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Hydrohalogenation of Platinum-Palladium/H-ZSM-5 Catalysts for n-Hexane Hydroconversion

机译:用于正己烷加氢转化的铂钯/ H-ZSM-5催化剂的加氢卤化反应

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摘要

Catalysts containing 0.3% Pt-, 0.3% Pd-, and 0.3% Pt-0.3% Pd-/H-ZSM-5 were prepared and modified via hydrochlorination or hydrofluorination and tested for n-hexane hydroconversion throughout a reaction temperature range of 250-500 degrees C. Bifunctionality parameters of the current catalysts were characterized via acid site strength distribution by NH3-temperature programmed desorption, metal(s) component dispersion by H-2 chemisorption, and temperature programmed reduction. Hydrochlorination was found to leach less structural zeolitic Al in the catalyst than hydrofluorination. HCl modification improved n-hexane hydroisomerization activity, whereas HF treatment was deteriorative via causing pore diffusion restriction by excessively formed debris. Acid sites density and strength were higher on hydrofluorination than on hydrochlorination. Surface area and metals dispersion were higher for hydrochlorinated catalyst but lower for the hydrofluorinated one. Maximum isohexanes production (70%) was realized on hydrochlorinated catalyst at 350 degrees C with 100% selectivity. Crystal unit cell d-spacing, obtained by XRD, was smaller by hydrofluorination than by hydrochlorination, whereas such d-spacing was increased through incorporating Pt and increased more via Pd addition during preparation.
机译:制备了含有0.3%Pt-,0.3%Pd-和0.3%Pt-0.3%Pd- / H-ZSM-5的催化剂,并通过氢氯化或氢氟化进行了改性,并测试了在250-200反应温度范围内的正己烷加氢转化率500℃。通过NH 3-程序升温脱附的酸位点强度分布,通过H-2化学吸附的金属成分分散和程序升温还原来表征当前催化剂的双官能度参数。发现氢氯化反应比氢氟化反应在催化剂中沥滤出较少的结构沸石铝。 HCl改性改善了正己烷的加氢异构化活性,而HF处理则由于形成过多的碎屑而导致了孔扩散限制,从而恶化了该效果。氢氟化作用的酸位密度和强度高于氢氯化作用。氯化催化剂的表面积和金属分散度较高,而氟化氢催化剂则较低。在350℃下以100%的选择性在盐酸催化剂上实现了最大的异己烷产量(70%)。通过XRD获得的晶体晶胞d间距通过氢氟化作用比通过氢氯化作用要小,而这种d间距通过掺入Pt得以增加,而在制备过程中通过添加Pd得以增加。

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