Mg/Fe类水滑石的磷酸根吸附性能及吸附机理

采用共沉淀法成功制备了Mg/Fe类水滑石(Mg/Fe-hlc),并研究了其对废水中磷酸根的吸附性能及吸附机理。研究结果表明:制备的Mg/Fe-hlc具有典型的类水滑石结构和较大的比表面积(156.7 m~2·g~(-1));Mg/Fe-hlc对磷酸根的吸附动力学过程符合准二级动力学模型;Langmuir和Tempkin方程都可以很好地拟合Mg/Fe-hlc对磷酸根的等温吸附数据,Langmuir方程拟合得到的最大吸附量可达47.38 mg·g~(-1);共存阴离子NO_3~-、Cl~-和SO_4~(2-)对磷吸附性能的影响很小;通过分析吸附磷酸根前后的Mg/Fe-hlc的结构和织构性质以及表面官能团变化,并结合溶液pH对磷酸根吸附影响实验结果,发现静电相互作用、配体交换和阴离子交换是Mg/Fe-htl吸附磷酸根的三种主要机制。     

纯相钙铝层状双氢氧化物对磷的吸附特性

采用乙醇辅助液相共沉淀法制备了纯相Ca-Al-LDH层状双金属氢氧化物,考察了Ca-Al-LDH的投加量、吸附时间、pH值、无机电解质(Na₂CO₃ ,KCl ,Na₂SO₄,KNO₃)和温度等因素对磷吸附的影响,结果表明,纯相Ca-Al-LDH对磷酸根离子具有很好的吸附性能,最大饱和吸附量可达160.78 mg/g,当pH值为5.1、温度为45 ℃、吸附时间为600 min、LDH投加量为0.6 g/L、磷初始浓度为80 mg/L时,磷的去除率高达95.88%;无机阴离子会抑制磷在吸附剂上的吸附,当Cl^-浓度从2.5 g/L升高到25 g/L时,Ca-Al-LDH对磷酸盐的最大饱和吸附量从69.96 mg/g降至53.18 mg/g,降低了23.99%;当SO₄^2-浓度从2.5 g/L升高到25 g/L时,Ca-Al-LDH对磷酸盐的最大饱和吸附量降低了24.79%,其它无机阴离子对磷在吸附剂上的吸附也有一定的影响。 Ca-Al-LDH对水中磷的吸附符合二级动力学方程和Langmuir等温模型。 采用扫描电子显微镜、傅里叶变换红外光谱仪和X射线衍射仪等技术手段对制备的纯相Ca-Al-LDH及其吸附磷酸根后的产物进行表征,揭示了Ca-Al-LDH对磷酸根的吸附可能是静电吸引、化学吸附和阴离子插层等过程协同作用的吸附机理。     

稀土硼酸盐的结构及其真空紫外(VUV)荧光性质

稀土硼酸盐在真空紫外(VUV)波段的吸收与化合物中硼酸根离子的结构有关,扩展Hückel计算表明,硼酸根离子中的B-O成键轨道与B-O反键轨道能量差按BO₄^5->B₂O₅^4->BO₃^3->B₃O₉^9-顺序减小,这与VUV激发光谱的实验结果一致,表明VUV激发过程对应于电子从B-O成键轨道向反键轨道的跃迁.     

12-磷钨杂多酸根柱撑水滑石合成及催化脂肪酸甲酯环氧化

研究了一种可用于脂肪酸甲酯环氧化的类水滑石催化剂. 采用共沉淀法合成类水滑石[Mg_1-xAl_x(OH)₂]^x+-(NO^3-)_x·mH₂O, 通过离子交换法制备出一种新的柱撑水滑石[Mg_1-x²⁺Al_x³⁺(OH)₂]^x+[PW₁₂O₄₀]_x/3^3- ·mH₂O化合物, 并由XRD,FT-IR, Raman, ICP和UV-Vis 进行了表征. 用制备的类水滑石应用于无羧酸环境下的催化脂肪酸甲酯环氧化反应, 结果表明, 柱撑水滑石较插层前转化率和选择性都有了明显的提高. 考察了反应温度、反应时间、催化剂重复使用等因素对环氧化反应的影响, 在60 ℃时反应16 h, 转化率和选择性分别达到56.1%和59.4%, 催化剂使用4 次后重复使用率仍高于90%. 对催化剂催化环氧化的机理进行了初步的探讨.     

镁铝类水滑石对阳离子染料中性红的吸附及机理研究

研究了镁铝类水滑石对中性红的吸附及其作用机理,考察了时间、pH、温度、电解质浓度等因素对吸附作用的影响。结果表明,镁铝类水滑石对中性红的吸附动力学符合准二级动力学方程,热力学符合Langmuir吸附等温式。在实验范围内,吸附量随溶液pH的增大而增加,随温度的升高而降低,随电解质浓度的增加先增加后降低。吸附过程是放热、熵减小的自发过程。镁铝类水滑石对中性红的吸附缘于为类水滑石与中性红分子中π电子的较强静电吸引作用。     

磁性阴离子交换树脂对水体中环丙沙星的吸附行为研究

制备不同Fe₃O₄含量的丙烯酸系强碱阴离子交换树脂为吸附剂,去除水环境中的环丙沙星(CPX),考察了不同Fe₃O₄含量的阴离子交换树脂对CPX的吸附行为。结果表明,树脂吸附使其准一级动力学和准二级动力学常数都有所增加,更符合一级动力学方程,R²>0.996,树脂中Fe₃O₄含量增加可增强吸附性能;Langmuir模型和Freundlich模型对系列树脂吸附CPX的过程均有较好的拟合效果,相关系数R²>0.93,树脂中Fe₃O₄含量的变化不会改变树脂对CPX的吸附机制;pH值<6.18时,吸附量逐渐增加,pH值在6～8之间时,吸附量最高,当pH>8.76时,吸附量下降明显。较高Fe₃O₄含量的磁性丙烯酸系阴离子交换树脂受NaCl影响较大。     

羟基磷灰石对牛血清白蛋白的吸附特性研究

研究了羟基磷灰石表面电位随溶液PO₄^3-浓度、Ca²⁺浓度、离子强度和pH的变化规律;测定了不同操作条件下牛血清白蛋白在羟基磷灰石上的吸附容量;吸附等温线的测定结果表明该吸附属于Langmuir型;通过对该吸附过程的动力学研究,计算得到的表观活化能和吸附热数值较低,表明该吸附是物理吸附.     

邻甲酚在类水滑石、焙烧及改性类水滑石上的吸附

用液相非稳态共沉淀法制备了Mg-Al 类水滑石(HTlc); Mg-Al HTlc 于450 ℃下焙烧得焙烧类水滑石(CHTlc); 采用结构重建法由CHTlc 制备了十二烷基硫酸根(DS－)插层(改性)类水滑石(DS·HTlc). 研究了邻甲酚在Mg-Al HTlc,CHTlc 和DS·HTlc 上的吸附行为: 邻甲酚在Mg-Al HTlc, CHTlc 和DS·HTlc 上的吸附动力学和等温式均分别符合准二级动力学方程和Freundlich 方程, 且吸附速率和吸附量大小均依次为: DS·HTlc>>CHTlc>HTlc; 在初始pH＝5.00～13.00 范围内, 邻甲酚在HTlc 和CHTlc 上的吸附量随pH 值的增加先增加后减小, 随温度的增加而增加, 邻甲酚在DS·HTlc 的吸附量随pH 值和温度的增加而降低; 邻甲酚在HTlc, CHTlc 和DS·HTlc 上的吸附量均随电解质(NaCl)浓度的增加而增加, 探讨了吸附机理. 研究结果表明, DS·HTlc 有望成为一种新型的高效酚类有机污染物处理剂.     

壳聚糖-Fe(Ⅲ)复合凝胶球去除磷酸根的影响因素与吸附机理

为改善当前环境水体中的磷污染现状,利用溶胶-滴定-真空冷冻干燥法制备了壳聚糖-铁(CS-Fe)复合凝胶球去除水中磷酸根。 对CS-Fe凝胶球的形貌结构进行了表征,研究了材料对磷酸根的吸附影响因素,并探索了反应机理。 结果表明,CS-Fe对磷酸根的吸附为自发、吸热、熵增过程;吸附过程符合拟一级动力学方程,吸附平衡时间为50 min;根据Langmuir模型计算最大吸附量为23.97 mg/g,脱附效率大于90%。 傅里叶红外光谱(FT-IR)、扫描电子显微镜-能量散射谱(SEM-EDS)、Zeta电势分析、X射线光电子能谱(XPS)等证明,CS-Fe形成利于磷酸根快速吸附的蜂窝状结构;吸附机理包含静电吸附和离子交换过程。 该吸附剂将金属化合物的吸附性能与壳聚糖大分子利于构建多孔材料的特点相结合,改善了吸附效果,球状材料更利于回收,避免二次污染,具有良好应用前景。     

改性层状双氢氧化物对铜离子(Ⅱ)和双酚A的协同吸附

采用离子交换法制备了十二烷基苯磺酸根(DBS^-)和柠檬酸根(Cit^3-)复合改性层状双氢氧化物(LDHs),简写为DBS-Cit-LDHs。 利用粉末X射线衍射分析、红外光谱分析、比表面积测定以及元素分析等技术手段对样品进行了表征。 结果表明,DBS^-和Cit^3-已柱撑进入LDHs层间。 研究了DBS-Cit-LDHs对水中重金属离子Cu²⁺和有机污染物双酚A(BPA)的协同吸附性能。 吸附实验结果表明,DBS-Cit-LDHs能同时高效去除Cu²⁺和BPA;对Cu²⁺的强吸附能力缘于DBS-Cit-LDHs层间Cit^3-与Cu²⁺形成了稳定配合物;对BPA的强吸附能力缘于分配作用,且吸附能力与样品比表面积无关。 DBS-Cit-LDHs对Cu²⁺的吸附动力学和热力学分别符合准二级动力学方程和Freundlich等温式;对BPA的吸附分别符合准一级动力学方程和Linear等温式。 二者吸附过程的ΔG^o和ΔH^o均为负值,表明吸附为自发放热过程。     

New method for the determination of adsorption space volume for sorbents with an arbitrary porous structure from excess gas adsorption isotherm measurements

A new method for the determination of adsorption space volume has been proposed, which is applicable to adsorbents with an arbitrary porous structure, including nonporous adsorbents with open surfaces. The method is based on the use of an experimental excess adsorption isotherm measured over a wide range of pressures in the equilibrium gaseous phase (as a rule up to 100–150 MPa) and the absolute adsorption isotherm equation with unspecified parameters in the most general form, given by statistical physics. The method has been tested for a number of adsorption systems, and it has been found that the result was always unambiguous, correct, and stable in the sense of input data.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2381–2385, December, 1995.     

Thermal-Adsorptive Concentration

Methods for concentrating dilute fluids using adsorption followed by partial thermal regeneration were studied using the simulation package ADSIM. The systems studied were NaCl in liquid water on Amberlite XD-2 resin and benzene vapor in nitrogen on activated carbon. Cycles studied included counter-current regeneration with pure hot fluid, co-current regeneration with pure hot fluid, a new process called Hot Feed Addition (HFA) consisting of co-current regeneration with pure hot fluid followed by hot feed, and cycling zone adsorption (co-current alternating hot and cold feeds with no pure regeneration fluid). The optimum system depends upon the conditions of the system and the value function chosen to evaluate the systems. For example, for benzene in nitrogen with hot regeneration gas at 467.4 K, cycling zone adsorption used no carrier gas, had the most concentrated benzene stream and a very pure nitrogen product, but the energy use was greater than the other processes. For liquid systems counter-current operation could produce the purest product, but regenerant requirements were high. With slightly lower purity requirements HFA reduced solvent usage and increased the concentration of the concentrated waste stream. For the liquid system all processes used approximately 3% or less of the energy that would be required for evaporation.     

大孔吸附树脂的吸附机理

大孔吸附树脂(macroprous adsorption resin, MAR)是近几十年发展起来的一种具有多孔立体结构、人工合成的有机高分子聚合物。由于其特殊的理化性质和吸附性能,已被广泛应用于化学、医药、环保和食品等领域。本文介绍了近年来国内外对大孔吸附树脂在吸附机理研究方面的进展,重点介绍了不同温度条件下大孔吸附树脂对靶标分子的吸附热力学行为模式,靶标分子在大孔吸附树脂表面及孔内的吸附扩散行为模式。此外,大孔吸附树脂性能参数和靶标分子结构参数之间构效关系也对其吸附选择性规律具有重要的影响。因此,大孔吸附树脂与底物间构效关系的匹配程度及其对选择性的影响是大孔吸附树脂分离理论研究的核心。本文最后介绍了可以准确客观描述吸附过程并具有一定使用范围的大孔吸附树脂吸附模型的建立和评价。     

多组分气体吸附平衡理论研究进展*

关于多组分气体吸附平衡理论的研究之所以重要,一是因为其在分离技术中的应用前景,二是因为其尚不成熟。本文对临界温度以下多组分气体吸附平衡理论研究的进展、各种数学模型的特点及适用范围作了评述,并探讨了含超临界值组分的气体吸附平衡理论所面临的问题及其研究方向。     

氨基酸在固/液界面的吸附作用

本文介绍了氨基酸在固/液界面吸附等温线的特点,氨基酸液相吸附热力学和活性炭、硅胶、二氧化钛、氧化铝、蒙脱土等自水中吸附氨基酸的机制。     

A common approach to adsorption and absorption: Polymolecular adsorption

The Brunauer-Emmett-Teller (BET) and Frenkel-Halsey-Hill equations are shown to be special cases of an equation obtained earlier for interphase equilibrium.Institute of Physical Chemistry, Russian Academy of Sciences, Moscow 117915. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 779–785, April, 1992.     

Thermodynamic parameters of adsorption described by the logarithmic Temkin isotherm

Thermodynamic analysis of the adsorption Temkin isotherm was performed. The equations that describe the dependence of the thermodynamic functions on the amount adsorbed were obtained. A relationship between the excess differential and mean molar thermodynamic functions was found. The thermodynamic approach does not contradict the molecular statistical theory and appears to be more general.     

Expressiveness of Adsorption Measurements for Characterization of Zeolitic Materials—A Review

This critical review concerns the author's results and experience in adsorption studies on molecular sieves comprising crystalline microporous aluminosilicates and aluminophosphates as well as amorphous mesoporous aluminosilicates. The discussion is mainly based on three distinctly different standard adsorbates: nitrogen, benzene, and water. The highlights or advantages and the shortcomings or limitations are considered from the points of view of the experimental procedures and expressiveness or concluding. The results are compared to several other zeolitic materials and adsorbates. Adsorption technique is a valuable tool for characterization of the molecular sieves. Since the measurements are very sensitive to modification of the materials, the investigations require sufficiently thorough procedures and the results a careful interpretation. A comparison between the results for larger series of materials yields valuable conclusions that are much more expressive than those from a single measurement or material. Dedicated to the memory of Professor Wolfgang Schirmer.     

Adsorption of Nitrogen on Silica Gel Over a Large Range of Temperatures

To study the mechanism of physical adsorption of supercritical gases, the adsorption equilibria of N₂ on silica gel for 103–298 K using 20 K increments and pressures up to 10 MPa were measured. A transition of the adsorption mechanism was proven on crossing the critical temperature, but the transition way observed is different from that observed with activated carbon. This causes a difference in the locations of the linear section of the n- _g isotherm at the near-critical temperature. Although the isotherm type is different on silica gel and on activated carbon in the sub-critical region, all isotherms in the supercritical region can be well modeled by a single model. It leads to the argument that the adsorption mechanism of supercritical gases is identical no matter what kind of adsorbent is used.