神华煤直接液化性能及固体酸催化可行性研究

STUDY ON DIRECT LIQUEFACTION PROPERTIES OF SHENHUA COAL AND FEASIBILITY WITH SO_4^(2-)/ZrO_2 SOLID ACID AS CATALYST

利用微型压热釜考察了气氛、温度、氢气初压及煤溶剂比等工艺条件对神华煤直接液化转化率和产物分布的影响,结合神华煤的溶剂抽提性能和产物表征,系统地研究了神华煤加氢液化性能,并通过与FeS和FeS+S等催化剂对比实验,初步探讨了SO42-/MxOy型固体酸催化煤加氢液化的可行性.结果表明,神华煤中以非共价键作用结合的小分子化合物含量较低,煤中的羟基主要位于大分子骨架结构中;神华煤具有良好的液化性能,400℃,煤/四氢萘比为1∶2,SO42-/ZrO2为催化剂时最高转化率达到76.3%,气氛、初压、液化温度及煤溶剂比对液化转化率具有较大影响,较高温度及强的供氢体系有利于提高煤的转化率及油气产率.三种催化剂的催化活性顺序为:FeS<FeS+S<SO42-/ZrO2,其中SO42-/ZrO2固体酸不仅具有良好的液化转化率,而且油气收率高,值得进一步研究开发.

Direct hydro-liquefaction properties of Shenhua coal and feasibility with SO4^2-/ZrO2 as catalyst were studied by a batch micro-autoclave. The effects of atmosphere, liquefaction temperature, initial pressure of hydrogen and the ratio of coal to solvent on liquefaction conversion and the distribution of products were investigated. The catalytic properties of SO4^2-/ZRO2 solid acid were compared with FeS and FeS＋S to verify the catalytic activity of SO4^2-/MxOy solid acid for the hydro-liquefaction of coal. In addition, the solvent extractable properties of Shenhua coal were determination. The results show that the extraction yield of Shenhua coal by CS2/NMP mixed solvent is 21.3%. The content of low-molecular weight compounds associated in the coal macromolecular network structure is lower,and hydroxyl group consisted in coal is linked in macromolecular framework. Shenhua coal has good liquefaction ability. The highest liquefaction conversion was obtained as 76.3% at optimized conditions which were 400℃, coal/tetralin 1/2,and SO4^2-/ZrO2 catalysis. There are great effects of atmosphere, initial pressure of hydrogen ,conversion temperature and ratio of coal to solvent on the liquefaction conversion of Shenhua coal. Higher temperature and stronger hydrogen donator are favorable to increasing the liquefaction conversion and the yield of oil and gas. The catalytic activity of four catalytic systems increase in turn non-catalytic （FeS （FeS ＋ S （SO42-/ZrO2 SO4^2-/ZrO2 solid acid shows the best catalytic ability for the direct hydro-liquefaction of coal and is worth to study and development.