高酸原油直接催化脱酸裂化成套技术开发和工业应用

DEVELOPMENT AND COMMERCIAL APPLICATION OF PACKAGED TECHNOLOGY FOR CATALYTIC DECARBOXYLATION AND CRACKING OF HIGH ACID CRUDE OIL

利用分子模拟技术和量子化学理论研究了各种石油酸中原子的电荷分布、键级和在不同催化材料上的反应行为,发现羧基可从石油酸分子中脱除,生成无腐蚀性的CO_2和烃类化合物,尤其在酸性裂化催化剂作用下脱羧基速率更快、更彻底。开发了高酸原油经脱盐、脱水后直接进入催化裂化提升管反应器与高温新型催化剂接触,瞬间汽化,同时实现脱酸和裂化反应,生成高价值石油产品的新工艺。工业应用结果:催化脱酸率大于99%,汽油、柴油可直接作为产品的调合组分,在平衡催化剂上金属污染物总量达40 620μg/g(其中镍为24 000μg/g)时,总轻油收率比常规加工技术提高1.36百分点,能耗(相对于原油)降低271.7 MJ/t,对工业应用装置没有特殊防腐要求。为炼油企业扩大原油资源选择范围、降本增效提供了有效技术保障。

Abstract： The charge distributions, bond orders on the atoms of various petroleum acids and their reaction behaviors over different catalytic materials were studied by means of molecular simulation technology and quantum chemistry theory. It was found that the carboxyl of petroleum acid could be removed over acidic catalysts to form noncorrosive carbon dioxide and hydrocarbons rapidly. A set of novel technologies to directly process high acid crude oil after desalting and dewatering was developed, which involves using FCC riser reactor and proprietary cracking catalyst to realize the catalytic decarboxylation and cracking reactions happened simultaneously, and high valuable products were produced. The commercial results showed that the rate of catalytic decarboxylation was more than 99%, the obtained gasoline and diesel fractions could be used as related blending components directly. Compared with conventional processing technology, at an equilibrium catalyst having a metal content of 40 620 μg/g （in which Ni 24 000 μg/g）, the total light oil yield increased by 1.36 percentage points, the energy consumption （based on crude） decreased by 271.7 MJ/t and without special anticorrosion requirements for the processing unit. This technology could provide effective technical support for the refining enterprises to expand the selection of crude oil resources, to reduce production cost and increase profit for better competition.