5,7-二羟基黄烷酮的流动氢化仪法合成

针对常规氢化反应釜合成匹诺塞林的合成工艺中容易发生过度还原生成副产物、不易控制反应的进程、重现性差、副产物难纯化分离等问题,为提高匹诺塞林合成收率,利用H-Cube TM流动氢化仪具有连续流动可实时监测从而实现高选择性、反应条件容易优化的特点,以5,7-二羟基黄酮为原料,四氢呋喃为溶剂,还原氢化得到5,7-二羟基黄烷酮.考察了反应液流速、温度、压力对反应收率的影响.结果表明,当反应温度为100℃,压力为2 000kPa,反应液流速为0.5mL/min时,5,7-二羟基黄烷酮的合成收率最高,达到96%,纯度为98.5%.影响黄烷酮合成收率因素顺序为温度>流速>压力.化合物的结构经过熔点、质谱分析法、氢-核磁共振确定,纯度经过液相色谱确证.该方法具有安全、易控制、操作简便、后处理简单等优点,更适合工业化生产.

连续流动氢化法合成新型双环醇类似物

以双环醇为原料,经酯化、叠氮化、还原和成盐反应合成了一个新型的双环醇类似物——5'-(氨基甲基)-7,7'-二甲氧基-4,4'-二苯并[d][1,3]二氧杂环-5-甲酸甲酯,总收率78%,其结构经1H NMR,13C NMR和MS表征。以连续流动氢化法替代传统还原法可以有效避免副反应的发生,收率由10%提高至95%。

The Induction Period of Hydrate Formation in a Flow System

The appearance of turbidity due to large numbers of critical size hydrate nuclei may significantly affect the outgoing light intensity and the flow resistance in the pipe loop. The induction period of hydrate formation was determined by analyzing the experimental data——either based on the shading ratio data of laser detector or based on the pressure drop data of the flow system. The induction period of CC12F2 (R12) in pure water and that of CH4 in (tetrahydrofuran ＋ water) systems were then measured with the above two methods. Experimental data show that the induction period depends on the driving force exponentially. Flow rate also has a significant influence on the hydrate nucleation. A new induction period model taking the driving force and liquid flow rate into account was proposed. And it is successfully applied to the calculation of the induction period, which is in good agreement with the experimental data obtained in this study.

Periodic Packing Mode for Trickle-Bed Reactors: Experiments and Modeling

A periodic packing mode of trickle-bed reactor (TBR) for the gas limited reaction was proposed. Hy-drogenation of 2-ethylanthraquinone over Pd/Al2O3 in a laboratory-scale TBR was taken as a test reaction for determining whether the periodic packing mode is advantageous. The effects of operating conditions and packing type on TBR performance were experimentally examined to demonstrate the cause-effect relationships. A mathe-matic model of TBR considering axial dispersion and fractional wetting was developed to quantitatively illuminate the reason of performance enhancement.

Contents of Selenium （Ⅳ） in Rice Samples after Oxidizing Acid Digestion

Se （Ⅳ） contents in rice samples after oxidizing acid digestion were investigated by flow injection-hydride generation atomic absorption spectrometric method （FI-HG-AAS）. The optimization was performed with varying the formation of gaseous hydrides and the specific pieces of instrumentation. The results of FI-HG-AAS showed good linear calibration curve at the working concentration between 0.10 and 2.00 μg/L （R^2〉0.999）. For 7 replicate determinations of 0.75 μg/L selenium standard solution spiked in deionized water, the precision and accuracy were 2.33% and 86.63%, respectively. The detection limit （3σ/S, n=7） was 0.01 lag/L. Oxidizing acid digestions of rice samples were carried out at the ratio of 5：3 between nitric acid and perchloric acid. This method was succeeded to determine Se （Ⅳ） in acid digestion of rice samples without pre-reduction step with hydrochloric acid and heating.

Continuous Flow Reactor for Hydroxylation of Benzene to Phenol by Hydrogen Peroxide

The direct hydroxylation of benzene to phenol catalyzed by activated carbon-supported Fe （Fe/AC） in acetonitrile using H2O2 as the oxidant was studied in a continuous flow reactor. Results showed that the continuous operation could obtain high phenol yield of 28.1%, coupled with the turnover frequency of 3 h^-1, and high selectivity of 98% under mild condition. The catalyst was characterized by N2 adsorption/desorption, Boehm titration, X-ray photoelectron spectra, and Fourier transform infrared spectroscopy. It was observed that iron may interact with the carboxyl group forming iron-carboxylate like species, which act as the active phase. The apparent activation energy obtained by fitting an Arrhenius model to the experimental data was 13.4 kJ/mol. The reaction order was calculated to be about i, 0.2 for benzene and 0.7 for H202.

Hydrodynamic regime as a major control on localization of uranium mineralization in sedimentary basins

Uranium deposits in sedimentary basins can be formed at various depths,from near surface to the basement.While many factors may have played a role in controlling the location of mineralization,examination of various examples in the world,coupled with numerical modeling of fluid flow,indicates that the hydrodynamic regime of a basin may have exerted a major control on the localization of uranium deposits.If a basin is strongly overpressured,due to rapid sedimentation,abundance of low-permeability sediments or generation of hydrocarbons,fluid flow is dominantly upward and uranium mineralization is likely limited at shallow depths.If a basin is moderately overpressured,upward moving fluids carrying reducing agents may meet downward moving,oxidizing,uranium-bearing fluids in the middle of the basin,forming uranium deposits at moderate depths.If a basin is weakly or not overpressured,either due to slow sedimentation or dominance of high-permeability lithologies,minor topographic disturbance or density variation may drive oxidizing fluids to the bottom of the basin,leaching uranium either from the basin or the basement,forming unconformity-type uranium deposits.It is therefore important to analyze the hydrodynamic regime of a basin in order to predict the most likely type and location of uranium deposits in the basin.