技术领域technical field
本发明涉及一种尾气脱硫脱硝一体化装置及方法，尤其涉及一种船舶尾气脱硫脱硝一体化装置及方法，属于船舶柴油尾气处理技术领域。The invention relates to an integrated device and method for tail gas desulfurization and denitrification, in particular to an integrated device and method for desulfurization and denitrification of ship tail gas, belonging to the technical field of ship diesel tail gas treatment.
背景技术Background technique
船舶柴油机燃用重油，在工作过程中会产生大量的NO和SO2，这些气体会对自然环境和人体健康构成极大威胁。国际海事组织(IMO)对于船舶排放一直以来都有严格的控制标准，众多科研机构对于船舶尾气控制技术进行了大量研究，取得了很多科研成果。The marine diesel engine burns heavy oil, which will produce a large amount of NO and SO2 in the working process, and these gases will pose a great threat to the natural environment and human health. The International Maritime Organization (IMO) has always had strict control standards for ship emissions. Many scientific research institutions have conducted a lot of research on ship exhaust control technology and achieved many scientific research results.
目前船舶柴油机脱硝主要是采用催化还原(SCR)技术，脱硫主要是采用湿法洗涤脱除技术。SCR技术和湿法洗涤脱除技术存在占地面积大、初投资成本高、耗能大、运行维护成本高等问题。船舶尾气脱硫脱硝一体化技术具有占地面积小、耗能低、运行维护方便等优点。因此，众多科研机构致力于脱硫脱硝一体化技术的研发，提出了多种一体化脱除技术，但是在技术上存在诸多问题。At present, the denitrification of marine diesel engines mainly adopts catalytic reduction (SCR) technology, and the desulfurization mainly adopts wet scrubbing and removal technology. SCR technology and wet scrubbing removal technology have problems such as large floor area, high initial investment cost, large energy consumption, and high operation and maintenance costs. The integrated technology of ship exhaust desulfurization and denitrification has the advantages of small footprint, low energy consumption, and convenient operation and maintenance. Therefore, many scientific research institutions are committed to the research and development of integrated desulfurization and denitrification technologies, and have proposed a variety of integrated removal technologies, but there are many technical problems.
在申请号为201010299518.1的专利《一种用于海洋船舶尾气一体化脱硫脱硝的方法》中采用等离子体的方法将废气中的NO和SO2经过除雾加湿和等离子氧化最终转化为硝酸和硫酸，最终在洗涤塔中转变为硝酸盐和硫酸盐，从而实现尾气净化。相比于臭氧氧化，等离子体法耗能较低，但等离子体技术相比其他技术耗能依然较高。其次，烟气中的灰分会污染放电电极，容易造成等离子体发生器失效。该技术的最终产物为硝酸盐和硫酸盐，IMO对于硝酸盐排海有严格的控制标准，因此该发明在应用中存在较大问题。In the patent application number 201010299518.1 "A method for integrated desulfurization and denitrification of marine ship tail gas", the method of plasma is used to convert NO and SO2 in the exhaust gas into nitric acid and sulfuricacid after demisting, humidification and plasma oxidation. Finally, it is converted into nitrate and sulfate in the scrubber, so as to realize the purification of tail gas. Compared with ozone oxidation, plasma method consumes less energy, but plasma technology still consumes more energy than other technologies. Secondly, the ash in the flue gas will contaminate the discharge electrode, which will easily cause the failure of the plasma generator. The final products of this technology are nitrate and sulfate. IMO has strict control standards for nitrate discharge into the sea, so there are big problems in the application of this invention.
在申请号为201210532709.7的专利《一种船用燃机烟气脱硫脱硝一体化方法及设备》中采用二氧化氯的方法脱除SO2和NO，该技术中二氧化氯由二氧化氯发生器产生，二氧化氯发生器系统组成较为复杂，用于制备二氧化氯的原材料具有很强的氧化性，属于高度危险的化学品，该原材料在船舶上的储存有很大困难。二氧化氯溶液的氧化性较强，容易使洗涤塔出现腐蚀，造成系统寿命下降。此外，二氧化氯溶液具有很强的刺激性气味，长期使用会严重污染船员的生活环境。In the patent application number 201210532709.7 "An integrated method and equipment for flue gas desulfurization and denitrification of marine combustion engines", the method of chlorine dioxide is used to remove SO2 and NO. In this technology, chlorine dioxide is produced by a chlorine dioxide generator , The composition of the chlorine dioxide generator system is relatively complex. The raw materials used to prepare chlorine dioxide are highly oxidizing and are highly dangerous chemicals. It is very difficult to store these raw materials on ships. Chlorine dioxide solution has a strong oxidizing property, which is easy to cause corrosion of the washing tower and reduce the life of the system. In addition, chlorine dioxide solution has a strong pungent odor, and long-term use will seriously pollute the living environment of the crew.
在申请号为201611256827.4的专利《一种低温等离子体预氧化联合SCR脱硫脱硝除尘降噪复合装置》中利用低温等离子体技术联合SCR系统实现尾气净化，该发明中低温等离子体技术耗能较高，放电电极会由于烟气中的灰分而失效。由于该发明有两台反应器，因此系统需占据较大的船舶有效空间。In the patent "A low-temperature plasma pre-oxidation combined with SCR desulfurization, denitrification, dust removal and noise reduction composite device" with application number 201611256827.4, low-temperature plasma technology combined with SCR system is used to achieve exhaust gas purification. The low-temperature plasma technology consumes high energy in this invention. Discharge electrodes can fail due to ash in the flue gas. Since the invention has two reactors, the system needs to occupy a larger effective space of the ship.
发明内容Contents of the invention
本发明的目的是为了开发高效、经济、能够满足IMO排放标准的一体化技术而提供的一种钠碱法船舶尾气脱硫脱硝一体化装置及方法。The purpose of the present invention is to provide an integrated device and method for desulfurization and denitrification of ship tail gas by sodium-alkali method for the purpose of developing an integrated technology that is efficient, economical, and capable of meeting IMO emission standards.
本发明的目的是这样实现的：The purpose of the present invention is achieved like this:
一种钠碱法船舶尾气脱硫脱硝一体化装置，包括NO氧化器3、洗涤塔4、废水处理主反应器14、中和反应器21，An integrated device for desulfurization and denitrification of ship tail gas by sodium-alkali method, including an NO oxidizer 3, a scrubber 4, a wastewater treatment main reactor 14, and a neutralization reactor 21,
船舶柴油机1连通烟气三通阀2，烟气三通阀2的一路连通到大气，另一路通过NO氧化器3连接洗涤塔4的底部；洗涤塔4通过废水驳运泵13与废水处理主反应器14顶部相连，铝合金粉末储存罐23和碱液缓冲罐25分别通过铝合金粉末加装电磁阀24和碱性溶液加装电磁阀26与废水处理主反应器14连接，废水处理主反应器14内设置有空气分布器15，空气分布器15与储气罐16相连，废水处理主反应器14内设导流挡板18，所述导流挡板18包括上部导流挡板和下部导流挡板，上部导流挡板和下部导流挡板交替放置，废水处理主反应器14的底部与渣滓收集柜17连接；The marine diesel engine 1 is connected to the flue gas three-way valve 2, one way of the flue gas three-way valve 2 is connected to the atmosphere, and the other way is connected to the bottom of the scrubber 4 through the NO oxidizer 3; the scrubber 4 is mainly reacted with the wastewater treatment through the wastewater transfer pump 13 The top of the device 14 is connected, and the aluminum alloy powder storage tank 23 and the lye buffer tank 25 are respectively connected to the main reactor 14 for wastewater treatment through the addition of an electromagnetic valve 24 for aluminum alloy powder and an additional electromagnetic valve 26 for alkaline solution, and the main reactor for wastewater treatment 14 is provided with an air distributor 15, the air distributor 15 is connected to the air storage tank 16, and the main reactor 14 for wastewater treatment is equipped with a guide baffle 18, and the guide baffle 18 includes an upper guide baffle and a lower guide The flow baffles, the upper baffles and the lower baffles are placed alternately, and the bottom of the wastewater treatment main reactor 14 is connected to the slag collection cabinet 17;
废水处理主反应器14的气体出口与中和反应器21相连，酸性溶液储存柜28通过电磁流量控制阀29与中和反应器21的相连，废水处理主反应器14的液体出口与中和反应器21相连，中和反应器21通过废水碱度传感器31与废水监测装置32相连，废水监测装置32与三通阀33相连，三通阀33的一路通过废水驳运泵13连接废水处理主反应器14，另一路连接舷外。The gas outlet of the wastewater treatment main reactor 14 is connected with the neutralization reactor 21, the acid solution storage cabinet 28 is connected with the neutralization reactor 21 through the electromagnetic flow control valve 29, the liquid outlet of the wastewater treatment main reactor 14 is connected with the neutralization reaction The neutralization reactor 21 is connected to the wastewater monitoring device 32 through the wastewater alkalinity sensor 31, the wastewater monitoring device 32 is connected to the three-way valve 33, and one of the three-way valves 33 is connected to the wastewater treatment main reactor through the wastewater transfer pump 13 14. Another way to connect the outboard.
本发明还包括这样一些结构特征：The present invention also includes such structural features:
1.所述洗涤塔4分为上下两层，上层通过洗涤液冷却器12和高位碱液循环泵11与洗涤塔4的底部连接，下层喷淋系统通过低位碱液循环泵9与洗涤塔4的底部连接；碱液罐7与碱液供给泵8连接，供给泵8一方面与碱液缓冲罐25相连，另一方面与碱液循环管路相连，碱液循环管路上设置有pH传感器9；1. The washing tower 4 is divided into upper and lower layers, the upper layer is connected with the bottom of the washing tower 4 through the washing liquid cooler 12 and the high-level lye circulation pump 11, and the lower floor spray system is connected with the washing tower 4 through the low-level lye circulation pump 9 The bottom of the lye tank 7 is connected with the lye supply pump 8, and the supply pump 8 is connected with the lye buffer tank 25 on the one hand, and is connected with the lye circulation pipeline on the other hand, and the lye circulation pipeline is provided with a pH sensor 9 ;
2.废水pH传感器20连接废水监测单元22并将信息反馈给废水监测单元22，铝合金粉末加装电磁阀24、碱性溶液加装电磁阀26均连接废水监测单元22并在废水监测单元22的作用下调节开度；废水碱度传感器31连接pH控制单元30并将信息反馈给pH控制单元30，电磁流量控制阀29连接pH控制单元30并在pH控制单元30的作用下调节开度；2. The wastewater pH sensor 20 is connected to the wastewater monitoring unit 22 and feeds information back to the wastewater monitoring unit 22. The aluminum alloy powder is equipped with a solenoid valve 24, and the alkaline solution is equipped with a solenoid valve 26. The opening is adjusted under the effect of the wastewater alkalinity sensor 31 is connected to the pH control unit 30 and the information is fed back to the pH control unit 30, and the electromagnetic flow control valve 29 is connected to the pH control unit 30 and the opening is adjusted under the action of the pH control unit 30;
3.所述上部导流挡板上设置有开孔；3. The upper guide baffle is provided with openings;
4.还包括安全阀27，所述安全阀27设置在废水处理主反应器14上；还包括滤网19，所述滤网19设置在废水处理主反应器14的液体出口上。4. It also includes a safety valve 27, which is arranged on the main reactor 14 for wastewater treatment; and a filter screen 19, which is arranged on the liquid outlet of the main reactor 14 for wastewater treatment.
一种钠碱法船舶尾气脱硫脱硝一体化方法，包括以下步骤：An integrated method for desulfurization and denitrification of ship tail gas by sodium-alkali method, comprising the following steps:
a、船舶柴油机1排出的废气经过烟气三通阀2和NO氧化器3，在NO氧化器3中NO被氧化为NO2；经过氧化的废气从洗涤塔4的底部进入，NO2和SO2与洗涤液反应转变为硝酸钠、亚硝酸钠、亚硫酸钠，之后废气通过除雾装置5和排气引风机6排入大气；所述洗涤液的pH为10～11，当洗涤液的pH不满足洗涤条件时，碱液罐7中的NaOH溶液加到洗涤液中，洗涤液通过碱液供给泵8分别从洗涤塔4的中部和上部进入并对废气进行洗涤，洗涤塔4中的洗涤液处于循环洗涤状态；a. The waste gas discharged from the marine diesel engine 1 passes through the flue gas three-way valve 2 and the NO oxidizer 3. In the NO oxidizer 3, NO is oxidized to NO2 ; the oxidized waste gas enters from the bottom of the scrubber 4, NO2 and SO2 react with the washing liquid to convert into sodium nitrate, sodium nitrite, and sodium sulfite, and then the waste gas is discharged into the atmosphere through the demisting device 5 and the exhaust fan 6; the pH of the washing liquid is 10-11, when the pH of the washing liquid is not When the washing conditions are satisfied, the NaOH solution in the lye tank 7 is added to the washing liquid, and the washing liquid enters from the middle and the upper part of the washing tower 4 respectively through the alkali liquid supply pump 8 and washes the exhaust gas. The washing liquid in the washing tower 4 In cycle washing state;
b、洗涤废水从废水处理主反应器14的上部进入，同时由铝合金粉末储存罐23和碱液缓冲罐25分别补充铝合金粉末和NaOH溶液，在碱性环境中铝合金粉末将洗涤废水中的硝酸盐和亚硝酸盐还原为NH3和N2，空气分布器15从废水处理主反应器14的底部充入空气，使废水中的亚硫酸盐氧化为硫酸盐，废水处理主反应器14产生的NH3和N2通过设置在导流挡板18顶部的气孔收集，之后和洗涤废水一同进入中和反应器21，废水pH控制单元22调节中和反应器21的溶液呈中性，NH3在中和反应器21中被水吸收转化为铵盐；b. The washing wastewater enters from the upper part of the wastewater treatment main reactor 14, while the aluminum alloy powder storage tank 23 and the lye buffer tank 25 are respectively supplemented with aluminum alloy powder and NaOH solution. In an alkaline environment, the aluminum alloy powder will dissolve the washing wastewater The nitrate and nitrite in the waste water are reduced to NH3 and N2 , the air distributor 15 is filled with air from the bottom of the wastewater treatment main reactor 14, and the sulfite in the wastewater is oxidized to sulfate, and the wastewater treatment main reactor 14 ProducedNH3 andN2 are collected through the air holes arranged on the top of the diversion baffle 18, and then enter the neutralization reactor 21 together with the washing wastewater, and the wastewater pH control unit 22 adjusts the solution of the neutralization reactor 21 to be neutral, and the NH3 is converted into ammonium salt by water absorption in the neutralization reactor 21;
c、废水经过处理后进入废水监测单元32，若水质合格，则废水直接排海；若水质不合格，则废水会再次循环到废水处理主反应器14进行二次处理。c. After the wastewater is treated, it enters the wastewater monitoring unit 32. If the water quality is qualified, the wastewater is directly discharged into the sea; if the water quality is unqualified, the wastewater will be recycled to the wastewater treatment main reactor 14 for secondary treatment.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
(1)本发明的一体化脱除技术只有一座洗涤塔，很大程度上减小了系统的占地面积，由于只有一座洗涤塔，减少了辅助机械，能耗明显降低，经济性显著提高；(1) The integrated removal technology of the present invention has only one washing tower, which greatly reduces the floor area of the system. Since there is only one washing tower, auxiliary machinery is reduced, energy consumption is significantly reduced, and economic efficiency is significantly improved;
(2)本发明采用NaOH溶液作为吸收液，烟气中的NO和SO2是通过洗涤塔内部发生酸碱中和反应脱除的，酸碱中和反应反应速率快、反应彻底、脱除效率很高，能够有效脱除烟气中的NO和SO2，使船舶排放满足IMO的标准；(2 ) The present invention adopts NaOH solution as the absorption liquid, and NO and SO in the flue gas are removed by the acid-base neutralization reaction inside the washing tower, and the acid-base neutralization reaction has fast reaction rate, complete reaction and high removal efficiency Very high, can effectively remove NO and SO2 in flue gas, so that ship emissions meet IMO standards;
(3)本发明能够有效处理废水中的硝酸盐和亚硝酸盐，使废水水质满足IMO的相关标准；(3) The present invention can effectively treat nitrate and nitrite in the waste water, so that the water quality of the waste water meets the relevant standards of IMO;
(4)本发明增加了废水在废水处理主反应器中流动时间，加强了废水流动的湍流强度，提高了废水的处理效率；(4) The present invention increases the flow time of waste water in the main reactor for waste water treatment, strengthens the turbulence intensity of waste water flow, and improves the treatment efficiency of waste water;
(5)本发明的消耗物为NaOH溶液、铝合金粉末等，消耗物为常见物质，其价格合理，在船舶上的储存和使用比较方便；(5) The consumables of the present invention are NaOH solution, aluminum alloy powder, etc., and the consumables are common substances with reasonable price and convenient storage and use on ships;
(6)本发明废水处理产生的渣滓主要成分是Al(OH)3，将渣滓收集后，在陆地上经过处理可以二次利用。(6) The main component of the dregs produced by the wastewater treatment in the present invention is Al(OH)3 . After the dregs are collected, they can be reused after being treated on land.
附图说明Description of drawings
图1是发明的钠碱法船舶尾气脱硫脱硝一体化装置的示意图；Fig. 1 is the schematic diagram of the inventive sodium-alkali process ship tail gas desulfurization and denitrification integrated device;
图2为废水处理主反应器中上部导流挡板示意图；Fig. 2 is a schematic diagram of the upper diversion baffle in the main reactor for wastewater treatment;
图3为空气分布器的俯视图。Figure 3 is a top view of the air distributor.
具体实施方式Detailed ways
本发明利用NaOH溶液作为洗涤液去除烟气中的NO和SO2；具体地，烟气中的NO在NO氧化器中被氧化为NO2，在洗涤塔中，烟气中的NO2和SO2被洗涤水吸收转化为硝酸、亚硝酸、亚硫酸，进而与该洗涤液中的NaOH发生酸碱中和反应，烟气中的NO和SO2转变为硝酸钠、亚硝酸钠、亚硫酸钠；本发明所提到的NO氧化器可采用臭氧氧化技术、催化氧化技术、等离子体技术等所有能将NO氧化为NO2的方法；本发明所述的洗涤水包括所有碱性洗涤溶液；本发明提到的铝合金粉末是指所有的以铝为反应主体的金属粉末；在废水处理主反应器中，铝合金粉末将废水中的硝酸盐、亚硝酸盐快速地还原为NH3和N2，该反应发生在pH为10～11的碱性环境中，铝合金粉末主要转化为氢氧化铝沉淀，最终收集在渣滓收集柜中。The present invention uses NaOH solution as a scrubbing solution to remove NO and SO2 in the flue gas; specifically, NO in the flue gas is oxidized to NO2 in the NO oxidizer, and in the scrubber, the NO2 and SO in the flue gas2 Absorbed by the washing water and transformed into nitric acid, nitrous acid and sulfurous acid, and then undergoes an acid-base neutralization reaction with NaOH in the washing liquid, and the NO and SO2 in the flue gas are transformed intosodium nitrate, sodium nitrite and sodium sulfite; The NO oxidizer mentioned in the invention can adopt all methods such as ozone oxidation technology, catalytic oxidation technology, and plasma technology that can oxidize NO into NO2 ; the washing water described in the present invention includes all alkaline washing solutions; the present invention provides The obtained aluminum alloy powder refers to all metal powders with aluminum as the main reaction; in the main reactor of wastewater treatment, the aluminum alloy powder quickly reduces the nitrate and nitrite in the wastewater to NH3 and N2 , the The reaction takes place in an alkaline environment with a pH of 10-11, and the aluminum alloy powder is mainly converted into aluminum hydroxide precipitate, which is finally collected in the dross collection cabinet.
本发明钠碱法船舶尾气脱硫脱硝一体化装置本系统包括：废气处理单元、碱液供给单元、废水处理单元和控制单元；废气处理单元你的主体为洗涤塔，该洗涤塔为两层设计，上层洗涤水的主要作用是脱除烟气中的NO和SO2，下层洗涤水的作用主要是降低烟气的温度，以利于废气吸收；碱液供给单元由碱液储存罐、碱液供给泵、高位碱液循环泵、低位碱液循环泵和洗涤液冷却器组成；所述的废水处理单元主要包括废水处理主反应器、储气罐、铝合金粉末储存罐、碱液缓冲罐、渣滓收集柜、中和反应器、酸性溶液储存柜和渣滓收集柜等；废水处理主反应器内部交替加装上下导流挡板，废水在处理器中呈现出上下蛇形流动，以减小废水处理主反应器的尺寸，增加铝合金粉末与废水的反应时间，同时会产生较强的湍流，提高废水中各组分的混合均匀度；废水处理主反应器上部挡板的上边缘设计开孔，便于产生的气体能够顺利排出，开孔的数量和孔径根据实际情况确定；废水pH控制单元通过控制碱性溶液加装电磁阀的开度维持废水主反应器的pH为10～11；废水处理控制单元通过控制酸性溶液的加入量，进而去除废水处理过程中产生的NH3，避免二次污染；在废水处理主反应器靠近废水入口的底部设置空气分布器，储气罐中的空气通过空气分布器形成大量的微小气泡，加快亚硫酸盐的氧化速度。The integrated device for desulfurization and denitrification of ship tail gas by sodium-alkali method of the present invention. The system includes: a waste gas treatment unit, a lye supply unit, a waste water treatment unit and a control unit; the main body of the waste gas treatment unit is a washing tower, which is designed in two layers. The main function of the upper layer of washing water is to remove NO and SO2 in the flue gas, and the function of the lower layer of washing water is mainly to reduce the temperature of the flue gas to facilitate the absorption of waste gas; the lye supply unit consists of a lye storage tank and an lye supply pump , a high lye circulation pump, a low lye circulation pump and a washing liquid cooler; the wastewater treatment unit mainly includes a wastewater treatment main reactor, a gas storage tank, an aluminum alloy powder storage tank, an lye buffer tank, and a dregs collection Cabinets, neutralization reactors, acid solution storage cabinets and waste collection cabinets, etc.; the interior of the main reactor for wastewater treatment is alternately installed with upper and lower guide baffles, and the wastewater presents a serpentine flow up and down in the processor to reduce the main waste water treatment. The size of the reactor increases the reaction time between the aluminum alloy powder and the wastewater, and at the same time generates strong turbulence, which improves the mixing uniformity of the components in the wastewater; the upper edge of the upper baffle of the wastewater treatment main reactor is designed with holes to facilitate The generated gas can be discharged smoothly, and the number and diameter of the openings are determined according to the actual situation; the wastewater pH control unit maintains the pH of the wastewater main reactor at 10-11 by controlling the opening of the alkaline solution and adding a solenoid valve; the wastewater treatment control unit By controlling the amount of acid solution added, the NH3 produced in the wastewater treatment process is removed to avoid secondary pollution; an air distributor is installed at the bottom of the wastewater treatment main reactor near the wastewater inlet, and the air in the air storage tank passes through the air distributor A large number of tiny bubbles are formed to accelerate the oxidation rate of sulfite.
本发明所提出的一体化脱除技术是一种湿法脱除方法，利用NaOH溶液作为吸收剂，在洗涤塔中，洗涤溶液的流向和烟气的流向呈逆向对流形式。在进入洗涤塔前，废气中的NO在NO氧化器中被氧化为NO2，随后进入洗涤塔，其中的NO2和SO2与洗涤液中的水反应生成硝酸、亚硝酸和亚硫酸，进一步地被洗涤液中的NaOH中和为硝酸盐溶液、亚硝酸盐溶液和亚硫酸盐溶液。洗涤塔排出的洗涤液经过废水处理主反应器处理，铝合金粉末将废液中的硝酸盐和亚硝酸盐还原为NH3和N2，将亚硫酸盐转化为硫酸盐，经过处理合格的废水排海，达到尾气净化的效果。在本发明中水处理单元是通过加入铝合金粉末和曝气等方法对废水进行无害化处理。本发明大大减少了系统占地面积，提高了反应的效率，系统耗能明显降低。The integrated removal technology proposed by the present invention is a wet removal method, using NaOH solution as an absorbent, and in the washing tower, the flow direction of the washing solution and the flow direction of the flue gas are in the form of reverse convection. Before entering the scrubber, NO in the exhaust gas is oxidized to NO2 in the NO oxidizer, and then enters the scrubber, where NO2 and SO2 react with water in the scrubbing liquid to form nitric acid, nitrous acid and sulfurous acid, further The NaOH in the ground was washed liquid is neutralized into nitrate solution, nitrite solution and sulfite solution. The washing liquid discharged from the washing tower is treated by the main reactor for wastewater treatment. The aluminum alloy powder reduces the nitrate and nitrite in the waste liquid to NH3 and N2 , and converts sulfite to sulfate. The qualified waste water after treatment Discharge the sea to achieve the effect of exhaust gas purification. In the present invention, the water treatment unit conducts harmless treatment of waste water by adding aluminum alloy powder, aeration and other methods. The invention greatly reduces the area occupied by the system, improves the efficiency of the reaction, and significantly reduces the energy consumption of the system.
本发明提供该脱硫脱硝一体化技术的具体实施步骤如下：The specific implementation steps of the desulfurization and denitrification integration technology provided by the present invention are as follows:
(1)船舶柴油机排出的尾气经过烟气三通阀和NO氧化器，从洗涤塔的塔底进入洗涤塔，烟气在洗涤塔中与NaOH溶液反应，之后烟气经过除雾装置和排气引风机排入大气。(1) The exhaust gas from the marine diesel engine passes through the flue gas three-way valve and NO oxidizer, and enters the scrubber from the bottom of the scrubber. The flue gas reacts with NaOH solution in the scrubber, and then the flue gas passes through the demisting device and exhaust The induced draft fan discharges into the atmosphere.
(2)NaOH溶液由碱液罐供给，混入洗涤液，洗涤液通过碱液供给泵和洗涤液冷却器分别从洗涤的中部和上部进入洗涤塔对烟气进行洗涤，洗涤塔中的洗涤液处于循环洗涤状态，当循环洗涤液的pH不满足洗涤条件时，新的NaOH溶液加到洗涤系统，多余的洗涤液排入废水处理主反应器。(2) The NaOH solution is supplied by the lye tank and mixed into the washing liquid. The washing liquid enters the washing tower from the middle and upper parts of the washing to wash the flue gas through the lye supply pump and the washing liquid cooler respectively. The washing liquid in the washing tower is at In the cycle washing state, when the pH of the circulating washing liquid does not meet the washing conditions, new NaOH solution is added to the washing system, and the excess washing liquid is discharged into the main reactor for wastewater treatment.
(3)洗涤废水从废水处理主反应器的上部进入，同时在废水处理主反应器中加入铝合金粉末和NaOH溶液，NaOH溶液调节洗涤水的pH为10～11，在碱性环境中铝合金粉末将废水中的硝酸盐和亚硝酸盐还原为NH3和N2。空气分布器从废水处理主反应器的底部充入空气，使废水中的亚硫酸盐氧化为硫酸盐，废水处理主反应器产生的NH3和N2通过在废水处理主反应器导流挡板顶部的气孔收集，之后和洗涤废水一同进入中和反应器，废水pH控制单元调节中和反应器的溶液呈中性，NH3在中和反应器中被水吸收转化为铵盐。(3) Washing wastewater enters from the upper part of the main reactor for wastewater treatment, and at the same time, aluminum alloy powder and NaOH solution are added to the main reactor for wastewater treatment. The NaOH solution adjusts the pH of the washing water to 10-11. The powder reduces nitrate and nitrite in wastewater to NH3 and N2 . The air distributor is filled with air from the bottom of the wastewater treatment main reactor to oxidize the sulfite in the wastewater to sulfate, and theNH3 andN2 produced by the wastewater treatment main reactor pass through the diversion baffle in the wastewater treatment main reactor The pores on the top are collected, and then enter the neutralization reactor together with the washing wastewater. The wastewater pH control unit adjusts the solution in the neutralization reactor to be neutral, and NH3 is absorbed by water in the neutralization reactor and converted into ammonium salt.
(4)废水经过处理后进入废水监测单元，若水质合格，则废水直接排海；若水质不合格，则废水会再次循环到废水处理主反应器进行二次处理。(4) After the wastewater is treated, it enters the wastewater monitoring unit. If the water quality is qualified, the wastewater will be directly discharged into the sea; if the water quality is not qualified, the wastewater will be recycled to the wastewater treatment main reactor for secondary treatment.
本发明涉及的主要化学反应有：Main chemical reaction that the present invention relates to has:
(1)洗涤塔:(1) Scrubber:
2NO2+H2O→HNO3+HNO22NO2 +H2 O→HNO3 +HNO2
SO2+H2O→H2SO3SO2 +H2 O→H2 SO3
HNO3+NaOH→NaNO3+H2OHNO3 +NaOH→NaNO3 +H2 O
HNO2+NaOH→NaNO2+H2OHNO2 +NaOH→NaNO2 +H2 O
H2SO3+2NaOH→Na2SO3+2H2OH2SO3+ 2NaOH→Na2SO3+ 2H2O
(2)废水处理主反应器：(2) Wastewater treatment main reactor:
3NO3—+2Al+3H2O→3NO2—+2Al(OH)3↓3NO3— +2Al+3H2 O→3NO2— +2Al(OH)3 ↓
NO2—+2Al+5H2O→3NH3↑+2Al(OH)3↓+OH—NO2— +2Al+5H2 O→3NH3 ↑+2Al(OH)3 ↓+OH—
2NO2—+2Al+4H2O→N2↑+2Al(OH)3↓+2OH—2NO2— +2Al+4H2 O→N2 ↑+2Al(OH)3 ↓+2OH—
Na2SO3+O2→Na2SO4Na2 SO3 +O2 →Na2 SO4
下面结合附图对本发明做详细地描述：The present invention is described in detail below in conjunction with accompanying drawing:
结合图1，1为船舶柴油机、2为烟气三通阀、3为NO氧化器、4为洗涤塔、5为除雾装置、6为排气引风机、7为碱液罐、8为碱液供给泵、9为pH传感器、10为低位碱液循环泵、11为高位碱液循环泵、12为洗涤液冷却器、13为废水驳运泵、14为废水处理主反应器、15为空气分布器、16为储气罐、17为渣滓收集柜、18为导流挡板、19为滤网、20为废水pH传感器、21为中和反应器、22为废水监测单元、23为铝合金粉末储存罐、24为铝合金粉末加装电磁阀、25为碱液缓冲罐、26为碱性溶液加装电磁阀、27为安全阀、28为酸性溶液储存柜、29为电磁流量控制阀、30为pH控制单元、31为废水碱度传感器、32为废水监测装置、33为三通阀。本发明是利用NaOH溶液作为吸收剂对船舶尾气中的NO和SO2进行脱除。首先船舶柴油机1排出的烟气进入NO氧化器3，在NO氧化器中NO被氧化为NO2，之后烟气从洗涤塔4的底部进入洗涤塔。NaOH溶液由碱液罐7提供，通过碱液泵8的将碱液供给洗涤液循环系统，在洗涤液循环系统中碱液分别通过低位洗涤液循环泵10、高位洗涤液循环泵11、洗涤液冷却器12，从洗涤塔的中部、上部进行喷淋洗涤，洗涤液将烟气中的NO和SO2转变为硝酸盐、亚硝酸盐和亚硫酸盐。当碱液循环系统的pH较低时，pH传感器9会通过控制单元启动碱液供给泵8向系统提供碱液，经过洗涤的烟气通过除雾装置5和排气引风机6排入大气。Combined with Figure 1, 1 is the marine diesel engine, 2 is the flue gas three-way valve, 3 is the NO oxidizer, 4 is the washing tower, 5 is the defogging device, 6 is the exhaust fan, 7 is the lye tank, and 8 is the alkali Liquid supply pump, 9 is pH sensor, 10 is low lye circulation pump, 11 is high lye circulation pump, 12 is washing liquid cooler, 13 is waste water transfer pump, 14 is main reactor for waste water treatment, 15 is air distribution device, 16 is a gas storage tank, 17 is a garbage collection cabinet, 18 is a diversion baffle, 19 is a filter screen, 20 is a wastewater pH sensor, 21 is a neutralization reactor, 22 is a wastewater monitoring unit, and 23 is an aluminum alloy powder Storage tank, 24 is aluminum alloy powder with electromagnetic valve, 25 is lye buffer tank, 26 is alkaline solution with electromagnetic valve, 27 is safety valve, 28 is acid solution storage cabinet, 29 is electromagnetic flow control valve, 30 31 is a wastewater alkalinity sensor, 32 is a wastewater monitoring device, and 33 is a three-way valve. The invention usesNaOH solution as an absorbent to remove NO and SO2 in ship tail gas. First, the flue gas discharged from the marine diesel engine 1 enters the NO oxidizer 3 , in which NO is oxidized to NO2 , and then the flue gas enters the scrubber 4 from the bottom of the scrubber 4 . The NaOH solution is provided by the lye tank 7, and the lye is supplied to the washing solution circulation system by the lye pump 8, and in the washing solution circulation system, the lye passes through the low-position washing liquid circulation pump 10, the high-position washing liquid circulation pump 11, and the washing liquid respectively. Cooler 12, spray and wash from the middle and upper parts of the washing tower, and the washing liquid converts NO and SO2 in the flue gas into nitrate, nitrite and sulfite. When the pH of the lye circulation system is low, the pH sensor 9 will start the lye supply pump 8 through the control unit to provide lye to the system, and the washed flue gas will be discharged into the atmosphere through the demisting device 5 and the exhaust fan 6.
洗涤产生的废水由废水驳运泵13驳运至废水处理主反应器14中，并从废水处理主反应器的顶部进入废水处理主反应器。合理控制驳运泵的扬程，使进入废水处理主反应器的废水不能跨越第一道导流挡板。储存在铝合金粉末储存罐23中的铝合金粉末通过电磁阀24加入废气处理主反应器。用于提升废水处理主反应器pH值的NaOH溶液存储在碱液缓冲罐25中，通过电磁阀26加入废水处理主反应器中。储气罐16中的空气通过空气分布器15进入废水处理主反应器，空气分布器15使空气形成微小气泡，增大空气与洗涤废水的接触面积，完成对废液中亚硫酸盐的氧化，同时促进铝合金粉末与洗涤水的混合，提高反应效率。为保证废水处理的高效进行，废水处理主反应器的pH需维持在10～11左右，废水处理的质量是通过废水处理控制单元22控制铝合金粉末加装电磁阀24和NaOH溶液加装电磁阀26实现的。其中铝合金粉末储存在铝合金粉末储存罐23中，NaOH溶液储存在碱液缓冲罐25中。当废水处理主反应器由于故障引起压力急剧升高时，位于废水处理主反应器顶部的废水处理主反应器安全阀27自动开启，泄放压力。废水处理主反应器正常工作，产生的氨气通过导流挡板上方的孔道收集，最后进入中和反应器21中，废水处理主反应器产生的渣滓收集到渣滓收集柜32中。从废水处理主反应器排出的废水进入中和反应器21。在废水pH控制单元30的调控下，储存在酸性溶液储存柜28中的酸性溶液通过电磁流量控制阀29进入中和反应器，调节中和反应器中的溶液至中性。从中和反应器排出的废水经过废水监测单元32，若废水水质合格，则直接排海；若水质不合格，则废水被循环至废水处理主反应器再次处理。The wastewater produced by washing is transferred to the wastewater treatment main reactor 14 by the wastewater transfer pump 13, and enters the wastewater treatment main reactor from the top of the wastewater treatment main reactor. Reasonably control the head of the transfer pump so that the wastewater entering the main reactor of wastewater treatment cannot cross the first diversion baffle. The aluminum alloy powder stored in the aluminum alloy powder storage tank 23 is fed into the exhaust gas treatment main reactor through the solenoid valve 24 . The NaOH solution used to increase the pH value of the main reactor for wastewater treatment is stored in the alkali buffer tank 25 and fed into the main reactor for wastewater treatment through a solenoid valve 26 . The air in the air storage tank 16 enters the main reactor for wastewater treatment through the air distributor 15, and the air distributor 15 makes the air form tiny bubbles, which increases the contact area between the air and the washing wastewater, and completes the oxidation of sulfite in the waste liquid. At the same time, it promotes the mixing of aluminum alloy powder and washing water to improve the reaction efficiency. In order to ensure efficient wastewater treatment, the pH of the main reactor for wastewater treatment needs to be maintained at about 10-11, and the quality of wastewater treatment is controlled by the wastewater treatment control unit 22. Add solenoid valve 24 for aluminum alloy powder and solenoid valve for NaOH solution 26 achieved. Wherein the aluminum alloy powder is stored in the aluminum alloy powder storage tank 23, and the NaOH solution is stored in the lye buffer tank 25. When the pressure of the wastewater treatment main reactor rises sharply due to a fault, the wastewater treatment main reactor safety valve 27 located at the top of the wastewater treatment main reactor automatically opens to release the pressure. The main reactor for wastewater treatment works normally, and the generated ammonia gas is collected through the channel above the diversion baffle, and finally enters the neutralization reactor 21 , and the dross produced by the main reactor for wastewater treatment is collected into the dross collection cabinet 32 . The wastewater discharged from the wastewater treatment main reactor enters the neutralization reactor 21 . Under the control of the wastewater pH control unit 30, the acid solution stored in the acid solution storage cabinet 28 enters the neutralization reactor through the electromagnetic flow control valve 29, and the solution in the neutralization reactor is adjusted to be neutral. The wastewater discharged from the neutralization reactor passes through the wastewater monitoring unit 32. If the quality of the wastewater is qualified, it will be directly discharged into the sea; if the quality of the wastewater is unqualified, the wastewater will be recycled to the wastewater treatment main reactor for further treatment.
本文中提供的钠碱法船舶尾气脱硫脱硝一体化装置的系统布置图仅作为系统的原理性示意，本发明仅以填料塔作为示范,但洗涤塔应该被广泛地理解为包括填料塔、喷淋塔等所有通过洗涤方式脱除有害气体的塔型，本发明中的洗涤液仅以NaOH溶液作为示意，但是应该广泛地理解为包括其他所有形式的碱性洗涤液；本发明废水处理单元用铝合金粉末作为示意，其含义应该包括所有的以铝为主的金属还原剂粉末；对于空气分布器和导流上挡板本文仅仅提供示意图，对于上述提到的所有可能的应用本发明的原理进行尾气处理的技术都应在本专利的保护范围。The system layout diagram of the sodium-alkali process ship tail gas desulfurization and denitrification integrated device provided in this article is only a schematic diagram of the system. The present invention only uses a packed tower as an example, but the washing tower should be broadly understood as including packed towers, spraying towers, etc. Towers and other towers that remove harmful gases by washing, the washing liquid in the present invention is only shown as NaOH solution, but it should be widely understood as including all other forms of alkaline washing liquid; the waste water treatment unit of the present invention uses aluminum Alloy powder is used as an illustration, and its meaning should include all metal reducing agent powders mainly based on aluminum; for the air distributor and the upper baffle plate of the guide, this paper only provides a schematic diagram, and all possible applications of the above-mentioned principles of the present invention are carried out The technologies for tail gas treatment should all be within the scope of protection of this patent.
虽然本文中已经结合实施例对本发明进行了描述，但应该理解的是，本发明不局限于所公开的实施方式，而是在如所附权利要求中限定的一样涵盖其特征的各种组合或者修改已经包含在本发明的范围内的一些其他应用。Although the invention has been described herein in connection with the examples, it is to be understood that the invention is not limited to the disclosed embodiments but encompasses various combinations or combinations of features thereof as defined in the appended claims. Modifying some other applications is already included within the scope of the invention.
综上：本发明公开了一种钠碱法船舶尾气脱硫脱硝一体化方法和装置，该系统主要包括：废气处理单元、碱液供给单元、废水处理主反应器、控制单元等。碱液供给单元主要包括碱液储存罐、碱液供给泵和洗涤液冷却器等。废水处理主反应器主要包括铝合金粉末储存罐、碱液缓冲罐和中和反应器等。在洗涤塔中，利用酸碱中和反应将烟气中的NO和SO2转变为硝酸盐、亚硝酸盐、亚硫酸盐，使船舶柴油机废气排放满足IMO的排放标准。在废水处理主反应器中，利用铝合金粉末将硝酸盐和亚硝酸盐转化为NH3和N2，将亚硫酸盐氧化为硫酸盐。废水处理主反应器中产生的NH3通过其上方的通道进入中和反应器，在中和反应器中碱性洗涤废水被酸性溶液中和，NH3溶与水形成铵盐，最终将符合IMO排放标准的洗涤水排海，本发明是一种洁净、低能耗、高效率的船舶尾气脱硫脱硝一体化技术。In summary: the present invention discloses an integrated method and device for desulfurization and denitrification of ship tail gas by sodium-alkali method. The system mainly includes: waste gas treatment unit, lye supply unit, main reactor for wastewater treatment, control unit, etc. The lye supply unit mainly includes lye storage tank, lye supply pump and washing liquid cooler. The main reactor for wastewater treatment mainly includes aluminum alloy powder storage tank, lye buffer tank and neutralization reactor. In the scrubber, the acid- base neutralization reaction is used to convert NO and SO2 in the flue gas into nitrate, nitrite, and sulfite, so that the exhaust gas emission of marine diesel engines meets the emission standards of IMO. In the wastewater treatment main reactor, aluminum alloy powder is used to convert nitrate and nitrite into NH3 and N2 , and oxidize sulfite to sulfate. TheNH3 produced in the wastewater treatment main reactor enters the neutralization reactor through the channel above it, and in the neutralization reactor, the alkaline washing wastewater is neutralized by the acidic solution, and theNH3 dissolves with water to form an ammonium salt, which will eventually comply with IMO Discharging standard washing water into the sea, the invention is a clean, low energy consumption and high efficiency integrated technology for desulfurization and denitrification of ship tail gas.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810514594.6ACN108704478A (en) | 2018-05-25 | 2018-05-25 | Sodium alkali ship tail gas denitration integrated device and method |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810514594.6ACN108704478A (en) | 2018-05-25 | 2018-05-25 | Sodium alkali ship tail gas denitration integrated device and method |
| Publication Number | Publication Date |
|---|---|
| CN108704478Atrue CN108704478A (en) | 2018-10-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810514594.6APendingCN108704478A (en) | 2018-05-25 | 2018-05-25 | Sodium alkali ship tail gas denitration integrated device and method |
| Country | Link |
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