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Abstract: The effect of cellulose crystallinity on the formation of a liquid intermediate and on its thermal degradation was studied thermogravimetrically and by Py-GC/MS using a control cellulose (Avicel, crystallinity at 60.5%) and ball-milled Avicel (low cellulose crystallinity at 6.5%). The crystallinity of the materials studied was quantified by XRD and FTIR. Thermogravimetric analyses (TGA) show the samples with lower crystallinity start to degrade at lower temperatures, exhibiting sharper DTG curves and lower thermal degradation activation energies. Scanning electron microscopy (SEM) studies of the solid residues formed in TGA tests showed that, while the conversion of the ball-milled cellulose (mostly amorphous cellulose) occurs through the formation of a liquid intermediate, in the conversion of the control the fibrous structure is conserved. Py-GC/MS studies showed major differences in the thermal behavior of the samples studied. At 300°C, amorphous cellulose yielded more levoglucosan. At temperatures between 350 and 450°C, higher yields of mono-anhydrosugars (levoglucosan and levoglucosenone) were obtained with the samples with higher crystallinity (control). The ball-milled cellulose produced more 5-(hydroxymethyl) furfural, 5-methylfurfural and furfural. The higher yields of these compounds are due to the acceleration of dehydration reactions when a liquid phase intermediate was formed. Fragmentation reactions responsible for the formation of light compounds (glycoaldehyde, acetic acid, methyl-vinyl-ketone and acetol) and the reactions responsible for the formation of cyclopentane do not seem to be affected by cellulose crystallinity and by the formation of a liquid intermediate. [Copyright &y& Elsevier]

Highlights • The maximum yield of oil phase organics (OPO) in CFP never exceeded the corresponding oil yield of thermal pyrolysis. • A path forward to obtain higher oil yields is not expected to come from process improvements. • For higher OPO yields, catalysts being able to convert the sugar fraction into OPO are required. Abstract Catalytic pyrolysis of woody biomass and cellulosic materials has been investigated by analyzing the effect of catalysts on aqueous phase (sugar rich) and oil phase (lignin rich) organics produced by the preceding thermal pyrolysis. Tests were done in a downer reactor using ZSM-5 and Na 2 O/γ-Al 2 O 3 as typical commercially available catalysts. Both catalysts converted the aqueous phase organics to coke, water and gas, and deoxygenated and cracked the oil phase organics. The maximum yield of oil phase organics when applying the catalysts never exceeded the corresponding oil yield of thermal pyrolysis (∼22% on carbon basis). Analysis of new results of ex-situ with in-situ catalysis, in combination with earlier reported data, indicates that a path forward to obtain higher oil yields is not expected to come from process improvements. The development of catalysts that can convert the aqueous phase organics (potentially ∼35% on carbon basis) into organic phase ones, instead of cracking and polymerizing them to respectively gas and char, should be considered. [ABSTRACT FROM AUTHOR]

The interactions between lignin and cellulose during the slow pyrolysis of their blends were studied by means of Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). Fast pyrolysis was studied using Pyrolysis-Gas Chromatography/Mass Spectroscopy (Py–GC/MS). Crystalline cellulose (Avicel), amorphous cellulose, organosolv lignin, and their blends containing 20, 50, and 80 wt.% of lignin were used for the experiments. Differential thermogravimetry (DTG) revealed that the interaction between crystalline cellulose and lignin resulted in a shift toward higher decomposition temperatures, but for lignin/amorphous cellulose mixtures this effect was small. No effect of adding lignin to cellulose was observed on the yields of bio-char. Cellulose-lignin interactions during fast pyrolysis in Py–GC/MS did occur. Products from cellulose fragmentation reactions (hydroxyl-acetaldehyde and acetol) were not influenced by the presence of lignin. In general, production of lignin derived phenolics remains quite similar at 500 °C, but the yield of many methoxylated monophenols increases at 350 °C in the presence of both types of cellulose. Importantly, it was found that the presence of lignin enhanced the yield of levoglucosan, but decreased the yield of some of their dehydration products (e.g., levoglucosenone, 5-Hydrosymethylfurfural, Furfural). This result could be explained by the reduction of residence time of cellulose products in liquid intermediates, a phase where most of the dehydration reactions occur. Lignin seems to enhance micro-explosions, decreasing in this way the residence time of cellulose derived products in the liquid intermediates. [ABSTRACT FROM AUTHOR]

• The effect of recycle gas atmosphere on biomass fast pyrolysis was investigated. • Recycle gas atmosphere did not have a notable effect on the product yields. • Recycle gas atmosphere did not lead to a bio-oil with improved quality. It has been reported that a deoxygenated bio-oil (ca. 0.12 kg kg−1 O on bio-oil basis) can be obtained simply by recycling the non-condensable gases (NCG) of biomass fast pyrolysis to a fluidized-bed reactor operated at atmospheric pressure [Mullen et al., 2013, Energy Fuels, 27, 3867–3874]. Such an unprecedented effect would (i) complicate the use of lab-scale research results obtained typically under inert gas (N 2 , He, Ar) atmosphere for the design of commercial scale pyrolysis units projected to utilize a recycle gas atmosphere (ii) obviate the need for catalytic pyrolysis or mild hydrotreatment processes. Considering these implications, further validation or refutation of the claimed deoxygenation effect of recycle gas atmosphere is needed. Therefore, fast pyrolysis experiments with pine wood were performed in a bench-scale fluidized bed reactor under N 2 atmosphere, recycle gas atmospheres (75 % and 90 % recycle gas volume fraction) at reactor temperatures of 430 °C and 500 °C. Mass balances were obtained and the bio-oils were analyzed using GC/MS, GPC, elemental analysis and Karl Fischer titration. No significant differences were observed in product yield and bio-oil composition (e.g. oxygen content) when going from a nitrogen gas atmosphere to a recycle gas atmosphere for both pyrolysis temperatures. [ABSTRACT FROM AUTHOR]