Catalytic pyrolysis of crude glycerol over a shaped H-ZSM-5 zeolite catalyst with (partial) recycling of the product oil was studied with the incentive to improve benzene, toluene, and xylene (BTX) yields. Recycling of the polycyclic aromatic hydrocarbon (PAH) fraction, after separation from BTX by distillation and co-feeding with the crude glycerol feed, was shown to have a positive effect on the BTX yield. Further improvements were achieved by hydrogenation of the PAH fraction using a Ru/C catalyst and hydrogen gas prior to co-pyrolysis, and BTX yields up to 16 wt% on feed were obtained. The concept was also shown to be beneficial to other biomass feeds such as e.g., Kraft lignin, cellulose, and Jatropha oil.
A time- and space-resolved deactivation study on the conversion of glycerol to aromatics over H-ZSM-5 was performed. For this purpose, glycerol was vaporized/pyrolyzed in a pyrolysis section followed by a catalytic aromatization step. Benchmark performance showed an induction period of ca. 20 min, followed by a rather constant BTX yield of ca. 25.4 ± 2.2C.% for 3–4 h time on stream (TOS). Subsequently, a rapid drop in BTX yield was observed due to catalyst deactivation. Severe coking leads to coverage of catalyst surface area and blockage of micropores, particularly at the entrance of the catalyst bed at short TOS, indicating the presence of an axial coke gradient in the fixed bed reactor. At longer TOS, coke was formed throughout the bed and negligible BTX yield was shown to be associated with the presence of coke at all bed positions. Besides coking, the acidity of the catalyst was also reduced, and dealumination occurred, both with a similar time–space evolution. The results were explained by a conversion-zone migration model, which includes a deactivation zone (with severely coked catalyst), a conversion zone (BTX formation), and an induction zone (a.o. (de-)alkylation reactions), and describes the time- and space-resolved evolution of coking and relevant changes in other catalyst characteristics.
The catalytic conversion of glycerol to aromatics (GTA, e.g., benzene, toluene, and xylenes, BTX) over a shaped H-ZSM-5/Al2O3 (60/40 wt%) catalyst was investigated in a continuous fixed-bed reactor to study the addition of the Al2O3 binder in the catalyst formulation on catalyst performance. The experiments were performed under N2 at 550 °C, a WHSV of glycerol (pure) of 1 h−1, and atmospheric pressure. The spent H-ZSM-5/Al2O3 catalysts were reused after an oxidative regeneration at 680 °C and in total 5 reaction-regeneration cycles were performed. Catalyst characterization studies show that the addition of the Al2O3 binder does not affect the surface area and crystallinity of the formulation, but increases the total pore volume (mesopores in particular) and total acidity (Lewis acidity in particular). The H-ZSM-5/Al2O3 (60/40 wt%) catalyst shows a considerably prolonged catalyst life-time (8.5 vs. 6.5 h for H-ZSM-5), resulting in a significant increase in the total BTX productivity (710 vs. 556 mg g−1 H-ZSM-5). Besides, the addition of the Al2O3 binder retards irreversible deactivation. For instance, after 3 regenerations, catalyst performance is comparable to the fresh one. However, after 4 regenerations, some irreversible catalyst deactivation occurs, associated with a reduction in total pore volume, crystallinity, and acidity (Brønsted acidity in particular), and meso-porosity of the Al2O3 binder. This study shows that both the stability and reusability of H-ZSM-5-based catalysts for GTA are remarkably enhanced when using a suitable binder.
Paper sludge contains papermaking mineral additives and fibers, which could be reused or recycled, thus enhancing the circularity. One of the promising technologies is the fast pyrolysis of paper sludge, which is capable of recovering > 99 wt.% of the fine minerals in the paper sludge and also affording a bio-liquid. The fine minerals (e.g., ‘circular’ CaCO3) can be reused as filler in consumer products thereby reducing the required primary resources. However, the bio-liquid has a lower quality compared to fossil fuels, and only a limited application, e.g., for heat generation, has been applied. This could be significantly improved by catalytic upgrading of the fast pyrolysis vapor, known as an ex-situ catalytic pyrolysis approach. We have recently found that a high-quality bio-oil (mainly ‘bio-based’ paraffins and low-molecular-weight aromatics, carbon yield of 21%, and HHV of 41.1 MJ kg-1) was produced (Chem. Eng. J., 420 (2021), 129714). Nevertheless, catalyst deactivation occurred after a few hours’ of reaction. As such, catalyst stability and regenerability are of research interest and also of high relevance for industrial implementation. This project aims to study the potential of the add-on catalytic upgrading step to the industrial fast pyrolysis of paper sludge process. One important performance metric for sustainable catalysis in the industry is the level of catalyst consumption (kgcat tprod-1) for catalytic pyrolysis of paper sludge. Another important research topic is to establish the correlation between yield and selectivity of the bio-chemicals and the catalyst characteristics. For this, different types of catalysts (e.g., FCC-type E-Cat) will be tested and several reaction-regeneration cycles will be performed. These studies will determine under which conditions catalytic fast pyrolysis of paper sludge is technically and economically viable.
