环己酮肟液相重排反应机理及动力学研究

研究了环己酮肟重排反应生成己内酰胺的机理及反应动力学方程。在建立用分光光度法测定环己酮肟浓度方法的基础上,实验研究了反应温度为20~45℃范围内的液相重排反应动力学。提出了此反应的化学反应动力学速率方程式: -r肟= k0exp (-E/RT)Ca肟Cb硫酸,其中环己酮肟反应级数a为2,硫酸反应级数b为1,活化能为-E/R = -19.86 kJmol-1, 频率因子k0为1.35×1027。通过实验研究证实了作为催化剂的硫酸参与重排反应的机理,认为重排反应过程中游离SO3不参与反应,仅作为水的吸收剂,此结论对环己酮肟液相重排反应的生产技术改造提供了有力依据,并在生产中得到了应用。     

B2O3/TiO2-ZrO2催化剂上环己酮肟的气相Beckmann重排反应

用共沉淀法制备了TiO2-ZrO2复合氧化物载体，BET，DTA，XRD表征结果表明，该复合载体具有较大的比表面和较好的热稳定性，对于环己酮肟气相Beckmann重排反应制己内酰胺，用复合载体制备的B2O3／TiO2-ZrO2催化剂，比分别以TiO2,ZrO2为载体所制备的B2O3/TiO2和B2O3／ZrO2催化剂具有更高的活性和选择性，实验表明，催化剂表面中等强度的酸位是环己酮肟气相Beckmann重排反应的有效活性中心。     

II. Yeast sequencing reports. Sequence of a segment of yeast chromosome II shows two novel genes,one almost entirely hydrophobic and the other extremely asparagine-serine rich

A 3·2 kb EcoRI fragment of yeast Saccharomyces cerevisiae was entirely sequenced. Two new open reading frames were identified. The first is extremely hydrophobic, and would likely be an integral membrane protein. It has significant similarity to only one reported gene, a gene of unknown function from Drosophila melanogaster. The second ORF is asparagine-rich and very serine-rich, with a remarkable stretch of nearly 26 consecutive asparagine residues comprised of the same codon. It has no significant similarity to any reported gene. The fragment maps to chromosome II on the left arm between the CDC27 and ILS1 loci. The nucleotide sequence reported in this paper has been deposited in the GenBank database with the Accession Number M89908.     

Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry     

The Structure of the Irreversibly Bound Adhesion Promoter-Substrate Interfacial Layer of γ-Aminopropylsilanetriol on Crystalline Si, as Measured by XPS and FTIR

The irreversibly bound interfacial layer deposited by the γ-aminopropysilanetriol adhesion promoter onto a crystalline silicon substrate, which remains even after profuse washing, was found by XPS to have resulted from the fragmentation and rearrangement of the original γ-aminopropylsilanetriol molecule. A mechanism is proposed, involving the homolytic scission of the terminal N-C bond. One of the subsequent reactions is believed to involve hydrogen loss by abstraction and the formation of a terminal vinyl group, which bonds to the substrate. Support for this mechanism is found in IR spectroscopy of this layer.     

Dehydration of aldoximes on rare earth exchanged (La<Superscript>3+</Superscript>, Ce<Superscript>3+</Superscript>, RE<Superscript>3+</Superscript>, Sm<Superscript>3+</Superscript>) Na–Y zeolites: A facile route for the synthesis of nitriles

Rare earth exchanged Na–Y zeolites, H-mordenite, K-10 montmorillonite clay and amorphous silica-alumina were effectively employed for the continuous synthesis of nitriles. Dehydration of benzaldoxime and 4-methoxybenzaldoxime were carried out on these catalysts at 473 K. Benzonitrile (dehydration product) was obtained in near quantitative yield with benzaldoxime whereas; 4-methoxybenzaldoxime produces both Beckmann rearrangement (4-methoxyphenylformamide) as well as dehydration products (4-methoxy benzonitrile) in quantitative yields. The production of benzonitrile was near quantitative under heterogeneous reaction conditions. The optimal protocol allows nitriles to be synthesized in good yields through the dehydration of aldoximes. Time on stream (TOS) studies show decline in the activity of the catalysts due to neutralization of acid sites by the basic reactant and product molecules and water formed during the dehydration of aldoximes.     

Kinetics of and catalyst decay accompanying the gas phase rearrangement of cyclohexanone-oxime over a hy ultrastable zeolite

The kinetics of the rearrangement of cyclohexanone-oxime has been studied in a fixed bed, glass tubular reactor at atmospheric pressure and temperatures of 240, 270, 300 and 335°C, using ultrastable HY zeolite catalyst. Several kinetic models, including the Langmuir-Hinshelwood type, have been derived and the best statistical fit has been obtained with a pseudo-first order kinetic equation. The rate constants and activation energies for the formation of the products caprolactam, cyclohexanone and 5-cyanopent-l-ene have been calculated. Based on the evolution of the selectivity with temperature, and the I.R. spectra of the poisoned catalyst, different decay models have been deduced and discussed.     

己内酰胺生产的绿色化

己内酰胺生产的绿色化关键是环己酮肟贝克曼重排工艺路线替代的开发。重点介绍了代替浓硫酸催化该反应的固体酸催化剂、催化剂的失活与再生、反应器工业化的方法的进展。提出采用多相催化剂取代发烟硫酸使环己酮肟转化为己内酰胺的工艺 ,该催化剂具有转化率和选择性高 ,易处理再生 ,且可用于连续化工业生产     

Heat Induced Structure Modifications in Polymer‐Layered Silicate Nanocomposites

Summary: The success of the use of layered silicates in polymer nanocomposites, to improve physical and chemical properties is strictly related to a deeper knowledge of the mechanistic aspects on which the final features are grounded. This work shows the temperature induced structural rearrangements of nanocomposites based on poly[ethylene‐co‐(vinyl acetate)] (EVA) intercalated‐organomodified clay (at 3–30 wt.‐% silicate addition) which occur in the range between 75 and 350 °C. In situ high temperature X‐ray diffraction (HT‐XRD) studies have been performed under both nitrogen and air to monitor the modifications of the nanocomposite structure at increasing temperatures under inert/oxidative atmosphere. Heating between 75 and 225 °C, under nitrogen or air, causes the layered silicate to migrate towards the nanocomposite surface and to increase its interlayer distance. The degradation of both the clay organomodifier and the VA units of the EVA polymer seems to play a key role in driving the evolution of the silicate phase in the low temperature range. The structural modifications of the nanocomposites in the high temperature range (250–350 °C), depended on the atmosphere, either inert or oxidizing, in which the samples were heated. Heating under nitrogen led to deintercalation and thus a decrease of the silicate interlayer space, whereas exfoliation was the main process under air leading to an increase of the silicate interlayer space.

Heat induced structural modification of EVA‐clay nanocomposite under nitrogen and air.     

基于注意力和卷积特征重排的图像修复

近年来,基于UNet与GAN（生成对抗网络）的深度学习网络模型在图像修复领域展现出了独特的优势,但是修复结果中仍然存在伪影、模糊、纹理细节退化、对于大面积破损难以修复、修复后的孔洞与背景图像不相容等现象。为了解决现有模型对大面积破损图像修复不友好以及修复后的图像存在退化现象等问题,通过对现有方法进行研究,改进了Shift-UNet（移位网络）模型：在UNet与GAN的基础上,在每一层编码器和解码器之间增加了改进之后的注意力机制Attention-UNet并融入shift-UNet,形成Attention-Shift-UNet;并且通过研究,将原来下采样部分的激活函数由Leaky_ReLU改为了SiLU函数。改进模型不仅在64×64的中心遮罩上取得了较好的效果,还实现了随机遮罩,遮罩面积由20%增加到80%。通过实验结果证明,该模型的修复效果更优,特别是针对大面积破损图像的修复。在CelebA、ParisArchitecture以及Paris Streetview数据集上经过测试,各评价指标都有明显的提高,其中结构相似性（SSIM）由原来的0.944 5提高到0.947 1,峰值信噪比（PSNR）由原来的27.992 7提高到28.553 6,L2损失由原来的0.001 7降低到0.001 5。