摘要
本课题主要是在前人研究基础上，进行了天然斜发沸石钾钙离子交换性能的研究。主要从热力学和动力学两部分对钙型斜发沸石钾离子的交换进行了试验，研究了不同外界条件对钾钙离子交换的影响，为寻求最佳的工作条件提供了一定的理论依据。
热力学试验研究表明：钙型斜发沸石钾离子交换的全交换量为164.42meq/100g沸石，该交换反应为不完全交换。绘制了离子交换等温线和Kielland图。结果表明在一定范围内温度越高越利于钙型斜发沸石对单—钾阳离子溶液中钾的吸附。并研究了不同温度下，钙型斜发沸石对海水中钾离子的吸附，得到试验范围内50℃为最佳交换温度。根据试验数据计算得到相关的离子交换热力学函数，并通过计算结果可以得知钙型斜发沸石的钾—钙离子交换为吸热反应，在一定温度范围内反应本身可以自发进行。
动力学试验研究表明：在试验范围内反应的控制机理为液膜控制。利用浅床技术，得到不同温度、浓度和流速下的动力学数据并绘制了动力学曲线。根据动力学数据计算出不同条件下的总传质系数和有效扩散系数。以上的试验结果表明，温度和浓度的升高，有利于钾离子的交换。另外溶液流速的增大也有利于钾离子的交换，但和温度和浓度相比效果并不明显。本课题还建立了离子交换传质模型并对模型进行了验证。
本课题的研究内容既填补了国内外该研究领域的空白，也可以帮助改进现有的海水提钾技术。钙型斜发沸石海水提钾可以使海水提钾的成本大大降低，也可以简化整个工艺的流程。试验结论为海水提钾技术最终实现工业化提供了必要的补充。
The task is the studies on the capability of K+-Ca2+ exchange on natural clinoptilolite, which is based on the predecessor's research. Two parts were studied which included thermodynamics and kinetics. The effect of different surroundings on the ion exchange was investigated. All the work can help us to find the best operation conditions.
In the studies of thermodynamics some conclusions had been drawn. The ability of potassium exchange was 164.42meq/100g clinoptilolite. The reaction belongs to incomplete exchange. The isotherm of ion exchange and the diag of Kielland had been got. It showed that the selectivity would be higher with the temperature increasing. The adsorption of potassium in the seawater on the Ca-form clinoptilolite was studied at different temperature and the best operation temperature was 50℃. The functions of thermodynamics had been got, which showed the reaction was endothermic and it can progress spontaneously in the experiment.
The studies of kinetics showed that the exchange process was controlled by film diffusion in the conditions of experiment. By the technique of shallow bed, the data and the curve of kinetics had been got under different conditions. The KD.a and D had been calculated. The results of experiments showed the increasing of temperature and concentration was in favor of the exchange of potassium. Although the increasing of flow can also be in favor of the exchange, the effect was not notable. The mass transfer model was founded in the research, and the data got from the model could be fit for the data got from the experiments well.
The task can supply the research blank of the Ca-form clinoptilolite, it also can help us to improve the technique of extracting potassium. This method can reduce the cost and cut short the circuit. In a word, this task is an indispensable complement for extracting potassium from seawater.
引文
[1] 中国科学院地质研究所：沸石矿物与应用研究(论文集)，科学出版社，1979
[2] 张铨吕，杨华蕊，韩成，等编著．天然沸石离子交换性能及其应用，科学出版社，1986
[3] 姜志新，宋正孝，等编著．离子交换分离工程．天津大学出版社，1989
[4] Ames, L.,L., Jr. and B. W. Mercer..Scientific communications, The use of clinoptilolite to removal potassium selectively from aqueous solutions of mixed salts, Econ. Geol., 1967, 56: 1135-1136
[5] Nishita, H. and Haug R. M..Influence of clinoptilolite on ~(90)Sr and ~(137)Cs uptakes by plants. Soil. Sci., 1972, 114: 149-157
[6] L.,L., Jr..Zeolite extraction of cesium from aqueous solutions. U. S. At. Energy Comm., H. W. , 1959, 25: 62607
[7] Nikashina, V. A., Zaborskaya, Ye. Yu., Mahalov, Ye. M. and Rubinshteen, R. N..Selective solution of strontium by natural clinoptilolite from aqueous solutions. Radiokhimiya, 1974, 16: 753-756
[8] Ames, L.,L., Jr. The cation sieve properities of clinoptilolite. Amer. Miner., 1960, 45: 689-700
[9] 张铨吕，韩成．天然沸石交换重金属阳离子的基础研究．岩石学研究，第一辑，1982：171-181
[10] Fujimori, K. and Moriya, Y..Removal and treatment of heavy metalsin industrial wastewater, Ⅰ. Neutralizing method and solidification by zeolite. Asahi Gerasukogyo Gijutsu Shoreikai Kenkyu, Hokoku, 1973, 23: 243-246
[11] Cohen. J. M.,Trace metal removal by wastewater treatment, Tech. Transfer, U. S. Environ Protect Agency, 1977, Jan: 2-7
[12] John D. Morgan, Donald H. Napper and Gregory G. Warr. Thermodynamics of Ion Exchange Selectivity at Interfaces. J. Phys. Chem., 1995,99:9458-9465
[13] D. Petruzzelli, F. G. Helfferich, L. Liberti. Kinetics of Ion Exchange with Intraparticle rate control: models accounting for interactions in the solid phase. Reactive Polymers, 7(1987): 1-13
[14] Roberto T. Pabalan and F. Paul Bertetetti. Experimental and Modeling Study of Ion Exchange Between Aqueous Solutions and the Zeolite Mineral Clinoptilolite. Journal of Solution Chermistry, 1999. 4 (28): 367-393
[15] 李增新，张启军．天然沸石的开发与应用．现代化工，1997：42-43
[16] 邢锋，丁浩，冯乃谦．天然沸石加工与改造技术的现状及应用前景．矿产综合利用，1996．12(6)：32-36
[17] 何杰，张秀云．皖南沸石基本物化性能及其住水处理中应用可能性研究．非金属矿，1998．2：20-22
[18] 吴瑞风，施和平，李曼尼．内蒙古天然沸是的开发及应用进展情况．现代化工，1997．6(26)：69-70
[19] 刘亦凡，汪玉英，梁旭生．等．NH_4~-改型天然斜发沸石及其离子交换性．离子交换与吸附，1997．13(3)：274-279
[20] 胡艳海，王继库，邵淑华．活性沸石对重金属离子的吸附及再生性研究．无机盐工业，1997．2：5-6
[21] 霍爱群、姜华，改性天然沸石用于饮用水体除铅机理探讨，无机盐工业，1998．30(2)：14-15
[22] 李曼尼，张翼民，杨文斌，等．白庙子斜发沸石上2K~-(z)Cu~(2-)(s)离子交换性能的热力学研究．内蒙古大学学报(自然科学版)，1998．1(29)：79～83
[23] 陈学玺，姜华，谷忠勇，等．W_∞-1沸石离子交换性能的研究．无机化学学报，1997．9(13)：340-343
[24] 王绍亭，陈涛编著．动量、热量与质量传递．天津科学技术出版社
[25] 朱炳辰．无机化工反应工程．(第二版)．华东化工学院，1985．7：259-272
[26] 文衍宣，王励生，金作美，等．离子交换法脱除磷矿废水中Mg~(2-)的动力学研究．高校化学工程学报，1999．12(13)：572-575
[27] 李曼尼，杨文斌，新民．钠型斜发沸石上Na~--Cu~(2-)离子交换过程动力学研究．物理化学学报，1997．3(13)：224-229
[28] 车如心，李冉冉．水处理中离子交换动力学的试验研究．大连铁道学院学报，1998．6(19)：98—100
[29] 李玉龙，孙彦，胡宗定，等．乳酸的离子交换动力学模型．天津大学学报，1999．5(32)：565-568
[30] 于连群，肖举强，付俊国，等．活化沸石除铁性能研究．铁道劳动安全卫生与环保，1997．2(24)：98-101
[31] 刘峙嵘，郭锦勇，周祥友．P951树脂吸附铂的动力学性质．山东冶金，1997．4(19)
[32] 王萍，严子春，邱熔处．氯化钠改性沸石吸附水中苯酚的研究．中国给水排水，2000．4(16)：11-13
[33] 朱伯儒，史作清，何炳林．大孔球形纤维素离子交换剂的制备及其对蛋白质的吸附富集性能研究．Ⅲ．球形纤维素阴离子交换剂对蛋白质的吸附富集性能研究．离子交换与吸附，1997．13(1)，43-47
[34] 文衍宣．磷矿脱镁废水中Mg~(2-)-NH_4~-交换动力学研究．四川大学学报(工程科学版)，2000．1，Vol．32，NO．1：101-104
[35] 王德华，费维扬．钠改型天然斜发沸石对铵离子的交换性能。离子交换与吸附，2002，18(2)：144～149
[36] 王仰东，傅乐峰等．高铝沸石的钙离子交换动力学研究．无机化学学报，2002．11．
Vol. 18, No. 11
[37] V.I. Starosta, F.M. Bobonich and I.S. Balog. Effect of Change in Sign of The Telectivity in The Ion-exchange Adsorption of Cobalt by Mordenite and Clinoptilolite. Theoretical and Experiment Chemistry, Vol. 37, No. 5, 2001
[38] Tarasevich, Yu. I: Krysenko, D.A: Polyakov. V. E. Selectivity of low- and high-silica clinoptilolites with respect to alkali and alkaline-earth metal cations. Colloid Journal of the Russion Academy of Sciences: Kolloidnyi Zhurnal, v 64, n 6, November/December, 2OO2, p 759-764
[39] 中少华，张术根，王大伟 天然沸石及其开发利用研究进展 矿产保护与利用 2000，4：34-38
[40] 许真玉，李三鸣，王齐放等 磷酸苯丙哌啉与树脂的交换动力学研究 中国药学杂志，2002，37(4)：280-283
[41] 王德华，费维扬．钠改型天然斜发沸石的铵离子交换平衡．离子交换与吸附，2002，18(4)：343-348
[42] 李玉龙，孙彦，胡定宗等．乳酸的离子交换动力学模型．天津大学学报，1999．5(32)：565-568
[43] 成都科学技术大学分析化学教研组编．分析化学试验．高等教育出版社，1998
[44] 印永嘉。物理化学简明手册．高等教育出版社，1988
[45] 天津市制盐工业研究所编．海盐工业分析．燃料化学工业出版社，1972