Critical evaluation of coupling particle size distribution with the shrinking core model

The shrinking core model (SCM) is widely used to model fluid-solid reactions such as the leaching of metals from minerals. In most cases, however, the particle size distribution (PSD) of the solid material was disregarded. In this paper the erroneous shift in the control regime when neglecting PSD was quantified and the dependence of the shift on the coefficients of variation (CV) and the type of PSD was analysed. By coupling the SCM with a Gamma PSD, it was found that neglecting the PSD would shift the control regime from chemical reaction to inert/ash layer diffusion, when the CV was between 0.7 and 1.2. For a system controlled by liquid film diffusion, neglect of the PSD, would shift the control regime to chemical reaction when CV is between 0.3 and 0.7 or to inert/ash layer diffusion when CV is greater (0.9-1.5). It was therefore postulated that some researchers had unknowingly made invalid conclusions about the control regime due to the neglect of PSD. However, an inert/ash layer diffusion-controlled process was insensitive to the neglect of PSD. When CV<0.3, neglect of the PSD would not cause any erroneous shifts, irrespective of the control regime. Experimental data confirmed the observation. For a given CV, the deviation in the fraction reacted from the mono-PSD increases with CV and decreases with time. The maximum deviation, which occurs at the beginning, is about 10% with a gamma PSD of CV=0.3. The percent deviation is dependent of the type of PSDs. Gamma PSD gives the lowest deviation while Gaudin-Schuhmann results in the largest deviation (maxi. ∼19%, with CV=0.3) in the first half of dissolution process. Log-normal distribution gives a larger deviation than gamma but quickly approaches the latter with time. The deviation for Rosin-Rammler is between log-normal and Gaudin-Schuhmann. For systems with CV less than 0.3, the SCM can be fairly used without considering PSD. When CV is greater than 0.3, particularly in the early stage of a dissolution process with a PSD other than gamma, PSD should be included to avoid substantial errors.     

纳米SiO2粉体的制备与研究

纳米SiO2粉体的制备是以硅酸钠和盐酸为原料，添加适宜的稳定剂(非离子表面活性剂)和分散剂，在适宜的pH值和温度下，采用化学沉淀法合成。研究表明，要得到性能优良纳米的SiO2粉体，最佳工艺条件为：温度20～40℃，pH=6，反应液质量浓度P1=20g／L，P2=1．20g／L，反应时间15min。结果表明：制备的纳米SiO2粒径30～50nm，比表面积大，分散性好，质量优良，可达到产业化的生产。     

棉籽油间歇式酯交换反应动力学的研究

生物柴油(棉籽油甲酯)可以由棉籽油与甲醇在催化剂KOH存在下通过酯交换反应制得。故对棉籽油间歇式酯交换反应动力学进行了研究,并考察了反应温度和催化剂浓度对产物棉籽油甲酯浓度的影响。用液相色谱法分析棉籽油的组成;用气相色谱法分析产物中棉籽油甲酯的含量。由实验数据绘制的动力学曲线得到酯交换反应在开始阶段为准二级反应,以后紧接转为一级反应和零级反应,与文献报导的棕榈油酯交换反应动力学结果一致。由实验数据求出酯交换反应在开始阶段的动力学参数,35℃、45℃时的反应速率常数分别为0.9179Lmol-1min-1和1.049Lmol-1min-1,酯交换反应的活化能为10.88kJmol-1。根据实验结果得到棉籽油酯交换反应的最佳反应温度为45℃,最佳催化剂为1.1%KOH。     

Photoelectric conversion of photosynthetic reaction center in multilayered films fabricated by layer-by-layer assembly

Multilayered protein films which contained ordered layers of photosynthetic reaction center (RC) from Rhodobacter Sphaeroides (RS601) were assembled by means of alternate electrostatic adsorption with positively charged poly(diallyldimethylammonium chloride) (PDDA). The assembly of RC was monitored by spectrometry and photocurrent measurement. Linear film growth was observed up to about 20 cycles of adsorption. For the monolayer film, the photocurrent was about 8.5 nA cm⁻². For the multilayered film, the total photocurrent was about 77 nA cm⁻² for the 24-layer RC film, while the average photocurrent increment per adsorption cycle was about 3.2 nA cm⁻². The overall light-to-electricity conversion efficiency for a 24-layer film was about eight times higher than that for the monolayer one. The effects of electrode potential and pH on the photocurrent were also measured to illustrate the light-to-electric converting mechanism.     

Reactive compatibilization of PE/PS blends. Effect of copolymer chain length on interfacial adhesion and mechanical behavior

This paper deals with in situ compatibilization of PE/PS blends via Friedel-Crafts reaction, performed at the interphase. Two polyethylenes having different molecular weights, and the same PS, were used along a wide range of catalyst concentration. The influence of the graft copolymer architecture and content on the efficiency of blend compatibilization was studied. The emulsifying effect, morphological aspects and mechanical behavior were also assessed for these blends. The amount of copolymer formed increases with catalyst concentration and the short chain length fraction of the homopolymers. The high molecular weight (MW) copolymers behaved as better compatibilizers as they showed, at the cmc, greater graft copolymer concentration than the low MW ones. A substantial increase in interfacial adhesion and particle size reduction was observed, even at catalyst concentrations as low as 0.3 wt%. In correspondence, mechanical properties, like ductility and yield strength, were enhanced by the effect of this Friedel-Crafts reaction's compatibilization.     

抗氧剂3114合成反应热力学和动力学的研究

研究了常温溶剂法合成抗氧剂3114反应热力学和动力学过程。控制温度在117±2℃,研究结果表明,反应是零级反应,反应速率常数k=1.91×10-3/min,反应的平衡常数K=138.4(mol/L)-6,反应活化能Ea=1366.2J/mol。     

Correlation of reactivity and electrical resistivity of coke

A correlation between the reactivity and electrical resistivity of a series of cokes was determined using cokes prepared from blends of medium- and high-volatile coals. After correcting for the ash yield of the coke and the density of the resistivity specimen, a statistically significant relation between reactivity and resistivity was established. As the resistivity test requires much less time to perform than the reactivity test, it can be considered as an alternative approach to reactivity testing currently performed for quality control purposes.     

Nanocrystalline CeO2 in SBA-15: Performance of Pt/CeO2/SBA-15 Catalyst for Water-gas-shift Reaction

CeO₂ particles confined within the pores of an SBA-15 mesoporous silica host were prepared by incipient wetness impregnation (IMP) and deposition precipitation (DP) methods. The materials were characterized by XRD, N₂-adsorption and temperature programmed reduction (TPR) to evaluate the structure, texture, and redox properties. The preparation procedure had significant impact on the assembling mode of CeO₂ inside the SBA-15 mesopores. A high dispersion of CeO₂ particles was achieved via DP, whereas the dispersion of CeO₂ prepared by IMP was found to be inhomogeneous and CeO₂ partially blocked the pores. The CO conversion in the water-gas-shift reaction was enhanced over 1 wt% Pt supported on CeO₂-modified SBA-15 obtained by DP.     

Studies on fluorinated polyurethanes by X-ray diffraction and density functional theory calculations with periodic boundary conditions

Thin-film wide-angle X-ray diffraction, small-angle X-ray scattering, and density functional theory calculations using B3LYP hybrid functional with the two-dimensional periodic boundary conditions (2D-PBC) have been applied to study the crystal structures of parent and fluorinated polyurethanes. The crystal structures from 2D-PBC-B3LYP calculation and experiments showed the hard-segment chains within crystallites adopted an extended-chain conformation for polyurethanes. Energetically, the parent polyurethane preferred an alternating hydrogen-bonded sheet structure while the fluorinated one adopted a progressive hydrogen-bonded sheet structure.     

水合肼生产中氧化反应的研究和应用

分析了尿素法生产水合肼的氧化反应历程及影响因素，改进了反应器，并找到了最佳的工艺控制条件：①控制n(尿素)：n(次氯酸钠)=(1．05～1．10)：1，各原料的消耗较低，总经济效益佳；②采用-5℃冷冻盐水移走尿素、次氯酸钠混合段内氯化反应放出的热量，控制物料混合终点温度在15～30℃；③采用列管式加热器，将氯化反应与水解反应在不同的设备中进行，水合肼的收率提高到83％～85％；④采用列管式加热器代替双夹套反应器，提高了加热强度，生产能力大，1套合成反应器可生产1万t／a80％的水合肼。