CET Volume 86 DOI: 10.3303/CET2186019 Paper Received: 19 September 2020; Revised: 25 January 2021; Accepted: 21 April 2021 Please cite this article as: Andersone A., Arshanitsa A., Akishin Y., Semenischev A., Telysheva G., 2021, Microwave Assisted Torrefaction of Plant Biomass of Different Origin with a Focus on Solid Products Valorisation for Energy and Beyond, Chemical Engineering Transactions, 86, 109-114 DOI:10.3303/CET2186019 CHEMICAL ENGINEERING TRANSACTIONS VOL. 86, 2021 A publication of The Italian Association of Chemical Engineering Online at www.cetjournal.it Guest Editors: Sauro Pierucci, Jiří Jaromír Klemeš Copyright © 2021, AIDIC Servizi S.r.l. ISBN 978-88-95608-84-6; ISSN 2283-9216 Microwave Assisted Torrefaction of Plant Biomass of Different Origin with a Focus on Solid Products Valorisation for Energy and Beyond Anna Andersonea, Alexandr Arshanitsaa*,Yegor Akishina,Aleksandr Semenischevb, Galina Telyshevaa aLatvian State Institute of Wood Chemistry, 27 Dzerbenes street, Riga, LV-1006, Latvia bEkokompozit Ltd., 27 Dzerbenes street, Riga, LV-1006, Latvia arshanica@edi.lv In the present paper, the microwave-assisted torrefaction of three types of the most widely spread lignocellulosic biomass feedstock, namely, wood, wheat straw, and peat, in the form of commercial fuel pellets, was studied using a laboratory-scale microwave torrefactor of original design. The torrefaction process, at temperatures varied in the range of 175-300 °C, was on-line monitored in terms of energy consumption and the temperature of the treated pellets. Elemental analysis, thermogravimetric analysis, Py- GC/MS and FTIR spectroscopy were used to characterize the biomass transformation and confirmed the simultaneous development of destruction and condensation processes in lignocarbohydrate complexes at microwave treatment. Torrefaction promoted the increase in the calorific value of all treated biomass. Higher heating values of the treated solid biomass compared to non-treated softwood, wheat straw, and peat increased by 24 %, 42 %, and 31 %, respectively. Biomass weight loss significantly depends on the structure and chemical composition of lignocellulosic matrixes of different origin. Wheat straw revealed itself as the most thermodegradable material. Therefore, although wheat straw had the highest calorific value, the overall output/input energy balance for the process of wheat straw torrefaction was less beneficial in comparison with that of peat and softwood. The microwave-assisted torrefaction promoted the increase in the hydrophobicity of the material and the improvement of its surface characteristics. Therefore, the possibility of torrefied biomass application as a natural sorbent for oil-derived products from the water surface was proposed. 1. Introduction Today, torrefaction or low-temperature pyrolysis is recognized as a key route for increasing the potential of plant biomass for large-scale production of renewable solid fuel with high energy density. The potential application of torrefied biomass includes small scale residential boilers, district heating systems (Kostas et al., 2017), and large power producers using co-firing technologies (Deutmeyer et al., 2012). An average co-firing share on the EU market could be about 70 Tg/y (Thrän et al., 2016). Finding the resources for fuel production beyond wood is an urgent task today. In this respect, wheat straw and peat, belonging to the category between fossil and renewables (Green et al., 2019), could be the most prospective due to their availability in high volumes. The use of microwave (MW) irradiation to supply heat energy for thermal conversion of biomass is recognized as a prospective decision (Hoa, 2018) because it will allow to avoid external heat carriers. Instead, volumetric heating of biomass owing to the electromagnetic energy transformation into heat energy directly inside a biomass particle with low thermal conductivity will occur and therefore will not be accompanied by the formation of additional pollutants: CO, CO2, NOX, and volatile organic compounds. In this work, the comparative effect of MW treatment on the torrefaction process of commercial pellets from softwood, wheat straw, and peat was studied, with a focus on the yield of solid products and their potential application as a fuel and a sorbent for collection of liquid fossil spills from the surface of the water area. 109 2. Materials, experimental setup, and procedures Commercial softwood pellets with a diameter of 6.0 mm, wheat straw, and peat pellets, both with a diameter of 8.0 mm, produced in Latvia, were used as objects of investigation (Table 1). Table 1: Characteristics of initial non-treated biomass pellets used as a feedstock for torrefaction Parameters Biomass Softwood Wheat straw Peat Moisture (%) 7.1 10.2 8.9 Ash content on dry matter (DM) (%) 0.3 5.0 3.4 Element composition on DM (%): C H N O 50.3 5.5 0.17 43.8 46.4 5.8 0.59 42.2 52.8 5.2 1.17 37.4 HHV on DM (MJ/kg) 19.8 18.4 20.9 A microwave laboratory device of original construction equipped with a magnetron (MW power 850 W at 2.45 GHz), a coaxial waveguide, a rotating reactor (V=1.3 L) placed in a tubular resonator (V=40 L), a condenser tool for the collection of the liquid fraction, an ejector for removing of gaseous products from the reactor, a thermocouple controller, and a power indicator SENECA S604E-6-MOD SENECA S604E-6-MOD, was applied for processing (Arshanitsa et al., 2016). The pellets (300 g) were heated in an argon atmosphere in the rotating reactor placed inside the resonator up to the maximum temperature varied in the range of 175-300 °C at constant MW power, followed by isothermal MW heating for 20 min. The yields of solid and condensable fractions were determined by weighing. Before the physico-chemical analysis, solid fractions were ground in a knife type crusher Retch 100, followed by oven-drying at 50 °C in a vacuum. The moisture, and ash content in non-treated and torrefied biomass were measured in accordance with LVS EN 1474-2:2010 and LVS EN 14775:2010, respectively. The higher heating values (HHV) of the torrefied biomass were calculated based on elemental analysis using regression equations (Toscano et al., 2009). Thermogravimetric (TG) analysis was performed in air media by the Mettler Toledo star system (10 °C/min). FTIR spectra of biomass were recorded by a Spectrum One FTIR spectrometer in the range of 4000-450 cm-1. The analytical pyrolysis (Py-GC/MS) of samples (torrefied and non-torrefied) was performed using a Frontier Lab Micro Double-shot Pyroliser Py- 2020 id (pyrolysis temperature 500 °C, heating rate 600 °C/min). 3. Results and discussion The results showed a significant difference in the structure and composition of the biomass samples under study in terms of the degree of plant cell degradation, and element and ash content, which predetermine the different dielectric losses of the presented biomass samples at MW treatment. Both softwood and wheat straw are characterized by the non-destructed morphological structure of plant cell, and the native molecular and supramolecular structure of the major cell wall components including cellulose and lignin. However, peat is formed from the biomass of terrestrial plants partly decomposed under conditions of high humidity and limited air access (initial stage of coalification) (UN, 2011; Sutton et al., 2005). Considering the elemental composition of the peat sample, its degree of decomposition (humification) can be characterized as low (H1- H3) (Fuchsman, 1980). Therefore, the cellular structure of the plant biomass introduced in the peat composition remained partly unchangeable. It was shown that, at the same regimes of treatment, the average MW assisted heating rate increased in the order: peatwood >wheat straw. • The carbonization of biomass as a result of the combined effect of thermodegradation and condensation processes promoted by MW irradiation was proved by FTIR spectroscopy, PY-GC/MS, hermogravimetric, and elemental analysis. • The calorific values of torrefied biomass increased up to 24, 42, 31% compared to those of non- treated biomass and corresponded to 24.5, 25.9, and 27.0 MJ/kg for wood, wheat straw, and peat, respectively. • Wheat straw revealed itself as the most thermodegradable biomass under study, characterized, respectively, by an inferior input/output energy balance at processing. • The decrease in the polar component content and the enhancement of the biomass porous structure achieved by its MW torrefaction at the temperature above 250 °C allows to propose them for testing as a sorbent for collection of the oil-derived products’ spill from the water surface. Acknowledgment The project ERAF No. 1.1.1.1/19/A/010: “Microwave pre-treatment of pelletized biofuels and development of new technologies for improved combustion of selectively activated fuel mixtures with efficient control of energy production and composition of emissions” is gratefully acknowledged. References Andersone A., Dižbite T., Telysheva G., Arshanitsa A., Grinshpan D., Savitskaja T., Solodovnik V., Kampars V., 2012, Lignins for Oil Spill Cleanup from Water Surface in Biorefinery Context, 8th International Conference on Renewable Resources & Biorefineries, Toulouse, France, 61–61. Arshanitsa A., Akishin Y., Zile E., Dizhbite T., Solodovnik V., Telysheva G., 2016, Microwave treatment combined with conventional heating of plant biomass pellets in a rotated reactor as a high rate process for solid biofuel manufacture, Renewable Energy, 91, 86–96. European Commission, 2015, Energy Union / Energy. 2030 Energy Strategy, ec.europa.eu/energy/topics/energy-strategy/energy-union_en. 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