CN113813960A - Dual-functional powder and preparation method and application thereof - Google Patents

Dual-functional powder and preparation method and application thereof Download PDF

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CN113813960A
CN113813960A CN202110952393.6A CN202110952393A CN113813960A CN 113813960 A CN113813960 A CN 113813960A CN 202110952393 A CN202110952393 A CN 202110952393A CN 113813960 A CN113813960 A CN 113813960A
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powder
flue gas
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mass ratio
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CN113813960B (en
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沈岳松
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Nanjing Tech University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
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    • 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
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur 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
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • 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
    • B01D2257/404—Nitrogen oxides other than 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
    • B01D2258/0283—Flue gases

Abstract

The invention provides a bifunctional powder and a preparation method and application thereof, and is characterized by comprising a catalysis component and a reduction component, wherein the mass ratio of the catalysis component to the reduction component is 1: (0.1-20) mixing and ball-milling to obtain; the catalytic component takes one or more of transition metal oxide, noble metal or metal ion exchange type molecular sieves and light rare earth ore metal as active components, and the high-specific-surface industrial waste residue as a carrier, wherein the metal ion exchange type molecular sieves are one or more of the transition metal and noble metal active components; the reducing component is composite reducing functional powder formed by mixing activated carbon powder, melamine, plastic powder or rubber powder. The DCR purification technology disclosed by the invention is high in denitration and desulfurization efficiency, free of ammonia and urea spraying, green and environment-friendly in the whole process, low in operation cost, simple in process, free of secondary pollution and free of corrosion to equipment.

Description

Dual-functional powder and preparation method and application thereof
Technical Field
The invention relates to a bifunctional powder, a preparation method and application thereof, in particular to a bifunctional powder containing a catalytic component and a reduction component, a preparation method thereof and an application method in dynamic catalytic removal of NOx and SOx, belonging to the technical fields of air pollution treatment, industrial pollution emission reduction, environmental catalytic materials and the like.
Background
NOxAnd SOxIs the main reason for causing haze, acid rain and deteriorating the quality of the atmosphere, and is the key point for controlling the atmospheric pollution. As the criterial index becomes stricter, NOxThe main development process of the treatment technology is as follows: the low-nitrogen combustion technology → the selective non-catalytic reduction (SNCR) technology → the selective catalytic reduction technology, and the denitration effects of the three technologies are as follows: SCR is more than SNCR and is more than low-nitrogen combustion, wherein the SCR denitration technology has high efficiency and good stability, becomes the mainstream technology and the development direction of industrial flue gas denitration at home and abroad at present, and the technical core is to use the integral denitration catalyst. SO (SO)xThe main treatment techniques include wet, dry and semi-dry desulfurization techniques. At present, the denitration and desulfurization of industrial coal-fired flue gas mainly adopts a 'denitration and desulfurization' segmented integrated process, although NO can be realizedxAnd SOxThe ultra-low emission of (2) meets the requirement of environmental protection, but the existing integrated process has large occupied space, high investment cost and high operating cost, brings huge economic pressure to enterprise users, and urgently needs low-cost technical innovation. In addition, the existing SCR denitration technology is difficult to stably operate under the complex smoke in the non-electric industry.
In recent years, research on a process and key materials for simultaneously denitrating and desulfurizing flue gas has been reported, and the research is representatively listed as follows:
the patent (ZL201510098577.5) discloses a denitration desulfurization dust collector of burning flue gas and method thereof, and wherein the device is connected with at least one denitration desulfurization dust collector module according to burning flue gas flow direction in order, and every denitration desulfurization dust collector module is including the gas mixing unit and the air cleaning unit that connect in order, the gas mixing unit includes gas mixing inner chamber and with gas mixing inner chamber's the flue gas inlet and the air intlet of intercommunication, the air cleaning unit includes the exhanst gas outlet, the exhanst gas outlet communicates with the flue gas inlet of next stage denitration desulfurization dust collector module. The denitration, desulfurization and dust removal method provided by the invention utilizes air and water to carry out step denitration, removes particulate matters, greatly reduces the concentration of oxynitride, and can remove sulfides by using various wet desulfurization methods.
The patent (ZL201810668695.9) discloses a high-efficiency denitration and desulfurization agent prepared from carboxymethyl chitosan, urea, ammonium carbonate, dicyanodiamide and water as raw materials, and the substance of the high-efficiency denitration and desulfurization agent is a means for mainly denitration and desulfurization by obtaining ammonia from different ammonia sources, and the patent does not relate to a use process.
The patent (ZL201710839256.5) discloses a flue gas denitration, desulfurization and dust removal process, which is implemented by introducing coarse-grained desulfurizer into flue gas from a combustion device, pre-desulfurizing the flue gas, and then feeding the flue gas into a denitration reactor; and (4) enabling the denitrated flue gas to enter air/flue gas for heat exchange and cooling. Humidifying the cooled flue gas, and then feeding the flue gas into a dry desulfurization tower, wherein the dry desulfurization tower uses a dry powder desulfurizer; the desulfurized flue gas containing dust such as desulfurizer and the like after reaction enters a bag-type dust remover for dust removal, the hot air from the air/flue gas heat exchanger is mixed with the flue gas before or after the dust remover, and the flue gas which is purified and mixed with the hot air is introduced into a chimney for emission. The patent mainly adopts a process of sectionally integrating a desulfurizing tower, a denitration reactor and a bag-type dust remover.
The patent (ZL201310703127.5) discloses a honeycomb low-temperature synchronous desulfurization and denitrification catalyst and a preparation method thereof, and the honeycomb low-temperature synchronous desulfurization and denitrification catalyst is used in a traditional fixed bed process, occupies large space and has high investment cost.
The patent (ZL201210369470.6) discloses a method for simultaneously desulfurizing and denitrating flue gas, which comprises the steps of mixing a large amount of active substances generated by the flue gas under ultraviolet radiation with SO in the flue gas2And NOxThe reaction is carried out to generate two important industrial products of stable sulfuric acid and nitric acid, thereby simultaneously removing SO2And NOxThe effect of (1).
The patent (ZL200710067082.1) discloses a method for combined desulfurization and denitrification of flue gas, wherein flue gas to be treated enters a photocatalytic reactor, and NO in the flue gas is oxidized into NO under the action of ultraviolet light and a catalyst2The flue gas after oxidation reaction enters a double-alkali absorption reactor, and SO in the flue gas2Absorbed by alkali solution to obtain Na2SO3With NO in the flue gas2Reaction of NO with2Reduction to N2And (4) discharging.
The representative patent technologies mostly adopt a sectional integrated denitration and desulfurization process route, and most of the representative patent technologies are still established on the traditional denitration and desulfurization process using ammonia as a reducing agent or alkali liquor as an absorbent.
Disclosure of Invention
The invention aims to meet the important requirements of air pollution comprehensive treatment and emission reduction of industrial pollutants, creatively provides a dual-functional powder containing catalysis and reduction components aiming at the problems of high investment, large occupied space, high operation cost, ammonia escape, secondary pollution and harmless treatment of waste denitration catalysts and the like of the existing 'denitration and desulfurization' segmented integration process used for industrial coal-fired flue gas, and also aims to provide a preparation method of the dual-functional powder.
The technical scheme of the invention is as follows: the bifunctional powder is characterized by comprising a catalyzing component and a reducing component, wherein the mass ratio of the catalyzing component to the reducing component is 1: (0.1 to 20); the catalytic component takes one or more of transition metal oxide, noble metal or metal ion exchange type molecular sieves and light rare earth ore metal as active components, and the high-specific-surface industrial waste residue as a carrier, wherein the metal ion exchange type molecular sieves are one or more of the transition metal and noble metal active components; the reducing component is composite reducing functional powder formed by mixing activated carbon powder, melamine, plastic powder or rubber powder, wherein the mass ratio of the activated carbon powder to the melamine to the plastic powder to the rubber powder is 1: (0.1-10): (0.1-10): (0.1-10).
Preferably, the light rare earth mineral metal is at least one of La or Ce; the transition metal oxide is at least WO3、SnO2、MoO3、CoO、V2O5、CuO、TiO2、ZrO2、Fe2O3、MnO2、NiO、Al2O3Or ZnO; the noble metal is at least one of Pt, Ru, Pd, Au or Ag; the industrial waste residue with high specific surface area is one or more of fly ash, steel slag powder, red mud powder or carbide slag.
Preferably, the mass of the active component in the catalytic component accounts for 1-30% of the mass of the carrier, wherein the mass ratio of the light rare earth mineral metal to other active components is 1 (0.1-10).
The invention also provides a method for preparing the bifunctional powder, which is characterized in that the catalytic component and the reducing component are mixed according to a metering ratio and subjected to ball milling, and the mixture is milled into the composite bifunctional powder with the particle size of 80-300 meshes through mechanochemical action.
The invention also provides application of the bifunctional powder in denitration and desulfurization of coal-fired flue gas, namely Dynamic Catalytic Removal (DCR) NOxAnd SOx. The method comprises the following specific steps: spraying bifunctional powder with reduction and catalysis in a flue region at 150-500 ℃, quickly blowing the bifunctional powder under the convective impact of flue gas, fully mixing and contacting with the flue gas, and further adsorbing and capturing NOxAnd SOxAnd promote them to produce harmless N2Water vapor, CO2Sulfate or sulfurous acid, thereby realizing simultaneous and efficient denitration and desulfurization.
Preferably, the spraying quality and the treatment of SO of the bifunctional powder are optimized2The mass ratio of the NO treatment solution to the NO treatment solution is 1000 (20-500)xThe mass ratio of (A) to (B) is 1000 to (17-300). The bifunctional powder is used for treating SO2And NOxThe capacity of the powder is that each kg of the bifunctional powder is used for treating 20-500 g of SO2And 17 to 300g of NOxThe spraying amount of the actual dual-function powder is along with NO in the smokexAnd SO2The concentration of the flue gas and the size of the flue gas. The effective activity using temperature is 100-500 ℃, and the applicable flue gas flow rate is 1-7 m/s.
The DCR denitration and desulfurization integrated application method is mainly applied to fire coalThe denitration and desulfurization treatment of the flue gas is applicable to NO in the industries of boilers, coal-electricity, coking, steel, sintering, waste incineration and the likexAnd SOxThe high-efficiency purification is little influenced by complex working conditions.
Has the advantages that:
the DCR denitration and desulfurization technology provided by the invention has the advantages of high efficiency, no ammonia and urea spraying, green and environment-friendly whole process, no secondary pollution, no hazardous waste disposal, low operation cost, simple process, no need of large transformation of an equipment body, low one-time investment of technical improvement engineering, very small interference from working conditions and wide application range. Compared with the existing 'SCR denitration and desulfurization tower' sectional process, the denitration and desulfurization efficiency is equivalent, and the NO of the coal-fired flue gas can be realizedxAnd SOxThe emission is ultra-low, but the investment cost is far lower than that of the existing denitration and desulfuration segmentation process, and no secondary pollution is caused.
Drawings
FIG. 1 is a process flow diagram of a DCR denitration and desulfurization technology.
Detailed Description
The following describes in detail an embodiment of the DCR denitration and desulfurization technique of the present invention with reference to fig. 1.
Selecting a feeding port in a flue area at 150-500 ℃, weighing bifunctional powder according to a metering ratio, spraying the bifunctional powder into the flue through the feeding port by a gas conveying pump, allowing the sprayed bifunctional powder to generate convection with flue gas, rapidly dispersing the powder under the impact of the flue gas, fully mixing and contacting the powder and the flue gas components in the flowing and advancing process, and further adsorbing and capturing NOxAnd SOxAnd promoting them to have sufficient catalytic reaction in a flue gas pipeline at 100-500 ℃ so as to react NOxReduction to N2Promoting SOxGenerating harmless sulfate or sulfite, and finally recycling and disposing together through a dust collector. Under the conditions that the flow velocity of flue gas is 1-7 m/s, the flow field is uniformly mixed and the temperature is balanced, the denitration efficiency can reach more than 80%, and the desulfurization efficiency can approach 100%.
Example 1
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1:0.1, wherein the catalytic component is rare earth Ce,Transition metal oxide (WO)3、SnO2、MoO3、CoO、V2O5The mass ratio of the mixture is 1:1:1:1:1), the carrier is fly ash, and the mass percentage of the active component is 1 percent by taking the mass of the carrier as a reference, wherein the mass ratio of the rare earth Ce to the transition metal oxide is 0.1; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:0.1:0.1: 0.1). The powder has the granularity of 300 meshes. At the feeding port of the 500 ℃ flue, the original NO of the inlet flue gas is actually measuredxConcentration of 465ppm, SOxConcentration is 645ppm, 200g SO per kg bifunctional powder2And 17g NOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is measured and sprayed in, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 100 DEG CxConcentration 15ppm, SOxThe concentration is 1ppm, and when the flow velocity of the flue gas is 7m/s, the denitration efficiency can reach 96.8%, and the desulfurization efficiency reaches 99.8%.
Example 2
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1:1, wherein the catalytic component is rare earth La and transition metal oxide (CuO, TiO)2、ZrO2、Fe2O3、MnO2The mass ratio of the mixture is 1:1:1:1:1), the steel slag powder is taken as a carrier, the mass percentage of active components is 5 percent by taking the mass of the carrier as a reference, wherein the mass ratio of the rare earth La to the transition metal oxide is 0.5; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (the mass ratio is 1:5:5: 5). The powder has a granularity of 120 meshes. At the feeding port of the 400 ℃ flue area, the original NO of the inlet flue gas is actually measuredxConcentration 500ppm, SOxThe concentration is 500ppm, 200g SO is processed by each kg of the dual-function powder2And 70g NOxThe powder material is based on the SO contained in the actual flue gas2And NOxMetered injection of the total quantity throughA gas delivery pump, which sprays the difunctional powder with corresponding amount into the flue through the feeding port, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 100 DEG CxConcentration 30ppm, SOxThe concentration is 2ppm, and when the flow velocity of the flue gas is 6m/s, the denitration efficiency can reach 94%, and the desulfurization efficiency reaches 99.6%.
Example 3
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1:5, wherein the catalytic component is rare earth Ce and transition metal oxide (NiO, Al)2O3、ZnO、Fe2O3、MnO2The mass ratio of the red mud powder is 1:1:1:1), the red mud powder is taken as a carrier, the mass percentage of the active component is 10 percent by taking the mass of the carrier as a reference, wherein the mass ratio of the rare earth Ce to the transition metal oxide is 1; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (the mass ratio is 1:10:10: 10). The powder has a granularity of 120 meshes. At the feeding port of the 350 ℃ flue area, the original NO of the inlet flue gas is actually measuredxConcentration 130ppm, SOxConcentration of 280ppm, 20g SO per kg bifunctional powder2And 100g NOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is measured and sprayed in, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 280 DEG CxConcentration 25ppm, SOxThe concentration is 3ppm, when the flow velocity of the flue gas is 6m/s, the medium-low temperature short-flow denitration efficiency can reach 80.7%, and the desulfurization efficiency can reach 98.9%.
Example 4
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1: 15, wherein the catalytic component comprises rare earth Ce and La (mass ratio is 1:1), noble metal (mixture of Pd and Au, mass ratio is 1:1), carbide slag powder is used as a carrier, the mass of the carrier is used as a reference,the mass percent of the active component is 1.1 percent, wherein the mass ratio of the rare earth to the noble metal is 10; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (the mass ratio is 1:5:8: 10). The powder has the granularity of 200 meshes. At the feeding port of the 300 ℃ flue area, the original NO of the inlet flue gas is actually measuredxConcentration 130ppm, SOxThe concentration is 280ppm, and 500g SO is treated by each kg of the dual-function powder2And 200g NOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is measured and sprayed in, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 100 DEG CxConcentration 15ppm, SOxThe concentration is 1ppm, and when the flow velocity of flue gas is 5m/s, the low-temperature denitration efficiency can reach 88.5%, and the desulfurization efficiency can reach 99.6%.
Example 5
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1:10, wherein the catalytic component is rare earth La and noble metal (a mixture of Pt and Ru in a mass ratio of 1:1), the fly ash, the steel slag powder, the red mud powder and the carbide slag powder are mixed to form a carrier in a mass ratio of 1:1:1:1, the mass percentage of the active component is 1.2 percent on the basis of the mass of the carrier, and the mass ratio of the rare earth to the noble metal is 9; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (the mass ratio is 1:5:5: 10). The granularity of the powder is 250 meshes. At the feeding port of the 500 ℃ flue area, the original NO of the inlet flue gas is actually measuredxAt a concentration of 470ppm, SOxThe concentration is 500ppm, 400g SO is processed by each kg of the double-function powder2And 200gNOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is measured and sprayed in, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 100 DEG CxAt a concentration of 3ppm, SOxThe concentration is 1ppm, and when the flow velocity of flue gas is 1m/s, the low-temperature denitration efficiency can reach 99.4%, and the desulfurization efficiency can reach 99.8%.
Example 6
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1: 15, wherein the catalytic component is a mixture of rare earth Ce and noble metal (Ru and Ag, the mass ratio is 1:1), the steel slag powder, red mud powder and carbide slag powder are mixed to form a carrier (the mass ratio is 1:1:1), the mass percentage of the active component is 1.8 percent on the basis of the mass of the carrier, and the mass ratio of the rare earth to the noble metal is 8; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (the mass ratio is 1:5:5: 5). The granularity of the powder is 280 meshes. At the feeding port of the 500 ℃ flue area, the original NO of the inlet flue gas is actually measuredxConcentration of 370ppm, SOxThe concentration is 480ppm, 200g SO is processed by each kg of the dual-function powder2And 170gNOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is measured and sprayed in, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 100 DEG CxConcentration of 4ppm, SOxThe concentration is 2ppm, and when the flow velocity of the flue gas is 3m/s, the low-temperature denitration efficiency can reach 98.9%, and the desulfurization efficiency can reach 99.6%.
Example 7
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1: 20, wherein the catalytic component is rare earth Ce and La (the mass ratio is 1:1), the Ru/Pd exchange type molecular sieve (the Ru/Pd molar ratio is 1:1), red mud powder and carbide slag powder are mixed to be a carrier (the mass ratio is 1:1), the mass percentage of the active component is 5 percent by taking the mass of the carrier as a reference, and the mass ratio of the rare earth to the molecular sieve is 7; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (the mass ratio is 1:5:5: 5). The granularity of the powder is 280 meshes. Inlet is actually measured at the feeding port of the 350 ℃ flue areaOriginal flue gas NOxAt a concentration of 350ppm, SOxThe concentration is 50ppm, and 450g SO is treated by each kg of the dual-function powder2And 250g NOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is measured and sprayed in, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 100 DEG CxConcentration 1ppm, SOxThe concentration is 0ppm, and when the flow velocity of the flue gas is 5m/s, the low-temperature denitration efficiency can reach 99.7%, and the desulfurization efficiency reaches 100%.
Example 8
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1: 15, wherein the catalytic component is rare earth Ce, a Cu/Fe exchange type molecular sieve (Cu/Fe molar ratio is 1:1), the fly ash is used as a carrier, the mass of the carrier is used as a reference, the mass percent of the active component is 30%, and the mass ratio of the rare earth/the molecular sieve is 1; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:1:1: 1). The powder has the granularity of 200 meshes. Actually measuring the original NO of the inlet flue gas at the feeding port of the flue region at 200 DEG CxConcentration 150ppm, SOxThe concentration is 500ppm, 200g SO is processed by each kg of the dual-function powder2And 300gNOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is measured and sprayed in, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 100 DEG CxConcentration 1ppm, SOxThe concentration is 2ppm, and when the flow velocity of the flue gas is 4m/s, the low-temperature denitration efficiency can reach 99.3%, and the desulfurization efficiency can reach 99.6%.
Example 9
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1: 8, wherein the catalytic component is rare earth Ce, using red mud powder as a carrier and taking the mass of the carrier as a reference, wherein the mass percent of active components is 10 percent, and the mass ratio of rare earth to the molecular sieve is 4; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:1:1: 3). The powder has 180-mesh granularity. Actually measuring the original NO of the inlet flue gas at the feeding port of the flue region at 200 DEG CxAt a concentration of 170ppm, SOxThe concentration is 350ppm, 200g SO is processed by each kg of the dual-function powder2And 170gNOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is measured and sprayed in, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, the powder and the flue gas components are fully mixed and contact to react under the impact of the flue gas, and the purified NO is detected at a monitoring port at 100 DEG CxConcentration 1ppm, SOxThe concentration is 1ppm, and when the flow velocity of flue gas is 5m/s, the low-temperature denitration efficiency can reach 99.4%, and the desulfurization efficiency can reach 99.7%.
Example 10
Selecting the components with the mass ratio of the catalytic component to the reducing component of 1: 17, wherein the catalytic component is rare earth La, WO3And Ag exchange type molecular sieve (W/Ag molar ratio is 10:1), carbide slag powder is taken as a carrier, the mass of the carrier is taken as a reference, the mass percent of active components is 6 percent, wherein rare earth/WO3The mass ratio of the molecular sieve to the molecular sieve is 2; the reducing component is mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:1:1: 1). The powder granularity is 230-mesh dual-function powder. At the feeding port of the 280 ℃ flue region, the original NO of the inlet flue gas is actually measuredxConcentration 230ppm, SOxThe concentration is 480ppm, and 400g SO is processed by each kg of the double-function powder2And 250gNOxThe powder material is based on the SO contained in the actual flue gas2And NOxThe total amount is metered and sprayed, the difunctional powder with the corresponding amount is sprayed into a flue through a feeding port by a gas delivery pump, the sprayed difunctional powder and the flue gas generate convection, and the powder and the flue gas components are fully mixed under the impact of the flue gasIn combination with the contact reaction, purified NO was detected at a monitoring port of 100 deg.CxConcentration 1ppm, SOxThe concentration is 2ppm, and when the flow velocity of the flue gas is 6m/s, the low-temperature denitration efficiency can reach 99.5%, and the desulfurization efficiency can reach 99.5%.

Claims (8)

1. The bifunctional powder is characterized by comprising a catalyzing component and a reducing component, wherein the mass ratio of the catalyzing component to the reducing component is 1: (0.1 to 20); wherein the catalytic component takes one or more of transition metal oxide, noble metal or metal ion exchange type molecular sieve and light rare earth ore metal as active components, and the industrial waste residue with high specific surface area as a carrier; wherein the metal ion exchange type molecular sieve is one or more metal ion exchange type molecular sieves in the transition metal and noble metal active components; the reducing component is composite reducing functional powder formed by mixing activated carbon powder, melamine, plastic powder or rubber powder, wherein the mass ratio of the activated carbon powder to the melamine to the plastic powder to the rubber powder is 1: (0.1-10): (0.1-10): (0.1-10).
2. The bifunctional powder of claim 1, wherein the light rare earth metal is at least one of La or Ce; the transition metal oxide is at least WO3、SnO2、MoO3、CoO、V2O5、CuO、TiO2、ZrO2、Fe2O3、MnO2、NiO、Al2O3Or ZnO; the noble metal is at least one of Pt, Ru, Pd, Au or Ag; the industrial waste residue with high specific surface area is one or more of fly ash, steel slag powder, red mud powder or carbide slag.
3. The bifunctional powder of claim 1, wherein the mass of the active component in the catalytic component accounts for 1-30% of the mass of the carrier, and the mass ratio of the light rare earth mineral metal to other active components is 1 (0.1-10).
4. The method for preparing the bifunctional powder of claim 1 is characterized in that the catalytic component and the reducing component are mixed, ball-milled and ground into the composite bifunctional powder with the particle size of 80-300 meshes according to the metering ratio.
5. The application of the bifunctional powder of claim 1 in denitration and desulfurization of coal-fired flue gas.
6. The application of claim 5, which comprises the following specific steps: spraying the bifunctional powder into a flue region at 150-500 ℃, blowing the bifunctional powder away under the convection impact of flue gas, fully mixing and contacting with the flue gas, and further adsorbing and capturing NOxAnd SOxAnd promote them to produce harmless N2Water vapor, CO2Sulfate or sulfurous acid, thereby realizing simultaneous and efficient denitration and desulfurization.
7. Use according to claim 6, characterized in that the spraying quality of the bifunctional powders and the treatment of SO are such that2The mass ratio is 1000 (20-500), the spraying mass of the double-function powder and the treated NO arexThe mass ratio of (A) to (B) is 1000 to (17-300).
8. The application of claim 6, wherein the flow velocity of the flue gas is 1-7 m/s.
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