WO2020192114A1 - Industrial flue-gas storage reduction and denitration system and method - Google Patents

Industrial flue-gas storage reduction and denitration system and method Download PDF

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WO2020192114A1
WO2020192114A1 PCT/CN2019/114547 CN2019114547W WO2020192114A1 WO 2020192114 A1 WO2020192114 A1 WO 2020192114A1 CN 2019114547 W CN2019114547 W CN 2019114547W WO 2020192114 A1 WO2020192114 A1 WO 2020192114A1
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flue gas
catalyst
storage
optionally
industrial flue
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PCT/CN2019/114547
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French (fr)
Chinese (zh)
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朱廷钰
徐文青
王艺晰
王健
杨阳
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中国科学院过程工程研究所
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Priority to JP2021550209A priority Critical patent/JP7223154B2/en
Publication of WO2020192114A1 publication Critical patent/WO2020192114A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • 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
    • B01D53/48—Sulfur compounds
    • 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
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/80—Semi-solid phase processes, i.e. by using slurries
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes

Definitions

  • This application belongs to the technical field of flue gas purification, and relates to an industrial flue gas storage reduction denitration system and method, for example, it relates to a system and method that divides denitration into a storage process and a reduction process according to the instantaneous change of NO x concentration.
  • the instantaneous emission concentration of NO x in industrial flue gas will fluctuate with the change of working conditions.
  • Related denitration technologies mainly include NH 3 -SCR, direct lye absorption method, ozone oxidation + lye absorption method, and activated carbon adsorption method And so on, can meet the denitrification requirements under the condition that the instantaneous emission concentration is basically constant.
  • the change rule of the instantaneous emission concentration of NO x in part of the flue gas changes periodically as shown in Figure 1.
  • the reduction efficiency of NH 3 -SCR generally does not exceed 95%.
  • the emission standard of 100 mg/m 3 cannot be met; and the amount of ammonia injection cannot be compared with the drastically changing NO
  • the instantaneous concentration of x is matched in real time, which is easy to cause secondary pollution due to ammonia leakage.
  • the ozone oxidation + lye absorption method needs to adjust the ozone concentration in real time according to the NO x emission concentration, but a certain response time is required in the process.
  • the NO x storage reduction technology proposed by Toyota Corporation of Japan has great advantages in the treatment of lean-burn engine (diesel and lean-burn gasoline engines) exhaust.
  • the NO x emission concentration in the exhaust of lean-burn engines changes periodically, and the concentration reaches its peak.
  • the tail gas has both higher oxygen content and lower CO, H 2 , hydrocarbon and other reducing gas content; when the instantaneous emission concentration of NO x is low, the tail gas also has a higher reducing gas content.
  • CN101422689B discloses a circulating fluidized bed nitrogen oxide storage reduction flue gas denitration method and device, including the following steps: a. The flue gas is accelerated or pressurized and then directly sprayed into a fluidized bed with a catalyst as the bed material In the storage reactor, the oxidation and absorption and storage of NO x are realized while driving the flow of the bed material; b. The gas-solid phase separation is realized by the gas-solid separator at the end of the storage reactor, and the gas phase can be directly discharged or enter the lower NO x The purification system performs purification, and the solid-phase catalyst enters the fluidized bed reduction regeneration reactor; c.
  • the NO x storage catalyst contacts with the reducing agent in the fluidized bed reduction regeneration reactor to reduce the stored NO x to achieve catalyst regeneration; d , The regenerated catalyst is introduced into the fluidized bed storage reactor.
  • this technical solution adopts a circulating fluidized bed reactor, and the circulating fluidized bed reactor wants to achieve the purpose of fluidizing the solid phase, which puts forward strict requirements on the physical properties of the material, such as the properties of the catalyst itself, and the molding production. For example, the particles with larger particle size will rise at the center and fall back at a certain height at the edge; the particle size of the particles with larger viscosity should be controlled below 20 ⁇ m.
  • CN105251326A discloses a reduction and oxidation combined denitration system and a denitration method thereof, including an SNCR denitration device, an SCR denitration device and an oxidation denitration device.
  • the SNCR denitration device includes a reducing agent storage device, a cyclone separator and a reducing agent injection device.
  • the SCR denitration device includes a reducing agent supplemental dose control device and a denitration catalyst layer, and the denitration catalyst layer is arranged in the tail of the boiler flue gas pipeline.
  • the oxidation denitrification device which is connected to the outlet of the boiler flue gas pipeline through a flue gas pipeline, includes an oxidation reaction device, a concentrated nitric acid absorption tower, and an alkali washing tower that are sequentially connected through the flue gas pipeline;
  • the flue gas after the denitration treatment of the device and the SCR denitration device undergoes deep denitration treatment.
  • the system still has the following shortcomings: 1. SNCR denitration device is suitable for high temperature denitration requirements, the reaction temperature window is 800-1100 °C, and the efficiency is generally not higher than 60%; 2.
  • SCR is suitable for working conditions with constant NO x instantaneous emission concentration , Otherwise there will be excessive NH 3 problems, which is easy to cause secondary pollution; 3.
  • Oxidative denitrification devices are generally ozone oxidative denitrification, and the ozone concentration must be adjusted in real time according to the changes in the instantaneous emission concentration of NO x , and in actual production The ozone concentration adjustment often has a hysteresis.
  • the storage reduction technology is used to treat industrial flue gas whose instantaneous NO x emission concentration changes drastically. It can be stored on the catalyst when the NO x instantaneous emission concentration is high; when the working conditions change, the NO x instantaneous emission concentration is low or When the emission is stopped, the NO x on the catalyst is slowly released and reduced to N 2 . This process realizes the regeneration of the catalyst. It solves the problems of slow response time of related industrial flue gas denitration technology to fluctuating flue gas conditions and difficulty in meeting emission standards for instantaneous high-concentration NO x treatment.
  • the present application aims to provide a dramatic change in the instantaneous concentration of industrial flue gas denitration storage reduction system and method, according to an instantaneous NO x concentration
  • the denitration is divided into storage process and reduction process, using the redox active component and storage component of the catalyst (redox active component/storage component/carrier), the instantaneous concentration of NO x in the flue gas fluctuates strongly
  • NO x is deposited on the surface of the catalyst in the form of nitrate or nitrite; when the instantaneous concentration of NO x in the flue gas is low, the reducing agent is sprayed, and the hot blast stove is turned on to heat the flue gas at this time.
  • x is slowly released and reduced to N 2 .
  • this application provides a storage reduction denitration method of industrial flue gas, the method comprising:
  • step (1) of the industrial flue gas instantaneous concentration of NO x emissions above step (2) of the industrial flue gas instantaneous concentration of NO x emissions is performed in accordance with the present application.
  • the instantaneous emission concentration of NO x in the industrial flue gas in step (1) is higher than 100 mg/m 3 , for example, it can be 150 mg/m 3 , 200 mg/m 3 , 250 mg/m 3 , 300 mg/m 3 , 350mg/m 3 , 400mg/m 3 , 450mg/m 3 , 500mg/m 3 , 550mg/m 3 , 600mg/m 3 , 650mg/m 3 , 700mg/m 3 , 750mg/m 3 , 800mg/m 3 , 950mg/m 3 or 1000mg/m 3 , and the peak concentration is 10000mg/m 3 .
  • the instantaneous emission concentration of NO x in the industrial flue gas in step (2) is 0-100 mg/m 3 , for example, it can be 10 mg/m 3 , 20 mg/m 3 , 30 mg/m 3 , 40 mg/m 3 , 50mg/m 3 , 60mg/m 3 , 70mg/m 3 , 80mg/m 3 or 90mg/m 3 .
  • the present application uses the storage components on the catalyst to store NO x with a higher instantaneous emission concentration on the catalyst, and releases and reduces it when the instantaneous emission concentration is low, effectively avoiding the related industrial flue gas caused by the sudden change of the instantaneous emission concentration
  • the denitrification technology has slow response time to fluctuating flue gas conditions, and the instantaneous high concentration cannot meet the emission standards.
  • the method includes the following steps:
  • the chemical reactions include but are not limited to the following reactions:
  • the chemical reactions include but are not limited to the following reactions:
  • the chemical reactions include but are not limited to the following reactions:
  • the method further includes performing dust removal and desulfurization treatment on the industrial flue gas before step (1).
  • the industrial flue gas concentration of NO x emissions instantaneous changes periodically.
  • the industrial flue gas is non-ferrous smelting flue gas or rotary kiln flue gas.
  • the temperature of industrial flue gas in the oxidation storage process in step (1) is 100°C to 250°C, for example 110°C, 120°C, 130°C, 140°C, 150°C, 160°C , 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C or 240°C.
  • the heating process in step (2) includes: raising the temperature of industrial flue gas in the oxidation storage process in step (1) to 350-450°C, for example, from 100°C to 350°C, 110°C to 110°C 350°C, 120°C to 360°C, 130°C to 360°C, 140°C to 380°C, 150°C to 380°C, 160°C to 400°C, 170°C to 400°C, 180°C to 420 °C, 190°C to 420°C, 200°C to 440°C, 210°C to 440°C, 220°C to 450°C, 230°C to 450°C, 240°C to 450°C or 250°C to 450°C .
  • the slow release process of NO x in step (2) is achieved by controlling the heating rate.
  • the heating rate is 5°C/min-30°C/min, for example, 5°C/min, 10°C/min, 15°C/min, 20°C/min, 25°C/min or 30°C/min. This application of the flue gas by slowly warmed to achieve the purpose of controlling the rate of release of NO x in the catalyst is.
  • the catalyst in step (1) includes a redox active component, a storage component and a carrier.
  • the redox active component includes a platinum-based catalyst, a manganese-based catalyst, and a copper-based catalyst.
  • the storage component includes a barium-based catalyst and a potassium-based catalyst.
  • the support includes an aluminum-based catalyst and a titanium-based catalyst.
  • the reducing agent in step (2) is selected from one or a mixture of at least two of hydrogen, carbon monoxide, propylene, or ammonia, for example, a mixture of hydrogen and carbon monoxide, a mixture of hydrogen and propylene, and a mixture of hydrogen and ammonia.
  • the present application provides a system for implementing the storage reduction denitration method as described in the first aspect.
  • the system includes a heating device and a storage reduction denitration reaction device that are sequentially connected.
  • a reductant injection device is arranged above the cavity, and the storage reduction denitration reaction device adopts a solidified bed reactor.
  • the storage reduction denitrification reaction tower provided by this application is a fixed bed, which can realize the in-situ storage and reduction process.
  • the reason why the circulating fluidized bed is not used is that the purpose of the circulating fluidized bed to fluidize the solid phase is that the physical properties of the material are There are relatively high requirements, that is, there are strict requirements on the properties and molding of the catalyst itself.
  • the particles with larger particle size will rise at the center and fall back at the edge at a certain height; while the particle size of the particles with larger viscosity needs to be controlled below 20 ⁇ m.
  • the system further includes a dust removal device and a desulfurization device connected in sequence, and the outlet of the desulfurization device is connected to the inlet of the heating device.
  • This application is equipped with a desulfurization device at the front end of the system to avoid the problem of catalyst vulcanization poisoning.
  • a flue gas online monitoring device is also provided on the connecting pipeline between the desulfurization device and the heating device.
  • the application is equipped with an online monitoring device, which can realize intelligent adjustment according to the change of the instantaneous emission concentration of NO x , and determine the opening or closing of the heating device and the reducing agent injection device.
  • This application is based on the instantaneous NO x concentration, the denitration process and into storage reduction process, firstly the instantaneous NO x emission concentration of gas-line monitoring of industrial flue gas detecting means.
  • the flue gas online monitoring device detects that the instantaneous emission concentration of NO x in the industrial flue gas is higher than 100 mg/m 3 , the heating device and the reductant injection device are turned off, the industrial flue gas undergoes an oxidation storage process, and the NO x in the flue gas It is stored on the catalyst in the form of nitrate or nitrite.
  • the heating device and the reductant injection device are turned on, and the industrial flue gas is released and reduced, and the NO x on the catalyst is released and combined Reduce to N 2 .
  • the system further includes a flue gas discharge chimney connected to the outlet of the storage reduction denitration reaction device.
  • the dust removal device is a cyclone dust collector, a bag dust collector or an electric bag dust collector.
  • the desulfurization device is a circulating fluidized bed semi-dry desulfurization device, an SDA desulfurization device or a wet desulfurization device.
  • the heating device is a hot blast stove.
  • the storage reduction denitration reaction device includes a cavity, and a guide vane is arranged at the flue gas inlet of the top of the cavity, and a gas rectifying device and a reducing agent are sequentially arranged below the guide vane.
  • Injection device, static mixing device and catalyst packing layer is sequentially arranged below the guide vane.
  • the storage reduction denitration reaction device further includes a control system electrically connected to the reducing agent injection device.
  • the catalyst filler layer includes at least one layer of catalyst filler, and optionally includes three layers of catalyst filler.
  • the efficient storage of NO x by the catalyst is realized.
  • the gas rectifying device and the static mixing device are made of stainless steel.
  • This application uses the storage components on the catalyst to store the NO x with a higher instantaneous emission concentration on the catalyst, and release and reduce it when the instantaneous emission concentration is low, effectively avoiding the correlation caused by the sudden change of the instantaneous emission concentration.
  • Industrial flue gas denitrification technology has slow response time to fluctuating flue gas conditions, and the instantaneous high concentration cannot meet the emission standards.
  • the total removal rate of NO x in a storage reduction cycle Can reach more than 95%.
  • Fig. 1 is a schematic diagram of the periodic change rule of the instantaneous emission concentration of NO x provided by the background art of the present application;
  • FIG. 2 is a schematic diagram of the structural connection of a storage reduction denitration device provided by a specific embodiment of the present application
  • 1- dust removal device 2- desulfurization device; 3- flue gas online monitoring device; 4- hot blast stove; 5- guide vane; 6-gas rectifier; 7- reductant injection device; 8- control system; 9- Static mixer; 10-catalyst packing layer; 11-storage reduction denitration reaction device; 12-chimney.
  • the present application provides an industrial flue gas storage reduction denitrification system.
  • the system includes a dust removal device 1, a desulfurization device 2, a hot blast stove 4, and a storage reduction denitration reaction. ⁇ 11 ⁇ Device 11.
  • a flue gas online monitoring device 3 is provided on the connecting pipeline of the desulfurization device 2 and the hot blast stove 4.
  • the lower part of the dust removal device 1 is provided with a flue gas inlet and the upper part is provided with a flue gas outlet;
  • the lower part of the desulfurization device 2 is provided with a flue gas inlet and the top is provided with a flue gas outlet;
  • the hot blast stove 4 is provided with a flue gas inlet in the lower part and a flue gas outlet on the upper part.
  • the upper part of the storage reduction denitration reaction device 11 is provided with a flue gas inlet, and the lower part is provided with a flue gas outlet.
  • the flue gas outlet of the dust removal device 1 is connected to the flue gas inlet of the desulfurization device 2
  • the flue gas outlet of the desulfurization device 2 is connected to the flue gas inlet of the hot blast stove 4
  • the connecting pipe between the desulfurization device 2 and the hot blast stove 4 is also connected with flue gas
  • the flue gas outlet of the hot blast stove 4 is connected to the flue gas inlet of the storage reduction denitrification reaction device 11
  • the flue gas outlet of the storage reduction denitrification reaction device 11 is connected to the flue gas inlet of the chimney 12.
  • the flue gas inlet of the storage reduction denitrification reaction device 11 is provided with a guide vane 5, and a gas rectifier 6, a reducing agent injection device 7, a static mixer 9 and a catalyst packing layer 10 are sequentially arranged below the guide vane 5.
  • the reduction denitration reaction device 11 also includes a control system 8 electrically connected to the reducing agent injection device 7. Both the gas rectifier 6 and the static mixer 9 are made of stainless steel.
  • the catalyst packing layer includes three layers of catalyst packing. Through the storage function of the three layers of catalyst packing layers, the efficient storage of NO x by the catalyst can be realized.
  • this application provides an industrial flue gas storage reduction denitration method, the specific operation includes the following steps:
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off.
  • the flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst.
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on . The flue gas is slowly raised from the flue gas temperature during the oxidation storage process to 350°C. Under the influence of the reducing agent and the temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
  • This embodiment provides an industrial flue gas storage reduction denitrification method, which is performed in the system provided in the specific implementation mode, and the specific operation includes the following steps:
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off.
  • the flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst, the flue gas temperature during the oxidation storage process is 100°C.
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on . The flue gas is slowly raised from 100°C to 350°C at a rate of 30°C/min. Under the influence of the reducing agent and temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
  • This embodiment can make the total removal rate of NO x in one storage and reduction cycle reach more than 95%.
  • This embodiment provides an industrial flue gas storage reduction denitrification method, which is performed in the system provided in the specific implementation mode, and the specific operation includes the following steps:
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off.
  • the flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst, the flue gas temperature during the oxidation storage process is 150°C.
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on. The flue gas is slowly raised from 150°C to 400°C at a rate of 20°C/min. Under the influence of the reducing agent and temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
  • This embodiment can make the total removal rate of NO x in one storage and reduction cycle reach 97.2%.
  • This embodiment provides an industrial flue gas storage reduction denitrification method, which is performed in the system provided in the specific implementation mode, and the specific operation includes the following steps:
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off.
  • the flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst, the flue gas temperature during the oxidation storage process is 200°C.
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on. The flue gas is slowly raised from 200°C to 420°C at a rate of 10°C/min. Under the influence of the reducing agent and temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
  • This embodiment can make the total removal rate of NO x within one storage and reduction cycle reach 96.4%.
  • This embodiment provides an industrial flue gas storage reduction denitrification method, which is performed in the system provided in the specific implementation mode, and the specific operation includes the following steps:
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off.
  • the flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst, the flue gas temperature during the oxidation storage process is 250°C.
  • the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on. The flue gas is slowly raised from 250°C to 450°C at a rate of 5°C/min. Under the influence of the reducing agent and temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
  • This embodiment can make the total removal rate of NO x within one storage and reduction cycle reach 96.8%.
  • the removal rate data provided in the above-mentioned embodiments are only parameter data made by laboratory regeneration evaluation, and not as guiding data for engineering regeneration evaluation. .
  • CN101422689B discloses a denitration method and device for flue gas storage reduction in circulating fluidized bed nitrogen oxides.
  • Industrial flue gas with the same composition as in Example 1 is used to perform the denitration method disclosed in CN101422689B.
  • the specific operation steps include:
  • the industrial flue gas is pressurized or accelerated by the flue gas compressor and sprayed into the fluidized bed storage reactor through the flue gas nozzle.
  • the powdered NO x trap catalyst is pre-placed in the fluidized bed NO x storage reactor through the catalyst inlet as the bed material ,
  • the flue gas drives the NO x trap catalyst to fluidize together.
  • stored in the NO x catalyst may be a nitrate, nitrite, or other forms of immobilized NO x (absorption, adsorption or oxidation absorption).
  • the flue gas in the fluidized bed storage reactor and the catalyst storing NO x enter the gas-solid separator through the flue gas outlet connecting pipe.
  • the gas-solid phase is separated in the gas-solid separator, and the gas phase can directly pass through the purified gas outlet Emissions that meet the standards or enter the lower-level circulating fluidized bed NO x storage reduction reactor for further treatment, and the solid-phase catalyst particles that store NO x enter the fluidized bed reduction regeneration reactor.
  • the reductant is sprayed into the fluidized bed reduction regeneration reactor through the reductant inlet and drives the solid phase catalyst to flow.
  • the temperature of the reactor is adjusted by the heater to maximize selective catalytic reduction of NO x to achieve, while achieving the regeneration of NO x trap catalyst.
  • the industrial flue gas storage reduction denitrification method provided by this application is a continuous cyclic process.
  • a catalyst is not required to store NO x .
  • Comparative Example 1 uses a fluidized bed reactor, which cannot realize the in-situ storage and reduction process, so it will cause energy waste;
  • Comparative Example 1 uses a fluidized bed reactor. Due to the short contact time between gas and solid in the fluidized bed, the storage efficiency and catalyst regeneration rate will be limited;
  • Comparative Example 1 only mentions that the device is suitable for use in conjunction with a circulating fluidized bed flue gas desulfurization device, and there is no desulfurization device, so it is very easy to cause catalyst sulfidation poisoning.

Abstract

Provided are an industrial flue-gas storage reduction and denitration system and method, said method comprising: (1) if the instantaneous emission concentration of NOx in industrial flue gas is relatively high, then passing the industrial flue gas into a catalyst layer, wherein the NOx is oxidized and stored by the catalyst in the form of nitrate or nitrite; (2) if the instantaneous emission concentration of NOx in industrial flue gas is relatively low, then heating the industrial flue gas and simultaneously spraying-in a reducing agent, releasing and reducing the stored NOx.

Description

一种工业烟气储存还原脱硝系统和方法Industrial flue gas storage reduction denitration system and method 技术领域Technical field
本申请属于烟气净化技术领域，涉及一种工业烟气储存还原脱硝系统和方法，例如涉及一种根据NO x瞬时浓度变化情况，将脱硝分为储存过程和还原过程的系统和方法。 This application belongs to the technical field of flue gas purification, and relates to an industrial flue gas storage reduction denitration system and method, for example, it relates to a system and method that divides denitration into a storage process and a reduction process according to the instantaneous change of NO x concentration.
背景技术Background technique
工业烟气中的NO x瞬时排放浓度会随着工况条件的改变呈波动性变化，相关脱硝技术主要包括NH 3-SCR、碱液直接吸收法、臭氧氧化+碱液吸收法、活性炭吸附法等，能够满足瞬时排放浓度基本恒定情况下的脱硝要求。而部分烟气中NO x的瞬时排放浓度的变化规律如图1所示呈周期性变化，以有色冶炼烟气、回转窑烟气为例，其NO x瞬时排放浓度不断变化，峰值最高可达10000mg/m 3，周期内同时存在NO x瞬时排放浓度为零的时刻。将在用的脱硝技术应用于此类烟气条件的治理主要存在以下问题： The instantaneous emission concentration of NO x in industrial flue gas will fluctuate with the change of working conditions. Related denitration technologies mainly include NH 3 -SCR, direct lye absorption method, ozone oxidation + lye absorption method, and activated carbon adsorption method And so on, can meet the denitrification requirements under the condition that the instantaneous emission concentration is basically constant. The change rule of the instantaneous emission concentration of NO x in part of the flue gas changes periodically as shown in Figure 1. Taking non-ferrous smelting flue gas and rotary kiln flue gas as examples, the instantaneous emission concentration of NO x changes continuously, and the peak value can reach the highest 10000mg/m 3 , there is a moment when the instantaneous emission concentration of NO x is zero in the cycle. The main problems in applying the denitration technology in use to the treatment of such flue gas conditions are as follows:
(1)NH 3-SCR的还原效率一般不超过95％，当NO x瞬时排放浓度达10000mg/m 3时，不能够满足100mg/m 3的排放标准；且喷氨量不能与剧烈变化的NO x瞬时浓度实时匹配，容易由于氨气泄露造成二次污染。 (1) The reduction efficiency of NH 3 -SCR generally does not exceed 95%. When the instantaneous emission concentration of NO x reaches 10,000 mg/m 3 , the emission standard of 100 mg/m 3 cannot be met; and the amount of ammonia injection cannot be compared with the drastically changing NO The instantaneous concentration of x is matched in real time, which is easy to cause secondary pollution due to ammonia leakage.
(2)碱液直接吸收法产生大量NO 3 -、NO 2 -超标废液。 (2) The direct absorption method of lye produces a large amount of NO 3 - and NO 2 - over - standard waste liquid.
(3)臭氧氧化+碱液吸收法需要根据NO x排放浓度实时调节臭氧浓度，但过程中需要一定的响应时间。 (3) The ozone oxidation + lye absorption method needs to adjust the ozone concentration in real time according to the NO x emission concentration, but a certain response time is required in the process.
(4)活性炭使用量大，吸附后需要再生或填埋处理。(4) The amount of activated carbon used is large, and it needs to be regenerated or landfilled after adsorption.
由日本丰田公司提出的NO x储存还原技术在治理稀燃发动机(柴油机和稀燃汽油机)尾气中有较大的优势，稀燃发动机尾气中NO x排放浓度呈周期性变化， 且浓度达峰值时尾气中同时具有较高的氧含量和较低的CO、H 2、碳氢化合物等还原性气体含量；NO x瞬时排放浓度较低时尾气中同时具有较高的还原性气体含量。 The NO x storage reduction technology proposed by Toyota Corporation of Japan has great advantages in the treatment of lean-burn engine (diesel and lean-burn gasoline engines) exhaust. The NO x emission concentration in the exhaust of lean-burn engines changes periodically, and the concentration reaches its peak. The tail gas has both higher oxygen content and lower CO, H 2 , hydrocarbon and other reducing gas content; when the instantaneous emission concentration of NO x is low, the tail gas also has a higher reducing gas content.
CN101422689B公开了一种循环流化床氮氧化物储存还原烟气的脱硝方法及其装置，包括如下步骤：a、将烟气经加速或者加压后直接喷入以催化剂为床料的流化床储存反应器中，在带动床料流动的同时实现NO x的氧化和吸收储存；b、通过设置在储存反应器尾部的气固分离器实现气固相分离，气相可以直接排放或者进入下级NO x净化系统进行净化，固相催化剂进入流化床还原再生反应器；c、存储NO x的催化剂在流化床还原再生反应器中与还原剂接触，还原被储存的NO x，实现催化剂再生；d、将再生后的催化剂引入流化床储存反应器。但该技术方案采用了循环流化床反应器，而循环流化床反应器想要实现将固相流化的目的对于物料物性例如催化剂本身性质、成型制作等都提出了严格要求。如粒度较大的颗粒存在中心处上升，一定高度在边缘处回落的返混现象；而粘性较大的颗粒粒度需控制在20μm以下等。这使得循环流化床在设计中需要注意输送分离高度的问题，即受催化剂物性和气体流速的影响，循环流化床反应器的设计要求比较高，否则达不到使固相流化的目的，就会造成循环率下降、气固接触时间短、催化剂利用率下降等问题。 CN101422689B discloses a circulating fluidized bed nitrogen oxide storage reduction flue gas denitration method and device, including the following steps: a. The flue gas is accelerated or pressurized and then directly sprayed into a fluidized bed with a catalyst as the bed material In the storage reactor, the oxidation and absorption and storage of NO x are realized while driving the flow of the bed material; b. The gas-solid phase separation is realized by the gas-solid separator at the end of the storage reactor, and the gas phase can be directly discharged or enter the lower NO x The purification system performs purification, and the solid-phase catalyst enters the fluidized bed reduction regeneration reactor; c. The NO x storage catalyst contacts with the reducing agent in the fluidized bed reduction regeneration reactor to reduce the stored NO x to achieve catalyst regeneration; d , The regenerated catalyst is introduced into the fluidized bed storage reactor. However, this technical solution adopts a circulating fluidized bed reactor, and the circulating fluidized bed reactor wants to achieve the purpose of fluidizing the solid phase, which puts forward strict requirements on the physical properties of the material, such as the properties of the catalyst itself, and the molding production. For example, the particles with larger particle size will rise at the center and fall back at a certain height at the edge; the particle size of the particles with larger viscosity should be controlled below 20μm. This makes the design of circulating fluidized bed need to pay attention to the problem of transport and separation height, that is, affected by the physical properties of the catalyst and the gas flow rate, the design requirements of the circulating fluidized bed reactor are relatively high, otherwise the purpose of solid phase fluidization will not be achieved. , It will cause problems such as decreased circulation rate, short gas-solid contact time, and decreased catalyst utilization rate.
CN105251326A公开了一种还原与氧化联合脱硝系统及其脱硝方法，包括SNCR脱硝装置、SCR脱硝装置以及氧化脱硝装置。所述SNCR脱硝装置包括还原剂储存装置、旋风分离器和还原剂喷射装置。所述SCR脱硝装置，包括还原剂补充剂量控制装置和脱硝催化剂层，所述脱硝催化剂层设于锅炉烟气管道尾部内。所述氧化脱硝装置，其与锅炉烟气管道出口通过烟气管道连接，包括 依次通过烟气管道连接的氧化反应装置、浓硝酸吸收塔和碱液洗涤塔；所述氧化脱硝装置对经过SNCR脱硝装置与SCR脱硝装置脱硝处理后的烟气进行深度脱硝处理。但该系统仍存在如下缺陷：1、SNCR脱硝装置适用于高温脱硝需求，反应温度窗口在800-1100℃，效率一般不高于60％；2、SCR适用于NO x瞬时排放浓度恒定的工况，否则会存在NH 3过量的问题，易造成二次污染；3、氧化脱硝装置一般为臭氧氧化脱硝，臭氧的浓度要根据NO x瞬时排放浓度变化情况做出实时的调节，而在实际生产中臭氧的浓度调节往往存在滞后现象。 CN105251326A discloses a reduction and oxidation combined denitration system and a denitration method thereof, including an SNCR denitration device, an SCR denitration device and an oxidation denitration device. The SNCR denitration device includes a reducing agent storage device, a cyclone separator and a reducing agent injection device. The SCR denitration device includes a reducing agent supplemental dose control device and a denitration catalyst layer, and the denitration catalyst layer is arranged in the tail of the boiler flue gas pipeline. The oxidation denitrification device, which is connected to the outlet of the boiler flue gas pipeline through a flue gas pipeline, includes an oxidation reaction device, a concentrated nitric acid absorption tower, and an alkali washing tower that are sequentially connected through the flue gas pipeline; The flue gas after the denitration treatment of the device and the SCR denitration device undergoes deep denitration treatment. However, the system still has the following shortcomings: 1. SNCR denitration device is suitable for high temperature denitration requirements, the reaction temperature window is 800-1100 ℃, and the efficiency is generally not higher than 60%; 2. SCR is suitable for working conditions with constant NO x instantaneous emission concentration , Otherwise there will be excessive NH 3 problems, which is easy to cause secondary pollution; 3. Oxidative denitrification devices are generally ozone oxidative denitrification, and the ozone concentration must be adjusted in real time according to the changes in the instantaneous emission concentration of NO x , and in actual production The ozone concentration adjustment often has a hysteresis.
将储存还原技术用于治理NO x瞬时排放浓度剧烈变化的工业烟气，可以在NO x瞬时排放浓度较高时将其储存在催化剂上；当工况条件改变，NO x瞬时排放浓度较低或停止排放时，将催化剂上的NO x缓慢释放并还原成N 2。该过程实现了对催化剂的再生。解决了相关工业烟气脱硝技术对于波动性烟气条件响应时间慢，对瞬时高浓度NO x治理难以达到排放标准等问题。 The storage reduction technology is used to treat industrial flue gas whose instantaneous NO x emission concentration changes drastically. It can be stored on the catalyst when the NO x instantaneous emission concentration is high; when the working conditions change, the NO x instantaneous emission concentration is low or When the emission is stopped, the NO x on the catalyst is slowly released and reduced to N 2 . This process realizes the regeneration of the catalyst. It solves the problems of slow response time of related industrial flue gas denitration technology to fluctuating flue gas conditions and difficulty in meeting emission standards for instantaneous high-concentration NO x treatment.
发明内容Summary of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics detailed in this article. This summary is not intended to limit the scope of protection of the claims.
鉴于将相关工业烟气脱硝技术应用于此类烟气条件治理中存在的问题，本申请的目的在于提供一种瞬时浓度变化剧烈的工业烟气储存还原脱硝系统和方法，根据NO x瞬时浓度变化情况，将脱硝分为储存过程和还原过程，利用催化剂(氧化还原活性组分/储存组分/载体)的氧化还原活性组分和储存组分，在烟气中NO x瞬时浓度波动性较强时，将NO x以硝酸盐或亚硝酸盐的形式赋存在催化剂表面；烟气中NO x瞬时浓度较低时，喷入还原剂，同时打开热风炉对烟气 加热，此时催化剂上的NO x被缓慢释放并还原成N 2。 In view of the related art applied to industrial flue gas denitration treatment in the presence of flue gas conditions such problems, the present application aims to provide a dramatic change in the instantaneous concentration of industrial flue gas denitration storage reduction system and method, according to an instantaneous NO x concentration In the case, the denitration is divided into storage process and reduction process, using the redox active component and storage component of the catalyst (redox active component/storage component/carrier), the instantaneous concentration of NO x in the flue gas fluctuates strongly At this time, NO x is deposited on the surface of the catalyst in the form of nitrate or nitrite; when the instantaneous concentration of NO x in the flue gas is low, the reducing agent is sprayed, and the hot blast stove is turned on to heat the flue gas at this time. x is slowly released and reduced to N 2 .
为达此目的，本申请采用以下技术方案：To achieve this goal, this application adopts the following technical solutions:
第一方面，本申请提供了一种工业烟气的储存还原脱硝方法，所述方法包括：In the first aspect, this application provides a storage reduction denitration method of industrial flue gas, the method comprising:
(1)工业烟气中NO x的瞬时排放浓度较高时，将工业烟气通入催化剂层，其中的NO x以硝酸盐或亚硝酸盐的形式被催化剂氧化储存； (1) When the instantaneous emission concentration of NO x in the industrial flue gas is high, pass the industrial flue gas into the catalyst layer, and the NO x in it is oxidized and stored by the catalyst in the form of nitrate or nitrite;
(2)工业烟气中NO x的瞬时排放浓度较低时，对工业烟气加热，同时喷入还原剂，释放并还原被储存的NO x。 (2) When the instantaneous emission concentration of NO x in the industrial flue gas is low, the industrial flue gas is heated and a reducing agent is injected at the same time to release and reduce the stored NO x .
作为本申请可选的技术方案，步骤(1)所述工业烟气中NO x的瞬时排放浓度高于步骤(2)所述工业烟气中NO x的瞬时排放浓度。 As an alternative aspect of the present application, the step (1) of the industrial flue gas instantaneous concentration of NO x emissions above step (2) of the industrial flue gas instantaneous concentration of NO x emissions.
可选地，步骤(1)所述工业烟气中NO x的瞬时排放浓度高于100mg/m 3，例如可以是150mg/m 3、200mg/m 3、250mg/m 3、300mg/m 3、350mg/m 3、400mg/m 3、450mg/m 3、500mg/m 3、550mg/m 3、600mg/m 3、650mg/m 3、700mg/m 3、750mg/m 3、800mg/m 3、950mg/m 3或1000mg/m 3，且峰值浓度为10000mg/m 3。 Optionally, the instantaneous emission concentration of NO x in the industrial flue gas in step (1) is higher than 100 mg/m 3 , for example, it can be 150 mg/m 3 , 200 mg/m 3 , 250 mg/m 3 , 300 mg/m 3 , 350mg/m 3 , 400mg/m 3 , 450mg/m 3 , 500mg/m 3 , 550mg/m 3 , 600mg/m 3 , 650mg/m 3 , 700mg/m 3 , 750mg/m 3 , 800mg/m 3 , 950mg/m 3 or 1000mg/m 3 , and the peak concentration is 10000mg/m 3 .
可选地，步骤(2)所述工业烟气中NO x的瞬时排放浓度为0～100mg/m 3，例如可以是10mg/m 3、20mg/m 3、30mg/m 3、40mg/m 3、50mg/m 3、60mg/m 3、70mg/m 3、80mg/m 3或90mg/m 3。 Optionally, the instantaneous emission concentration of NO x in the industrial flue gas in step (2) is 0-100 mg/m 3 , for example, it can be 10 mg/m 3 , 20 mg/m 3 , 30 mg/m 3 , 40 mg/m 3 , 50mg/m 3 , 60mg/m 3 , 70mg/m 3 , 80mg/m 3 or 90mg/m 3 .
本申请利用催化剂上的储存组分将瞬时排放浓度较高的NO x储存在催化剂上，在瞬时排放浓度较低时释放并加以还原，有效避免了由于瞬时排放浓度剧烈变化引起的相关工业烟气脱硝技术对于波动性烟气条件响应时间慢、瞬时高浓度不能达到排放标准等问题。 The present application uses the storage components on the catalyst to store NO x with a higher instantaneous emission concentration on the catalyst, and releases and reduces it when the instantaneous emission concentration is low, effectively avoiding the related industrial flue gas caused by the sudden change of the instantaneous emission concentration The denitrification technology has slow response time to fluctuating flue gas conditions, and the instantaneous high concentration cannot meet the emission standards.
具体地，所述方法包括如下步骤：Specifically, the method includes the following steps:
(Ⅰ)当在线监测装置检测NO x瞬时排放浓度高于100mg/m 3，且峰值浓度可达10000mg/m 3时，利用催化剂上的氧化活性组分将通入储存还原脱硝装置中的NO氧化成NO 2； (Ⅰ) When the on-line monitoring device detects that the instantaneous emission concentration of NO x is higher than 100mg/m 3 , and the peak concentration can reach 10000mg/m 3 , the oxidation active component on the catalyst is used to oxidize the NO in the storage reduction denitrification device Into NO 2 ;
所述的化学反应包括但不限于以下反应：The chemical reactions include but are not limited to the following reactions:
NO(g)→NO(ad)NO(g)→NO(ad)
O 2(g)→O 2(ad)→2O(ad) O 2 (g)→O 2 (ad)→2O(ad)
O(ad)+NO(g)→NO 2(g) O(ad)+NO(g)→NO 2 (g)
O(ad)+NO(ad)→NO 2(ad) O(ad)+NO(ad)→NO 2 (ad)
NO 2(g)→NO 2(ad) NO 2 (g)→NO 2 (ad)
(Ⅱ)利用催化剂上的储存组分与氧化后的NO 2反应，使其以硝酸盐或亚硝酸盐的形式储存在催化剂上； (II) Utilize the storage components on the catalyst to react with the oxidized NO 2 to store it on the catalyst in the form of nitrate or nitrite;
所述的化学反应包括但不限于以下反应：The chemical reactions include but are not limited to the following reactions:
BaCO 3+2NO 2(ad)+O(ad)→Ba(NO 3) 2+CO 2(g) BaCO 3 +2NO 2 (ad)+O(ad)→Ba(NO 3 ) 2 +CO 2 (g)
K 2CO 3+2NO(ad)+O(ad)→2KNO 2+CO 2(g) K 2 CO 3 +2NO(ad)+O(ad)→2KNO 2 +CO 2 (g)
K 2CO 3+2NO(ad)+3O(ad)→2KNO 3+CO 2(g) K 2 CO 3 +2NO(ad)+3O(ad)→2KNO 3 +CO 2 (g)
K 2CO 3+2NO 2(ad)+O(ad)→2KNO 3+CO 2(g) K 2 CO 3 +2NO 2 (ad)+O(ad)→2KNO 3 +CO 2 (g)
(Ⅲ)当在线监测装置检测NO x瞬时排放浓度为0～100mg/m 3时，加热装置与还原剂喷射装置处于开启状态时，催化剂上的NO x缓慢释放并还原成N 2。 (Ⅲ) When the on-line monitoring device detects that the instantaneous emission concentration of NO x is 0-100 mg/m 3 , and the heating device and the reductant injection device are turned on, the NO x on the catalyst is slowly released and reduced to N 2 .
可选地，所述的化学反应包括但不限于以下反应：Optionally, the chemical reactions include but are not limited to the following reactions:
3Ba(NO 3) 2+10NH 3(g)→8N 2(g)+3BaO+15H 2O 3Ba(NO 3 ) 2 +10NH 3 (g)→8N 2 (g)+3BaO+15H 2 O
作为本申请可选的技术方案，所述方法还包括在步骤(1)之前对所述工业 烟气进行除尘和脱硫处理。As an optional technical solution of the present application, the method further includes performing dust removal and desulfurization treatment on the industrial flue gas before step (1).
作为本申请可选的技术方案，所述工业烟气中NO x的瞬时排放浓度呈周期性变化。 As an alternative aspect of the present application, the industrial flue gas concentration of NO x emissions instantaneous changes periodically.
可选地，所述工业烟气为有色冶炼烟气或回转窑烟气。Optionally, the industrial flue gas is non-ferrous smelting flue gas or rotary kiln flue gas.
作为本申请可选的技术方案，步骤(1)所述氧化储存过程的工业烟气温度为100℃～250℃，例如可以是110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃或240℃。As an optional technical solution of this application, the temperature of industrial flue gas in the oxidation storage process in step (1) is 100°C to 250°C, for example 110°C, 120°C, 130°C, 140°C, 150°C, 160°C , 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃ or 240℃.
可选地，步骤(2)所述加热过程包括：由步骤(1)所述氧化储存过程的工业烟气温度升温至350～450℃，例如可以从100℃升温至350℃、110℃升温至350℃、120℃升温至360℃、130℃升温至360℃、140℃升温至380℃、150℃升温至380℃、160℃升温至400℃、170℃升温至400℃、180℃升温至420℃、190℃升温至420℃、200℃升温至440℃、210℃升温至440℃、220℃升温至450℃、230℃升温至450℃、240℃升温至450℃或250℃升温至450℃。Optionally, the heating process in step (2) includes: raising the temperature of industrial flue gas in the oxidation storage process in step (1) to 350-450°C, for example, from 100°C to 350°C, 110°C to 110°C 350°C, 120°C to 360°C, 130°C to 360°C, 140°C to 380°C, 150°C to 380°C, 160°C to 400°C, 170°C to 400°C, 180°C to 420 ℃, 190℃ to 420℃, 200℃ to 440℃, 210℃ to 440℃, 220℃ to 450℃, 230℃ to 450℃, 240℃ to 450℃ or 250℃ to 450℃ .
可选地，步骤(2)所述NO x缓慢释放过程通过控制升温速率实现，进一步可选地，所述的升温速率为5℃/min～30℃/min，例如可以是5℃/min、10℃/min、15℃/min、20℃/min、25℃/min或30℃/min。本申请通过对烟气进行缓慢升温来达到控制催化剂中NO x释放速率的目的。 Optionally, the slow release process of NO x in step (2) is achieved by controlling the heating rate. Further optionally, the heating rate is 5°C/min-30°C/min, for example, 5°C/min, 10℃/min, 15℃/min, 20℃/min, 25℃/min or 30℃/min. This application of the flue gas by slowly warmed to achieve the purpose of controlling the rate of release of NO x in the catalyst is.
作为本申请可选的技术方案，步骤(1)所述催化剂包括氧化还原活性组分、储存组分和载体。As an optional technical solution of this application, the catalyst in step (1) includes a redox active component, a storage component and a carrier.
可选地，所述氧化还原活性组分包括铂基催化剂、锰基催化剂和铜基催化剂。Optionally, the redox active component includes a platinum-based catalyst, a manganese-based catalyst, and a copper-based catalyst.
可选地，所述储存组分包括钡基催化剂和钾基催化剂。Optionally, the storage component includes a barium-based catalyst and a potassium-based catalyst.
可选地，所述载体包括铝基催化剂和钛基催化剂。Optionally, the support includes an aluminum-based catalyst and a titanium-based catalyst.
步骤(2)所述的还原剂选自氢气、一氧化碳、丙烯或氨气中的一种或至少两种的混合物，例如可以是氢气和一氧化碳的混合物、氢气和丙烯的混合物、氢气和氨气的混合物、一氧化碳和丙烯的混合物、一氧化碳和氨气的混合物或丙烯和氨气的混合物。The reducing agent in step (2) is selected from one or a mixture of at least two of hydrogen, carbon monoxide, propylene, or ammonia, for example, a mixture of hydrogen and carbon monoxide, a mixture of hydrogen and propylene, and a mixture of hydrogen and ammonia. A mixture, a mixture of carbon monoxide and propylene, a mixture of carbon monoxide and ammonia, or a mixture of propylene and ammonia.
第二方面，本申请提供了一种实现如第一方面所述的储存还原脱硝方法的系统，所述系统包括顺次连接的加热装置和储存还原脱硝反应装置，所述储存还原脱硝反应装置的腔体上方设置有还原剂喷射装置，所述储存还原脱硝反应装置采用固化床反应器。本申请提供的储存还原脱硝反应塔为固定床，可以实现原位储存和还原过程，不使用循环流化床的原因在于，循环流化床想要实现将固相流化的目的对于物料物性是有比较高的要求的，即对催化剂本身性质、成型制作都有严格要求。如粒度较大的颗粒存在中心处上升，一定高度在边缘处回落的返混现象；而粘性较大的颗粒粒度需控制在20μm以下等问题。这使得循环流化床在设计中需要注意输送分离高度的问题，即受催化剂物性和气体流速的影响，循环流化床反应器的设计要求比较高，否则达不到使固相流化的目的，而且极易造成循环率下降、气固接触时间短、催化剂利用率下降等问题。因此，本申请选择了固定床反应器作为储存还原脱硝反应塔。In the second aspect, the present application provides a system for implementing the storage reduction denitration method as described in the first aspect. The system includes a heating device and a storage reduction denitration reaction device that are sequentially connected. A reductant injection device is arranged above the cavity, and the storage reduction denitration reaction device adopts a solidified bed reactor. The storage reduction denitrification reaction tower provided by this application is a fixed bed, which can realize the in-situ storage and reduction process. The reason why the circulating fluidized bed is not used is that the purpose of the circulating fluidized bed to fluidize the solid phase is that the physical properties of the material are There are relatively high requirements, that is, there are strict requirements on the properties and molding of the catalyst itself. For example, the particles with larger particle size will rise at the center and fall back at the edge at a certain height; while the particle size of the particles with larger viscosity needs to be controlled below 20μm. This makes the design of circulating fluidized bed need to pay attention to the problem of transport and separation height, that is, affected by the physical properties of the catalyst and the gas flow rate, the design requirements of the circulating fluidized bed reactor are relatively high, otherwise the purpose of solid phase fluidization will not be achieved. , And it is easy to cause problems such as decreased circulation rate, short gas-solid contact time, and decreased catalyst utilization rate. Therefore, this application selects a fixed bed reactor as the storage reduction denitration reaction tower.
作为本申请可选的技术方案，所述系统还包括顺次连接的除尘装置和脱硫装置，所述脱硫装置出口连接所述加热装置入口。本申请在系统前端设有脱硫装置，避免催化剂硫化中毒问题。As an optional technical solution of the present application, the system further includes a dust removal device and a desulfurization device connected in sequence, and the outlet of the desulfurization device is connected to the inlet of the heating device. This application is equipped with a desulfurization device at the front end of the system to avoid the problem of catalyst vulcanization poisoning.
可选地，所述脱硫装置与所述加热装置的连接管路上还设置有烟气在线监测装置。本申请设有在线监测装置，可根据NO x瞬时排放浓度变化情况来实现 智能调节，决定加热装置和还原剂喷射装置的开启或关闭。 Optionally, a flue gas online monitoring device is also provided on the connecting pipeline between the desulfurization device and the heating device. The application is equipped with an online monitoring device, which can realize intelligent adjustment according to the change of the instantaneous emission concentration of NO x , and determine the opening or closing of the heating device and the reducing agent injection device.
本申请根据NO x瞬时浓度变化情况，将脱硝分为储存过程和还原过程，首先利用烟气在线监测装置检测工业烟气中的NO x瞬时排放浓度。当烟气在线监测装置检测工业烟气中的NO x瞬时排放浓度高于100mg/m 3时，加热装置和还原剂喷射装置处于关闭状态，工业烟气发生氧化储存过程，烟气中的NO x以硝酸盐或亚硝酸盐的形式储存在催化剂上。当烟气在线监测装置检测工业烟气中NO x瞬时排放浓度为0～100mg/m 3时，开启加热装置和还原剂喷射装置，工业烟气发生释放还原过程，催化剂上的NO x释放出来并还原成N 2。 This application is based on the instantaneous NO x concentration, the denitration process and into storage reduction process, firstly the instantaneous NO x emission concentration of gas-line monitoring of industrial flue gas detecting means. When the flue gas online monitoring device detects that the instantaneous emission concentration of NO x in the industrial flue gas is higher than 100 mg/m 3 , the heating device and the reductant injection device are turned off, the industrial flue gas undergoes an oxidation storage process, and the NO x in the flue gas It is stored on the catalyst in the form of nitrate or nitrite. When the flue gas online monitoring device detects that the instantaneous emission concentration of NO x in the industrial flue gas is 0-100 mg/m 3 , the heating device and the reductant injection device are turned on, and the industrial flue gas is released and reduced, and the NO x on the catalyst is released and combined Reduce to N 2 .
可选地，所述系统还包括与所述储存还原脱硝反应装置出口连接的烟气排放烟囱。Optionally, the system further includes a flue gas discharge chimney connected to the outlet of the storage reduction denitration reaction device.
作为本申请可选的技术方案，所述除尘装置为旋风除尘器、布袋除尘器或电袋除尘器。As an optional technical solution of this application, the dust removal device is a cyclone dust collector, a bag dust collector or an electric bag dust collector.
可选地，所述脱硫装置为循环流化床半干法脱硫装置、SDA脱硫装置或湿法脱硫装置。Optionally, the desulfurization device is a circulating fluidized bed semi-dry desulfurization device, an SDA desulfurization device or a wet desulfurization device.
可选地，所述的加热装置为热风炉。Optionally, the heating device is a hot blast stove.
作为本申请可选的技术方案，所述储存还原脱硝反应装置包括腔体，所述腔体顶部烟气入口处设置有导流叶片，所述导流叶片下方依次设置有气体整流装置、还原剂喷射装置、静态混合装置和催化剂填料层。As an optional technical solution of the present application, the storage reduction denitration reaction device includes a cavity, and a guide vane is arranged at the flue gas inlet of the top of the cavity, and a gas rectifying device and a reducing agent are sequentially arranged below the guide vane. Injection device, static mixing device and catalyst packing layer.
可选地，所述储存还原脱硝反应装置还包括与所述还原剂喷射装置电性连接的控制系统。Optionally, the storage reduction denitration reaction device further includes a control system electrically connected to the reducing agent injection device.
可选地，所述催化剂填料层包括至少一层催化剂填料，可选包括三层催化剂填料。通过三层催化剂填料层的储存作用，实现催化剂对NO x的高效储存。 Optionally, the catalyst filler layer includes at least one layer of catalyst filler, and optionally includes three layers of catalyst filler. Through the storage function of the three-layer catalyst packing layer, the efficient storage of NO x by the catalyst is realized.
可选地，所述气体整流装置和静态混合装置均为不锈钢材质。Optionally, the gas rectifying device and the static mixing device are made of stainless steel.
本申请所述的数值范围不仅包括上述例举的点值，还包括没有例举出的上述数值范围之间的任意的点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。The numerical range described in this application not only includes the above-exemplified point values, but also includes any point value between the above-mentioned numerical ranges that are not exemplified. Due to the limitation of space and for the sake of brevity, this application will not exhaustively list all the points. The specific point value included in the range.
与现有技术相比，本申请的有益效果为：Compared with the prior art, the beneficial effects of this application are:
(1)本申请利用催化剂上的储存组分将瞬时排放浓度较高的NO x储存在催化剂上，在瞬时排放浓度较低时释放并加以还原，有效避免了由于瞬时排放浓度剧烈变化引起的相关工业烟气脱硝技术对于波动性烟气条件响应时间慢，瞬时高浓度不能达到排放标准等问题，采用本申请提供的工业烟气储存还原脱硝方法，在一个储存还原周期内NO x的总去除率可达到95％以上。 (1) This application uses the storage components on the catalyst to store the NO x with a higher instantaneous emission concentration on the catalyst, and release and reduce it when the instantaneous emission concentration is low, effectively avoiding the correlation caused by the sudden change of the instantaneous emission concentration. Industrial flue gas denitrification technology has slow response time to fluctuating flue gas conditions, and the instantaneous high concentration cannot meet the emission standards. Using the industrial flue gas storage reduction denitrification method provided in this application, the total removal rate of NO x in a storage reduction cycle Can reach more than 95%.
(2)本申请实现了催化剂在反应过程中不断再生，避免了副产物二次污染问题。(2) This application realizes that the catalyst is continuously regenerated during the reaction process, and the problem of secondary pollution by by-products is avoided.
在阅读并理解了详细描述和附图后，可以明白其他方面。After reading and understanding the detailed description and drawings, other aspects can be understood.
附图说明Description of the drawings
图1是本申请背景技术提供的NO x瞬时排放浓度的周期性变化规律示意图； Fig. 1 is a schematic diagram of the periodic change rule of the instantaneous emission concentration of NO x provided by the background art of the present application;
图2是本申请一个具体实施方式提供的储存还原脱硝装置的结构连接示意图；2 is a schematic diagram of the structural connection of a storage reduction denitration device provided by a specific embodiment of the present application;
其中：1-除尘装置；2-脱硫装置；3-烟气在线监测装置；4-热风炉；5-导流叶片；6-气体整流器；7-还原剂喷射装置；8-控制系统；9-静态混合器；10-催化剂填料层；11-储存还原脱硝反应装置；12-烟囱。Among them: 1- dust removal device; 2- desulfurization device; 3- flue gas online monitoring device; 4- hot blast stove; 5- guide vane; 6-gas rectifier; 7- reductant injection device; 8- control system; 9- Static mixer; 10-catalyst packing layer; 11-storage reduction denitration reaction device; 12-chimney.
下面对本申请进一步详细说明。但下述的实例仅仅是本申请的简易例子， 并不代表或限制本申请的权利保护范围，本申请的保护范围以权利要求书为准。The application is described in further detail below. However, the following examples are only simple examples of this application, and do not represent or limit the scope of protection of this application. The scope of protection of this application is subject to the claims.
具体实施方式detailed description
下面结合附图并通过具体实施方式来进一步说明本申请的技术方案。The technical solutions of the present application will be further described below in conjunction with the drawings and specific implementations.
在一个具体实施方式中，本申请提供了一种工业烟气储存还原脱硝系统，所述系统如图2所示，包括依次连接的除尘装置1、脱硫装置2、热风炉4、储存还原脱硝反应装置11。所述脱硫装置2和热风炉4的连接管路上设有烟气在线监测装置3。In a specific embodiment, the present application provides an industrial flue gas storage reduction denitrification system. As shown in Figure 2, the system includes a dust removal device 1, a desulfurization device 2, a hot blast stove 4, and a storage reduction denitration reaction.装置11。 Device 11. A flue gas online monitoring device 3 is provided on the connecting pipeline of the desulfurization device 2 and the hot blast stove 4.
所述除尘装置1下部设有烟气入口，上部设有烟气出口；脱硫装置2下部设有烟气入口，顶部设有烟气出口；热风炉4下部设有烟气入口，上部设有烟气出口；储存还原脱硝反应装置11上部设有烟气入口，下部设有烟气出口。The lower part of the dust removal device 1 is provided with a flue gas inlet and the upper part is provided with a flue gas outlet; the lower part of the desulfurization device 2 is provided with a flue gas inlet and the top is provided with a flue gas outlet; the hot blast stove 4 is provided with a flue gas inlet in the lower part and a flue gas outlet on the upper part. Gas outlet; the upper part of the storage reduction denitration reaction device 11 is provided with a flue gas inlet, and the lower part is provided with a flue gas outlet.
除尘装置1的烟气出口与脱硫装置2的烟气入口相连，脱硫装置2的烟气出口与热风炉4的烟气入口相连，脱硫装置2和热风炉4的连接管路上还外接有烟气在线监测装置3，热风炉4的烟气出口与储存还原脱硝反应装置11的烟气入口相连，储存还原脱硝反应装置11的烟气出口与烟囱12烟气入口相连。The flue gas outlet of the dust removal device 1 is connected to the flue gas inlet of the desulfurization device 2, the flue gas outlet of the desulfurization device 2 is connected to the flue gas inlet of the hot blast stove 4, and the connecting pipe between the desulfurization device 2 and the hot blast stove 4 is also connected with flue gas In the online monitoring device 3, the flue gas outlet of the hot blast stove 4 is connected to the flue gas inlet of the storage reduction denitrification reaction device 11, and the flue gas outlet of the storage reduction denitrification reaction device 11 is connected to the flue gas inlet of the chimney 12.
所述储存还原脱硝反应装置11的烟气入口设有导流叶片5，导流叶片5下方依次设有气体整流器6、还原剂喷射装置7、静态混合器9和催化剂填料层10，所述储存还原脱硝反应装置11还包括与所述的还原剂喷射装置7电性连接的控制系统8。气体整流器6和静态混合器9均为不锈钢材质。The flue gas inlet of the storage reduction denitrification reaction device 11 is provided with a guide vane 5, and a gas rectifier 6, a reducing agent injection device 7, a static mixer 9 and a catalyst packing layer 10 are sequentially arranged below the guide vane 5. The reduction denitration reaction device 11 also includes a control system 8 electrically connected to the reducing agent injection device 7. Both the gas rectifier 6 and the static mixer 9 are made of stainless steel.
本申请对催化剂填料层10的催化剂填料层数不作具体限定，本领域的技术人员需要根据工业烟气的实际工况对催化剂层数进行实时调整，示例性地，如图2所示，所述的催化剂填料层包括三层催化剂填料，通过三层催化剂填料层 的储存作用，可以实现催化剂对NO x的高效储存。 This application does not specifically limit the number of catalyst filler layers of the catalyst filler layer 10, and those skilled in the art need to adjust the number of catalyst layers in real time according to the actual working conditions of industrial flue gas. Illustratively, as shown in FIG. The catalyst packing layer includes three layers of catalyst packing. Through the storage function of the three layers of catalyst packing layers, the efficient storage of NO x by the catalyst can be realized.
在另一个具体实施方式中，本申请提供了一种工业烟气储存还原脱硝方法，具体操作包括以下步骤：In another specific embodiment, this application provides an industrial flue gas storage reduction denitration method, the specific operation includes the following steps:
(1)工业烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度高于100mg/m 3时，关闭热风炉和还原剂喷射装置。烟气流过储存还原脱硝反应装置中的催化剂填料层，与催化剂上的氧化活性组分和储存组分发生所述氧化储存过程，烟气中的NO x以硝酸盐或亚硝酸盐的形式储存在催化剂上。 (1) After the industrial flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off. The flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst.
(2)工业烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度在0～100mg/m 3的范围内，开启热风炉和还原剂喷射装置。烟气由氧化储存过程时的烟气温度缓慢升温至350℃，在还原剂和温度的影响下催化剂上的NO x被缓慢释放并还原成N 2。 (2) After the industrial flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on . The flue gas is slowly raised from the flue gas temperature during the oxidation storage process to 350°C. Under the influence of the reducing agent and the temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
实施例1Example 1
本实施例提供了一种工业烟气储存还原脱硝方法，在具体实施方式提供的系统进行，具体操作包括以下步骤：This embodiment provides an industrial flue gas storage reduction denitrification method, which is performed in the system provided in the specific implementation mode, and the specific operation includes the following steps:
(1)工业烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度高于100mg/m 3时，关闭热风炉和还原剂喷射装置。烟气流过储存还原脱硝反应装置中的催化剂填料层，与催化剂上的氧化活性组分和储存组分发生所述氧化储存过程，烟气中的NO x以硝酸盐或亚硝酸盐的形式储存在催化剂上，所述氧化储存过程烟气温度为100℃。 (1) After the industrial flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off. The flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst, the flue gas temperature during the oxidation storage process is 100°C.
(2)工业烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度在0～100mg/m 3的范围内，开启热风炉和还原 剂喷射装置。烟气由100℃缓慢升温至350℃，升温速率为30℃/min，在还原剂和温度的影响下催化剂上的NO x被缓慢释放并还原成N 2。 (2) After the industrial flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on . The flue gas is slowly raised from 100°C to 350°C at a rate of 30°C/min. Under the influence of the reducing agent and temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
该实施例可以使一个储存、还原周期内NO x总的去除率达到95％以上。 This embodiment can make the total removal rate of NO x in one storage and reduction cycle reach more than 95%.
实施例2Example 2
本实施例提供了一种工业烟气储存还原脱硝方法，在具体实施方式提供的系统进行，具体操作包括以下步骤：This embodiment provides an industrial flue gas storage reduction denitrification method, which is performed in the system provided in the specific implementation mode, and the specific operation includes the following steps:
(1)烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度高于100mg/m 3时，关闭热风炉和还原剂喷射装置。烟气流过储存还原脱硝反应装置中的催化剂填料层，与催化剂上的氧化活性组分和储存组分发生所述氧化储存过程，烟气中的NO x以硝酸盐或亚硝酸盐的形式储存在催化剂上，所述氧化储存过程烟气温度为150℃。 (1) After the flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off. The flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst, the flue gas temperature during the oxidation storage process is 150°C.
(2)烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度在0～100mg/m 3的范围内，开启热风炉和还原剂喷射装置。烟气由150℃缓慢升温至400℃，升温速率为20℃/min，在还原剂和温度的影响下催化剂上的NO x被缓慢释放并还原成N 2。 (2) After the flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on. The flue gas is slowly raised from 150°C to 400°C at a rate of 20°C/min. Under the influence of the reducing agent and temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
该实施例可以使一个储存、还原周期内NO x总的去除率达到97.2％。 This embodiment can make the total removal rate of NO x in one storage and reduction cycle reach 97.2%.
实施例3Example 3
本实施例提供了一种工业烟气储存还原脱硝方法，在具体实施方式提供的系统进行，具体操作包括以下步骤：This embodiment provides an industrial flue gas storage reduction denitrification method, which is performed in the system provided in the specific implementation mode, and the specific operation includes the following steps:
(1)烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度高于100mg/m 3时，关闭热风炉和还原剂喷射装置。烟气流过储存还原脱硝反应装置中的催化剂填料层，与催化剂上的氧化活 性组分和储存组分发生所述氧化储存过程，烟气中的NO x以硝酸盐或亚硝酸盐的形式储存在催化剂上，所述氧化储存过程烟气温度为200℃。 (1) After the flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off. The flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst, the flue gas temperature during the oxidation storage process is 200°C.
(2)烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度在0～100mg/m 3的范围内，开启热风炉和还原剂喷射装置。烟气由200℃缓慢升温至420℃，升温速率为10℃/min，在还原剂和温度的影响下催化剂上的NO x被缓慢释放并还原成N 2。 (2) After the flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on. The flue gas is slowly raised from 200°C to 420°C at a rate of 10°C/min. Under the influence of the reducing agent and temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
该实施例可以使一个储存、还原周期内NO x总的去除率达到96.4％。 This embodiment can make the total removal rate of NO x within one storage and reduction cycle reach 96.4%.
实施例4Example 4
本实施例提供了一种工业烟气储存还原脱硝方法，在具体实施方式提供的系统进行，具体操作包括以下步骤：This embodiment provides an industrial flue gas storage reduction denitrification method, which is performed in the system provided in the specific implementation mode, and the specific operation includes the following steps:
(1)烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度高于100mg/m 3时，关闭热风炉和还原剂喷射装置。烟气流过储存还原脱硝反应装置中的催化剂填料层，与催化剂上的氧化活性组分和储存组分发生所述氧化储存过程，烟气中的NO x以硝酸盐或亚硝酸盐的形式储存在催化剂上，所述氧化储存过程烟气温度为250℃。 (1) After the flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is higher than 100 mg/m 3 , the hot blast stove and the reductant injection device are turned off. The flue gas flows through the catalyst packing layer in the storage reduction denitrification reaction device, and the oxidation storage process occurs with the oxidation active components and storage components on the catalyst, and the NO x in the flue gas is stored in the form of nitrate or nitrite On the catalyst, the flue gas temperature during the oxidation storage process is 250°C.
(2)烟气通过除尘装置和脱硫装置后经在线监测装置检测NO x的瞬时排放浓度，如果NO x瞬时排放浓度在0～100mg/m 3的范围内，开启热风炉和还原剂喷射装置。烟气由250℃缓慢升温至450℃，升温速率为5℃/min，在还原剂和温度的影响下催化剂上的NO x被缓慢释放并还原成N 2。 (2) After the flue gas passes through the dust removal device and the desulfurization device, the instantaneous emission concentration of NO x is detected by the online monitoring device. If the instantaneous emission concentration of NO x is within the range of 0-100 mg/m 3 , the hot blast stove and the reductant injection device are turned on. The flue gas is slowly raised from 250°C to 450°C at a rate of 5°C/min. Under the influence of the reducing agent and temperature, the NO x on the catalyst is slowly released and reduced to N 2 .
该实施例可以使一个储存、还原周期内NO x总的去除率达到96.8％。 This embodiment can make the total removal rate of NO x within one storage and reduction cycle reach 96.8%.
本领域的技术人员需要了解的是NO x总的去除率受众多因素影响，上述实施例中提供的去除率数据仅为实验室再生评价做出的参数数据，不作为工程再 生评价的指导性数据。 Those skilled in the art need to understand that the total removal rate of NO x is affected by many factors. The removal rate data provided in the above-mentioned embodiments are only parameter data made by laboratory regeneration evaluation, and not as guiding data for engineering regeneration evaluation. .
对比例1Comparative example 1
CN101422689B公开了一种循环流化床氮氧化物储存还原烟气的脱硝方法及其装置，采用与实施例1相同组成的工业烟气进行CN101422689B公开的脱硝方法，具体操作步骤包括：CN101422689B discloses a denitration method and device for flue gas storage reduction in circulating fluidized bed nitrogen oxides. Industrial flue gas with the same composition as in Example 1 is used to perform the denitration method disclosed in CN101422689B. The specific operation steps include:
工业烟气经烟气压缩机加压或加速后通过烟气喷嘴喷入流化床储存反应器，粉体NO x阱催化剂通过催化剂入口预先置于流化床NO x储存反应器内作为床料，烟气带动NO x阱催化剂一起流化。在NO x储存流化床反应器内实现NO x阱催化剂对NO x的储存，并从烟气中消除NO x，催化剂上存储的NO x可以为硝酸盐、亚硝酸盐或者其他形式的固定化的NO x(吸收、吸附或者氧化吸收)。 The industrial flue gas is pressurized or accelerated by the flue gas compressor and sprayed into the fluidized bed storage reactor through the flue gas nozzle. The powdered NO x trap catalyst is pre-placed in the fluidized bed NO x storage reactor through the catalyst inlet as the bed material , The flue gas drives the NO x trap catalyst to fluidize together. In the NO x storage fluidized bed reactor to achieve NO x stored on the NO x trap catalyst, and eliminates NO x from the flue gas, stored in the NO x catalyst may be a nitrate, nitrite, or other forms of immobilized NO x (absorption, adsorption or oxidation absorption).
流化床储存反应器中的烟气和储存NO x的催化剂通过烟气出口连接管进入气固分离器，气固相在气固分离器中实现气固相分离，气相可以直接通过净化气体出口达标排放或者在未达标情况下进入下级循环流化床NO x储存还原反应器进一步处理，储存NO x的固相催化剂颗粒进入流化床还原再生反应器。 The flue gas in the fluidized bed storage reactor and the catalyst storing NO x enter the gas-solid separator through the flue gas outlet connecting pipe. The gas-solid phase is separated in the gas-solid separator, and the gas phase can directly pass through the purified gas outlet Emissions that meet the standards or enter the lower-level circulating fluidized bed NO x storage reduction reactor for further treatment, and the solid-phase catalyst particles that store NO x enter the fluidized bed reduction regeneration reactor.
通过还原剂入口向流化床还原再生反应器中喷入还原剂，并带动固相催化剂流动，根据还原剂还原能力和催化剂的催化性能的强弱，通过加热器调节反应器的温度，最大限度实现NO x的选择性催化还原，同时实现NO x阱催化剂的再生。 The reductant is sprayed into the fluidized bed reduction regeneration reactor through the reductant inlet and drives the solid phase catalyst to flow. According to the reducing ability of the reductant and the catalytic performance of the catalyst, the temperature of the reactor is adjusted by the heater to maximize selective catalytic reduction of NO x to achieve, while achieving the regeneration of NO x trap catalyst.
综合分析本申请提供的工业烟气储存还原脱硝方法与对比例1提供的循环流化床氮氧化物储存还原烟气的脱硝方法可以发现：Comprehensive analysis of the industrial flue gas storage reduction denitrification method provided in this application and the denitration method of circulating fluidized bed nitrogen oxide storage reduction flue gas provided in Comparative Example 1 reveals:
(1)本申请提供的工业烟气储存还原脱硝方法是持续进行的循环过程，针对具有周期性排放特点的工业烟气，当NO x瞬时排放浓度较低时并不需要催化 剂将NO x储存，而对比例1采用了流化床反应器，无法实现原位储存和还原过程，因此会产生能源浪费的问题； (1) The industrial flue gas storage reduction denitrification method provided by this application is a continuous cyclic process. For industrial flue gas with periodic emission characteristics, when the instantaneous emission concentration of NO x is low, a catalyst is not required to store NO x . However, Comparative Example 1 uses a fluidized bed reactor, which cannot realize the in-situ storage and reduction process, so it will cause energy waste;
(2)对比例1采用了流化床反应器，由于流化床气固间接触时间短，储存的效率以及催化剂再生率都会受到限制；(2) Comparative Example 1 uses a fluidized bed reactor. Due to the short contact time between gas and solid in the fluidized bed, the storage efficiency and catalyst regeneration rate will be limited;
(3)工业烟气中催化剂用量大，可能存在烟气不足以将全部催化剂流化进入到下一反应器，从而导致物料循环性差，催化剂再生率低，甚至堵塞反应器的现象发生；(3) The amount of catalyst in the industrial flue gas is large, and the flue gas may not be enough to fluidize all the catalyst into the next reactor, resulting in poor material circulation, low catalyst regeneration rate, and even blockage of the reactor;
(4)对比例1只提到所述装置适用于与循环流化床烟气脱硫装置衔接使用，并没有设置脱硫装置，因此极易造成催化剂硫化中毒。(4) Comparative Example 1 only mentions that the device is suitable for use in conjunction with a circulating fluidized bed flue gas desulfurization device, and there is no desulfurization device, so it is very easy to cause catalyst sulfidation poisoning.
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。The applicant declares that the above are only specific implementations of this application, but the scope of protection of this application is not limited to this, and those skilled in the art should understand that any person skilled in the art disclosed in this application Within the technical scope, easily conceivable changes or substitutions fall within the scope of protection and disclosure of this application.

Claims (11)

  1. 一种工业烟气的储存还原脱硝方法，其中，所述方法包括：A storage reduction denitration method of industrial flue gas, wherein the method includes:
    (1)工业烟气中NO x的瞬时排放浓度较高时，将工业烟气通入催化剂层，其中的NO x以硝酸盐或亚硝酸盐的形式被催化剂氧化储存； (1) When the instantaneous emission concentration of NO x in the industrial flue gas is high, pass the industrial flue gas into the catalyst layer, and the NO x in it is oxidized and stored by the catalyst in the form of nitrate or nitrite;
    (2)工业烟气中NO x的瞬时排放浓度较低时，对工业烟气加热，同时喷入还原剂，释放并还原被储存的NO x。 (2) When the instantaneous emission concentration of NO x in the industrial flue gas is low, the industrial flue gas is heated and a reducing agent is injected at the same time to release and reduce the stored NO x .
  2. 根据权利要求1所述的储存还原脱硝方法，其中，步骤(1)所述工业烟气中NO x的瞬时排放浓度高于步骤(2)所述工业烟气中NO x的瞬时排放浓度； The storage according to claim 1, reduction denitration process wherein, (1) the instantaneous emission concentration of NO x in industrial flue gas is higher than the step of the step (2) the instantaneous concentration of NO x emissions from industrial flue gas;
    可选地，步骤(1)所述工业烟气中NO x的瞬时排放浓度高于100mg/m 3，且峰值浓度为10000mg/m 3； Optionally, the instantaneous emission concentration of NO x in the industrial flue gas in step (1) is higher than 100 mg/m 3 , and the peak concentration is 10000 mg/m 3 ;
    可选地，步骤(2)所述工业烟气中NO x的瞬时排放浓度为0～100mg/m 3。 Optionally, the instantaneous emission concentration of NO x in the industrial flue gas in step (2) is 0-100 mg/m 3 .
  3. 根据权利要求1或2所述的储存还原脱硝方法，其中，步骤(2)所述NO x释放过程通过控制升温速率实现缓慢释放，进一步可选地，所述的升温速率为5℃/min～30℃/min。 The storage reduction denitrification method according to claim 1 or 2, wherein the NO x release process in step (2) realizes slow release by controlling the heating rate, and further optionally, the heating rate is 5°C/min~ 30°C/min.
  4. 根据权利要求1或2所述的储存还原脱硝方法，其中，所述方法还包括在步骤(1)之前对所述工业烟气进行除尘和脱硫处理。The storage reduction denitration method according to claim 1 or 2, wherein the method further comprises performing dust removal and desulfurization treatment on the industrial flue gas before step (1).
  5. 根据权利要求1-4任一项所述的储存还原脱硝方法，其中，所述工业烟气中NO x的瞬时排放浓度呈周期性变化； Storage according to any one of claims 1-4 reduction denitration method, wherein the concentration of industrial flue gas instantaneous emission of NO x varies periodically;
    可选地，所述工业烟气为有色冶炼烟气或回转窑烟气。Optionally, the industrial flue gas is non-ferrous smelting flue gas or rotary kiln flue gas.
  6. 根据权利要求1-5任一项所述的储存还原脱硝方法，其中，步骤(1)所述氧化储存过程的工业烟气温度为100℃～250℃；The storage reduction denitration method according to any one of claims 1 to 5, wherein the temperature of the industrial flue gas in the oxidation storage process in step (1) is 100°C to 250°C;
    可选地，步骤(2)所述的工业烟气加热过程包括：由步骤(1)所述氧化 储存过程的工业烟气温度升温至350～450℃。Optionally, the industrial flue gas heating process in step (2) includes: raising the temperature of the industrial flue gas in the oxidation storage process in step (1) to 350-450°C.
  7. 根据权利要求1-6任一项所述的储存还原脱硝方法，其中，步骤(1)所述催化剂层包括氧化还原活性组分、储存组分和载体；The storage reduction denitration method according to any one of claims 1 to 6, wherein the catalyst layer in step (1) comprises a redox active component, a storage component and a carrier;
    可选地，所述氧化还原活性组分包括铂基催化剂、锰基催化剂和铜基催化剂；Optionally, the redox active component includes a platinum-based catalyst, a manganese-based catalyst, and a copper-based catalyst;
    可选地，所述储存组分包括钡基催化剂和钾基催化剂；Optionally, the storage component includes a barium-based catalyst and a potassium-based catalyst;
    可选地，所述载体包括铝基催化剂和钛基催化剂；Optionally, the carrier includes an aluminum-based catalyst and a titanium-based catalyst;
    步骤(2)所述的还原剂选自氢气、一氧化碳、丙烯或氨气中的一种或至少两种的混合物。The reducing agent in step (2) is selected from one or a mixture of at least two of hydrogen, carbon monoxide, propylene or ammonia.
  8. 一种实现权利要求1-7任一项所述储存还原脱硝方法的系统，其中，所述系统包括顺次连接的加热装置和储存还原脱硝反应装置，所述储存还原脱硝反应装置的腔体上方设置有还原剂喷射装置，所述储存还原脱硝反应装置采用固化床反应器。A system for realizing the storage-reduction denitration method of any one of claims 1-7, wherein the system includes a heating device and a storage-reduction denitration reaction device connected in sequence, and the cavity of the storage-reduction denitration reaction device is above the A reductant injection device is provided, and the storage reduction denitration reaction device adopts a solidified bed reactor.
  9. 根据权利要求8所述的系统，其中，所述脱硫装置与所述加热装置的连接管路上还设置有烟气在线监测装置；The system according to claim 8, wherein the connecting pipeline between the desulfurization device and the heating device is also provided with a flue gas online monitoring device;
    可选地，所述系统还包括顺次连接的除尘装置和脱硫装置，所述脱硫装置出口连接所述加热装置入口；Optionally, the system further includes a dust removal device and a desulfurization device connected in sequence, and the outlet of the desulfurization device is connected to the inlet of the heating device;
    可选地，所述系统还包括与所述储存还原脱硝反应装置出口连接的烟气排放烟囱。Optionally, the system further includes a flue gas discharge chimney connected to the outlet of the storage reduction denitration reaction device.
  10. 根据权利要求8或9所述的系统，其中，所述除尘装置为旋风除尘器、布袋除尘器或电袋除尘器；The system according to claim 8 or 9, wherein the dust removal device is a cyclone dust collector, a bag dust collector or an electric bag dust collector;
    可选地，所述脱硫装置为循环流化床半干法脱硫装置、SDA脱硫装置或湿 法脱硫装置；Optionally, the desulfurization device is a circulating fluidized bed semi-dry desulfurization device, an SDA desulfurization device or a wet desulfurization device;
    可选地，所述的加热装置为热风炉。Optionally, the heating device is a hot blast stove.
  11. 根据权利要求8-10任一项所述的系统，其中，所述储存还原脱硝反应装置包括腔体，所述腔体顶部烟气入口处设置有导流叶片，所述导流叶片下方依次设置有气体整流装置、还原剂喷射装置、静态混合装置和催化剂填料层；The system according to any one of claims 8-10, wherein the storage reduction denitration reaction device comprises a cavity, and a guide vane is provided at the flue gas inlet at the top of the cavity, and the guide vane is sequentially arranged below There are gas rectifying device, reducing agent injection device, static mixing device and catalyst packing layer;
    可选地，所述储存还原脱硝反应装置还包括与所述还原剂喷射装置电性连接的控制系统；Optionally, the storage reduction denitration reaction device further includes a control system electrically connected to the reducing agent injection device;
    可选地，所述催化剂填料层包括至少一层催化剂填料，可选包括三层催化剂填料；Optionally, the catalyst filler layer includes at least one layer of catalyst filler, and optionally includes three layers of catalyst filler;
    可选地，所述气体整流装置和静态混合装置均为不锈钢材质。Optionally, the gas rectifying device and the static mixing device are made of stainless steel.
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CN114470850A (en) * 2022-01-29 2022-05-13 成都易态科技有限公司 Yellow phosphorus furnace gas purification and utilization method
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