钒渣中钒和钛的连续滴定

不管用富氧顶吹、底吹、侧吹和雾化处理含钒铁水,均可得到不同品位V_2O_5的钒渣,测定钒渣中钒和钛系常规分析。过去测定其中的钛,国内外文献报道几乎全部采用分离除钒的手段,以消除钒对测定钛的干扰。作者所拟定的快速测定钒渣中钒、铁和钛的方法,尤其是不分离钒直接测定钒渣中钛的方法。虽经使用多年效果甚好,但工作要求我们寻求钒钛连测的途径。我们将测定钒后的溶液中,以还原铁粉将钛(Ⅳ)还原至钛(Ⅲ),控制钒为四价,中性红为指示剂,以重铬酸钾为滴定剂,拟定了钒渣中钒和钛的连续滴定法。本法适于含V_2O_5 10—36％的钒渣分析。方法简便、快速、条件宽容。一、分析步骤 1.钒渣中钒的测定称0.2000g试样于500mL锥形瓶中,加热溶于15—20mL磷酸中,冷却,加100mL15％硫酸,2—3g过硫酸铵,煮沸除去多余     

钛铁中钛铝的测定

目前钛铁合金中钛的测定,国家标准使用铝片还原,硫氰酸盐指示终点,硫酸高铁滴定.由于低价钛不稳定,在还原及滴定时须在氮气保护下进行,否则将造成一定误差且终点不易判别,操作极为不便.钛铁中铝的测定用8-羟基喹啉容量法.须经多次沉淀分离,测定流程较长.成本高.本文研究了铁、铝、钛、锰、铋与EDTA及过氧化氢之间的络合平衡关系,制定出在铁、铝、锰存在下测钛及锰存在下测铝的EDTA连续滴定方法.     

高钛炉渣中的Fe(Ⅲ)的测定

高钛炉渣中Fe(Ⅱ)的测定,由于共存金属铁及低价钛化物的干扰和本身赋存状态的复杂性,至今尚难寻求准确可靠的分析方法。而高钛炉渣中Fe(Ⅲ)的测定,一般认为它在试样中不可能存在而未予研究,文献在介绍钛渣中低价钛合量测定时,也以不存在Fe(Ⅲ)为前提。在高炉冶炼的强还原气氛和1450—1500℃的高温下,可认为不存在Fe(Ⅲ)化物,加之钒钛矿高温还原性能良好,高价铁化物在软熔带已还原为FeO和部份金属铁,而且呈高     

钛渣中低价钛的测定

钛渣中低价钛的测定,国内外资料均有报导,多采用三价铁、四价铈和五价钒作为氧化剂,但实验结果不够稳农,分析步骤冗长。本文以试样中不存在高价铁为前提,先用5%硫酸浸取,选择分解试样中金属铁和硫化物,以消除干扰。不经过滤,直接在浸取液中,加入已知量的过量三氯化铁标准液,作为低价钛的氧化剂,继而以氢氟酸和盐酸等使试样完全分解。最后用硫氰酸盐为指示剂,以硝酸亚汞标准溶液返滴定过量的三氯化铁。由两种标准溶液用量的差数,求得低价钛的含量。     

高钛炉渣中Ti(Ⅱ)的测定

高钛炉渣中低价钛的测定,对干认识钒钛矿高炉冶炼过程机理、改善工艺流程都有重要意义。至今低价钛合量及分量的测定仍用Табакова的高价铁盐法,尚未见到Ti(Ⅱ)直接测定的报道,本实验用气体容量法直接测定高钛炉渣中Ti(Ⅱ)含量。     

电感耦合等离子体原子发射光谱（ICP-AES）法测定石煤钒矿石中钒、铁、钛的含量

研究一种快速准确测定石煤钒矿石中钒、铁、钛含量的方法对石煤钒矿检测行业的发展和石煤钒矿资源的开发利用、综合评价具有重要的意义。本研究试样经过氧化钠在650℃完全熔融后保持1-3min,取出冷却,热水浸提,盐酸酸化,定容稀释,选择V 292.402nm 、Fe 259.940nm 、Ti 334.941nm为分析谱线,利用电感耦合等离子体原子发射光谱法（ ICP-AES ）,建立了石煤钒矿石中同时测定钒、铁、钛含量的方法。试验优化了钒、铁、钛元素的分析谱线和背景校正模式,采用全程序样品空白稀释配置的校准曲线消除盐度钠基影响;研究了坩埚、熔剂种类、直接碱熔与灼烧-碱熔前处理方式、酸度效应的影响。结果表明,方法检出限为0.009%～0.019%,定量限为0.027%～0.057%;铁、钛、钒3元素浓度在0.10～30.0μg/mL时,校准曲线线性回归方程的相关系数均大于0.9999;采用国家一级标准物质（GBW 07876、GBW 07877、GBW 07878）进行验证,相对标准偏差( RSD%,n =12) 为 0.49～0.87,且测定值与标准值吻合。该方法具有快速简便、精密度好、准确度高、同时测定钒、铁、钛等优点,满足石煤钒矿石化学分析检测需求,且可为石煤钒矿化学分析标准方法的建立提供技术支撑。     

库仑滴定剂三价铊的应用——钒的库仑滴定和钒、钛连续库仑滴定

本文报告库仑滴定剂三价铊的应用——钒的库仑滴定和钒、钛连续库仑滴定。实验证明,大量铁、钛、铬均不干扰钒的测定。选择性相当好。同时,钒和钛用三价铊作库仑滴定时,有两个明显分开的突跃范围。因此,亦可用于钒和钛的连续库仑滴定。本法用于微量钒的测定,在几十微克时,相对误差在±0.3％左右。测定结果与标准样品数据相符。     

低价钒试剂促进的有机反应及其在有机合成中的应用

综述了近年来低价钒试剂促进的有机反应及其在有机合成中的应用。重点讨论了低价钒试剂促进下的碳-碳键的形成反应，如卤代烃的还原偶联、醛(酮)的还原偶联、羰基化合物的脱氧烷基化及脱氧偶联反应等。另外，还介绍了催化量的低价钒度剂在促进有机反应方面的应用。     

低价钛促进的酮腈的分子内还原偶联反应

自二十世纪七十年代,McMurry等发现低价钛试剂能引起羰基化合物的还原偶联反应以来,低价钛试剂在有机合成中的应用越来越受到人们的重视,已经发现低价钛试剂能引起不少官能团化合物的还原偶联反应.我们最近几年发现低价钛试剂能引起一些α,β-不饱和化合物和多官能团化合物的还原偶联环化反应.本文报道一酮二腈的分子内还原偶联反应.     

库仑滴定剂醌

将氢醌在0.5-10N硫酸介质及鉑阳极上电解产生醌可以作为库仑滴定剂。氢醌氧化的电流-电极电势曲线说明电流效率易接近100%,实验也证明此点。用电生醌分别进行毫克量亚钛和二价钒的库仑滴定,误差为千分之几。用小型锌汞齐还原器可将四价或五价钒定量还原到二价,迅速方便。铬、鉬干扰钒的测定,而锰、钛不干扰。     

New methodological approach for the vanadium K-edge X-ray absorption near-edge structure interpretation: application to the speciation of vanadium in oxide phases from steel slag

This paper presents a comparison between several methods dedicated to the interpretation of V K-edge X-ray absorption near-edge structure (XANES) features. V K-edge XANES spectra of several V-bearing standard compounds were measured in an effort to evaluate advantages and limits of each method. The standard compounds include natural minerals and synthetic compounds containing vanadium at various oxidation state (from +3 to +5) and in different symmetry (octahedral, tetrahedral, and square pyramidal). Correlations between normalized pre-edge peak area and its centroid position have been identified as the most reliable method for determining quantitative and accurate redox and symmetry information for vanadium. This methodology has been previously developed for the Fe K edge. It is also well adapted for the V K edge and is less influenced by the standard choice than other methods. This methodology was applied on an "environmental sample," i.e., a well-crystallized leached steel slag containing vanadium as traces. Micro-XANES measurements allowed elucidating the microdistribution of vanadium speciation in leached steel slag. The vanadium exhibits an important evolution from the unaltered to the altered phases. Its oxidation state increases from +3 to +5 together with the decrease of its symmetry (from octahedral to tetrahedral).     

Multielemental analysis of metallurgical samples by thermal neutron activation

Instrumental neutron activation analysis (INAA) was applied to investigated a total of 16 samples of raw materials, intermediate and final products involved in metallurgical processes in Romanian Iron and Stell works Sidex Galatzy: iron ores and pellets from different regions of the world, cast iron, slag and steels. A series of chemical elements was determined in the analyzed samples: Al, As, Ce, Co, Cr, Fe, La, Mn, Na, Sc, Sm, V, W. A qualitative discussion regarding the passing of from elements with different chemical affinity for oxygen compared to that of iron, from the raw materials to slag or to finite products is presented.     

Fe3+/V5+/TiO2复合纳米微粒光催化性能的研究

采用溶胶凝胶法制备了Fe^3 /V^5 /TiO2复合纳米微粒作为光催化剂。光降解反应结果表明，其掺杂催化剂Fe^3 /V^5 /TiO2的光催化活性明显提高。光电化学研究显示，铁离子可以成为电荷陷阱，促进空穴的界面传递反应。适量钒离子掺杂使TiO2电极的光电流升高，导带中电子浓度的增大，加快了界面的电子传递反应。共掺杂催化剂中，Fe^3 、V^5 分别提供了空穴与电子的陷阱，同时加快了电子与空穴的界面传递反应，从 更有效地提高光催化活性。双组份共掺杂为提高TiO2光催化活性提供新的途径。     

超细Fe-V-O催化剂的制备、表征及其吸附性能

分别采用共沉淀法和溶胶-凝胶法制备了Fe-V-O催化剂，用DTA-TG、TEM、XRD、IR和TPR等方法对微粒的组成、表面结构及晶格氧活性进行了表征．用化学吸附-IR和TPD方法考察了乙烷在Fe-V-O催化剂表面上的吸附性能．结果表明：溶胶-凝胶法制备的Fe-V-O催化剂为超细微粒，粒子大小为10-20nm，其比表面、晶格氧的活泼性均大于共沉法制备的Fe-V-O催化剂．乙烷能够以-CH3中的H原子吸附于催化剂表面Lewis碱位V＝O链的端氧上形成两种分子吸附态，随吸附温度的升高，乙烷的吸附强度逐渐增大，其乙烷吸附量远大于共沉法制备的Fe-V-O催化剂．     

Experimental studies of biomass gasification with air

In this work,experimental studies of biomass gasification under different operating conditions were carried out in an updraft gasifier combined with a copper slag reformer.The influence of gasification temperature,equivalence ratio(ER) and copper slag catalyst addition on gas production and tar yield were investigated.The experimental results showed that the content of H2 and CO,gas yield and LHV increased,while the tar yield and the content of CO2,CH4 and C2Hx in the gas product decreased with the temperature.At 800C,with the increase of ER,the LHV,the tar yield and the content of H2,CO,CH4 and C2Hx in gas products decreased,while the gas yield and the content of CO2 increased.Copper slag was introduced into the secondary reformer for tar decomposition.The Fe3O4 phase in the fresh copper slag was reduced to FeO(Fe2+) and metallic Fe by the gas product.Fe species(FeO and metallic Fe) acted as the active sites for tar catalytic decomposition.The catalytic temperature had a significant influence on tar conversion and the composition of the gas product.Typically,the tar conversion of about 17%-54% could be achieved when the catalytic temperature was varied from 750 to 950 C.Also,the content of H2 and CO increased with the catalytic temperature,while that of CO2,CH4 and C2Hx in the gas product decreased.It was demonstrated that copper slag was a good catalyst for upgrading the gas product from biomass gasification.     

掺杂Fe作为第二种金属组分的V-HMS催化剂的苯羟基化反应

采用浸渍法在V-HMS中引入第二种金属组分(Fe、Al、Cu、Ni、Co、Mo、Cr)以提高催化剂在H2O2为氧化剂的苯羟基化反应中的催化性能.筛选发现,Fe在所研究的金属组分中最为有效.进一步采用共合成法制备了一系列FexVy-HMS催化剂.采用粉末X射线衍射、N2物理吸附、透射电子显微镜、NH3程序升温脱附、H2程序升温还原等手段对催化剂的结构和性质进行表征,结果表明,HMS仍保持介孔结构,Fe的加入在催化剂中产生了新的酸性位和更强的氧化还原性.在苯羟基化反应中,钒物种是反应活性物种,铁物种起助剂作用,其中Fe0.04V0.06-HMS具有最高的催化活性,苯酚收率由不含Fe的Fe0.00V0.06-HMS的13.1%提高到18.1%.提出了Fe、V参与反应过程的可能机理.     

高钙高铁煤灰熔融及黏温特性研究

以金鸡滩煤为原料,沙子为添加剂,研究不同比例添加剂下高钙高铁煤灰熔融及黏温特性变化;通过XRD、高温热台显微镜与扫描电镜-能谱等分析方法研究矿物质转变对其灰熔融及黏温特性影响。结果表明,煤灰熔点随添加剂量的增加先降低后升高,辉石类低温共熔物生成是其降低的主要原因;原煤熔渣黏度波动与钙铝黄长石生成有关,而含铁矿物质析出导致其黏度迅速增加;添加沙子后,煤灰熔渣临界温度显著下降,熔渣由结晶渣向玻璃渣转变。原煤熔渣中Fe、Ca元素分布不均匀,添加沙子后均匀程度明显改善,与黏温曲线测试结果吻合。实验结果表明,沙子是改善高钙高铁煤黏温特性的一种有效添加剂。     

"True" iron(V) and iron(VI) porphyrins: a first theoretical exploration

We present here a first theoretical characterization of iron(V) (S = (3)/(2)) and iron(VI) (S = 0) porphyrin intermediates. The Fe(V) calculations exhibit exceptionally narrow convergence radii and we believe that for this reason they have long eluded researchers working on high-valent iron intermediates. The Fe(V)-N(nitrido) bond distance in the DFT(PW91/TZP) optimized geometry of Fe(V)(P)(N) is 1.722 A, comparable to and slightly longer than the Fe(IV)-O bond distance of 1.684 A in Fe(IV)(P)(O) and the Fe(IV)-N(imido) bond distance of 1.698 A in Fe(IV)(P)(NH). In contrast, the Fe(VI)-N(nitrido) bond distances in [Fe(VI)(P)(N)](+) (S = 0) and Fe(VI)(P)(N)(F) (S = 0) are dramatically shorter, 1.508 and 1.533 A, respectively, consistent with the formal triple bond character of the Fe(VI)-N(nitrido) bond. The nitrido ligand appears to be uniquely capable of stabilizing a "true" Fe(V) center, in the sense defined in the paper. All three unpaired electrons in Fe(V)(P)(N) are completely localized on the Fe(V)-N(nitrido) axis, with the Fe and N gross atomic spin populations being 1.579 and 1.550, respectively. In contrast, an axial ligand set consisting of an oxide and a fluoride do not stabilize an Fe(V) ground state but favor an electronic structure best described as an Fe(IV)-oxo porphyrin pi-cation radical.     

Synthesis and analytical properties of 3,4-dihydroxybenzaldehyde guanylhydrazone (3,4-DBGH)

Synthesis and analytical properties of 3,4-dihydroxy-benzaldehyde guanylhydrazone are described. The reagent was tested with 43 cations but only Co(II), Fe(II), Fe(III), Mo(VI), W(VI) and V(V) gave colored complexes. Spectral characteristics of the reagent are presented. Procedure for a selective a determination of Co(II), a sensitive determination of Fe(III) and determination of Mo(VI), W(VI) and V(V) in presence of large amounts of Fe(III) are reported. The method was applied for the determination (a) of Co(II) in presence of other cations at excess (b) of Fe(III) in a city drinking water sample without preconcentration and (c) of Mo(VI) in a standard steel sample.     

Reversed-phase ion-pair high performance liquid chromatographic determination of Co(III)-, Ni(II)-, V(V)- and Fe(III)-2-(2-benzothiazolylazo)-5-(3-sulforpropyl)aminophenol chelates

The separation and determination of Co(III), Ni(II), V(V) and Fe(III) chelates with 2-(2-benzothiazolylazo)-5-(3-sulfopropyl)aminophenol (BTASPAP) by reversed-phase ion-pair HPLC was investigated. In the presence of the oxidant potassium iodate, BTASPAP reacts with Co(III), Ni(II), V(V) and Fe(III) to form stable, negatively charged, water-soluble chelates. The chelates were separated on a C(18) siloxane bonded phase and eluted within 7 min with acetonitrile-acetate-water (36:1:63 v/v) containing 0.2 mol 1(-1) acetic acid-sodium acetate buffer (pH 3.0) and 1.0 mmol 1(-1) tetrabutylammonium bromide. The detection limits of Co(III), Ni(II), V(V) and Fe(III) at 565 nm are 0.3, 0.8, 0.3 and 1.0 ng (signal-to-noise ratio = 2), respectively. The method was applied to the determination of Co, Ni, V and Fe in four samples of standard alloys.