Biomass gasification is a favourable process to produce a H₂-rich fuel gas from biogenic waste materials. In particular, the dual bubbling fluidized bed (DBFB) technology consists of the separation of the combustion chamber, fed with air, from the gasification chamber, fed with steam, allowing to obtain a concentrated syngas stream without N₂ dilution. In a previous work, an innovative design of a DBFB reactor was developed and its hydrodynamics tested in a cold model; in this work, the novel gasifier was realized at pilot scale (100 kWth) and operated for preliminary biomass gasification tests. The results showed a high-quality syngas, composed of H₂ = 35%, CO = 23%, CO₂ = 20%, and CH₄ = 11%, as a confirmation of the design efficacy in the separation of the reaction chambers. The dry gas yield obtained was 1.33 Nm³/kg of biomass feedstock and the carbon conversion was 73%. Tars were sampled and measured both in the raw syngas, giving a content of 12 g/Nm³, and downstream from a traditional conditioning system composed of a cyclone and a water scrubber, showing a residual tar content of 3 g/Nm³, mainly toluene. The preliminary tests showed promising results; further gasification tests are foreseen to optimize the main process parameters. Full article

The fractionation of components of lignocellulosic biomass is important to be able to take advantage of biomass resources. The hydrothermal–ethanol method has significant advantages for fraction separation. The first step of hydrothermal treatment can separate hemicellulose efficiently, but hydrothermal treatment affects the efficiency of ethanol treatment to delignify lignin. In this study, the efficiency of lignin removal was improved by an ultrasonic-assisted second-step ethanol treatment. The effects of ultrasonic time, ultrasonic temperature, and ultrasonic power on the ultrasonic ethanol treatment of hydrothermal straw were investigated. The separated lignin was characterized by solid product composition analysis, FT-IR, and XRD. The hydrolysate was characterized by GC-MS to investigate the advantage on the products obtained by ethanol treatment. The results showed that an appropriate sonication time (15 min) could improve the delignification efficiency. A proper sonication temperature (180 °C) can improve the lignin removal efficiency with a better retention of cellulose. However, a high sonication power 70% (840 W) favored the retention of cellulose and lignin removal. Full article

The COVID-19 pandemic exacerbated the use of medical protective equipment, including face masks, to protect the individual from the virus. This work studies the feasibility of using these materials as fuel for thermochemical processes for the production of syngas. A preliminary physic-chemical characterization was made by means of moisture and ash determination, thermogravimetric analysis, X-ray fluorescence. Afterward, pyrolysis and gasification tests were executed in a laboratory-scale fluidized bed reactor with chirurgical and FFP2 masks investigating four temperature levels and three different operating conditions (fluidizing agents and dry/wet sample). A qualitative and quantitative analysis of condensable aromatic hydrocarbons in the produced gas, collected during the test campaign, was performed employing a gas chromatograph-mass spectrometer. The experimental data from the tests were used to propose a hybrid approach to simulate the gasification process, based on experimental laws for the devolatilization step and a thermodynamic equilibrium approach for char gasification. The resulting data were compared with a thermodynamic equilibrium model, showing that the new approach captures non-equilibrium effects always present in real gasifiers operation. Full article

In this work, the influence of temperature on textural, morphological, and crystalline characterization of bio-adsorbents produced by hydrothermal carbonization (HTC) of corn stover was systematically investigated. HTC was conducted at 175, 200, 225, and 250 °C, 240 min, heating rate of 2.0 °C/min, and biomass-to-H₂O proportion of 1:10, using a reactor of 18.927 L. The textural, morphological, crystalline, and elemental characterization of hydro-chars was analyzed by TG/DTG/DTA, SEM, EDX, XRD, BET, and elemental analysis. With increasing process temperature, the carbon content increased and that of oxygen and hydrogen diminished, as indicated by elemental analysis (C, N, H, and S). TG/DTG analysis showed that higher temperatures favor the thermal stability of hydro-chars. The hydro-char obtained at 250 °C presented the highest thermal stability. SEM images of hydro-chars obtained at 175 and 200 °C indicated a rigid and well-organized fiber structure, demonstrating that temperature had almost no effect on the biomass structure. On the other hand, SEM images of hydro-chars obtained at 225 and 250 °C indicated that hydro-char structure consists of agglomerated micro-spheres and heterogeneous structures with nonuniform geometry (fragmentation), indicating that cellulose and hemi-cellulose were decomposed. EDX analysis showed that carbon content of hydro-chars increases and that of oxygen diminish, as process temperature increases. The diffractograms (XRD) identified the occurrence of peaks of higher intensity of graphite (C) as the temperature increased, as well as a decrease of peaks intensity for crystalline cellulose, demonstrating that higher temperatures favor the formation of crystalline-phase graphite (C). The BET analysis showed 4.35 m²/g surface area, pore volume of 0.0186 cm³/g, and average pore width of 17.08 μm. The solid phase product (bio-adsorbent) obtained by hydrothermal processing of corn stover at 250 °C, 240 min, and biomass/H₂O proportion of 1:10, was activated chemically with 2.0 M NaOH and 2.0 M HCl solutions to investigate the adsorption of CH₃COOH. The influence of initial acetic acid concentrations (1.0, 2.0, 3.0, and 4.0 mg/mL) was investigated. The kinetics of adsorption were investigated at different times (30, 60, 120, 240, 480, and 960 s). The adsorption isotherms showed that chemically activated hydro-chars were able to recover acetic acid from aqueous solutions. In addition, activation of hydro-char with NaOH was more effective than that with HCl. Full article

This work aims to systematically investigate the influence of process temperature, biomass-to-water ratio, and production scales (laboratory and pilot) on the chemical composition of aqueous and gaseous phases and mass production of chemicals by hydrothermal processing of Açaí (Euterpe oleraceae, Mart.) seeds. The hydrothermal carbonization was carried out at 175, 200, 225, and 250 °C at 2 °C/min and a biomass-to-water ratio of 1:10; at 250 °C at 2 °C/min and biomass-to-water ratios of 1:10, 1:15, and 1:20 in technical scale; and at 200, 225, and 250 °C at 2 °C/min and a biomass-to-water ratio of 1:10 in laboratory scale. The elemental composition (C, H, N, S) in the solid phase was determined to compute the HHV. The chemical composition of the aqueous phase was determined by GC and HPLC and the volumetric composition of the gaseous phase using an infrared gas analyzer. For the experiments in the pilot test scale with a constant biomass-to-water ratio of 1:10, the yields of solid, liquid, and gaseous phases varied between 53.39 and 37.01% (wt.), 46.61 and 59.19% (wt.), and 0.00 and 3.80% (wt.), respectively. The yield of solids shows a smooth exponential decay with temperature, while that of liquid and gaseous phases showed a smooth growth. By varying the biomass-to-water ratios, the yields of solid, liquid, and gaseous reaction products varied between 53.39 and 32.09% (wt.), 46.61 and 67.28% (wt.), and 0.00 and 0.634% (wt.), respectively. The yield of solids decreased exponentially with increasing water-to-biomass ratio, and that of the liquid phase increased in a sigmoid fashion. For a constant biomass-to-water ratio, the concentrations of furfural and HMF decreased drastically with increasing temperature, reaching a minimum at 250 °C, while that of phenols increased. In addition, the concentrations of CH₃COOH and total carboxylic acids increased, reaching a maximum concentration at 250 °C. For constant process temperature, the concentrations of aromatics varied smoothly with temperature. The concentrations of furfural, HMF, and catechol decreased with temperature, while that of phenols increased. The concentrations of CH₃COOH and total carboxylic acids decreased exponentially with temperature. Finally, for the experiments with varying water-to-biomass ratios, the productions of chemicals (furfural, HMF, phenols, cathecol, and acetic acid) in the aqueous phase is highly dependent on the biomass-to-water ratio. For the experiments at the laboratory scale with a constant biomass-to-water ratio of 1:10, the yields of solids ranged between 55.9 and 51.1% (wt.), showing not only a linear decay with temperature but also a lower degradation grade. The chemical composition of main organic compounds (furfural, HMF, phenols, catechol, and acetic acid) dissolved in the aqueous phase in laboratory-scale study showed the same behavior as those obtained in the pilot-scale study. Full article

Agricultural by-products have several disadvantages as fuel, such as low calorific values and high ash contents. To address these disadvantages, this study examined the mixing of agricultural by-products and spent coffee grounds, for use as a solid fuel, and the improvement of fuel characteristics through torrefaction. Pepper stems and spent coffee grounds were first dried to moisture contents of <15% and then combined, with mixing ratios varying from 9:1 to 6:4. Fuel pellets were produced from these mixtures using a commercial pelletiser, evaluated against various standards, and classified as grade A, B, or Bio-SRF. The optimal ratio of pepper stems to spent coffee grounds was determined to be 8:2. The pellets were torrefied to improve their fuel characteristics. Different torrefaction temperatures improved the mass yields of the pellets to between 50.87% and 88.27%. The calorific value increased from 19.9% to 26.8% at 290 °C. The optimal torrefaction temperature for coffee ground pellets was 230 °C, while for other pellets, it was 250 °C. This study provides basic information on the potential enhancement of agricultural by-products for fuel applications. Full article

This work investigates the effect of production scales (laboratory, bench, and pilot) by pyrolysis of Açaí (Euterpe oleracea Mart.) seeds at 450 °C and 1.0 atmosphere, on the yields of reaction products and acid value of bio-oils. The experiments were carried out in batch mode using a laboratory scale reactor of 143 mL, a bench scale reactor of 1.5 L, and a pilot scale reactor of 143 L (≈1:10:1000). The bio-oil was obtained in pilot scale, fractionated by distillation to produce biofuel-like fractions. The distillation of bio-oil was carried out in a laboratory column. The physical-chemistry properties (density, kinematic viscosity, acid value, and refractive index) of bio-oils and distillation fractions were determined. The qualitative analysis was determined by FT-IR and the chemical composition by GC-MS. The pyrolysis showed bio-oil yields from 4.37 to 13.09 (wt.%), decreasing with reactor volume. The acid value of bio-oils varied from 68.31 to 70.26 mg KOH/g. The distillation of bio-oil produced gasoline, light kerosene, and kerosene-like fuel fractions, and the yields were 16.16, 19.56, and 41.89 (wt.%), respectively. The physical-chemistry properties of distillation fractions increase with temperature. The FT-IR analysis of bio-oils and distillation fractions identified the presence of functional groups characteristic of hydrocarbons (alkenes, alkanes, aromatics, and aromatics rings) and oxygenates (carboxylic acids, ketones, esters, ethers, alcohols, phenols). The GC-MS identified 48.24 (area.%) hydrocarbons and 51.76 (area.%) oxygenates in the bio-oil produced in bench scale and 21.52 (area.%) hydrocarbons and 78.48 (area.%) oxygenates in the bio-oil produced in pilot scale. The gasoline-like fraction was composed by 64.0 (area.%) hydrocarbons and 36.0 (area.%) oxygenates, light kerosene-like fraction by 66.67 (area.%) hydrocarbons and 33.33 (area.%) oxygenates, and kerosene-like fraction by 19.87 (area.%) hydrocarbons and 81.13 (area.%) oxygenates. Full article

Chemical looping gasification (CLG) is a promising process for the thermochemical solid to liquid conversion route using lattice oxygen, provided by a solid oxygen carrier material, to produce a nitrogen free synthesis gas. Recent advances in lab-scale experiments show that CLG with biomass has the possibility to produce a carbon neutral synthesis gas. However, all experiments have been conducted in externally heated units, not enabling autothermal operation. In this study, the modification of an existing pilot plant for demonstrating autothermal operation of CLG is described. Energy and mass balances are calculated using a validated chemical looping combustion process model extended for biomass gasification. Based on six operational cases, adaptations of the pilot plant are designed and changes discussed. A reactor configuration using two circulating fluidized bed reactors with internal solid circulation in the air reactor is proposed and a suitable operating strategy devised. The resulting experimental unit enables a reasonable range of operational parameters within restrictions imposed from autothermal operation. Full article

This paper aims to investigate the usage of waste from Absorbent Hygienic Products (AHP) as a fuel for gasification or pyrolysis, two attractive routes to obtain valuable products and dispose of this kind of waste. The study experimentally investigated the devolatilization of coarsely shredded materials from diapers, in a laboratory-scale bubbling fluidized bed made of sand, as a representative preparatory step of the above-mentioned thermochemical conversions. Two versions of shredded materials were considered: as-manufactured diapers (AHPam, as a reference), and the cellulosic fraction of sterilized used diapers (AHPus). Results were presented, obtained from physical-chemical characterization of AHPam and AHPus (TGA, CHNS/O, proximate and ultimate analyses, XRF, ICP-AES, SEM-EDS), as well as from their devolatilizations at 500–600–700–800 °C under two different atmospheres (air plus nitrogen, or pure nitrogen as a reference). Generally, temperature influenced syngas composition the most, with better performances under pure nitrogen. At 700–800 °C under pure nitrogen, the highest syngas quality and yield were obtained. For AHPam and AHPus, respectively: (i) H₂ equaled 29.5 vol% and 23.7 vol%, while hydrocarbons equaled 14.8 vol% and 7.4 vol% on dry, dilution-free basis; (ii) 53.7 Nl and 46.0 Nl of syngas were produced, per 100 g of fuel. Overall, AHP emerged as an interesting fuel for thermochemical conversions. Full article

There has been intense debate over the depletion of fossil fuel reserves in recent decades as well as the greenhouse gas emissions that are causing climate change. At the same time, new legislation in Greece, national policies, European policies, and realistic needs, need effective waste management and the protection of national resources. As a result, it seems a necessity to exploit waste treatments, while expanding the use of renewable energy sources. In this study, an attempt is made to focus our interest and research on a specific biomass waste stream, namely the waste biomass from the agricultural-livestock sector. The possibility of processing these wastes through the technology of biomass biorefinery with anaerobic digestion as its central process will be studied. The technology of anaerobic digestion is a process widely used for the treatment of agricultural residues and livestock waste as well as for the exploitation of energy crops (energy development, soil enhancement) mainly in countries in Europe and globally. This study reviews the biorefinery biomass technology, the energy production technology, production of biofuels, and new materials from waste biomass at the behest of the circular economy and bioeconomy. Additionally, this research will be an introduction in maximizing the potential of the full utilization of agricultural and livestock waste, and the by-products that can be produced from these processes. Full article

Biomass pellets are a potential renewable and clean energy source. With the advantages of perfect combustion performance and easy storage and transport, biomass pellets have gradually replaced fossil fuels and become widely used. Rapid and accurate determination of biomass pellets’ quality is critical to efficient energy use. Laser-induced breakdown spectroscopy (LIBS) combined with chemometric methods were utilized. The gross calorific value (CV) and ash content (Ash), volatile matter (VM) and fixed carbon (FC) were firstly measured and analyzed. LIBS spectra and their corresponding elements of biomass pellet samples were analyzed. Three quantitative analysis models for quality indexes including partial least-squares regression (PLSR), least squares-support vector machines (LS-SVM), extreme learning machines (ELM) were further built. All models performed well, especially the LS-SVM model which obtained the best determination results, with all R² values over 0.95. Concurrently, the modeling performance of ash was slightly better than that of the other three quality indexes, which further confirmed the feasibility of using relevant elements to predict biomass quality indexes. The overall results indicated that LIBS coupled with suitable chemometrics could be an alternative promising method to determine quality indexes of biomass pellets and further improve energy utilization by using biomass materials with better quality. Full article