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Direct liquefaction of high-sulfur coals: Effect of the catalyst, the solvent, and the mineral matter

机译:高硫煤直接液化:催化剂,溶剂和矿物质的影响

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摘要

Two low-rank coals with high sulfur contents (Gediz subbituminous coal: 7.6 wt % S:dry basis. Çayirhan lignite: 5.7 wt% S:dry basis.) were subjected to hydroliquefaction. Liquefaction conditions included dry or solvent mediated runs under pressurized hydrogen without added catalyst or with the impregnated catalyst precursor ammonium heptamolybdate (AHM). Gediz coal having higher sulfur content gave 90% conversion in the absence of catalyst and solvent. Maximum conversion (98%) and maximum oil + gas yield (70%) from this coal were obtained by impregnating AHM onto coal and carrying out liquefaction in H 2/tetralin system at 450 °C for 30 min. Under the same conditions, Çayirhan lignite gave 85% conversion and 70.5% oil + gas yield. The superior hydrodesulfurization effect of impregnated AHM on the oil fraction when used in the absence of solvent (less than 0.1% S in lignite's oil and less than 1% S in subbituminous coal's oil following one-stage hydrogenation) is a promising finding of this work. AHM was found to be much more effective in liquefaction of Çayirhan lignite and this has been ascribed to the well-dispersion of AHM throughout this lignite's structure via a cation-exchange mechanism through oxygen functionalities. Strong evidence for the catalytic effect of clay minerals in coal structure on char-forming reactions during liquefaction was observed by making use of liquefaction reactions of demineralized coal samples. It was also observed that tetralin had a retarding effect on the condensation and subsequent cross-linking reactions.
机译:将两种具有高硫含量的低级煤(Gediz次烟煤:S:干重为7.6 wt%。Çayirhan褐煤:S:干重为5.7 wt%)进行液化。液化条件包括在加压氢气中进行干燥或溶剂介导的操作,无需添加催化剂,也无需浸渍催化剂前体七钼酸铵(AHM)。在没有催化剂和溶剂的情况下,具有较高硫含量的Gediz煤的转化率为90%。通过将AHM浸渍到煤上并在H 2 /四氢化萘系统中于450°C下液化30分钟,可获得该煤的最大转化率(98%)和最大油+气产率(70%)。在相同条件下,Çayirhan褐煤的转化率为85%,油气产量为70.5%。在没有溶剂的情况下(一步加氢后,褐煤油中的S含量低于0.1%,次烟煤油中的S含量低于1%)时,浸渍的AHM对油馏分具有优异的加氢脱硫效果,这是这项工作的有希望的发现。发现AHM在Çayirhan褐煤的液化中要有效得多,这归因于AHM通过氧官能团通过阳离子交换机制在整个褐煤结构中的良好分散。通过使用软化煤样品的液化反应,观察到了煤结构中粘土矿物对液化过程中炭形成反应的催化作用的有力证据。还观察到四氢化萘对缩合和随后的交联反应具有阻滞作用。

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