离子交换法海水提钾过程优化
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摘要
离子交换法由于具有良好的选择性和较高的产品回收率,在海水提钾领域已得到广泛应用。随着离子交换设备的不断发展与更新,连续离子交换技术开始应用于海水提钾工艺中。计算机技术的迅猛发展使连续离子交换分离技术进行模拟研究成为可能。由于数学模型的设计和优化不受实验条件的限制,因此更有利于分离过程复杂机理的研究。连续离子交换法海水提钾过程模拟研究是以单柱吸附和洗脱过程的模拟为基础进行的,因此本文分别对单柱吸附和洗脱过程进行模拟研究,考察不同操作参数和因素对实验的影响,为连续离子交换法海水提钾工艺的模拟研究提供理论支持与参考。
通过查阅文献选取数学模型和模拟所需的相关参数,在此基础上利用COMSOL仿真模拟软件对单柱钾离子吸附和洗脱过程分别进行模拟。将模拟结果与实验结果相对照,可见平衡扩散模型的模拟效果要优于理想模型。
在单柱吸附模拟过程中,选定进料浓度、柱长、柱径和离子交换等温线方程的基础上,随着孔隙率的减小,穿透曲线的穿透时间基本保持不变,保留时间不断增大;而随着传质系数的增大,穿透曲线的穿透时间不断减小,保留时间基本不变;不同流速对穿透曲线的影响较为复杂,随着进料流速的增大,穿透时间不断减小,保留时间也不断减小。
单柱洗脱模拟过程与吸附类似,但所得结果有不同。孔隙率的变化对模拟结果的影响不大,但使流出曲线发生平移的总趋势还是存在的,不影响其穿透时间;而随着传质系数的增大,穿透时间减小的速率不断减小。
The ion exchange method has been widely used in the field of extracting potassium from seawater, owning to the good selectivity and high product recovery. With the development of the ion exchange device, the technology of continuous ion exchange has applied to the process of extracting potassium from seawater. The rapid development of computer technology has made the simulation of continuous ion exchange possible. Design and optimization of mathematical models without restriction of experimental conditions, therefore, are propitious to the study of the complex mechanism of separation. Based on the simulation of batch adsorption and elution process, simulation of extraction potassium process from seawater by continuous ion exchange was researched. In this paper, the simulations of batch adsorption and elution process were studied, while the effects of different operating parameters and factors were investigated. The above research will provide theoretical support and reference for the simulation of extraction potassium process from seawater by continuous ion exchange.
The mathematical models and simulation parameters were selected by referring to the literature. Base on the above, the simulations of batch adsorption and elution process were carried out with COMSOL software. Contrasting the simulation results with experiment data, it can been shown that the equilibrium diffusion model is better than the ideal model.
When the feed concentration, length and diameter of column, and ion-exchange isotherm equation are selected, the process of batch adsorption was simulated through the mathematical model. It can be seen with the porosity decreases the penetration time of the breakthrough curve remain unchanged and retention time increasing. With the increasing of mass transfer coefficients, the through time of the curve gradually decreased and retention time basically unchanged. This paper also study the effect of different velocity on breakthrough curve, the results found the influence is very complicated. It was as follow with the increasing of incoming velocity, the through time and retention time also will decrease.
The simulation of elution process is similar to the adsorption process, but the results are different. With the change in porosity, the results of simulation have little influence. The trend of making the elution curve translation still exists, but the penetration time was not been influenced. With the increasing of mass transfer coefficients, the rate of the penetrate time continuously decreased.
通过查阅文献选取数学模型和模拟所需的相关参数,在此基础上利用COMSOL仿真模拟软件对单柱钾离子吸附和洗脱过程分别进行模拟。将模拟结果与实验结果相对照,可见平衡扩散模型的模拟效果要优于理想模型。
在单柱吸附模拟过程中,选定进料浓度、柱长、柱径和离子交换等温线方程的基础上,随着孔隙率的减小,穿透曲线的穿透时间基本保持不变,保留时间不断增大;而随着传质系数的增大,穿透曲线的穿透时间不断减小,保留时间基本不变;不同流速对穿透曲线的影响较为复杂,随着进料流速的增大,穿透时间不断减小,保留时间也不断减小。
单柱洗脱模拟过程与吸附类似,但所得结果有不同。孔隙率的变化对模拟结果的影响不大,但使流出曲线发生平移的总趋势还是存在的,不影响其穿透时间;而随着传质系数的增大,穿透时间减小的速率不断减小。
The ion exchange method has been widely used in the field of extracting potassium from seawater, owning to the good selectivity and high product recovery. With the development of the ion exchange device, the technology of continuous ion exchange has applied to the process of extracting potassium from seawater. The rapid development of computer technology has made the simulation of continuous ion exchange possible. Design and optimization of mathematical models without restriction of experimental conditions, therefore, are propitious to the study of the complex mechanism of separation. Based on the simulation of batch adsorption and elution process, simulation of extraction potassium process from seawater by continuous ion exchange was researched. In this paper, the simulations of batch adsorption and elution process were studied, while the effects of different operating parameters and factors were investigated. The above research will provide theoretical support and reference for the simulation of extraction potassium process from seawater by continuous ion exchange.
The mathematical models and simulation parameters were selected by referring to the literature. Base on the above, the simulations of batch adsorption and elution process were carried out with COMSOL software. Contrasting the simulation results with experiment data, it can been shown that the equilibrium diffusion model is better than the ideal model.
When the feed concentration, length and diameter of column, and ion-exchange isotherm equation are selected, the process of batch adsorption was simulated through the mathematical model. It can be seen with the porosity decreases the penetration time of the breakthrough curve remain unchanged and retention time increasing. With the increasing of mass transfer coefficients, the through time of the curve gradually decreased and retention time basically unchanged. This paper also study the effect of different velocity on breakthrough curve, the results found the influence is very complicated. It was as follow with the increasing of incoming velocity, the through time and retention time also will decrease.
The simulation of elution process is similar to the adsorption process, but the results are different. With the change in porosity, the results of simulation have little influence. The trend of making the elution curve translation still exists, but the penetration time was not been influenced. With the increasing of mass transfer coefficients, the rate of the penetrate time continuously decreased.
引文
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[3]成思危.试论用天然沸石由海水中直接提取钾盐的方法[J].无机盐工业,1980(6):1-6.
[4]袁俊生,杨树娥,邓会宁.连续离子交换技术及其在海水提钾的应用.盐业与化工,2007,36(3):27-30.
[5]姜志新,谌竟清,宋正孝.离子交换分离工程[M].天津:天津大学出版社,1992.
[6]张铨昌,杨华蕊,韩成.天然沸石离子交换性能及其应用[M].北京:科学出版社,1986.185-191.
[7]闻瑞梅.高纯水的制备及检测技术[M].北京:科学出版社,1999: 101-126.
[8]马建标,何炳林.离子交换树脂在分析化学中的应用[[J].分析测试学报,1993, 12(1):79-86.
[9]王秋萍,宋崇立,姜长印等.除Cs用无机离子交换剂的筛选[J].离子交换与吸附,2000,16(3):225-233.
[10]李丹,邓天龙,孙柏.无机离子交换法从卤水中提锂的研究进展[J].广东微量元素科学;2007,1.
[11]闫明,钟辉,张艳.卤水中分离提取铷、铯的研究进展[J].盐湖研究.2006,3.
[12]徐世平,张继荣,宋崇立.用无机离子交换法从酸性高放废液中去除铯研究进展[J].辐射防护通讯;2000,6.
[13] Kamatsu M, Potassium-selective adsorbent and its Production, JP 03一205315,1991.
[14]孙汉章.从海水中提取钾盐.青岛海洋大学学报,1994,24(1):231一235
[15]李艳,李涛,王丽娜等.离子筛材料的合及其对盐湖卤水中锂的选择吸附性[J].过程工程学报,2006,6(5):724-728.
[16] Tanaka Y. Technology for removing potassium from concentrated seawater by electrodialysis and solar salt dissolved in brine. Separation Science and Technology, 1993,28(11):2023-2034.
[17]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.
[18] Nishita, H. and Haug R. M.. Influence of clinoptilolite on 90Sr and 137Cs uptakes by plants.Soil. Sci. 1972,114: 149-157.
[19] L.,L., Jr..Zeolite extraction of cesium from aqueous solutions.U. S. At. Energy Comm.,H. W. ,1959,25:62607.
[20] 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.
[21] Ames,L.,L.,Jr. The cation sieve properities of clinoptilolite. Amer. Miner, 1960,45:689-700.
[22] 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.
[23] Ames. Some zeolites equilibria with alkali metal cations. Amer Miner,1964,49 (3):35-39.
[24] Nikashina, VA, Zsborskays, YeYu, Mahalov, YeMandRubinshteen, RN. Selective solution of strontium by natural clinoptilolite from aqueous solutions [J], Radiokhimiya, 1974, (16):753-756.
[25] KnollH. Ger (Wdst). 1971, 81-91.
[26] Fujimori, KandMoriya, Y. Removal and treatment of heavy metallic industrial waste water,Ⅰ. Neutralizing method and solidification by zeolite [J], Asahi Gerasukogyo Gijutsu Shoreikai Kenkyu, Hokoku, 1973, (23):243-246.
[27] Cohen, J M. Trace metal removal by waste water treatment, Tech. Transfer, U.S. Environ Protect Agency, 1977, (Jan):3-7.
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