Langmuir吸附等温线方程的改进及其在沸石吸附重金属中的应用

从试验数据分析出发,基于经典Langmuir吸附等温线方程,通过引入虚拟重金属离子和平衡吸附面积分配参数的概念,并将传统的平衡吸附量概念转化为平衡吸附面积,成功建立了可用于分析重金属离子在沸石材料上多元吸附过程的改进式半经验吸附等温线方程和数据分析方法,并应用到重金属元素(Cu、Pb、Cd、Ni)在合成沸石上的吸附过程,结果令人满意。方程拟合结果表明:在一元吸附体系下,四种重金属离子的极限吸附面积顺序依次为Ni^2+>Cu^2+>Pb^2+>Cd^2+。在多元吸附体系中,由于重金属离子间的相互干扰,重金属离子的总极限吸附面积均小于各重金属离子在一元吸附体系下的极限吸附面积之和。在任何多元吸附系统中,无论初始浓度高低,Cu离子均占有吸附面积分配的优势,且随着初始浓度的增加其优势愈加明显或至少保持相对稳定。Pb离子的竞争优势主要体现在较高初始浓度,并且也随着初始浓度的增加而增加。Cd离子和Ni离子的优势地位则主要体现在较低初始浓度,且随着初始浓度的增加而逐步降低。     

基于正交实验的凹凸棒/生物炭复合材料镉吸附性能

以凹凸棒与碱木质素为原料,采用炭化活化法制备凹凸棒/生物炭(ATP/C)复合材料,并设计正交试验对制备工艺进行优化,得出较优制备条件为:反应温度600℃、反应时间60 min、ATP与K2CO3质量比为1:2、ATP与LG质量比为1:2.利用XRD和SEM等技术对材料形貌以及结构等进行表征分析.详细考察投放量、初始浓度...     

Adsorption of carbon dioxide by coconut activated carbon modified with Cu/Ce

A series of the coconut activated carbons(CAC) based absorbents modified with Cu and Ce(Cu/CAC,Cu/Ce/CAC) were prepared by impregnation technology for carbon dioxide capture.The adsocrption equilibriums of CO2 on Cu/CAC and Cu/Ce/CAC were measured.The results showed that the adsorption capacity of CO2 onto the activated carbon modified with Cu/Ce increased with the decreasing temperature in the same pressure.The adsorption capacity of CO2 on Cu/CAC was higher than that of the blank CAC,and compared with the Cu/CAC,the adsorption capacity of CO2 of Cu/Ce/CAC with the mass ratio of Cu/Ce=30 was improved at 298 and 303 K.In addition,the adsorption equilibrium data for CO2 at various temperatures was fitted to Langmuir,Freundlich and D-R isotherm models.It was found that the D-R equation was the best model for fitting the adsorption data on Cu/Ce/CAC at different temperatures.     

Biosorption of La^3＋ and Ce^3＋ by Agrobacterium sp.HN1

The Agrobacterium sp.HN1 was isolated from the soil and used to adsorb rare earth ions La3+ and Ce3+.The results showed that the pretreatments of Agrobacterium sp.HN1 did not enhance the adsorption of La3+ and Ce3+.The pH,temperature,time and bacterial age affected the dynamics of adsorption of La3+ and Ce3+.The optimum adsorption conditions for Agrobacterium sp.HN1 were as follows:15 mg/L La3+ of initial concentration,10 mg/L Ce3+,300 mg/L(dry wt.cell) biomass for sorption,6.8 pH,30 oC temperature,150 r/min rotational speed,2 h adsorption time and 28 h bacterial age.The adsorption kinetics of La3+ and Ce3+ for Agrobacterium sp.HN1 followed the pseudo-second order equation.     

Adsorption and desorption properties of D151 resin for Ce(Ⅲ)

The present research is aimed at the development of D151 resin as an adsorbent that it can be used in the adsorption of Ce(Ⅲ) ions.The adsorption and desorption behaviors of Ce(Ⅲ) on D151 resin have been investigated by chemistry analysis.The influence of operational conditions such as contact time,initial concentration of Ce(Ⅲ),initial pH of solution and temperature on the adsorption of Ce(Ⅲ) had also been examined.The results show that the optimal adsorption condition of D151 for Ce(Ⅲ) was achieved at pH=6.50 in HAc-NaAc medium.The maximum uptake capacity of Ce(Ⅲ) was 392 mg/g resin at 298 K.The adsorption of Ce(Ⅲ) followed both the Langmuir isotherm and Freundlich isotherm,and the correlation coefficients had been evaluated.Even kinetics on the adsorption of Ce(Ⅲ) had been studied.The adsorption rate constant k298 K valued was 1.3×10-5 s-1.The calculation data of thermodynamic parameters which ΔS0 value of 91.34 and ΔH0 value of 7.07 kJ/mol indicate the endothermic nature of the adsorption process.While,a decrease of Gibb’s free energy(ΔG0) with increasing temperature indicated the spontaneous nature of the adsorption process.Finally,Ce(Ⅲ) could be eluted by using 0.5 mol/L HCl solution and the elution percentage was as high as 100%.Adsorption mechanism was also proposed for the adsorption of Ce(Ⅲ) ions onto D151 resin using infrared spectroscopy technique.     

碳羟磷灰石(CHAP)吸附废水中锰离子的动力学研究

主要研究了碳羟磷灰石(CHAP)对二价锰离子的吸附性能。从pH、吸附时间及初始Mn2+浓度3方面对吸附能力的影响进行吸附试验。试验结果表明:在常温常压,CHAP吸附Mn2+的最佳pH值为6,最佳吸附时间为60 min,吸附量达到22.44mg/g。CHAP对Mn2+的吸附过程符合准二级反应动力学模型。CHAP吸附Mn2+的能力随着废水中Mn2+浓度增加而增加,最大的吸附量达24.29mg/g,CHAP对Mn2+的吸附符合Langmuir吸附等温式。     

Adsorption of carbon dioxide by coconut activated carbon modified with Cu/Ce

A series of the coconut activated carbons (CAC) based absorbents modified with Cu and Ce (Cu/CAC, Cu/Ce/CAC) were prepared by impregnation technology for carbon dioxide capture. The adsocrption equilibriums of CO₂ on Cu/CAC and Cu/Ce/CAC were measured. The results showed that the adsorption capacity of CO₂ onto the activated carbon modified with Cu/Ce increased with the decreasing temperature in the same pressure. The adsorption capacity of CO₂ on Cu/CAC was higher than that of the blank CAC, and compared with the Cu/CAC, the adsorption capacity of CO₂ of Cu/Ce/CAC with the mass ratio of Cu/Ce=30 was improved at 298 and 303 K. In addition, the adsorption equilibrium data for CO₂ at various temperatures was fitted to Langmuir, Freundlich and D-R isotherm models. It was found that the D-R equation was the best model for fitting the adsorption data on Cu/Ce/CAC at different temperatures.     

Adsorption and desorption properties of D151 resin for Ce(III)

The present research is aimed at the development of D151 resin as an adsorbent that it can be used in the adsorption of Ce(III) ions. The adsorption and desorption behaviors of Ce(III) on D151 resin have been investigated by chemistry analysis. The influence of operational conditions such as contact time, initial concentration of Ce(III), initial pH of solution and temperature on the adsorption of Ce(III) had also been examined. The results show that the optimal adsorption condition of D151 for Ce(III) was achieved at pH=6.50 in HAc-NaAc medium. The maximum uptake capacity of Ce(III) was 392 mg/g resin at 298 K. The adsorption of Ce(III) followed both the Langmuir isotherm and Freundlich isotherm, and the correlation coefficients had been evaluated. Even kinetics on the adsorption of Ce(III) had been studied. The adsorption rate constant k_{298 K} valued was 1.3×10^?5 s^?1. The calculation data of thermodynamic parameters which ΔS⁰ value of 91.34 and ΔH⁰ value of 7.07 kJ/mol indicate the endothermic nature of the adsorption process. While, a decrease of Gibb's free energy (ΔG⁰) with increasing temperature indicated the spontaneous nature of the adsorption process. Finally, Ce(III) could be eluted by using 0.5 mol/L HCl solution and the elution percentage was as high as 100%. Adsorption mechanism was also proposed for the adsorption of Ce(III) ions onto D151 resin using infrared spectroscopy technique.     

Comparison of Arsenate, Lead, and Cadmium Adsorption onto Aged Biofilter Media

Many biological water treatment plants for removal of iron and manganese from groundwater are in place for quite a long time, and thus their filters are aged—naturally coated with metal oxides and associated biomass. The particular reactivity and high adsorption capacity of these biogenic surface coatings make them potentially applicable for cost effective removal of arsenic and other heavy metals from contaminated water. However, the nature of interaction between various toxic elements and the composite materials in biological filters is not well understood. This study combines macroadsorption experiments with electron probe analysis to evaluate the adsorption properties of the biogenic surface coatings of an aged biofilter medium (BFM) for cationic lead and cadmium as well as arsenate anion. Results of batch adsorption showed that BFM has higher adsorption capacity for lead and cadmium as compared to arsenate anion. At pH 5.5, the maximum adsorption capacities of the medium for As(V), Pb(II), and Cd(II) were 17.03-, 80.77-, and 179.05-mg/g surface coatings, respectively. However, the column performance of BFM for Cd(II) was rather low. In particular, the breakthrough adsorption capacities (qb) of the BFM for As(V), Pb(II), and Cd(II) were 0.247-, 31.168-, and 4.084-mg/g surface coatings, respectively. These values represent about 1.5, 38.6, and 2.3% of the respective theoretical maximum adsorption capacities (qmax) of BFM for these metals. Data from the X-ray electron probe analysis corroborated well with that of the macroadsorption experiments. Results of this study strongly suggest that the Mn/Fe ratio and the presence of preadsorbed competing ions were two of the principal characteristics of the BFM, governing its affinity and adsorption capacity for different toxic metals.     

Investigation of Cadmium Desorption from Different-Sized Sediments

Using the adsorptive reaction kinetics equation and the mass conservation equation, formulas for calculating the particulate heavy metal concentration (or the residual adsorption content of unit weight of sediment) and the dissolved heavy metal concentration were deduced. Furthermore, equations for calculating the equilibrium particulate heavy metal concentration (or the equilibrium residual adsorption content of unit weight of sediment) and the equilibrium dissolved heavy metal concentration were formulated. On the basis of these theoretically deduced formulas and through laboratory reactor modeling of artificially contaminated sediments with cadmium in suspension, heavy metal desorption rates from nonuniform sediment particles were studied. Both theoretical analysis and experimental results indicate that adsorption and desorption of heavy metal pollutants to and from sediment particles are partly reversible. It is also noticed from the experiments that the adsorption and desorption rates of heavy metals to and from sediments are dependent on the content of active adsorption components in the sediments. The greater the content of active adsorption components, the higher the adsorption rate of the sediments and the lower the desorption rate. The total amount of heavy metal desorbed from sediments is directly proportional to the concentration of suspended sediment particles.     

Effects of Sediment Concentration and Initial Phosphorus Loading on Phosphate Adsorption in the Chongqing Reach of the Yangtze River

The results are presented from a laboratory and theoretical study to investigate the effects of sediment concentration and initial phosphorus loading on adsorption isotherm and capacity. The tested aquatic sediment was collected from the Chongqing reach of the Yangtze River. The adsorption isotherm of dissolved phosphate was approximated by the Langmuir equation. Using mass conservation and Langmuir adsorption kinetic equations, the authors derived formulas for calculating both the particulate and dissolved phosphate concentration. Kinetic experiments on fine sediment samples (<0.008?mm) show that the adsorption process is time dependent and takes place in three stages, namely, an initial fast stage followed by a gradual adsorption, leading to the eventual equilibrium. The results indicate that larger initial phosphate loading causes longer duration, higher adsorption rate, and less adsorption percentages on both the first and second stages. The sediment concentration mainly influences the adsorption rate of the first stage, in which the adsorption rate significantly increases with the increasing sediment concentration.     

废FCC催化剂吸附苯酚废水

将炼油厂排放的废FCC(fluid catalytic cracking,流化催化裂化)催化剂粉末(含稀土元素2%)进行酸浸处理,其中的稀土及有价金属进入浸出液后得以回收,粉末残渣经过水洗、干燥后,分析其结构,并进行吸附苯酚废水的实验,考察吸附时间、苯酚的初始浓度、吸附温度及吸附方式等对苯酚吸附量的影响,分析废FCC催化剂残渣对苯酚的等温吸附特性。结果表明,吸附达到平衡需要60 min;pH在7.0~8.0时,苯酚的吸附量较大;苯酚的初始浓度越高,吸附量越大;温度对苯酚吸附量的影响较显著;Freundlich方程和Langmuir方程都可用于描述废FCC催化剂残渣对苯酚的等温吸附特征,Langmuir方程更为准确,通过计算,理论饱和吸附量为36.751 mg/g,实验测得饱和吸附容量为35.540 mg/g。     

Adsorption behavior of Cd(II) from aqueous solutions onto gel-type weak acid resin

The adsorption and desorption behaviors of Cd(II) on gel-type weak acid resin (GTWAR) have been investigated. The influence of operational conditions such as contact time, initial concentration of Cd(II), initial pH of solution and temperature on the adsorption of Cd(II) has also been examined. The results show that the optimal adsorption condition of GTWAR for Cd(II) is achieved at pH = 5.95 in HAc–NaAc medium. The maximum uptake capacity of Cd(II) is 282 mg/g GTWAR at 298 K. The adsorption of Cd(II) follows the Langmuir isotherm and Freundlich isotherm, and the correlation coefficients have been evaluated. Even kinetics on the adsorption of Cd(II) has been studied. The apparent activation energy E_a and adsorption rate constant k₂₉₈ values are 2.95 kJ/mol and 3.02 × 10^− 5 s^− 1, respectively. The calculation data of thermodynamic parameters which ΔS value of 110 J/(mol K) and ΔH value of 13.1 kJ/mol indicate the endothermic nature of the adsorption process. Whilst, a decrease of Gibb's free energy (ΔG) with increasing temperature indicates the spontaneous nature of the adsorption process. Finally, Cd(II) can be eluted by using 0.5 mol/L HCl solution and the gel-type weak acid resin can be regenerated and reused. The sample was described by IR spectroscopy and scanning electron micrographs (SEM).     

Kinetics of hydrochloric acid leaching of smithsonite

The dissolution kinetics of smithsonite ore in hydrochloric acid solution has been investigated. As such, the effects of particle size (−180 + 150, −250 + 180, −320 + 250, −450 + 320 μm), reaction temperature (25, 30, 35, 40, and 45°C), solid to liquid ratio (25, 50, 100, and 150 g/L) and hydrochloric acid concentration (0.25, 0.5, 1, and 1.5 M) on the dissolution rate of zinc were determined. The experimental data conformed well to the shrinking core model, and the dissolution rate was found to be controlled by surface chemical reaction. From the leaching kinetics analysis it can be demonstrated that hydrochloric acid can easily and readily dissolve zinc present in the smithsonite ore, without any filtration problems. The activation energy of the process was calculated as 59.58 kJ/mol. The order of the reaction with respect to HCl concentration, solid to liquid ratio, and particle size were found to be 0.70, −0.76 and −0.95, respectively. The optimum leaching conditions determined for the smithsonite concentrate in this work were found to be 1.5 M HCl, 45°C, −180 + 150 μm, and 25 g/L solid to liquid (S/L) ratio at 500 rpm, which correspond to more than 95% zinc extraction. The rate of the reaction based on shrinking core model can be expressed by a semi-empirical equation as:

纳滤膜对稀土离子的动态吸附行为及截留特性

采用经碳纳米管改性的亲水化纳滤膜浓缩提取稀土浸出液中的稀土离子,探究纳滤膜表面对La3+、Nd3+、Pr3+、Ce3+和Y3+5种稀土离子吸附动力学行为,考察稀土离子半径的大小对纳滤膜吸附性能和截留性能的影响.结果表明,Freundlich吸附方程比Langmuir方程能更好地描述稀土离子在纳滤膜表面上的动态吸附行为,用Freundlich吸附方程拟合后的结果相关度系数R2能达到0.999以上;在初始浓度为5×105 μg/L,温度为25 ℃,运行压力为0.6 MPa的实验条件下,纳滤膜对稀土离子的浓缩提取过程中,初始阶段的截留机理取决于纳滤膜表面的吸附作用和膜孔的机械筛分效应,膜面吸附达到平衡后以膜孔的机械筛分效应为主,此时La3+、Nd3+、Pr3+、Ce3+和Y3+的截留率分别为94.21 %、81.25 %、85.80 %、89.90 %和81.18 %,表明经碳纳米管改性的亲水化纳滤膜能高效浓缩截留稀土浸出液中的稀土离子.      

The effect of pH on cadmium extraction by Lix 34

The pH dependence of the extraction of cadmium from nitrate solution using LIX 34 diluted with Kermac 470B has been studied. The optimum pH for cadmium extraction in the system studied is in the neighborhood of 8.3. Below pH 7, the reagent forms a two-to-one ligand to cadmium ion chelate, whereas, at pH greater than 7, the extraction mechanism is extremely complicated due to the presence of NH₃, NH₄⁺ and some other unknown buffers. Moreover, the difference between the initial and equilibrated aqueous pH values, ΔpH, can be estimated by the following equation

$\text{Delta;}\text{pH}\text{=}\text{log}\text{1}\text{1 +(i?2)}\text{[}\text{cd}\text{]}{}_0\text{[}\text{NH}{}_3\text{]}{}^{\mathrm{<mtext>I</mtext>}}$

where i is the average co-ordination number of cadmium by ammonia in the aqueous phase. [Cd]₀ represents the equilibrium cadmium concentration in the organic phase and [NH₃]^I denotes the initial aqueous ammonia concentration.     

253MA耐热不锈钢EAF-AOD-LF-板坯连铸生产工艺实践

253MA钢（/%:0.05～0.10C,1.2～2.0Si,20～22Cr,10～12Ni,0.14～0.20N,0.03～0.08Ce）是在21Cr-11Ni不锈钢的基础上,通过N合金化和添加稀土元素Ce开发的耐热奥氏体不锈钢。由于该钢种的熔点偏低,钢液的流动性差。因此,氮气合金化、稀土合金化是冶炼过程中的工艺难点。通过对稀土加入方式、过程脱氧、以及精确控N模型等研究,采用AOD全程氮气搅拌,AOD出钢前按照1.8～2.2 m3/t钢吹氩降氮,钢中[O]可降低到15×10^-6～20×10^-6,LF按13 m/t钢喂入铈线,实现了253MA不锈钢的批量生产。     

Global analysis of the effects of temperature and denaturant on the folding and unfolding kinetics of the N-terminal domain of the protein L9

The folding and unfolding kinetics of the N-terminal domain of the ribosomal protein L9 have been measured at temperatures between 7 and 85 degrees C and between 0 and 6 M guanidine deuterium chloride. Stopped-flow fluorescence was used to measure rates below 55 degrees C and NMR lineshape analysis was used above 55 degrees C. The amplitudes and rate profiles of the stopped-flow fluorescence experiments are consistent with a two-state folding mechanism, and plots of ln(k) versus guanidine deuterium chloride concentration show the classic v-shape indicative of two-state folding. There is no roll over in the plots when the experiments are repeated in the presence of 400 mM sodium sulfate. Temperature and denaturant effects were fit simultaneously to the simple model k=D exp(-DeltaG*/RT) where DeltaG* represents the change in apparent free energy between the transition state and the folded or unfolded state and D represents the maximum possible folding speed. DeltaG* is assumed to vary linearly with denaturant concentration and the Gibbs-Helmholtz equation is used to model stability changes with temperature. Approximately 60% of the surface area buried upon folding is buried in the transition state as evidenced by changes in the heat capacity and m value between the unfolded state and the transition state. The equilibrium thermodynamic parameters, DeltaCp degrees, m and DeltaG degrees, all agree with the values calculated from the kinetic experiments, providing additional evidence that folding is two-state. The folding rates at 0 M guanidine hydrochloride show a non-Arrhenius temperature dependence typical of globular proteins. When the folding rates are examined along constant DeltaG degrees/T contours they display an Arrhenius temperature dependence with a slope of -8600 K. This indicates that for this system, the non-Arrhenius temperature dependence of folding can be accounted for by the anomalous temperature dependence of the interactions which stabilize proteins.     

Thermodynamics of cadmium- and zinc-rich alloys in the Cd−La,Cd−Ce,Cd−Pr,Zn−La,Zn−Ce and Zn−Pr systems

The thermodynamics of the cadmium- and zinc-rich alloys in the Cd?La, Cd?Ce, Cd?Pr, Zn?La, Zn?Ce, and Zn?Pr systems have been studied with a high-temperature galvanic cell method. The values of the standard free energy of formation (kcal per mole) of the intermetallic compounds are given by the equations: $$\begin{gathered} (LaCd_{11} ), \Delta Gf^ \circ = - 72.3 + 43.6 \times 10^{ - 3} T (670^ \circ to 804^ \circ K) \hfill \\ (CeCd_{11} ), \Delta Gf^ \circ = - 70.5 + 44.6 \times 10^{ - 3} T (638^ \circ to 884^ \circ K) \hfill \\ (PrCd_{11} ), \Delta Gf^ \circ = - 69.1 + 44.8 \times 10^{ - 3} T (635^ \circ to 825^ \circ K) \hfill \\ (LaZn_{11} ), \Delta Gf^ \circ = - 92.6 + 48.0 \times 10^{ - 3} T (705^ \circ to 793^ \circ K) \hfill \\ (CeZn_{11} ), \Delta Gf^ \circ = - 87.9 + 45.0 \times 10^{ - 3} T (710^ \circ to 1018^ \circ K) \hfill \\ (PrZn_{11} ), \Delta Gf^ \circ = - 85.3 + 42.7 \times 10^{ - 3} T (696^ \circ to 875^ \circ K) \hfill \\ \end{gathered} $$ Equations are also given for the partial molar excess free energies of the lanthanide in dilute solutions of the lanthanide in liquid cadmium or zinc. The enthalpy of formation of the intermetallic compounds is discussed in terms of the crystalline structure of these intermetallic compounds. It is shown that the enthalpy of formation is a linear function of the ration/V _c , wheren is the number of zinc or cadmium atoms which are near-neighbors of the lanthanide atom andV _c is the volume of the cage formed by the near-neighbor cadmium or zinc atoms. A linear dependence of the enthalpy of formation onn/V _c is also found for the intermetallic compounds in several other binary systems. These empirical correlations are discussed in terms of a model which involves localized bonds between the lanthanide and zinc or cadmium atoms.     

CL-P204萃淋树脂对溶液中钒的吸附性能研究

探究CL-P204萃淋树脂对溶液中V(Ⅳ)的吸附效果。考察溶液pH、反应时间、初始浓度、温度对钒吸附容量的影响,并对吸附过程进行了动力学和热力学分析。结果表明,CL-P204萃淋树脂在298K、pH=1.6的条件下,吸附8h即可达到平衡,对V(Ⅳ)的最大吸附容量为34.2mg/g。树脂循环使用4次后对钒依然有良好的吸附效果。CL-P204萃淋树脂对钒的吸附过程符合准二级动力学方程和Langmuir等温吸附方程,是吸热熵增加的自发反应。