不同惰性填料复极性固定床电解槽处理对硝基酚钠废水行为比较

分别以磺化煤、果壳、PVC塑料、回收旧塑料等4种密度与活性炭相当的惰性填料替代工程上广泛使用的石英砂,结合适当的反冲洗解决复极性固定床电解槽(BPBC,b ipolar packed bed cell)存在的电极污染及填料分层问题.并以含有对硝基酚钠的废水降解实验考察其应用的可行性.结果表明,以回收旧塑料及磺化煤作为填料的BPBC处理效果优于石英砂的,而果壳、PVC塑料的与石英砂的处理效果相当.反冲洗后,以磺化煤、果壳、PVC塑料和回收旧塑料作填料的电解槽再生率均大于石英砂的.     

氟离子对TiO2/膨润土光催化降解酸性桃红的影响

研究了在紫外光照射下, 添加氟离子对P25(锐钛矿)和TiO2/膨润土光催化降解酸性桃红(SRB)的影响. 紫外可见光谱测定结果表明无氟的反应体系, pH值越小, 光降解速率越快; pH值固定, 添加氟离子越多, 反应速率越快, 在TiO2/膨润土催化剂上, 当氟离子浓度达到一定程度时, 反应速率不再变化. 在P25和TiO2/膨润土催化剂上, 添加氟离子对H2O2的产生量影响不同, 通过电子顺磁共振(EPR)技术探测到了超氧自由基和羟基自由基, 这两个体系添加氟离子对其产生强度影响不同, 这可能是因为TiO2/膨润土催化剂为层状结构, BET 比表面积较大, 经XRD和TEM测试表明其晶粒直径约为57.9 nm. TiO2/膨润土催化剂连续循环使用11次, 光催化活性基本不变, 这个现象说明TiO2/膨润土催化剂既易于从分散体系中分离出来, 而且其稳定性也好, 它是一个有应用前途的催化剂.     

CeO2对CuCl/活性炭吸附剂C2H4/C2H6吸附分离性能促进作用

通过等体积浸渍方法制备了添加CeO₂助剂的用于C₂H₄/C₂H₆吸附分离的CuCl/活性炭(AC)吸附剂,使用氮气吸附-脱附曲线、X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、能量分散X射线光谱(EDX)等分析方法对吸附剂进行了表征.结果表明,吸附剂表面Cu(II)在氮气气氛焙烧过程中被部分还原成Cu(I).重点研究了Ce元素的添加对于吸附剂的C₂H₄/C₂H₆吸附分离性能的影响,等温吸附曲线结果表明添加了CeO₂的吸附剂通过降低乙烷的吸附容量从而显著提高了吸附分离性能. XRD及XPS结果表明,和未添加助剂样品相比,其表面晶体团簇较小,分散性更好, Cu(II)还原程度更高.添加CeO₂的吸附剂样品5Ce50Cu(CeO₂和CuCl2的质量分数(w)分别为5%和50%)获得了最好的吸附分离效果,相对于未添加CeO₂的样品50Cu,其在660 kPa下的吸附选择性由4.2提升到8.7.     

巧用T形三通管探究多种气体的性质

密度明显大于空气的气体,其在空气中能够下沉;密度明显小于空气的气体,其在空气中则上升;密度与空气接近的气体,其在空气中则比较均匀地向四周运动。     

一种快速同位素稀释定量方法及其在示踪方面的应用

同位素稀释法定量分析中,当待测样品中某一目标同位素的丰度被示踪剂影响而不能保持天然丰度时,需要测量样品中各同位素的丰度比。在待测样品量或测量时间有限时,常规同位素稀释法的应用受到局限。为了降低样品消耗量、简化测量步骤、减小记忆效应影响、提高测量效率,本研究建立了一种可省略待测样品丰度比测量环节的快速同位素稀释定量方法。基于物质的量守恒原理,通过关联的运算,得到待测样品后,只需进行一次添加同位素稀释剂后混合样品的丰度比测量即可完成目标同位素的定量分析。以天然丰度Xe标准气体作为模拟样品,6次测量值与标称值的相对偏差均小于1%,相对标准偏差(RSD)为0.4%,与使用常规同位素稀释法得到的测量结果完全相符。此外,以¹²⁸Xe作为示踪同位素,得到的示踪同位素扩散曲线符合气体在封闭空间的扩散规律。本方法适用于有3种或更多稳定同位素的元素,既保证了测量结果的准确性,又可缩短分析时间,减少样品消耗量。     

拐点法计算气体在高分子中的扩散系数

根据Fick扩散的基本假定,推导了从微分渗透曲线上的拐点值计算气体在高分子薄膜中扩散系数的公式。此法不需要达到稳态扩散,因此,可成倍地缩短实验时间。 用气体色谱仪测定丙烯气体在聚酰胺1010和聚酰胺1010/聚乙烯/聚乙烯与马来酸酐接枝共聚物的共混物的扩散系数,由本法计算的结果与滞后时间法、t_(1/2)法相一致,也符合实验值。     

疏水性二氧化硅气凝胶吸附水中微量苯酚和甲醛的研究

气凝胶是一种新型纳米多孔非晶材料,其密度低、比表面积大、孔隙率高,可以作为吸附剂.本文研究了稻壳灰为硅源制成的合甲基的疏水性二氧化硅气凝胶对水中微量苯酚和甲醛的吸附性能.结果表明,疏水性气凝胶对水中微量苯酚和甲醛具有一定的吸附能力,实验中对苯酚的吸附容量是1.93mg/g,要大于对甲醛的吸附容量0.92mg/g;增大气凝胶的疏水化程度可以增加其对水中微量苯酚和甲醛的平衡吸附容量;苯酚的吸附平衡等温曲线符合Langmuir和Freundlich方程,甲醛的吸附平衡等温曲线符合Freundlich方程.     

石英砂固体分散剂制样的裂解气相色谱法测定涤/毛纤维混纺比列

基于纵型微型炉裂解器的裂解气相色谱法(Py-GC)建立了涤/毛纤维混纺比例的测定方法。以石英砂为固体质量分散剂,将样品加入其中碾磨成粉末后称量进样,在550℃的裂解温度下得到相应的裂解色谱图,依据各自特征裂解谱图与释放气体分析曲线可识别涤纶与羊毛纤维;选择涤/毛二元混纺纤维裂解谱图上涤纶的特征裂解产物——联苯为定量峰,计算混纺纤维中涤纶的质量百分含量,进而推算出羊毛纤维的含量。样品和石英砂的最佳配比为0.02 g∶4 g,涤纶质量在0.0256~0.2048 mg范围内联苯的线性良好,相关系数R2=0.9952。对不同涤/毛混纺比例的实际样品进行了测定,相对标准偏差RSD<3%(n=3);本法与国标法所得结果的偏差小于5%。结果表明,本方法简便、准确,适合涤/毛二元混纺纤维混纺比例的质控分析。     

碳纳米管/活性炭复合微球的制备及其对VB12的吸附应用

采用反相乳液法制备碳纳米管/壳聚糖复合微球(CNTs/CTS), 并对其进一步炭化、活化制得碳纳米管/活性炭复合微球(CNTs/AC). 以此复合微球为吸附材料, 探索了其对中分子代表物质VB12的吸附. 研究结果表明, 碳纳米管含量70%(w)的复合微球经水蒸气适当活化后球形度好、吸附性能优异, 其对VB12的吸附量达23.59 mg·g-1, 分别是活性炭和大孔吸附树脂的5.4和2.7倍. 分析表明这是由于碳纳米管/活性炭复合微球具有发达的中孔结构.     

气相色谱法测定苯系物含量

报道用活性炭做捕集苯系物的吸附剂,以二硫化炭为解吸剂,用毛细管气相色谱法研究活性炭对苯系物的吸、脱附效率,样品的存放寿命,共存干扰物实验,方法的精密度及最小检出浓度。实验结果表明:活性炭捕集效率为100％,解吸率稳定在90％以上,能可靠地测出小于1.0mg/m~3的苯系物单个组分,其相对标准偏差均小于10％,方法具有取样手段先进,检测灵敏度高,抗干扰能力强等特点。     

Experimental and numerical investigations of 99TcO4− diffusion in compacted SPV 200 bentonite

Journal of Radioanalytical and Nuclear Chemistry - Diffusion characteristics in bentonite are essential to quantify the transport of radionuclides through buffer/backfill materials in waste...     

Diffusion of 137Cs in compacted bentonite: Effect of pH and concentration

The effect of pH and concentration on the diffusion of ¹³⁷Cs in the compacted bentonite is studied with capillary method at the ionic strength of 0.1M NaClO₄. The apparent diffusion coefficient increases with increasing concentrations if the sorption of radionuclides is largely dependent on the radionuclide concentrations. The apparent diffusion coefficient decreases with increasing pH because most of the radionuclide sorption on the bentonite increases with increasing pH. The interlaminary space contributes significantly to the radionuclide diffusion and sorption in compacted bentonite. The relationship of the apparent diffusion coefficient and the effective diffusion coefficient of ¹³⁷Cs is also discussed.     

Optimisation of a gas chromatographic method for trace gaseous impurities in nitrogen trifluoride by column sequence reversal

Highly reactive fluorinated gaseous matrices require special equipment and techniques for the gas chromatographic analysis of trace impurities in these gases. The impurities that were analysed at the low mg/L levels included dioxygen (O2), dinitrogen (N2), carbon dioxide (CO2), carbon monoxide (CO), sulfur hexafluoride (SF6), methane (CH4) and nitrous oxide (N2O). Carbon tetrafluoride (CF4) is also present in the product at levels of 20-400mg/L and had to be analysed as well. This paper compares the use of a custom-built dual-channel gas chromatograph utilising single column back flush switching on one channel for the determination of O2, N2, CH4 and CO with column sequence reversal on a second channel for the determination of CO2, N2O, SF6 and CF4 to a similar system using a combination of dual-column back flush and heart-cut configurations. Pulsed discharge helium ionisation detectors were used on both channels in both configurations.     

柱后切换及程序升温气相色谱法测定六氟化硫气体中痕量一氧十氟化二硫

本工作提供了用柱后切换和程序升温技术测定纯六氟化硫气体中痕量有毒杂质Ｓ２Ｆ１０Ｏ含量的气相色谱方法。用火焰光度检测器检测，进样量为 １ｍＬ时，Ｓ２Ｆ１０Ｏ最小检测浓度为５×１０－７（ｍｏｌ／ ｍｏｌ）。     

SF6气体的富集与解吸方法

介绍SF6的低温富集及高温解吸方法.测定了SF6在Porapak Q和PorapakT两种吸附剂上的动态吸附系数(kd).结果显示,Porapak Q对SF6的吸附性能明显优于Porapak T,温度是影响kd值的主要因素之一,温度和kd的关系符合Arrhenius方程,实验范围内的样品气流量对kd的影响较小.SF6解吸前需预抽真空至30 kPa,然后放入热水浴中恒温30 min,用N2洗提,逐段收集洗提气体,洗提流量为2mL/min.当解吸体积为7 mL时,回收率可达到90％以上,富集系数可达到102量级.     

NMR study of the reversible trapping of SF6 by cucurbit[6]uril in aqueous solution

The complexation of sulfur hexafluoride (SF(6)), a highly potent greenhouse gas, by cucurbit[6]uril (CB) was studied at various temperatures in Na(2)SO(4) aqueous solutions by (19)F and (1)H NMR. CB shows a remarkable affinity for SF(6), suggesting that it is a suitable molecular container for the design of materials tailored for SF(6) trapping. At 298 K, the equilibrium constant characterizing the inclusion of SF(6) by CB is 3.1 x 10(4) M(-1) and the residence time of SF(6) within the CB cavity is estimated to be of the order of a few seconds. The enthalpic and entropic contributions to the free energy of encapsulation were determined and are discussed. This work also reports on the interest of SF(6) in the framework of the spin-spy methodology. The advantages and drawbacks of solution-state (19)F NMR of SF(6) with respect to (129)Xe NMR are discussed. SF(6) comes forward as a versatile and informative spin-spy molecule for probing systems in solution because its detection limit by (19)F NMR reaches the micromolar range with standard equipment and because quantitative integral measurements, relaxation time measurements, and demanding experiments, such as translational diffusion coefficient measurements, are easily carried out in addition to chemical shift measurements. Solution-state (19)F NMR of SF(6) emerges as a promising alternative to (129)Xe NMR for probing cavities and for other applications relying on the encapsulation of an NMR active gaseous probe.     

Gas chromatographic analysis of trace gas impurities in tungsten hexafluoride

Highly reactive fluorinated gaseous matrices require special equipment and techniques for the gas chromatographic analysis of trace impurities in these gases. The impurities that were analysed at the low-microg/l levels included oxygen, nitrogen, carbon dioxide, carbon monoxide, sulfur hexafluoride and hydrogen. This paper describes the use of a system utilising backflush column switching to protect the columns and detectors in the analysis of trace gas impurities in tungsten hexafluoride. Two separate channels were used for the analysis of H2, O2, N2, CO, CO2 and SF6 impurities with pulsed discharge helium ionisation detection.     

The effect of ionic strength on the diffusion of 125I in Gaomiaozi bentonite

The diffusion of ¹²⁵I^? in compacted Gaomiaozi (GMZ) bentonite was investigated by capillary in-diffusion method. Apparent and effective diffusion coefficients and accessible porosity of iodide in GMZ bentonite were obtained, and the effect of ionic strength on diffusion parameters was studied. The apparent diffusion coefficients of iodide in compacted GMZ bentonite are in the range of 1.0–6.0 × 10^?10 m² s^?1 under the conditions of dry bulk density 1,500 kg m^?3 and temperature 298 K, and increase with increasing ionic strength. This effect was explained through the analysis of microscopic structure of compacted bentonite. The iodide can only diffuse in unbound interparticle pore solution of compacted bentonite. The apparent diffusion coefficient is a function of accessible porosity which is decided by the thickness of diffusion double layer, and the thickness is in turn controlled by ionic strength.     

A new experimental design to investigate the concentration dependent diffusion of Eu(III) in compacted bentonite

The 'in-diffusion method was used to study the diffusion behavior of Eu(III) in compacted bentonite. The results (K _d, apparent and effective diffusion coefficients) derived from the capillary method are in good agreement with the literature data for similar bentonite dry densities and similar radionuclide concentrations, and fits the Fick's second law very well. The method was used to study the effect of solution concentration (10^-7-10^-3 mol/l) on the diffusion and sorption behavior in compacted bentonite. The experiments were carried out in synthetic groundwater, at room temperature. The results suggested that the diffusion of Eu(III) in the bentonite was independent on the density of bentonite, but dependent on the solution concentration. In agreement to the literature, the K _d values from the capillary experiments are in most cases lower than those from batch experiments, they are about one-half to one-third the value to those from batch experiments. The difference between the K _dvalues from capillary and batch experiments are a strong function of the bulk density of the bentonite. The results suggest that the content of interlaminary space plays a very important role to the transport of Eu(III) in compacted bentonite.     

S_2OF_(10)气体标准样品制备方法和测定方法研究

提出了一系列的安全、方便、可靠、在线和可连续操作的热解吸／色谱分析柱制备Ｓ２ＯＦ１０纯品、指数稀释法配制Ｓ２ＯＦ１０标准样品、应用定量校正系数测定样品中痕量Ｓ２ＯＦ１０的方法和技术。分别采用气相色谱、红外光谱、气相色谱／质谱等方法对色谱制备的Ｓ２ＯＦ１０纯品进行了纯度分析和测定。配制Ｓ２ＯＦ１０标准气体的体积分数范围为８．０×１０－７～２．６×１０－４。气相色谱测定Ｓ２ＯＦ１０的定量校正系数为０．１９７,测定方法的相对误差范围为１．８％～２０％。