CN114540858A - Jet plasma coupling multistage electrocatalysis integrated ammonia synthesis device and method - Google Patents
Jet plasma coupling multistage electrocatalysis integrated ammonia synthesis device and method Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 44
- 230000008878 coupling Effects 0.000 title claims abstract description 15
- 238000010168 coupling process Methods 0.000 title claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 94
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000003860 storage Methods 0.000 claims abstract description 42
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 30
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000010453 quartz Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052961 molybdenite Inorganic materials 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 230000001276 controlling effect Effects 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000009616 inductively coupled plasma Methods 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
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- 238000002360 preparation method Methods 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
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- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011943 nanocatalyst Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000011268 retreatment Methods 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 230000001360 synchronised effect Effects 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000126 substance Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 241000772991 Aira Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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Abstract
The invention discloses a jet plasma coupling multistage electrocatalysis integrated ammonia synthesis device and methodxAnd the water-soluble NO is improved by means of a gas storage tank, exhaust gas recirculation and the likexConcentration, providing reaction raw materials for the electrocatalytic process; then theRealize multistage catalysis through a plurality of H type electrolytic cell series connection, adopt the high catalytic activity nitrogen phosphorus of preparing to mix molybdenum disulfide electrocatalyst simultaneously to furthest improves the conversion efficiency of electrocatalysis process, finally with N in the air2Real-time conversion to NH in electrolyte3The high-efficiency conversion from renewable solar energy to high-grade chemical energy is realized, and the problem of energy consumption in the plasma process is solved.
Description
Technical Field
The invention relates to the field of synthetic ammonia, in particular to an integrated synthetic ammonia device and method with jet plasma coupling and multistage electrocatalysis.
Background
In the modern society, with environmental pollution caused by industrial development and population growth, development of a green and environment-friendly renewable energy source becomes a focus of global attention. The ammonia gas is used as an excellent hydrogen energy storage carrier and an important nitrogen fertilizer raw material in agricultural production, has wide application in the fields of agriculture and energy storage, and how to efficiently prepare the clean and environment-friendly ammonia gas becomes a major problem in the fields of energy and environment. Currently, the ammonia production method applied industrially is still the Haebi method developed in the last century, which continuously provides the human society with the required ammonia gas resource for over a century, however, the method not only has harsh reaction conditions and consumes a large amount of energy, but also emits nearly 3 hundred million tons of carbon dioxide every year; the large amount of high nitrogen ammonia wastewater generated in the production process causes great pollution to the environment. Therefore, at present, the energy and environment problems are increasingly outstanding, and a clean and efficient ammonia preparation method capable of replacing the Haeberg method is urgently developed.
At present, a plurality of experimental researches directly convert nitrogen into ammonia gas by an electro-catalysis method, the experimental conditions are mild, the method is simple and environment-friendly, and no harmful pollutant is discharged. However, since the electrocatalysis method is excessively dependent on the performance of the catalyst, nitrogen-nitrogen triple bonds (N ≡ N,948kJ/mol) with stable structures cannot be effectively broken, so that the problems of poor treatment capability and low yield exist, and the requirement of human beings on ammonia cannot be met; based on this, the invention couples the plasma with strong processing ability with the electric catalysis, and uses the air with rich source as the airAs raw materials, N can be realized2To NH3The transformation of (3). The strong processing capability of the plasma is utilized, so that the effective breakage of nitrogen-nitrogen triple bonds is guaranteed, the ammonia can be efficiently synthesized without pollution, meanwhile, the plasma can be well combined with renewable energy sources such as solar energy, wind energy and the like, and an experimental basis can be provided for replacing the Haebi method in the future.
Disclosure of Invention
The invention aims to further optimize and perfect an experimental system for coupling plasma and electrocatalysis, integrate the solar-driven plasma discharge and electrocatalysis processes and a corresponding tail gas recirculation system into an integrated device, and realize N in the air2To NH in the electrolyte3The multi-stage catalysis is realized by connecting a plurality of H-shaped electrolytic cells in series, the nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst with high catalytic activity is prepared, and finally, the plasma-coupled multi-stage nitrogen-phosphorus-doped molybdenum disulfide electrocatalysis integrated high-efficiency ammonia synthesis is realized.
The purpose of the invention is realized by the following technical scheme: an integrated ammonia synthesis device with jet plasma coupled with multistage electrocatalysis comprises a multi-air inlet jet plasma reactor, a multistage electrocatalysis system based on a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst and a tail gas recirculation system;
the multi-air-inlet jet plasma reactor comprises two air inlets, wherein one air inlet is an air inlet and is connected with an air compressor, and the other air inlet is an air circulation air inlet and is connected with a circulation air pump for air circulation; the multi-air inlet jet flow plasma reactor is used for converting N in air2And O2Conversion to NOxThe outlet of the reactor is connected with a gas pipe through a stainless steel flange and a quartz cover, and NO is addedxInputting the gas into a gas storage tank;
the multistage electro-catalysis system comprises an electrochemical workstation and an H-shaped electrolytic cell; a plurality of H-shaped electrolytic cells are connected in series, the air outlet of the cathode reaction chamber of the upper H-shaped electrolytic cell is connected with the air inlet of the cathode reaction chamber of the lower H-shaped electrolytic cell, and each H-shaped electrolytic cell is connected with an electric generatorChemical workstation, implementing NOxTo NH3The transformation of (3); the H-shaped electrolytic cell of the first stage is connected with a gas storage tank; the last stage of H-shaped electrolytic cell is connected with a circulating air pump;
the working electrode of the H-shaped electrolytic cell adopts a nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst, and the preparation process of the nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst is as follows: firstly obtaining phosphorus-doped molybdenum disulfide through a plasma enhanced vapor deposition method, a hydrothermal method and a phosphating method in sequence, and finally carrying out ammonia plasma doping on the phosphorus-doped molybdenum disulfide to obtain a nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst, wherein the plasma doping process is as follows:
placing the phosphorized molybdenum disulfide catalyst in a tubular furnace, pumping to negative pressure and heating, introducing ammonia gas, and then discharging through inductively coupled plasma, wherein in the discharging process, the etching effect on the surface of the catalyst is obvious in the ammonia gas atmosphere, and the generated N-containing free radical has high activity, can replace S atoms in molybdenum disulfide to realize N atom doping, so as to obtain the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst;
the tail gas recirculation system comprises a first mass flow meter, a pressure gauge, a pressure regulating valve, a gas storage tank, a vent valve, a second mass flow meter and a circulating gas pump; the first mass flow meter is arranged at an air inlet of the reactor and used for controlling the air inlet flow; the plasma discharge gas is adjusted by a second mass flow meter and a pressure regulating valve and then is introduced into a gas storage tank, flows through all levels of H-shaped electrolytic cells and then flows back to the multi-gas-inlet jet flow plasma reactor again through a circulating gas pump; the tail gas recycling system enables the N which does not participate in the reaction to be contained2、O2And NO mainly comprising NOxThe tail gas participates in the discharge again, and the gas after the plasma retreatment is more easily converted into water-soluble NOxAnd the gas conversion rate is improved.
Further, the device also comprises a solar power supply system, wherein the solar power supply system comprises a solar panel, a storage battery and a transformer; the solar panel is connected with a storage battery, and the storage battery supplies power to the multi-air-inlet jet plasma reactor through a transformer.
Furthermore, the air inlets of the multi-air-inlet jet flow plasma reactor are a plurality of uniformly-distributed tangential air inlets, a rotating airflow is formed inside the reactor, the disturbance of air in the air cavity of the reactor is increased, the discharge effect and the plasma area are enhanced, and the gas treatment efficiency is improved.
Further, since the discharge gas contains a large amount of NO, the gas is easily oxidized to NO in an oxygen-containing atmosphere2Standing and buffering the discharge gas via a gas storage tank to make the water-soluble NO in the discharge gasxIncrease in content of NOxFixed in solution.
Further, the preparation method of the nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst comprises the following steps:
(1) cutting carbon cloth with proper size, placing the carbon cloth in a quartz tube, pumping the quartz tube to negative pressure, introducing methane, hydrogen and argon into the quartz tube according to a certain proportion, heating, starting cooling water, and discharging inductively coupled plasma for a period of time to form uniformly distributed graphene on the carbon cloth, wherein the graphene is recorded as VG/CC;
(2) uniformly mixing 1.2g of sodium molybdate, 1.56g of thioacetamide and 60ml of deionized water, then transferring the mixture into a reaction kettle, placing the obtained VG/CC into the mixed solution, carrying out hydrothermal treatment at 200 ℃ in an oven for 12 hours to obtain a molybdenum disulfide nano structure growing on vertical graphene, and recording the molybdenum disulfide nano structure as MoS2/VG/CC；
(3) The obtained MoS2placing/VG/CC and 1g sodium hypophosphite at two ends of a quartz boat respectively, and placing into a quartz tube, wherein MoS2the/VG/CC is positioned in the downwind direction, the sodium hypophosphite is positioned in the upwind direction, negative pressure is pumped, the reaction is maintained for one hour at 300 ℃, and the phosphorus-doped molybdenum disulfide catalyst is obtained after the reaction is finished;
(4) putting the phosphorus-doped molybdenum disulfide catalyst in a tubular furnace, pumping to negative pressure, introducing ammonia gas, heating, and discharging by inductively coupled plasma to obtain the nitrogen-phosphorus-doped molybdenum disulfide nano catalyst, which is recorded as N, P-MoS2/VG/CC。
The invention also provides a jet plasma coupling multistage electrocatalysis integrated ammonia synthesis method, which is a multistage catalysis operation mode in which gas discharge and electrocatalysis processes are synchronously carried out, and comprises the following steps:
(1) connecting the multi-air-inlet jet flow plasma reactor with a power supply, respectively connecting two air inlets with an air compressor and a circulating air pump, starting the air compressor, introducing air into the multi-air-inlet jet flow plasma reactor, and controlling the air inlet flow by a first mass flow meter;
(2) turning on a plasma power supply, adjusting power input into two ends of the multi-air-inlet jet flow plasma reactor, realizing stable discharge of plasma, and converting N in air2And O2Conversion to NOxInputting into a gas storage tank;
(3) the air outlet of the air storage tank is connected with the air inlet of the first-stage H-shaped electrolytic cell, the air outlet of the upper-stage H-shaped electrolytic cell is connected with the next-stage H-shaped electrolytic cell through an air pipe, and the last-stage H-shaped electrolytic cell is connected with a circulating air pump; each electrolytic cell is respectively connected with an electrochemical workstation, and a piece of nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst is clamped on a working electrode clamp of each H-shaped electrolytic cell to be used as a working electrode.
(4) Adjusting pressure regulating valve and communicating valve, make pipeline gas pressure maintain stably, open the electrochemistry workstation, the operation CV makes system current carry out electro-catalysis process at different levels after stable, including first order electro-catalysis, second level electro-catalysis, third level electro-catalysis … Nth level electro-catalysis, open magnetic stirrers simultaneously, through magnetic stirrers with electrolyte misce bene, realize plasma discharge and electro-catalysis's synchronous going on, after waiting to react, collect the reaction liquid in every H type electrolytic cell and carry out the detection of ammonia productivity.
Further, the electrocatalytic reaction is carried out at an overpotential of 0.1V to 0.5V for 1 hour, and the ammonia yield is measured by an ultraviolet-spectrophotometer.
The invention has the beneficial effects that:
(1) integrating devices; through the integrated design, including the connection of a plasma reactor and an electrolytic cell, the construction of a tail gas recovery system and the like, the solar-driven plasma discharge and electrocatalysis process are integrated into an integrated device, so that the plasma discharge is realizedSynchronous operation with electrocatalysis process, realizes N in the air2To NH in the electrolyte3Real-time transformation of (2).
(2) The conversion efficiency is high; conversion efficiency includes both air to water soluble NOxIncluding NO in solution2 -,NO3 -To NH3The conversion efficiency of (a). The former improves the conversion of air to water-soluble NO through the strong processing capacity of multi-air inlet jet plasma, the standing function of the air storage tank and the tail gas recycling of the tail gas recycling systemxThe conversion efficiency of the method provides sufficient raw materials for the subsequent electrocatalysis process; in the latter, nitrogen-phosphorus-doped molybdenum disulfide catalyst with high catalytic activity is used as a working electrode of electrocatalytic reaction, so that the reaction rate of ammonia synthesis in the electrolyte is increased; meanwhile, a multi-stage catalytic system established by connecting a plurality of H-type electrolytic cells in series promotes the NO conversion process to the maximum extent2 -,NO3 -Conversion to NH3Finally, jointly increase N2To NH3The conversion efficiency of (2).
(3) Low energy consumption and no pollution; clean and renewable solar energy is used as power supply energy of the plasma reactor, so that huge energy consumption required by plasma discharge is effectively eliminated; meanwhile, a plasma coupling electrocatalysis method is adopted to realize carbon neutralization in the reaction process; in addition, NO in the exhaust gas is reducedxThe recycling is carried out, and zero pollution and zero emission can be realized in the whole process.
(4) The reaction design is reasonable; the experimental system effectively solves the barriers that nitrogen-nitrogen triple bonds are difficult to break and the synthetic ammonia reaction activity is low in the current research, utilizes plasma to break bonds of nitrogen and oxygen in the air for reforming, avoids direct participation of nitrogen in the reaction, dissolves the reformed oxynitride in electrolyte for electrocatalytic reaction, and greatly improves the reaction rate of the synthetic ammonia.
Drawings
FIG. 1 is a schematic diagram of an integrated ammonia synthesis device with jet plasma coupling and multistage electrocatalysis.
In the figure: 1. a solar panel; 2. a storage battery; 3. a transformer; 4. an air compressor; 5. a first mass flow meter; 6. a multi-inlet jet plasma reactor; 7. a stainless steel flange; 8. a quartz cover; 9. a pressure gauge; 10. a pressure regulating valve; 11. a gas storage tank; 12. a vent valve; 13. a second mass flow meter; 14. an electrochemical workstation; 15. a magnetic stirrer; an H-type electrolytic cell; 17. a magnetic stirrer; 18. a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst; 19. second-stage electrocatalysis; 20. third-stage electrocatalysis; 21. the Nth stage of electrocatalysis; 22. and a circulating air pump.
FIG. 2 is a graph comparing experimental performance: (a) the single-stage catalytic synthesis ammonia yield and the corresponding Faraday efficiency under different overpotentials; (b) the ammonia yield and the corresponding Faraday efficiency are synthesized by multistage catalysis under different overpotentials; (c) the ammonia yield and the corresponding Faraday efficiency are synthesized by multi-stage catalysis of different catalysts under the overpotential of 0.3V;
FIG. 3 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of nitrogen-phosphorus-doped molybdenum disulfide.
FIG. 4 is a nitrogen phosphorus doped molybdenum disulfide X-ray photoelectron spectrum (top: N, P-MoS)2/VG/CC; the following: MoS2/VG/CC)。
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
The invention provides a jet plasma coupling multistage electrocatalysis integrated ammonia synthesis device and a method, and integrates a solar-driven plasma discharge and electrocatalysis process and a corresponding tail gas recirculation system into an integrated device. Firstly, air is converted into NO by utilizing solar energy to drive jet plasmaxAnd the water-soluble NO is improved by means of a gas storage tank, exhaust gas recirculation and the likexConcentration, providing reaction raw materials for the electrocatalytic process; then, a plurality of H-shaped electrolytic cells are connected in series to realize multi-stage catalysis, and the prepared high-catalytic-activity nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst is adopted to improve the conversion efficiency of the electrocatalysis process to the maximum extent and finally make N in the air2Real-time conversion to NH in electrolyte3The high-efficiency conversion from renewable solar energy to high-grade chemical energy is realized, and the problem of energy consumption in the plasma process is solved.
As shown in fig. 1, the integrated ammonia synthesis device with jet plasma coupling and multistage electrocatalysis comprises a solar power supply system, a multi-air inlet jet plasma reactor 6, a multistage electrocatalysis system based on nitrogen-phosphorus doped molybdenum disulfide electrocatalysts and a tail gas recirculation system;
the multi-inlet jet plasma reactor 6 comprises two inlets, wherein one inlet is an air inlet and is connected with the air compressor 4, and the other inlet is an air circulation inlet and is connected with the circulation air pump 22 for air circulation; the air inlets of the multi-air-inlet jet plasma reactor 6 are a plurality of uniformly-distributed tangential air inlets, and a rotating airflow is formed inside the reactor, so that the disturbance of air in the air cavity of the reactor and the plasma discharge area are increased, the discharge effect is enhanced, and the gas treatment efficiency is improved. The multi-air inlet jet flow plasma reactor 6 is used for discharging N in the air2And O2Conversion to NOxAnd is input into an air storage tank 11; the discharge gas is kept still and buffered by the gas storage tank 11, so that the water-soluble NO in the discharge gasxIncrease in content of NOxFixed in solution to provide reaction raw materials for electrocatalytic process.
The multi-stage electro-catalytic system includes an electrochemical workstation 14 and an H-type electrolyzer 16; a plurality of H-shaped electrolytic cells 16 are connected in series, the air outlet of the cathode reaction chamber of the previous H-shaped electrolytic cell 16 is connected with the air inlet of the cathode reaction chamber of the next H-shaped electrolytic cell 16, and each H-shaped electrolytic cell 16 is connected with an electrochemical workstation 14 to realize NOxTo NH3The transformation of (3); the first stage H-shaped electrolytic cell 16 is connected with the gas storage tank 11; the last stage of the H-shaped electrolytic cell 16 is connected with a circulating air pump 22;
unlike other reactions, a large amount of NO is generated during the plasma process in the present coupled systemxThe single-stage electrocatalysis process can not effectively convert and utilize the NO, and NO is maximally converted and utilized by establishing a multi-stage catalysis systemxMulti-stage absorption in electrolyte and greatly increased NH3The synthesis efficiency of (2).
The working electrode of the H-shaped electrolytic cell 16 adopts a nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst 18, and the preparation process of the nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst 18 is as follows: firstly obtaining phosphorus-doped molybdenum disulfide by a plasma enhanced vapor deposition method, a hydrothermal method and a phosphorization method in sequence, and finally carrying out ammonia plasma doping on the phosphorus-doped molybdenum disulfide to obtain a nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst, wherein the plasma doping process is as follows:
placing the phosphatized molybdenum disulfide catalyst in a tubular furnace, pumping to negative pressure and heating, introducing ammonia gas, discharging through inductively coupled plasma, and replacing S atoms in molybdenum disulfide with generated N-containing free radicals to realize N atom doping to obtain a nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst 18;
the preparation method of the nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst 18 specifically comprises the following steps:
(1) cutting carbon cloth with proper size, placing the carbon cloth in a quartz tube, pumping the quartz tube to negative pressure, introducing methane, hydrogen and argon into the quartz tube according to a certain proportion, heating, starting cooling water, and discharging inductively coupled plasma for a period of time to form uniformly distributed graphene on the carbon cloth, wherein the graphene is recorded as VG/CC;
(2) uniformly mixing 1.2g of sodium molybdate, 1.56g of thioacetamide and 60ml of deionized water, then transferring the mixture into a reaction kettle, placing the obtained VG/CC into the mixed solution, carrying out hydrothermal treatment at 200 ℃ in an oven for 12 hours to obtain a molybdenum disulfide nano structure growing on vertical graphene, and recording the molybdenum disulfide nano structure as MoS2/VG/CC；
(3) The obtained MoS2placing/VG/CC and 1g sodium hypophosphite at two ends of a quartz boat respectively, and placing into a quartz tube, wherein MoS2the/VG/CC is positioned in the downwind direction, the sodium hypophosphite is positioned in the upwind direction, the negative pressure is pumped, the reaction is maintained for one hour at the temperature of 300 ℃, and the phosphorus-doped molybdenum disulfide catalyst is obtained after the reaction is finished;
(4) putting the phosphorus-doped molybdenum disulfide catalyst in a tube furnace, pumping to negative pressure, introducing ammonia gas, heating, and discharging by inductively coupled plasma to obtain the nitrogen-phosphorus-doped molybdenum disulfide nano catalyst, which is recorded as N, P-MoS2/VG/CC。
The tail gas recycling system comprises a first mass flow meter 5, a pressure regulating valve 10,The air storage tank 11, the second mass flow meter 13 and the air circulation pump 22; the first mass flow meter 5 is arranged at an air inlet of the reactor and used for controlling the flow of the inlet air; the plasma discharge gas is adjusted by a second mass flow meter 13 and a pressure regulating valve 10 and then is introduced into a gas storage tank 11, then flows through each stage of H-shaped electrolytic cell 16 and then flows back to the multi-gas inlet jet flow plasma reactor 6 again through a circulating gas pump 22; the tail gas recycling system enables the N which does not participate in the reaction to be contained2、O2And NO mainly comprising NOxThe tail gas participates in the discharge again, and the gas after the plasma retreatment is more easily converted into water-soluble NOxAnd the gas conversion rate is improved. By means of tail gas recovery, the gas conversion rate is improved, and harmful NO is avoidedxAnd (4) discharging gas.
The solar power supply system comprises a solar panel 1, a storage battery 2 and a transformer 3; the solar panel 1 is connected with the storage battery 2, and the storage battery 2 supplies power to the multi-air-inlet jet plasma reactor 6 through the transformer 3.
The invention also provides a jet plasma coupling multistage electrocatalysis integrated ammonia synthesis method, which is a multistage catalysis operation mode in which gas discharge and electrocatalysis processes are synchronously carried out, and comprises the following steps:
(1) connecting a multi-air-inlet jet flow plasma reactor 6 with a power supply, respectively connecting two air inlets with an air compressor 4 and a circulating air pump 22, starting the air compressor 4, introducing air into the multi-air-inlet jet flow plasma reactor 6, and controlling the flow rate of the inlet air by a first mass flow meter 5;
(2) turning on a plasma power supply, adjusting the power input into two ends of the multi-air-inlet jet flow plasma reactor 6, realizing the stable discharge of the plasma, and converting N in the air2And O2Conversion to NOxAnd is input into an air storage tank 11;
(3) the air outlet of the air storage tank 11 is connected with the air inlet of the first-stage H-shaped electrolytic cell 16, the air outlet of the previous-stage H-shaped electrolytic cell 16 is connected with the next-stage H-shaped electrolytic cell 16 through an air pipe, and the last-stage H-shaped electrolytic cell 16 is connected with the circulating air pump 22; each of which is connected to an electrochemical workstation 14 and a piece of nitrogen-phosphorus doped molybdenum disulfide electrocatalyst 18 is clamped as the working electrode on the working electrode holder of each H-cell 16.
(4) Adjusting a pressure regulating valve 10 and a communicating valve 12 to maintain the pressure of the pipeline gas stable, opening an electrochemical workstation 14, operating CV to stabilize the system current, then performing a multistage electrocatalysis process to realize the synchronous operation of plasma discharge and electrocatalysis, wherein the electrocatalysis reaction is performed for 1 hour under the overpotential of 0.1V-0.5V, and after the reaction is finished, collecting the reaction liquid in each H-shaped electrolytic cell to detect the ammonia yield through an ultraviolet-spectrophotometer.
Examples 1 to 5
As shown in (a) of fig. 2, a jet plasma reactor is connected with a power supply, three air inlets are respectively connected with an air compressor and a circulating air pump, the outlet end of the reactor is fixed with a quartz cover through a flange, an air outlet of the quartz cover is connected with an air inlet of an air storage tank through an air pipe, an air outlet of the air storage tank is connected with an air inlet of an H-shaped electrolytic cell, and the pressure of pipeline gas is regulated by a pressure regulating valve and a communicating valve, so that the gas flow is kept stable;
clamping a prepared nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst on a working electrode clamp of an H-shaped electrolytic cell to serve as a working electrode, wherein the microstructure of the electrocatalyst is shown in figure 3, respectively filling a certain amount of 0.1M KOH solution into the H-shaped electrolytic cell, placing the H-shaped electrolytic cell on a magnetic stirrer to be continuously stirred by using a magnetic stirrer, connecting an electrochemical workstation with the H-shaped electrolytic cell, starting an air compressor, and controlling the air inflow through a mass flowmeter; and (3) turning on a plasma power supply, adjusting power input into two ends of the three-air-inlet jet flow plasma reactor, realizing stable discharge of plasma, simultaneously starting an electrochemical workstation, operating CV to stabilize system current, carrying out a single-stage electrocatalysis process for 1 hour under an overpotential of 0.1V/0.2V/0.3V/0.4V/0.5V, and collecting reaction liquid in an H-shaped electrolytic cell for ammonia yield detection after the reaction is finished.
Examples 6 to 10
As shown in (b) of fig. 2, connecting a jet plasma reactor with a power supply, connecting three air inlets with an air compressor and a circulating air pump respectively, fixing the outlet end of the reactor with a quartz cover through a flange, connecting the air outlet of the quartz cover with the air inlet of an air storage tank through an air pipe, connecting the air outlet of the air storage tank with the air inlet of a first-stage H-shaped electrolytic cell, connecting the air outlet of a previous-stage electrolytic cell with a next-stage electrolytic cell through an air pipe, and regulating the pressure of pipeline gas through a pressure regulating valve and a communicating valve to maintain the gas flow stably;
respectively clamping a prepared nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst on working electrode clamps of two H-shaped electrolytic cells to serve as working electrodes, wherein the microcosmic appearance of the working electrodes is shown in figure 3, respectively filling a certain amount of 0.1M KOH solution into the two H-shaped electrolytic cells, placing the H-shaped electrolytic cells on a magnetic stirrer to be continuously stirred by a magnetic stirrer, respectively connecting two electrochemical working stations with the corresponding H-shaped electrolytic cells, starting an air compressor, and controlling the gas flow through a mass flow meter; and (3) turning on a plasma power supply, adjusting power input into two ends of the three-air-inlet jet flow plasma reactor, realizing stable discharge of plasma, simultaneously starting an electrochemical workstation, operating CV to stabilize system current, carrying out a two-stage electrocatalysis process for 1 hour under an overpotential of 0.1V/0.2V/0.3V/0.4V/0.5V, and collecting reaction liquid in each H-shaped electrolytic cell after reaction is finished to detect the ammonia yield.
Examples 11 to 14
As shown in (c) of fig. 2, connecting a jet plasma reactor with a power supply, connecting three air inlets with an air compressor and a circulating air pump respectively, fixing the outlet end of the reactor with a quartz cover through a flange, connecting the air outlet of the quartz cover with the air inlet of an air storage tank through an air pipe, connecting the air outlet of the air storage tank with the air inlet of a first-stage H-shaped electrolytic cell, connecting the air outlet of a previous-stage electrolytic cell with a next-stage electrolytic cell through an air pipe, and regulating the pressure of pipeline gas through a pressure regulating valve and a communicating valve to maintain the gas flow stably;
clamping CC, VG/CC and MoS on working electrode clamps of two H-shaped electrolytic cells2/VG/CC、N,P-MoS2/VG/CC as working electrode, wherein MoS2/VG/CC and N, P-MoS2/VG/CC X-ray photoelectricityThe energy spectrum chart is shown in fig. 4, a certain amount of 0.1M KOH solution is respectively filled into two H-shaped electrolytic cells, the H-shaped electrolytic cells are placed on a magnetic stirrer and continuously stirred by a magnetic stirrer, two electrochemical workstations are respectively connected with the corresponding H-shaped electrolytic cells, an air compressor is started, and the gas flow is controlled by a mass flow meter; and (3) turning on a plasma power supply, adjusting power input into two ends of the three-air-inlet jet flow plasma reactor, realizing stable discharge of plasma, simultaneously turning on an electrochemical workstation, operating CV to stabilize system current, performing a two-stage electrocatalysis process for 1 hour under an overpotential of 0.3V, and collecting reaction liquid in each H-shaped electrolytic cell after the reaction is finished to detect the ammonia yield.
Example 15
Connecting a jet plasma reactor with a power supply, connecting three air inlets with an air compressor and a circulating air pump respectively, fixing the outlet end of the reactor with a quartz cover through a flange, connecting the air outlet of the quartz cover with the air inlet of an air storage tank through an air pipe, connecting the air outlet of the air storage tank with the air inlet of a first-stage H-shaped electrolytic cell, connecting the air outlet of a previous-stage electrolytic cell with a next-stage electrolytic cell through the air pipe, and regulating the gas pressure of a gas path system through a pressure valve to maintain the stable gas flow;
respectively filling a certain amount of 0.1M KOH solution into the two H-shaped electrolytic cells, placing the H-shaped electrolytic cells on a magnetic stirrer, continuously stirring the H-shaped electrolytic cells by using a magnetic stirrer, opening a gas cylinder, introducing air, and controlling the flow of the gas by using a mass flow meter; and (3) turning on a plasma power supply, adjusting power input into two ends of the three-air-inlet jet flow plasma reactor, realizing stable discharge of the plasma, and collecting reaction liquid in the two H-shaped electrolytic cells after 1 hour to detect the ammonia yield.
Example 16
Clamping the prepared nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst serving as a working electrode on working electrode clamps of two electrolytic cells, wherein the microstructure of the electrocatalyst is shown in fig. 3, respectively filling a certain amount of 0.1M KOH solution into the two H-shaped electrolytic cells, placing the H-shaped electrolytic cells on a magnetic stirrer, continuously stirring the H-shaped electrolytic cells by using a magnetic stirrer, respectively connecting two electrochemical workstations with the corresponding H-shaped electrolytic cells, opening a gas cylinder, directly introducing air into the electrolytic cells, and controlling the gas flow through a mass flow meter; starting an electrochemical workstation, operating CV to stabilize the system current, carrying out a two-stage electrocatalysis process for 1 hour under an overpotential of 0.1V-0.5V, and collecting reaction liquid in two H-shaped electrolytic cells to carry out ammonia yield detection after the reaction is finished.
The method further optimizes and perfects an experimental system for coupling the plasma with the electro-catalysis: the multistage addition and the application of the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst further improve the ammonia yield. Experiments have shown that at 0.5v overpotential, ammonia conversion efficiency of the two-stage catalysis (7294.06 μ g/h) is 1.6 times higher than that of the single-stage catalysis (4596.36 μ g/h), and both are far ahead of the current research level. The invention can be optimized and perfected continuously in the future, and is expected to achieve better effect.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.
Claims (7)
1. The jet plasma coupling multistage electrocatalysis integrated ammonia synthesis device is characterized by comprising a multi-air-inlet jet plasma reactor (6), a multistage electrocatalysis system based on a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst and a tail gas recirculation system;
the multi-air-inlet jet flow plasma reactor (6) comprises two air inlets, wherein one air inlet is an air inlet and is connected with an air compressor (4), and the other air inlet is an air circulation air inlet and is connected with a circulation air pump (22) for air circulation; the multi-air inlet jet flow plasma reactor (6) is used for discharging N in the air2And O2Conversion to NOxAnd is input into an air storage tank (11);
the multi-stage electro-catalytic system comprises an electrochemical workstation (14) and an H-type electrolytic cell (16); a plurality of H-shaped electrolytic cells (16) are effectively connected in series and matched, and the air outlet of the cathode reaction chamber of the H-shaped electrolytic cell (16) at the previous stage is connected with the air outlet of the cathode reaction chamberIs connected with the air inlet of the cathode reaction chamber of the next stage H-shaped electrolytic cell (16), and each H-shaped electrolytic cell (16) is connected with an electrochemical workstation (14) to realize NOxTo NH3The transformation of (3); the first-stage H-shaped electrolytic cell (16) is connected with the gas storage tank (11); the last stage of H-shaped electrolytic cell (16) is connected with a circulating air pump (22);
the working electrode of the H-shaped electrolytic cell (16) adopts a nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst (18), and the preparation process of the nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst (18) is as follows: firstly obtaining phosphorus-doped molybdenum disulfide by a plasma enhanced vapor deposition method, a hydrothermal method and a phosphorization method in sequence, and finally carrying out ammonia plasma doping on the phosphorus-doped molybdenum disulfide to obtain a nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst, wherein the plasma doping process is as follows:
placing the phosphorized molybdenum disulfide catalyst in a tubular furnace, pumping to negative pressure and heating, introducing ammonia gas, discharging through inductively coupled plasma, and replacing S atoms in molybdenum disulfide with generated N-containing free radicals to realize N atom doping to obtain a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst (18);
the tail gas recirculation system comprises a first mass flow meter (5), a pressure regulating valve (10), a gas storage tank (11), a second mass flow meter (13) and a circulating gas pump (22); the first mass flow meter (5) is arranged at an air inlet of the reactor and used for controlling the flow of inlet air; the plasma discharge gas is adjusted by a second mass flow meter (13) and a pressure adjusting valve (10), then is introduced into a gas storage tank (11), then flows through H-shaped electrolytic cells (16) at all stages, and then flows back to the multi-gas-inlet jet flow plasma reactor (6) again through a circulating gas pump (22); the tail gas recycling system enables the N which does not participate in the reaction to be contained2、O2And NO mainly comprising NOxThe tail gas participates in the discharge again, and the gas after the plasma retreatment is more easily converted into water-soluble NOxAnd the gas conversion rate is improved.
2. A jet plasma coupled multistage electrocatalytic integrated ammonia plant according to claim 1, characterized in that it further comprises a solar power supply system comprising solar panels (1), accumulators (2) and transformers (3); the solar panel (1) is connected with the storage battery (2), and the storage battery (2) supplies power to the multi-air-inlet jet plasma reactor (6) through the transformer (3).
3. The jet plasma coupled multistage electrocatalytic integrated ammonia synthesis device according to claim 1, wherein the gas inlets of the multi-gas inlet jet plasma reactor (6) are a plurality of uniformly distributed tangential gas inlets, a rotating gas flow is formed inside the reactor, the disturbance of the gas in the gas cavity of the reactor and the plasma discharge area are increased, the discharge effect is enhanced, and the gas treatment efficiency is improved.
4. A jet plasma coupled multistage electrocatalytic integrated ammonia synthesis device according to claim 1, wherein the discharge gas is statically placed and buffered through a gas storage tank (11) so as to enable water-soluble NO in the discharge gas to be obtainedxIncrease in content of NOxFixed in solution.
5. The integrated ammonia synthesis device with jet plasma coupling multistage electrocatalysis as claimed in claim 1, wherein the preparation method of the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst (18) comprises the following steps:
(1) cutting carbon cloth with proper size, placing the carbon cloth in a quartz tube, pumping the quartz tube to negative pressure, introducing methane, hydrogen and argon into the quartz tube according to a certain proportion, heating, starting cooling water, and discharging inductively coupled plasma for a period of time to form uniformly distributed graphene on the carbon cloth, wherein the graphene is recorded as VG/CC;
(2) uniformly mixing 1.2g of sodium molybdate, 1.56g of thioacetamide and 60ml of deionized water, then transferring the mixture into a reaction kettle, placing the obtained VG/CC into the mixed solution, carrying out hydrothermal reaction for 12 hours at 200 ℃ in an oven to obtain a molybdenum disulfide nano structure growing on vertical graphene, and recording the molybdenum disulfide nano structure as MoS2/VG/CC；
(3) The obtained MoS2placing/VG/CC and 1g sodium hypophosphite at two ends of the quartz boat respectively and placing into the quartz tubeWherein MoS2the/VG/CC is positioned in the downwind direction, the sodium hypophosphite is positioned in the upwind direction, negative pressure is pumped, the reaction is maintained for one hour at 300 ℃, and the phosphorus-doped molybdenum disulfide catalyst is obtained after the reaction is finished;
(4) putting the phosphorus-doped molybdenum disulfide catalyst in a tube furnace, pumping to negative pressure, heating, introducing ammonia gas, and discharging through inductively coupled plasma to obtain the nitrogen-phosphorus-doped molybdenum disulfide nano catalyst, which is recorded as N, P-MoS2/VG/CC。
6. A jet plasma coupled multistage electrocatalytic integrated ammonia synthesis method based on the device of any one of claims 1 to 5, characterized in that the method is a multistage catalytic operation mode in which gas discharge and electrocatalytic processes are carried out synchronously, and comprises the following steps:
(1) connecting a multi-air-inlet jet flow plasma reactor (6) with a power supply, respectively connecting two air inlets with an air compressor (4) and a circulating air pump (22), starting the air compressor (4), introducing air into the multi-air-inlet jet flow plasma reactor (6), and controlling the air inlet flow by a first mass flow meter (5);
(2) turning on a plasma power supply, adjusting the power input into two ends of the multi-air inlet jet flow plasma reactor (6), realizing stable discharge of the plasma, and converting N in the air2And O2Conversion to NOxAnd is input into an air storage tank (11);
(3) the air outlet of the air storage tank (11) is connected with the air inlet of the first-stage H-shaped electrolytic cell (16), the air outlet of the upper-stage H-shaped electrolytic cell (16) is connected with the lower-stage H-shaped electrolytic cell (16) through an air pipe, and the last-stage H-shaped electrolytic cell (16) is connected with the circulating air pump (22); wherein each electrolytic cell is respectively connected with an electrochemical workstation (14), and a piece of nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst (18) is clamped on a working electrode clamp of each H-shaped electrolytic cell (16) to be used as a working electrode.
(4) Adjusting a pressure regulating valve (10) and a communicating valve (12) to maintain the pressure of the pipeline gas stable, opening an electrochemical workstation (14), operating CV to stabilize the system current and then performing each level of electrocatalysis process, realizing the synchronous operation of plasma discharge and electrocatalysis, and collecting the reaction liquid in each H-shaped electrolytic cell after the reaction is finished to detect the ammonia yield.
7. The integrated ammonia synthesis method by coupling jet plasma with multistage electrocatalysis according to claim 6, characterized in that the electrocatalysis reaction is carried out for 1 hour under overpotential of 0.1V-0.5V, and the ammonia yield is detected by an ultraviolet-spectrophotometer.
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