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The conversion of biomass primary pyrolysis vapors over several β-zeolites with silica-to-alumina ratios (SAR) varying from 21 to 250 was carried out in a flow microreactor to investigate the effect of number of acid sites on product speciation and deactivation of the catalyst. Experiments were conducted using a horizontal fixed bed semi-batch reactor in which up to 40 discrete 50 mg boats of biomass were pyrolyzed and the vapors upgraded over 0.5 g of the catalyst. Products were measured with a molecular beam mass spectrometer (MBMS). These studies were complemented using a tandem micropyrolyzer connected to a GCMS (py-GCMS) for speciation and quantifying the products. In the py-GCMS experiments, several 0.5 mg loads of pine were pyrolyzed sequentially and the vapors upgraded over 4 mg of catalyst. In all of these experiments, real-time measurements of the products formed were conducted as the catalyst aged and deactivated during upgrading. The results from these experiments showed that: (1) fresh catalyst for β-zeolites with lower SAR (more acid sites) produced primarily aromatic hydrocarbons and olefins with no detectable oxygen-containing species; (2) a suite of oxygenated products was observed from fresh catalysts with high SAR (few acid sites), indicating that 0.5 g of these catalyst materials did not have sufficient acid sites to deoxygenate vapors produced from pyrolysis of 50 mg of pine. This suite of oxygen containing products consisted of furans, phenol and cresols. The amount of coke deposited on each catalyst and the yield of aromatic hydrocarbons increased with the number of acid sites. However, while the catalysts were active, the biomass selectivity towards coke and hydrocarbons remained essentially constant on the catalysts of varying SAR. [ABSTRACT FROM AUTHOR]

The torrefaction of Loblolly pine (Pinus taeda) was examined at 250 and 300 °C, to determine the effects of treatment temperatures on the chemical structure of the torrefied Loblolly pine. Solid-state cross-polarization/magic angle spinning (CP/MAS) 13C nuclear magnetic resonance (NMR) spectroscopy was used to characterize the torrefied and native Loblolly pine. The NMR results indicate that aryl-ether bonds in lignin were cleaved during the torrefaction. The methyl carbons in hemicellulose acetyl groups were no longer present after the torrefaction at 250 °C for 4 h, which is consistent with HPLC carbohydrate analysis of the torrefied wood which indicated that the hemicellulose fraction of pine was completely absent, whereas the cellulose and lignin remained largely intact. Under these conditions the torrefied wood has a relatively high energy yield of 81.29% and a HHV of 24.06 MJ kg−1. After torrefaction at 300 °C for 4 h, the cellulose and hemicellulose in the wood were completely eliminated, the residue contains enriched amounts of carbonyl groups, aromatic carbons and methoxyl groups, which represent complex condensed aromatics, these aromatics units were linked with aliphatic C–O and C–C bonds and the product has a very high HHV of 32.34 MJ kg−1. [ABSTRACT FROM AUTHOR]

A common goal in present and future forestry, biofuels and biomaterials practices, is the need to valorize lignocellulose processes to maximize value and optimize autonomic economy. Consequently, a key focus of modern biorefining is the on-site utilization of all residual materials generating products of the highest possible value. The LignoBoost process, recently demonstrated on the pilot-scale at Kraft pulp mills, injects CO2 into pulping liquors which results in a lower solution pH and thereby precipitates lignin. The present paper compares and evaluates the pyrolysis of pulping liquor lignins precipitated by sulfuric acid (pH 3) and the aforementioned CO2 method (pH 10.5 and 9.5). The CO2 based process yielded lignin that showed superior pyrolysis properties including low gas formation and increased bio-oil yields, close to 40%, consisting primarily of low (∼150 g mol−1) molecular weight compounds. Subsequent NMR analysis showed that the oils exhibit favorable changes in functionalities, e.g. loss of aromatic and gain in aliphatic carbon percentages as well as decrease in carboxyl and methoxyl (oxygen containing) groups. Moreover, NMR results further confirmed previously hypothesized lignin pyrolysis reactions, while at the same time showed the potential of CO2 precipitated lignin for pyrolysis and subsequent liquid biofuel production. [ABSTRACT FROM AUTHOR]