异丁烷与丁烯在炭化树脂负载PW_(12)催化剂上的烷基化

探讨了炭化树脂负载杂多酸PW1 2 催化剂制备的适宜条件 ,反应工艺条件对催化剂催化异丁烷与丁烯烷基化反应及产物分布的影响 ,分析了催化剂具有较高活性的原因 ,进行了催化剂稳定性实验。并与其它类固体酸催化剂进行了对比。     

异丁烷与丁烯烷基化反应工艺

讨论了异丁烷与丁烯烷基化反应工艺在清洁燃料生产过程中的地位、作用和发展趋势;简介了目前石油炼制工业中使用的液体酸烷基化工艺;详细介绍了正在研究开发的固体酸烷基化技术;对在烷基化反应中应用的新型固体酸催化材料和新催化反应工艺的探索和进展进行了综述。     

Isobutane/2-butene alkylation on MCM-22 catalyst. Influence of zeolite structure and acidity on activity and selectivity

The catalytic behavior of the novel MCM-22 zeolite for the continuous alkylation of isobutane with 2-butene has been investigated at a temperature of 50°C, 2.5 MPa total pressure, and a variety of olefin space velocities. At high olefin conversions the MCM-22 zeolite showed a very high initial cracking activity attributable to strong Brønsted acid sites, as well as to the existence of strong diffusional restrictions of the TMP's (formed inside the zeolite) to exit through the channels. At short times on stream (TOS), TMP's account for ca. 40% of the C₈ fraction. The olefin conversion and the cracking activity rapidly decline with TOS, while the alkylate product became richer in dimethylhexenes, indicating a predominance of 2-butene dimerization and a loss of hydrogen transfer activity as the catalyst aged. Moreover, MCM-22 gives less TMP's than large-pore zeolites (USY, beta, mordenite), but more than the mediumpore ZSM-5 at similar 2-butene conversion. The latter catalyst was much more selective for olefin dimerization than for isobutane alkylation, presumably because formation of the bulkier TMP's was strongly impeded in its smaller pores.     

Dehydrocyclization of 1-hexene to benzene on Cu3Pt(111)

The disproportionation ofn-butane (and of isobutane) was catalyzed by sulfated zirconium oxide containing 1.5 wt% Fe, 0.5 wt% Mn, and 4.0 wt% sulfate at 2.0 atm and temperatures in the range of 30–60C. The reaction accompanies isomerization, which under some conditions is as much as one or two orders of magnitude faster than disproportionation. The conversion to each of the products increased with time on stream in a flow reactor, and then declined. The time on stream for maximum conversion was the same for each product. The results suggest that the disproportionation and isomerization reactions proceed through a common C₈ intermediate. Rates of the disproportionation reaction were determined at the time on stream corresponding to the maximum conversion at each temperature; for example, the rate of conversion ofn-butane into isopentane at 60C with ann-butane partial pressure of 0.58 atm was about 1×10^–7 mol/(g of catalyst s).     

Preparation of superacid of iron-supported zirconia for reaction of butane to isobutane

A highly active superacid of 2 wt% Fe-supported ZrO₂ for the skeletal isomerization of butane to isobutane was obtained by sfexposing Fe₂O₃/ZrO₂ to 1 N H₂SO₄ followed by calcining in air at 700°C for more than 24 h; the Fe₂O₃/ZrO₂ was prepared by impregnating zirconia gel with a solution of Fe(NO₃)₃ followed by drying at 300°C (2 wt% Fe). A much lower activity was observed with the opposite procedure, where the first impregnation was sulfation of the gel, followed by a second impregnation with the iron compound. It was proved from analysis of the sulfur content in the catalysts that residual sulfur species were not related with generation of the superacidic sites. XPS showed the catalyst to be Fe₂O₃ supported on ZrO₂.Superacids by metal oxides, VIII. For previous publications VI and VII in this series see refs. [10,11].     

Kinetic Study of the Steam Reforming of Isobutane Using a Pt–CeO2–Gd2O3 Catalyst

Steam reforming of isobutane on a 0.5% Pt–Ce_0.8Gd_0.2O_1.9 catalyst was carried out from 300 to 700 °C under integral conditions with a gas hourly space velocity (GHSV) of 12,000 h⁻¹. The major products were H₂, CO₂, CO and CH₄. The other products produced were ethane, ethylene, propane and propylene with a total molar composition of less than 1.5%. A complete conversion of isobutane was achieved at 700 °C, Kinetic data was obtained by changing the partial pressure of the reactants and the temperature under differential conditions with a GHSV of 55,400 h⁻¹. This was done after observing stable isobutane steam reforming for 160 h and under conditions where the mass transfer limitations were insignificant. An empirical Langmuir–Hinshelwood type model that best fit the kinetic data available was developed.     

酸催化合成烷基化油的研究进展

综述了分别以硫酸、氢氟酸等无机酸、固体酸和离子液体为催化剂合成烷基化油的最新研究进展,并对这些催化剂的结构和酸性能对烷基化油的组成和性质的影响规律进行了分析和评述。指出离子液体作为绿色催化剂用于烷基化油的合成表现出易与产物分离、催化活性高、烷基化产物中C8组分含量高、辛烷值高等突出优点,是较有应用前景的烷基化油合成用催化剂。     

The solid-state rearrangement of the Wells-Dawson K6P2W18O62·10H2O to a stable Keggin-type heteropolyanion phase: a catalyst for the selective oxidation of isobutane to isobutene

The thermal and structural stability of the Wells-Dawson-type heteropoly compound K₆P₂W₁₈O₆₂·10H₂O was examined by FT-IR spectroscopy, X-ray powder diffraction, thermogravimetric analysis and HRTEM. It was found that calcination at temperatures higher than 850 K led to the formation of a Keggin-type compound K₃PW₁₂O₄₀, containing small amounts of an additional phase originated from the high-temperature interaction between potassium phosphate (K₃PO₄ formed during the decomposition of the K₆P₂W₁₈O₆₂·10H₂O) and the Keggin-type compound itself. The Keggin-type product showed a higher activity in the selective oxidative dehydrogenation of isobutane to isobutene compared to both the Wells-Dawson precursor and to pure, authentic K₃PW₁₂O₄₀. This higher activity can be tentatively attributed to the presence of an amorphous layer of unknown stoichiometry at the surface of the thermally rearranged Wells-Dawson compound.     

异丁烷催化脱氢反应机理与失活动力学研究进展

异丁烯是化工行业重要的基础原料,国内外对异丁烯的需求量逐年递增。仅靠石油催化裂解已无法满足对异丁烯的需求,开展异丁烷脱氢制异丁烯工艺的研究备受关注。综述Cr系异丁烷脱氢催化剂的研究进展,探讨Cr系催化剂的活性中心以及发生在活性中心上的多种反应机理和相应的动力学模型,详述催化剂的失活机理,总结积炭的形成过程,指出Cr系异丁烷催化脱氢反应和失活机理以及相关动力学方面研究的不足,并对未来研究前景进行展望。