羟基磷灰石的制备及其对水中氟离子的吸附

本研究利用红外光谱(FTIR)、扫描电镜(SEM)和X射线粉末衍射(XRD)观察了共沉淀法合成羟基磷灰石(HAP)的形貌及其晶型结构,并探讨了Ca/P摩尔比、反应时间及反应温度等因素对羟基磷灰石吸附水中氟离子性能的影响。结果表明,n(Ca/P)=1.5/1、反应时间1 h、反应温度40℃、陈化时间48 h、煅烧温度200℃、煅烧时间2 h时,HAP除氟效果最佳,吸附效率和吸附容量分别达到68.8%和6.88 mg/g。实验数据Langmuir等温模式拟合效果优于Freundlich模式,热力学参数计算可知,HAP对氟离子的吸附是自发(ΔG00),吸热(ΔH00),熵增(ΔS00)的过程。HAP对氟离子的吸附符合拟二级反应动力学过程。     

沉水植物黑藻对沉积物氨氮吸附/释放特征的影响

氮素是主要的湖泊营养盐,而沉水植物作为湖泊生态系统主要的组成部分,对系统中氮素的跨界面迁移有着重要的影响。在实验室模拟条件下,通过沉积物氨氮释放动力学、吸附热力学和吸附动力学实验,研究了沉水植物黑藻(Hydrilla verticilla)对沉积物氨氮吸附/释放特征的影响,得到如下结论:(1)一级动力学反应模型能较好地拟合沉积物氨氮释放的动力学过程,种植沉水植物没有影响氨氮释放的趋势,但增强了沉积物释放氨氮的能力;(2)分别用多个模型对沉积物氨氮吸附热力学和动力学过程进行拟合,结果均表明种植沉水植物以后,沉积物对氨氮吸附的趋势没有影响,但吸附强度有所下降。     

Dehalogenation Potential of Municipal Waste Incineration Fly Ash

BACKGROUND, AIMS AND SCOPE: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novo synthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. RESULTS AND DISCUSSION: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300 degrees C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene --> pentachlorobenzene --> 1,2,3,5-tetrachlorobenzene --> 1,3,5-trichlorobenzene --> 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2 as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer CONCLUSIONS: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3 to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. RECOMMENDATIONS AND OUTLOOK: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study.     

超高交联吸附树脂对有机物质甲苯的吸附热力学研究

比较了2种超高交联聚苯乙烯吸附树脂NDa99与ZH-04对甲苯的静态吸附行为.结果表明,在288～293 K和研究的浓度范围内,ZH-04、NDa99对甲苯的吸附平衡数据符合Freundlich和Langmuir吸附等温方程.吸附为放热过程,适当降低温度有利于吸附,并计算了甲苯在ZH-04和NDa99树脂上的吸附焓变、自由能变和熵变,对吸附行为进行了合理的解释,为废水处理提供一定的理论依据.     

黄河兰州段沉积物对水体中萘的吸附行为及影响

为研究典型有机污染物在黄河兰州段沉积物的吸附规律及影响,以黄河兰州段的沉积物为供试样品,选择萘（naphthalene）为代表性有机污染物,采用批量试验法研究了污染物萘在黄河沉积物上的吸附动力学、吸附热力学、初始质量浓度、pH、离子强度、粒径等影响因素以及解吸动力学.结果表明:黄河沉积物对萘的吸附动力学更符合准二级动力学模型,且吸附过程主要分为快吸附（0~4 h）和慢吸附（4~8 h）两个阶段,在8 h左右达到平衡;Freundlich模型能较好地拟合热力学吸附特征.在25~45℃的温度范围内,E（吸附平均自由能）为0.288~0.316 kJ/mol（< 8 kJ/mol）,吸附过程中,ΔGθ（吉布斯自由能）小于0,ΔSθ（熵变）与ΔHθ（焓变）均大于0,说明萘在黄河沉积物上的吸附是一个自发的混乱度增大的吸热过程,且以物理吸附为主.影响因素分析结果显示,随着沉积物粒径的增大,萘在其上的吸附量逐渐减小;增大吸附体系中的离子强度时,萘在沉积物上的吸附过程受到抑制;当萘初始浓度增大时,吸附量增加;酸性条件抑制吸附过程,碱性环境促进吸附过程;黄河沉积物对萘的解吸量远小于吸附量,存在解吸滞后现象.研究显示,萘在黄河沉积物中的吸附速率受内部扩散、表面吸附和液膜扩散的共同影响,并且吸附过程同时受到沉积物粒径和溶液的pH和离子强度的影响.      

水中Cu~(2+)、Ni~(2+)与腐殖酸、膨润土的相互作用研究

研究了Cu2+、Ni2+与腐殖酸以及膨润土与腐殖酸的共存吸附剂的相互作用,考察了相互作用时间、初始pH、温度对相互作用的影响.结果表明,金属离子的去除率随时间增加而增大,吸附量随温度升高而增大.初始pH对Cu2+、Ni2+的去除率影响很大,pH在中性范围附近Cu2+、Ni2+的去除率可以达到最大.吸附动力学实验表明,Cu2+、Ni2+在腐殖酸及共存吸附剂上的吸附符合伪二级吸附速率模型,并得到Cu2+在腐殖酸及共存吸附剂上吸附的活化能Ea分别为17.01和38.49 kJ.mol-1,Ni2+在腐殖酸及共存吸附剂上吸附的活化能Ea分别为15.15和13.35 kJ.mol-1,表明吸附过程以物理吸附为主.Cu2+、Ni2+在腐殖酸及共存吸附剂上的吸附符合Langmuir等温线模型.得到的ΔH0、ΔS0和ΔG0表明金属离子在腐殖酸及共存吸附剂上的吸附是一个吸热、熵增、自发的过程.     

黄棕壤不同粒级组分对镉的吸附动力学与热力学研究

采用一次平衡法研究了黄棕壤不同粒级组分(粘粒≤2 μm、粉粒2～20 μm、细砂粒20～200 μm、粗砂粒200～2000 μm)对镉的吸附动力学与热力学,并采用拉格朗日假一级动力学方程、假二级动力学方程、颗粒内扩散模型对试验数据进行拟合.结果表明,2种温度下各粒级组分对镉的吸附均可分为快反应和慢反应2个阶段,0～15 min内为快反应阶段,吸附量达到饱和吸附量的95%以上,此后为慢反应阶段;随着温度由25℃升高到45℃,各组分对镉的饱和吸附量增加了4.86%～25.3%;各组分对镉的吸附动力学符合拉格朗日假二级动力学方程,吸附过程以化学吸附为主;二级动力学吸附速率常数表明,随着各组分粒级增大,吸附速率降低;在试验温度范围内随着温度升高,吸附速率加快;吸附过程的限速步骤为颗粒间扩散;各粒级组分对镉的吸附为吸热反应,反应能自发进行.     

温度对好氧颗粒污泥吸附铅离子的影响

由活性污泥培养得到好氧颗粒污泥,研究了温度对好氧颗粒污泥吸附Pb²⁺的影响.结果表明,好氧颗粒污泥主要含有C、H、N、O、P等元素,其经验结构式为C_5.7H_10.9O3.9NS_0.04.好氧颗粒污泥表面主要由球状细菌组成,具有明显的孔隙结构.在20～40℃时,Pb²⁺在好氧颗粒污泥上的吸附过程可以由Langmuir和Freundlich等温方程进行拟合（R²>0.914）.Pb2+最大吸附量Qmax由80.65 mg·g-1（20℃）增至97.09　mg·g-1（40℃）.吸附过程的表观自由能变ΔG<0、 ΔH>0、 ΔS>0,表明Pb2+在好氧颗粒污泥表面的吸附为吸热、熵增的自发过程.红外扫描分析(FTIR)结果表明,吸附过程Pb2+主要与—OH、蛋白质中的—COOH以及PO发生作用,与含氮官能团无关.     

凹凸棒石对十八胺吸附的实验研究

利用天然凹凸棒石对难降解的十八胺进行吸附研究,并对天然凹凸棒石粘土结构和性质进行分析表征,重点研究了固液比、时间、p H值和温度对十八胺在凹凸棒石上吸附的影响.结果表明,十八胺在凹凸棒石上的吸附受p H和温度的影响明显,并且符合准二级动力学方程和Langmuir吸附等温线,由Langmuir吸附等温线(293 K)得出的饱和吸附容量为143.92 mg·g-1.凹凸棒石作为天然粘土有望成为处理十八胺的理想吸附材料.     

榕树树叶对废水中亚甲基蓝的吸附研究

本研究以榕树树叶为吸附剂,考察了在投加量、p H、温度、吸附时间不同因素下对亚甲基蓝去除率的影响。建立正交实验,结果表明榕树树叶粉末吸附亚甲基蓝的最佳条件是当初始浓度为100mg/L,投加量为0.5g、p H为8、温度为35℃、吸附时间为75min时,去除率最高,达到99.05%。吸附动力学过程可用准一级反应动力学方程来描述,等温吸附过程可由Freundlich吸附等温式来描述,榕树树叶粉末对亚甲基蓝的吸附过程是一个吸热过程。实验证明榕树叶是一种具有潜力的亚甲基蓝吸附剂。