Hydro-pyrolysis and catalytic upgrading of biomass and Its hydroxy residue fast pyrolysis vapors

Fast pyrolysis of Miscanthus, its hydrolysis residue and lignin were carried with a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) followed by online vapor catalytic upgrading with sulfated ZrO2, sulfated TiO2 and sulfated 60 wt.% ZrO2-TiO2. The most evident influence of the catalyst on the vapor phase composition was observed for aromatic hydrocarbons,light phenols and heavy phenols. A larger amount of light phenols was detected, especially when 60 wt.% ZrO2-TiO2 was present. Thus, a lower average molecular weight and lower viscosity of bio-oil could be obtained with this catalyst. Pyrolysis was also performed at different pressures of hydrogen. The pressure of H2 has a great effect on the overall yield and the composition of biomass vapors. The peak area percentages of both aromatic hydrocarbons and cyclo-alkanes are enhanced with the increasing of H2 pressure. The overall yields are higher with the addition of either H2 or sulfated catalysts. This is beneficial as phenols are valuable chemicals, thus, increasing the value of bio-oil. The results show that the hydrolysis residue has the potential to become a resource for phenol production

Impact of Zr Incorporation into the Ni/AlSBA-15 Catalyst on Its Activity in Cellulose Conversion to Hydrogen-Rich Gas

This work focused on the investigation of the effect of zirconium incorporation into the structure of the Ni/AlSBA-15 catalyst on its performance in high-temperature conversion of cellulose (the main component of lignocellulosic feedstock) to hydrogen-rich gas. The modified supports were prepared by direct incorporation of zirconium and impregnation methods. The obtained results exhibited that introduction of zirconium into the structure of Ni/AlSBA-15 allowed for a considerable increase in the amount of hydrogen produced in the studied process in comparison to unmodified Ni/AlSBA-15 material. The characterization of physicochemical properties of the investigated materials (X-ray diffraction, scanning electron microscopy–energy-dispersive X-ray spectroscopy, time-of-flight secondary ion mass spectrometry, temperature-programmed reduction, temperature-programmed desorption of ammonia, etc.) showed that the preparation of mesoporous Ni/ZrAlSBA-15 with the use of the direct synthesis method led to obtaining the catalyst with a higher surface area and pore volume and smaller crystallites of an active phase in comparison to the material containing nickel supported on ZrAlSBA-15 with zirconium introduced by impregnation. Despite that the mesoporous catalyst prepared by impregnation possessed higher acidity, its structure underwent partial collapse during the preparation procedure

Supercritical extraction of biomass-A green and sustainable method to control the pyrolysis product distribution

This research demonstrates that supercritical extraction of the biomass has a remarkable and complex influence on Scots pine tree fractions changing the surface concentration of water, lipids, and metals simultaneously. Surprisingly, this surface composition modification makes a considerable impact on the pyrolysis of the bulk biomass mechanism, leading to the alternation of the volatile and inorganic matter composition. The unique combination of time-of-flight secondary-ion mass spectrometry analysis and utilization of pyrolysis gas chromatography−mass spectrometry data on the thermal behavior of woody biomass demonstrates, for the first time, the extraordinary influence of surface adsorbed metals on the composition of pyrolysis products. ScCO2 could extract the surface metals in the form of fatty acid salts, demonstrating a sustainable and environmentally friendly pretreatment method for controlling the pyrolysis products

The effect of particle size, temperature and residence time on the yields and reactivity of olive stones from torrefaction

Olive stones obtained as a by-product from olive oil extraction in combination with the favourable climate in Mediterranean countries are value-added feedstocks for the energy sector due to low moisture content ( 20 wt. %), suitable calorific value ( 18.7 MJ kg−1 as received) and high bulk density (about 750 kg m−3). The torrefaction process at Arigna Fuels with high energy efficiency of (above 90%) improves biomass properties for conversion to a high-value fuel for use in solid fuel stoves. This study reports the effect of moisture content, organic composition, inorganic matter, particle size, heat treatment temperature and residence time on product yields, O2/CO2 reactivity, calorific value, composition and thermal conductivity value of torrefied olive stones. Results showed that both lignocellulosic content and ash composition equally influenced the reactivity of torrefied material. For the first time, time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that the structure of torrefied material from small olive stone particles contains more cellulose than lignin when compared to large grains. Importantly from a technological standpoint, the lower heating values of torrefied olive stones (21.8 MJ kg−1) [1] from a small scale reactor were within the range of values for torrefied woodchip briquettes containing high starch binder content which was an energy increase of 15% when compared to the raw feedstock. The results showed that olive stones of particle size ≤ 2 mm produced during torrefaction at 270 °C for 30 min are the most suitable material and conditions for briquetting due to high solid yield, low reactivity and low thermal conductivity values. These conditions are recommended for the pilot plant operation using olive stones from the Mediterranean region