富含介孔Ni/W-USY/Al2O3催化剂的费托蜡加氢裂化性能

Investigation of performance of Ni/W-USY/Al2O3 catalyst with full mesoporous in Fischer Tropsch wax hydrocracking

  • 摘要: 制备了富含介孔的Ni/W-USY/Al2O3催化剂并开展费托合成蜡加氢裂化实验,从反应性能、产品特性以及催化剂性质变化三方面对该催化剂进行评价。312 h运行实验结果表明,催化剂初始活性较高,120 h后趋于稳定,无明显失活现象,重质蜡转化率为73.95%时,轻质油选择性达到98.46%,裂解气以C3,4为主;石脑油、煤油、柴油为无色透明液体,以正构烷烃和甲基、多甲基取代的异构烷烃为主,异构烃含量分别达到63.98%、52.26%、48.90%;对反应前后催化剂分析发现,新鲜催化剂的金属分散性较好、介孔含量高,加氢活性中心以WS2、NiWS为主,随着反应由高活性到稳定阶段过渡,WS2部分迁移并与Ni形成更多Ni-S-W键,部分W-S键断裂释放出S后形成W-W键,使得稳定后催化剂的NiWS活性中心增加而WS2活性中心降低,并引起L酸密度降低而B酸密度增加。

     

    Abstract: Ni/W-USY/Al2O3 with full mesoporous structure was prepared and used for hydrocracking of Fischer Fropsch wax. The catalyst was evaluated for its reaction performance, product characteristics and catalyst properties change. In a 312 h experiment, the result showed that the catalyst possessed high initial activity, and maintained stable after 120 h, and did not show obvious deactivation afterward. When the heavy wax conversion reached 73.95% at the stable stage, the fuel oil selectivity reached to 98.46% and C3, 4 constituted the most cracked gas. Gasoline, kerosene and diesel, as the products, were transparent and composed of paraffins and iso-paraffins substituted by methyl-groups. The iso-paraffin contents in the three products were 63.98%, 52.26% and 48.90% respectively. The fresh catalyst contained two main active states of WS2 and NiWS, had good metal dispersion and rich mesoporous structure. With transition from high activity to stable state of the catalyst property, part of W migrated and formed more Ni-S-W bonds with Ni, and some W-S bonds broke to form W-W bonds after releasing S, resulting in the increase of active states of NiWS and the decrease of WS2, and forming more Brönsted acid sites and less Lewis acid sites.

     

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