WO2019062449A1 - 干法脱硫脱硝剂及其生产方法和应用 - Google Patents

干法脱硫脱硝剂及其生产方法和应用 Download PDF

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WO2019062449A1
WO2019062449A1 PCT/CN2018/103025 CN2018103025W WO2019062449A1 WO 2019062449 A1 WO2019062449 A1 WO 2019062449A1 CN 2018103025 W CN2018103025 W CN 2018103025W WO 2019062449 A1 WO2019062449 A1 WO 2019062449A1
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desulfurization
denitration agent
parts
weight
denitration
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PCT/CN2018/103025
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English (en)
French (fr)
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童裳慧
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中晶环境科技股份有限公司
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Priority to JP2020517788A priority Critical patent/JP6961810B2/ja
Priority to US16/650,791 priority patent/US11058993B2/en
Publication of WO2019062449A1 publication Critical patent/WO2019062449A1/zh

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8637Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8892Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/60Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81Solid phase processes
    • B01D53/82Solid phase processes with stationary reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • B01J35/23
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/40Alkaline earth metal or magnesium compounds
    • B01D2251/402Alkaline earth metal or magnesium compounds of magnesium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • B01D2251/602Oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20707Titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20715Zirconium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20723Vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/2073Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20738Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20746Cobalt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/40Mixed oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/92Dimensions
    • B01D2255/9202Linear dimensions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to a dry desulfurization and denitration agent, a production method and application thereof, in particular to a dry desulfurization and denitration agent, a production method thereof and a flue gas dry desulfurization and denitration method.
  • CN101954284A discloses a method for preparing an activated carbon desulfurization catalyst, which comprises mixing a copper-containing compound, an iron-containing compound, a cobalt-containing compound and a zinc-containing compound, and then dispersing the activated carbon in a solution, and finally preparing a desulfurization catalyst.
  • the catalyst has a high desulfurization efficiency.
  • the preparation method is complicated and requires a large amount of raw material components, and in particular, there is no mention whether the catalyst has the ability to remove nitrogen oxides.
  • CN102527369A discloses a preparation method of activated carbon-supported rare earth metal oxide reduction denitration catalyst, wherein activated carbon is used as denitration catalyst carrier, and rare earth metal ruthenium or ruthenium and osmium components are used as catalytic active components to reduce nitrogen oxides.
  • the denitration rate can be maintained above 95% at higher airspeeds.
  • this patent document does not relate to whether the catalyst can be desulfurized.
  • the catalyst uses a relatively expensive rare earth metal compound as an active component, which increases the cost.
  • CN1597094A discloses a preparation method of a honeycomb activated carbon-based catalyst for desulfurization and denitration, by adding a phenol resin or a furan resin binder to an activated carbon powder, and then carbonizing after extrusion molding, and immersing in ammonium metavanadate and The catalyst is prepared by drying, calcining and oxidizing in a mixed solution of oxalic acid.
  • the catalyst has a sulfur capacity of 67 to 90 mg SO 2 /100 g of catalyst, and the NO conversion rate is 55 to 90%, and there is still room for improvement.
  • An object of the present invention is to provide a dry desulfurization denitration agent which has high desulfurization and denitration efficiency and does not use rare earth metals, and thus has a low cost.
  • Another object of the present invention is to provide a method for producing a desulfurization and denitration agent, which is simple in process, energy-saving and environmentally friendly.
  • Still another object of the present invention is to provide a method for dry flue gas desulfurization and denitrification which can improve the use effect of a desulfurization and denitration agent.
  • the present invention achieves the above object by the following technical solutions.
  • the invention provides a dry desulfurization denitration agent, characterized in that the desulfurization denitration agent comprises the following components based on 100 parts by weight of a desulfurization denitration agent:
  • the desulfurization denitration agent comprises the following components based on 100 parts by weight of the desulfurization denitration agent:
  • the desulfurization denitration agent comprises the following components based on 100 parts by weight of the desulfurization denitration agent:
  • TiO 2 and ZrO 2 are used as a carrier; V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 and KMnO 4 are used as active ingredients.
  • the desulfurization and denitration agent has an average particle diameter of 0.8 to 15 ⁇ m.
  • the invention also provides a method for producing the above-mentioned desulfurization and denitration agent, comprising the following steps:
  • V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 and KMnO 4 are added to a slurry containing TiO 2 and ZrO 2 , and stirred at a rotation speed of 100 to 300 rpm for 10 to 60 hours. Forming a mixed slurry; wherein, TiO 2 , ZrO 2 , V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 and MnO 2 are all nano-scale oxides;
  • the paste is dried at 100 to 130 ° C and ground into fine particles; the fine particles are calcined at 350 to 1000 ° C for 2 to 6 hours to obtain the desulfurization and denitration agent.
  • the addition rate of the ammonia water is from 0.2 to 20 mL/min.
  • the dropping rate of the potassium permanganate solution is 0.2 to 20 mL/min.
  • the invention also provides a method for dry flue gas desulfurization and denitrification, which fully contacts the flue gas with the desulfurization and denitration agent, and then contacts with the dry powder of the magnesium oxide containing absorbent to remove nitrogen oxides and sulfur dioxide in the flue gas.
  • the magnesium oxide comprises 70 to 85% by weight of active magnesium oxide, and the content of nano-sized magnesium oxide in the magnesium oxide is 10 to 20% by weight.
  • the flue gas before the contact with the desulfurization denitration agent has a sulfur dioxide content of 1000 to 3000 mg/Nm 3 , a nitrogen oxide content of 100 to 600 mg/Nm 3 , a flow rate of 2 to 5 m/s, and The temperature is 110 to 170 °C.
  • the dry desulfurization and denitration agent of the present invention can convert low-cost nitrogen oxides into high-priced nitrogen oxides such as nitrogen dioxide, and oxidize sulfur dioxide to sulfur trioxide, and then absorb it with an absorbent such as magnesium oxide to achieve a desulfurization and denitration effect.
  • the desulfurization and denitration agent of the invention has good desulfurization and denitration effect, low energy consumption and low cost.
  • the nanoscale means 1 to 100 nm, preferably 10 to 60 nm.
  • the desulfurization and denitration agent of the present invention is a desulfurization and denitration catalyst.
  • the desulfurization denitration agent may include a carrier and an active component.
  • the support may be a nano-sized amphoteric oxide, preferably a combination of TiO 2 and ZrO 2 .
  • the active components include nanoscale metal oxides and KMnO 4 .
  • the nanoscale metal oxide includes V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 . These active components are supported on a carrier to form a desulfurization denitration agent.
  • These active components are combined to oxidize sulfur dioxide to sulfur trioxide, and catalytically oxidize the low-valent nitrogen oxide NO to NO 2 or the like. Such a combination can fully exert catalytic oxidation, thereby improving the desulfurization and denitration effect.
  • the invention adopts vanadium, cobalt, iron and manganese as active components of the desulfurization and denitration agent; they exist in the form of V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 , and can provide catalytic reaction activity. Position, and adsorb the reactants SO 2 and NO, and promote the reaction.
  • Ti is the main carrier of the active component and is present in the form of TiO 2 .
  • Ti also adsorbs NO, increasing the possibility of adsorption of the reactants on the surface of the desulfurization and denitrification agent.
  • ZrO 2 and TiO 2 are combined together as a carrier, and Zr can replace the position of Ti in the original crystal lattice to form ZrTiO 4 .
  • a new acidity and alkalinity will be formed on the carrier.
  • SO 2 and NO invade the desulfurization and denitration agent, these alkaline sites will attract SO 2 and NO to form an encroachment target, thereby effectively protecting the active site of the active component. .
  • the desulfurization denitration agent comprises 30 to 60 parts by weight of TiO 2 , 9 to 30 parts by weight of ZrO 2 , 2 to 10 parts by weight of V 2 O 5 , 2 to 10, based on 100 parts by weight of the desulfurization denitration agent.
  • CoO by weight, 1 to 8 parts by weight of Co 2 O 3 , 2 to 10 parts by weight of Fe 2 O 3 , 5 to 15 parts by weight of MnO 2 , and 2 to 10 parts by weight of KMnO 4 .
  • the desulfurization and denitration agent comprises 35 to 60 parts by weight of TiO 2 , 10 to 20 parts by weight of ZrO 2 , 6 to 10 parts by weight of V 2 O 5 , 2.5 to 7 parts by weight of CoO, and 1.5 to 6 parts by weight of Co 2 O 3 . 3 to 8 parts by weight of Fe 2 O 3 , 6 to 12 parts by weight of MnO 2 , and 3 to 8 parts by weight of KMnO 4 .
  • the desulfurization and denitration agent comprises 50 to 52 parts by weight of TiO 2 , 10 to 15 parts by weight of ZrO 2 , 8 to 10 parts by weight of V 2 O 5 , 3 to 6 parts by weight of CoO, and 3 to 5 parts by weight of Co 2 O. 3 , 6 to 8 parts by weight of Fe 2 O 3 , 7 to 9.5 parts by weight of MnO 2 , and 5 to 8 parts by weight of KMnO 4 .
  • Controlling the active components in the above range can significantly improve their oxidation effects on sulfur dioxide and low-cost nitrogen oxides in the flue gas, thereby improving the desulfurization and denitration effect.
  • the desulfurization and denitration agent is made of a raw material including the above-described TiO 2 , ZrO 2 , V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 and KMnO 4 .
  • the desulfurization denitration agent is made only of the above-mentioned raw materials of TiO 2 , ZrO 2 , V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 and KMnO 4 .
  • the desulfurization and denitration agent of the present invention has an average particle diameter of 0.8 to 15 ⁇ m, preferably 1 to 5 ⁇ m.
  • the average particle size can be obtained by sieving.
  • V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 and MnO 2 may have a size of 2 to 100 nm and a specific surface area of 100 to 300 m 2 /g.
  • the desulfurization and denitration agent of the present invention can be produced using nano metal oxides.
  • a nano-sized metal oxide of V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , and MnO 2 is prepared.
  • Common methods include a sol-gel method, a hydrolysis method, a hydrothermal synthesis method, and the like, and a sol-gel method is preferably employed.
  • a nitrate solution of vanadium, cobalt, iron, and manganese is used as a precursor, and these nitrates are respectively hydrolyzed in a solution, condensed into a sol solution, and then heated to remove the solvent to be converted into a gel, thereby finally obtaining a crystal form and a particle size.
  • the production method of the present invention comprises (1) a mixing step; (2) a reaction step: (3) a drying calcination step and the like.
  • the mixing step of the present invention is: adding V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 and KMnO 4 to a slurry containing TiO 2 and ZrO 2 and stirring at a rotation speed of 100 to 300 rpm. ⁇ 60 hours, a mixed slurry was formed.
  • the rotation speed is preferably 200 to 250 rpm; and the stirring time is preferably 10 to 48 hours.
  • TiO 2 , ZrO 2 , V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 and MnO 2 are all nano-scale oxides.
  • the reaction step of the present invention comprises: adding a concentration of 2 to 19% by weight, preferably 5 to 10% by weight, of ammonia water to the mixed slurry under the action of ultrasonic waves having an oscillation frequency of 15 to 200 kHz, preferably 50 to 100 kHz, until the reaction system is The pH is 7 to 9.5, for example, 7 to 8; after stirring for 2 to 6 hours, preferably 2 to 3 hours, the potassium permanganate solution is added dropwise until the pH of the reaction system is 4 to 6, for example, 5 to 5.5. Stirring is continued for 2 to 6 hours, preferably 2 to 3 hours, vacuum filtration, and washing with water to obtain a paste.
  • the rate of addition of the aqueous ammonia may be 0.2 to 20 mL/min, preferably 3 to 10 mL/min; and the dropping rate of the potassium permanganate solution is 0.2 to 20 mL/min, preferably 1 to 5 mL/min. This is advantageous in obtaining a nano metal oxide having a uniform size.
  • the potassium permanganate solution used in the present invention is preferably an acidic potassium permanganate solution.
  • the dry calcination step of the present invention comprises drying the paste at 100 to 130 ° C, for example, 105 to 110 ° C to obtain a dried product; and then grinding the dried product into fine particles.
  • the fine particles are calcined at 350 to 1000 ° C, preferably 500 to 800 ° C for 2 to 6 hours, for example, for 2 to 3 hours to obtain a desulfurization denitration agent.
  • the method for dry flue gas desulfurization and denitration of the present invention comprises the steps of flue gas desulfurization and denitrification: contacting the flue gas with the above desulfurization and denitration agent, and then contacting with the dry powder containing magnesium oxide, thereby removing sulfur dioxide and nitrogen in the flue gas. Oxide.
  • the sulfur dioxide may have a sulfur dioxide content of from 1,000 to 3,000 mg/Nm 3 , preferably from 1,500 to 2,500 mg/Nm 3 , more preferably from 1,600 to 2,000 mg/Nm 3 .
  • the nitrogen oxide content may be from 100 to 600 mg/Nm 3 , preferably from 150 to 500 mg/Nm 3 , more preferably from 300 to 450 mg/Nm 3 .
  • the oxygen content may be 10 to 25 vol%, preferably 15 to 20 vol%.
  • the temperature may be from 110 to 170 ° C; preferably from 120 to 135 ° C. Further, the flow rate of the flue gas may be 2 to 5 m/s, preferably 2.5 to 3.5 m/s.
  • the above flue gas parameters all indicate the parameters at the flue gas inlet; the parameters at the flue gas outlet are determined according to the actual desulfurization and denitrification conditions.
  • the use of the above process parameters is beneficial to improve the efficiency of desulfurization and denitrification.
  • the flue gas is in full contact with the desulfurization and denitration agent, converts the low-cost nitrogen oxides in the flue gas into nitrogen dioxide, and converts the sulfur dioxide into sulfur trioxide to form a pretreatment flue gas.
  • the magnesium oxide of the present invention may include light burned magnesium oxide, micron-sized magnesium oxide, and/or nano-sized magnesium oxide.
  • the magnesium oxide comprises 70 to 85 wt% of active magnesium oxide, preferably 80 to 85% of active magnesium oxide; and the content of nanometer magnesia in the magnesium oxide is 10 to 20 wt. % is preferably 15 to 20% by weight.
  • the desulfurization and denitration efficiency can be improved by utilizing the unique properties of some nanoparticles of nanometer magnesia. This is more conducive to the formation of magnesium nitrate and magnesium sulfate, thereby improving the flue gas desulfurization and denitration effect.
  • the absorbent may include only the above magnesium oxide; the absorbent may further include a modifier such as calcium oxide and silica.
  • the modifier is a micron-sized, nano-scale metal oxide.
  • the absorbent of the present invention is in the form of a powder.
  • the particle diameter may be from 0.8 to 15 ⁇ m, preferably from 1 to 5 ⁇ m. In this way, the absorbent can be directly mixed with the flue gas, thereby removing the sulfur dioxide and the nitrogen oxides from the flue gas, thereby completing the desulfurization and denitration of the flue gas without requiring a large amount of industrial wastewater, and not generating a large amount of industrial waste liquid.
  • the dry powder of the absorbent is thoroughly mixed with the pretreatment flue gas in the flue gas pipeline, and then enters the absorption tower for desulfurization and denitration treatment, and the flue gas after desulfurization and denitration is discharged by the chimney.
  • the desulfurization denitration agent was produced according to the formulation of Table 1.
  • V 2 O 5 , CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 (all of which are nano-sized metal oxides) and KMnO 4 are added to a slurry containing TiO 2 and ZrO 2 at a rotation speed of 250 pm. Stir for 45 hours to form a mixed slurry. Under the action of ultrasonic waves with an oscillation frequency of 70 kHz, 10% by weight of ammonia water was added to the mixed slurry until the pH of the reaction system was 7; after stirring for 3 hours, potassium permanganate solution was added dropwise until the pH of the reaction system was reached.
  • the value was 5, stirring was continued for 2 hours, vacuum filtration, and washing with water to obtain a paste.
  • the addition rate of ammonia water was 5 mL/min; the drop rate of potassium permanganate solution was 2 mL/min.
  • the paste was dried at 100 ° C and ground into fine particles; the fine particles were calcined at 500 ° C for 3 hours to obtain a desulfurization denitration agent H1.
  • the flue gas is catalytically oxidized by the desulfurization and denitration agent, and is absorbed by the dry powder of magnesium oxide.
  • the flow rate of the flue gas is 2.5 m/s; the other parameters of the flue gas inlet and the parameters of the flue gas outlet are shown in Tables 2 and 3.
  • Serial number project Quantity unit 1 Export smoke volume (working conditions) 42353 m 3 /h 2 exhaust temperature 65 °C 3 Sulfur dioxide emission concentration twenty three Mg/Nm 3 4 Desulfurization efficiency 99.51 % 5 NOx emission concentration 50 Mg/Nm 3 6 Denitration efficiency 96 % 7 Output of by-products 5.34 t/h
  • the concentration of sulfur dioxide is 23 mg/Nm 3 and the concentration of nitrogen oxides is 50 mg/Nm 3 .
  • the desulfurization denitration agent H2 was obtained according to the formulation of Table 4, and the other conditions were the same as in Example 1.
  • the flue gas is catalytically oxidized by the desulfurization and denitration agent, and is absorbed by the dry powder of magnesium oxide.
  • the flue gas inlet parameters are the same as in the first embodiment, and the parameters of the flue gas outlet are shown in Table 5.
  • Serial number project Quantity unit 1 Export smoke volume (working conditions) 41341 m 3 /h 2 exhaust temperature 65 °C 3 Sulfur dioxide emission concentration 19 Mg/Nm 3 4 Desulfurization efficiency 99.60 % 5 NOx emission concentration 43 Mg/Nm 3 6 Denitration efficiency 96.02 % 7 Output of by-products 5.43 t/h
  • the concentration of sulfur dioxide is 19 mg/Nm 3 and the concentration of nitrogen oxides is 43 mg/Nm 3 .
  • the desulfurization denitrification agent H3 was obtained according to the formulation of Table 6, and the other conditions were the same as in Example 1.
  • the flue gas is catalytically oxidized by the desulfurization and denitration agent, and is absorbed by a dry powder of magnesium oxide.
  • the flue gas inlet parameters are the same as in the first embodiment, and the parameters of the flue gas outlet are shown in Table 7.
  • Serial number project Quantity unit 1 Export smoke volume (working conditions) 40324 m 3 /h 2 exhaust temperature 65 °C 3 Sulfur dioxide emission concentration 13 Mg/Nm 3 4 Desulfurization efficiency 99.73 % 5 NOx emission concentration 29 Mg/Nm 3 6 Denitration efficiency 97.39 % 7 Output of by-products 5.7 t/h
  • the purified flue gas has a sulfur dioxide concentration of 13 mg/Nm 3 and a nitrogen oxide concentration of 29 mg/Nm 3 .
  • the desulfurization efficiency reached 99.73% and the denitration efficiency was 97.39%.

Abstract

本发明公开了一种干法脱硫脱硝剂及其生产方法和应用。基于100重量份脱硫脱硝剂,该脱硫脱硝剂包括以下组分:30~60重量份TiO2,10~30重量份ZrO2,2~10重量份V2O5,2~10重量份CoO,1~8重量份Co2O3,2~10重量份Fe2O3,5~15重量份MnO2,2~10重量份KMnO4。本发明的干法脱硫脱硝剂对烟气的二氧化硫和氮氧化物的催化氧化效果好,脱硫脱硝效率高。

Description

干法脱硫脱硝剂及其生产方法和应用 技术领域
本发明涉及一种干法脱硫脱硝剂及其生产方法和应用,尤其是一种干法脱硫脱硝剂及其生产方法和烟气干法脱硫脱硝方法。
背景技术
随着世界经济发展,工业化和城市化脚步加快,烟气排放量逐年增加。由此,大气污染现已成为21世纪最严重的污染问题。工业废气酸化污染是大气污染的主要原因,其污染范围广,污染物产生量大,造成环境酸化。环境酸化是由SO 2、NO x形成,酸雨为主要表现形式。20世纪60年代,很多工业发达地区环境受到工业废气影响,降水pH值降到5以下,之后污染范围不断扩大,生态环境遭到严重破坏。进入21世纪以来,中国经济迅速发展,但排废气量也在全球范围内居高不下,各工业城市环境污染日益加剧。
有鉴于此,开发一种可靠的烟气脱硫脱硝技术是非常必要的。CN101954284A公开了一种活性炭脱硫催化剂的制备方法,其将含铜化合物、含铁化合物、含钴化合物与含锌化合物混合后,再将活性炭分散在溶液中,最后制得脱硫催化剂。该催化剂具有较高的脱硫效率,。但制备方法较为复杂,且所需原料成分较多,尤其是并未提及该催化剂是否具有脱除氮氧化物的能力。CN102527369A公开了一种活性炭负载稀土金属氧化物还原脱硝催化剂的制备方法,以活性炭为脱硝催化剂载体,以稀土金属铈,或镧与铈双组分为催化活性组分,对氮氧化物进行还原,在较高空速下能保持脱硝率95%以上。但是,该专利文献未涉及该催化剂是否可以脱硫。此外,该催化剂采用价格较高的稀土金属化合物作为活性组分,增加了成本。CN1597094A公 开了一种用于脱硫脱硝的蜂窝状活性炭基催化剂的制备方法,通过在活性炭粉中添加酚醛树脂或呋喃树脂粘接剂,再挤压成型后进行炭化,并浸渍于偏钒酸铵和草酸混合的溶液中,经干燥、焙烧、氧化制备得到催化剂。该催化剂的硫容为67~90mgSO 2/100g催化剂,NO转化率达55~90%,仍然存在提高的空间。
发明内容
本发明的一个目的在于提供一种干法脱硫脱硝剂,其脱硫脱硝效率高、并且不使用稀土金属,因而成本较低。
本发明的另一个目的在于提供一种脱硫脱硝剂的生产方法,其工艺简单,节能环保。
本发明的再一个目的在于提供一种烟气干法脱硫脱硝的方法,其可以改善脱硫脱硝剂的使用效果。
本发明采用如下技术方案实现上述目的。
本发明提供一种干法脱硫脱硝剂,其特征在于,基于100重量份脱硫脱硝剂,该脱硫脱硝剂包括以下组分:
Figure PCTCN2018103025-appb-000001
根据本发明的脱硫脱硝剂,优选地,基于100重量份脱硫脱硝剂,该脱硫脱硝剂包括以下组分:
Figure PCTCN2018103025-appb-000002
Figure PCTCN2018103025-appb-000003
根据本发明的脱硫脱硝剂,优选地,基于100重量份脱硫脱硝剂,该脱硫脱硝剂包括以下组分:
Figure PCTCN2018103025-appb-000004
根据本发明的脱硫脱硝剂,优选地,TiO 2和ZrO 2作为载体;V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2和KMnO 4作为活性成分。
根据本发明的脱硫脱硝剂,优选地,所述脱硫脱硝剂的平均粒径为0.8~15微米。
本发明还提供上述脱硫脱硝剂的生产方法,包括如下步骤:
(1)将V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2和KMnO 4加入含有TiO 2和ZrO 2的浆液中,在转速为100~300rpm下搅拌10~60小时,形成混合浆液;其中,TiO 2、ZrO 2、V 2O 5、CoO、Co 2O 3、Fe 2O 3和MnO 2均为纳米级氧化物;
(2)在震荡频率为15~200kHz的超声波作用下,将浓度为2~19wt%氨水加入所述混合浆液,直至反应体系的pH值为7~9.5;继续搅拌2~6小时后,滴加高锰酸钾溶液,直至反应体系的pH值为4~6,继续搅拌2~6小时,真空抽滤,加水洗涤,得到膏状物;
(3)将所述膏状物在100~130℃下干燥,研磨成微小颗粒;将该微小颗粒在350~1000℃下煅烧2~6小时,得到所述脱硫脱硝剂。
根据本发明的生产方法,优选地,步骤(2)中,氨水的加入速度为0.2~20mL/min。
根据本发明的生产方法,优选地,步骤(2)中,高锰酸钾溶液的滴加速度为0.2~20mL/min。
本发明也提供一种烟气干法脱硫脱硝的方法,将烟气与所述脱硫脱硝剂充分接触,然后与含有氧化镁的吸收剂干粉接触,从而脱除烟气中的氮氧化物和二氧化硫;所述氧化镁包括70~85wt%的活性氧化镁,且纳米级氧化镁在所述氧化镁中的含量为10~20wt%。
根据本发明的方法,优选地,与脱硫脱硝剂接触之前的烟气的二氧化硫含量为1000~3000mg/Nm 3、氮氧化物含量为100~600mg/Nm 3、流速为2~5m/s、且温度为110~170℃。
本发明的干法脱硫脱硝剂能够将低价氮氧化物为二氧化氮等高价氮氧化物,并将二氧化硫氧化为三氧化硫,然后以氧化镁等吸收剂吸收,从而达到脱硫脱硝效果。本发明的脱硫脱硝剂的脱硫脱硝效果好,能耗低,成本较低。
具体实施方式
下面结合具体实施例对本发明作进一步的说明,但本发明的保护范围并不限于此。
在本发明中,纳米级表示1~100nm,优选为10~60nm。
<干法脱硫脱硝剂>
本发明的脱硫脱硝剂为一种脱硫脱硝催化剂。该脱硫脱硝剂可以包括载体和活性组分。载体可以为纳米级两性氧化物,优选为TiO 2和ZrO 2的组合。活性组分包括纳米级金属氧化物和KMnO 4。纳米级金属氧化物包括V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2。将这些活性组分负载在载体上,从而形成脱硫脱硝剂。这些活性组分配合将二氧化硫氧化为三氧化硫,并将低价氮氧化物NO催化氧化为NO 2等。这样的组合可以充分发挥催化氧化作用,进而改善脱硫脱硝效果。
本发明采用钒、钴、铁、锰作为脱硫脱硝剂的活性组分;它们以V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2的形式存在,能够提供催化反应的活性位,并对反应物SO 2、NO进行吸附,并促进反应进行。
Ti作为活性组分的主要载体,以TiO 2形式存在。Ti同样对NO进行吸附,增加反应物在脱硫脱硝剂表面吸附的可能性。ZrO 2和TiO 2结合一起作为载体,Zr能取代原有晶格中Ti的位置,形成ZrTiO 4。此时载体上将形成新的酸度和碱度,SO 2、NO在侵占脱硫脱硝剂时,这些碱性点位会吸引SO 2、NO,形成侵占靶位,从而有效保护活性组分的活性位。
根据本发明的一个实施方式,基于100重量份脱硫脱硝剂,该脱硫脱硝剂包括30~60重量份TiO 2,9~30重量份ZrO 2,2~10重量份V 2O 5,2~10重量份CoO,1~8重量份Co 2O 3,2~10重量份Fe 2O 3,5~15重量份MnO 2,和2~10重量份KMnO 4。优选地,该脱硫脱硝剂包括35~60重量份TiO 2,10~20重量份ZrO 2,6~10重量份V 2O 5,2.5~7重量份CoO,1.5~6重量份Co 2O 3,3~8重量份Fe 2O 3,6~12重量份MnO 2,和3~8重量份KMnO 4。更优选地,该脱硫脱硝剂包括50~52重量份TiO 2,10~15重量份ZrO 2,8~10重量份V 2O 5,3~ 6重量份CoO,3~5重量份Co 2O 3,6~8重量份Fe 2O 3,7~9.5重量份MnO 2,和5~8重量份KMnO 4。将活性组分控制在上述范围,可以显著改善它们对烟气中的二氧化硫和低价氮氧化物的氧化效果,从而提高脱硫脱硝效果。本发明中,脱硫脱硝剂由包括上述TiO 2、ZrO 2、V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2和KMnO 4的原料制成。根据本发明一个优选的实施方式,脱硫脱硝剂仅由上述TiO 2、ZrO 2、V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2和KMnO 4的原料制成。
本发明的脱硫脱硝剂的平均粒径为0.8~15微米,优选为1~5微米。平均粒径可以采用筛分法获得。在成型的脱硫脱硝剂中,V 2O 5、CoO、Co 2O 3、Fe 2O 3和MnO 2的尺寸可以为2~100nm,比表面积可以达到100~300m 2/g。
<生产方法>
本发明的脱硫脱硝剂可以采用纳米金属氧化物进行生产。首先制备V 2O 5、CoO、Co 2O 3、Fe 2O 3和MnO 2的纳米级金属氧化物。常见方法有溶胶-凝胶法、水解法、水热合成法等,优选采用溶胶-凝胶法。例如,以钒、钴、铁、锰的硝酸盐溶液为前驱物,分别以这些硝酸盐在溶液中水解、缩合成溶胶液,然后加热去除溶剂而转化成凝胶,最终制得晶型、粒度可控且粒子均匀度高的纳米级金属氧化物。这些方法都是本领域熟知的,这里不再赘述。
本发明的生产方法包括(1)混合步骤;(2)反应步骤:(3)干燥煅烧步骤等。
本发明的混合步骤为:将V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2和KMnO 4加入含有TiO 2和ZrO 2的浆液中,在转速为100~300rpm下搅拌10~60小时,形成混合浆液。转速优选为200~250rpm;搅拌时间优选为10~48小时。根据本发明的一个实施方式,TiO 2、ZrO 2、V 2O 5、 CoO、Co 2O 3、Fe 2O 3和MnO 2均为纳米级氧化物。
本发明的反应步骤包括:在震荡频率为15~200kHz、优选为50~100kHz的超声波作用下,将浓度为2~19wt%、优选为5~10wt%氨水加入所述混合浆液,直至反应体系的pH值为7~9.5,例如7~8;继续搅拌2~6小时、优选为2~3小时后,滴加高锰酸钾溶液,直至反应体系的pH值为4~6、例如5~5.5,继续搅拌2~6小时、优选为2~3小时,真空抽滤,加水洗涤,得到膏状物。氨水的加入速度可以为0.2~20mL/min,优选为3~10mL/min;高锰酸钾溶液的滴加速度为0.2~20mL/min,优选为1~5mL/min。这样有利于获得尺寸均匀的纳米金属氧化物。本发明采用的高锰酸钾溶液优选为酸性高锰酸钾溶液。
本发明的干燥煅烧步骤包括:将所述膏状物在100~130℃、例如105~110℃下干燥,得到干燥物;然后将干燥物研磨成微小颗粒。将所述微小颗粒在350~1000℃、优选为500~800℃下煅烧2~6小时、例如2~3小时,得到脱硫脱硝剂。
<烟气干法脱硫脱硝方法>
本发明的烟气干法脱硫脱硝的方法包括烟气脱硫脱硝步骤:将烟气与上述脱硫脱硝剂充分接触,然后与含有氧化镁的吸收剂干粉接触,从而脱除烟气中的二氧化硫和氮氧化物。
在本发明的方法中,烟气的二氧化硫含量可以为1000~3000mg/Nm 3、优选为1500~2500mg/Nm 3、更优选为1600~2000mg/Nm 3。氮氧化物含量可以为100~600mg/Nm 3、优选为150~500mg/Nm 3、更优选为300~450mg/Nm 3。氧含量可以为10~25vol%、优选为15~20vol%。温度可以为110~170℃;优选为120~135℃。此外,烟气的流速可以为2~5m/s,优选为2.5~3.5m/s。上述烟气参 数均表示烟气入口处的参数;烟气出口处的参数根据实际脱硫脱硝情况而定。采用上述工艺参数,有利于改善脱硫脱硝效率。烟气与脱硫脱硝剂充分接触,将烟气中的低价氮氧化物转化为二氧化氮等,并将二氧化硫转化为三氧化硫,从而形成预处理烟气。
本发明的氧化镁可以包括轻烧氧化镁、微米级氧化镁和/或纳米级氧化镁。根据本发明的一个实施方式,所述氧化镁包括70~85wt%的活性氧化镁,优选为80~85%的活性氧化镁;且纳米级氧化镁在所述氧化镁中的含量为10~20wt%,优选为15~20wt%。通过利用纳米级氧化镁的一些纳米微粒独有的性质,可以提高脱硫脱硝效率。这样更有利于硝酸镁、硫酸镁的形成,从而改善烟气脱硫脱硝效果。在本发明中,所述吸收剂可以仅包括上述氧化镁;所述吸收剂还可以包括氧化钙和二氧化硅等改性剂。改性剂是微米级、纳米级的金属氧化物。为了提高去除效率,本发明的吸收剂为粉末状。其粒径可以为0.8~15微米,优选为1~5微米。这样可以直接将吸收剂与烟气混合,进而对烟气进行二氧化硫和氮氧化物的脱除,从而在不需要大量工业废水的情况下完成烟气的脱硫脱硝,并且不产生大量工业废液。例如,将吸收剂干粉与预处理烟气在烟气管道充分混合,然后进入吸收塔进行脱硫脱硝处理,脱硫脱硝后的烟气由烟囱排出。
实施例1
按照表1的配方生产脱硫脱硝剂。将V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2(以上化合物均为纳米级金属氧化物)和KMnO 4加入含有TiO 2和ZrO 2的浆液中,在转速为250pm下搅拌45小时,形成混合浆液。在震荡频率为70kHz的超声波作用下,将浓度为10wt%氨水加入所述混合浆液,直至反应体系的pH值为7;继续搅拌3小时后,滴加高锰酸钾溶液,直至反应体系的pH值为5,继续搅拌2小时,真空抽滤, 加水洗涤,得到膏状物。氨水的加入速度为5mL/min;高锰酸钾溶液的滴加速度为2mL/min。将所述膏状物在100℃下干燥,研磨成微小颗粒;将该微小颗粒在500℃下煅烧3小时,得到脱硫脱硝剂H1。
表1、脱硫脱硝剂H1的配方
TiO 2 56.0重量份
ZrO 2 15.0重量份
V 2O 5 4.0重量份
CoO 5.0重量份
Co 2O 3 5.0重量份
Fe 2O 3 3.0重量份
MnO 2 7.0重量份
KMnO 4 5.0重量份
采用该脱硫脱硝剂对烟气进行催化氧化,并采用氧化镁干粉进行吸收。烟气的流速为2.5m/s;烟气入口的其他参数、烟气出口的参数如表2和3所示。
表2、烟气入口参数
序号 参数 单位 数值
1 入口烟气量(工况) m 3/h 120000
2 入口烟气量(标况) Nm 3/h 80294
3 入口烟温 135
4 SO 2入口浓度 mg/Nm 3 2000
5 入口一氧化氮浓度 mg/Nm 3 450
6 烟气含湿量 5.7
表3、烟气出口参数
序号 项目 数量 单位
1 出口烟气量(工况) 42353 m 3/h
2 排烟温度 65
3 二氧化硫排放浓度 23 mg/Nm 3
4 脱硫效率 99.51
5 氮氧化物排放浓度 50 mg/Nm 3
6 脱硝效率 96
7 副产物的产出量 5.34 t/h
净化后的烟气中,二氧化硫的浓度是23mg/Nm 3,氮氧化物的浓度是50mg/Nm 3。脱硫效率达到99.51%,脱硝效率为96%。
实施例2
按照表4的配方得到脱硫脱硝剂H2,其余条件与实施例1相同。采用该脱硫脱硝剂对烟气进行催化氧化,并采用氧化镁干粉进行吸收。烟气入口参数同实施例1,烟气出口的参数如表5所示。
表4、脱硫脱硝剂H2的配方
TiO 2 52.0重量份
ZrO 2 15.0重量份
V 2O 5 6.0重量份
CoO 5.0重量份
Co 2O 3 5.0重量份
Fe 2O 3 5.0重量份
MnO 2 7.0重量份
KMnO 4 5.0重量份
表5、烟气出口参数
序号 项目 数量 单位
1 出口烟气量(工况) 41341 m 3/h
2 排烟温度 65
3 二氧化硫排放浓度 19 mg/Nm 3
4 脱硫效率 99.60
5 氮氧化物排放浓度 43 mg/Nm 3
6 脱硝效率 96.02
7 副产物的产出量 5.43 t/h
净化后的烟气中,二氧化硫的浓度是19mg/Nm 3,氮氧化物的浓度是43mg/Nm 3。脱硫效率达到99.60%,脱硝效率为96.02%。
实施例3
按照表6的配方得到脱硫脱硝剂H3,其余条件与实施例1相同。采用该脱硫脱硝剂对烟气进行催化氧化,并采用氧化镁干粉进行吸 收。烟气入口参数同实施例1,烟气出口的参数如表7所示。
表6、脱硫脱硝剂H3的配方
TiO 2 48.0重量份
ZrO 2 15.0重量份
V 2O 5 8.0重量份
CoO 5.0重量份
Co 2O 3 5.0重量份
Fe 2O 3 7.0重量份
MnO 2 7.0重量份
KMnO 4 5.0重量份
表7、烟气出口参数
序号 项目 数量 单位
1 出口烟气量(工况) 40324 m 3/h
2 排烟温度 65
3 二氧化硫排放浓度 13 mg/Nm 3
4 脱硫效率 99.73
5 氮氧化物排放浓度 29 mg/Nm 3
6 脱硝效率 97.39
7 副产物的产出量 5.7 t/h
净化后的烟气,二氧化硫的浓度是13mg/Nm 3,氮氧化物的浓度是29mg/Nm 3。脱硫效率达到99.73%,脱硝效率为97.39%。
本发明并不限于上述实施方式,在不背离本发明的实质内容的情况下,本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。

Claims (10)

  1. 一种干法脱硫脱硝剂,其特征在于,该脱硫脱硝剂由包括以下组分的原料制成:基于100重量份脱硝剂,
    Figure PCTCN2018103025-appb-100001
  2. 根据权利要求1所述的脱硫脱硝剂,其特征在于,该脱硫脱硝剂由包括以下组分的原料制成:基于100重量份脱硝剂,
    Figure PCTCN2018103025-appb-100002
  3. 根据权利要求1所述的脱硫脱硝剂,其特征在于,该脱硫脱硝剂由包括以下组分的原料制成:基于100重量份脱硝剂,
    Figure PCTCN2018103025-appb-100003
    Figure PCTCN2018103025-appb-100004
  4. 根据权利要求1所述的脱硫脱硝剂,其特征在于,TiO 2和ZrO 2作为载体;V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2和KMnO 4作为活性成分。
  5. 根据权利要求1所述的脱硫脱硝剂,其特征在于,所述脱硫脱硝剂的平均粒径为0.8~15微米。
  6. 根据权利要求1~5任一项所述的脱硫脱硝剂的生产方法,其特征在于,包括如下步骤:
    (1)将V 2O 5、CoO、Co 2O 3、Fe 2O 3、MnO 2和KMnO 4加入含有TiO 2和ZrO 2的浆液中,在转速为100~300rpm下搅拌10~60小时,形成混合浆液;其中,TiO 2、ZrO 2、V 2O 5、CoO、Co 2O 3、Fe 2O 3和MnO 2均为纳米级氧化物;
    (2)在震荡频率为15~200kHz的超声波作用下,将浓度为2~19wt%氨水加入所述混合浆液,直至反应体系的pH值为7~9.5;继续搅拌2~6小时后,滴加高锰酸钾溶液,直至反应体系的pH值为4~6,继续搅拌2~6小时,真空抽滤,加水洗涤,得到膏状物;
    (3)将所述膏状物在100~130℃下干燥,研磨成微小颗粒;将该微小颗粒在350~1000℃下煅烧2~6小时,得到所述脱硫脱硝剂。
  7. 根据权利要求6所述的生产方法,其特征在于,步骤(2)中,氨水的加入速度为0.2~20mL/min。
  8. 根据权利要求6所述的生产方法,其特征在于,步骤(2)中,高锰酸钾溶液的滴加速度为0.2~20mL/min。
  9. 一种烟气干法脱硫脱硝的方法,其特征在于,将烟气与权利要求1~5任一项所述的脱硫脱硝剂充分接触,然后与含有氧化镁的吸收剂干粉接触,从而脱除烟气中的氮氧化物和二氧化硫;所述氧化镁包括70~85wt%的活性氧化镁,且纳米级氧化镁在所述氧化镁中的含量为10~20wt%。
  10. 根据权利要求9所述的方法,其特征在于,与脱硫脱硝剂接触之前的烟气的二氧化硫含量为1000~3000mg/Nm 3、氮氧化物含量为100~600mg/Nm 3、流速为2~5m/s、且温度为110~170℃。
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