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WO2023070756A1 - Procédé de désulfuration d'ammoniac et appareil de désulfuration d'ammoniac - Google Patents

Procédé de désulfuration d'ammoniac et appareil de désulfuration d'ammoniac Download PDF

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Publication number
WO2023070756A1
WO2023070756A1 PCT/CN2021/130671 CN2021130671W WO2023070756A1 WO 2023070756 A1 WO2023070756 A1 WO 2023070756A1 CN 2021130671 W CN2021130671 W CN 2021130671W WO 2023070756 A1 WO2023070756 A1 WO 2023070756A1
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Prior art keywords
ammonia
flue gas
desulfurizer
desulfurization device
desulfurization
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PCT/CN2021/130671
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English (en)
Chinese (zh)
Inventor
罗静
徐天奇
刘凡
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江南环保集团股份有限公司
江苏新世纪江南环保股份有限公司
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Publication of WO2023070756A1 publication Critical patent/WO2023070756A1/fr

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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
    • B01D53/77—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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • 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
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • 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
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Definitions

  • the invention belongs to the technical field of environmental protection, and in particular relates to a method and a device for desulfurizing flue gas containing SO2 and SO3 based on the ammonia method.
  • limestone or lime is used as the desulfurization absorbent.
  • the limestone can be crushed, ground into powder, and mixed with water to make an absorption slurry.
  • lime powder can be stirred with water to make absorption slurry.
  • the absorption slurry can be contacted and mixed with the flue gas, and the SO2 in the flue gas can react with the calcium carbonate or calcium hydroxide in the slurry to generate calcium sulfite, and the calcium sulfite can be further combined with the oxidized
  • the air reacts to form calcium sulfate (commonly known as gypsum), which is eventually discharged.
  • the ammonia desulfurization technology of flue gas belongs to the new clean technology of circular economy, which has obvious advantages such as high desulfurization efficiency, no secondary pollution, resource recovery of sulfur dioxide, and meeting the requirements of circular economy.
  • it has been successfully applied to a desulfurization device with a single flue gas volume equivalent to a 500MW generating set, and has developed rapidly.
  • the SO2 - containing flue gas can fully contact and react with the ammonia-containing solution, so that most of the SO2 in the flue gas can be absorbed, and the net flue gas can be discharged through the top chimney of the desulfurization tower.
  • the ammonium sulfite solution obtained by absorbing SO2 in the flue gas can form an ammonium sulfate slurry with a certain solid content after oxidation, concentration and crystallization.
  • the ammonium sulfate slurry can undergo solid-liquid separation, drying process and packaging to become a solid ammonium sulfate product.
  • the advantages of ammonia desulfurization can include:
  • the SO 2 removed from the flue gas can be converted into ammonium sulfate fertilizer, turning waste into treasure.
  • ammonium sulfate fertilizer there is basically no waste water, solid waste, and no secondary pollution, which is in line with the concept of environmental protection.
  • the desulfurizer can be readily available liquid chemical raw materials, which can avoid solid limestone mining, transportation and by-product gypsum, and the operating environment at the production site can be better.
  • ammonia desulfurization process can be mainly divided into three processes: absorption, oxidation, and concentration (crystallization).
  • ammonium sulfite solution can be used as the absorbing liquid to absorb sulfur dioxide in the flue gas to obtain a mixed solution of ammonium sulfite and ammonium bisulfite, which becomes ammonium sulfite solution after neutralization by adding ammonia.
  • Ammonium sulfite can be oxidized to ammonium sulfate by passing oxidizing air through the ammonium sulfite solution.
  • the ammonium sulfate solution is concentrated, crystallized, solid-liquid separated and dried to obtain the final solid product ammonium sulfate.
  • ammonia desulfurization process since ammonia is easy to volatilize, when there is free ammonia in the absorption liquid, ammonia, SO 2 and SO 3 can exist in the gas phase at the same time, so it is easy to form the mist of ammonium sulfite and ammonium sulfate. With this fog as the core, the saturated water vapor in the flue gas can condense on these fogs to form dense white fog. On the one hand, it can cause ammonia loss, and on the other hand, it can cause secondary pollution. This is a key technical problem that has not been well resolved in the past for a long time in the ammonia desulfurization process.
  • ammonia is volatile.
  • the pH value of the solution is the highest at the contact point at the top of the absorption zone, and the SO in the gas phase 2 has the lowest concentration and ammonia has the highest concentration in the gas phase. This means that the amount of ammonia overflowing the desulfurization tower with the tail gas is large. This will not only cause waste loss of ammonia, but also cause new pollution.
  • Patent document CN106000043A proposes a single-tower six-stage cascade purification desulfurization and dust removal integrated device with ultra-low emissions, which includes an oxidation section, a concentration section, an absorption section, a purification water washing section, a demister section, a partition, and a wet electricity section.
  • the electric section further removes the tiny mist droplets carried in the flue gas after demisting through electrostatic adsorption, so as to ensure that the flue gas can still achieve standard emission when the flue gas working conditions change, and it is used as an insurance measure for this device.
  • This process has large investment and high operating costs, and there is room for further improvement in the effect of wet electricity control of ammonia escape and aerosol.
  • Patent document CN106474895A proposes a method and device for deep removal of sulfur oxides in flue gas, wherein the flue gas is sequentially subjected to primary desulfurization and secondary desulfurization from bottom to top, and in the primary desulfurization, calcium carbonate slurry and flue gas
  • primary desulfurization calcium carbonate slurry and flue gas
  • secondary desulfurization sodium-based desulfurizer, magnesium-based desulfurizer, potassium-based desulfurizer or calcium hydroxide are atomized in the form of solution or slurry, sprayed into the flue gas, and desulfurization reaction is carried out.
  • the new Calcium carbonate slurry is supplemented to control the pH value of the circulating slurry, and the concentration of sulfur oxides in the flue gas at the outlet of the desulfurization tower is controlled by adjusting the desulfurizing agent solution or slurry of the secondary desulfurization.
  • Patent document CN101053744A proposes a segmented sodium-calcium double-alkali desulfurization process and device, in which calcium-based desulfurization and sodium-alkali flue gas desulfurization are combined in one reactor, so that the flue gas is pre-desulfurized by calcium-based, and then Sodium base is used for fine desulfurization to ensure discharge requirements.
  • Patent document CN112708475A proposes a process combining ammonia desulfurization and alkali desulfurization, wherein the combination of ammonia desulfurization and alkali desulfurization is applied to remove H2S in coal gas instead of SO in flue gas 2 , where the reaction conditions and process flow for removing H 2 S from coal gas are completely different from those for removing SO 2 from flue gas.
  • the object of the present invention is to propose an ammonia-based method and device for desulfurization of flue gas containing SO 2 and SO 3 , wherein SO 2 and SO 3 in the flue gas can be removed synergistically, which can solve the problem of flue gas Improvements in gas tailing and aerosol generation.
  • the first aspect of the present invention relates to a method for removing SO by ammonia desulfurization and solving flue gas tailing and aerosol, which is characterized in that ammonia is used as the main desulfurizer, and metal alkaline desulfurization is added to the ammonia desulfurization device at the same time agent as an auxiliary desulfurization agent.
  • the second aspect of the present invention relates to an ammonia desulfurization method, which is characterized in that the flue gas containing SO2 and SO3 is desulfurized by using an ammonia desulfurization device, wherein ammonia is used as the first desulfurizer, and metal alkali is used
  • An active desulfurizing agent is used as the second desulfurizing agent, preferably, the first desulfurizing agent is a main desulfurizing agent and the second desulfurizing agent is an auxiliary desulfurizing agent.
  • the added amount of metal basic desulfurizer can be ⁇ 45%, preferably ⁇ 25%, more preferably ⁇ 10%.
  • the percentage of the added amount of the metal basic desulfurizer can be understood as the ratio of the sub-desulfurization amount and the total desulfurization amount of the metal basic desulfurizer (or auxiliary desulfurizer) under the situation of fully participating in the desulfurization reaction. Ratio, the total desulfurization amount is equal to the sum of the sub-desulfurization amount and another sub-desulfurization amount when the ammonia desulfurizer (or main desulfurizer) fully participates in the desulfurization reaction.
  • the volume of the second desulfurizing agent solution may be smaller than the volume of the first desulfurizing agent solution added to the ammonia desulfurization device, for example, the ratio of the volume of the second desulfurizing agent solution to the volume of the first desulfurizing agent solution may be 1:2-5.
  • the metal alkaline desulfurizer may include at least one of metal hydroxides, metal oxides and carbonates.
  • these substances may be used in the form of a mixture, or sequentially used separately from each other, or supplied to the ammonia desulfurization unit at different parts of the ammonia desulfurization unit.
  • the metal hydroxide may include at least one of sodium hydroxide and potassium hydroxide.
  • the metal oxide may include at least one of potassium oxide and sodium oxide.
  • the carbonate may include at least one of potassium carbonate and sodium carbonate.
  • a metal base desulfurizer may be employed in solution.
  • the metallic alkaline desulfurizer may be employed in the form of powder particles.
  • the ammonia-based desulfurization device includes a flue gas cooling unit, a flue gas absorption unit, and a fine particle control unit in sequence along the flue gas flow direction, wherein the flue gas
  • the cooling unit has a flue gas inlet for inputting raw flue gas.
  • ammonia may be added to the absorption liquid used in the flue gas absorption unit.
  • the ammonia-based desulfurization device may include an oxidation device for oxidizing the absorption liquid, and the oxidation device and the flue gas absorption unit form an absorption liquid circulation through an associated pipeline, wherein ammonia is added to the absorption In the liquid cycle, especially in the oxidation plant and/or in the pipeline of the absorption liquid cycle.
  • a metallic alkaline desulfurizer may be added to the water wash circulating fluid for the fine particulate matter control unit.
  • the ammonia-based desulfurization device may include a water washing circulation tank that can be supplied with process water, and the water washing circulation tank and the fine particle control unit form a water washing cycle through an associated pipeline, wherein the metal alkaline desulfurization agent Added to the water washing cycle, especially can be added to the water washing cycle tank and/or added to the pipeline of the water washing cycle.
  • the pH value of the water washing circulation tank can be controlled within the range of 3-10, for example, 4-8.
  • a mist eliminator may be used to remove mist in the flue gas absorption unit.
  • a demister can be used to remove mist in the fine particulate matter control unit.
  • a third aspect of the present invention relates to an ammonia-based desulfurization device, characterized in that the ammonia-based desulfurization device is configured to desulfurize flue gas containing SO2 and SO3 , wherein the ammonia-based desulfurization device includes A first desulfurizing agent supply system and a second desulfurizing agent supply system, the first desulfurizing agent supply system is configured to supply ammonia as the first desulfurizing agent to the ammonia desulfurization device, and the second desulfurizing agent supply system is configured to use
  • the first desulfurizing agent is a main desulfurizing agent and the second desulfurizing agent is an auxiliary desulfurizing agent.
  • the first desulfurizing agent supply system and the second desulfurizing agent supply system can be configured such that the added amount of metal alkaline desulfurizing agent is ⁇ 45%, preferably ⁇ 25%, more preferably ⁇ 10%.
  • the second desulfurizing agent supply system may be configured to supply the metallic alkaline desulfurizing agent in solution.
  • the first desulfurizer supply system may be configured to add ammonia to the absorption liquid for the flue gas absorption unit.
  • the ammonia-based desulfurization device may include oxidation equipment for oxidizing the absorption liquid, and the oxidation equipment and the flue gas absorption unit form an absorption liquid circulation through an associated pipeline, wherein the first desulfurization
  • the agent supply system is configured for adding ammonia to the absorption liquid circuit, in particular to the oxidation device.
  • the ammonia-based desulfurization device may include an oxidation air supply system configured to supply compressed air to oxidation equipment.
  • the second desulfurizing agent supply system may be configured to add the metal alkaline desulfurizing agent into the water washing circulating fluid for the fine particulate matter control unit.
  • the ammonia-based desulfurization device may include a water washing circulation tank that can be supplied with process water, and the water washing circulation tank and the fine particle control unit form a water washing cycle through an associated pipeline, wherein the second desulfurizer
  • the supply system is configured for adding the metallic alkaline desulfurizer into the water wash cycle, especially into the water wash cycle tank.
  • At least one unit among the flue gas cooling unit, the flue gas absorption unit, and the fine particle control unit may be provided with a circulating liquid spray layer, and the circulating liquid spray layer is configured to be used in the corresponding Spray circulating fluid in the unit.
  • the flue gas cooling unit, the flue gas absorption unit and the fine particulate matter control unit may respectively be provided with at least one circulating liquid spray layer.
  • the flue gas cooling unit, the flue gas absorption unit and the fine particle control unit may be configured as separate units.
  • the flue gas cooling unit, the flue gas absorption unit, and the fine particle control unit are respectively used as separate towers and can be connected in series, and the flue gas can flow from the previous tower (for example, in the tower The flue gas outlet at the top) is piped to the flue gas inlet of the next tower (for example at the lower part of the tower).
  • At least two units among the flue gas cooling unit, the flue gas absorption unit and the fine particle control unit may be integrated together.
  • the flue gas cooling unit, flue gas absorption unit and fine particle control unit can be integrated into an ammonia desulfurization tower.
  • the ammonia desulfurization unit may comprise towers in series, one of which may be configured as an ammonia desulfurization tower, and the other tower may be configured as an alkaline scrubber.
  • the first desulfurizing agent or main desulfurizing agent or ammonia desulfurization can be passed through the ammonia desulfurization tower.
  • further desulfurization can be carried out by means of a second desulfurizing agent or an auxiliary desulfurizing agent or a metallic alkaline desulfurizing agent.
  • the flue gas cooling unit, the flue gas absorption unit and the fine particle control unit may be arranged sequentially from bottom to top in the ammonia desulfurization tower.
  • the ammonia desulfurization unit may further include an ammonium sulfate treatment system configured to treat the ammonium sulfate solution or slurry output from the ammonia desulfurization unit.
  • the flue gas containing sulfur oxides can first enter the flue gas cooling unit, and the flue gas is in contact with the spray liquid circulating in the flue gas cooling unit, and the temperature of the flue gas is reduced; the flue gas with reduced temperature then enters the flue gas Gas absorption unit, in which the flue gas absorption unit is in contact with the first desulfurizer or the main desulfurizer, and most of the sulfur oxides in the flue gas are removed; then, the residual sulfur oxides enter the fine particle control unit along with the flue gas , where it can be further removed, and fine particles in the flue gas can be eliminated at the same time.
  • the main desulfurizer is preferably added to the flue gas absorption unit, and the auxiliary desulfurizer is preferably added to the fine particle control unit.
  • the flue gas containing SO 2 and SO 3 from a coal-fired boiler in a thermal power plant can be desulfurized, or the flue gas containing SO 2 and SO 3 from a chemical process (such as from an oil refinery flue gas) for desulfurization.
  • the main desulfurizer can remove most of the sulfur oxides in the flue gas (at least half of the total amount of sulfur oxides in the original flue gas), and the auxiliary desulfurizer can remove a small part of sulfur oxides (less than half of the total amount of sulfur oxides in the original flue gas, such as at most 30%, preferably at most 25% or 15%).
  • SO 2 and SO 3 in flue gas can be removed synergistically, improvements can be achieved in solving flue gas tailing and aerosol generation, especially can significantly reduce or even substantially eliminate flue gas Tailing and aerosol generation.
  • the process flow can be simplified and the investment can be reduced.
  • the metal alkaline desulfurizer is used for further desulfurization or auxiliary desulfurization, for example, the additional auxiliary desulfurization function in the fine particle control unit can be used.
  • the energy-saving effect is achieved, so that the whole process and device can be more environmentally friendly.
  • Fig. 1 is a schematic diagram of an ammonia desulfurization device according to an embodiment of the present invention.
  • FIG. 1 shows an ammonia desulfurization device according to an exemplary embodiment of the present invention.
  • the ammonia desulfurization device can be used to treat the flue gas of coal-fired boilers in thermal power plants, or can be used to treat other chemical flue gases containing sulfur oxides.
  • the ammonia desulfurization process involved in the present invention is different from the traditional simple ammonia desulfurization, but additionally utilizes metal alkaline desulfurization agent on the basis of ammonia desulfurization.
  • the ammonia-based desulfurization device includes an ammonia-based desulfurization tower 1, and the ammonia-based desulfurization tower includes a flue gas cooling unit 4, a flue gas absorption unit 5, and a fine particle control unit 6 sequentially from bottom to top.
  • the flue gas cooling unit 4 has a flue gas inlet 9 .
  • the flue gas containing SO 2 and SO 3 as the original flue gas, usually has a relatively high temperature, and enters the flue gas cooling unit 4 through the flue gas inlet 9 .
  • the flue gas cooling unit 4 forms a concentrated liquid circulation through the associated pipeline 12 and the circulation pump 21 arranged in the pipeline 12 .
  • the concentrated liquid can be sprayed against the flow direction of the flue gas on the upper part of the flue gas cooling unit 4 through a spray layer not shown in the figure.
  • the original flue gas After the original flue gas enters from the flue gas inlet 9, it passes through the solution or slurry contained in the flue gas cooling unit 4, and the residual heat of the original flue gas can evaporate and concentrate the solution or slurry. At the same time, the original flue gas is cooled and dust is removed in the flue gas cooling unit 4 .
  • the substance contained in the flue gas cooling unit 4 may be a solution or a slurry of ammonium sulfate, wherein the slurry has a solid content.
  • the concentrated solution or slurry mainly containing ammonium sulfate contained in the flue gas cooling unit 4 can be output to the ammonium sulfate treatment system 16 schematically shown in FIG. 1 through the circulation pump 21 and the branch pipeline 12a.
  • the output solution or slurry can be treated in the ammonium sulfate treatment system 16 .
  • the solution or slurry may be crystallized by evaporation into a solid ammonium sulfate product and finally packaged into bags of ammonium sulfate fertilizer having a predetermined weight.
  • the solution or slurry may be directly filled as a salable commodity.
  • the flue gas absorption unit 5 is separated from the flue gas cooling unit 4 through a gas-liquid separator 11a.
  • the flue gas can enter the flue gas absorption unit 5 from the flue gas cooling unit 4 through the gas-liquid separator 11a, but the liquid cannot basically enter the flue gas cooling unit 4 from the flue gas absorption unit 5 through the gas-liquid separator 11a, or In the case of intentional design, it can only pass through the gas-liquid separator 11a from the flue gas absorption unit 5 into the flue gas cooling unit 4 in a controlled manner within a predetermined degree.
  • the ammoniated absorption liquid absorbs the sulfides in the flue gas, especially SO 2 .
  • the flue gas absorption unit 5 , the oxidation device 2 as well as the associated lines 23 , 24 and the circulation pump 22 arranged in the line 23 form an absorption liquid circuit 7 .
  • the absorption liquid in the flue gas absorption unit 5 is transported from the lower part of the flue gas absorption unit 5 to the oxidation device 2 via the pipeline 24, and is oxidized in the oxidation device 2.
  • the oxidation device 2 can be connected with an oxidation air supply system 14, and the compressed air with a predetermined pressure is delivered to the oxidation device 2 through the oxidation air supply system 14, so as to oxidize the absorption liquid delivered to the oxidation device 2.
  • the oxidation device 2 can be connected to the first desulfurizer supply system 13 constituted as an ammonia supply system, and ammonia can be added to the oxidation device 2 through the ammonia supply system.
  • Ammonia as a desulfurizing agent may be elemental ammonia, ammonia water, ammonium bicarbonate or the like. For example, ammonia water with a concentration of 20% (mass) can be used as the first desulfurizing agent.
  • the first desulfurizing agent may be a primary desulfurizing agent.
  • the absorption liquid oxidized in the oxidation device 2 can be sent to the flue gas absorption unit 5 through the circulation pump 22 and the pipeline 23 . In the embodiment shown in FIG.
  • the absorption liquid containing ammonium sulfite can remove sulfides in the flue gas, especially sulfur dioxide.
  • the absorption liquid which has absorbed sulfur dioxide contains ammonium bisulfite. Ammonium bisulfite can be converted to ammonium sulfite by adding ammonia.
  • a mist eliminator 18a may be provided on the upper part of the smoke absorption unit 5 to demist the smoke flowing through the mist eliminator 18a.
  • the secondary oxidation air used in the oxidation device 2 can be sent from the oxidation device 2 to the flue gas cooling unit 4 of the ammonia desulfurization tower 1 through a pipeline 25 .
  • the oxidized absorption liquid in the oxidation device 2 can be replenished into the flue gas cooling unit 4 through the circulation pump 22 and the branch pipeline 29 .
  • the absorption liquid can be added to the flue gas cooling unit 4 from the flue gas absorption unit 5, for example, through a branch line of the pipeline 24 leading to the flue gas cooling unit 4 .
  • the fine particle control unit 6 is separated from the smoke absorption unit 5 by a gas-liquid separator 11b.
  • the flue gas can enter the fine particulate matter control unit 6 from the flue gas absorption unit 5 through the gas-liquid separator 11b, but the liquid basically cannot enter the flue gas absorption unit 5 from the fine particulate matter control unit 6 through the gas-liquid separator 11b, or In the case of intentional design, it can only pass through the gas-liquid separator 11b from the fine particle control unit 6 and enter the smoke absorption unit 5 in a controlled manner within a predetermined degree.
  • the fine particle control unit 6 , the water washing circulation tank 3 , the associated pipelines 27 , 28 and the circulation pump 26 can form a water washing cycle 10 .
  • the water washing circulation tank 3 can be connected with a process water supply system 15 , and the process water supply system 15 can deliver process water to the water washing circulation tank 3 .
  • the water washing circulation liquid can be delivered from the water washing circulation tank 3 to the fine particle control unit 6 via the circulation pump 26 and the pipeline 27, for example, sprayed in the fine particle control unit 6 through a spray layer not shown.
  • the water washing circulation liquid can be returned to the water washing circulation tank 3 through the pipeline 28 at the lower part of the fine particle control unit 6 .
  • the flue gas can be washed with circulating fluid in the fine particle control unit 6 to remove fine particles.
  • the smoke absorption unit 5 can obtain supplementary liquid from the fine particulate matter control unit 6 and/or the water washing circulation tank 3, so that the amount of the absorption liquid can be kept within a predetermined range, for example, substantially stable.
  • the liquid replenished into the smoke absorption unit 5 from the fine particle control unit 6 and/or the water washing circulation tank 3 becomes a component of the absorption liquid.
  • the water washing circulation tank 3 may be connected to the oxidation device 2 through a pipeline 30 for replenishing liquid to the oxidation device.
  • the pipeline 28 may have a branch pipeline leading to the smoke absorption unit 5, for supplementing liquid from the fine particle control unit 6 to the smoke absorption unit 5; and/or the water washing circulation tank 3 may have a pipeline leading to the smoke absorption unit 5 for supplementing liquid from the water washing circulation tank 3 to the smoke absorption unit 5 .
  • the water washing circulation tank 3 may be connected to a second desulfurizing agent supply system 17 .
  • the second desulfurizing agent supply system 17 can deliver metal alkaline desulfurizing agent to the water washing circulation tank 3 .
  • the metal alkaline desulfurizer can be added to the water washing circulation tank in the form of powder particles or in the form of solution, for example.
  • Metal alkaline desulfurizer can be used as auxiliary desulfurizer.
  • the pH value of the liquid in the washing circulation tank 3 can be controlled within the range of 3-10, for example, 4-8.
  • the metal alkaline desulfurizing agent may include at least one of metal hydroxides, metal oxides and carbonates.
  • the metal hydroxide may include at least one of sodium hydroxide and potassium hydroxide.
  • the metal oxide may include at least one of potassium oxide and sodium oxide.
  • the carbonate may include at least one of potassium carbonate and sodium carbonate.
  • a mist eliminator 18b may be provided on the upper part of the fine particle control unit 6 to demist the flue gas flowing through the mist eliminator 18b.
  • the net flue gas demisted by the mist eliminator 18b can be discharged from the ammonia desulfurization tower 1 to the environment through the chimney 8 .
  • the metallic alkaline desulfurizer as a second desulfurizer or an auxiliary desulfurizer, can be directly or indirectly added to the flue gas absorption unit 5 .
  • the metal basic desulfurizer as the second desulfurizer or auxiliary desulfurizer, can be directly or indirectly added to the flue gas absorption unit 5, and the rest directly or indirectly into the fine particulate matter control unit 6.
  • the part of the metal alkaline desulfurizer can be added to the oxidation device 2 , or can be added to the pipeline 23 or 24 connected to the oxidation device 2 .
  • all of the metal basic desulfurization agent or the rest of the metal basic desulfurization agent can be added to the pipeline 27 or 28 connected to the water washing circulation tank 3 .
  • All or most of the first desulfurization agent or main desulfurization agent or ammonia desulfurization agent can be directly or indirectly added to the flue gas absorption unit 5 .
  • Ammonia addition locations can be single or multiple.
  • a small amount of ammonia can be added in the flue gas cooling unit 4 of the ammonia desulfurization tower 1 , and/or a small amount of ammonia can be added in the fine particle control unit 6 of the ammonia desulfurization tower 1 .
  • the flue gas cooling unit 4, the flue gas absorption unit 5 and the fine particulate matter control unit 6 can be constituted as separate towers respectively, and these towers can be connected in series, and the flue gas can flow from the front to the The flue gas outlet of one tower (eg at the top of the tower) is piped to the flue gas inlet of the next tower (eg at the lower part of the tower).
  • the flue gas cooling unit 4, the flue gas absorption unit 5, and the fine particle control unit 6 can be configured similarly to the embodiment shown in Figure 1, and they are integrated into an ammonia desulfurization tower 1, but the fine The particle control unit 6 is not provided with the second desulfurizing agent supply system 17 for delivering the metal alkaline desulfurizing agent to the water washing circulation tank 3 .
  • the ammonia desulfurization tower 1 desulfurization is achieved only by the first desulfurizer or main desulfurizer or ammonia.
  • the ammonia-based desulfurization device also includes an auxiliary desulfurization device separate from the ammonia-based desulfurization tower 1, the auxiliary desulfurization device has a circulating fluid and is equipped with a second desulfurizing agent supply system 17 for delivering a metal alkaline desulfurizing agent to the circulating fluid.
  • the flue gas can be transported from the flue gas outlet of the ammonia desulfurization tower 1 to the auxiliary desulfurization device, and further desulfurized by metal alkaline desulfurizer in the auxiliary desulfurization device.
  • the net flue gas can be discharged into the environment from the flue gas outlet of the auxiliary desulfurization device.
  • the structure of the auxiliary desulfurization device can be constructed similarly to the fine particle control unit 6 shown in FIG. 1, wherein the auxiliary desulfurization device also has a circulation tank with a process water inlet and the already mentioned second desulfurizer supply system 17.
  • the circulating fluid of the auxiliary desulfurization device can be directly or indirectly output to the fine particle control unit 6 of the ammonia desulfurization tower 1 in addition to the circulation operation (for example, the circulating fluid of the auxiliary desulfurization device can be output from its circulation tank to the ammonia desulfurization
  • the water washing circulation tank 3) of the tower 1 and/or the flue gas absorption unit 5 for example, the circulating liquid of the auxiliary desulfurization device can be output from its circulation tank to the oxidation device 2 of the ammonia desulfurization tower 1).
  • the ammonia desulfurization device can have the following design parameters:
  • the designed circulation volume of the concentrate liquid circulation is 20m 3 /h
  • the circulation volume of the absorption liquid circulation is 175m 3 /h
  • the circulation volume of the water washing cycle is 55m 3 /h.
  • Ammonia water with a concentration of 20% (mass) is used as the main desulfurizer
  • a sodium hydroxide solution with a concentration of 20% (mass) is used as the auxiliary desulfurizer
  • the amount of the auxiliary desulfurizer is 10%.
  • the designed flue gas parameters are as follows:
  • the solution composition of each zone of the ammonia-based desulfurization device is controlled mainly through coordinated control of the addition of ammonia as the first desulfurizer and sodium hydroxide as the second desulfurizer, so as to control ammonia escape and aerosol, and reduce smoke Gas smearing phenomenon.
  • the net flue gas SO 2 concentration is 21 mg/Nm 3
  • the total dust (including aerosol) concentration is 3 mg/Nm 3
  • the SO 3 concentration is 2 mg/Nm 3
  • the amount of ammonia slip It is 0.8mg/Nm 3 , basically no tailing phenomenon.
  • the second desulfurizing agent supply system 17 was disconnected from the water-washing circulation tank 3, and thus no metal alkaline desulfurizing agent was supplied.
  • the net flue gas SO 2 concentration is 30 mg/Nm 3
  • the total dust (including aerosol) concentration is 19 mg/Nm 3
  • the SO 3 concentration is 5 mg/Nm 3
  • the ammonia escape amount is 4 mg/Nm 3 , the tailing phenomenon is serious.

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Abstract

L'invention concerne un procédé de désulfuration d'ammoniac. Un gaz de combustion contenant du SO2 et du SO3 est désulfuré au moyen d'un appareil de désulfuration d'ammoniac, l'ammoniac étant utilisé comme premier agent de désulfuration et un agent de désulfuration alcalin métallique étant utilisé en tant que second agent de désulfuration. Le procédé de désulfuration peut éliminer de manière synergique le SO2 et le SO3 de gaz de combustion, et permettre d'obtenir des améliorations dans la résolution de résidus de gaz de combustion et dans la génération d'aérosol.
PCT/CN2021/130671 2021-10-25 2021-11-15 Procédé de désulfuration d'ammoniac et appareil de désulfuration d'ammoniac WO2023070756A1 (fr)

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CN117443163A (zh) * 2023-09-19 2024-01-26 湖北蔚天环保科技有限公司 一种单塔、单槽、多循环、高浓度二氧化硫脱硫系统
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CN119607875A (zh) * 2025-02-12 2025-03-14 上海鲁源控制设备有限公司 一种吸收氧化一体化设备

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