供氢剂与分散型催化剂协同作用的研究

以辽河渣油为原料，四氢萘为供氢剂，二烷基二硫代氨基甲酸钼为油溶性催化剂在高压釜中进行裂化反应，比较了临氢裂化，临氢供氢裂化，催化加氢裂化以及供氢剂与分散型催化剂共同存在下的加氢裂化，在同样生焦量的情况下，渣油裂化转化率的顺序为：临氢催化供氢过程＞临氢催化过程＞临氢供氢过程＞临氢过程，同时发现供氢剂与分散型催化剂在渣油加氢裂化过程中具有协同作用，与单独使用分散型催化剂的改质反应相比，供氢剂的协同作用不但可以在低转化率下延迟生焦诱导期，提高渣油生焦前的最大转化率，而且在高转化率下对渣油的缩合反应有更大的抑制作用。由420－440℃四集总表观动力学模型计算出的动力学速率常数和活化能表明，供氢剂与分散型催化剂产生的协同作用提高了沥青质和焦生成的活化能，极大地抑制了沥青质和焦生成 速率，而对可溶质生成馏分油的裂化反应的抑制作用很小。

SYNERGISM BETWEEN HYDROGEN DONORS AND DISPERSED CATALYSTS IN HYDROCRACKING OF RESIDUE

Liaohe vacuum residue was placed in magnetic-stirred autoclave as feed, tetrahydronaphthalene as hydrogen donor and oil-soluble MoDTC as dispersed catalyst, the comparison of hydrocracking reaction systems among LHVR, LHVR hydrogen donor, LHVR dispersed catalyst, LHVR dispersed catalyst hydrogen donor had been investigated. It is shown that the relation between the coke yield and cracking yield of LHVR depended on different reaction system, the order of cracking yields of LHVR at the same coke yield displayed in this way: LHVR dispersed catalyst hydrogen donor>LHVR dispersed catalyst> LHVR hydrogen donor>LHVR. It is found that there existed synergism between hydrogen donors and dispersed catalysts, and that the synergism had effective inhibition of coke, not only delayed induction time of coke formation and enhanced the maximum conversion before coke formation, but also improved considerably the deep upgrading of residue. Four-lumping kinetic reaction network was suggested and the analysis based on four-lumping reactions of LHVR presented the synergism increased activation energy of formation of coke and formation of asphaltene so that the rate of coking and forming asphaltene decreased to a great extent.