Insight into volatile-char interaction mechanisms of biomass torrefaction based on three major components.

Volatile-char interaction is an important phenomenon in biomass thermal conversion process, which significantly contributes to the decomposition, deoxygenation and upgrading of biomass. However, the deep insight into volatile-char interaction mechanisms between hemicellulose, cellulose and lignin is currently unclear. In this work, above mechanism was studied through systematic single-/bi-component torrefactions and the follow-up char analysis. Results demonstrate that only hemicellulose volatile and cellulose char interaction exists during torrefaction at 250 °C, causing over 19.9 wt% of mass loss and 27.3 wt% of O removal for cellulose. This volatile-char interaction causes significant depolymerization and amorphization of cellulose by hydrolysis, acid hydrolysis and esterification reactions. The depolymerized and amorphous cellulose partly thermally decomposes to dehydrated sugars and aromatic compounds through dehydroxylation and aromatization reactions. A volatile-char interaction mechanism model is thus developed. This work provides theoretical insight into biomass thermal conversion and provides basis for the development of new thermochemical method.

Microwave absorber utilization to improve grinding and particle surface structure characteristics of torrefied switchgrass particles for bioenergy applications.

Torrefaction treatment improves biomass grindability by transforming the fibrous herbaceous to a more brittle and lighter coal-like material. Microwave-assisted torrefaction is a promising technology for biomass conversion into energy, fuels, and chemicals. The study applied microwave absorbers in the torrefaction process to improve the thermochemical characteristics and grindability of switchgrass. Switchgrass in two particle sizes was torrefied in a microwave reactor with biochar added as a microwave absorber under inert conditions. After torrefaction, the geometric mean particle and size distribution and selected physical characteristics were evaluated, and the grindability of the torrefied ground and chopped with and without biochar were compared with those of untreated switchgrass. The geometric diameter results decreased, and the specific energy required for grinding torrefied switchgrass with biochar was significantly reduced with extended residence times and at a torrefaction temperature of 300 °C. After grinding, the lowest grinding energy of 32.82 kJ at 300 °C/20 min was recorded with torrefied ground switchgrass/biochar. The 10% biochar added/250 °C resulted in deep cell wall disarrangement, whereas at a torrefaction temperature of 300 °C, large surface deformation and carbonized weight fractions were observed.

Key fuel characteristics and techno-economic aspects of torrefied rubberwood biomass pellets produced by incorporating various cassava-based binders at varied doses.

Improving energy content and hydrophobic nature of woody biomass can be pursued through torrefaction. This gives torrefied biomass with a low bulk density, potentially increasing storage and transport costs. To overcome this issue, densifying the torrefied biomass is necessary. However, poor binding of particles makes densification challenging without using a binder. Therefore, the aim of this study was to investigate the physicochemical characteristics and techno-economic aspects of torrefied rubberwood biomass (TRWB) when pelletized using various cassava-based binders at different blending ratios. The selected binders included cassava starch (CS), cassava pulp (CP), and cassava chip (CC). Each binder at 5%, 10%, or 15% (wt.) was mixed with TRWB and water before pelletizing using a flat die machine. The results revealed that pelletizing TRWB with different cassava-based binders at various blending ratios influenced the physicochemical characteristics of the TRWB pellets, particularly dimensions, bulk density, fuel and atomic ratios, and energy content. The TRWB pellets demonstrated energy densities in the range of 7.95-11.39 GJ/m3, and their mechanical durability and fine content fell within acceptable ranges. The TRWB pellets maintained their shape during 120 min of water soaking, with water absorption levels varying by binder dose. The pelletizing ability, material, and energy costs of TRWB pellets depend on binder type and dose. CP can be applied as a binder for pelletizing torrefied rubberwood biomass. However, the mechanical durability of the product needs to be above the user requirement or standard.

An Optimized Method for Evaluating the Preparation of High-Quality Fuel from Various Types of Biomass through Torrefaction.

The pretreatment for torrefaction impacts the performance of biomass fuels and operational costs. Given their diversity, it is crucial to determine the optimal torrefaction conditions for different types of biomass. In this study, three typical solid biofuels, corn stover (CS), agaric fungus bran (AFB), and spent coffee grounds (SCGs), were prepared using fluidized bed torrefaction. The thermal stability of different fuels was extensively discussed and a novel comprehensive fuel index, "displacement level", was analyzed. The functional groups, pore structures, and microstructural differences between the three raw materials and the optimally torrefied biochar were thoroughly characterized. Finally, the biomass fuel consumption for household heating and water supply was calculated. The results showed that the optimal torrefaction temperatures for CS, AFB, and SCGs were 240, 280, and 280 °C, respectively, with comprehensive quality rankings of the optimal torrefied biochar of AFB (260) > SCG (252) > CS (248). Additionally, the economic costs of the optimally torrefied biochar were reduced by 7.03-19.32%. The results indicated that the displacement level is an index universally applicable to the preparation of solid fuels through biomass torrefaction. AFB is the most suitable solid fuel to be upgraded through torrefaction and has the potential to replace coal.

Turning trash into treasure: Torrefaction of mixed waste for improved fuel properties. A case study of metropolitan city.

Solid waste management is one of the biggest challenges of the current era. The combustible fractions in the waste stream turn out to be a good energy source if converted into refuse-derived fuel. Researchers worldwide are successfully converting it into fuel. However, certain challenges are associated with its application in gasifiers, boilers, etc. to co-fire it with coal. These include high moisture content, low calorific value, and difficulty to transport and store. The present study proposed torrefaction as a pretreatment of the waste by heating it in the range of 200 °C-300 °C in the absence of oxygen at atmospheric pressure. The combustible fraction from the waste stream consisting of wood, textile, paper, carton, and plastics termed as mixed waste was collected and torrefied at 225 °C, 250 °C, 275 °C, and 300 °C for 15 and 30 min each. It was observed that the mass yield and energy yield decreased to 45% and 62.96% respectively, but the energy yield tended to increase by the ratio of 1.39. Proximate analysis showed that the moisture content and volatile matter decreased for torrefied samples, whereas the ash content and fixed carbon content increased. Similarly, the elemental analysis revealed that the carbon content increased around 23% compared to raw samples with torrefaction contrary to hydrogen and oxygen, which decreased. Moreover, the higher heating value (HHV) of the torrefied samples increased around 1.3 times as compared to the raw sample. This pretreatment can serve as an effective solution to the current challenges and enhance refuse-derived fuel's fuel properties.

Machine learning models for predicting biochar properties from lignocellulosic biomass torrefaction.

This study developed six machine learning models to predict the biochar properties from the dry torrefaction of lignocellulosic biomass by using biomass characteristics and torrefaction conditions as input variables. After optimization, gradient boosting machines were the optimal model, with the highest coefficient of determination ranging from 0.89 to 0.94. Torrefaction conditions exhibited a higher relative contribution to the yield and higher heating value (HHV) of biochar than biomass characteristics. Temperature was the dominant contributor to the elemental and proximate composition and the yield and HHV of biochar. Feature importance and SHapley Additive exPlanations revealed the effect of each influential factor on the target variables and the interactions between these factors in torrefaction. Software that can accurately predict the element, yield, and HHV of biochar was developed. These findings provide a comprehensive understanding of the key factors and their interactions influencing the torrefaction process and biochar properties.

Experimental strategy for the preparation of adsorbent materials from torrefied palm kernel shell oriented to CO2 capture.

In this study, an experimental strategy to obtain biochar and activated carbon from torrefied palm kernel shell as an efficient material for CO2 removal was evaluated. Biochar was obtained by slow pyrolysis of palm kernel shell at different temperatures (350 °C, 550 °C, and 700 °C) and previously torrefied palm kernel shell at different temperatures (220 °C, 250 °C, and 280 °C). Subsequently, activated carbons were prepared by physical activation with CO2 from previously obtained biochar samples. The CO2 adsorption capacity was measured using TGA. The experimental results showed that there is a correlation between the change in the O/C and H/C ratios and the functional groups -OH and C=O observed via FTIR in the obtained char, indicating that both dehydration and deoxygenation reactions occur during torrefaction; this favors the deoxygenation reactions and makes them faster through CO2 liberation during the pyrolysis process. The microporous surface area shows a significant increase with higher pyrolysis temperatures, as a product of the continuous carbonization reactions, allowing more active sites for CO2 removal. Pyrolysis temperature is a key factor in CO2 adsorption capacity, leading to a CO2 adsorption capacity of up to 75 mg/gCO2 for biochar obtained at 700 °C from non-torrefied palm kernel shell (Char700). Activated carbon obtained from torrefied palm kernel shell at 280 °C (T280-CHAR700-AC) exhibited the highest CO2 adsorption capacity (101.9 mg/gCO2). Oxygen-containing functional groups have a direct impact on CO2 adsorption performance due to electron interactions between CO2 and these functional groups. These findings could provide a new experimental approach for obtaining optimal adsorbent materials exclusively derived from thermochemical conversion processes.

Effects of water washing and KOH activation for upgrading microalgal torrefied biochar.

Torrefaction is an effective pathway for microalgal solid biofuel upgrading, and alkali metal activation is also an efficient method to enhance fuel properties. This study explores the comparison of torrefaction alone and KOH activation combined with torrefaction to determine a better operation for biochar production from the microalga Nannochloropsis Oceanica. The results indicate that the HHV ranges of KOH-activated biochar and unactivated biochar are 25.611-32.792 MJ·kg-1 and 25.024-26.389 MJ·kg-1, respectively. Furthermore, KOH-activated biochar is better than unactivated biochar, with less residue, broader pyrolysis and combustion temperature ranges, higher elemental carbon, and less combined carbon. Moreover, KOH-activated biochar is close to the unactivated one from the viewpoint of expense calculation and life cycle assessment and thus possesses a better comprehensive performance. Overall, KOH activation is an efficient method for upgrading microalgal solid biofuel. The results are conducive to exploring further modification of microalgal solid biofuel production with better properties, thus leading to a greener and more efficient approach for upgrading fuel performance.

Enhancing fuel characteristics and combustion performance of cellulose-rich straws through CO2-assisted torrefaction.

Cellulose-rich straws of corn and rice were torrefied under carbon dioxide, and the fuel characteristics and combustion performance of the obtained biochar were investigated. A high severity resulted in surface collapse, greater pore volume, elimination of oxygen, elevated calorific value, and improved hydrophobicity in biochar. Following carbon dioxide torrefaction, the cellulose content in solid biochar experienced a slight decrease when the temperature was raised to 220 °C for longer residence durations. At 300 °C, the cellulose content in the biochar was nearly eliminated, while the relative proportion of non-sugar organic matter in corn stover and rice straw increased to 87.40 % and 77.27 %, respectively. The maximum calorific values for biochar from corn and rice straws were 22.38 ± 0.03 MJ/kg and 18.72 ± 0.05 MJ/kg. The comprehensive combustion indexes of rice and corn straw samples decreased to 1.06 × 10-7 and 1.31 × 10-7 after torrefaction at 300 °C, respectively. In addition, the initial decomposition temperatures increased by 38 °C and 45 °C, while the ultimate combustion temperatures rose by 13 °C and 16 °C for corn and rice straws, respectively. These results imply an extended combustion timeframe for the torrefied samples.

Effect of torrefaction on fuel properties of biopellets.

The study aimed to determine the effects of torrefaction on the fuel properties of pellets. Therefore, firstly, torrefaction parameters of rose (Rosa Damascena Mill.) oil distillation solid waste and red pine sawdust were determined through the torrefaction optimization process in terms of temperature and holding time. Then, using the selected torrefaction parameters, 14 different raw and torrefied pellets containing RP, PS, and Turkish Elbistan Lignite were prepared in different weight ratios. Finally, the fuel properties of the prepared raw and torrefied pellets, namely dimensions, proximate analyses, higher heating values, tensile strength, durability, abrasive resistance, and water uptake resistances, were investigated. The findings demonstrated that the higher heating values and carbon content of raw biomass samples increased while their volatile matter content decreased. The use of lignite at high concentrations led to an increase in ash content and a decrease in the strength and durability of pellets, which should be emphasized. In addition, red pine sawdust was used in place of solid waste from rose oil distillation solid waste to produce pellets with greater strength. All pellet mixtures with torrefaction had higher heating values and energy densities despite the fact that their mass and energy efficiency had decreased. It was determined that torrefaction increased the pellets' resistance to absorbing water and gave them a more hydrophobic structure. Thus, it was determined that torrefaction could enhance the crucial fuel parameters of the biomass samples.

Alteration of biomass toxicity in torrefaction - A XDS-CALUX bioassay study.

Torrefaction constitutes one of the promising technologies for the management of waste biomass and the production of high-carbon products for combustion, gasification, adsorption of pollutants or soil treatment. Unfortunately, waste biomass may be contaminated with toxic persistent organic pollutants, such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) and dioxin-like biphenyls (dl-PCB). Literature does not provide consistent measurements on how the low-temperature thermochemical processing, such as torrefaction, affects the toxicity of biomass. This contribution assesses how a torrefaction treatment, conducted at 200 °C, modifies the toxicity due to PCDD/PCDF/dl-PCB in biomass. We deploy the XDS-CALUX biotest on five types of waste biomass (sewage sludge, tree bark, cattle manure, spent coffee ground, common reed), before and after treatment. The content of total dioxin- & biphenyl fraction compounds in the raw biomass, investigated in this study, varies from 0.14 to 3.67 pg BEQ·g-1d.m., and in the torrefied biomass between 0.17 and 6.00 pg BEQ·g-1d.m.; BEQ stands for bioanalytical equivalent. This increase is statistically insignificant at p = 0.05, taking into account all types of examined biomass. This proves that low-temperature torrefaction cannot detoxify biomass, i.e., chars, produced from biomass characterized by elevated concentration of PCDD/PCDF/dl-PCB, will reflect the contamination of the feedstocks. With respect to heavy metals, we conclude that only the content of Cd in biomass, and, to a lesser extent, the abundance of Cu and Fe, modify the toxicity of this material during its thermochemical treatment at low temperature.

Effects of cation types in persulfate on physicochemical and adsorptive properties of biochar prepared from persulfate-pretreated bamboo.

The adsorption behaviors of biochar are largely impacted by biomassfeedstock. In this study, two biochars were prepared from torrefaction of ammonium persulfate- and potassium persulfate-pretreated bamboo and then activated by cold alkali, which are named as ASBC and KSBC, respectively. The two biochars were characterized by different instruments, and their adsorption properties over cationic methylene blue (MB) were compared. The type of persulfates little affected the specific surface areas, but significantly impacted O (29.54 % vs. 35.113 %) and N (12.13 % vs. 3.74 %) contents, functional groups, and zeta potentials of biochars. MB adsorption onto ASBC/KSBC is a single-layer chemical endothermic process and ASBC/KSBC exhibit high adsorption capacity over MB (475/881 mg·g-1) at 303 K. Obviously, the sorption capacity of MB onto KSBC much surpasses that of MB onto ASBC. These results indicate biomass pre-treatment is a cheap and convenient method to prepare biochars with unique physicochemical and adsorptive properties.

Catalytic torrefaction effect on waste wood boards for sustainable biochar production and environmental remediation.

Wood boards used in construction are generally treated with toxic chemicals, making them unsuitable for further use and causing environmental pollution. This study evaluates the possibility of using catalytic torrefaction as a pretreatment to improve wood pyrolysis and combustion for greener biochar production. Waste beech boards were impregnated with different K2CO3 solutions (0-0.012 M), then torrefied between 5 and 60 min at 275 °C. The ICP-AES showed that the board's surface held more potassium than the core. Torrefaction coupled with potassium decreased the C-O and -OH stretches. Thermogravimetric analysis of torrefied wood showed that the board's internal heating degraded the core more than the surface. The exothermic reactions made potassium's catalytic action more efficient in the core. Interactions between the potassium content and torrefaction duration decreased the pyrolysis' maximum devolatilization temperature. During combustion, potassium decreased the ignition temperature by up to 9% and 3% at the surface and core, respectively, while the torrefaction increased it. The catalytic torrefaction significantly decreased the devolatilization peak during combustion, thus making the wood's combustion similar to that of coal, having only the char oxidation step. These findings highlight the advantages and challenges of waste wood's catalytic-torrefaction for biochar production to reduce environmental pollution.

Waste to Energy: Steam explosion-based torrefaction process to produce solid biofuel for power generation utilizing various waste biomasses.

Currently, humankind is facing a serious environmental and climate crisis, which has accelerated the research on producing bioenergy from waste biomass as a carbon-neutral feedstock. In this study, the aim was to develop an upcycling strategy for waste biomass to solid-type biofuel conversion for power generation. Various types of waste biomass (i.e., waste wood after lumbering, sawdust-type mushroom waste wood, kudzu vine, and empty fruit bunches from palm) were used as sustainable feedstocks for steam explosion-based torrefaction. The reaction conditions were optimized for each waste biomass by controlling the severity index (Ro); the higher heating value increased proportional to the Ro increase. Additionally, component analysis revealed that steam explosion torrefaction mainly degraded hemicellulose, and most of the torrefied waste biomass met the Bio-Solid Refuse Fuel quality standard. The results provide not only a viable waste-to-energy strategy but also insights to address global climate change.

Solidification characteristics of solid biofuel densified by two-step torrefaction process.

Coal coke, which is used widely in industrial furnaces, emits large amounts of CO2. To utilize solid biofuels as alternatives to coal coke, the fuel ratio of the biofuels must be improved to generate functions, such as deoxidization, permeability, and carbon pickup. In this study, an innovative densification molding method is proposed; it uses a two-step torrefaction process with a high CO2 reduction effect. The molding method consists of the following two-step torrefaction process at torrefaction temperatures of 463-773 K: In the first step, raw biomass is torrefied to remove some of the volatile matter that inhibits densified molding. In the second step, the torrefied biomass is densified at the above temperature. The purpose of the second torrefaction step is to further enhance the fuel ratio due to the conversion of volatile matter to fixed carbon and to develop the thermal softening of lignin. Solid biofuel densified using a two-step torrefaction process was produced from a Japanese cedar sample, and it was found that its fuel ratio was significantly improved. Furthermore, the mechanism of the adhesive effect during carbonization was elucidated by analyzing the structure of the densified solid biofuel using Raman spectroscopy.

Substituting Solid Fossil Fuels with Torrefied Timber Products.

As a push towards alternative and renewable resources for heat and power generation, biomass and thermally treated fuels from biomass may be viable options in the upcoming economic reality. This study the verified mass and energy balance of spruce woody biomass after low temperature pyrolysis between 250 and 550 °C. The results showed that low-temperature pyrolysis can yield high-grade biochar suitable for substitution of fossil fuels. Crucially, the net calorific value of biochar processed at 350 °C substantially exceeded that of brown coal. An economic analysis was carried out on the assumption of the current economic reality in the Czech Republic. It was shown that even if the price of the biochar slightly increased, it would still be beneficial to invest in torrefaction technology over paying carbon credits.

Gas-Pressurized Torrefaction of Lignocellulosic Solid Wastes: Deoxygenation and Aromatization Mechanisms of Cellulose.

A novel gas-pressurized (GP) torrefaction method at 250 °C has recently been developed that realizes the deep decomposition of cellulose in lignocellulosic solid wastes (LSW) to as high as 90% through deoxygenation and aromatization reactions. However, the deoxygenation and aromatization mechanisms are currently unclear. In this work, these mechanisms were studied through a developed molecular structure calculation method and the GP torrefaction of pure cellulose. The results demonstrate that GP torrefaction at 250 °C causes 47 wt.% of mass loss and 72 wt.% of O removal for cellulose, while traditional torrefaction at atmospheric pressure has almost no impact on cellulose decomposition. The GP-torrefied cellulose is determined to be composed of an aromatic furans nucleus with branch aliphatic C through conventional characterization. A molecular structure calculation method and its principles were developed for further investigation of molecular-level mechanisms. It was found 2-ring furans aromatic compound intermediate is formed by intra- and inter-molecular dehydroxylation reactions of amorphous cellulose, and the removal of O-containing function groups is mainly through the production of H2O. The three-ring furans aromatic compound intermediate and GP-torrefied cellulose are further formed through the polymerization reaction, which enhances the removal of ketones and aldehydes function groups in intermediate torrefied cellulose and form gaseous CO and O-containing organic molecules. A deoxygenation and aromatization mechanism model was developed based on the above investigation. This work provides theoretical guidance for the optimization of the gas-pressurized torrefaction method and a study method for the determination of molecular-level structure and the mechanism investigation of the thermal conversion processes of LSW.

Utilization of Torrefied and Non-Torrefied Short Rotation Willow in Wood-Plastic Composites.

The torrefaction process is widely used in the energy field, but the characteristics of the torrefied wood also have positive effects on the production of wood plastic composites. In this study, short-rotation shrub willow was torrefied at 225 and 300 °C and incorporated into polypropylene composites filled with changing levels of weight percent (wt%) of non-torrefied and torrefied (5, 15, 25, and 40 wt%) wood. Nine different formulations were extruded for mechanical, thermal, and water absorption properties. The tensile properties of composites were not affected by any level of torrefaction, while higher flexure properties were in favor of lower wt% of torrefied wood. The slowest rate of thermal degradation was confirmed for the highest wt% of torrefied wood with a torrefaction temperature of 300 °C. In contrast, the presence of torrefied wood in composites did not show a difference in crystallization or melting temperatures. The most noticeable contribution of torrefaction temperature and wt% was found for water-absorbing properties, where the higher torrefaction temperature and largest wt% of torrefied wood in the composite resulted in decreased water uptake.

Effect of Torrefaction on the Physiochemical Characteristics and Pyrolysis of the Corn Stalk.

Torrefaction of biomass is one of the most promising pretreatment methods for deriving biofuels from biomass via thermochemical conversion processes. In this work, the changes in physicochemical properties and morphology features of the torrefied corn stalk, the changes in physicochemical properties and morphology features of the torrefied corn stalk were investigated. The results of this study showed that the elemental content and proximate analysis of the torrefied corn stalk significantly changed compared with those of the raw corn stalk. In particular, at 300 °C, the volatile content decreased to 41.79%, while the fixed carbon content and higher heating value increased to 42.22% and 21.31 MJ/kg, respectively. The H/C and O/C molar ratios of torrefied corn stalk at the 300 °C were drastically reduced to 0.99 and 0.27, respectively, which are similar to those of conventional coals in China. Numerous cracks and pores were observed in the sample surface of torrefied corn stalk at the torrefaction temperature range of 275 °C-300 °C, which could facilitate the potential application of the sample in the adsorption process and promote the release of gas products in pyrolysis. In the pyrolysis phase, the liquid products of the torrefied corn stalk decreased, but the H2/CO ratio and the lower heating value of the torrefied corn stalk increased compared with those of the raw corn stalk. This work paves a new strategy for the investigation of the effect of torrefaction on the physiochemical characteristics and pyrolysis of the corn stalk, highlighting the application potential in the conversion of biomass.

Torrefaction interpretation through morphological and chemical transformations of agro-waste to porous carbon-based biofuel.

In the current study, two agro-waste lignocellulosic corncob (CC) and rice husk (RH) were thermally torrefied at 200-300 °C into a porous carbon-enriched biofuel. The scanning electron microscopy (SEM) of produced biofuel confirmed the rounded, homogenous, and spherical structure of the produced biofuels with higher porosity at a temperature between 250 and 300 °C with 60 min retention time. Brunauer-Emmett-Teller (BET) analysis indicated the high surface area (CC: 1.19-2.87 m2 g-1 and RH: 1.22-2.67 m2 g-1) and pore volume (CC: 1.23-2.81 ×10-3 m3 g-1 and RH: 1.46-2.58 ×10-3 m3 g-1). Crystallinity index decline percent (CC= 62.87% and RH=57.10%) estimated thermal stability and rise in amorphous cellulose reformation during (250-300 °C)/60 min that would efficiently hydrolyze during oxidative pyrolysis carbon reactive sites the rise in surface area and total pore's volume, having higher conversion rate as compared to raw materials. Carbon content was upgraded to 94% by eliminating hydrogen and oxygen from lignocellulosic agro-waste to produce energy-dense CC and RH. The lignin macromolecule transformation extent was estimated by O/C trend, which was equal to 63% and 47% for CC and RH, respectively, at 300 °C for 60 min. Due to low bulk density and pre-grinding energy requirements, torrefied biofuel with decomposed fibrous structure have lower transportation costs.