method for controlling aerosol production during absorption in ammonia desulfurization

专利摘要:
The present invention relates to apparatus and methods for controlling aerosol production during ammonia desulphurization absorption by removing sulfur dioxide in the exhaust gas with an ammonium sulfite-containing absorption circulating liquid. control aerosol production during absorption in ammonia desulphurization. Efficient desulphurization and dust removal can be achieved by staging solution composition control and reaction condition control. At the same time, ammonia escape and aerosol production during absorption can be controlled. the exhaust gas may be subjected to preliminary temperature lowering and purification, and may be allowed to contact an absorption circulating liquid and a fine particle wash circulating fluid sequentially. Solution composition levels and reaction temperatures can be controlled.
公开号:BR102018009209A2
申请号:R102018009209-0
申请日:2018-05-07
公开日:2018-10-23
发明作者:Jing Luo；Tianqi XU；Jinyong Wang；Yongying LUO
申请人:Jiangnan Environmental Protection Group Inc.；
IPC主号:

专利说明:

(54) Title: METHOD TO CONTROL AEROSOL PRODUCTION DURING ABSORPTION IN DEMANDING AMMONIA (51) Int. Cl .: B01D 53/14; B01D 53/50; B01D 53/78; F23J 15/04 (30) Unionist Priority: 09/07/2017 CN 201710800599.0, 07/09/2017 CN 201710800599.016 / 03/2018 US 15 / 923,031 (73) Holder (s): JIANGNAN ENVIRONMENTAL PROTECTION GROUP INC.
(72) Inventor (s): JING LUO; TIANQI XU; JINYONG WANG; YONGYING LUO (85) National Phase Start Date:
05/07/2018 (57) Abstract: The present invention relates to apparatus and methods to control the production of aerosol during absorption in ammonia desulfurization, removing sulfur dioxide in the exhaust gas with a circulating liquid of absorption containing ammonium sulfite, in order to control aerosol production during absorption in ammonia desulfurization. Efficient desulfurization and dust removal can be achieved by controlling the solution composition in stages and controlling the reaction condition. At the same time, ammonia leakage and aerosol production during absorption can be controlled. The discharge gas can be subjected to a preliminary temperature decrease and purification, and it can be allowed to contact a liquid of absorption circulation and a liquid of washing of fine particles sequentially. The levels of solution compositions and reaction temperatures can be controlled.
1/78
METHOD TO CONTROL AEROSOL PRODUCTION DURING ABSORPTION OF SULFUR DIOXIDE FROM A DISCHARGE GAS, AND APPARATUS TO CONTROL AEROSOL PRODUCTION IN DEMANDING AMMONIA.
[001] This application claims priority under 35 U.S.C. § 119 of Chinese Patent Application Number 201710800599.0, filed on September 7, 2017, which is hereby incorporated in its entirety.
FIELD OF TECHNIQUE [002] This description refers to the field of environmental technology, and specifically to a method to control aerosol production during absorption in ammonia desulfurization. BACKGROUND [003] Several countries in the world discharge sulfur dioxide to varying degrees. Emissions of sulfur dioxide are huge in China, have a huge impact on the environment and society, and the total sulfur dioxide emission in 2014 was 19.74 million tons, and in 2015, 18.591 million tons, classifying first in the world, resulting in huge economic loss and a serious impact on the ecological environment and people's health in China.
[004] Currently, there are hundreds of relatively mature desulfurization technologies, in which the wet desulfurization process is the most widely used, accounting for approximately 85% of the total installed desulfurization capacity in the world. Common wet exhaust gas desulfurization technologies are limestone-plaster, double alkali, sodium carbonate, ammonia, magnesium oxide, and the like. Ammonia desulfurization is a wet desulfurization process that uses ammonia as an absorbent, and this method can produce an ammonium sulfate fertilizer that uses SO2, and is a type of treatment scheme Petition 870180138231, of 10/05/2018, . 5/16
2/78 green discharge gas with low energy consumption, high added value and recycling of resources. There is a large amount of ammonia waste water generated during production in the chemical industry, and therefore using ammonia desulfurization for boiler exhaust gas in the chemical industry has its unique advantages.
[005] The ammonia desulfurization process mainly includes three procedures, absorption, oxidation and crystallization concentration:
[006] Absorb sulfur dioxide with ammonium sulfite to obtain a mixed solution of ammonium sulfite and ammonium bisulfite, to which ammonia is added to obtain ammonium sulfite:
NH ₄ 2SO3 + H2O + SO2 = 2NH ₄ HSO3 NH _4X H2-xSO ₃ + 2-xN H ₃ = NH ₄₂ SO ₃ [007] Supply oxidation air to the solution to oxidize ammonium sulfite to provide ammonium sulfate:
NH ₄₂ SO ₃ + 1 / 2O2 = NH ₄₂ SO ₄ ; and [008] Submit the ammonium sulfate solution to concentration, crystallization, solid-liquid separation and drying, thereby obtaining the final ammonium sulfate product.
[009] The three procedures, absorption, oxidation and concentration, seem simple. In fact, they influence each other. Conventionally, in order to ensure absorption efficiency, the contents of ammonium sulfite and free ammonia have been maintained at a high level, and the content of ammonium sulphate has been kept at a low level in the absorption liquid, which is conductive to absorption, but not conductive to oxidation and concentration, and the pH of the absorption liquid was maintained at approximately 7, thereby leading to a serious escape of ammonia and aerosols during absorption.
[0010] In order to ensure the absorption efficiency, convincePetition 870180037264, of 07/05/2018, p. 10/187
3/78 finally, the temperature absorption was controlled to not be higher than 4013 by cooling with process water, adjusting a heater, decreasing the temperature with a diluted ammonium sulfate solution, and other measures that are conductive for absorption , but not conductive for oxidation and concentration. At a low temperature, ammonium sulfite in a high concentration cannot be completely directly oxidized to ammonium sulfate quickly, but the same in a lower concentration can be subjected to oxidation and evaporation and concentration processes to obtain a product, with a large amount of evaporation, large energy consumption, a long flow process, a lot of equipment, a large footprint, a high cost of operation, and poor economic efficiency of the device. Furthermore, generally the water content of the boiler exhaust gas is maintained at not less than 7%. The water content of sulfur recovery exhaust gas, incineration exhaust gas and other industrial exhaust gas is still more than 25%. Therefore, if the absorption efficiency is deliberately exercised by reducing the absorption temperature to less than 4013, not only is the energy consumption high, but the water in the exhaust gas will also condense. Condensed water is excess, it is not conductive to wash the plunger and wash the tower wall, and it needs to be discharged in the form of waste water.
[0011] As for a dry method for sulfuric acid discharge gas, due to a low water content and a low concentration of sulfur dioxide, the absorption temperature can be controlled at 3013-5013.
[0012] The ammonia desulfurization processes for exhaust gas can involve the following technical problems:
1. Escape from ammonia and aerosols
Petition 870180037264, of 05/07/2018, p. 11/187
4/78 [0013] Unlike the limestone-plaster method based on limestone as the raw material, ammonia is easy to volatilize, when free ammonia is present in the absorption liquid, ammonia, SO2 and SO3 are simultaneously present in the phase of gas. Therefore, a mist of ammonium sulphite and ammonium sulphate is easily formed, and the water vapor saturated in the exhaust gas condenses over the mist using the mist with a core, thereby forming a dense white mist, which by on the one hand it causes ammonia loss, and on the other hand it causes secondary pollution.
[0014] So far ammonia desulfurization has failed to be effectively widespread, for which the main reason is that previous efforts have focused on capturing aerosols produced during absorption, and not suppressing or reducing aerosol production during absorption, resulting in a system investment, high operating cost and unstable operation.
2. Oxidation of ammonium sulfite [0015] The oxidation of ammonium sulfite is different from other sulfites, and NH4 + at a certain concentration has a damping effect on the oxidation process. Literature for example, Zhou, J., W. Li, and W. Xiao, Kinetics Of Heterogeneous Oxidation Of Concentrated Ammonium Sulfite, Chemical Engineering Science, Volume 55, Issue 23, December 2000, Pages 5637-5641, Pergamon Press, Oxford, England, 2000, which is hereby incorporated by reference in its entirety illustrates this unique property, that is, NhV significantly blocks the dissolution of O2 in aqueous solutions. When the salt concentration is less than 0.5 mol / L, approximately 5% by weight, the oxidation rate of ammonium sulfite increases with increasing concentration; and when this limit is exceeded, the oxidation rate decreases with increasing concentration. In addition, when the concentration of the total ammonium salt is 3-4 mol / L,
Petition 870180037264, of 05/07/2018, p. 12/187
5/78 and the concentration of ammonium sulfite is less than 0.15 mol / l, the solution of the oxidation reaction is a fast reaction of the ^nth order, that is, the oxidation rate is irrelevant to the sulfite content of ammonium.
[0016] The oxidation reaction of ammonium sulphite actually also occurs during absorption, but due to a low O2 content in the exhaust gas, a low temperature and a slow reaction speed, the oxidation rate is generally 40% -70% under continuous cycling conditions. However, additionally improving the oxidation rate to no less than 95% to meet the post-treatment processing requirements is still necessary, so that an oxidation tank / oxidation section / oxidizing jet was used to fully oxidize the ammonium sulfite in an oxidation air condition in excess and pressurized, and some manufacturers have chosen to add a catalyst to the absorption liquid to promote oxidation, but this will affect product quality.
3. Recovery of exhaust gas that entrains ammonia [0017] Unlike other alkaline substances, ammonia is easily volatile. In traditional countercurrent contact type absorption towers, or spray towers, packaged towers or plate towers, in order to ensure the desulphurisation efficiency and the final emission index, the pH value of a solution is the highest, the concentration of SO2 in the gas phase is the lowest and the concentration of ammonia in the gas phase will be the highest at a contact point at the top of the absorption zone. This means that the amount of ammonia that spills with the exhaust gas outside the desulfurization tower will be large. This will cause ammonia waste and loss, but it also causes new pollution.
[0018] As for aerosol and ammonia leakage problems, well-known research institutions and engineering companies
Petition 870180037264, of 05/07/2018, p. 13/187
6/78 proposed a variety of schemes to control or eliminate, such as wet electricity, multistage water washing, multistage de-combining; however, these methods address the problem not of sources that produce aerosols, and ammonia leakage during absorption, only focusing on how to eliminate ammonia leakage and aerosols produced during absorption, making the number of tower sections more and more the most complex system, which not only has poor treatment effects, but also has a substantial increase in investment and operating costs.
[0019] The absorption, oxidation and concentration of the ammonia desulfurization device interact with each other, absorption requires a high pH value of the solution and a high content of ammonium sulfite, oxidation requires a concentration of total ammonium salt relatively low and low ammonium sulfite content, and the concentration requires a high ammonium sulfate content. Controlling the escape of ammonia and aerosols requires a low pH value and a solution that does not contain free ammonia.
[0020] As the requirements of the solution compositions for different processes are different, more reasonable technologies to control aerosol production are highly required to achieve synergistic control of absorption, oxidation and concentration, meet emission requirements while reducing investment, simplify the technological process and reduce the difficulty of operation.
[0021] A Chinese patent for invention with an application number of CN 02136906.2 describes a method and device for removing and recovering SO2 in exhaust gas, in which the concentration of ammonium sulfite is controlled between 0.1% -5% by weight, for example, between 0.5% and 2.0%, to create favorable conditions for oxidation, reduce energy consumption and oxidation investment,
Petition 870180037264, of 05/07/2018, p. 14/187
7/78 and ensure high desulfurization efficiency. An ammonia ratio in the absorption liquid to sulfur is 1.3-1.8 molar ratio, the absorption gas to liquid ratio is 2000-5000 volume ratio. Hot exhaust gas heat is used to concentrate the ammonium sulfate solution, and when the temperature of the hot exhaust gas is reduced to 50Ό-55Ό, the ammonium sulfate concentration can be increased to 40% -50% by weight , which will be sent to an ammonium sulphate crystallizer and processed into a commercial ammonium sulphate fertilizer. The oxidation section is provided with a longitudinal partition, so that the unoxidized ammonium sulfite solution and oxidized ammonium sulfite solution are separated as far apart as possible, in order to prevent the occurrence of countermixing. In this method: 1 the concentration of the absorption liquid is low, and the method is only suitable for discharge gas that contains low sulfur; 2 the method is not concerned with ammonia leakage control and aerosol production during absorption, it is necessary to provide a reheater to eliminate white smoke; 3 crystallization is influenced by the volume of air that dries and the content of dust, and the amount of crystallization is small and not stable, and the like.
[0022] A Chinese patent for invention with an application number of CN 201310634675.7 describes a desulfurization and denitrification system and a desulfurization and denitrification method with this, in which the absorption section includes a circulation liquid spray layer. level I, a level II circulation liquid spray layer, a fill absorption layer and a level III circulation liquid spray layer arranged from the bottom to the top sequentially, in which the level spray spray layer Level I circulation fluid is a fixed ammonia absorption layer for efficiently absorption 870180037264, 05/07/2018, p. 15/187
8/78 sorb SO2, the fixed ammonia absorption layer is a separate ammonia absorption circulation system, the level II circulation liquid spray layer and the fill absorption layer are used to prevent the escape of ammonia and to absorb SO2, and the level III circulation liquid spray layer is used to prevent ammonia from escaping. However, the solution compositions are not specified, and the effect of controlling ammonia and aerosol leakage is limited by adding layered ammonia.
[0023] A Chinese patent for invention with an application number of CN 201510009642.2 describes a method for achieving integrated desulphurization and dust removal with ultrasonic waves to achieve ultra-low emissions, in which the exhaust gas which has been subjected to temperature reduction and desulfurization is completely washed providing a droplet washing system for the absorption liquid, the droplet in the absorption liquid in the discharge gas is captured and removed, followed by de-embedding; after de-stemming, the discharge gas is washed out by the droplet of the absorption liquid, followed by de-stemming; the aforementioned preliminarily purified exhaust gas is subject to agglutination and / or coagulation so that the particle size of fine particles is increased, and the increased fine particles are removed by agglutination and / or a layer de-stemmer; and the use of multistage water washing and multistage de-spraying ensures total dust is qualified with great investment and high operating cost, which cannot control ammonia leakage and aerosol production from the aspect of the mechanism.
[0024] A Chinese patent for invention with an application number of CN 201510680578.0 describes a desulphurisation, denitrification and dusting system for double circulation of amôPetição 870180037264, from 07/05/2018, pg. 16/187
9/78 nia, which includes a wash absorption tower 1 and an oxidation circulation tank 9; the wash absorption tower 1 consists of an efficient water mist removal section 2, an improved ammonia mist removal section 3, an absorption liquid de-stemming section 4, a secondary absorption section 5, a primary absorption 6 and a temperature wash and decrease 7 sequentially; when the exhaust gas enters the primary absorption section 6, SO2 is primarily removed using an ammonium sulfate solution containing ammonium nitrate with a density of 1.1 to 1.15 kg / L and a pH value of 6 , 5 to 7 as an absorption liquid; and when the exhaust gas enters the secondary absorption section 5, SO2 is secondarily removed using an ammonium sulfate solution containing ammonium nitrate with a density of 1.05 to 1.1 kg / L and a pH value of 5.5 to 6 as an absorption liquid. The technological process is complex, with excess ammonia used during absorption, significant escape of aerosol and ammonia, and final emission targets that are difficult to guarantee by water washing and de-stemming.
[0025] A Chinese patent for invention with an order number of CN 201610390173.8 describes a desulfurization and dust removal device integrated with a single tower that has six gradient purification sections to achieve ultra low emissions, including: an oxidation section, a concentration section, an absorption section, a purified water wash section, a de-stemming section, a partition and a wet electrical section; in which the tiny droplets charged by the unburdened exhaust gas are additionally removed via the electrostatic absorption action on the wet electrical section, to ensure that the discharge gas discharge pattern is met when working conditions for the exhaust gas vary, and
Petition 870180037264, of 05/07/2018, p. 17/187
10/78 the section is used as a means of guarantee for this device. The process requires a large investment, has a high operating cost, and is an inefficient electrical method of controlling ammonia leakage and aerosol emissions.
[0026] A Chinese patent for invention with an application number of CN 201610177178.2 describes a desulfurization and dust removal process to achieve ultra-low emissions, a device therein includes a desulfurization tower 1; an exhaust gas inlet 2 and an exhaust gas outlet 9 are provided on the desulphurization tower 1; a temperature wash-down section 3, a primary absorption section 4, a secondary absorption section 5, a primary de-stemming section 6, a secondary de-stemming section 7, and a tertiary de-stemming section 8 are arranged in series on the direction of flow of exhaust gas between the inlet gas 2 and the outlet gas 9; the exhaust gas containing SO2 of fuel coal at 120Ό-180Ό is subject to de-nitrification and dust removal, then enters the wash and temperature decrease section 3 of the exhaust gas inlet 2, and is sprayed with a solution of ammonium sulfate with a density of 1200-1250 g / L and a pH value of 3-5, in order to reduce the temperature of the exhaust gas to be 45Ό-60Ό; the discharge gas flows into the primary absorption section 4, and is sprayed with an absorption liquid with a density of 1100-1250 g / L and a pH value of 5.5-6.5; and when the discharge gas enters the secondary absorption section 5, it is sprayed with an absorption liquid with a pH value of 5.0-5.8 and a density of 1030-1100 g / L, and then the gas discharge enters the primary de-section 6, the secondary de-section 7 and the tertiary de-section 8 sequentially, and is discharged from the gas outlet
Petition 870180037264, of 05/07/2018, p. 18/187
11/78 discharge 9. The hot discharge gas is subjected to gradient elution controlling the density, pH and similar values of the absorption liquid, then subjected to the removal of mist droplets using a single de-aerator and other devices, and sulfur, smoke dust and the like in the exhaust gas can be effectively removed thereby achieving ultra low emissions. However, the process does not specify solution compositions and absorption temperatures, and it cannot yet control ammonia leakage and aerosol production from the source.
[0027] A Chinese patent for invention with an application number of CN 201611014433.8 describes a method to reduce aerosol production in ammonia desulfurization, of which the specific steps are: 1) direct the aqueous ammonia into an absorption tower ammonia, initiating a primary absorption and circulation pump for spray washing, in order to desulfurize the majority of SO2 in the exhaust gas; 2) direct the aqueous ammonia into the ammonia absorption tower for spray washing, where the spray liquid is additionally reacted with SO2 exhaust gas to remove pollutants in the exhaust gas; 3) passing the exhaust gas which has been subjected to secondary absorption through a water washing and spraying device to wash away impurities such as aerosols entrained in the exhaust gas; and 4) finally purifying the exhaust gas, which has been subjected to water washing, against impurities such as residual aerosol liquid foams entrained in the exhaust gas during washing and spraying, and discharging the discharge gas a liquid in the standard. In step 1, the pH value of the absorption solution is strictly controlled at 5.5-, 5, and the density is controlled at 1.15-1.25 g / ml. In step 2, the pH value of the absorption solution is strictly controlled at 5.0-6.0, and the density is controlled at 1.0-1.20 g / ml. The process
Petition 870180037264, of 05/07/2018, p. 19/187
12/78 does not specify solution compositions and absorption temperatures, and still cannot completely control ammonia leakage and aerosol production from the source. Also, the discharge gas which has been subjected to simple water washing and de-stemming cannot meet or cannot easily meet the requirements of ultra-low emission standards or higher requirements in China.
[0028] A Chinese patent for invention with an order number of CN201611207184.4 describes a process to save water and control the aerosol phenomenon in the ammonia desulfurization process, in which the boiler exhaust gas enters a desulfurization tower , the discharge gas containing SO2 which entered the desulphurization tower is sprayed with a spray liquid of ammonium sulphate / ammonium sulphite solution with a concentration of 5% -35%, followed by passing through a layer of filling, contacting the cooling water over the filler layer, and then contacting a water wash and spray layer, during which the cooling water at the bottom of the filler layer falls over a container of liquid accumulation of water wash and reversely flows to a cooling water tower, then enters a water wash tank, and is directed to a water wash and spray layer through a washing water infusion pump for recycling; the system has advantages such as a simple flow process, a good cooling effect and a low operating cost, the spray cooling water absorbs substances such as (NH4) 2SO4, SO2, and NH3 particles in the exhaust gas boiler, the water vapor saturated in the boiler exhaust gas condenses, using (NH4) 2SO4 particles as the nuclei to form water droplets, so that (NH4) 2SO4 particles in the boiler exhaust gas are captured , through
Petition 870180037264, of 05/07/2018, p. 20/187
13/78 this by inhibiting aerosol formation, and making the concentration of particles in the boiler exhaust gas discharged in the ammonia desulfurization process less than 30 mg / m ³ . The process does not specify the solution compositions, pH values and absorption temperatures, it still cannot completely control ammonia leakage and aerosol production from the source, moreover, the low temperature wash energy consumption is high, and the concentration of particles in the purified exhaust gas is less than 30 mg / m ³ , which cannot meet the latest emission standards.
[0029] A Chinese patent for invention with an application number of CN 201310340885.5 describes a method for controlling the emission of aerosol in ammonia desulfurization and a dedicated absorption tower for this, in which the exhaust gas which has been subjected to spraying with atomized water and decreased temperature and has been cooled to 100Ό to 120Ό is allowed to flow into a desulfurization zone of a desulfurization absorption tower, the discharge gas in the desulfurization zone from the bottom to the top is allowed to contact with a liquid countercurrent desulfurization ejected from top to bottom to absorb SO2 in the exhaust gas, and fillers or sieve plates are provided within the desulfurization zone; the discharge gas after being desulfurized enters a filling wash zone, in which the washing water is injected to remove the crude grain aerosols produced by ammonia desulfurization; the discharge gas after being subjected to desulfurization and removal of raw grain aerosol enters a water-vapor phase transition zone, steam is injected in the middle of the water-steam phase transition zone in order to establish an environment of supersaturated water vapor required for the water-steam transition, so that the fine-grained aerosol particles that are not removed condense and grow and are removed by a develPetition 870180037264, from 07/05/2018, p. 21/187
14/78 wire strainer at the exhaust gas outlet of the water-vapor phase transition zone; and the purified exhaust gas is discharged through a flue from the exhaust gas outlet at the top of the desulfurization absorption tower. The surface gas velocity of the discharge gas is 2.0-3.0 m / s and an operating liquid to air ratio is 2 to 8 L / Nm ³ ; and the desulfurization liquid has a pH value of 5.2-6.0 and a temperature of 4513-5513; The desulphurizing agent in the desulphurisation liquid is ammonium sulphate or ammonium sulphite in a concentration of 10% by weight for supersaturated, the ratio of washing water spray liquid in the filling wash zone is 0.6-3, 0 L / Nm ³ , the temperature of the exhaust gas after being washed through the filling layer is reduced to 5013-5513, and in a modality and, at the outputs of the absorption tower, the minimum mass concentration of PM10 is 45mg / m ³ and the minimum SO2 concentration is 135 mg / Nm ³ . The process still cannot completely control ammonia leakage and aerosol production from the source, moreover, the particles and SO2 in the purified exhaust gas cannot meet the latest emission standards, and the phase transition energy consumption steam is high. [0030] A Chinese patent for invention with an application number of CN 201610966033.0 describes a device and method for removing aerosols in ammonia desulfurization, the device including a desulfurization tower 1, wherein the interior of the desulfurization tower 1 is provided with an absorption reaction zone 2, an oxidation water wash zone 3 and a water wash and purification zone 4 from bottom to top sequentially; an oxidation and spray water wash layer 22 is provided within the oxidation water wash zone 3, and the concentration of ammonium sulphate dissolved in a water oxidation water wash liquid is controlled by <3% ; the temPetição 870180037264, of 05/07/2018, p. 22/187
15/78 water wash and purification time <50Ό; and the strong oxidizer includes hydrogen peroxide or hypochlorite. The process does not specify the solution compositions, pH values and absorption temperatures, and still cannot completely control ammonia leakage and aerosol production from the source, moreover, the investment in washing oxidation water is large, the operating cost is high, and there is a certain security risk.
BRIEF DESCRIPTION OF THE DRAWINGS [0031] The objects and advantages of the invention will become apparent when considering the following detailed description taken in conjunction with the accompanying drawings, in which equal reference characters refer to equal parts throughout, and in which:
[0032] Figure 1 is a schematic view of apparatus and methods in accordance with the principles of the invention.
[0033] Figure 2 is a schematic view of Example 1.
[0034] Figure 3 is a schematic view of Example 2.
Reference numbers:
absorption tower oxidation container fine particle wash circulation pre-wash zone absorption zone fine particle control zone absorption circulation liquid purified exhaust gas outlet discharge gas inlet prewash spray layer absorption spray gun fine particle spray layer a
Petition 870180037264, of 05/07/2018, p. 23/187
16/78 fine particle spray layer b fine particle wash liquid de-flower absorption circulation tank gas-liquid separator a gas-liquid separator b gas-liquid dispersion enhancer ammonia oxidation air process water ammonium sulphate post-processing system DETAILED DESCRIPTION
DEFINITIONS [0035] Escape from ammonia means ammonia or one or more species containing ammonia / amine that escape with the discharge of the gas flow. The species are derived from ammonia or species that contain ammonia / amine that have been added to the gas stream.
[0036] Dust means a particulate material fine enough to float along gaseous flows, when manipulated, processed, or contacted. This includes, but is not limited to, aerosols, which include solid aerosol particles and liquid aerosol particles, soot, charcoal, unburned coal, fine minerals, sand, gravel, salts, and any combination thereof.
[0037] Discharge means a gas flow that leaves an industrial or chemical process. This includes, but is not limited to, exhaust gas, waste gas, exhaust gases from furnaces, furnaces, boilers, and / or generators. This may comprise combustion products derived from the combustion of air and flammable material, residual material from chemical processes, which may include water, nitrogen, and pollutants, such as particulate matter, soot, carbon monoxide, Petition 870180037264, 07/05/2018 , p. 24/187
17/78 no, nitrogen oxides, and sulfur oxides. The discharge from one process can be a gaseous input to another.
[0038] Oxidation Rate means the percentage, calculated per mole percent, of a given material that has been converted to a more oxidized species identified in the material. For example, in a mixture containing species containing ammonia and sulfur oxides, if X mol% of the mixture is out of ammonium sulfate, Y mol% is ammonium sulfite, and Z mol% is some other species containing ammonia , sulfur, and / or oxygen with a greater oxidation potential than ammonium sulphate, because ammonium sulphate is the most oxidized species identified, the oxidation rate of the mixture would be X mol%.
[0039] Ammonia Recovery Rate means that fraction or percentage of ammonia added to a gas cleaning process that is subsequently captured and extracted from the process.
[0040] Spray Cover is a spray divergence from a nozzle or a network of nozzles. The greater the divergence, the greater the spray coverage.
[0041] In the event that the above definitions or a description stated elsewhere in this application is inconsistent with a meaning (explicit or implicit) that is commonly used, presented in a dictionary, or stated in a source incorporated by reference in this application, the claim and the claim terms are specifically understood to be considered in accordance with the definition or description in this application, and not in accordance with the common definition, dictionary definition, or the definition that has been incorporated by reference. In the event that a claim term can only be understood if it is considered by a dictionary, a definition presented in the Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition, 2005, (John Wiley & Sons, Inc.) should control, whether there provided.
Petition 870180037264, of 05/07/2018, p. 25/187
18/78 [0042] All ranges and parameters described herein are understood to encompass any and all sub-ranges included here, and each number between the end points. For example, a range declared from 1 to 10 should be considered to include any and all sub-ranges between (and inclusive) the minimum value of 1 and the maximum value of 10; that is, all sub-bands that start with a minimum value of 1 or more (for example, 1 to 6.1), and end with a maximum value of 10 or less (for example, 2.3 to 9.4, 3 to 8, 4 to 7), and finally each number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within the range. All percentages, ratios and proportions here are by weight unless otherwise specified. Unless otherwise stated, the term molecular weight means average molecular weight (mw).
[0043] Apparatus and methods for controlling aerosol production in ammonia desulfurization are provided. The apparatus may include, and the methods may involve, a gas purification and removal system. The gas purification and removal system can be configured to apply an ammonium salt gradient to the exhaust gas. The apparatus may include, and the methods may involve, an oxidation system. The apparatus may include, and the methods may involve, an auxiliary system.
[0044] The oxidation system may include an oxidation vessel that is configured to force oxidation of an input ammonium solution to generate a plurality of outputs of varying degrees of oxidation of the ammonium solution. The oxidation vessel can provide the outlets for the gas purification and removal system to define the gradient.
[0045] The auxiliary system may include an ammonium sulphate post-processing system. The auxiliary system can include an ammonia supply system. The auxiliary system can include a process water system.
Petition 870180037264, of 05/07/2018, p. 26/187
19/78 [0046] The device may include a tower. The tower can house the gas purification and removal system. The tower can include a prewash zone. The tower may include an absorption zone. The tower can include a fine particle control zone.
[0047] The apparatus may include a component arranged between the absorption zone and the pre-wash zone. The component can allow only the gas to pass. The apparatus can include a plurality of spray layers. The prewash zone can include a spray layer of a plurality. The absorption zone can include a spray layer of a plurality. The fine particle control zone can include a spray layer of a plurality. The tower can be configured to provide divisive control of solution compositions for the spray layers. Partition control can include providing different compositions for different spray layers. The different compositions can be selected or adjusted to select or adjust the gradient.
[0048] The oxidation system may include the spray layers. The oxidation system can be configured to control an interaction between (a) the sprayed liquid in one of the different spray layers and (b) the discharge gas in the respective different spray layers to naturally oxidize the liquid to generate a plurality of outputs of different degrees of oxidation of the ammonium solution to define the gradient.
[0049] The oxidation system can be configured to control an operating temperature of one or more of the pre-wash zone, the absorption zone, and the fine particle control zone to control the gradient.
[0050] The oxidation system can be an oxidation system that does not include a forced oxidation container.
Petition 870180037264, of 05/07/2018, p. 27/187
20/78 [0051] The oxidation system can be configured to prorate the pre-wash liquid into the absorption zone.
[0052] Each zone can include a single spray layer. Each zone can include a plurality of spray layers. [0053] The apparatus may include a component arranged between the absorption zone and the fine particle control zone. The component can allow only the gas to pass.
[0054] The device may include a component disposed within the absorption zone. The component can allow only the gas to pass.
[0055] The apparatus may include a component disposed within the fine particle control zone. The component can allow only the gas to pass.
[0056] The device can include a plurality of layers of devices. A plunger layer of the plurality can be arranged within the fine particle control zone. The plunger layer of the plurality can be arranged in each spray layer of the prewash zone and the absorption zone. [0057] A plunger from the plurality of plunger layers may include a deflector.
[0058] A plunger from the plurality of plunger layers may include a crest.
[0059] A plunger from the plurality of plunger layers may include a filler.
[0060] A plunger from the plurality of plunger layers may include a wire sieve.
[0061] A plunger of the plurality of plunger layers may include a combination of one or more of a deflector; a crest; filling; and wire sieve.
[0062] Each spray layer in the absorption zone can
Petition 870180037264, of 05/07/2018, p. 28/187
21/78 have a liquid-to-gas ratio that is not less than 0.2 L / Nm ³ . Each spray layer in the absorption zone can have a spray coverage that is not less than 110%.
[0063] Each spray layer in the fine particle control zone can have a liquid-to-gas ratio that is not less than 0.1 L / Nm ³ . Each spray layer in the fine particle control zone can have a spray coverage that is not less than 105%.
[0064] Each spray layer in the absorption zone can have a liquid to gas ratio that is not less than 0.2 L / Nm ³ ; and a spray coverage that is not less than 110%; and, each spray layer of the fine particle control zone can have a liquid-to-gas ratio that is not less than 0.1 L / Nm ³ ; and a spray coverage that is not less than 105%.
[0065] The oxidation system can include a plurality of sections. Each section can correspond to an ammonium salt of a different composition. The oxidation system can be configured to provide for a fine particulate washing circulation liquid and an absorption circulation liquid a composition of the plurality of compositions to form the ammonium salt gradient.
[0066] A section can be defined by a layer of the oxidation system.
[0067] A section can be defined by a component of the oxidation system.
[0068] A section can occupy a different position in the oxidation system.
[0069] The oxidation system may include 0, 1,2, 3, 4, 5 or more layers of gas-liquid dispersion enhancers.
[0070] The oxidation system may include a liquid stage. O
Petition 870180037264, of 05/07/2018, p. 29/187
22/78 liquid stage can have a height that is greater than 3 m. The oxidation system can be configured to provide no less than 20% excess oxidation air.
[0071] The tower can be configured to cool and flush the exhaust gas using the circulating washing liquid in the pre-wash zone, while simultaneously increasing a concentration of the circulating washing liquid. The tower can be configured to pass the discharge gas through the absorption zone, in which the discharge gas is washed and desulfurized by the absorption circulation liquid. The tower can be configured to pass the discharge gas through the fine particle control zone, in which the fine particles are removed by a fine particulate circulation washing liquid. The tower may be configured to discharge the exhaust gas. The tower can be configured to replenish the circulating washing liquid in the pre-washing zone of the fine particulate circulation washing liquid. The tower can be configured to rinse impurities on the tower wall. The tower can be configured to refill the absorption circulation liquid. The tower can be configured to oxidize the absorption circulation liquid in the oxidation system. The tower can be configured to extract circulating liquids with different compositions from an oxidation system in different sections for distribution to different zones.
[0072] The fine particles circulation washing liquid can be a major constituent of circulation washing liquid replenishment fluids.
[0073] The tower can be configured to rinse the impurities by spraying the fine particles circulation washing liquid. The impurity can be a chemical impurity. Impurity can be a physical impurity. The impurity may be inside the tower. The impurity
Petition 870180037264, of 05/07/2018, p. 30/187
23/78 can be on structures inside the tower.
[0074] The tower can be configured to rinse impurities by spraying process water.
[0075] The tower can be configured to replenish the absorption circulation liquid with the liquid from the fine particle control zone.
[0076] The tower can be configured to replenish the absorption circulation liquid with the process water. The tower can be configured to replenish process water with liquid from the fine particle control zone.
[0077] The tower can be configured to provide a surface discharge gas speed in the range of 1-5 m / s.
[0078] The tower can be configured to provide a temperature in the pre-wash zone in the range of 40Ό to 80G.
[0079] The tower can be configured to receive a discharge gas that has an SO2 concentration as high as 30,000 mg / Nm ³ .
[0080] The tower may be configured to discharge purified exhaust gas that complies with: all GB13223-2011 emission requirements, Emission Standard Of Air Pollutantes For Thermal Power Plants, Ministry of Environmental Protection of The People's Republic of China , 2011, which is hereby incorporated by reference in its entirety. For example, GB132232011 requires that in key areas of China, dust, sulfur dioxide and nitrogen oxide emissions from coal-fired boilers should not be higher than 20, 50 and 100 mg / Nm ³ (6% oxygen content , dry basis), respectively. And, under Environment and Development No. 164 (Full Implementation Of The Work Plan For Ultra-Low Emission And Energy Conservation Of Coal-Fired Power Plants, Ministry Of Environmental Protection, Development and Reform
Petition 870180037264, of 05/07/2018, p. 31/187
24/78 commission, Energy Bureau of The People's Republic of China, Released on December 11, 2015, which is hereby incorporated by reference in its entirety), in China, by 2020, coal-fired power plants must achieve ultra-low emissions (namely under the condition of emission concentration of 6% content of oxygen, dust, sulfur dioxide, nitrogen oxide should not be more than 10, 35, 50 mg / m ³ ). Also, in relation to the ammonia-based desulfurization and electrostatic degreasing presented in PCT / US2002 / 039095, which involves a method to remove SO2 / NO / NO2 from the gas flow as follows:
A. Oxidize some or all of the gas flow to NO2; So,
B. Wash some or all of SO2, NO and NO2 in the gas stream with washing liquid that contains ammonia, and has a pH between 6 and 8,
C. Use an aerosol removal device to remove some or all of the ammonia aerosol generated in the washing step; and
D. Removing ammonium sulfate from the washing liquid as a fertilizer, the tower can cost 10-20% less to build; an operating cost that is 5-10% less; and a performance ratio that is 15-30% lower.
[0081] The tower can be configured to discharge the exhaust gas that has an SO2 concentration not greater than 200 mg / Nm ³ . The tower can be configured to discharge the exhaust gas that has an SO2 concentration not greater than 100 mg / Nm ³ . The tower can be configured to discharge the exhaust gas that has an SO2 concentration not greater than 35 mg / Nm ³ . The tower may be configured to discharge the exhaust gas that has an SO2 concentration not greater than 5 mg / Nm ³ .
Petition 870180037264, of 05/07/2018, p. 32/187
25/78 [0082] The tower can be configured to discharge the exhaust gas that has a total dust concentration, including aerosols, not greater than 20 mg / Nm ³ . The tower can be configured to discharge the exhaust gas that has a total dust concentration, including aerosols, not greater than 10mg / Nm ³ . The tower may be configured to discharge the exhaust gas that has a total dust concentration, including aerosols, not greater than 5mg / Nm ³ . The tower can be configured to discharge the exhaust gas that has a total dust concentration, including aerosols not greater than 2mg / Nm ³ .
[0083] The tower can be configured to discharge the exhaust gas that has an ammonia concentration not greater than 5 mg / Nm ³ . The tower may be configured to discharge the exhaust gas that has an ammonia concentration not greater than 2 mg / Nm ³ .
[0084] The tower can be configured to discharge the exhaust gas that has an ammonia concentration not greater than 1 mg / Nm ³ .
[0085] The tower can be configured to discharge the exhaust gas that has an ammonia concentration not greater than 0.5 mg / Nm ³ .
[0086] The apparatus may include a drying device. The drying device may be configured to receive an absorption liquid. The drying device can be configured to produce a solid product that includes an ion from a circulating liquid. The ion can include chloride. The ion can include fluoride.
[0087] The drying device can be configured to reduce the circulating liquid chloride ion concentration to less than 50,000 mg / L. The drying device can be configured to reduce the concentration of liquid fluoride ions from
Petition 870180037264, of 05/07/2018, p. 33/187
26/78 circulation to less than 20,000 mg / L. The drying device can be configured to reduce the circulating fluoride ion concentration to 300-3000 mg / L. The drying device can be configured to reduce the circulating liquid chloride ion concentration to 10,000-31,000 mg / L.
[0088] The tower can be configured to spray, in a spraying layer in the absorption zone, the absorption circulation liquid that has a mass fraction ratio of ammonium sulfate to ammonium sulfite that is in the range of 1, 5-199 to 1. [0089] The tower can be configured to spray, in a spray layer in the fine particle absorption zone, the fine particulate circulation washing liquid that has a mass fraction ratio of sulfate ammonium to ammonium sulfite that is in the range of 3-1.999 to 1.
[0090] Methods may include applying an ammonium salt gradient to the exhaust gas. Methods may include applying a reaction condition gradient to the exhaust gas.
[0091] The application of an ammonium salt gradient may include applying a first concentration of ammonium salt in a first stage. The application of an ammonium salt gradient may include applying a second concentration of ammonium salt in a second stage. The first stage may be upstream, in relation to the exhaust gas, from the second stage.
[0092] The salt may include ammonium sulfite. The salt may include ammonium bisulfite. The salt may include ammonium sulfate.
[0093] The first concentration may be greater than the second concentration.
[0094] The application of a first concentration of ammonium salt in a first stage may include spraying on the discharge gas absorption circulation liquid in an absorption process 870180037264, from 05/07/2018, pg. 34/187
27/78 sulfur dioxide sorption.
[0095] The application of a second concentration of ammonium salt in a second stage may include spraying on the discharge liquid absorption circulation liquid in the sulfur dioxide absorption process.
[0096] The application of a first concentration of ammonium salt in a first stage may include spraying a fine particulate washing liquid over the discharge gas in a fine particle washing process.
[0097] The application of a second concentration of ammonium salt in a second stage may include spraying a fine particulate washing liquid over the discharge gas in the fine particle washing process.
[0098] The application of a reaction condition gradient can include providing a first temperature in a first stage. The application of a reaction condition gradient can include providing a second temperature in a second stage. The first stage may be upstream, in relation to the exhaust gas, from the second stage.
[0099] The first temperature can be higher than the second temperature.
[00100] The provision of a first temperature in a first stage may include adjusting a first temperature in a sulfur dioxide absorption process. The provision of a second temperature in a second stage may include adjusting a second temperature in a fine particle washing process.
[00101] The application of a reaction condition gradient can include providing a first pH in a first stage. The application of a reaction condition gradient can include providing a second pH in a second stage. The first stage may be upstream,
Petition 870180037264, of 05/07/2018, p. 35/187
28/78 in relation to the exhaust gas, of the second stage.
[00102] The first pH can be higher than the second pH.
[00103] The provision of a first pH in a first stage may include spraying on the exhaust gas absorption circulation liquid in a sulfur dioxide absorption process.
[00104] The provision of a second pH in a second stage may include spraying on the discharge gas absorption circulation liquid in the sulfur dioxide absorption process.
[00105] The provision of a first pH in a first stage may include spraying a fine particle washing liquid over the discharge gas in a fine particle washing process.
[00106] The provision of a second pH in a second stage may include spraying a fine particle washing liquid over the discharge gas in the fine particle washing process.
[00107] The method may include cooling and purifying the exhaust gas. The method may include, after cooling and purification, absorbing sulfur dioxide. The method may include, after absorption, removing the exhaust gas with a fine particulate washing liquid. The application of an ammonium salt gradient can be performed after purification and cooling. Both absorption and removal may include spraying ammonium sulfite. Both absorption and removal may include spraying ammonium sulfate.
[00108] Absorption may include spraying over the discharge gas absorption circulation liquid. The fine particulate wash circulation liquid may have a pH that is lower than a discharge gas absorption circulation liquid pH. The fine particulate wash liquid can have a lower ammonium sulfite concentration than a
Petition 870180037264, of 05/07/2018, p. 36/187
29/78 ammonium from the absorption circulation liquid.
[00109] The reaction condition can be a temperature gradient. The temperature gradient can be defined by an absorption temperature and a wash temperature. Applying a reaction condition gradient can include controlling the absorption temperature and the wash temperature to reduce energy consumption. Applying a reaction condition gradient can include maintaining an absorption efficiency. Applying a reaction condition gradient may include maintaining a limit on ammonia leakage. The application of a reaction condition gradient may include maintaining a limit on aerosol leakage.
[00110] The absorption temperature can be in the range of 30Ό to 70Ό.
[00111] The absorption temperature can be in the range of 35Ό to 60Ό.
[00112] The absorption temperature can be in the range of 45Ό to 55Ό.
[00113] The washing temperature can be in the range of 28Ό to 68Ό.
[00114] The washing temperature can be in the range of 30Ό to 55Ό.
[00115] The washing temperature can be in the range of 40Ό to 50Ό.
[00116] Absorption may include spraying an absorption circulation liquid at a lower stage. Absorption may include spraying an absorption circulation liquid at an upper stage which is downstream, in relation to the discharge gas, from the lower stage. The absorption circulation liquid in one or both of the lower and upper stages may include 0.15% -4.95% ammonium sulfite. The absorption circulation liquid in one or both of the lower and upper stages 870180037264, of 05/07/2018, p. 37/187
30/78 rior may include 5% -38% ammonium sulphate. The absorption circulation liquid in one or both of the lower and upper stages may have a pH value in the range of 4-6.6. The concentration of liquid ammonium sulfite in the upper stage of absorption circulation may be lower than the concentration of ammonium sulfite in the lower stage of the absorption circulation liquid.
[00117] The pH of the upper stage absorption circulation liquid may be lower than the lower stage pH of the absorption circulation liquid.
[00118] Absorption may include spraying an absorption circulation liquid at a lower stage. Absorption may include spraying an absorption circulating liquid at an upper stage which is downstream, in relation to the discharge gas, from the lower stage. The absorption circulation liquid in one or both of the lower and upper stages may include 0.15% -4.95% ammonium sulfite. The absorption circulation liquid in one or both of the lower and upper stages may include 5% -38% ammonium sulfate. The absorption circulation liquid in one or both of the lower and upper stages may have a pH value in the range of 4-6.6. The pH of the upper stage absorption circulation liquid may be lower than the lower stage pH of the absorption circulation liquid.
[00119] Absorption may include spraying the absorption circulation liquid in a single stage.
[00120] Absorption may include spraying the absorption circulation liquid in only two stages.
[00121] At a stage of removal, the fine particulate wash circulation liquid may include 0.003% -1% ammonium sulfite. At a stage of removal, the fine particle washing circulation liquid can include 0.3% -38% ammonium sulfate. At a stage of removal, the particulate wash circulation liquid
Petition 870180037264, of 05/07/2018, p. 38/187
Thin 31/78 can have a pH in the range of 3-5.4.
[00122] Removal may include spraying the fine particles washing circulation liquid in two stages. In one stage of the stages the fine particulate washing liquid can include 0.1% -1% ammonium sulfite. In one stage of the stages the fine particulate washing liquid can include 5% 38% ammonium sulfate.
[00123] The apparatus and methods provide to control ammonia leakage and aerosol production at the source, in which the sulfur dioxide in the exhaust gas is removed with an absorption liquid containing ammonium sulfite, and the ammonia desulfurization It is performed by converting ammonia to ammonium sulfite by adding ammonia to an absorption circulating liquid. Furthermore, using a staged solution composition control and reaction condition control, a synergistic control of absorption, oxidation, and concentration can be achieved. This can simplify the technological process, reducing investment, and forming the technology of this description.
[00124] Illustrative principles of the invention such as those below can be used alone or in combination, or in combination with other principles illustrated here:
1. The gas purification process may include an absorption circulation and a fine particulate wash circulation, and the circulation liquid during gas purification may include an absorption circulating liquid and a particulate wash circulation liquid thin. The absorption circulating liquid can be used primarily for desulfurization and to control aerosol production during desulfurization. The fine particulate wash circulation liquid can further assist desulphurization efficiency, while fine particle control is performed.
Petition 870180037264, of 05/07/2018, p. 39/187
32/78
2. The reaction conditions can be controlled, the pH value of the absorption circulation liquid can be reduced to no more than 6.6, and the absorption temperature can be controlled in 3013-7013, so that the escape ammonia and aerosols during absorption are reduced, and the total dust at the outlet after de-escalation in the absorption zone is not greater than 100 mg / Nm3. This can reduce energy consumption, reduce or avoid the discharge of waste water, and provide stable long-term operation of the device.
3. The ammonium sulfite content of the absorption circulation liquid can be controlled. This can control aerosol production during absorption, create favorable conditions for oxidation, and reduce energy consumption and the cost associated with oxidation.
4. The exhaust gas heat can be used to concentrate the ammonium sulfate solution. The ammonium sulfate content of the absorption circulating liquid may be increased to not less than 5% generally, for example to not less than between 15% and 35%. This can maintain the absorption efficiency and control the production of aerosol while helping the concentration process. A process configured to accept raw exhaust gas that has an SO2 concentration greater than 10,000 mg / Nm3 only needs crystallization by saturation. For a discharge gas with a higher SO2 concentration, part of the solution can be sent to an evaporation crystallization device for treatment, in order to reduce the investment and energy consumption in a post-processing sulfate system. ammonium.
5. The oxidation system, which can include different layers, different devices, or both, can be implemented according to the desired solution composition control. The liquid
Petition 870180037264, of 05/07/2018, p. 40/187
33/78 of the fine particle washing circulation and the absorption circulation liquid can be removed from the oxidation container of the oxidation system in different positions, each corresponding to a different layer, or different devices.
[00125] The control of aerosol production during absorption can help the described processes. The control means can include precise dividing control of the solution composition. The absorption circulating liquid can be provided with 1 stage or multiple stages. One or more stages may include ammonium sulphite and ammonium sulphate, and the fine particulate wash circulation liquid may be provided with one or more stages. One or more stages can include ammonium sulfite and ammonium sulfate. The fine particulate wash circulation liquid may have a pH value that is lower than an absorption circulation liquid pH value and an ammonium sulfite content that is less than an ammonium sulfite content in the absorption circulation liquid. The absorption temperature can be controlled within an appropriate range to reduce energy consumption while ensuring absorption efficiency and controlling the escape of ammonia and aerosols, and the total dust at the outlet after deflection in the absorption zone can be no greater than than 100 mg / Nm ³ .
[00126] The composition of the dividing solution can be controlled by forced oxidation through an oxidation and / or natural oxidation vessel and / or by making the pre-wash liquid enter the absorption zone and / or by controlling the operating temperature.
[00127] The absorption temperature can be reduced by conventional means such as cooling process water and mixing with cold wind, and increased by conventional means such as mixing with hot wind.
[00128] A method to control aerosol production during
Petition 870180037264, of 05/07/2018, p. 41/187
34/78 absorption in ammonia desulfurization may include removing sulfur dioxide in the exhaust gas with an absorption circulating liquid containing ammonium sulfite, in order to control aerosol production during absorption in ammonia desulfurization. [00129] The aerosol may include precipitated solid crystal grains by evaporating droplets of circulating absorption liquid in hot exhaust gas, and solid particles formed by reacting gaseous NH3 escaped from volatile aqueous ammonia in the circulating absorption liquid with SO2 in the gas of discharge, which are mainly composed of (NH4) 2SO3, NH4HSO3, NH4HSO4, and (NH4) 2SO4. The higher the pH value of the circulating absorption liquid and / or the higher the operating temperature, the more severe the aerosol is.
[00130] The aerosol has a specific relationship with the total dust content at the outlet, the higher the aerosol content, the higher the total dust content at the outlet. Devices that cannot or do not control aerosols well may not be able to meet ultra-low emission requirements, for example, GB13223-2011, and the purified exhaust gas may form a white dragon when discharged into the atmosphere. This can extend a few kilometers or even tens of kilometers, causing serious fog pollution.
[00131] Efficient desulfurization and dust removal can be achieved by controlling the composition of the solution in stages and controlling the reaction condition, and currently ammonia leakage and aerosol production can be controlled.
[00132] The control of solution composition in stages may include concentration gradient control of ammonium sulfite, ammonium bisulfite, ammonium sulfate, or a combination thereof.
[00133] The exhaust gas subject to a decrease in temperature. Petition 870180037264, of 07/05/2018, p. 42/187
35/78 Preliminary cleaning and purification may be allowed to contact a liquid of absorption circulation and a liquid of circulation of washing of fine particles sequentially in order to achieve a synergistic control of absorption, oxidation and concentration. The absorption circulating liquid can be provided with 1 stage or multiple stages as required, where one or more stages may include ammonium sulfite and ammonium sulfate. The fine particle washing circulation liquid can be provided with 1 stage or multiple stages. One or more stages contain ammonium sulfite and ammonium sulfate.
[00134] The fine particulate wash circulation liquid may have a pH value that is lower than an absorption circulation liquid pH value, and an ammonium sulfite content that is less than a content of ammonium sulfite in the absorption circulation liquid.
[00135] An absorption temperature and a wash temperature can be controlled within an appropriate range to reduce energy consumption, while currently maintaining absorption efficiency and controlling the escape of ammonia and aerosols.
[00136] The absorption circulation liquid can have any suitable number of stages, for example, 1-2 stages, or 1 stage. When choosing multiple stages, one or more stages of composition of the absorption circulation liquid can include 0.15% 4.95% ammonium sulfite and 5% -38% ammonium sulfate, with a pH value of 4- 6.6, and the ammonium sulfite content of an upper stage of the absorption circulation liquid may be lower than the ammonium sulfite content of a lower stage of the absorption circulation liquid. The pH value of an upper stage of the absorption circulation liquid may be lower than the pH value of a lower stage of the absorption circulation liquid.
Petition 870180037264, of 05/07/2018, p. 43/187
36/78 [00137] One or more stages of fine particle washing circulation liquid composition may include 0.003% -1% ammonium sulfite and 0.3% -38% ammonium sulfate, with a pH value 3-5.4.
[00138] The fine particles washing circulation liquid can have any suitable number of stages, for example, 2 stages. One of the stages can be a circulating liquid with a high concentration of ammonium sulfate content, in which ammonium sulfite is 0.1% -1% and ammonium sulfate is 5% -38%; and the other stage can be a diluted solution, in which the ammonium sulfite content is not more than 0.1%. A diluted solution stage can be included. A process water stage can be included.
[00139] The absorption temperature can be any suitable temperature, for example, from 30Ό to 70Ό, from 35Ό to 60 Ό, or from 45Ό to 55Ό.
[00140] The washing temperature can be any temperature, for example, from 28Ό to 68Ό, 30Ό to 55Ό, or from 40 ° C to 50Ό.
[00141] The auxiliary system may include an ammonium sulphate post-processing system, an ammonia supply system, and a process water system.
[00142] The apparatus and methods may use a divider control, and may include a pre-wash zone, an absorption zone, and a fine particle control zone, in which each of the pre-wash zone, the zone absorption, and the fine particle control zone is provided with one or more layers of spray layer, and a gas-liquid separator such as a liquid receiver, a partition with a gas cap, a gas distribution plate gas and a liquid receiving container, which only allows gas to pass through it and allows the liquid to be removed from the side or bottom, is provided between the absorption zone
Petition 870180037264, of 05/07/2018, p. 44/187
37/78 and the prewash zone.
[00143] A gas-liquid separator that allows only the gas to pass through it, and allows the liquid to be removed from the side or the bottom, can be provided between the absorption zone and the fine particles control zone, inside absorption zone and within the fine particle control zone, as follows:
when the original exhaust gas flow is more than 800,000 Nm ³ / h, the gas-liquid separator which only allows the gas to pass through it and allows the liquid to be removed from the side or the bottom can be provided within the absorption zone and within the fine particle control zone;
when the SO2 concentration of the original exhaust gas is more than 6,000 mg / Nm ³ , a gas-liquid separator which only allows the gas to pass through it and allows the liquid to be removed from the side or the bottom can be provided within the absorption zone; and when the total original exhaust gas dust is more than 100 mg / Nm ³ , a gas-liquid separator which only allows the gas to pass through it and allows the liquid to be removed from the side or bottom can be provided within the fine particle control zone.
[00144] The fine particle control zone can be provided with one or more layers of deaerators, and each layer of the prewash zone and the absorption zone can be provided with one or more layers of deaerators. Deaerators can use deflectors, ridges, fillers and wire sieve forms, or their combination forms.
[00145] The ratio of liquid to gas and the spray coverage on each layer of the absorption zone can be controlled, so that the sulfur dioxide, particles and free ammonia are total. Petition 870180037264, from 07/05/2018, pg. 45/187
38/78 or almost completely absorbed. Specifically, for example, the liquid-to-gas ratio may not be less than 0.2 L / Nm ³ and the spray coverage may not be less than 110% in each layer of the absorption zone; and the liquid-to-gas ratio may not be less than 0.1 L / Nm ³ and the spray coverage may not be less than 105% on each layer of the fine particle control zone.
[00146] The oxidation system can be established with layers or devices according to the requirements of the solution composition control. The fine particles washing circulation liquid and the absorption circulation liquid can be removed from the oxidation container of the oxidation system in different positions or different devices.
[00147] In some embodiments, the absorption circulation liquid and the fine particles washing circulation liquid in a high concentration of ammonium sulfate and ammonium sulfite can be removed from the oxidation container of the oxidation system in different positions. The absorption circulation liquid can include 1-3 levels. The fine particle washing circulation liquid, in a high concentration of ammonium sulfate and ammonium sulfite, can include 1-2 stages. The fine particulate wash circulation liquid, in a low concentration, can circulate separately from the fine particulate wash circulation tank, and can be provided with 1-3 levels.
[00148] In some embodiments, the absorption circulation liquid can be removed from an absorption circulation tank, and can include 1-4 levels. The fine particulate wash circulation liquid in a high concentration of ammonium sulphate and ammonium sulphite can be removed from the oxidation vessel of the oxidation system and can be 1-2 stages. The washing circulation liquid
Petition 870180037264, of 05/07/2018, p. 46/187
39/78 of fine particles in a low concentration of ammonium sulfate can be circulated separately from the fine particle wash circulation tank. The separate circulation can be omitted, for example, if the sulfur dioxide concentration of the inlet exhaust gas is lower than 2,000 mg / Nm ³ (dry base, 6% O2), and the emission concentration of dioxide sulfur content of the clean gas is higher than 100 mg / Nm ³ (dry base, 6% O2), and the fine particulate wash circulation liquid can be sprayed at 1-3 levels.
[00149] In some embodiments, process water can be used as the last level (further downstream) of the fine particulate washing liquid.
[00150] 1-5 layers of gas-liquid dispersion enhancers can be provided within the oxidation vessel of the oxidation system. The liquid-gas dispersion enhancer can use one or more structured fillings, random fillers, perforated plates, gas caps, aeration heads, and the like, or any combination thereof.
[00151] The oxidation container can have a liquid level greater than 3 m and not less than 20% of excess oxidation air. [00152] The methods can include the following illustrative process:
the exhaust gas enters the prewash zone and is cooled and flushed with a circulation wash liquid in the pre-wash zone while the circulation wash liquid is concentrated, and then the exhaust gas passes through the absorption zone where the discharge gas is washed and desulfurized by the absorption circulation liquid, passes through the fine particle control zone where the fine particles are removed by a fine particulate circulation washing liquid respectively, and is then discharged;
Petition 870180037264, of 05/07/2018, p. 47/187
40/78 the circulation washing liquid in the prewash zone is mainly replenished by the fine particulate circulation washing liquid, and the fine particulate circulation washing liquid and / or process water is used to rinse impurities on a tower wall, and the absorption circulation liquid is replenished by the circulation wash liquid in the fine particle and / or process water control zone; and the absorption circulation liquid is oxidized in the oxidation system, and solutions with different compositions are removed from the oxidation container of the oxidation system in different positions or different apparatus respectively for circulation.
[00153] Process water can be replenished from one or both of the fine particle control zone and the fine particle wash circulation tank, or it can be replenished with rinse water.
[00154] The solution composition can be controlled by forced oxidation through an oxidation and / or natural oxidation vessel and / or by making the pre-wash liquid enter the absorption zone and / or by controlling the operating temperature. Under normal circumstances, the temperature of the exhaust gas is 110Ό-180 ^ο Ο, the oxygen content in the exhaust gas is 3% -7%, and the water content is 710%, at this time it is necessary to control forced oxidation part of the circulating liquid to control the solution composition within a desired range; however, in the case where the discharge gas temperature is above 200Ό and / or the oxygen content in the discharge gas is above 8%, the natural oxidation of the absorption circulation liquid by the discharge gas can meet the requirements, and at this time it is not necessary to control forced oxidation during circulation and absorption.
[00155] If the gas speed of the absorption tower is high, the airPetition 870180037264, dated 07/05/2018, pg. 48/187
41/78 creeping of liquid by the gas is serious, or the sealing of trays from one zone to another zone is weak, so that the pre-wash circulation liquid and the absorption circulation liquid flow between each other, and it is also possible to obtain an ideal solution composition. [00156] Implementations can include staged solution composition control and reaction condition control, in order to achieve efficient desulfurization and dust removal, while at the same time efficient desulfurization, ammonia escape and the production of aerosol during absorption are controlled. The desulfurization material can include ammonium sulfite. The absorption circulation liquid can be a mixed solution of weakly acidic ammonium sulfate-ammonium sulphate, and the fine particle wash circulation liquid can be a mixed solution of more acidic ammonium sulfate-ammonium sulfite in more concentrated concentrations. low. This can help to achieve synergistic control of absorption, oxidation and concentration.
[00157] The sulfur dioxide in the discharge gas can be removed by the absorption circulation liquid containing ammonium sulfite, and the absorption circulation liquid after absorbing SO2 can be converted to ammonium sulfite by adding ammonia and then subjected to ammonia desulfurization.
[00158] The absorption tower can have an exhaust gas inlet, and the various zones, positioned based on exhaust gas parameters in one or more of the following stages: inlet, after pre-wash control (if there is such stage), after absorption, after fine particle control, after discharge. Positioning may also depend on whether or not there is a pre-wash control zone, the number of spray layers in the zones, the degree of oxidation of absorption liquid in the oxidation system, and the degree of enrichment for post-processing. The position of enPetition position 870180037264, of 07/05/2018, p. 49/187
42/78 discharge gas inlet can be 10% -40% of the tower height, the height of the prewash zone can be 10% -40% of the tower height, the height of the absorption zone can be 10 % -35% of the tower height, and the height of the fine particle control zone can be 15% -70% of the tower height.
[00159] The ratio of the diameter of the absorption tower to the diameter of the oxidation container can be 0.5-3, and the height of the oxidation container can be 0.3-6 times the diameter of the absorption tower.
[00160] The surface gas velocity of the absorption tower can be 1 m / s-5 m / s. The operating temperature of the prewash zone can be 4013-8013.
[00161] The absorption temperature can be controlled according to the exhaust gas parameters, and for the boiler exhaust gas, this is usually controlled at 4013-6013. For sulfur recovery exhaust gas and incineration exhaust gas, this is generally controlled at 5013-7013. For a dry method for sulfuric acid discharge gas, this is generally controlled at 3013-4513.
[00162] When the system is under the condition that the SO2 concentration in the original exhaust gas is not greater than 30,000 mg / Nm ³ , the purified exhaust gas can meet the most stringent standard emission requirements or process requirements worldwide , and the device can be tuned and designed according to specific design requirements to reduce investment and operating costs and improve the performance-price ratio.
[00163] The purified exhaust gas can have SO2 not greater than 200 mg / Nm ³ , for example, not greater than 100 mg / Nm ³ , or 35 mg / Nm ³ , or 5 mg / Nm ³ .
[00164] The purified exhaust gas may have a total dust (containing aerosols) not greater than 20 mg / Nm ³ , for example 10
Petition 870180037264, of 05/07/2018, p. 50/187
43/78 mg / Nm ³ , or 5 mg / Nm ³ , or 2 mg / Nm ³ .
[00165] The purified exhaust gas may have an ammonia leak not greater than 5 mg / Nm ³ , for example 2 mg / Nm ³ , or 1 mg / Nm ³ , or 0.5 mg / Nm ³ .
[00166] When the emission index requirements are low, the investment and operating costs can be reduced by reducing the levels of the absorption circulation and the fine particles washing circulation and / or the number of spray layers and / or number circulations, and / or increasing the ammonium sulfite content and the pH values of the absorption liquid.
[00167] When the emission index requirements are strict, a qualified emission can be achieved, or production requirements of subsequent operating procedures can be met, increasing the levels of the absorption circulation and the fine particle wash circulation and / or number of spray layers and / or number of circulations, and / or precisely to control the ammonium sulfite content and pH values of the absorption liquid. [00168] The mass fraction ratio of ammonium sulfate to ammonium sulfite in one or more stages of the absorption circulation liquid can be 1.5-199: 1, for example, 9-99: 1.
[00169] The ratio of mass fraction of ammonium sulphate to ammonium sulphite in one or more stages of the fine particulate circulation washing liquid can be 3-1999: 1, for example, 9-999: 1. [00170 ] When it is necessary to control harmful ions such as chloride ions and fluoride ions in the circulation solution, a portion of the fine particle circulation wash liquid can be directly prepared as ammonium sulfate. The content of chloride ions in the circulating solution can be less than 50,000 mg / L, for example, 10,000-31,000 mg / L, and the concentration of fluoride ions can be less than 20,000 mg / L, for example, 300-3,000 mg / L.
Petition 870180037264, of 05/07/2018, p. 51/187
44/78 [00171] Selected illustrative modalities:
1. A method to control aerosol production during absorption in ammonia desulfurization, in which the sulfur dioxide in the exhaust gas is removed with an absorption circulation liquid containing ammonium sulfite, in order to control the production of aerosol during absorption in ammonia desulfurization.
2. The mode 1 method in which efficient desulfurization and dust removal are achieved by controlling the composition of the solution in stages and controlling the reaction condition, while at the same time efficient desulfurization and dust removal, ammonia escape and aerosol production are controlled.
3. The mode 2 method in which the solution composition control in stages includes a concentration gradient control of ammonium sulfite, ammonium bisulfite, ammonium sulfate, or a combination thereof.
4. The method of mode 2 in which the discharge gas subject to a preliminary temperature decrease and purification is allowed to contact the absorption circulation liquid and a fine particles washing circulation liquid sequentially in order to achieve a synergistic control absorption, oxidation and concentration, the absorption circulation liquid is provided with 1 stage or multiple stages as required, where one or more 1 stage contains ammonium sulphite and ammonium sulphate, and the fine particles washing circulation liquid it is provided with 1 stage or multiple stages as required, where one or more stages contains ammonium sulphite and ammonium sulphate.
5. The method of mode 4 in which the fine particle washing circulation liquid has a pH value being lower than an absorption circulation liquid pH value and an ammonium sulfite content being less than one content
Petition 870180037264, of 05/07/2018, p. 52/187
45/78 ammonium sulfite in the absorption circulation liquid.
6. The mode 2 method in which an absorption temperature and a wash temperature are controlled within an appropriate range to reduce energy consumption while ensuring absorption efficiency and controlling the escape of ammonia and aerosols.
7. The method of modality 4 in which when multiple levels are chosen for the absorption circulation liquid, one or more 1 stage of composition includes 0.15% -4.95% ammonium sulfite and 5% -38% ammonium sulfate, with a pH value of 4-6.6, the ammonium sulfite content of a higher level of the absorption circulation liquid is lower than the ammonium sulfite content of a lower level of the liquid absorption circulation, and / or the pH value of a higher level of the absorption circulation liquid is lower than the pH value of a lower level of the absorption circulation liquid.
8. Mode 4 method in which the absorption circulation liquid is 1 to 2 stages, for example, 1 stage.
9. The method of modality 4 in which one or more stages of composition of the fine particle washing circulation liquid includes 0.003% -1% ammonium sulfite and 0.3% -38% ammonium sulfate, with a value pH of 3-5.4.
10. The method of mode 9 in which the fine particles washing circulation liquid is 2 stages, and 1 stage contains high concentration ammonium sulfate, where ammonium sulfite is 0.1% -1% and ammonium sulfate is 5% -38%.
11.0 method of mode 6 in which the absorption temperature is 30Ό to 70Ό, for example, 35Ό to 6 0 6, or 45Ό to 55O.
12. The method of mode 6 in which the temperature of
Petition 870180037264, of 05/07/2018, p. 53/187
46/78 wash is 28Ό to 68Ό, for example, 30Ό to 55 Ό, or 40Ό to 50Ό
13. A device to control the production of aerosol in ammonia desulfurization to implement the method of any of the modalities 1 to 12, in which the device includes a gas purification and removal system, an oxidation system, and an auxiliary system .
14. The mode 13 device in which the auxiliary system includes an ammonium sulphate post-processing system, an ammonia supply system, and a process water system.
15.0 mode 13 device in which an absorption tower of the gas purification and removal system uses a divider control, and includes a pre-wash zone, an absorption zone, and a fine particle control zone, in which each one of the prewash zone, the absorption zone, and the fine particle control zone is provided with one or more layers of spray layer, and an apparatus / component which only allows the gas to pass through it is provided between the absorption zone and the prewash zone.
16. The device of modality 15 in which an apparatus / component which only allows gas to pass through it is provided between the absorption zone and the fine particle control zone, as required.
17. The device of mode 15 in which an apparatus / component which only allows gas to pass through it is provided within the absorption zone as required.
18. The device of mode 15 in which an apparatus / component which only allows gas to pass through it is provided within the fine particle control zone as required.
Petition 870180037264, of 05/07/2018, p. 54/187
47/78
19. The device of mode 15 in which the fine particle control zone is provided with one or more layers of deaerators, and each layer of the prewash zone and the absorption zone is provided with one or more layers of deaerators as required; drawers use deflectors, ridges, fillers and wire sieve forms, or their combination forms.
20. The device of modality 15 in which the liquid to gas ratio per layer is not less than 0.2 L / Nm ³ and the spray coverage is not less than 110% in the absorption zone; and the liquid-to-gas ratio is not less than 0.1 L / Nm ³ and the spray coverage is not less than 105% on each layer of the fine particle control zone.
21.0 device of modality 13 in which the oxidation system is arranged with layers or devices according to the requirements of the solution composition control, and the fine particles washing circulation liquid and the absorption circulation liquid are removed from a oxidation container of the oxidation system in different positions or different devices.
22. The device of mode 21 wherein 1-5 layers of gas-liquid dispersion enhancers are provided within the oxidation vessel of the oxidation system.
23. The mode 22 device in which the gas-liquid dispersion enhancer can use one of structured fillers, random fillers, perforated plates, gas caps, and aeration heads, or any combination thereof.
24. The mode 21 device in which the oxidation container of the oxidation system has a liquid level greater than 3 m and not less than 20% excess oxidation air.
25. The provision of any of the modalities 13-24,
Petition 870180037264, of 05/07/2018, p. 55/187
48/78 where:
the exhaust gas enters the prewash zone and is cooled and flushed with a circulating wash liquid in the pre-wash zone while the circulating wash liquid is concentrated, and then the exhaust gas passes through the absorption zone where the discharge gas is washed and desulfurized by the absorption circulation liquid, passes through the fine particle control zone where the fine particles are removed by a fine particulate circulation washing liquid respectively, and is then discharged;
the circulation washing liquid in the prewash zone is mainly replenished with the fine particles circulation washing liquid, and the fine particles circulation washing liquid and / or process water is used to rinse impurities on the wall tower, and the absorption circulating liquid is replenished by the circulating washing liquid in the control zone for fine particles and / or process water; and the absorption circulation liquid is oxidized in the oxidation system, and solutions with different compositions are removed from the oxidation container of the oxidation system in different positions or different apparatus respectively for circulation.
26. The device of mode 25 in which the process water is replenished from the fine particle control zone.
27. The device of mode 25 in which the preliminary temperature reduction and purification solution is to decrease the temperature and remove the dust with the circulating washing liquid.
28. The device of mode 15 in which the discharge gas inlet position is 10% -40% of the tower height, the height of the prewash zone is 10% -40% of the tower height, the height gives
Petition 870180037264, of 05/07/2018, p. 56/187
49/78 absorption zone is 10% -35% of the tower height, and the height of the fine particle control zone is 15% -70% of the tower height.
29. The device of mode 21 in which the ratio of the diameter of the absorption tower to the diameter of the oxidation vessel is 0.5-3, and the height of the oxidation vessel is 0.3-6 times the diameter of the oxidation tower. absorption.
30. The device of mode 25 in which the surface gas velocity of the absorption tower is 1 m / s-5 m / s; and / or the operating temperature of the prewash zone is 40Ό to 80 “C.
31. The mode 25 device in which the SO2 concentration in the original exhaust gas is <30,000 mg / Nm ³ .
32. The mode 31 device in which the purified exhaust gas can meet the most stringent emission standard requirements or process requirements worldwide, and the device is optimized and designed according to specific design requirements to reduce investment costs and operation and perfect the performance-price ratio.
33. The mode 31 device in which the purified exhaust gas has SO2 of <200 mg / Nm ³ , for example, <100 mg / Nm ³ , <35 mg / Nm ³ , or £ 5 mg / Nm ³ .
34. The 32 mode device where the purified exhaust gas has total dust (containing aerosols) of <20 mg / Nm ³ , for example, £ 10 mg / Nm ³ , or £ 5 mg / Nm ³ , or £ 2 mg / Nm ³ .
35. The 32 mode device where the ammonia leak in the purified exhaust gas is <5 mg / Nm ³ , for example, £ 2 mg / Nm ³ , or £ 1 mg / Nm ³ , or <0.5 mg / Nm ³ .
36. The device of modality 25 in which when harmful ions such as chloride and fluoride ions in a circulating solution need to be controlled, a part of an absorption liquid is directly made into a solid product using an apparatus 870180037264, from 07 / 05/2018, p. 57/187
50/78
Drying son.
37. The mode 36 device in which the content of chloride ions in the circulating solution is less than 50,000 mg / L, for example, 10,000-31,000 mg / L, and the concentration of fluoride ions is less than 20,000 mg / L, for example, 300-3,000 mg / L.
38. The mode 21 device in which the solution composition is controlled by forced oxidation through a oxidation and / or natural oxidation vessel and / or by making the pre-wash liquid enter the absorption zone and / or by controlling the operating temperature .
39. The device of mode 25 in which the mass fraction ratio of ammonium sulfate to ammonium sulfite in one or more stages of the absorption circulation liquid is 1.5-199: 1.
40. The device of mode 20 in which the mass fraction ratio of ammonium sulfate to ammonium sulfite in one or more stages of the fine particulate circulation washing liquid is 3-1999: 1.
[00172] The devices and methods described here are illustrative. The apparatus and methods according to the invention will now be described in connection with the figures, which form a part thereof. The figures show illustrative characteristics of apparatus and method steps according to the principles of the invention. It should be understood that other modalities can be used and that structural functional and procedural modifications can be made without departing from the scope and spirit of the present invention.
[00173] The method steps can be performed in an order other than the order shown and / or described here. The modalities may omit steps shown and / or described in connection with the illustrative methods. The modalities may include steps that are neither shown nor described in connection with the illusPetition methods 870180037264, 05/07/2018, p. 58/187
51/78 approaches. The illustrative method steps can be combined. For example, an illustrative method may include steps shown in connection with another illustrative method.
[00174] Some devices may omit features shown and / or described in connection with the illustrative devices. The modalities may include features that are neither shown nor described in connection with the illustrative methods. Features of illustrative devices can be combined. For example, an illustrative embodiment may include features shown in connection with another illustrative embodiment.
[00175] The apparatus and methods of the invention will be described in connection with the modalities and characteristics of illustrative devices. The devices will now be described with reference to the accompanying drawings in the figures, which form a part thereof. [00176] As shown in Figure 1, a method to control aerosol production during absorption in ammonia desulfurization is performed by removing sulfur dioxide in the discharge gas with an absorption circulation liquid containing ammonium sulfite, in order to control aerosol production during absorption in ammonia desulfurization.
[00177] Efficient desulphurization and dust removal can be achieved by a staged solution composition control and reaction condition control, and currently ammonia leakage and aerosol production are controlled.
[00178] The solution composition control in stages can include a concentration gradient control of ammonium sulfite, ammonium bisulfite, ammonium sulfate, or a combination thereof. [00179] The exhaust gas may enter a pre-wash zone, and the exhaust gas, subject to a preliminary temperature decrease and purification in the pre-wash zone, may be allowed 870180037264, from 07/05/2018, pg . 59/187
52/78 had to contact an absorption circulation liquid 7 and a fine particle wash circulation liquid 15 sequentially, to achieve synergistic control of absorption, oxidation and concentration. The absorption circulation liquid can be provided with a single stage that includes 1% ammonium sulfite and 22% ammonium sulfate with a pH value of 6.1 and an absorption temperature of 50 ° C. The fine particle washing circulation liquid can be provided with three levels, the lowest level being a mixed solution of high concentration ammonium sulfate-ammonium sulfite including 0.17% ammonium sulfite and 22% ammonium sulfate with a pH value of 4.5 and a wash temperature of 49.3 ° C, the second level is a mixed solution of ammonium sulphate-ammonium sulphite including 0.01% ammonium sulphite and 1 , 5% ammonium sulfate with a pH value of 4.3 and a wash temperature of 48 ° C, and the third level is process water.
[00180] The device can be configured to control the production of aerosol during absorption in ammonia desulfurization. The apparatus may include a gas purification and removal system, an oxidation system, and an auxiliary system. The auxiliary system may include an ammonium sulphate post-processing system, an ammonia supply system, and a process water system. [00181] The gas purification and removal system may include an absorption tower 1, a fine particulate wash circulation tank 3, a pre-wash circulation pump, and a fine particulate wash circulation pump. The absorption tower 1 can use a divider control and can be divided into a prewash zone 4, an absorption zone 5, and a fine particle control zone 6, where the prewash zone 4, the absorption zone 5, and the fine particle control zone 6 may be provided with three, three, and five spray layers, respectively, and
Petition 870180037264, of 05/07/2018, p. 60/187
53/78 a gas-liquid separator at 17 which only allows the gas to pass through it, and allows the liquid to be led out of the side or the bottom, can be provided between the absorption zone 5 and the prewash 4. The fine particle control zone can be divided into three spray layers, in which a gas-liquid separator b 18 which only allows the gas to pass through it, and allows the liquid to be carried out on the side or the bottom, it can be provided between the second spray layer and the third spray layer. The fine particulate wash circulation liquid 15 in layers 1-2 can be mixed with the absorption circulation liquid 7, followed by flowing into an oxidation vessel.
[00182] The fine particle control zone can be provided with seven layers of de-aerators, where three layers are below the gas-liquid separator b including a baffle layer and two crest layers, and four layers are below one purified exhaust gas outlet 8 which includes a baffle layer, two crest layers and a wire sieve layer. [00183] In each layer of the absorption zone, the liquid to gas ratio can be 1.5 L / Nm ³ , and the spray coverage can be 300%. In several layers of the fine particle control zone, the liquid to gas ratios can be 0.15 L / Nm ³ , 1.1 L / Nm ³ , 1.3 L / Nm ³ , 0.15 L, respectively / Nm ³ , and 1.5 L / Nm ³ , and the spray coverage can be, respectively, 105%, 250%, 280%, 105%, and 300%.
[00184] The oxidation system can include an oxidation container 2, in which the oxidation device 2 can be layered according to the requirements of the solution composition control. The fine particulate wash circulation liquid 15 and the absorption circulation liquid 7 can be removed from the container
Petition 870180037264, of 05/07/2018, p. 61/187
54/78 of oxidation in different positions. Five layers of gas-liquid dispersion enhancers can be provided within the oxidation vessel. The gas-liquid dispersion enhancer uses a perforated plate.
[00185] The oxidation container can have a liquid level of 8 m, and 200% excess oxidation air.
[00186] The apparatus and methods may involve the following illustrative process:
the exhaust gas enters the prewash zone 4 and is cooled and flushed with a circulating washing liquid in the prewash zone 4 while the circulating washing liquid is concentrated, and then the discharge gas passes through the absorption zone 5 where the discharge gas is washed and desulfurized by the absorption circulation liquid 7, passes through the fine particle control zone 6 where the fine particles are removed by the fine particulate circulation washing liquid 15 respectively, and then it is discharged;
the circulation washing liquid in the prewash zone 4 is mainly replenished with the fine particulate circulation washing liquid 15, the fine particulate circulation washing liquid 15 and / or process water 23 is used to rinse impurities on the tower wall and the like, and the absorption circulation liquid is replenished by the fine particles circulation washing liquid 15 and / or process water 23; and the absorption circulation liquid 7 is oxidized within the oxidation container 2, and solutions with different compositions are removed from the oxidation container 2 in different positions respectively for circulation.
[00187] The sulfur dioxide in the exhaust gas can be removed with an absorption circulating liquid containing sulfur of
Petition 870180037264, of 05/07/2018, p. 62/187
55/78 ammonia, ammonia can be converted to ammonium sulfite after being added to the absorption circulation liquid for ammonia desulfurization, and at the same time ammonia can be added to the prewash zone as needed to ensure that free indicators of acid in the ammonium sulfate product meet GB535 requirements.
[00188] Process water 23 can be refilled from the fine particle control zone 6 and the fine particle wash circulation tank 3. The discharge gas inlet position can be 12% of the tower height of the tower of absorber 1. The height of the prewash zone 4 can be 20% of the tower height. The height of the absorption zone 5 can be 15% of the tower height. The height of the fine particle control zone 6 can be 65% of the tower height.
[00189] The diameter ratio of the absorption tower 1 to the oxidation container 2 can be 1.5, and the height of the oxidation container 2 can be 1.4 times the diameter of the absorption tower 1.
[00190] The surface gas velocity of absorption tower 1 can be 2.75 m / s; and the operating temperature of the prewash zone 4 can be 55 ° C.
[00191] The exhaust gas flow can be 186,000 Nm ³ / h, the SO2 concentration can be 3,000 mg / Nm ³ , the total dust concentration can be 19.6 mg / Nm ³ , SO2 in the purified exhaust gas it can be 79.4 mg / Nm ³ , the total dust (including aerosol) can be 6.5 mg / Nm ³ , and the ammonia leak can be 1.8 mg / Nm ³ .
[00192] The solution composition can be controlled mainly by forced oxidation inside the oxidation container 2 and controlling the operating temperature.
[00193] The mass fraction ratio of ammonium sulfate to ammonium sulfite in the absorption circulation liquid 7 can be 22: 1. [00194] The mass fraction ratio of ammonium sulfate to southPetition 870180037264, from 07 / 05/2018, p. 63/187
56/78 ammonium phyto in the lowest fine particulate circulation washing liquid 15 can be 129.4: 1.
EXAMPLES [00195] The following examples, which are presented for purposes of illustration and are not intended to limit the scope of the invention. The application of the principles of the invention is not limited to the conditions presented in the examples, and it will be understood that the principles encompass various changes and modifications in the examples described herein, and that such changes and modifications can be made without departing from the spirit and scope of the invention.
EXAMPLE 1
1. Method for Controlling Aerosol Production During Absorption in Ammonia Desulfurization [00196] The sulfur dioxide in the exhaust gas was removed with an absorption circulation liquid containing ammonium sulfite in order to control aerosol production. during absorption in ammonia desulfurization.
[00197] Efficient desulfurization and dust removal were achieved by controlling the composition of the solution in stages and controlling the reaction condition, and currently ammonia leakage and aerosol production have been controlled.
[00198] The solution composition control in stages included one or more concentration gradient control of ammonium sulfite, ammonium bisulfite, ammonium sulfate.
[00199] The discharge gas entered a prewash zone of an absorption tower, and the discharge gas, subject to a preliminary temperature decrease and purification in the prewash zone, was allowed to be contacted by a liquid absorption circulation flow 7 and a fine particle washing circulation liquid 15 sequentially in order to achieve a synergistic absorption control, oxyPetition 870180037264, from 07/05/2018, pg. 64/187
57/78 dation and concentration. The absorption circulation liquid was provided with two levels, which were removed from an oxidation vessel in different positions and supplied using separate pumps. The first level of absorption circulation liquid included 1.5% ammonium sulfite and 24% ammonium sulfate with a pH value of 6.3 and an absorption temperature of 51 ° C, and the second level of liquid Absorption circulation flow included 0.9% ammonium sulfite and 24% ammonium sulfate with a pH value of 5.5 and an absorption temperature of 50.8 ° C. The fine particle washing circulation liquid was provided with three levels, where the first level was a mixed solution of high concentration ammonium sulfate-ammonium sulfite including 0.15% ammonium sulfite and 24% ammonium sulfate with a pH value of 4.5 and a wash temperature of 50.5 ° C, the second level was a mixed solution of diluted ammonium sulfate sulfate including 0.02% ammonium sulfite and 2% ammonium sulfate with a pH value of 4.2 and a wash temperature of 49.8 ° C, and the third level was process water.
2. Device to Control Aerosol Production During Absorption in Ammonia Desulfurization [00200] The device mainly included a gas purification and removal system, an oxidation system, and an auxiliary system. The auxiliary system included an ammonium sulphate post-processing system, an ammonia supply system, and a process water system.
[00201] The gas purification and removal system included an absorption tower 1, a fine particles washing circulation tank 3, a pre-washing circulation pump, and a fine particles washing circulation pump. The absorption tower 1 used a divider control and was mainly divided into a pre-wash zone 4, an absorption zone 5, and a control zone of
Petition 870180037264, of 05/07/2018, p. 65/187
58/78 fine particles 6, where the prewash zone 4, the absorption zone 5, and the fine particle control zone 6 were provided with three, three, and four spray layers, respectively, and a separator gas-liquid to 17 which only allowed gas to pass through it was provided between the absorption zone 5 and the pre-wash zone 4. A liquid-gas separator 17, which only allows gas to pass through the same, it was also provided between the absorption zone 5 and the fine particle control zone 6. The fine particle control zone 6 was divided into three spray layers, in which a gas-liquid separator b 18, which it only allows gas to pass through it, it was provided between the first spray layer and the second spray layer. The first spray liquid layer and the absorption circulation liquid entered the oxidation vessel, respectively.
[00202] The fine particle control zone was provided with five layers of deaerators, in which two layers were below the gas-liquid separator b, and included a deflector layer and a ridge layer, and three layers were below a purified exhaust gas outlet 8, and included a ridge layer and two layers of wire sieve.
[00203] The absorption zone was provided with two layers of deflector fans.
[00204] In each layer of the absorption zone, the liquid to gas ratio was 1.6 L / Nm ³ , and the spray coverage was 320%. In several layers of the fine-particle control zone from top to bottom, the liquid-to-gas ratios were 0.2 L / Nm ³ , 1.2 L / Nm ³ , 1.3 L / Nm ³ , and 1 respectively , 6 L / Nm ³ , and spray coverage were 110%, 260%, 290%, and 320%, respectively.
[00205] The oxidation system included an oxidation container 2, in which the oxidation device 2 was arranged in layers of accordion 870180037264, of 05/07/2018, p. 66/187
59/78 with the requirements of the solution composition control. The fine particle washing circulation liquid 15 and the absorption circulation liquid 7 were removed from the oxidation vessel 2 in different positions. Five layers of gas-liquid dispersion improvers were provided inside the oxidation vessel. The gas-liquid dispersion improver used a perforated plate and an aeration head.
[00206] The oxidation vessel had a liquid level of 9.3 m, and 250% excess oxidation air.
3. Processes and Method Parameters to Control the Production of
Aerosol During Absorption in Ammonia Desulfurization [00207] The apparatus and methods may involve the following illustrative process:
[00208] The exhaust gas entered a prewash zone 4, and was cooled and rinsed by a circulating washing liquid in the prewash zone 4, while the circulating washing liquid was concentrated, and then the discharge gas passed through the absorption zone 5, where the discharge gas was washed and desulfurized by the absorption circulation liquid 7, passed through the fine particle control zone 6, where the fine particles are removed by the washing liquid fine particle circulation 15, and then was discharged.
[00209] The circulating washing liquid in the prewash zone 4 was mainly replenished with the fine particulate circulation washing liquid 15. The fine particulate circulation washing liquid 15 and / or process water 23 was used to rinse the impurities on the tower walls and the like, and the absorption circulation liquid was replenished by the fine particulate circulation washing liquid 15 and / or process water 23.
[00210] The absorption circulation liquid 7 has been oxidized within the
Petition 870180037264, of 05/07/2018, p. 67/187
60/78 oxidation vessel 2, and solutions with different compositions were removed from oxidation vessel 2 in different positions respectively into an absorption zone 5 and the fine particle control zone 6 for circulation.
[00211] Process water 23 has been replenished from the fine particle control zone 6 and the fine particle wash circulation tank 3.
[00212] The second level of fine particles washing circulation liquid 15 (a mixed solution of diluted ammonium sulfate-ammonium sulfite) was mixed with the first level of fine particles washing circulation liquid 15 (a mixed solution ammonium sulfate-high-concentration ammonium sulfite) through a pipe, and then sprayed in a spray layer in the fine particle control zone 6 of absorption tower 1. [00213] The absorbent was 20% ammonia, which was refilled within the prewash zone 4 and the oxidation vessel 2. The sulfur dioxide in the exhaust gas was removed with an absorption circulation liquid containing ammonium sulphite. The ammonia was converted to ammonium sulfite after being added to the oxidation vessel for ammonia desulfurization, and currently ammonia has been added in the prewash zone to ensure that the free acid indicators in the ammonium sulfate product meet GB535 requirements .
[00214] Oxidizing air was added to oxidation vessel 2, and the outlet gas from oxidation vessel 2 was introduced into absorption zone 4 of absorption tower 1 for natural oxidation of the absorption liquid.
[00215] The discharge gas inlet position was 11% of the tower height of the absorber tower 1, the height of the prewash zone 4 was 21% of the tower height, the height of the absorption zone 5 went to 20%
Petition 870180037264, of 05/07/2018, p. 68/187
61/78 of the tower height, and the height of the fine particle control zone 6 was 59% of the tower height.
[00216] The diameter ratio of the absorption tower 1 to the oxidation vessel 2 was 1.1, and the height of the oxidation vessel 2 was 1.2 times the diameter of the absorption tower 1.
[00217] The surface gas velocity of absorption tower 1 was 2.68 m / s; and the operating temperature of the prewash zone 4 was 56 ° C.
[00218] The exhaust gas flow was designated to be 510,000 Nm ³ / h, the SO2 concentration was designated to be 5,000 mg / Nm ³ , and the total dust concentration was designated to be no greater than 25 mg / Nm ³ .
[00219] During the test, the SO2 in the purified exhaust gas was 21 mg / Nm ³ , the total dust (including aerosol) was 1.3 mg / Nm ³ , and the ammonia leak was 0.8 mg / Nm ³ .
[00220] The solution compositions in different zones were controlled mainly by forced oxidation inside the oxidation vessel 2, natural oxidation in the absorption zone 4, controlling the operating temperature and other means.
Table 1. Device design parameters
Number Process indicator unity Numeric value 1 Discharge gas flow Nm ³ / h 510,000 2 Discharge gas inlet temperature ° C 140-160 3 Concentration of SO2 in the exhaust gas mg / Nm ³ 5,000 4 Dust concentration at the exhaust gas inlet mg / Nm ³ <25 5 SO2 concentration in the outlet exhaust gas mg / Nm ³ <35
Petition 870180037264, of 05/07/2018, p. 69/187
62/78
Number Process indicator unity Numeric value 6 Dust concentration in the exhaust gas mg / Nm ³ <5 7 Exhaust ammonia concentration in the exhaust gas mg / Nm ³ <1 8 Ammonia Recovery Rate % > 99.3
4. Implementation Effect [00221] The exhaust gas under different working conditions was subjected to ammonia desulfurization and dust removal using the device and method of Example 1. Table 2 shows the test methods and test instruments. Table 3 shows the operating parameters and test results.
Table 2. Test methods for each indicator and list of main instruments
Naked-mere Item ofMon-ramento Standard analytical method name and number Instrument name and type Number ofinstrument 1 Dust and smoke Determination of particulates and sampling methods for gaseous pollutants from gas discharged from stationary source GB / T16157-1996 Laoying 3012H dust and smoke sampler Electronic scales BS224S, AB204-S 8042448,0824449618360886, and 1119051201 2 SO ₂ Determination of sulfur dioxide from gas discharged fromstationary sourceFixed potential electrolysis method HJ / T 57-2000 Exhaust gas analyzer Testo 350 10 ^# , and 1 ^#
Petition 870180037264, of 05/07/2018, p. 70/187
63/78
Naked-mere Item ofMon-ramento Standard analytical method name and number Instrument name and type Number ofinstrument 3 NOx Determination of nitrogen oxides from gas discharged from stationary sourceFixed potential electrolysis method HJ / T 693-2014 Exhaust gas analyzer Testo 350 10 ^# , and 1 ^# 4 Ammonia Ambient air and discharged gasammonia Nessler reagent spectrophotometryHJ 533-2009 Laoying 3072H type spectrophotometer722 02085809, and 2c5BP363 5 Oxygen content of exhaust gas Electrochemical method - Specifications and test procedures for monitoring systemscontinuous emission of exhaust gas emitted from stationary sources (Appendix B) (HJ / T 76-2007) Exhaust gas analyzer Testo 350 10 ^# , and 1 ^# 6 Gas temperature ofdischarge Platinum resistance methodDetermination ofparticulates and methods of sampling gaseous pollutants from gas discharged from stationary sources (GB / T 161571996) TES-1310 /
Petition 870180037264, of 05/07/2018, p. 71/187
64/78
Naked-mere Item ofMon-ramento Standard analytical method name and number Instrument name and type Number ofinstrument 7 Waste gas humiditycharge Specifications and testing procedures for systemsmonitoringcontinuous emission of exhaust gas emitted from stationary sources (Appendix B) (HJ / T 76-2007) Laoying 3012H dust and smoke sampler 8042448, and 08244496 8 Sulfateammonia Ammonium sulphate (GB 535-1995) Analytical balance, pH meter and other laboratory instrumentsconventional Tabe a 3. Device operation parameters and test results
Number Item unity Test result comments 1 Discharge gas volume in absorption tower Standard state, wet basis, and real O2 x10 ⁴ m ³ / h 45.67 - Standard state, dry basis, and 6% O2 x10 ⁴ m ³ / h 41.34 - 2 System resistance Pan 1021 - 3 Original exhaust gas parameters SO2 concentration (standard state, dry basis, and 6% O ₂ ) mg / Nm ³ 4230 Average value during test O ₂ (V / V) % - - Temperature ° C 127.3 Average value during test Moisture content (V / V) % 9.05 -
Petition 870180037264, of 05/07/2018, p. 72/187
65/78
Number Item unity Test result comments Dust and smoke concentration (standard state, dry basis, and 6% O2) mg / Nm ³ 23.6 - 4 Gas parametersdischargepurified SO2 concentration (standard state, dry basis, and 6% O ₂ ) mg / Nm ³ 21 Average value during test O ₂ (V / V) % - - Temperature ° C 49.8 Average value during test Moisture content (V / V) % 14.23 - Dust and smoke concentration (standard state, dry basis, and 6% O2) mg / Nm ³ 1.3 Including solid particles and soluble solid particles Free ammonia leak (standard state, dry basis, and 6% O2) mg / Nm ³ 0.8 - 5 Absorption tower desulfurization efficiency % 99.5 6 Absorption tower dust removal efficiency % 94.5 - 7 Ammonia consumption (on the basis of 20% ammonia) t / h 4.669 8 Use of ammonia % 99.45 - 9 Ammonium sulfate by-product Nitrogen content % 21.1 Moisture % 0.25 - Free acid content % 0.03 -
Petition 870180037264, of 05/07/2018, p. 73/187
66/78
EXAMPLE 2
1. Method to Control Aerosol Production During absorption in ammonia desulfurization [00222] Sulfur dioxide in the exhaust gas was removed with an absorption circulation liquid containing ammonium sulfite, in order to control aerosol production during absorption in ammonia desulfurization.
[00223] Efficient desulfurization and dust removal were achieved by controlling the composition of the solution in stages and controlling the reaction condition, and currently ammonia leakage and aerosol production have been controlled.
[00224] The solution composition control in stages included a concentration gradient control of one or more of ammonium sulfite, ammonium bisulfite, ammonium sulfate.
[00225] The exhaust gas enters a pre-wash zone. The discharge gas, subject to a preliminary temperature decrease and purification in the prewash zone, was allowed to contact with an absorption circulation liquid 7 and a fine particles washing circulation liquid 15 sequentially, in order to achieve a synergistic control of absorption, oxidation and concentration. The absorption circulation liquid was provided with two levels, which were removed from an absorption circulation tank 16 in different positions and supplied using separate pumps. The first level of absorption circulation liquid included 2% ammonium sulfite and 27% ammonium sulfate with a pH value of 6.4 and an absorption temperature of 49 ° C, and the second level of circulation liquid Absorption rate included 1.1% ammonium sulfite and 27.9% ammonium sulfate with a pH value of 5.7 and an absorption temperature of 48.7 ° C. The fine particles washing circulation liquid was provided with four levels, where the first level was a solution
Petition 870180037264, of 05/07/2018, p. 74/187
67/78 mixed ammonium sulphate-high concentration ammonium sulphite including 0.2% ammonium sulphite and 28.8% ammonium sulphate with a pH value of 4.9 and a wash temperature of 48.5 ° C, the second level was a mixed solution of diluted ammonium sulfate-ammonium sulfite including 0.03% ammonium sulfite and 3.7% ammonium sulfate with a pH value of 4.3 and a washing temperature of 4 , 2 ° C, the third level was a mixed solution of diluted ammonium sulphate of lower concentration including 0.005% ammonium sulphite and 0.5% ammonium sulphate with a pH value of 4.25 and a wash temperature of 48.1 ° C, and the fourth level was process water.
2. Device to Control Aerosol Production During Absorption in Ammonia Desulfurization [00226] The device mainly included a gas purification and removal system, an oxidation system, and an auxiliary system. The auxiliary system included an ammonium sulphate post-processing system, an ammonia supply system, and a process water system.
[00227] The gas purification and removal system included an absorption tower 1, an absorption circulation tank 16, a fine particulate wash circulation tank 3, a fine particulate wash circulation tank b 3, a pre-wash circulation pump, an absorption circulation pump, and a fine particle wash circulation pump. The absorption tower 1 used a divider control and was mainly divided into a prewash zone 4, an absorption zone 5, and a fine particle control zone 6, where the prewash zone 4, the absorption zone 5, and the fine particle control zone 6 were provided with three, four and five spray layers, respectively, and a gas-liquid separator at 17 which only allowed the gas
Petition 870180037264, of 05/07/2018, p. 75/187
68/78 to pass through it was provided between the absorption zone 5 and the pre-wash zone 4. A gas-liquid separator at 17 which only allowed the gas to pass through it was also provided between the absorption zone 5 and the fine particle control zone 6. A gas-liquid separator b 18 which only allowed gas to pass through it was provided between the first absorption (two spray layers) and the second absorption (two spray layers ) in the absorption zone 5, between the first spray layer and the second spray layer in the fine particle control zone 6, and between the third spray layer and the fourth spray layer in the fine particle control zone. The absorption circulation liquid 7 entered the absorption circulation tank. The first layer of fine particulate circulation washing liquid 15 entered the oxidation vessel 2. The second layer and the third layer of fine particulate circulation washing liquid 15 entered the fine particle washing circulation tank at 3. The fourth layer and the fifth layer of fine particulate wash liquid entered the fine particulate wash circulation tank b 3.
[00228] The fine particle control zone was provided with seven layers of deaerators, two layers of which were below the gas-liquid separator b 18 between the first spray layer and the second spray layer including two ridge layers , two layers were below the gas-liquid separator b 18 between the third spray layer and the fourth spray layer including a ridge layer and a wire sieve layer, and three layers were below a gas outlet. purified discharge 8 including a crest layer and two layers of wire sieves.
[00229] The absorption zone was provided with a deflection layer 870180037264, from 07/05/2018, p. 76/187
69/78 depleting tor and a depleting crest layer.
[00230] In each layer of the absorption zone, the liquid to gas ratio was 2.1 L / Nm ³ , and the spray coverage was 400%. In several layers of the fine-particle control zone from top to bottom, the liquid-to-gas ratios were 0.16 L / Nm ³ , 2.1 L / Nm ³ , 1.4 L / Nm ³ , 1 respectively, 4 L / Nm ³ , and 2.1 L / Nm ³ , and spray coverage was 110%, 400%, 300%, 300%, and 400%, respectively.
[00231] The absorption circulation tank 16 has been adjusted with layers according to the requirements of the solution composition control. The first level of absorption circulation liquid 7 and the second level of absorption circulation liquid 7 were removed from an absorption circulation tank 2 in different positions. Two layers of gas-liquid dispersion improvers were provided inside the absorption circulation tank 16, which were structured fillers.
[00232] The oxidation system included an oxidation vessel 2. Five layers of gas-liquid dispersion improvers were provided inside the oxidation vessel. The gas-liquid dispersion enhancer used a perforated plate and an aeration head. [00233] The liquid level inside oxidation vessel 2 was 10 m.
[00234] The oxidation air added in the absorption circulation tank 16 and in the oxidation container 2 was in excess of 350%. [00235] The ammonium sulfate post-processing system was provided with a drying tower, through which part of the fine particles circulation washing liquid was converted directly to ammonium sulfate, in order to control the ion content chloride and fluoride ions in various circulation solutions.
3. Processes and Method Parameters to Control the Production of
Petition 870180037264, of 05/07/2018, p. 77/187
70/78
Aerosol During Absorption in Ammonia Desulfurization [00236] The specific processes of the method or device above were as follows:
[00237] The exhaust gas entered the prewash zone 4 and was cooled and washed by a circulating wash liquid in the prewash zone 4 while the circulating wash liquid was concentrated, and then the discharge gas was passed through the absorption zone 5, where the exhaust gas was washed and desulfurized by the absorption circulation liquid 7, passed through the fine particle control zone 6, where the fine particles are removed by the particulate circulation washing liquid 15, respectively, and was then discharged.
[00238] The circulating washing liquid in the prewash zone 4 was mainly replenished with the fine particles circulating washing liquid 15, and the fine particles circulating washing liquid 15 and / or process water 23 was used to rinse impurities on a tower wall, and the absorption circulation liquid was replenished by the fine particles circulation washing liquid 15 and / or process water 23.
[00239] The absorption circulation liquid 7 was oxidized inside the absorption circulation tank 16, and solutions with different compositions were removed from the absorption circulation tank 16 in different positions respectively for the first absorption and the second absorption.
[00240] Process water 23 was replenished from the fine particle control zone 6 and the fine particle wash circulation tank 3.
[00241] The second level and the third level of fine particulate washing circulation liquid 15 (a mixed solution of diluted ammonium sulfate-ammonium sulfite) was refilled inside the container 870180037264, from 05/07/2018, p. 78/187
71/78 oxidation agent 2.
[00242] The fourth level of fine particles washing circulation liquid 15 has been refilled inside the fine particles washing circulation tank 3.
[00243] The first level of fine particles washing circulation liquid 15 has been refilled inside the absorption circulation tank 16.
[00244] The absorbent was liquid ammonia and was mainly replenished inside the absorption circulation tank 16. The sulfur dioxide in the discharge gas was removed with an absorption circulation liquid containing ammonium sulfite, and the ammonia was converted in ammonium sulphite after being added to the absorption circulation tank 16 for ammonia desulfurization.
[00245] Ammonia was added in the prewash zone 4 to adjust the pH value to ensure that the free acid indicators in the ammonium sulphate product met GB535 requirements. Ammonia was added to oxidation vessel 2 to adjust the pH value.
[00246] Oxidizing air was added to the oxidation vessel 2 and absorption circulation tank 16, and the exhaust gases from the oxidation vessel 2 and absorption circulation tank 16 were introduced into the absorption zone 4 of the tower. absorption 1 for natural oxidation of the absorption liquid.
[00247] The discharge gas inlet position was 7% of the tower height of the absorber tower 1, the height of the prewash zone 4 was 17% of the tower height, the height of the absorption zone 5 was 25% of the tower height, and the height of the fine particle control zone 6 was 58% of the tower height.
[00248] The diameter ratio of the absorption tower 1 to the oxidation vessel 2 was 0.85, and the height of the oxidation vessel 2 was
Petition 870180037264, of 05/07/2018, p. 79/187
72/78
1.25 times the diameter of the absorption tower 1.
[00249] The surface gas velocity of absorption tower 1 was 2.64 m / s; and the operating temperature of the prewash zone 4 was 51 ° C.
[00250] The exhaust gas flow was designed to be 350,000 Nm ³ / h, the SO2 concentration was designed to be 15,000 mg / Nm ³ , the hydrogen chloride content was designed to be 100 mg / Nm ³ , and the total dust concentration is designed to be no greater than 30 mg / Nm ³ .
[00251] The exhaust gas had a high sulfur dioxide content. After calculation and analysis with water balance, 10% -20% of the high concentration fine particulate circulation washing liquid was required to be fed into an evaporation crystallization system for separate treatment, and the rest of the circulating washing liquid of fine particles of high concentration was concentrated and crystallized in the prewash zone of the absorption tower. Taking into account that the tower was designed so that the hydrogen chloride content of the exhaust gas was up to 100 mg / Nm ³ , a drying device was selected (instead of the evaporation crystallization system) in which 10% -20 % of the high concentration fine particulate circulation washing liquid was dried directly inside the drying apparatus to control the concentration of chloride ions to be 10,000-30,000 mg / L and to control the concentration of fluoride ions to be 500-2,800 mg / L in the circulating liquid.
[00252] During the test, the SO2 in the purified exhaust gas was 3.4 mg / Nm ³ , the total dust (including aerosol) was 0.9 mg / Nm ³ , and the ammonia leak was 0.25 mg / Nm ³ Nm ³ .
[00253] The solution compositions in different zones were controlled mainly through forced oxidation within the REPETITION 870180037264, of 07/05/2018, p. 80/187
73/78 oxidation vessel 2, forced oxidation inside the absorption circulation tank 16, natural oxidation in the absorption zone 4, controlling the operating temperature and other means.
Table 4. Device design parameters
Number Process indicator unity Numeric value 1 Discharge gas flow Nm ³ / h 350000 2 Discharge gas inlet temperature ° C 130-142 3 Concentration of SO2 in exhaust gas mg / Nm ³ 15000 4 Dust concentration at the exhaust gas inlet mg / Nm ³ <30 5 Concentration of SO2 in exhaust gas mg / Nm ³ <5 6 Dust concentration in the exhaust gas mg / Nm ³ <2 7 Exhaust ammonia concentration in the exhaust gas mg / Nm ³ <0.5 8 Ammonia Recovery Rate % > 99
4. Implementation Effect [00254] The exhaust gas under different working conditions was subjected to ammonia desulfurization and dust removal using the device and method of Example 2. Table 5 shows the test methods and test instruments. Table 6 shows the operating parameters and test results.
Petition 870180037264, of 05/07/2018, p. 81/187
74/78
Table 5. Test methods for each indicator and list of main instruments
Naked-mere Mon-ramento Standard name and analytical method number Instrument name and type Instrument number 1 Dust and smoke Determination of particulates and sampling methods for gaseous pollutants from gas discharged from stationary source GB / T16157-1996 Laoying 3012H dust and smoke sampleElectronic scales BS224S, AB204-S 8042448,0824449618360886,1119051201 2 SO ₂ Determination of sulfur dioxide from gas discharged fromstationary sourceFixed potential electrolysis method HJ / T 57-2000 Testo 350 exhaust gas analyzer 10 ^# , and 1 ^# 3 NOx Determination of nitrogen oxide from gas discharged from stationary sourceFixed potential electrolysis method HJ / T 693-2014 Exhaust gas analyzer Testo 350 10 ^# , and 1 ^# 4 Ammonia Ambient air and gas dischargedammonia Nessler reagent spectrophotometryHJ 533-2009 Laoying 3072H spectrophotometer722 02085809, and 2c5BP363
Petition 870180037264, of 05/07/2018, p. 82/187
75/78
Naked-mere Mon-ramento Standard name and analytical method number Instrument name and type Instrument number 5 Oxygen content of exhaust gas Electrochemical method - Specifications and test procedures for monitoring systemscontinuous emission of exhaust gas emitted from stationary sources (Appendix B) (HJ / T 76-2007) Exhaust gas analyzer Testo 350 10 ^# , and 1 ^# 6 Discharge gas temperature Platinum resistance methodDetermination ofparticulates and methods of sampling gaseous pollutants from gas discharged from stationary sources (GB / T 161571996) TES-1310 / 7 Discharge gas humidity Test specifications and testing procedures for monitoring systemscontinuous emission of exhaust gas emitted from stationary sources (Appendix B) (HJ / T 76-2007) Laoying 3012H dust and smoke sampler 8042448,08244496
Petition 870180037264, of 05/07/2018, p. 83/187
76/78
Naked-mere Mon-ramento Standard name and analytical method number Instrument name and type Instrument number 8 Sulfateinammonia Ammonium sulphate (GB 535-1995) Analytical balance, pH meter and other measuring instrumentsconventional laboratory Tabe to 6. Device operation parameters and test results
Number-ro Item unity Resultof test comments 1 Discharge gas volume inabsorption tower Standard state, wet basis, and real O2 x10 ⁴ m ³ / h 31.44 - Standard state, dry basis, and 6% O2 x10 ⁴ m ³ / h 28.95 - 2 System resistance Pan 1850 - 3 Original exhaust gas parameters SO2 concentration (standard state, dry basis, and 6% O2) mg / Nm ³ 12285 Average valueduring test O ₂ (V / V) % - - Temperature ° C 128 Average valueduring test Moisture content (V / V) % 7.92 - Dust and smoke concentration (standard state, dry basis, and 6% O2) mg / Nm ³ 27.5 -
Petition 870180037264, of 05/07/2018, p. 84/187
77/78
Number-ro Item unity Resultof test comments 4 Purified exhaust gas parameters SO2 concentration (standard state, dry basis, and 6% O2) mg / Nm ³ 3.4 Average valueduring test O ₂ (V / V) % - - Temperature ° C 48.2 Average valueduring test Moisture content (V / V) % 13.75 - Dust and smoke concentration (standard state, dry basis, and 6% O2) mg / Nm ³ 0.9 Including solid particles and soluble solid particles Escape free ammonia (standard state, dry basis, and 6% O2) mg / Nm ³ 0.25 - 5 Absorption tower desulfurization efficiency % 99.97 6 Absorption tower dust removal efficiency % 96.7 - 7 Ammonia consumption (on the basis of 99.6% liquid ammonia) t / h 1.907 8 Use of ammonia % 99.75 - 9 Sulfate by-productammonium Nitrogen content % 21.2 moisture % 0.3 - Contentof acidfree % 0.05 -
Petition 870180037264, of 05/07/2018, p. 85/187
[00255] Thus, apparatus and methods for controlling aerosol production during the absorption of sulfur dioxide from a discharge gas have been provided. Persons skilled in the art will appreciate that the present invention can be practiced by others than the examples described, which are presented for purposes of illustration rather than limitation. The present invention is limited only by the claims that follow.
Petition 870180037264, of 05/07/2018, p. 86/187
1/7

权利要求:
Claims (15)
[1]
1. Method for controlling the production of aerosol during the absorption of sulfur dioxide from a discharge gas, characterized by the fact that it comprises applying a gradient of ammonium salt to the discharge gas.
[2]
2/7 in which the application of a second concentration of ammonium salt in a second stage comprises spraying the absorption circulation liquid over the discharge gas in the sulfur dioxide absorption process; and / or where the application of a first concentration of ammonium salt in a first stage comprises spraying the fine particles washing circulation liquid onto the exhaust gas in a fine particles washing process; and / or in which the application of a second concentration of ammonium salt in a second stage comprises spraying the fine particles washing circulation liquid onto the discharge gas in the fine particles washing process.
2. Method according to claim 1, characterized by the fact that it also comprises applying a gradient of reaction condition, which comprises providing:
a first pH in a first stage; and a second pH in a second stage;
where the first stage is upstream, in relation to the exhaust gas, from the second stage, and the first pH is greater than the second pH.
[3]
3/7
3. Method according to claim 1, characterized by the fact that the application of an ammonium salt gradient comprises applying:
a first concentration of ammonium salt in a first stage; and a second concentration of ammonium salt in a second stage;
where the first stage is upstream, in relation to the exhaust gas, from the second stage.
[4]
4/7 prewash zone, absorption zone, and fine particle control zone including a plurality spray layer;
where the tower is configured to provide divisive control of solution compositions for the spray layers.
4. Method according to claim 3, characterized in that the salt includes ammonium sulfite, ammonium bisulfite, or ammonium sulfate.
[5]
5/7 control an operating temperature of the zone of fine particles to control the gradient; and / or where the oxidation system is configured to control an operating temperature of the zone of fine particles to control the gradient; and / or where the oxidation system does not include a forced oxidation container; and / or in which the oxidation system is configured to route the prewash liquid into the absorption zone.
5% -38% ammonium sulfate; and has a pH value in the range of 4-6.6;
wherein the concentration of ammonium sulfite in the upper stage absorption circulation liquid is lower than the concentration of ammonium sulfite in the lower stage of absorption circulation liquid.
Petition 870180138231, of 10/05/2018, p. 7/16
5. Method according to claim 4, characterized in that the application of a first concentration of ammonium salt in a first stage comprises spraying the absorption circulation liquid onto the discharge gas in a process of absorption of dioxide sulfur; and / or
Petition 870180138231, of 10/05/2018, p. 6/16
[6]
6/7 absorption.
6. Method according to claim 4, characterized by the fact that:
absorption includes:
spray an absorption circulation liquid at a lower stage;
spray an absorption circulation liquid at an upper stage which is downstream, in relation to the discharge gas, from the lower stage; and the absorption circulation liquid in one or both of the lower and upper stages:
comprises:
0.15% -4.95% ammonium sulfite; and
[7]
7/7
7. Apparatus to control the production of aerosol in ammonia desulfurization, characterized by the fact that it comprises:
a gas purification and removal system that is configured to apply an ammonium salt gradient to the exhaust gas;
an oxidation system; and an auxiliary system.
[8]
8. Apparatus according to claim 7, characterized by the fact that the oxidation system includes an oxidation container that is configured for:
forced oxidation of the input ammonium solution to generate a plurality of outputs of different degrees of oxidation of the ammonium solution; and providing the outlets for the gas purification and removal system to define the gradient; and / or where the auxiliary system comprises:
an ammonium sulphate post-processing system;
an ammonia supply system; and a process water system.
[9]
9. Apparatus according to claim 7, characterized by the fact that it also comprises:
a tower that:
houses the gas purification and removal system; and includes:
a prewash zone;
an absorption zone; and a fine particle control zone;
a component disposed between the absorption zone and the pre-wash zone that allows only the gas to pass; and a plurality of spray layers, each of the
Petition 870180138231, of 10/05/2018, p. 8/16
[10]
10. Apparatus according to claim 9, characterized by the fact that the oxidation system:
includes spray layers; and is configured to control an interaction between the sprayed liquid in a different spray layer and the discharge gas in a different spray layer to naturally oxidize the liquid to generate a plurality of outputs of different degrees of oxidation of ammonium solution to define the gradient; and / or where the oxidation system is configured to control an operating temperature of the prewash zone to control the gradient; and / or where the oxidation system is configured to control an operating temperature of the absorption zone to control the gradient; and / or where the oxidation system is configured to control an operating temperature of the fine particle control zone to control the gradient; and / or where the oxidation system is configured to control an operating temperature of the prewash zone and to control an operating temperature of the fine particle zone, to control the gradient; and / or where the oxidation system is configured to control an operating temperature of the absorption zone to control the gradient; and / or where the oxidation system is configured to conform 870180138231, of 05/10/2018, pg. 9/16
[11]
11. Apparatus according to claim 9, characterized by the fact that each zone includes a single spray layer; and / or wherein a zone of the zones includes a plurality of spray layers; and / or still comprising a component disposed between the absorption zone and the fine particle control zone that allows only the gas to pass; and / or still comprising a component disposed within the absorption zone that allows only the gas to pass; and / or even comprising a component disposed within the fine particle control zone that allows only the gas to pass.
[12]
Apparatus according to claim 9, characterized by the fact that it comprises a plurality of layers of deaerators;
on what:
a plurality release layer is arranged in the fine particle control zone; and a plurality de-stemming layer is arranged on each spray layer of the prewash zone and the
Petition 870180138231, of 10/05/2018, p. 10/16
[13]
Apparatus according to claim 12, characterized by the fact that a plunger of the plurality of plunger layers includes a deflector; and / or wherein a plunger of the plurality of plunger layers includes a ridge; and / or wherein a plunger of the plurality of plunger layers includes filling; and / or where a deaerator of the plurality of layers of deaerators includes a wire sieve and / or where a deaerator of the plurality of layers of deaerators includes a structure selected from the group consisting of:
a deflector; a crest; filling; wire sieve; and a combination of one or more of a deflector; a crest; filling; and wire sieve.
[14]
14. Apparatus according to claim 9, characterized by the fact that:
in each spray layer of the absorption zone: a liquid-to-gas ratio is not less than 0.2
L / Nm ³ ; and spray coverage is not less than 110%; and, in each spray layer of the fine particle control zone:
a liquid-to-gas ratio is not less than 0.1
L / Nm ³ ; and spray coverage is not less than 105%.
Petition 870180138231, of 10/05/2018, p. 11/16
[15]
15. Apparatus according to claim 7, characterized by the fact that the oxidation system:
includes a plurality of sections, each section corresponding to an ammonium solution of a different composition;
is configured, to form the ammonium salt gradient, to provide:
for a fine particle washing circulation liquid a composition of the different compositions; and to an absorption circulation liquid a composition of the different compositions to form the ammonium salt gradient.
Petition 870180138231, of 10/05/2018, p. 12/16

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR102018009209A2|2018-10-23|method for controlling aerosol production during absorption in ammonia desulfurization

---

CA2971655C|2018-07-03|Method and apparatus for effectively removing sulfur oxides and dust in gas by ammonia-based process

---

US20110052453A1|2011-03-03|Removal of carbon dioxide from a flue gas stream

---

BRPI0718179B1|2018-06-05|WET DESULFURIZATION AND WITHDRAWAL OF SINTERIZATION COMBUSTION GAS DUST.

---

BR102018009282A2|2019-03-06|CARBON CATCH

---

CN105013311A|2015-11-04|Flue gas desulfurization dust and mist removal method

---

CN204891568U|2015-12-23|Distributed SOx/NOx control device of boiler flue gas integration

---

US11224838B2|2022-01-18|Controlling aerosol production during absorption in ammonia-based desulfurization

---

CN101422693A|2009-05-06|Sulphuric acid tail-gas deep desulfurization method

---

US20170029343A1|2017-02-02|Sulfur enhanced nitrogen production from emission scrubbing

---

CN101844037A|2010-09-29|Tower for flue gas desulfurization in homogeneous air-humidifying method

---

CN106582236A|2017-04-26|Method and device for combined removal of SO2/NOx/PM2.5/Hg in coal-fired smoke

---

CN101862587A|2010-10-20|Wet flue-gas desulfurization tower based on baffle air distribution

---

CN102065982B|2013-11-27|Improved alkanolamines for CO2 removal from gas streams

---

CN214972862U|2021-12-03|Device for removing sulfur oxides in high-humidity flue gas

---

CN105056746A|2015-11-18|Implementing method for integrated distributed desulfurization and denitrification process of boiler flue gas

---

CN101306316A|2008-11-19|Boiler flue gas countercurrent direct purification method

---

BR122018069706B1|2021-10-26|METHOD TO CONTROL AEROSOL PRODUCTION DURING ABSORPTION OF SULFUR DIOXIDE FROM A DISCHARGE GAS

---

CN201823468U|2011-05-11|Twin tower ammonia desulfurization device

---

TW202010565A|2020-03-16|Aerosol generation controlling method during absorption process of ammonia desulfurization capable of realizing highly efficient desulfurization and dust removal while controlling ammonia escape and aerosol generation

---

CZ291174B6|2003-01-15|Method for suppressing the formation of sulfuric acid aerosols in exhaust gas purification systems

---

CN205730768U|2016-11-30|A kind of defogger system

---

CN112675669A|2021-04-20|Device and method for removing sulfur oxides in high-humidity flue gas

---

CN104667719A|2015-06-03|Flue gas countercurrent direct-discharge-type purification method

同族专利:

---

公开号 | 公开日

---

KR102302849B1|2021-09-16|

---

WO2019047625A1|2019-03-14|

---

EA202090619A1|2020-07-24|

---

JP2018161650A|2018-10-18|

---

PH12018000126A1|2019-04-01|

---

US20190270048A1|2019-09-05|

---

KR20190027701A|2019-03-15|

---

US20190126197A1|2019-05-02|

---

BR122018069706A2|2019-09-10|

---

US10369517B2|2019-08-06|

---

US10357741B2|2019-07-23|

---

CN108722163B|2019-06-07|

---

AU2018328418B2|2021-04-01|

---

CN108722163A|2018-11-02|

---

BR102018009209B1|2020-05-26|

---

JP6917337B2|2021-08-11|

---

CA3009243A1|2018-08-28|

---

US10112145B1|2018-10-30|

---

SG10201807441QA|2019-04-29|

---

MX2018005296A|2019-01-17|

---

MA49547A|2020-05-20|

---

CA3009243C|2019-11-05|

---

AR112527A1|2019-11-06|

---

IL273095D0|2020-04-30|

---

US20190070554A1|2019-03-07|

---

EP3401004A1|2018-11-14|

---

AU2018328418A1|2020-03-26|

---

CL2018001239A1|2018-07-06|

---

US10449488B2|2019-10-22|

---

JP2021094559A|2021-06-24|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2810627A|1953-02-26|1957-10-22|Texas Gulf Sulphur Co|Recovery of sulfur dioxide from gases and production of ammonium sulphate|

---

US3752877A|1969-08-27|1973-08-14|Parsons Co Ralph M|Recovery of sulfur compounds from tail gases|

---

US3645671A|1969-10-24|1972-02-29|Exxon Research Engineering Co|Flue gas desulfurization with ammonium sulfite|

---

JPS5513770B2|1973-09-26|1980-04-11|

---

US4250160A|1977-08-15|1981-02-10|Exxon Research & Engineering Co.|Production of ammonium sulfate|

---

US4378977A|1978-11-09|1983-04-05|Linde Aktiengesellschaft|Removal of undesired gaseous components from hot waste gases|

---

DE2943130A1|1978-11-09|1981-05-07|Linde Ag, 6200 Wiesbaden|METHOD FOR REMOVING UNWANTED GAS-SHAPED COMPONENTS FROM HOT EXHAUST GAS|

---

US4248842A|1979-03-05|1981-02-03|International Telephone & Telegraph Corporation|Removal of contaminants and recovery of by-products from hot waste gas stream|

---

US4324776A|1980-12-08|1982-04-13|General Electric Company|Mid-temperature H2 S removal process|

---

US4552747A|1984-06-20|1985-11-12|Gaa Engineered Systems, Inc.|Temperature moderation of an oxygen enriched Claus sulfur plant|

---

US4690807A|1985-08-15|1987-09-01|General Electric Environmental Services, Inc.|Process for the simultaneous absorption of sulfur oxides and production of ammonium sulfate|

---

US4777024A|1987-03-06|1988-10-11|Fuel Tech, Inc.|Multi-stage process for reducing the concentration of pollutants in an effluent|

---

DE3733319C2|1987-10-02|1989-09-14|Krupp Koppers Gmbh, 4300 Essen, De|

---

FR2625113B1|1987-12-23|1993-10-22|Rhone Poulenc Chimie|CATALYSTS FOR TREATMENT OF GASEOUS EFFLUENTS AND METHOD FOR TREATING SUCH EFFLUENTS|

---

US5019361A|1988-11-09|1991-05-28|Union Carbide Canada Limited|Removal and recovery of sulphur dioxide from gas streams|

---

US5342592A|1989-07-04|1994-08-30|Fuel Tech Europe Ltd.|Lance-type injection apparatus for introducing chemical agents into flue gases|

---

US5362458A|1993-03-22|1994-11-08|General Electric Environmental Services, Incorporated|Process for the simultaneous absorption of sulfur oxides and production of ammonium sulfate|

---

JPH08299755A|1995-05-01|1996-11-19|Nitto Kikai Kk|Flue gas desulfurization method and device therefor|

---

US5632967A|1995-09-19|1997-05-27|Goar, Allison & Associates, Inc.|Process for the high pressure degassing of hydrogen sulfide from liquid sulfur|

---

FR2740704B1|1995-11-03|1997-12-26|Elf Aquitaine|PROCESS FOR THE QUASI TOTAL ELIMINATION OF THE SULFUR H2S, SO2, COS AND / OR CS2 COMPOUNDS CONTAINED IN A RESIDUAL SULFUR PLANT GAS, WITH RECOVERY OF THE SAID COMPOUNDS IN THE FORM OF SULFUR|

---

US6991771B2|1996-10-09|2006-01-31|Powerspan Corp.|NOx, Hg, and SO2 removal using ammonia|

---

US6508998B1|1996-10-28|2003-01-21|Gaa Engineered Systems, Inc.|Temperature moderation of an oxygen enriched claus sulfur plant using an ejector|

---

DE19731062C2|1997-07-19|2001-07-12|Lurgi Lentjes Bischoff Gmbh|Process for the removal of acid gases from flue gases, in particular from power plant waste gases and waste gases from waste incineration plants|

---

US6066304A|1998-08-06|2000-05-23|Delores Pircon|Process for removing sulfur dioxide out of a gas|

---

US6221325B1|1998-09-08|2001-04-24|Marsulex Environmental Technologies, Llc|Process for controlling ammonia slip in the reduction of sulfur dioxide emission|

---

US6776974B1|1999-10-22|2004-08-17|Monsanto Enviro-Chem Systems, Inc.|Process for the production of sulfur|

---

CN1096285C|2000-07-17|2002-12-18|史汉祥|Special device for processing so2 containing fume|

---

GB0021409D0|2000-08-31|2000-10-18|Boc Group Plc|Treatment of a gas stream containing hydrogen sulphide|

---

US6531104B1|2000-11-21|2003-03-11|Alstom Ag|Process for the absorption of sulfur oxides and the production of ammonium sulfate|

---

US6569398B2|2001-04-30|2003-05-27|Gaa Engineered Systems, Inc.|Method for treating hydrogen sulfide-containing waste gases|

---

US20030059352A1|2001-08-07|2003-03-27|Maurice Karras|Process and apparatus for scrubbing sulfur dioxide from flue gas and conversion to fertilizer|

---

CN1164480C|2001-09-26|2004-09-01|南化集团研究院|Combined production of high concentration sulphuric acid by using acid gas containing hydrogen sulfide and sulphur|

---

AT391546T|2001-11-09|2008-04-15|Clean Diesel Tech Inc|CONTINUOUS ADJUSTABLE CONTROL OF ENVIRONMENTAL POLLUTION, REDUCING CHEMICALS FOR COMBUSTION SOURCES|

---

US6936231B2|2001-12-06|2005-08-30|Powerspan Corp.|NOx, Hg, and SO2 removal using ammonia|

---

CN1139422C|2001-12-30|2004-02-25|国家环境保护总局华南环境科学研究所|Wet urea additive process for simultanously desulfurizing and denitrification|

---

CN1251965C|2002-06-25|2006-04-19|南化集团研究院|Preparation of high-concntration surlfuric acid using hydrogen sulfide contained acidic gas|

---

CN1178735C|2002-09-09|2004-12-08|华东理工大学|Removing and recovering process and device for SO2 in flue gas|

---

NO323121B1|2003-07-22|2007-01-08|Knutsen Oas Shipping As|Method and apparatus for securing a vessel's cargo area against overpressure|

---

CN1283346C|2003-09-17|2006-11-08|镇江市江南环保设备研究所|Fuel coal smoke low oxidation rate desulfur method|

---

CN1321723C|2003-09-17|2007-06-20|镇江市江南环保设备研究所|Method of separating and recovering sulfur dioxide in smoke using ammonia method|

---

CN2640584Y|2003-09-17|2004-09-15|镇江市江南环保设备研究所|Integrated equipment for desulfurizing and discharging smoke|

---

CN2640585Y|2003-09-19|2004-09-15|镇江市江南环保设备研究所|Reinforced desulfurizing tower for smoke|

---

CN2668235Y|2003-09-19|2005-01-05|镇江市江南环保设备研究所|High-speed smoke gas desulfurizing tower|

---

EP3069780B1|2004-01-20|2018-04-11|Fluor Technologies Corporation|Methods for acid gas enrichment|

---

US7351392B2|2004-03-03|2008-04-01|Shell Oil Company|Process for the high recovery efficiency of sulfur from an acid gas stream|

---

CN100532250C|2004-03-03|2009-08-26|国际壳牌研究有限公司|Process for the high efficiency recovery of sulfur from an acid gas stream|

---

EA010173B1|2004-04-22|2008-06-30|Флуор Текнолоджиз Корпорейшн|Methods of converting cos-containing streams in claus plants|

---

EA012470B1|2004-11-09|2009-10-30|Флуор Текнолоджиз Корпорейшн|Configuration and method for so|

---

EA013217B1|2004-04-22|2010-04-30|Флуор Текнолоджиз Корпорейшн|Configurations amd methods for effluent gas treatment|

---

KR100599882B1|2004-06-08|2006-07-13|한국과학기술연구원|Desulfurization for simultaneous removal of hydrogen sulfide and sulfur dioxide|

---

CN2746972Y|2004-12-07|2005-12-21|镇江市江南环保设备研究所|Multi-functional and combination type desulfurization tower|

---

CN2746971Y|2004-12-07|2005-12-21|镇江市江南环保设备研究所|Desulfurization and denitration integrated flue-gas purification tower|

---

CN2772609Y|2004-12-07|2006-04-19|镇江市江南环保设备研究所|Oxidizing tower of smoke ammonia devulcanizer|

---

CN2754711Y|2004-12-07|2006-02-01|镇江市江南环保设备研究所|Smoke desulfurized filling tower from ammonia method|

---

CN2746973Y|2004-12-07|2005-12-21|镇江市江南环保设备研究所|Demister of nitrogen method desulfurization tower|

---

EP1871511A4|2005-04-20|2011-05-04|Fluor Tech Corp|Configurations and methods for claus plant operation with variable sulfur content|

---

CN2778373Y|2005-04-22|2006-05-10|胡恩龙|Ejection sieve plate absorber|

---

CN100428979C|2005-06-28|2008-10-29|江苏世纪江南环保有限公司|Ammonia desulfurizing process and apparatus with crystallization inside tower|

---

CN2799059Y|2005-06-28|2006-07-26|镇江市江南环保设备研究所|Inside-crystallizing ammonia-processed desulfurization tower|

---

CN2799060Y|2005-06-28|2006-07-26|镇江市江南环保设备研究所|Empty tower type ammonia processed desulfurization tower|

---

CN100395006C|2005-06-28|2008-06-18|江苏世纪江南环保有限公司|Void tower type ammonia desulfurizing process and apparatus|

---

CN100460045C|2006-05-31|2009-02-11|中国石油化工股份有限公司|Process for disposing SOx in discharge gas|

---

CN100475313C|2007-02-13|2009-04-08|西安中宇软件科技有限责任公司|Device for the recovery and diffluence of sulfur dioxide and the system and method thereof|

---

CN101274204B|2007-03-28|2011-06-22|成都华西化工研究所|Absorbing agent for removing and recovering sulfur dioxide from gaseous mixture|

---

CN100588608C|2007-04-30|2010-02-10|中国石油集团工程设计有限责任公司|The improvement low-temperature Claus sulfur recovery method|

---

CN201030298Y|2007-05-21|2008-03-05|江苏晟宜环保科技有限公司|One-segment type low-sulfur oxidizing catalyst reactor|

---

JP5121927B2|2007-06-21|2013-01-16|フルオー・テクノロジーズ・コーポレイシヨン|Air demand feedback control system and method for sulfur recovery unit|

---

CN201052456Y|2007-07-02|2008-04-30|江苏晟宜环保科技有限公司|Wrapped-tube catalytic oxidation reactor|

---

CN101085410A|2007-07-16|2007-12-12|娄爱娟|Method and device for reclaiming sulfur dioxide from countercurrent flue gas|

---

CN101352642A|2007-07-25|2009-01-28|上海智方环保工程有限公司|Flue gas desulfurization system by lime-sodium alkaline method|

---

CN201109711Y|2007-10-31|2008-09-03|镇海石化工程有限责任公司|Pool for storing underground liquid sulphur|

---

CN201129965Y|2007-11-20|2008-10-08|镇海石化工程有限责任公司|Sulfur condenser for sulfur recovery|

---

CN101274196B|2007-12-11|2010-12-08|镇海石化工程有限责任公司|Desulphurization method of amine liquid with high removal rate of hydrogen sulfide|

---

CN201132102Y|2007-12-11|2008-10-15|镇海石化工程有限责任公司|Ammine-burning device for recovering sulfur|

---

CN101456540B|2007-12-14|2012-07-25|山东三维石化工程股份有限公司|Liquid sulfur pool high temperature resistant and corrosion proof structure|

---

CN101182926B|2007-12-14|2011-01-26|镇海石化工程有限责任公司|Stove-fuel flow online control device and method thereof|

---

CN101274750B|2007-12-29|2010-06-30|江苏晟宜环保科技有限公司|Tail gas-recycled sulfur recovery method|

---

CN201179415Y|2008-02-14|2009-01-14|娄爱娟|Flue gas desulfurization purification column|

---

CN101576261B|2008-05-07|2011-05-11|北京丰汉工程咨询有限公司|Combustion and catalytic reduction method for acid gas|

---

CN101574614B|2008-05-07|2012-07-18|北京丰汉工程咨询有限公司|Desulphurization method for acid gas|

---

CN101575103A|2008-05-07|2009-11-11|北京丰汉工程咨询有限公司|Method for processing ammonium sulfate in acid gas desulfurization process|

---

CN201231130Y|2008-07-29|2009-05-06|中冶集团北京冶金设备研究设计总院|Flue gas desulfurization device for producing ammonia sulfate fertilizer|

---

CN101642629A|2008-08-08|2010-02-10|山东三维石化工程股份有限公司|Method for controlling amine solvent regeneration system|

---

DE102008050088A1|2008-10-06|2010-04-22|Uhde Gmbh|Process for desulfurization|

---

CN201320447Y|2008-10-27|2009-10-07|江苏新世纪江南环保有限公司|Integrated smoke purification device for desulphurization and denitration|

---

CN201333376Y|2008-11-14|2009-10-28|江苏新世纪江南环保有限公司|Flue gas desulfurization and denitration purifying device|

---

CN101422693A|2008-11-24|2009-05-06|贵州开磷（集团）有限责任公司|Sulphuric acid tail-gas deep desulfurization method|

---

CN101418246B|2008-12-05|2013-04-03|华陆工程科技有限责任公司|Low temperature methanol washing integrated Claus sulfur recovery system and process|

---

CN101456541B|2008-12-16|2011-05-25|山东三维石化工程股份有限公司|Selecting and packing method of catalyst for sulphur preparation|

---

CN201423237Y|2009-01-23|2010-03-17|江苏新世纪江南环保有限公司|Ammonia bubble crystallized flue gas desulfurizing device|

---

CN201380039Y|2009-01-23|2010-01-13|江苏新世纪江南环保有限公司|Double-tower flue gas desulphurization device|

---

CN201380038Y|2009-01-23|2010-01-13|江苏新世纪江南环保有限公司|Grid-type wet desulphurization device|

---

CN201380037Y|2009-01-23|2010-01-13|江苏新世纪江南环保有限公司|Flue-gas cleaner with functions of desulphurization, denitration, concentration and crystal|

---

CN201380040Y|2009-01-23|2010-01-13|江苏新世纪江南环保有限公司|Combined device for purifying coal-fired flue gas|

---

CN101530727B|2009-03-13|2012-11-07|北京航星世纪科技发展有限公司|Desulfurization process containing H<2>S acidic gas|

---

CN101519192B|2009-03-27|2011-02-09|成都赛普瑞兴科技有限公司|Low temperature Claus sulfur recovery process and device therefor|

---

CN101524620B|2009-04-13|2010-06-09|山西晋丰环保工程设计有限公司|Segment-based ammonia method flue gas desulfurization device|

---

CN101579600B|2009-05-04|2011-04-20|何金整|Ammonia desulfurization technology and device utilizing high potential energy|

---

CN101884872A|2009-05-13|2010-11-17|张波|Double-oxidation, double-loop and double-demisting desulfurization tower and processing device|

---

CN101579602B|2009-06-12|2011-05-04|山西晋丰环保工程设计有限公司|Energy-saving and high-quality ammonia desulphurization process for ammonia sulfate recovery|

---

CN101585511A|2009-06-25|2009-11-25|中国石油化工集团公司|Sulfur recycling technique|

---

CN101670231B|2009-07-23|2011-08-24|何金整|Device and process for converting calcium process desulfurization into temperature difference crystallizing ammonia process desulfurization|

---

CN201492952U|2009-08-12|2010-06-02|江苏新世纪江南环保有限公司|Flue gas heat source heat pipe-type evaporation device of byproduct in ammonia process of flue gas desulfurization|

---

CN201537456U|2009-08-12|2010-08-04|江苏新世纪江南环保有限公司|Flue gas heat exchange type evaporator of flue gas desulfurization side product by ammonia method|

---

CN101637685B|2009-08-24|2012-07-18|成都德美工程技术有限公司|Comprehensive treatment method of sulfur-containing flue gas|

---

CN102019186A|2009-09-10|2011-04-20|湖北双剑催化剂有限公司|New process for medium-temperature high-pressure sulfur tolerant shift catalyst|

---

CN102049186B|2009-10-27|2013-01-23|中国石油化工股份有限公司|Method for desulfurizing high-concentration flue gas|

---

CN201529488U|2009-10-30|2010-07-21|江苏新世纪江南环保有限公司|Gas ammonia washing combined sintering smoke desulphurization device|

---

CN201529487U|2009-10-30|2010-07-21|江苏新世纪江南环保有限公司|Gas cleaning device for liquid phase catalysis de-nitration|

---

CN101745303A|2009-12-30|2010-06-23|王建敏|Improved smoke removal purifier|

---

DE102010013052A1|2010-03-22|2011-09-22|Uhde Gmbh|Apparatus and method for the condensation, separation and storage of liquid sulfur in a Claus plant|

---

CN102205202A|2010-03-29|2011-10-05|北京丰汉工程咨询有限公司|Processing method for acid gas containing H2S|

---

US20110243822A1|2010-03-31|2011-10-06|Airborne Technologies Inc.|Flue gas clean up methods|

---

CN102211762B|2010-04-06|2012-11-21|山东三维石化工程股份有限公司|Method for preparing sulfur and processing tail gas by taking ammonium bisulfite as intermediate|

---

CN101791517B|2010-04-08|2012-05-23|北京至清时光环保工程技术有限公司|Method for recycling sulfur from acid gases containing hydrogen sulfide|

---

US8444943B2|2010-04-30|2013-05-21|Black & Veatch Corporation|Methods and apparatus for sulfur recovery from acid gases|

---

US8206669B2|2010-07-27|2012-06-26|Air Products And Chemicals, Inc.|Method and apparatus for treating a sour gas|

---

CN102381685A|2010-08-25|2012-03-21|中国石油化工股份有限公司|Degassing technique for liquid sulfur|

---

CN101934191B|2010-09-06|2013-01-09|江苏新世纪江南环保股份有限公司|Method for desulfurizing and denitrating smoke simultaneously through ammonia method|

---

CN101955828B|2010-09-07|2012-11-21|山东三维石化工程股份有限公司|Method for removing hydrogen sulfide from natural gas|

---

CN101972592B|2010-09-08|2012-12-05|江苏新世纪江南环保股份有限公司|Process for removing smoke dust by wet ammonia flue gas desulphurization and device thereof|

---

CN102451604A|2010-10-18|2012-05-16|袁俊海|Secondary Claus and SCOT tail gas treatment process|

---

CN201880482U|2010-11-19|2011-06-29|上海弗卡斯环保工程有限公司|Stepped spray tower for desulfurization by ammonia method|

---

CN102000490B|2010-11-25|2012-07-25|东南大学|Control method for aerosol in flue gas desulfurization by utilizing ammonia method and master desulfurizing tower|

---

CN102061206A|2010-12-02|2011-05-18|山东三维石化工程股份有限公司|Pressure reduction gas desulfurization method|

---

CN102012034A|2010-12-06|2011-04-13|山东三维石化工程股份有限公司|Multifunctional exhaust incinerator for sulfur recovery facility|

---

CN201944861U|2010-12-06|2011-08-24|山东三维石化工程股份有限公司|Multifunctional tail gas incinerator for sulfur recovery unit|

---

US8361432B2|2010-12-08|2013-01-29|Fluor Enterprises, Inc.|Reactor, a retained catalyst structure, and a method for improving decomposition of polysulfides and removal of hydrogen sulfide in liquid sulfur|

---

PL2463014T3|2010-12-10|2018-10-31|General Electric Technology Gmbh|A wet scrubber comprising deflector plates, and a method of cleaning a process gas|

---

CN201912884U|2011-01-06|2011-08-03|江苏新世纪江南环保有限公司|Ammonia desulfurizer with two-level gas distributors|

---

CN201912885U|2011-01-06|2011-08-03|江苏新世纪江南环保有限公司|Desulfurizing and impurity removing integrated purifying device for sintering flue gas|

---

CN201949808U|2011-01-12|2011-08-31|江苏新世纪江南环保有限公司|Flue gas desulfurization device for realizing online oil and dust separation|

---

US8329128B2|2011-02-01|2012-12-11|Alstom Technology Ltd|Gas treatment process and system|

---

CN102092688A|2011-02-12|2011-06-15|李金山|Technological process for producing acid with sulfur-containing gas|

---

CN102120137B|2011-02-16|2012-12-26|安徽淮化股份有限公司|System and process for capturing and absorbing sulfur dioxide and carbon dioxide at normal pressure by using ammonia method|

---

CN102198365B|2011-05-11|2013-07-24|北京丰汉工程咨询有限公司|Processing method of acid gas|

---

JP5755047B2|2011-06-22|2015-07-29|三菱重工業株式会社|Exhaust gas treatment system and exhaust gas treatment method|

---

CN102381686A|2011-07-29|2012-03-21|山东三维石化工程股份有限公司|Treatment process of high-ammonia and low-sulfur gas|

---

CN102423613B|2011-08-23|2013-10-02|武汉兴能环保技术有限公司|Ammonia desulfurization method for effectively removing chlorine and fluorine ions and heavy metal ions|

---

CN102380305A|2011-09-30|2012-03-21|合肥宁垣工程技术有限责任公司|Technology and apparatus for desulphurizing acidic gas|

---

CN102423597B|2011-10-14|2014-06-11|华南理工大学|Intelligent anti-blocking demister used for wet flue gas desulfurization|

---

CN202538627U|2011-12-27|2012-11-21|合肥宁垣工程技术有限责任公司|Device for removing desulfurization and denitration aerosol|

---

CN202460375U|2012-01-04|2012-10-03|江苏新世纪江南环保股份有限公司|Desulfurated dust-laden tail gas washing and recovering device|

---

CN202460420U|2012-01-04|2012-10-03|江苏新世纪江南环保股份有限公司|Breathing bucket device for purifying tail gas exhausted by storage tank|

---

CN202460438U|2012-01-04|2012-10-03|江苏新世纪江南环保股份有限公司|Desulfurizing liquid oxidation and purification combined device|

---

CN102489140B|2012-01-04|2013-12-25|江苏新世纪江南环保股份有限公司|Flue gas desulphurization and denitration reactant integrated supply method and apparatus|

---

CN102631827A|2012-04-11|2012-08-15|山东三维石化工程股份有限公司|Zero-emission sulfur recovery technology combined with low-temperature methanol washing acid gas treatment|

---

CN202912691U|2012-06-15|2013-05-01|洛阳瑞泽石化工程有限公司|Liquid sulfur collector for sulfur recovery device|

---

CN202725003U|2012-06-28|2013-02-13|北京中科创新园环境技术有限公司|Compound type multifunctional ammonia desulphurization device|

---

CN103521060B|2012-07-04|2017-01-25|江苏新世纪江南环保股份有限公司|Method for desulfurization of sulfur recovery tail gas by using boiler flue gas ammonia method|

---

CN202754802U|2012-07-23|2013-02-27|重庆万盛煤化有限责任公司|Sulphur coal claus sulfur recovery system|

---

CN202829575U|2012-08-06|2013-03-27|中国石油化工股份有限公司|Sulfur recycling device|

---

CN202751942U|2012-08-08|2013-02-27|上海河图工程股份有限公司|Sulphur tail gas absorption and purification combined device|

---

CN102847431B|2012-08-14|2014-10-22|北京丰汉工程咨询有限公司|Method for treating claus technical tail gas|

---

CN202924730U|2012-09-05|2013-05-08|山东三维石化工程股份有限公司|Inner floating ball type sulfur sealing tank|

---

CN102872709A|2012-09-17|2013-01-16|江苏和亿昌环保工程科技有限公司|Process of efficiently capturing aerosol in desulfurized flue gas|

---

CN103663386B|2012-09-19|2015-05-20|中国石油化工股份有限公司|Method for reducing SO2 emission concentration of sulfur device|

---

CN102895870B|2012-09-28|2015-03-04|美景（北京）环保科技有限公司|Treatment system and treatment method for removing hydrogen sulfide from acid gas|

---

CN102910593B|2012-10-30|2014-09-17|美景（北京）环保科技有限公司|System and method for treating waste acid gas|

---

CN102908890A|2012-11-15|2013-02-06|王正中|Device for preventing ammonia escape in ammonia desulfurization and denitration of flue gases|

---

CN102923670B|2012-11-22|2015-03-04|山东三维石化工程股份有限公司|Liquid sulfur degasification process|

---

CN102942162B|2012-12-06|2014-08-13|山东三维石化工程股份有限公司|Liquid-phase treatment process of tail gas from sulfur recovery|

---

CN202953829U|2012-12-11|2013-05-29|内蒙古大唐国际克什克腾煤制天然气有限责任公司|Acid gas desulfurizing device|

---

CN103041679B|2013-01-15|2015-02-04|美景（北京）环保科技有限公司|Waste gas treatment system of acid gas containing ammonia|

---

CN103112831B|2013-02-26|2015-05-13|镇海石化工程股份有限公司|Liquid sulphur degassing device and liquid sulphur degassing method|

---

CN203159221U|2013-03-19|2013-08-28|镇海石化工程股份有限公司|Supporting structure for sulfur reactor|

---

CN103223292B|2013-04-15|2015-04-22|江苏新世纪江南环保股份有限公司|Ammonia process flue gas treatment method for acidic tail gas and device|

---

US9370745B2|2013-04-24|2016-06-21|Jiangsu New Century Jiangnan Environmental Protection Co., Ltd|Flue gas-treating method and apparatus for treating acidic tail gas by using ammonia process|

---

CN103204477B|2013-04-25|2014-10-15|山东三维石化工程股份有限公司|Liquid sulphur collecting method for sulfur recovery|

---

CN203264545U|2013-04-25|2013-11-06|江苏新世纪江南环保股份有限公司|Ammonia escape preventing device used in flue gas ammonia desulphurization and denitrification process|

---

CN104138713A|2013-05-10|2014-11-12|杭州林达化工技术工程有限公司|Method, device and reactor for recovery of sulfur from acidic gas|

---

CN103263841B|2013-05-27|2015-06-10|史秦博苑|Method for removing aerosol in ammonia washing desulphurization of flue gas|

---

CN103301705B|2013-06-06|2015-08-19|江苏新世纪江南环保股份有限公司|A kind of desulfurization fume fine particulates control device and method|

---

CN203291675U|2013-06-19|2013-11-20|江苏新世纪江南环保股份有限公司|Flue gas desulfurization absorber with aerosol controlling function|

---

CN103301732B|2013-06-20|2015-01-21|义马煤业集团煤生化高科技工程有限公司|Device and process for recycling and treating hydrogen sulfide-containing chemical acid waste gas|

---

CN203329558U|2013-06-20|2013-12-11|江苏新世纪江南环保股份有限公司|Wet-type flue gas desulfurization tail gas repurifying device|

---

CN104249995B|2013-06-25|2016-04-13|中国石油化工股份有限公司|Reduce sulfur recovery facility SO 2the method of emission concentration|

---

CN103418223A|2013-07-26|2013-12-04|新汶矿业集团有限责任公司|Comprehensive desulphurization technology in coal chemical industry|

---

CN103463949B|2013-08-08|2015-12-23|江苏新世纪江南环保股份有限公司|The method and apparatus of a kind of flue gas desulphurization system process greasy dirt, flue dust|

---

CN103482583B|2013-09-10|2015-09-02|山东三维石化工程股份有限公司青岛分公司|SWSR-1 sulfur recovery technology|

---

CN103446859B|2013-09-12|2014-10-29|中国海洋石油总公司|Treatment method of acid gases in coal-made natural gas|

---

DE102013015280A1|2013-09-16|2015-03-19|Rwe Power Aktiengesellschaft|Process and system for gas scrubbing of aerosol-containing process gases|

---

CN203612955U|2013-09-26|2014-05-28|上海河图工程股份有限公司|Liquid sulfur degassing device|

---

US9364781B2|2013-10-11|2016-06-14|Alstom Technology Ltd|Method and apparatus for wet desulfurization spray towers|

---

CN104555939A|2013-10-15|2015-04-29|中国石油化工股份有限公司|Purified gas treatment process of sulfur recovery device|

---

CN104555940B|2013-10-15|2016-08-17|中国石油化工股份有限公司|Reduce the recovery technology of sulfur of sulfur dioxide emissions|

---

CN105642098B|2013-12-03|2018-08-31|张波|A kind of desulfurization denitration method|

---

CN103721553A|2014-01-07|2014-04-16|江苏新世纪江南环保股份有限公司|Method for efficiently removing acid gas sulfide by ammonia process desulfurization technique|

---

CN103822217B|2014-02-14|2016-06-01|江苏新世纪江南环保股份有限公司|A kind of sour gas pretreatment technology|

---

CN103939918B|2014-04-11|2017-01-25|江苏新世纪江南环保股份有限公司|Incineration method for acid gas and liquid purification|

---

CN204352660U|2014-04-16|2015-05-27|南京新世纪江南环保科技发展有限公司|The special demister of a kind of high-efficiency ammonia desulfurization|

---

CN203781842U|2014-04-18|2014-08-20|中石化南京工程有限公司|New sulfur recovery device|

---

CN104259713B|2014-09-12|2016-02-17|江苏创力电梯部件有限公司|Traction machine supporting component welding tooling|

---

CN104208992B|2014-09-17|2017-02-01|宁波市化工研究设计院有限公司|Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur|

---

CN204151066U|2014-09-18|2015-02-11|中石化南京工程有限公司|A kind of sulphur recovery new device processing alkylation spent acid|

---

CN104258713B|2014-10-08|2017-02-15|美景（北京）环保科技有限公司|Acid gas treatment system and method based on ammonia-process desulfurization|

---

CN204134465U|2014-10-08|2015-02-04|美景（北京）环保科技有限公司|A kind of Acidic Gas Treating system based on the ammonia process of desulfurization|

---

CN104368231A|2014-10-10|2015-02-25|江苏新世纪江南环保股份有限公司|Method for controlling chlorine / fluorine content in flue gas desulfurization absorption liquid|

---

CN204233957U|2014-10-30|2015-04-01|中国石油化工股份有限公司|A kind of novel sulfurizedization hydrogen waste gas pollution control and treatment system|

---

CN204198421U|2014-11-14|2015-03-11|镇海石化工程股份有限公司|A kind of molten sulfur pond gas recovery system|

---

CN104353258B|2014-11-18|2016-01-06|镇海石化工程股份有限公司|Subtract top pumped vacuum systems and technique|

---

CN104528659B|2014-12-17|2017-04-12|田晓良|Sulfur recycling process for circularly treating low-concentration acidy gas by utilizing liquid sulfur|

---

CN104524948B|2015-01-08|2016-09-07|江苏新世纪江南环保股份有限公司|A kind of ultrasonic wave desulphurizing and dust-removing integral minimum discharge method|

---

CN104946296A|2015-05-18|2015-09-30|江苏新世纪江南环保股份有限公司|Gasoline-oxidation ammonia-process desulfurization method|

---

CN104927894A|2015-05-18|2015-09-23|江苏新世纪江南环保股份有限公司|Diesel oxidation ammonia desulfurization method|

---

CN104923046A|2015-05-20|2015-09-23|江苏新世纪江南环保股份有限公司|Coke oven flue gas desulfurization, denitration and waste heat recovery integrated method|

---

CN108176224A|2015-05-20|2018-06-19|江苏新世纪江南环保股份有限公司|A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method and device|

---

CN105110819B|2015-07-22|2019-04-05|江苏新世纪江南环保股份有限公司|A method of sulfenyl urea compound fertilizer is produced using ammonia process of desulfurization by-product|

---

CN105126573B|2015-07-22|2017-10-13|江苏新世纪江南环保股份有限公司|A kind of a variety of acid gas integral ammonia method desulfurizing methods of oil refining apparatus|

---

CN105148712B|2015-10-10|2017-11-14|中石化南京工程有限公司|A kind of classification Absorption Desulfurization device of ammoniacal ammonium sulphate method|

---

CN105195002A|2015-10-19|2015-12-30|云南亚太环境工程设计研究有限公司|Ammonia process type double-cycle desulfurization and denitrification dust removal system|

---

CN205562498U|2015-12-15|2016-09-07|南京新世纪江南环保科技发展有限公司|Sealed pH meter interface|

---

CN205257271U|2015-12-17|2016-05-25|江苏常州酞青新材料科技有限公司|Feeding machine mechanism|

---

CN205549846U|2015-12-17|2016-09-07|南京新世纪江南环保科技发展有限公司|Double -deck defroster subassembly|

---

CN205235588U|2015-12-17|2016-05-18|南京新世纪江南环保科技发展有限公司|Defroster mounting|

---

CN205252721U|2015-12-17|2016-05-25|南京新世纪江南环保科技发展有限公司|Double -deck defroster subassembly of buckle blade|

---

CN205252720U|2015-12-17|2016-05-25|南京新世纪江南环保科技发展有限公司|House rigde mounting structure of defroster module|

---

CN205252722U|2015-12-17|2016-05-25|南京新世纪江南环保科技发展有限公司|Defroster subassembly|

---

CN205262780U|2015-12-29|2016-05-25|南京新世纪江南环保科技发展有限公司|Can sealed thief hatch|

---

CN205245200U|2015-12-29|2016-05-18|南京新世纪江南环保科技发展有限公司|Chimney water smoke connects and draws dish|

---

CN105841168A|2016-03-23|2016-08-10|江苏新世纪江南环保股份有限公司|Integrated treatment method for malodorous VOCs gas of refining devices|

---

CN105757688A|2016-03-23|2016-07-13|江苏新世纪江南环保股份有限公司|Method and system for treating VOCs gas in sewage treatment plant|

---

CN108144428A|2017-03-15|2018-06-12|江苏新世纪江南环保股份有限公司|A kind of method and device of ammonia process efficient removal gas sulphur oxide and dirt|

---

CN106955574A|2017-03-27|2017-07-18|江苏科行环保科技有限公司|A kind of flue gas ammonia method desulfurizing multi-region oxidation technology and device|

---

CN107213769B|2017-05-25|2019-09-20|江苏新世纪江南环保股份有限公司|A kind of ammonia method desulfurizing method and device of locellus ammonification|

---

CN108722163B|2017-09-07|2019-06-07|江苏新世纪江南环保股份有限公司|A kind of method that ammonia process of desulfurization control absorption process aerosol generates|

---

CN109045981A|2018-09-29|2018-12-21|石家庄宇清环保科技有限公司|A kind of ammonia process of desulfurization High-efficiency oxidation device|CN108722163B|2017-09-07|2019-06-07|江苏新世纪江南环保股份有限公司|A kind of method that ammonia process of desulfurization control absorption process aerosol generates|

---

EP3421115A3|2017-09-22|2019-05-01|Jiangnan Environmental Protection Group Inc.|Apparatus and method for ammonia-based desulfurization|

---

CN109806751B|2019-03-25|2021-08-24|周岩|Low-energy-consumption coal-fired boiler flue gas whitening system|

---

CN110201508A|2019-05-09|2019-09-06|山东明晟化工工程有限公司|A kind of the escaping of ammonia and ammonia process of desulfurization aerosol combination treatment method|

---

CN110975575A|2019-12-12|2020-04-10|宾采尔环境技术有限公司|Spray tower for industrial waste gas treatment and spray method thereof|

---

CN110935279A|2019-12-19|2020-03-31|济宁明升新材料有限公司|Heat pump type white smoke eliminating device and method thereof|

---

CN111957183A|2019-12-26|2020-11-20|江苏新世纪江南环保股份有限公司|Improved ammonia desulphurization method for controlling aerosol generation in absorption process|

---

CN111167293A|2020-01-07|2020-05-19|无锡市华星电力环保修造有限公司|Method and equipment for FWGD cooperative fine particulate matter and SO3 removal|

---

CN111111413A|2020-01-13|2020-05-08|江苏远东环保工程有限公司|Desulfurization system and process for ultralow emission of waste gas in carbon black industry|

---

US20210370227A1|2020-05-26|2021-12-02|ThioSolv, LLC|Process for removal of sulfur dioxide and ammoniafrom a vent gas stream|

---

CN111659237A|2020-06-16|2020-09-15|王波|Energy-saving environment-friendly integrated flue gas purification and dust removal device and method thereof|

---

CN111939726A|2020-07-17|2020-11-17|淮阴工学院|Filler absorption tower and application method thereof|

---

CN112023648A|2020-08-18|2020-12-04|衡阳百赛化工实业有限公司|Secondary zinc oxide production line tail gas desulphurization unit|

---

CN113262625A|2021-05-11|2021-08-17|江苏新世纪江南环保股份有限公司|Ammonia desulphurization and decarburization integrated device and method|

法律状态:
2018-10-23| B03B| Publication of an application: publication anticipated [chapter 3.2 patent gazette]|

---

2019-01-29| B27A| Filing of a green patent (patente verde)|

---

2019-02-26| B27B| Request for a green patent granted|

---

2019-07-02| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

---

2019-12-10| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

---

2020-04-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-05-26| 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 07/05/2018, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

CN201710800599.0|2017-09-07|

---

CN201710800599.0A|CN108722163B|2017-09-07|2017-09-07|A kind of method that ammonia process of desulfurization control absorption process aerosol generates|

---

US15/923,031|2018-03-16|

---

US15/923,031|US10112145B1|2017-09-07|2018-03-16|Method for controlling aerosol production during absorption in ammonia desulfurization|BR122018069706-7A| BR122018069706B1|2017-09-07|2018-05-07|METHOD TO CONTROL AEROSOL PRODUCTION DURING ABSORPTION OF SULFUR DIOXIDE FROM A DISCHARGE GAS|