D113大孔树脂吸附Ni~(2+)的动力学与热力学研究

研究了D113大孔树脂吸附Ni2+的动力学与热力学的特性。动力学研究表明,在298K温度下,D113大孔树脂对Ni2+的吸附符合拟一级动力学方程和拟二级动力学方程,颗粒扩散过程为吸附的控速步骤。热力学研究表明,在实验温度下,D113大孔树脂对Ni2+的吸附符合Langmuir等温方程,吸附焓变ΔHθ=15.1306kJ/mol,熵变ΔSθ=0.1002kJ/mol.K,反应吉布斯自由能ΔGθ随温度升高向负方向增加。热力学参数表明吸附过程为吸热和自发的。     

垃圾填埋场衬垫对Cr(Ⅵ)和Zn(Ⅱ)吸附的动力学研究

通过静态平衡吸附试验对垃圾填埋场衬垫土壤材料对Cr(Ⅵ)和Zn(Ⅱ)的吸附进行了观察.在试验中考察了溶液的初始浓度、pH值和溶液的温度对吸附的影响,通过动力学实验确定了动力学参数,并探讨了天然黏土材料对重金属Cr(Ⅵ)和Zn(Ⅱ)的吸附机理.结果显示,黏土对重金属的吸附过程可以通过伪二阶动力模式来描述.根据对lnk2与1/T线形图斜率的计算,可以确定Cr(Ⅵ)和Zn(Ⅱ)的活化能(Ea)分别为22.7 kJ·mol1-和26.88 kJ·mol-1.活化能的计算结果说明,温度的升高能促进黏土材料对Cr(Ⅵ)和zn(Ⅱ)的吸附,同时也表明吸附很可能是一个化学吸附.热力学参数(△H0,△S0,△G0)值可以通过图1gKD与1/T的斜率与截距来计算.热力学参数值的结果表明,天然黏土材料对Cr(Ⅵ)和Zn(Ⅱ)的吸附是吸热反应.     

阳离子表面活性剂聚集行为的热力学研究

为了深入了解阳离子表面活性剂溶液在复杂体系中的物理化学性质,以十六烷基三甲基氯化铵(CTAC)和十六烷基三甲基溴化铵(CTAB)为模型,通过电导法和表面张力法研究其在水相体系中的聚集行为。测定两种表面活性剂的临界胶束浓度CMC、胶束离解度β、胶束聚集数n和表面过剩吸附量Γs。由CMC与温度T的关系,应用准相分离模型计算了胶束化热力学参数ΔmicG0、ΔmicH0和ΔmicS0,结果表明ΔmicG0为负值,而且随温度变化很小,ΔmicH0的值相对于TΔmicS0来说小得多,表明胶束化过程为熵驱动过程。     

水化普通硅酸盐水泥吸附水中氟化物的动力学与热力学解析

以水化普通硅酸盐水泥颗粒为除氟吸附剂,对其吸附水中氟化物的动力学和热力学过程进行了解析.结果表明:水化普通硅酸盐水泥对氟化物的吸附平衡时间为192 h,20℃时其吸附容量为14.63 mg/g,4℃时为13.14 mg/g.吸附速率特性与准二级动力学模型拟合性较好且吸附速率由颗粒内部扩散速率控制,吸附行为均满足Langmuir吸附等温式.吸附焓变为16.56 kJ/mol,表明该吸附过程是以化学吸附为主的吸热反应;吸附熵变为正值,说明该吸附过程是熵推动为主的过程;吉布斯自由能在4和20℃时均为负值,说明该吸附反应是一个自发过程.脱附研究与XRD分析结果也证实,该吸附反应以化学吸附过程为主.      

Adsorption of caesium from aqueous solution using cerium molybdate–pan composite

In this study, a cerium molybdate–polyacrylonitrile (CM–PAN) composite ion exchanger was synthesised and its characteristics were determined by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetry (TGA), specific area measurement (BET), X-ray fluorescence and CHN elemental analyses. The adsorption of caesium from aqueous solutions by CM–PAN composite was investigated under batch and continuous conditions. The distribution coefficient of caesium on the composite sorbent was studied as a function of pH, solution temperature and the presence of interfering cations, and the optimum conditions for a batch system were determined. Pseudo-first- and second-order sorption kinetic models were used to investigate the kinetics of adsorption and the results pointed to the pseudo-second-order model for caesium sorption kinetics. The intraparticle diffusion model was used to the predict rate-limiting step of the ion exchange process in order to specify the sorption mechanism. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models were fitted to the experimental sorption data, where the Freundlich model showed a good agreement. The adsorption thermodynamic parameters, standard enthalpy, entropy and Gibbs’ free energy were calculated and the reaction was found to be endothermic and spontaneous. Finally, the dynamic sorption capacities of the sorbent at two breakthroughs were calculated from the continuous system.     

Physicochemical aspects of using natural scavengers in removing methylene blue (basic dye) from solution

Effluent from dyeing and finishing processes is an important source of water pollution. The effectiveness of bentonite, kaolinite and sediment from a local deposit in removing methylene blue as a cationic dye from aqueous solutions has been investigated. The adsorption equilibrium (isotherm) has been determined according to Freundlich and Langmuir equations. The optimum amount is 0.5 g for all adsorbents, and the optimum pH ranges are 2–8 for bentonite and 2–6 for kaolinite and sediment. With respect to kinetic modelling, the adsorption of methylene blue on various adsorbents was fitted to a second-order equation. Also, the thermodynamic parameters were determined. The negative free energy values indicate the feasibility of the process and spontaneous nature of adsorption. The positive ΔH° values indicate the endothermic nature of the process. Thus, Egyptian clay minerals and sediments have a great tendency to remove the dye from solutions.     

硝酸铵与硝铵磷热稳定性对比研究

为了研究硝铵磷的热稳定性,用DSC－TG同步热分析仪测试了硝酸铵的热分解过程,根据升温速率分别为5,10,15 K／min的DSC和TG－DTG曲线,利用Ozawa法和Kissinger法求得的硝酸铵的活化能基本一致。用Rogers公式和Arrhenius公式求得指前因子和速率常数分别为1．62×1010 s－1,1．07×10－18 s－1（120℃）;硝酸铵在升温速率为5 K／min时,分解峰值温度的活化焓、活化熵、活化自由能分别为102．76 kJ／mol ,－62．35 J／（K·mol ）,134．98 kJ／mol;对比了硝酸铵和硝铵磷的DSC曲线,结果表明硝铵磷的吸热分解峰值温度低于硝酸铵,热稳定性更好。     

重金属铜在黑土和棕壤中解吸行为的比较

采用一次平衡法研究吸附态Cu²⁺在黑土和棕壤上的解吸行为并进行了比较.结果表明,与棕壤相比,黑土吸附态Cu²⁺解吸有更长的滞后阶段,黑土在Cu²⁺的吸附量低于729.00mg·kg^-1(Cu²⁺处理浓度小于40 mg·L^-1),棕壤在Cu²⁺的吸附量低于393.29 mg·kg^-1(Gu²⁺处理浓度小于20 mg·L^-1)时,土壤吸附态Cu²⁺几乎不发生解吸.2种土壤吸附态Cu²⁺的解吸率均较低,尤其是黑土.在试验所采用的Gu²⁺处理浓度范围内,黑土与棕壤吸附态Cu²⁺的最高解吸率分别为6.60%和13.56%.Freundlich方程为描述2种土壤Cu²⁺等温解吸过程的最佳方程.黑土和棕壤吸附态Cu²⁺的解吸速率均较快,在40min左右基本达到平衡.描述黑土和棕壤解吸动力学过程的最优模型为双常数速率方程,其次为Elovich方程.     

煤燃烧复杂体系中痕量元素迁移转化的热力学

用热力学平衡模拟方法研究了贵州六盘水烟煤燃烧过程中痕量元素Ni、Cr、Hg、As、Se和Sb在凝聚相和气相中的迁移转化.研究的体系为气相和包含氧化物和硫化物熔融体、熔融盐及固溶体凝聚相的复杂体系.分别研究了燃烧过程的3个阶段:燃烧初期的还原性气氛、燃烧完全的氧化性气氛以及燃后冷凝气氛中痕量元素迁移转化规律.用10K小步长法计算了在1 30 0K以下痕量元素从气相迁移至凝聚相的形态及其凝聚顺序.比较计算结果与文献报道的实验数据,结果吻合.在研究煤燃烧过程中痕量元素的迁移转化时,在凝聚相加入氧化物和硫化物熔融体、固溶体及熔融盐模型大大提高了热力学平衡模拟方法的准确度和真实性.     

Phenol removal from aqueous environments by natural & chemically modified kaolin clay

Natural, acid and base modified kaolin clays were studied for the sake of phenol and 4-chlorophenol removal from aqueous environments and their application to real ground and industrial wastewater samples. Scanning electron microscope (SEM), infrared spectroscopy (IR), X-ray diffraction (XRD), Thermo Gravimetric Analysis (TGA), Differential Thermal Analysis (DTA), and Surface area analysis were employed for characterization of the adsorbents microstructure. Operating factors such as adsorbent dose, solution pH, initial phenol concentration, and contact time were studied. The experimental data displayed that the increase of the adsorbent dose, contact time, and pH value from 2 to 7 increases the efficiency of the removal process. Optimal conditions for phenolic removal were; contact time of 300 min, primary phenol solution of 25 mg/L, pH 7 and 2.5 g/L as an appropriate adsorbent dose using crude (natural), acid modified and base modified kaolin clays. The higher phenolic removal efficiencies were obtained at 5 mg/L as 90, 97, 96.2%, respectively, for the adsorbents in the previously mentioned order. The adsorption capacity in the removal of phenol and 4-chlorophenol were 7.481 and 4.195, 8.2942 and 3.211, and 8.05185 and 18.565 mg/g, respectively, for the adsorbents in the same mentioned order. The adsorption equilibrium data were fitted and analyzed with four isotherm models, namely, Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm equations. The adsorption process of phenol on studied adsorbents was exothermic, spontaneous and thermodynamically favorable proved by the negative values of their thermodynamic parameters ΔH° and ΔG°. The correlation coefficient (R²) for all concentrations was higher than 0.94, which indicates that in the studied system, the data suitably fit the first-order kinetics. The % desorption capacity was amounted to 96%, 91.11%, and 87.06% of adsorbed phenol, respectively, for the adsorbents in the previous order using 0.1N NaOH and 10% V/V ethanol solutions as eluents at 25°C, indicating the reusability of the adsorbents. Kaolin and its modified forms can be introduced as eco-friendly and low-cost adsorbents in water remediation implementation.