Selective Synthesis of Distillates by Transfer Hydrocracking of Heavy Oils.

研究发现，一种特殊的活性炭，通过适当的活化方法，具有高比表面积、高孔体积和高密度的自由基位点，并携带金属或金属硫酸盐，对真空渣油或天然沥青等重质烃的转移加氢裂化制馏出物表现出优异的催化活性。重碳氢化合物在油中和碳表面都发生裂解，生成低分子量的石蜡、芳烃、烯烃、自由基和有机硫化合物。另一方面，高芳香族、高分子量的沥青被吸附在活性炭上分解脱氢，得到轻烃和焦炭。焦化过程中产生的氢原子在碳表面移动到达金属部位。在金属上，部分氢原子与烯烃或有机硫化合物反应生成石蜡或脱硫化合物。金属上更多的原子结合形成氢气，进入液态。后半部分的氢运动是可逆的。它是由液体中氢的浓度控制的，它与气相中氢的压力成正比。因此”。通过在一定氢气压力下进行碳催化反应，使重油加氢裂化过程不耗氢。模型化合物（二苯丙烷为氢受体，四氢萘为氢供体）在同一催化剂上的反应证实了这一概念。为了制备出性能优良的碳催化剂，对煤进行了多种活化试验。用氢对煤进行高温处理，制得一种载铁时具有良好加氢活性的多孔炭；用CO_2在850℃下对褐煤进行处理，制得一种对重油裂解和沥青脱氢具有高活性的多孔炭。利用含铁量为5 wt%的三氧化二碳，实现了阿拉维麻质原油真空渣油的完全转化，得到了80%的油。%煤气和10%焦炭。在此基础上，提出了一种新型的煤-石油协同加工系统。少

It was found that a special kind of active carbon, which was activated by proper methods to give high specific surface area, pore volume and high density of radical site and which carry metal or metal sulfate, showed excellent catalytic activity for the transfer hydrocracking of heavy hydrocarbons such as vacuum residue or natural asphalt to make distillate. Cracking of heavy hydrocarbons proceeded both in the oil and on the carbon surface to give paraffins, aromatics, olefins, free radicals and organo-sulfur compounds, with low molecular weight. On the other hand, asphalten, which is high aromatic and high molecular weight, was adsorbed -on active carbon to be decomposed an'd to be dehydrogenated making light hydrocarbons and coke. Hydrogen atoms which was generated during coking moved on the carbon surface to reach metal site. On the metal, some part of hydrogen atoms reacted with olefins or organo-sulfur compounds to make paraffins or de-sulfured compounds, . and other part of hydro … More gen atoms on the metal site combined to fokm hydrogen gas to go out into liquid phase. The latter part of hydrogen movement was a reversible phenomenon. It was controled by the concentratiori of hydrogen in the liquid, which was proportional to the pressure of hydrogen in the gas phase. Therefore'. by conducting the carbon catalyied reaction under certain hydrogen pressure, the hydrocracking of heavy oil proceed without any hydrogen consumption. This concept was confirmed by the reaction of model compounds (diphenyl propane as a hydrogen acceptor and tetra-hydro naphthalene as a hydrogen donor) on the same catalyst.In order to make excellent carbon catalyst, a variety of activation of coal were tried. By treating a coal with hydrogen at high temperature, a porous carbon which has excellent hydrogenation activity, when it carried iron, was made while brown coal was treated with CO_2 at 850ﾟC, a porous barbon which was highly active for cracking heavy oil and for dehydrogenating asphalten was developed. By using tliis carbon (with 5 wt% Fe) complete conversion of vacuum residue of Aravian fleavy Crude was attained to give 80 % oil, 8. % gas and 10 % coke.Based on this concept, a new coal-petroleum co-processing system was postulated. Less