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    • 专利摘要:
    "Method and apparatus for effective removal of sulfur oxides and dust in gas by ammonia-based process". This invention belongs to the technical field of environmental protection. A method and apparatus for effectively removing sulfur oxides and dust in a gas by an ammonia process is provided. Further provided are a fine particle control section, a mixing structure or apparatus, as well as gas-liquid dispersion enhancer layers.
    公开号:BR102017013527B1
    申请号:R102017013527
    申请日:2017-06-22
    公开日:2019-09-03
    发明作者:Xu Changxiang；Luo Jing
    申请人:Jiangnan Environmental Prot Group Inc；Jiangsu New Century Jiangnan Environmental Prot Inc Ltd；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for METHOD AND APPARATUS FOR REMOVING SULFUR OXIDES AND DUST IN GAS THROUGH AMMONIA-BASED PROCESSES.
    FIELD OF TECHNIQUE [0001] The present invention relates to the technical field of environmental protection and, in particular, to a method and apparatus for the effective removal of sulfur oxides and dust in gas through an ammonia process.
    PREVIOUS TECHNIQUE [0002] At the moment, the gypsum-limestone method is the main process for removing sulfur dioxide in gas in the world. This method generates a large amount of waste water and plaster waste in the process of desulfurization. 0.7 ton of carbon dioxide is generated to remove 1 ton of sulfur dioxide. The treatment of this wastewater and waste requires high capital and operating costs. While desulfurization with ammonia does not generate waste water or waste, and ammonia as the added desulfurization agent is converted into an ammonium sulfate fertilizer. This makes the refuse profitable and the sales revenue for the ammonium sulfate fertilizer is typically greater than the cost of purchasing ammonia. However, the popularization and application of this advanced technique has been limited for a long period of time due to problems such as ammonia leak, aerosol, etc., present in ammonia desulfurization. The present invention has fundamentally eliminated ammonia leakage and aerosol formation through an innovative process process, and the significant technical challenge that prevents the development and popularization of ammonia desulfurization has been fully resolved. It can obtain SO2 <35 mg / Nm 3 , total powder (including aerosol) <5 mg / Nm 3 and ammonia exhaust <2 mg / Nm 3 in combustion gas
    Petition 870190038870, of 04/25/2019, p. 4/16
    2/21 so clean; however, the structural design of the absorber is simpler and capital expenditures less.
    [0003] Jiangsu New Century Jiangnan Environmental Protection Inc. (JNEP) has started to develop ammonia desulfurization since 1998 and has since established more than 300 sets of ammonia desulfurization apparatus, comprising 80% of ammonia desulfurization market share in China and is the proponent and leader in ammonia desulfurization. This company is dedicated to the development of ammonia desulfurization technology, a technique that is continuously in progress. Technical challenges such as ammonia leakage, aerosol formation, etc., were fundamentally resolved, and this technique was developed until the fourth generation. When using this technique, under the conditions that the SO 2 concentration <30,000 mg / Nm 3 and the total powder concentration <50 mg / Nm 3 in crude flue gas, SO 2 <35 mg / Nm 3 can be obtained, total powder (including aerosol) <5 mg / Nm 3 and ammonia exhaust <2 mg / Nm 3 in clean flue gas. This company revealed two patents for methods of removing SO2 in flue gas burned with coal (CN 1283346C and CN 1321723C) in 2003, which proposed requirements for parameters of dust removal with cooling and desulfurization by absorption and for concentration of SO2 in gas tail was less than 100 mg / Nm 3 . However, the escape of ammonia in the tail gas reached 12 mg / Nm 3 , no attention was paid to aerosol discharge, and the ammonia recovery rate was low. In response, this company revealed “Process and apparatus of ammonia desulfurization with crystallization in tower” (CN100428979C) in 2005, where an absorber was designed for a structure of multiple sections, which were sequentially an oxidation section, a crystallization section, a absorption cooling section, a main absorption section, a mist separation dehydration section. Through
    Petition 870170046786, of 07/05/2017, p. 7/35
    3/21 of these innovations, crystallization was carried out using the flue gas evaporation capacity in order to reduce the device's operational energy consumption. The SO 2 concentration in the tail gas discharged was less than 200 mg / Nm 3 , the ammonia content in the tail gas was up to 3 mg / Nm 3 and the ammonium sulfate fertilizer as the by-product satisfies the product requirement first grade of GB535 standard. Ammonia recovery was greatly increased, but the amount of aerosol discharge was still large. This company later unveiled “Apparatus and method for controlling fine particulates in de-sulfurized flue gas” (CN103301705B) in 2013, which revealed a method and apparatus for removing flue gas mist and removing water wash mist after absorption. Small particles can be effectively removed. An absorption mist separator removed most liquid droplets greater than 10 pm and gas with larger droplets removed was passed to dust with water washing, small particles developed into large particles after washing with water and were removed. The efficiency of removing small particles and dust can be 60% or more. Although this technique can efficiently remove small particles, the ultra-low emission index in China requires that total dust (including aerosol) <10 mg / Nm 3 and the dust removal efficiency needs to be further improved.
    [0004] Based on the 4 core patents described above and 64 other ancillary patents, this company continues to tackle key problems against the significant technical challenge of ammonia and aerosol leakage within the present invention by totally taking the technical focus away from how to eliminate ammonia leak and aerosol generated for innovative investigation of the absorption process, eradicating ammonia leak and aerosol formation. Through technical means such as segmented control, ammonia feeding with multiple points
    Petition 870170046786, of 07/05/2017, p. 8/35
    4/21 plos, etc., gas discharged after treatment meets the requirements that SO 2 <35 mg / Nm 3 , total powder (including aerosol) <5 mg / Nm 3 and ammonia exhaust <2 mg / Nm 3 . The technique of the present invention has been verified through industrial tests.
    SUMMARY OF THE INVENTION [0005] The present invention relates to the fact that the prior art does not reach the key point of ammonia-based desulfurization techniques and where it does not solve the significant technical challenges of ammonia and aerosol leakage from the formation, but only focuses on how to eliminate escaped ammonia and formed aerosol. This results in the increase of several sections within the absorber and complication of the system. It not only leads to poorer treatment effect, but also to a substantial increase in capital and operating costs. Based on systematic investigation of ammonia desulfurization techniques, the present invention focuses on reasons for ammonia escape and aerosol formation and uses segmented control techniques and ammonia feeding at multiple points in order to fundamentally solve these problems. In this way, the technique of the present invention is formed. It obtains SO 2 <35 mg / Nm 3 and total powder (including aerosol) <5 mg / Nm 3 , ammonia leakage <2 mg / Nm 3 and ammonia recovery rate> 99% in clean flue gas subjected to desulfurization dust removal using the method of the present invention. Still, the process flow is simple, the investment is low, the degree of automation is high, the by-product is qualified, no waste water is discharged, there is no secondary pollution and synergistic control of various pollutants can be obtained.
    [0006] Finally, the invention solves the technical problems described above through the technical solutions that follow.
    [0007] A method and apparatus for the effective removal of sulfur oxides and dust in gas through a process with ammonia, characterized
    Petition 870170046786, of 07/05/2017, p. 9/35
    5/21 as follows. The device uses segmented control and ammonia feeding process at multiple points to fundamentally control ammonia leakage and aerosol formation in order to obtain an effective desulfurization and dust removal effect. Under conditions where the SO 2 concentration <30,000 mg / Nm 3 and the total powder concentration <50 mg / Nm 3 in crude flue gas, SO 2 <35 mg / Nm 3 , total powder (including aerosol) can be obtained ) <5 mg / Nm 3 and ammonia leakage <2 mg / Nm 3 in clean flue gas. The device consists of a gas cleaning and pollutant removal system, an oxidation system, an ammonium sulphate after-treatment system, an ammonia supply system and an auxiliary system.
    [0008] The gas cleaning and pollutant removal system uses segmented control and is mainly divided into a prewash section, an absorption section and a small particle control section, and each of the prewash section , the absorption section and the small particle control section are provided with a plurality of spray layers, the prewash section concentrates a washing liquid in circulation, reducing the flue gas temperature and the absorption section absorbs and removes sulfur dioxide in flue gas. Absorption solutions with different compositions are used in the respective sections in order to control ammonia leakage and aerosol formation in the respective sections.
    [0009] The gas cleaning and pollutant removal system uses ammonia feed at multiple points and has sufficient reaction to prevent ammonia escape and aerosol formation. An ammonia-containing desulfurization agent is added from a plurality of points, including the top layer, the middle layer and the bottom layer of an oxidation system oxidation tank, the prewash section, spray absorption layers
    Petition 870170046786, of 07/05/2017, p. 10/35
    6/21 tion and inputs and outputs of the respective recirculation pumps. A mixing frame or apparatus can be provided at each ammonia feed point and a mixer used exclusively for liquid ammonia is provided when anhydrous ammonia is directly added to a solution to obtain ammonia feed at multiple points and sufficient reaction and prevent leakage of ammonia and aerosol formation. The absorption circulation liquid of the absorption section has a pH value greater than 4.6. The circulating washing liquid from the prewash section has a pH value of less than 5.5 for the crystallization process inside the absorber, and the circulating washing liquid from the prewash section has a value of pH less than 6 for crystallization process outside the absorber.
    [0010] The oxidation system is layered according to the requirement for segmented control, so the replacement liquid and an absorption circulation liquid from the prewash section are removed from different positions of the oxidation tank of the system. oxidation and 2 to 8 layers of gas-liquid dispersion enhancers are provided in the oxidation tank in such a way that both ensure absorption efficiency and ammonia escape control and aerosol formation. The gas-liquid dispersion enhancer can employ a form of any of a structured packaging, random packaging, a perforated plate, a bubble cap, an aeration head and the like or a combined form thereof. The oxidation tank and the pre-wash recirculation tank are respectively placed at the bottom of the tower or outside the tower as needed. The liquid level of the oxidation tank is greater than 5 meters, oxidation air is excessive by 20% or more, the actual residence time of the solution is greater than 20 minutes, the oxidation rate of the absorption circulating liquid it's bigger
    Petition 870170046786, of 07/05/2017, p. 11/35
    7/21 than 90% and the oxidation ratio of the circulating wash liquid of the prewash section is greater than 92%.
    [0011] The small particle control section is provided with a mist separator, each layer of the prewash section and the absorption section is provided with a mist separator as needed; and the mist separator employs a form of a baffle plate, a ridge, packaging or mesh or a combined form thereof.
    [0012] The process flow used by the device is as follows:
    [0013] the flow gas enters from a prewash section of a gas cleaning and pollutant removal system and is cooled and rinsed by a circulating wash liquid from the prewash section while the washing liquid circulation of the pre-wash liquid is concentrated and the process gas is further passed through an absorption section for desulfurization through washing with an absorption circulation liquid and a small particle control section for removal of small particles through a small particle circulation washing liquid before being discharged;
    [0014] the circulation washing liquid of the pre-wash section is replaced from an absorption circulation liquid, the absorption circulation liquid is replaced from a circulation wash liquid of the small particle control section and Process water is mainly replenished from the small particle control section; and [0015] the absorption circulation liquid is oxidized in the oxidation system and solutions with different oxidation ratios are removed from different positions of the oxidation tank of the oxidation system for absorption by circulation.
    [0016] The liquid-to-gas ratio of each layer in the
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    8/21 absorption is not less than 0.2 L / m 3 and the spray coverage is not less than 110%. The liquid-to-gas ratio of each layer of the small particle control section is not less than 0.1 L / m 3 and the spray coverage is not less than 100%.
    [0017] The surface gas velocity of the absorber is 1 m / s to 5 m / s;
    and / or the operating temperature of the prewash section is 35 ° C to 80 ° C;
    and / or the operating temperature of the absorption section is 30 ° C to 70 ° C; and / or the operating temperature of the small particle control section is 30 ° C to 65 ° C.
    [0018] The circulation washing liquid from the pre-wash section is concentrated (crystallized) in the prewash section or is subjected to evaporative crystallization outside the absorber and is processed into a commercial ammonium sulfate through an after-treatment system. of ammonium sulfate. An integrated drying tower is used to directly produce ammonium sulfate from a portion of the circulating washing liquid in the prewash section when it is necessary to control harmful ions such as chlorine, fluorine and the like in the solution.
    [0019] In this system, under the condition that the SO 2 concentration <30,000 mg / Nm 3 and the total powder concentration <50 mg / Nm 3 in crude flue gas, SO 2 <35 mg / Nm 3 can be obtained and total powder (including aerosol) <5 mg / Nm 3 , ammonia leakage <2 mg / Nm 3 and ammonia recovery> 99% in cleaning flue gas.
    [0020] The present invention has positive and progressive effects as follows.
    [0021] 1. Total powder (containing aerosol) and SO 2 in flue gas treated using the method of the present invention meet the requirements for ultra low emission, which are SO 2 <35 mg / Nm 3 and total powder (including
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    9/21 indo aerosol) <5 mg / Nm 3 in cleaning flue gas. The cleaning flue gas can be discharged through a chimney on top of an absorber or returned to the existing battery for discharge.
    [0022] 2. Free ammonia <2 mg / Nm 3 in the flue gas treated using the method of the present invention and the recovery and utilization of ammonia is 99% or more.
    [0023] 3. The quality of ammonium sulfate as a by-product meets GB535 standard.
    [0024] 4. The method of the present invention has a simple process flow, low energy consumption, no waste water discharge, no secondary pollution, synergistic control of various pollutants such as SO 2 , dust, SO 3 , free ammonia , etc., can be obtained and capital and operating costs can be reduced.
    BRIEF DESCRIPTION OF THE DRAWINGS [0025] Fig. 1 is a schematic diagram of a method and apparatus.
    [0026] Fig. 2 is a schematic diagram of the apparatus and method of Example 1.
    Description of reference numerals:
    [0027] I. Gas cleaning and pollutant removal system; II. Oxidation system; III. Ammonia supply system; IV. Ammonium sulfate after-treatment system; 1. Absorber; 2. Pre-wash recirculation pump; 3. Absorption section; 4. prewash section; small particle control section; 6. Top layer absorption recirculation pump; 7. Crude combustion gas; 8. Oxidation tank; 9. Bubble cover tray; 10. Oxidation air; 11. Pre-wash recirculation tank; 12. Mist separator; 13. Cleaning flue gas; 14. Bottom absorption recirculation pump; 15. Sulfate slurry
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    10/21 ammonium; 16. Flue gas outlet; 17. Crystallization pump; primary solid-liquid separation; 181. Primary solid-liquid separation; 182. Secondary solid-liquid separation; 183; integrated drying tower; 184. Packaging machine; 19. Commercial ammonium sulfate; 20. Flue gas inlet; 21. Spray layer; 22. Small particle control section recirculation tank; 23. Small particle control section recirculation pump; 24. Process water; 25. Continuous emission monitoring system (CEMS); 26. Gas-liquid dispersion enhancer; 31. Evaporative crystallization system; 32. Absorption circulation liquid; 33. Pre-wash section circulation washing liquid; 34. Small particle control section circulation washing liquid; 35. Pre-wash section replacement fluid.
    DESCRIPTION OF MODALITIES [0028] The present invention will be further described below by way of example, but the present invention will therefore not be limited to the scope of the example. The experimental method without specific conditions shown in the example below will be selected according to conventional methods and conditions or according to instructions of the goods.
    PREFERRED EMBODIMENTS [0029] Segmented control processes and ammonia feeding at multiple points are used to fundamentally control ammonia leakage and aerosol formation in order to obtain an effective desulfurization and dust removal effect. Provided that the SO 2 concentration <30,000 mg / Nm 3 and the total powder concentration <50 mg / Nm 3 in crude flue gas, SO 2 <35 mg / Nm 3 , total powder (including aerosol) can be obtained ) <5 mg / Nm 3 and ammonia leakage <2 mg / Nm 3 in cleaning flue gas.
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    11/21 [0030] The device comprises a gas cleaning and pollutant removal system I, an oxidation system II, an ammonium sulphate III post-treatment system, an IV ammonia supply system and an auxiliary system.
    [0031] The gas cleaning and pollutant removal system I comprises an absorber 1, an evaporative crystallization system 31 (optional), a recirculation tank 22 of a small particle control section, a recirculation pump 23 of a small particle control section and a pre-wash recirculation tank 11. The oxidation system II comprises an oxidation tank 8, an upper layer absorption recirculation pump 6 and a lower layer absorption recirculation pump 14. O ammonium sulphate III post-treatment system comprises primary solid-liquid separation 181, secondary solid-liquid separation 182, an integrated drying tower 183 and a packaging machine 184. The oxidation tank 8 and the recirculation tank prewash 11 are respectively placed at the bottom of the tower or outside the absorber as needed.
    [0032] The absorber 1 of the gas cleaning and pollutant removal system I uses segmented control and is divided into a prewash section 4, an absorption section 3 and a small particle control section 5. Each of the prewash section 4, absorption section 3 and small particle control section 5 is provided with a plurality of spray layers 21, the prewash section 4 concentrates a circulating washing liquid 33 while reducing the raw flue gas temperature 7, the absorption circulating liquid 32 of the absorption section 3 absorbs and removes sulfur dioxide in the flue gas and the small particle control section 5 removes small particles. Absorption liquids with different compositions are used in their respective
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    12/21 tions to control ammonia leakage and aerosol formation.
    [0033] Ammonia feeding at multiple points is used and the reaction is sufficient to prevent ammonia escape and aerosol formation. An ammonia-containing desulfurizing agent is added from a plurality of points, including the upper chamber, the intermediate layer or the lower layer of the oxidation tank 8 (absorption recirculation tank), the pre-wash section 4, the layers of spraying of absorption section 3 and inlets and outlets of the respective recirculation pumps.
    [0034] The process flow used by the device is as follows.
    [0035] Crude combustion gas 7 enters from a prewash section 4 of an absorber 1 of a gas cleaning and pollutant removal system I and is cooled and washed by a recirculating washing liquid 33 from the section pre-wash, while the circulating washing liquid 33 of the prewash section is concentrated and the flue gas is still passed through an absorption section 3 for desulfurization by washing with absorption circulating liquid 32 and a small particle control section 5 for removing small particles by washing with a circulating washing liquid from the small particle control section 34 and mist separator respectively before being discharged.
    [0036] Circulating wash liquid 33 from the pre-wash section is replaced from an absorption circulating liquid 32, Absorption circulating liquid 32 is replaced from a circulating wash liquid 34 from the control section small particle and process water 24 is replenished from a recirculation tank 22 of the small particle control section 5.
    [0037] Absorption circulation liquid 32 is oxidized in the tank
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    13/21 of oxidation 8. Most of the solution is removed from the top of the oxidation tank 8 and pumped back to the top of the absorber section 4 of the absorber 1 for absorption circulation and the minority is used as the liquid of replacement 35 of the prewash section and removal of solution from the bottom is pumped to the bottom of the absorption section 4 of the absorber 1 for circulation absorption.
    [0038] Circulating wash liquid 33 from the pre-wash section is concentrated and crystallized in the prewash section 4 or the concentrated solution is crystallized in an evaporative crystallization system 31 outside the absorber and the slurry is then processed in a commercial ammonium sulphate 19 using a post-treatment system of ammonium sulphate IV using a primary liquid-solid separator 181, a secondary solid-liquid separator 182, an integrated dryer drying tower 183 and a packaging machine 184. However , 0.5% of the circulation washing liquid 33 of the prewash section is directly administered to the integrated drying tower for drying and the total chlorine and fluorine content in the circulation liquid in the apparatus is controlled to be <30,000 mg / L. The mother liquor of the solid-liquid separation is returned to the evaporative crystallization system.
    [0039] A plurality of layers of mist separators 12 are provided in the first small particle control section 5 and in the absorption section 3. The mist separator 12 employs a plate shape with a baffle, a ridge or mesh or a combination of the same.
    [0040] A mixing structure is provided at each ammonia feed point to obtain multi-point ammonia feed and efficient reaction and to prevent ammonia escape and aerosol formation. The pH values of the absorption circulation liquid 32
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    14/21 of absorption section 3 are 4.6 to 5.8 at the top and 5.2 to 6.4 at the bottom. The pH value of the circulating washing liquid 33 of the prewash section is 5 to 5.4.
    [0041] 2 to 8 layers of liquid-liquid dispersion enhancers 26 are provided in the oxidation tank 8 and the liquid-gas dispersion enhancer employs a structured packaging and a perforated plate. The liquid level of the oxidation tank 8 is greater than 5 meters, oxidation air is excessive by more than 20%, the residence time of the solution> 20 minutes, the oxidation ratio of the absorption circulating liquid 32> 90% and the oxidation ratio of the circulating washing liquid 33 of the prewash section is> 92%.
    [0042] The liquid-to-gas ratio of an absorption liquid in each layer of absorption section 3 is not less than 0.2 L / m 3 and the spray coverage is not less than 110%. The liquid-to-gas ratio of a distribution liquid in each layer of the small particle control section 5 is not less than 0.1 L / m 3 and the spray coverage is not less than 100%.
    [0043] The surface gas velocity of the absorber is 1 m / s to 5 m / s;
    and / or the operating temperature of the prewash section 4 is 35 ° C to 80 ° C;
    and / or the operating temperature of absorption section 3 is 30 ° C to 70 ° C;
    and / or the operating temperature of the small particle control section 5 is 30 ° C to 65 ° C.
    Example 1
    1. An apparatus for the effective removal of sulfur oxides and dust in gas using an ammonia-based process [0044] The apparatus comprises a gas cleaning system and
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    15/21 pollutant removal I, an oxidation system II, an ammonium sulphate III post-treatment system and an IV ammonia supply system and an auxiliary system.
    [0045] The gas cleaning and pollutant removal system I comprises an absorber 1, a recirculation tank 22 of a small particle control section, a recirculation pump 23 of a small particle control section and a tank of prewash recirculation 11. The oxidation system II comprises an oxidation tank 8, an upper layer absorption recirculation pump 6 and a lower layer absorption recirculation pump 14. The sulfate after-treatment system ammonium III comprises primary solid-liquid separation 181, secondary solid-liquid separation 182, an integrated drying tower 183 and a packaging machine 184.
    [0046] The absorber 1 of the gas cleaning and pollutant removal system I uses segmented control and is divided into a prewash section 4, an absorption section 3 and a small particle control section 5. The prewash 4, the absorption section 3 and the small particle control section 5 are provided with 2/5/2 spray layers 21, respectively, the prewash section 4 concentrates a circulating washing liquid 33 while reducing the raw flue gas temperature 7 and absorption section 3 absorbs and removes sulfur dioxide in flue gas in order to control ammonia leakage and aerosol formation. The small particle control section 5 controls small particles.
    [0047] Ammonia feeding at multiple points is used and the reaction is sufficient to prevent ammonia escape and aerosol formation. An ammonia-containing desulphurizing agent is added from the top and bottom layers of the
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    16/21 oxidation 8, from the prewash section 4, from the prewash recirculation tank 11, from the inlets and outlets of the upper / lower layer absorption recirculation pumps 6/14 and the outlet pump prewash recirculation 2.
    [0048] CEMSs 25 are mounted on a flue gas inlet 20 and a flue gas outlet 16. The CEMS at the flue gas inlet detects flue gas in terms of temperature, pressure, flow rate, oxide concentration nitrogen content, sulfur dioxide concentration, water content, oxygen content and dust content. The CEMS at the flue gas outlet detects flue gas in terms of temperature, pressure, flow rate, nitrogen oxide concentration, sulfur dioxide concentration, water content, oxygen content, free ammonia content and powder.
    [0049] The liquid-to-gas ratio in each layer of a liquid distributor in the absorption section 3 is 1.2 L / m 3 , the spray coverage is 125% and the total spray coverage of the absorption section it is not less than 500%.
    [0050] The liquid-to-gas ratio in each layer of the small particle control section 5 is 1.1 L / m 3 and the spray coverage is 140%.
    [0051] 2 layers of mist separators 12 are provided in the upper part of the absorption section 3 and the mist separator employs 1 layer of a peak plus 1 layer of a plate with deflector. 3 layers of mist separators are provided at the top of a mist separation section of the small particle control section 5 and the mist separator employs 2 layers of ridges plus 1 layer of a mesh.
    Table 1. Device Design Parameters
    At the. Process Index unity Value 1 Quantity of combustion gas Nm 3 / h 510000
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    17/21
    so boiler 2 Flue gas inlet temperature ° C 130-150 3 Flue gas SO 2 concentration mg / Nm 3 4500 5 Dust concentration in the flue gas at the outlet mg / Nm 3 <20 6 Concentration of SO 2 in the flue gas at the outlet mg / Nm 3 <35 7 Dust concentration in the flue gas at the outlet mg / Nm 3 <5 8 Recovery and use of % > 99 ammonia
    2. A method for effective removal of sulfur oxides and dust in gas through the ammonia process [0052] The process flow of the same is as follows.
    [0053] Crude flue gas 7 enters a prewash section 4 of a gas cleaning and pollutant removal system 1 from a flue gas inlet 20 and is brought into countercurrent contact with a flushing liquid circulation 33 of the prewash section to remove dust, SO 3 and a part of SO 2 in the flue gas, then enters an absorption section 3 and is brought into countercurrent contact with an absorption circulation liquid 32 to allow that SO2 of the flue gas is absorbed and still enters a small particle control section 5 to remove a small amount of free ammonia and aerosol in the flue gas as well as atomized droplets, and finally cleaning flue gas 13 is directly discharged flue gas outlet 16 at the top of the tower.
    [0054] The absorption circulation liquid is under the oxidation of
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    18/21 compressed air 10 and sulfites in the mixed liquid are oxidized to sulfates. The solution at the top has an oxidation ratio of 93%, a density of 1.15 g / L and a pH of 4.75. The solution at the bottom has an oxidation rate of 92%, a density of 1.12 g / L and a pH of 5.7.
    [0055] The oxidation air 10 is administered to the lower part of the oxidation system through a pipe and exhaust gas from the oxidation system is administered to the prewash section 4 of absorber 1 and is used for agitation.
    [0056] Process water 24 is replenished in the recirculation tank 22 of the small particle control section.
    [0057] Practical operational parameters of raw flue gas 7 and cleaning flue gas 13 and quality parameters of the ammonium sulfate product can be seen in Tables 4-6.
    [0058] The surface gas velocity of absorber 1 is 3.1 m / s; the operating temperature of the prewash section 4 is 53 ° C;
    the operating temperature of absorption section 3 is 49 ° C; and the operating temperature of the small particle control section 5 is 47 ° C.
    Effect Example 1 [0059] Flue gas under different processing conditions is subjected to desulfurization with ammonia and dust removal using the apparatus and method of Example 1. Table 2 are operational parameters and test results in processing condition 1 ; and Table 3 are operational parameters and test results in processing condition 2.
    Table 2. Operating Parameters and Test Results in Processing Condition 1
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    19/21
    At the. Item unity Test result Grades 1 Amount of flue gas fromintegrated absorber Normal conditions, wet basis, real O 2 x10 4 m 3 / h 35.96 - Normal conditions, dry basis, O 2 6% x10 4 m 3 / h 38.88 - 2 System resistance Pan 1021 - 3 Raw flue gas parameters Concentration ofSO2(Normal conditions, dry basis, O2 6%) mg / Nm 3 811.78 Average during test O2 (V / V) % - - Concentration ofSO3 (Conditionsnormal, dry basis, O2 6%) mg / Nm 3 9.8 Average during test Temperature Ç 127.3 Average during test Moisture content(V / V) % 7.70Dust concentration (Normal conditions, dry basis, O2 6%) mg / Nm 3 9.74 Flue gas parameters ofcleaning Concentration ofSO2 (Conditionsnormal, dry basis, O2 6%) mg / Nm 3 15.73 Average during test O2 (V / V) % -Concentration ofSO3 (Conditionsnormal, dry basis, O2 6%) mg / Nm 3 0.8 Average during test Temperature Ç 47 Average during test Moisture content(V / V) % 14.23Dust concentration mg / Nm 3 1.9 Including partici-
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    20/21
    (Normal conditions, dry basis, O 2 6%) solid particles and soluble solid particles Exhaust-free ammonia (Conditionsnormal, dry basis, O2 6%) mg / Nm 3 0.06Exhaust ammonium salts(Normal conditions, dry basis, O2 6%) mg / Nm 3 0.435 Integrated absorber desulfurization efficiency % 98.05 SO2 concentration of crude flue gas is less than the projected value 6 Integrated absorber dust removal efficiency % 80.57 Efficiency of SO3 removal from integrated absorber % 91.88 Energy consumption (excluding ammonium sulphate system) kWh / h 882.19 Ammonia consumption (anhydrous ammonia) t / h 0.189 Converted intoanhydrous ammonia 10 Ammonia recovery % 99.8811 Ammonium sulfate by-product Nitrogen content % 21.2Moisture % 0.2Free acid content % 0.02
    Table 3. Operating Parameters and Test Results in Processing Condition 2
    At the. Section Tested item unity FirstPeriod Second period 1 Flue gas inlet Flue gas temperature ° C 110 120 2 Average flue gas flow rate m / s 11.2 11.5 3 Sectional duct area m 2 16 16 4 Integral pressure kPa 1.38 1.49
    Petition 870170046786, of 07/05/2017, p. 25/35
    21/21
    5Flue gas moisture content % 7.5 7.5 6 Dry flue gas under normal conditions m 3 / h 4.67χ10 5 4.56χ10 5 7 Oxygen content % 3.75 3.76 8 Powder Discharge concentration measured 3 mg / m 3 43.7 44.8 9 Discharge rate kg / h 20.4 20.4 10 SO2 Discharge concentration measured 3 mg / m 3 2.97χ10 3 2.98χ10 3 11 Discharge rate kg / h 1.39χ10 3 1.36χ10 3 12 Gas outletcombustion Flue gas temperature ° C 46 46 13 Sectional duct area m 2 13.2 13.2 14 Integral pressure KPa 0.03 0.4 15 Measured amount of flue gas m 3 / h 6.46χ10 5 6.32χ10 3 16 Flow rate of dry flue gas under normal conditions m 3 / h 4.74χ10 5 4.64χ10 3 17 Oxygen content of flue gas % 3.93 3.94 18 Powder Discharge concentration at 6% oxygen 3 mg / m 3 4.31 4.76 19 Discharge rate kg / h 2.33 2.51 20 SO2 Discharge concentration at 6% oxygen 3 mg / m 3 5.03 7.54 21 Discharge rate kg / h 2.71 3.98 22 Ammonia Discharge concentration at 6% oxygen 3 mg / m 3 0.250 <0.235 23 Desulfurization efficiency % 99.81 99.71 24 Dust removal efficiency % 88.58 87.70 25 Absorber pressure drop kPa 1.35 1.45
    Note: the first period is on the morning of May 18, 2016 and the second period is on the afternoon of May 18, 2016.
    权利要求:
    Claims (15)
    [1]
    claims
    1. Method for the effective removal of sulfur oxides and dust in gas through an ammonia process, characterized by the fact that the method uses segmented control and multipoint ammonia feeding process to fundamentally control ammonia leakage and aerosol formation to achieve an effective desulfurization and dust removal effect; under the condition that the SO2 concentration <30,000 mg / Nm 3 and the total dust concentration <50mg / Nm 3 in crude combustion gas (7), is carried out, in clean gas, so that SO2 <35mg / Nm 3 , total powder <5mg / Nm 3 , and ammonia leakage <2mg / Nm 3 ;
    the process flow used by the method is as follows:
    the flue gas enters from a pre-wash section (4) and is cooled and washed by a circulating washing liquid from the prewash section (33), while the circulating washing liquid is concentrated and the flue gas combustion is also passed through an absorption section (3) for desulfurization by washing with an absorption circulating liquid (32) and a small particle control section (5) for removing small particles through a washing liquid. small particle circulation (34) respectively and is then discharged;
    the circulation wash liquid of the prewash section (33) is replaced from an absorption circulation liquid (32), the absorption circulation liquid (32) is replaced from a circulation wash liquid of the section small particle control (34) and process water (24) is mainly replenished from the small particle control section (5);
    the absorption circulation liquid (32) is oxidized in the oxidation system (II), and the absorption circulation liquid (32) and the circulation wash liquid with different oxidation ratios
    Petition 870190038870, of 04/25/2019, p. 5/16
    [2]
    2/7 are removed from different positions of the oxidation tank (8) for absorption by circulation;
    the circulating washing liquid from the prewash section (33) is concentrated in the prewash section (4) or subjected to evaporative crystallization outside the absorber (1) and is processed into a commercial ammonium sulfate (19) through an ammonium (IV) sulfate after-treatment system; an integrated drying tower (183) is used to directly produce ammonium sulphate from a part of the absorption washing liquid when it is necessary to control the concentration of chlorine, fluorine in the solution.
    2. Method according to claim 1, characterized by the fact that the small particle control section (5) is provided with mist separators (12), each layer of the pre-wash section (4) and the absorption section ( 3) is provided with mist separators (12) as needed; and the mist separator (12) employs a form of a baffle plate, a ridge, packaging or mesh or a combined form thereof.
    [3]
    3. Method according to claim 1, characterized by the fact that a structure or mixing apparatus is provided at each ammonia feed point and when anhydrous ammonia is directly added to the absorption circulation liquid (32) and the absorption liquid circulating washing, a mixer exclusively used for liquid ammonia is provided to obtain ammonia feed at multiple points and sufficient reaction and to prevent ammonia escape and aerosol formation; the absorption circulation liquid (32) of the absorption section (3) has a pH value greater than 4.6; the circulation wash liquid of the prewash section (33) has a pH value of less than 5.5 for a crystallization process inside the absorber (1) and a pH value of less than 6 for the crystallization process outside the absorber (1).
    Petition 870190038870, of 04/25/2019, p. 6/16
    3/7
    [4]
    4. Method according to claim 1, characterized by the fact that the gas-liquid dispersion enhancer (26) employs a form of any of a structured packaging, random packaging, a perforated plate, a bubble cap, a aeration head or a combined form thereof; the liquid level of the oxidation tank (8) is greater than 5 m, the oxidized air is excessive by 20% or more, and / or an actual residence time of the absorption circulating liquid (32) is greater than 20 minutes , and / or the oxidation ratio of the absorption circulation liquid (32) is greater than 90%, and / or the oxidation ratio of the circulation wash liquid of the prewash section (33) is greater than 92% .
    [5]
    5. Method according to claim 1, characterized in that the liquid-to-gas ratio of each layer of the absorption section (3) is not less than 0.2 L / m 3 and the spray coverage is not less than 110%; the liquid-to-gas ratio of each layer of the small particle control section (5) is not less than 0.1 L / m 3 and the spray coverage is not less than 100%.
    [6]
    Method according to claim 1, characterized in that the surface velocity of the gas in the absorber (1) is from 1 m / s to 5 m / s.
    [7]
    7. Method according to claim 6, characterized by the fact that an operating temperature of the pre-wash section (4) is from 35 ° C to 80 ° C; an operating temperature of the absorption section (3) is 30 ° C to 70 ° C, and / or an operating temperature of the small particle control section (5) is 30 ° C to 65 ° C.
    [8]
    8. Method according to claim 1, characterized by the fact that the total powder includes aerosol, and / or circulation washing liquid from the prewash section (33) is crystallized in the
    Petition 870190038870, of 04/25/2019, p. 7/16
    4/7 pre-wash (4).
    [9]
    9. Apparatus for a method for the effective removal of sulfur oxides and dust in gas using an ammonia process as defined in any one of claims 1 to 8, characterized by the fact that it uses segmented control and an ammonia feed process multipoint to fundamentally control ammonia leakage and aerosol formation in order to achieve an effective desulphurization and dust removal effect; the device consists of a gas cleaning and pollutant removal system (I), an oxidation system (II), an after-treatment system with ammonium sulfate (IV), an ammonia supply system (III) and an auxiliary system;
    the gas cleaning and pollutant removal system (I) uses segmented control and is, in principle, divided into a prewash section (4), an absorption section (3) and a small particle control section ( 5), and each prewash section (4), absorption section (3) and small particle control section (5) is provided with a plurality of spray layers (21), the prewash section ( 4) concentrates a washing liquid circulating the prewash section (33) while reducing the flue gas temperature and the absorption section (3) absorbs and removes sulfur dioxide from the flue gas, controlling ammonia leakage and aerosol formation in the respective sections;
    the gas cleaning and pollutant removal system (I) uses multipoint ammonia feed and allows sufficient reaction to prevent ammonia escape and aerosol formation; a desulfurizing agent containing ammonia is added to a plurality of points, wherein the plurality of points includes at least two of: an upper layer of an oxidation tank (8) in the oxidation system (II), an intermediate layer of the tank of oxidation (8) in the oxidation system (II) and a lower layer of the oxidation tank (8)
    Petition 870190038870, of 04/25/2019, p. 8/16
    5/7 in the oxidation system (II), the prewash section (4), spray absorption layers, a prewash recirculation pump inlet (2), a prewash recirculation pump outlet wash (2), an absorption recirculation pump inlet, an absorption recirculation pump outlet, a wash recirculation pump inlet, a wash recirculation pump outlet;
    the oxidation tank (8) in the oxidation system (II) is layered according to the requirement of segmented control, the pre-wash section replacement fluid (35) and an absorption circulation liquid (32) are removed from different positions of the oxidation tank (8) and 2 to 8 layers of liquid-gas dispersion enhancers (26) are provided in the oxidation tank (8) in order to ensure the absorption efficiency and control the exhaust ammonia and aerosol formation.
    [10]
    10. Apparatus according to claim 9, characterized by the fact that the small particle control section (5) is provided with mist separators (12), each layer of the pre-wash section (4) and the absorption section ( 3) is provided with mist separators (12) as needed; and the mist separator (12) employs a form of a baffle plate, a ridge, packaging or mesh or a combined form thereof.
    [11]
    11. Apparatus according to claim 9, characterized by the fact that a structure or mixing apparatus is provided at each ammonia feed point and, when anhydrous ammonia is directly added to the absorption circulation liquid (32) and the liquid for circulation washing, a mixer used exclusively for anhydrous ammonia is provided to obtain multipoint ammonia feed, sufficient reaction and prevention of ammonia leakage and aerosol formation; the absorption circulation liquid (32) from the section
    Petition 870190038870, of 04/25/2019, p. 9/16
    6/7 absorption (3) has a pH value greater than 4.6; the circulation wash liquid of the prewash section (33) has a pH value of less than 5.5 for the crystallization process inside the absorber (1), and a pH of less than 6 for the process of crystallization crystallization out of the absorber (1).
    [12]
    Apparatus according to claim 9, characterized in that the gas-liquid dispersion enhancers (26) employ a form of any structured packaging, random packaging, perforated plate, bubble cap, aeration head, and the like, or a combined form thereof; the liquid level of the oxidation tank (8) is greater than 5 m, the oxidizing air is excessive by 20% or more, and / or the actual residence time of the absorption circulating liquid (32) is greater than 20 minutes and / or the oxidation ratio of the absorption circulation liquid (32) is greater than 90%, and / or the oxidation ratio of the circulation wash liquid of the prewash section (33) is greater than 92%.
    [13]
    13. Apparatus according to claim 9, characterized by the fact that the liquid to gas ratio of each layer of the absorption section (3) is not less than 0.2 L / m 3 and the spray coverage is not less than 110%; the net to gas ratio of each layer of the small particle control section (5) is not less than 0.1 L / m 3 , and the spray coverage is not less than 100%.
    [14]
    Apparatus according to claim 9, characterized in that the surface gas velocity of the absorber (1) is from 1 m / s to 5 m / s.
    [15]
    Apparatus according to claim 14, characterized by the fact that a temperature of an operating temperature of the prewash section (4) is 35 ° C to 80 ° C and / or an operating temperature of the absorption section ( 3) is 30 ° C to 70 ° C, and / or an operating temperature of the small particle control section
    Petition 870190038870, of 04/25/2019, p. 10/16
    7/7 (5) is from 30 ° C to 65 ° C.
    Petition 870190038870, of 04/25/2019, p. 11/16
    1/2
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    法律状态:
    2017-10-03| B03B| Publication of an application: publication anticipated [chapter 3.2 patent gazette]|
    2018-04-24| B27A| Filing of a green patent (patente verde) [chapter 27.1 patent gazette]|
    2018-05-15| B27B| Request for a green patent granted [chapter 27.2 patent gazette]|
    2018-09-04| B25A| Requested transfer of rights approved|Owner name: JIANGNAN ENVIRONMENTAL PROTECTION GROUP INC. (KY) |
    2018-12-04| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-03-26| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-07-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-09-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/06/2017, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/06/2017, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201710154157.3A|CN108144428A|2017-03-15|2017-03-15|A kind of method and device of ammonia process efficient removal gas sulphur oxide and dirt|
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