Cellulose

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Cellulose is the most globally abundant biopolymer, accounting for 1.5x1012 tonnes of

annually available biomass. [1] As such, there has been considerable interest in recent

years in the development of new technologies for the utilization of cellulose as a

feedstock for the production of fine chemicals [2-5] and hydrogen.[6-10] Amongst these

technologies, hydrothermal conversion is of growing interest since pre-drying of

feedstocks are avoided and the water gas shift can be performed in situ using platinum

group metal catalysts. Furthermore, the unique properties of hot compressed water can be

tuned to control decomposition pathways.

Upon hydrolysis to glucose, the decomposition of cellulose in hot compressed water

is known to follow the same path of glucose decomposition, forming a large number of

organic acids, aldehydes, ketones, furfurals, and phenolic structures as intermediates. [11-

13] Kabyemela et al., have investigated the kinetics of the decomposition of glucose, the

monomer of cellulose, in subcritical water at short residence times and proposed basic

non-catalytic pathways for its initial decomposition as presented in Figure 1. These

pathways have formed the backbone of current understanding on the decomposition of

cellulosic biomass in hot compressed water thus far. While it is known that gas products

originate from short chain aldehydes and acids [12], which acid/aldehydes the gas is

primarily produced from, and through which intermediates is of great interest. More work

is required on understanding which pathways contribute to the gas formation. Since each

chemical intermediate has a different rate of gasification, understanding which pathways

generate more easily gasified intermediates is an im...

... middle of paper ...

...viour in terms of how it controls the

gasification pathways of cellulose.

In the present study, the effect of headspace fraction is studied to determine if the

altered phase behaviour of the solution affects decomposition pathways, and how these

may lead to gasification. The effects of sodium carbonate concentration and headspace

fraction at 315oC are studied. Sodium carbonate concentrations were studied between 0

and 1M concentration in the presence of 1% by weight, 5%Pt/Al2O3 as metal catalyst.

Headspace fractions between 49 and 93% of the reactor volume were studied at sodium

carbonate concentrations of 0, 50, 100 and 500 mM. Finally, the relationship between the

headspace fraction and changes in the liquid phase composition are discussed in terms of

the balance between free radical and ionic reaction pathways that mediate the

decomposition of cellulose.

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