气流床煤气化炉内流动、混合与反应过程的研究进展

气流床气化过程涉及高温高压下湍流多相流动与复杂化学反应过程的相互作用,涵盖喷嘴雾化与弥散、复杂多相射流流动、炉内湍流混合、复杂气化反应、火焰结构及温度分布等诸多方面,是世界各国研究的热点.对近年来世界各国在气流床气化过程研究上取得的进展进行了综述,包括喷嘴雾化与颗粒弥散机理与雾化过程的影响因素、撞击流驻点偏移规律和撞击面振荡规律、撞击火焰结构与炉内三维温度场、典型煤种气化反应特性与石油焦气化特性以及气流床气化过程模拟.对气流床气化过程未来的研究重点进行了展望.     

Preparation and certification of a reference material for the determination of nutrients in seawater

There is an urgent need for natural water reference materials certified for nutrients. In 1996, NRC collected seawater for a proposed CRM at a depth of 200 m in the North Atlantic; this was immediately filtered through 0.05-m cartridge filters into 50-L carboys. The water was later homogenized in the NRC laboratories in Ottawa and stabilized via gamma irradiation. Over six years of stability testing no significant deterioration was detected. In addition to the usual customary standard colorimetric procedures, alternative analytical methods were developed to enable the certification process. The production of a CRM called MOOS-1 will be discussed. Certified values, with uncertainty components addressing the homogeneity, stability, and characterization of the material, were calculated to be: orthophosphate=1.56±0.07 µmol L^–1, silicate=26.0±1.0 µmol L^–1, nitrite=3.06±0.15 µmol L^–1, and nitrite and nitrate=23.7±0.9 µmol L^–1.     

Generalized criterion of solvent polarity as a tool for control of chromatographic process

The generalized (reductive) criterion of solvent polarity was obtained by the method of multiparametric optimization of the Snyder index P", Hildebrand parameter _T , permittivity _r , and solvatochromism parameter E _T (30). Possibilities of employing this criterion for estimation of the elution power of normal and reversed mobile phases used in high-performance liquid chromatography were considered.     

Investigating metal-organic framework as a new pseudo-capacitive material for supercapacitors

A new application of metal organic framework （MOF） as a pseudo-capacitive material for supercapacitors is investigated. To this end, a simple nickel-based MOF, formulated Ni3（btc）2.12H2O, is synthesized via a hydrothermal reaction. As an electro-active material, such nickel-based MOF exhibits superior pseudo- capacitive behavior in KOH aqueous electrolyte with a high specific capacitance of 726 F g-1. Also, it displays good electrochemical stability with 94.6% of the initial capacitance over consecutive 1000 cycles. In addition, a simple asymmetric supercapacitor with a high energy density of 16.5 Wh kg-1 is successfully built using the nickel-based MOF as positive electrode and commercial activated carbon as negative electrode in KOH electrolyte.     

Regression models with process variables and parallel blocks of raw material measurements

The topic of this paper is regression models based on designed experiments, where additional spectroscopic measurements are also available. This particular case describes a situation with two spectral blocks with no natural order: The blocks are parallel. Three methods are described, which combine least squares regression of the design variables with PCA or PLS on the spectra. The methods properties are explored in two simulation studies based on real experiments. The results show that the methods are equal when it comes to prediction, but interpretability varies. One of the methods, LS‐ParPLS, is especially interesting when it comes to interpretability because it splits the spectral information into two parts; information that is common in both blocks and information that is unique for each block. Copyright © 2008 John Wiley & Sons, Ltd.     

Selenium in electrolytic manganese as a reference material for the quality control of aluminium melts

Electrolytic manganese is an important alloying element for aluminium and steel melts. It is mainly added to melts of aluminium in the holding furnace as tablets or minitablets (compressed compacts of manganese and aluminium powders). Selenium derivates are usually added during the production of electrolytic manganese, so some selenium is present in the alloys produced when electrolytic manganese is added to the aluminium furnace. Since the selenium contents of many alloys are of concern from health and environmental perspectives, their values should be provided. In this work, a laboratory reference material (LRM) based on electrolytic manganese was produced to assure our routine quality control method, where selenium is analysed by hydride generation followed by optical emission spectrometry with inductively coupled plasma (HG–ICP–OES). Therefore, the present paper describes in detail the preparation procedure for and the results from homogeneity and stability studies performed on electrolytic manganese LRM. For this purpose, a commercial electrolytic manganese lot was selected and the main factors involved in the preparation of the material (pretreatment step, homogenization, bottling and storage) were carefully studied and established in order to guarantee the long-term stability of the LRM. The results obtained showed that the LRM developed was a fit-for-purpose material for the quality control of the routine analysis of selenium.     

好氧颗粒污泥中凝胶型聚多糖的特性研究进展

凝胶型聚多糖(PS)是好氧颗粒污泥(AGS)中重要的结构性物质,具有稳定性强、可生化性低、交联度高等特点。鉴于AGS技术广阔的应用前景与"多糖机制"的最新突破,本文首先介绍了主要胞外聚合物(EPS)的含量范围与空间分布,重点综述了以颗粒体多糖(Granulan)与类海藻酸(ALE)为代表的凝胶型PS的化学组成、可能来源与结构性功能,并指出有针对性地开展分子动力学研究与微生物基因测序是该领域研究的发展方向。     

Preparation and analysis of a reference material for the measurement of oxygen in copper

The preparation and analysis of the oxygen mass fraction of three pure copper reference materials (BAM-379/1, BAM-379/2, BAM-379/3) intended for the calibration of spark emission spectrometry are described here. Data of homogeneity testing and round robin certification in collaboration with 12 independent laboratories from metalworking industry and research are reported. Problems with the establishment of traceability in this special case are discussed. Received: 20 July 2001 Accepted: 13 October 2001     

Structure and electronic properties for a newly synthesized red fluorescent material

The ground-state structure and electronic properties of a newly synthesized red fluorescent material, 2-[3-(2-{4-[(2-hydroxy-ethyl)-methyl-amino]-phenyl}-vinyl)-5, 5-dimethyl-cyclohex-2-enylidene]-malononitrile (A31), are investigated using a hybrid density-functional theory (DFT) approach, B3LYP, and the 6-31G* basis set. We have obtained four geometrical isomers. The theoretical infrared (IR) spectrum calculated by B3LYP/6-31G* level of theory is in very good agreement with our experimental measurement. The cation and anion are optimized to clarify the effects of the hole and electron injections and the energies needed by injections are estimated.     

构建一维铜基配位聚合物作为锂离子电池正极材料

合成了一种新型的一维(1D)羰基配位聚合物[Cu(BGPD)(DMA)(H₂O)]·DMA(记为Cu-BD,H₂BGPD=N,N''-双(甘氨酰)均苯四甲酸二酰亚胺,DMA=二甲基乙酰胺),并考察了其用作锂离子电池正极材料的电化学性能。电化学测试结果表明,Cu-BD正极在50 mA·g^-1的电流密度下循环100圈后仍然保留50 mAh·g^-1的比容量,具有较好的循环稳定性。Cu-BD电极反应机理研究表明,BGPD配体和Cu(II)离子在充放电过程中都可能参与了电子转移过程。     

Rapid one-step derivatization of Se(VI) to a piazselenol for the spectrofluorimetric determination of selenium in biological material

A spectrofluorimetric method for the determination of total selenium in biological samples has been developed. After oxidative destruction, the sample is reacted with a mixture of bromide and 2,3-diamino-1,4-dibromonaphthalene (Br₂-DAN) without pH adjustment. Selenium(VI) is rapidly reduced by bromide to Se(IV) which then forms 4,7-dibromo-5,6-benzopiazselenol (Br₂-DAN-Se). The conversion of Se(VI) to Br₂-DAN-Se is completed in 6 min at 100°C. The piazselenol is extracted to cyclohexane and the fluorescence measured at 577 nm with excitation at 518 nm. The procedure has been validated by determinations on reference materials with selenium concentrations ranging from 4 to 1460 ng g⁻¹. The advantages of the method are the fast reduction of Se(VI) by hydrobromic acid and the properties of Br₂-DAN, which permit the piazselenol formation to be carried out in a strongly acidic medium and at high temperature. The limit of detection is 0.6 ng g⁻¹ as estimated by three times the standard deviation of the blank determination (n = 7).

The rate of reduction of Se(VI) to Se(IV) in hydrobromic acid was investigated as a function of concentration and temperature. The new kinetic data together with previous kinetic and equilibrium data for the piazselenol formation were used to model and optimize the simultaneous reduction-derivatization procedure.     

Preparation and photocatalytic activity of TiO2-coated granular activated carbon composites by a molecular adsorption-deposition method

TiO₂ nanoparticle-coated granular activated carbon (GAC) composite photocatalysts (CPs) were successfully prepared by a molecular adsorption-deposition (MAD) method. The CPs were detected by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), BET surface area and UV-Vis adsorption spectroscopy, and their photoactivity was evaluated by methyl orange (MO) photodegradation. The results show that small-sized TiO₂ nanoparticles were dispersed well, deposited on the surface of GAC, and showed slight blue shift in comparison with pure TiO₂. With the increase in TiO₂ content, the CPs showed band gaps in lower energy, smaller surface areas and the higher content of Ti³⁺ ions. Compared with pure TiO₂ and others CPs samples, CPs-382 sample showed the highest photoactivity due to the optimum TiO₂ content and surface area besides the synergic effect of photocatalytic degradation of TiO₂ and adsorptive property of GAC. In addition, the CPs could be very easily reclaimed, recycled and reused for methyl orange removal while high photoactivity is preserved. Supported by the Natural Science Foundation of Hunan Province (Grant No. 06JJ50150), the Scientific Research Fund of Science and Technology Department of Hunan Province (Grant No. 2007GK3060) and Jishou University (Grant No. JSDXKYZZ200648)     

Preparation and homogeneity study of a mussel candidate reference material for certification of organotin compounds

Organotin compounds are currently determined in various environmental matrices (in particular water, sediment and shellfish) to form the basis of control measures for the levels of contamination, as required in some EC Directives. Accurate measurements are a prerequisite for the enforcement of this legislation, which implies that good quality control of determinations should be ensured. One of the tools for achieving accuracy is to use certified reference materials (CRMs). With regard to tin species, however, CRMs are rather scarce and mainly concern sediment and fish matrices certified for their butyltin content. The present study deals with the preparation of a mussel candidate reference material and the verification of its homogeneity prior to the certification of the contents of butyl- and phenyl-tin compounds. 100kg of mussels (Mytilus edulis) were collected, carefully washed with fresh water in order to eliminate matrix salts and immediately frozen by immersion in liquid nitrogen. The mussels were shelled (in the frozen state) and the edible part was stored in thermally sealed polyethylene bags which were stored at –25 °C. The frozen material was ground in a Teflon-coated grinding mill, spread on sterilized flat trays and freeze-dried. The freeze-dried material was then ground for 15 days in a zirconia ball mill and sieved on a titanium sieve to separate the fibrous part. Successively, the material was mixed for 15 days under argon atmosphere in a special polyethylene-lined mixing drum and bottled in brown Pyrex-glass bottles. 21 bottles were selected during the course of the bottling procedure to verify the within- and between-bottle homogeneity of the overall batch. The within-bottle homogeneity was verified by determining the organotin (butyl- and phenyltins) content for subsamples of 500 mg in ten replicates from one bottle, whereas the between-bottle homogeneity was controlled by one organotin measurement from each of 20 bottles. The analyses were performed by GC-MS. The results showed that the homogeneity of the material makes it suitable as a candidate reference material.     

Mixing device for polymer blends of very different molecular weights using a mixing nozzle process

A new method of blending two polymers with very different molecular weights, i.e. different melt viscosities, in which the polymer mixture is forced to pass through a nozzle with a conical taper is proposed in this study. High density polyethylenes with very high and very low molecular weights were used as the samples in the blending process, and the parameters that affected the homogeneity of the blended polymers were studied. The homogeneity was found to be better at a lower shear rate, smaller orifice diameter, higher compression ratio of the cross-sectional area of the nozzle entrance and orifice, and a small length-to-diameter ratio of the orifice. This blending process, the nozzle blend, was found to make the droplets of a high molecular weight component extend to thin fibers along the conical section of the nozzle. The nozzle blend system has been proved to be useful in obtaining both macroscopic and microscopic homogeneity, and has been estimated to be comparable to a few minutes of roll-mill blending.     

A novel oligothiophene derivative as a hole‐transport with emitting material for OLED

A novel oligothiophene derivative containing the triphenylamine moiety with high glass transition temperature (T_g; 135 °C), 5,5′‐{bis[4‐di(4‐thiophenyl)amino]phenyl}‐2,2′‐bithiophene (TTPA‐dimer) was synthesized by the dimerization of tris[4‐(2‐thienyl)phenyl]amine (TTPA) with a palladium catalysis. Some types of electroluminescent (EL) devices that use the amorphous material for a hole‐ and an electron‐transporting with an emitting layer were fabricated. These devices emitted a bright green‐yellowish light (λ_emi; around 510 nm) with a small full width at half maximum (FWHM) rather than that of Alq₃. The single layer EL device showed a maximum luminance of 221 cd/m² at 8 V (0.06 lm/W at 100 cd/m²). On the other hand, the double layer (TTPA‐dimer/Alq₃) EL device that used Alq₃ as the electron transport material was increased up to 10830 cd/m² at 12 V (0.89 lm/W at 300 cd/m²) and with a lower turn‐on voltage (3.2 V at 0.1 cd/m²) than other types of EL devices. Copyright © 2003 John Wiley & Sons, Ltd.     

Comparison of three sequential extraction procedures to describe metal fractionation in anaerobic granular sludges

In the last few decades, several sequential extraction procedures have been developed to quantify the chemical status of metals in the solid phase. In this study, three extraction techniques (modified [A. Tessier, P.G.C. Campbell, M. Bisson, Anal. Chem. 51 (1979) 844]; [R.C. Stover, L.E. Sommers, D.J. Silvera, J. Water Pollut. Con. F. 48 (1976) 2165]; and the Bureau Communautaire de Reference (BCR) [K.F. Mossop, C.M. Davidson, Anal. Chim. Acta 478 (2003) 111]) were applied to study the distribution of trace (Co, Ni, Zn and Cu) and major (Mn and Fe) elements in two different anaerobic granular sludges from full-scale methanogenic wastewater treatment plants. The Stover scheme displayed a higher number of fractions that induces a poor recovery compared to the other schemes. The sequential extraction scheme recommended by BCR and the modified Tessier scheme gave similar trends and are sufficiently repeatable and reproducible for application in fractionation studies. However, the BCR scheme seems to be of limited utilisation to study anaerobic matrixes because the extraction stage for its reducible fraction may release substantial amounts of trace elements bound to the organic/sulfides fraction, and consequently, the recovery of trace elements in the oxide fraction may be overestimated at the expense of the oxidisable fraction. As a final conclusion, the modified Tessier scheme seems to be the most suitable scheme to study the metal partitioning in anaerobic granular sludges.     

炉前煤低温干馏工艺中的挥发分除尘

为了寻求优化的炉前煤低温干馏工艺中的挥发分除尘方案,在使用400目金属滤网对间歇式粉煤固体热载体热解装置挥发分除尘研究的基础上,将颗粒床过滤器用于该过程的除尘研究。热态除尘实验表明,颗粒床的使用有效地降低了滤网的过滤负荷。选用2mm石英砂和φ5mm×2mm瓷环作为滤料,通过对比实验发现,两种滤料除尘效率均在90％以上;随着过滤操作的进行,由于颗粒床内粉尘的沉积使其过滤效率有所提高,而对气、液收率的影响很小。结果表明,颗粒床与滤网结合可作为粉煤炉前低温干馏工艺中可供选择的挥发分除尘方案。     

加替沙星纯度标准物质研制

研制加替沙星纯度标准物质。采用质量平衡法和氢谱定量核磁法对加替沙星纯度标准物质候选物进行纯度定值,采用卡尔费休法和热重分析法准确测量了影响主成分纯度的水分含量,并考察了水分含量的稳定性。开展了加替沙星纯度定值、均匀性检验、稳定性考察以及不确定度评估。结果表明,加替沙星纯度标准物质的纯度值为93.1%,扩展不确定度为0.6%(k=2),水分含量为6.6%,特性量值均匀性良好,6个月稳定性可靠,被认定为国家二级标准物质,编号为GBW(E) 100476。研制的加替沙星纯度标准物质填补了国内空白,同时也为吸湿性较强的药物纯度标准物质研制过程中水分测定提供了参考与借鉴。     

Production of a calibrant certified reference material for determination of the estrogenic mycotoxin zearalenone

Several previous interlaboratory studies in the field of mycotoxin analysis have revealed considerable problems, apparent as high between-laboratory standard deviations, or rather non-comparable and non-traceable results. A major reason is lack of proper calibrants for external calibration. Public awareness of substances that mimic or interfere with the activity of natural hormones (endocrine disrupters) has led to increased interest in mycotoxins with estrogenic potential, e.g. zearalenone (ZON). During a large-scale standard measurement and testing (SMT) project of the European Commission (EC) dealing with the preparation and certification of reference materials for determination of the mycotoxin ZON in maize, a ZON calibrant in acetonitrile was prepared and intensively checked for purity, homogeneity, and stability. Preparation of the material, study of its homogeneity and stability, and characterisation of the calibrant on the basis of its preparation, with discussion of the results obtained, are described in this paper. The certified value of 9.95 µg mL^–1 for ZON in acetonitrile and its corresponding expanded uncertainty of ±0.30 µg mL^–1 were calculated in compliance with the Guide to the Expression of Uncertainty in Measurement (GUM).