TW202007435A - Oxidation method and device of ammonia desulfurization solution achieving multi-stage circulation of absorption liquid and controlling the generation of aerosols during the ammonia desulfurization process - Google Patents
Oxidation method and device of ammonia desulfurization solution achieving multi-stage circulation of absorption liquid and controlling the generation of aerosols during the ammonia desulfurization process Download PDFInfo
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本發明屬於環保技術領域，具體涉及一種用於對氨法脫硫溶液進行氧化處理的方法和裝置。本發明還涉及這種裝置的運行方法。The invention belongs to the technical field of environmental protection, and in particular relates to a method and a device for oxidizing an ammonia desulfurization solution. The invention also relates to a method of operating such a device.
世界各國都不同程度排放二氧化硫，中國二氧化硫排放量大，對環境和社會造成一定影響。排放的二氧化硫除了造成經濟損失之外，還嚴重影響生態環境和人民健康。Countries in the world emit sulfur dioxide to varying degrees. China has a large amount of sulfur dioxide emissions, which has a certain impact on the environment and society. In addition to causing economic losses, the emitted sulfur dioxide also seriously affects the ecological environment and people's health.
目前比較成熟的脫硫技術達上百種，其中，濕法脫硫製程應用最廣，占世界脫硫總裝機容量的85%左右。常見的濕法煙氣脫硫技術有石灰石―石膏法、雙鹼法、碳酸鈉法、氨法、氧化鎂法等。氨法脫硫是採用氨作為吸收劑的一種濕法脫硫製程，該法可利用SO2 生產硫酸銨化肥，是一種低能耗、高附加值、實現資源循環利用的綠色煙氣治理方案。化工行業在生產過程中有大量可利用的氨水產生，因此化工行業鍋爐尾氣採用氨法脫硫有其獨特的優勢。There are hundreds of mature desulfurization technologies. Among them, the wet desulfurization process is the most widely used, accounting for about 85% of the world's total desulfurization installed capacity. Common wet flue gas desulfurization technologies include limestone-gypsum method, double alkali method, sodium carbonate method, ammonia method, magnesium oxide method, etc. Ammonia desulfurization is a wet desulfurization process that uses ammonia as an absorbent. This method can use SO 2 to produce ammonium sulfate fertilizers. It is a green flue gas treatment plan with low energy consumption, high added value, and resource recycling. A large amount of available ammonia is produced in the chemical industry during the production process. Therefore, the ammonia industry desulfurization of boiler tail gas in the chemical industry has its unique advantages.
氨法脫硫過程主要分吸收、氧化、濃縮（結晶）三個過程，首先用亞硫酸銨吸收二氧化硫得到亞硫酸銨與亞硫酸氫銨混合溶液，其中的亞硫酸氫銨在加氨中和之後又得到亞硫酸銨。二氧化硫的吸收和加氨中和過程可以通過以下化學式簡化地表達： (NH4 )2 SO3 + H2 O + SO2 = 2NH4 HSO3 (NH4 )X H(2-x)SO3 + (2-x)NH3 = (NH4 )2 SO3 在氧化過程中，對溶液通入氧化空氣，將亞硫酸（氫）銨氧化，得到硫酸（氫）銨： (NH4 )2 SO3 + 1/2O2 = (NH4 )2 SO4 硫酸銨溶液經濃縮、結晶、固液分離、乾燥即得最終產品硫酸銨。The ammonia desulfurization process is divided into three processes: absorption, oxidation, and concentration (crystallization). First, ammonium sulfite is used to absorb sulfur dioxide to obtain a mixed solution of ammonium sulfite and ammonium bisulfite. The ammonium bisulfite is neutralized by adding ammonia Ammonium sulfite is also obtained. The process of sulfur dioxide absorption and ammonia addition neutralization can be simplified by the following chemical formula: (NH 4 ) 2 SO 3 + H 2 O + SO 2 = 2NH 4 HSO 3 (NH 4 ) X H(2-x)SO 3 + (2-x)NH 3 = (NH 4 ) 2 SO 3 In the oxidation process, the solution is fed with oxidizing air to oxidize (hydrogen) ammonium sulfite to obtain (NH 4 ) 2 SO 3 + 1/2O 2 = (NH 4 ) 2 SO 4 ammonium sulfate solution is concentrated, crystallized, solid-liquid separated, and dried to obtain the final product ammonium sulfate.
氨法脫硫使用氨作為吸收劑，吸收廢氣中的二氧化硫後產生亞硫酸氫銨和亞硫酸銨溶液，該溶液是易分解和不穩定的，因此需要將其氧化成硫酸氫銨和硫酸銨溶液。氨法脫硫主要步驟之一就是將脫硫吸收液中的亞硫酸（氫）銨氧化成硫酸（氫）銨。如果氧化不徹底，會影響煙氣中的SO2 回收率，容易產生氣溶膠。Ammonia desulfurization uses ammonia as an absorbent to produce ammonium bisulfite and ammonium sulfite solution after absorbing sulfur dioxide in exhaust gas. This solution is easily decomposed and unstable, so it needs to be oxidized into ammonium bisulfate and ammonium sulfate solution . One of the main steps of ammonia desulfurization is to oxidize the (hydrogen) ammonium sulfite in the desulfurization absorbent to ammonium (hydrogen) sulfate. If the oxidation is not thorough, it will affect the recovery rate of SO 2 in the flue gas and easily generate aerosol.
亞硫酸銨氧化是氨法脫硫的主要步驟之一，亞硫酸銨氧化和其他亞硫酸鹽相比明顯不同，一定濃度下，NH4 + 對氧化過程有阻尼作用。文獻Chemical Engineering Science，2000，Volume 55, Issue 23, December 2000, Pages 5637-5641, Pergamon Press, Oxford, England, 2000闡述了這一獨特性質，NH4 + 顯著阻礙O2 在水溶液中的溶解。當鹽濃度小於0.5mol/L即約5(重量)%時，亞硫酸銨氧化速率隨其濃度增加而增加，而當超過這個極限值時，氧化速率隨濃度增加而降低。Ammonium sulfite oxidation is one of the main steps of ammonia desulfurization. Ammonium sulfite oxidation is obviously different from other sulfites. At a certain concentration, NH 4 + has a damping effect on the oxidation process. The literature Chemical Engineering Science, 2000, Volume 55, Issue 23, December 2000, Pages 5637-5641, Pergamon Press, Oxford, England, 2000 describes this unique property, NH 4 + significantly hinders the dissolution of O 2 in aqueous solution. When the salt concentration is less than 0.5 mol/L, that is, about 5% by weight, the oxidation rate of ammonium sulfite increases as the concentration increases, and when this limit is exceeded, the oxidation rate decreases as the concentration increases.
亞硫酸銨的氧化過程即是亞硫酸銨與氧氣結合產生硫酸銨的過程，低濃度的亞硫酸銨較容易氧化，具有較高的氧化速率，但在亞硫酸銨或硫酸銨濃度較高的溶液中，亞硫酸銨的氧化速率較低，受漿液溫度、O/S比、氣液接觸面積、pH值、鹽濃度、氧氣溶解速率等多種因素影響。The oxidation process of ammonium sulfite is the process of combining ammonium sulfite and oxygen to produce ammonium sulfate. Low concentration ammonium sulfite is easier to oxidize and has a higher oxidation rate, but in a solution with a higher concentration of ammonium sulfite or ammonium sulfate Among them, the oxidation rate of ammonium sulfite is low, which is affected by various factors such as slurry temperature, O/S ratio, gas-liquid contact area, pH value, salt concentration, and oxygen dissolution rate.
溶液中氧氣的溶解速率越高，對亞硫酸銨的氧化越有利。氧氣在水中的溶解度很小，在標準狀態下，每100cm3 的水可溶解3.08cm3 氧氣，在50℃時可溶解2.08cm3 氧氣。在含有高濃度的硫酸銨鹽溶液中，溶液的黏度遠大於水，氧氣的溶解度和溶解速率更低。如何提高氧氣在含有硫酸銨鹽溶液中的利用率、降低氧化空氣用量和壓力是亞硫酸銨氧化的一個難題。The higher the dissolution rate of oxygen in the solution, the more beneficial it is to the oxidation of ammonium sulfite. Oxygen solubility in water is very small, in the standard state, per 100cm 3 of water soluble 3.08cm 3 oxygen, dissolved oxygen 2.08cm 3 at 50 ℃. In a solution containing a high concentration of ammonium sulfate, the viscosity of the solution is much greater than that of water, and the solubility and dissolution rate of oxygen are lower. How to improve the utilization rate of oxygen in the solution containing ammonium sulfate, reduce the amount and pressure of oxidized air is a problem of ammonium sulfite oxidation.
亞硫酸銨氧化反應實際上在吸收過程中也會產生，只不過由於煙氣中O2 含量低，溫度低，反應速度慢，在不斷循環的條件下，氧化率一般為40-70%。這種氧化率是不足夠的，需要將氧化率進一步提高到90%以上，以滿足後處理加工要求。這存在較大的難度。在先前技術中普遍使用氧化槽/氧化段/噴射氧化器，部分技術商選擇往吸收液中加入催化劑來促進氧化，但這樣會影響產品的質量。The ammonium sulfite oxidation reaction actually occurs during the absorption process, but due to the low O 2 content in the flue gas, the temperature is low, and the reaction speed is slow. Under the condition of continuous circulation, the oxidation rate is generally 40-70%. This oxidation rate is not sufficient, and the oxidation rate needs to be further increased to more than 90% to meet the post-processing requirements. This is more difficult. In the prior art, oxidation tanks/oxidation sections/jet oxidizers are commonly used, and some technicians choose to add a catalyst to the absorption liquid to promote oxidation, but this will affect the quality of the product.
中國發明專利申請CN103212348A提出一種亞硫酸銨的氧化製程及裝置，該裝置包括底部帶有漿液排出泵的氧化槽，還包括：與該氧化槽頂部連通的加氨管道；設置在該氧化槽內且位於下部的氧化風管；設置在該氧化槽內且位於中部的若干層間隔佈置的多孔板。在此，將亞硫酸銨漿液送入漿液槽中，加氨水調節該亞硫酸銨漿液的pH值為6~8，再從氧化槽的頂部送入氧化槽中，該亞硫酸銨漿液從氧化槽的頂部緩慢流向氧化槽的底部；氧化空氣經氧化風管射流成小氣泡進入硫酸銨漿液中，再經多孔板破碎後與硫酸銨漿液接觸進行氧化反應；氧化反應結束後由漿液排出泵泵出。在此，多孔板設置為2～5層，每層間距為1～4m，多孔板的孔徑為2~20mm，孔心距為孔徑的2~5倍，亞硫酸銨漿液在氧化槽中的停留時間為10~60min，氧化空氣的風量滿足氧化過程中O/S比為2~5。該製程及裝置存在氧化空氣用量大、氧化時間長、氧化率難以保證、氧化pH高導致氨逃逸、產生氣溶膠等缺點。Chinese invention patent application CN103212348A proposes an ammonium sulfite oxidation process and device. The device includes an oxidation tank with a slurry discharge pump at the bottom, and also includes: an ammonia addition pipe connected to the top of the oxidation tank; Oxidation air duct located at the lower part; several layers of porous plates arranged in the oxidation tank and located in the middle. Here, the ammonium sulfite slurry is sent to the slurry tank, and ammonia water is added to adjust the pH value of the ammonium sulfite slurry to 6-8, and then sent to the oxidation tank from the top of the oxidation tank, and the ammonium sulfite slurry is sent from the oxidation tank The top of the pump slowly flows to the bottom of the oxidation tank; the oxidized air jets into small bubbles through the oxidizing air pipe and enters into the ammonium sulfate slurry, and then is crushed by the porous plate to contact the ammonium sulfate slurry for oxidation reaction; after the oxidation reaction is completed, the slurry is discharged from the pump . Here, the perforated plate is set to 2 to 5 layers, the distance between each layer is 1 to 4m, the pore size of the perforated plate is 2 to 20mm, the hole center distance is 2 to 5 times the pore size, and the ammonium sulfite slurry stays in the oxidation tank The time is 10~60min, and the air volume of the oxidized air meets the O/S ratio of 2~5 during the oxidation process. The process and the device have the disadvantages of large amount of oxidized air, long oxidation time, difficult to guarantee the oxidation rate, high oxidation pH leading to ammonia escape, and aerosol generation.
中國發明專利申請CN1408464A提出一種煙氣中SO2 的脫出和回收方法及裝置，其中，控制亞硫酸銨的濃度在0.1~5(重量)%之間，最好在0.5~2.0(重量)%之間，以創造最有利於氧化的條件，降低氧化的能耗和投資。在此，產生的亞硫酸銨溶液與空氣進行氧化反應，得到硫酸銨溶液。壓縮空氣的壓力一般在0.05~0.2Mpa(表壓)，壓縮空氣的流量是亞硫酸銨氧化理論需要量的1～5倍，常見的是2~4倍，氧化反應停留時間一般在1～3小時之間，最好在2小時左右。在此條件下，氧化率可大於95%。硫酸銨溶液的濃度一般為5~20(重量)%。該製程存在氧化空氣用量大、氧化時間長、氧化率難以保證、後處理車間的空氣質量、氧化液濃度低、投資大、運行成本高等缺點。Chinese invention patent application CN1408464A proposes a method and device for the extraction and recovery of SO 2 in flue gas, in which the concentration of ammonium sulfite is controlled between 0.1 and 5 wt%, preferably between 0.5 and 2.0 wt% In order to create the most favorable conditions for oxidation, reduce energy consumption and investment in oxidation. Here, the generated ammonium sulfite solution undergoes an oxidation reaction with air to obtain an ammonium sulfate solution. The pressure of compressed air is generally 0.05~0.2Mpa (gauge pressure), the flow rate of compressed air is 1~5 times of the theoretical requirement of ammonium sulfite oxidation, and the common is 2~4 times. The residence time of oxidation reaction is generally 1~3 Between hours, it is best to be around 2 hours. Under this condition, the oxidation rate can be greater than 95%. The concentration of the ammonium sulfate solution is generally 5-20% by weight. This process has the disadvantages of large amount of oxidized air, long oxidation time, difficult to ensure oxidation rate, air quality of post-treatment workshop, low concentration of oxidizing liquid, large investment, high operating cost and so on.
中國實用新型專利CN206810043U提出一種氨法脫硫多級氧化槽，槽體上端設有回流液入口，底部設有外接循環泵的氧化液出口，槽體內部設有若干層氧化裝置，包括：空氣分佈器、氧化液均布器、曝氣裝置；曝氣裝置包括若干設置在槽板上，貫通槽板兩側的曝氣頭。曝氣頭分割氣泡，更新氣液接觸面，提高液傳質效率，加強氧化效果；氧化射流器具有自吸空氣功能，且降低一級氧化系統的空氣消耗量，還將硫銨回流液噴入到液面以下，增強漿液擾動，提高氧化效率。通過三級氧化系統實現分級氧化功能。但該製程未明確氧化條件，結構複雜，投資大。Chinese utility model patent CN206810043U proposes an ammonia desulfurization multi-stage oxidation tank, with a reflux liquid inlet at the upper end of the tank body, an oxidation liquid outlet at the bottom with an external circulation pump, and several layers of oxidation devices inside the tank body, including: air distribution Device, oxidizing liquid distributor, and aeration device; the aeration device includes several aeration heads arranged on the trough plate and penetrating through both sides of the trough plate. The aeration head divides the bubbles, updates the gas-liquid contact surface, improves the liquid mass transfer efficiency, and enhances the oxidation effect; the oxidation jet has a self-priming air function, and reduces the air consumption of the first-level oxidation system, and also sprays the ammonium sulfate reflux liquid into Below the liquid level, the slurry disturbance is enhanced and the oxidation efficiency is improved. The graded oxidation function is realized through a three-stage oxidation system. However, the process does not specify the oxidation conditions, the structure is complex, and the investment is large.
因此，有必要選擇更合適的氧化製程及裝置，降低氧化系統的投資和運行成本，達到最佳的氧化效果，提高氨回收率，控制氣溶膠的產生。Therefore, it is necessary to choose a more appropriate oxidation process and device, reduce the investment and operating costs of the oxidation system, achieve the best oxidation effect, improve the ammonia recovery rate, and control the generation of aerosols.
在已知的先前技術中，未完全掌握氨法脫硫氧化技術的關鍵，難以或甚至不能實現氧化裝置低投資和低運行成本，難以或甚至不能達到最佳的氧化效果和保證氨回收率並控制氣溶膠的產生。In the known prior art, the key to the ammonia desulfurization and oxidation technology is not fully grasped, it is difficult or even impossible to achieve low investment and low operating cost of the oxidation device, it is difficult or even impossible to achieve the best oxidation effect and ensure the recovery rate of ammonia and Control the production of aerosols.
本發明的目的在於，提出一種用於對氨法脫硫溶液進行氧化處理的方法和裝置以及一種用於運行該裝置的方法。The object of the present invention is to propose a method and device for oxidizing an ammonia desulfurization solution and a method for operating the device.
為此，本發明提供一種氨法脫硫溶液氧化的方法，其特徵在於：在氧化過程中使用低成本的加壓空氣，採用多級空氣分佈，對吸收液進行強制氧化，實現多級循環，達到高效低成本氧化的目的。To this end, the present invention provides an ammonia desulfurization solution oxidation method, characterized in that: low-cost pressurized air is used in the oxidation process, multi-stage air distribution is adopted, and the absorption liquid is subjected to forced oxidation to achieve multi-stage circulation. To achieve the purpose of efficient and low-cost oxidation.
本發明還提供一種用於對氨法脫硫吸收液進行氧化處理的方法，其特徵在於， 吸收液從氨法脫硫吸收塔輸送到氧化塔，已被氧化處理的吸收液或者說氧化液從氧化塔輸送到氨法脫硫吸收塔，由此實現吸收液的多級循環；並且 在氧化塔中的氧化過程中，使用加壓空氣作為氧化空氣，並且採用多級空氣分佈，對吸收液進行強制氧化，實現氧化空氣的多級循環，較佳以將完成對吸收液進行氧化的氧化空氣輸送到氨法脫硫吸收塔，用於對氨法脫硫吸收塔中的吸收液進行二次氧化。The invention also provides a method for oxidizing the ammonia desulfurization absorption liquid, characterized in that the absorption liquid is transferred from the ammonia desulfurization absorption tower to the oxidation tower, and the oxidation-treated absorption liquid or oxidation liquid The oxidation tower is sent to the ammonia desulfurization absorption tower, thereby achieving multi-stage circulation of the absorption liquid; and in the oxidation process in the oxidation tower, pressurized air is used as the oxidation air, and the multi-stage air distribution is adopted to carry out the absorption liquid Forced oxidation to achieve multi-stage circulation of oxidized air, preferably to send the oxidized air that has completed the oxidation of the absorption liquid to the ammonia desulfurization absorption tower for secondary oxidation of the absorption liquid in the ammonia desulfurization absorption tower .
按本發明方法的一種進一步方案，加壓空氣的壓力為0.05~0.3MPa，較佳為0.07~0.23MPa。只要不另外說明，則壓力為表壓力，或者說相對於環境的相對壓力。According to a further solution of the method of the present invention, the pressure of the pressurized air is 0.05 to 0.3 MPa, preferably 0.07 to 0.23 MPa. Unless otherwise stated, the pressure is gauge pressure, or relative pressure with respect to the environment.
按本發明方法的一種進一步方案，空氣分佈的級數為1~6級，較佳為2~5級，例如為3級、4級、5級。According to a further solution of the method of the present invention, the level of air distribution is 1 to 6, preferably 2 to 5, for example, 3, 4, and 5.
按本發明方法的一種進一步方案，一個或多個空氣分佈級採用篩板，篩板開有小孔，單孔面積4~400mm2 ，較佳9~225mm2 ，例如為50、100mm2 、150mm2 、200mm2 。較佳篩板開孔率為1~15%，更佳為1.5~10%，例如為2%、3%、5%、8%或9%。特別佳多個空氣分佈級的篩板開孔率自下向上遞增。According to a further solution of the method of the present invention, one or more air distribution stages use a sieve plate, the sieve plate is provided with small holes, and the single hole area is 4 to 400 mm 2 , preferably 9 to 225 mm 2 , for example, 50, 100 mm 2 , 150 mm 2 , 200mm 2 . The opening ratio of the sieve plate is preferably 1 to 15%, more preferably 1.5 to 10%, for example, 2%, 3%, 5%, 8% or 9%. It is particularly preferred that the aperture ratio of the sieve plate of multiple air distribution levels increases from bottom to top.
按本發明方法的一種進一步方案，控制輸入的氧化空氣加入量，使得氧化空氣的加入量為吸收液中的亞硫酸（氫）銨氧化所需理論氧化劑量的1.2~20倍，較佳2~8倍，例如3倍、4倍、5倍或6倍。According to a further solution of the method of the present invention, the amount of oxidizing air input is controlled so that the amount of oxidizing air added is 1.2 to 20 times the theoretical oxidant amount required for the oxidation of (hydrogen) ammonium sulfite in the absorption liquid, preferably 2 to 8 times, for example 3 times, 4 times, 5 times or 6 times.
按本發明方法的一種進一步方案，通過多級循環控制吸收液的成分，使得要被氧化處理的吸收液中的亞硫酸（氫）銨的含量為0.1~8(重量)%，較佳為0.2~5(重量)%，硫酸銨含量為2~38(重量)%。According to a further solution of the method of the present invention, the composition of the absorption liquid is controlled by multi-stage circulation so that the content of ammonium sulfite (hydrogen) sulfite in the absorption liquid to be oxidized is 0.1-8% by weight, preferably 0.2 ~5(wt)%, ammonium sulfate content is 2~38(wt)%.
按本發明方法的一種進一步方案，控制氧化塔的容積，使得吸收液在氧化塔中的氧化時間為5~90min，較佳為10~70min，例如為20min、30min、40min、50min、60min、80min。According to a further solution of the method of the present invention, the volume of the oxidation tower is controlled so that the oxidation time of the absorption liquid in the oxidation tower is 5 to 90 min, preferably 10 to 70 min, for example, 20 min, 30 min, 40 min, 50 min, 60 min, 80 min .
按本發明方法的一種進一步方案，將已被氧化處理的吸收液中的亞硫酸銨和亞硫酸銨氫銨的氧化率控制在90~99.9%或者更高。According to a further solution of the method of the present invention, the oxidation rate of ammonium sulfite and ammonium bisulfite in the absorption liquid that has been oxidized is controlled to be 90-99.9% or higher.
按本發明方法的一種進一步方案，通過氧化強化設備強化吸收液在氧化塔中的氧化。According to a further embodiment of the method of the present invention, the oxidation of the absorption liquid in the oxidation tower is enhanced by an oxidation enhancement device.
本發明還提出一種氨法脫硫溶液氧化的裝置，其特徵在於，包括氧化空氣系統、氧化系統，氧化系統包括氧化塔（罐），該氧化塔包括塔體，在塔體內形成氧化室，在塔體上設有吸收液入口、氧化液出口、氧化空氣入口和氧化空氣出口。The present invention also provides an ammonia desulfurization solution oxidation device, which is characterized by including an oxidation air system and an oxidation system. The oxidation system includes an oxidation tower (tank). The oxidation tower includes a tower body, and an oxidation chamber is formed in the tower body. The tower body is provided with an absorption liquid inlet, an oxidation liquid outlet, an oxidation air inlet and an oxidation air outlet.
本發明還提出一種用於對氨法脫硫吸收液進行氧化處理的裝置，其包括氧化空氣系統和氧化塔，該氧化塔包括塔體，在塔體內形成氧化室，在塔體上設有用於輸入要被氧化處理的吸收液的吸收液入口、用於輸出已被氧化處理的吸收液的氧化液出口、氧化空氣入口和氧化空氣出口，該氧化空氣系統與氧化空氣入口連接，該氧化空氣出口連接至氨法脫硫吸收塔，其中， 該裝置構造成，使得吸收液從氨法脫硫吸收塔輸送到氧化塔，使得已被氧化處理的吸收液或者說氧化液從氧化塔輸送到氨法脫硫吸收塔，由此實現吸收液的多級循環；並且 該氧化空氣系統構造成，使得在氧化塔中的氧化過程中，使用加壓空氣作為氧化空氣，並且採用多級空氣分佈，對吸收液進行強制氧化，實現氧化空氣的多級循環，較佳以將完成對吸收液進行氧化的氧化空氣輸送到氨法脫硫吸收塔，用於對氨法脫硫吸收塔中的吸收液進行二次氧化。The invention also provides a device for oxidizing the ammonia desulfurization absorption liquid, which includes an oxidizing air system and an oxidizing tower, the oxidizing tower includes a tower body, an oxidation chamber is formed in the tower body, and the tower body is provided with An absorbing liquid inlet that inputs the absorbing liquid to be oxidized, an oxidizing liquid outlet that outputs the oxidized absorbing liquid, an oxidizing air inlet, and an oxidizing air outlet, the oxidizing air system is connected to the oxidizing air inlet, and the oxidizing air outlet It is connected to an ammonia desulfurization absorption tower, wherein the device is configured such that the absorption liquid is transferred from the ammonia desulfurization absorption tower to the oxidation tower, so that the oxidized absorption liquid or the oxidation liquid is transferred from the oxidation tower to the ammonia method Desulfurization absorption tower, thereby achieving multi-stage circulation of absorption liquid; and the oxidizing air system is configured such that during the oxidation in the oxidation tower, pressurized air is used as oxidizing air, and multi-stage air distribution is adopted to absorb The liquid is forcedly oxidized to achieve a multi-stage circulation of oxidized air. Preferably, the oxidized air that has completed the oxidation of the absorption liquid is sent to an ammonia desulfurization absorption tower for the second process of the absorption liquid in the ammonia desulfurization absorption tower. Secondary oxidation.
按本發明的裝置的一種進一步方案，在氧化塔內設有1層、2層、3層或更多層氣液分散強化器。較佳氣液分散強化器的形式為規整填料、散堆填料、開孔板、氣帽和曝氣頭之中的任一種或任意多種的組合。According to a further embodiment of the device of the present invention, one, two, three or more layers of gas-liquid dispersion intensifiers are provided in the oxidation tower. A preferred form of the gas-liquid dispersion intensifier is any one or any combination of structured packing, random packing, perforated plate, gas cap and aeration head.
按本發明的裝置的一種進一步方案，該裝置還包括氧化強化設備，較佳該氧化強化設備是音波產生設備、超音波產生設備、紅外線產生設備、紫外線產生設備和電子束產生設備之中的任一種或者任意多種的組合。According to a further aspect of the device of the present invention, the device further includes an oxidation strengthening device, preferably the oxidation strengthening device is any of a sonic wave generating device, an ultrasonic wave generating device, an infrared ray generating device, an ultraviolet ray generating device and an electron beam generating device One or any combination of multiple.
按本發明的裝置的一種進一步方案，在氨法脫硫吸收塔的洗滌降溫段設置空氣分佈器，該空氣分佈器包括母管、支管，在支管上開有小孔，單孔面積為25~625mm2 ，較佳為64~400mm2 ，例如為50mm2 、100mm2 、150mm2 、200mm2 、250mm2 、300mm2 、350mm2 、400mm2 、450mm2 、500mm2 。According to a further solution of the device of the present invention, an air distributor is provided in the washing and cooling section of the ammonia desulfurization absorption tower. The air distributor includes a mother pipe and a branch pipe, and a small hole is opened on the branch pipe, and the single hole area is 25~ 625mm 2, preferably 64 ~ 400mm 2, for example, 50mm 2, 100mm 2, 150mm 2 , 200mm 2, 250mm 2, 300mm 2, 350mm 2, 400mm 2, 450mm 2, 500mm 2.
本發明還提出一種用於運行本發明的裝置的方法，其特徵在於，該方法包括以下製程步驟： 1) 將來自氨法脫硫吸收塔的要被氧化處理的吸收液輸送到氧化塔中； 2) 由氧化空氣系統提供加壓的氧化空氣到氧化塔中，其中，氧化空氣與吸收液接觸，將吸收液中的亞硫酸銨和亞硫酸氫銨氧化為硫酸銨和硫酸氫銨； 3) 將已被氧化處理的吸收液加氨後，一部分輸送到氨法脫硫吸收塔的洗滌降溫段進行噴淋，對洗滌降溫段進行沖洗，另一部分輸送到氨法脫硫吸收塔吸收段； 4) 將反應後的氧化空氣輸送到氨法脫硫吸收塔的洗滌降溫段和/或吸收段，其中，在輸送到氨法脫硫吸收塔的洗滌降溫段的情況下，在攪拌洗滌降溫液的同時，對洗滌降溫液進行二次氧化。The present invention also provides a method for operating the device of the present invention, characterized in that the method includes the following process steps: 1) The absorption liquid from the ammonia desulfurization absorption tower to be oxidized is sent to the oxidation tower; 2) The pressurized oxidizing air is supplied to the oxidation tower by the oxidizing air system, where the oxidizing air contacts the absorption liquid to oxidize the ammonium sulfite and ammonium bisulfite in the absorption liquid to ammonium sulfate and ammonium bisulfate; 3) After adding ammonia to the absorption liquid that has been oxidized, a part of it is sent to the washing and cooling section of the ammonia desulfurization absorption tower for spraying, the washing and cooling section is washed, and the other part is sent to the absorption section of the ammonia desulfurization absorption tower; 4 ) The oxidized air after the reaction is sent to the washing and cooling section and/or absorption section of the ammonia desulfurization absorption tower, wherein, in the case of being sent to the washing and cooling section of the ammonia desulfurization absorption tower, the At the same time, the washing cooling liquid is subjected to secondary oxidation.
按本發明的另一個方面，提出一種氨法脫硫溶液氧化的裝置，其中，該裝置包括氧化空氣系統、氧化罐以及在氧化罐中的氣液分散強化器，該氧化罐包括吸收液入口、氧化液出口、氧化空氣入口和氧化空氣出口。According to another aspect of the present invention, an ammonia desulfurization solution oxidation device is proposed, wherein the device includes an oxidation air system, an oxidation tank, and a gas-liquid dispersion intensifier in the oxidation tank. The oxidation tank includes an absorption liquid inlet, Oxidizing liquid outlet, oxidizing air inlet and oxidizing air outlet.
按本發明的裝置的一種進一步方案，該氣液分散強化器包括1個、2個、3個或更多個篩板層，該篩板層分別包括篩板；和/或該氣液分散強化器的形式為規整填料、散堆填料、開孔板、氣帽和曝氣頭之中的任一種或任意多種的組合。According to a further aspect of the device of the present invention, the gas-liquid dispersion intensifier includes 1, 2, 3 or more sieve plate layers, each of which includes a sieve plate; and/or the gas-liquid dispersion strengthener The form of the device is any one or any combination of regular packing, random packing, perforated plate, gas cap and aeration head.
按本發明的裝置的一種進一步方案，該裝置還包括與氧化罐耦合的氧化強化設備；較佳該氧化強化設備是音波產生設備、尤其是超音波產生設備，較佳超音波產生設備構造成用於發射超音波頻率為50~100kHz的超音波。According to a further aspect of the device of the present invention, the device further includes an oxidation strengthening device coupled to the oxidation tank; preferably the oxidation strengthening device is a sound wave generating device, especially an ultrasonic wave generating device, preferably the ultrasonic wave generating device is configured to use It is used to transmit supersonic wave with supersonic frequency of 50~100kHz.
按本發明的裝置的一種進一步方案，超音波頻率為60~85kHz，並且超音波產生設備構造成用於提供12~40W/L、較佳18~24W/L的聲強。According to a further solution of the device of the present invention, the ultrasonic frequency is 60 to 85 kHz, and the ultrasonic generating device is configured to provide a sound intensity of 12 to 40 W/L, preferably 18 to 24 W/L.
按本發明的裝置的一種進一步方案，該氧化強化設備包括紅外線產生設備和/或紫外線產生設備和/或電子束產生設備。According to a further embodiment of the device according to the invention, the oxidation strengthening device includes an infrared generating device and/or an ultraviolet generating device and/or an electron beam generating device.
按本發明的裝置的一種進一步方案，該裝置還包括：煙氣脫硫塔洗滌降溫段和設置在洗滌降溫段中的空氣分佈器，該空氣分佈器包括母管、支管，在支管上開有小孔，較佳單孔面積為25~625mm2 ，更佳為64~400mm2 。According to a further solution of the device of the present invention, the device further includes: a flue gas desulfurization tower scrubbing cooling section and an air distributor provided in the scrubbing cooling section, the air distributor includes a mother pipe and a branch pipe, and the branch pipe is provided with holes, hole area is preferably 25 ~ 625mm 2, more preferably 64 ~ 400mm 2.
按本發明的裝置的一種進一步方案，該裝置包括氧化空氣系統和氧化塔，該氧化塔包括：氧化塔體；在氧化塔體內形成的氧化室，該氧化室構造成用於提供多級空氣分佈，該多級空氣分佈對吸收液進行強制氧化；在氧化塔體上的用於從氨法脫硫吸收塔輸入吸收液的入口；在氧化塔體上的用於將氧化處理的吸收液提供至氨法脫硫吸收塔的出口；在氧化塔體上的氧化空氣入口和在氧化塔體上的氧化空氣出口；其中，氧化空氣系統構造成用於輸送加壓的空氣到氧化空氣入口中；並且其中，該氧化空氣出口構造成用於輸送氧化空氣到氨法脫硫吸收塔中。According to a further embodiment of the device of the present invention, the device includes an oxidizing air system and an oxidizing tower, the oxidizing tower includes: an oxidizing tower body; an oxidizing chamber formed in the oxidizing tower body, the oxidizing chamber configured to provide a multi-stage air distribution , The multi-stage air distribution compulsorily oxidizes the absorption liquid; the inlet on the oxidation tower body is used to input the absorption liquid from the ammonia desulfurization absorption tower; the oxidation tower body is used to provide the oxidation treatment absorption liquid to An ammonia desulfurization absorption tower outlet; an oxidation air inlet on the oxidation tower body and an oxidation air outlet on the oxidation tower body; wherein the oxidation air system is configured to deliver pressurized air to the oxidation air inlet; and Wherein, the oxidized air outlet is configured to transport oxidized air to the ammonia desulfurization absorption tower.
按本發明的另一個方面，提出一種用於運行按本發明的裝置的方法，其中，該方法包括： 將來自氨法脫硫吸收塔的吸收液輸送到氧化罐中； 由氧化空氣系統提供氧化空氣到氧化罐中； 使得氧化空氣與吸收液接觸，以便將吸收液中的亞硫酸銨和亞硫酸氫銨氧化為硫酸銨和硫酸氫銨； 將吸收液的第一部分從吸收液出口輸送到氨法脫硫吸收塔的洗滌降溫段； 在洗滌降溫段中利用該第一部分沖洗煙氣； 將吸收液的第二部分從吸收液出口輸送到氨法脫硫吸收塔的吸收段； 將空氣從氧化空氣出口輸送到洗滌降溫段，以便對洗滌降溫液進行二次氧化；並且 攪拌洗滌降溫液。According to another aspect of the present invention, a method for operating the device according to the present invention is provided, wherein the method comprises: transferring the absorption liquid from the ammonia desulfurization absorption tower to an oxidation tank; the oxidation is provided by an oxidation air system Air into the oxidation tank; make the oxidizing air contact with the absorption liquid to oxidize the ammonium sulfite and ammonium bisulfite in the absorption liquid to ammonium sulfate and ammonium bisulfate; transport the first part of the absorption liquid from the absorption liquid outlet to ammonia The cooling and cooling section of the process desulfurization absorption tower; the first part is used to wash the flue gas in the cooling and cooling section; the second part of the absorption liquid is sent from the absorption liquid outlet to the absorption section of the ammonia desulfurization absorption tower; the air is oxidized The air outlet is sent to the washing cooling section to perform secondary oxidation of the washing cooling liquid; and the washing cooling liquid is stirred.
按本發明的另一個方面，提出一種用於運行按本發明的裝置的方法，其中，該方法包括： 將來自氨法脫硫吸收塔的吸收液輸送到氧化罐中； 由氧化空氣系統提供氧化空氣到氧化罐中； 使得氧化空氣與吸收液接觸，以便將吸收液中的亞硫酸銨和亞硫酸氫銨氧化為硫酸銨和硫酸氫銨； 將吸收液的第一部分從吸收液出口輸送到氨法脫硫吸收塔的洗滌降溫段； 在洗滌降溫段中利用該第一部分沖洗煙氣； 將吸收液的第二部分從吸收液出口輸送到氨法脫硫吸收塔的吸收段； 將空氣從氧化空氣出口輸送到氨法脫硫吸收塔的吸收段，以便對吸收液進行二次氧化。According to another aspect of the present invention, a method for operating the device according to the present invention is provided, wherein the method comprises: transferring the absorption liquid from the ammonia desulfurization absorption tower to an oxidation tank; the oxidation is provided by an oxidation air system Air into the oxidation tank; make the oxidizing air contact with the absorption liquid to oxidize the ammonium sulfite and ammonium bisulfite in the absorption liquid to ammonium sulfate and ammonium bisulfate; transport the first part of the absorption liquid from the absorption liquid outlet to ammonia The cooling and cooling section of the process desulfurization absorption tower; the first part is used to wash the flue gas in the cooling and cooling section; the second part of the absorption liquid is sent from the absorption liquid outlet to the absorption section of the ammonia desulfurization absorption tower; the air is oxidized The air outlet is sent to the absorption section of the ammonia desulfurization absorption tower to perform secondary oxidation of the absorption liquid.
按本發明的方法的一種進一步方案，該方法還包括：將空氣從氧化空氣出口輸送到氨法脫硫吸收塔的吸收段，以便對吸收液進行二次氧化。According to a further solution of the method of the present invention, the method further comprises: transporting air from the oxidized air outlet to the absorption section of the ammonia desulfurization absorption tower to perform secondary oxidation of the absorption liquid.
按本發明的方法的一種進一步方案，該方法還包括：將空氣從氧化空氣出口輸送到洗滌降溫段，以便對洗滌降溫液進行二次氧化。According to a further solution of the method of the present invention, the method further comprises: sending air from the oxidizing air outlet to the washing cooling section, so as to perform secondary oxidation on the washing cooling liquid.
按本發明的方法的一種進一步方案，該方法還包括：在吸收液離開吸收液出口之後並且在吸收液進入脫硫吸收塔之前，給吸收液補充氨。According to a further aspect of the method of the present invention, the method further includes: after the absorption liquid leaves the absorption liquid outlet and before the absorption liquid enters the desulfurization absorption tower, supplementing the absorption liquid with ammonia.
按本發明的另一個方面，提出一種用於運行按本發明的裝置的方法，其中，該方法包括： 將來自氨法脫硫吸收塔的吸收液輸送到氧化罐中； 由氧化空氣系統提供氧化空氣到氧化罐中； 使得氧化空氣與吸收液接觸，以便將吸收液中的亞硫酸銨和亞硫酸氫銨氧化為硫酸銨和硫酸氫銨； 將吸收液的第一部分從吸收液出口輸送到氨法脫硫吸收塔的洗滌降溫段； 在洗滌降溫段中利用該第一部分沖洗煙氣； 將吸收液的第二部分從吸收液出口輸送到氨法脫硫吸收塔的吸收段； 將空氣從氧化空氣出口輸送到洗滌降溫段，以便對洗滌降溫液進行二次氧化；並且 攪拌洗滌降溫液。According to another aspect of the present invention, a method for operating the device according to the present invention is provided, wherein the method comprises: transferring the absorption liquid from the ammonia desulfurization absorption tower to an oxidation tank; the oxidation is provided by an oxidation air system Air into the oxidation tank; make the oxidizing air contact with the absorption liquid to oxidize the ammonium sulfite and ammonium bisulfite in the absorption liquid to ammonium sulfate and ammonium bisulfate; transport the first part of the absorption liquid from the absorption liquid outlet to ammonia The cooling and cooling section of the process desulfurization absorption tower; the first part is used to wash the flue gas in the cooling and cooling section; the second part of the absorption liquid is sent from the absorption liquid outlet to the absorption section of the ammonia desulfurization absorption tower; the air is oxidized The air outlet is sent to the washing cooling section to perform secondary oxidation of the washing cooling liquid; and the washing cooling liquid is stirred.
按本發明的另一個方面，提出一種用於運行按本發明的裝置的方法，其中，該方法包括： 將來自氨法脫硫吸收塔的吸收液輸送到氧化罐中； 由氧化空氣系統提供氧化空氣到氧化罐中； 使得氧化空氣與吸收液接觸，以便將吸收液中的亞硫酸銨和亞硫酸氫銨氧化為硫酸銨和硫酸氫銨； 將吸收液的第一部分從吸收液出口輸送到氨法脫硫吸收塔的洗滌降溫段； 在洗滌降溫段中利用該第一部分沖洗煙氣； 將吸收液的第二部分從吸收液出口輸送到氨法脫硫吸收塔的吸收段； 將空氣從氧化空氣出口輸送到氨法脫硫吸收塔的吸收段，以便對吸收液進行二次氧化。According to another aspect of the present invention, a method for operating the device according to the present invention is provided, wherein the method comprises: transferring the absorption liquid from the ammonia desulfurization absorption tower to an oxidation tank; the oxidation is provided by an oxidation air system Air into the oxidation tank; make the oxidizing air contact with the absorption liquid to oxidize the ammonium sulfite and ammonium bisulfite in the absorption liquid to ammonium sulfate and ammonium bisulfate; transport the first part of the absorption liquid from the absorption liquid outlet to ammonia The cooling and cooling section of the process desulfurization absorption tower; the first part is used to wash the flue gas in the cooling and cooling section; the second part of the absorption liquid is sent from the absorption liquid outlet to the absorption section of the ammonia desulfurization absorption tower; the air is oxidized The air outlet is sent to the absorption section of the ammonia desulfurization absorption tower to perform secondary oxidation of the absorption liquid.
按本發明的方法的一種進一步方案，該方法還包括：將空氣從氧化空氣出口輸送到氨法脫硫吸收塔的吸收段，以便對吸收液進行二次氧化。According to a further solution of the method of the present invention, the method further comprises: transporting air from the oxidized air outlet to the absorption section of the ammonia desulfurization absorption tower to perform secondary oxidation of the absorption liquid.
按本發明的方法的一種進一步方案，該方法還包括：將空氣從氧化空氣出口輸送到洗滌降溫段，以便對洗滌降溫液進行二次氧化。According to a further solution of the method of the present invention, the method further comprises: sending air from the oxidizing air outlet to the washing cooling section, so as to perform secondary oxidation on the washing cooling liquid.
按本發明的方法的一種進一步方案，其中，該方法還包括：在吸收液離開吸收液出口之後並且在吸收液進入脫硫吸收塔之前，給吸收液補充氨。A further solution of the method according to the invention, wherein the method further comprises: after the absorption liquid leaves the absorption liquid outlet and before the absorption liquid enters the desulfurization absorption tower, supplement the absorption liquid with ammonia.
按本發明的另一個方面，提出一種含氨脫硫溶液氧化的方法，其中，該方法包括： 在罐中的空氣分佈級上朝溶液擴散空氣；並且然後 向煙氣脫硫塔的多個不同區段提供溶液。According to another aspect of the present invention, a method for oxidizing an ammonia-containing desulfurization solution is proposed, wherein the method includes: diffusing air toward the solution at an air distribution stage in a tank; and then to a plurality of different flue gas desulfurization towers The section provides a solution.
按本發明的方法的一種進一步方案，該提供包括：在塔的洗滌降溫段中噴淋溶液；和/或該提供包括：在塔的吸收段中噴淋溶液。According to a further aspect of the method of the present invention, the providing includes: spraying the solution in the cooling and cooling section of the tower; and/or the providing includes spraying the solution in the absorption section of the tower.
按本發明的方法的一種進一步方案，該方法還包括：從塔的吸收段的出口接收溶液。According to a further solution of the method of the present invention, the method further comprises: receiving the solution from the outlet of the absorption section of the tower.
按本發明的方法的一種進一步方案，在該提供之前，該方法還包括：向溶液補充氨。According to a further aspect of the method of the present invention, before the providing, the method further comprises: supplementing the solution with ammonia.
按本發明的方法的一種進一步方案，其中，該方法還包括：提供表壓力為0.05~0.3MPa、較佳為0.07~0.23MPa的空氣，用於該擴散。A further solution of the method according to the invention, wherein the method further comprises: providing air with a gauge pressure of 0.05 to 0.3 MPa, preferably 0.07 to 0.23 MPa, for the diffusion.
按本發明的方法的一種進一步方案，其中，該擴散包括：在1~6個空氣分佈級中分佈空氣。A further solution of the method according to the invention, wherein the diffusion comprises: distributing air in 1 to 6 air distribution stages.
按本發明的方法的一種進一步方案，該擴散包括：在空氣分佈級中使得空氣通過篩板，並且篩板開有小孔，單孔面積為4~400mm2 ，較佳為9~225mm2 ，較佳篩板開孔率為1~15%，更佳為1.5~10%。According to a further solution of the method of the present invention, the diffusion includes: passing air through the sieve plate in the air distribution stage, and the sieve plate is provided with small holes, and the single hole area is 4 to 400 mm 2 , preferably 9 to 225 mm 2 , Preferably, the aperture ratio of the sieve plate is 1 to 15%, and more preferably 1.5 to 10%.
按本發明的方法的一種進一步方案，該空氣分佈級包含於多個空氣分佈級之中，各空氣分佈級垂直地佈置，各空氣分佈級分別包括具有相應開孔率的篩板，並且各級的開孔率自下向上遞增。According to a further solution of the method of the present invention, the air distribution stage is included in a plurality of air distribution stages, each air distribution stage is arranged vertically, each air distribution stage includes a sieve plate having a corresponding opening rate, and each level The opening rate of the air increases from bottom to top.
按本發明的方法的一種進一步方案，該方法還包括：使得空氣以不低於溶液中的亞硫酸銨和亞硫酸氫銨氧化所需的理論氧化劑量流入該罐中，較佳空氣量為該理論氧化劑量的1.2~20倍，更佳2~8倍。According to a further solution of the method of the present invention, the method further comprises: allowing air to flow into the tank with a theoretical oxidant amount not less than that required for the oxidation of ammonium sulfite and ammonium bisulfite in the solution, preferably the amount of air is The theoretical oxidant amount is 1.2-20 times, more preferably 2-8 times.
按本發明的方法的一種進一步方案，該方法還包括： 使得溶液經過該塔循環； 在溶液經過該塔循環之後將溶液輸送到該罐中；並且 控制循環，使得通過該輸送，該溶液具有0.1~8(重量)%、尤其是0.2~5(重量)%的亞硫酸銨和亞硫酸氫銨並且具有2~38(重量)%的硫酸銨。According to a further aspect of the method of the present invention, the method further comprises: circulating the solution through the column; transferring the solution to the tank after the solution has been circulated through the column; and controlling the circulation so that the solution has a value of 0.1 through the transfer ~8% by weight, especially 0.2~5% by weight of ammonium sulfite and ammonium bisulfite and having 2~38% by weight of ammonium sulfate.
按本發明的方法的一種進一步方案，該方法還包括：選擇該罐的容積，使得溶液在氧化罐中的氧化時間為5~90min，較佳10~70min。According to a further solution of the method of the present invention, the method further comprises: selecting the volume of the tank so that the oxidation time of the solution in the oxidation tank is 5 to 90 minutes, preferably 10 to 70 minutes.
按本發明的方法的一種進一步方案，該方法還包括： 在溶液包含亞硫酸銨和亞硫酸氫銨的第一亞硫酸鹽含量的情況下將溶液輸送到該罐中； 在溶液包含亞硫酸銨和亞硫酸氫銨的第二亞硫酸鹽含量的情況下將溶液從該罐中取出； 其中，第一亞硫酸鹽質量含量大於第二亞硫酸鹽質量含量，且第一亞硫酸鹽質量含量≤第二亞硫酸鹽質量含量+10%）特別是≤第二亞硫酸鹽質量含量+0.1%。例如當第二亞硫酸鹽質量含量為1.0%時，第一亞硫酸鹽質量含量≤11.0%，特別是≤1.1%。According to a further aspect of the method of the present invention, the method further comprises: delivering the solution to the tank if the solution contains the first sulfite content of ammonium sulfite and ammonium bisulfite; and the solution contains ammonium sulfite And the second sulfite content of ammonium bisulfite, the solution is taken out of the tank; wherein, the first sulfite mass content is greater than the second sulfite mass content, and the first sulfite mass content ≤ Mass content of second sulfite +10%) Especially ≤ mass content of second sulfite +0.1%. For example, when the mass content of the second sulfite is 1.0%, the mass content of the first sulfite is ≤11.0%, especially ≤1.1%.
按本發明的方法的一種進一步方案，該方法還包括：通過氧化強化設備強化溶液的氧化。According to a further solution of the method of the present invention, the method further includes: strengthening the oxidation of the solution by the oxidation strengthening device.
按本發明的另一個方面，提供一種氨法脫硫吸收液氧化的方法，其中，該方法包括： 在脫硫吸收塔中吸收液與煙氣反應； 在該反應之後，將吸收液輸送到氧化塔中； 在該輸送之後，在氧化塔中氧化吸收液；並且 在該氧化之後，將氧化液返回到脫硫吸收塔中。According to another aspect of the present invention, a method for oxidation of an ammonia desulfurization absorption liquid is provided, wherein the method includes: the absorption liquid reacts with flue gas in a desulfurization absorption tower; after the reaction, the absorption liquid is transported to oxidation In the tower; after the transportation, the absorption liquid is oxidized in the oxidation tower; and after the oxidation, the oxidation liquid is returned to the desulfurization absorption tower.
按本發明的方法的一種進一步方案，該氧化包括：將加壓空氣、吸收液在多級分佈器中進行分佈。According to a further embodiment of the method of the present invention, the oxidation includes: distributing the pressurized air and the absorption liquid in a multi-stage distributor.
在此需要指出的是，在本申請中記載的各技術特徵可以任意組合，只要這種組合是技術上可行的。所有這些組合都是在本申請中記載的技術內容。It should be pointed out here that the technical features described in this application can be arbitrarily combined as long as such a combination is technically feasible. All these combinations are the technical contents described in this application.
在如第1圖所示的用於對氨法脫硫吸收液進行氧化處理的裝置中，在氧化過程中可以使用低成本的加壓空氣作為氧化空氣，並且採用多級空氣分佈，對吸收液進行強制氧化，實現吸收液和氧化空氣的多級循環，達到高效低成本氧化的目的。In the device for oxidizing the ammonia desulfurization absorption liquid as shown in FIG. 1, low-cost pressurized air can be used as the oxidation air during the oxidation process, and a multi-stage air distribution is adopted to absorb the absorption liquid. Perform forced oxidation to achieve multi-stage circulation of absorption liquid and oxidized air, to achieve the purpose of efficient and low-cost oxidation.
如第1圖所示的裝置包括氧化空氣系統13和氧化塔1，該氧化塔1包括塔體，在塔體內形成氧化室，在塔體上設有氧化室吸收液入口4、氧化液出口10、氧化空氣入口9和氧化空氣出口5。The device shown in FIG. 1 includes an oxidation air system 13 and an
在氧化塔1內設有4層氣液分散強化器2。氣液分散強化器2的形式為2層開孔板+2層曝氣頭。In the
如第1圖所示的裝置還包括氧化強化設備3，該氧化強化設備是超音波產生設備。超音波頻率為60~85kHz，聲強為20W/L。The device shown in FIG. 1 further includes an oxidation strengthening device 3, which is an ultrasound generating device. The ultrasonic frequency is 60~85kHz, and the sound intensity is 20W/L.
加壓空氣的壓力可以為0.06~0.18MPa（表壓力）。The pressure of pressurized air can be 0.06~0.18MPa (gauge pressure).
在氧化塔中，空氣分佈的級數為4級。In the oxidation tower, the level of air distribution is 4 levels.
空氣分佈級採用篩板，篩板開有小孔，單孔面積121~196mm2 。自下向上，四層篩板開孔率分別為2.1%、2.3%、2.3%、2.5%。The air distribution level adopts sieve plate, the sieve plate has small holes, and the area of single hole is 121~196mm 2 . From bottom to top, the opening rate of the four-layer sieve plate is 2.1%, 2.3%, 2.3%, 2.5%.
氧化空氣加入量調節為吸收液中的亞硫酸（氫）銨氧化所需理論氧化劑量的4倍。The amount of oxidizing air added is adjusted to 4 times the theoretical oxidant amount required for the oxidation of ammonium sulfite (hydrogen) sulfite in the absorption solution.
吸收液中的亞硫酸（氫）銨含量調節為0.5~2.5(重量)%，硫酸（氫）銨含量調節為19~25(重量)%。The content of ammonium sulfite (hydrogen) sulfite in the absorption solution is adjusted to 0.5 to 2.5% by weight, and the content of ammonium sulfite is adjusted to 19 to 25% by weight.
吸收液在氧化塔的停留時間為30~42min。The residence time of the absorption liquid in the oxidation tower is 30~42min.
按一種有利的實施方式，已被氧化處理的吸收液或者說氧化液在進入氨法脫硫吸收塔之前通過靜態混合器補充氨或含氨吸收液。與此不同，在CN103212348A中在進入氧化塔之前給漿液加氨，這帶來一系列與之相關的技術缺陷，低pH有利於亞硫酸銨的氧化，高pH下氧化成本高，氧化率難以保證，且高pH漿液在氧化過程中由於空氣的氣提作用容易產生氨逃逸和氣溶膠。According to an advantageous embodiment, the absorption liquid or the oxidation liquid that has been oxidized is supplemented with ammonia or an ammonia-containing absorption liquid by a static mixer before entering the ammonia desulfurization absorption tower. In contrast, in CN103212348A, ammonia is added to the slurry before entering the oxidation tower, which brings a series of related technical defects. Low pH is conducive to the oxidation of ammonium sulfite. The oxidation cost is high at high pH, and the oxidation rate is difficult to guarantee And, during the oxidation process of high pH slurry, it is easy to produce ammonia escape and aerosol due to the air stripping effect of air.
在第1圖中還示出氨法脫硫吸收塔6，其包括洗滌降溫段11和吸收段12。洗滌降溫段11設有洗滌噴淋裝置7。吸收段12設有吸收噴淋裝置8。Also shown in FIG. 1 is an ammonia
該裝置在運行時可以包括以下的具體製程步驟： 1) 吸收液進入氧化塔1。 2) 氧化空氣系統13提供的氧化空氣進入氧化塔1，與吸收液接觸，將吸收液中的亞硫酸（氫）銨氧化為硫酸（氫）銨。 3) 已被氧化處理的吸收液（或者說氧化液）一部分進入氨法脫硫吸收塔6的洗滌降溫段11的洗滌噴淋裝置7，與煙氣逆流接觸，在使得煙氣降溫的同時，氧化液得到濃縮，並對洗滌降溫段進行沖洗，另一部分進入氨法脫硫吸收塔6的吸收段12的吸收噴淋裝置8。 4) 反應後的氧化空氣通過氧化空氣出口5送入氨法脫硫吸收塔6的洗滌降溫段11，在攪拌洗滌降溫液的同時，可對洗滌降溫液進行二次氧化。The device may include the following specific process steps during operation: 1) The absorption liquid enters the
吸收液中的亞硫酸（氫）銨氧化率根據製程需要可以控制在96.5~99.5%或者更高。The oxidation rate of ammonium sulfite (hydrogen) sulfite in the absorption liquid can be controlled at 96.5~99.5% or higher according to the process requirements.
在氨法脫硫吸收塔的洗滌降溫段也可以設置空氣分佈器，該空氣分佈器包括母管、支管，在支管上開有小孔，孔徑10~20mm。An air distributor can also be provided in the washing and cooling section of the ammonia desulfurization absorption tower. The air distributor includes a mother pipe and a branch pipe, and a small hole is opened on the branch pipe, and the hole diameter is 10-20 mm.
在氧化塔內有多層氣液分散強化器（例如形式為篩板），對氧化空氣和吸收液（氧化液）有均布作用，實現多級氧化（多級循環），同時，吸收液（氧化液）在氨法脫硫吸收塔與氧化塔之間還有循環。在氧化塔內通過氣液分散強化器實現氧化空氣的多次分佈，從而實現氧化空氣的多次均勻分佈，並使其與吸收液多次逆流接觸，有利於氧化。In the oxidation tower, there are multiple layers of gas-liquid dispersion intensifiers (for example, in the form of sieve plates), which have a uniform distribution effect on the oxidized air and the absorption liquid (oxidation liquid) to achieve multi-stage oxidation (multi-stage circulation). (Liquid) There is also a circulation between the ammonia desulfurization absorption tower and the oxidation tower. In the oxidation tower, multiple distributions of oxidized air are realized by a gas-liquid dispersion intensifier, thereby achieving multiple uniform distributions of oxidized air, and multiple countercurrent contact with the absorption liquid, which is beneficial to oxidation.
以下說明本發明的另一實施例。The following describes another embodiment of the present invention.
在氧化過程中使用低成本的加壓空氣，採用多級空氣分佈，對吸收液進行強制氧化，實現多級循環，達到高效低成本氧化的目的。In the oxidation process, low-cost pressurized air is used, and multi-stage air distribution is adopted to perform forced oxidation of the absorption liquid to achieve multi-stage circulation and achieve the purpose of efficient and low-cost oxidation.
加壓空氣壓力為0.105MPa。The pressurized air pressure is 0.105MPa.
空氣分佈的級數為3級。The level of air distribution is 3 levels.
空氣分佈級採用篩板，篩板開有小孔，單孔面積16~64mm2 。自下向上，三層篩板開孔率分別為5.2%、5.3%、5.5%。The air distribution level adopts sieve plate, the sieve plate has small holes, and the single hole area is 16~64mm 2 . From bottom to top, the three-layer sieve plate opening rate is 5.2%, 5.3%, 5.5%.
氧化空氣加入量為吸收液中的亞硫酸（氫）銨氧化所需理論氧化劑量的5.2倍。The added amount of oxidized air is 5.2 times the theoretical oxidant amount required for the oxidation of (hydrogen) ammonium sulfite in the absorption liquid.
吸收液中的亞硫酸（氫）銨含量為0.3~1(重量)%，硫酸銨含量為20~23(重量)%。The content of ammonium sulfite (hydrogen) sulfite in the absorption liquid is 0.3~1% by weight, and the content of ammonium sulfate is 20~23% by weight.
氧化時間為52min。The oxidation time is 52 min.
該裝置包括氧化空氣系統13和氧化塔1，該氧化塔1包括塔體，在塔體內形成氧化室，在塔體上設有吸收液入口4、氧化液出口10、氧化空氣入口9和氧化空氣出口5。The device includes an oxidation air system 13 and an
在氧化室內設有3層氣液分散強化器2。氣液分散強化器2的形式為2層開孔板+1層規整填料。A three-layer gas-liquid dispersion intensifier 2 is provided in the oxidation chamber. The form of the gas-liquid dispersion intensifier 2 is 2 layers of perforated plates + 1 layer of structured packing.
該裝置還包括氧化強化設備，該氧化強化設備是紫外線產生設備。The device also includes oxidation strengthening equipment, which is ultraviolet generating equipment.
該吸收液入口4和氧化液出口10分別設置有旋塞閥，該閥門的過流部分的材質為316襯氟塑膠。The absorption liquid inlet 4 and the
具體製程步驟可以包括： 1) 吸收液進入氧化塔1。 2) 氧化空氣系統13提供的氧化空氣進入氧化塔的氧化空氣入口9，與吸收液接觸，將吸收液中的亞硫酸（氫）銨氧化為硫酸（氫）銨。 3) 已被氧化處理的吸收液（或者說氧化液）一部分進入氨法脫硫吸收塔6的洗滌降溫段11的洗滌噴淋裝置7，與煙氣逆流接觸，在使得煙氣降溫的同時，氧化液得到濃縮，並對塔壁及支撐梁進行沖洗；另一部分補充氨後進入氨法脫硫吸收塔6的吸收段12的吸收噴淋裝置8。 4) 反應後的氧化空氣通過氧化空氣出口5送入氨法脫硫吸收塔6的吸收段12。The specific process steps may include: 1) The absorption liquid enters the
吸收液中的亞硫酸（氫）銨氧化率97.5~99%。The oxidation rate of ammonium sulfite (hydrogen) sulfite in the absorption liquid is 97.5~99%.
在氨法脫硫吸收塔6的洗滌降溫段11設置攪拌器。An agitator is provided in the washing and
處理的鍋爐煙氣量為500000Nm3 /h(標態、濕基、實際氧)，SO2 濃度1750mg/Nm3 ，氧化塔直徑為5.6m，高度10.5m，進入氧化塔的氧化液流量為650m3 /h。The flue gas volume of the treated boiler is 500000Nm 3 /h (standard state, wet basis, actual oxygen), the concentration of SO 2 is 1750mg/Nm 3 , the diameter of the oxidation tower is 5.6m, the height is 10.5m, and the flow rate of the oxidizing liquid entering the oxidation tower is 650m 3 /h.
最後要指出的是，本發明的上述各個實施例僅僅用於理解本發明，而不對本發明的保護範圍構成限制。對於本領域技術人員來說，在上述實施例的基礎上可以做出修改，所有這些修改都不脫離本發明的保護範圍。Finally, it should be pointed out that the above-mentioned embodiments of the present invention are only for understanding the present invention, and do not limit the protection scope of the present invention. For those skilled in the art, modifications can be made on the basis of the foregoing embodiments, and all these modifications do not deviate from the protection scope of the present invention.
1‧‧‧氧化塔2‧‧‧氣液分散強化器3‧‧‧氧化強化設備4‧‧‧氧化室吸收液入口5‧‧‧氧化空氣出口6‧‧‧氨法脫硫吸收塔7‧‧‧洗滌噴淋裝置8‧‧‧吸收噴淋裝置9‧‧‧氧化空氣入口10‧‧‧氧化液出口11‧‧‧洗滌降溫段12‧‧‧吸收段13‧‧‧氧化空氣系統1‧‧‧Oxidation tower 2‧‧‧Gas-liquid dispersion intensifier 3‧‧‧Oxidation intensification equipment 4‧‧‧Observation chamber inlet of oxidation chamber 5‧‧‧ Oxidation air
下面借助實施例參照附圖更詳細地闡述本發明，但本發明不限制於所說明的和所描述的實施例。示意性的附圖簡要說明如下： 第1圖為按本發明的實施例的用於對氨法脫硫吸收液進行氧化處理的裝置的示意圖。In the following, the invention is explained in more detail with reference to the accompanying drawings, but the invention is not restricted to the illustrated and described embodiments. The schematic drawings are briefly described as follows: FIG. 1 is a schematic diagram of an apparatus for oxidizing an ammonia desulfurization absorption liquid according to an embodiment of the present invention.
1‧‧‧氧化塔 1‧‧‧Oxidation tower
2‧‧‧氣液分散強化器 2‧‧‧Gas-liquid dispersion intensifier
3‧‧‧氧化強化設備 3‧‧‧oxidation strengthening equipment
4‧‧‧氧化室吸收液入口 4‧‧‧ Oxidation chamber absorption liquid inlet
5‧‧‧氧化空氣出口 5‧‧‧ Oxidized air outlet
6‧‧‧氨法脫硫吸收塔 6‧‧‧Ammonia desulfurization absorption tower
7‧‧‧洗滌噴淋裝置 7‧‧‧ Washing and spraying device
8‧‧‧吸收噴淋裝置 8‧‧‧absorption spray device
9‧‧‧氧化空氣入口 9‧‧‧oxidized air inlet
10‧‧‧氧化液出口 10‧‧‧Export of oxidizing liquid
11‧‧‧洗滌降溫段 11‧‧‧Washing and cooling section
12‧‧‧吸收段 12‧‧‧ Absorption section
13‧‧‧氧化空氣系統 13‧‧‧oxidized air system
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