal reaction tube. The gas enters from one side of the horizontal reaction tube, passes through the catalyst stack and is discharged from the other side. Since the catalyst stack does not generally fill the entire quartz tube cross section, a small portion of the gas diffuses into the stack and most of the gas is swept over the top of the stack, the catalyst stack produces less resistance to gas flow, and the operating pressure of such devices is nearly atmospheric. And as the flow rate of the reducing gas increases, most of the gas is blown from the upper or shallow surface of the catalyst stack, and the middle and lower layers of the catalyst stack still cannot be contacted with fresh reducing gas.
The existing reduction device for the horizontal reaction tube with the gas circuit and the heating device has the following defects: 1. since the catalyst particles are microscopic in size, 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 layers of the 1cm thick stacked particles is not less than 10000. The dense stack layer causes the reducing gas containing hydrogen to mainly blow the outer surface or shallow layer of the stack layer, and the middle-lower layer particles of the stack layer mainly depend on the diffusion of the gas, so that the catalyst particles positioned at different depths are insufficiently reduced or the reduction speed is slow. 2. The reactor layers of the horizontal reactor are uneven in heating, so that the particle reduction of different depths of the reactor layers is uneven, the effect of catalyst treatment among different batches is inconsistent, and the catalyst is affected to be applied to civil large-batch fuel cells. 3. At present, the upper flange, the lower flange and the downstream pipeline of the reaction tube do not solve the problem of corrosion by HCl and H 2 O. Safety problems of corrosive leakage can only be avoided by frequent detection and frequent replacement of the equipment. 4. The process operation and safety of the existing platinum-carbon catalyst catalytic reduction equipment are linked, and unmanned on duty and linkage cannot be satisfied. Only through the manual judgment, the efficiency is low, and the safety accident is easy to occur.
The invention patent application with publication number CN114572971A discloses a method for preparing graphene on the surface of copper powder, which comprises the steps of mixing copper powder with substances only containing carbon, hydrogen, oxygen and copper elements according to a certain proportion, placing the substances into a heating zone of a tubular furnace, and calcining under the combined action of mixed atmosphere of high-purity hydrogen and high-purity argon under the 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 aims to solve the technical problems that: the problems of insufficient reduction, slow reduction speed or uneven reduction of platinum-carbon-containing catalyst particles for hydrogen fuel cells in a hydrogen-containing atmosphere; corrosion of equipment accessories by the reduction products of chloroplatinic acid aqueous compounds (HCl and H 2 O) leads to the risk of leakage of flammable and explosive hydrogen; the platinum carbon catalyst particles for fuel cells are artificially inefficient and erroneous in the reduction operation.
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 for containing a catalyst stacking layer is arranged in the quartz tube, and the sand core is provided with a plurality of holes;
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;
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 reducing product falls onto the lower flange through the gap of the sand core, and finally the reducing product is treated by the tail gas treatment unit.
The advantages are that: according to the invention, the vertical quartz reaction tube is adopted, the catalyst is flatly paved on the sand core in the reaction tube, and the reducing gas can fully contact with the catalyst 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 small holes inside can enable reduction products HCl and H 2 O to flow into the lower end of the reaction tube in time, so that the problem that partial catalyst cannot react with reduction gas due to accumulation of the reduction products in the catalyst is avoided, and the problems of slow reduction speed and uneven reduction 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 respectively and sequentially arranged on the pipeline between the reducing gas pipe and the mixing tank, and the flowing 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 respectively and sequentially arranged on the pipeline between the reducing gas pipe and the mixing tank, 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 control system further 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 gauge and the first pressure sensor are arranged on a pipeline between the mixing tank and the reaction tube; the second pressure gauge and the second pressure sensor are 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, are respectively sleeved in a sleeve made of ceramic materials, and are respectively inserted into catalyst stacks 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 at 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, four openings are formed in the upper flange, wherein one opening is an air inlet communicated with the output end of the mixing tank, and the other three openings can be respectively inserted into temperature sensors;
the lower flange is provided with an air 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 smaller than 170 degrees.
Preferably, the heating furnace adopts three sections of hearths with independent temperature control, 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 neutralization 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 of: the method comprises the following steps:
s1, cleaning the inner wall and the sand core in a reduction reaction tube 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 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, installing an upper flange and a 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 three thermocouples into the reaction tube from the tube orifice of the upper flange, immersing the ceramic sleeves in the bed layer, and then putting the thermocouples into the ceramic sleeves;
s4, opening an air inlet valve of the inert gas, setting the flow of the inert gas, wherein the flow is based on the loading amount of the catalyst, the airspeed range is 300-3000 h -1, purging for 5-20min, closing the air inlet valve of the inert gas after purging is finished, opening a vacuum pump, pumping 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 airspeed range is 300-3000 h -1; setting the temperature of the heating furnace at the same time, wherein the temperature range is 200-1000 ℃, the temperature rising rate is 3-12 ℃/min, and stopping rising after the fourth temperature sensor, the fifth temperature sensor and the sixth temperature sensor reach the 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 kept for more than 10mins, the temperature of the catalyst stack layer is considered to be stable and uniform, and then the catalyst stack layer is kept for 1-5 hours;
S6, after the catalyst is reduced for a certain time at the temperature and the pressure, setting the cooling rate of the heating furnace to be 1-5 ℃/min, and closing an air inlet valve of the reducing gas after the temperature is reduced to be below 50 ℃ detected by the first temperature sensor; step S4, purging with inert gas again, and discharging inflammable and explosive reducing gas;
And S7, after the reaction is finished, opening the upper flange, taking out the catalyst bed layer into liquid, and performing liquid sealing.
Preferably, when the measured value of the first pressure sensor exceeds 0.02mpa by 80%, the PLC processor will start the vacuum pump, and the pressure of the equipment and the pipeline of the whole device will be reduced rapidly and integrally; and maintaining the vacuum pump to continuously run, and if the flow of the upstream air flow of the upper flange is too large, the measured value of the first pressure sensor exceeds 0.02mpa by 80%, and the PLC processor downwards regulates the set flow of the first flow controller and the second flow controller.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, through the control of a process flow and a PLC, the pressure of the internal reducing gas is ensured not to exceed the upper limit of the safe pressure of the quartz tube in the reduction treatment process. Under the premise, the vertical quartz reaction tube is adopted, the catalyst is flatly paved on the sand core in the reaction tube, and the reducing gas can fully contact with the catalyst 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 small holes inside can enable reduction products HCl and H 2 O to flow into the lower end of the reaction tube in time, so that the problem that partial catalyst cannot react with reduction gas due to accumulation of the reduction products in the catalyst is avoided, and the problems of slow reduction speed and uneven reduction are solved.
(2) The invention solves the problem of corrosiveness of the reduction product by the sealing structure design of the upper flange, the lower flange, the mixing tank and the alkali liquor neutralization tank of the reaction tube, the material selection of the inner cavity surface spraying and contact atmosphere.
(3) The invention is connected with a plurality of sensors through the PLC processor, receives temperature and pressure signals when the whole device operates, can control the start and stop of equipment such as a first electromagnetic valve, a second electromagnetic valve, a first flow controller, a second flow controller, a vacuum pump and the like to adjust the temperature and pressure inside the device, and realizes unmanned guard and safety linkage of platinum-carbon catalyst particles for fuel cells in reduction operation through the linkage control. Meanwhile, the hydrogen sensor arranged on the outer side of the device can monitor the hydrogen content outside the device in real time, and can timely treat the hydrogen leakage caused by overpressure or accidents when flammable and explosive hydrogen is leaked.
(4) The invention can keep the space velocity range of the catalyst at 300-3000 h -1, and improve the reduction efficiency of the catalyst while ensuring the safety of the reaction tube. If the upper space velocity is exceeded, the pressure in the upper part of the bed will be too high, which may lead to rupture of the reaction tube. Below the lower space velocity, a lower reduction rate will result, which in turn may lead to insufficient catalyst reduction.
Drawings
FIG. 1 is a schematic diagram of a connection according to an embodiment of the present invention;
FIG. 2 is a schematic view of a reaction tube according to an embodiment of the present invention;
FIG. 3 is an enlarged view of part of A of FIG. 2;
FIG. 4 is an enlarged view of part B of FIG. 2;
FIG. 5 is an enlarged view of part of C of FIG. 2;
FIG. 6 is a partial enlarged view of D of FIG. 2;
FIG. 7 is a top view of the upper flange of the reactor tube of an embodiment of the present invention;
In the figure: 1. a reducing gas input unit; 11. a reducing gas pipe; 12. a first electromagnetic valve; 13. a first flow controller; 14. a first one-way valve; 2. a purge unit; 21. an inert gas tube; 22. a second electromagnetic 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. a clamp; 46. opening holes; 47. a bracket; 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 detector; 8. polytetrafluoroethylene.
Detailed Description
In order to facilitate the understanding of the technical scheme of the present invention by those skilled in the art, the technical scheme of the present invention will be further described with reference to the accompanying drawings.
The terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined 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 an exhaust gas treatment unit 6;
The reducing gas input unit 1 includes a reducing gas pipe 11, a first solenoid 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 sequentially passing through a first electromagnetic valve 12, a first flow controller 13 and a first one-way valve 14. The reducing gas pipe 11 is internally provided with pure hydrogen or mixed gas containing hydrogen and inert gas, 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 between the two, and the first one-way valve 14 can prevent the gas from flowing back into the reducing gas pipe 11 to pollute the internal gas.
The purge unit 2 includes an inert gas pipe 21, a second solenoid 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 a second electromagnetic valve 22, a second flow controller 23 and a second one-way valve 24 in sequence. The inert gas pipe 21 is internally provided with pure nitrogen gas or pure argon gas or mixed gas of the pure nitrogen gas and the pure argon gas, the second electromagnetic valve 22 can control the communication or closing of the inert gas pipe 21 and the mixing tank 3, the second flow controller 23 can control the flow between the inert gas pipe 21 and the mixing tank, and the second one-way valve 24 can prevent the gas from flowing back into the inert gas pipe 21 to pollute the internal gas.
Referring to fig. 2 to 7, the reaction tube 4 is of a vertical structure including 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 by the clamp 45, the lower flange 43 is arranged at the lower end of the quartz tube 41 and is fixed by the clamp 45, and the upper flange 42 and the lower flange 43 are respectively fixed with the quartz tube 41 by the detachable clamp 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 holding a catalyst. The pore diameter gap range of the sand core 44 of this embodiment is 10-30 μm, and the inner diameter range of the quartz tube 41 is 30-160mm. When in use, 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, one of which 46 is an air inlet for communication with the output of the mixing tank 3. The other three openings 46 may be respectively inserted with temperature sensors.
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 inner bottom surface of the lower flange 43 is tapered with a slope of less than 170 ° so as to collect the reduction product of the catalyst reduction reaction and output from the gas outlet 48.
The bottom of the reaction tube 4 is also provided with a bracket 47 for supporting the reaction tube 4.
Meanwhile, in order to ensure the tightness of the inside of the quartz tube 41, an O-shaped sealing ring 410 and a sealing gasket 49 are arranged between the upper flange 42 and 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 embodiment has the characteristic of acid and alkali corrosion resistance, and polytetrafluoroethylene 8 or modified materials thereof are sprayed on the inner cavity surfaces of the upper flange 42 and the lower flange 43, so that the upper flange 42 and the lower flange 43 can resist acid and alkali corrosion. The integral device of the reaction tube 4 can avoid the problem that the reduction products HCl and H2O of chloroplatinic acid hydrate (Cl6H2Pt.xH2O) are corrosive to equipment, so that the reaction can be safely carried out without frequent equipment replacement.
The heating furnace 5 surrounds the circumference of the reaction tube 4, the heating furnace 5 adopts three sections of hearths with independent temperature control, and the three sections of independent temperature control can reach a longer constant temperature zone, thereby being beneficial to the temperature uniformity of the catalyst bed. 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 heatable and controllable temperature of the heating furnace 5 ranges 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 air 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 through the vacuum pump 63 for discharging tail gas.
The alkali liquor neutralization tank 61 is made of 316L stainless steel, and polytetrafluoroethylene 8 or modified materials thereof are sprayed on the surface of the inner cavity of the alkali liquor neutralization tank 61, so that the alkali liquor neutralization tank can resist corrosion of acid and alkali. The inside holds 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. The adsorbent tank 62 is provided with an adsorbent, and the adsorbent of the internal quartz is activated carbon or color-changing silica gel.
The vacuum pump 63 is a corrosion-resistant diaphragm pump with a vacuum limit of 200mbar and an aeration rate of not less than 120L/min.
The pipeline connecting the devices is made of polytetrafluoroethylene 8 or modified material thereof, and can resist corrosion of acid and alkali.
The control system 7 includes a PLC processor (not shown), a touch screen (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 detector 711.
The PLC processors are connected to the touch panel, 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, respectively.
A first pressure gauge 71 and a first pressure sensor 72 are both provided on the pipe between the mixing tank 3 and the reaction tube 4 for monitoring the pressure value at the upper flange 42; a second pressure gauge 73 and a second pressure sensor 74 are both provided on the piping between the canister 62 and the vacuum pump 63 for monitoring the pressure value at the lower flange 43. Because 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 of the first pressure sensor 72 is typically no lower than the pressure measurement of the second pressure sensor 74. The pressure of 0.02MPa (gauge pressure) is more easily exceeded at the upper flange 42 than at the lower flange 43, and there is a tendency that the gas leaks due to exceeding 0.02MPa at the upper flange 42 of the reaction tube 4. When the measured value of the first pressure sensor 72 exceeds 0.02mpa by 80%, the PLC processor activates the vacuum pump 63. The pressure of the equipment and the pipeline of the whole device can be quickly and integrally reduced. Maintaining the vacuum pump 63 continuously running, if the flow of the air flow upstream of the upper flange 42 is too high, resulting in a measured value of the second pressure sensor 74 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 for reducing the flow rate and thus the pressure.
The first, second and third temperature sensors 75, 76 and 77 are installed in the reaction tube 4 to be inserted through the three openings 46 of the upper flange 42, respectively, and the first, second and third temperature sensors 75, 76 and 77 measure temperatures of the catalyst stack layers 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 substances.
The fourth temperature sensor 78, the fifth temperature sensor 79 and the sixth temperature sensor 710 are respectively installed on three independent hearths of the heating furnace 5 from top to bottom in sequence and are used for monitoring the temperature of the heating furnace 5.
The hydrogen detector 711 is located above the device, and the hydrogen detector 711 is exposed to air for detecting the concentration of hydrogen gas that may leak out, thereby confirming whether the device leaks.
The PLC processor is also connected to the first solenoid valve 12, the first flow controller 13, the second solenoid 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 device of the present embodiment 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 tightly attached to the inner wall of the reaction tube 4.
S3, installing the upper flange 42 and the lower flange 43 on the top and the bottom of the reaction tube 4, and fixing the sealing gasket 49 and the O-ring. The ceramic bushings 411 of three thermocouples were vertically inserted into the reaction tube 4 from the nozzle of the upper flange 42 and immersed inside the bed, and then the thermocouples were put into the ceramic bushings 411 again.
S4, opening an air inlet valve of the inert gas, setting the flow rate of the inert gas, wherein the flow rate is based on the filling amount of the catalyst, the air airspeed range of the embodiment 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 equipment and pipelines of the whole device is rapidly and integrally reduced. Maintaining the vacuum pump 63 continuously running, if the flow of the air flow upstream of the upper flange 42 is excessive, resulting in a measured value of the first pressure sensor 72 exceeding 0.02mpa by 80%, the PLC processor will down-regulate the set flow rates of the first flow controller 13 and the second flow controller 23. After the purging is completed, the inlet valve of the inert gas is closed, the vacuum pump 63 is maintained or opened, the suction is performed for 3 to 5 minutes, and then the vacuum pump 63 is closed.
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 air airspeed range of the embodiment is 300-3000 h < -1 >. Setting the temperature of the heating furnace 5 to be 200-1000 ℃, heating the heating furnace at a heating rate of 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 of the first temperature sensor 75, the second temperature sensor 76 and the third temperature sensor 77 at the positions of different radiuses of the catalyst stack layer is within + -2 ℃ and kept for more than 10 minutes, the temperature of the catalyst stack layer can be considered to be stable and uniform, and the catalyst stack layer is kept for 1-5 hours. In the above process, when the measured value of the first pressure sensor 72 exceeds 0.02mpa×80%, the PLC processor activates the vacuum pump 63. The pressure of the equipment and the pipeline of the whole device can be quickly and integrally reduced. Maintaining the vacuum pump 63 continuously running, if the measured value of the first pressure sensor 72 exceeds 0.02mpa by 80% due to the excessive flow rate of the upstream air flow, the PLC processor will down-regulate the set flow rates of the first flow controller 13 and the second flow controller 23.
S6, after the catalyst is reduced for a certain time at the temperature and the pressure, setting the cooling rate of the heating furnace 5 to be 1-5 ℃/min, cooling to the temperature below 50 ℃ detected by the first temperature sensor 75, and closing the air inlet valve of the reducing gas. And (4) carrying out inert gas purging again according to the step (S4) to discharge inflammable and explosive reducing gas.
And S7, after the reaction is finished, opening the upper flange 42, taking out the catalyst bed layer into liquid, and performing liquid seal to prevent oxygen in the air from affecting the catalyst.
In this embodiment, the vertical reaction tube 4 made of quartz is adopted, and the catalyst is tiled on the sand core 44 in the reaction tube 4, and the reducing gas can fully contact with the catalyst after entering the reaction tube 4 from the upper flange 42, so that the problem of insufficient reduction of the catalyst is avoided. Meanwhile, the reaction tube 4 with the vertical structure and the sand core 44 with small holes inside can enable reduction products HCl and H2O to timely flow into the lower end of the reaction tube 4, so that the problem that partial catalyst cannot react with reduction gas due to accumulation of the reduction products in the catalyst is solved, and the problems of slow reduction speed and uneven reduction are solved.
The embodiment can keep the space velocity range of the catalyst at 300-3000 h -1, and improve the reduction efficiency of the catalyst while ensuring the safety of the reaction tube 4. If the upper space velocity is exceeded, the pressure in the upper part of the bed will be too high, which may lead to rupture of the reaction tube 4. Below the lower space velocity, a lower reduction rate will result, which in turn may lead to insufficient catalyst reduction.
The corrosion problem of the reduction products is solved by spraying polytetrafluoroethylene 8 or modified materials thereof on the surfaces of the inner cavities of the upper flange 42, the lower flange 43, the mixing tank 3 and the alkali liquor neutralization tank 61 of the reaction tube 4.
The first temperature sensor 75, the second temperature sensor 76 and the third temperature sensor 77 monitor temperatures of different depths of the catalyst and send data to the PLC processor, the fourth temperature sensor 78, the fifth temperature sensor 79 and the sixth temperature sensor 710 monitor temperatures of three sections of independent hearths of the heating furnace 5 and send data to the PLC processor, and the PLC controller can automatically adjust a temperature range when the catalyst undergoes a reduction reaction.
The first and second pressure sensors 72 and 74 monitor the pressures at the upper flange 42 and the flange, respectively, and send data to a PLC controller capable of controlling the start and stop of the first and second solenoid valves 12, 22, the first and second flow controllers 13, 23, and the vacuum pump 63 to adjust the pressures according to whether the first and second pressure sensors 72 and 74 exceed 0.02 Mpa. Through linkage control, unmanned guard 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 characteristics 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.
The above-described embodiments merely represent embodiments of the invention, the scope of the invention is not limited to the above-described embodiments, and it is obvious to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (6)
1. A reduction processing apparatus for carbon carries platinum catalyst which 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 pile layer is arranged in the quartz tube (41), and the sand core (44) is provided with a plurality of holes;
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 tube (4), and the lower flange (43) of the reaction tube (4) is communicated with the tail gas treatment unit (6); the heating furnace (5) surrounds the circumference of the reaction tube (4);
The reducing gas enters the reaction tube (4) from the upper flange (42) after passing through the mixing tank (3), moves downwards and performs reduction reaction with the catalyst stack layer, the reducing product falls onto the lower flange (43) through the gap of the sand core (44), and finally the reducing product is treated by the tail gas treatment unit (6);
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 respectively and sequentially arranged on the pipeline between the reducing gas pipe (11) and the mixing tank (3), and the flowing direction of the first one-way valve (14) is from the reducing gas pipe (11) to the mixing tank (3);
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 end of the inert gas pipe (21) is communicated with the input end of the mixing tank (3) through a pipeline, the second electromagnetic valve (22), the second flow controller (23) and the second one-way valve (24) are respectively and sequentially arranged on the pipeline between the reducing gas pipe (11) and the mixing tank (3), and the circulation direction of the second one-way valve (24) is from the inert gas pipe (21) to the mixing tank (3);
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 the vacuum pump (63);
The system further comprises 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 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 openings (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 ceramic sleeve (411) and are respectively inserted into catalyst stack 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 located 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.
2. The reduction treatment device for a carbon-supported platinum catalyst according to claim 1, wherein: four openings (46) are formed in the upper flange (42), wherein one opening (46) is an air inlet and is communicated with the output end of the mixing tank (3), and the other three openings (46) can be respectively inserted into a temperature sensor;
An air outlet (48) is formed in the lower flange (43), and the air 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 smaller than 170 degrees.
3. The reduction treatment device for a carbon-supported platinum catalyst according to claim 1, wherein: 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 3-6 times of the height of a catalyst bed in the reaction tube (4).
4. The reduction treatment device for a carbon-supported platinum catalyst according to claim 1, wherein: polytetrafluoroethylene (8) is sprayed on the surfaces of the inner cavities of the upper flange (42), the lower flange (43), the mixing tank (3) and the alkali liquor neutralization tank (61).
5. A method using the reduction treatment device for a carbon-supported platinum catalyst according to any one of claims 1 to 4, characterized by: the method comprises the following steps:
s1, cleaning the inner wall and the sand core (44) in a 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 a sand core (44) of the reaction tube (4), and enabling a 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, installing an upper flange (42) and a lower flange (43) at 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 opening of the upper flange (42), immersing the three thermocouples in the bed, and then putting 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 based on the loading amount of the catalyst, the airspeed range is 300-3000 h < -1 >, purging is carried out for 5-20min, after purging is finished, closing the air inlet valve of the inert gas, opening a 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 airspeed range is 300-3000 h < -1 >; setting the temperature of the heating furnace (5) at the temperature range of 200-1000 ℃ and the temperature rising rate of 3-12 ℃/min, and stopping rising 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 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 layer is +/-2 ℃ and kept for more than 10 minutes, the temperature of the catalyst stack layer is considered to be stable and uniform, and the catalyst stack layer is kept for 1-5 hours;
s6, after the catalyst is reduced for a certain time at the temperature and the pressure, setting the cooling rate of the heating furnace (5) to be 1-5 ℃/min, cooling to the temperature below 50 ℃ detected by the first temperature sensor (75), and closing an air inlet valve of the reducing gas; step S4, purging with inert gas again, and discharging inflammable and explosive reducing gas;
And S7, after the reaction is finished, opening the upper flange (42), taking out the catalyst bed layer into liquid, and performing liquid seal.
6. The method according to claim 5, wherein: 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 equipment and pipelines of the whole device is rapidly and integrally reduced; maintaining the vacuum pump (63) continuously running, if the flow of the air flow upstream of the upper flange (42) is excessive, so that the measured value of the first pressure sensor (72) exceeds 0.02mpa by 80%, and the PLC processor downwards regulates the set flow of the first flow controller (13) and the second flow controller (23).
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| CN111509240A (en) * | 2020-05-19 | 2020-08-07 | 深圳市通用氢能科技有限公司 | Carbon-supported platinum catalyst powder and preparation method and application thereof |
| CN218160459U (en) * | 2022-09-15 | 2022-12-27 | 安徽科幂仪器有限公司 | Reduction treatment device for carbon-supported platinum catalyst |
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| US20070003822A1 (en) * | 2005-06-30 | 2007-01-04 | Shyam Kocha | Voltage cycling durable catalysts |
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| CN111509240A (en) * | 2020-05-19 | 2020-08-07 | 深圳市通用氢能科技有限公司 | Carbon-supported platinum catalyst powder and preparation method and application thereof |
| CN218160459U (en) * | 2022-09-15 | 2022-12-27 | 安徽科幂仪器有限公司 | Reduction treatment device for carbon-supported platinum catalyst |
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| Title |
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| 燃料电池型一氧化碳传感器的研究;张小水;刘红霞;高胜国;张娴;;陶瓷学报;20080915(第03期);全文 * |
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