Catalytic desulfurization of a model sulfur-containing compound benzothiophene (BT) through partial oxidation in supercritical water (SCW) was investigated in a bomb reactor at 623-723K and 30-40MPa over sulfided CoMo/-Al2O3. Vacuum residuum was used to confirm the desulfurization rate and efficiency, and the desulfurization mechanism of vacuum residuum was determined by the pyrolysis temperature (TR) of the vacuum residuum (VR). For T>TR, obvious reduction of sulfides up to 67% was obtained. The thermodynamic equilibrium of in situ H2 generation was a controlling factor of the desulfurization pathway.

The wet ammonia desulfurization process can be retrofitted for combined removal of SO2 and NO from the flue gases by adding soluble cobalt(Ⅱ) salt into the aqueous ammonia solution. Activated carbon is used to catalyze the reduction of hexamminecobalt(Ⅲ) to hexamminecobalt(Ⅱ) to maintain the capability of removing NO of the hexamminecobalt solution. The effects of temperature, pH, activated carbon particle size, and superficial liquid flow velocity on hexamminecobalt(Ⅲ) conversion have been investigated. An apparent activation energy is obtained. According to the experimental results, the catalytic reduction reaction rate increases with temperature. The batch reactor experiments show that the best pH range lies in between 3.5 and 6.5. In a fixed-bed reactor, superficial liquid flow velocity obviously affects the reaction and a high yield of cobalt(Ⅱ) is obtained at a pH value lower than 9.0. The experiments manifest that the hexamminecobalt solution coupled with catalytic regeneration of hexamminecobalt(Ⅱ) can maintain a high nitric oxide removal efficiency during a period of time.

The effect ofpartial internal wetting ofcatalyst pellets on apparent reaction kinetics at elevated temperatures and pressures is investigated experimentally and by modeling for benzene hydrogenation. A new method that combines adsorption and chemical reaction is introduced to study the kinetics influenced by capillary condensation ofreagents at steady-state conditions. It is shown that the extent ofliquid filling in the pellet interior has a critical effect on the global kinetics, and the current state of the catalyst depends on the history. Under certain conditions two steady states ofthe effectiveness factor exist. Moreover, either a decrease in temperature or increase in total pressure can increase the effectiveness factor. The model exhibits good agreement with experimental results.

Gas phase propylene epoxidation on gold catalysts has attracted wide attention from industry and academia due to its high selectivity. However, it suffers from low propylene conversion and rapid catalyst deactivation. Experiments showed that propylene conversion could be increased by raising H2, O2, or C3H6 concentration in the feed, but the feed compositions were within the explosion limit. It was also shown that the activity of the used catalyst could be fully recovered, but the regeneration temperature was 280℃, much higher than that for reaction. Therefore a microchannel reactor was devised to suppress explosion and was constructed with Fecralloy, to raise the temperature rapidly for catalyst regeneration by electric heating. In two minutes the temperature of the reactor could be raised from 50 to 300℃. Catalysts were coated on the alloy belt by dip coating, and the performance of the reactor was evaluated under different operating conditions. Results showed that in the microreactor the overall reaction rate was controlled mainly by the intrinsic reaction rate, and also influenced by film diffusion to a certain extent. The deactivated catalyst was regenerated in the microchannel reactor and the activity was fully recovered.

Five models for fishbone-type carbon nanofibers (f-CNFs) have been proposed and their geometries have been optimized through molecular dynamics and molecular mechanics simulations. The angle between graphene layers and fiber axis can take the values 9.71, 19.60, 30.03, 41.99, and 56.43, which agree satisfactorily with the experimentally determined values. With reduction of the angle, the interlayer spacing of graphene sheets increases from 0.3376nm to 0.3392nm accordingly, due to the strain of the graphitic cones. In addition, X-ray diffraction (XRD) simulations are also implemented. With the high-resolution transmission electron microscopy (HRTEM) results taken into account, the XRDsimulations verify that f-CNFs can adopt not only a regular arrangement but also a turbostratic way, and our models are good approximations for describing the bulk microstructures of f-CNFs.

The impact of some engineering aspects such as space velocity, catalyst metal loading, hydrogen, and temperature on carbon nanotube (CNT) production rate, productivity, and morphology in carbon monoxide disproportionation has been studied. The morphology and quality of the CNTs produced were examined by high resolution transmission electron microscopy (TEM). It was found that space velocity and metal loading have significant effects on the production rate and CNT productivity. The presence of H2 dramatically increased the productivity, but altered the CNT structure. The synthesis temperature also influenced the carbon productivity and structure. The results were interpreted according to the traditional model for CNT growth, and the implications for large-scale CNT production were suggested.

Understanding the mechanism of liquid-phase evaporation in a three-phase fixed-bed reactor is of practical importance, because the reaction heat is usually 7-10 times the vaporization heat of the liquid components. Evaporation, especially the liquid dryout, can largely influence the reactor performance and even safety. To predict the vanishing condition of the liquid phase, Raoult's law was applied as a preliminary approach, with the liquid vanishing temperature defined based on a liquid flow rate of zero. While providing correct trends, Raoult's law exhibits some limitation in explaining the temperature profile in the reactor. To comprehensively understand the whole process of liquid evaporation, a set of experiments on inlet temperature, catalyst activity, liquid flow rate, gas flow rate, and operation pressure were carried out. A liquid-region length-predicting equation is suggested based on these experiments and the principle of heat balance.

用过渡态及Kirkwood介电模型考察近临界水中醋酸甲酯（MeAc）水解动力学3实验结果表明。临界溶剂化作用使本体系在623K附近出现反应活化体积（△V≠）极负值现象，同时反应表观活化能降低至（23.5±8.29）kg/mol利用lnka与反应场的线性关系可修正压力因素对水解动力学的影响。并证实了近临界水介质中MeAc水解SN2反应机理的可靠性。

Electrosynthesis of glyoxylic acidby electroreduction of oxalic acidhas long been well known. However, attempts to commercialize the process have encountered problems due to rapid deactivation of the cathode. The cathode activity can be continuously restored by adding small amounts of chemical activators to the catholyte. In this paper the structural e5ect of chemical activator on electrode reaction is studied. The results show that (1) It is the cation of the chemical activator, but not the anion that a5ects the current e6ciency and the reaction selectivity. (2) The more symmetrical the cation, or the shorter the longest alkyl chain, the higher the current e6ciency and the reaction selectivity become. (3) Mechanism of the activation is discussed. Adsorption of the cations of the activator on the cathode surface protects the electrode. (4) Quantitative characterization of the activator molecule is given using some topological indices, with which the activation ability can be predicted, and screening of the proper activator is made possible.

超（近）临界水作为优良的有机反应溶剂适合于针对酸碱催化类型有机反应绿色工艺的开发。（本课题以具备工业生产背景的醋酸甲酯水解作为研究体系，在一管式反应器中#将原料5%质量分数置于体系的超。近（临）界条件下（523～673K，23～32MPa）进行反应操作实验结果表明，在无外加酸性催化剂情况下，水解反应以接近1的选择性，150～300s内达到热力学平衡限制同时在系统临界点附近#溶剂化作用对反应动力学影响显著。根据SN2反应机理对反应动力学方程进行了回归。