Adsorption of U(VI) onto kaolin studied by batch method

Adsorption of U(VI) on purified kaolin was studied by batch methods under ambient conditions, including contact time, pH, fulvic acid, etc. Three kinetic models were used to model the kinetic adsorption which was very well described by the pseudo-second-order rate equation, and the activation energy of adsorption was 52.20 kJ/mol. The Freundlich and Dubinin–Radushkevich models fitted the experimental data better than the Langmuir model for the adsorption and desorption isotherms. The thermodynamic parameters indicated that the adsorption of U(VI) on kaolin was an endothermic and spontaneous process.     

The removal of uranium(VI) from aqueous solutions onto activated carbon: kinetic and thermodynamic investigations

The adsorption of uranium(VI) from aqueous solutions onto activated carbon has been studied using a batch adsorber. The parameters that affect the uranium(VI) adsorption, such as contact time, solution pH, initial uranium(VI) concentration, and temperature, have been investigated and optimized conditions determined (contact time 240 min; pH 3.0+/-0.1; initial uranium concentration 100 mg/L; temperature 293.15 K). The experimental data were analyzed using sorption kinetic models (pseudo-first- and pseudo-second-order equations) to determine the equation that fits best our experimental results. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of activated carbon and experimental results showed this to be 28.30 mg/g. The Freundlich, Langmuir, and Dubinin-Radushkevich (D-R) models have been applied and the data correlate well with Freundlich model and that the sorption is physical in nature (the activation energy Ea=7.91 kJ/mol). Thermodynamic parameters (DeltaHads0=-50.53 kJ/mol, DeltaSads0=-98.76 J/mol K, DeltaGads(293.15 K)0=-21.61 kJ/mol) showed the exothermic heat of adsorption and the feasibility of the process.     

纳米γ-Al_2O_3吸附Ge(Ⅳ)的机理及性能

研究了纳米γ-Al2O3吸附剂对Ge(Ⅳ)的吸附行为,考察了吸附平衡时间、温度和溶液的pH值等因素对吸附过程的影响.结果表明,纳米Al2O3对Ge(Ⅳ)的吸附在2min时基本达到平衡,在pH=4～11范围内,Ge(Ⅳ)可以被纳米Al2O3定量富集,吸附率大于95%;吸附于纳米Al2O3上的Ge(Ⅳ)可以用0.3mol/LK3PO4和1mol/LH2SO4混合溶液洗脱,5min后基本达到解析平衡,解析率能达到97%;该吸附过程符合准二级反应动力学模型,计算了不同温度下的吸附速率常数,并求得纳米Al2O3对Ge(Ⅳ)的吸附活化能(Ea)为11.63kJ/mol;该体系的吸附过程符合Freundlich等温式,由D-R等温式求得常温下纳米Al2O3对Ge(Ⅳ)的平均吸附能为10.87kJ/mol.Ge(Ⅳ)吸附反应的ΔG0为负值,焓变ΔH0为正值,说明该吸附过程是自发的吸热反应.     

原位合成羟基磷灰石/壳聚糖复合吸附剂及除氟特性研究

利用原位共沉淀法合成了羟基磷灰石/壳聚糖复合吸附剂,通过扫描电镜、X射线粉末衍射、红外光谱和N2吸附-脱附曲线,研究复合前后羟基磷灰石的理化特征变化。实验结果表明与壳聚糖复合后羟基磷灰石的晶型并没有改变,只是结晶度有所降低,且复合后表面形成了不规则的凹凸结构,表面粗糙度增加。比表面积从106.75m2/g增加到127.58m2/g。复合吸附剂孔径大部分集中在10~50nm,属于介孔结构。利用Langmuir和Freundlich吸附等温方程对实验数据进行了拟合,对比相关系数R2值,Langmuir模型能更好地描述该吸附过程。复合吸附剂对氟离子的吸附符合拟二级反应动力学方程。计算了吸附热力学和动力学参数值,探讨了复合吸附剂对氟离子的吸附机理。ΔG0<0、ΔH0>0和ΔS0>0,说明复合吸附剂对氟离子的吸附是自发的、吸热的熵增过程,温度升高有利于吸附。吸附活化能(Ea)=15.03kJ·mol-1,迁移能(E)=7.639kJ·mol-1,说明该吸附过程以物理吸附为主。     

还原态氧化石墨烯对Zn(Ⅱ)的吸附动力学与热力学

以乙二胺(EDA)还原氧化石墨烯(GO)制得一种吸附材料,即还原态氧化石墨烯(RGO)。 采用批量平衡法研究了RGO对Zn(Ⅱ)的吸附动力学与热力学,利用Lagergren准一级及准二级动力学方程、Langmuir和Freundlich等温方程对实验数据进行了拟合分析。 研究结果表明,Lagergren准二级吸附动力学模型能够较好地描述实验结果,表明该吸附过程以化学吸附为主。 RGO的吸附在所研究的Zn(Ⅱ)浓度范围内更符合Langmuir等温吸附经验式,ΔH0=-21.60 kJ/mol,吸附焓变小于零,表明该吸附为放热过程;吸附吉布斯自由能变化ΔG0为正值,表明该吸附是一个非自发的过程。     

717型阴离子交换树脂吸附水溶性芳香族有机污染物研究

研究了717型阴离子交换树脂对苯酚、苯甲酸和十二烷基苯磺酸钠(SDBS)等水溶性芳香族污染物吸附过程的基本化学问题.研究结果表明:717型树脂对苯酚、苯甲酸和SDBS的吸附过程均符合Lagergren二级吸附动力学方程,吸附速率均随着温度的升高而加快,吸附表观活化能Ea分别为13.2kJ/mol、59.5kJ/mol和48.1kJ/mol,吸附过程△H0和△S0均为正值,△G0均为负值,吸附能够自发进行;吸附等温模型符合Langmuir等温式;318K时,717型树脂在pH=9.1对SDBS的饱和吸附容量为360mg/g;在pH=10.2,对苯酚和苯甲酸的饱和吸附容量分别为194mg/g和286mg/g.用浓度均为0.5mol/L,体积比为5∶1的NaCl-NaOH混合溶液可快速洗脱树脂上吸附的污染物,洗脱率达98％以上.该树脂对水溶性芳香族污染物吸附容量大,易于再生和循环利用,可用于环境水体中水溶性芳香族有机污染物的吸附治理.     

Adsorption of direct dyes from aqueous solutions by carbon nanotubes: determination of equilibrium, kinetics and thermodynamics parameters

This study examined the feasibility of removing direct dyes C.I. Direct Yellow 86 (DY86) and C.I. Direct Red 224 (DR224) from aqueous solutions using carbon nanotubes (CNTs). The effects of dye concentration, CNT dosage, ionic strength and temperature on adsorption of direct dyes by CNTs were also evaluated. Pseudo second-order, intraparticle diffusion and Bangham models were adopted to evaluate experimental data and thereby elucidate the kinetic adsorption process. Additionally, this study used the Langmuir, Freundlich, Dubinin and Radushkevich (D-R) and Temkin isotherms to describe equilibrium adsorption. The adsorption percentage of direct dyes increased as CNTs dosage, NaCl addition and temperature increased. Conversely, the adsorption percentage of direct dyes decreased as dye concentration increased. The pseudo second-order model best represented adsorption kinetics. Based on the regressions of intraparticle diffusion and Bangham models, experimental data suggest that the adsorption of direct dyes onto CNTs involved intraparticle diffusion, but that was not the only rate-controlling step. The equilibrium adsorption of DR86 is best fitted in the Freundlich isotherm and that of DR224 was best fitted in the D-R isotherm. The capacity of CNTs to adsorb DY86 and DR224 was 56.2 and 61.3 mg/g, respectively. For DY86, enthalpy (DeltaH(0)) and entropy (DeltaS(0)) were 13.69 kJ/mol and 139.51 J/mol K, respectively, and those for DR224 were 24.29 kJ/mol and 172.06 J/mol K, respectively. The values of DeltaH(0), DeltaG(0) and E all indicate that the adsorption of direct dyes onto CNTs was a physisorption process.     

COS hydrolysis in the presence of oxygen： Experiment and modeling

A mathematical model of COS hydrolysis on Al2O3, with fouling of catalyst, has been developed. Kinetic studies were carried out in a fixed bed reactor under atmospheric pressure and low temperature （40-70℃）. The effects of the COS inlet concentration, temperature, and relative humidity were analyzed. Experimental results of breakthrough curves were used to obtain kinetic parameters, which accounted for effects of S deposition on the inner-face of the catalyst. The model described the experimental breakthrough curves satisfactorily and well explained the performance of COS hydrolysis in the presence of oxygen. The exothermic heat of adsorption and activation energy, assuming Arrhenius type of temperature dependence of the equilibrium constant, were determined. Activation energy of COS hydrolysis and H2S oxidation were 35.9 kJ/mol, 19.6 kJ/mol; adsorption heat of H2O and H2S on Al2O3 were 45.1 and 60.1 kJ/mol respectively. Deactivation coefficient （α） was used to quantify the behavior of COS hydrolysis at different operating conditions. The effect of relative humidity on α is significant in the relative humidity range under study. Experimental data accorded well with model data in the studied range.     

D301大孔树脂吸附钒(V)的性能研究

研究了D301大孔树脂对钒的吸附性能.结果表明,pH值对D301树脂吸附钒的影响很大,与钒在溶液中的赋存状态有关,且在pH=2时吸附效果最好:测得吸附热力学参数分别为:△H=8.97kJ/mol,△G_(313)=-5.69kJ/mol,△G_(303)=-5.2kJ/mol,△G_(293)=-4.9kJ/mol,△S=46.84J/mol·K.等温吸附服从Freundlich经验式;考察了溶液浓度、搅拌速率对交换过程的影响,并对实验数据运用相关理论模型进行拟合,结果显示钒(V)在D301树脂上吸附交换过程控制步骤为颗粒扩散控制,反应级数n为0.2391.     

Characterization and determination of the thermodynamic and kinetic properties of the adsorption of the molybdenum(VI)-calmagite complex onto active carbon

The extraction of the Mo(VI)-calmagite complex by adsorption onto active carbon is investigated in the present paper. Thermodynamic and kinetic properties and different adsorption isotherms were determined. The adsorption studies have shown that both the empirical Freundlich and the classical Langmuir isotherms successfully fit the experimental results. The overall adsorption process was exothermic and spontaneous in the temperature range from 283 to 323 K; namely, DeltaH(0) and DeltaS(0) values were found to be -8.15 kJ mol(-1) and -3.86 J mol(-1) K, respectively. The high activation energy demanded for desorption of the Mo(VI)-calmagite complex surface indicated that the overall process was controlled by the slow desorption, while a fast and low activated adsorption of the complex onto active carbon surface was fairly favored. These features indicate that active carbon may be very useful for preconcentration of molybdenum from diluted solutions.     

三聚磷酸二氢铝吸附Cd~(2+)的动力学研究

采用动态吸附法研究三聚磷酸二氢铝吸附镉离子的动力学行为并进行吸附活化状态热力学参数分析。结果表明,当三聚磷酸二氢铝粒径小于150μm、搅拌器转速大于200r/min、Cd2+的初始浓度为500mg/L时,三聚磷酸二氢铝对镉离子的化学吸附符合二级反应动力学方程,吸附速率常数k与温度T之间的关系符合Arrhenius方程式,吸附的活化能为Ea=27.93kJ/mol,吸附的频率因子A=65.33L/mg·min,ln(k/T)与1/T之间的关系符合Eyring公式,其活化焓ΔH=25.44kJ/mol,活化熵ΔS=-218.54J/mol·K。     

高容量亚胺基二乙酸型螯合树脂的制备及吸附性能

以甲基丙烯酸缩水甘油酯(GMA)为单体, 氯甲基化的交联聚苯乙烯树脂(CMCPS)为大分子引发剂, CuBr/2,2'-联吡啶(Bpy)为催化剂, 采用表面引发原子转移自由基聚合(SI-ATRP)技术, 使甲基丙烯酸缩水甘油酯聚合在CMCPS树脂表面, 制得了环氧化聚合物. 将该聚合物与亚胺基二乙酸(IDA)反应, 制备了高容量亚胺基二乙酸型螯合树脂(IDA-PGMA-CMCPS), 用元素分析对其进行了表征. 考察了螯合树脂对Cu²⁺的吸附性能及动力学和热力学参数. 该螯合树脂表面IDA接枝密度达8.15 mg/m². 研究结果表明, 树脂对Cu²⁺的吸附量随离子浓度和温度的升高而增加, 当pH值为2.2时, 对Cu²⁺离子的吸附效果最佳. 树脂的静态饱和吸附容量为1339.66 mg/g, Langmuir和Freundlich方程均呈现良好的拟合度. 通过热力学平衡方程计算ΔG<0, ΔH=270.60 kJ/mol, ΔS>0, 表明该吸附过程是自发、 吸热、 熵增加的过程. 动力学研究结果表明, 准二级动力学方程能较好拟合动力学实验结果, 该过程符合准二级动力学模型.     

The rate of O2 and CO binding to a copper complex, determined by a "flash-and-trap" technique, exceeds that for hemes

The observation and fast time-scale kinetic determination of a primary dioxygen-copper interaction have been studied. The ability to photorelease carbon monoxide from [Cu(I)(tmpa)(CO)](+) in mixtures of CO and O(2) in tetrahydrofuran (THF) between 188 and 218 K results in the observable formation of a copper-superoxide species, [Cu(II)(tmpa)(O(2)(-))](+) lambda(max) = 425 nm. Via this "flash-and-trap" technique, temperature-dependent kinetic studies on the forward reaction between dioxygen and [Cu(I)(tmpa)(thf)](+) afford activation parameters DeltaH = 7.62 kJ/mol and DeltaS = -45.1 J/mol K. The corresponding reverse reaction proceeds with DeltaH = 58.0 kJ/mol and DeltaS = 105 J/mol K. Overall thermodynamic parameters are DeltaH degrees = -48.5 kJ/mol and DeltaS degrees = -140 J/mol K. The temperature-dependent data allowed us to determine the room-temperature second-order rate constant, k(O2) = 1.3 x 10(9) M(-1) s(-1). Comparisons to copper and heme proteins and synthetic complexes are discussed.     

Adsorption of Ni(II) on clays

The present work investigates the adsorptive interactions of Ni(II) ions with kaolinite, montmorillonite, and their poly(oxo zirconium) and tetrabutylammonium derivatives in aqueous medium. Batch adsorption studies were carried out with various Ni(II) concentrations, amount of clay adsorbents, pH, agitation time and temperature. The adsorption is strongly dependent on pH of the medium with enhanced adsorption as the pH turns from acidic to alkaline side till precipitation sets in. The process was very fast initially and maximum adsorption was observed within 180 min of agitation. The kinetics of the interactions, tested with pseudo first order Lagergren equation, second order kinetics, Elovich equation, liquid film diffusion model and intra-particle diffusion mechanism, showed better agreement with second order kinetics (k2 = 1.3 x 10(-2) to 5.3 x 10(-2) g/(mg min)). The adsorption data gave good fits with Langmuir and Freundlich isotherms and yielded Langmuir monolayer capacity of 2.75 to 21.14 mg/g and Freundlich adsorption capacity of 0.70 to 3.40 mg(1-1/n) l(1/n)/g for the clay adsorbents. The adsorption process was exothermic with Delta H in the range of -24.0 to -45.1 kJ/mol accompanied by decrease in entropy (DeltaS: -118.2 to -160.5 J/(mol K)) and Gibbs energy (Delta G: -34.6 to -49.5 kJ/mol). The results have shown that montmorillonite has the largest adsorption capacity followed by ZrO-montmorillonite, TBA-montmorillonite, kaolinite, ZrO-kaolinite and TBA-kaolinite. Introduction of ZrO- and TBA- groups into the clays reduced their adsorption capacity by blocking the available adsorption sites.     

玉米秸热解动力学研究

生物质能具有低硫和二氧化碳零排放的特点，其在能源结构中的地位越来越重要。作为一种高效生物质能转化途径，热化学转化可获得气、液和固态多种能源产物。其中，热解是热化学转化中最为基本的过程，是气化、液化及燃烧过程的初始和伴生反应，对热解的分析有助于热化学转化过程控制及高效转化工艺的开发。热解动力学是表征热解过程中反应过程参数对原料转化率影响的重要手段，通过动力学分析可深入了解反应过程和机理，预测反应速率及难易程度，为生物质热化学转化工艺的研究开发提供重要的基础数据。国外对纤维素热解动力学已进行了一些研究，但生物质作为纤维素、半纤维素、木质素等的复杂聚合物，其热解行为与单纯纤维素差别较大。因此本文的热解研究集中在玉米秸这种常见的软质秸秆类生物质原料。     

ADSORPTION OF MACROPOROUS PHOSPHONIC ACID RESIN FOR INDIUM

The adsorption kinetics and mechanism of a nrovel chelate resin, macroporous phosphonic acid resin (PAR) for In(Ill) were investigated Tile statically saturated adsorption capacity is 216mg&#183;g^-1resin at 298K in HAc-NaAc medium. Tire apparent adsorption rate constant is k298=4.84&#215;10^-5 s^-1. Tile adsorption behavior of PAR for In(Ill) obeys the Freundlich isotherm. The thermodynamic adsorption parameters, enthalpy change △H, free energy change △G and entropychange △S of PAR for In(Ⅲ) are 11.5kmol, -12.6kJmol and 80.8Jmol.K, respectively. The apparent activation energy is Ea=3.5k.l/mol. Tire molar coordination ratio of the functional group of PAR to In(Ⅲ) is about 3:1.     

多壁碳纳米管对稀土元素的吸附性能

研究了改性多壁碳纳米管(MWCNTs)对稀土元素的吸附。 采用硝酸、次氯酸钠、过氧化氢、高锰酸钾4种方法对MWCNTs进行改性,考察了改性MWCNTs对稀土元素的吸附能力。 采用紫外-可见分光光度法测定稀土元素的浓度,比较了未处理和不同方法处理的MWCNTs对稀土元素的吸附能力。实验结果表明,NaClO改性的MWCNTs对稀土元素的吸附能力最强。以稀土元素钐(Sm)、钆(Gd)、镱(Yb)为代表,研究了NaClO改性MWCNTs对稀土元素的吸附性能。 考察了溶液pH值、离子强度、吸附剂用量、温度等因素对吸附性能的影响。当溶液pH值在2~7范围内,NaClO改性的MWCNTs对Sm、Gd、Yb的吸附随pH值增大而增强。 当离子强度和MWCNTs的用量增大时,对稀土元素的吸附能力降低。3种元素在NaClO改性的MWCNTs上的吸附均为放热过程,其反应焓变ΔH分别为：-6.44、-5.63和8.31 kJ/mol。吸附等温线符合Langmuir和Freundlich等温吸附方程。     

邻-氨基酚修饰吸附树脂对2-氨基吡啶的静态吸附热力学及动力学特征

合成了两种邻-氨基酚修饰超高交联吸附树脂(MOAR-1、MOAR-2),并用该树脂对水溶液中2-氨基吡啶的静态吸附热力学和动力学特征进行研究。热力学研究结果表明,Freundlich吸附等温方程能够对静态吸附等温线进行很好地拟合。吸附焓变ΔH<0,其绝对值小于60kJ/mol,表明以物理吸附为主以及该吸附剂容易脱附的特征;ΔG<0,说明吸附是自发行为;ΔS<0,表明吸附质分子在树脂表面上的运动受到了限制。两种树脂对2-氨基吡啶的吸附量随着温度的升高而降低,适当降低温度有利于吸附。动力学研究的结果表明:吸附符合一级动力学方程,吸附速率随温度升高而增大。表观活化能Ea<4.0kJ/mol,说明吸附较容易进行。     

Absolute and relative-rate kinetics experiments and direct dynamics computations for the reaction of Br atoms with CH2ClBr

Kinetics of the reaction Br + CH2ClBr <--> CHClBr + HBr (1, -1) were studied experimentally in the forward direction. The absolute reaction kinetics method of laser flash photolysis coupled with Br atom resonance fluorescence detection and three different relative-rate methods with gas-chromatographic analysis were applied to carry out the experiments. The rate constants determined were found to obey the Arrhenius law in the wide temperature range of T = 293-785 K providing the kinetic expression k1 = (2.8 +/- 0.1) x 10(13) exp[-(47.6 +/- 0.3) kJ mol(-1)/RT] cm3 mol(-1) s(-1) (the errors given refer to 1sigma precision). An ab initio direct dynamics method was used to study reaction (1, -1) theoretically. The electronic structure information including geometries, gradients, and force constants was obtained at the MP2 level of theory; and energies were improved at higher theoretical levels. Rate constants were calculated using the canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-1000 K. Theory substantially underestimates k1 compared to experiment. The agreement was found good with k(-1) reported previously predicting positive temperature dependence. The experimental kinetic parameters were utilized in thermochemical calculations yielding the recommended standard enthalpy of formation of delta(f)H degrees (298) (CHClBr) = (140 +/- 4) kJ mol(-1) (with 2sigma accuracy given).     

Thermal Degradation Kinetics of N,N＇-Di（diethoxythiophosphoryl）-1,4-phenylenediamine

The non-isothermal degradation kinetics of N,N＇-di（diethoxythiophosphoryl）-1,4-phenylenediamine in N2 was studied by TG-DTG techniques.The kinetic parameters,including the activation energy and pre-exponential factor of the degradation process for the title compound were calculated by means of the Kissinger and Flynn-Wall-Ozawa（FWO）method and the thermal degradation mechanism of the title compound was also studied with the Satava-Sestak methods.The results indicate that the activation energy and pre-exponential factor are 152.61 kJ/mol and 9.06×101 4s -1with the Kissinger method and 154.08 kJ/mol with the Flynn-Wall-Ozawa method,respectively.It has been shown that the degradation of the title compound follows a kinetic model of one-dimensional diffusion or parabolic law,the kinetic function is G（α）=α2and the reaction order is n=2.