WO2023221647A1 - 一种控制氨法脱碳***氨逃逸的装置及方法 - Google Patents

一种控制氨法脱碳***氨逃逸的装置及方法 Download PDF

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WO2023221647A1
WO2023221647A1 PCT/CN2023/083695 CN2023083695W WO2023221647A1 WO 2023221647 A1 WO2023221647 A1 WO 2023221647A1 CN 2023083695 W CN2023083695 W CN 2023083695W WO 2023221647 A1 WO2023221647 A1 WO 2023221647A1
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ammonia
liquid
desulfurization
washing
gas
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PCT/CN2023/083695
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English (en)
French (fr)
Inventor
罗静
张军
祁丽昉
王金勇
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江南环境科技公司
江苏新世纪江南环保股份有限公司
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Priority to AU2023222850A priority Critical patent/AU2023222850A1/en
Priority to CA3210444A priority patent/CA3210444A1/en
Priority to MX2023010155A priority patent/MX2023010155A/es
Priority to IL305522A priority patent/IL305522A/en
Publication of WO2023221647A1 publication Critical patent/WO2023221647A1/zh

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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
    • B01D53/14—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 by absorption
    • B01D53/1406—Multiple stage absorption
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/14—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 by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • B01D53/185—Liquid distributors
    • 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
    • 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
    • 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
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
    • 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
    • B01D53/62—Carbon 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
    • B01D53/75—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/26—Carbonates or bicarbonates of ammonium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/102—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2

Definitions

  • the invention belongs to the field of environmental protection technology, and specifically relates to a device and method for controlling ammonia escape in an ammonia desulfurization and decarbonization system.
  • ammonium bicarbonate is a typical compound fertilizer that can provide nitrogen fertilizer and CO 2 to plants at the same time. It is especially suitable for the needs of modern agriculture and greenhouse plant growth in soilless cultivation. It truly realizes the resource utilization of CO 2 and realizes carbon cycle. Secondary pollution and CO2 environmental accidents that may be caused by carbon underground storage can be avoided.
  • ammonia absorbs CO 2 more efficiently and ammonium bicarbonate is easier to regenerate, which can significantly reduce decarbonization costs.
  • Ammonia decarbonization technology has always been the focus of research and is also the best way to solve greenhouse gases; however, ammonia is volatile, and decarbonization needs to be carried out under alkaline conditions, resulting in an increase in ammonia escape. If not solved, a large amount of ammonia will escape, which will not only increase the cost of decarbonization, but also cause secondary pollution.
  • Patent CN113262625A proposes an integrated desulfurization and decarbonization device that uses desulfurization circulating liquid for washing to reduce part of the free ammonia in the process gas, and the washing liquid is returned to the desulfurization tower to be used as an absorbent for desulfurization.
  • desulfurization circulating fluid For free ammonia in process gas, simply using desulfurization circulating fluid to clean it will still cause a large amount of ammonia to escape. After washing with desulfurization circulating solution and then washing with process water, a large amount of ammonia-containing solution will be produced.
  • Returning to the desulfurization functional area to be used as a desulfurization absorbent will destroy the water balance of the desulfurization system and generate wastewater.
  • Patent CN101600489B proposes a method of pickling ammonia using SO2 from flue gas, cooling the process gas with the help of a cooling liquid, and absorbing the sulfur dioxide of the process gas into the cooling liquid, thereby obtaining a cooling liquid containing sulfate .
  • Ammonia is removed from the process gas that has been treated in the CO2 absorber.
  • the main product generated after the cooling liquid absorbs sulfur dioxide is sulfite.
  • sulfuric acid needs to be added to the cooling liquid to control the pH value of the cooling liquid, which greatly increases the difficulty of device control.
  • this patent does not consider the material balance of desulfurization and decarbonization as an overall system, but only partially removes sulfur dioxide to obtain sulfate.
  • the present invention has developed a device and method for controlling the escape of ammonia in an ammonia decarbonization system based on the operation experience of ammonia desulfurization and decarbonization.
  • Ammonia is used as the desulfurization and decarburization agent.
  • the gas first enters the desulfurization device for desulfurization.
  • the final gas enters the decarbonization device to remove the carbon dioxide in the gas.
  • the decarbonized gas contains free ammonia, and the acidic ammonium sulfate liquid and acidic water washing liquid used for ammonia desulfurization absorb the free ammonia in the gas.
  • the invention effectively controls the escape of ammonia in the ammonia decarbonization system.
  • the ammonia recovered by washing can also be used for desulfurization, thus saving ammonia consumption.
  • the invention develops a device and method for controlling ammonia escape in an ammonia decarbonization system, using ammonia to remove sulfur oxides and CO 2 to generate ammonium sulfate fertilizer and ammonium bicarbonate fertilizer.
  • the ammonia desulfurization and decarbonization device is equipped with an ammonia desulfurization functional area, an ammonia decarbonization functional area, and an ammonia escape control functional area.
  • the ammonia desulfurization functional area includes a washing and cooling section, an absorption circulation section, a particulate matter control section, and an ammonia decarbonization functional area. It includes a cooling section and an absorption circulation section.
  • the ammonia escape control functional area includes an acidic ammonium sulfate liquid washing system and an acidic water washing system.
  • the absorption circulation section of the ammonia desulfurization functional area is connected to the acidic ammonium sulfate liquid washing system of the ammonia escape control functional area through pipelines.
  • the particulate matter control section of the ammonia desulfurization functional area or the cooling section of the ammonia decarbonization functional area is connected to the ammonia escape area through pipelines. Control the connection of the acidic water washing system in the functional area.
  • the ammonia decarburization absorption cycle section adopts multi-stage absorption, in which less or no ammonia is added in the last stage to reduce the escape of NH 3 after decarburization.
  • Ammonia is used as the desulfurization and decarbonization agent.
  • the gas first enters the desulfurization functional zone for desulfurization to generate ammonium sulfate fertilizer.
  • the desulfurized gas enters the decarbonization functional zone to remove carbon dioxide in the gas and generate ammonium bicarbonate fertilizer for decarbonization.
  • the final gas contains free ammonia, and the free ammonia in the absorbed gas is washed and absorbed with acidic ammonium sulfate liquid and acidic water washing liquid derived from ammonia desulfurization.
  • the acidic ammonium sulfate liquid adopts the ammonia desulfurization functional zone to absorb the circulating section solution, the ammonium sulfate concentration is 10-38wt%, pH 4.5-6.5; the acidic water washing liquid adopts the ammonia desulfurization functional zone particulate matter control section solution or the ammonia decarbonization functional zone for cooling Section solution, ammonium sulfate concentration 0-5wt%, pH 3-7. After washing in the ammonia escape control functional area, the concentrations of acidic ammonium sulfate liquid and acidic water washing liquid remain basically unchanged.
  • the pH of acidic ammonium sulfate liquid is 4.6-6.9, and the pH of acidic water washing liquid is 3.5-7.5.
  • the temperature of the acidic ammonium sulfate liquid and acidic water washing liquid is 20-60°C, preferably 30-50°C.
  • Acidic ammonium sulfate liquid and acidic water washing liquid scrubbers are provided with a liquid distributor and a gas-liquid contact component.
  • the liquid distributor is preferably a trough distributor, and the gas-liquid contact component is preferably a filler.
  • the acidic ammonium sulfate liquid and acidic water washing liquid of ammonia desulfurization Before using the acidic ammonium sulfate liquid and acidic water washing liquid of ammonia desulfurization to absorb free ammonia in the gas, it also includes washing with process water to absorb free ammonia.
  • the process water is preferably desalted water or solution in the cooling section of the ammonia decarbonization functional area or drainage from the acidic water washing system in the ammonia escape control functional area.
  • the acidic ammonium sulfate liquid washing of ammonia desulfurization is equipped with at least one layer of liquid distributor.
  • the solution after gas-liquid contact washing is recovered and returned to the desulfurization system.
  • the acidic water washing liquid of ammonia desulfurization is equipped with at least one layer of liquid distributor.
  • the solution after gas-liquid contact washing is recovered and returned to the desulfurization system or decarbonization system.
  • At least one layer of liquid distributor is installed for process water washing, and the ammonia-containing solution produced is returned to the desulfurization system or decarbonization system.
  • each section is provided with at least one spray layer, and equipment/components that allow gas to pass are provided between sections.
  • the particulate matter removal section it is divided into two parts. The first part of spray washing uses a high concentration solution containing ammonium sulfate for circulating washing, and the second part uses a dilute solution containing ammonium sulfate for circulating washing. There is a device/component between the two parts that allows the passage of gas.
  • each section is provided with at least one spray layer, and equipment/components that allow gas to pass are provided between sections.
  • a method for controlling the escape of ammonia in an ammonia decarbonization system which is characterized in that the gas after ammonia decarburization contains free ammonia, and the ammonia desulfurization is washed and absorbed with acidic ammonium sulfate liquid and acidic water washing liquid of ammonia desulfurization. Free ammonia in the gas after carbon.
  • Embodiment 2 The method according to Embodiment 1, characterized in that, before using the acidic ammonium sulfate liquid and acidic water washing liquid desulfurized by the ammonia method to absorb free ammonia in the gas, it also includes washing with process water to absorb free ammonia, and the process
  • the water is preferably desalted water, washing condensed water, or acidic water washing liquid drainage.
  • Embodiment 3 The method according to Embodiment 1, characterized in that the ammonia-containing solution produced by washing the acidic ammonium sulfate liquid and acidic water washing liquid of ammonia desulfurization is returned to the desulfurization system or decarbonization system.
  • Embodiment 4 The method according to Embodiment 1, characterized in that the acidic ammonium sulfate liquid washing for ammonia desulfurization is provided with at least one layer of liquid distributor, and the solution after gas-liquid contact washing is recovered and returned to the desulfurization system.
  • Embodiment 5 The method according to Embodiment 1, characterized in that the acidic water wash of ammonia desulfurization is provided with at least one layer of liquid distributor, and the solution after gas-liquid contact washing is recovered and returned to the desulfurization system or decarbonization system.
  • Embodiment 6 The method according to Embodiment 2, characterized in that the process water washing is provided with at least one layer of liquid distributor, The generated ammonia-containing solution is returned to the desulfurization system or decarbonization system.
  • Embodiment 7 The method according to Embodiment 1, characterized in that, between the washing of the acidic ammonium sulfate liquid and the acidic water washing liquid used for ammonia desulfurization, equipment or components that only allow gas to pass are provided.
  • Embodiment 8 The method according to Embodiment 2, characterized in that equipment or components that only allow gas to pass are provided between the acidic ammonium sulfate liquid desulfurized by ammonia and process water washing.
  • ammonia decarburization absorption cycle section includes multi-stage absorption, in which less or no ammonia is added in the last stage to reduce the escape of NH 3 after decarburization.
  • NH 3 content in the gas after being treated by the absorption circulation section of the ammonia decarburization functional zone is 200 to 2000 ppm; preferably 400 to 1500 ppm; more preferably 500 to 1000 ppm.
  • liquid-to-gas ratio of the process water is usually 5-25, preferably 10-20, and more preferably 12-18.
  • liquid-gas ratio of the acidic ammonium sulfate liquid is usually 1-20, preferably 1-10, and more preferably 2-6.
  • liquid-to-gas ratio of the acidic water washing liquid is usually 1-15, preferably 1-8, and more preferably 2-5.
  • gas-liquid contact parts are provided in the acidic ammonium sulfate liquid and acidic water washing liquid scrubbers, and the gas-liquid contact parts are preferably fillers.
  • Embodiment 2 The method according to Embodiment 2, characterized in that acid is added to the process water, washing condensate water, and acidic washing liquid drainage to adjust the pH.
  • the acid is sulfuric acid.
  • a device for controlling ammonia escape in an ammonia desulfurization and decarbonization system which is characterized in that it includes an ammonia desulfurization functional area, Ammonia decarbonization functional area, ammonia escape control functional area,
  • the ammonia desulfurization functional area includes a washing and cooling section, an absorption circulation section, and a particulate matter control section.
  • the ammonia decarbonization functional area includes a cooling section and an absorption cycle section.
  • the ammonia escape control functional area includes the ammonia escape control section, including the acidic ammonium sulfate liquid washing system and the acidic water washing system.
  • the absorption circulation section of the ammonia desulfurization functional area is connected to the acidic ammonium sulfate washing system of the ammonia escape control functional area through pipelines.
  • the particulate matter control section of the ammonia desulfurization functional area or the cooling section of the ammonia decarbonization functional area is connected to the ammonia escape control functional area through pipelines. Escape control functional area acid wash system connection.
  • ammonia decarburization absorption cycle section includes multi-stage absorption, in which less or no ammonia is added in the last stage to reduce the escape of NH 3 after decarburization.
  • the device according to embodiment 21, characterized in that the ammonia escape control functional area may also include a process water washing system.
  • the process water washing system is connected to the process water pipe through a pipeline and is connected to the absorption circulation section of the ammonia desulfurization device or the ammonia desulfurization device. Carbon device absorption cycle section connection.
  • Figure 1 shows Embodiment 1 of the present invention.
  • process water is also used for washing to absorb free ammonia.
  • FIG. 2 shows Embodiment 2 of the present invention, in which the acidic ammonium sulfate liquid and acidic water washing liquid used for ammonia desulfurization are used to wash free ammonia in the absorbed gas.
  • Figure 3 shows a comparative example, using process water for washing to absorb free ammonia.
  • Process gas 1 desulfurization functional area 2, desulfurization washing and cooling section 2-1, desulfurization absorption circulation section 2-2, desulfurization particulate matter control section 2-3, desulfurization circulation pump a 3, desulfurization circulation pump b 4, desulfurization circulation pump c 5 , Desulfurization circulation tank 6, oxidation air 7, desulfurization system and ammonia addition 8, ammonium sulfate discharge pump 9, desulfurization circulation pump d 10, desulfurization heat exchanger 11, tail gas after desulfurization 12, decarbonization absorption tower 13, decarbonization circulation pump 14. Ammonium bicarbonate discharge pump 15. Add ammonia to the decarburization system 16. Tail gas after decarburization 17. Ammonia washing tower 18.
  • the gas after ammonia decarburization contains free ammonia.
  • the present invention specifically uses acidic ammonium sulfate liquid and acidic water washing liquid for ammonia desulfurization to wash and absorb free ammonia in the gas after ammonia decarburization.
  • the present invention also includes washing with process water to absorb free ammonia before using the acidic ammonium sulfate liquid and acidic water washing liquid desulfurized by ammonia method to absorb free ammonia.
  • the process water is preferably desalted water and washing condensed water.
  • the flow rate of the acidic ammonium sulfate liquid, acidic water washing liquid or process water used for washing and absorption can be appropriately adjusted as needed.
  • the liquid-gas ratio of the process water is usually 5-25, preferably 10-20. More preferably, 12-18 is used; the liquid-to-gas ratio of the acidic ammonium sulfate liquid is usually 1-20, preferably 1-10, and more preferably 2-6; the liquid-to-gas ratio of the acidic water washing liquid is usually 1-20, preferably 1-15, and more Preferably 2-10.
  • V process gas flow after ammonia decarburization (working conditions, that is, gas flow under operating conditions (temperature, pressure, etc.)), m 3 /h.
  • the treatment carried out according to the method of the present invention mainly removes free ammonia contained in the gas after decarburization by the ammonia method, and has little effect on the SO 2 content and CO 2 content.
  • the pH of the acidic ammonium sulfate liquid is 4.5-6.5, and the ammonium sulfate concentration is 10-38wt%, preferably 12-35wt%, more preferably 15-30wt%, most preferably 17-28wt%;
  • the pH of the acidic water wash liquid is 3-7, and the ammonium sulfate concentration is 0-5wt%, preferably 0-3wt%, more preferably 0-1wt%, most preferably 0-0.6wt%.
  • the temperature of the acidic ammonium sulfate liquid and the acidic water washing liquid is 20-60°C, preferably 30-50°C.
  • the NH 3 content in the gas after being treated by the decarbonization absorption tower is 200 to 2000 ppm; preferably 400 to 1500 ppm; more preferably 500 to 1000 ppm.
  • the SO 2 content in the gas after being treated by the decarbonization absorption tower is 0 to 20 mg/Nm 3 ; preferably 0 to 15 mg/Nm 3 ; more preferably 0 to 10 mg/Nm 3 .
  • the CO 2 content in the gas after being treated by the decarbonization absorption tower is 0-20v%; preferably 1-10v%; more preferably 2-7v%.
  • the NH 3 content in the gas after being treated by the method of the present invention is 0 to 30 ppm; preferably 0 to 20 ppm; more preferably 0 to 10 ppm.
  • the method for controlling the escape of ammonia in an ammonia-based decarbonization system protected by the present invention is preferably carried out in a device for controlling the escape of ammonia from an ammonia-based desulfurization and decarbonization system as defined by the present invention.
  • the method and device of the present invention achieve beneficial economic effects in addition to technical effects, especially reducing ammonia escape and particularly significantly reducing ammonia consumption.
  • the ammonia consumption loss can be reduced by 96%-99%, preferably 97%-99%. %, specifically as shown in the following examples.
  • the testing method for the SO 2 content in the gas in the present invention is HJ 629-2011 Fixed pollution source waste gas. Determination of sulfur dioxide. Non-dispersive infrared absorption method;
  • the test method for CO2 content is HJ 870-2017 Determination of carbon dioxide in exhaust gas from fixed pollution sources, non-dispersive infrared absorption method;
  • test method for NH 3 content is HJ 533-2009 Determination of Ammonia in Ambient Air and Exhaust Gas Nessler's Reagent Spectrophotometry.
  • the present invention specifically provides Examples 1 and 2 and comparative examples to further illustrate the technical solution of the present invention and its beneficial effects.
  • the process gas 1 containing sulfur oxides and CO2 enters the desulfurization functional zone 2, and sequentially passes through the desulfurization washing and cooling section 2-1, the desulfurization absorption cycle section 2-2, and the desulfurization particulate matter control section 2-3.
  • the cooling section 2-1 uses the desulfurization circulation pump-a 3 to perform a spray cycle. While the tail gas is cooled, the ammonium sulfate solution is concentrated. The concentrated and precipitated solid ammonium sulfate slurry is sent to the ammonium sulfate discharge pump 9 to produce ammonium sulfate 26.
  • desulfurization circulation pump-b 4 Use desulfurization circulation pump-b 4, desulfurization circulation pump-c 5, and desulfurization circulation tank 6 to perform absorption spray circulation to absorb sulfur oxides (sulfur dioxide and sulfur trioxide) in the exhaust gas.
  • the desulfurization circulation pump-c 5 sends out part of the ammonium sulfate solution 20 and is cooled to 35°C by the cooler 32 and then goes to the ammonium sulfate washing section 18-2 of the ammonia tower.
  • the washed solution 21 returns to the desulfurization circulation tank 6.
  • the desulfurization circulation pump-d 10 is used to perform the washing spray cycle, and the desulfurization heat exchanger 11 is used to control the washing temperature and the temperature of the desulfurized tail gas 12.
  • the particulate matter control section 2-3 of the ammonia desulfurization functional area realizes the cooling function of ammonia decarbonization.
  • the acidic solution 23 condensed from the flue gas is cooled to 35°C by the cooler 33 and then used as the acid water washing section 18-3 of the ammonia washing tower to replenish water.
  • the washed solution 24 is returned to the desulfurization circulation tank 6.
  • To desulfurize After the ammonia added to the system 8 is measured, it goes to the desulfurization circulation tank 6 to add ammonia.
  • the oxidizing air 7 goes to the desulfurization circulation tank 6 to oxidize the solution.
  • the tail gas 12 enters the decarbonization absorption tower 13, uses the decarbonization circulation pump 14 for absorption circulation, and uses the ammonium carbonate discharge pump 15 to deliver the finished product ammonium carbonate 27.
  • the decarbonization absorption tower 13 adds ammonia after metering.
  • the tail gas 17 enters the ammonia washing tower 18, passes through the process water washing section 18-1, the ammonium sulfate washing section 18-2, and the acid liquid washing section 18-3 in sequence, and uses ammonia washing in the ammonia washing tower process water washing section 18-1.
  • the circulating pump-a 19 performs process water washing.
  • the ammonia washing tower process water washing section 18-1 is equipped with a trough distributor 31-1 and a filler 30-1. The process water is replenished through the external process water pipe 28, and the washed ammonia-containing solution 29 Go to decarburization tower 13.
  • the ammonium sulfate washing section 18-2 of the ammonia washing tower is equipped with a trough distributor 31-2 and a filler 30 -2, the washed solution (that is, returned to the desulfurization liquid) 21 returns to the desulfurization circulation tank 6.
  • the acidic solution condensed from the flue gas (i.e., the desulfurization particulate matter control section solution) 23 sent out by the desulfurization circulating pump-d 10 is used as water replenishment for the acidic water washing section 18-3 of the ammonia washing tower.
  • the acidic water washing section 18-3 of the ammonia washing tower is equipped with a trough type distributor 31-3 and filler 30-3, the washed solution (that is, returned to the acidic solution) 24 returns to the desulfurization circulation tank 6. After washing, 25% of the clean flue gas is discharged.
  • the acidic ammonium sulfate liquid 20 has a flow rate of 350m 3 /h, pH 6.4, and an ammonium sulfate concentration of 18 wt%.
  • the acidic ammonium sulfate liquid returned after entering the ammonia washing tower for washing has a pH of 6.9, and the ammonium sulfate concentration remains basically unchanged.
  • the flow rate of the acidic washing liquid 23 is adjusted according to the pH value of the washing liquid in the acid washing section 18-3 of the ammonia washing tower.
  • the pH is 3.8 and the ammonium sulfate concentration is 2wt%.
  • the acidic washing liquid returned after entering the ammonia washing tower for washing has a pH of 4.2 and the ammonium sulfate concentration remains basically unchanged.
  • the ammonia washing circulation pump b 22 has a circulation capacity of 500m 3 /h to ensure the ammonia washing effect.
  • the flow rate of process water 28 is adjusted according to the pH value of the washing liquid in the process water washing section 18-1 of the ammonia washing tower.
  • the circulation volume of the ammonia washing circulation pump a 19 is 1200m 3 /h to ensure the ammonia washing effect.
  • the pH of the demineralized water is 6.9, and the pH of the solution returned after entering the ammonia washing tower is 7.9.
  • Desulfurization and decarburization use 99.6% liquid ammonia as the absorbent.
  • the parameters of process gas 1 are shown in the table below:
  • the amount of ammonia escaped is 4.98t/year, and the ammonia consumption loss is about 20,000 yuan/year.
  • the amount of ammonia escaped is 8.96t/year, and the ammonia consumption loss is about 36,000 yuan/year.
  • the amount of ammonia escaped is 248t/year, and the ammonia consumption loss is about 992,000 yuan/year.

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Abstract

一种控制氨法脱碳***氨逃逸的装置及方法，以氨为脱硫和脱碳剂，气体首先进入脱硫装置进行脱硫，生成硫酸铵化肥，脱硫后的气体进入脱碳装置中，脱除气体中的二氧化碳，生成碳酸氢铵化肥。脱碳后的气体中含有游离氨，用氨法脱硫的酸性硫酸铵液和酸性水洗液吸收气体中的游离氨。该装置及方法有效地控制氨法脱碳***的氨逃逸，同时，洗涤回收的氨还可再用于脱硫，节约了氨耗。

Description

一种控制氨法脱碳***氨逃逸的装置及方法 技术领域
本发明属于环保技术领域，具体涉及一种控制氨法脱硫脱碳***氨逃逸的装置及方法。
背景技术
近年来，温室效应逐渐成为了人类面对的最严峻的问题之一，二氧化碳是最重要的温室气体，化石能源使用是其主要的排放源，我国CO2排放总量已位居世界第一，而且中国能源结构以煤为主的局面还将持续一段时间，煤炭能源仍将是新能源调峰及能源安全的基础，我国已向世界承诺2030年碳达峰，2060年实现碳中和。对排放烟气中CO2进行捕集封存和资源化，对于控制和减少温室气体的排放，应对温室效应、全球变暖问题具有重要意义。
目前，世界范围内主要采用的碳捕集技术是有机胺法，但存在运行成本高、***三废排放量大且难处理的等问题。国内外也一直积极探索新的脱碳技术，与有机胺法相比，氨法具有再生容易、运行成本低、脱碳的副产物即为重要的碳酸氢铵化肥。碳酸氢铵是一个典型的复合肥，可同时向植物提供氮肥和CO2，特别适合于无土栽培的现代农业、大棚植物生长的需要，真正实现了CO2的资源化利用，实现碳循环，可以避免碳地下储存可能造成的二次污染和CO2环境事故。与有机胺脱碳产物相比，氨吸收CO2的效率高、碳酸氢铵更容易再生，可大幅降低脱碳成本。
氨法脱碳技术一直是研究的重点，也是解决温室气体的最佳方法；但氨易挥发，脱碳需在偏碱性条件下进行，造成氨逃逸量增加。如不加以解决，大量的氨逃逸，不仅造成脱碳成本的增加，也造成二次污染。
专利CN113262625A提出一种脱硫脱碳一体化装置，用脱硫循环液进行洗涤，以减少工艺气体中部分游离氨，洗涤液返回脱硫塔用于脱硫的吸收剂。对于工艺气体中的游离氨，简单地使用脱硫循环液进行洗净，仍然会造成大量的氨逃逸。采用脱硫的循环溶液洗涤后，再用工艺水洗涤，会产生大量含氨溶液，返回脱硫功能区用做脱硫的吸收剂会破坏脱硫***的水平衡，产生废水。
专利CN101600489B提出一种使用来自烟气的SO2对氨进行酸洗的方法，借助于冷却液体来冷却工艺气体，并且将工艺气体的二氧化硫吸收到冷却液体中，从而获得包含着硫酸盐的冷却液体。使包含着氨的工艺气体与包含着硫酸盐的冷却液体接触而 从已在CO2吸收器中经过处理的工艺气体去除氨。冷却液体吸收二氧化硫后生成的主要应为亚硫酸盐，为达到除氨效果，还需要将硫酸添加到冷却液体以控制冷却液体的pH值，这大大增加了装置控制难度。而且该专利未将脱硫脱碳作为整体***考虑其物料平衡，仅仅为了获得硫酸盐而部分的去除二氧化硫。
本发明针对上述问题，结合氨法脱硫脱碳运行经验，开发了一种控制氨法脱碳***氨逃逸的装置及方法，以氨为脱硫和脱碳剂，气体首先进入脱硫装置进行脱硫，脱硫后的气体进入脱碳装置中，脱除气体中的二氧化碳。脱碳后的气体中含有游离氨，用氨法脱硫的酸性硫酸铵液和酸性水洗液吸收气体中的游离氨。本发明有效地控制氨法脱碳***的氨逃逸，同时，洗涤回收的氨还可在用于脱硫，节约了氨耗。
发明内容
本发明开发了一种控制氨法脱碳***氨逃逸的装置及方法，采用氨脱除硫氧化物和CO2，生成硫酸铵化肥和碳酸氢铵化肥。氨法脱硫脱碳装置设置氨法脱硫功能区、氨法脱碳功能区、氨逃逸控制功能区，氨法脱硫功能区包括洗涤降温段、吸收循环段、颗粒物控制段，氨法脱碳功能区包括冷却降温段、吸收循环段，氨逃逸控制功能区包括酸性硫酸铵液洗涤***、酸性水洗***。氨法脱硫功能区的吸收循环段通过管道与氨逃逸控制功能区酸性硫酸铵液洗涤***连接，氨法脱硫功能区的颗粒物控制段或氨法脱碳功能区的冷却降温段通过管道与氨逃逸控制功能区酸性水洗***连接。氨法脱碳吸收循环段采用多级吸收，其中最后一级少加氨或不加氨，以减少脱碳后的NH3逃逸。
采用氨为脱硫和脱碳剂，气体首先进入脱硫功能区中进行脱硫，生成硫酸铵化肥，脱硫后的气体进入脱碳功能区中，脱除气体中的二氧化碳，生成碳酸氢铵化肥，脱碳后的气体中含有游离氨，用氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤吸收气体中的游离氨。酸性硫酸铵液采用氨法脱硫功能区吸收循环段溶液，硫酸铵浓度10-38wt％，pH 4.5-6.5；酸性水洗液采用氨法脱硫功能区颗粒物控制段溶液或氨法脱碳功能区冷却降温段溶液，硫酸铵浓度0-5wt％，pH 3-7。在氨逃逸控制功能区洗涤后，酸性硫酸铵液和酸性水洗液浓度基本不变，酸性硫酸铵液pH 4.6-6.9，酸性水洗液pH 3.5-7.5。
酸性硫酸铵液、酸性水洗液温度20-60℃，优选30-50℃。
酸性硫酸铵液、酸性水洗液洗涤前通过冷却器冷却降温后再洗涤。
酸性硫酸铵液、酸性水洗液洗涤器中设置液体分布器、气液接触部件，液体分布器优选槽式分布器，气液接触部件优选填料。
在用氨法脱硫的酸性硫酸铵液和酸性水洗液吸收气体中的游离氨前，还包括用工艺水进行洗涤，吸收游离氨。工艺水优选脱盐水或氨法脱碳功能区冷却降温段溶液或氨逃逸控制功能区酸性水洗***排水。
氨法脱硫的酸性硫酸铵液洗涤至少设置1层液体分布器，气液接触洗涤后的溶液回收，返回脱硫***。
氨法脱硫的酸性水洗液洗涤至少设置1层液体分布器，气液接触洗涤后的溶液回收，返回脱硫***或脱碳***。
工艺水洗涤至少设置1层液体分布器，产生的含氨溶液返回脱硫***或脱碳***。
用氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤之间，设有仅允许气体通过的集液器。
用氨法脱硫的酸性硫酸铵液和工艺水洗涤之间，设有仅允许气体通过的集液器。
上述功能区，可以组合成一个塔中或多个塔中。在脱硫功能区，每个段设置至少一层喷淋层，段与段之间设有允许气体通过的设备/部件。在颗粒物去除段，分成两个部分，第一部分喷淋洗涤采用含硫酸铵的高浓度溶液循环洗涤，第二部分采用含硫酸铵的稀溶液循环洗涤。两个部分之间设有允许气体通过的设备/部件。在脱碳功能区，每个段设置至少一层喷淋层，段与段之间设有允许气体通过的设备/部件。
本发明还涉及如下实施方案：
1.一种控制氨法脱碳***氨逃逸的方法，其特征在于，氨法脱碳后的气体中含有游离氨，用氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤吸收该氨法脱碳后的气体中的游离氨。
2.如实施方案1所述的方法，其特征在于，在用氨法脱硫的酸性硫酸铵液和酸性水洗液吸收气体中的游离氨前，还包括用工艺水进行洗涤，吸收游离氨，工艺水优选脱盐水、洗涤冷凝水、酸性水洗液排水。
3.如实施方案1所述的方法，其特征在于，氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤产生的含氨溶液返回脱硫***或脱碳***。
4.如实施方案1所述的方法，其特征在于，氨法脱硫的酸性硫酸铵液洗涤至少设置1层液体分布器，气液接触洗涤后的溶液回收，返回脱硫***。
5.如实施方案1所述的方法，其特征在于，氨法脱硫的酸性水洗液洗涤至少设置1层液体分布器，气液接触洗涤后的溶液回收，返回脱硫***或脱碳***。
6.如实施方案2所述的方法，其特征在于，工艺水洗涤至少设置1层液体分布器， 产生的含氨溶液返回脱硫***或脱碳***。
7.如实施方案1所述的方法，其特征在于，用氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤之间，设有仅允许气体通过的设备或部件。
8.如实施方案2所述的方法，其特征在于，用氨法脱硫的酸性硫酸铵液和工艺水洗涤之间，设有仅允许气体通过的设备或部件。
9.如实施方案1所述的方法，其特征在于，氨法脱碳吸收循环段包括多级吸收，其中最后一级少加氨或不加氨，以减少脱碳后的NH3逃逸。
10.如实施方案1所述的方法，其特征在于，经氨法脱碳功能区吸收循环段处理后气体中NH3含量为200至2000ppm；优选400至1500ppm；更优选500至1000ppm。
11.如实施方案1所述的方法，其特征在于，在经过氨逃逸控制功能区处理之后气体中NH3含量为0至30ppm；优选0至20ppm；更优选0至10ppm。
12.如实施方案1所述的方法，其特征在于，酸性硫酸铵液pH 4.5-6.5，硫酸铵浓度10-38wt％；酸性水洗液pH 3-7，硫酸铵浓度0-5wt％。
13.如实施方案1所述的方法，其特征在于，酸性硫酸铵液、酸性水洗液温度20-60℃，优选30-50℃。
14.如实施方案1所述的方法，其特征在于，酸性硫酸铵液、酸性水洗液洗涤前通过冷却器冷却降温后再洗涤。
15.如实施方案2所述的方法，其特征在于，工艺水的液气比通常采用5-25，优选10-20，更优选12-18。
16.如实施方案1所述的方法，其特征在于，酸性硫酸铵液的液气比通常采用1-20，优选1-10，更优选2-6。
17.如实施方案1所述的方法，其特征在于，酸性水洗液的液气比通常采用1-15，优选1-8，更优选2-5。
18.如实施方案1所述的方法，其特征在于，酸性硫酸铵液、酸性水洗液洗涤器中设置气液接触部件，气液接触部件优选填料。
19.如实施方案2所述的方法，其特征在于，工艺水、洗涤冷凝水、酸性水洗液排水的pH不大于8。
20.如实施方案2所述的方法，其特征在于，工艺水、洗涤冷凝水、酸性水洗液排水加入酸调节pH，优选该酸是硫酸。
21.一种控制氨法脱硫脱碳***氨逃逸的装置，其特征在于，包括氨法脱硫功能区、 氨法脱碳功能区、氨逃逸控制功能区，
其中，
氨法脱硫功能区包括洗涤降温段、吸收循环段、颗粒物控制段，
氨法脱碳功能区包括冷却降温段、吸收循环段，
氨逃逸控制功能区包括氨逃逸控制段包括酸性硫酸铵液洗涤***、酸性水洗***，
氨法脱硫功能区的吸收循环段和通过管道与氨逃逸控制功能区酸性硫酸铵液洗涤***连接，氨法脱硫功能区的颗粒物控制段或氨法脱碳功能区的冷却降温段通过管道与氨逃逸控制功能区酸性水洗***连接。
22.如实施方案21所述的装置，其特征在于，氨法脱碳吸收循环段包括多级吸收，其中最后一级少加氨或不加氨，以减少脱碳后的NH3逃逸。
23.如实施方案21所述的装置，其特征在于，氨逃逸控制功能区还可包括工艺水洗***，工艺水洗***通过管道与工艺水管连接，并与氨法脱硫装置吸收循环段或氨法脱碳装置吸收循环段连接。
24.如实施方案21所述的装置，其特征在于，氨法脱硫功能区、氨法脱碳功能区各段，可以组合成一个塔中或多个塔中，段与段之间设有允许气体通过的设备/部件。
25.如实施方案21所述的装置，其特征在于，氨法脱硫功能区颗粒物控制段可部分或全部实现氨法脱碳功能区冷却降温段功能。
附图说明
图1为本发明实施例1，在用氨法脱硫的酸性硫酸铵液和酸性水洗液吸收气体中的游离氨前，还用工艺水进行洗涤，吸收游离氨。
图2为本发明实施例2，用氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤吸收气体中的游离氨。
图3为对比例，用工艺水进行洗涤，吸收游离氨。
工艺气1、脱硫功能区2、脱硫洗涤降温段2-1、脱硫吸收循环段2-2、脱硫颗粒物控制段2-3、脱硫循环泵a 3、脱硫循环泵b 4、脱硫循环泵c 5、脱硫循环槽6、氧化空气7、去脱硫***加氨8、硫酸铵排出泵9、脱硫循环泵d 10、脱硫换热器11、脱硫后尾气12、脱碳吸收塔13、脱碳循环泵14、碳铵排出泵15、去脱碳***加氨16、脱碳后尾气17、洗氨塔18、工艺水洗涤段18-1、硫酸铵洗涤段18-2、酸液洗涤段18-3、洗氨循环泵a 19、脱硫吸收段硫酸铵溶液20、返回脱硫液21、洗氨循环泵b 22、 脱硫颗粒物控制段溶液23、返回酸性溶液24、净烟气25、产成品硫酸铵26、产成品碳酸氢铵27、工艺水28、含氨溶液29、工艺水洗涤段填料30-1、硫酸铵洗涤段填料30-2、酸液洗涤段填料30-3、工艺水洗涤段槽式分布器31-1、硫酸铵洗涤段槽式分布器31-2、酸液洗涤段槽式分布器31-3、去洗氨的脱硫吸收段硫酸铵溶液换热器32、去洗氨的脱硫颗粒物控制段溶液换热器33。
具体实施方式
在本发明控制氨法脱碳***氨逃逸的方法中，氨法脱碳后的气体中含有游离氨。本发明具体采用氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤吸收该氨法脱碳后的气体中的游离氨。此外，本发明还在用氨法脱硫的酸性硫酸铵液和酸性水洗液吸收气体中的游离氨前，还包括用工艺水进行洗涤，吸收游离氨，工艺水优选脱盐水、洗涤冷凝水。
在本发明的方法中，用于洗涤吸收的酸性硫酸铵液、酸性水洗液或工艺水的流量可以根据需要进行合适地调节，工艺水的液气比通常采用5-25，优选10-20，更优选12-18；酸性硫酸铵液的液气比通常采用1-20，优选1-10，更优选2-6；酸性水洗液的液气比通常采用1-20，优选1-15，更优选2-10。
液气比＝Q/V,
Q，液体循环量，L/h
V，氨法脱碳后的工艺气体流量(工况条件，即操作条件下(温度、压力等条件下)的气体流量)，m3/h。
根据本发明方法进行的处理主要脱除氨法脱碳后的气体中含有的游离氨，而对SO2含量和CO2含量影响较小。
在本发明的方法中，酸性硫酸铵液pH为4.5-6.5，硫酸铵浓度为10-38wt％，优选12-35wt％，更优选15-30wt％，最优选17-28wt％；酸性水洗液pH为3-7，硫酸铵浓度为0-5wt％，优选0-3wt％，更优选0-1wt％，最优选0-0.6wt％。
在本发明的方法中，酸性硫酸铵液、酸性水洗液温度为20-60℃，优选30-50℃。
经脱碳吸收塔处理后气体中NH3含量为200至2000ppm；优选400至1500ppm；更优选500至1000ppm。
经脱碳吸收塔处理后气体中SO2含量为0至20mg/Nm3；优选0至15mg/Nm3；更优选0至10mg/Nm3。
经脱碳吸收塔处理后气体中CO2含量为0-20v％；优选1-10v％；更优选2-7v％。
在经过本发明的方法处理之后气体中NH3含量为0至30ppm；优选0至20ppm；更优选0至10ppm。
本发明所保护的一种控制氨法脱碳***氨逃逸的方法优选在本发明所限定的一种控制氨法脱硫脱碳***氨逃逸的装置中进行。
本发明的方法和装置实现了除了技术效果以外的有益经济效果，特别是减少氨逃逸，特别显著地减少了氨耗，具体地可以使氨耗损失减少96％-99％，优选97％-99％，具体地如以下实施例所示。
本发明中气体中SO2含量测试方法为HJ 629-2011固定污染源废气.二氧化硫的测定.非分散红外吸收法；
CO2含量测试方法为HJ 870-2017固定污染源废气二氧化碳的测定非分散红外吸收法；
NH3含量测试方法为HJ 533-2009环境空气和废气氨的测定纳氏试剂分光光度法。
本发明中所提及的所有浓度以重量计，除非另外说明。
实施例
本发明具体提供实施例1和2及对比例以进一步说明本发明的技术方案及其有益效果。
实施例1
如图1，含硫氧化物、CO2的工艺气1进入脱硫功能区2，依次经过脱硫洗涤降温段2-1、脱硫吸收循环段2-2、脱硫颗粒物控制段2-3，在脱硫洗涤降温段2-1用脱硫循环泵-a 3进行喷淋循环，尾气降温的同时提浓硫酸铵溶液，提浓并析出固体的硫酸铵浆液经硫酸铵排出泵9送出产硫酸铵26。用脱硫循环泵-b 4和脱硫循环泵-c 5、脱硫循环槽6进行吸收喷淋循环，吸收尾气中的硫氧化物(二氧化硫及三氧化硫)。脱硫循环泵-c 5送出部分硫酸铵溶液20经冷却器32冷却至35℃后去洗氨塔硫酸铵洗涤段18-2，洗涤后的溶液21回脱硫循环槽6。利用脱硫循环泵-d 10进行洗涤喷淋循环，利用脱硫换热器11控制洗涤温度及脱硫后尾气12的温度。氨法脱硫功能区颗粒物控制段2-3实现氨法脱碳的冷却降温功能。烟气冷凝的酸性溶液23经冷却器33冷却至35℃后作为洗氨塔酸性水洗段18-3补水，洗涤后的溶液24回脱硫循环槽6。去脱硫 ***加氨8经计量后去脱硫循环槽6加氨。氧化空气7去脱硫循环槽6将溶液氧化。
脱硫后尾气12进入脱碳吸收塔13，用脱碳循环泵14进行吸收循环，用碳铵排出泵15送出产成品碳酸铵27。去脱碳***加氨16经计量后去脱碳吸收塔13加氨。
脱碳后尾气17进入洗氨塔18，依次经过工艺水洗涤段18-1、硫酸铵洗涤段18-2、酸液洗涤段18-3，在洗氨塔工艺水洗段18-1利用洗氨循环泵-a 19进行工艺水洗涤，洗氨塔工艺水洗段18-1设有槽式分布器31-1和填料30-1，工艺水通过外界工艺水管28补水，洗涤后的含氨溶液29去脱碳塔13。脱硫循环泵-c 5送出的部分脱硫吸收段硫酸铵溶液20进洗氨塔硫酸铵洗涤段18-2，洗氨塔硫酸铵洗涤段18-2设有槽式分布器31-2和填料30-2，洗涤后的溶液(即返回脱硫液)21回脱硫循环槽6。脱硫循环泵-d 10送出的烟气冷凝的酸性溶液(即脱硫颗粒物控制段溶液)23作为洗氨塔酸性水洗段18-3补水，洗氨塔酸性水洗段18-3设有槽式分布器31-3和填料30-3，洗涤后的溶液(即返回酸性溶液)24回脱硫循环槽6。洗涤后净烟气25排出。
酸性硫酸铵液20流量350m3/h，pH 6.4，硫酸铵浓度18wt％，进入洗氨塔洗涤后返回的酸性硫酸铵液pH 6.9，硫酸铵浓度基本不变。
酸性水洗液23流量根据洗氨塔酸性水洗段18-3水洗液pH值调整，pH 3.8，硫酸铵浓度2wt％，进入洗氨塔洗涤后返回的酸性水洗液pH 4.2，硫酸铵浓度基本不变，其中洗氨循环泵b 22循环量500m3/h，以保证洗氨效果。
工艺水28流量根据洗氨塔工艺水洗段18-1水洗液pH值调整，其中洗氨循环泵a 19循环量1200m3/h，以保证洗氨效果。采用除盐水pH 6.9，进入洗氨塔洗涤后返回的溶液pH7.9。
脱硫脱碳采用99.6％的液氨作为吸收剂，工艺气1参数见下表：
脱硫并冷却后气体12参数见下表：
经脱碳吸收塔处理后气体17主要参数见下表：
经洗氨塔处理后气体25主要参数见下表：
氨逃逸量4.98t/年，氨耗损失约2万元/年。
实施例2
如图2，同实施例1，但不设洗氨塔的工艺水洗段18-1。脱硫脱碳参数一致，经洗氨塔处理后气体25主要参数见下表：
氨逃逸量8.96t/年，氨耗损失约3.6万元/年。
对比例
如图3，同实施例1，但不设洗氨塔的硫酸铵洗涤段18-2和酸性溶液水洗段18-3。脱硫脱碳参数一致，经洗氨塔处理后气体25主要参数见下表：
氨逃逸量248t/年，氨耗损失约99.2万元/年。
从以上本发明实施例和对比例的比较可以看出，经过本发明方法和装置处理的气体中氨逃逸量显著下降，使得氨耗损失极大地降低，从而实现了优异的技术效果和经济效果。
唯以上所述者，仅为本发明的较佳实施例而已，举凡熟悉此项技艺的专业人士在了解本发明的技术手段之后，自然能依据实际的需要，在本发明的教导下加以变化。因此凡依本发明申请专利范围所作的同等变化与修饰，都应仍属本发明专利涵盖的范围内。

Claims (25)

  1. 一种控制氨法脱碳***氨逃逸的方法，其特征在于，氨法脱碳后的气体中含有游离氨，用氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤吸收该氨法脱碳后的气体中的游离氨。
  2. 如权利要求1所述的方法，其特征在于，在用氨法脱硫的酸性硫酸铵液和酸性水洗液吸收气体中的游离氨前，还包括用工艺水进行洗涤，吸收游离氨，工艺水优选脱盐水、洗涤冷凝水、酸性水洗液排水。
  3. 如权利要求1所述的方法，其特征在于，氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤产生的含氨溶液返回脱硫***或脱碳***。
  4. 如权利要求1所述的方法，其特征在于，氨法脱硫的酸性硫酸铵液洗涤至少设置1层液体分布器，气液接触洗涤后的溶液回收，返回脱硫***。
  5. 如权利要求1所述的方法，其特征在于，氨法脱硫的酸性水洗液洗涤至少设置1层液体分布器，气液接触洗涤后的溶液回收，返回脱硫***或脱碳***。
  6. 如权利要求2所述的方法，其特征在于，工艺水洗涤至少设置1层液体分布器，产生的含氨溶液返回脱硫***或脱碳***。
  7. 如权利要求1所述的方法，其特征在于，用氨法脱硫的酸性硫酸铵液和酸性水洗液洗涤之间，设有仅允许气体通过的设备或部件。
  8. 如权利要求2所述的方法，其特征在于，用氨法脱硫的酸性硫酸铵液和工艺水洗涤之间，设有仅允许气体通过的设备或部件。
  9. 如权利要求1所述的方法，其特征在于，氨法脱碳吸收循环段包括多级吸收，其中最后一级少加氨或不加氨，以减少脱碳后的NH3逃逸。
  10. 如权利要求1所述的方法，其特征在于，经氨法脱碳功能区吸收循环段处理后气体中NH3含量为200至2000ppm；优选400至1500ppm；更优选500至1000ppm。
  11. 如权利要求1所述的方法，其特征在于，在经过氨逃逸控制功能区处理之后气体中NH3含量为0至30ppm；优选0至20ppm；更优选0至10ppm。
  12. 如权利要求1所述的方法，其特征在于，酸性硫酸铵液pH 4.5-6.5，硫酸铵浓度10-38wt％；酸性水洗液pH 3-7，硫酸铵浓度0-5wt％。
  13. 如权利要求1所述的方法，其特征在于，酸性硫酸铵液、酸性水洗液温度20-60℃，优选30-50℃。
  14. 如权利要求1所述的方法，其特征在于，酸性硫酸铵液、酸性水洗液洗涤前通过冷却器冷却降温后再洗涤。
  15. 如权利要求2所述的方法，其特征在于，工艺水的液气比通常采用5-25，优选10-20，更优选12-18。
  16. 如权利要求1所述的方法，其特征在于，酸性硫酸铵液的液气比通常采用1-20，优选1-10，更优选2-6。
  17. 如权利要求1所述的方法，其特征在于，酸性水洗液的液气比通常采用1-15，优选1-8，更优选2-5。
  18. 如权利要求1所述的方法，其特征在于，酸性硫酸铵液、酸性水洗液洗涤器中设置气液接触部件，气液接触部件优选填料。
  19. 如权利要求2所述的方法，其特征在于，工艺水、洗涤冷凝水、酸性水洗液排水的pH不大于8。
  20. 如权利要求2所述的方法，其特征在于，工艺水、洗涤冷凝水、酸性水洗液排水加入酸调节pH，优选该酸是硫酸。
  21. 一种控制氨法脱硫脱碳***氨逃逸的装置，其特征在于，包括氨法脱硫功能区、氨法脱碳功能区、氨逃逸控制功能区，
    其中，
    氨法脱硫功能区包括洗涤降温段、吸收循环段、颗粒物控制段，
    氨法脱碳功能区包括冷却降温段、吸收循环段，
    氨逃逸控制功能区包括氨逃逸控制段包括酸性硫酸铵液洗涤***、酸性水洗***，
    氨法脱硫功能区的吸收循环段和通过管道与氨逃逸控制功能区酸性硫酸铵液洗涤***连接，氨法脱硫功能区的颗粒物控制段或氨法脱碳功能区的冷却降温段通过管道与氨逃逸控制功能区酸性水洗***连接。
  22. 如权利要求21所述的装置，其特征在于，氨法脱碳吸收循环段包括多级吸收，其中最后一级少加氨或不加氨，以减少脱碳后的NH3逃逸。
  23. 如权利要求21所述的装置，其特征在于，氨逃逸控制功能区还可包括工艺水洗***，工艺水洗***通过管道与工艺水管连接，并与氨法脱硫装置吸收循环段或氨法脱碳装置吸收循环段连接。
  24. 如权利要求21所述的装置，其特征在于，氨法脱硫功能区、氨法脱碳功能区各段，可以组合成一个塔中或多个塔中，段与段之间设有允许气体通过的设备/部件。
  25. 如权利要求21所述的装置，其特征在于，氨法脱硫功能区颗粒物控制段可部分或全部实现氨法脱碳功能区冷却降温段功能。
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