氨基酸螯合吸附树脂对苯酚的吸附行为研究

合成了一种L-酪氨酸修饰的螯合吸附树脂(AJS-02),并与超高交联树脂NDA-150作对比,研究了其对苯酚的吸附和脱附行为.静态实验结果表明,在研究的浓度范围内,吸附平衡数据符合Langmuir等温吸附方程且吸附为放热过程.溶液的初始浓度为100 mg/L、吸附温度为288 K时,苯酚在AJS-02和NDA-150上的平衡吸附量分别为76.98和91.97 mg/g,苯酚在两种树脂上的吸附是比表面积和表面官能团共同作用的结果.动力学数据表明吸附动力学符合液膜扩散方程和颗粒内扩散方程,液膜扩散为吸附速率的主要控制步骤.动态吸附-脱附实验表明,AJS-02树脂对苯酚的动态穿透吸附量和饱和吸附量分别为5.26×10-2和6.60×10-2mmol/mL,采用95%乙醇作脱附剂,脱附率可达91.5%以上.     

由Langmuir方程计算标准吸附平衡常数

在Langmuir方程中,参数b被定义为吸附与解吸速率常数的比值,即吸附平衡常数.长期以来,人们习惯用吸附平衡常数b进行吸附热力学参数计算.但实际上b并不符合标准平衡常数的特征.本文提出了由Langmuir方程计算标准吸附平衡常数的方法.     

黄姜黄色素在大孔树脂上的吸附动力学研究

采用静态法考察了8种大孔吸附树脂对黄姜黄色素的吸附及解吸特性,筛选出LX-18G树脂具有较高的吸附选择性和良好的脱附性能.以LX-18G树脂对黄姜色素的吸附平衡和吸附动力学进行了深入探讨,测定了不同温度下黄姜色素在该树脂上的吸附等温线,以及不同温度,初始液浓度和转速下的吸附动力学曲线.结果表明,Langmuir方程可更好地描述黄姜色素在该树脂上的吸附平衡.吸附动力学规律可用二级速率方程表示,液膜扩散和颗粒内扩散分别是吸附初期和吸附后期的主要速率控制步骤,吸附活化能为5.37kJ/mol.     

法拉第吸脱附偶联过程循环伏安行为的有限元分析

法拉第吸脱附偶联过程的电化学行为较为复杂,难以定量获得其表界面反应动力学信息. 本文通过COMSOL有限元软件对法拉第吸脱附偶联过程的循环伏安行为进行数值分析,研究了反应物或产物不同吸附条件下的循环伏安行为. 结果表明：当反应物或产物弱吸附时,可通过阴、阳极峰电流之差实现饱和吸附量的定量表征. 随着吸附平衡常数的增大,反应由弱吸附向强吸附过渡,峰电流由扩散峰与吸脱附峰相互重叠过渡到相互分离的吸脱附“前波”或“后波”特征. 该吸脱附特征峰的形状和位置与电势依赖的吸附平衡常数有关. 吸附平衡常数及其电势依赖程度越大,吸脱附峰偏离扩散峰越远,吸脱附峰越尖锐. 该模型为法拉第吸脱附偶联过程的循环伏安研究提供了一种定量研究方法,能够帮助研究者从复杂的吸脱附伏安行为中定量获得饱和吸附量和吸附平衡常数等信息,并对涉及吸脱附的电催化研究具有一定指导意义.     

玻璃硅烷化处理对罗丹明6G和亚甲基蓝吸附行为的影响

利用六甲基二硅烷胺对平面玻璃光波导(高折射率透明导光薄膜介质)进行硅烷化处理, 得到水接触角大于90°的疏水表面. 然后使用时间分辨光波导分光光谱技术研究水溶液中的罗丹明6G (R6G)和亚甲基蓝(MB)分子在疏水玻璃表面的吸附行为, 并与亲水玻璃条件下测得的结果进行对比. 对利用疏水玻璃光波导测得的R6G的吸附-脱附动力学曲线进行Langmuir拟合得到了R6G的吸附速率常数, 脱附速率常数以及吸附自由能. 并且发现与亲水玻璃情况相比, 吸附速率常数增大, 脱附速率常数减小, 吸附自由能更负. 在疏水玻璃表面形成的R6G和MB吸附层的吸光度与亲水玻璃情况相比显著升高, 表明这两种分子更倾向于吸附在疏水玻璃表面. 实验结果还发现玻璃硅烷化处理能够有效抑制这两种染料分子在表面的聚合反应.     

复合功能吸附树脂对2,4-二硝基苯酚的吸附特性

研究了NDA-99复合功能吸附树脂对2,4-二硝基苯酚的吸附及脱附行为.结果表明,该树脂对2,4-二硝基苯酚的吸附与脱附效果较好.在283-313K和研究的浓度范围内,吸附行为符合Freundlich和Langmuir等温式,该树脂对2,4-二硝基苯酚的动态吸附量为161.8mg/g.用质量分数为10%NaOH溶液作脱附剂,温度333K,体积为5BV(床体积)时,脱附率为96.7%,树脂可反复使用,并回收2,4-二硝基苯酚.     

吸附法和溶胶-凝胶法固定化醇脱氢酶比较研究

采用吸附法与溶胶-凝胶(sol-gel)包埋法固定化醇脱氢酶(ADH),对两种方法固定化的ADH的活性进行了比较.采用大孔硅胶为载体对ADH进行吸附,研究了吸附动力学和吸附平衡,得到了吸附动力学曲线和吸附等温线,ADH在硅胶上的吸附等温线可以用Langmuir方程拟合.并且考察了硅胶孔径对ADH吸附量的影响,发现大孔径的硅胶对ADH有着较大吸附量.同时采用sol-gel法对ADH进行包埋固定化.在PH 7.0、25℃下,对两种固定化酶催化甲醛转化为甲醇的反应活性进行比较.由实验测得的反应初速度及拟合得到的米氏常数表明吸附法固定化ADH表现出比sol-gel法固定化ADH高的催化活性.     

耐盐吸附树脂对增塑剂DIBP生产废水预处理的研究

采用耐盐吸附树脂NDA-66预处理增塑剂DIBP生产废水,研究了不同吸附剂对DIBP生产废水中主要污染物邻苯二甲酸的吸附脱附效果。实验结果表明,5种吸附剂中,NDA-66树脂对邻苯二甲酸处理效果最好,且符合Freundlich方程和Langmuir方程;动态吸附脱附过程中,单柱吸附量为7BV,最佳流速为1.5BV/h,最佳脱附剂为1BV 8%Na OH+2BV蒸馏水,温度为328K,脱附率能达到99%以上;放大实验过程中,NDA-66耐盐吸附树脂对增塑剂DIBP生产废水中邻苯二甲酸吸附稳定性较好。     

多胺型阴离子交换纤维吸附铬(VI)的动力学

以聚丙烯腈纤维为原料, 采用化学改性法, 制备了多胺型阴离子交换纤维. 研究该纤维对Cr(VI)的吸附特性. 在研究的温度及浓度范围内, 该纤维对Cr(VI)吸附的平衡数据符合Langmuir和Freundlich吸附等温方程, 对Cr(VI)有较强的亲和力, 吸附反应易于进行. 重点研究了该纤维对Cr(VI)的吸附动力学特性, 分别采用Lagergren一级动力学方程、修正伪一级动力学方程、伪二级动力学方程和颗粒内扩散方程进行拟合, 计算相应的速率常数. 研究表明, 该吸附是一个快速吸附过程, 20 min即可接近吸附平衡, 吸附过程符合伪二级动力学方程, 以化学吸附为主, 该纤维能够多次反复对Cr(VI)进行吸附.     

超高交联吸附树脂对气体中三氯乙烯的吸附研究

研究了超高交联吸附树脂NDA-201对气体中三氯乙烯(TCE)的静态吸附行为.分别采用Langmuir、Freundlich和Dubimn-Astakov模型方程对吸附平衡数据进行了拟合分析,并探讨了吸附机理.实验结果表明,Dubinin-Astakov方程能较好地拟合吸附平衡数据,表明微孔填充在吸附过程中起着很重要的作用.此外,研究了气体中TCE在NDA-201上的动态吸附行为,并用半经验方程Yoon-Nelson模型对穿透曲线进行拟合,实验数据与模拟值吻合良好.     

吸附等温方程参数估算方法的分析

采用定容容量法,在温度6~60℃、平衡压力达106Pa的条件下,测得N2和O2在5A分子筛上系统的吸附相平衡数据。通过Langmuir和Toth等温方程关联这些相平衡数据,结果表明:线性化拟合的方法不可靠,其中用1/q~1/P形式线性化Langmuir方程,会得到误差很大的结果;用非线性法在各温度下单独拟合的等温方程和实验结果吻合很好,但是参数不符合其物理意义,进一步处理则误差较大。应当用非线性最小二乘法将所有温度下的相平衡数据一起拟合吸附等温方程。Langmuir和Toth方程都能用于描述体系的平衡吸附量随温度和压力的变化关系,而Toth方程的误差更小。     

Removal of boron from aqueous solution by clays and modified clays

In order to increase the adsorption capacities of bentonite, sepiolite, and illite for the removal of boron form aqueous solution, the clay samples were modified by nonylammonium chloride. Specific surface areas of the samples were determined as a result of N2 adsorption-desorption at 77 K using the BET method. X-ray powder diffraction analysis of the clays and modified clays was used to determine the effects of modifying agents on the layer structure of the clays. The surface characterization of clays and modified clay samples was conducted using the FTIR technique before and after the boron adsorption. For the optimization of the adsorption of boron on clays and modified clays, the effect of pH and ionic strength was examined. The results indicate that adsorption of boron can be achieved by regulating pH values in the range of 8-10 and high ionic strength. In order to find the adsorption characteristics, Langmuir, Freundlich, and Dubinin-Radushkevich adsorption isotherms were applied to the adsorption data. The data were well described by Freundlich and Dubinin-Radushkevich adsorption isotherms while the fit of Langmuir equation to adsorption data was poor. It was reached that modification of bentonite and illite with nonylammonium chloride increased the adsorption capacity for boron sorption from aqueous solution.     

Preparation of magnetic composite adsorbents from laterite nickel ore for organic amine removal

Magnetic composite adsorbent (MCA) was prepared successfully using laterite nickel ore. The effectiveness of MCA as an adsorbent was evaluated for removal trimethylamine from aqueous environment. In this technological route, the utilization of solid wastes, wastewater treatment and adsorbent recovery were considered comprehensively. The MCA was characterized by techniques, including XRD, SEM, TEM, EDS, VSM and adsorption-desorption of nitrogen at 77 K. The adsorption processes were best described by pseudo-second-order kinetic model and controlled by intraparticle and surface diffusion processes. Langmuir and Freundlich isotherm models were used to match the adsorption equilibrium data. Freundlich isotherm was the best fitting curve for the sorption equilibrium data. The adsorption mechanism was further interpreted by Gibbs free energy, entropy and enthalpy calculated by thermodynamic equation. The negative values of Gibbs free energy changes (ΔG) manifest that the adsorbing process is spontaneous. The results show that laterite nickel ore can be made into MCA for organic amine removal from polluted water.     

On the Applicability of the Langmuir Equation to Estimation of Adsorption Equilibrium Constants on a Powdered Solid from Aqueous Solution

The Langmuir adsorption equation has become popular for summarizing solution-solid adsorption data and estimating adsorption equilibrium constants. The applicability of the Langmuir equation to estimation of adsorption equilibrium constants at solid-aqueous solution interfaces was theoretically examined in terms of (1) comparisons of solid-solution adsorption with solid-gas adsorption, (2) deductions of the Langmuir mathematical expression for the nonelectrolyte/solvent exchange, the phase exchange, the ion exchange, and the simple association reactions, and (3) the fitting procedure. The restrictive assumptions underlying the Langmuir equation for solid-gas adsorption may not be valid for adsorption of solute of small molecules or ions by a powdered solid surface from the aqueous solution phase. The fit of adsorption data to the Langmuir mathematical expression cannot be ascertained solely by the linearity of the commonly used equilibrium concentration/amount adsorbed versus the equilibrium concentration plot and does not provide the actual mechanism of the loss of small molecules or ions from aqueous solution. Therefore, the parameters of fitting to the Langmuir mathematical expression may not provide an unambiguous chemical meaning. In addition, we attempt to bring attention to the importance of the standard states of surface phase and solution phase. Copyright 2000 Academic Press.     

不同锌铝比水滑石的合成及其吸附脱除水中邻苯二甲酸性能

采用共沉淀法合成一系列具有不同锌铝比的水滑石,并利用X射线衍射(XRD)、扫描电镜(SEM)、热重(TG)、氮气吸脱附及电感耦合等离子体质谱(ICP-MS)等表征手段对其结构与组成进行了测试。将上述水滑石材料用于吸附脱除水中邻苯二甲酸污染物,考察了不同锌铝比水滑石吸附邻苯二甲酸性能的差异。结果表明,在较低锌铝比时,随着水滑石锌铝比的增加,其对邻苯二甲酸的吸附量逐渐增大;当锌铝比较大时(6),随着锌铝比的增加,水滑石的吸附量基本保持不变。进一步选取锌铝比为6的水滑石,分别对其吸附邻苯二甲酸的动力学和热力学进行了研究,发现其吸附等温线和吸附动力学数据分别符合Freundlich等温吸附模型和准二级动力学模型,且循环吸附性能较好。     

不同锌铝比水滑石的合成及吸附脱除水中邻苯二甲酸性能的研究

采用共沉淀法合成一系列具有不同锌铝比的水滑石,并利用X射线衍射（XRD）、扫描电镜（SEM）、热重（TG）、氮气吸脱附及电感耦合等离子体质谱（ICP-MS）等表征手段对其结构与组成进行了测试。将上述水滑石材料用于吸附脱除水中邻苯二甲酸污染物,考察了不同锌铝比水滑石吸附邻苯二甲酸性能的差异。结果表明,在较低锌铝比时,随着水滑石锌铝比的增加,其对邻苯二甲酸的吸附量逐渐增大;当锌铝比较大时（>6）,随着锌铝比的增加,水滑石的吸附量基本保持不变。进一步选取锌铝比为6的水滑石,分别对其吸附邻苯二甲酸的动力学和热力学进行了研究,发现其吸附等温线和吸附动力学数据分别符合Freundlich等温吸附模型和准二级动力学模型,且循环吸附性能较好。     

羧甲基壳聚糖微球对活性艳红X-3B的吸附行为研究

用交联的壳聚糖微球(CTS)与氯乙酸在碱性条件下反应,合成了羧甲基壳聚糖树脂(CMCT)。其吸附染料活性艳红X-3B的实验结果表明,CMCT和CTS均对偶氮染料活性艳红X-3B有较好的去除能力。实验条件下,最大平衡吸附量分别为611.5mg/g和365.2mg/g,说明羧甲基的引入提高了壳聚糖的吸附能力。等温吸附可以用Langmuir方程较好的描述,表明为单分子层吸附。动力学过程用二级吸附动力学模拟具有很好的线性相关性,通过二级吸附模型计算出的平衡吸附量与实验值相符。流动床实验表明,CMCT和CTS对浓度为100mg/L的X-3B溶液吸附的穿透点分别为6000ml/g和3375ml/g,用0.1mol/L的氢氧化钠溶液洗脱,洗脱峰集中,洗脱率都在90%以上。洗脱再生后的CMCT和CTS树脂均可重复使用。     

Adsorption characteristics of poly(styrene-co-divinylbenzene) resin functionalized with methoxy and phenoxy groups for phenol

Two macroporous crosslinked poly(styrene-co-divinylbenzene) resins functionalized with methoxy and phenoxy groups, PVBME and PVBPE were prepared and their adsorption characteristics for phenol were studied in hexane as well as in aqueous solution. It was shown that the equilibrium adsorption capacity of phenol onto PVBPE was a little larger than that onto PVBME at the same temperature and equilibrium concentration. The adsorption onto PVBME in hexane can be correlated to Langmuir isotherm model, whereas the semi-empirical Freundlich isotherm model characterized the adsorption onto PVBPE better. The adsorption thermodynamic parameters were calculated and it was found that the adsorption enthalpy, adsorption free energy, and adsorption entropy were all negative, and the adsorption thermodynamic parameters onto PVBPE were more negative than the corresponding ones onto PVBME. The relationship of the adsorption capacity with the equilibrium concentration was linear in aqueous solution. The adsorption was hypersensitive to the solution pH in aqueous solution, and the optimum pH was determined to be 6.0. The adsorption dynamics of phenol onto PVBPE in aqueous solution was investigated and it was seen that the adsorption can be well fitted by the pseudo-first-order rate equation.     

Adsorption-desorption isotherm hysteresis of beta-lactoglobulin A with a weakly hydrophobic surface.

Adsorption-desorption isotherms of bovine beta-lactoglobulin A (beta-lact A) on a weakly hydrophobic stationary phase (C1-ether) were measured by frontal analysis. The adsorption isotherms obtained at different pH were found to be dramatically different in shape, column capacity and desorption reversibility. At pH 4.5, an S-shaped adsorption isotherm was observed whereas at pH 6.0 a Langmuir isotherm was found. In addition, the desorption isotherm at pH 6.0 was found to overlap with the adsorption isotherm, and the adsorption-desorption process of beta-lact A under this condition could be characterized by a fully reversible Langmuir model. The desorption isotherm at pH 4.5, however, did not retrace the adsorption isotherm, resulting in hysteresis loops. A higher aggregate (tetramer) of beta-lact A is shown to be in an equilibrium with the beta-lact A protomer (dimer) at pH 4.5 whereas the dimer alone is predominant at pH 6.0. It is further shown that changes in the absorption coefficient between the adsorption and the desorption cycles for the tetramer at pH 4.5 can account for the hysteresis. The results demonstrate that pH can be a sensitive parameter in protein adsorption isotherm behavior and ultimately the behavior of species in preparative-scale chromatography.     

Fe3O4@HTlc的制备及其对甲基橙的吸附研究

采用液相非稳态共沉淀法制备了磁性镁铝类水滑石(Fe3O4@HTlc),采用透射电子显微镜、粉末X射线衍射仪、傅里叶变换红外光谱仪、振动样品磁强计、比表面分析仪、微电泳仪等对样品的形貌和结构进行了表征,并比较了 Fe3O4@HTlc和HTlc对甲基橙的吸附性能。结果表明,Fe3O4@HTlc为顺磁性、具有核-壳结构和较大比表面积、带有正电荷的近球状颗粒。甲基橙在Fe3O4@HTlc和HTlc上的吸附动力学曲线均符合准一级动力学方程;吸附等温线均符合Langmuir吸附等温式;298 K时Fe3O4@HTlc和HTlc对甲基橙的饱和吸附量分别为138.89和147.06 mg/g,但Fe3O4@HTlc对甲基橙有较强吸附推动力和较短的吸附平衡时间。二者对甲基橙的吸附量均随温度的升高和pH (5~11)的增加而降低。