Microwave pyrolysis of biomass for bio-oil production: Scalable processing concepts

The pursuit of sustainable hydrocarbon alternatives to fossil fuels has prompted an acceleration in the development of new technologies for biomass processing. Microwave pyrolysis of biomass has long been recognised to provide better quality bio-products in shorter timescales compared to conventional pyrolysis. Although this topic has been widely assessed and many investigations are currently ongoing, this article gives an overview beyond the physico-chemical pyrolysis process and covers engineering aspects and the limitations of microwave heating technology. Herein, we provide innovative scalable concepts to perform the microwave pyrolysis of biomass on a large scale, including essential energy and material handling requirements. Furthermore, some of the possible socio-economic and environmental implications derived from the use of this technology in our society are discussed. Such potential concepts are expected to assist the needs of the industrial bioenergy community to move this largely studied process upwards in scale

Biofuel characteristics of chars produced from rapeseed, whitewood, and seaweed via thermal conversion technologies – Impacts of feedstocks and process conditions

Understanding the suitability of different conversion technologies for different types of biomass feedstocks is crucial in delivering the full valorisation of different types of biomass feedstocks. Optimal valorisation pathways can be identified by investigating the formation of products and the most efficient application technologies of these products. This is therefore novel research reporting an extensive comparative study on the biomass processing pathways (hydrothermal conversion, pyrolysis, and torrefaction) for three distinct biomass feedstocks (Rapeseed residue, Whitewood, Seaweed–Laminaria Digitata) to optimise char formation under a wide range of processing conditions and their biofuel characteristics in the bioenergy applications. The results demonstrates that Whitewood gradually decomposes during all three conversion processes to produce chars (hydrochars/biochars) that have a lower O/C-H/C ratio as process temperature increases. The char formation from Whitewood follows the dehydration process in the Van Krevelen diagram. Char formation from Rapeseed residue and L. digitata via pyrolysis also follows a similar dehydration and demethanation pathway at higher temperatures (550 °C for Rapeseed residue and 400 °C for L. digitata). However, char formation from Rapeseed residue and L. digitata via hydrothermal conversion predominantly follows the decarboxylation pathway producing structures with a higher H/C ratio and lower O/C ratio. The intrinsic reactivity analysis of these chars showed that the temperature of initial weight loss and the onset of ignition for the raw biomass sample was shifted to a higher temperature for the chars produced by hydrothermal conversion or pyrolysis, regardless of biomass feedstocks. The chars produced from Whitewood (with hydrothermal conversion, pyrolysis and torrefaction) and Rapeseed residue (with pyrolysis) have a potential application in bioenergy production due to the significant enhancement of char products. However, the chars produced from L. digitata appear less promising for bioenergy applications due to relatively low energy yield, carbon recovery, inferior char structures and a high inherent ash content

Exploring the utilisation of natural biosorbents for effective methylene blue removal

This paper presents a comprehensive analysis of the adsorbent capacity of five distinctly different biosorbents derived from untreated biomasses. The optimal adsorption capacity of seaweed (Laminaria digitata), horse chestnut husk, hazelnut husk, rapeseed residue, and whitewood to remove methylene blue (MB) dye was assessed by analysing the effects of particle size, pH, temperature, and initial dye concentrations. Furthermore, the adsorption kinetics, isotherms, and adsorption thermodynamics were investigated. The results showed that relatively high MB adsorption capacity was achieved by Laminaria digitata (~180 mg/g), in addition to a reasonable MB adsorption capacity of horse chestnut husk (~130 mg/g), hazelnut husk (~110 mg/g), and rapeseed residue (~80 mg/g). However, whitewood provides a relatively low adsorption capacity of below 20 mg/g. The best fit with experimental results regardless of biosorbent type was a pseudo-second-order kinetic model with the lowest mean absolute percentage error (ε, MAPE 0.99). Although the pseudo-second-order kinetic model is often associated with chemisorption, the low enthalpy values (<29.30 kJ/mol) typically suggest that the adsorption process is more characteristic of physisorption, which involves weaker van der Waals forces rather than the stronger covalent bonds of chemisorption. This proposed a multi-step adsorption process involving both physisorption and chemisorption. The adsorption isotherm of Langmuir showed superior fitting results for Laminaria digitata and hazelnut husk. In contrast, rapeseed residue and horse chestnut husk fit better with the Freundlich adsorption isotherm. The Langmuir adsorption isotherms showed a maximum adsorption capacity of ~500 mg/g for Laminaria digitata, followed by horse chestnut husk (~137 mg/g), hazelnut husk (~120 mg/g), and rapeseed residue (~85 mg/g). The Gibbs free energy was negative for Laminaria digitata < horse chestnut husk < hazelnut husk < 0, which suggests that the removal of MB is thermodynamically favourable, as the adsorption process occurs spontaneously. The results of the study indicate that MB dye removal using untreated biomasses has the potential to be a low-cost valorisation option in the holistic whole life cycle valorisation pathway for Laminaria digitata, horse chestnut husk, and hazelnut husk

Microwave pyrolysis of biomass within a liquid medium

A new approach to pyrolysis is demonstrated that uses microwave heating combined with an external liquid media at atmospheric pressure. The liquid acts as the inerting medium instead of the traditional inert gas, and also acts as a heat-sink to maintain the external temperature at the normal boiling point of the liquid. The ability to regulate the external temperature using a liquid offers significant advantages over established pyrolysis technologies and is only possible due to the selective and volumetric heating that occurs with microwaves. The new concept overcomes many of the challenges encountered in traditional and gas-based microwave pyrolysis processes, producing a bio-oil that naturally partitions into a sugar-rich aqueous phase and a phenol-rich organic phase. Energy requirements are as low as 2 kJ/g for 50% volatilisation, comparable to microwave pyrolysis using inert gases. It is shown that the new concept works effectively with both microwave-transparent and microwave-absorbent solvents. The liquid media also acts to eliminate arcing and prevent carbonaceous residues from forming, phenomena which have so far proved challenging for the scale-up of microwave pyrolysis processes

Hydrothermal conversion of different lignocellulosic biomass feedstocks – effect of the process conditions on hydrochar structures

Five biomass feedstocks (Coffee residues, Rice waste, Whitewood, Zilkha black, and Lignin) were hydrothermally processed in a semi-continuous flow rig using 9 different processing conditions (75, 150, 250 °C, and 1, 50, 240 bar). Solid residues produced at low temperature (<150 °C) did not show significant structural changes. At more severe conditions, structural changes could be linked to the lignocellulosic composition and divided into three categories: (i) biomass with higher hemicellulose-cellulose and lower cellulose-lignin structures, (ii) lower hemicellulose-cellulose and higher cellulose-lignin structures, and (iii) only cellulose-lignin structures. Both hemicellulose and cellulose structures in category (i) and (ii) were successfully degraded under subcritical conditions (250 °C and 50 bar) to produce hydrochar with higher lignin content. Biomasses with higher levels of lignin did not show the same degree of transformation. Category (i) produced a low hydrochar yield (39 wt%) due to the degradation of higher hemicellulose-cellulose structures. Category (ii) had higher hydrochar yields (58–62 wt%) due to the lower amount of cellulose and hemicellulose. Category (iii) had the highest hydrochar yields (73–90 wt%) thanks to the lack of hemicellulose and lower cellulosic structures. A novel concept called “displacement”, based on a thermogravimetric profiling method, was used to quantify changes in the pyrolysis behaviour of the hydrochar compared to the original feedstock. The degree of “displacement” correlated with hydrochar yield and reactivity, the highest level of displacement was observed with category (i- higher hemicellulose-cellulose biomasses) while the lowest displacement was observed with category (iii- higher lignin biomasses). This novel technique could be used to quantify the effects of hydrothermal treatment on any given biomass