【作者】 喻赛波；

【导师】 陈孟林； 何星存；

【作者基本信息】 广西师范大学 ， 有机化学， 2004， 硕士

【摘要】 本文综述了糖蜜酒精废液的现行治理方法和催化湿式氧化法、超临界水氧化法、催化超临界水氧化法的特点及其在有机废水处理中的研究情况，在此基础上针对糖蜜酒精废液的特点提出了催化亚临界水氧化法处理糖蜜酒精废液的新思路，进行了基于催化亚临界水氧化技术应用问题的基础性研究，主要的研究内容和得到的结论如下：1、对糖蜜酒精废液的特征进行了分析，结果表明：糖蜜酒精废液是一种高浓度的酸性有机废水，在亚临界水氧化过程中可产生大量的热量，能够维持反应的自热，其在110℃时开始有部分有机物发生聚合，在约167℃左右开始有部分分解而析出碳，有氧气存在时，240℃以上的温度下观察不到聚合物或碳的析出。为避免酸性物质对反应釜的腐蚀，在进行催化亚临界水氧化前需调节废液的pH值并将形成的悬浮物除去。2、对糖蜜酒精废液的中和-絮凝预处理进行了研究。首先用石灰乳将废水中和至pH=8.00左右，然后以阴离子型聚丙烯酰胺（PHP-2）或PHP-2与聚合氯化铝(PAC)的复配物为絮凝剂进行絮凝沉降，均可取得良好的处理效果，较适宜的絮凝沉降操作参数为：PHP-2投加量为0. 9mg/L废水，搅拌时间为6 min，搅拌速度为200rpm，20 min基本能将悬浮物沉降完全；如用PHP-2与PAC进行复配， PAC投加量为30 mg/L废水的絮凝效果最好，5~7 min能将悬浮物基本沉降完全。3、进行了亚临界水氧化催化剂的研制，结果显示：铜、锰元素的氧化物对糖蜜酒精废液的氧化降解具有明显的催化效果，且其复合催化剂CuO/MnO2/γ-Al2O3的催化效果比单组分催化剂的催化效果好。该催化剂适宜的制备条件为：老化温度为60℃，老化时间为8h，焙烧温度为600℃，焙烧时间为8h，铜、锰元素和γ-Al2O3物质的量比为2∶1∶8。4、对以CuO/MnO2/γ-Al2O3为催化剂的催化亚临界水氧化法处理糖蜜酒精废液过程的影响因素进行了研究，结果表明：增加氧气浓度、反应温度、反应停<WP=3>留时间、催化剂投加量均能提高废液CODCr的去除率。在这些影响因素中，反应温度和反应停留时间的影响最为显著，氧气浓度的影响在实际供氧量超过理论所需氧量的4.7倍以上时变得不明显，当催化剂投加量小于10mg/L废水时，随催化剂投加量的增大，CODCr的去除率增加，但当催化剂投加量大于10mg/L废水时对CODCr的去除率无明显影响，因此催化剂投加量以10mg/L废水为宜。5、对催化亚临界水氧化法处理糖蜜酒精废液的动力学进行了初步探索，研究表明：以CuO/MnO2/γ-Al2O3为催化剂、在亚临界水条件下处理糖蜜酒精废液的催化氧化过程中，在实际供氧量超过理论需氧量的4.7倍以上时氧气的反应级数是0，CODCr的反应级数为1，反应的活化能为5.36Х104J/mol，指前因子为6.74Х103min-1。更多还原

【Abstract】 In this dissertation, the current treatment technologies of molasses alcohol wastewater are reviewed. The characteristics of the Catalytic Wet Air Oxidation (CWAO), the Supercritical Water Oxidation (SCWO) and the Catalytic Supercritical Water Oxidation (CSCWO), with their study status in the treatment of organic wastewater are elaborated. And then, according to the characteristic of molasses alcohol wastewater, a new technique for treating the molasses alcohol wastewater, Catalytic Subcritical Water Oxidation (CSWO), is put forward and the basic study on the application of CSWO is carried through. The content and conclusion of the research are listed below.1. The characteristic of molasses alcohol wastewater is analyzed. The results are as follows: molasses alcohol wastewater is a kind of high concentration acid organic wastewater, and there is a great quantity of heat to be produced, which can maintain the heat required by the reaction, when it is in the process of CSWO. At the temperature of 110℃, it was found that some organics polymerized and at the temperature of 167℃, some organics were decomposed to produce carbon. When there is oxygen, it won’t polymerize and precipitate carbon over the temperature of 240℃. The acidity of the wastewater should be adjusted and the suspended solids should be eliminated before the CSWO in order to avoid the erosion of the reactor by acid substances.2. The neutralization-sedimentation treatment of the molasses alcohol wastewater is researched. Firstly, the wastewater was neutralized by cream of lime to adjust the pH value to 8, and then the suspended solids were flocculated and precipitated by the anionic polyacrylamide (PHP-2) or the composition of PHP-2 and poly aluminum chloride (PAC). The best operation parameters were: the chemicals feeding quantity of PHP-2: 0.9mg/L wastewater, the time of stirring: 6 min, the speed of stirring: 200rpm. The suspended solids were precipitated in 20min. Furthermore, when the PAC was added into the system and the PAC feeding quantity amounted 30mg/l wastewater, it <WP=5>acquired the best effect and the suspended solids were precipitated in 5~7min.3. The catalysts of CSWO are investigated. The result shows that the oxides of copper and manganese have the obvious catalytic effect on the oxidation of the molasses alcohol wastewater. And the effect of the composite catalyst, CuO /MnO2/γ-Al2O3, is better than the single catalyst. The optimal conditions to prepare the composite catalyst are: the aging temperature: 60℃, the aging time: 8h, the calcination temperature: 600℃, and the calcination time: 8h. The ratio of Cu, Mn and γ-Al2O3 is 2∶1∶8.4. The affecting factors of treatment of the molasses alcohol wastewater by CSWO using the CuO/MnO2/γ-Al2O3 as catalyst are studied. The result shows that, the removal ratio of CODCr can be improved by increasing the concentration of oxygen, reaction temperature, reaction time and the quantity of catalyst, in which, the reaction temperature and time have the most distinct effect. The effect of concentration of oxygen becomes unconspicuous when the actual quantity of oxygen exceeds 4.7 times of theoretic oxygen. The removal ratio would also be improved by increasing the quantity of catalyst when the concentration of catalyst is below 10mg/L, but the effect would be unnoticeable when the concentration exceeds 10mg/L. So the optimum of the dosage of the catalyst is 10mg/L wastewater.5. The kinetics of treatment of molasses alcohol wastewater by CSWO is studied. The study shows that, the reaction order is 0 and 1 for oxygen and CODCr, respectively. When we choose CuO/MnO2/γ-Al2O3 as catalyst and the actual quantity of oxygen exceeds 4.7 times of theoretic oxygen in the process of treatment of molasses alcohol wastewater by CSWO, the activate energy is 5.36×104J/mol and preexponential factor is 6.74×103min-1.更多还原