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  • Deoxy-liquefaction of switchgrass in supercritical water with calcium formate as an in-situ hydrogen donor.

Deoxy-liquefaction of switchgrass in supercritical water with calcium formate as an in-situ hydrogen donor.

Bioresource technology (2013-07-10)
Hema Ramsurn, Ram B Gupta
ABSTRACT

Switchgrass was liquefied in supercritical water (SCW) using Ca(HCOO)2 as an in-situ source of hydrogen to enhance deoxygenation and the quality of the biocrude obtained. In SCW, Ca(HCOO)2 produces hydrogen via decomposition and hydrolysis reactions, and simultaneously switchgrass hydrolyzes to form oxygenated hydrocarbon compounds. Because of the close proximity of the newly-formed hydrogen and active hydrocarbons, hydrodeoxygenation occurred whereby some of the oxygenated compounds were upgraded by the removal of oxygen in the form of water. The analysis of the so-formed biocrude revealed the presence of benzene, polyaromatic hydrocarbons, and alkyl phenolics. The benzene formation is attributed to the hydrogenation of phenols but also due to the Diels-Alder alkene addition, followed by dehydrogenation. The addition of Ca(HCOO)2 doubled the yield of biocrude (10 wt%) and increased the heating value from 28 to 34 kJ/g. Formic acid amount increased in the aqueous biocrude due to the enhanced decomposition of xylose and glucose.

MATERIALS
Product Number
Brand
Product Description

Supelco
Calcium formate, Standard for quantitative NMR, TraceCERT®, Manufactured by: Sigma-Aldrich Production GmbH, Switzerland
Sigma-Aldrich
Cesium formate, 98%
Supelco
Ammonium formate, eluent additive for LC-MS, LiChropur, ≥99.0%
Sigma-Aldrich
Ammonium formate, BioUltra, ≥99.0% (calc. based on dry substance, NT)
Sigma-Aldrich
Thallium(I) formate, 97%
Sigma-Aldrich
Ammonium formate, ≥99.995% trace metals basis
Sigma-Aldrich
Calcium formate, BioUltra, ≥99.0% (T)
Sigma-Aldrich
Ammonium formate, reagent grade, 97%
Sigma-Aldrich
Sodium formate, 99.998% trace metals basis
Sigma-Aldrich
Sodium formate-13C, 99 atom % 13C
Sigma-Aldrich
Potassium formate, ReagentPlus®, 99%
Sigma-Aldrich
Potassium formate, BioUltra, ≥99.0% (NT)
Sigma-Aldrich
Formic acid, reagent grade, ≥95%
Sigma-Aldrich
Formic acid, ACS reagent, ≥88%
Sigma-Aldrich
Formic acid, ≥95%, FCC, FG
Sigma-Aldrich
Formic acid solution, BioUltra, 1.0 M in H2O
Sigma-Aldrich
Sodium formate, BioUltra, ≥99.0% (NT)
Sigma-Aldrich
Ammonium formate solution, BioUltra, 10 M in H2O
Sigma-Aldrich
Formic acid, puriss. p.a., ACS reagent, reag. Ph. Eur., ≥98%
Sigma-Aldrich
Sodium formate, reagent grade, 97%
Sigma-Aldrich
Formic acid, ACS reagent, ≥96%
Sigma-Aldrich
Sodium formate, ACS reagent, ≥99.0%
Sigma-Aldrich
Formic acid, puriss., meets analytical specifications of DAC, FCC, 98.0-100%