多组分粒子流化床半湿式烟气脱硫研究

在借鉴国内外现有主要烟气脱硫技术优点的基础上,该研究提出了一种应用多组分粒子流化床(MSFB)的半湿式烟气脱硫技术.在常温下,该研究探讨了MSFB的各种粒子的流态化特性,还进一步研究了多种粒子混合条件下流态化的机理,明确了MSFB正常操作的区域.通过合理的简化与理论上的解析,该研究对MSFB上段自由空间内液滴的传热问题进行了分析,认为MSFB烟气脱硫装置中,液滴下落过程的温度变化极微,可以忽略不计.通过热力学关系的分析,该文提出了MSFB烟气脱硫系统正常稳定操作应遵循的条件,并研究了实验过程中死床现象出现的原因.在250℃进口烟温下,该文通过一系列的实验,研究了MSFB中密相床内浆液的干燥机理.在150℃ˉ250℃较低温度范围内,该文实施了利用Ca(OH)<,2>脱硫剂浆液的模拟烟气脱硫试验,脱硫效率可达95%以上.该文还介绍了该技术的工业示范情况,比较系统地总结了在实际应用中MSFB所遇到的问题及相应采取的解决方案.对MSFB应用于工业实践的具体案例,该文通过细致的技术经济分析,以及与应用NaOH废液时的经济性的比较分析,证明了MSFB半湿式烟气脱硫的良好的技术经济性能. 

锌电极在碱性溶液中阳极溶解的中间步骤的研究

用恒电位下电流衰减和动电位扫描方法研究了锌电极在KOH溶液中阳极溶解过程的中间吸附步骤；用旋转圆盘电极动电位扫描法考察了不同扫描速度下传质过程的影响。在接近于锌的阳极活性溶解的电位区，在恒电位下，衰减的电流的对数lgi与时间t呈线性关系，在电流降的最初350ms（毫秒）的时间内，这一直线的斜率(partial deriv)lgi/(partial deriv)t与氢氧根离子浓度[OH~-]成直线关系。在随后的350ms至1000ms的时间内，直线的斜率((partial deriv)lgi/(partial deriv)t)'与[OH~-]~2成直线关系。在用动电位法快速扫描时，在动电位极化曲线上，出现一个尖锐的电流峰ip，扫描速度S越大，ip也越大，相应的峰电位φ_p也越往正方向推移。峰电位φ_p与扫描速度的对数lgS呈线性关系，当S = 1200-9000 mV/sec., 这一直线的斜率(partial deriv)φ_p/(partial deriv)lgS = 120 mV；当扫描速度稍慢，S = 100-1200 mV/sec., 直线的斜率((partial deriv)φ_p/(partial deriv)lgS)' = 60 mV。峰电位φ_p与lg[OH~-]也呈直线关系，在很快扫描速度下(S > 1200 mV/sec.)，斜率(partial deriv)φ_p/(partial deriv)lg[OH~-] = -120 mV；当扫描速度稍慢 (100-1200 mV/sec.)，φ_p与lg a_(OH~-)近似地也呈直线关系，其斜率(partial deriv)φ_p/(partial deriv)lga_(OH~-) = -84 mV。在较快的扫描速度下(例如500 mV/sec.)，峰电流ip与电极转速ω无关，表明在快速扫描时，锌电极表面上进行电化学反应与溶液中的传质过程无关，因而所得结果可反映不受扩散干扰的锌的阳极溶解动力学。设在KOH溶液中，锌的阳极溶解过程前二步的电化学吸附反应如下：Zn + OH~- <-> (ZnOH)_吸 + e~- 1-θ_1-θ_2 θ_1 (ZnOH)_吸 + OH~- <-> [Zn(OH)_2]_吸 + e~- θ_1 θ_2则由理论的动力学方程式与上述实验结果基本上相符。

海水主要无机阴离子对镉在针铁矿表面吸附影响研究

镉具有生物富集性和毒性，是地下水和海洋水体中重要的污染物之一，对人类健康构成了严重威胁。针铁矿是土壤、陆地和海洋底泥中一种常见矿物，矿物对镉的吸附能力强弱是影响镉在环境中迁移转化的重要因素，因此开展在不同介质下镉在针铁矿表面吸附机理研究，具有重要的环境意义。 本研究通过实验室序批式吸附试验，溶解度测定试验，X射线衍射分析和表面络合模型，考察在海水中主要共存阴离子在其自然浓度条件下，镉在针铁矿表面吸附机理：如表面沉淀，沉淀，表面三重络合或共沉淀等。 试验研究结果表明：随pH值升高，针铁矿对Cd的吸附量显著增加；Cl-、SO42-和NO3-在pH=8时抑制针铁矿对镉的吸附；影响程度为Cl- > SO42- > NO3-；Cl-和SO42-在低pH值条件下促进镉的吸附；HCO3-在pH 4~10范围内促进镉吸附；pH=8时，对于SO42和NO3-，其与镉加入顺序的不同对吸附结果具有显著影响，先加入镉时，镉的吸附量明显大于先加入阴离子和镉与阴离子同时加入时镉的吸附量。 在pH5-9范围内，镉的溶解度随pH增加急剧下降，在pH=8时，溶液中溶解镉浓度大于吸附实验中镉初始浓度，表明吸附实验中，镉没有到达产生Cd(OH)2(s)沉淀的最低镉浓度，可能产生Cd(OH)2表面沉淀。Cl-、SO42-和NO3-对镉的溶解均有一定促进作用，其影响程度Cl- > SO42- > NO3-，与吸附试验中对镉吸附影响顺序一致。 对负载镉的针铁矿进行X射线衍射试验，结果显示：没有发现β-Cd(OH)2(s)、γ-Cd(OH)2(s)等晶体存在，发现了CdCO3(s)晶体，但不能排除有无定型Cd(OH)2(s)形式存在。由于试验过程中有CO2进入，与镉形成CdCO3(s)沉淀或形成表面沉淀，影响实验结果，揭示了在自然条件下，镉与CO2作用在针铁矿表面形成CdCO3(s)过程。

铀矿坑水样中铀电沉积层的表征

描述了硫酸铵溶液中铀矿坑水样品中铀的电沉积层特性。电沉积液为10ml0.8M的硫酸铵溶液,电流密度0.6A/cm2,pH值为2.5,电镀1h。电沉积经化学分离后的水样品和电沉积的纯硝酸铀酰样品进行了比较,并对二者分别做了红外(IR)光谱、扫描电镜(SEM)、元素分析以及α能谱测量。IR谱上铀酰离子的反对称伸缩振动峰在887cm-1附近,使电沉积在不锈钢片上的铀主要以铀酰离子水合物的形式存在,有一部分NH4+以NH3的形式替代水合物中的水,使电沉积层中铀的化合物形式为UO2(OH)2.xNH3.yH2O或者UO2(OH)2-x.(ONH4)x.yH2O,铀酰离子通过链的形式形成聚合结构。SEM照片显示电沉积层均匀,没堆积成团现象出现。α谱表明电沉积层中铀的同位素主要是238U和234U,相应的α能量峰4198和4773keV很显著,没其它峰的干扰。

环境样品的低水平放射性测量

环境样品中的低水平放射性测量在环境放射性现状调查和探矿中有广泛的应用。本论文对CSR环境水样品的放射性利用γ能谱方法进行了测量；对铀矿坑水样铀电沉积层用红外谱图和扫描电镜进行了表征，并且对其进行了α能谱测量；对便携式钾40探测器样机在不同条件下进行了测试。 CSR环境水样品经过采集，静置，预处理和封装，用高纯锗探测器在低本底大铅室内对水样品进行了测量，每个样品测量86400秒。标准源由中国原子能科学研究院提供，用相对比较的方法，给出样品中天然铀、钍、镭和钾的放射性活度。测量结果表明，CSR环境水样品中的放射性处于兰州地区本底水平，在样品中没有发现人工放射性核素。 对铀矿坑水样中的铀进行离子交换化学分离，在0.8M的硫酸铵溶液中进行电沉积，电流密度为0.6A cm-2,pH值为2.5；和同样条件下电沉积的硝酸铀酰进行对比，并对二者分别作了红外光谱、扫描电镜、元素分析以及α能谱测量，红外谱上铀酰离子的反对称伸缩振动峰在887cm-1附近，电沉积在不锈钢片上的铀主要以铀酰离子水合物的形式存在，电沉积层中铀化合物形式为UO2(OH)2•xNH3•yH2O或者UO2(OH)2-x•(ONH4)x•yH2O。扫描电镜照片显示电沉积层均匀，没有成团现象出现。α谱表明电沉积层中铀的同位素主要是238U和234U，相应的α能量峰分别为4198keV和4773keV。 对研制的40K探测器样机在屏蔽和未加屏蔽的条件下进行了测试，测量配制的40K标准源，绘出标准曲线，在同样的条件下测量未知钾含量的样品，根据峰面积计算40K的含量。研制的40K探测器样机基本满足样品中钾含量测量的需要，在野外测量时，在一定程度上受本底的影响

On configuration of exchanged La3+ on ZSM-5: A theoretical approach to the improvement in hydrothermal stability of La-modified ZSM-5 zeolite

Density functional calculations have been employed to investigate the locating and binding of lanthanum cation, i.e., La(OH)(2)(+), on HZSM-5 zeolite. Through geometry optimization, it was determined that lanthanum ions are favorably accommodated in the two 6-T rings of the straight channels (Clusters 1 and 2, see Sec. III A for details). Cluster 1 was found to exist in prior to Cluster 2 due to the preference of Al substitution in the T11 site (Cluster 1) rather than in the T8 site (Cluster 2). Geometry-optimization of Cluster 1 containing another two lanthanide ions Nd3+ and Yb3+ was also carried out and it was found that a monotonic decrease in Ln-O bond length will take place as the atomic number increases, conforming well to the rule of lanthanide contraction. Some of the optimized parameters are comparable to the corresponding experimental values in Y zeolite, which confirms that the optimized configurations are acceptable. The average frequencies of hydroxyls attached to La3+ or Yb3+ in Cluster 1 fall at 3609.16 and 3579.76 cm(-1), respectively, with the gap of these two frequencies close to that in the sodalite cage of Y zeolite. Compared to H-form zeolite, the charges on both Al and O atoms in Ln-ZSM-5 zeolite show an obvious increase, which will undoubtedly lead to a stronger mutual interaction and hence enhance the stability of the [AlO4](-) anion. Moreover, the Ln(OH)(2)(+) seem to have thickened the zeolite framework, which can effectively retard the process of dealumination. Through the evaluation of the possibility for dimer formation, it turned out that when the exchange degree arrived to approximately 0.28, lanthanum monomers began to aggregate into dimers, and were completely converted into dimers when the exchange degree approached 0.60. (C) 2003 American Institute of Physics.

zero point of charge of cupric hydroxide and surface area determination by dye adsorption

zero point of charge of freshly precipitated cu(oh)2 has been determined to lie at pH 7.7 by means of microclectrophoresis technique. Day aged hydroxide shows an acid zpc shift to pH 7.3. these experimental values approximate the equivalence points of cu+ and oh_ ,which can be estimated from the solubility diagram constructed fo gu(oh)2 and cuo.

Controllable synthesis of metal hydroxide and oxide nanostructures by ionic liquids assisted electrochemical corrosion method

Cu(OH)(2) nanowires have been synthesized by anodic oxidation of copper through a simple electrolysis process employing ionic liquid as an electrolyte. Controlling the electrochemical conditions can qualitatively modulate the lengths, amounts, and shapes of Cu(OH)(2) nanostructures. A rational mechanism based on coordination self-assembly and oriented attachment is proposed for the selective formation of the polycrystalline Cu(OH)(2) nanowires. In addition, the FeOOH nanoribbons, Ni(OH)(2) nanosheets, and ZnO nanospheres were also synthesized by this route, indicative of the universality of the electrochemical route presented herein. The morphologies and structures of the synthesized nanostructures have been characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), powder X-ray diffraction (XRD). Fourier transform infrared spectra (FT-IR), and thermogravimetric (TG). (C) 2007 Elsevier Masson SAS. All rights reserved

Self-Assembly from Two-Dimensional Layered Networks to Tetranuclear Structures: Syntheses, Structures, and Properties of Four Copper-Thiacalix[4]arene Compounds

Two new copper-thiacalix[4]arene compounds, [Cu-2(1)-Cl-2(H(4)TC4A)](CH3OH) (1) and [Cu(I)2Cl(2)(H(4)PTC4A)](CH3OH)(CHCl3)(0.5) (2) (where H(4)TC4A = p-tert-butylthiacalix[4]arene and H(4)PTC4A = p-phenylthiacalix[4]arene), were synthesized by the solvothermal method in the mixed CH3OH/CHCl3 (1: 1) solvent and reassembled in air at room temperature to two other structures, [(Cu4Cl3)-Cl-II(HCO2)(TC4A)(CH3-OH)(2)(H2O)](CHCl3)(CH3OH)(2.7) (3) and [(Cu4Cl4)-Cl-II(PTC4A)(CH3OH)(4)] (4), respectively. All these four compounds were characterized by TG analyses, FTIR spectroscopy, and singlecrystal X-ray diffraction analyses. Compounds 1 and 2 feature two-dimensional layered networks, while compounds 3 and 4 are assembled by some tetranuclear units.

Synthesis and reactivity of rare earth metal alkyl complexes stabilized by anilido phosphinimine and amino phosphine ligands

Anilido phosphinimino ancillary ligand H2L1 reacted with one equivalent of rare earth metal trialkyl [Ln{CH2Si(CH3)(3)}(3)(thf)(2)] (Ln = Y, Lu) to afford rare earth metal monoalkyl complexes [L(1)LnCH(2)Si(CH3)(3)(THF)] (1a: Ln = Y; 1b: Ln = Lu). In this process, deprotonation of H2L1 by one metal alkyl species was followed by intramolecular C-H activation of the phenyl group of the phosphine moiety to generate dianionic species L-1 with release of two equivalnts of tetramethylsilane. Ligand L-1 coordinates to Ln(3+) ions in a rare C,N,N tridentate mode. Complex 1a reacted readily with two equivalents of 2,6-diisopropylaniline to give the corresponding bis-amido complex [(HL1)LnY(NHC(6)H(3)iPr(2)-2,6)(2)] (2) selectively, that is, the C-H activation of the phenyl group is reversible. When 1a was exposed to moisture, the hydrolyzed dimeric complex [{(HL1)Y(OH)}(2)](OH)(2) (3) was isolated. Treatment of [Ln{CH2Si(CH3)(3)}(3)-(thf)(2)] with amino phosphine ligands HL2-R gave stable rare earth metal bisalkyl complexes [(L2-R)Ln{CH2Si(CH3)(3)}(2)(thf)] (4a: Ln=Y, R=Me; 4b: Ln=Lu, R=Me; 4c: Ln=Y, R=iPr; 4d: Ln=Y, R=iPr) in high yields. No proton abstraction from the ligand was observed. Amination of 4a and 4c with 2,6-diisopropylaniline afforded the bis-amido counterparts [(L2-R)Y(NHC(6)H(3)iPr(2)-2,6)(2)(thf)] (5a: R=Me; 5b: R=iPr).

Cu掺杂的NiO的制备及其超级电容器性能

采用低热固相反应法合成掺杂Cu的Ni(OH)2,将其在300℃下热处理得到相应的NiO.电化学测试表明∶掺杂量为n(Ni)∶n(Cu)=100∶0.25时,NiO电极的比容量最高,为99-120 F/g,具有良好的充放电性能,而不掺杂的只有83-111 F/g,因此掺杂Cu有利于提高NiO的电化学性能.

Hydrothermal synthesis of ZrW2O8 nanorods

Negative thermal expansion ZrW2O8 nanorods were synthesized by a rapid low-temperature hydrothermal route, followed with a heat treatment at 500 degrees C for 6h. Acidity of the HCl addition to the mixed solution in the hydrothermal condition strongly affects the formation of the precursor ZrW2O7(OH)(2)(H2O)(2). High acidity of HCl in the range of 5-10 N facilitates the nucleation of ZrW2O7(OH)(2)(H2O)(2), but constrains its growth. Low acidity of HCl addition (< 5 N) only obtained the products ZrO2 and WO3 by firing the precursors. FE-SEM images revealed that the shape and size of ZrW2O8 were modeled after its precursor ZrW2O7(OH)(2)(H2O)(2).

Polypropylene as a carbon source for the synthesis of multi-walled carbon nanotubes via catalytic combustion

Multi-walled carbon nanotubes (MWCNTs) were efficiently synthesized by catalytic combustion of polypropylene (PP) using nickel compounds (such as Ni2O3, NiO, Ni(OH)(2) and NiCO3 (.) 2Ni(OH)(2)) as catalysts in the presence of organic-modified montmorillonite (OMMT) at 630-830 degrees C. Morphologies of the sample undergoing different combustion times were observed to investigate actual process producing MWCNTs by this method. The obtained MWCNTs were characterized by X-ray diffraction (XRD), transmission electron microscope and Raman spectroscopy. The yield of MWCNTs was affected by the composition of PP mixtures with OMMT and nickel compounds and the combustion temperature. The proton acidic sites from the degraded OMMT layers due to the Hoffman reaction of the modifiers at high temperature played an important role in the catalytic degradation of PP to supply carbon sources that are easy to be catalyzed by nickel catalyst for the growth of MWCNTs. The XRD measurements demonstrated that the nickel compounds were in situ reduced into the Ni(0) state with the aid of hydrogen gas and/or hydrocarbons in the degradation products of PP, and the Ni(O) was really the active site for the growth of MWCNTs. The combination of nickel compounds with OMMT was a key factor to efficiently synthesize MWCNTs via catalytic combustion of PP.

Solvent extraction of scandium(III), yttrium(III), lanthanum(III) and gadolinium(III) using Cyanex 302 in heptane from hydrochloric acid solutions

The extractions of the selected rare earths (Sc, Y, La and Gd) from hydrochloric acid solutions have been investigated using bis(2,4,4-trimethylpentyl)-mono thiophosphinic acid (Cyanex 302, HL) in heptane as an extractant. The results demonstrate that the extractions of rare earths occur via the following reaction: Sc(OH)(2+) + 2[(HL)(2)]((O)) double left right arrow [Sc(OH)L-2 (.) 2(HL)]((O)) + 2H(+) Y3+ + 3[(HL)(2)]((O)) double left right arrow [Y(HL2)(3)]((O)) + 3H(+) La(OH)(2)(+) + 3[(HL)(2)](O) double left right arrow [La(OH)(2)L (.) 5(HL)]((O)) + H+ Gd(OH)(2+) + 3[(HL)(2)]((O)) double left right arrow [Gd(OH)L-2 (.) 4(HL)]((O)) + 2H(+) The pH(1/2) values and equilibrium constants of the extracted complexes have been deduced by taking into account the aqueous phase complexation of the metal ion with hydroxyl ligands and plausible complexes extracted into the organic phase. According to the pH(1/2) values, it is possible to realize mutual separation among Sc(III), Y(III), La(III) and Gd(III) with Cyanex 302 by controlling aqueous acidity.

Hexagonal nanodisks of cadmium hydroxide and oxide with nanoporous structure

In this work we demonstrate that hexagonal nanodisks of cadmium hydroxide with nanoporous structures could be fabricated by a facile hydrothermal treatment without using any templates or organic additives. With this method, the length of the hexagonal edge and thickness of the nanodisks can be adjusted through controlling the experimental conditions such as the pH value of the mother liquor and the initial concentration of the cadmium ion. On the basis of our experimental observations and understandings of the nanocrystal growth, the formation of the nanodisks is believed to mainly originate from the oriented attachment of small particles. Furthermore, the hexagonal Cd(OH)(2) nanodisks can be converted to CdO semiconductors with similar morphology by calcinations.