Catalytic hydrothermal liquefaction (HTL) of cardboard was carried out in a 300 mL Parr batch reactor using 5 wt % Ni(NO3)2, Ca(NO3)2, and NiCl2 in a temperature range of 225–300 °C for H2, biocrude, and bio-oil production. A slurry with cardboard to water weight ratio of 1:30, 1:10, 1:4, or 1:1.5 was loaded in the reactor and pressurized with N2 (40 or 200 psi). HTL was performed at various temperatures for 120 min. While HTL was in progress, gas samples were withdrawn periodically and analyzed by GC. The maximum H2 yield of 11.46 mL/g of cardboard was obtained using Ni(NO3)2 at 300 °C in 30 min. The percent liquefaction of biomass was quantified by TOC. The liquefaction yields were found to be dependent on reaction temperature, residence time, cardboard to water ratio, and operating pressure. The highest biocrude yield of 47.14% was observed at 275 °C in 30 min. Light bio-oil (LBO) and heavy bio-oil (HBO) were extracted by dichloromethane and acetone, respectively, and characterized by GC/MS and elemental analyzer. LBO contained mainly C4–C11 oxygenated hydrocarbons with a higher heating value (HHV) of 27.71 MJ/kg. HBO consisted of C17–C22 oxygenated compounds with a HHV of 29.62 MJ/kg.
Hydrothermal liquefaction (HTL) processing of lignocellulosic biomass to bio-oil produces aqueous co-product (AP) which contains significant (~40 wt%) carbon from the original feedstock. This study evaluates macro and micronutrient composition of AP from Ca(NO 3 ) 2 catalyzed HTL of cardboard (CbAP) to cultivate bacteria. HPLC, GC-MS and ICP-MS analysis of CbAP revealed presence of C1-C3 carboxylic acids, aldehydes, ketones, phenolics, sub-optimal phosphorous and bio-incompatible levels of calcium. Dilutions (5 -80 vol%) of detoxified CbAP (DTP-CbAP) in potassium phosphate buffer (pH 7.2) were supplemented with 50 mg·mL −1 of yeast extract and inoculated with metabolically versatile Enterobacter species. The cultures were incubated at 25˚C under aerobic conditions. A maximum 9.4 fold increase in the dry cell weight was observed in DTP-CbAP-15 vol%. Co-liquefaction of the bacteria with cardboard in 1:1 and 1:3 weight ratios each produced ~33% more total bio-oil. These had higher HHVs of 34.11 and 31.05 MJ·kg −1, respectively compared with bio-oil from cardboard feedstock alone which had HHV of 30.61 MJ·kg −1. The study highlights the challenges in cultivating microbes in AP from HTL of lignocellulosic biomass (LCB) and the possibility to integrate microbial capture and recycle of the AP carbon for enhanced bio-oil production and quality.
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