浅析降低电石生产能耗的影响因素

讨论石灰原料、碳素原料以及炉料配比和操作对电石生产的影响。     

Rapid and Sensitive Determination of Timosaponin AIII in Rat Plasma by LC-MS/MS and Its Pharmacokinetic Application

A rapid sensitive and selective liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for determination of timosaponin AIII (TA-III) in rat plasma, using ginsenoside Re as an internal standard (IS). TA-III and the IS were detected in MRM mode with a negative ionization electrospray mass spectrometer. The calibration curves were linear over the concentration ranges from 11.14 to 1114 ng/mL and the lower limit of quantification (LLOQ) was 11.14 ng/mL. Intra-day and inter-day precisions (RSD) were within 10%, and accuracy ranged from 6.4% to 9.1%. The extraction recovery at three concentrations ranged from 92.3% to 95.5%. The validated method was successfully applied to monitor the concentrations of TA-III in rat plasma after intragastric administration. The best fit pharmacokinetic model to estimate the pharmacokinetic parameters was a single compartment model with weight of 1/x² for oral administration groups of rats for TA-III.     

硫酸钙和氯化钾复分解制取硫酸钾

介绍在氨水存在条件下,用KCI和CaSO4制取K2SO4的方法。实验表明,优化的制备条件是:硫酸钙的粒度为180目以上,氨水初始浓度为36％～40％,反应温度为0～10℃,时间90～120 min,并分步加入KCl,经过一段法和二段法制得纯度91％和99.8％的硫酸钾。     

Kinetic Study of Metal-Catalyzed Reaction of Solid Calcium Oxide with Gas Mixtures of Methane and Water Vapor to Form Hydrogen

With noble metal catalysts (Pd, Pt, Rh, Ir) present, hydrogen is formed by the interaction of solid calcium oxide with gas mixtures of methane and water vapor, according to CaO + CH₄ + 2H₂O CaCO₃ + 4H₂. Among the metals, Ir and Rh are so active that the reaction takes place at temperatures as low as 600 K. Rate data obtained with these metals show a nearly first order with respect to CH₄ pressure, while a negative order with respect to H₂O vapor pressure. The apparent activation energies are 171 and 217 kJ/mol for the Ir- and Rh-catalyzed reactions, respectively. On the other hand, Ni does not catalyze the reaction below 733 K, probably due to its strong interaction with H₂O vapor.     

Conversion of Oak to Cellular Silicon Carbide Ceramic by Gas-Phase Reaction with Silicon Monoxide

Oak has been converted to a porous biocarbon template by annealing in an inert atmosphere above 800°C. Subsequent infiltration with gaseous SiO at 1550–1600°C under flowing argon of atmospheric pressure finally resulted in the formation of a porous, cellular β-SiC ceramic. The conversion retains the biomorphic cellular morphology of oak tissue. While pores in the cell walls with a diameter less than ∼1 μm vanished, two distinct pore channel maxima representing tracheidal cells and large vessels remained in the SiC ceramic. Depending on the cellular morphology of different kinds of wood, e.g., strut thickness and pore size distribution, gas-phase conversion to single-phase β-SiC can be used to manufacture cellular ceramics with a wide range of pore channel diameters.     

丙烯酸与透明质酸共聚制备耐盐性凝胶

将丙烯酸与透明质酸钠盐共聚制备了新型聚丙烯酸凝胶,对凝胶性质进行了测定。当丙烯酸添加量为6 mL、交联剂与单体摩尔比为0.015、透明质酸添加量为0.18 g时,凝胶有最好耐盐性及凝胶强度,在0.9%质量分数NaCl溶液中这种接枝共聚物的吸水率为122.695 g/g,在磷酸缓冲液中的吸水率为90.298 g/g;同时凝胶的机械强度也有了明显的改善,达到401.485kPa。添加透明质酸后所得凝胶有更好的耐盐性且透明度好,适于应用于眼科材料。     

Investigations of the reduction of NO to N2 by reaction with Fe

The paper presents the results of the investigation of nitric oxide reduction by its reaction with metallic iron, within the temperature range of 750-1200 °C. Experiments were carried out in a one-dimensional tubular flow reactor externally heated in an electrical furnace. The spherical and cylindrical iron samples of well-defined and fixed surface area were placed in the center of the reactor. Mixtures NO/N₂, NO/O₂/N₂, NO/CO₂/N₂ of different molar compounds fractions were continuously fed into the reactor. The surfaces and cross-sections of partly oxidized iron samples were observed using a scanning microscope. The rate of nitric oxide reduction in the first stage of iron oxidization was measured. The obtained values lie between those presented in the literature and measured in the fluidized bed reactor and thermogravimetrically. A very strong influence of oxygen but a very weak one of carbon dioxide on the efficiency of NO reduction was observed within the investigated range of temperature.     

Gas-phase oxydehydrogenation of ethylbenzene with nitrobenzene by hydrogen transfer catalyzed reaction to produce styrene and aniline

Gas-phase catalytic hydrogen transfer reaction between ethylbenzene and nitrobenzene, to produce styrene and aniline, has been carried out at 360–460°C on amorphous AlPO₄, SiO₂, Al₂O₃, and on a natural sepiolite, as well as on the corresponding 20 wt% supported nickel catalysts. The influence of Cu as a second metal was also studied. Reactions were also carried out without nitrobenzene, under nonoxidative conditions. Catalytic activity under oxidative conditions was always comparatively higher than in nonoxidative conditions. In both cases, styrene yield and selectivity values obtained with support materials directly used as catalysts were better than those obtained with the corresponding Ni or Ni–Cu supported metal catalysts, with the only exception of SiO₂. The best results were obtained when amorphous AlPO₄ was used as the catalyst. The catalytic activity obtained in both oxidative and nonoxidative conditions, was closely associated to acid–base properties of the catalysts studied. Furthermore, a very similar linear correlation between A and E _a known as “compensation effect” was obtained and a common dehydrogenation mechanism was considered for oxidative and nonoxidative conditions. However, without considering the catalyst, nitrobenzene plays an important role as hydrogen acceptor, not only shifting the ethylbenzene dehydrogenation equilibrium but also avoiding secondary reactions by lowering the level of available hydrogen, especially when supported metals are being used as catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

WO3催化H2O2氧化环己醇合成己二酸

以WO3为催化剂,H2O2氧化环己醇合成己二酸。探讨了催化剂用量、H2O2用量、反应温度和时间等条件对反应的影响。优化条件：n（环己醇）∶n（H2O2）∶n（WO3）=100∶600∶4、反应温度100℃、反应时间6h。己二酸分离收率达67.6%,纯度99.8%;催化剂重复使用5次后,己二酸收率仍可达60.2%。     

A novel non-phosgene approach to the synthesis of methyl N-phenyl carbamate by a reaction of methanol with phenylurea

A novel non-phosgene process for the synthesis of methyl N-phenyl carbamate (MPC) by a reaction of phenylurea with methanol was studied. The reaction between phenylurea and methanol was found to be a spontaneous reaction that took place in the absence of catalyst and gave MPC as the main product. Addition of a catalyst markedly influenced the reaction behavior. A basic catalyst greatly enhanced the yield of MPC, whereas an acidic catalyst promoted the formation of aniline and methyl carbamate. Moderate strength of basicity showed the best catalytic performance in the cases studied. The mechanism of reaction and catalyst functioning was discussed.     

Functional Ionic Liquids Catalyzed the Esterification of Ricinoleic Acid with Methanol to Prepare Biodiesel: Optimization by Response Surface Methodology

An efficient route to preparing biodiesel by the esterification of ricinoleic acid (RA) with methanol was investigated in the work. Six kinds of functional ionic liquids (IL) were selected as catalysts. The effects of reaction variables (reaction time, temperature, IL load, and the ratio of reaction substrates) were also evaluated and optimized using response surface methodology (RSM). Among IL tested, 1‐butylsulfonic‐3‐methylimidazolium trifluoromethanesulfonate showed the highest catalytic efficiency for the esterification. Reaction variables were optimized using RSM as follows: IL load 4 % (relative to the weight of RA), molar ratio of methanol to RA 9.2:1, 67 °C, and 28 min. Under the optimized conditions, the esterification degree of RA was 92.3 ± 1.7 %.     

Surface organometallic chemistry on metals in water: Chemical modification of platinum catalyst surface by reaction with hydrosoluble organotin complexes: application to the selective dehydrogenation of isobutane to isobutene

Surface organo-metallic chemistry on metals can be a new route to generate supported bimetallic catalysts. According to previous works on Pt–Sn catalysts, the reaction of tetra n-butyl-tin on the reduced platinum surface leads to well-defined bimetallic catalysts which are very active and selective in the dehydrogenation of isobutane into isobutene. The presence of tin not only isolates the surface platinum atoms from each other (EXAFS) and thus prevents a fast deactivation by decreasing the processes of C–C bond cleavage but also favors the regeneration processes under air. So far the catalyst preparations were carried out either in the gas phase or in organic solution (e.g. heptane). However, in order to meet the industrial criteria of process simplicity, there is a need to carry out such catalyst preparation in water.

In this work, Pt–Sn/Al₂O₃ and Pt–Sn/SiO₂ catalysts was prepared by reacting tris n-butyl-tin hydroxide on the platinum surface, in water solution under atmospheric pressure of hydrogen. The kinetics of the reaction was followed by measuring the amount of butane evolved as a function of time. The solids obtained were characterized by CO, O₂ or H₂ chemisorption and electron microscopy (CTEM and EDAX). Clearly, the (n-Bu)₃Sn(OH) reacts selectively on the platinum surface and not with the support, with evolution of butane, leading to a bimetallic catalyst where the platinum atoms are isolated from each other by the tin atoms. Very high selectivities (>95%) and activities were obtained for the reaction of isobutane dehydrogenation into isobutene and it was concluded that surface organo-metallic chemistry on metal in water can be an alternative route to prepare well-defined supported bimetallic Pt–Sn catalysts.     

Solid-state reactivity of iron molybdate artificially contaminated by antimony ions and its relation with catalytic activity in the selective oxidation of isobutene to methacrolein

Catalysts were prepared by impregnation of Fe₂(MoO₄)₃ with different quantities of antimony butoxide. BET surface area measurement, XRD, Mössbauer spectroscopy, CTEM-AEM, XPS and ISS were used to characterize phase and surface architectures and their changes after calcination and catalytic reaction. Before calcination, antimony was present as pure oxide or hydroxide, partly as particles and partly as an incomplete monolayer on the surface of Fe₂(MoO₄)₃. After calcination at 400°C, antimony got detached from the Fe₂(MoO₄)₃ surface and aggregated very intensively, partly as Sb₂O₄ and partly, through reaction with the iron molybdate, as a mixture of distorted FeSbO₄ and MoO₃. After reaction or calcination at 500°C, more distorted FeSbO₄ and MoO₃ are formed, separated from Fe₂(MoO₄)₃. Selective oxidation of isobutene to methacrolein was carried out on the calcined material. Impregnated catalysts show considerably improved catalytic performances compared to the pure Fe₂(MoO₄)₃ phase or mechanical mixtures of it with α-Sb₂O₄. The catalytic performances are explained by several catalytic cooperations via spillover oxygen. These cooperative effects involve all the oxide phases present in the material having worked as catalyst: Fe₂(MoO₄)₃ (pure or possibly contaminated by small amounts of antimony oxide), FeSbO₄, MoO₃ and Sb_yO_x.

     

Analysis of process parameters on the characteristics of liposomes prepared by ethanol injection with a view to process scale-up: Effect of temperature and batch volume

Liposomes have been extensively used as carriers of several compounds, due to their structural versatility in terms of size, composition, surface charge, lamellarity, and facility to incorporate hydrophilic and hydrophobic substances. Among the methodologies for liposomes production, the ethanol injection technique is probably the most suitable for implementation at industrial scale, mainly due to its simplicity. The effects of the aqueous phase temperature and preparation volume on the characteristics of liposomes produced by this technique were evaluated, seeking to attain criteria for its implementation in large scale. The aqueous phase temperature significantly affects the final characteristics of liposomes obtained by this methodology. By varying this parameter, it is possible to control size distribution and polydispersity of the lipid vesicles. Subsequently, process scale-up was carried out using a 10-fold scale ratio. The adapted power per unit of volume (P/V) scale-up criterion showed to be appropriate to reproduce in larger scale the final characteristics of liposomes produced in smaller scale. The results demonstrate that using the ethanol injection technique, it is possible to obtain a relatively narrow distribution of small unilamellar vesicles, appropriately modulating the experimental conditions. Therefore, the preparation of vesicles with the desired diameter and size distribution was essentially fulfilled.     

Brazing of SiO2-BN modified with in situ synthesized CNTs to Ti6Al4V alloy by TiZrNiCu brazing alloy

Brazing SiO₂-BN ceramic to Ti6Al4V is often associated with the problem of brittle continuous phases and high residual stress at the reaction layer of SiO₂-BN, inducing low joining strength. To overcome these problems, SiO₂-BN ceramic modified with in situ synthesized carbon nanotubes (CNTs) were joined to Ti6Al4V by TiZrNiCu alloy. Results show that CNTs can improve the wettability of TiZrNiCu on SiO₂-BN rapidly, and break the continuous reaction layer of SiO₂-BN into fine sizes. Residual stress can also be reduced by low CTE of CNTs and fine size phases among reaction layer. The shear strength of SiO₂-BN/Ti6Al4V joints with CNTs modified is 35.3?MPa at 970?°C for 10?min, which is 3 times higher than that of the joints without CNTs modified.     

Molecular evolution of a defined DNA sequence with accumulation of mutations in a single round by a dual approach to random chemical mutagenesis (DuARCheM)

Directed evolution has paved the way to a new era of protein and nucleic acid molecules with improved and enhanced properties. The utmost important component of directed evolution is random mutations in a defined DNA sequence. The utility of random chemical mutagenesis in directed evolution studies is dwindling due to the inherent flaws with whole-organism mutagenesis and the in vitro approach. Here, we report a novel Dual Approach to Random Chemical Mutagenesis (DuARCheM) to introduce random mutations in a defined DNA fragment. DuARCheM involves in vivo chemical mutagenesis and in vitro genetic manipulations. The resulting library revealed an accumulation of mutations in its members. These results imply that the parent mutation is carried in the further generations within the same library. This method might help to change random chemical mutagenesis because the combination of in vivo and in vitro approaches mimics the amplification and mutation that is performed by PCR-based mutagenesis, and at the same time the mutations are confined to the desired gene. Moreover, the mutagen pressure is greater in chemical mutagenesis than in a Taq-polymerase-based error-prone system. Concomitant amplification and mutation in the DuARCheM method leads to a better spectrum of mutants because the plasmid construct is exponentially amplified in the presence of mutagen pressure, unlike in the in vitro chemical mutagenesis system in which the template molecule does not replicate. This work is able to nullify all the disadvantages that are associated with random chemical mutagenesis, and could make random chemical mutagenesis an indispensable tool in directed evolution studies.     

The conversion of methane to ethylene and ethane with near total selectivity by low temperature (< 610 ° C) oxydehydrogenation over a calcium-nickel-potassium oxide catalyst

The catalytic oxidative coupling of methane to C₂, C₃ and C₄ paraffins and olefins has been accomplished with close to 100% selectivity at methane conversions of about 10% per pass. Essentially no carbon oxides are formed and the mechanism appears to be a surface catalyzed reaction. Temperatures of < 600 ° C are used and the presence of steam is important. The catalyst comprises a ternary mixture of calcium, nickel and potassium oxides. Method of preparation and composition of the catalyst are critical for its performance. Presence of a carbidic carbon on the catalyst surface may be important.     

New thermoplastic vulcanizate,composed of polypropylene and ethylene–vinyl acetate copolymer crosslinked by tetrapropoxysilane: evolution of the blend morphology with respect to the crosslinking reaction conversion

A thermoplastic vulcanizate (TPV) is tailored by a dynamic vulcanization process. TPVs can be processed as thermoplastics and have properties similar to conventional vulcanized rubbers. The main objective of our recent works was to tailor, by using the reactive extrusion process, a new TPV composed of polypropylene homopolymer (PP) as thermoplastic phase and ethylene–vinyl acetate copolymer (EVA) as elastomer phase, which is crosslinked by tetrapropoxysilane (TPOS) as crosslinking agent in the presence of dibutyl tin oxide (DBTO) as catalyst. Crosslinking is carried out through a transesterification reaction between the ester groups of EVA and the alkoxysilane groups of TPOS. This exchange reaction is catalyzed by DBTO at temperatures above 100 °C. The main advantage of this chemistry that it is non‐radical, and so prevent the degradation of PP, in comparison with crosslinking reactions using peroxides as initiators. Different reactive blends were prepared in the internal mixer of a Haake Plasticorder. In order to know how the crosslinking reaction has advanced, the EVA gel content and the volume swelling rate of the blend were measured. The aim of this study was to get a better understanding of the dispersion mechanism of EVA in the major phase during its dynamic vulcanization in the presence of PP in the minor phase. This paper deals with the correlation that exists between the evolution of the two‐phase blend morphology and the extent of the crosslinking reaction on the elastomer phase during the elaboration of a TPV. In particular, we showed that the correlation was almost the same for the elaboration of the TPV in the internal mixer of the Haake Plasticorder (discontinuous process) and in a twin‐screw extruder (continuous process). Copyright © 2004 Society of Chemical Industry