WO2021134927A1 - Dry process of integrated flue gas desulfurization and denitration - Google Patents

Dry process of integrated flue gas desulfurization and denitration Download PDF

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WO2021134927A1
WO2021134927A1 PCT/CN2020/080339 CN2020080339W WO2021134927A1 WO 2021134927 A1 WO2021134927 A1 WO 2021134927A1 CN 2020080339 W CN2020080339 W CN 2020080339W WO 2021134927 A1 WO2021134927 A1 WO 2021134927A1
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flue gas
dry powder
dust removal
desulfurization
dry
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French (fr)
Chinese (zh)
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童裳慧
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童裳慧
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/80—Semi-solid phase processes, i.e. by using slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/83—Solid phase processes with moving reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to a dry integrated flue gas desulfurization and denitration process.
  • Nitrogen oxide is a general term for various nitrogen oxide compounds such as nitric oxide (NO), nitrogen dioxide (NO 2 ), nitrous oxide (N 2 O 3 ), etc., which are used in atmospheric environments such as strong light, low temperature, and low wind. It can react with hydrocarbons to produce secondary pollutants such as ozone, formaldehyde, and peroxyacetyl nitrate, which can eventually form highly toxic blue or brown photochemical smog.
  • the integrated removal of sulfur dioxide and nitrogen oxides has been a research hotspot in recent years.
  • the removal of nitrogen oxides in flue gas, especially the effective removal of NO, is a difficult point in research.
  • the nitrogen oxides in the flue gas are removed by first oxidation and then reduction, with a high removal rate, and the product is harmless N 2 , which has no secondary pollution to the environment.
  • the oxidation of NO requires the participation of oxidants, and commonly used oxidants include ozone. Ozone is mostly used as the gas-phase oxidant, but its cost is high, the investment is large, and there are dangerous factors in the operation of the equipment.
  • CN107551782A discloses a method for dry flue gas denitration, which includes the following steps: (1) pre-dust removal step: pre-dust the flue gas to be treated to remove most of the dust particles, thereby forming flue gas to be denitrified; (2) oxidation Step: Use a denitration catalyst to oxidize the nitrogen monoxide in the flue gas to be denitrated into nitrogen dioxide in the catalytic bed equipment, thereby forming an oxidation flue gas; the denitration catalyst includes a carrier and an active ingredient; the carrier is a nano-scale amphoteric oxidation Material, selected from one or more of TiO 2 , ZrO 2 or HfO 2 ; the active ingredients include CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 and KMnO 4 ; (3) Absorption step: adopt The denitration agent with magnesium oxide as the main component performs dry denitration on the oxidation flue gas in the absorption device, thereby forming a treated flue
  • CN106422772A discloses an ammonia gasification system for SCR flue gas denitration, which is used in the ammonia gasification and ammonia injection process of the SCR flue gas denitration process.
  • the system includes an ammonia tank, an ammonia pump, an ammonia metering control device and a number of ammonia spray guns connected in sequence.
  • the ammonia in the ammonia tank is pressurized by the ammonia pump and sent to the ammonia metering control device.
  • the ammonia metering control device adjusts the flow and pressure of the ammonia and then sends it to the ammonia spray gun.
  • the ammonia in the ammonia spray gun compresses the air in the compressed air tank.
  • the atomized ammonia is completely gasified under the heat of the denitrification original flue gas, and the gasified ammonia is mixed with the denitrification original flue gas to form a denitrification reaction.
  • ammonia flue gas mixture it is difficult to ensure the mixing degree of the injected ammonia water with the flue gas after gasification, which will affect the denitration efficiency and the utilization rate of the reducing agent.
  • CN109107347A discloses a desulfurization and denitrification process, including the following steps: (1) boiler flue gas is pretreated by flue gas pretreatment equipment; (2) induced draft fan sends the pretreated flue gas to a spray tower, and the absorption liquid is The mixed solution of sodium chlorite and sodium hypochlorite solution; (3) The flue gas is discharged after spraying, washing, foam absorption, and filtering in the spray tower; (4) The absorption liquid in the circulation tank is regularly pumped out and sent to waste liquid treatment The equipment is recycled.
  • the purpose of the present invention is to provide a dry integrated flue gas desulfurization and denitration process.
  • the invention uses hydrogen peroxide as the oxidant, and uses calcium hydroxide (or calcium oxide) and ammonium bisulfite to perform integrated flue gas desulfurization and denitrification in a dense coherent tower, and the denitrification efficiency is further improved.
  • the operating cost of the process of the present invention is relatively low.
  • the present invention provides a dry integrated flue gas desulfurization and denitration process, which includes the following steps:
  • the original flue gas is pretreated by pre-dust removal equipment to obtain dust removal flue gas;
  • the oxidizing flue gas is passed into the absorption tower, while the absorbent dry powder and ammonium bisulfite dry powder are sprayed into the absorption tower, and water is sprayed into the absorption tower at the same time, thereby humidifying the absorbent dry powder and ammonium bisulfite dry powder And dry powder of absorbent and dry powder of ammonium bisulfite contact and react with the oxidizing flue gas, thereby forming desulfurization and denitration flue gas; wherein the dry powder of ammonium bisulfite added per unit time is connected to the unit time in step (1)
  • the molar ratio of nitric oxide contained in the incoming raw flue gas is 3.2 ⁇ 4.9:1;
  • the desulfurization and denitration flue gas is subjected to dust removal treatment through a dust removal device to obtain purified flue gas.
  • the H 2 O 2 in the hydrogen peroxide aqueous solution added per unit time in step (2) is the same as the H 2 O 2 in the hydrogen peroxide solution per unit time in step (1).
  • the molar ratio of nitric oxide contained in the flue gas is 1 to 4:1; the concentration of the aqueous hydrogen peroxide solution is 15 to 35 wt%.
  • the oxidant is sprayed into the flue gas pipe through a first spray device, and performs an oxidation reaction with the dust removal flue gas;
  • the contact time between the oxidant and the dust removal flue gas is 1-30s.
  • the flow velocity of the dust removal flue gas in the flue gas pipeline is 6-15 m/s.
  • the dry ammonium bisulfite powder added per unit time in step (3) and the original flue gas passed in per unit time in step (1) contained
  • the molar ratio of nitric oxide is 3.2 to 3.9:1.
  • the dry powder of the absorbent is calcium oxide or calcium hydroxide.
  • the dry powder of absorbent added per unit time in step (3) and the sulfur dioxide contained in the original flue gas passed in per unit time in step (1) is the dry powder of absorbent added per unit time in step (3) and the sulfur dioxide contained in the original flue gas passed in per unit time in step (1)
  • the molar ratio is the calcium-sulfur ratio, which is 1 to 2:1.
  • the contact time between the dry powder of absorbent and the dry powder of ammonium bisulfite in the absorption tower and the oxidation flue gas is 5-30 seconds.
  • the flow rate of the oxidation flue gas in the absorption tower is 1-7 m/s.
  • the dry integrated flue gas desulfurization and denitration process according to the present invention preferably includes the following specific steps:
  • the original flue gas is pretreated by a pre-dust removal device to obtain dust removal flue gas; wherein the pre-dust removal device is an electrostatic precipitator; the dust removal flue gas is passed into the flue gas pipeline;
  • the hydrogen peroxide aqueous solution is supplied to the first spraying device through the oxidant supply device, and then the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the first spraying device, and is in contact with the dust removal flue gas. Oxidation reaction to obtain oxidized flue gas; wherein, the first spray device is an atomizer;
  • the present invention uses hydrogen peroxide to oxidize NO in the flue gas into high-valence nitrogen oxides, and uses ammonium bisulfite dry powder and absorbent dry powder to remove nitrogen oxides and SO 2 in a dense coherent tower to generate harmless product N 2.
  • Ammonium sulfate and calcium sulfate no secondary pollution.
  • the desulfurization efficiency of the invention can reach 99.7%, and the denitration efficiency can reach 98.8%.
  • the water consumption of the present invention is small, and the by-product is a powdery product, which not only reduces water consumption, but also saves the process steps of the by-product crystallization and purification.
  • Figure 1 is a schematic diagram of the structure of the dry integrated desulfurization and denitrification device of the present invention.
  • the "wt%" in the present invention is a weight percentage.
  • the process of the present invention includes a pre-dust removal step, an oxidation step, a desulfurization and denitration step, a dust removal step and the like.
  • a cycle step is also included.
  • the process of the invention is suitable for the treatment of flue gas containing sulfur and nitrogen such as coal-fired boilers, steel sintering machines, pellets, industrial kilns and the like. The details are described below.
  • the original flue gas is pretreated by a pre-dust removal equipment to obtain dust removal flue gas. Pass the dust removal flue gas into the flue gas pipe.
  • the pre-dust removal efficiency can reach more than 90%.
  • the dust content in the original flue gas is 80-200 mg/Nm 3 , preferably 90-180 mg/Nm 3 , and more preferably 100-160 mg/Nm 3 .
  • the pre-dust removal equipment may adopt a bag filter, a cyclone dust collector or an electric dust collector, and is preferably an electric dust collector.
  • the pre-dust removal treatment adopts a wet electrostatic precipitator for dust removal. After the pre-dust removal step, large and small particles in the flue gas can be removed.
  • the dust content in the dust removal flue gas is 5-20 mg/Nm 3 , preferably 6-18 mg/Nm 3 , and more preferably 7-16 mg/Nm 3 .
  • the hydrogen peroxide can more fully react with the nitric oxide (NO) in the flue gas to form high-valence nitrogen oxides such as NO 2 and N 2 O 5 .
  • the oxygen content in the original flue gas is 5 to 23 vol%, preferably 8 to 20 vol%.
  • the hydrogen peroxide aqueous solution can more fully react with the NO in the flue gas to form high-valence nitrogen oxides such as NO 2 and N 2 O 5. It is appropriate to control the oxygen content of the flue gas within the scope of the present invention. If the oxygen content in the flue gas is too low, the desulfurization and denitrification effect cannot be guaranteed; if the oxygen content is too high, energy consumption and cost will be increased.
  • the temperature of the raw flue gas before the pre-dust removal treatment may be 90-150°C, preferably 100-130°C, more preferably 110-120°C.
  • the original flue gas flow rate is 180,000-2,000,000 Nm 3 /h, preferably 200,000-2,000,000 Nm 3 /h, and more preferably 200,000-1800000 Nm 3 /h.
  • the moisture content of the original flue gas is 5-15%, preferably 5-12%. Controlling the flue gas temperature, flue gas humidity and flow rate within the above range is more conducive to the hydrogen peroxide aqueous solution to forcibly oxidize NO to high-valence nitrogen oxides such as NO 2 and N 2 O 5 , thereby improving the denitration efficiency.
  • the sulfur content of the original flue gas is 500 to 4500 mg/Nm 3 , preferably 600 to 4500 mg/Nm 3 , and more preferably 600 to 4000 mg/Nm 3 .
  • the sulfur-containing material in the original flue gas is mainly sulfur dioxide.
  • the nitrogen oxides in the original flue gas are mainly NO.
  • Controlling the concentration of sulfur dioxide and nitrogen oxides in the flue gas within the above range is more conducive to the forced oxidation of NO by hydrogen peroxide to high-valence nitrogen oxides such as NO 2 and N 2 O 5 , and is conducive to dry absorbent powder (calcium oxide or Calcium hydroxide) and ammonium bisulfite dry powder react with sulfur dioxide and high-valence nitrogen oxides, thereby improving desulfurization efficiency and denitration efficiency.
  • dry absorbent powder calcium oxide or Calcium hydroxide
  • the original flue gas in the present invention can be sulfur-containing and NO-containing flue gas from coal-fired boilers, steel sintering machines, pellets, industrial kilns and the like.
  • the dust removal flue gas and the oxidant are contacted in the flue gas pipe to carry out an oxidation reaction, thereby forming an oxidation flue gas.
  • the invention uses hydrogen peroxide as the oxidant, which can rapidly chemically react with the low-valent nitrogen oxides in the flue gas, and has a fast reaction speed and high efficiency. Hydrogen peroxide is used in the form of an aqueous solution of hydrogen peroxide.
  • the molar ratio of the H 2 O 2 in the hydrogen peroxide aqueous solution added per unit time to the nitrogen monoxide contained in the original flue gas passed in the unit time in step (1) is 1 to 4: 1, It is preferably 1.1 to 3:1, more preferably 1.2 to 1.5:1. This can take into account the oxidation effect and save the hydrogen peroxide solution.
  • the concentration of the aqueous hydrogen peroxide solution is 15 to 35 wt%, preferably 20 to 35 wt%, more preferably 27.5 wt% or 35 wt%, and still more preferably 27.5 wt%.
  • the concentration of the hydrogen peroxide aqueous solution of the present invention can take into account the oxidation effect and save the hydrogen peroxide aqueous solution.
  • the contact time between the aqueous hydrogen peroxide solution and the dust removal flue gas is 1-30s, preferably 1-10s, and more preferably 1-3s.
  • the flow velocity of the dust removal flue gas in the flue gas duct is 6-15m/s, preferably 9-13m/s, more preferably 10-12m/s. This is conducive to the oxidation of NO in the flue gas.
  • the hydrogen peroxide aqueous solution is supplied to the first spraying device through the oxidant supply device, and the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the first spraying device, and then combined with the dust removal fume The gas contacts and reacts in the flue gas pipe to form an oxidized flue gas.
  • the first spray device is an atomizer, which is located in the flue gas duct.
  • the oxidation step is carried out in the flue gas pipeline before the absorption tower.
  • the first spray device is used for receiving the hydrogen peroxide aqueous solution and spraying the hydrogen peroxide aqueous solution into the flue gas pipe, so that the hydrogen peroxide can fully contact and react with the dust removal flue gas better.
  • the first spray device is arranged in the flue gas pipeline, which can increase the contact time of the hydrogen peroxide aqueous solution and the flue gas, thereby promoting the rapid oxidation reaction of hydrogen peroxide to low-valent nitrogen oxides (mainly NO).
  • Hydrogen peroxide oxidizes nitric oxide (NO) in the flue gas to high-valence nitrogen oxides such as nitrogen dioxide (NO 2 ) and dinitrogen pentoxide (N 2 O 5 ), which facilitates the reaction with dry ammonium bisulfite powder.
  • NO nitric oxide
  • N 2 O 5 dinitrogen pentoxide
  • the oxidized flue gas is passed into the absorption tower, while the absorbent dry powder and ammonium bisulfite dry powder are sprayed into the absorption tower, and water is sprayed into the absorption tower at the same time, so as to humidify the absorbent dry powder and ammonium bisulfite dry powder; and the absorbent dry powder
  • the dry powder of ammonium bisulfite contacts and reacts with the oxidation flue gas, thereby forming desulfurization and denitration flue gas. This is beneficial to improve desulfurization efficiency and denitration efficiency, without secondary pollution, and more environmentally friendly.
  • the molar ratio of the dry ammonium bisulfite powder added per unit time to the NO contained in the original flue gas passed in the unit time in the pre-dust removal step is 3.2 to 4.9:1, preferably 3.2 to 3.9:1 , More preferably 3.5 to 3.9:1. This helps to improve the denitration efficiency. If the amount of ammonium bisulfite is too small, the denitration efficiency will be low. If the amount of ammonium bisulfite is too much, on the one hand, the denitration efficiency will not be greatly improved, but will increase the cost; on the other hand, too much ammonium bisulfite will affect the absorption of the absorbent dry powder and reduce the desulfurization efficiency.
  • the absorbent dry powder is calcium oxide dry powder or calcium hydroxide dry powder.
  • the molar ratio of the absorbent dry powder (calcium oxide or calcium hydroxide) added per unit time to the sulfur dioxide contained in the original flue gas passed in the unit time in the pre-dust removal step is the calcium-sulfur ratio, which can be 1 ⁇ 2:1 , Preferably 1.1 to 1.8:1, more preferably 1.1 to 1.5:1. This is conducive to the absorption of sulfur dioxide by the absorbent dry powder and the absorption of sulfuric acid, the reaction product of the dry ammonium bisulfite powder, thereby helping to improve the desulfurization efficiency and the denitration efficiency.
  • the contact time of the absorbent dry powder, the dry ammonium bisulfite powder and the oxidation flue gas in the absorption tower is 5-30s, preferably 6-15s, more preferably 9-12s.
  • the flow velocity of the oxidation flue gas in the absorption tower is 1 to 7 m/s, preferably 2 to 5 m/s, more preferably 3 to 5 m/s, for example 4 m/s. This is conducive to the full reaction of dry ammonium bisulfite powder with nitrogen oxides, and at the same time, it is beneficial to the absorption of sulfur dioxide by the dry powder of absorbent and the absorption of sulfuric acid, the reaction product of dry ammonium bisulfite powder.
  • the absorbent dry powder is calcium oxide dry powder or calcium hydroxide dry powder, preferably calcium hydroxide dry powder.
  • Calcium hydroxide is also called slaked lime or slaked lime.
  • the particle size of the dry calcium oxide powder or the dry calcium hydroxide powder is 100-400 mesh, preferably 150-350 mesh, more preferably 200-250 mesh.
  • the particle size of the dry powder of ammonium bisulfite is 100-400 mesh, preferably 150-350 mesh, more preferably 200-300 mesh. This is beneficial to improve desulfurization efficiency and denitration efficiency.
  • the absorbent dry powder is supplied by the absorbent dry powder supply device.
  • the dry ammonium bisulfite powder is supplied by the ammonium bisulfite dry powder supply equipment.
  • the water used for the dry powder of humidifying absorbent and the dry powder of ammonium bisulfite is supplied by the second spraying device. Both the absorbent dry powder and the ammonium bisulfite dry powder are solid powders. In this way, the water consumption is small, and the by-product is a powdery product, which not only reduces water consumption, but also saves the process steps for crystallization and purification of the by-product.
  • water is sprayed into the absorption tower through a humidifier.
  • the presence of water makes the humidified dry powder of absorbent and the dry powder of ammonium bisulfite used synergistically.
  • water can promote the reduction and oxidation of nitrogen oxides in the flue gas by the dry powder of ammonium bisulfite;
  • water can promote the absorption of sulfur dioxide by the dry powder of absorbent and the absorption of sulfuric acid, the reaction product of the dry powder of ammonium bisulfite. This can significantly improve the effect of flue gas desulfurization and denitrification.
  • a proper amount of moisture is beneficial to flue gas desulfurization and denitrification, but excessive moisture will cause the dry powder of absorbent to agglomerate, thereby affecting the effect of flue gas desulfurization and denitration.
  • the oxidized flue gas is passed into the absorption tower, while the absorbent dry powder and ammonium bisulfite dry powder are respectively sprayed into the absorption tower through the absorbent dry powder supply device and the ammonium bisulfite dry powder supply device, and At the same time, water is sprayed into the absorption tower through the second spray device to humidify the absorbent dry powder and ammonium bisulfite dry powder, and the absorbent dry powder and ammonium bisulfite dry powder contact and react with the oxidizing flue gas in the absorption tower, Thereby forming desulfurization and denitrification flue gas.
  • the absorption tower is a dense phase dry tower; the second spray device is a humidifier.
  • the NO in the dust removal flue gas is oxidized by the hydrogen peroxide agent, and the resulting products include NO 2 , N 2 O 5 , HNO 3 , HNO 2 and H 2 O.
  • oxidized flue gas is obtained.
  • the dry powder of ammonium bisulfite and the dry powder of absorbent are used to fully react with the oxidizing flue gas. The principle is as follows:
  • the dust removal equipment is a bag filter. Filtered by a filter bag, purified flue gas that meets the dust emission requirements is obtained. The particulate matter intercepted on the filter bag is blown to the dust hopper of the dust collector, and part of it is sent to the ash silo. Mainly by-products such as calcium sulfate and ammonium sulfate are discharged into the ash silo.
  • the unreacted dry powder of absorbent and dry powder of ammonium bisulfite are recycled to the absorption tower.
  • unreacted dry powder of absorbent and dry powder of ammonium bisulfite may be recycled to the absorption tower through a circulation device.
  • the purified flue gas is discharged through the exhaust device, and the exhaust device of the present invention is a chimney.
  • the unreacted dry absorbent powder and ammonium bisulfite dry powder are sent from the bottom of the absorption tower or the dust hopper of the dust collector to the absorption tower through a circulation device.
  • the dry integrated flue gas desulfurization and denitration process includes the following specific steps:
  • the original flue gas is pretreated by a pre-dust removal device to obtain dust removal flue gas; wherein the pre-dust removal device is an electrostatic precipitator; the dust removal flue gas is passed into the flue gas pipeline;
  • the hydrogen peroxide aqueous solution is supplied to the first spraying device through the oxidant supply device, and then the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the first spraying device, and is in contact with the dust removal flue gas. Oxidation reaction to obtain oxidized flue gas; wherein, the first spray device is an atomizer;
  • FIG. 1 shows a schematic diagram of a device used in a dry integrated flue gas desulfurization and denitration process of the present invention. It can be seen from the figure that the flue gas desulfurization and denitrification device of the present invention includes: absorbent dry powder supply equipment 1, ammonium bisulfite dry powder supply equipment 2, oxidant supply equipment 3, atomizer 4, electrostatic precipitator 5, dense coherent tower 6, Humidifier 7, bag filter 8, ash warehouse 9 and chimney 10.
  • the original flue gas from the sintering machine is used to remove particulate matter with an electrostatic precipitator 5 to obtain dust-removing flue gas with a dust content of 11 mg/Nm 3 , which is passed into the flue gas pipeline.
  • the original flue gas (inlet flue gas) parameters and process parameters are shown in Table 1.
  • the hydrogen peroxide aqueous solution (concentration is 27.5wt%) is supplied to the atomizer 4 through the oxidant supply device 3; then the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the atomizer 4 and combined with the dust removal smoke The gas contacts and reacts in the flue gas pipe to form an oxidized flue gas.
  • the aqueous hydrogen peroxide solution oxidizes low-valence nitrogen oxides (such as NO) in the flue gas to form high-valence nitrogen oxides (such as NO 2 and N 2 O 5 ).
  • the desulfurization and denitration flue gas is dedusted by the bag filter 8 to obtain purified flue gas.
  • the purified flue gas is discharged through the chimney 10.
  • the parameters of the flue gas purification and the desulfurization efficiency and denitration efficiency are shown in Table 2.
  • the unreacted dry powder of absorbent and dry powder of ammonium bisulfite are sent to the dense coherent tower 6 for recycling, and the by-products such as calcium sulfate and ammonium sulfate enter the ash silo 9.

Abstract

A dry process of integrated flue gas desulfurization and denitration, comprising: (1) passing a flue gas through a pre-dedusting device for pretreatment, so as to obtain a dedusted flue gas; (2) contacting the dedusted flue gas with an oxidant in a flue gas pipeline for an oxidation reaction, so as to obtain an oxidized flue gas; (3) introducing the oxidized flue gas into an absorption column, simultaneously spraying an absorbent dry powder and an ammonium bisulphate dry powder into the absorption column, and simultaneously spraying water into the absorption column by means of a second spraying device, the absorbent dry powder and the ammonium bisulphate dry powder contacting and reacting with the oxidized flue gas, thereby forming a desulfurized and denitrated flue gas, the molar ratio of the ammonium bisulphate dry powder added per unit time to the nitrogen monoxide contained in the flue gas introduced in step (1) per unit time being 3.2 to 4.9 : 1; and (4) passing the desulfurized and denitrated flue gas through a dedusting device for dedusting treatment, so as to obtain a purified flue gas.

Description

干法一体化烟气脱硫脱硝工艺Dry integrated flue gas desulfurization and denitrification process 技术领域Technical field
本发明涉及一种干法一体化烟气脱硫脱硝工艺。The invention relates to a dry integrated flue gas desulfurization and denitration process.
背景技术Background technique
当前大气环境污染的主要污染源为大量排放的燃煤烟气，主要污染物成分为氮氧化物和SO 2等。氮氧化物是一氧化氮(NO)、二氧化氮(NO 2)、三氧化二氮(N 2O 3)等多种氮氧化合物的总称，其在强光、低温、少风等大气环境下可与碳氢化合物发生反应，产生臭氧、甲醛、过氧乙酰硝酸酯等二次污染物，最终可形成毒性很大的蓝色或棕色光化学烟雾。 At present, the main source of atmospheric pollution is a large amount of coal-fired flue gas, and the main pollutants are nitrogen oxides and SO 2 . Nitrogen oxide is a general term for various nitrogen oxide compounds such as nitric oxide (NO), nitrogen dioxide (NO 2 ), nitrous oxide (N 2 O 3 ), etc., which are used in atmospheric environments such as strong light, low temperature, and low wind. It can react with hydrocarbons to produce secondary pollutants such as ozone, formaldehyde, and peroxyacetyl nitrate, which can eventually form highly toxic blue or brown photochemical smog.
将二氧化硫和氮氧化物的一体化进行脱除是近几年来的研究热点。烟气中氮氧化物的脱除，尤其是NO的有效脱除，是研究难点。采用先氧化后还原脱除烟气中的氮氧化物，脱除率高，产物为无害的N 2，对环境无二次污染。NO的氧化需要氧化剂的参与，常用的氧化剂包括臭氧。气相氧化剂多采用臭氧，但其存在价格高，投入大，设备运行过程存在危险因素。 The integrated removal of sulfur dioxide and nitrogen oxides has been a research hotspot in recent years. The removal of nitrogen oxides in flue gas, especially the effective removal of NO, is a difficult point in research. The nitrogen oxides in the flue gas are removed by first oxidation and then reduction, with a high removal rate, and the product is harmless N 2 , which has no secondary pollution to the environment. The oxidation of NO requires the participation of oxidants, and commonly used oxidants include ozone. Ozone is mostly used as the gas-phase oxidant, but its cost is high, the investment is large, and there are dangerous factors in the operation of the equipment.
CN107551782A公开了一种干法烟气脱硝的方法，包括如下步骤：(1)预除尘步骤：将待处理烟气进行预除尘以除去大部分粉尘颗粒，从而形成待脱硝烟气；(2)氧化步骤：采用脱硝催化剂在催化床设备中将待脱硝烟气中的一氧化氮氧化为二氧化氮，从而形成氧化烟气；所述脱硝催化剂包括载体和活性成分；所述载体为纳米级两性氧化物，选自TiO 2、ZrO 2或HfO 2中的一种或多种；所述活性成分包括CoO、Co 2O 3、Fe 2O 3、MnO 2和KMnO 4；(3)吸收步骤：采用以氧化镁为主要成分的脱硝剂在吸收装置中对所述氧化烟气进行干法脱硝， 从而形成处理后烟气。上述方法需要采用贵金属，成本较高。 CN107551782A discloses a method for dry flue gas denitration, which includes the following steps: (1) pre-dust removal step: pre-dust the flue gas to be treated to remove most of the dust particles, thereby forming flue gas to be denitrified; (2) oxidation Step: Use a denitration catalyst to oxidize the nitrogen monoxide in the flue gas to be denitrated into nitrogen dioxide in the catalytic bed equipment, thereby forming an oxidation flue gas; the denitration catalyst includes a carrier and an active ingredient; the carrier is a nano-scale amphoteric oxidation Material, selected from one or more of TiO 2 , ZrO 2 or HfO 2 ; the active ingredients include CoO, Co 2 O 3 , Fe 2 O 3 , MnO 2 and KMnO 4 ; (3) Absorption step: adopt The denitration agent with magnesium oxide as the main component performs dry denitration on the oxidation flue gas in the absorption device, thereby forming a treated flue gas. The above method requires the use of precious metals, and the cost is relatively high.
CN106422772A公开了一种用于SCR烟气脱硝的氨水气化系统，用于SCR烟气脱硝工艺的氨水气化及氨喷射过程。该系统包括依次连接的氨水槽、氨水泵、氨水计量控制装置及若干氨水喷枪。工作时，氨水槽中的氨水通过氨水泵增压后送至氨水计量控制装置，由氨水计量控制装置调节氨水的流量和压力后送至氨水喷枪，氨水喷枪中的氨水在压缩空气罐中压缩空气的推动下以雾化形式喷入原烟气烟道内，在脱硝原烟气的热量作用下，雾化后的氨水完全气化，气化后的氨水与脱硝原烟气混合后，为脱硝反应提供氨烟气混合气体。该发明中喷射的氨水气化后难以保证与烟气的混合程度，会对脱硝效率和还原剂的利用率产生影响。CN106422772A discloses an ammonia gasification system for SCR flue gas denitration, which is used in the ammonia gasification and ammonia injection process of the SCR flue gas denitration process. The system includes an ammonia tank, an ammonia pump, an ammonia metering control device and a number of ammonia spray guns connected in sequence. When working, the ammonia in the ammonia tank is pressurized by the ammonia pump and sent to the ammonia metering control device. The ammonia metering control device adjusts the flow and pressure of the ammonia and then sends it to the ammonia spray gun. The ammonia in the ammonia spray gun compresses the air in the compressed air tank. In the form of atomization, sprayed into the original flue gas flue under the promotion of the denitrification of the original flue gas, the atomized ammonia is completely gasified under the heat of the denitrification original flue gas, and the gasified ammonia is mixed with the denitrification original flue gas to form a denitrification reaction. Provide ammonia flue gas mixture. In the present invention, it is difficult to ensure the mixing degree of the injected ammonia water with the flue gas after gasification, which will affect the denitration efficiency and the utilization rate of the reducing agent.
CN109107347A公开了一种脱硫脱硝工艺，包括以下步骤：(1)锅炉烟气通过烟气预处理设备进行预处理；(2)引风机将预处理过后的烟气送入喷淋塔，吸收液为亚氯酸钠与次氯酸钠溶液的混合液；(3)烟气在喷淋塔内经过喷淋、水洗、泡沫吸收、过滤后排放；(4)循环池中的吸收液定期抽出送往废液处理设备进行回收处理。该工艺中吸收剂为亚氯酸钠和次氯酸钠的混合溶液，其脱硫效率约91 ～99％、脱硝效率约86 ～90％；而且该工艺需要使用氢氧化钠调节吸收液pH值在指定范围内，操作不便。此外，需要多次净化吸收脱硝效率才能达到90％。 CN109107347A discloses a desulfurization and denitrification process, including the following steps: (1) boiler flue gas is pretreated by flue gas pretreatment equipment; (2) induced draft fan sends the pretreated flue gas to a spray tower, and the absorption liquid is The mixed solution of sodium chlorite and sodium hypochlorite solution; (3) The flue gas is discharged after spraying, washing, foam absorption, and filtering in the spray tower; (4) The absorption liquid in the circulation tank is regularly pumped out and sent to waste liquid treatment The equipment is recycled. The process of absorbent mixed solution of sodium chlorite and sodium hypochlorite, desulfurization efficiency of about 91 to 99%, the denitration efficiency of about 86% to 90%; and the process requires the use of sodium hydroxide to adjust the pH of the absorption liquid within a specified range , Inconvenient operation. In addition, multiple purification and absorption denitration efficiency are required to reach 90%.
发明内容Summary of the invention
本发明的目的在于提供一种干法一体化烟气脱硫脱硝工艺。本发明采用过氧化氢为氧化剂，并采用氢氧化钙(或氧化钙)和亚硫酸氢铵在密相干塔中进行烟气一体化脱硫脱硝，脱硝效率得到进一步提高。此外，本发明的工艺运行成本较低。The purpose of the present invention is to provide a dry integrated flue gas desulfurization and denitration process. The invention uses hydrogen peroxide as the oxidant, and uses calcium hydroxide (or calcium oxide) and ammonium bisulfite to perform integrated flue gas desulfurization and denitrification in a dense coherent tower, and the denitrification efficiency is further improved. In addition, the operating cost of the process of the present invention is relatively low.
本发明提供一种干法一体化烟气脱硫脱硝工艺，包括以下步骤：The present invention provides a dry integrated flue gas desulfurization and denitration process, which includes the following steps:
(1)将原烟气通过预除尘设备进行预处理，得到除尘烟气；(1) The original flue gas is pretreated by pre-dust removal equipment to obtain dust removal flue gas;
(2)将所述除尘烟气与氧化剂在烟气管道内接触以进行氧化反应，得到氧化烟气；其中，所述氧化剂为过氧化氢水溶液；(2) Contacting the dust removal flue gas with an oxidant in a flue gas pipe to perform an oxidation reaction to obtain an oxidized flue gas; wherein the oxidant is an aqueous hydrogen peroxide solution;
(3)将所述氧化烟气通入吸收塔，同时将吸收剂干粉和亚硫酸氢铵干粉喷入吸收塔，且同时向吸收塔内喷入水，从而加湿吸收剂干粉和亚硫酸氢铵干粉；并且吸收剂干粉和亚硫酸氢铵干粉与所述氧化烟气接触并反应，从而形成脱硫脱硝烟气；其中，单位时间内加入的亚硫酸氢铵干粉与步骤(1)中单位时间内通入的原烟气中所含一氧化氮的摩尔比为3.2～4.9:1；和(3) The oxidizing flue gas is passed into the absorption tower, while the absorbent dry powder and ammonium bisulfite dry powder are sprayed into the absorption tower, and water is sprayed into the absorption tower at the same time, thereby humidifying the absorbent dry powder and ammonium bisulfite dry powder And dry powder of absorbent and dry powder of ammonium bisulfite contact and react with the oxidizing flue gas, thereby forming desulfurization and denitration flue gas; wherein the dry powder of ammonium bisulfite added per unit time is connected to the unit time in step (1) The molar ratio of nitric oxide contained in the incoming raw flue gas is 3.2～4.9:1; and
(4)将所述脱硫脱硝烟气通过除尘设备进行除尘处理，得到净化烟气。(4) The desulfurization and denitration flue gas is subjected to dust removal treatment through a dust removal device to obtain purified flue gas.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，步骤(2)中单位时间内加入的过氧化氢水溶液中的H 2O 2与步骤(1)中单位时间内通入的原烟气中所含一氧化氮的摩尔比为1～4:1；过氧化氢水溶液的浓度为15～35wt％。 According to the dry integrated flue gas desulfurization and denitrification process of the present invention, preferably, the H 2 O 2 in the hydrogen peroxide aqueous solution added per unit time in step (2) is the same as the H 2 O 2 in the hydrogen peroxide solution per unit time in step (1). The molar ratio of nitric oxide contained in the flue gas is 1 to 4:1; the concentration of the aqueous hydrogen peroxide solution is 15 to 35 wt%.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，步骤(2)中，将所述氧化剂通过第一喷淋设备喷淋到烟气管道内，并与除尘烟气进行氧化反应；所述氧化剂与除尘烟气接触时间为1～30s。According to the dry integrated flue gas desulfurization and denitrification process of the present invention, preferably, in step (2), the oxidant is sprayed into the flue gas pipe through a first spray device, and performs an oxidation reaction with the dust removal flue gas; The contact time between the oxidant and the dust removal flue gas is 1-30s.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，步骤(2)中，所述除尘烟气在烟气管道内的流速为6～15m/s。According to the dry integrated flue gas desulfurization and denitrification process of the present invention, preferably, in step (2), the flow velocity of the dust removal flue gas in the flue gas pipeline is 6-15 m/s.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，步骤(3)中单位时间内加入的亚硫酸氢铵干粉与步骤(1)中单位时间内通入的原烟气中所含一氧化氮的摩尔比为3.2～3.9:1。According to the dry integrated flue gas desulfurization and denitrification process of the present invention, preferably, the dry ammonium bisulfite powder added per unit time in step (3) and the original flue gas passed in per unit time in step (1) contained The molar ratio of nitric oxide is 3.2 to 3.9:1.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，步骤(3)中，所述吸收剂干粉为氧化钙或氢氧化钙。According to the dry integrated flue gas desulfurization and denitration process of the present invention, preferably, in step (3), the dry powder of the absorbent is calcium oxide or calcium hydroxide.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，步骤(3)中单位时间内加入的吸收剂干粉与步骤(1)中单位时间内通入的原烟气中所含二氧化硫的摩尔比为钙硫比，其为1～2:1。According to the dry integrated flue gas desulfurization and denitration process of the present invention, preferably, the dry powder of absorbent added per unit time in step (3) and the sulfur dioxide contained in the original flue gas passed in per unit time in step (1) The molar ratio is the calcium-sulfur ratio, which is 1 to 2:1.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，步骤(3)中，所述吸收塔内吸收剂干粉、亚硫酸氢铵干粉与氧化烟气接触时间为5～30s。According to the dry integrated flue gas desulfurization and denitrification process of the present invention, preferably, in step (3), the contact time between the dry powder of absorbent and the dry powder of ammonium bisulfite in the absorption tower and the oxidation flue gas is 5-30 seconds.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，步骤(3)中，所述氧化烟气在吸收塔内的流速为1～7m/s。According to the dry integrated flue gas desulfurization and denitrification process of the present invention, preferably, in step (3), the flow rate of the oxidation flue gas in the absorption tower is 1-7 m/s.
根据本发明的干法一体化烟气脱硫脱硝工艺，优选地，包括如下具体步骤：The dry integrated flue gas desulfurization and denitration process according to the present invention preferably includes the following specific steps:
(1)将原烟气通过预除尘设备进行预处理，得到除尘烟气；其中，所述预除尘设备为静电除尘器；将除尘烟气通入烟气管道内；(1) The original flue gas is pretreated by a pre-dust removal device to obtain dust removal flue gas; wherein the pre-dust removal device is an electrostatic precipitator; the dust removal flue gas is passed into the flue gas pipeline;
(2)将过氧化氢水溶液通过氧化剂供给设备供给至第一喷淋设备，然后将过氧化氢水溶液通过第一喷淋设备喷淋至烟气管道内，并与所述除尘烟气接触以进行氧化反应，得到氧化烟气；其中，所述第一喷淋设备为雾化器；(2) The hydrogen peroxide aqueous solution is supplied to the first spraying device through the oxidant supply device, and then the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the first spraying device, and is in contact with the dust removal flue gas. Oxidation reaction to obtain oxidized flue gas; wherein, the first spray device is an atomizer;
(3)将氧化烟气通入吸收塔，同时将吸收剂干粉和亚硫酸氢铵干粉分别通过吸收剂干粉供给设备和亚硫酸氢铵干粉供给设备喷入至吸收塔，且同时通过第二喷淋设备向吸收塔内喷入水，从而加湿吸收剂干粉和亚硫酸氢铵干粉，并且吸收剂干粉和亚硫酸氢铵干粉与所述氧化烟气在吸收塔内接触并反应，从而形成脱硫脱硝烟气；其中，所述吸收塔为密相干塔；所述第二喷淋设备为加湿器；和(3) Pass the oxidation flue gas into the absorption tower, and at the same time spray the absorbent dry powder and ammonium bisulfite dry powder into the absorption tower through the absorbent dry powder supply equipment and the ammonium bisulfite dry powder supply equipment, and at the same time through the second spray The shower device sprays water into the absorption tower to humidify the absorbent dry powder and ammonium bisulfite dry powder, and the absorbent dry powder and ammonium bisulfite dry powder contact and react with the oxidation flue gas in the absorption tower, thereby forming desulfurization and denitration fumes Gas; wherein, the absorption tower is a dense-phase dry tower; the second spray device is a humidifier; and
(4)将所述脱硫脱硝烟气通过除尘设备进行除尘处理，得到净化烟气；其中，所述除尘设备为布袋除尘器。(4) Pass the desulfurization and denitration flue gas through a dust removal device for dust removal treatment to obtain purified flue gas; wherein the dust removal device is a bag filter.
本发明采用过氧化氢将烟气中的NO氧化为高价态的氮氧化物， 利用亚硫酸氢铵干粉和吸收剂干粉在密相干塔中脱除氮氧化物和SO 2，生成无害产物N 2、硫酸铵和硫酸钙，无二次污染。本发明的脱硫效率可达99.7％，脱硝效率可达98.8％。与湿法工艺相比，本发明用水量小，副产物为粉末状产物，不仅降低水的消耗，还节省了副产物结晶提纯的工艺步骤。 The present invention uses hydrogen peroxide to oxidize NO in the flue gas into high-valence nitrogen oxides, and uses ammonium bisulfite dry powder and absorbent dry powder to remove nitrogen oxides and SO 2 in a dense coherent tower to generate harmless product N 2. Ammonium sulfate and calcium sulfate, no secondary pollution. The desulfurization efficiency of the invention can reach 99.7%, and the denitration efficiency can reach 98.8%. Compared with the wet process, the water consumption of the present invention is small, and the by-product is a powdery product, which not only reduces water consumption, but also saves the process steps of the by-product crystallization and purification.
附图说明Description of the drawings
图1为本发明的干法一体化脱硫脱硝装置的结构示意图。Figure 1 is a schematic diagram of the structure of the dry integrated desulfurization and denitrification device of the present invention.
1-吸收剂干粉供给设备；2-亚硫酸氢铵干粉供给设备；3-氧化剂供给设备；4-雾化器；5-静电除尘器；6-密相干塔；7-加湿器；8-布袋除尘器；9-灰仓；10-烟囱。1- Absorbent dry powder supply equipment; 2- Ammonium bisulfite dry powder supply equipment; 3- Oxidizer supply equipment; 4- Atomizer; 5- Electrostatic precipitator; 6-Dense phase dry tower; 7- Humidifier; 8- Bag Dust collector; 9-ash warehouse; 10-chimney.
具体实施方式Detailed ways
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。The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.
本发明的“wt％”为重量百分比。The "wt%" in the present invention is a weight percentage.
本发明的工艺包括预除尘步骤、氧化步骤、脱硫脱硝步骤、除尘步骤等。任选地，还包括循环步骤。本发明的工艺适用于燃煤锅炉、钢铁烧结机、球团、工业窑炉等含硫和氮的烟气的处理。下面进行详细介绍。The process of the present invention includes a pre-dust removal step, an oxidation step, a desulfurization and denitration step, a dust removal step and the like. Optionally, a cycle step is also included. The process of the invention is suitable for the treatment of flue gas containing sulfur and nitrogen such as coal-fired boilers, steel sintering machines, pellets, industrial kilns and the like. The details are described below.
<预除尘步骤><Pre-dust removal step>
将原烟气通过预除尘设备进行预处理，得到除尘烟气。将除尘烟气通入烟气管道内。预除尘效率可达90％以上。原烟气中的含尘量为80～200mg/Nm 3，优选为90～180mg/Nm 3，更优选为100～160mg/Nm 3。预除尘设备可以采用布袋式除尘器、旋流式除尘器或者电除尘器，且 优选为电除尘器。根据本发明的一个具体实施方式，预除尘处理采用湿式静电除尘器进行除尘。经过预除尘步骤，可以脱除烟气中较大及微小的颗粒。除尘烟气中含尘量为5～20mg/Nm 3，优选为6～18mg/Nm 3，更优选为7～16mg/Nm 3。当除尘烟气中的含尘量为上述范围时，能够使过氧化氢与烟气中的一氧化氮(NO)更加充分地反应，从而形成NO 2、N 2O 5等高价态氮氧化物。 The original flue gas is pretreated by a pre-dust removal equipment to obtain dust removal flue gas. Pass the dust removal flue gas into the flue gas pipe. The pre-dust removal efficiency can reach more than 90%. The dust content in the original flue gas is 80-200 mg/Nm 3 , preferably 90-180 mg/Nm 3 , and more preferably 100-160 mg/Nm 3 . The pre-dust removal equipment may adopt a bag filter, a cyclone dust collector or an electric dust collector, and is preferably an electric dust collector. According to a specific embodiment of the present invention, the pre-dust removal treatment adopts a wet electrostatic precipitator for dust removal. After the pre-dust removal step, large and small particles in the flue gas can be removed. The dust content in the dust removal flue gas is 5-20 mg/Nm 3 , preferably 6-18 mg/Nm 3 , and more preferably 7-16 mg/Nm 3 . When the dust content in the dust removal flue gas is in the above range, the hydrogen peroxide can more fully react with the nitric oxide (NO) in the flue gas to form high-valence nitrogen oxides such as NO 2 and N 2 O 5 .
在本发明中，原烟气中的氧气含量为5～23vol％，优选为8～20vol％。当烟气中氧气含量为上述范围时，能够使过氧化氢水溶液与烟气中的NO更加充分地反应形成NO 2、N 2O 5等高价态氮氧化物。烟气的氧气含量控制在本发明的范围内是合适的，烟气中氧气含量过低，不能保证脱硫脱硝效果；氧气含量过高，则增加能耗和成本。 In the present invention, the oxygen content in the original flue gas is 5 to 23 vol%, preferably 8 to 20 vol%. When the oxygen content in the flue gas is in the above range, the hydrogen peroxide aqueous solution can more fully react with the NO in the flue gas to form high-valence nitrogen oxides such as NO 2 and N 2 O 5. It is appropriate to control the oxygen content of the flue gas within the scope of the present invention. If the oxygen content in the flue gas is too low, the desulfurization and denitrification effect cannot be guaranteed; if the oxygen content is too high, energy consumption and cost will be increased.
在本发明中，预除尘处理之前的原烟气的温度可以为90～150℃，优选为100～130℃，更优选为110～120℃。原烟气流量为180000～2000000Nm 3/h，优选为200000～2000000Nm 3/h，更优选为200000～1800000Nm 3/h。原烟气的含湿量为5～15％，优选为5～12％。将烟气温度、烟气湿度和流速控制在上述范围，更加有利于过氧化氢水溶液将NO强制氧化为NO 2、N 2O 5等高价态氮氧化物，从而提高脱硝效率。 In the present invention, the temperature of the raw flue gas before the pre-dust removal treatment may be 90-150°C, preferably 100-130°C, more preferably 110-120°C. The original flue gas flow rate is 180,000-2,000,000 Nm 3 /h, preferably 200,000-2,000,000 Nm 3 /h, and more preferably 200,000-1800000 Nm 3 /h. The moisture content of the original flue gas is 5-15%, preferably 5-12%. Controlling the flue gas temperature, flue gas humidity and flow rate within the above range is more conducive to the hydrogen peroxide aqueous solution to forcibly oxidize NO to high-valence nitrogen oxides such as NO 2 and N 2 O 5 , thereby improving the denitration efficiency.
在本发明中，原烟气的含硫量为500～4500mg/Nm 3，优选为600～4500mg/Nm 3，更优选为600～4000mg/Nm 3。原烟气中含硫的物质主要为二氧化硫。原烟气的氮氧化物NO x浓度为200～600mg/Nm 3，优选为220～550mg/Nm 3。原烟气中的氮氧化物主要为NO。将烟气的二氧化硫和氮氧化物浓度控制在上述范围，更加有利于过氧化氢将NO强制氧化为NO 2、N 2O 5等高价态氮氧化物，并有利于吸收剂干粉(氧化钙或氢氧化钙)和亚硫酸氢铵干粉与二氧化硫和高价态氮氧化物反应，从而提高脱硫效率和脱硝效率。 In the present invention, the sulfur content of the original flue gas is 500 to 4500 mg/Nm 3 , preferably 600 to 4500 mg/Nm 3 , and more preferably 600 to 4000 mg/Nm 3 . The sulfur-containing material in the original flue gas is mainly sulfur dioxide. Original flue nitrogen oxides of the NO x concentration 200 ~ 600mg / Nm 3, preferably 220 ~ 550mg / Nm 3. The nitrogen oxides in the original flue gas are mainly NO. Controlling the concentration of sulfur dioxide and nitrogen oxides in the flue gas within the above range is more conducive to the forced oxidation of NO by hydrogen peroxide to high-valence nitrogen oxides such as NO 2 and N 2 O 5 , and is conducive to dry absorbent powder (calcium oxide or Calcium hydroxide) and ammonium bisulfite dry powder react with sulfur dioxide and high-valence nitrogen oxides, thereby improving desulfurization efficiency and denitration efficiency.
本发明中的原烟气可以为来自燃煤锅炉、钢铁烧结机、球团、工 业窑炉等含硫和含NO烟气。The original flue gas in the present invention can be sulfur-containing and NO-containing flue gas from coal-fired boilers, steel sintering machines, pellets, industrial kilns and the like.
<氧化步骤><oxidation step>
将除尘烟气与氧化剂在烟气管道中接触以进行氧化反应，从而形成氧化烟气。本发明采用过氧化氢作为氧化剂，能迅速与烟气中的低价氮氧化物发生化学反应，反应速度快，效率高。过氧化氢以过氧化氢水溶液形式使用。The dust removal flue gas and the oxidant are contacted in the flue gas pipe to carry out an oxidation reaction, thereby forming an oxidation flue gas. The invention uses hydrogen peroxide as the oxidant, which can rapidly chemically react with the low-valent nitrogen oxides in the flue gas, and has a fast reaction speed and high efficiency. Hydrogen peroxide is used in the form of an aqueous solution of hydrogen peroxide.
在本发明中，单位时间内加入的过氧化氢水溶液中的H 2O 2与步骤(1)中单位时间内通入的原烟气中含一氧化氮的摩尔比为1～4:1，优选为1.1～3:1，更优选为1.2～1.5:1。这样能够兼顾氧化效果和节约过氧化氢水溶液。 In the present invention, the molar ratio of the H 2 O 2 in the hydrogen peroxide aqueous solution added per unit time to the nitrogen monoxide contained in the original flue gas passed in the unit time in step (1) is 1 to 4: 1, It is preferably 1.1 to 3:1, more preferably 1.2 to 1.5:1. This can take into account the oxidation effect and save the hydrogen peroxide solution.
过氧化氢水溶液的浓度为15～35wt％，优选为20～35wt％，更优选为27.5wt％或35wt％，再优选为27.5wt％。采用本发明的过氧化氢水溶液的浓度能够兼顾氧化效果和节约过氧化氢水溶液。The concentration of the aqueous hydrogen peroxide solution is 15 to 35 wt%, preferably 20 to 35 wt%, more preferably 27.5 wt% or 35 wt%, and still more preferably 27.5 wt%. The concentration of the hydrogen peroxide aqueous solution of the present invention can take into account the oxidation effect and save the hydrogen peroxide aqueous solution.
过氧化氢水溶液与除尘烟气接触时间为1～30s，优选为1～10s，更优选为1～3s。除尘烟气在烟气管道内的流速为6～15m/s，优选为9～13m/s，更优选为10～12m/s。这样有利于烟气中的NO的氧化。The contact time between the aqueous hydrogen peroxide solution and the dust removal flue gas is 1-30s, preferably 1-10s, and more preferably 1-3s. The flow velocity of the dust removal flue gas in the flue gas duct is 6-15m/s, preferably 9-13m/s, more preferably 10-12m/s. This is conducive to the oxidation of NO in the flue gas.
根据本发明的一个实施方式，通过氧化剂供给设备将过氧化氢水溶液供给至第一喷淋设备，并将过氧化氢水溶液通过第一喷淋设备进行喷淋至烟气管道内，然后与除尘烟气在烟气管道内接触并反应，以形成氧化烟气。根据本发明的一个具体实施方式，第一喷淋设备为雾化器，其位于烟气管道内。According to an embodiment of the present invention, the hydrogen peroxide aqueous solution is supplied to the first spraying device through the oxidant supply device, and the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the first spraying device, and then combined with the dust removal fume The gas contacts and reacts in the flue gas pipe to form an oxidized flue gas. According to a specific embodiment of the present invention, the first spray device is an atomizer, which is located in the flue gas duct.
在本发明中，氧化步骤在吸收塔之前的烟气管道内进行。第一喷淋设备用以接收过氧化氢水溶液，并将过氧化氢水溶液喷淋至烟气管道内，从而使得过氧化氢更好地与除尘烟气进行充分接触并反应。将第一喷淋设备设置于烟气管道内，这样可以增加过氧化氢水溶液与烟 气的接触时间，从而促进过氧化氢对低价氮氧化物(主要为NO)的快速氧化反应。In the present invention, the oxidation step is carried out in the flue gas pipeline before the absorption tower. The first spray device is used for receiving the hydrogen peroxide aqueous solution and spraying the hydrogen peroxide aqueous solution into the flue gas pipe, so that the hydrogen peroxide can fully contact and react with the dust removal flue gas better. The first spray device is arranged in the flue gas pipeline, which can increase the contact time of the hydrogen peroxide aqueous solution and the flue gas, thereby promoting the rapid oxidation reaction of hydrogen peroxide to low-valent nitrogen oxides (mainly NO).
过氧化氢将烟气中的一氧化氮(NO)氧化为二氧化氮(NO 2)、五氧化二氮(N 2O 5)等高价态氮氧化物，便于与亚硫酸氢铵干粉反应。利用过氧化氢氧化NO的氧化原理如下： Hydrogen peroxide oxidizes nitric oxide (NO) in the flue gas to high-valence nitrogen oxides such as nitrogen dioxide (NO 2 ) and dinitrogen pentoxide (N 2 O 5 ), which facilitates the reaction with dry ammonium bisulfite powder. The oxidation principle of NO using hydrogen peroxide is as follows:
NO+H 2O 2→NO 2+H 2O(主) NO+H 2 O 2 →NO 2 +H 2 O (main)
2NO+3H 2O 2→N 2O 5+3H 2O(主) 2NO+3H 2 O 2 →N 2 O 5 +3H 2 O (main)
2NO+3H 2O 2→2HNO 3+2H 2O(副) 2NO+3H 2 O 2 → 2HNO 3 +2H 2 O (assist)
2NO+H 2O 2→2HNO 2(副) 2NO+H 2 O 2 →2HNO 2 (assist)
<脱硫脱硝步骤><Desulfurization and Denitration Step>
将氧化烟气通入吸收塔，同时将吸收剂干粉和亚硫酸氢铵干粉喷入吸收塔，且同时向吸收塔内喷入水，从而加湿吸收剂干粉和亚硫酸氢铵干粉；并且吸收剂干粉、亚硫酸氢铵干粉与所述氧化烟气接触并反应，从而形成脱硫脱硝烟气。这样有利于提高脱硫效率和脱硝效率，并无二次污染，更环保。The oxidized flue gas is passed into the absorption tower, while the absorbent dry powder and ammonium bisulfite dry powder are sprayed into the absorption tower, and water is sprayed into the absorption tower at the same time, so as to humidify the absorbent dry powder and ammonium bisulfite dry powder; and the absorbent dry powder The dry powder of ammonium bisulfite contacts and reacts with the oxidation flue gas, thereby forming desulfurization and denitration flue gas. This is beneficial to improve desulfurization efficiency and denitration efficiency, without secondary pollution, and more environmentally friendly.
在本发明中，单位时间内加入的亚硫酸氢铵干粉与预除尘步骤中单位时间内通入的原烟气中所含NO的摩尔比为3.2～4.9:1，优选为3.2～3.9:1，更优选为3.5～3.9:1。这样有利于提高脱硝效率。若亚硫酸氢铵用量太少，则脱硝效率较低。若亚硫酸氢铵用量太多，一方面，脱硝效率不会有太大提高，反而增加成本；另一方面，亚硫酸氢铵用量太多反而会影响吸收剂干粉的吸收，降低脱硫效率。In the present invention, the molar ratio of the dry ammonium bisulfite powder added per unit time to the NO contained in the original flue gas passed in the unit time in the pre-dust removal step is 3.2 to 4.9:1, preferably 3.2 to 3.9:1 , More preferably 3.5 to 3.9:1. This helps to improve the denitration efficiency. If the amount of ammonium bisulfite is too small, the denitration efficiency will be low. If the amount of ammonium bisulfite is too much, on the one hand, the denitration efficiency will not be greatly improved, but will increase the cost; on the other hand, too much ammonium bisulfite will affect the absorption of the absorbent dry powder and reduce the desulfurization efficiency.
在本发明中，吸收剂干粉为氧化钙干粉或氢氧化钙干粉。单位时间内加入的吸收剂干粉(氧化钙或氢氧化钙)与预除尘步骤中单位时间内通入的原烟气中所含二氧化硫的摩尔比为钙硫比，其可以为1～2:1，优选为1.1～1.8:1，更优选为1.1～1.5:1。这样有利于吸收剂干粉 对二氧化硫的吸收以及对亚硫酸氢铵干粉的反应产物硫酸的吸收，从而有利于提高脱硫效率和脱硝效率。In the present invention, the absorbent dry powder is calcium oxide dry powder or calcium hydroxide dry powder. The molar ratio of the absorbent dry powder (calcium oxide or calcium hydroxide) added per unit time to the sulfur dioxide contained in the original flue gas passed in the unit time in the pre-dust removal step is the calcium-sulfur ratio, which can be 1～2:1 , Preferably 1.1 to 1.8:1, more preferably 1.1 to 1.5:1. This is conducive to the absorption of sulfur dioxide by the absorbent dry powder and the absorption of sulfuric acid, the reaction product of the dry ammonium bisulfite powder, thereby helping to improve the desulfurization efficiency and the denitration efficiency.
在本发明中，吸收剂干粉、亚硫酸氢铵干粉与氧化烟气在所述吸收塔中的接触时间为5～30s，优选为6～15s，更优选为9～12s。氧化烟气在吸收塔内的流速为1～7m/s，优选为2～5m/s，更优选为3～5m/s，例如4m/s。这样有利于亚硫酸氢铵干粉与氮氧化物充分反应，同时有利于吸收剂干粉对二氧化硫的吸收以及对亚硫酸氢铵干粉的反应产物硫酸的吸收。在本发明中，吸收剂干粉为氧化钙干粉或氢氧化钙干粉，优选为氢氧化钙干粉。氢氧化钙又称为消石灰或熟石灰。氧化钙干粉或氢氧化钙干粉的粒度为100～400目，优选为150～350目，更优选为200～250目。亚硫酸氢铵干粉的粒度为100～400目，优选为150～350目，更优选为200～300目。这样有利于提高脱硫效率和脱硝效率。In the present invention, the contact time of the absorbent dry powder, the dry ammonium bisulfite powder and the oxidation flue gas in the absorption tower is 5-30s, preferably 6-15s, more preferably 9-12s. The flow velocity of the oxidation flue gas in the absorption tower is 1 to 7 m/s, preferably 2 to 5 m/s, more preferably 3 to 5 m/s, for example 4 m/s. This is conducive to the full reaction of dry ammonium bisulfite powder with nitrogen oxides, and at the same time, it is beneficial to the absorption of sulfur dioxide by the dry powder of absorbent and the absorption of sulfuric acid, the reaction product of dry ammonium bisulfite powder. In the present invention, the absorbent dry powder is calcium oxide dry powder or calcium hydroxide dry powder, preferably calcium hydroxide dry powder. Calcium hydroxide is also called slaked lime or slaked lime. The particle size of the dry calcium oxide powder or the dry calcium hydroxide powder is 100-400 mesh, preferably 150-350 mesh, more preferably 200-250 mesh. The particle size of the dry powder of ammonium bisulfite is 100-400 mesh, preferably 150-350 mesh, more preferably 200-300 mesh. This is beneficial to improve desulfurization efficiency and denitration efficiency.
在本发明中，吸收剂干粉由吸收剂干粉供给设备供给。亚硫酸氢铵干粉由亚硫酸氢铵干粉供给设备供给。加湿吸收剂干粉和亚硫酸氢铵干粉所用的水由第二喷淋设备供给。吸收剂干粉和亚硫酸氢铵干粉均为固体粉末。这样用水量小，而且副产物为粉末状产物，不仅降低水的消耗，还节省了副产物结晶提纯的工艺步骤。In the present invention, the absorbent dry powder is supplied by the absorbent dry powder supply device. The dry ammonium bisulfite powder is supplied by the ammonium bisulfite dry powder supply equipment. The water used for the dry powder of humidifying absorbent and the dry powder of ammonium bisulfite is supplied by the second spraying device. Both the absorbent dry powder and the ammonium bisulfite dry powder are solid powders. In this way, the water consumption is small, and the by-product is a powdery product, which not only reduces water consumption, but also saves the process steps for crystallization and purification of the by-product.
在本发明中，通过加湿器将水喷入至吸收塔内。在该吸收塔内，水的存在使得加湿后的吸收剂干粉和亚硫酸氢铵干粉协同使用。一方面，水可以促进亚硫酸氢铵干粉还原氧化烟气中的氮氧化物，另一方面，水可以促进吸收剂干粉对二氧化硫的吸收以及对亚硫酸氢铵干粉的反应产物硫酸的吸收。这样可以显著改善烟气脱硫脱硝效果。适量的水分对烟气脱硫脱硝是有利的，但是，过多的水分则导致吸收剂干粉团聚，从而影响烟气脱硫脱硝效果。In the present invention, water is sprayed into the absorption tower through a humidifier. In the absorption tower, the presence of water makes the humidified dry powder of absorbent and the dry powder of ammonium bisulfite used synergistically. On the one hand, water can promote the reduction and oxidation of nitrogen oxides in the flue gas by the dry powder of ammonium bisulfite; on the other hand, water can promote the absorption of sulfur dioxide by the dry powder of absorbent and the absorption of sulfuric acid, the reaction product of the dry powder of ammonium bisulfite. This can significantly improve the effect of flue gas desulfurization and denitrification. A proper amount of moisture is beneficial to flue gas desulfurization and denitrification, but excessive moisture will cause the dry powder of absorbent to agglomerate, thereby affecting the effect of flue gas desulfurization and denitration.
根据本发明的一个实施方式，将氧化烟气通入吸收塔，同时将吸 收剂干粉和亚硫酸氢铵干粉分别通过吸收剂干粉供给设备和亚硫酸氢铵干粉供给设备喷入至吸收塔，且同时通过第二喷淋设备向吸收塔内喷入水，从而加湿吸收剂干粉和亚硫酸氢铵干粉，并且吸收剂干粉和亚硫酸氢铵干粉与所述氧化烟气在吸收塔内接触并反应，从而形成脱硫脱硝烟气。根据本发明的一个具体实施方式，吸收塔为密相干塔；第二喷淋设备为加湿器。According to one embodiment of the present invention, the oxidized flue gas is passed into the absorption tower, while the absorbent dry powder and ammonium bisulfite dry powder are respectively sprayed into the absorption tower through the absorbent dry powder supply device and the ammonium bisulfite dry powder supply device, and At the same time, water is sprayed into the absorption tower through the second spray device to humidify the absorbent dry powder and ammonium bisulfite dry powder, and the absorbent dry powder and ammonium bisulfite dry powder contact and react with the oxidizing flue gas in the absorption tower, Thereby forming desulfurization and denitrification flue gas. According to a specific embodiment of the present invention, the absorption tower is a dense phase dry tower; the second spray device is a humidifier.
如前所述，利用过氧化氢氧化剂将除尘烟气中的NO进行氧化，所得产物包括NO 2、N 2O 5、HNO 3、HNO 2和H 2O。这样得到氧化烟气。然后，采用亚硫酸氢铵干粉和吸收剂干粉与氧化烟气进行充分反应。原理如下： As mentioned above, the NO in the dust removal flue gas is oxidized by the hydrogen peroxide agent, and the resulting products include NO 2 , N 2 O 5 , HNO 3 , HNO 2 and H 2 O. In this way, oxidized flue gas is obtained. Then, the dry powder of ammonium bisulfite and the dry powder of absorbent are used to fully react with the oxidizing flue gas. The principle is as follows:
4NH 4HSO 3+2NO 2→N 2+2(NH 4) 2SO 4+2H 2SO 4(主) 4NH 4 HSO 3 +2NO 2 →N 2 +2(NH 4 ) 2 SO 4 +2H 2 SO 4 (main)
10NH 4HSO 3+2N 2O 5→2N 2+5(NH 4) 2SO 4+5H 2SO 4(主) 10NH 4 HSO 3 +2N 2 O 5 →2N 2 +5(NH 4 ) 2 SO 4 +5H 2 SO 4 (main)
10NH 4HSO 3+4HNO 3→2N 2+5(NH 4) 2SO 4+5H 2SO 4+2H 2O(副) 10NH 4 HSO 3 +4HNO 3 →2N 2 +5(NH 4 ) 2 SO 4 +5H 2 SO 4 +2H 2 O(Associate)
6NH 4HSO 3+4HNO 2→2N 2+3(NH 4) 2SO 4+3H 2SO 4+2H 2O(副) 6NH 4 HSO 3 +4HNO 2 →2N 2 +3(NH 4 ) 2 SO 4 +3H 2 SO 4 +2H 2 O(Associate)
4NH 4HSO 3+2NO+O 2→N 2+2(NH 4) 2SO 4+2H 2SO 4(副) 4NH 4 HSO 3 +2NO+O 2 →N 2 +2(NH 4 ) 2 SO 4 +2H 2 SO 4 (assistant)
SO 2+H 2O→H 2SO 3(主) SO 2 +H 2 O→H 2 SO 3 (main)
3H 2SO 3+2Ca(OH) 2→Ca(HSO 3) 2+CaSO 3+4H 2O(主) 3H 2 SO 3 +2Ca(OH) 2 →Ca(HSO 3 ) 2 +CaSO 3 +4H 2 O (main)
Ca(HSO 3) 2+2CaSO 3+2O 2+Ca(OH) 2→4CaSO 4+2H 2O(主) Ca(HSO 3 ) 2 +2CaSO 3 +2O 2 +Ca(OH) 2 →4CaSO 4 +2H 2 O (main)
NO+NO 2+Ca(OH) 2→Ca(NO 2) 2+H 2O(副) NO+NO 2 +Ca(OH) 2 →Ca(NO 2 ) 2 +H 2 O(Associate)
Ca(NO 2) 2+O 2→Ca(NO 3) 2(副) Ca(NO 2 ) 2 +O 2 →Ca(NO 3 ) 2 (assistant)
N 2O 5+Ca(OH) 2→Ca(NO 3) 2+H 2O(副) N 2 O 5 +Ca(OH) 2 →Ca(NO 3 ) 2 +H 2 O(Associate)
HNO 2+HNO 3+1/2O 2+Ca(OH) 2→Ca(NO 3) 2+2H 2O(副) HNO 2 +HNO 3 +1/2O 2 +Ca(OH) 2 →Ca(NO 3 ) 2 +2H 2 O(Associate)
H 2SO 4+Ca(OH) 2→CaSO 4+2H 2O H 2 SO 4 +Ca(OH) 2 →CaSO 4 +2H 2 O
<除尘步骤和循环步骤><Dust removal step and cycle step>
通过除尘设备将所述脱硫脱硝烟气进行除尘处理，得到净化烟 气。根据本发明的一个实施方式，所述除尘设备为布袋除尘器。经过滤袋过滤，得到符合粉尘排放要求的净化烟气。滤袋上被拦截的颗粒物被吹扫至除尘器灰斗，一部分送入灰仓。主要是硫酸钙和硫酸铵等副产物排入灰仓内。The desulfurization and denitration flue gas is subjected to dedusting treatment by the dust removal equipment to obtain purified flue gas. According to an embodiment of the present invention, the dust removal equipment is a bag filter. Filtered by a filter bag, purified flue gas that meets the dust emission requirements is obtained. The particulate matter intercepted on the filter bag is blown to the dust hopper of the dust collector, and part of it is sent to the ash silo. Mainly by-products such as calcium sulfate and ammonium sulfate are discharged into the ash silo.
将未反应完全的吸收剂干粉和亚硫酸氢铵干粉循环至所述吸收塔。具体地，可以将未反应完全的吸收剂干粉和亚硫酸氢铵干粉通过循环设备循环至所述吸收塔。The unreacted dry powder of absorbent and dry powder of ammonium bisulfite are recycled to the absorption tower. Specifically, unreacted dry powder of absorbent and dry powder of ammonium bisulfite may be recycled to the absorption tower through a circulation device.
净化烟气经排气设备排出，本发明的排气设备为烟囱。根据本发明的一个实施方式，将所述未反应完全的吸收剂干粉和亚硫酸氢铵干粉从所述吸收塔的底部或除尘器灰斗通过循环设备送入所述吸收塔。The purified flue gas is discharged through the exhaust device, and the exhaust device of the present invention is a chimney. According to one embodiment of the present invention, the unreacted dry absorbent powder and ammonium bisulfite dry powder are sent from the bottom of the absorption tower or the dust hopper of the dust collector to the absorption tower through a circulation device.
根据本发明的一个实施方式，干法一体化烟气脱硫脱硝工艺包括以下具体步骤：According to an embodiment of the present invention, the dry integrated flue gas desulfurization and denitration process includes the following specific steps:
(1)将原烟气通过预除尘设备进行预处理，得到除尘烟气；其中，所述预除尘设备为静电除尘器；将除尘烟气通入烟气管道内；(1) The original flue gas is pretreated by a pre-dust removal device to obtain dust removal flue gas; wherein the pre-dust removal device is an electrostatic precipitator; the dust removal flue gas is passed into the flue gas pipeline;
(2)将过氧化氢水溶液通过氧化剂供给设备供给至第一喷淋设备，然后将过氧化氢水溶液通过第一喷淋设备喷淋至烟气管道内，并与所述除尘烟气接触以进行氧化反应，得到氧化烟气；其中，所述第一喷淋设备为雾化器；(2) The hydrogen peroxide aqueous solution is supplied to the first spraying device through the oxidant supply device, and then the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the first spraying device, and is in contact with the dust removal flue gas. Oxidation reaction to obtain oxidized flue gas; wherein, the first spray device is an atomizer;
(3)将氧化烟气通入吸收塔，同时将吸收剂干粉和亚硫酸氢铵干粉分别通过吸收剂干粉供给设备和亚硫酸氢铵干粉供给设备喷入至吸收塔，且同时通过第二喷淋设备向吸收塔内喷入水，从而加湿吸收剂干粉和亚硫酸氢铵干粉，并且吸收剂干粉和亚硫酸氢铵干粉与所述氧化烟气在吸收塔内接触并反应，从而形成脱硫脱硝烟气；其中，所述吸收塔为密相干塔；所述第二喷淋设备为加湿器；(3) Pass the oxidation flue gas into the absorption tower, and at the same time spray the absorbent dry powder and ammonium bisulfite dry powder into the absorption tower through the absorbent dry powder supply equipment and the ammonium bisulfite dry powder supply equipment, and at the same time through the second spray The shower device sprays water into the absorption tower to humidify the absorbent dry powder and ammonium bisulfite dry powder, and the absorbent dry powder and ammonium bisulfite dry powder contact and react with the oxidation flue gas in the absorption tower, thereby forming desulfurization and denitration fumes Gas; wherein, the absorption tower is a dense-phase dry tower; the second spray device is a humidifier;
(4)将所述脱硫脱硝烟气通过除尘设备进行除尘处理，得到净 化烟气；其中，所述除尘设备为布袋除尘器；和(4) Pass the desulfurization and denitration flue gas through dust removal equipment for dust removal treatment to obtain purified flue gas; wherein, the dust removal equipment is a bag filter; and
(5)将未反应完全的吸收剂干粉和亚硫酸氢铵干粉循环至所述吸收塔内。(5) Circulating the unreacted dry powder of absorbent and dry powder of ammonium bisulfite to the absorption tower.
实施例1Example 1
图1示出了本发明的一种干法一体化烟气脱硫脱硝工艺所采用的装置的示意图。由图可知，本发明的烟气脱硫脱硝装置包括：吸收剂干粉供给设备1、亚硫酸氢铵干粉供给设备2、氧化剂供给设备3、雾化器4、静电除尘器5、密相干塔6、加湿器7、布袋除尘器8、灰仓9和烟囱10。Figure 1 shows a schematic diagram of a device used in a dry integrated flue gas desulfurization and denitration process of the present invention. It can be seen from the figure that the flue gas desulfurization and denitrification device of the present invention includes: absorbent dry powder supply equipment 1, ammonium bisulfite dry powder supply equipment 2, oxidant supply equipment 3, atomizer 4, electrostatic precipitator 5, dense coherent tower 6, Humidifier 7, bag filter 8, ash warehouse 9 and chimney 10.
(1)将来自烧结机的原烟气采用静电除尘器5除去颗粒物质，得到含尘量为11mg/Nm 3的除尘烟气，通入烟气管道内。原烟气(入口烟气)参数及工艺参数如表1所示。 (1) The original flue gas from the sintering machine is used to remove particulate matter with an electrostatic precipitator 5 to obtain dust-removing flue gas with a dust content of 11 mg/Nm 3 , which is passed into the flue gas pipeline. The original flue gas (inlet flue gas) parameters and process parameters are shown in Table 1.
(2)将过氧化氢水溶液(浓度为27.5wt％)通过氧化剂供给设备3供给至雾化器4；然后将过氧化氢水溶液通过雾化器4喷淋至烟气管道内，并与除尘烟气在烟气管道内接触并反应，从而形成氧化烟气。过氧化氢水溶液将烟气中的低价态氮氧化物(如NO)氧化形成高价态氮氧化物(如NO 2和N 2O 5)。 (2) The hydrogen peroxide aqueous solution (concentration is 27.5wt%) is supplied to the atomizer 4 through the oxidant supply device 3; then the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the atomizer 4 and combined with the dust removal smoke The gas contacts and reacts in the flue gas pipe to form an oxidized flue gas. The aqueous hydrogen peroxide solution oxidizes low-valence nitrogen oxides (such as NO) in the flue gas to form high-valence nitrogen oxides (such as NO 2 and N 2 O 5 ).
(3)将氧化烟气通入密相干塔6，同时将吸收剂干粉(氢氧化钙)和亚硫酸氢铵干粉分别通过吸收剂干粉供给设备1和亚硫酸氢铵干粉供给设备2喷入密相干塔6内，且同时通过加湿器7向密相干塔6内喷入水，从而加湿吸收剂干粉和亚硫酸氢铵干粉，并且吸收剂干粉和亚硫酸氢铵干粉与氧化烟气接触10s并发生反应，从而形成脱硫脱硝烟气。(3) Pass the oxidizing flue gas into the dense coherent tower 6, and at the same time spray the absorbent dry powder (calcium hydroxide) and ammonium bisulfite dry powder through the absorbent dry powder supply equipment 1 and the ammonium bisulfite dry powder supply equipment 2 respectively into the dense coherent tower 6. In the coherent tower 6, and at the same time spray water into the dense coherent tower 6 through the humidifier 7, so as to humidify the absorbent dry powder and ammonium bisulfite dry powder, and the absorbent dry powder and ammonium bisulfite dry powder are in contact with the oxidized flue gas for 10s and occur Reaction to form desulfurization and denitration flue gas.
(4)将脱硫脱硝烟气采用布袋除尘器8进行除尘处理，得到净化烟气。净化烟气通过烟囱10排出。净化烟气的参数及脱硫效率和 脱硝效率如表2所示。将未反应完全的吸收剂干粉和亚硫酸氢铵干粉送入密相干塔6进行循环利用，副产物硫酸钙和硫酸铵等进入灰仓9。(4) The desulfurization and denitration flue gas is dedusted by the bag filter 8 to obtain purified flue gas. The purified flue gas is discharged through the chimney 10. The parameters of the flue gas purification and the desulfurization efficiency and denitration efficiency are shown in Table 2. The unreacted dry powder of absorbent and dry powder of ammonium bisulfite are sent to the dense coherent tower 6 for recycling, and the by-products such as calcium sulfate and ammonium sulfate enter the ash silo 9.
表1Table 1
参数parameter 数值Numerical value 单位unit
装置入口烟气量(工况)Device inlet flue gas volume (working condition) 575824575824 m 3/h m 3 /h
装置入口烟气量(标况湿)Device inlet flue gas volume (standard humidity) 400000400000 Nm 3/h Nm 3 /h
脱硫脱硝装置入口烟气温度Inlet flue gas temperature of desulfurization and denitrification device 120120 ℃°C
SO 2入口浓度 SO 2 inlet concentration 25002500 mg/Nm 3 mg/Nm 3
NO入口浓度NO inlet concentration 240240 mg/Nm 3 mg/Nm 3
烟气含湿量 Smoke moisture content 1010 ％%
烟气含氧量Oxygen content of flue gas 1818 ％%
烟气含尘量Dust content of flue gas 120120 mg/Nm 3 mg/Nm 3
烟道内烟气流速Flow rate of flue gas in flue 1212 m/sm/s
空塔烟气流速Empty tower flue gas flow rate 3.83.8 m/sm/s
H 2O 2/NO摩尔比 H 2 O 2 /NO molar ratio 1.51.5 ——
NH 4HSO 3/NO摩尔比 NH 4 HSO 3 /NO molar ratio 3.53.5 ——
钙硫比Calcium-sulfur ratio 1.31.3 ——
H 2O 2质量分数 H 2 O 2 mass fraction 27.527.5 ％%
氧化剂喷入量Oxidizer injection volume 594594 kg/hkg/h
亚硫酸氢铵纯度Purity of Ammonium Bisulfite 9999 ％%
亚硫酸氢铵粒度Particle size of ammonium bisulfite 200～300200～300 目Item
亚硫酸氢铵用量Dosage of ammonium bisulfite 11101110 kg/hkg/h
吸收剂(消石灰)纯度Absorbent (slaked lime) purity 9090 ％%
吸收剂(消石灰)粒度Absorbent (slaked lime) particle size 200～300200～300 目Item
消石灰(氢氧化钙)用量Slaked lime (calcium hydroxide) dosage 16701670 kg/hkg/h
表2Table 2
参数parameter 单位unit 数值Numerical value
排烟温度exhaust temperature ℃°C 4040
脱硫效率Desulfurization efficiency ％% 99.799.7
脱硝效率Denitration efficiency ％% 98.898.8
比较例1Comparative example 1
除亚硫酸氢铵干粉用量不同之外，其他工艺参数与实施例1均相同。本比较例的亚硫酸氢铵干粉用量参见表3。所得净化烟气参数及脱硫效率和脱硝效率参见表4。Except for the difference in the amount of dry ammonium bisulfite powder, other process parameters are the same as in Example 1. Refer to Table 3 for the dosage of dry ammonium bisulfite powder in this comparative example. See Table 4 for the obtained purified flue gas parameters and desulfurization efficiency and denitration efficiency.
表3table 3
参数parameter 数值Numerical value 单位unit
NH 4HSO 3/NO摩尔比 NH 4 HSO 3 /NO molar ratio 5.55.5 ——
表4Table 4
项目project 单位unit 数值Numerical value
排烟温度exhaust temperature ℃°C 4040
脱硫效率Desulfurization efficiency ％% 99.599.5
脱硝效率Denitration efficiency ％% 98.998.9
比较例2Comparative example 2
除亚硫酸氢铵干粉用量不同之外，其他工艺参数与实施例1均相同。本比较例的亚硫酸氢铵干粉用量参见表5。所得净化烟气参数及脱硫效率和脱硝效率参见表6。Except for the difference in the amount of dry ammonium bisulfite powder, other process parameters are the same as in Example 1. Refer to Table 5 for the dosage of dry ammonium bisulfite powder in this comparative example. See Table 6 for the obtained purified flue gas parameters and desulfurization efficiency and denitration efficiency.
表5table 5
参数parameter 单位unit 数值Numerical value
NH 4HSO 3/NO摩尔比 NH 4 HSO 3 /NO molar ratio —— 2.62.6
表6Table 6
项目project 单位unit 数值Numerical value
排烟温度exhaust temperature ℃°C 4040
脱硫效率Desulfurization efficiency ％% 99.599.5
脱硝效率Denitration efficiency ％% 88.388.3
比较例3Comparative example 3
除亚硫酸氢铵干粉用量不同之外，其他工艺参数与实施例1均相同。本比较例的亚硫酸氢铵干粉用量参见表7。所得净化烟气参数及脱硫效率和脱硝效率参见表8。Except for the difference in the amount of dry ammonium bisulfite powder, other process parameters are the same as in Example 1. Refer to Table 7 for the dosage of dry ammonium bisulfite powder in this comparative example. See Table 8 for the obtained purified flue gas parameters and desulfurization efficiency and denitration efficiency.
表7Table 7
参数parameter 单位unit 数值Numerical value
NH 4HSO 3/NO摩尔比 NH 4 HSO 3 /NO molar ratio —— 33
表8Table 8
项目project 单位unit 数值Numerical value
排烟温度exhaust temperature ℃°C 4040
脱硫效率Desulfurization efficiency ％% 99.699.6
脱硝效率Denitration efficiency ％% 91.791.7
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。The present invention is not limited to the above-mentioned embodiments. Without departing from the essence of the present invention, any modifications, improvements, and replacements that can be imagined by those skilled in the art fall within the scope of the present invention.

Claims (10)

  1. 一种干法一体化烟气脱硫脱硝工艺，其特征在于，包括以下步骤：A dry integrated flue gas desulfurization and denitration process is characterized in that it comprises the following steps:
    (1)将原烟气通过预除尘设备进行预处理，得到除尘烟气；(1) The original flue gas is pretreated by pre-dust removal equipment to obtain dust removal flue gas;
    (2)将所述除尘烟气与氧化剂在烟气管道内接触以进行氧化反应，得到氧化烟气；其中，所述氧化剂为过氧化氢水溶液；(2) Contacting the dust removal flue gas with an oxidant in a flue gas pipe to perform an oxidation reaction to obtain an oxidized flue gas; wherein the oxidant is an aqueous hydrogen peroxide solution;
    (3)将所述氧化烟气通入吸收塔，同时将吸收剂干粉和亚硫酸氢铵干粉喷入吸收塔，且同时向吸收塔内喷入水，从而加湿吸收剂干粉和亚硫酸氢铵干粉；并且吸收剂干粉和亚硫酸氢铵干粉与所述氧化烟气接触并反应，从而形成脱硫脱硝烟气；其中，单位时间内加入的亚硫酸氢铵干粉与步骤(1)中单位时间内通入的原烟气中所含一氧化氮的摩尔比为3.2～4.9:1；和(3) The oxidizing flue gas is passed into the absorption tower, while the absorbent dry powder and ammonium bisulfite dry powder are sprayed into the absorption tower, and water is sprayed into the absorption tower at the same time, thereby humidifying the absorbent dry powder and ammonium bisulfite dry powder And dry powder of absorbent and dry powder of ammonium bisulfite contact and react with the oxidizing flue gas, thereby forming desulfurization and denitration flue gas; wherein the dry powder of ammonium bisulfite added per unit time is connected to the unit time in step (1) The molar ratio of nitric oxide contained in the incoming raw flue gas is 3.2～4.9:1; and
    (4)将所述脱硫脱硝烟气通过除尘设备进行除尘处理，得到净化烟气。(4) The desulfurization and denitration flue gas is subjected to dust removal treatment through a dust removal device to obtain purified flue gas.
  2. 根据权利要求1所述的干法一体化烟气脱硫脱硝工艺，其特征在于，步骤(2)中单位时间内加入的过氧化氢水溶液中的H 2O 2与步骤(1)中单位时间内通入的原烟气中所含一氧化氮的摩尔比为1～4:1；过氧化氢水溶液的浓度为15～35wt％。 The dry integrated flue gas desulfurization and denitrification process according to claim 1, characterized in that the H 2 O 2 in the hydrogen peroxide aqueous solution added per unit time in step (2) is the same as that in step (1) per unit time The molar ratio of nitric oxide contained in the original flue gas introduced is 1 to 4:1; the concentration of the aqueous hydrogen peroxide solution is 15 to 35 wt%.
  3. 根据权利要求1所述的干法一体化烟气脱硫脱硝工艺，其特征在于，步骤(2)中，将所述氧化剂通过第一喷淋设备喷淋到烟气管道内，并与除尘烟气进行氧化反应；所述氧化剂与除尘烟气接触时间为1～30s。The dry integrated flue gas desulfurization and denitration process according to claim 1, characterized in that, in step (2), the oxidant is sprayed into the flue gas pipeline through the first spray device, and is combined with the dust removal flue gas The oxidation reaction is carried out; the contact time between the oxidant and the dust removal flue gas is 1-30s.
  4. 根据权利要求1所述的干法一体化脱硫脱硝工艺，其特征在于，步骤(2)中，所述除尘烟气在烟气管道内的流速为6～15m/s。The dry integrated desulfurization and denitration process according to claim 1, wherein in step (2), the flow velocity of the dust removal flue gas in the flue gas pipe is 6-15 m/s.
  5. 根据权利要求1所述的干法一体化烟气脱硫脱硝工艺，其特征在于，步骤(3)中单位时间内加入的亚硫酸氢铵干粉与步骤(1)中 单位时间内通入的原烟气中所含一氧化氮的摩尔比为3.2～3.9:1。The dry integrated flue gas desulfurization and denitrification process according to claim 1, wherein the dry powder of ammonium bisulfite added per unit time in step (3) and the original smoke passed in per unit time in step (1) The molar ratio of nitric oxide contained in the gas is 3.2 to 3.9:1.
  6. 根据权利要求1所述的干法一体化烟气脱硫脱硝工艺，其特征在于，步骤(3)中，所述吸收剂干粉为氧化钙或氢氧化钙。The dry integrated flue gas desulfurization and denitration process according to claim 1, wherein in step (3), the dry powder of the absorbent is calcium oxide or calcium hydroxide.
  7. 根据权利要求6所述的干法一体化烟气脱硫脱硝工艺，其特征在于，步骤(3)中单位时间内加入的吸收剂干粉与步骤(1)中单位时间内通入的原烟气中所含二氧化硫的摩尔比为钙硫比，其为1～2:1。The dry integrated flue gas desulfurization and denitrification process according to claim 6, characterized in that the dry powder of absorbent added per unit time in step (3) and the original flue gas passed in per unit time in step (1) The molar ratio of sulfur dioxide contained is the calcium-sulfur ratio, which is 1 to 2:1.
  8. 根据权利要求1所述的干法一体化烟气脱硫脱硝工艺，其特征在于：步骤(3)中，所述吸收塔内吸收剂干粉、亚硫酸氢铵干粉与氧化烟气接触时间为5～30s。The dry integrated flue gas desulfurization and denitrification process according to claim 1, characterized in that: in step (3), the contact time between the dry powder of absorbent and the dry powder of ammonium bisulfite and the oxidation flue gas in the absorption tower is 5～ 30s.
  9. 根据权利要求1所述的干法一体化烟气脱硫脱硝工艺，其特征在于，步骤(3)中，所述氧化烟气在吸收塔内的流速为1～7m/s。The dry integrated flue gas desulfurization and denitration process according to claim 1, wherein in step (3), the flow rate of the oxidation flue gas in the absorption tower is 1-7 m/s.
  10. 根据权利要求1～9任一项所述的干法一体化烟气脱硫脱硝工艺，其特征在于，包括如下具体步骤：The dry integrated flue gas desulfurization and denitration process according to any one of claims 1-9, characterized in that it comprises the following specific steps:
    (1)将原烟气通过预除尘设备进行预处理，得到除尘烟气；其中，所述预除尘设备为静电除尘器；将除尘烟气通入烟气管道内；(1) The original flue gas is pretreated by a pre-dust removal device to obtain dust removal flue gas; wherein the pre-dust removal device is an electrostatic precipitator; the dust removal flue gas is passed into the flue gas pipeline;
    (2)将过氧化氢水溶液通过氧化剂供给设备供给至第一喷淋设备，然后将过氧化氢水溶液通过第一喷淋设备喷淋至烟气管道内，并与所述除尘烟气接触以进行氧化反应，得到氧化烟气；其中，所述第一喷淋设备为雾化器；(2) The hydrogen peroxide aqueous solution is supplied to the first spraying device through the oxidant supply device, and then the hydrogen peroxide aqueous solution is sprayed into the flue gas pipe through the first spraying device, and is in contact with the dust removal flue gas. Oxidation reaction to obtain oxidized flue gas; wherein, the first spray device is an atomizer;
    (3)将氧化烟气通入吸收塔，同时将吸收剂干粉和亚硫酸氢铵干粉分别通过吸收剂干粉供给设备和亚硫酸氢铵干粉供给设备喷入至吸收塔，且同时通过第二喷淋设备向吸收塔内喷入水，从而加湿吸收剂干粉和亚硫酸氢铵干粉，并且吸收剂干粉和亚硫酸氢铵干粉与所述氧化烟气在吸收塔内接触并反应，从而形成脱硫脱硝烟气；其中，所述吸收塔为密相干塔；所述第二喷淋设备为加湿器；和(3) Pass the oxidation flue gas into the absorption tower, and at the same time spray the absorbent dry powder and ammonium bisulfite dry powder into the absorption tower through the absorbent dry powder supply equipment and the ammonium bisulfite dry powder supply equipment, and at the same time through the second spray The shower device sprays water into the absorption tower to humidify the absorbent dry powder and ammonium bisulfite dry powder, and the absorbent dry powder and ammonium bisulfite dry powder contact and react with the oxidation flue gas in the absorption tower, thereby forming desulfurization and denitration fumes Gas; wherein, the absorption tower is a dense-phase dry tower; the second spray device is a humidifier; and
    (4)将所述脱硫脱硝烟气通过除尘设备进行除尘处理，得到净 化烟气；其中，所述除尘设备为布袋除尘器。(4) Pass the desulfurization and denitrification flue gas through dust removal equipment for dust removal treatment to obtain purified flue gas; wherein, the dust removal equipment is a bag filter.
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