预硫化加氢催化剂钝化技术研究进展

钝化是预硫化加氢催化剂的关键处理过程。预硫化催化剂经过钝化处理后,有效抑制了自热性质和硫的脱离,便于催化剂的存储和运输,并保持催化剂的活性,有利于器外预硫化催化剂的大规模生产。介绍了气相、液相和固相3种钝化方式、钝化机理及其应用和研究进展。     

煤基石脑油加氢研究

采用三段加氢工艺对煤基石脑油进行了加氢处理,重点研究了反应温度、压力、空速对一段加氢效果的影响,并对该段催化剂的使用寿命进行了考查,初步探讨了三段加氢反应温度对加氢性能的影响。研究结果表明经过三段加氢后的产品溴值小于1.0 g Br/100 g,总硫小于0.5μg/g,可用于汽油调和组分、芳烃抽提或环保溶剂油。     

Effects of partial hydrogenation, epoxidation, and hydroxylation on the fuel properties of fatty acid methyl esters

The properties of biodiesel depend on the chemical structure of individual fatty acid methyl esters (FAME). In this work the chemical structure of fatty acid chains was modified by catalytic hydrogenation, epoxidation and hydroxylation under controlled conditions. Hydrolysis of ester functionality or oxidation of fatty acid chain was not observed during these reactions. The properties of hydrogenated FAME strongly depend on the hydrogenation time. The total saturated fatty acid (SFA) percentage increased from 29.3% to 76.2% after 2 h of hydrogenation. This hydrogenated FAME showed higher oxidation stability and higher cetane number but poor cold flow properties. Formation of trans FAME was observed during hydrogenation. Both hydroxylation and epoxidation resulted in a decrease of unsaturated fatty acid methyl ester (UFA) fraction. The percentages of total unsaturated FAME decreased 39% in the epoxidation reaction and 44% in the hydroxylation reaction. The addition of hydroxyl groups to the unsaturated regions of the fatty acid chain yields biodiesel with better cold flow properties, increased lubricity and slightly increased oxidative stability. However, epoxy FAME shows some interesting properties such as higher oxidation stability, higher cetane number and acceptable cold flow properties, which met the limits of ASTM D6751 biodiesel specifications.     

Aromatics saturation by sulfided Nickel---Molybdenum hydrotreating catalysts

The effect of H₂S on the rates of toluene hydrogenation of sulfided Mo, Ni, Ni---Mo and Ni---Mo---P/alumina catalysts has been determined at 6 MPa, 350°C over a large range of H₂S partial pressure. In those conditions, Ni/alumina is nearly inactive. For the three other catalysts, similar trends are found with in particular no effect of H₂S at high partial pressure. In the presence of NH₃, the effect of H₂S remains globally the same.     

Characteristics of carbon dioxide hydrogenation in a fluidized bed reactor

Characteristics of CO₂ hydrogenation were investigated in a fluidized bed reactor (0.052 m IDxl.5 m in height). Coprecipitated Fe-Cu-K-Al catalyst (d_ρ=75–90 Μm) was used as a fluidized solid phase. It was found that the CO₂ conversion decreases but the CO selectivity increases, whereas the space-time-yield attains maximum values with increasing gas velocity. The CO₂ conversion has increased, but CO selectivity has decreased with increasing hydrogenation temperature, pressure or H₂/CO₂ ratio in the fluidized bed reactor. Also, the CO, conversion and olefin selectivity appeared to be higher in the fluidized bed reactor than those of the fixed bed reactor. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University     

Simulation of gas exothermic chemical reaction in porous media reactor with lattice Boltzmann method

Exothermic reactor is the main part in a chemical heat pump. It involves complex multi-component exothermal chemical reaction in catalyst-filled porous media. The lattice Boltzmann method (LBM) is developed to simulate the characteristics of fluid flow, heat and mass transfer coupling chemical reaction in the exothermic reactor of the isopropanol/acetone/hydrogen chemical heat pump system. Fractal theory is used to structure a porous medium model in the reactor. The simulation results show that LBM is suitable for the simulation and the conversion has an optimal value with different inlet velocities.     

负载型Pd/SBA—15催化剂催化性能研究

将负载型催化剂Pd/SBA—15用于催化邻氯硝基苯加氢。考察了反应温度、催化剂用量对Pd/SBA—15催化性能的影响,并考察了催化剂的使用寿命。实验结果表明,Pd/SBA—15催化剂表现出很好的催化性能,有望应用于工业生产。     

器外预硫化加氢催化剂放热研究

将氧化态NiMo/Al2O3加氢催化剂器外预硫化,然后使用TA-MS、HPDSC、XRD进行表征,以考察催化剂在惰性气体下的放热行为及组分相应的变化.结果表明,硫化剂与催化剂中的活性组分在惰性气体氛围加热的条件下结合成有机金属氧硫化物,适当提高加热温度能显著提高器外预硫化催化剂的活性和持硫率.但温度过高,有机金属氧硫化物分解,催化剂的活性降低.有机金属氧硫化物的生成是器外预硫化效果的关键,本实验制备的器外预硫化催化剂具有良好的活性.     

Electrochemically hydrogenated TiO2 nanotubes with improved photoelectrochemical water splitting performance

One-dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as photoanode for photoelectrochemical (PEC) water splitting. In this work, we report a facile and eco-friendly electrochemical hydrogenation method to modify the electronic and PEC properties of ATO nanotube films. The hydrogenated ATO (ATO-H) electrodes present a significantly improved photocurrent of 0.65 mA/cm² in comparison with that of pristine ATO nanotubes (0.29 mA/cm²) recorded under air mass 1.5 global illumination. The incident photon-to-current efficiency measurement suggests that the enhanced photocurrent of ATO-H nanotubes is mainly ascribed to the improved photoactivity in the UV region. We propose that the electrochemical hydrogenation induced surface oxygen vacancies contribute to the substantially enhanced electrical conductivity and photoactivity.     

The selective hydrogenation of butyne-1,4-diol by supported palladiums: a comparative study on slurry, fixed bed, and monolith downflow bubble column reactors

The present study was carried out to asses performance of a Pd-monolith downflow bubble column (DBC) reactor, and compare it with that of the slurry and the fixed bed DBC. The selective hydrogenation of butyne-1,4-diol to cis-2-butene-1,4-diol over palladium catalyst was chosen as a model reaction. In principle, the monolith DBC allowed the reaction to take place under kinetic control regime. Comparison with DBC employing 5% Pd/C powder and 1% Pd-on-Raschig ring catalysts revealed a better performance of the monolith DBC (1% Pd loading) with advantage of smaller reaction volume and intensified reaction rate. In the monolith DBC, improved hydrogen transport was possible, as the interface between bubbles and the channel wall was very thin, thus, the length of the diffusion path was very short. In addition, the interfacial surface area at both gas–liquid and liquid–solid interface in the monolith was also very high. The reaction kinetics was well represented by the Langmuir–Hinshelwood mechanism. As an alternative to conventional three-phase reactors, the monolith DBC was simple due to its inherent characteristic operation and no specially designed device.