Rates of Exchange of Cs+ and Sr2+ for Poorly Crystalline Sodium Titanium Silicate (CST) in Nuclear Waste Systems

The compound sodium titanium silicate, popularly known as CST, is highly selective for Cs⁺. It was synthesized for the purpose of removing ¹³⁷Cs from basic nuclear waste systems. This compound has a tunnel structure in which the Cs⁺ ion just fits but diffusion through the tunnels is relatively slow. CST loses its ability to sequester Cs⁺ in the strongly basic nuclear waste solutions. However, replacement of titanium with 25 mol% of niobium increases the selectivity to a satisfactory level. It has been found that producing a less crystalline form of Nb-CST greatly improves the rate of Cs⁺ removal. Additionally, the non-niobium CST is selective for strontium both as Sr²⁺ and Sr(OH)⁺. It is suggested that both radioisotopes of cesium and strontium may be efficiently extracted by a combination of a mixture of poorly crystalline CST and Nb-CST.     

累托石对模拟核素Sr~(2+)、Cs~+、Co~(2+)的吸附性能研究

分析湖北钟祥杨榨累托石矿床的累托石土样的基本物化特性的基础上,进行了累托石对模拟核素Sr2+、Cs+、Co2+的静态吸附性能的研究。实验表明,累托石的阳离子交换容量(CEC)为36.04 mmol/100 g,胀缩度为23.89%,渗透系数为6.94×10-8cm/s。在中性条件下,累托石对模拟核素Sr2+、Cs+、Co2+的平衡吸附量分别为70,48,20 mg/g。累托石对核素的吸附量会随着吸附时间的增加而逐渐趋于稳定。弱碱性条件下累托石的吸附效果更好。     

Mg2+/NH4 + Ion Exchange Kinetics under Isothermal Supersaturated Conditions

Ion Exchange Isothermal Supersaturation process (IXISS) allows the recovery of the salt from the elution solution without any additional reagent or step. This work focuses on the batch elution kinetics of magnesium with ammonium from two commercial resins under supersaturated conditions – i.e., conditions far above from the solubility of magnesium. The Mg²⁺/NH₄ ⁺ exchange was measured by chemical analysis and the salt crystallization was monitored by the turbidity of the solution. The stability of the supersaturated solution was evaluated as a function of the functional group and matrix type of the ion exchanger. The effective diffusion coefficients were calculated by fitting the experimental data to the unreacted core model. The values calculated were dependent on the stability of the intraparticular solution.     

Adsorption of Radioactive Ions 137Cs+, 85Sr2+, and 60Co2+ on Natural Magnetite and Hematite

Abstract

Natural magnetite and hematite have been used as granular sorbents for ¹³⁷Cs⁺, ⁸⁵Sr²⁺, and ⁶⁰Co²⁺ at tracer concentration levels in aqueous solutions of constant pH (range 2–10) at 25°C. The kinetics of adsorption, up to the first 60 to 90 min, followed a first-order equation. At pH 6–8 about 50% Cs, 30% Co, and 18% Sr is removed from the solution with magnetite and 78% Co with hematite. The difference in the sorption capabilities of magnetite and hematite is discussed in terms of crystal structures of these oxides.     

Removal of Cs1+, Sr2+ and Co2+ from aqueous solutions by adsorption on natural clinoptilolite

The adsorption properties of local clinoptilolite (Serbia) towards Cs⁺, Co²⁺, and Sr²⁺ were investigated by batch equilibration technique. The influence of equilibration time, initial metal cation concentration, solution pH and presence of EDTA on these properties was studied and discussed. Kinetic data were found to be well fitted with pseudo-second order kinetic model. Cs⁺ is preferably adsorbed by the natural clinoptilolite, followed by Sr²⁺ and Co²⁺. The Langmuir adsorption isotherm was used to determine the adsorption capacities from both single and mixed metal solutions. At pH range of 3–12 the adsorption of Cs⁺ remains almost constant, while at low pH (2–3) the adsorption is lesser. At initial pH range of 2–10 adsorption of Sr²⁺ remains approximately stable, whereas at initial pH > 10 adsorption increases significantly. The adsorption of Co²⁺ is low at low pH but increased remarkably with increasing pH and precipitated at pH > 8. Cs⁺ adsorption on the clinoptilolite was not affected by the presence of EDTA, while the presence of EDTA hinders the adsorption of Co²⁺ and Sr²⁺ on clinoptilolite.     

Monosodium Titanate in Hydrous Titanium Oxide Spheres for the Removal of Strontium and Key Actinides from Salt Solutions at the Savannah River Site

Abstract

Fine powders of monosodium titanate effectively remove strontium and plutonium from alkaline salt supernatant. At the Savannah River Site, larger, porous particles with monosodium titanate were desired for continuous column operations. The internal gelation process was used to make hydrous titanium oxide microspheres with 32 and 50 wt% monosodium titanate. With actual supernatant, the microspheres with 50 wt% monosodium titanate produced average batch distribution coefficients of 35,000 mL/g for plutonium and 99,000 mL/g for strontium. These microspheres were tested using a simulant and a flow rate of 5.3 bed volumes per hour. The plutonium removal dropped from 99% to 94% while the strontium removal remained nearly 100%. The microspheres exhibited good flow performance and no particle degradation.     

Non-stationary radiotracer method for diffusion coefficients of Cs+, Ba2+, Eu3+ tracers in Nafion-117 membrane

The ion-exchange kinetics of A^z+_sol ? Na⁺_mem (A^z+ = Cs⁺/Ba²⁺/Eu³⁺) in Nafion-117 have been measured using non-stationary radiotracer technique for trace concentrations of A^z+ ions in external solution. A method based on non-steady state Nernst–Planck approach has been developed and used to fit the experimental ion-exchange profiles to obtain the diffusion coefficients (DCs) of these ions. The DCs, thus obtained, have been found to be appreciably lower than the literature-reported self-diffusion coefficients, indicating slower rate of ion-exchange. The results show that membrane DCs of these ions are modified by bulk electrolyte solution.     

Adsorptive Removal of Nitrate and Phosphate from Water by a Purolite Ion Exchange Resin and Hydrous Ferric Oxide Columns in Series

Elevated concentrations of nitrate and phosphate in surface and ground waters can lead to eutrophication, and nitrate can also cause health hazards to humans. The adsorption process is generally considered to be an efficient technique in removing these ions provided that the adsorbent is highly selective for these ions. Removal of nitrate and phosphate from a synthetic water (50 mg N/L as nitrate, 15 mg P/L as phosphate) and a wastewater (12.9 mg N/L as nitrate, 5.9 mg P/L as phosphate) using a Purolite A500P anion exchange resin and a hydrous ferric oxide (HFO) columns (60 cm height, 2 cm diameter, flow rate 1 m/h) in series containing 1–10% (w/w) of these adsorbents and the remainder anthracite (90–99%) were studied. Data from batch adsorption experiment at various concentrations of adsorbents satisfactorily fitted to Langmuir adsorption isotherm for nitrate and phosphate on Purolite with adsorption maxima of 64 mg N/g and 7 mg P/g and only for phosphate on HFO with adsorption maxima of 14 mg P/g. Both batch and column experiments showed that Purolite selectively removed nitrate and HFO selectively removed phosphate. The Purolite column BTC time was greater for nitrate than for phosphate. At the highest percentage by weight of Purolite almost all nitrate was removed in batch study and up to 1000 min in column study, but it was not able to remove a comparatively high percentage of phosphate. However, when the effluent from the Purolite column was passed through the HFO column almost all phosphate was removed. The two columns when set up in series also removed almost all nitrate and phosphate from the wastewater.     

NO与乙二胺合钴离子气液反应动力学研究

用乙二胺合钴水溶液实现NO的液相催化氧化,乙二胺合钴离子作氧化催化剂,废气中残存的氧气作氧化剂,使NO的氧化和吸收同时进行。采用搅拌反应器分别在有氧和无氧时,对NO与乙二胺合钴离子气液反应动力学进行研究,结果表明当乙二胺合钴浓度大于0.02mol/L时,过程为气膜控制。氧的存在有利于NO的吸收,其分压越大,越有利于NO的氧化和脱除。气体中有氧存在时,最佳NO脱除温度为50℃,并推得吸收反应动力学方程。     

Influence of Na+, K+, Mg2+, Ca2+, and Fe3+on filterability and settleability of drilling sludge

Solid–liquid separation is a vital step in drilling sludge disposal, and the filterability and settleability of drilling sludge are the main evaluating indicators for the separation process. The influence of Na~+,K~+,Mg~(2+),Ca~(2+),and Fe~(3+) on drilling sludge filterability and settleability was investigated in our research. The water content,filtration rate, supernatant volume and supernatant turbidity were measured to evaluate the filterability and settleability of drilling sludge. Meanwhile, the zeta potential, specific surface area of sludge flocs, particle size distribution and Fourier-transformed infrared spectra were employed to clarify the influencing mechanism.The experimental results showed that the filterability and settleability of drilling sludge were related to concentration and types of cations. Mg~(2+),Ca~(2+),and Fe~(3+) performed better than Na~+, K~+, and the cations with smaller hydrated radius got superior solid–liquid separation behavior at same valence. Finally, the spectra indicated that no chemical adsorption occurred between inorganic cations and drilling sludge flocs. The variation of surface charge and flocs growth after adding different inorganic cations were the reasons for the changes of the filterability and settleability.     

Competitive Adsorption of Ag+, Pb2+, Ni2+, and Cd2+ Ions on Vermiculite

Competitive adsorption of Ag⁺, Pb²⁺, Ni²⁺, and Cd² ions on vermiuculite in a binary, ternary, and quaternary mixture was investigated in batch experiments. The effects of the presence of Ag⁺, Ni²⁺, and Cd²⁺ ions on the adsorption of Pb²⁺ ions were investigated in terms of the equilibrium isotherm. Experimental results indicated that Pb²⁺ ions always favorably adsorbed on vermiculite over Ag⁺, Ni²⁺, and Cd²⁺ ions. The adsorption equilibrium data of Pb²⁺ ions better fitted the Langmuir model than the Freundlich model. The results showed that the pseudo-second-order kinetics model was in good agreement with the experimental results for all metal ions, and the adsorption rate among the metal ions followed Ag⁺ > Pb²⁺ > Ni²⁺ > Cd²⁺. The desorption and regenration study indicated that vermiculite can be used repeatedly and be suitable for the design of a continuous process.     

球型Co2+印迹壳聚糖树脂的吸附特性及动力学研究

以Co2 和壳聚糖为原料,环氧氯丙烷和异丙醇为交联剂,制备了球形Co2 印迹壳聚糖树脂。研究了pH值、温度等因素对该印迹树脂吸附的影响及其吸附动力学。结果表明,pH值小于3.5时,印迹CTS树脂无吸附能力,pH值在3.5～6.0之间,印迹CTS树脂的吸附量随pH值升高而增大。印迹CTS树脂的吸附符合二级吸附动力学方程:t/Q=0.0077 0.0048 t。球形印迹壳聚糖树脂的吸附是以多分子层不均匀吸附模式为主,符合Freundlich方程。在30～90℃的温度范围内,树脂的吸附量随温度升高而增加,70℃时达到最大值,随后呈下降趋势。     

Synergistic effects during CO oxidation over mixed oxides. Study of (Fe2O3+SnO2) and (Mn2O3+SnO2) systems

Based on the comparative evaluation of the catalytic activity of Fe₂O₃, Mn₂O₃ and SnO₂ and their mixed oxides (Fe₂O₃+SnO₂) and (Mn₂O₃+SnO₂), it is shown that the system (Mn₂O₃+SnO₂) shows strong synergistic effects during CO oxidation reaction. Such effects are not observed for the analogous system (Fe₂O₃+SnO₂). Based on the calcination and reduction behaviour of these two mixed oxide systems and the redox potentials of the involved cations, the possible reasons for the observance of synergistic effects for the (Mn₂O₃+SnO₂) system are discussed.     

TWC Behaviour of Platinum Supported on High and Low Surface Area Cerium/Zirconium Mixed Oxides

The catalytic activity as TWC of two Pt catalysts supported on one high and one low surface area Ce_0.68Zr_0.32O₂ mixed oxide has been investigated. The catalyst behaviour was studied both fresh and after thermal ageing, and correlated to the textural and the Pt dispersion changes. The results show that the catalyst with the highest surface area is not necessarily the catalyst which has the best performances as TWC. The different behaviour of the catalysts has been attributed mainly to differences in the platinum dispersion and/or the reducibility of the samples, both related to the platinum/support interaction.     

微波辐射对球型Co2+印迹壳聚糖树脂吸附特性的影响及动力学研究

以Co2 和壳聚糖为原料,环氧氯丙烷和异丙醇为交联剂,在微波辐射下制备了球形Co2 印迹壳聚糖树脂.研究了微波辐射时间、温度等因素对该印迹树脂吸附的影响及其吸附动力学.结果表明,随着微波辐射时间的增加,制得的印迹CTS树脂的吸附量增大,辐射5 min时吸附量达到最高,5 min后随微波时间的延长吸附量反而减少.印迹CTS树脂的吸附符合二级吸附动力学方程:t/Q=0.0009 0.0024t.球形印迹壳聚糖树脂的吸附是以多分子层不均匀吸附模式为主,符合Freundlich方程.在30～90 ℃的温度范围内,树脂的吸附量随温度升高而增加,70 ℃时达到最大值,随后呈下降趋势.     

谷壳对水中铜镉离子的生物吸附研究

研究了农业副产物谷壳对水中Cu2+、Cd2+的生物吸附过程及其影响因素,以间歇实验的方式考察了吸附时间、溶液初始pH值、谷壳用量、谷壳粒径、吸附温度、金属离子初始浓度等物化参数对吸附过程的影响,研究了其吸附热力学和动力学。结果表明谷壳对Cu2+、Cd2+的吸附均符合Langmuir和Freundlich等温吸附模式,都遵循拟二级动力学模型。利用谷壳做生物吸附剂去除废水中重金属离子,既是对农作物副产物的合理利用,也是重金属废水净化的一种有效方法,谷壳有望成为一种低成本有效、效果好的净化重金属废水的新型生物吸附剂。     

壳聚糖及Zn2+模板壳聚糖膜与Zn2+螯合反应的动力学及机理探讨

分别用壳聚糖及Zn2 模板壳聚糖膜与Zn2 螯合反应,在30、40、50、60、70℃测定出锌离子浓度随时间变化的数据,由dc/dt=-kcn进行拟合,以线性相关系数为判据,得到该螯合反应的积分动力学模式函数:2c=-kt。表观活化能E壳(131.96 kJ/mol)>E膜(89.92 kJ/mol),表明Zn2 模板壳聚糖膜对Zn2 具有较强的“记忆”能力。并用红外光谱(IR)光电子能谱(XPS)对壳聚糖与Zn2 的螯合机理进行了探讨。结果表明Zn2 壳聚糖螯合物的配位原子是-NH2中的N,壳聚糖分子链上的-OH没有参与配位反应。     

电解锰渣中Mn2+的固化及动力学研究

电解锰渣(EMR)中大量可溶性锰会带来严重的环境问题,需要对其进行固化处理.本文利用CaO固化电解锰渣中Mn2+及其动力学机制,系统考察了CaO添加量、液固比、温度和反应时间对Mn2+固化率的影响.通过XRD、SEM-EDS对原EMR和预处理EMR的物相组成、表面形貌检测分析,探讨固化反应机理.结果表明,在CaO与EM...     

石灰调质污泥恒温干燥特性及动力学模型研究

对添加石灰的市政污泥进行恒温干燥实验,研究在不同的石灰添加量和不同的温度条件下污泥干燥特性、有效水分扩散系数和干燥活化能。结果表明:高温干燥时,石灰添加量的增加对平均干燥速率以及有效扩散系数的提高影响显著,低温干燥时影响不显著;石灰的添加可以降低干燥活化能;基于Modified Page模型建立的通用干燥模型能准确地描述石灰调质污泥的干燥特性;模型方程预测值和实验值吻合,均方根误差为0.32%。     

The influence of simultaneous divalent cations (Mg2+, Co2+ and Sr2+) substitution on the physico-chemical properties of carbonated hydroxyapatite

Bone is generally known as calcium-apatite which contains considerable amounts of various trace elements, mainly carbonate. Thus, bone is usually referred as carbonated hydroxyapatite (CHA). The incorporation of dopants into calcium-apatite has been proposed. This approach provides a safer and efficient platform for enhancing bone remodelling. However, reports that emphasize on the influence of multi-dopant substitutions into the CHA structure particularly in the form of as-synthesized powders are limitedly available. The present study investigates the influence of simultaneous substitution of divalent cations, Mg²⁺, Co²⁺ and Sr²⁺ into CHA structure by a nanoemulsion method. Several combinations of ions were doped into the CHA structure. The XRD and FTIR results confirmed that the phase purity and crystallinity were not affected by the simultaneous incorporation of multi-doped ions; all powders remained as amorphous B-type CHA. Despite the small amount of dopants used, all the three cations were successfully substituted into the Ca²⁺ site of CHA structure. The crystallite size of the as-synthesized powder decreased as the amount of incorporated dopants increased. Interestingly, the particle shape showed the transformation from near spherical structures into needle-like structures with increasing amount of dopants. Our finding highlights that the incorporation of these cations into the CHA structure results in crystal imperfections, which cause a substantial dislocation of the crystal lattice, as seen by the alteration of the lattice parameters, crystallite and particle sizes of the as-synthesized powders.