WO2023001139A1 - Method and device for treating nitrous oxide tail gas by using fuel cell - Google Patents

Method and device for treating nitrous oxide tail gas by using fuel cell Download PDF

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Publication number
WO2023001139A1
WO2023001139A1 PCT/CN2022/106440 CN2022106440W WO2023001139A1 WO 2023001139 A1 WO2023001139 A1 WO 2023001139A1 CN 2022106440 W CN2022106440 W CN 2022106440W WO 2023001139 A1 WO2023001139 A1 WO 2023001139A1
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Prior art keywords
fuel cell
cathode
nitrous oxide
gas
cell tube
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PCT/CN2022/106440
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French (fr)
Chinese (zh)
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肖睿
崔东旭
吴石亮
李桃
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东南大学
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Publication of WO2023001139A1 publication Critical patent/WO2023001139A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/402—Dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0208—Other waste gases from fuel cells
    • 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

Definitions

  • the invention relates to the technical field of nitrous oxide tail gas treatment, in particular to a method and device for treating nitrous oxide tail gas by using a fuel cell.
  • N 2 O is listed as one of the six major greenhouse gases because it can seriously deplete the ozone layer and cause the greenhouse effect, with a global warming potential (GWP) 310 times that of CO 2 .
  • GWP global warming potential
  • the removal pathways of N 2 O include high temperature thermal decomposition, non-selective catalytic reduction and direct catalytic decomposition.
  • direct catalytic decomposition is considered to be the most promising approach, because N2O is decomposed into nitrogen and oxygen under the action of the catalyst without producing secondary pollutants.
  • the decomposition catalysts of nitrous oxide mainly include supported noble metal catalysts, molecular sieve catalysts, semiconductor photocatalysts and metal oxide catalysts.
  • perovskite-based metal oxide catalysts are not only low in cost, but also exhibit good thermal stability at operating temperatures of 500–850 °C.
  • SOFC is an energy device that can directly and efficiently convert the chemical energy of fuel into electrical energy.
  • some perovskite materials that can be used as catalysts for the decomposition of nitrous oxide are also widely used in the cathode of solid oxide fuel cells (SOFC) with similar temperatures, such as La ⁇ Sr 1- ⁇ MnO 3 , La ⁇ Sr 1- ⁇ CoO 3 , La ⁇ Sr 1- ⁇ FeO 3 , and La ⁇ Sr 1- ⁇ Co ⁇ Fe 1- ⁇ O 3 .
  • SOFC solid oxide fuel cells
  • the uneven temperature will aggravate the mismatch of expansion between the electrode and the electrolyte material, thereby destroying the SOFC mechanical structure and bringing safety problems to the entire system.
  • Patent CN105396460B provides a comprehensive purification system for nitrogen oxides. Under high temperature conditions, the mixture of coke and activated carbon is used to completely remove NO x in the treated gas, and at the same time partially remove N 2 O; and then under medium and low temperature conditions Utilize the N 2 O efficient decomposition catalyst to catalytically decompose the remaining N 2 O in the gas into N 2 and O 2 .
  • the system is a two-step removal process, and the N 2 O treatment process is quite satisfactory, but additional equipment is still required to treat the tail gas, and the treated tail gas has not been used in any way, and there is a certain loss of energy and efficiency.
  • Patent CN111330437A provides a method and system for synergistic purification of various pollutants in the production of adipic acid.
  • a dryer is used to reduce the water vapor content in the tail gas, and then it enters a heat exchanger for preheating and adds a certain amount of air and ammonia.
  • the catalytic reaction is then carried out in a fixed bed reactor.
  • This system realizes the joint treatment of NO X and N 2 O. Compared with the traditional process, the system is also greatly simplified.
  • nitrous oxide is a pollutant
  • the ratio of nitrogen and oxygen produced by direct decomposition is 2:1, and it can also be used for secondary treatment. Reuse, improve the dual utilization efficiency of matter and energy.
  • Patent CN111013382A provides a tail gas treatment device and method of an adipic acid production plant.
  • This system uses a pretreatment system, a tail gas pressurization system, a purification system, a low-temperature rectification system, and a catalytic decomposition system to process adipic acid from the tail gas of adipic acid production.
  • the nitrous oxide is recovered. Although the nitrous oxide in the system has been reused, the system is too complicated and consumes a lot of energy.
  • fluidized beds Compared with fixed beds, fluidized beds have higher heat and mass transfer rates and larger gas-solid contact areas, and are widely used in gas-solid two-phase reactions.
  • the fluidized bed reactor also has the advantages of high reaction intensity and easy scale-up.
  • the present invention provides a method and device for treating nitrous oxide tail gas by using a fuel cell, which improves the decomposition rate of nitrous oxide and improves the safety and stability of the fuel cell system.
  • a device for treating nitrous oxide tail gas using a fuel cell comprising a solid oxide fuel cell, the structure of which includes a casing, a fuel cell tube, and a cathode bed material; the casing is provided with a cathode A gas inlet and a cathode gas outlet, the cathode gas includes nitrous oxide to be treated; at least one fuel cell tube is arranged in the housing, and an anode gas inlet and an anode gas outlet are arranged at both ends of the fuel cell tube; A cavity is formed between the inner wall of the housing and the outer wall of the cathode of at least one fuel cell tube, and the cathode bed material is filled in the cavity; an air distribution plate is arranged in the housing, and the cathode gas is supplied by the cathode The gas inlet flows through the air distribution plate and then enters the cavity, which can promote the cathode bed material to be in a fluidized state; the two ends of the
  • the cathode bed material is a perovskite-based metal oxide granular catalyst.
  • a heating or heat preservation device is arranged outside the shell.
  • the fuel cell tube adopts an anode support, metal support or electrolyte support structure, and the cathode and anode of the fuel cell tube are respectively connected to corresponding electronic loads during use.
  • a method of using a fuel cell to treat nitrous oxide tail gas The fuel cell tube is heated to 620°C-720°C, and then the anode gas and the nitrous oxide-containing gas used as the cathode gas are respectively input into the fuel cell tube and the cavity
  • the cathode gas makes the cathode bed material in a fluidized state, and uses the fluidized cathode bed material as a catalyst to promote the decomposition reaction of nitrous oxide, and at the same time promotes the uniform distribution of heat released by the decomposition reaction, and promotes the uniform distribution of the temperature of the fuel cell tube.
  • the oxygen released by the decomposition reaction of nitrous oxide increases the oxygen concentration in the cathode gas, thereby increasing the output power of the fuel cell tube.
  • the cathode bed material adopts cerium oxide particles coated with lanthanum strontium iron powder (LSF), and the particle diameter is 100-300 ⁇ m.
  • the fuel cell tube is heated by an electric heating furnace, or high-temperature gas is passed into the fuel cell tube for heating.
  • the present invention provides a device and method for co-processing nitrous oxide gas with a fixed oxide fuel cell and a cathode fluidized bed.
  • the solid oxide fuel cell uses nitrous oxide as the cathode gas, and the cathode gas drives the cathode bed material to form a fluidized state.
  • the cathode bed material acts as a catalyst to increase the contact area with the cathode gas, improve the catalytic effect, and promote the nitrous oxide.
  • the temperature field distribution of the whole device is more uniform, which realizes the clean and efficient treatment of nitrous oxide, and obtains a higher conversion rate of nitrous oxide; the content of nitrous oxide is higher in the treatment
  • the oxygen concentration can be increased after the nitrous oxide is decomposed, and the performance of the oxide fuel cell will also be improved accordingly.
  • the present invention does not need to add additional catalytic decomposition equipment, and at the same time, the high-performance fixed oxide fuel cell can build a multi-cell stack to supply power for other systems, realize the efficient treatment and application of nitrous oxide, and the process cost is low , the fixed oxide fuel cell of the present invention has the characteristics of being easy to scale up, the capacity of the device is flexible, and the application prospect is wide.
  • Fig. 1 is a structural schematic diagram of a specific embodiment of the device of the present invention.
  • Fig. 2 is a schematic diagram of fuel cell performance under different working conditions of a specific embodiment of the method of the present invention.
  • Fig. 3 is a graph showing the temperature distribution of the fuel cell under different working conditions in a specific embodiment of the method of the present invention.
  • Fig. 4 is a diagram of the decomposition rate of nitrous oxide under different working conditions of the specific embodiment of the method of the present invention.
  • a device for treating nitrous oxide tail gas using a fuel cell of the present application includes a solid oxide fuel cell, the structure of which is shown in Figure 1, including a housing 4, a fuel cell tube 2 and a cathode bed material 3; A cathode gas inlet 5 and a cathode gas outlet 1 are provided, and the cathode gas includes nitrous oxide to be treated; at least one fuel cell tube 2 is arranged in the casing 4, and an anode gas inlet 9 and an anode gas inlet 9 are arranged at both ends of the fuel cell tube 2 .
  • a cavity 10 is formed between the inner wall of the casing 4 and the cathode outer wall of at least one fuel cell tube 2, and the cathode bed material 3 is filled in the cavity 10;
  • the casing 4 is provided with an air distribution plate 6, and the cathode gas
  • the cathode gas flows from the inlet 5 through the air distribution plate 6 and then enters the cavity 10, which can make the cathode bed material 3 in a fluidized state; the two ends of the fuel cell tube 2 are fixedly connected to the air distribution plate 6 and the housing 4 respectively.
  • the above-mentioned cathode bed material 3 is a perovskite-based metal oxide granular catalyst, or a granular catalyst such as monometallic, bimetallic or molecular sieve, which can be used for the decomposition reaction of nitrous oxide.
  • a heating or heat preservation device 7 is arranged outside the housing 4 .
  • the above-mentioned fuel cell tube 2 adopts an anode support, metal support or electrolyte support structure.
  • the anode material of the fuel cell tube 2 is NiO/8% yttria stabilized yttrium oxide (8YSZ)
  • the electrolyte material is yttrium oxide (8YSZ)
  • the barrier layer is gadolinium oxide stabilized cerium oxide (GDC)
  • the cathode material is lanthanum Strontium cobalt iron (LSCF) and cerium oxide (GDC) mixture.
  • LSCF lanthanum Strontium cobalt iron
  • GDC cerium oxide
  • the above-mentioned air distribution plate 6 can be made of porous sand core made of quartz, zirconia or alumina.
  • a method of using a fuel cell to treat nitrous oxide tail gas of the present application is to heat the fuel cell tube 2 to 620°C-720°C, and then input anode gas and cathode gas into the fuel cell tube 2 and cavity 10 respectively.
  • the gas containing nitrous oxide; the cathode gas makes the cathode bed material 3 in a fluidized state, and uses the fluidized cathode bed material 3 as a catalyst to promote the decomposition reaction of nitrous oxide, and at the same time promotes the uniform distribution of heat released by the decomposition reaction, and promotes the fuel
  • the temperature of the battery tube 2 is evenly distributed, and at the same time, the oxygen concentration in the cathode gas is increased by utilizing the oxygen released by the decomposition reaction of nitrous oxide, thereby increasing the output power of the fuel cell tube 2 .
  • one fuel cell tube 2 is provided, and the heating or heat preservation device 7 can specifically adopt an electric heating furnace or a heat preservation box, and use an electric heating furnace to heat the fuel cell tube 2, or pass into the fuel cell tube 2
  • the high-temperature gas is used for heating and the heat preservation box is used for heat preservation.
  • the cathode bed material 3 is made of cerium oxide particles coated with lanthanum strontium iron powder (LSF), and the diameter of the particles is 100-300 ⁇ m.
  • the filling height is half the height of the cavity 10 .
  • cathode bed material 3 sieve cerium oxide particles with a particle size of 100-300 ⁇ m, and then impregnate and mix it with a certain proportion of ferric nitrate, lanthanum nitrate, strontium carbonate, citric acid and polyethylene glycol aqueous solution in equal volumes, Then place it in a drying oven at 130°C to dry to obtain gel-wrapped cerium oxide particles, then place the sample in a muffle furnace at 800°C, calcinate for 2 hours in an air atmosphere, and obtain it after cooling and sieving.
  • the anode gas is selected as hydrogen
  • the cathode gas is selected as nitrous oxide or air.
  • the cathode gas flow rate to 50ml, 100ml, 200ml, 300ml and 400ml respectively, and the temperature of the heating or heat preservation device 7 to be 620°C, 670°C and 720°C respectively.
  • the output performance of the fuel cell tube in the fluidized state is tested after the voltage of the fuel cell tube is stabilized.
  • the maximum power of the battery at 620°C with three cathode gases and three flow rates is shown in Figure 2.
  • the test results show that the order of the maximum discharge power of the battery is "nitrous oxide-fluidized bed” > "air-fixed bed” > “nitrous oxide Nitrogen-fixed bed”, the battery output performance reaches the highest at 400ml/min gas velocity, which are 2040 mW, 1615 mW and 1083 mW respectively.
  • the cathode gas flow rate is less than 200ml/min, the filled cathode bed material is still in a fixed state.
  • Fig. 3 the left and right respectively show the whole solid oxide fuel cell under the two states of "nitrous oxide-fixed bed” and "nitrous oxide-fluidized state” when the temperature of heating or heat preservation device 7 is set at 620°C
  • the surface temperature distribution as can be seen from the figure, under the 300ml/min gas velocity fixed bed mode, the temperature at the bottom of the battery is lower than that at the top, and the temperature difference is greater than 50°C. Good heat transfer can be achieved through fluidization, and the entire solid oxide fuel cell The temperature field is very uniform.
  • Figure 4 shows the decomposition rate of nitrous oxide at three reaction temperatures of 300ml/min under the two working conditions of "nitrous oxide-fixed bed” and "nitrous oxide-fluidized bed". It can be seen from the figure that no cathode is added When the bed material is used, the conversion rate of nitrous oxide is lower than 30%, that is, the oxygen content in the cathode gas is 13%, which is far lower than the oxygen content in the air; the cathode bed material is in a fluidized bed condition (fluidized state) nitrous oxide The decomposition rate is 100%, that is, the oxygen concentration in the cathode gas can reach 33%, thus explaining the difference in fuel cell performance in Figure 2. The test results show that the fluidized cathode bed material can significantly improve the conversion rate of nitrous oxide.
  • the fluidization of the cathode material can enhance the reaction intensity in the cavity, which can not only improve the decomposition rate of nitrous oxide and achieve high efficiency of nitrous oxide Decomposition can even the temperature field on the surface of the fuel cell, solve the temperature unevenness caused by the decomposition and heat generation of nitrous oxide, and at the same time improve the output performance of the fuel cell and the safety of the fuel cell.
  • the cathode gas can be a mixed gas with different nitrous oxide content.
  • it may also include one or more gases such as nitrogen, oxygen, argon, nitrogen dioxide, etc.
  • nitrogen, oxygen, argon, nitrogen dioxide, etc. When the content of nitrous oxide in the tail gas When it is low, an appropriate amount of air or oxygen can be added.
  • the state of the cathode bed material can be suitable for bubbling fluidization, turbulent bed, fast bed or dilute phase bed.
  • the number of battery tubes can be set in multiples according to actual needs.

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Abstract

The present invention relates to a method and a device for treating nitrous oxide tail gas by using a fuel cell. The device comprises a solid oxide fuel cell with a structure comprising a shell, a fuel cell tube and a cathode bed material, wherein a cathode gas inlet and a cathode gas outlet are provided on the shell, and cathode gas comprises nitrous oxide to be treated; at least one fuel cell tube is provided in the shell, a cavity is formed between an inner wall of the shell and an outer wall of a cathode of the at least one fuel cell tube, and is filled with the cathode bed material; an air distribution plate is provided in the shell, and the cathode gas flows into the cavity from the cathode gas inlet and is guided by the air distribution plate, which can promote the cathode bed material to be in a fluidized state; and two ends of the fuel cell tube are fixedly connected with the air distribution plate and the shell, respectively. The fluidization of the cathode bed material enhances the reaction strength inside the cavity, and also solves an uneven temperature phenomenon caused by the heat release of nitrous oxide decomposition, thus improving the decomposition rate of nitrous oxide and the safety of the fuel cell.

Description

使用燃料电池处理氧化亚氮尾气的方法及装置Method and device for treating nitrous oxide tail gas using fuel cell 技术领域technical field
本发明涉及氧化亚氮尾气处理技术领域，尤其是一种使用燃料电池处理氧化亚氮尾气的方法及装置。The invention relates to the technical field of nitrous oxide tail gas treatment, in particular to a method and device for treating nitrous oxide tail gas by using a fuel cell.
背景技术Background technique
N 2O被列为六大温室气体之一，因为它会严重消耗臭氧层并引起温室效应，其中全球变暖潜能值（GWP）是 CO 2的 310 倍。在硝酸和己二酸的生产过程中，产生的废气中一氧化二氮的含量可达50%，如果废气不进行处理，每生产1吨己二酸将排放约0.25吨一氧化二氮气体。 N 2 O is listed as one of the six major greenhouse gases because it can seriously deplete the ozone layer and cause the greenhouse effect, with a global warming potential (GWP) 310 times that of CO 2 . During the production of nitric acid and adipic acid, the content of nitrous oxide in the waste gas produced can reach 50%. If the waste gas is not treated, about 0.25 tons of nitrous oxide gas will be emitted for every ton of adipic acid produced.
N 2O的去除途径包括高温热分解、非选择性催化还原和直接催化分解。其中，直接催化分解被认为是最有前景的途径，因为N 2O在催化剂的作用下被分解为氮气和氧气，不会产生二次污染物。一氧化二氮的分解催化剂主要有负载型贵金属催化剂、分子筛催化剂、半导体光催化剂和金属氧化物催化剂等几种。其中钙钛矿基金属氧化物催化剂不仅成本低，而且在500-850℃的操作温度下表现出良好的热稳定性。 The removal pathways of N 2 O include high temperature thermal decomposition, non-selective catalytic reduction and direct catalytic decomposition. Among them, direct catalytic decomposition is considered to be the most promising approach, because N2O is decomposed into nitrogen and oxygen under the action of the catalyst without producing secondary pollutants. The decomposition catalysts of nitrous oxide mainly include supported noble metal catalysts, molecular sieve catalysts, semiconductor photocatalysts and metal oxide catalysts. Among them, perovskite-based metal oxide catalysts are not only low in cost, but also exhibit good thermal stability at operating temperatures of 500–850 °C.
SOFC是一种能将燃料的化学能直接高效转化为电能的能源装置。现有技术中，一些可作为一氧化二氮分解催化剂的钙钛矿材料也被广泛用于温度相近的固体氧化物燃料电池（SOFC）的阴极，如La δSr 1- δMnO 3、La δSr 1- δCoO 3、La δSr 1- δFeO 3、和 La δSr 1- δCo εFe 1- εO 3。但在SOFC中直接使用一氧化二氮作为氧化剂时，由于气体与催化剂的接触面积小，一氧化二氮的转化率较低。一氧化二氮分解是放热反应2N 2O = 2N 2+ O 2 (H 298 =-163 kJ/mol) ，它将影响 SOFC 阴极表面的温度场分布。温度不均会加剧电极与电解质材料间膨胀度的不匹配，进而破坏SOFC机械结构，给整个***带来安全性问题。 SOFC is an energy device that can directly and efficiently convert the chemical energy of fuel into electrical energy. In the prior art, some perovskite materials that can be used as catalysts for the decomposition of nitrous oxide are also widely used in the cathode of solid oxide fuel cells (SOFC) with similar temperatures, such as La δ Sr 1- δ MnO 3 , La δ Sr 1- δ CoO 3 , La δ Sr 1- δ FeO 3 , and La δ Sr 1- δ Co ε Fe 1- ε O 3 . However, when nitrous oxide is directly used as an oxidant in SOFC, the conversion rate of nitrous oxide is low due to the small contact area between the gas and the catalyst. Nitrous oxide decomposition is an exothermic reaction 2N 2 O = 2N 2 + O 2 (H 298 =-163 kJ/mol), which will affect the temperature field distribution on the cathode surface of SOFC. The uneven temperature will aggravate the mismatch of expansion between the electrode and the electrolyte material, thereby destroying the SOFC mechanical structure and bringing safety problems to the entire system.
专利CN105396460B提供了一种氮氧化合物综合净化***，在高温条件下，利用焦炭和活性炭的混合物，将处理气中的NO x脱除完全，同时部分脱除N 2O；然后在中低温条件下利用N 2O高效分解催化剂将气体中剩余的N 2O催化分解为N 2和O 2。该***为两步脱除工艺，N 2O的处理过程中规中矩，但是仍然需要额外增加设备处理尾气，处理后的尾气也没有得到任何利用，存在一定的能量及效率损失。 Patent CN105396460B provides a comprehensive purification system for nitrogen oxides. Under high temperature conditions, the mixture of coke and activated carbon is used to completely remove NO x in the treated gas, and at the same time partially remove N 2 O; and then under medium and low temperature conditions Utilize the N 2 O efficient decomposition catalyst to catalytically decompose the remaining N 2 O in the gas into N 2 and O 2 . The system is a two-step removal process, and the N 2 O treatment process is quite satisfactory, but additional equipment is still required to treat the tail gas, and the treated tail gas has not been used in any way, and there is a certain loss of energy and efficiency.
专利CN111330437A提供了一种己二酸生产中多种污染物协同净化的方法及***，首先使用干燥器降低尾气中水汽含量，然后进入换热器进行预热并加入一定量的空气和氨气，随后在固定床反应器中进行催化反应。此***实现了NO X和N 2O的联合处理，***较传统工艺也大幅简化，但是氧化亚氮虽然是一种污染物，但是直接分解产生的氮氧比例为2:1，还可以进行二次利用，提升物质和能量的双重利用效率。 Patent CN111330437A provides a method and system for synergistic purification of various pollutants in the production of adipic acid. First, a dryer is used to reduce the water vapor content in the tail gas, and then it enters a heat exchanger for preheating and adds a certain amount of air and ammonia. The catalytic reaction is then carried out in a fixed bed reactor. This system realizes the joint treatment of NO X and N 2 O. Compared with the traditional process, the system is also greatly simplified. However, although nitrous oxide is a pollutant, the ratio of nitrogen and oxygen produced by direct decomposition is 2:1, and it can also be used for secondary treatment. Reuse, improve the dual utilization efficiency of matter and energy.
专利CN111013382A提供了一种己二酸生产装置尾气处理装置及方法，此***通过前级预处理***、尾气增压***、纯化***、低温精馏***以及催化分解***，将己二酸生产尾气中的氧化亚氮进行回收。虽然***中的氧化亚氮得到了二次利用，但是***过于复杂，且能耗较高。Patent CN111013382A provides a tail gas treatment device and method of an adipic acid production plant. This system uses a pretreatment system, a tail gas pressurization system, a purification system, a low-temperature rectification system, and a catalytic decomposition system to process adipic acid from the tail gas of adipic acid production. The nitrous oxide is recovered. Although the nitrous oxide in the system has been reused, the system is too complicated and consumes a lot of energy.
与固定床相比，流化床具有更高的传热传质速率和更大的气固接触面积，被广泛应用于气固两相反应。此外，流化床反应器还具有反应强度高、易于放大的优点。Compared with fixed beds, fluidized beds have higher heat and mass transfer rates and larger gas-solid contact areas, and are widely used in gas-solid two-phase reactions. In addition, the fluidized bed reactor also has the advantages of high reaction intensity and easy scale-up.
技术问题technical problem
针对现有技术的不足，本发明提供了一种使用燃料电池处理氧化亚氮尾气的方法及装置，提高氧化亚氮分解率，并提升燃料电池***安全性和稳定性。Aiming at the deficiencies of the prior art, the present invention provides a method and device for treating nitrous oxide tail gas by using a fuel cell, which improves the decomposition rate of nitrous oxide and improves the safety and stability of the fuel cell system.
技术解决方案technical solution
本发明采用的技术方案如下：一种使用燃料电池处理氧化亚氮尾气的装置，包括固体氧化物燃料电池，其结构包括壳体、燃料电池管和阴极床料；所述壳体上设有阴极气体入口和阴极气体出口，阴极气体包括待处理的氧化亚氮；所述壳体内设置有至少一根所述燃料电池管，所述燃料电池管两端设有阳极气体入口和阳极气体出口；所述壳体内壁与至少一根所述燃料电池管的阴极外壁之间形成腔体，所述阴极床料填充于所述腔体内；所述壳体内设有布风板，阴极气体由所述阴极气体入口流入经所述布风板导流后进入腔体内，可促使所述阴极床料处于流化状态；所述燃料电池管两端分别与布风板、壳体固定连接。The technical scheme adopted in the present invention is as follows: a device for treating nitrous oxide tail gas using a fuel cell, comprising a solid oxide fuel cell, the structure of which includes a casing, a fuel cell tube, and a cathode bed material; the casing is provided with a cathode A gas inlet and a cathode gas outlet, the cathode gas includes nitrous oxide to be treated; at least one fuel cell tube is arranged in the housing, and an anode gas inlet and an anode gas outlet are arranged at both ends of the fuel cell tube; A cavity is formed between the inner wall of the housing and the outer wall of the cathode of at least one fuel cell tube, and the cathode bed material is filled in the cavity; an air distribution plate is arranged in the housing, and the cathode gas is supplied by the cathode The gas inlet flows through the air distribution plate and then enters the cavity, which can promote the cathode bed material to be in a fluidized state; the two ends of the fuel cell tube are respectively fixedly connected with the air distribution plate and the casing.
其进一步技术方案为：所述阴极床料为钙钛矿基金属氧化物颗粒状催化剂。Its further technical scheme is: the cathode bed material is a perovskite-based metal oxide granular catalyst.
所述壳体外部设置加热或保温装置。A heating or heat preservation device is arranged outside the shell.
所述燃料电池管采用阳极支撑、金属支撑或电解质支撑结构，使用时将燃料电池管阴极和阳极分别连接到相应的电子负载上。The fuel cell tube adopts an anode support, metal support or electrolyte support structure, and the cathode and anode of the fuel cell tube are respectively connected to corresponding electronic loads during use.
一种使用燃料电池处理氧化亚氮尾气的方法，将燃料电池管加热到620℃-720℃，然后分别向燃料电池管和腔体中输入阳极气体和用作阴极气体的含氧化亚氮的气体；阴极气体使阴极床料处于流化状态，利用流化状态的阴极床料作为催化剂促进氧化亚氮的分解反应，同时促进分解反应释放的热量分布均匀，促使燃料电池管温度均匀分布，同时利用氧化亚氮分解反应释放的氧气提升阴极气体中氧气浓度，从而提升燃料电池管的输出功率。A method of using a fuel cell to treat nitrous oxide tail gas. The fuel cell tube is heated to 620°C-720°C, and then the anode gas and the nitrous oxide-containing gas used as the cathode gas are respectively input into the fuel cell tube and the cavity The cathode gas makes the cathode bed material in a fluidized state, and uses the fluidized cathode bed material as a catalyst to promote the decomposition reaction of nitrous oxide, and at the same time promotes the uniform distribution of heat released by the decomposition reaction, and promotes the uniform distribution of the temperature of the fuel cell tube. The oxygen released by the decomposition reaction of nitrous oxide increases the oxygen concentration in the cathode gas, thereby increasing the output power of the fuel cell tube.
其进一步技术方案为：阴极床料采用包覆镧锶铁粉体（LSF）的氧化铈颗粒，颗粒直径100-300μm。Its further technical proposal is: the cathode bed material adopts cerium oxide particles coated with lanthanum strontium iron powder (LSF), and the particle diameter is 100-300 μm.
利用电加热炉对燃料电池管加热，或者向燃料电池管内通入高温气体进行加热。The fuel cell tube is heated by an electric heating furnace, or high-temperature gas is passed into the fuel cell tube for heating.
有益效果Beneficial effect
本发明的有益效果如下：本发明提出了一种固定氧化物燃料电池与阴极流化床协同处理氧化亚氮气体的装置及方法。将固体氧化物燃料电池以氧化亚氮作为阴极气体，以阴极气体驱动阴极床料形成流化态，阴极床料一方面作为催化剂增加了与阴极气体的接触面积提高了催化效果可促进氧化亚氮的分解反应，另一方面通过流化状态促使整个装置的温度场分布更加均匀，实现了氧化亚氮的清洁高效处理，并获得了较高的氧化亚氮转化率；处理氧化亚氮含量较高的尾气时，氧化亚氮分解后可以提升氧气浓度，氧化物燃料电池性能也会随之提升。The beneficial effects of the present invention are as follows: the present invention provides a device and method for co-processing nitrous oxide gas with a fixed oxide fuel cell and a cathode fluidized bed. The solid oxide fuel cell uses nitrous oxide as the cathode gas, and the cathode gas drives the cathode bed material to form a fluidized state. On the one hand, the cathode bed material acts as a catalyst to increase the contact area with the cathode gas, improve the catalytic effect, and promote the nitrous oxide. On the other hand, through the fluidization state, the temperature field distribution of the whole device is more uniform, which realizes the clean and efficient treatment of nitrous oxide, and obtains a higher conversion rate of nitrous oxide; the content of nitrous oxide is higher in the treatment When the exhaust gas is exhausted, the oxygen concentration can be increased after the nitrous oxide is decomposed, and the performance of the oxide fuel cell will also be improved accordingly.
本发明和传统尾气处理方法相比，无需额外增加催化分解设备，同时高性能的固定氧化物燃料电池可构建多电池堆，为其他***供电，实现氧化亚氮的高效处理和应用，工艺成本低廉，本发明的固定氧化物燃料电池具有易于放大的特点，装置容量大小灵活，应用前景广泛。Compared with the traditional tail gas treatment method, the present invention does not need to add additional catalytic decomposition equipment, and at the same time, the high-performance fixed oxide fuel cell can build a multi-cell stack to supply power for other systems, realize the efficient treatment and application of nitrous oxide, and the process cost is low , the fixed oxide fuel cell of the present invention has the characteristics of being easy to scale up, the capacity of the device is flexible, and the application prospect is wide.
附图说明Description of drawings
图1为本发明装置具体实施例的结构示意图。Fig. 1 is a structural schematic diagram of a specific embodiment of the device of the present invention.
图2为本发明方法具体实施例的不同工况下燃料电池性能示意图。Fig. 2 is a schematic diagram of fuel cell performance under different working conditions of a specific embodiment of the method of the present invention.
图3为本发明方法具体实施例的不同工况下燃料电池的温度分布图。Fig. 3 is a graph showing the temperature distribution of the fuel cell under different working conditions in a specific embodiment of the method of the present invention.
图4为本发明方法具体实施例的不同工况下氧化亚氮分解率图。Fig. 4 is a diagram of the decomposition rate of nitrous oxide under different working conditions of the specific embodiment of the method of the present invention.
图中：1、阴极气体出口；2、燃料电池管；3、阴极床料；4、壳体；5、阴极气体入口；6、布风板；7、加热或保温装置；8、阳极气体出口；9、阳极气体入口；10、腔体。In the figure: 1. Cathode gas outlet; 2. Fuel cell tube; 3. Cathode bed material; 4. Shell; 5. Cathode gas inlet; 6. Air distribution plate; 7. Heating or heat preservation device; 8. Anode gas outlet ; 9, anode gas inlet; 10, cavity.
本发明的实施方式Embodiments of the present invention
以下结合附图说明本发明的具体实施方式。The specific embodiments of the present invention will be described below in conjunction with the accompanying drawings.
本申请的一种使用燃料电池处理氧化亚氮尾气的装置，包括固体氧化物燃料电池，其结构如图1所示，包括壳体4、燃料电池管2和阴极床料3；壳体4上设有阴极气体入口5和阴极气体出口1，阴极气体包括待处理的氧化亚氮；壳体4内设置有至少一根燃料电池管2，燃料电池管2两端设有阳极气体入口9和阳极气体出口8；壳体4内壁与至少一根燃料电池管2的阴极外壁之间形成腔体10，阴极床料3填充于腔体10内；壳体4内设有布风板6，阴极气体由阴极气体入口5流入经布风板6导流后进入腔体10内，可促使阴极床料3处于流化状态；燃料电池管2两端分别与布风板6、壳体4固定连接。A device for treating nitrous oxide tail gas using a fuel cell of the present application includes a solid oxide fuel cell, the structure of which is shown in Figure 1, including a housing 4, a fuel cell tube 2 and a cathode bed material 3; A cathode gas inlet 5 and a cathode gas outlet 1 are provided, and the cathode gas includes nitrous oxide to be treated; at least one fuel cell tube 2 is arranged in the casing 4, and an anode gas inlet 9 and an anode gas inlet 9 are arranged at both ends of the fuel cell tube 2 . Gas outlet 8; a cavity 10 is formed between the inner wall of the casing 4 and the cathode outer wall of at least one fuel cell tube 2, and the cathode bed material 3 is filled in the cavity 10; the casing 4 is provided with an air distribution plate 6, and the cathode gas The cathode gas flows from the inlet 5 through the air distribution plate 6 and then enters the cavity 10, which can make the cathode bed material 3 in a fluidized state; the two ends of the fuel cell tube 2 are fixedly connected to the air distribution plate 6 and the housing 4 respectively.
上述阴极床料3为钙钛矿基金属氧化物颗粒状催化剂、或者单金属、双金属或分子筛等可用作氧化亚氮分解反应的颗粒状催化剂。The above-mentioned cathode bed material 3 is a perovskite-based metal oxide granular catalyst, or a granular catalyst such as monometallic, bimetallic or molecular sieve, which can be used for the decomposition reaction of nitrous oxide.
上述壳体4外部设置加热或保温装置7。A heating or heat preservation device 7 is arranged outside the housing 4 .
上述燃料电池管2采用阳极支撑、金属支撑或电解质支撑结构。具体地，燃料电池管2的阳极材料NiO/8%氧化钇稳定的氧化钇（8YSZ），电解质材料为氧化钇（8YSZ），隔断层为氧化钆稳定的氧化铈（GDC），阴极材料为镧锶钴铁（LSCF）和氧化铈（GDC）混合物。使用时将燃料电池管2阴极和阳极分别连接到相应的电子负载上。The above-mentioned fuel cell tube 2 adopts an anode support, metal support or electrolyte support structure. Specifically, the anode material of the fuel cell tube 2 is NiO/8% yttria stabilized yttrium oxide (8YSZ), the electrolyte material is yttrium oxide (8YSZ), the barrier layer is gadolinium oxide stabilized cerium oxide (GDC), and the cathode material is lanthanum Strontium cobalt iron (LSCF) and cerium oxide (GDC) mixture. When in use, the cathode and anode of the fuel cell tube 2 are respectively connected to corresponding electronic loads.
上述布风板6可采用石英或氧化锆或氧化铝材质多孔砂芯。The above-mentioned air distribution plate 6 can be made of porous sand core made of quartz, zirconia or alumina.
本申请的一种使用燃料电池处理氧化亚氮尾气的方法，将燃料电池管2加热到620℃-720℃，然后分别向燃料电池管2和腔体10中输入阳极气体和用作阴极气体的含氧化亚氮的气体；阴极气体使阴极床料3处于流化状态，利用流化状态的阴极床料3作为催化剂促进氧化亚氮的分解反应，同时促进分解反应释放的热量分布均匀，促使燃料电池管2温度均匀分布，同时利用氧化亚氮分解反应释放的氧气提升阴极气体中氧气浓度，从而提升燃料电池管2的输出功率。A method of using a fuel cell to treat nitrous oxide tail gas of the present application is to heat the fuel cell tube 2 to 620°C-720°C, and then input anode gas and cathode gas into the fuel cell tube 2 and cavity 10 respectively. The gas containing nitrous oxide; the cathode gas makes the cathode bed material 3 in a fluidized state, and uses the fluidized cathode bed material 3 as a catalyst to promote the decomposition reaction of nitrous oxide, and at the same time promotes the uniform distribution of heat released by the decomposition reaction, and promotes the fuel The temperature of the battery tube 2 is evenly distributed, and at the same time, the oxygen concentration in the cathode gas is increased by utilizing the oxygen released by the decomposition reaction of nitrous oxide, thereby increasing the output power of the fuel cell tube 2 .
作为具体实施例方式，燃料电池管2设置1根，加热或保温装置7具体可采用电加热炉或保温箱体，利用电加热炉对燃料电池管2加热，或者向燃料电池管2内通入高温气体进行加热利用保温箱体进行保温。阴极床料3采用包覆镧锶铁粉体（LSF）的氧化铈颗粒，颗粒直径100-300μm。填充高度为腔体10高度的一半。阴极床料3的制备方法：筛分粒径为100-300μm的氧化铈颗粒，随后将其与一定比例的硝酸铁、硝酸镧、碳酸锶、柠檬酸和聚乙二醇水溶液等体积浸渍混合，然后置于130℃干燥箱中干燥获得凝胶包裹的氧化铈颗粒，再将样品置于800℃的马弗炉中，在空气氛围下煅烧2小时，冷却筛分后获得。As a specific embodiment, one fuel cell tube 2 is provided, and the heating or heat preservation device 7 can specifically adopt an electric heating furnace or a heat preservation box, and use an electric heating furnace to heat the fuel cell tube 2, or pass into the fuel cell tube 2 The high-temperature gas is used for heating and the heat preservation box is used for heat preservation. The cathode bed material 3 is made of cerium oxide particles coated with lanthanum strontium iron powder (LSF), and the diameter of the particles is 100-300 μm. The filling height is half the height of the cavity 10 . The preparation method of cathode bed material 3: sieve cerium oxide particles with a particle size of 100-300 μm, and then impregnate and mix it with a certain proportion of ferric nitrate, lanthanum nitrate, strontium carbonate, citric acid and polyethylene glycol aqueous solution in equal volumes, Then place it in a drying oven at 130°C to dry to obtain gel-wrapped cerium oxide particles, then place the sample in a muffle furnace at 800°C, calcinate for 2 hours in an air atmosphere, and obtain it after cooling and sieving.
以下通过试验研究温度、阴极气体成分和阴极床料状态对电池输出性能的影响，从而进一步说明本申请的氧化亚氮尾气处理方法的优越性。In the following, the effects of temperature, cathode gas composition and cathode bed material state on the output performance of the battery are studied through experiments, so as to further illustrate the superiority of the nitrous oxide tail gas treatment method of the present application.
试验中，选择阳极气体为氢气，选择阴极气体为氧化亚氮或空气。In the test, the anode gas is selected as hydrogen, and the cathode gas is selected as nitrous oxide or air.
选取了三种试验工况：不添加阴极床料并以纯氧化亚氮作为阴极气体（记为：氧化亚氮-固定床，Fixed electrode-N 2O），不添加阴极床料并以空气作为阴极气体（记为：空气-固定床，Fixed electrode-Air）和添加25g阴极床料即填充高度为腔体高度的一半，并以纯氧化亚氮作为阴极气体（记为：氧化亚氮-流化床，Fluidizeded electrode-N 2O）。随后调整参数获得对比试验结果，设置阴极气体流量分别为50ml、100ml、200ml、300ml和400ml、加热或保温装置7温度分别为620℃、670℃和720℃几种工况***极床料处于不同流化状态下的燃料电池管的输出性能，待燃料电池管电压稳定后进行测试。 Three test conditions were selected: no cathode bed material was added and pure nitrous oxide was used as the cathode gas (denoted as: nitrous oxide-fixed bed, Fixed electrode-N 2 O), no cathode bed material was added and air was used as the cathode Gas (denoted as: air-fixed bed, Fixed electrode-Air) and adding 25g of cathode bed material means that the filling height is half of the chamber height, and pure nitrous oxide is used as cathode gas (denoted as: nitrous oxide-fluidized bed , Fluidized electrode-N 2 O). Then adjust the parameters to obtain comparative test results, set the cathode gas flow rate to 50ml, 100ml, 200ml, 300ml and 400ml respectively, and the temperature of the heating or heat preservation device 7 to be 620°C, 670°C and 720°C respectively. The output performance of the fuel cell tube in the fluidized state is tested after the voltage of the fuel cell tube is stabilized.
620℃下三种阴极气体在三种流量下电池最大功率如图2所示，试验结果显示电池最大放电功率顺序为“氧化亚氮-流化床”>“空气-固定床”>“氧化亚氮-固定床”，在400ml/min气速下电池输出性能达到最高，分别为2040 mW、1615 mW和1083 mW。试验观测到当阴极气体流速小于200ml/min时，填充的阴极床料仍然为固定态。当气速到达200ml/min后，阴极床料呈现流态化，电池性能相比于100ml/min气速提高18.5%。试验结果表明氧化亚氮分解可以提高燃料电池的输出性能，而流态化可以进一步扩大氧化亚氮分解为电池性能所带来的优势。其中，“流化床”、“固定床”借用流化床反应器中的术语，意思是阴极床料在对应气流作用下处于流化态或固定态。The maximum power of the battery at 620°C with three cathode gases and three flow rates is shown in Figure 2. The test results show that the order of the maximum discharge power of the battery is "nitrous oxide-fluidized bed" > "air-fixed bed" > "nitrous oxide Nitrogen-fixed bed", the battery output performance reaches the highest at 400ml/min gas velocity, which are 2040 mW, 1615 mW and 1083 mW respectively. Experiments have observed that when the cathode gas flow rate is less than 200ml/min, the filled cathode bed material is still in a fixed state. When the gas velocity reaches 200ml/min, the cathode bed material becomes fluidized, and the battery performance increases by 18.5% compared with the gas velocity of 100ml/min. The test results show that the nitrous oxide decomposition can improve the output performance of the fuel cell, and the fluidization can further expand the advantages brought by the nitrous oxide decomposition to the battery performance. Wherein, "fluidized bed" and "fixed bed" borrow terms from fluidized bed reactors, which means that the cathode bed material is in a fluidized state or a fixed state under the corresponding air flow.
图3中左、右分别为设定加热或保温装置7温度为620℃下，“氧化亚氮-固定床”和“氧化亚氮-流化态”两种状态下，整个固体氧化物燃料电池表面温度分布，从图中可以看出，300ml/min气速固定床模式下电池底部温度低于顶部温度，温差大于50℃，通过流化可以实现很好的热量传递，整个固体氧化物燃料电池的温度场都非常均匀。In Fig. 3, the left and right respectively show the whole solid oxide fuel cell under the two states of "nitrous oxide-fixed bed" and "nitrous oxide-fluidized state" when the temperature of heating or heat preservation device 7 is set at 620°C The surface temperature distribution, as can be seen from the figure, under the 300ml/min gas velocity fixed bed mode, the temperature at the bottom of the battery is lower than that at the top, and the temperature difference is greater than 50°C. Good heat transfer can be achieved through fluidization, and the entire solid oxide fuel cell The temperature field is very uniform.
图4为“氧化亚氮-固定床”和“氧化亚氮-流化床”两种工况下三种反应温度下300ml/min时氧化亚氮分解率，从图中可以看出不添加阴极床料时，氧化亚氮转化率均低于30%，即阴极气体中氧气含量13%，远低于空气中氧气含量；阴极床料处于流化床工况下（流化态）氧化亚氮分解率均为100%，即阴极气体中氧气浓度可达33%，从而解释了图2中燃料电池性能的差异性。此试验结果表明流化态阴极床料可以明显提升氧化亚氮的转化率。Figure 4 shows the decomposition rate of nitrous oxide at three reaction temperatures of 300ml/min under the two working conditions of "nitrous oxide-fixed bed" and "nitrous oxide-fluidized bed". It can be seen from the figure that no cathode is added When the bed material is used, the conversion rate of nitrous oxide is lower than 30%, that is, the oxygen content in the cathode gas is 13%, which is far lower than the oxygen content in the air; the cathode bed material is in a fluidized bed condition (fluidized state) nitrous oxide The decomposition rate is 100%, that is, the oxygen concentration in the cathode gas can reach 33%, thus explaining the difference in fuel cell performance in Figure 2. The test results show that the fluidized cathode bed material can significantly improve the conversion rate of nitrous oxide.
因此使用本申请具有流化床阴极床料的固体氧化物燃料电池处理氧化亚氮尾气的工艺方法，通过阴极材料流化增强腔体内反应强度，不仅可以提升氧化亚氮分解率实现氧化亚氮高效分解，又可以均匀燃料电池表面的温度场，解决因氧化亚氮分解放热所产生的温度不均现象，同时还可以提升燃料电池的输出性能和燃料电池的安全性。Therefore, using the process method of the present application for treating nitrous oxide tail gas with a solid oxide fuel cell with a fluidized bed cathode bed material, the fluidization of the cathode material can enhance the reaction intensity in the cavity, which can not only improve the decomposition rate of nitrous oxide and achieve high efficiency of nitrous oxide Decomposition can even the temperature field on the surface of the fuel cell, solve the temperature unevenness caused by the decomposition and heat generation of nitrous oxide, and at the same time improve the output performance of the fuel cell and the safety of the fuel cell.
实际应用时，阴极气体可采用不同氧化亚氮含量的混合气体，除氧化亚氮外还可能包括氮气、氧气、氩气、二氧化氮等一种或多种气体，当尾气中氧化亚氮含量较低时可以补充适量的空气或氧气。阴极床料的状态可适用于鼓泡流态化、湍流床、快速床或稀相床。电池管的数量根据实际需要可是设置多根。In practical applications, the cathode gas can be a mixed gas with different nitrous oxide content. In addition to nitrous oxide, it may also include one or more gases such as nitrogen, oxygen, argon, nitrogen dioxide, etc. When the content of nitrous oxide in the tail gas When it is low, an appropriate amount of air or oxygen can be added. The state of the cathode bed material can be suitable for bubbling fluidization, turbulent bed, fast bed or dilute phase bed. The number of battery tubes can be set in multiples according to actual needs.

Claims (7)

  1. 一种使用燃料电池处理氧化亚氮尾气的装置，其特征在于，包括固体氧化物燃料电池，其结构包括壳体（4）、燃料电池管（2）和阴极床料（3）；所述壳体（4）上设有阴极气体入口（5）和阴极气体出口（1），阴极气体包括待处理的氧化亚氮；所述壳体（4）内设置有至少一根所述燃料电池管（2），所述燃料电池管（2）两端设有阳极气体入口（9）和阳极气体出口（8）；所述壳体（4）内壁与至少一根所述燃料电池管（2）的阴极外壁之间形成腔体（10），所述阴极床料（3）填充于所述腔体（10）内；所述壳体（4）内设有布风板（6），阴极气体由所述阴极气体入口（5）流入、经所述布风板（6）导流后进入腔体（10）内，可促使所述阴极床料（3）处于流化状态；所述燃料电池管（2）两端分别与布风板（6）、壳体（4）固定连接。A device for treating nitrous oxide tail gas using a fuel cell, characterized in that it includes a solid oxide fuel cell, and its structure includes a shell (4), a fuel cell tube (2) and a cathode bed material (3); the shell The body (4) is provided with a cathode gas inlet (5) and a cathode gas outlet (1), and the cathode gas includes nitrous oxide to be treated; at least one fuel cell tube ( 2), the two ends of the fuel cell tube (2) are provided with an anode gas inlet (9) and an anode gas outlet (8); the inner wall of the housing (4) and at least one of the fuel cell tubes (2) A cavity (10) is formed between the outer walls of the cathode, and the cathode bed material (3) is filled in the cavity (10); the housing (4) is provided with an air distribution plate (6), and the cathode gas is The cathode gas inlet (5) flows into the cavity (10) after being diverted by the air distribution plate (6), which can promote the cathode bed material (3) to be in a fluidized state; the fuel cell tube (2) The two ends are respectively fixedly connected with the air distribution plate (6) and the housing (4).
  2. 根据权利要求1所述的使用燃料电池处理氧化亚氮尾气的装置，其特征在于，所述阴极床料（3）为钙钛矿基金属氧化物颗粒状催化剂。The device for treating nitrous oxide tail gas using a fuel cell according to claim 1, characterized in that the cathode bed material (3) is a perovskite-based metal oxide granular catalyst.
  3. 根据权利要求1所述的使用燃料电池处理氧化亚氮尾气的装置，其特征在于，所述壳体（4）外部设置加热或保温装置（7）。The device for treating nitrous oxide tail gas using a fuel cell according to claim 1, characterized in that a heating or heat preservation device (7) is arranged outside the housing (4).
  4. 根据权利要求1所述的使用燃料电池处理氧化亚氮尾气的装置，其特征在于，所述燃料电池管（2）采用阳极支撑、金属支撑或电解质支撑结构，使用时将燃料电池管（2）阴极和阳极分别连接到相应的电子负载上。The device for treating nitrous oxide tail gas using a fuel cell according to claim 1, characterized in that the fuel cell tube (2) adopts an anode support, metal support or electrolyte support structure, and the fuel cell tube (2) The cathode and anode are respectively connected to corresponding electronic loads.
  5. 一种利用权利要求1所述的装置处理氧化亚氮尾气的方法，其特征在于，将燃料电池管（2）加热到620℃-720℃，然后分别向燃料电池管（2）和腔体（10）中输入阳极气体和用作阴极气体的含氧化亚氮的气体；阴极气体使阴极床料（3）处于流化状态，利用流化状态的阴极床料（3）作为催化剂促进氧化亚氮的分解反应，同时促进分解反应释放的热量分布均匀，促使燃料电池管（2）温度均匀分布，同时利用氧化亚氮分解反应释放的氧气提升阴极气体中氧气浓度，从而提升燃料电池管（2）的输出功率。A method for treating nitrous oxide tail gas using the device according to claim 1, characterized in that the fuel cell tube (2) is heated to 620°C-720°C, and then the fuel cell tube (2) and the cavity ( 10) Input the anode gas and the nitrous oxide-containing gas used as the cathode gas; the cathode gas makes the cathode bed material (3) in a fluidized state, and uses the fluidized cathode bed material (3) as a catalyst to promote the nitrous oxide At the same time, it promotes the uniform distribution of the heat released by the decomposition reaction, and promotes the uniform distribution of the temperature of the fuel cell tube (2). output power.
  6. 根据权利要求5所述的处理氧化亚氮尾气的方法，其特征在于，阴极床料（3）采用包覆镧锶铁粉体的氧化铈颗粒，颗粒直径100-300μm。The method for treating nitrous oxide tail gas according to claim 5, characterized in that the cathode bed material (3) is cerium oxide particles coated with lanthanum strontium iron powder, and the particle diameter is 100-300 μm.
  7. 根据权利要求5所述的处理氧化亚氮尾气的方法，其特征在于，利用电加热炉对燃料电池管（2）加热，或者向燃料电池管（2）内通入高温气体进行加热。The method for treating nitrous oxide tail gas according to claim 5, characterized in that an electric heating furnace is used to heat the fuel cell tube (2), or a high-temperature gas is introduced into the fuel cell tube (2) for heating.
PCT/CN2022/106440 2021-07-21 2022-07-19 Method and device for treating nitrous oxide tail gas by using fuel cell WO2023001139A1 (en)

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