钠基膨润土吸附亚甲基蓝的热力学与动力学研究

利用钠基膨润土吸附亚甲基蓝水溶液,探讨了不同参数如接触时间、初始pH值、温度等对其吸附性能的影响。结果表明,室温下,pH10,钠基膨润土吸附60min,其吸附量达198.71mg/g,且吸附量随温度的升高而增大。通过计算不同温度下的热力学参数?G,?H和?S,证实该吸附为一自发的吸热过程。其等温吸附平衡更符合Langmuir模型;吸附动力学更适合准二级反应方程。     

静态法和X射线吸收精细结构光谱技术研究腐殖酸对Eu(III)在高庙子膨润土上的吸附影响

膨润土由于其高吸附性和低渗透性而受到广泛的研究. 在本文中, 利用XRD、FTIR和酸碱滴定对我国内蒙古高庙子膨润土进行了详细的表征和分析. 用静态法研究在温度为25± 2 ℃和0.01 mol/L NaClO4溶液中, pH值、腐殖酸、接触时间和Eu(III)初始浓度对Eu(III)在钠基膨润土上的吸附影响. 研究结果表明Eu(III)的吸附受pH值影响明显. 在低pH值条件下, 腐殖酸对Eu(III)的吸附影响微弱, 而在高pH值条件下腐殖酸降低Eu(III)的吸附. X射线吸收精细结构光谱(XAFS)技术对吸附在膨润土上的Eu(III)局域微观结构研究结果表明, 在pH为4.15条件下, Eu在膨润土上与其周围的氧原子间的距离大约为2.39 Å. 本文中的研究结果对于评估其他三价镧系和锕系元素在作为填充材料的膨润土上的吸附和迁移具有重要的意义.     

静态法和X射线吸收精细结构光谱技术研究腐殖酸对Eu(Ⅲ)在高庙子膨润土上的吸附影响

膨润土由于其高吸附性和低渗透性而受到广泛的研究.在本文中,利用XRD、FTIR和酸碱滴定对我国内蒙古高庙子膨润土进行了详细的表征和分析.用静态法研究在温度为25±2℃和0.01mol/L NaClO4溶液中,pH值、腐殖酸、接触时间和Eu(Ⅲ)初始浓度对Eu(Ⅲ)在钠基膨润土上的吸附影响.研究结果表明Eu(Ⅲ)的吸附受pH值影响明显.在低pH值条件下,腐殖酸对Eu(III)的吸附影响微弱,而在高pH值条件下腐殖酸降低Eu(Ⅲ)的吸附.X射线吸收精细结构光谱(XAFS)技术对吸附在膨润土上的Eu(Ⅲ)局域微观结构研究结果表明,在pH为4.15条件下,Eu在膨润土上与其周围的氧原子间的距离大约为2.39.本文中的研究结果对于评估其他三价镧系和锕系元素在作为填充材料的膨润土上的吸附和迁移具有重要的意义.     

溴化铵改性膨润土脱除气态单质汞的特性及机理分析

采用溴化铵对钠基膨润土进行改性制得脱汞吸附剂,在固定床实验装置上对所制备的吸附剂进行脱汞性能测试。脱汞实验结果表明,钠基膨润土较钙基膨润土在脱汞性能上提高不大,而溴化铵改性的钠基膨润土(Br-Ben/Na)脱汞性能得到明显提高,脱汞效率达到97.7%。吸附温度的升高有利于对Hg0的脱除,在140℃下,10%Br-Ben/Na吸附剂的脱汞率能长时间保持在90%以上,说明在此吸附过程中化学吸附占主导性作用。通过N2吸附/脱附、X射线衍射(XRD)、元素分析仪和傅里叶变换红外光谱(FT-IR)分析等结果表明,改性后的膨润土比表面积下降,平均孔径增大;铵根离子进入到膨润土的层间置换出层间钠离子,煅烧活化过程中层间的铵根离子并未分解,而在层间与膨润土结合为某吸附活性组分协助Br-与Hg0反应,提高了膨润土的脱汞性能。     

邻菲咯啉改性膨润土吸附水中镉离子的研究

通过邻菲咯啉改性膨润土,对水中镉离子进行吸附性能的研究.探讨了投加量、pH值、接触时间、温度等影响因素对改性膨润土吸附镉离子的影响.实验结果表明:在25℃,250 r/min,pH 5.5,NaNO3浓度0.01 mol/L,投加量为5.0 g/L,镉离子质量浓度100 mg/L的条件下,未改性膨润土对水中镉离子的吸附...     

两种有机物改性膨润土对Cu2+和Zn2+的吸附-解吸研究

选用天然有机物料(猪粪降解液)和有机化学试剂[十六烷基三甲基溴化胺(HDTMA)]对钠基膨润土进行表面改性,比较了膨润土对两类有机物的吸附特性,以及两种有机物改性膨润土对Cu2+、Zn2+吸附-解吸性能的差异。结果表明,膨润土对HDTMA和猪粪降解液是优惠吸附,且前者最大吸附量为382.4mg/g,是后者的4.19倍。HDTMA改性膨润土对Cu2+、Zn2+的最大吸附量均大于猪粪降解液改性膨润土,前者分别为后者的1.12倍(Cu2+)和1.09倍(Zn2+),且两种吸附剂对Cu2+的最大吸附量和吸附速率均大于Zn2+。Zn2+在两种改性膨润土上的解吸率均高于Cu2+,且Cu2+、Zn2+在猪粪改性膨润土上的解吸率均要高于在HDTMA改性膨润土的。两种有机物改性的钠基膨润土对重金属离子具有良好的吸附性能,可以用于含重金属废水的处理和重金属污染土壤的钝化修复,而猪粪降解液改性膨润土是环境友好的重金属钝化剂。     

微波改性膨润土对水中PFOS的吸附热力学和动力学研究

以十六烷基三甲基溴化铵(CTMAB)微波改性膨润土(CTMAB-膨润土)作为吸附剂。在初始浓度为50~100mg/L,温度为288~308K时,研究了CTMAB-膨润土对PFOS的吸附热力学和动力学规律。结果表明,吸附反应2h后,CTMAB-膨润土对PFOS吸附量达到平衡吸附量的80%,随后吸附速率逐渐变缓并在吸附反应进行约4h后达到平衡;PFOS在CTMAB-膨润土上的吸附过程符合伪二级动力学方程和Langmuir等温吸附模型。通过热力学分析发现?H~00、?G~00、?S~00、E_a=26.7k J/mol,表明PFOS在CTMAB-膨润土上的吸附属于易于自发进行的物理吸附过程,吸附过程吸热,但吸附热较小,温度对吸附过程的影响较小。吸附饱和的CTMAB-膨润土可在NaOH溶液中脱附再生,经4次脱附后,PFOS的吸附量为140.6mg/g,具有良好的再生使用性,可以循环使用。     

复合改性膨润土对2,4,6-三氯苯酚和Pb~(2+)的吸附行为研究

本文主要以钠基膨润土为原料,用十六烷基二甲基苄基氯化铵和乙二胺四乙酸二钠盐对膨润土进行复合改性,制得改性膨润土,用XRD对其结构进行表征,研究了改性后的膨润土对2,4,6-三氯苯酚和Pb~(2+)的吸附行为,结果表明,改性后的膨润土对2,4,6-三氯苯酚和Pb~(2+)的吸附性能明显提高,吸附等温线较好地符合Langmuir模型,改性膨润土对2,4,6-三氯苯酚和Pb~(2+)的最大吸附量分别为238.1mg/g和191.20mg/g,吸附动力学符合准二级反应动力学方程,其二级反应速率常数为分别为8.34×10~(-5)g/mgámin和5.62×110~(-5)g/mgámin,改性膨润土对2,4,6-三氯苯酚的吸附为吸热反应,而对Pb~(2+)的吸附为放热反应。     

X-5大孔树脂吸附熊果酸的动力学与热力学特性研究

研究了熊果酸在X-5树脂上吸附的动力学和热力学特性,从物理化学的角度探讨了树脂吸附天然产物的机理。动力学结果表明,在pH=6.36时,熊果酸在X-5树脂上吸附量最大,吸附量为0.1016mmol/g。热力学结果表明,不同温度下熊果酸在X-5树脂上的等温吸附符合Langmuir方程和Freundlich方程,吸附热焓变?Hm=58.77kJ/mol,熵变?Sm=0.23kJ/mol·K,吉布斯自由能?Gm随温度升高向负方向增加。以上热力学参数表明,熊果酸在X-5树脂上的吸附属于自发的物理吸附过程,且在X-5大孔树脂吸附熊果酸过程中,液固界面间增加了随机性吸附。     

钠基膨润土的制备

膨润土是以蒙脱石为主要成分的粘土矿 ,在药学中作为制剂辅料具有乳化、增稠、助悬、吸附的功能 ,是优良的药用辅料[1] .膨润土根据所含的可交换阳离子的种类和数量 ,又可分为钙基膨润土和钠基膨润土 .钠基膨润土比钙基膨润土具有更好的膨胀性、阳离子交换性、分散性和粘性[2 ] 我国膨润土资源十分丰富 ,但 90 %是钙基膨润土 .通过化学改型 ,可使膨润土作为助悬剂、软膏基质及乳化剂具有更优异的性能 .因此 ,我们对天然钙基膨润土的改型条件进行了考察 .1　实验部分1 1　材料及仪器材料 :辽宁黑山膨润土原矿粉 (蒙脱石含量 6 2 5 % ,ｐＨ …     

Sorption of Eu(III) on GMZ bentonite in the absence/presence of humic acid studied by batch and XAFS techniques

Bentonite has been extensively studied because of its strong sorption ability and low permeability. In this work, the Na-bentonite from Gaomiaozi County (China) has been characterized by XRD, FTIR and acid-base titration. The sorption of Eu(III) on Na-bentonite in the absence/presence of humic acid (HA) was studied at T = 25 ± 2 °C and in 0.01 mol/L NaClO₄ solution. The effects of pH, HA, contact time and initial Eu(III) concentrations were also investigated. The results indicate that the sorption of Eu(III) on Na-bentonite was dependent on pH values. The presence of HA had little effect on Eu(III) sorption at low pH values, but decreased Eu(III) sorption at high pH values. X-ray absorption fine structure spectroscopy (XAFS) was applied to characterize the local structural environment of the adsorbed Eu(III) on bare Na-bentonite and HA-bentonite hybrids. The results indicate that Eu(III) was bound to O atoms at a distance of about 2.39 Å at pH 4.15. The results are crucial for the evaluation of the sorption and migration of other trivalent lanthanides and actinides in bentonite as backfill materials.     

STUDY OF THE INFLUENCE OF HUMIC SUBSTANCES ON THE SORPTION OF RARE EARTH ELEMENTS AT THE KAOLINITE AND BENTONITE SURFACES

The isotherms for sorption of fulvic acid from weathered coal,and the distribution ratios,Rd,of ^169Yb at various concentration of fulvic acid on Na-bentonite and Na-Kaolinite have been measured.Meantime,the dependences of Rd of ^169 Yb on pH values at a constant initial concentration of FA were obtained.It was not found that the parallel relationship between the high affinity of humic substance to the clay and the high uptake of metal which has strong ability to complex with this humic substance.     

Adsorption of uranium from aqueous solution using HDTMA+-pillared bentonite: isotherm, kinetic and thermodynamic aspects

The ability of hexadecyltrimethylammonium cation pillared bentonite (HDTMA⁺-bentonite) has been explored for the removal and recovery of uranium from aqueous solutions. The adsorbent was characterized using small-angle X-ray diffraction, high resolution transmission electron microscopy, and Fourier transform infrared spectroscopy. The influences of different experimental parameters such as solution pH, initial uranium concentration, contact time, dosage and temperature on adsorption were investigated. The HDTMA⁺-bentonite exhibited the highest uranium sorption capacity at initial pH of 6.0 and at 80?min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, ??G° (308?K), ??H°, and ??S° were determined to be ?31.64, ?83.84?kJ/mol, and ?169.49?J/mol/K, respectively, which demonstrated the sorption process of HDTMA⁺-bentonite towards U(VI) was feasible, spontaneous, and exothermic in nature. The adsorption on HDTMA⁺-bentonite was more favor than Na-bentonite, in addition the saturated monolayer sorption capacity increased from 65.02 to 106.38?mg/g at 298?K after HDTMA⁺ pillaring. Complete removal (??100%) of U(VI) from 1.0?L simulated nuclear industry wastewater containing 10.0?mg U(VI) ions was possible with 1.5?g HDTMA⁺-bentonite.     

Investigation of Co(II) sorption on GMZ bentonite from aqueous solutions by batch experiments

In this study, a local bentonite from Gaomiaozi county (Inner Mongolia, China) was converted to Na-bentonite and was characterized by FTIR and XRD to determine its chemical constituents and micro-structure. The removal of cobalt from aqueous solutions by Na-bentonite was investigated as a function of contact time, pH, ionic strength, foreign ions and temperature by batch technique under ambient conditions. The results indicated that the sorption of Co(II) was strongly dependent on pH. At low pH, the sorption of Co(II) was dominated by outer-sphere surface complexation or ion exchange whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich, and D-R models were used to simulate the sorption isotherms of Co(II) at the temperatures of 293.15, 313.15 and 333.15 K, respectively. The thermodynamic parameters (∆G°, ∆S°, ∆H°) of Co(II) sorption on GMZ bentonite calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on GMZ bentonite was an exothermic and spontaneous process. The Na-bentonite is a suitable material for the preconcentration and solidification of Co(II) from aqueous solutions.     

Adsorption of thorium from aqueous solution by HDTMA+-pillared bentonite

The ability of hexadecyltrimethylammonium cation pillared bentonite (HDTMA⁺-bentonite) has been explored for the removal and recovery of thorium from aqueous solutions. The adsorbent was characterized using small-angle X-ray diffraction, high resolution transmission electron microscopy and Fourier transform infrared spectroscopy. The influences of different experimental parameters such as solution pH, initial thorium concentration, contact time and temperature on adsorption were investigated. The HDTMA⁺-bentonite showed the highest thorium sorption capacity at initial pH of 3.5 and contact time of 60?min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, ?G° (298?K), ?H° and ?S° were determined to be ?31.78, ?23.71?kJ/mol and 27.10?J/mol?K, respectively, which demonstrated the sorption process of HDTMA⁺-bentonite towards Th(VI) was feasible, spontaneous and exothermic in nature. The adsorption on HDTMA⁺-bentonite was more favor than Na-bentonite, in addition the saturated monolayer sorption capacity increased from 17.88 to 31.20?mg/g at 298?K after HDTMA⁺ pillaring. The adsorbed HDTMA⁺-bentonite could be effectively regenerated by 0.1?mol/L HCl solution for the removal and recovery of Th(VI). Complete removal (99.9?%) of Th(VI) from 1.0?L industry wastewater containing 16.8?mg Th(VI) ions was possible with 7.0?g HDTMA⁺-bentonite.     

Adsorption of Acid Blue 193 from aqueous solutions onto Na-bentonite and DTMA-bentonite

Dodecyltrimethylammonium bromide-modified bentonite (DTMA-bentonite) was prepared and tested as an adsorbent for an acid dye (Acid Blue 193, AB193) removal from aqueous solution in comparison with Na-bentonite. The effect of various experimental parameters was investigated using a batch adsorption technique. In this manner, the adsorption isotherms, adsorption kinetics, and temperature and pH effects upon Acid Blue 193 adsorption on Na-bentonite and DTMA-bentonite were thoroughly examined. Results show that a pH value of 1.5 is favorable for the adsorption of Acid Blue 193. The isothermal data could be well described by the Freundlich equation. The dynamical data fit well with the pseudo-second-order kinetic model. The adsorption capacity of DTMA-bentonite (740.5 mg g(-1)) was found to be around 11 times higher than that of Na-bentonite (67.1 mg g(-1)) at 20 degrees C. Thermodynamic parameters such as activation energy (E(a)) and change in the free energy (DeltaG(0)), the enthalpy (DeltaH(0)), and the entropy (DeltaS(0)) were also evaluated. The overall adsorption process was exothermic but it is only spontaneous at 20 degrees C. The results indicate that Na-bentonite and DTMA-bentonite could be employed as low-cost alternatives to activated carbon in wastewater treatment for the removal of color which comes from textile dyes.     

Sorption of Am(Ⅲ) on Na-bentonite:Effect of pH,ionic strength,temperature and humic acid

Sorption of Am(Ⅲ) on Na-bentonite as a function of contact time,pH,ionic strength,humic acid(HA) and temperature was investigated under ambient conditions.The results showed that the sorption was strongly dependent on pH and ionic strength. Am(Ⅲ) sorption can be described well by pseudo-second-order model.The presence of HA takes a positive effect at low pH;but a negative influence under high pH range.Enthalpy,entropy and Gibbs free energy(i.e.,△H~0,△S~0 and△G~0) calculated from sorption isotherms suggested that sorption process of Am(Ⅲ) was spontaneous and endothermic.     

Uranium adsorption studies on hydrothermal carbon produced by chitosan using statistical design method

A new hydrothermal cross-linking chitosan (HCC) was prepared by hydrothermal reaction at a mild temperature (180 °C) to diminish the solubility in acid solution, and the amine groups were almost retained during the hydrothermal reaction characterized by FT-IR and the dissolution rate in pH 3 solution decreased from 89.6 to 12.6 %. The effects of initial pH, contact time, initial concentration and temperature on the sorption capacity are discussed using 24 full-factorial central composite design using response-surface methodology. The HCC showed the highest uranium sorption capacity at initial pH of 7.92 and contact time of 273.6 min with 24 full-factorial central composite design and the maximum adsorption capacity was 273 mg/g. The adsorption process could be well defined by the Langmuir isotherm and the thermodynamic parameters, ?G°(298 K), ?H° and ?S°, demonstrated shown that the sorption process of U(VI) onto HCC was feasible, spontaneous and endothermic in nature.     

Oxidative decarboxylation of levulinic acid by silver(I)/persulfate

The oxidative decarboxylation of levulinic acid (LA) by silver(I)/persulfate [Ag(I)/S?O?2?] has been investigated in this paper. The effects of buffer solution, initial pH value, time and temperature and dosages of Ag(I)/S?O?2? on the decarboxylation of LA were examined in batch experiments and a reaction scheme was proposed on basis of the reaction process. The experimental results showed that a solution of NaOH-KH?PO? was comparatively suitable for the LA decarboxylation reaction by silver(I)/persulfate. Under optimum conditions (temperature 160 °C, pH 5.0, and time 0.5 h), the rate of LA conversion in NaOH-KH?PO? solutions with an initial concentration of 0.01 mol LA reached 70.2%, 2-butanone (methyl ethyl ketone) was the single product in the gas phase and the resulted molar yield reached 44.2%.