Date of Award
Doctor of Philosophy
Robert C. Brown
Sugars are the feedstocks for many promising advanced cellulosic biofuels. Traditional sugars derived from starch and sugar crops are limited in their availability. In principle, more plentiful supply of sugars can be obtained from depolymerization of cellulose, the most abundant form of biomass in the world. Breaking the glycosidic bonds between the pyranose rings in the cellulose chain to liberate glucose has usually been pursued by enzymatic hydrolysis although a purely thermal depolymerization route to sugars is also possible. Fast pyrolysis of pure cellulose yields primarily levoglucosan, an anhydrosugar that can be hydrolyzed to glucose. However, naturally occurring alkali and alkaline earth metals (AAEM) in biomass are strongly catalytic toward ring-breaking reactions that favor formation of light oxygenates over anhydrosugars.
Removing the AAEM by washing was shown to be effective in increasing the yield of anhydrosugars; but this process involves removal of large amount of water from biomass that renders it energy intensive and thereby impractical. In this work passivation of the AAEM (making them less active or inactive) using mineral acid infusion was explored that will increase the yield of anhydrosugars from fast pyrolysis of biomass. Mineral acid infusion was tried by previous researchers, but the possibility of chemical reactions between infused acid and AAEM in the biomass appears to have been overlooked, possibly because metal cations might be expected to already be substantially complexed to chlorine or other strong anions that are found in biomass. Likewise, it appears that previous researchers assumed that as long as AAEM cations were in the biomass, they would be catalytically active regardless of the nature of their complexion with anions.
On the contrary, we hypothesized that AAEM can be converted to inactive or less active salts using mineral acids. Various biomass feedstocks were infused with mineral (hydrochloric, nitric, sulfuric and phosphoric acids) and organic acids (formic and acetic acids) followed by analytical pyrolysis on a micropyrolyzer/GC/MS/FID system. It was found that sulfuric and phosphoric acids are very effective in passivating the AAEM thereby increasing the yield of anhydrosugars. An excellent correlation was discovered between the amount of acid required to obtain the maximum yield of anhydrosugars and the amount of AAEM contained in the biomass feedstock. In the micro-scale studies, up to 56% of the cellulose contained in the biomass was converted into anhydrosugars which is close to the 57% conversion obtained from pure cellulose pyrolysis.
It is known that LG polymerization and subsequent charring occur at temperatures above 275Â°C depending on the vapor pressure of LG in the gas stream. A study of pyrolysis of acid-infused biomass feedstocks at various temperatures revealed that LG recovery is best at lower temperatures than the conventional pyrolysis temperature range of 450-500Â°C.
Pyrolysis of acid-infused biomass failed in a continuous fluidized bed reactor due to clogging of the bed. The feedstock formed vitreous material along with the fluidizing sand that was formed from poor pyrolysis of lignin. However, more investigation of this phenomenon is a subject for future work. Pyrolysis experiments on an auger type reactor were successful in producing bio-oils with unprecedented amounts of sugars. Though there was increase in charring when compared to the control feedstock, pyrolysis of red oak infused with 0.4 wt% of sulfuric acid produced bio-oil with 18wt% of sugars.
One of the four fractions of bio-oil collected contained most of the sugars, which shows significant potential for separating the sugars from bio-oil using simple means. This work points towards a new pathway for making advanced biofuels viz. upgrading pyrolytic sugars from biomass that could compete with enzymatic sugars from biomass.
Najeeb M. Kuzhiyil
Kuzhiyil, Najeeb M., "Pyrolytic sugars from cellulosic biomass" (2013). Graduate Theses and Dissertations. 13644.