Journal
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
Volume 7, Issue 9, Pages 8387-8396Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.9b00024
Keywords
Hydrothermal carbonization; Hydrochar; Pyrolysis; Boehm titration; Electron storage capacity; Acidic oxygen-containing functional groups
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Funding
- Ohio University
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Hydrothermal carbonization (HTC) is a thermochemical process, where biomass is treated with subcritical water. Hydrochar, the solid product of HTC, is a carbon-rich material containing acidic functional groups. In order to increase total surface area, one of the common practices is to pyrolyze it. However, dehydration occurs during pyrolysis, which may affect the acidic functional groups on hydrochar. In addition, biochars have recently been shown to possess significant electron storage capacities (ESC), but it was unknown whether pyrolyzed hydrochars also possess ESC and to what extent. In this article, the effect of pyrolysis temperature on acidic oxygen-containing functional groups and ESC of pyrolyzed hydrochars is evaluated. Hydrochars were prepared from cellulose and wood at 220 and 260 degrees C. These hydrochars were then pyrolyzed at 400, 500, and 600 degrees C under an N 2 atmosphere. Afterward, the changes in functional groups were evaluated by BET analysis, ultimate analysis, ESC measurement, pH, pH at point of zero charge (pH(PZC)), Boehm titration, and FTIR analysis. The hydrochars showed relatively low surface areas mostly due to the lack of pores or pores being clogged with volatiles. The surface area was increased by an order of magnitude after pyrolysis; however, acidic oxygen-containing functional groups decreased significantly with increasing pyrolysis temperature. ESC was also decreased with increasing pyrolysis temperature, ranging from 1.44 (cellulose at 600 degrees C) to 3.25 (wood at 400 degrees C) mmol/g. This result suggests that a portion of the ESC of the pyrolyzed wood hydrochars originated from cellulose. A linear correlation between ESC and lactonic group was observed for pyrolyzed hydrochars.
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