【作者】 马静颖；

【导师】 倪明江； 严建华； 岑可法；

【作者基本信息】 浙江大学 ， 工程热物理， 2006， 博士

【摘要】 化工、制药、造纸等行业的发展排放了大量的含低熔点碱金属盐和碱土金属盐的高浓度有机废液，这些废液往往毒性较高，如果直接排放将造成严重的环境污染，而常规的生化处理方法等又无法解决此类污染问题。焚烧法是一种有效的高浓度有机废液处理方法，但是在将传统的焚烧法应用于处理含盐高浓度有机废液时，却遇到了低熔点碱金属盐和碱土金属盐造成的焚烧炉结焦、结渣等问题。因此，开发一种更为可靠、更为有效的含盐高浓度有机废液处理方法已是废液污染治理的迫切需求。本文结合蒸发脱盐预处理和流化床焚烧的优点，开发了蒸发结晶脱盐和流化床焚烧处理含盐高浓度有机废液的方法，有效地解决了焚烧过程中碱金属盐和碱土金属盐导致的结焦问题，为含盐高浓度有机废液的连续稳定无害化处理提供了一种可靠、可行的方法，具有重要的环保效益和应用价值。 本文在全面综述含盐高浓度有机废液排放和处理技术现状的基础上，首先建立了蒸发结晶脱盐和循环流化床焚烧方法的系统，然后对含盐有机废液处理过程中涉及的化学分析方法进行了探讨，建立了离子色谱快速测定高浓度有机废液中常见碱金属、碱土金属离子含量的方法。在此基础上，搭建试验台架，对蒸发脱盐过程的有机物挥发和无机盐脱除效果进行了全面的试验研究；并分别进行了蒸发残液的萃取分离和脱盐后的有机废液蒸气流化床焚烧特性的试验研究；最后建立了废液蒸发和焚烧机理的动力学反应模型。 含氯化钠的苯酚模拟废液通过蒸发结晶可以达到脱盐的效果。有机物的析出率与苯酚的初始浓度、氯化钠的初始浓度及蒸发速度有关。由于有“盐析”效应，氯化钠初始浓度的升高有利于挥发性有机物和半挥发性有机物的挥发。蒸发速度从1.67ml／min提高到2.73ml／min，氯化钠的总去除率在99.88％～99.99％。在蒸发比为0.97的情况下，蒸发结晶技术对氯化钠、硫酸钠和碳酸钠均具有高于99.0％的去除率；降低蒸发比、提高原废液中氯化钾的浓度能提高氯化钾中钾离子的去除率。当模拟废液中含有氯化钠、硫酸钠和氯化钾这些中性碱金属盐时，有机物的析出率都很高。 如果有机废液中主要含挥发性较大的有机物时，蒸发量可以达到比较大，则蒸发残液体积少，残液中含有高浓度的无机盐和高沸点有机物，在蒸发结晶—流化床焚烧工艺中，蒸发产生的残液可喷入流化床焚烧炉中焚烧处理。当有机废液中含有大量高沸点有机物时，蒸发量不能达到很大，则残液中无机盐的量较高，这些蒸发残液可通过溶剂萃取的方法进行有机物和无机盐的分离。以含氯化钠的对硝基苯酚作为模拟废液，乙酸乙酯的萃取效率较正辛醇的高。当油水比为1∶5时，含30,000mg／L氯化钠和1,000mg／L对硝基苯酚的模拟废液经过1min剧烈振荡和10min静置后的一级萃取效率和二级萃取效率分别达到97.12％和99.89％。萃取效率受到水油比、氯化钠初始浓度、萃取剂等因素的影响。萃取对无机盐的去除效果均很明显。当实际的废液含水量很低，有机物和无机盐含量都很高时（如一些垃圾、危险废弃物的浸出液等），萃取—焚烧工艺也可以使用。 蒸发脱盐后的有机废液蒸气直接通入流化床焚烧炉进行焚烧处理。流化床的床料采用氧化铝空心小球。有机物焚烧分解产物利用在线烟气分析仪进行测定。通过CO和CO₂含量的变化确定焚烧效果。结果显示焚烧处理的效率受到焚烧温度、烟气停留时间、有机废液蒸气中有机物浓度等因素的影响。如：当焚烧炉的温度从650℃升高到800℃时，进样时间为18min时的焚烧效率从88.74％升高到99.80％；CO的浓度则从200ppm下降到0.6ppm。焚烧更多还原

【Abstract】 Great deals of organic salty liquid wastes are discharged by industries of chemical engineering, pharmacy and paper making, which are easy to lead irreversible environmental pollution. High concentration organic liquid wastes cannot be disposed effectively by routine treatment methods. Incineration is a very potential method for disposal of these liquid wastes. However, low-melting point alkali metal and alkaline-earth metal salts bring the problems of agglomeration, fouling, sintering and defluidization during incineration. So, development and study of organic salty liquid wastes is strigent need in this field.A new wastewater incineration system with evaporation-desalination pretreatment equipment was put forward to treat organic salty liquid wastes in this dissertation. Volatilization of VOCs（volatile organic compounds） and SVOCs（semi-volatile organic compounds） and desalination were analyzed roundly. Analysis of ion chromatography and COD（chemical oxygen demand） was discussed. Extraction for dedalination of evaporation residues and incineration of desalinated organic steam were also studied. In addition, kinetics of evaporation and combustion reactions were investigated.An ion chromatographic method for the determination of alkali and alkaline-earth metal cations in high concentration organic wastewater was developed. The separation of cations was achieved on an IonPac CS12A column with 20 mmol/L methanesulfonic acid as the eluent. The detection was performed by a conductivity detector. Na⁺、 K⁺、 Mg²⁺ and Ca²⁺ could be identified within 14 minutes. A C18 cleanup column was used for direct sample injection. The method is sensitive, selective, and simple, which is convenient to be used for determination of cations in the samples in the incineration of liquid wastes. Determination of COD in these organic liquid wastes is dominant for design of burner and estimation of incineration efficiency. High-speed catalytic method for organic liquid with high concentration of chloride ion and organic compounds was presented in this dissertation. Relative error is 0.15%～5.8% when the concentration of CY is 20,000～60,000mg/L. Accuracy of the method is good, the relative error is less than 2% and the recovery is 98%～102%. There is no "prominent difference" between standard method and high-speed catalytic method.Simulated phenol liquid wastes containing sodium chloride was evaporated and concentrated and sodium chloride was crystallized in different parameters. The experimental results showed that the higher initial concentration of sodium chloride increases the ratio of volatilization of VOCs and SVOCs, which is due to the effect of "salting out". When evaporation speed was increased from 1.67 ml/min to 2.73 ml/min, the total removal coefficient of sodium chloride was about 99.88%～99.99%. When the ratio of evaporation was 0.97, the efficiency of removal of NaCl, Na₂SO₄, and Na₂CO₃ was higher than 99.0%; while, the efficiency of removal of KCl was lower due to high mechanical and selective schlepp in vapour. The efficiency could be improved by reducing the ratio of evaporation or increasing the concentration of KCl. Volatile organic compounds had high ratio of volatilization when the pH of the wastewater was neutral and acidic. The volatilization ratio of organic compounds is affected by initial content of phenol, NaCl and evaporation velocity.Evaporation residues contain high concentration inorganic salts and non-volatile organic compounds, which can be incinerated after desalination. Simulated para-nitrophenol （PNP） liquid更多还原