Fine structural changes of fluid catalytic catalysts and characterization of coke formed resulting from heavy oil devolatilization

Coke formation from heavy oil cracking and the associated change in the porous structure of fluid catalytic cracking (FCC) catalysts has been studied using a comprehensive range of techniques, including 2D and 3D imaging and carbon/coke characterization techniques. The carbon/coke formed from heavy oil devolatilization has been investigated with a range of oil-to-FCC catalyst ratios (1:3, 1:2, 1:1, 2:1 and 3:1) to simulate the ageing of FCC catalysts in an operating oil refinery. Carbon/coke was formed on all used FCC catalyst samples and was found to generally increase in quantity with the increasing oil-to-FCC catalyst ratios. Coke formation has been correlated with the observed porosity change of the FCC catalyst. Higher quantities of carbon/coke formed on the FCC catalyst due to higher oil-to-FCC catalyst ratios (simulated increase in time on-stream) leads to a decrease of total pore volume and surface area. X-Ray computed tomography (X-Ray CT) studies allowed 3-dimensional imaging of used catalyst particles and showed that the zeolite component of the FCC catalyst remains evenly distributed throughout the FCC particle from the centre to the exterior for pristine and used FCC catalyst particles. This technique showed that while the interior porous structure of the FCC catalyst particle is not affected by the coking, the exterior porous structure is substantially modified for all used FCC catalyst samples. This process of pore collapse and/or clogging at the surface of the particles is likely to have a significant effect on the deactivation of FCC catalysts that is commonly observed. The deeper insight into this process gained through this study is important for understanding how FCC catalysts change with time-on-stream and eventually deactivate and may allow for future catalysts to be developed that are more resistant to deactivation.