Hydrogenation of Heavy Oil through Partial Oxidation in Supercritical Water

我们开发了一种在超临界水中部分氧化重油的加氢工艺。超临界水中的烃类部分氧化和水-气变换(WGS)反应是该工艺发展的关键反应。在本研究中，我们对这些反应进行了基础研究。1)超临界水中烃类部分氧化反应的研究在400ﾟC下，采用间歇式反应器对正十六烷在超临界水中的部分氧化反应进行了研究，考察了水密度对n-C16部分氧化反应的影响，结果表明，随着水密度的增加，生成CO的选择性增加。在超临界水中，甲醇和甲烷的部分氧化反应也采用流动装置进行，反应温度为380ﾟC~400ﾟC，反应压力为10 Mpa~25 Mpa。在较低的转化率和较高的水密度下，CO生成的选择性增加。2)反应…的测定用流动仪测定了超临界水中水-气变换反应的反应速率，实验条件为反应温度380ﾟC-400ﾟC，反应压力10-30 MPa。3)超临界水中WGS反应催化加氢的研究采用间歇式反应器，考察了超临界水中烃类(萘、咔唑、重油等)的WGS反应催化加氢反应。在SCW+CO气氛下，碳氢化合物的催化加氢速率高于在SCW+H2气氛下的催化加氢速率。此外，在SCW+CO2+H2气氛下，烃类的催化加氢速率高于在SCW+H2气氛下的催化加氢速率。这些结果表明，WGS反应为超临界水中烃类的催化加氢提供了活性物种。以上结果表明，超临界水中部分氧化催化加氢和水-气变换反应是一种有效的烃类加氢方法。较少

We have developed a hydrogenation process of heavy oil through partial oxidation in supercritical water. For the development of the process, partial oxidation of hydrocarbon and water-gas shift (WGS) reaction in supercritical water are key reactions. In this research, we conducted the basic study of these reactions. The results are as follows.1) Study on partial oxidation of hydrocarbon in supercritical waterPartial oxidation of n-hexadecane (n-C_<16>) in supercritical water was conducted using batch reactors at 400ﾟC and the effect of water density on the partial oxidation of n-C16 was investigated, In the result, the selectivity of CO formation increased with increasing water density.Partial oxidation of methanol and methane in supercritical water was also conducted using a flow apparatus at 380ﾟC - 400ﾟC of reaction temperatures and 10 MPa - 25 MPa of reaction pressures. At lower conversion and higher water density, the selectivity of CO formation increased.2) Measurement of reactio … More n rate of water-gas shift (WGS) reaction in supercritical waterThe reaction rate of WGS reaction in supercritical water was measured using a flow apparatus at 380ﾟC - 400ﾟC of reaction temperatures and 10 MPa - 30 MPa of reaction pressures. The rate of WGS reaction was changed specifically at the critical point of water and increased slightly with increasing water density.3) Study on catalytic hydrogenation of hydrocarbons through WGS reaction in supercritical waterCatalytic hydrogenation of hydrocarbons (naphthalene, carbazole, heavy oil, and so on) through WGS reaction in supercritical water was investigated using batch reactors. The rate of catalytic hydrogenation of hydrocarbons under SCW+CO atmosphere was higher than that under SCW+H_2 atmosphere. Furthermore, the rate of catalytic hydrogenation of hydrocarbons under SCW + CO_2 +H_2 atmosphere was higher than that under SCW+h_2 atmosphere. These results suggest that WGS reaction provides an active species for a catalytic hydrogenation of hydrocarbon in supercritical water.The above results indicate that catalytic hydrogenation through partial oxidation and water-gas shift reaction in supercritical water is an effective method for hydrogenation of hydrocarbons. Less