The use of H-ZSM-5 with various binders (Al2O3, SiO2, and kaolinite, 10 wt% on catalyst formulation) for the catalytic conversion of glycerol to bio-based aromatics (GTA) was investigated in a continuous bench-scale unit at a pyrolysis temperature of 450 °C, catalytic upgrading temperature of 500 °C, WHSV of pure glycerol of 1 h−1, and atmospheric pressure, and their performance was compared to H-ZSM-5 (SiO2/Al2O3 molar ratio of 28). The latter gave a peak BTX carbon yield of ca. 31.1C.%, a life-time of ca. 220 min, and a total BTX productivity of ca. 312 mg BTX g−1H-ZSM-5. The introduction of binders affects catalyst performance, which is the most profound and promising for the H-ZSM-5/Al2O3 catalyst. It shows a prolonged catalyst life-time of ca. 320 min and a higher total BTX productivity of ca. 518 mg BTX g−1H-ZSM-5, compared to the H-ZSM-5 without a binder. Catalyst characterization studies show that the addition of the binder does not have a major effect on the specific surface area, total pore volume, and total acidity. Other relevant properties were affected, though, such as micropore volume (SiO2), a reduced Brønsted acidity (Al2O3, and SiO2), and reduced crystallinity (SiO2). Coke formation causes severe catalyst deactivation, ultimately leading to an inactive catalyst for BTX formation. Catalyst characterization studies after an oxidative regeneration showed that the textural properties of the regenerated catalysts were close to those of the original catalysts. However, some dealumination of H-ZSM-5 occurs, resulting in decreased crystallinity and acidity, causing irreversible deactivation, which needs attention in future catalyst development studies.
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.
Glycerol is an attractive bio-based platform chemical that can be converted to a variety of bio-based chemicals. We here report a catalytic co-conversion strategy where glycerol in combination with a second (bio-)feed (fatty acids, alcohols, alkanes) is used for the production of bio-based aromatics (BTX). Experiments were performed in a fixed bed reactor (10 g catalyst loading and WHSV of (co-)feed of 1 h-1) at 550 °C using a technical H-ZSM-5/Al2O3 catalyst. Synergistic effects of the co-feeding on the peak BTX carbon yield, product selectivity, total BTX productivity, catalyst life-time, and catalyst regenerability were observed and quantified. Best results were obtained for the co-conversion of glycerol and oleic acid (45/55 wt%), showing a peak BTX carbon yield of 26.7 C%. The distribution of C and H of the individual co-feeds in the BTX product was investigated using an integrated fast pyrolysis-GC-Orbitrap MS unit, showing that the aromatics are formed from both glycerol and the co-feed. The results of this study may be used to develop optimized co-feeding strategies for BTX formation. This journal is
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.
De maatschappij raakt zich in toenemende mate bewust dat het huidige lineaire economisch model niet meer houdbaar is. Het gebruik van petrochemische producten resulteert in een toename van CO2 in de atmosfeer. Verder neemt de hoeveelheid afval, met name plastics, verontrustende vormen aan en raken de oceanen zienderogen meer vervuild. Om de bovengenoemde problemen te tackelen is een transitie naar biobased en circulair essentieel. Naast dat we voor het maken van (consumenten) producten meer gebruik moeten maken van natuurlijke, hernieuwbare grondstofstromen zullen we de huidige materialen tevens veel beter moeten recyclen teneinde de druk op het milieu te verminderen. Een belangrijk thema in het recyclen van plastics is de chemische recycling. Een bekend voorbeeld waar op dit moment onderzoek naar verricht wordt is de depolymerisatie van PET naar de monomeren, GEVOLGD DOOR de scheiding van additieven en kleurstoffen en vervolgens weer een polymerisatie tot het gewenste plastic. In dit project wordt een andere methode voor chemische recycling onderzocht, namelijk de katalytische pyrolyse van (mengsels) van plastics tot de aromaten benzeen, tolueen en xylenen (BTX). Deze aromaten zijn veel gebruikte intermediairen voor tal van hoogwaardige plastics, zoals polyesters, polyamides en polyurethanen. Ruwweg 40% van alle huidige plastics is opgebouwd uit BTX. De techniek kan gebruikt worden voor mengsels van plastics en, door toepassing van de ex situ approach kunnen ook sterk vervuilde plastic stromen omgezet worden naar BTX. In samenwerking met het bedrijf BioBTX gaat de Rijksuniversiteit Groningen een kinetische studie doen naar de omzetting van plastics door gebruik te maken van tweetal geselecteerde plastic voedingen en een modelsysteem (etheen, propeen en mengels) voor de omzetting naar BTX middels een katalytische pyrolyse. De resultaten van deze studie zullen gebruikt worden voor een techno-economische evaluatie om te inventariseren of het proces commercieel aantrekkelijk is en geschikt voor verdere opschaling richting pilot/demoplant.
