Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

Grain Growth Behavior of 5Cr21Mn9Ni4N Steel Micro-Alloyed by Rare Earth

Grain growth behavior of 5Cr21Mn9Ni4NRE steel was experimentally studied at various solid solution treatment temperatures and holding for different times. The experimental results show that the 5Cr21Mn9Ni4NRE steel has the feature of sharp austenite grain coarsening after solid solution treatment at the temperature above 1150 ℃. RE added in the steel has the benefit to restrain grain growth and increase grain growth activation energy.     

不饱和烃硅氢加成催化剂固载化研究进展

综述了各类负载过渡金属的催化剂体系及其在不饱和烃硅氢加成反应中的应用。负载过渡金属的催化剂具有良好的可回收性和选择性，研究主要集中在开发价廉、使用安全、环境友好和高催化性能的活性炭、氧化物或有机聚合物等负载过渡金属催化剂，并取得很好的结果。     

Ni catalyst promotion of a Cis-selective Pd catalyst for canola oil hydrogenation

A Ni catalyst was added to a cis-selective Pd catalyst in an attempt to further improve the Pd catalyst's cis-selectivity and activity for canola oil hydrogenation. The system was tested under reaction conditions known to be suitable for cis-selective hydrogenation with the Pd catalyst (50 ppm Pd, 70 °C, and 5.2 MPa). Although inactive on its own under these conditions, the addition of 100 ppm Ni increased the hydrogenation activity (from 2.12 to 2.49 10⁻² min⁻¹). Further addition of Ni up to 1000 ppm resulted in no further improvements in activity. The trans isomer contents of the oils hydrogenated with Pd and the Pd/Ni systems were similar. The level of conjugated dienes decreased rapidly during hydrogenation with both Pd alone and with the Pd/Ni combination and no changes in conjugation were detected in the presence of the Ni catalyst alone. The increased activity of the Pd/Ni system over Pd alone was attributed to adsorption of catalyst poisons from the oil by Ni.     

粘土矿物用于乙烯聚合催化剂的研究 Ⅰ.以凹凸棒石粘土为载体的乙烯聚合催化剂

研究了以凹凸棒石粘土为载体,负载TiCl4制备的乙烯聚合催化剂的结构、性能及制备规律。结果表明,催化剂中Ti的负载量随焙烧温度的提高而逐渐降低,聚合活性随焙烧温度的提高呈上升趋势,但过高的焙烧温度也会导致粘土晶体结构的彻底破坏而不利于活化粘土活性的提高;通过采用烷基铝等有机金属化合物处理粘土同样可以极大地改善粘土性质,提高催化活性。不同助催化剂对以凹凸棒石粘土为载体的催化剂的聚合性能有较大影响。     

HAT-095催化剂运行末期的优化探索

通过优化工艺条件,严控进料质量、改造循环氢压缩机油系统、调整二甲苯塔操作等措施,使催化剂在运行末期,也能发挥出良好的催化性能,并延长催化剂使用寿命;提高了催化剂处理C10芳烃的能力,降低重芳烃产率,提高经济效益。为催化剂运行末期操作和正常操作提供有益的探索。     

Exit effect on hydrodynamics of the internal circulating fluidized bed riser

This is the first time an extensive investigation has been carried out regarding the effects of riser exit geometry on pressure drop and solid behaviour inside the Internal Circulating Fluidized Bed (ICFB) riser, using different riser exit geometries at several operating conditions.The Radioactive Particle-Tracking (RPT) technique was used for solid concentration measurements and solid residence time distribution at the exit zone. Experiments were conducted using Geldart B particles, in the gas superficial velocity range of 4 to 10 m/s. Axial solid hold-up, solid residence time distribution in the exit zone, and the reflux ratio factor k_m, (defined earlier by [E.H. Van der Meer, R.B. Thorpe, J.F. Davidson, Flow patterns in the square cross-section riser of a circulating fluidized bed and the effect of riser exit design, Chem. Eng. Sc. 55 (19) (2000) 4079-4099]), were the main criteria used to investigate the impact of gas-solid separator devices implemented at the ICFB riser exit.Solid residence time distribution results and axial solid hold-up profiles provided clear evidence that the separator device at the riser exit strongly influences the hydrodynamic structure of the ICFB riser. The V-shaped riser exit geometry was found to be the optimum of all the configurations studied.     

Catalytic oxidation of naphthalene using a Pt/Al2O3 catalyst

Polycylic aromatic hydrocarbons (PAHs) are listed as carcinogenic and mutagenic priority pollutants, belonging to the environmental endocrine disrupters. Most PAHs in the environment stem from the atmospheric deposition and diesel emission. Consequently, the elimination of PAHs in the off-gases is one of the priority and emerging challenges. Catalytic oxidation has been widely used in the destruction of organic compounds due to its high efficiency (or conversion of reactants), its economic benefits and good applicability.

This study investigates the application of the catalytic oxidation using Pt/γ-Al₂O₃ catalysts to decompose PAHs and taking naphthalene (the simplest and least toxic PAH) as a target compound. It studies the relationships between conversion, operating parameters and relevant factors such as treatment temperatures, catalyst sizes and space velocities. Also, a related reaction kinetic expression is proposed to provide a simplified expression of the relevant kinetic parameters.

The results indicate that the Pt/γ-Al₂O₃ catalyst used accelerates the reaction rate of the decomposition of naphthalene and decreases the reaction temperature. A high conversion (over 95%) can be achieved at a moderate reaction temperature of 480 K and space velocity below 35,000 h⁻¹. Non-catalytic (thermal) oxidation achieves the same conversion at a temperature beyond 1000 K. The results also indicate that Rideal–Eley mechanism and Arrhenius equation can be reasonably applied to describe the data by using the pseudo-first-order reaction kinetic equation with activation energy of 149.97 kJ/mol and frequency factor equal to 3.26 × 10¹⁷ s⁻¹.     

大孔径石蜡加氢精制催化剂的制备

采用氨吸附-程序升温脱附(NH3-TPD)、低温N2吸附(BET)、压汞法以及加氢精制活性评价等技术,探索SiO2-Al2O3载体在制备过程中孔结构和表面性质的变化。实验结果表明,采用特殊扩孔剂制备载体,当焙烧温度为700℃时,平均孔径可达到17.3nm,其中孔径大于20nm的孔占总孔体积的13.2%;同时载体表面上的中、强酸中心也全部丧失,均为弱酸中心。采用该载体制备的MoNiP/SiO2-Al2O3石蜡加氢精制催化剂,在MoO3用量减少了约1/4的情况下,比目前工业上使用的催化剂具有更高的脱金属能力和加氢精制活性。     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.