不同分子结构渣油加氢反应性能研究

分别以石蜡基青海原油渣油（简称青海渣油）和中间基沙特阿拉伯轻质原油渣油（简称沙轻渣油）为原料，采用RHT系列渣油加氢催化剂进行了1 500 h 稳定性试验，采用傅里叶变换离子回旋共振质谱仪和核磁共振波谱仪分析原料和加氢生成油的分子结构差异及试验后催化剂（简称试验旧剂）上积炭组成。结果表明：青海渣油分子芳烃侧链多且长，通过初期快速升温可使其侧链断裂，改善其内扩散性能，且生焦倾向降低；沙轻渣油分子芳烃含量高，侧链较短，低温时即可达到较高杂质脱除率，高温则易生成结焦前躯物，造成催化剂快速失活；与青海渣油相比，沙轻渣油加氢试验旧剂的积炭量更大，硬炭比例更高。对青海渣油加氢反应的温度分布进行优化，快速升高脱金属催化剂床层温度，降低脱硫剂反应温度，形成前高后低的温度分布，结果表明优化后方案的加氢生成油性质更优。

STUDY OF HYDROGENATION PERFORMANCE OF RESIDUES WITH DIFFERENT HYDROCARBON STRUCTURES

The 1 500 h experiment of catalyst stability was conducted with residue of paraffin-base Qinghai crude oil (Qinghai residue) and residue of intermediate-base Saudi Arabia light crude oil (Saudi Arabia residue) as feedstock,respectively. The differences of the molecular structures of the feedstock and products were analyzed by Fourier transform ion cyclotron resonance mass spectrometer and NMR techniques，as well as the coke- composition of post-reaction catalyst in experiment （used catalyst）. According to the results in this study，Qinghai residue has high content of saturated hydrocarbon and long numerous side-chains on aromatic rings. The accessibility of Qinghai residue can be improved by cracking its side-chains with rapidly–rising temperature at the start of run. Besides，the tendency of coking is declined. The molecular of Saudi Arabia residue has high content of aromatics with short side-chains. It can achieve high removal rate of impurity at low temperature, but it tends to form coking-precursor when the temperature is high，which is one of the main factors causing deactivation of catalyst rapidly. Saudi Arabia residue has lager amount of coke-composition of used catalyst and high proportion of hard coke compared to Qinghai residue. The reaction temperature distribution of Qinghai residue hydrogenation was optimized. The temperature of the demetallization catalyst bed was increased rapidly，while the temperature of the desulfurization catalyst bed was decreased，forming the distribution of the high temperature down to low temperature. The data showed that the hydrogenated products with the optimized temperature had better properties.