Examples on the real-world field application of Raman spectroscopy with systematic analysis of the intensity variation of D and G bands corresponding to the change of excitation laser energy to characterize and compare coke species from various industrial processes are presented. The findings indicate the different degree of sp2 and sp3 hybridized bonding structures of amorphous carbon collected from different industrial processes as well as heavy carbonaceous deposits generated by industrial catalysts. This spectroscopic methodology is practical and highly beneficial in identifying coke formation mechanisms in industrial processes, as well as supporting design strategies to abate the undesired coke formation on industrial catalysts.
Fluid Catalytic Cracking (FCC) has maintained its crucial role in refining decades after its initial introduction owing to the flexibility it has as a process as well as the developments in its key enabler, the FCC catalyst. Boron-based technology (BBT) for passivation of contaminant metals in FCC catalysts represents one such development. In this contribution we describe Fourier Transform Infrared Spectroscopy (FTIR) characterization of boron-containing catalysts to identify the phase and structural information of boron. We demonstrate that FTIR can serve as a sensitive method to differentiate boron trioxide and borate structures with a detection limit at the 1000 ppm level. The FTIR analysis validates that the boron in the FCC catalysts studied are in the form of small borate units and confirms that the final FCC catalyst product contains no detectable isolated boron trioxide phase. Since boron trioxide is regulated in some parts of the world, this novel FTIR methodology can be highly beneficial for further FCC catalyst development and its industrial application at refineries around the world. This new method can also be applied on systems beyond catalysts, since the characterization of boron-containing materials is needed for a wide range of other applications in the fields of glass, ceramics, semiconductors, agriculture, and pharmaceuticals.
Structural analysis and catalytic testing revealed that zeolite Beta from template-free synthesis introduces new possibilities in catalysis, as a result of its unprecedentedly high density of active sites with exceptional stability and distinctively ordered nature. Highly active and selective catalysts were obtained either by using it in the Al-rich form (e.g. alkylation) or after post-synthesis treatments (e.g. acylation). Such versatility made possible by this novel synthesis route constitutes a new toolbox for catalysis.
A ferrierite-type layered aluminosilicate, Al-RUB-36, was prepared for the first time and its interlayer expansion resulted in new zeolite catalysts denoted Al-COE-3 and Al-COE-4. Decane hydroconversion tests demonstrated the highly active and shape-selective nature of the new Al-COE-4 catalyst with an unprecedented isomerization yield, highlighting the potential of this material as a hydroisomerization catalyst. This is the first report on achieving shape-selectivity via interlayer expansion.
Refiners around the globe are either considering or are actively replacing a portion of their crude oil inputs originating from fossil sources with alternative sources, including recycled materials (plastics, urban waste, mixed solid waste) and renewable materials (bio-mass waste, vegetable oils). In this paper, we explore such replacement, specifically focusing on the fluid catalytic cracking (FCC) operation. Five pyrolysis oils, obtained from municipal solid waste (MSW) and biogenic material (olive stones/pits), were fully characterized and tested at 10% loading against a standard fluid catalytic cracking (FCC) vacuum gasoil (VGO) feed in a bench scale reactor using an industrially available fluid catalytic cracking catalyst based on ultrastable Y zeolite to simulate fluid catalytic cracking co-processing. Despite having unique feed properties, including high Conradson carbon (e.g., up to 19.41 wt%), water (e.g., up to 5.7 wt%), and contaminants (e.g., up to 227 ppm Cl) in some cases, the five pyrolysis oils gave similar yield patterns as vacuum gasoil. Gasoline was slightly (ca. 1 wt%) higher in all cases and LPG slightly (ca. 1 wt%) lower. Olefinicity in the LPG streams were unchanged, bottoms and light cycle oil (LCO) showed no significant changes, while dry gas was slightly (up to −0.2 wt%) lower. Coke selectivity was also unchanged (maximum −7.7 wt%, relatively), suggesting minimal to no heat balance concerns when co-processing in an industrial fluid catalytic cracking unit. The results demonstrate the applicability of municipal solid waste and biogenic originating pyrolysis oils into a refinery. A catalyst design concept is explored, based on higher rare Earth oxide exchange and/or utilization of ZSM-5 zeolite, that would further minimize the impacts of replacing fossil oils with pyrolysis oils, namely one that shifts the 1% higher gasoline into LPG.