链状高分子金属配合物催化氧化苯乙烯

利用链状Salen型高分子希夫碱金属配合物PLSBM(M:CoⅡ,MnⅡ,ZnⅡ,CuⅡ)作为催化剂,催化分子氧氧化苯乙烯.结果表明,在不添加任何助剂和共还原剂的条件下,氧化产物以苯甲醛(Ⅰ)和环氧苯乙烷(Ⅱ)为主,PLSBCuⅡ具有最佳的催化活性和产物选择性.考察了影响氧化反应的因素,发现在反应温度为90℃、反应时间为9h和催化剂与苯乙烯用量比为1mg∶2mL时,苯乙烯具有最优的转化率(61％)和产物选择性(Ⅰ:57％,Ⅱ:36％).     

Semi-closed synthesis of nitrogen and oxygen Co-doped mesoporous carbon for selective aqueous oxidation

Heteroatom-doped meso/micro-porous carbon materials are conventionally produced by harsh carbonization under an inert atmosphere involving specific precursors, hard/soft templates, and heteroatom-containing agents. Herein, we report a facile synthesis of N and O co-doped meso/micro-porous carbon (NOMC) by template-free carbonization of a small-molecule precursor in a semi-closed system. The semi-closed carbonizaiton process yields hydrophilic NOMCs with large surface area in a high yield. The porous structure as well as the elemental composition of NOMCs can be modulated by changing the holding time at a particular temperature. NOMCs as metal-free heterogeneous catalysts can selectively oxidize benzyl alcohol and its derivatives into aldehydes/ketones with>85％conversion in aqueous solution, which is much higher than that of the control sample obtained in tube furnace (21％conversion), mainly due to their high N content, high percentage of pyridinic N, and large surface area. The presence of O-containing moieties also helps to improve the hydrophilicity and dispersion ability of catalysts and thus facilitates the mass transfer process during aqueous oxidation. The NOMC catalysts also dispayed excellent activity for a wide range of substrates with a selectivity of>99％.     

Spatio-temporal dissolved oxygen dynamics in the Orbetello lagoon by fuzzy pattern recognition

This paper models the dissolved oxygen (DO) dynamics in the Orbetello lagoon as a function of the physico-chemical and ecological system variables, including the submerged vegetation, nutrients, and hydrodynamics. It should be viewed as the concluding sequel to a previous paper describing the dynamics of the lagoon ecosystem [Giusti, E., Marsili-Libelli, S., 2006. An integrated model for the Orbetello lagoon ecosystem, Ecol. Model. 196, 379–394] by introducing the missing DO dynamics. The model considers the oxygen demand originating from the decay of carbonaceous and nitrogenous compounds, as well as photosynthesis and natural reaeration by winds and currents as the oxygen producing processes. With a fixed-parameter set the model could accurately reproduce each single circadian DO cycle, but in the long run it failed to extend this fit and could not accommodate the large DO fluctuations induced by the seasonal variability. In order to enhance the model flexibility, a fuzzy pattern recognition algorithm was designed to classify the circadian DO patterns into four typical behaviours, related to the season, and estimate the corresponding parameters, with the overall model output being a fuzzy combination of these sets. The paper discusses several methods to patch the parameter sets and compares their performance in tracking long-term DO variations. A final assessment of the model validity is obtained by incorporating the whole DO dynamics (model, fuzzy pattern recognition and parameter combination) into the general lagoon model and producing a consistently correct series of DO daily distributions over a yearly cycle. Thus the paper contains both a practical and a methodological aspect. The practical one is the linking of all the lagoon dynamics to the dissolved oxygen kinetics in order to clarify to what extent macroalgae and macrophytes influence the oxygen balance. The methodological aspect consists of extending the validity of short-term models to long time-horizons through a patching technique supported by fuzzy pattern recognition.     

氧和氮等离子体改性细旦涤纶的清洁工艺比较

该文对氧、氮低温等离子体改性细旦涤纶进行了研究,分别探讨了氧、氮等离子体放电参数对提高细旦涤纶上染率的影响,得出了2种工艺的最佳放电参数。实验结果表明:经氧、氮等离子体改性后,细旦涤纶的上染率分别提高了17%和5%,说明氧等离子体改性可显著减少印染废水中的污染物排放量,有利于环境治理,氮等离子体改性效果次之。      

有机碳源和溶解氧对亚硝酸盐生物硝化的影响研究

从城市污水处理厂的活性污泥中纯化分离到高活性硝化菌株N-20（Nitrobacter sp．）,在一种新型材料Carbon Foam的表面挂膜;通过对菌株N-20进行摇瓶试验,选择添加有机碳源的种类,将其在pH7．5～8．0、温度28℃的条件下,分别以NaNO2和K2HPO4为氮源和磷源,通过生物滤塔中的液相连续试验,考察在不同DO的条件下有机碳源对硝化作用的影响规律。结果表明,以葡萄糖作为有机碳源,DO≥2mg／L,葡萄糖低于20mg／L时,生物滤塔内可进行正常硝化,NO2^--N的硝化去除率维持在90％左右,随着葡萄糖浓度的增加,硝化去除率下降到70％;DO≤2mg／L,葡萄糖对硝化作用的抑制增强,当葡萄糖为200mg／L时,生物滤塔中NO^2-—N的硝化去除率仅为32％。     

天然水体腐殖质对双酚A光降解影响的研究

以中压汞灯模拟太阳光光源,研究了双酚A(BPA)在水体腐殖质中的光降解过程,探讨了不同来源的腐殖质、腐殖质浓度、BPA初始浓度、溶解氧等因素对BPA光解速率的影响,实验结果表明,BPA在纯水体系中直接光解很慢,但在腐殖质溶液中光解迅速,符合拟一级动力学反应,改变BPA初始浓度对BPA光解速率的影响不明显,增大溶解氧浓度会抑制BPA光解,通过活性氧分子探针鉴定了腐殖质吸收光辐射产生的羟基与单线态氧,利用GC-MS鉴定了双酚A在Nordic湖富里酸(NOFA)中的光敏化降解产物,推测出BPA敏化降解的可能历程为能量转移导致的直接光解、羟基加成和羟基氧化。     

砷酸钙化合物的溶解度及其稳定性随pH值的变化

通过混合沉淀和溶解实验详细研究了pH值和Ca/As摩尔比对石灰沉淀法处理高浓度含砷废水的影响.沉淀后溶液中的As浓度随pH值的变化趋势与混合液的Ca/As摩尔比有关,在Ca/As=1·50和1·67时,沉淀后溶液中的As浓度在pH=7附近达到最低,然后随pH值的升高而呈现出增大的趋势;在Ca/As=2·00和4·00时,沉淀后溶液中的As浓度随pH值的升高而降低,且2种Ca/As摩尔比条件下的实验结果基本一致.混合沉淀过程中生成的砷酸钙化合物的组成与结构取决于溶液的Ca/As摩尔比和pH值.在低pH值和低Ca/As摩尔比条件下形成的沉淀物要比在高pH值和高Ca/As摩尔比条件下形成的沉淀物的颗粒要大,而且结晶程度要好.在Ca/As摩尔比为1·0~4·0和不同pH值条件下,主要生成Ca_3(AsO_4)_2·3H_2O、Ca_3(AsO_4)_2·2·25H_2O、Ca_5(AsO-4)_3OH和Ca_4(OH)-2(AsO_4)2·4H_2O,溶度积分别等于10~(-21·14)、10~(-21·40)、10~(-40·12)和10~(-27·49).     

曝气生物滤池内的自养反硝化作用

采用多孔介质——火山岩为载体的上向流曝气生物滤池(BAF),研究了限制供氧条件下,无有机碳源时反应器的硝化反硝化特性.结果表明,在 10～30℃范围内,20℃为临界点,低于20℃时,硝化速率缓慢;高于 20℃后,硝化速率加快.温度从 20℃升高到 30℃,硝化速率增长仅为10%,这一特性与悬浮生长反应器内温度对硝化速率的影响完全不同.此外,稳定运行的 BAF 内存在大量氮流失现象,分析认为,限制供氧和无有机碳源时,生物膜内发生了以 Anammox反应为主的自养反硝化作用,大量的氮以 N₂的形式流失.     

东平湖DOM荧光特征及与氢氧同位素指标的相关性

本研究在运用三维荧光光谱示踪平水期东平湖DOM荧光特征的基础上,进一步分析其与氢氧同位素指标的相关性,并在此基础上尝试对大气降水的DOC贡献进行估算,以期为东平湖的污染控制及治理提供依据.结果表明,东平湖平水期DOM主要由类蛋白组分（C1和C4）和类腐殖质组分（C2和C3）构成,以类酪氨酸组分C1为主,C1所占比重将近50%.平水期东平湖DOM同时受陆源、内源及大气降水的影响,但以内源输入为主;外源输入中大气降水补给与大汶河输入所占比例相当;大气降水中的溶解性有机碳输入可能会对东平湖DOM产生不可忽视的影响,需进一步系统研究.氢氧稳定同位素与溶解态有机碳以及类腐殖质荧光之间呈显著相关关系,可以在一定程度上指示DOM的变化趋势.     

BOD微生物膜的再利用研究初探

对失去大部分活性的微生物膜进行再培养,以研究膜再利用的可能性。试验结果初部表明:在1/2MS培养基中加入一定量的植物激素,不仅可以使膜的电位值(I0)显著升高,且活性强,稳定性好,可使膜重复利用。