Biofuels produced via thermochemical conversions of waste biomass could be sustainable alternatives to fossil fuels but currently require costly downstream upgrading to be used in existing infrastructure. In this work, we explore how a low-cost, abundant clay mineral, bentonite, could serve as an in situ heterogeneous catalyst for two different thermochemical conversion processes: pyrolysis and hydrothermal carbonization (HTC). Avocado pits were combined with 20 wt% bentonite clay and were pyrolyzed at 600 °C and hydrothermally carbonized at 250 °C, commonly used conditions across the literature. During pyrolysis, bentonite clay promoted Diels–Alder reactions that transformed furans to aromatic compounds, which decreased the bio-oil oxygen content and produced a fuel closer to being suitable for existing infrastructure. The HTC bio-oil without the clay catalyst contained 100% furans, mainly 5-methylfurfural, but in the presence of the clay, approximately 25% of the bio-oil was transformed to 2-methyl-2-cyclopentenone, thereby adding two hydrogen atoms and removing one oxygen. The use of clay in both processes decreased the relative oxygen content of the bio-oils. Proximate analysis of the resulting chars showed an increase in fixed carbon (FC) and a decrease in volatile matter (VM) with clay inclusion. By containing more FC, the HTC-derived char may be more stable than pyrolysis-derived char for environmental applications. The addition of bentonite clay to both processes did not produce significantly different bio-oil yields, such that by adding a clay catalyst, a more valuable bio-oil was produced without reducing the amount of bio-oil recovered.
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Catalytic pyrolysis of raw and hydrothermally carbonized Chlamydomonas debaryana microalgae for denitrogenation and production of aromatic hydrocarbons
Pyrolysis of raw and hydrothermally carbonized (HTC) Chlamydomonas debaryana with and without activated carbon (AC) or β-zeolite as the catalyst were studied. Monoaromatic hydrocarbon yields from the pyrolysis of raw and HTC treated algae without a catalyst were relatively low at optimum yields of 11.2% and 12.0% obtained at 600 °C, respectively. The maximum yields of monoaromatic hydrocarbons from the AC catalyzed pyrolysis of raw and HTC treated algae were 43.8% obtained at 600 °C and 43.5% obtained at 800 °C, respectively, compared to 32.3% and 32.7% for the maximum yields from the β-zeolite catalyzed pyrolysis at 500 °C and 600 °C, respectively. However, β-zeolite catalyzed pyrolysis produced higher yields of total hydrocarbons (aromatic + aliphatic) for raw and HTC algae compared to AC catalyzed pyrolysis. This means while β-zeolite was more effective in producing total hydrocarbon content, AC was more effective in aromatization of oxygenates. The combination of HTC pretreatment and catalytic pyrolysis were effective in reducing nitrogen content in bio-oil. The yields of nitriles and nitrogenous compounds were negligible for the AC catalyzed pyrolysis of HTC treated algae at 600 °C, compared to 8.3% using the β-zeolite at the same temperature. The AC catalyst had a lower tendency towards coking
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- Award ID(s):
- 1736173
- PAR ID:
- 10085388
- Date Published:
- Journal Name:
- Fuel
- ISSN:
- 0016-2361
- Page Range / eLocation ID:
- 234-242
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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