H3PW12O40 acid dispersed on its Cs salt: improvement of its catalytic properties by mechanical mixture and grinding

Acidic cesium salts Cs_x H_3-xPW₁₂O₄₀ have been prepared by grinding together amounts of H₃PW₁₂O₄₀ and porous Cs₃PW₁₂O₄₀ compounds in varying stoichiometries. It is shown that this procedure leads to a dispersion of the acid on top of the high surface area Cs₃PW₁₂O₄₀ salt (160 m² g^-1), and, subsequently, yields high surface area materials which exhibit a much higher catalytic activity for n-butane isomerisation at 473 K when compared with samples prepared directly by chemical precipitation. This improvement holds particularly true with low Cs content (x < 2). This revised version was published online in July 2006 with corrections to the Cover Date.     

Two-Phase Calorimetry. II. Studies on the Thermodynamics of Cesium and Strontium Extraction by Mixtures of H+CCD− and PEG-400 in FS-13

Abstract

Thermochemical characterization of the partitioning of cesium and strontium from nitric acid solutions into mixtures of the acid form of chlorinated cobalt dicarbollide (H⁺CCD^?) and polyethylene glycol (PEG-400) in FS-13 diluent has been completed using isothermal titration microcalorimetry and radiotracer distribution methods. The phase transfer reaction for Cs⁺ is a straightforward (H⁺ for Cs⁺) cation exchange reaction. In contrast, the extraction of Sr²⁺ does not proceed in the absence of the co-solvent molecule PEG-400. This molecule is believed to facilitate the dehydration of the Sr²⁺ aquo cation to overcome its resistance to partitioning. The phase transfer reactions for both Cs⁺ and Sr²⁺ are enthalpy driven (exothermic), but partially compensated by an unfavorable entropy. The results of the calorimetry studies suggest that the PEG-400 functions as a stoichiometric phase transfer reagent rather than acting simply as a phase transfer catalyst or phase modifier. The calorimetry results also demonstrate that the extraction of Sr²⁺ is complex, including evidence for both the partitioning of Sr(NO₃)⁺ and endothermic ion pairing interactions in the organic phase that contribute to the net enthalpic effect. The thermodynamics of the liquid-liquid distribution equilibria are discussed mainly considering the basic features of the ion solvation thermochemistry.     

用于羟醛缩合反应的固体碱催化剂的制备及表征

采用溶胶凝胶法制备载体二氧化锆,并通过浸渍法负载铯制备固体碱催化剂,将其应用于以醋酸甲酯、甲醛为原料合成丙烯酸甲酯的反应。考察了不同温度,负载不同含量的硝酸铷、硝酸铯对催化剂性能的影响。利用微反色谱实验装置测试合成丙烯酸甲酯固体碱催化剂的催化活性,结果表明,负载铯比铷催化效果要好;催化剂最优条件：氧化锆负载20%铯,反应温度为380℃时,可使收率达到29.2%。     

Chromatographic partitioning of cesium by a macroporous silica‐calix[4]arene‐crown supramolecular recognition composite

A macroporous silica‐based 1,3‐[(2,4‐diethyl‐heptylethoxy)oxy]‐2,4‐crown‐6‐calix[4]arene (Calix[4]arene‐R14) supramolecular recognition polymeric composite, (Calix[4]+Oct)/SiO₂‐P, was synthesized. It was performed by impregnating and immobilizing Calix[4]arene‐R14 and n‐octanol into the pores of the macroporous SiO₂‐P particles support. n‐Octanol was used to modify Calix[4]arene‐R14 through hydrogen bonding. The effect of eight typical fission products contained in highly active liquid waste (HLW) on the adsorption of Cs(I), one of the heat generators, was investigated at 298 K by examining the effect of contact time and the HNO₃ concentration in a range of 0.3–7.0 M. (Calix[4]+Oct)/SiO₂‐P showed excellent adsorption ability and high selectivity for Cs(I) at 4.0 M HNO₃ over the tested elements. The partitioning of Cs(I) from a simulated HLW was operated by (Calix[4]+Oct)/SiO₂‐P packed column. Cs(I) was able to be effectively eluted by water and separated from the tested metals. It is demonstrated that (Calix[4]+Oct)/SiO₂‐P is promising to apply in chromatographic separation of Cs(I) from HLW. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

平行板静电场法铯离子引出的实验研究

为研究平行板静电场法离子引出的规律，利用对由YAG四倍频脉冲激光(266nm)一步电离产生的铯等离子体进行了多次离子引出实验。结果发现，离子引出时间随外加引出电压的增加而减小，随离子初始密度的增加而增长。通过对实验数据的分析，获得了在此实验条件下光致瞬态铯等离子体离子引出时间与外加引出电压和离子初始密度之间关系的经验公式。但是，离子引出时间并非一直随电压的增加线性减小。在外加电压超过1200V以后发现离子引出时间有增加的趋势。在外加电压高于1000V以后观察到溅射离子峰的存在．并讨论了溅射现象的存在对离子引出时间的影响。通过对离子引出与收集和溅射现象的分析获得了本实验条件下平行板静电场法离子引出中外加电压的最佳值。     

Cesium-adsorption capacity and hydraulic conductivity of sealing geomaterial made with marine clay,bentonite, and zeolite

Great amounts of soil and waste contaminated with radioactive cesium have been generated due to the decontamination work after the Fukushima Daiichi Nuclear Power Plant accident. The aim of this study is to develop a sealing geomaterial for use at the disposal facilities of the soil and waste constructed in the maritime environment. The geomaterial consists of marine clay, bentonite, and zeolite. The hydraulic conductivity and cesium-adsorption performance of the geomaterial were examined through laboratory tests with different proportions of bentonite and zeolite added to marine clay. It was concluded that the hydraulic conductivity could be reduced to the required level by increasing the amount of bentonite and that the cesium-adsorption capacity could be enhanced by increasing the amount of zeolite.     

Extracting Performance of Cesium by 25,27‐Bis(2‐Propyloxy) Calix[4]‐26,28‐Crown‐6 (iPr‐C[4]C‐6) in n‐octanol

Abstract

In this work, the extraction of cesium(Cs⁺) in nitric acid and in a simulated high level liquid waste (HLLW) by iPr‐C[4]C‐6 was investigated in the diluent n‐octanol. The slope of the extractant dependency equals 1, indicating that the complex has 1∶1[Cs⁺ · iPr‐C[4]C‐6]Cs⁺ to ligand. 0.025 mol/L iPr‐C[4]C‐6 in n‐octanol (abbreviated to iPr‐C[4]C‐6‐n‐octanol) has a stronger extracting ability to Cs when acidities are between 1.0 mol/L and 4.0 mol/L. The stripping properties of Cs loading in 0.025 mol/L iPr‐C[4]C‐6‐n‐octanol was studied. Cs loading in iPr‐C[4]C‐6‐n‐octanol can be stripped easily into the aqueous phase because the distribution ratios of Cs are lower than 0.5 when pH is between 2 and 10 in the aqueous phase. On the above basis, the better parameters were selected and the cold cascade test for removing Cs from the simulated HLLW was investigated on miniature centrifugal contactor. The results of the test are attractive. The removing ratio of Cs from the simulated HLLW is 99.5% and the stripping ratio of Cs loading in 0.025 mol/L iPr‐C[4]C‐6‐n‐octanol is 99.2%. The results show that 0.025 mol/L iPr‐C[4]C‐6‐n‐octanol is an effective process for removing Cs from HLLW.     

Evaluation of Elution Parameters for Cesium Ion Exchange Resins

Abstract

Cesium ion exchange is one of the planned processes for treating and disposing of waste at the U.S. Department of Energy Hanford Site. Radioactive supernatant liquids from the waste tanks will undergo ultrafiltration, followed by cesium ion exchange using a regenerable organic ion exchange resin. Two resins, SuperLig^®644 and a resorcinol‐formaldehyde resin, are being evaluated for cesium removal and cesium elution characteristics. The main purpose of this study is to optimize the cesium elution to provide a resin that, after undergoing elution, would meet the U.S. Department of Energy/Office of River Protection Project‐Waste Treatment Plant processing and resin disposal criteria. Columns of each resin type were loaded to greater or equal to 90% breakthrough with a Hanford waste stimulant and eluted with nitric acid. The temperature, flow rate, and nitric acid concentration were varied to determine the optimal elution conditions. Temperature and eluant flow rate were the most important elution parameters. As would be predicted based upon kinetic consideration alone, decreasing the eluant flow rate and increasing the temperature provided the optimal elution conditions. Varying the nitric acid concentration did not have a significant effect on the elution completion; however, elutions performed using both high acid concentration (1 M) and elevated temperature (45°C) resulted in resin degradation, causing gas generation and resin bed disruption.     

A rapid-detection method for radioactive cesium in the air

We propose a method of rapidly detecting radioactive cesium floating in the air for the purpose of alerting people active in the ‘difficult-to-return zone’ of Fukushima to changes in airborne radioactivity. With this purpose in mind, we set requirement specifications and created a new system concept. The targeted detection limit was 30 Bq/m³ and the mandatory level of measurement time was 48 min with a target level of 12 min, and these periods are 10 times faster than those of conventional air monitors. The system consists of a conventional gamma-spectrometer with a novel shaped shield. The targeted peak region of the measured energy spectrum is analyzed. After the basic design and confirmation of feasibility, we perform some experiments in the normal environment of Yokohama city and the difficult-to-return zone of Fukushima. Using the results, we conducted the design improvement and performance evaluation. As a result, the system performance is found to satisfy requirements. We thus conclude that this system is a promising candidate for rapid detection of airborne radioactivity in the difficult-to-return zone of Fukushima.