Biomass gasification in supercritical water:

Chemistry of decomposition of alcohols and acids

Why we are studying this

Objective of this study

To meet the current energy demand and decrease the carbon footprint on the
planet there is a great need to find alternative renewable energy sources.
Biomass is one of the promising candidates for renewable energy sources.
Supercritical water is an interesting medium for the production of H2/CH4 rich
products (with high energetic value) from diluted, wet biomass that has a low
overall heating value. SCWG technology has potential to convert municipality
sludge, organic waste streams etc. that have negative market value into energy
rich gaseous stream.

The objective of this study is to contribute to the understanding of

the chemistry of biomass gasification in supercritical water by
elucidating the relationship between molecular structure (chain
length, functional groups) and gasification behavior. Carboxylic
acids and alcohols are frequently observed as intermediate
products from the hydrothermal gasification of a wide variety of
organic compounds, wastes and biomass and hence chosen for our
study as model compounds.

What we have found

We found that chain length of alcohol and acid has no significant effect on
gasification efficiency however it does have effect on gas composition.
Differences in gas compositions can be explained by the -scission reaction
pathway. In case of alcohols decomposition into CO is dominate while in case of
acids decarboxylation reaction is dominant. We found that concentration has no
much effect on gasification efficiency of alcohols while a significant decrease in
gasification efficiency is observed with increase in concentration of acids
suggesting first order kinetics in case of alcohols while zero order kinetics in case
of acids. Later in our modeling of methanol gasification, we validated the
occurrence of first order kinetics. Based on the experimental results, reaction
pathways of the individual compounds are proposed. We found that
homogeneous catalyst KOH enhances gasification efficiency of studied alcohols
and acids by enhancing extraction of hydrogen atom which seems to be the
major initiation reaction. We found that increasing electron releasing OH group
increases the gasification however the position of OH group has no influence on
the gasification suggesting C-OH cleavage is not the major route of the gas
formation. We developed a quantitative kinetic model for the gas formation in
the SCWG of methanol considering the catalytic wall effect. It is figured out that
major reaction responsible for the methanol gasification under supercritical
water is decomposition of methanol into CO and H2.

Who I am
Myself, Shushil Kumar graduated cum laude as
Master of Science in Process Technology from
University of Twente. I wrote my master thesis
on the topic presented in this flyer. After my
graduation, I decided to pursue an academic
carreer as a PhD-student in the group of
Prof.dr. S.R.A. Kersten, at University of Twente.