WO2023020295A1 - 一种双功能粉剂及其制备方法和应用 - Google Patents

一种双功能粉剂及其制备方法和应用 Download PDF

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WO2023020295A1
WO2023020295A1 PCT/CN2022/110404 CN2022110404W WO2023020295A1 WO 2023020295 A1 WO2023020295 A1 WO 2023020295A1 CN 2022110404 W CN2022110404 W CN 2022110404W WO 2023020295 A1 WO2023020295 A1 WO 2023020295A1
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powder
dual
flue gas
component
mass ratio
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沈岳松
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Nanjing Tech University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01D53/8603—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
    • 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
    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to a dual-function powder and its preparation method and application, in particular to a dual-function powder containing catalytic and reducing components, its preparation method and its application method in dynamic catalytic removal of NOx and SOx, which belongs to air pollution Treatment, industrial pollution reduction and environmental catalytic materials and other technical fields.
  • NO x and SO x are the main causes of smog, acid rain and deterioration of air quality, and are the focus of air pollution control.
  • the main development process of NO x control technology is: low nitrogen combustion technology ⁇ selective non-catalytic reduction (SNCR) technology ⁇ selective catalytic reduction technology
  • the denitrification effect of the three technologies is: SCR > SNCR >Low-nitrogen combustion.
  • SCR denitrification technology has high efficiency and good stability, and has become the mainstream technology and development direction of industrial flue gas denitrification at home and abroad.
  • the core of the technology is the use of packaged denitrification catalysts.
  • the main technologies for SO x treatment are wet, dry and semi-dry desulfurization technologies.
  • the denitrification and desulfurization of industrial coal-fired flue gas mainly adopts the segmented integrated process of "denitrification + desulfurization". Although it can achieve ultra-low emissions of NO x and SO x and meet environmental protection requirements, the existing integrated process occupies an area of Large space, high investment costs, and high operating costs have brought huge economic pressure to enterprise users, and low-cost technological innovations are urgently needed. In addition, the existing SCR denitrification technology is difficult to operate stably under the complex flue gas of the non-electric industry.
  • the patent discloses a denitrification, desulfurization and dust removal device for combustion flue gas and its method, wherein the device is connected with at least one denitrification, desulfurization and dust removal module in sequence according to the flow direction of combustion flue gas, and each denitrification, desulfurization and dust removal module includes sequential A gas mixing unit and an air cleaning unit that are connected secondaryly, the gas mixing unit includes a gas mixing inner chamber and a smoke inlet and an air inlet communicating with the gas mixing inner chamber, the air cleaning unit includes a smoke outlet, and the smoke The outlet is connected with the flue gas inlet of the next-level denitrification, desulfurization and dust removal module.
  • the denitrification, desulfurization and dust removal method provided by the present invention utilizes air and water cascade denitrification to remove particulate matter while greatly reducing the concentration of nitrogen oxides.
  • the system can also use a variety of wet desulfurization methods to remove sulfide.
  • the patent discloses a high-efficiency denitrification and desulfurization agent prepared from carboxymethyl chitosan, urea, ammonium carbonate, dicyandiamide and water. Its essence is to obtain ammonia from different ammonia sources.
  • the main means of denitrification and desulfurization, the patent does not involve the use of technology.
  • the patent discloses a flue gas denitrification, desulfurization and dust removal process.
  • the specific implementation process is to introduce the flue gas from the combustion device into a coarse particle desulfurizer, and enter the denitrification reactor after pre-desulfurization; the flue gas after denitrification The gas enters the air/flue gas for heat exchange and cooling.
  • the cooled flue gas enters the dry desulfurization tower after humidity adjustment, and the dry desulfurization tower uses dry powder desulfurization agent; after desulfurization, the flue gas containing dust such as post-reaction desulfurization agent enters the bag filter for dust removal, and comes from the air/flue gas exchange
  • the hot air from the heater is mixed with the flue gas before or after the dust collector, and the purified flue gas mixed with the hot air is introduced into the chimney for discharge.
  • This patent mainly adopts the process of segmented integration of desulfurization tower, denitrification reactor and bag filter.
  • the patent discloses a honeycomb low-temperature synchronous desulfurization and denitrification catalyst and its preparation method. It still uses the traditional fixed-bed process, which occupies a large space and has high investment costs.
  • the patent discloses a flue gas simultaneous desulfurization and denitrification method, which reacts a large amount of active substances produced by flue gas under ultraviolet radiation with SO 2 and NO x in the flue gas to generate two kinds of stable sulfuric acid and nitric acid.
  • An important industrial product so as to achieve the effect of removing SO 2 and NO x at the same time.
  • the patent discloses a method of combined flue gas desulfurization and denitrification.
  • the flue gas to be treated enters the photocatalytic reactor, and the NO in the flue gas is oxidized to NO 2 under the action of ultraviolet light and catalyst, and the oxidation reaction Finally, the flue gas enters the double-alkali absorption reactor, the SO 2 in the flue gas is absorbed by the lye, the Na 2 SO 3 in the product reacts with the NO 2 in the flue gas, and the NO 2 is reduced to N 2 to be discharged.
  • the purpose of the present invention is to meet the major demands of comprehensive control of air pollution and reduction of industrial pollutants.
  • the investment is high, the floor space is large, and the operating cost is high. High, there are problems such as ammonia escape, secondary pollution and harmless disposal of waste denitrification catalysts, and a kind of dual-functional powder containing catalytic and reducing two-components is creatively proposed.
  • Another purpose of the present invention is to provide the above-mentioned dual-functional powder
  • Another object of the present invention is to provide the application of the above-mentioned dual-functional powder in the denitrification and desulfurization of coal-fired flue gas.
  • the technical solution of the present invention is: a dual-function powder, characterized in that it contains two components of catalysis and reduction, and the mass ratio of the catalysis component to the reduction component is 1: (0.1-20); wherein the catalysis component is transition One or more of metal oxides, precious metals or metal ion exchange molecular sieves and light rare earth metals are active components, and high specific surface industrial waste is used as a carrier, among which metal ion exchange molecular sieves are the active components of the above transition metals and precious metals One or more metal ion-exchange molecular sieves in the components; the reducing component is a composite reducing functional powder made of activated carbon powder, melamine, plastic powder or rubber powder, wherein activated carbon powder, melamine, plastic powder and The mass ratio of the rubber powder is 1:(0.1-10):(0.1-10):(0.1-10).
  • the light rare earth metal is at least one of La or Ce;
  • the transition metal oxide is at least WO 3 , SnO 2 , MoO 3 , CoO, V 2 O 5 , CuO, TiO 2 , ZrO 2 , Fe 2 One of O 3 , MnO 2 , NiO, Al 2 O 3 or ZnO;
  • the precious metal is at least one of Pt, Ru, Pd, Au or Ag;
  • the high specific surface industrial waste slag is fly ash, steel slag One or more of powder, red mud powder or carbide slag.
  • 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 ore metal to other active components is 1:(0.1-10).
  • the present invention also provides a method for preparing the above-mentioned dual-functional powder, which is characterized in that the catalytic component and the reducing component are mixed and ball-milled according to the metering ratio, and the composite dual-functional powder with a particle size of 80 to 300 meshes is ground into a compound bifunctional powder through mechanochemical action. Functional powder.
  • the present invention also provides the application of the above-mentioned dual-function powder in denitrification and desulfurization of coal-fired flue gas, dynamic catalytic removal (Dynamic Catalytic Removal, DCR for short) of NO x and SO x .
  • the specific steps are as follows: In the flue area at 150-500 °C, spray the dual-function powder with both reduction and catalysis. Under the convective impact of the flue gas, the dual-function powder is quickly blown away and fully mixed with the flue gas.
  • the mass ratio of the injection mass of the above-mentioned dual-function powder to the SO 2 treatment is 1000:(20-500), and the mass ratio to the NO x treatment is 1000:(17-300).
  • the ability of the dual-function powder to treat SO2 and NOx is 20-500g of SO2 and 17-300g of NOx per kg of the dual-function powder.
  • concentration of SO 2 changes and the size of flue gas changes.
  • the effective and active use temperature is 100-500°C, and the applicable flue gas flow rate is 1-7m/s.
  • the DCR denitrification and desulfurization integrated application method described in the present invention is mainly applied to the denitrification and desulfurization treatment of coal-fired flue gas, and is suitable for efficient purification of NOx and SOx in industries such as boilers, coal power, coking, steel, sintering, and waste incineration. Less affected by complex working conditions.
  • the DCR denitrification and desulfurization technology provided by the invention has high efficiency, does not need to spray ammonia and urea, is environmentally friendly throughout the process, has no secondary pollution, no hazardous waste disposal, low operating cost, simple process, no need for major transformation of the equipment body, and a technical transformation project once Low permanent investment, very little interference by working conditions, and wide application.
  • the denitrification and desulfurization efficiency is equivalent, and both can achieve ultra-low emissions of coal-fired flue gas NOx and SOx , but the investment cost is much lower than the existing denitrification and desulfurization segmental process , no secondary pollution.
  • Figure 1 is a process flow chart of DCR denitrification and desulfurization technology.
  • the feed port In the flue area at 150-500°C, select the feed port, weigh the dual-function powder according to the metering ratio, and spray it into the flue through the gas delivery pump through the feed port.
  • the injected dual-function powder and flue gas Convection occurs, and under the impact of the flue gas, the powder is quickly dispersed.
  • the powder is fully mixed and contacted with the flue gas components, and then adsorbs and captures NOx and SOx , and promotes them to be heated at 100-500°C.
  • a sufficient catalytic reaction occurs in the flue gas pipeline, thereby reducing NO x to N 2 , prompting SO x to generate harmless sulfate or sulfite, which are finally recovered and disposed of through the dust collector.
  • the flue gas flow rate is 1-7m/s, the flow field is uniformly mixed, and the temperature is balanced, the denitrification efficiency can reach more than 80%, and the desulfurization efficiency can be close to 100%.
  • a bifunctional powder with a mass ratio of catalytic component to reducing component of 1:0.1 wherein the catalytic component is rare earth Ce, transition metal oxides (WO 3 , SnO 2 , MoO 3 , CoO, A mixture of V 2 O 5 , the mass ratio is 1:1:1:1:1), the carrier is fly ash, based on the carrier mass, the mass percentage of the active component is 1%, and the rare earth Ce/transition metal oxidation
  • the mass ratio of substances is 0.1; the reducing component is a mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:0.1:0.1:0.1).
  • the particle size of the powder is 300 mesh double function powder.
  • the measured NOx concentration of the imported original flue gas is 465ppm, and the SOx concentration is 645ppm.
  • the ability to treat 200g SO 2 and 17g NOx per kg of dual-function powder, the powder is based on the actual flue gas
  • the total amount of SO 2 and NO x contained is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of the impact, the powder and the flue gas components are fully mixed and contacted.
  • the concentration of NOx after purification is 15ppm and the concentration of SOx is 1ppm at the monitoring port at 100°C.
  • a bifunctional powder with a mass ratio of catalytic component to reducing component of 1:1 wherein the catalytic component is rare earth La, transition metal oxides (CuO, TiO 2 , ZrO 2 , Fe 2 O 3.
  • the mixture of MnO2 , the mass ratio is 1:1:1:1:1)
  • the steel slag powder is the carrier
  • the mass percentage of the active component is 5% based on the mass of the carrier, wherein the rare earth La/transition metal oxide
  • the mass ratio is 0.5;
  • the reduction component is a mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:5:5:5).
  • the particle size of the powder is 120 mesh dual function powder.
  • the measured NOx concentration of imported raw flue gas is 500ppm
  • the SOx concentration is 500ppm.
  • the ability to treat 200g SO 2 and 70g NOx per kg of dual-function powder is based on the actual smoke
  • the total amount of SO 2 and NO x contained in the gas is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of gas, the powder and the flue gas components are fully mixed and contacted.
  • the concentration of NOx after purification is 30ppm and the concentration of SOx is 2ppm at the monitoring port at 100°C.
  • the oxide mass ratio is 1;
  • the reducing component is a mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:10:10:10).
  • the particle size of the powder is 120 mesh dual function powder.
  • the measured NOx concentration of the imported original flue gas is 130ppm, and the SOx concentration is 280ppm.
  • the ability to treat 20g SO2 and 100g NOx per kg of dual-function powder, the powder is based on the actual smoke
  • the total amount of SO 2 and NO x contained in the gas is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of gas, the powder and the flue gas components are fully mixed and contacted.
  • the NOx concentration after purification is 25ppm and the SOx concentration is 3ppm at the monitoring port at 280°C.
  • the bifunctional powder with the mass ratio of the catalytic component and the reducing component as 1:15, wherein the catalytic component is rare earth Ce and La (the mass ratio is 1:1), and the noble metal (Pd, Au mixture, the mass ratio is 1:1), calcium carbide slag powder is the carrier, based on the mass of the carrier, the mass percentage of the active component is 1.1%, and the mass ratio of rare earth/precious metal is 10; the reducing component is activated carbon powder, melamine, Mixed powder of plastic powder and rubber powder (mass ratio 1:5:8:10).
  • the particle size of the powder is 200 mesh dual function powder.
  • the measured NOx concentration of imported raw flue gas is 130ppm, and the SOx concentration is 280ppm.
  • the ability to treat 500g SO 2 and 200g NOx per kg of dual-function powder, the powder is based on the actual flue gas
  • the total amount of SO 2 and NO x contained in the gas is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of gas, the powder and the flue gas components are fully mixed and contacted.
  • the concentration of NOx after purification is 15ppm and the concentration of SOx is 1ppm at the monitoring port at 100°C.
  • a bifunctional powder with a component distribution ratio of 1:10 for the mass ratio of the catalytic component to the reducing component wherein the catalytic component is a mixture of rare earth La and noble metal (Pt, Ru, the mass ratio is 1:1), Fly ash, steel slag powder, red mud powder and calcium carbide slag powder are mixed as the carrier (mass ratio is 1:1:1:1), based on the mass of the carrier, the mass percentage of the active component is 1.2%, of which the rare earth/ The mass ratio of precious metal is 9; the reducing component is the mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:5:5:10).
  • the particle size of the powder is 250 mesh dual function powder.
  • the measured NOx concentration of the imported original flue gas is 470ppm, and the SOx concentration is 500ppm.
  • the ability to treat 400g SO 2 and 200gNOx per kg of dual-function powder, the powder is based on the actual flue gas
  • the total amount of SO 2 and NO x contained is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of the flue gas, the powder and the flue gas components are fully mixed and contacted.
  • the NOx concentration after purification is 3ppm and the SOx concentration is 1ppm at the monitoring port at 100°C.
  • a bifunctional powder with a component distribution ratio of 1:15 for the mass ratio of the catalytic component to the reducing component wherein the catalytic component is a mixture of rare earth Ce and noble metal (Ru, Ag, the mass ratio is 1:1), Steel slag powder, red mud powder and calcium carbide slag powder are mixed as a carrier (mass ratio is 1:1:1), based on the carrier mass, the mass percentage of active components is 1.8%, and the mass ratio of rare earth/precious metal is 8;
  • the reducing component is a mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:5:5:5).
  • the particle size of the powder is 280 mesh dual function powder.
  • the measured NOx concentration of the imported original flue gas is 370ppm, and the SOx concentration is 480ppm.
  • the ability to treat 200g SO 2 and 170gNOx per kg of dual-function powder, the powder is based on the actual flue gas
  • the total amount of SO 2 and NO x contained is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of the flue gas, the powder and the flue gas components are fully mixed and contacted.
  • the NOx concentration after purification is 4ppm and the SOx concentration is 2ppm at the monitoring port at 100°C.
  • the flue gas flow rate is 3m/s
  • the low-temperature denitrification efficiency It can reach 98.9%
  • the desulfurization efficiency can reach 99.6%.
  • a bifunctional powder with a mass ratio of catalytic component to reducing component of 1:20 wherein the catalytic component is rare earth Ce and La (mass ratio is 1:1), Ru/Pd exchanged molecular sieve (Ru/Pd molar ratio is 1:1), red mud powder and calcium carbide slag powder are mixed as the carrier (mass ratio is 1:1), based on the mass of the carrier, the mass percentage of the active component is 5%, of which the rare earth Molecular sieve mass ratio is 7; the reduction component is a mixed powder of activated carbon powder, melamine, plastic powder and rubber powder (mass ratio is 1:5:5:5).
  • the particle size of the powder is 280 mesh dual function powder.
  • the measured NOx concentration of the imported raw flue gas is 350ppm, and the SOx concentration is 50ppm.
  • the ability to treat 450g SO 2 and 250g NOx per kg of dual-function powder, the powder is based on the actual smoke
  • the total amount of SO 2 and NO x contained in the gas is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of the flue gas, the powder and the flue gas components are fully mixed and contacted.
  • the concentration of NOx after purification is 1ppm and the concentration of SOx is 0ppm at the monitoring port at 100°C.
  • the flue gas flow rate is 5m/s, the low-temperature denitrification The efficiency can reach 99.7%, and the desulfurization efficiency can reach 100%.
  • the bifunctional powder with the mass ratio of catalytic component and reducing component as 1:15, wherein the catalytic component is rare earth Ce, Cu/Fe exchange type molecular sieve (Cu/Fe molar ratio is 1:1 ), with fly ash as the carrier, based on the carrier mass, the mass percentage of the active component is 30%, wherein the rare earth/molecular sieve mass ratio is 1; the reducing component is the mixture of activated carbon powder, melamine, plastic powder and rubber powder Powder (mass ratio 1:1:1:1).
  • the particle size of the powder is 200 mesh dual function powder. At the feed port of the flue area at 200°C, the measured NOx concentration of the imported original flue gas is 150ppm, and the SOx concentration is 500ppm.
  • the ability to treat 200g SO 2 and 300gNOx per kg of dual-function powder is based on the actual flue gas
  • the total amount of SO 2 and NO x contained is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of the flue gas, the powder and the flue gas components are fully mixed and contacted.
  • the concentration of NOx after purification is 1ppm and the concentration of SOx is 2ppm at the monitoring port at 100°C.
  • the flue gas flow rate is 4m/s, the low-temperature denitrification efficiency It can reach 99.3%, and the desulfurization efficiency can reach 99.6%.
  • a bifunctional powder with a component distribution ratio of 1:8 for the mass ratio of the catalytic component to the reducing component, wherein the catalytic component is rare earth Ce, and the Co/Pt exchange type molecular sieve (the Co/Pt molar ratio is 1:1 ), with red mud powder as the carrier, based on the carrier mass, the mass percentage of the active component is 10%, wherein the rare earth/molecular sieve mass ratio is 4; the reduction component is the mixture of activated carbon powder, melamine, plastic powder and rubber powder Powder (mass ratio 1:1:1:3).
  • the particle size of the powder is 180 mesh dual function powder.
  • the measured NOx concentration of the imported raw flue gas is 170ppm, and the SOx concentration is 350ppm.
  • the ability to treat 200g SO 2 and 170gNOx per kg of dual-function powder, the powder is based on the actual flue gas
  • the total amount of SO 2 and NO x contained is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of the flue gas, the powder and the flue gas components are fully mixed and contacted.
  • the NOx concentration after purification is 1ppm and the SOx concentration is 1ppm at the monitoring port at 100°C.
  • the selected component distribution ratio is a dual-functional powder with a mass ratio of catalytic component to reducing component of 1:17, wherein the catalytic component is rare earth La, WO 3 and Ag exchanged molecular sieve (W/Ag molar ratio is 10: 1), with calcium carbide slag powder as the carrier, based on the carrier mass, the mass percentage of the active component is 6%, wherein the mass ratio of rare earth/ WO3 and molecular sieve is 2; the reducing components are activated carbon powder, melamine, plastic powder And the mixed powder of rubber powder (mass ratio is 1:1:1:1).
  • the particle size of the powder is 230 mesh dual-function powder.
  • the measured NOx concentration of the imported raw flue gas is 230ppm, and the SOx concentration is 480ppm.
  • the ability to treat 400g SO 2 and 250gNOx per kg of dual-function powder, the powder is based on the actual flue gas
  • the total amount of SO 2 and NO x contained is metered and injected, and the corresponding amount of dual-function powder is sprayed into the flue through the gas delivery pump through the feeding port.
  • the injected dual-function powder convects with the flue gas, Under the impact of the flue gas, the powder and the flue gas components are fully mixed and contacted.
  • the NOx concentration after purification is 1ppm and the SOx concentration is 2ppm at the monitoring port at 100°C.
  • the flue gas flow rate is 6m/s, the low-temperature denitrification efficiency It can reach 99.5%, and the desulfurization efficiency reaches 99.5%.

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Abstract

本发明提供一种双功能粉剂及其制备方法和应用，其特征在于包含催化和还原双组分，催化组分与还原组分的质量比为1：(0.1～20)混合球磨得到；其中催化组分是以过渡金属氧化物、贵金属或金属离子交换型分子筛中的一种或几种和轻稀土矿金属为活性组分，高比表面工业废渣为载体，其中金属离子交换型分子筛为上述的过渡金属和贵金属活性组分中的一种或多种金属离子交换型分子筛；还原组分是以活性炭粉、三聚氰胺、塑料粉或橡胶粉混配而成的复合还原功能粉体。适用于燃煤烟气的同时脱硝脱硫治理，本发明的DCR净化技术脱硝脱硫效率高，无需喷氨和尿素，全过程绿色环保，运行成本低，工艺简单无二次污染，对设备无腐蚀性。

Description

一种双功能粉剂及其制备方法和应用 技术领域
本发明涉及一种双功能粉剂及其制备方法和应用，尤其涉及一种包含催化和还原双组分的双功能粉剂及其制备方法和在动态催化脱除NOx和SOx的应用方法，属于大气污染治理、工业污染减排及环境催化材料等技术领域。
背景技术
NO x和SO x是造成雾霾、酸雨及恶化大气质量的主要原因，是大气污染治理的重点。随着环评指标的日趋严格，NO x治理技术的主要发展历程为：低氮燃烧技术→选择性非催化还原(SNCR)技术→选择性催化还原技术，三种技术的脱硝效果为：SCR＞SNCR＞低氮燃烧，其中，SCR脱硝技术效率高、稳定性好，成为当前国内外工业烟气脱硝的主流技术和发展方向，技术核心是使用整装脱硝催化剂。SO x治理的主要技术有湿法、干法及半干法脱硫技术。目前，工业燃煤烟气的脱硝脱硫主要采用的是“脱硝+脱硫”的分段集成工艺，虽然能实现NO x和SO x的超低排放，达到环保要求，但是，现有集成工艺占地空间大，投资费用高，运行费用高，给企业用户带来了巨大的经济压力，亟待进行低成本技术革新。此外，现有SCR脱硝技术难以在非电行业复杂烟气下稳定运行。
近年来，针对烟气同时脱硝脱硫的工艺及关健材料研究已有先关报道，代表性列举如下：
专利(ZL201510098577.5)公开了一种燃烧烟气的脱硝脱硫除尘装置及其方法，其中该装置按照燃烧烟气流动方向顺次连接有至少一个脱硝脱硫除尘模块，每个脱硝脱硫除尘模块包括顺次连接的气体混合单元和空气清洗单元，所述气体混合单元包括气体混合内腔以及与气体混合内腔连通的烟气进口及空气进口，所述空气清洗单元包括烟气出口，所述烟气出口与下一级脱硝脱硫除尘模块的烟气进口连通。本发明所提供的脱硝脱硫除尘的方法利用空气与水梯级脱硝，把颗粒物去除干净的同时大幅降低氮氧化合物的浓度，系统又可以引用多种湿法脱硫的方法脱去硫化物。
专利(ZL201810668695.9)公开了一种以羧甲基壳聚糖、尿素、碳酸铵、二氰二胺和水为原料配制而成的高效脱硝脱硫剂，其实质还是以不同氨源获取氨为 主要脱硝脱硫的手段，专利也没有涉及使用工艺。
专利(ZL201710839256.5)公开了一种烟气脱硝脱硫除尘工艺方法，其具体实施工艺是将来自燃烧装置的烟气，引入粗颗粒脱硫剂，经预脱硫后进入脱硝反应器；脱硝后的烟气进入空气/烟气换热降温。降温后的烟气再经调湿后进入干式脱硫塔，干式脱硫塔使用干粉脱硫剂；脱硫后的含有反应后脱硫剂等粉尘的烟气进入布袋除尘器除尘，来自空气/烟气换热器的热空气在除尘器前或后与烟气混合，经净化并混合了热空气的烟气导入烟囱排放。该专利主要采用的是脱硫塔、脱硝反应器和布袋除尘器分段集成的工艺。
专利(ZL201310703127.5)公开了一种蜂窝状低温同步脱硫脱硝催化剂及制备方法，使用的还是传统固定床工艺，占地空间大，投资成本较高。
专利(ZL201210369470.6)公开了一种烟气同时脱硫脱硝方法，将烟气在紫外线辐射下产生的大量活性物质与烟气中的SO 2和NO x发生反应，生成稳定的硫酸和硝酸两种重要的工业产物，从而达到同时去除SO 2和NO x的效果。
专利(ZL200710067082.1)公开了一种烟气联合脱硫脱硝的方法，待处理的烟气进入光催化反应器，在紫外光和催化剂的作用下将烟气中的NO氧化为NO 2，氧化反应后烟气进入双碱法吸收反应器，烟气中SO 2被碱液吸收，生成物中的Na 2SO 3与烟气中的NO 2反应，将NO 2还原为N 2排出。
以上代表性的专利技术大多采用的是分段集成的脱硝脱硫工艺路线，大部分还是建立在以氨为还原剂或以碱液为吸收剂的传统脱硝脱硫工艺上。
发明内容
本发明的目的是面向大气污染综合治理和工业污染物减排的重大需求，针对目前工业燃煤烟气使用的“脱硝+脱硫”分段集成工艺存在的投资高，占地空间大，运行成本高，存在氨逃逸，废弃脱硝催化剂的二次污染及无害化处置等问题，创造性地提出了一种包含催化和还原双组分的双功能粉剂，本发明的另一目的是提供上述双功能粉剂的制备方法，本发明的另一目的是提供上述双功能粉剂在燃煤烟气的脱硝脱硫中的应用。
本发明的技术方案为：一种双功能粉剂，其特征在于包含催化和还原双组分，催化组分与还原组分的质量比为1：(0.1～20)；其中催化组分是以过渡金属氧化 物、贵金属或金属离子交换型分子筛中的一种或几种和轻稀土矿金属为活性组分，高比表面工业废渣为载体，其中金属离子交换型分子筛为上述的过渡金属和贵金属活性组分中的一种或多种金属离子交换型分子筛；还原组分是以活性炭粉、三聚氰胺、塑料粉或橡胶粉混配而成的复合还原功能粉体，其中活性炭粉、三聚氰胺、塑料粉与橡胶粉的质量比为1：(0.1～10)：(0.1～10)：(0.1～10)。
优选所述的轻稀土矿金属至少为La或Ce中的一种；过渡金属氧化物至少为WO 3、SnO 2、MoO 3、CoO、V 2O 5、CuO、TiO 2、ZrO 2、Fe 2O 3、MnO 2、NiO、Al 2O 3或ZnO中的一种；贵金属至少为Pt、Ru、Pd、Au或Ag中的一种；所述的高比表面工业废渣为粉煤灰、钢渣粉、赤泥粉或电石渣中的一种或多种。
优选所述的催化组分中活性组分的质量占载体质量的1～30％，其中轻稀土矿金属与其他活性组分的质量比为1:(0.1～10)。
本发明还提供了制备上述的双功能粉剂的方法，其特征在于是将催化组分和还原组分按计量比混合球磨，通过机械力化学作用，磨制成粒径为80～300目的复合双功能粉体。
本发明还提供了上述双功能粉剂在燃煤烟气的脱硝脱硫中的应用，动态催化脱除(Dynamic Catalytic Removal，简称DCR)NO x和SO x。其具体步骤如下：在150～500℃的烟道区域，喷入兼具还原与催化的双功能粉剂，在烟气的对流冲击下，双功能粉剂被快速吹散，与烟气充分地混合接触，进而吸附捕捉NO x和SO x，并促使它们发生快速的催化反应，生成无害的N 2、水蒸气、CO 2、硫酸盐或亚硫酸，从而实现同时高效的脱硝脱硫。
优选上述双功能粉剂的喷入质量与处理SO 2质量比为1000:(20-500)，与处理NO x的质量比为1000:(17～300)。所述的双功能粉剂处理SO 2和NO x的能力为每kg双功能粉料处理20～500g的SO 2和17～300g的NO x，实际双功能粉剂的喷入量随烟气中NO x和SO 2的浓度变化及烟气量大小而变化。有效活性使用温度为100～500℃，适用烟气流速为1～7m/s。
本发明所述的DCR脱硝脱硫一体化应用方法主要应用于燃煤烟气的脱硝脱硫治理，适用于锅炉、煤电、焦化、钢铁、烧结、垃圾焚烧等行业NO x和SO x的高效净化，受复杂工况影响小。
有益效果：
本发明提供的DCR脱硝脱硫技术效率高，无需喷氨和尿素，全过程绿色环保，无二次污染，无危废处置，运行成本低，工艺简单，无需设备本体大的改造，技改工程一次性投资低，受工况干扰非常小，适用面广。与现有“SCR脱硝+脱硫塔”分段工艺相比，脱硝脱硫效率相当，都能实现燃煤烟气NO x和SO x超低排放，但投资成本远低于现有脱硝脱硫分段工艺，无二次污染。
附图说明
图1是DCR脱硝脱硫技术工艺流程图。
具体实施方式
以下参照附图1，对本发明DCR脱硝脱硫技术实施方式进行详细说明。
在150～500℃烟道区域，选取喂料口，按照计量比，称取双功能粉料，通过气体输送泵，经喂料口将其喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂被快速冲散，在流动行进过程中，粉剂与烟气组分充分混合接触，进而吸附捕捉NO x和SO x，并促使它们在100～500℃的烟气管道内发生充分地催化反应，从而将NO x还原为N 2，促使SO x生成无害的硫酸盐或亚硫酸盐，最终经收尘器一并回收处置。在烟气流速为1～7m/s，流场混合均匀、温度均衡的条件下，脱硝效率能达到80％以上，脱硫效率能接近100％。
实施例1
选取组分配比为催化组分与还原组分的质量比为1：0.1的双功能粉料，其中，催化组分为稀土Ce、过渡金属氧化物(WO 3、SnO 2、MoO 3、CoO、V 2O 5的混合物，质量比为1:1:1:1:1)、载体为粉煤灰，以载体质量为基准，活性组分的质量百分比为1％，其中稀土Ce/过渡金属氧化物质量比为0.1；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:0.1:0.1:0.1)。粉料粒度为300目的双功能粉剂。在500℃烟道喂料口，实测进口原始烟气NO x浓度为465ppm，SO x浓度为645ppm，以每kg双功能粉料处理200g SO 2和17g NO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净 化后的NO x浓度为15ppm，SO x浓度为1ppm，在烟气流速为7m/s时，脱硝效率能达到96.8％，脱硫效率达到99.8％。
实施例2
选取组分配比为催化组分与还原组分的质量比为1：1的双功能粉料，其中，催化组分为稀土La、过渡金属氧化物(CuO、TiO 2、ZrO 2、Fe 2O 3、MnO 2的混合物，质量比为1:1:1:1:1)，钢渣粉为载体，以载体质量为基准，活性组分的质量百分比为5％，其中稀土La/过渡金属氧化物质量比为0.5；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:5:5:5)。粉料粒度为120目的双功能粉剂。在400℃烟道区域喂料口，实测进口原始烟气NO x浓度为500ppm，SO x浓度为500ppm，以每kg双功能粉料处理200g SO 2和70g NO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净化后的NO x浓度为30ppm，SO x浓度为2ppm，在烟气流速为6m/s时，脱硝效率能达到94％，脱硫效率达到99.6％。
实施例3
选取组分配比为催化组分与还原组分的质量比为1：5的双功能粉料，其中，催化组分为稀土Ce、过渡金属氧化物(NiO、Al 2O 3、ZnO、Fe 2O 3、MnO 2的混合物，质量比为1:1:1:1:1)，赤泥粉为载体，以载体质量为基准，活性组分的质量百分比为10％，其中稀土Ce/过渡金属氧化物质量比为1；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:10:10:10)。粉料粒度为120目的双功能粉剂。在350℃烟道区域喂料口，实测进口原始烟气NO x浓度为130ppm，SO x浓度为280ppm，以每kg双功能粉料处理20g SO 2和100g NO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在280℃的监测口检测净化后的NO x浓度为25ppm，SO x浓度为3ppm，在烟气流速为6m/s时，中低温短流程脱硝效率能达到80.7％，脱硫效率达到98.9％。
实施例4
选取组分配比为催化组分与还原组分的质量比为1：15的双功能粉料，其中，催化组分为稀土Ce和La(质量比为1:1)，贵金属(Pd、Au的混合物，质量比为1:1)，电石渣粉为载体，以载体质量为基准，活性组分的质量百分比为1.1％，其中稀土/贵金属质量比为10；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:5:8:10)。粉料粒度为200目的双功能粉剂。在300℃烟道区域喂料口，实测进口原始烟气NO x浓度为130ppm，SO x浓度为280ppm，以每kg双功能粉料处理500g SO 2和200g NO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净化后的NO x浓度为15ppm，SO x浓度为1ppm，在烟气流速为5m/s时，低温脱硝效率能达到88.5％，脱硫效率达到99.6％。
实施例5
选取组分配比为催化组分与还原组分的质量比为1：10的双功能粉料，其中，催化组分为稀土La、贵金属(Pt、Ru的混合物，质量比为1:1)，以粉煤灰、钢渣粉、赤泥粉和电石渣粉混合为载体(质量比为1:1:1:1)，以载体质量为基准，活性组分的质量百分比为1.2％，其中稀土/贵金属质量比为9；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:5:5:10)。粉料粒度为250目的双功能粉剂。在500℃烟道区域喂料口，实测进口原始烟气NO x浓度为470ppm，SO x浓度为500ppm，以每kg双功能粉料处理400g SO 2和200gNO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净化后的NO x浓度为3ppm，SO x浓度为1ppm，在烟气流速为1m/s时，低温脱硝效率能达到99.4％，脱硫效率达到99.8％。
实施例6
选取组分配比为催化组分与还原组分的质量比为1：15的双功能粉料，其中，催化组分为稀土Ce、贵金属(Ru、Ag的混合物，质量比为1:1)，以钢渣粉、赤泥粉和电石渣粉混合为载体(质量比为1:1:1)，以载体质量为基准，活性组分的 质量百分比为1.8％，其中稀土/贵金属质量比为8；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:5:5:5)。粉料粒度为280目的双功能粉剂。在500℃烟道区域喂料口，实测进口原始烟气NO x浓度为370ppm，SO x浓度为480ppm，以每kg双功能粉料处理200g SO 2和170gNO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净化后的NO x浓度为4ppm，SO x浓度为2ppm，在烟气流速为3m/s时，低温脱硝效率能达到98.9％，脱硫效率达到99.6％。
实施例7
选取组分配比为催化组分与还原组分的质量比为1：20的双功能粉料，其中，催化组分为稀土Ce和La(质量比为1:1)，Ru/Pd交换型分子筛(Ru/Pd摩尔比为1:1)，以赤泥粉和电石渣粉混合为载体(质量比为1:1)，以载体质量为基准，活性组分的质量百分比为5％，其中稀土/分子筛质量比为7；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:5:5:5)。粉料粒度为280目的双功能粉剂。在350℃烟道区域喂料口，实测进口原始烟气NO x浓度为350ppm，SO x浓度为50ppm，以每kg双功能粉料处理450g SO 2和250g NO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净化后的NO x浓度为1ppm，SO x浓度为0ppm，在烟气流速为5m/s时，低温脱硝效率能达到99.7％，脱硫效率达到100％。
实施例8
选取组分配比为催化组分与还原组分的质量比为1：15的双功能粉料，其中，催化组分为稀土Ce，Cu/Fe交换型分子筛(Cu/Fe摩尔比为1:1)，以粉煤灰为载体，以载体质量为基准，活性组分的质量百分比为30％，其中稀土/分子筛质量比为1；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:1:1:1)。粉料粒度为200目的双功能粉剂。在200℃烟道区域喂料口，实测进口原始烟气NO x浓度为150ppm，SO x浓度为500ppm，以每kg双功能粉料处 理200g SO 2和300gNO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净化后的NO x浓度为1ppm，SO x浓度为2ppm，在烟气流速为4m/s时，低温脱硝效率能达到99.3％，脱硫效率达到99.6％。
实施例9
选取组分配比为催化组分与还原组分的质量比为1：8的双功能粉料，其中，催化组分为稀土Ce，Co/Pt交换型分子筛(Co/Pt摩尔比为1:1)，以赤泥粉为载体，以载体质量为基准，活性组分的质量百分比为10％，其中稀土/分子筛质量比为4；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:1:1:3)。粉料粒度为180目的双功能粉剂。在200℃烟道区域喂料口，实测进口原始烟气NO x浓度为170ppm，SO x浓度为350ppm，以每kg双功能粉料处理200g SO 2和170gNO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净化后的NO x浓度为1ppm，SO x浓度为1ppm，在烟气流速为5m/s时，低温脱硝效率能达到99.4％，脱硫效率达到99.7％。
实施例10
选取组分配比为催化组分与还原组分的质量比为1：17的双功能粉料，其中，催化组分为稀土La，WO 3和Ag交换型分子筛(W/Ag摩尔比为10:1)，以电石渣粉为载体，以载体质量为基准，活性组分的质量百分比为6％，其中稀土/WO 3和分子筛的质量比为2；还原组分为活性炭粉、三聚氰胺、塑料粉及橡胶粉的混合粉体(质量比为1:1:1:1)。粉料粒度为230目的双功能粉剂。在280℃烟道区域喂料口，实测进口原始烟气NO x浓度为230ppm，SO x浓度为480ppm，以每kg双功能粉料处理400g SO 2和250gNO x的能力，粉料依据实际烟气含有的SO 2和NO x总量计量喷入，通过气体输送泵，经喂料口将对应量的双功能粉料喷入烟道，喷入的双功能粉剂与烟气发生对流，在烟气的冲击下，粉剂与烟气组分充分混合接触反应，在100℃的监测口检测净化后的NO x浓度为1ppm，SO x浓度为2ppm，在烟气流速为6m/s时，低温脱硝效率能达到99.5％，脱硫效率达到99.5％。

Claims (8)

  1. 一种双功能粉剂，其特征在于包含催化和还原双组分，催化组分与还原组分的质量比为1：(0.1～20)；其中所述的催化组分是以过渡金属氧化物、贵金属或金属离子交换型分子筛中的一种或几种和轻稀土矿金属为活性组分，高比表面工业废渣为载体；其中金属离子交换型分子筛为上述的过渡金属和贵金属活性组分中的一种或多种金属离子交换型分子筛；所述的还原组分是以活性炭粉、三聚氰胺、塑料粉或橡胶粉混配而成的复合还原功能粉体，其中活性炭粉、三聚氰胺、塑料粉与橡胶粉的质量比为1：(0.1～10)：(0.1～10)：(0.1～10)。
  2. 根据权利要求1所述的双功能粉剂，其特征在于所述的轻稀土矿金属至少为La或Ce中的一种；过渡金属氧化物至少为WO 3、SnO 2、MoO 3、CoO、V 2O 5、CuO、TiO 2、ZrO 2、Fe 2O 3、MnO 2、NiO、Al 2O 3或ZnO中的一种；贵金属至少为Pt、Ru、Pd、Au或Ag中的一种；所述的高比表面工业废渣为粉煤灰、钢渣粉、赤泥粉或电石渣中的一种或多种。
  3. 根据权利要求1所述的双功能粉剂，其特征在于所述的催化组分中活性组分的质量占载体质量的1～30％，其中轻稀土矿金属与其他活性组分的质量比为1:(0.1～10)。
  4. 一种制备如权利要求1所述的双功能粉剂的方法，其特征在于是将催化组分和还原组分按计量比混合球磨，磨制成粒径为80～300目的复合双功能粉体。
  5. 一种利用如权利要求1所述的双功能粉剂在燃煤烟气的脱硝脱硫中的应用。
  6. 根据权利要求5所述的应用，其具体步骤如下：在150～500℃的烟道区域，喷入双功能粉剂，在烟气的对流冲击下，双功能粉剂被吹散，与烟气充分地混合接触，进而吸附捕捉NO x和SO x，并促使它们发生快速的催化反应，生成无害的N 2、水蒸气、CO 2、硫酸盐或亚硫酸，从而实现同时高效的脱硝脱硫。
  7. 根据权利要求6所述的应用，其特征在于双功能粉剂的喷入质量与处理SO 2质量比为1000:(20-500)，双功能粉剂的喷入质量与处理NO x的质量比为1000:(17～300)。
  8. 根据权利要求6所述的应用，其特征在于所述的烟气流速为1～7m/s。
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