负载化非茂单活性中心催化剂乙烯聚合的研究

在硅胶上负载了双(N-环己基-3-叔丁基水杨醛亚胺基)二氯化锆配合物,得到负载化非茂单活性中心催化剂。该催化剂用于乙烯聚合,考察了配合物用量、共聚单体1-己烯用量、聚合温度、聚合压力、聚合时间、三乙基铝用量对乙烯聚合性能的影响及对聚合物的相对分子质量、相对分子质量分布、熔体流动指数和密度的影响。实验结果表明,负载化非茂单活性中心催化剂保持了原均相催化剂的乙烯聚合性能;该催化剂在淤浆聚合工艺中聚合平稳,所得聚合物的颗粒形态良好。     

催化裂化技术现状及发展趋势

详述了国内外最新渣油催化裂化、多产柴油催化裂化、低碳烯烃催化裂化、生产清洁燃料催化裂化及催化剂的技术进展，同时根据我国实际情况对今后催化裂化技术的发展提出了建议。     

磷铝杂原子固体酸催化剂催化合成乙酸异丙酯

以丙烯和乙酸为原料 ,自制的磷铝杂原子固体酸作催化剂催化合成了乙酸异丙酯 ,考察了反应温度、反应压力、反应空速 (LHSV)及催化剂用量对酯化反应的影响 ,同时考察了固体酸催化剂的重复使用性。确定了最佳合成条件 :反应压力 1 5MPa,反应温度 1 60℃ ,反应空速2 0h-1,催化剂用量 2 0g。在此条件下 ,酯化率可达 91 5 % ,乙酸异丙酯选择性达 99 0 % ,且催化剂的重复使用性良好。     

合成直链烷基苯环境友好固体酸催化剂的研究 Ⅲ .催化剂失活原因分析

采用固定床反应器,对催化剂的稳定性进行了初步评价。在120℃、空速相同、液固反应条件下,高苯烯比时催化剂的稳定性明显高于低苯烯比时;在苯烯比和空速相同、液固反应条件下,相对低温反应时,催化剂的稳定性明显高于高温反应。IR分析结果表明,同新鲜和反应后未失活的催化剂相比,失活后催化剂的活性组分特征衍射峰消失,出现的新的特征衍射峰可能同—CH基的振动有关。TG分析结果表明,失活后催化剂在空气流中焙烧,失重幅度比新鲜催化剂大。     

改性Raney Cu催化一乙醇胺脱氢合成甘氨酸

一乙醇胺在氢氧化钠的水溶液中〔w(NaOH)=12%～18%〕,用含有铬和锗等贵金属改性的RaneyCu催化剂脱氢合成甘氨酸。反应温度150～180℃,反应压力0 8～1 2MPa,反应时间2～4h。实验结果表明:改性RaneyCu催化剂比普通RaneyCu有更好的活性和使用寿命,使一乙醇胺的平均转化率从92%提高到97%,有效使用寿命(一乙醇胺的转化率≥90%)从5次延长到15次以上。     

Rutile-type TiO2 thin film for high-k gate insulator

We investigated rutile-type titanium dioxide (TiO₂) films for possible use as a high-k gate insulator. The TiO₂ thin films were directly deposited on Si substrates using a RF magnetron sputtering method with a sintered oxide target. A single phase of rutile-type TiO₂ whose dielectric constant of approximately 75 was obtained when the film was deposited in an inert gas atmosphere and annealed at 800 °C in an oxidizing gas atmosphere. The oxygen ions were deficient in the as-deposited film, and consequently, a sufficient oxygen supply was needed to crystallize the film to a single phase of rutile during the post-annealing. However, the interfacial SiO₂ layer between the TiO₂ and the Si substrate simultaneously grew thicker than 2 nm. As the interfacial SiO₂ grew, the leakage current was decreased and the equivalent oxide thickness was increased, in the Au/rutile-type TiO₂/Si capacitor. Therefore, we concluded that the growth of the interfacial SiO₂ layer thicker than 2 nm is inevitable to form the single phase of rutile-type TiO₂ and to decrease the leakage.     

Microstructure and properties of MoSi2–MoB and MoSi2–Mo5Si3 molybdenum silicides

MoSi₂-based intermetallics containing different volume fractions of MoB or Mo₅Si₃ were fabricated by hot-pressing MoSi₂, MoB, and Mo₅Si₃ powders in vacuum. Both classes of alloys contained approximately 5 vol.% of dispersed silica phase. Additions of MoB or Mo₅Si₃ caused the average grain size to decrease. The decrease in the grain size was typically accompanied by an increase in flexure strength, a decrease in the room temperature fracture toughness, and a decrease in the hot strength (compressive creep strength) measured around 1200 °C, except when the Mo₅Si₃ effectively became the major phase. Oxidation measurements on the two classes of alloys were carried out in air. Both classes of alloys were protected from oxidation by an in-situ adherent scale that formed on exposure to high temperature. The scale, although not analyzed in detail, is commonly recognized in MoSi₂ containing materials as consisting mostly of SiO₂. The MoB containing materials showed an increase in the scale thickness and the cyclic oxidation rate at 1400 °C when compared with pure MoSi₂. However, in contrast with the pure MoSi₂ material, oxidation at 1400 °C began with a weight loss followed by a weight gain and the formation of the protective silica layer. The Mo₅Si₃ containing materials experienced substantial initial weight losses followed by regions of small weight changes. Overall, the MoB and Mo₅Si₃ additions to MoSi₂ tended to be detrimental for the mechanical and oxidative properties.     

New approach to environmentally benign epoxidation: the solid-phase-system using urea–H2O2 and recyclable dodecatungstate on apatite

On the basis of new concept using a solid disperse phase we have developed an efficient catalytic solid-phase-system for epoxidations of alkenes using urea–hydrogen peroxide (urea–H₂O₂) complex and cetylpyridinium dodecatungstate ((CetylPy)₁₀[H₂W₁₂O₄₂]) catalyst on fluorapatite (FAp). The recovered solid catalyst phase was reused to keep the catalytic activity after several times. In the conceptual idea it is a key point that in situ solid-phase-activation of the catalyst with urea–H₂O₂ proceeds to form microcrystals of the active species dispersed on the solid phase. The dispersion of the catalyst on FAp in the case of tungstic acid (H₂WO₄) was suggested by EPMA analysis. We proposed the peroxo type of species keeping the parent polyoxometalate framework as novel active species from FT-IR spectroscopic studies. FAp phase plays important roles of dispersing the active species on its surface to have high catalytic activity and of stabilizing the active species to lead to high reusability.     

GS-08乙苯脱氢催化剂在广石化的应用

乙苯脱氢催化剂GS-08催化剂在广州石化总研制的首次应用。     

Ru-catalyzed anode materials for direct hydrocarbon SOFCs

A solid oxide fuel cell using a thin ceria-based electrolyte film with a Ru-catalyzed anode was directly operated on hydrocarbons, including methane, ethane, and propane, at 600 °C. The role of the Ru catalyst in the anode reaction was to promote the reforming reaction of the unreacted hydrocarbons by the produced steam and CO₂, which avoided interference from steam and CO₂ in the gas-phase diffusion of the fuels. The resulting peak power density reached 750 mW cm⁻² with dry methane, which was comparable to the peak power density of 769 mW cm⁻² with wet (2.9 vol.% H₂O) hydrogen. More important was the fact that the cell performance was maintained at a high level regardless of the change in the methane utilization from 12 to 46% but was significantly reduced by increasing the hydrogen utilization from 13 to 42%. While the anodic reaction of hydrogen was controlled by the slow gas diffusion, the anodic reaction of methane was not subject to the onset of such a gas-diffusion process.