技术领域technical field
本发明属于循环流化床锅炉技术领域，具体涉及一种超超临界CFB锅炉脱硫废水零排放处理系统及方法。The invention belongs to the technical field of circulating fluidized bed boilers, and in particular relates to a zero-discharge treatment system and method for ultra-supercritical CFB boiler desulfurization wastewater.
背景技术Background technique
近年来，循环流化床(CFB)锅炉因其燃料适应性好和节能环保的优势得到了迅速发展，是我国劣质煤燃料实现高效清洁利用的重要途径，其发展趋势向高参数大容量方向靠拢。截止目前我国超临界CFB锅炉机组已投产13台，达到世界领先水平，随着研究的深入和市场需要，超超临界CFB锅炉已成为世界各国的重点研究对象。SO2作为电厂排放的污染物之一，会对人体、植物乃至环境都造成巨大的伤害，严格控制SO2的排放是全球可持续发展的必然选择。对于SO2污染物的处理，超超临界CFB锅炉一般采用炉内喷石灰石脱硫技术，属于干法脱硫技术，该方法腐蚀性较低且没有废水排放，但是脱硫效率不够高、反应速度慢且吸收剂消耗大，SO2排放浓度无法达到部分地区的环保要求，特别是当燃用一些高硫低热值的劣质燃料如煤矸石、洗煤泥、油页岩、石煤、石油焦等CFB锅炉适用的燃料时更为明显，SO2超标排放将造成排污成本和投资运行费用大幅提高。并且石灰石利用率低，大量石灰石粉加入锅炉炉膛中以降低SO2排放浓度，带来的高Ca/S会影响锅炉燃烧，导致锅炉燃烧效率降低，增加煤耗，受热面系统磨损加重，造成其他锅炉部件积灰严重，最终影响锅炉长期稳定运行，并且形成的灰渣综合应用价值较低，还会造成新的固体废弃物处理问题。In recent years, circulating fluidized bed (CFB) boilers have developed rapidly due to their advantages in fuel adaptability, energy saving and environmental protection. They are an important way to realize efficient and clean utilization of inferior coal fuels in my country, and their development trend is closer to the direction of high parameters and large capacity. . Up to now, 13 supercritical CFB boiler units have been put into production in my country, reaching the world's leading level. With the deepening of research and market demand, ultra-supercritical CFB boilers have become the key research objects of countries all over the world. As one of the pollutants emitted by power plants, SO2 will cause great harm to the human body, plants and even the environment. Strict control of SO2 emissions is an inevitable choice for global sustainable development. For the treatment ofSO2 pollutants, ultra-supercritical CFB boilers generally adopt limestone spraying desulfurization technology in the furnace, which belongs to dry desulfurization technology. This method is less corrosive and has no waste water discharge, but the desulfurization efficiency is not high enough, the reaction speed is slow and the The consumption of solvent is large, and the concentration of SO2 emissions cannot meet the environmental protection requirements of some areas, especially when burning some inferior fuels with high sulfur and low calorific value, such as coal gangue, coal washing slime, oil shale, stone coal, petroleum coke, etc. CFB boilers are suitable It is more obvious when using fuel, and the excessive discharge of SO2 will cause a substantial increase in pollution discharge costs and investment and operation costs. Moreover, the utilization rate of limestone is low. A large amount of limestone powder is added to the boiler furnace to reduce the concentration of SO2 emissions. The high Ca/S brought by it will affect the combustion of the boiler, resulting in reduced combustion efficiency of the boiler, increased coal consumption, and increased wear of the heating surface system, causing other boilers Serious ash accumulation on parts will eventually affect the long-term stable operation of the boiler, and the comprehensive application value of the formed ash is low, and it will also cause new solid waste disposal problems.
采用湿法烟气脱硫技术则可以解决上述问题。石灰石—石膏湿法烟气脱硫技术是现阶段世界上技术最成熟且应用最广泛的脱硫技术，适用于任何机组容量和含硫量煤种的烟气脱硫。采用此种技术脱硫效率高，对负荷变化适用性好，设有旁路不影响锅炉机组运行，不受煤种限制，且脱硫后的副产物石膏杂质含量少质量较优，应用价值高可为电厂带来较为可观的收入。为了保证设备安全运行，防止设备腐蚀加快和影响石膏品质，在脱硫的过程中需定期排放一定量的脱硫废水进脱硫废水处理系统，脱硫废水水质呈弱酸性，含盐量高达25000～55000mg/L，悬浮物含量高达数万mg/L，含有大量Cl－、F－、SO32－、SO42－、Ca2+、Mg2+等离子与悬浮物，化学需氧量(COD)、亚硝酸盐、氟化物、重金属元素(As、Pb、Hg、Cd、Cr、Ni、Co、Zn等)均超标，极易结垢并且具有强腐蚀性，必须经过处理达标后才能排放。Using wet flue gas desulfurization technology can solve the above problems. Limestone-gypsum wet flue gas desulfurization technology is the most mature and widely used desulfurization technology in the world at this stage, and is suitable for flue gas desulfurization of any unit capacity and coal type with sulfur content. This technology has high desulfurization efficiency and good applicability to load changes. The bypass does not affect the operation of the boiler unit, and is not limited by coal types. The by-product gypsum after desulfurization has less impurity content and better quality, and has high application value. Power plants generate considerable income. In order to ensure the safe operation of equipment and prevent equipment corrosion from accelerating and affecting the quality of gypsum, a certain amount of desulfurization wastewater must be discharged regularly into the desulfurization wastewater treatment system during the desulfurization process. , the content of suspended solids is as high as tens of thousands mg/L, containing a large amount of Cl－ , F－ , SO32－ , SO42－ , Ca2+ , Mg2+ and other ions and suspended solids, chemical oxygen demand (COD), sub Nitrate, fluoride, and heavy metal elements (As, Pb, Hg, Cd, Cr, Ni, Co, Zn, etc.) all exceed the standard, are easily scaled and are highly corrosive, and must be treated to meet the standard before they can be discharged.
现有的脱硫废水处理方法主要包括化学沉淀法、生物处理法、烟道蒸发法和蒸汽浓缩蒸发法等。国内多数电厂均采用化学沉淀法处理脱硫废水，但废水经此方法处理后仍含高浓度盐分直接排放会影响环境；生物处理法系统复杂、造价较高、易形成有毒的有机硒和有机汞，引起二次污染。烟道蒸发法和蒸汽浓缩蒸发法都可实现脱硫废水零排放，但前者系统腐蚀较重、处理能力受限并且粉煤灰利用受影响；后者的多效蒸发技术尽管能带来较高的传热系数和热效率，操作灵活方便，但也具有设备易结垢、能耗较高、运行和投资成本费用高昂等缺点。The existing desulfurization wastewater treatment methods mainly include chemical precipitation method, biological treatment method, flue evaporation method and steam concentration evaporation method. Most power plants in China use the chemical precipitation method to treat desulfurization wastewater, but the wastewater still contains high concentrations of salt after being treated by this method, and the direct discharge will affect the environment; the biological treatment system is complicated, the cost is high, and it is easy to form toxic organic selenium and organic mercury. cause secondary pollution. Both the flue evaporation method and the steam concentration evaporation method can achieve zero discharge of desulfurization wastewater, but the former has serious system corrosion, limited processing capacity and affected the utilization of fly ash; although the latter’s multi-effect evaporation technology can bring higher The heat transfer coefficient and thermal efficiency are flexible and convenient to operate, but it also has the disadvantages of easy fouling of equipment, high energy consumption, high operation and investment costs, etc.
发明内容Contents of the invention
本发明针对现有的超超临界CFB锅炉采用炉内喷石灰石脱硫技术所带来的上述问题以及现有脱硫废水处理方法的不足之处，提出了一种利用超超临界CFB锅炉旋风分离器出口高温烟气作为热源驱动脱硫废水蒸发结晶，并利用后屏过热器进口的过热蒸汽预热脱硫废水的脱硫废水零排放处理系统及方法，该系统能提高脱硫效率、有效避免系统设备结垢、采用高温烟气作热源可只采用一效蒸发器即能充足蒸发脱硫废水降低投资运行费用，克服了多效蒸发设备投资费用高和能耗大的缺陷，为超超临界CFB锅炉脱硫废水零排放提供了一种新型的安全高效途径。Aiming at the above-mentioned problems caused by the limestone spraying technology in the furnace of the existing ultra-supercritical CFB boiler and the shortcomings of the existing desulfurization wastewater treatment method, the present invention proposes a method that utilizes the outlet of the cyclone separator of the ultra-supercritical CFB boiler. High-temperature flue gas is used as a heat source to drive the evaporation and crystallization of desulfurization wastewater, and the superheated steam imported from the rear screen superheater is used to preheat the desulfurization wastewater zero-discharge treatment system and method. The system can improve desulfurization efficiency and effectively avoid scaling of system equipment. High-temperature flue gas can be used as a heat source to fully evaporate desulfurization wastewater by using only one-effect evaporator to reduce investment and operation costs. A new safe and efficient way.
为达到上述目的，本发明采取的技术方案是：For achieving the above object, the technical scheme that the present invention takes is:
一种超超临界CFB锅炉脱硫废水零排放处理系统，包括依次设置的化学预处理系统、膜过滤系统、电渗析系统、脱硫废水预热系统、脱硫废水蒸发器、固液分离装置和蒸汽冷凝装置；A zero-discharge treatment system for ultra-supercritical CFB boiler desulfurization wastewater, including a chemical pretreatment system, a membrane filtration system, an electrodialysis system, a desulfurization wastewater preheating system, a desulfurization wastewater evaporator, a solid-liquid separation device, and a steam condensation device arranged in sequence ;
所述的化学预处理系统包括缓冲池、软化箱、压滤机和调节器，缓冲池、软化箱和调节器依次连接，软化箱将污泥送至压滤机，压滤机的出口端排出污泥；调节器与膜过滤系统相连；The chemical pretreatment system includes a buffer tank, a softening tank, a filter press and a regulator, the buffer tank, the softening tank and the regulator are connected in sequence, the softening tank sends the sludge to the filter press, and the outlet of the filter press discharges Sludge; the regulator is connected to the membrane filtration system;
所述的电渗析系统将处理后的脱硫废水先经真空脱气机脱气处理后再经废水泵输送至脱硫废水预热系统；In the electrodialysis system, the treated desulfurization wastewater is first degassed by a vacuum degasser and then transported to the desulfurization wastewater preheating system through a wastewater pump;
所述的脱硫废水预热系统包括预热器，预热器与脱硫废水蒸发器相连；The desulfurization wastewater preheating system includes a preheater connected to the desulfurization wastewater evaporator;
所述的脱硫废水蒸发器产生的盐浆母液被引至固液分离装置，产生的二次蒸汽被送至蒸汽冷凝装置；The salt slurry mother liquor produced by the desulfurization wastewater evaporator is led to the solid-liquid separation device, and the secondary steam generated is sent to the steam condensing device;
所述的蒸汽冷凝装置包括冷凝器和回用水池，冷凝器入口端连接脱硫废水蒸发器的蒸汽引出管，冷凝器的冷凝水出口端连接回用水池。The steam condensing device includes a condenser and a water reuse pool, the inlet of the condenser is connected to the steam outlet pipe of the desulfurization wastewater evaporator, and the condensed water outlet of the condenser is connected to the water reuse pool.
所述的软化箱设有电动搅拌装置，用于投入的组合试剂与脱硫废水进行化学反应。The softening tank is equipped with an electric stirring device, which is used for the chemical reaction between the input combination reagent and the desulfurization wastewater.
所述的膜过滤系统采用微滤装置。The membrane filtration system adopts a microfiltration device.
所述的预热器设有过热蒸汽引入管和引出管，过热蒸汽引入管连接超超临界CFB锅炉中后屏过热器进口联箱，过热蒸汽引出管连接超超临界CFB锅炉中空预器内布置的蒸汽吹灰器。The preheater is provided with a superheated steam inlet pipe and an outlet pipe, the superheated steam inlet pipe is connected to the superheater inlet header of the ultra-supercritical CFB boiler, and the superheated steam outlet pipe is connected to the ultra-supercritical CFB boiler hollow preheater. steam sootblower.
所述的脱硫废水蒸发器设有高温烟气引入管和高温烟气引出管，脱硫废水蒸发器的高温烟气引入管连接超超临界CFB锅炉中旋风分离器出口位置的高温烟气排出管，高温烟气引出管连接至超超临界CFB锅炉尾部烟道。The desulfurization wastewater evaporator is provided with a high-temperature flue gas inlet pipe and a high-temperature flue gas outlet pipe, the high-temperature flue gas inlet pipe of the desulfurization wastewater evaporator is connected to the high-temperature flue gas outlet pipe at the outlet of the cyclone separator in the ultra-supercritical CFB boiler, The high-temperature flue gas outlet pipe is connected to the tail flue of the ultra-supercritical CFB boiler.
所述的固液分离装置包括离心机和干燥机。The solid-liquid separation device includes a centrifuge and a dryer.
所述的固液分离装置设有一条废水母液引出管连接脱硫废水蒸发器。The solid-liquid separation device is provided with a wastewater mother liquor outlet pipe connected to the desulfurization wastewater evaporator.
一种采用超超临界CFB锅炉脱硫废水零排放处理系统的处理方法，包括以下步骤：A treatment method using an ultra-supercritical CFB boiler desulfurization wastewater zero-discharge treatment system, comprising the following steps:
1)经石灰石—石膏湿法烟气脱硫后的脱硫废水进入缓冲池，进行曝气处理，均匀水质；之后脱硫废水进入软化箱，向箱内添加NaOH溶液、Na2CO3溶液和有机硫的组合试剂，去除废水中的重金属离子，同时生成相应沉淀，调节pH值至9～11；软化箱中生成的污泥被送至压滤机进行压滤后排出；脱硫废水经软化箱处理后进入调节器，通过加入盐酸溶液将pH值调节至6～8；1) The desulfurization wastewater after limestone-gypsum wet flue gas desulfurization enters the buffer tank for aeration treatment to make the water quality uniform; after that, the desulfurization wastewater enters the softening tank, and NaOH solution, Na2 CO3 solution and organic sulfur are added to the tank Combining reagents to remove heavy metal ions in wastewater, and generate corresponding precipitates at the same time, adjust the pH value to 9-11; the sludge generated in the softening tank is sent to the filter press for pressure filtration and discharged; desulfurization wastewater is treated in the softening tank and then enters Regulator, adjust the pH value to 6-8 by adding hydrochloric acid solution;
2)调节器的废水进入膜过滤系统进行过滤处理，降低脱硫废水的污染指数；2) The wastewater from the regulator enters the membrane filtration system for filtration treatment to reduce the pollution index of desulfurization wastewater;
3)膜过滤系统处理后的废水被送至电渗析系统，使脱硫废水在电场力作用下分别通过阳离子交换膜和阴离子交换膜从而分别进行脱硫废水的淡化和浓缩，产生的淡水直接回收用于电厂锅炉补给水，产生的浓水则送至真空脱气机脱除脱硫废水中的不凝性气体和沸点低于水的易挥发组分，经真空脱气机脱气处理后的脱硫废水送至废水泵，废水泵将脱硫废水送至预热器进行预热；3) The wastewater treated by the membrane filtration system is sent to the electrodialysis system, so that the desulfurization wastewater passes through the cation exchange membrane and the anion exchange membrane under the action of the electric field to desalinate and concentrate the desulfurization wastewater, and the fresh water produced is directly recycled for use in Power plant boiler feed water, the concentrated water produced is sent to the vacuum degasser to remove non-condensable gases and volatile components with a boiling point lower than water in the desulfurization wastewater, and the desulfurization wastewater after degassing treatment by the vacuum degasser is sent to To the waste water pump, the waste water pump sends the desulfurization waste water to the preheater for preheating;
4)脱硫废水通过废水泵被送至预热器，预热后的脱硫废水被送至脱硫废水蒸发器；4) The desulfurization wastewater is sent to the preheater through the wastewater pump, and the preheated desulfurization wastewater is sent to the desulfurization wastewater evaporator;
5)进入脱硫废水蒸发器的脱硫废水被加热蒸发，脱硫废水蒸发器处理后的脱硫废水浓液被送至固液分离装置，产生的二次蒸汽送至蒸汽冷凝装置；5) The desulfurization wastewater entering the desulfurization wastewater evaporator is heated and evaporated, the concentrated liquid of desulfurization wastewater treated by the desulfurization wastewater evaporator is sent to the solid-liquid separation device, and the secondary steam generated is sent to the steam condensing device;
6)脱硫废水经脱硫废水蒸发器蒸发处理后形成的浓盐浆液进入固液分离装置进行固液分离，经离心机和干燥机处理后得到固体结晶盐，分离出的废水母液引入脱硫废水蒸发器进行再次蒸发；脱硫废水蒸发器产生的二次蒸汽被送至蒸汽冷凝装置中的冷凝器，冷凝形成的冷凝水进入回用水池。6) The concentrated salt slurry formed after the desulfurization wastewater is evaporated by the desulfurization wastewater evaporator enters the solid-liquid separation device for solid-liquid separation, and the solid crystalline salt is obtained after being treated by a centrifuge and a dryer, and the separated wastewater mother liquor is introduced into the desulfurization wastewater evaporator Evaporate again; the secondary steam generated by the desulfurization wastewater evaporator is sent to the condenser in the steam condensing device, and the condensed water formed by condensation enters the reuse water pool.
步骤6)固液分离得到的废水母液送至脱硫废水蒸发器内继续蒸发；电渗析系统后设有的真空脱气机用于脱除脱硫废水中的不凝性气体和沸点低于水的易挥发组分。Step 6) The waste water mother liquid obtained by solid-liquid separation is sent to the desulfurization waste water evaporator to continue to evaporate; the vacuum degasser provided after the electrodialysis system is used to remove non-condensable gases in the desulfurization waste water and the volatile gases with a boiling point lower than water. volatile components.
预热器的热源采用超超临界CFB锅炉中后屏过热器进口联箱处的过热蒸汽；过热蒸汽用于预热脱硫废水后，再引至空预器中布置的蒸汽吹灰器进行空预器吹灰；The heat source of the preheater is the superheated steam at the inlet header of the rear screen superheater in the ultra-supercritical CFB boiler; after the superheated steam is used to preheat the desulfurization wastewater, it is then led to the steam soot blower arranged in the air preheater for air preheating. sootblower
脱硫废水蒸发器的热源是超超临界CFB锅炉中旋风分离器出口位置的高温烟气；加热脱硫废水后的高温烟气通过高温烟气引出管送至超超临界CFB锅炉尾部烟道继续参与烟气流程。The heat source of the desulfurization wastewater evaporator is the high-temperature flue gas at the outlet of the cyclone separator in the ultra-supercritical CFB boiler; the high-temperature flue gas after heating the desulfurization wastewater is sent to the tail flue of the ultra-supercritical CFB boiler through the high-temperature flue gas outlet pipe to continue to participate in the flue gas. gas flow.
本发明具有以下优点和有益效果：The present invention has the following advantages and beneficial effects:
本发明针对采用湿法烟气脱硫技术的超超临界CFB锅炉脱硫废水系统研究其零排放处理工艺，包括依次连接的化学预处理系统、膜过滤系统、电渗析系统、脱硫废水预热系统、脱硫废水蒸发器、固液分离装置和蒸汽冷凝装置。脱硫废水蒸发器产生的二次蒸汽进入冷凝器进行冷凝，产生的冷凝水送至回用水池，可回用于电厂或达标排放；而处理后的母液被引至固液分离装置。电渗析系统处理过的脱硫废水先经真空脱气机脱除不凝性气体后再通过废水泵输送至预热器。The present invention studies its zero-emission treatment process for the ultra-supercritical CFB boiler desulfurization wastewater system using wet flue gas desulfurization technology, including a chemical pretreatment system, a membrane filtration system, an electrodialysis system, a desulfurization wastewater preheating system, and a desulfurization wastewater system connected in sequence. Waste water evaporator, solid-liquid separation unit and steam condensing unit. The secondary steam generated by the desulfurization waste water evaporator enters the condenser for condensation, and the condensed water generated is sent to the reuse water pool, which can be reused in the power plant or discharged up to standard; and the treated mother liquor is led to the solid-liquid separation device. The desulfurization wastewater treated by the electrodialysis system is firstly degassed by a vacuum degasser to remove non-condensable gases, and then transported to the preheater by a wastewater pump.
进一步的，脱硫废水蒸发器的热源采用超超临界CFB锅炉中旋风分离器后的高温烟气，大约850℃左右，能大幅提高传热温差且极大地降低能耗，有效利用烟气热量，避免热能浪费，节约能源和成本，减少设备投资和运行费用。其加热脱硫废水后的高温烟气通过高温烟气引出管连接至超超临界CFB锅炉尾部烟道继续参与烟气流程，实现高温烟气的有效利用。且处理后的脱硫废水被回收利用，产生的固体结晶盐可作为工业盐出售，为超超临界CFB锅炉脱硫废水零排放提供了一种经济高效的方法，利于节能减排。Furthermore, the heat source of the desulfurization wastewater evaporator is the high-temperature flue gas after the cyclone separator in the ultra-supercritical CFB boiler, which is about 850°C, which can greatly increase the heat transfer temperature difference and greatly reduce energy consumption, effectively use the heat of the flue gas, and avoid Heat energy waste, save energy and cost, reduce equipment investment and operating costs. The high-temperature flue gas after heating the desulfurization wastewater is connected to the tail flue of the ultra-supercritical CFB boiler through the high-temperature flue gas outlet pipe to continue to participate in the flue gas process to realize the effective utilization of high-temperature flue gas. And the treated desulfurization wastewater is recycled, and the solid crystalline salt produced can be sold as industrial salt, which provides an economical and efficient method for zero discharge of desulfurization wastewater from ultra-supercritical CFB boilers, which is conducive to energy saving and emission reduction.
进一步的，预热器的热源采用超超临界CFB锅炉中后屏过热器进口联箱处的过热蒸汽，该处过热蒸汽一般用于空预器吹灰，但因吹灰后汽温会上升因此需要加大减温水量。由此，先将此处的过热蒸汽用于预热脱硫废水后，再引至空预器中布置的蒸汽吹灰器进行空预器吹灰，将使汽温不再升高并节约减温水量，可提高电厂经济效益。Furthermore, the heat source of the preheater is the superheated steam at the inlet header of the rear screen superheater in the ultra-supercritical CFB boiler. The superheated steam here is generally used for soot blowing of the air preheater, but the steam temperature will rise after soot blowing. It is necessary to increase the amount of cooling water. Therefore, the superheated steam here is first used to preheat the desulfurization wastewater, and then lead to the steam soot blower arranged in the air preheater for soot blowing of the air preheater, so that the steam temperature will no longer rise and the desuperheating water will be saved The amount can improve the economic benefit of the power plant.
膜过滤系统采用微滤装置，过滤处理优于机械过滤，出水水质浊度值远小于普通机械过滤的出水水质。The membrane filtration system adopts a microfiltration device, and the filtration treatment is superior to mechanical filtration, and the turbidity value of the effluent quality is much lower than that of ordinary mechanical filtration.
进一步的，化学预处理系统包括缓冲池、软化箱、压滤机和调节器。其中缓冲池的作用是收集经湿法烟气脱硫后的脱硫废水，并进行曝气处理均匀水质，使后续设备运行稳定；软化箱的作用是通过添加NaOH溶液、Na2CO3溶液和有机硫(TMT-15)的组合试剂，去除废水中的重金属离子如Pb3+、Fe3+、Cr3+、Cd2+、Ni+、Hg2+、Pb2+、Cu2+，同时生成相应沉淀，调节pH值至10.0左右。同时软化箱还设有电动搅拌装置，便于投入的组合试剂与脱硫废水进行彻底的化学反应；压滤机的作用是将软化箱中生成的含重金属元素沉淀与悬浮物等污泥进行压滤后排出；调节器的作用是通过加入盐酸溶液将pH值回调至6～8。Further, the chemical pretreatment system includes a buffer tank, a softening tank, a filter press and a regulator. Among them, the role of the buffer pool is to collect the desulfurization wastewater after wet flue gas desulfurization, and perform aeration treatment to uniform the water quality, so that the subsequent equipment can run stably; the role of the softening tank is to add NaOH solution, Na2 CO3 solution and organic sulfur (TMT-15) combination reagent, remove heavy metal ions such as Pb3+ , Fe3+ , Cr3+ , Cd2+ , Ni+ , Hg2+ , Pb2+ , Cu2+ in wastewater, and generate corresponding For precipitation, adjust the pH to about 10.0. At the same time, the softening box is also equipped with an electric stirring device, which is convenient for the chemical reaction between the input combination reagent and the desulfurization wastewater; the function of the filter press is to filter the sludge containing heavy metal elements and suspended matter generated in the softening box. Discharge; the function of the regulator is to adjust the pH value to 6-8 by adding hydrochloric acid solution.
进一步的，膜过滤系统的作用是过滤脱硫废水，去除脱硫废水中的悬浮物、高分子有机物、胶体、颗粒、微粒，降低脱硫废水的污染指数。经预处理后的脱硫废水的水质指标可得到控制，重金属元素、无机盐、结垢性离子等均被完全去除，废水硬度得到去除，避免其进入后续设备出现结垢和腐蚀而影响传热造成危害。并且膜过滤系统采用微滤装置，过滤处理优于传统的机械过滤如絮凝沉淀和介质过滤，能截留0.1～10微米间的微粒和细菌等，出水水质浊度值远小于普通机械过滤的出水水质。Furthermore, the function of the membrane filtration system is to filter desulfurization wastewater, remove suspended solids, high molecular organic matter, colloids, particles, and particles in the desulfurization wastewater, and reduce the pollution index of the desulfurization wastewater. The water quality index of the pretreated desulfurization wastewater can be controlled, heavy metal elements, inorganic salts, scaling ions, etc. are completely removed, the hardness of the wastewater is removed, and the scaling and corrosion of subsequent equipment are prevented from affecting heat transfer. harm. In addition, the membrane filtration system adopts a microfiltration device. The filtration treatment is superior to traditional mechanical filtration such as flocculation sedimentation and media filtration. It can intercept particles and bacteria between 0.1 and 10 microns, and the turbidity value of the effluent quality is much lower than that of ordinary mechanical filtration. .
进一步的，电渗析系统具有一根淡水排出管和一根浓水排出管，脱硫废水经过电渗透系统处理后产生的淡水可回收用于锅炉补给水，浓水则送至真空脱气机。电渗析系统相比于其他的减量浓缩工艺电耗和药剂费用最低，因此可有效控制投资成本提高经济效益。它是基于离子交换和依靠电位差，使脱硫废水在电场力作用下分别通过阳离子交换膜和阴离子交换膜从而分别进行脱硫废水的淡化和浓缩，可用于分离和提纯脱硫废水，对其进行浓缩减量化处理。Furthermore, the electrodialysis system has a fresh water discharge pipe and a concentrated water discharge pipe. The fresh water generated after the desulfurization wastewater is treated by the electroosmosis system can be recycled for boiler makeup water, and the concentrated water is sent to the vacuum degasser. Compared with other volume reduction and concentration processes, the electrodialysis system has the lowest power consumption and reagent costs, so it can effectively control investment costs and improve economic benefits. It is based on ion exchange and depends on the potential difference, so that the desulfurization wastewater passes through the cation exchange membrane and the anion exchange membrane under the action of the electric field to desalinate and concentrate the desulfurization wastewater respectively. It can be used to separate and purify the desulfurization wastewater, and to concentrate and reduce Quantization processing.
进一步的，电渗透系统后设置有真空脱气机，可用于脱除脱硫废水中的不凝性气体和沸点低于水的易挥发组分，经真空脱气机脱气处理后的脱硫废水通过废水泵送至预热器进行预热。Further, a vacuum degasser is installed behind the electroosmosis system, which can be used to remove non-condensable gases and volatile components with a boiling point lower than water in the desulfurization wastewater. The desulfurization wastewater after degassing by the vacuum degasser passes The waste water is pumped to the preheater for preheating.
进一步的，固液分离装置包括离心机和干燥机，装置的排液管连接脱硫废水蒸发器。脱硫废水蒸发器中产出的浓盐浆液通过离心机进行固液分离，分离出的工业结晶盐可用于出售，分离出的废水盐液通过排液管送至脱硫废水蒸发器内进行再次蒸发，浓缩盐液提升纯度。Further, the solid-liquid separation device includes a centrifuge and a dryer, and the discharge pipe of the device is connected to the desulfurization wastewater evaporator. The concentrated salt slurry produced in the desulfurization wastewater evaporator is separated from solid and liquid by a centrifuge, and the separated industrial crystalline salt can be sold, and the separated wastewater salt solution is sent to the desulfurization wastewater evaporator through the drain pipe for re-evaporation. Concentrated brine enhances purity.
进一步的，超超临界CFB锅炉脱硫废水零排放处理系统还包括蒸汽冷凝装置，连接脱硫废水蒸发器的蒸汽引出管，蒸汽冷凝装置产生的冷凝水经排液管送至回用水池，可作为锅炉补给水回用于电厂或水质达标后排放。Furthermore, the ultra-supercritical CFB boiler desulfurization wastewater zero discharge treatment system also includes a steam condensing device connected to the steam outlet pipe of the desulfurization wastewater evaporator. The condensed water generated by the steam condensing device is sent to the reuse water pool through the drain pipe, which can be used as a boiler The make-up water is reused in the power plant or discharged after the water quality reaches the standard.
附图说明Description of drawings
图1为本发明的整体结构示意图。Figure 1 is a schematic diagram of the overall structure of the present invention.
附图中标记及相应的零部件名称：Marks and corresponding component names in the attached drawings:
1-缓冲池，2-软化箱，3-压滤机，4-调节器，5-膜过滤系统，6-电渗析系统，7-真空脱气机，8-废水泵，9-预热器，10-脱硫废水蒸发器，11-固液分离装置，12-冷凝器，13-回用水池，14-超超临界CFB锅炉，15-后屏过热器，16-空预器，17-旋风分离器。1-buffer tank, 2-softening tank, 3-filter press, 4-regulator, 5-membrane filtration system, 6-electrodialysis system, 7-vacuum degasser, 8-wastewater pump, 9-preheater , 10-desulfurization wastewater evaporator, 11-solid-liquid separation device, 12-condenser, 13-reuse water pool, 14-ultra-supercritical CFB boiler, 15-rear screen superheater, 16-air preheater, 17-cyclone Splitter.
具体实施方式Detailed ways
下面结合附图对本发明作进一步的详细描述，但本发明的实施方式不限于此。The present invention will be described in further detail below in conjunction with the accompanying drawings, but the embodiments of the present invention are not limited thereto.
如图1所示，本发明一种超超临界CFB锅炉脱硫废水零排放处理系统，包括依次连接的化学预处理系统、膜过滤系统5、电渗析系统6、脱硫废水预热系统、脱硫废水蒸发器10、固液分离装置11和蒸汽冷凝装置。As shown in Figure 1, an ultra-supercritical CFB boiler desulfurization wastewater zero-discharge treatment system of the present invention includes a chemical pretreatment system, a membrane filtration system 5, an electrodialysis system 6, a desulfurization wastewater preheating system, and a desulfurization wastewater evaporation system connected in sequence Device 10, solid-liquid separation device 11 and steam condensing device.
化学预处理系统，包括缓冲池1、软化箱2、压滤机3和调节器4，缓冲池1出口端连接至软化箱2，软化箱2出口端连接至压滤机3和调节器4，调节器4出口端连接至膜过滤系统5。The chemical pretreatment system includes a buffer tank 1, a softening tank 2, a filter press 3 and a regulator 4, the outlet of the buffer tank 1 is connected to the softening tank 2, and the outlet of the softening tank 2 is connected to the filter press 3 and the regulator 4, The outlet end of the regulator 4 is connected to a membrane filtration system 5 .
膜过滤系统5采用微滤装置，其出口端连接至电渗析系统6。The membrane filtration system 5 adopts a microfiltration device, and its outlet end is connected to an electrodialysis system 6 .
电渗析系统6处理后的脱硫废水先经真空脱气机7脱气处理后再经废水泵8输送至预热器9。The desulfurization wastewater treated by the electrodialysis system 6 is first degassed by the vacuum degasser 7 and then transported to the preheater 9 by the wastewater pump 8 .
脱硫废水预热系统主要装置为预热器9，设有过热蒸汽引入管和引出管，过热蒸汽引入管连接至超超临界CFB锅炉14中后屏过热器15的进口联箱，过热蒸汽引出管连接至超超临界CFB锅炉14中空预器16内布置的蒸汽吹灰器。预热器9出口端连接至脱硫废水蒸发器10。The main device of the desulfurization wastewater preheating system is a preheater 9, which is provided with a superheated steam inlet pipe and an outlet pipe. It is connected to the steam soot blower arranged in the air preheater 16 of the ultra-supercritical CFB boiler 14 . The outlet end of the preheater 9 is connected to the desulfurization wastewater evaporator 10 .
脱硫废水蒸发器10设有高温烟气引入管和高温烟气引出管，高温烟气引入管连接至超超临界CFB锅炉14中旋风分离器17出口位置，高温烟气引出管连接至超超临界CFB锅炉14的尾部烟道。脱硫废水蒸发器10产生的盐浆母液被引至固液分离装置11，产生的二次蒸汽被送至冷凝器12。The desulfurization wastewater evaporator 10 is provided with a high-temperature flue gas inlet pipe and a high-temperature flue gas outlet pipe. The high-temperature flue gas inlet pipe is connected to the outlet of the cyclone separator 17 in the ultra-supercritical CFB boiler 14, and the high-temperature flue gas outlet pipe is connected to the ultra-supercritical CFB boiler 14. The tail flue of the CFB boiler 14. The salt slurry mother liquid produced by the desulfurization wastewater evaporator 10 is led to the solid-liquid separation device 11 , and the secondary steam generated is sent to the condenser 12 .
固液分离装置11包括离心机和干燥机。固液分离装置11的排液管连接至脱硫废水蒸发器10，将分离出的废水盐液送至脱硫废水蒸发器10继续蒸发。The solid-liquid separation device 11 includes a centrifuge and a dryer. The liquid discharge pipe of the solid-liquid separation device 11 is connected to the desulfurization wastewater evaporator 10, and the separated wastewater brine is sent to the desulfurization wastewater evaporator 10 for further evaporation.
蒸汽冷凝装置包括冷凝器12和回用水池13，冷凝器12入口端连接脱硫废水蒸发器10的蒸汽引出管，冷凝器12的冷凝水出口端连接回用水池13。The steam condensing device includes a condenser 12 and a water reuse pool 13 , the inlet of the condenser 12 is connected to the steam outlet pipe of the desulfurization wastewater evaporator 10 , and the condensed water outlet of the condenser 12 is connected to the water reuse pool 13 .
采用上述系统的脱硫废水零排放处理方法，包括以下步骤：The zero-discharge treatment method for desulfurization wastewater using the above system includes the following steps:
(1)经石灰石—石膏湿法烟气脱硫后的脱硫废水进入缓冲池1，进行曝气处理，均匀水质；之后脱硫废水进入软化箱2，向箱内添加NaOH溶液、Na2CO3溶液和有机硫(TMT-15)的组合试剂，去除废水中的重金属离子如Pb3+、Fe3+、Cr3+、Cd2+、Ni+、Hg2+、Pb2+、Cu2+，同时生成相应沉淀，调节pH值至10.0左右。同时软化箱还设有电动搅拌装置，便于投入的组合试剂与脱硫废水进行彻底的化学反应。软化箱中生成的含重金属元素沉淀、其他难溶沉淀及悬浮物等污泥被送至压滤机3进行压滤后排出。脱硫废水经软化箱2处理后进入调节器4，通过加入盐酸溶液将pH值调节至6～8。(1) The desulfurization wastewater after limestone-gypsum wet flue gas desulfurization enters the buffer tank 1 for aeration treatment to ensure uniform water quality; after that, the desulfurization wastewater enters the softening tank 2, and NaOH solution, Na2 CO3 solution and The combined reagent of organic sulfur (TMT-15) removes heavy metal ions such as Pb3+ , Fe3+ , Cr3+ , Cd2+ , Ni+ , Hg2+ , Pb2+ , Cu2+ in wastewater, and at the same time A corresponding precipitate is generated, and the pH value is adjusted to about 10.0. At the same time, the softening box is also equipped with an electric stirring device, which is convenient for the thorough chemical reaction between the input combination reagent and the desulfurization wastewater. The sludge containing heavy metal element precipitation, other insoluble precipitation and suspended matter generated in the softening tank is sent to the filter press 3 for pressure filtration and then discharged. The desulfurization wastewater is treated by the softening tank 2 and enters the regulator 4, where the pH value is adjusted to 6-8 by adding hydrochloric acid solution.
(2)调节器4的废水进入膜过滤系统5进行过滤处理，去除脱硫废水中的悬浮物、高分子有机物、胶体、颗粒，降低脱硫废水的污染指数。经预处理系统处理后的脱硫废水水质指标得到有效控制，重金属元素、无机盐、结垢性离子等均被完全去除，废水硬度得到去除，可避免设备腐蚀和结垢的发生。(2) The wastewater from the regulator 4 enters the membrane filtration system 5 for filtration treatment to remove suspended solids, high-molecular organic matter, colloids, and particles in the desulfurization wastewater, and reduce the pollution index of the desulfurization wastewater. The water quality indicators of the desulfurization wastewater treated by the pretreatment system are effectively controlled, heavy metal elements, inorganic salts, scaling ions, etc. are completely removed, and the hardness of the wastewater is removed, which can avoid equipment corrosion and scaling.
(3)膜过滤系统5处理后的废水被送至电渗析系统6，其相比于其他的减量浓缩工艺电耗和药剂费用最低，因此可有效控制投资成本提高经济效益。使脱硫废水在电场力作用下分别通过阳离子交换膜和阴离子交换膜从而分别进行脱硫废水的淡化和浓缩，便于分离和提纯并浓缩减量脱硫废水化。产生的淡水直接回收用于电厂锅炉补给水，产生的浓水则送至真空脱气机7脱除脱硫废水中的不凝性气体和沸点低于水的易挥发组分，经真空脱气机7脱气处理后的脱硫废水送至废水泵8，废水泵8将脱硫废水送至预热器9进行预热。(3) The wastewater treated by the membrane filtration system 5 is sent to the electrodialysis system 6, which has the lowest power consumption and pharmaceutical costs compared to other reduction and concentration processes, so it can effectively control investment costs and improve economic benefits. The desulfurization wastewater passes through the cation exchange membrane and the anion exchange membrane respectively under the action of the electric field to desulphurize and concentrate the desulfurization wastewater, which is convenient for separation, purification and concentration reduction desulfurization wastewater. The fresh water produced is directly recovered for boiler feed water in the power plant, and the concentrated water produced is sent to the vacuum degasser 7 to remove non-condensable gases and volatile components with a boiling point lower than water in the desulfurization wastewater, and then passed through the vacuum degasser 7. The desulfurized wastewater after degassing is sent to the wastewater pump 8, and the wastewater pump 8 sends the desulfurized wastewater to the preheater 9 for preheating.
(4)脱硫废水通过废水泵8被送至预热器9，用于预热的热源是超超临界CFB锅炉14中后屏过热器15进口联箱处的过热蒸汽，过热蒸汽用于预热脱硫废水后，再通过过热蒸汽引出管引至空预器中布置的蒸汽吹灰器进行空预器吹灰，预热后的脱硫废水被送至脱硫废水蒸发器10。(4) The desulfurization wastewater is sent to the preheater 9 through the wastewater pump 8, and the heat source for preheating is the superheated steam at the inlet header of the rear panel superheater 15 in the ultra-supercritical CFB boiler 14, and the superheated steam is used for preheating After desulfurization wastewater, it is led to the steam soot blower arranged in the air preheater through the superheated steam outlet pipe for soot blowing of the air preheater, and the preheated desulfurization wastewater is sent to the desulfurization wastewater evaporator 10 .
(5)进入脱硫废水蒸发器10的脱硫废水被来自超超临界CFB锅炉14中旋风分离器17出口的高温烟气加热蒸发，加热脱硫废水后的高温烟气通过高温烟气引出管引至超超临界CFB锅炉14尾部烟道继续参与烟气流程。脱硫废水蒸发器10处理后的脱硫废水浓液被送至固液分离装置11，产生的二次蒸汽送至蒸汽冷凝装置。(5) The desulfurization wastewater entering the desulfurization wastewater evaporator 10 is heated and evaporated by the high-temperature flue gas from the outlet of the cyclone separator 17 in the ultra-supercritical CFB boiler 14. The tail flue of the supercritical CFB boiler 14 continues to participate in the flue gas flow. The concentrated desulfurization wastewater treated by the desulfurization wastewater evaporator 10 is sent to the solid-liquid separation device 11, and the secondary steam generated is sent to the steam condensing device.
(6)脱硫废水经脱硫废水蒸发器10蒸发处理后形成的浓盐浆液进入固液分离装置11进行固液分离，经离心机和干燥机处理后得到固体结晶盐，可作为工业盐出售创造附加的经济收益，分离出的废水母液引入脱硫废水蒸发器10进行再次蒸发。脱硫废水蒸发器10产生的二次蒸汽被送至蒸汽冷凝装置中的冷凝器12，冷凝形成的冷凝水进入回用水池13，可回收用于电厂锅炉补给水补充热力系统的水汽损失，实现脱硫废水的重复利用和零排放处理。(6) The concentrated salt slurry formed after the desulfurization wastewater is evaporated by the desulfurization wastewater evaporator 10 enters the solid-liquid separation device 11 for solid-liquid separation, and the solid crystalline salt is obtained after being treated by a centrifuge and a dryer, which can be sold as industrial salt to create additional economic benefits, the separated waste water mother liquor is introduced into the desulfurization waste water evaporator 10 for re-evaporation. The secondary steam generated by the desulfurization waste water evaporator 10 is sent to the condenser 12 in the steam condensing device, and the condensed water formed by condensation enters the reuse water pool 13, and can be recovered for power plant boiler make-up water to supplement the water vapor loss of the thermal system to achieve desulfurization Wastewater reuse and zero discharge treatment.
进一步的，固液分离得到的废水母液送至脱硫废水蒸发器10内继续蒸发，浓缩盐液，提升纯度。Further, the waste water mother liquid obtained by solid-liquid separation is sent to the desulfurization waste water evaporator 10 to continue to evaporate, concentrate the brine, and improve the purity.
进一步的，电渗析系统6后设有的真空脱气机7可脱除脱硫废水中的不凝性气体和沸点低于水的易挥发组分。Further, the vacuum degasser 7 provided after the electrodialysis system 6 can remove non-condensable gases and volatile components with a boiling point lower than water in the desulfurization wastewater.
优选的，预热器9的热源采用超超临界CFB锅炉14中后屏过热器15进口联箱处的过热蒸汽，该处过热蒸汽一般用于空预器吹灰，但因吹灰后汽温会上升因此需要加大减温水量。先将此处的过热蒸汽用于预热脱硫废水后，再引至空预器16中布置的蒸汽吹灰器进行空预器吹灰，将使汽温不再升高并节约减温水量，可提高电厂经济效益。Preferably, the heat source of the preheater 9 adopts the superheated steam at the inlet header of the rear panel superheater 15 in the ultra-supercritical CFB boiler 14, where the superheated steam is generally used for soot blowing of the air preheater, but due to the temperature of the steam after soot blowing It will rise, so it is necessary to increase the amount of cooling water. First use the superheated steam here to preheat the desulfurization wastewater, and then lead it to the steam soot blower arranged in the air preheater 16 for soot blowing in the air preheater, so that the steam temperature will no longer rise and the amount of desuperheating water will be saved. It can improve the economic benefit of the power plant.
优选的，脱硫废水蒸发器10的热源是超超临界CFB锅炉14中旋风分离器17出口位置的高温烟气，可有效利用烟气热量，避免热能浪费，大幅提高传热温差，极大地降低能耗并提高蒸发器的换热效率，节约能源与运行成本，减少设备投资费用。加热脱硫废水后的高温烟气通过高温烟气引出管送至超超临界CFB锅炉14尾部烟道继续参与烟气流程。Preferably, the heat source of the desulfurization wastewater evaporator 10 is the high-temperature flue gas at the exit position of the cyclone separator 17 in the ultra-supercritical CFB boiler 14, which can effectively utilize the heat of the flue gas, avoid waste of heat energy, greatly increase the heat transfer temperature difference, and greatly reduce energy consumption. Reduce energy consumption and improve the heat transfer efficiency of the evaporator, save energy and operating costs, and reduce equipment investment costs. The high-temperature flue gas after heating the desulfurization wastewater is sent to the tail flue of the ultra-supercritical CFB boiler 14 through the high-temperature flue gas outlet pipe to continue to participate in the flue gas process.
本发明以超超临界CFB锅炉旋风分离器出口位置的高温烟气为热源对脱硫废水进行蒸发结晶，以超超临界CFB锅炉后屏过热器进口联箱处的过热蒸汽作为预热脱硫废水的热源，并加设拥有微滤装置的膜过滤系统和用于浓缩减量的电渗析系统，克服了现有多效蒸发技术存在的能耗大、设备投资费用高的缺陷，能提高脱硫效率、有效避免设备结垢、减少系统处理负荷、显著提高经济效益、节约能源与运行成本。且超超临界CFB锅炉采用湿法烟气脱硫后的副产物石膏杂质含量少质量较优，应用价值高可为电厂带来较为可观的收入，脱硫废水经处理后的水质达标被电厂回收利用，产生的固体结晶盐可作为工业盐出售，实现超超临界CFB锅炉脱硫废水零排放，利于节能环保和可持续发展。In the present invention, the high-temperature flue gas at the outlet of the ultra-supercritical CFB boiler cyclone separator is used as a heat source to evaporate and crystallize the desulfurization wastewater, and the superheated steam at the inlet header of the superheater of the rear screen superheater of the ultra-supercritical CFB boiler is used as the heat source for preheating the desulfurization wastewater , and add a membrane filtration system with a microfiltration device and an electrodialysis system for concentration and weight reduction, which overcomes the defects of large energy consumption and high equipment investment costs in the existing multi-effect evaporation technology, and can improve desulfurization efficiency and effectively Avoid equipment fouling, reduce system processing load, significantly improve economic benefits, save energy and operating costs. In addition, the by-product gypsum after wet flue gas desulfurization of the ultra-supercritical CFB boiler has less impurity content and better quality, and its high application value can bring considerable income to the power plant. The solid crystalline salt produced can be sold as industrial salt, realizing zero discharge of ultra-supercritical CFB boiler desulfurization wastewater, which is conducive to energy saving, environmental protection and sustainable development.
需说明的是，上述实施例仅为本发明较佳的实施方式，但本发明并不受上述实施例限制，凡在本发明的原理和精神实质下对以上实施例所作的任何简单修改、组合、等效替换、变更、简化，均应包含在本发明的保护范围内。It should be noted that the above-mentioned embodiments are only preferred implementation modes of the present invention, but the present invention is not limited by the above-mentioned embodiments. , equivalent replacement, modification, and simplification shall all be included in the protection scope of the present invention.
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| CN201810651108.5ACN108558110A (en) | 2018-06-22 | 2018-06-22 | A kind of ultra supercritical CFB boiler desulfurization wastewater zero-discharge treatment system and method |
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