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吸附过程中的多元平衡与动力学研究

The Study of Multi-equilibrium and Kinetics in the Adsorption Processes

【作者】 樊建新

【导师】 申大忠;

【作者基本信息】 山东师范大学 , 分析化学, 2010, 硕士

【摘要】 本论文采用多元线性回归等化学计量学方法对模拟废水体系在脱除过程中的一系列紫外可见吸收光谱进行全面解析,从而获得吸附过程中的各组分之间的竞争或协同作用的吸附机理。第二章膨润土对阳离子染料的吸附等温线和动力学研究。以膨润土为吸附剂,研究了孔雀石绿、番红花红、罗丹明B及其混合染料的脱色情况。研究表明,膨润土对阳离子染料有很好的吸附性能,在三种染料的初始浓度为500μmol/L的条件下,加入膨润土的量分别为0.64, 0.98和1.05 g/L时番红花红、孔雀石绿和罗丹明B的脱色率均能达到95%。混合吸附体系中,各染料之间存在竞争吸附,膨润土投加量不足的情况下,吸附常数较大的染料优先被吸附,在三元混合吸附过程中出现罗丹明B和孔雀石绿被解吸的现象。吸附动力学的研究结果表明,单组分染料吸附动力学和混合体系中总动力学过程符合二级动力学模型。同时,单染料体系中的吸附等温线和多元混合体系中总的吸附等温线符合Langmuir等温吸附模型。第三章有机-膨润土吸附阴离子染料动力学和等温线研究。为提高膨润土吸附染料的性能,以聚二甲基二烯丙基氯化铵(PDADMA)和钠基膨润土为原料,合成阳离子型的PDADMA改性膨润土,它对阴离子染料废水的吸附能力有了很大提高。以此聚电解质改性的膨润土为吸附剂研究了阴离子染料酸性大红、酸性湖蓝和靛红及其混合溶液的脱色情况,在各染料初始浓度为100μmol/L的条件下,加入PDADMA改性膨润土的量分别为0.42, 0.68和0.75 g/L时,酸性大红、酸性湖蓝和靛红的脱色率都达到95%以上。在单染料吸附体系中,每种染料的吸附等温线均符合Langmuir吸附模型,吸附常数分别为4.31×106,0.372×106和0.629×106 L/mol,最大吸附量为228.7,176.3和149.2μmol/g。混合吸附体系中每种染料的吸附等温线符合扩展的Langmuir吸附模型,而各染料的吸附量总和和平衡浓度总和之间的关系符合Langmuir吸附模型。吸附动力学的研究结果表明,单组分染料吸附动力学和混合体系中总动力学过程符合二级动力学模型。第四章浊点萃取法用于模拟染料废水脱色研究。基于表面活性剂的浊点现象所建立浊点萃取是一种绿色环保的萃取方法。本文选用非离子表面活性剂TX-114作浊点萃取剂,研究了由酸性大红、活性紫和曙红构成的单元和混合染料模拟有色废水的萃取脱色过程,讨论了表面活性剂浓度、染料浓度、盐浓度、平衡温度、平衡时间等因素对萃取效率的影响。结果表明,提高表面活性剂浓度、盐浓度有利于提高萃取效率,而染料浓度增加则使萃取效率略有下降。在由活性紫、酸性大红和曙红构成的单元和多元混合染料体系中,酸性大红的萃取效率明显较活性紫高,混合染料体系的萃取脱色行为与单染料体系的萃取脱色行为相差不大。第五章CPC和双酚A同时存在时膨润土吸附研究。膨润土作为一种吸附剂已经被广泛应用于废水中有机物的初步处理,但是膨润土对一些有机物的吸附性能不是很好,如双酚A。但是在阳离子表面活性剂存在的条件下,膨润土对双酚A的吸附量远远大于没有表面活性剂存在的吸附量,溶液中阳离子表面活性剂的浓度对膨润土吸附双酚A的过程有很大的影响。当CPC浓度为600mg/l时,实验条件下,双酚A的去除率达到最大值95%,膨润土对双酚A的吸附等温线符合Langmuir吸附模型,吸附动力学过程符合二级动力学反应过程。溶液的pH值和离子浓度对CPC和双酚A的去除率有影响,但是影响不大。总之,在阳离子表面活性剂CPC存在的条件下,膨润土对双酚A的吸附效果良好。

【Abstract】 In this thesis, a multiple linear regression method was employed to analyze the spectrophotometric data in color removal processes. The residual color profiles, the color removal efficiencies, as well as the thermodynamic and kinetic data of single dyes in the mixture of dyes were obtained.Chapter 2:Adsorption kinetics and isotherm of cationic dyes onto bentonite from single and multisolute systems .The adsorption of Malachite green (MG),Rhodamin B (RM) and Safranine T (SF) onto bentonite from single and multisolute systems was studied. The experimental results show that bentonite is an excellent adsorbent for the cationic dyes used. Under our experimental conditions, the dosage of bentonite needed to remove 95% dyes from initial concentration of 500μmol/L was 0.64, 0.98 and 1.04g/L for SF, MG and RM, respectively. Competitive adsorption was observed in the multisolute dye solutions. In the region of insufficient dosage of bentonite, the dye with a larger adsorption constant is preferentially removed by adsorption. Because of the competitive adsorption of SF, The desorption of RM and MG was observed in the kinetics curves in the adsorption from binary and ternary dye solutions. The adsorption kinetics of dyes from single solutions, and the total amount of dyes adsorbed from binary and ternary dye solutions, can be well fitted by a pseudo-second model. In the case of adsorption from binary and ternary dye solutions, the total adsorption isotherms were fitted well by Langmuir model but the isotherm of each dye had different shape.Chapter 3: Adsorption kinetics and isotherm of anionic dyes onto organobentonite from single and multisolute systems The performances of polydiallydimethylammonium modified bentonite as an adsorbent to remove anionic dyes, namely Acid Scarlet GR(AS-GR), Acid Turquoise Blue 2G (ATB-2G) and Indigo Carmine (IC), were investigated in single, binary and ternary dye systems. In adsorption from single dye solutions with initial concentration of 100μmol/L, the dosage of PDADMA-bentonite needed to remove 95% dye was 0.42, 0.68 and 0.75g/L for AS-GR, ATB-2G and IC, respectively. The adsorption isotherms of the three dyes obeyed the Langmuir isotherm model with the equilibrium constants of 0.372, 0.629 and 4.31 L/μmol, the saturation adsorption amount of 176.3, 149.2 and 228.7μmol/g for ATB-2G, IC and AS-GR, respectively. In adsorption from mixed dye solutions, the isotherm of each individual dye followed an expanded Langmuir isotherm model and the relationship between the total amount of dyes adsorbed and the total equilibrium dye concentration was interpreted well by Langmuir isotherm model. In the region of insufficient dosage of PDADMA-bentonite, the dye with a larger affinity was preferentially removed by adsorption. Desorption was observed in the kinetic curve of the dye with lower affinity on PDADMA-bentonite surface by the competitive adsorption. The kinetics in single dye solution and the total adsorption of dyes in binary and ternary dye systems nicely followed pseudo-second-order kinetic model.Chapter 4: Color removal of simulated dye wastewaters by cloud point extractionCloud point extraction, which is based one the cloud point phenomenon of surfactant solution, is a new environmentally kind liquid-liquid extraction method. An attempt was made to remove color from simulated wastewater containing Acid Scarlet GR,Reactive violet K-3R and eosin by cloud point extraction using a nonionic surfactant of Triton X-114. The influence of the concentrations (surfactant, slat and dye), equilibrium temperature and equilibrium time on the extraction efficiency were tested. The experimental results show that the extraction efficiency to dye increases with increasing concentration of TX-114 and salt or decreasing initial dye concentration. The extraction efficiency to Acid Scarlet GR is higher than that to Reactive violet K-3R in both single and ternary dye solutions.Chapter 5: Simultaneous removal of bisphenol-A and cationic surfactantfrom water by bentonite in one-step process.Bentonite as an adsorbent was applied widely to removal the contamination in the wastewater,however, the adsorption amount is little when bentonite was appied to adsorb some contamination,such as bisphenol-A.In the thesis, we added cationic surfactant CPC to solution in order to hence adsorption capacity of bisphenol A onto bentonite. The influence of the concentrations (CPC) on the removal efficiency was tested. Experiments show that, the addition of CPC can greatly improve adsorption of bisphenol A onto bentonite,when concentration of CPC is 600mg/l,the removal efficiency will reach to 95% .adsorption isotherm of bisphenol-A is fitted to Langmuir and Frundlish adsorption equation , and adsorption kinetics followed pseudo-second-order kinetic model.

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