Chemical modification of biomass residues during hydrothermal carbonization - What makes the difference, temperature or feedstock?

Hydrothermal carbonization (HTC) of biomass may be a suitable technique to increase its carbon sequestration potential when applied to soils. However, the properties of end products of HTC (hydrochars) could be significantly influenced by feedstock source and temperature during the carbonization process. This study focused on chemical modification of wheat straw, poplar wood and olive residues through HTC at different temperatures (180 degrees C, 210 degrees C and 230 degrees C). Besides general properties such as pH, electrical conductivity (EC), ash content, elemental composition and yield, we evaluated bulk chemical composition (C-13 NMR) and contribution of specific compounds (lignin and black carbon). Moreover, the possible environmental risk of using hydrochars was assessed by determining their polycyclic aromatic hydrocarbon (PAH) and their dioxin contents. Our results showed that hydrochars were generally acidic with a pH value below 5. The highest EC (1710 mu S/cm) and ash content (10.9%) were found in wheat straw derived hydrochars. Hydrochar yields and C recovery decreased with increasing temperature to about 50% and 75%, respectively for all feedstocks at 230 degrees C. N recovery increased with increasing temperature but N content of feedstock is more important. H/C and O/C ratios showed a linear decrease with increasing production temperature for all feedstocks. O-alkyl C decreased while alkyl C and aromatic C increased with increasing temperature and no significant feedstock dependence could be observed. Carboxyl C was not influenced by feedstock and temperature. Lignin content decreased with increasing temperature, while its oxidation degree and the content of black carbon and PAH contents increased. We conclude that transformation of biomass was most advanced at 230 degrees C only. Feedstock did not significantly influence the chemical composition of the hydrochars apart from N content and recovery. Instead, HTC temperature is the main driver determining the chemical composition of hydrochars. Environmental risk of investigated hydrochars is low with respect to PAH and dioxin contents. Despite the advanced biomass transformation during the HTC process at 230 degrees C, chemical properties indicated that the end product might have a less stable structure than pyrochar. Considering the higher hydrochar yields and C and N recoveries, its C and N sequestration potential in soil could have some advantages over hydrochars but this still remains to be evaluated. (C) 2012 Elsevier Ltd. All rights reserved.