CN104016529B - Based on the Coal Chemical Industry salt-containing waste water treatment method of multi-stage countercurrent pole-reversing electroosmosis device - Google Patents
Based on the Coal Chemical Industry salt-containing waste water treatment method of multi-stage countercurrent pole-reversing electroosmosis device Download PDFInfo
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Abstract
本发明涉及工业废水处理工艺领域。本发明的基于多级逆流倒极电渗析器的煤化工含盐废水处理方法，包括以下步骤：1)将煤化工含盐废水使用臭氧催化氧化处理；2)将步骤1)臭氧催化氧化后的废水依次经多介质过滤和膜过滤处理；3)将步骤2)膜过滤出水经多级逆流倒极电渗析器处理，实现煤化工含盐废水的深度处理与脱盐回用；其中，所述多级逆流倒极电渗析器包括：电渗析膜堆单元、频繁倒极控制单元和在线监测与过程控制单元。本发明具有淡水回收率高、浓水排放量低、运行成本低、系统运行稳定等优点，可避免常规技术存在淡水回收率低、浓缩倍数低、处理成本高、膜污染严重和系统运行不稳定等问题。
The invention relates to the technical field of industrial wastewater treatment. The method for treating salty wastewater from coal chemical industry based on multi-stage countercurrent inverted electrodialyzers of the present invention comprises the following steps: 1) treating the salty wastewater from coal chemical industry with ozone catalytic oxidation; The waste water is treated by multi-media filtration and membrane filtration in sequence; 3) the membrane-filtered water in step 2) is treated by a multi-stage countercurrent reverse electrode electrodialyzer to realize the advanced treatment and desalination reuse of the salty wastewater in the coal chemical industry; wherein, the multi-stage The level countercurrent reverse electrode electrodialyzer includes: electrodialysis membrane stack unit, frequent reverse electrode control unit and on-line monitoring and process control unit. The invention has the advantages of high fresh water recovery rate, low concentration water discharge, low operating cost, stable system operation, etc., and can avoid the low fresh water recovery rate, low concentration multiple, high treatment cost, serious membrane pollution and unstable system operation in the conventional technology And other issues.
Description
技术领域technical field
本发明涉及工业废水处理工艺领域，具体地，本发明涉及基于多级逆流倒极电渗析器的煤化工含盐废水处理方法。The invention relates to the field of industrial wastewater treatment technology, in particular, the invention relates to a method for treating salty wastewater in coal chemical industry based on a multi-stage countercurrent inverted electrode electrodialyzer.
背景技术Background technique
煤化工含盐废水主要来源于生产过程中煤气洗涤废水、循环水系统排水、化学水站排水等，有时还包括生化处理后的有机废水，其特点是含盐量高、污染物以总含盐量为主，部分废水中还含有难降解的有机物。这类废水TDS通常在5000mg/L左右，甚至更高，无法直接回用。目前，这类工业废水虽然COD、氨氮等达到环保外排标准，但水里面含有NaCl、Na2SO4、CaCl2、MgSO4、MgCl2等盐类，直接回用会引起设备结垢、腐蚀和软泥沉积等，需进行脱盐处理。虽然可用于煤灰增湿及冲洗路面或冲厕所，但消耗量也很有限。因此，需要对煤化工含盐废水进行深度处理和脱盐回用，实现废水循环利用和减少外排。Coal chemical industry saline wastewater mainly comes from coal gas washing wastewater, circulating water system drainage, chemical water station drainage, etc. in the production process, and sometimes organic wastewater after biochemical treatment, which is characterized by high salt content, pollutants with total salt content Most of the waste water contains refractory organic matter. The TDS of this kind of wastewater is usually around 5000mg/L, or even higher, and cannot be reused directly. At present, although COD and ammonia nitrogen of this kind of industrial wastewater meet the environmental protection discharge standards, the water contains NaCl, Na 2 SO 4 , CaCl 2 , MgSO 4 , MgCl 2 and other salts, and direct reuse will cause scaling and corrosion of equipment and ooze deposits, etc., need to be desalinated. Although it can be used to humidify coal ash and flush roads or flush toilets, the consumption is also very limited. Therefore, it is necessary to carry out advanced treatment and desalination reuse of coal chemical industry salty wastewater, so as to realize the recycling of wastewater and reduce effluent.
尽管目前关于煤化工废水处理的报道较多，但大多是研究如何实现煤化工废水达标排放。如王奉军(小氮肥,2010,38(1):1-4)报道了A/O法处理煤化工废水的应用；王文标等(广东化工,2010,37(6):186-188)报道了采用氯碱氧化/混凝气浮/HBF-N联合工艺处理安徽某煤化工企业综合废水，出水可达到一级排放标准；唐秀华(中国给水排水,2011,27(16):85-87)报道了强化生物脱碳脱氮及回用工艺处理煤化工废水，并采用臭氧生物活性炭技术作为深度处理单元，出水水质虽然达到《城市污水再生利用工业用水水质》标准，但仍无法作为工业循环水再利用。近年来有关煤化工废水处理与应用的发明专利，如《煤化工废水的生化处理方法》(CN201310198071)、《一种高浓度含酚氨煤化工废水的萃取脱酚方法》(CN103496757)、《煤化工废水外循环移动床反应器和曝气生物滤池联用短程脱氮系统及方法》(CN103351078)、《煤气化废水深度处理系统》(CN201310475332)等，大多是提出利用生物法、臭氧氧化、萃取等方法或联合使用，目的是使煤化工废水实现达标排放。Although there are many reports on the treatment of coal chemical wastewater, most of them focus on how to achieve the standard discharge of coal chemical wastewater. For example, Wang Fengjun (Xiao Nitrogen Fertilizer, 2010, 38(1): 1-4) reported the application of A/O method to treat coal chemical wastewater; Wang Wenbiao et al. (Guangdong Chemical Industry, 2010, 37(6): 186-188) reported the application The chlor-alkali oxidation/coagulation air flotation/HBF-N combined process was used to treat the comprehensive wastewater of a coal chemical enterprise in Anhui, and the effluent could meet the first-class discharge standard; The biological decarbonization, denitrification and reuse process treats coal chemical industry wastewater, and uses ozone bio-activated carbon technology as the advanced treatment unit. Although the effluent water quality meets the "Urban Sewage Recycling Industrial Water Quality" standard, it still cannot be reused as industrial circulating water. In recent years, invention patents related to the treatment and application of coal chemical wastewater, such as "Biochemical Treatment Method of Coal Chemical Wastewater" (CN201310198071), "A Method for Extracting and Dephenolizing Coal Chemical Wastewater Containing High Concentration Phenol and Ammonia" (CN103496757), "Coal Chemical Wastewater Chemical wastewater external circulation moving bed reactor and biological aerated filter combined with short-range denitrification system and method" (CN103351078), "coal gasification wastewater advanced treatment system" (CN201310475332), etc., most of which propose the use of biological methods, ozone oxidation, Extraction and other methods or combined use, the purpose is to make the coal chemical industry wastewater discharge up to standard.
煤化工含盐废水尽管可达到国家和地方废水排放标准(COD<100mg/L，SS<60mg/L,pH6～9)，但这类工业废水中仍存在部分难降解有机物、微生物、胶体、颗粒悬浮物、Ca2+和Mg2+及其他高价离子、无机盐等。目前，通常采用膜分离或热浓缩工艺富集废水中的杂质，清水回用于循环水系统，浓水外排。如谢晓和凌怡敏(水处理信息报导，2010,6:15-20)探讨了煤化工废水零排放策略，指出国外处置高含盐废水及废水零排放的措施有：自然蒸发塘、深井灌注、焚烧、蒸汽驱动的多效蒸发、机械压缩循环蒸发技术(MVC)等；而国内采用节水工艺提高用水效率，以及通过膜技术如反渗透膜(RO)、电渗析(ED)、微滤(MF)、超滤(UF)和膜生物反应器(MBR)工艺等技术处理，最大限度地减少高含盐废水量。郭森等(煤化工,2011,1:27-30)探讨了煤化工含盐废水的处理方法，认为反渗透膜技术和热浓缩工艺可用于煤化工含盐废水的处理。近年来有关高含盐工业废水处理与零排放的发明专利，如《利用循环水余热处理高含盐废水的装置及方法》(CN103553166)、《利用废热烟气处理高含盐废水的方法》(CN103553170)、《一种农化高浓含盐废水处理工艺》(CN103601331)，大多是利用热浓缩工艺来实现高含盐废水减排。Although the salty wastewater of coal chemical industry can meet the national and local wastewater discharge standards (COD<100mg/L, SS<60mg/L, pH6~9), there are still some refractory organic substances, microorganisms, colloids, and particles in this kind of industrial wastewater Suspended matter, Ca 2+ and Mg 2+ and other high-valent ions, inorganic salts, etc. At present, membrane separation or thermal concentration processes are usually used to enrich the impurities in wastewater, the clean water is reused in the circulating water system, and the concentrated water is discharged outside. For example, Xie Xiao and Ling Yimin (Water Treatment Information Report, 2010, 6:15-20) discussed the zero-discharge strategy of coal chemical industry wastewater, and pointed out that foreign measures to deal with high-salt wastewater and zero-discharge wastewater include: natural evaporation ponds, deep well injection, Incineration, steam-driven multi-effect evaporation, mechanical compression cycle evaporation technology (MVC), etc.; while water-saving processes are used in China to improve water efficiency, and membrane technologies such as reverse osmosis (RO), electrodialysis (ED), microfiltration ( MF), ultrafiltration (UF) and membrane bioreactor (MBR) processes to minimize the amount of high-saline wastewater. Guo Sen et al. (Coal Chemical Industry, 2011, 1:27-30) discussed the treatment methods of coal chemical industry saline wastewater, and believed that reverse osmosis membrane technology and thermal concentration process can be used for the treatment of coal chemical industry saline wastewater. In recent years, invention patents related to the treatment of high-salt industrial wastewater and zero discharge, such as "The device and method for treating high-salt wastewater by using the waste heat of circulating water" (CN103553166), "The method of using waste heat and flue gas to treat high-salt wastewater" ( CN103553170), "A Treatment Process for Agrochemical High-Concentration Salt-Containing Wastewater" (CN103601331), most of them use thermal concentration process to reduce the discharge of high-concentration salt-containing wastewater.
目前煤化工含盐废水主要是采用热浓缩和膜技术处理，但热浓缩工艺普遍存在设备庞大、能耗高的问题，而且废水热浓缩过程中氯离子对设备的腐蚀及钙镁离子的结垢，会造成维护费用高，而且加大企业的投资和运行风险。采用超滤-反渗透双膜法处理煤化工废水，仅有60％-70％的淡水回用，剩余30％-40％的浓水还需外排。由于废水中有机物浓度较高，容易形成膜污染，需要经常进行化学清洗，造成膜使用寿命缩短，膜材料损耗大，系统无法长期稳定运行，投资运行成本高。而且外排废水中盐分大，外排很容易造成土壤板结，严重时会使土壤盐碱化。电渗析技术虽然在苦咸水淡化、海水浓缩制盐等获得应用，但由于受到反渗透技术的冲击，目前该技术处于停滞和萎缩状态。采用常规电渗析技术处理煤化工含盐废水，由于煤化工含盐废水中的杂质含量高，还含有少量难降解有机物，必然会导致电渗析过程脱盐效率低、膜污染严重、系统难以长期稳定运行、维护成本高等问题。总之，现有脱盐技术用于煤化工含盐废水处理，其设备投资和运行成本都较高，经济上不合算。需进一步研究高效、低成本的废水处理技术，提高这类废水的回收利用率。At present, the salty wastewater of coal chemical industry is mainly treated by thermal concentration and membrane technology, but the thermal concentration process generally has the problems of large equipment and high energy consumption, and the corrosion of equipment by chloride ions and the scaling of calcium and magnesium ions in the process of thermal concentration of wastewater , It will cause high maintenance costs, and increase the investment and operation risks of enterprises. Using ultrafiltration-reverse osmosis double-membrane method to treat coal chemical wastewater, only 60%-70% of fresh water is reused, and the remaining 30%-40% of concentrated water needs to be discharged. Due to the high concentration of organic matter in wastewater, it is easy to form membrane fouling, and frequent chemical cleaning is required, resulting in shortened membrane life, large loss of membrane materials, long-term stable operation of the system, and high investment and operation costs. Moreover, the discharged wastewater contains a lot of salt, which can easily cause soil compaction, and in severe cases, it will cause soil salinization. Although electrodialysis technology has been applied in the desalination of brackish water and salt production from seawater concentration, due to the impact of reverse osmosis technology, this technology is currently stagnant and shrinking. Conventional electrodialysis technology is used to treat coal chemical industry saline wastewater. Due to the high content of impurities and a small amount of refractory organic matter in coal chemical industry saline wastewater, the electrodialysis process will inevitably lead to low desalination efficiency, serious membrane pollution, and difficulty in long-term stable operation of the system. , High maintenance costs and other issues. In short, the existing desalination technology is used for the treatment of salty wastewater in coal chemical industry, and its equipment investment and operation costs are high, which is not economically cost-effective. It is necessary to further study efficient and low-cost wastewater treatment technologies to improve the recycling rate of such wastewater.
发明内容Contents of the invention
针对煤化工含盐废水的水质特点，本发明提出了一种采用多级逆流倒极电渗析处理煤化工含盐废水的新方法，该方法把倒极电渗析与臭氧催化氧化、多介质过滤、膜过滤等技术耦合，实现煤化工含盐废水的深度处理与脱盐回用。采用该技术处理煤化工含盐废水，具有淡水产率高、浓水排放量小、降低电渗析膜污染和提高系统运行稳定性等特点，其中淡水产率超过85％，浓水浓缩10倍以上。该方法可避免常规超滤-反渗透技术处理煤化工含盐废水时存在淡水回收率低、浓缩倍数低、运行成本高、膜污染严重和系统运行不稳定等问题，可促进煤化工等行业含盐废水深度处理与脱盐回用的工程化应用。Aiming at the water quality characteristics of the coal chemical industry's saline wastewater, the present invention proposes a new method for treating the coal chemical industry's saline wastewater by using multi-stage countercurrent electrodialysis. Membrane filtration and other technologies are coupled to realize advanced treatment and desalination reuse of salty wastewater from coal chemical industry. Using this technology to treat coal chemical industry salty wastewater has the characteristics of high fresh water yield, small concentrated water discharge, reduced electrodialysis membrane pollution, and improved system operation stability. Among them, the fresh water yield exceeds 85%, and the concentrated water is concentrated by more than 10 times. . This method can avoid the problems of low fresh water recovery rate, low concentration multiple, high operating cost, serious membrane fouling and unstable system operation in the treatment of coal chemical industry saline wastewater by conventional ultrafiltration-reverse osmosis technology. Engineering application of salt wastewater advanced treatment and desalination reuse.
具体地，本发明的基于多级逆流倒极电渗析器的煤化工含盐废水处理方法，包括以下步骤：Specifically, the coal chemical industry saline wastewater treatment method based on the multi-stage countercurrent inverted electrode electrodialyzer of the present invention comprises the following steps:
1)将煤化工含盐废水使用臭氧催化氧化处理；1) Treat the salty wastewater from the coal chemical industry with ozone catalytic oxidation;
2)将步骤1)臭氧催化氧化后的废水依次经多介质过滤、精密过滤和膜过滤处理；2) The waste water after step 1) ozone catalytic oxidation is sequentially processed through multi-media filtration, precision filtration and membrane filtration;
3)将步骤2)膜过滤出水经多级逆流倒极电渗析器处理，实现煤化工含盐废水的深度处理与脱盐回用；3) Process the membrane-filtered water in step 2) through a multi-stage countercurrent reverse electrode electrodialyzer to realize advanced treatment and desalination reuse of salty wastewater from coal chemical industry;
其中，所述多级逆流倒极电渗析器包括：电渗析膜堆单元、频繁倒极控制单元和在线监测与过程控制单元；Wherein, the multi-stage countercurrent reverse electrode electrodialyzer includes: an electrodialysis membrane stack unit, a frequent reverse electrode control unit, and an on-line monitoring and process control unit;
所述电渗析单元包括：电渗析膜堆3、输液泵、流量计、压力表、管路、储液罐4、组装框架和整流器5；所述电渗析膜堆3包括：若干交替排列的抗污染离子交换膜、隔板、膜堆两侧的电极板、夹紧装置，共同构成电渗析膜堆3的极室、脱盐室和浓缩室；由两个以上所述膜堆组成一组，同一组膜堆由一个整流器5并联供电；两组以上的膜堆3进行串联；所述储液罐4包括极水罐、浓水罐、淡水罐；所述不同膜堆3的不同隔室间的管路串联，控制其浓水/淡水的流向相反，由此构成多级/逆流体系，以减小膜堆3中相邻隔室间的浓差扩散，提高废水脱盐率与浓缩倍数。The electrodialysis unit includes: an electrodialysis membrane stack 3, an infusion pump, a flow meter, a pressure gauge, pipelines, a liquid storage tank 4, an assembly frame and a rectifier 5; the electrodialysis membrane stack 3 includes: several anti- Contaminated ion exchange membranes, separators, electrode plates on both sides of the membrane stack, and clamping devices together constitute the electrode chamber, desalination chamber and concentration chamber of the electrodialysis membrane stack 3; a group consisting of two or more membrane stacks, the same Group membrane stacks are powered by a rectifier 5 in parallel; more than two groups of membrane stacks 3 are connected in series; the liquid storage tank 4 includes a pole water tank, a concentrated water tank, and a fresh water tank; The pipelines are connected in series to control the flow direction of concentrated water/fresh water to be opposite, thus forming a multi-stage/countercurrent system to reduce the concentration difference between adjacent compartments in the membrane stack 3 and increase the desalination rate and concentration ratio of wastewater.
所述倒极控制单元包括：PLC单元6、自动控制阀和整流器5，用于完成电渗析膜堆3倒极过程中自动控制阀开启或关闭、整流器5正负极换向信号输出，以及电渗析过程控制；通过触摸屏进行膜堆3的倒极时间间隔、电源关闭或开启的延时时间以及手动自动模式的设定。The inversion control unit includes: a PLC unit 6, an automatic control valve and a rectifier 5, which are used to open or close the automatic control valve during the inversion process of the electrodialysis membrane stack 3, output the positive and negative reversing signals of the rectifier 5, and the electric Dialysis process control: through the touch screen, set the time interval of membrane stack 3 reversal, the delay time of power off or on, and the setting of manual and automatic modes.
所述参数在线监测与过程控制单元包括：电导率传感器1、温度传感器2、无纸记录仪、PLC单元6、自动控制阀；所述多个电导率传感器1安装在膜堆中淡水和/或浓水的出水管，用于在线监测一组膜堆3淡水脱盐率和浓水浓缩倍数；通过PLC单元6把电导率传感器1的数据传输到无纸记录仪保存，并与预设值进行比较，由PLC单元6输出信号控制对应自动控制阀开启或关闭，实现不同隔室溶液在膜堆3中循环或部分循环，使管路中淡水/浓水返回另一组膜堆3处理或直接排放；所述温度传感器2，用来监测膜堆极室溶液的温度。The parameter online monitoring and process control unit includes: conductivity sensor 1, temperature sensor 2, paperless recorder, PLC unit 6, automatic control valve; the plurality of conductivity sensors 1 are installed in fresh water and/or The concentrated water outlet pipe is used to monitor the fresh water desalination rate and concentrated water concentration multiple of a group of membrane stacks 3 online; the data of the conductivity sensor 1 is transmitted to the paperless recorder through the PLC unit 6 for storage, and compared with the preset value The output signal of the PLC unit 6 controls the opening or closing of the corresponding automatic control valve to realize the circulation or partial circulation of solutions in different compartments in the membrane stack 3, so that the fresh water/concentrated water in the pipeline is returned to another group of membrane stacks 3 for processing or directly discharged ; The temperature sensor 2 is used to monitor the temperature of the membrane stack electrode chamber solution.
本发明所述的煤化工含盐废水，包括但不限于来源于煤化工行业生产过程中的煤气洗涤废水、循环水系统排水、化学水站排水等，有时还包括生化处理后的有机废水，其特点是含盐量高(TDS通常在5000mg/L左右甚至更高)，还含有部分难降解有机物，这类废水需要进一步深度处理和电渗析脱盐才能实现回用。煤化工含盐废水中含有部分难降解有机物，以及细菌、胶体、颗粒悬浮物、Ca2+和Mg2+及其他高价离子、其他可溶性无机盐等，虽然达到了外排标准，但会造成大量的水资源浪费，要实现这种工业废水资源化与循环利用，必需进一步去除废水中的残余有机物和无机盐等。本发明提出了一种采用多级逆流倒极电渗析处理煤化工含盐废水的方法，其特征在于经过常规处理达标排放的煤化工含盐废水，先采用臭氧催化氧化、多介质过滤、膜过滤等技术处理，并采用多级逆流倒极电渗析脱盐，实现煤化工含盐废水的深度处理与脱盐回用。其目的是利用多级逆流倒极电渗析与臭氧催化氧化、多介质过滤和膜过滤等技术的耦合与协同作用，发挥不同技术优势和克服单一技术的局限性。本发明提出的电渗析处理煤化工含盐废水的新方法，可避免常规超滤-反渗透技术处理煤化工含盐废水时存在淡水回收率低、浓缩倍数低、处理成本高、膜污染严重和系统运行不稳定等问题。该方法具有对原水适应性强、淡水回收率高、浓水浓缩倍数高等特点，大幅度提高煤化工含盐废水的淡水回收率和减少浓水排放量，该技术还适用于化工、油田、纺织、造纸等行业含盐废水的深度处理与脱盐回用。The coal chemical industry saline wastewater described in the present invention includes, but is not limited to, coal gas washing wastewater, circulating water system drainage, chemical water station drainage, etc. from the production process of the coal chemical industry, and sometimes organic wastewater after biochemical treatment. It is characterized by high salt content (TDS is usually around 5000mg/L or even higher), and contains some refractory organic matter. This type of wastewater requires further advanced treatment and electrodialysis desalination to achieve reuse. Coal chemical industry saline wastewater contains some refractory organic matter, as well as bacteria, colloids, suspended particles, Ca 2+ and Mg 2+ and other high-valent ions, and other soluble inorganic salts. Waste of water resources, in order to realize the recycling and recycling of industrial wastewater, it is necessary to further remove the residual organic matter and inorganic salts in the wastewater. The present invention proposes a method for treating salty wastewater from coal chemical industry by multi-stage countercurrent reverse electrode electrodialysis, which is characterized in that the salty wastewater from coal chemical industry that is discharged up to standard after conventional treatment is firstly treated with ozone catalytic oxidation, multi-media filtration, and membrane filtration and other technologies, and adopt multi-stage countercurrent reverse electrode electrodialysis desalination to realize advanced treatment and desalination reuse of salty wastewater from coal chemical industry. Its purpose is to use the coupling and synergistic effect of multi-stage countercurrent reverse electrode electrodialysis and ozone catalytic oxidation, multi-media filtration and membrane filtration to give full play to the advantages of different technologies and overcome the limitations of a single technology. The new method of electrodialysis treatment of coal chemical industry saline wastewater proposed by the present invention can avoid the low recovery rate of fresh water, low concentration multiple, high treatment cost, serious membrane pollution and System instability and other problems. This method has the characteristics of strong adaptability to raw water, high recovery rate of fresh water, and high concentration multiple of concentrated water. Advanced treatment and desalination reuse of saline wastewater in , paper and other industries.
所述多级逆流倒极电渗析处理煤化工含盐废水的方法，其特点是，所述的多级逆流倒极电渗析脱盐单元，采用煤化工含盐废水处理的专用电渗析器和电渗析膜堆优化组合，可显著提高淡水回收率、降低浓水排放量、减小膜污染和提高系统运行稳定性。The method for treating saline wastewater in the coal chemical industry by multi-stage countercurrent inverted electrodialysis is characterized in that the multi-stage countercurrent inverted electrodialysis desalination unit adopts a special electrodialyzer and electrodialysis device for the treatment of coal chemical saline wastewater. The optimized combination of membrane stacks can significantly increase fresh water recovery rate, reduce concentrated water discharge, reduce membrane fouling and improve system operation stability.
所述用于煤化工含盐废水处理的多级逆流倒极电渗析单元，其特点是，所述专用电渗析器由电渗析膜堆单元、倒极控制单元、在线监测与过程控制单元等共同构成。电渗析系统通过多个电渗析膜堆串联或并联，实现煤化工含盐废水的多级脱盐或浓缩处理；通过膜堆间不同隔室的管路连接与溶液流向控制，使每组电渗析膜堆的淡水与浓水流向相反，减小相邻淡水与浓水隔室间的浓差扩散，提高淡水脱盐率和浓水浓缩倍数；通过PLC控制系统、整流器和自动控制阀(如电动阀、气动阀或电磁阀)等，共同实现电渗析脱盐单元自动倒极，且倒极周期可根据煤化工含盐废水水质和处理目标进行调节，减小电渗析过程的浓差极化和膜污染。采用所述的多级逆流倒极电渗析单元处理煤化工含盐废水，可实现淡水产率大于85％，浓水浓缩10倍以上。The multi-stage countercurrent reverse electrode electrodialysis unit for the treatment of salty wastewater in coal chemical industry is characterized in that the special electrodialyzer is composed of electrodialysis membrane stack unit, reverse electrode control unit, on-line monitoring and process control unit, etc. constitute. The electrodialysis system realizes multi-stage desalination or concentration treatment of salty wastewater in the coal chemical industry through multiple electrodialysis membrane stacks connected in series or in parallel; through the pipeline connection and solution flow control of different compartments between the membrane stacks, each set of electrodialysis membranes The flow direction of fresh water and concentrated water in the stack is opposite, reducing the concentration difference between adjacent fresh water and concentrated water compartments, increasing the desalination rate of fresh water and the concentration multiple of concentrated water; through PLC control system, rectifier and automatic control valve (such as electric valve, Pneumatic valve or solenoid valve), etc., jointly realize the automatic pole reversal of the electrodialysis desalination unit, and the pole reversal cycle can be adjusted according to the water quality and treatment objectives of the coal chemical industry's saline wastewater, so as to reduce the concentration polarization and membrane fouling in the electrodialysis process. The use of the multi-stage countercurrent reverse electrode electrodialysis unit to treat coal chemical industry saline wastewater can achieve a fresh water yield of greater than 85% and concentration of concentrated water by more than 10 times.
所述多级逆流倒极电渗析单元，是指至少2个或2个以上电渗析膜堆串联及其组合，提高淡水脱盐率和浓水浓缩倍数，可实现煤化工含盐废水脱盐率为80％-95％，满足工业水回用标准，且脱盐率可根据处理目标进行调节。The multi-stage countercurrent reverse electrode electrodialysis unit refers to at least two or more electrodialysis membrane stacks connected in series and their combination, which can increase the desalination rate of fresh water and the concentration multiple of concentrated water, and can achieve a desalination rate of 80% of the salty wastewater in the coal chemical industry. %-95%, meeting the industrial water reuse standard, and the desalination rate can be adjusted according to the treatment target.
本发明所述的抗污染离子交换膜是在离子膜表面覆盖与本体膜带相反电荷的薄膜层，利用静电作用和减小膜表面粗糙度，抑制污染物在膜表面的吸附沉积。The anti-pollution ion exchange membrane of the present invention covers the surface of the ion membrane with a thin film layer with opposite charges to the bulk membrane, and uses electrostatic action and reduces the surface roughness of the membrane to inhibit the adsorption and deposition of pollutants on the membrane surface.
本发明的多级逆流倒极电渗析处理煤化工含盐废水的方法，利用多介质过滤、精密过滤和膜过滤等进一步处理经臭氧催化氧化后的出水，去除废水中残余的少量胶体、悬浮物、菌体、大分子有机物等。其中，所述多介质过滤使用石英砂、活性炭和粉煤灰作为过滤介质；所述膜过滤采用微滤、超滤和纳滤膜技术中的一种或几种。通过优选膜组件及其组合，提高膜过滤出水水质，减小后续倒极电渗析脱盐过程的膜污染。The multi-stage countercurrent electrodialysis treatment method for coal chemical industry saline wastewater of the present invention uses multi-media filtration, precision filtration and membrane filtration to further treat the effluent after ozone catalytic oxidation to remove a small amount of colloid and suspended matter remaining in the wastewater , bacteria, macromolecular organic matter, etc. Wherein, the multimedia filtration uses quartz sand, activated carbon and fly ash as filter media; the membrane filtration adopts one or more of microfiltration, ultrafiltration and nanofiltration membrane technologies. By optimizing the membrane module and its combination, the water quality of the membrane filtered water is improved, and the membrane pollution in the subsequent electrodialysis desalination process is reduced.
所述臭氧催化氧化单元，采用高效催化剂来提高臭氧氧化效率，可促进难降解有机物的氧化去除，大幅度降低煤化工含盐废水中残余的难降解有机物。具体地，所述臭氧催化氧化在臭氧催化塔中进行，其中填充碳基复合型高效催化剂(如KL-CO3)，催化剂使用寿命为1-3年。所述臭氧催化氧化技术，具有催化氧化效率高、不带入其他杂质、对高含盐工业废水中难降解有机物去除效果好等优点。该臭氧催化氧化单元可弥补电渗析脱盐单元不能去除有机物的不足，提高电渗析产水水质和减小电渗析膜污染。本发明提出采用臭氧催化氧化处理煤化工含盐废水，具有催化氧化效率高、不带入其他杂质、对废水中难降解有机物去除效果好等优点。同时不排除其他高级氧化技术如(电)芬顿、湿式氧化法、紫外催化氧化等的使用，其目标是去除煤化工含盐废水中残余的有机物、硫化物和Fe2+等，使难降解有机物发生开环和氧化降解、以及杀灭细菌等。The ozone catalytic oxidation unit uses a high-efficiency catalyst to improve the ozone oxidation efficiency, which can promote the oxidation and removal of refractory organic matter, and greatly reduce the residual refractory organic matter in the salty wastewater of coal chemical industry. Specifically, the ozone catalytic oxidation is carried out in an ozone catalytic tower, which is filled with a carbon-based composite high-efficiency catalyst (such as KL-CO3), and the service life of the catalyst is 1-3 years. The ozone catalytic oxidation technology has the advantages of high catalytic oxidation efficiency, no other impurities, and good removal effect on refractory organic matter in high-salt industrial wastewater. The ozone catalytic oxidation unit can make up for the inability of the electrodialysis desalination unit to remove organic matter, improve the water quality of the electrodialysis water and reduce the pollution of the electrodialysis membrane. The invention proposes to use ozone catalytic oxidation to treat coal chemical industry salty wastewater, which has the advantages of high catalytic oxidation efficiency, no other impurities, good removal effect on refractory organic matter in wastewater, and the like. At the same time, the use of other advanced oxidation technologies such as (electric) Fenton , wet oxidation, and ultraviolet catalytic oxidation is not excluded. Organic matter undergoes ring-opening and oxidative degradation, and kills bacteria.
所述多级逆流倒极电渗析与臭氧催化氧化、多介质过滤、膜过滤等单元技术耦合，可预先去除煤化工含盐废水中的细菌、颗粒悬浮物、胶体、大分子有机物、Ca2+和Mg2+及高价离子等，减小后续电渗析膜污染，膜清洗周期延长3-6个月。同时可降低水处理运行成本和提高系统运行稳定性。The multi-stage countercurrent inverted electrodialysis is coupled with ozone catalytic oxidation, multi-media filtration, membrane filtration and other unit technologies, which can pre-remove bacteria, suspended particles, colloids, macromolecular organic matter, and Ca 2+ in coal chemical industry saline wastewater And Mg 2+ and high-valent ions, etc., reduce subsequent electrodialysis membrane pollution, and extend the membrane cleaning cycle by 3-6 months. At the same time, it can reduce the operating cost of water treatment and improve the stability of system operation.
本发明提出了一种采用多级逆流倒极电渗析处理煤化工含盐废水的方法，并与臭氧催化氧化、多介质过滤、膜过滤等技术耦合与协同作用，实现煤化工含盐废水的深度处理与脱盐回用。具有淡水回收率高、浓水排放量低、运行成本低、系统运行稳定等优点，可避免常规超滤-反渗透技术处理煤化工含盐废水时存在淡水回收率低、浓缩倍数低、处理成本高、膜污染严重和系统运行不稳定等问题。其中产生淡水可作为生产工艺水、循环冷却水或锅炉水等；少量浓水可进一步蒸发或用于洗煤、冲渣等，不会对环境造成污染。The present invention proposes a method for treating salty wastewater from coal chemical industry by multi-stage countercurrent electrodialysis, which is coupled and synergistic with technologies such as ozone catalytic oxidation, multi-media filtration, and membrane filtration to realize the depth of salty wastewater from coal chemical industry Treatment and desalination for reuse. It has the advantages of high fresh water recovery rate, low concentrated water discharge, low operating cost, and stable system operation, and can avoid the low fresh water recovery rate, low concentration multiple, and treatment cost of conventional ultrafiltration-reverse osmosis technology in the treatment of coal chemical industry salty wastewater. High, serious membrane fouling and unstable system operation. The fresh water produced can be used as production process water, circulating cooling water or boiler water, etc.; a small amount of concentrated water can be further evaporated or used for coal washing, slag washing, etc., without polluting the environment.
本发明与现有技术相比的优点在于：The advantage of the present invention compared with prior art is:
(1)本发明采用多级逆流倒极电渗析用于煤化工含盐废水处理，与臭氧催化氧化、多介质过滤、膜过滤等技术耦合与协同作用，实现煤化工含盐废水的深度处理与脱盐回用，对原水适应范围广、抗冲击性强、系统运行稳定。(1) The present invention uses multi-stage countercurrent electrodialysis for the treatment of salty wastewater in the coal chemical industry, and is coupled and synergistic with technologies such as ozone catalytic oxidation, multi-media filtration, and membrane filtration to realize the advanced treatment and integration of salty wastewater in the coal chemical industry. Desalination and reuse, wide adaptability to raw water, strong impact resistance, and stable system operation.
(2)本发明提出的煤化工含盐废水深度处理与脱盐回用处理工艺，具有淡水回收率高、浓水浓缩倍数高、运行成本低等特点。系统产水率大于85％，而外排浓水量小于15％。(2) The advanced treatment and desalination reuse treatment process of coal chemical industry saline wastewater proposed by the present invention has the characteristics of high recovery rate of fresh water, high concentration ratio of concentrated water, and low operating cost. The water production rate of the system is greater than 85%, while the discharge of concentrated water is less than 15%.
(3)本发明提出的煤化工含盐废水深度处理与脱盐回用处理工艺，采用高效臭氧氧化催化剂，可提高废水中难降解有机物的去除率，显著减小后续处理过程的膜污染和提高产水水质。(3) The advanced treatment and desalination and reuse treatment process of coal chemical industry salty wastewater proposed by the present invention adopts a high-efficiency ozone oxidation catalyst, which can improve the removal rate of refractory organic matter in wastewater, significantly reduce membrane fouling in subsequent treatment processes and improve production efficiency. water quality.
附图说明Description of drawings
图1为本发明的煤化工含盐废水处理方法流程图。Fig. 1 is a flow chart of the method for treating salty wastewater from coal chemical industry according to the present invention.
图2为本发明的多级逆流倒极电渗析器的电渗析单元示意图。Fig. 2 is a schematic diagram of the electrodialysis unit of the multi-stage countercurrent inverted electrode electrodialyzer of the present invention.
附图标记reference sign
1、电导率传感器 2、温度传感器1. Conductivity sensor 2. Temperature sensor
3、电渗析膜堆 4、储液罐(含极水罐、淡水罐、浓水罐)3. Electrodialysis membrane stack 4. Liquid storage tank (including polar water tank, fresh water tank, concentrated water tank)
5、电控柜(含整流器) 6、PLC单元5. Electric control cabinet (including rectifier) 6. PLC unit
具体实施方式Detailed ways
本说明书中公开得任一特征，除非特别叙述，均可被其他等效或具有类似目的的替代特征加以替换。除非特别叙述，每个特征只是一系列等效或者类似特征中的一个例子而已。所述仅仅是为了帮助理解本发明，不应该视为对本发明的具体限制。Any feature disclosed in this specification, unless specifically stated, can be replaced by other alternative features that are equivalent or have similar purposes. Unless expressly stated otherwise, each feature is only one example of a series of equivalent or similar features. The description is only to help the understanding of the present invention, and should not be regarded as a specific limitation on the present invention.
如图1所示，本发明提出采用多级逆流倒极电渗析处理煤化工含盐废水，并利用臭氧催化氧化、多介质过滤、膜过滤等技术耦合与协同作用，实现煤化工含废水的深度处理与脱盐回用。即煤化工含盐废水先经臭氧催化氧化处理去除大部分难降解有机物(COD)，其清液经过多介质过滤和精密过滤后进入膜过滤单元，经膜过滤去除细菌、颗粒悬浮物、大分子有机物和高价离子等，膜过滤产水则进一步经多级逆流倒极电渗析脱盐。整个处理系统产水率大于85％，外排浓水小于15％。其产水可用于生产工艺水、循环冷却水补水和锅炉用水。本发明提出的煤化工含盐废水深度处理与脱盐回用方法，也可用于化工、冶金、纺织、油田、造纸等行业含盐废水的深度处理与脱盐回用。As shown in Figure 1, the present invention proposes to use multi-stage countercurrent reverse electrode electrodialysis to treat coal chemical industry saline wastewater, and utilizes the coupling and synergistic effects of ozone catalytic oxidation, multi-media filtration, membrane filtration and other technologies to realize the depth of coal chemical industry wastewater Treatment and desalination for reuse. That is, the salty wastewater from the coal chemical industry is first treated with ozone catalytic oxidation to remove most of the refractory organic matter (COD). The clear liquid enters the membrane filtration unit after multi-media filtration and precision filtration. Organic matter and high-valent ions, etc., and the water produced by membrane filtration is further desalted by multi-stage countercurrent reverse electrode electrodialysis. The water production rate of the whole treatment system is greater than 85%, and the concentrated water discharged outside is less than 15%. The produced water can be used for the production of process water, circulating cooling water replenishment and boiler water. The method for advanced treatment and desalination reuse of salty wastewater in coal chemical industry proposed by the present invention can also be used for advanced treatment and desalination reuse of salty wastewater in industries such as chemical industry, metallurgy, textile, oil field, and papermaking.
如图2所示，所述用于煤化工含盐废水处理的专用电渗析器包括：电渗析膜堆单元、频繁倒极控制单元、在线监测与过程控制单元；所述电渗析单元包括：多个电渗析膜堆3、输液泵、流量计、压力表、管路、储液罐4、组装框架和整流器5；所述电渗析膜堆3包括：若干交替排列的抗污染离子交换膜、隔板、膜堆两侧的电极板、夹紧装置，共同构成电渗析膜堆3的极室、脱盐室和浓缩室；所述膜堆由2或2个以上膜堆为1组，同一组膜堆3由一个整流器5并联供电，且根据膜堆脱盐率大小，把2组或2组以上膜堆3进行串联；所述储液罐4包括极水罐、浓水罐、淡水罐；所述电渗析膜堆单元，不同膜堆3不同隔室间的管路串联，控制其浓水/淡水的流向相反，即淡水由第一组的第1级进水、最后一组的最后1级出水，浓水从最后一组的最后1级进水、第一组的第1级出水，由此构成多级/逆流体系，以减小膜堆3中相邻隔室间的浓差扩散，提高废水脱盐率与浓缩倍数。所述倒极控制单元包括：PLC单元6、自动控制阀、整流器5，用于完成电渗析膜堆3倒极过程中自动控制阀开启/关闭、整流器5正负极换向等信号输出、以及电渗析过程控制；通过触摸屏可方便进行膜堆3倒极时间间隔、电源关闭/开启延时时间、手动/自动模式的设定。所述参数在线监测与过程控制单元包括：电导率传感器1、温度传感器2、无纸记录仪、PLC单元6、自动控制阀；所述多个电导率传感器1安装在膜堆中淡水/浓水的出水管，用于在线监测一组膜堆3淡水脱盐率和浓水浓缩倍数；通过PLC单元6把电导率传感器1的数据传输到无纸记录仪保存，并与预设值进行比较，由PLC单元6输出信号控制对应自动控制阀开启/关闭，实现不同隔室溶液在膜堆3中循环或部分循环，使管路中淡水/浓水返回另一组膜堆3进一步处理或直接排放；所述温度传感器2，用来监测膜堆极室溶液的温度；当监测温度大于系统预设值时，由PLC单元6输出信号控制系统断电/停机保护、输出报警信号。As shown in Figure 2, the special electrodialyzer for the treatment of salty wastewater in the coal chemical industry includes: an electrodialysis membrane stack unit, a frequent electrode reversal control unit, an online monitoring and process control unit; the electrodialysis unit includes: An electrodialysis membrane stack 3, an infusion pump, a flow meter, a pressure gauge, a pipeline, a liquid storage tank 4, an assembly frame and a rectifier 5; Plates, electrode plates on both sides of the membrane stack, and clamping devices together constitute the electrode chamber, desalination chamber and concentration chamber of the electrodialysis membrane stack 3; The stack 3 is powered by a rectifier 5 in parallel, and according to the desalination rate of the membrane stack, two or more membrane stacks 3 are connected in series; the liquid storage tank 4 includes a pole water tank, a concentrated water tank, and a fresh water tank; In the electrodialysis membrane stack unit, the pipelines between different membrane stacks and 3 different compartments are connected in series to control the flow direction of concentrated water/fresh water in the opposite direction, that is, the fresh water enters from the first stage of the first group and the last stage of the last group exits. Concentrated water enters from the last stage of the last group and exits from the first stage of the first group, thereby forming a multistage/countercurrent system to reduce the concentration difference between adjacent compartments in the membrane stack 3 and improve Wastewater desalination rate and concentration multiple. The inverting control unit includes: a PLC unit 6, an automatic control valve, and a rectifier 5, which are used to complete the opening/closing of the automatic control valve during the inverting process of the electrodialysis membrane stack 3, the rectifier 5 positive and negative commutation and other signal outputs, and Electrodialysis process control; through the touch screen, it is convenient to set the time interval of membrane stack 3 reversal, power off/on delay time, and manual/automatic mode. The parameter online monitoring and process control unit includes: conductivity sensor 1, temperature sensor 2, paperless recorder, PLC unit 6, automatic control valve; the plurality of conductivity sensors 1 are installed in the fresh water/concentrated water in the membrane stack The water outlet pipe is used for online monitoring of fresh water desalination rate and concentrated water concentration multiple of a group of membrane stacks 3; through PLC unit 6, the data of conductivity sensor 1 is transmitted to the paperless recorder for storage, and compared with the preset value, by The output signal of the PLC unit 6 controls the opening/closing of the corresponding automatic control valve to realize the circulation or partial circulation of solutions in different compartments in the membrane stack 3, so that the fresh water/concentrated water in the pipeline is returned to another group of membrane stacks 3 for further processing or directly discharged; The temperature sensor 2 is used to monitor the temperature of the membrane stack electrode chamber solution; when the monitored temperature is greater than the system preset value, the PLC unit 6 outputs a signal to control the system power-off/shutdown protection and outputs an alarm signal.
实施例1模拟煤化工含盐废水的电渗析脱盐Example 1 Simulation of Electrodialysis Desalination of Coal Chemical Industry Salt Wastewater
采用电渗析技术处理模拟煤化工含盐废水，考察浓水、淡水不同初始Cl-离子时对脱盐率、能耗和膜堆电压等的影响。研究表明，当淡水中Cl-初始浓度为600mg/L，而浓水初始浓度分别为1200、5000和8000mg/L时，在恒压条件下，随淡水含盐量降低其电阻增大，可导致电流密度下降。在150min时淡水中Cl-离子浓度可降到250mg/L以下，当浓水中Cl-离子浓度较高时，其Cl-离子脱除速度减慢，其原因推测是浓水中Cl-离子反向扩散造成；不同初始浓度的浓水电流效率都呈现前脱盐前期较高(85％以上)，随着脱盐进行其电流效率逐渐下降到60％以下。淡水初始浓度为1200mg/L时，控制浓水初始Cl-离子浓度为1200、5000、8000和12000mg/L，同样在恒电位下操作，淡水中Cl-离子去除率随浓水中Cl-离子浓度增加而降低，意味着把淡水中Cl-离子脱除到指定浓度需要更长时间。结果表明，当淡水中Cl-离子浓度较高时，其单位时间内离子的绝对迁移量大于初始浓度较低的含盐废水；其次，浓水、淡水的浓度相差较大也会导致离子反向扩散加剧，从而降低其电流效率；当淡水浓度较高时其电流效率虽然呈现类似的变化趋势，但其下降幅度比淡水初始浓度低时要慢。Electrodialysis technology was used to treat simulated coal chemical industry saline wastewater, and the effects of different initial Cl- ions in concentrated water and fresh water on desalination rate, energy consumption and membrane stack voltage were investigated. Studies have shown that when the initial concentration of Cl- in fresh water is 600 mg/L, and the initial concentration of concentrated water is 1200, 5000 and 8000 mg/L, under constant pressure conditions, the resistance increases with the reduction of the salt content of fresh water, which can lead to The current density drops. In 150 minutes, the concentration of Cl- ions in fresh water can be reduced to below 250 mg/L. When the concentration of Cl- ions in concentrated water is high, the removal rate of Cl- ions slows down. The reason is speculated to be the reverse diffusion of Cl- ions in concentrated water. As a result, the current efficiencies of concentrated water with different initial concentrations are all higher (above 85%) in the early stage of desalination, and their current efficiencies gradually drop below 60% as desalination proceeds. When the initial concentration of fresh water is 1200mg/L, control the initial concentration of Cl- ions in the concentrated water to 1200, 5000, 8000 and 12000 mg/L, and also operate under constant potential, the removal rate of Cl- ions in the fresh water increases with the concentration of Cl- ions in the concentrated water The reduction means that it takes longer to remove Cl- ions in fresh water to a specified concentration. The results show that when the concentration of Cl- ions in fresh water is high, the absolute migration of ions per unit time is greater than that of saline wastewater with a lower initial concentration; secondly, the large difference in concentration between concentrated water and fresh water will also lead to ion reversal. Diffusion intensifies, thereby reducing its current efficiency; when the freshwater concentration is high, its current efficiency shows a similar trend, but its decline is slower than when the initial concentration of freshwater is low.
实施例2实际煤化工含盐废水的电渗析脱盐Example 2 Electrodialysis desalination of actual coal chemical industry saline wastewater
以煤化工曝气生物滤池外排水为例，虽然达到了工业废水外排标准，由于含Cl-离子等无机盐、少量难降解有机物、颗粒悬浮物和细菌等而限制其循环利用，需进一步去除Cl-等无机离子及其他污染物。采用电渗析技术进行脱盐处理，采用恒电位操作、浓水和淡水都采用采用5μm PP棉过滤后直接作为电渗析系统进水，经过10批次连续脱盐实验发现，随电渗析的进行，与模拟废水相似，在相同脱盐条件下淡水中Cl-离子下降到小于250mg/L达到回用标准。但在每批次实验中电流密度都随脱盐过程进行都呈下降趋势，不同批次下降趋势较为相似，恒电位下不同批次的初始电流密度略有下降，推测随电渗析脱盐过程可能发生膜污染。进一步拆膜堆发现，在阴离子交换膜两面都可明显观察褐黄色的污染物覆盖层，但阳离子交换膜表面没有观察到明显膜污染现象，分析原因是阴离子交换膜由于带正电荷，而煤化工含盐废水中带负电荷有机物通过静电作用吸附到膜表面而形成。阴离子交换膜表面形成的膜污染导致煤化工含盐废水电渗析过程难以持续稳定运行，需要进一步探讨其膜污染形成机理及其防治方法。Taking the external drainage of the biological aerated filter in the coal chemical industry as an example, although it has reached the industrial wastewater discharge standard, its recycling is limited due to the presence of inorganic salts such as Cl- ions, a small amount of refractory organic matter, suspended particles and bacteria, etc. Remove inorganic ions such as Cl- and other pollutants. Electrodialysis technology is used for desalination treatment, and constant potential operation is adopted. Concentrated water and fresh water are filtered with 5μm PP cotton and then directly used as water for electrodialysis system. After 10 batches of continuous desalination experiments, it is found that with the progress of electrodialysis, the same as the simulation Wastewater is similar, and under the same desalination conditions, the Cl-ion in fresh water drops to less than 250mg/L to meet the reuse standard. However, in each batch of experiments, the current density showed a downward trend with the desalination process, and the downward trend of different batches was similar. The initial current density of different batches decreased slightly under constant potential. pollute. Further dismantling of the membrane stack found that brownish-yellow pollutant coatings could be observed on both sides of the anion exchange membrane, but no obvious membrane fouling was observed on the surface of the cation exchange membrane. Negatively charged organic matter in saline wastewater is formed by electrostatic adsorption to the membrane surface. Membrane fouling formed on the surface of the anion exchange membrane makes it difficult for the electrodialysis process of coal chemical industry to operate continuously and stably. It is necessary to further explore the formation mechanism and prevention methods of the membrane fouling.
除了测量浓水和淡水中的COD变化外，进一步通过考察电渗析过程中淡水中有机物的迁移。如浓水用不含有机物的煤化工模拟废水、淡水与前相同，电渗析实验发现阴离子与淡室煤化工废水接触面可观察到明显的膜污染，而与模拟废水接触面没有观察到膜污染，表明淡水中有机污染物绝大部分被阴膜截留在淡水中而不会被电渗析过程浓缩。在该体系中同样没有观察到阳膜表面发生污染。由于阴膜表面的膜污染程度降低，在10批次电渗析脱盐实验中没有观察到明显的电流密度、脱盐率、电流效率下降等现象。但随着电渗析脱盐过程的进行，其膜污染必然逐渐加剧，也必然会影响电渗析运行的稳定性。In addition to measuring the COD changes in concentrated water and fresh water, the migration of organic matter in fresh water during electrodialysis was further investigated. For example, the simulated coal chemical wastewater and fresh water that do not contain organic matter are used for the concentrated water as before, and the electrodialysis experiment found that obvious membrane fouling can be observed on the contact surface between the anion and the dilute coal chemical wastewater, but no membrane fouling is observed on the contact surface with the simulated wastewater. , indicating that most of the organic pollutants in fresh water are trapped in the fresh water by the negative membrane and will not be concentrated by the electrodialysis process. In this system also no fouling of the surface of the cathodic membrane was observed. Due to the reduction of membrane fouling on the surface of the negative membrane, no obvious decrease in current density, desalination rate, and current efficiency was observed in 10 batches of electrodialysis desalination experiments. However, with the progress of the electrodialysis desalination process, the membrane fouling will inevitably increase gradually, which will inevitably affect the stability of the electrodialysis operation.
实施例3多级逆流倒极电渗析处理实际煤化工含盐废水Example 3 Multi-stage countercurrent reverse electrode electrodialysis treatment of actual coal chemical industry salty wastewater
针对国内大型钢铁企业煤化工曝气生物滤池外排水(简称煤化工含盐废水)，虽然达到了外排标准，但废水中还含有少量难降解有机物、可溶性无机盐、Ca2+和Mg2+离子、悬浮物、胶体、色度及其他杂质等，经沙滤后直接采用多级逆流倒极电渗析处理，系统连续5天后，发现在同样施加电压下电流密度逐渐下降，导致电渗析脱盐速率急剧下降，单位废水脱盐率也大幅度降低，膜电阻显著升高，导致电渗析脱盐系统难以持续运行。拆电渗析膜堆发现，离子交换膜表面污染严重，尤其是阴离子交换膜表面可见一层黄褐色胶体状吸附层，而且通过化学清洗，离子交换膜性能恢复效果不理想。结果表明，煤化工含盐废水需进行预处理，减少造成膜污染的组分后再采用电渗析技术进一步脱盐。Aiming at the external drainage of coal chemical aerated biological filter of large-scale iron and steel enterprises in China (abbreviated as coal chemical saline wastewater), although the discharge standard has been met, the wastewater still contains a small amount of refractory organic matter, soluble inorganic salts, Ca 2+ and Mg 2 + Ions, suspended solids, colloids, chroma and other impurities, etc., are directly treated by multi-stage countercurrent reverse electrode electrodialysis after sand filtration. After the system has been running for 5 days, it is found that the current density gradually decreases under the same applied voltage, resulting in electrodialysis desalination. The rate drops sharply, the desalination rate per unit of wastewater is also greatly reduced, and the membrane resistance is significantly increased, making it difficult for the electrodialysis desalination system to continue to operate. Dismantling the electrodialysis membrane stack found that the surface of the ion exchange membrane was seriously polluted, especially a yellow-brown colloidal adsorption layer was visible on the surface of the anion exchange membrane, and the performance recovery effect of the ion exchange membrane was not ideal after chemical cleaning. The results show that the salty wastewater from the coal chemical industry needs to be pretreated to reduce the components that cause membrane fouling, and then use electrodialysis technology for further desalination.
由此，本发明了提出了一种采用多级逆流倒极电渗析处理煤化工含盐废水的方法，并与臭氧催化氧化、多介质过滤、膜过滤等技术耦合与协同作用。即煤化工含盐废水经臭氧催化氧化、多介质过滤、膜过滤等预处理后，可去除大部分难降解有机物、硬度、色度和颗粒悬浮物等，其中废水中COD从100mg/L左右下降到小于20mg/L，废水由浅黄褐色变为无色透明，可显著减小后续电渗析膜污染。再经多级逆流电渗析脱盐脱盐处理，其脱盐率可稳定达到90％以上，其中Cl-离子浓度小于250mg/L，满足工业废水回用标准。结果表明，电渗析系统经过3-6个月连续运行，阴离子交换膜、阳离子交换膜都没有出现明显的膜污染，其脱盐率、电流效率、单位能耗等都在系统运行过程中基本保持稳定。由此证明，本发明提出的煤化工含盐废水深度处理与脱盐回用方法，对煤化工含盐废水处理具有较好适应性，应用前景好且适合大规模推广应用。Therefore, the present invention proposes a method for treating salty wastewater of coal chemical industry by using multi-stage countercurrent electrodialysis, which is coupled and synergistic with technologies such as ozone catalytic oxidation, multi-media filtration, and membrane filtration. That is, after pretreatment of coal chemical industry salty wastewater by ozone catalytic oxidation, multi-media filtration, membrane filtration, etc., most of the refractory organic matter, hardness, chroma and suspended particles can be removed, among which the COD in the wastewater is reduced from about 100mg/L When the concentration is less than 20mg/L, the wastewater changes from light yellowish brown to colorless and transparent, which can significantly reduce subsequent electrodialysis membrane pollution. After multi-stage countercurrent electrodialysis desalination and desalination treatment, the desalination rate can reach more than 90% stably, and the Cl- ion concentration is less than 250mg/L, which meets the industrial wastewater reuse standard. The results show that after 3-6 months of continuous operation of the electrodialysis system, there is no obvious membrane fouling in the anion exchange membrane and cation exchange membrane, and the desalination rate, current efficiency, and unit energy consumption are basically stable during the operation of the system . This proves that the advanced treatment and desalination reuse method of coal chemical industry saline wastewater proposed by the present invention has good adaptability to the treatment of coal chemical industry saline wastewater, has good application prospects and is suitable for large-scale popularization and application.
本发明未详细阐述部分属于本领域公知技术。Parts not described in detail in the present invention belong to the well-known technology in the art.
当然，本发明还可以有多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明的公开做出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明的权利要求的保护范围。Certainly, the present invention can also have multiple embodiments, without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the disclosure of the present invention, but these corresponding All changes and deformations should belong to the protection scope of the claims of the present invention.
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