利用纳米铁还原固定土壤中铼的机理研究
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摘要
为严重的环境危害,但是采用常用的吸附等方法却很难将其固定,因此本工作的目的是研究零价纳米铁还原固定锝的方法及其机理。鉴于非放射性元素铼与锝的物理化学性质相似,故本文实验选用元素铼替代锝,在利用纳米铁还原固定铼的实验基础上对其反应结果和机理进行分析和探讨,为进一步深入了解整个反应的本质提供了理论和实践依据。
本文首先介绍了纳米铁粉的发展历史和典型的制备方法,同时研究了实验室液相还原法制备零价纳米铁微粒过程及在反应体系中添加表面活性剂所产生的影响,并利用激光粒度仪(LS)、X射线粉末衍射仪(XRD)、扫描电镜(SEM)等分析手段进行了全面表征,得到了具有实用性的稳定纳米铁粉。之后,在土壤介质中,利用所制得的稳定纳米铁粉还原高铼酸钾。以批实验和柱实验的形式,通过分光光度法进行测量和分析,定量计算出在不同反应时间和不同ReO_4~-离子初始浓度条件下纳米铁粉对ReO_4~-离子的去除率。在实验的基础上进行拟一级反应动力学拟合,并研究淀粉投加量、纳米铁微粒的投加量、ReO_4~-离子的初始浓度、表面活性剂溶液的初始pH值以及温度对反应的影响。
通过本研究工作可得到结论,实验室自制的稳化高效纳米铁粉对土壤中ReO_4~-离子的还原固定效果十分理想,经计算拟合可知该反应符合准一级反应动力学。
As a radioactive element, Technetium is of a long half-life period and complicated chemical behavior, whose oxide-the TcO_4~- ion- endangers the environment horribly by easy transference. However, it is hard to fix the TcO4- ion through regular absorption methods. Hence, this assignment focuses on the methods of reduction that nanometer iron acts on the technetium,as well as the mechanism for the utter destination. Since the physiochemical properties of both Rhenium, which is a non radioactive element and Technetium are the same nearly, it is reasonable to displace technetium with rhenium for text object. Besides, on the base of the reduction, its results and mechanism will be analyzed and argued in this thesis. All the work above helps master the reacting essence theoretically and practically.
This thesis firstly introduces the development history and classical preparing methods of nanometer iron powder, furthermore studies the influences from adding surfactants into the reacting system during which, named liquid phase reduction in the laboratory, prepares the zero valence nanometer iron particles, and concurrently finishes the corresponding characterization by apparatus, such as LS, XRD, SEM and etc. Finally, the stabile nanometer iron powder of application is attained. Then within the soil as media, stabile nanometer iron powder prepared already is used to restore the potassium per-rhenium. The removal rate of the ReO_4~- ion is calculated quantitatively in the way of batch text and pillar text under different reacting time and different initial concentrations of the ReO_4~- ion, after being measured and analyzed through spectrophotometry. In the last, it is needed to fit the hypothetical first grade reaction kinetics on the foundation of experiment, and observe the reacting influence of starch quantity added, nanometer iron particles quantity added, initial concentration of ReO_4~- ion, initial pH value of surfactant solution and the temperature.
Therefore, the conclusion from this study is drawn up, which is that the relatively sound effect of both restore and reduction comes from the experiment carried out on the ReO_4~- ion in soil, using the stabile effective nanometer iron powder prepared myself in laboratory, in addition, this reaction is accordant with the standard first grade reaction kinetics.
本文首先介绍了纳米铁粉的发展历史和典型的制备方法,同时研究了实验室液相还原法制备零价纳米铁微粒过程及在反应体系中添加表面活性剂所产生的影响,并利用激光粒度仪(LS)、X射线粉末衍射仪(XRD)、扫描电镜(SEM)等分析手段进行了全面表征,得到了具有实用性的稳定纳米铁粉。之后,在土壤介质中,利用所制得的稳定纳米铁粉还原高铼酸钾。以批实验和柱实验的形式,通过分光光度法进行测量和分析,定量计算出在不同反应时间和不同ReO_4~-离子初始浓度条件下纳米铁粉对ReO_4~-离子的去除率。在实验的基础上进行拟一级反应动力学拟合,并研究淀粉投加量、纳米铁微粒的投加量、ReO_4~-离子的初始浓度、表面活性剂溶液的初始pH值以及温度对反应的影响。
通过本研究工作可得到结论,实验室自制的稳化高效纳米铁粉对土壤中ReO_4~-离子的还原固定效果十分理想,经计算拟合可知该反应符合准一级反应动力学。
As a radioactive element, Technetium is of a long half-life period and complicated chemical behavior, whose oxide-the TcO_4~- ion- endangers the environment horribly by easy transference. However, it is hard to fix the TcO4- ion through regular absorption methods. Hence, this assignment focuses on the methods of reduction that nanometer iron acts on the technetium,as well as the mechanism for the utter destination. Since the physiochemical properties of both Rhenium, which is a non radioactive element and Technetium are the same nearly, it is reasonable to displace technetium with rhenium for text object. Besides, on the base of the reduction, its results and mechanism will be analyzed and argued in this thesis. All the work above helps master the reacting essence theoretically and practically.
This thesis firstly introduces the development history and classical preparing methods of nanometer iron powder, furthermore studies the influences from adding surfactants into the reacting system during which, named liquid phase reduction in the laboratory, prepares the zero valence nanometer iron particles, and concurrently finishes the corresponding characterization by apparatus, such as LS, XRD, SEM and etc. Finally, the stabile nanometer iron powder of application is attained. Then within the soil as media, stabile nanometer iron powder prepared already is used to restore the potassium per-rhenium. The removal rate of the ReO_4~- ion is calculated quantitatively in the way of batch text and pillar text under different reacting time and different initial concentrations of the ReO_4~- ion, after being measured and analyzed through spectrophotometry. In the last, it is needed to fit the hypothetical first grade reaction kinetics on the foundation of experiment, and observe the reacting influence of starch quantity added, nanometer iron particles quantity added, initial concentration of ReO_4~- ion, initial pH value of surfactant solution and the temperature.
Therefore, the conclusion from this study is drawn up, which is that the relatively sound effect of both restore and reduction comes from the experiment carried out on the ReO_4~- ion in soil, using the stabile effective nanometer iron powder prepared myself in laboratory, in addition, this reaction is accordant with the standard first grade reaction kinetics.
引文
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[2] Matteazzi P,Basset D, Miani F,et al . Mechanosynthesis of nanophase materials [J]. Nanostructured Materials, 1993,2(3):217.
[3] Del Bianco L,Herando A, Navrro E,et al. Structural configuration and magnetic effects in as-milled and annealed nanocrystalline iron [J]. Journal De Physique, 1998,8(2):107-110.
[4] Malow T R, Koch C C, Miraglia P Q,et al . Compressive mechanical behavior of nanocrystalline Fe investigated with an automated ball indentation technique [J]. Materials Science &Engineering A:Structural Materials : Properties ,Microstructure and Processing, 1998,A252(1):36-43.
[5] Shingu P H. Metastability of amorphous phases and its application to the consolidation of rapidly quenched powders [J]. Materials Science and Engineering,1988,29:137-141.
[6]陈洪,徐祖耀,翟少岩等.机械球磨制备Fe纳米晶及其M?sbauer效应[J].金属学报,1995,31(2):73-76.
[7]江万权,朱春玲,陈祖耀等.超细Fe粒子对磁性粒子浓悬浮液体系磁流变性能的增强[J].化学物理学报, 2001,14(5):629-632.
[8] Islamgaliev R K,Chmelik F,Gibadulin I F et al . Nanocrystalline structure formation in germanium subjected to severe plastic deformation [J]. Nanostructured Materials, 1994,4(4):387-395.
[9] Rempel A A, Nazarova S Z. Magnetic properties of iron nanoparticles in submicrocrystalline copper [J]. Materials Science Forum, 1999,307:217-222.
[10]魏智强,温贤伦,吴现成等.直流电弧等离子体法制备镍纳米粉[J].兰州大学学报, 2003,39(5):38-40.
[11] Cui Zuolin,Zhang Zhikun. Ce-Ni nanoparticles with shell structure for hydrogen storage [J]. Nanostructured Materials, 1996,7:355-361.
[12]郝春成,催作林,张志琨.纳米铁氧化过程中的尺寸和压力效应[J].功能材料, 1997,28(5):471-473.
[13]陈克正,张志琨等.氢电弧等离子体法制备的纳米镍铈粒子的催化特性[J].功能材料,1996,27(6):562-564.
[14]张现平,张志琨,催作林.氢电弧等离子体法制备碳包铁纳米粒子[J].功能材料,1996,27(6):562~564.
[15]潘成福,候登录,张民.纳米Fe微粒的溅射制备及粒度计算[J].磁记录材料, 1999,(2):8-9.
[16]Gleiter H. Nanocrystalline materials [J].Progress in Materials Science, 1989,33(4):223.
[17]李发伸,杨文平,薛德胜.纳米Fe微粒的制备及研究[J].兰州大学学报,1994,30(1):144-146.
[18] Sanchez-lopez J C,Fernandez A. Role of oxide passivation layers in nanocrystalline metal powders and consolidated materials[J].Materials Science Forum, 1997,269(2):827-832.
[19] Quintela M A L,Liz L,Blanco J. Phase stability and structure of non-toxic microemulsions [J]. Progress in Colloid & Polymer Science, 1993,93:294.
[20]张朝平
[21]柳学全,徐教仁等.纳米级金属铁颗粒的制取[J].粉末冶金技术,1996,14(1):26-29.
[22]赵新清,梁勇,胡壮麟.纳米铁微粒表面氧化物的结构及磁性[J].金属学报,2001,37(6):633-636.
[23]刘思林,滕荣厚,徐教仁等.用热分解法制备纳米级铁粉[J].粉末冶金技术,1999,9(2):28-30.
[24]曹茂盛,邓启刚,鞠刚等.α-Fe纳米粉末制备及其表征[J].化学通报,2000(2):42-43.
[25]曾京辉,郑化桂,曾恒兴.纳米α-Fe金属粉合成[J].磁记录材料,1998,4:14-17.
[26] Santos A,Macedo W A A,Ardisson J D,et al . Fe-Al2O3 nanocomposite: synthesis and magnetic properties [J]. Materials Research Society Symposium– Proceedings, 2000,581:333-338.
[27] Chuan-Bao Wang,Wei-Xian Zhang. Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs[J]. Environment Science Technology ,1997,31(7):2154-2156.
[28]程起林,赵斌,古宏晨.液相还原法制备Fe-Cr纳米粉[J].华东理工大学学报,1999,25(5):499-502.
[29]李国栋,熊翔,黄伯云.纳米粉体大气环境团聚机理及无团聚纳米粉体的制备[J].中南大学学报, 2004,35(4):527-531.
[30] Israelachivili J N. Intermolecular and Surface Forces [M]. 2ndEd,London:Academic Press,1991.
[31]高濂,孙静,刘阳桥.纳米粉体的分散及表面改性[M].北京:化学工业出版社,2003.
[32]卢寿慈.粉体加工技术[M].北京:中国轻工业出版社,1999.
[33]付铁岩,孙晋良,陈来等.纳米催化剂FeS的制备及其在气相生长炭纤维中的应用[J].材料科学与工程学报, 2005,23(5):549-551.
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