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Review of fast pyrolysis of biomass and product upgrading
... Typically, reactors used for slow pyrolysis include cylindrical fixed-bed, batch, rotatory kiln, and packed bed. The bubbling fluidized bed, circulating fluidized bed, vortex, conical spouted bed, ablative and auger reactor are examples that are typical for either fast or flash pyrolysis (Bridgwater, 2012;Gholizadeh et al., 2020). Regardless of the reactor type, the external heat is generated by either the burning biomass, electric heaters, or gas burners and transferred directly or indirectly to the biomass within a furnace (Wu et al., 2014). ...
... The amount of biochar produced varies with factors such as temperature, pressure, and feedstock composition, but remains consistent regardless of whether the reaction lasts for hours or days (Brewer & Brown, 2012). To attain thermodynamic control during slow pyrolysis, it is recommended to employ extended vapor residence times (> 10 min) and operate at lower temperatures (290 -400 °C), as proposed by Bridgwater (2012). Various pyrolysis reactors are engineered to meet these criteria, with cylindrical fixed-bed, batch, rotatory kiln, and packed bed being among the most utilized designs. ...
... In conventional pyrolysis, biomass is converted into biochar, bio-oil, and synthesis gas, requiring an external energy source to heat the reactor due to its endothermic nature (Bridgwater, 2012). However, providing the necessary energy for pyrolysis via heat transfer becomes increasingly challenging as the system is scaled up. ...
Biochar, a carbon-rich substance produced through thermal decomposition of biomass, is gaining recognition for its potential in environmental and energy fields. To create biochar, biomass sources can be derived from both plants (lignocellulosic) and animals/sludge (non-lignocellulosic). Biochar production methods have made notable progress with advancements in pyrolysis techniques such as slow, fast, flash, microwave-assisted, and torrefaction, as well as gasification and hydrothermal carbonization, leading to enhanced efficiency and product quality. Pyrolysis, among these methods, offers considerable potential for biomass utilization. Over several decades, academic research has focused on understanding biomass pyrolysis mechanisms and improving technical processes. Therefore, this review begins by discussing pyrolysis mechanisms for both lignocellulosic and non-lignocellulosic biomass, along with reactor types employed in the process. It emphasizes the critical role of specific biomass types and conversion parameters—such as temperature, residence time, and heating rate—in determining biochar quality, addressing these factors to tailor biochar for distinct environmental needs. Furthermore, sustainable considerations, economic aspects, and future prospects for large-scale industrial production enhancement using existing methodologies are explored. This paper's significance lies in its role of consolidating and disseminating valuable information. By synthesizing existing research and elucidating various biochar production technologies, it facilitates the advancement of these technologies towards enhanced sustainability and efficiency.
... Consequently, several methodologies have been developed to facilitate the cleavage of these aromatic C─O ether bonds. Generally, lignin can be depolymerized by catalytic hydrogenolysis, [9] pyrolysis, [10] gasification, and oxidation. [11] Among the developed methodologies, hydrogenolysis has emerged as a particularly promising strategy due to its high atom economy. ...
... Inspired by its excellent performance in the CTH of benzyl phenyl ether, Ru/h-BN was employed to catalyze the CTH of other aromatic compounds containing ether bonds using 2propanol as the hydrogen resource ( (Table 2, entry 9). To further expand the applicability of the constructed Ru/h-BN, two substrates with methoxy group at the ortho-position of the ether bond, i.e., 1-methoxy-2-phenoxybenzene and 3-(benzyloxy)-4-methoxyphenol, were employed to investigate the impact of steric hindrance ( Table 2, entry [10][11]. Although these two substrates could be successfully cleaved, the reaction temperature should be improved to 200°C owing to the steric hindrance effect of ortho-position methoxy group. ...
Catalytic transfer hydrogenolysis (CTH) of aromatic ether bonds provides a promising strategy for sustainably converting lignin into useful chemicals. Design of innovative catalysts with high activity is the key for this route. Herein, we constructed the hexagonal boron nitride (h‐BN)‐supported Ru nanoparticles (Ru/h‐BN) as the heterogeneous catalyst for the CTH of aromatic ether bonds. Notably, the fabricated Ru/h‐BN catalyst could efficiently catalyze CTH of various types of aromatic ether bonds contained in lignin (i.e., 4‐O‐5, α‐O‐4, β‐O‐4, and aryl‐O‐CH3) employing 2‐propanol as the hydrogen resource without using extra acidic or basic additives. Besides, the Ru/h‐BN catalyst demonstrated superior performance compared to commercial Ru/C. Systematic investigation revealed that electron‐enriched Ru sites and the B atoms on h‐BN collaboratively promoted the CTH reaction. Besides, a mechanism study indicated that the direct cleavage of aromatic ether bonds was the primary reaction pathway over Ru/h‐BN.
... Activación del carbón Para generar carbón activado el proceso consiste en eliminar las impurezas del material precursor y aumentar su porosidad. Esto se puede hacer mediante diferentes métodos, como:Activación física: Se trata de calentar el material precursor a altas temperaturas en presencia de un gas oxidante, como el vapor de agua o el dióxido de carbono(Bridgwater, 2012a).Activación química: Se trata de impregnar el material precursor con un agente químico, como el ácido clorhídrico o el hidróxido de potasio, y luego calentarlo(Demirbas, 2001).2.4.2. Aplicaciones del carbón activadoEl carbón activado tiene una amplia gama de aplicaciones, incluyendo:Puricación de agua: Se utiliza para eliminar impurezas, contaminantes y malos olores del agua(Faix y Fortmann, 1991).Puricación de gases: Se utiliza para eliminar gases contaminantes del aire(Crittenden et al. 2018).Decoloración: Se utiliza para eliminar colorantes de líquidos y soluciones(Bridgwater, 2012a).Extracción: Se utiliza para extraer sustancias de líquidos y soluciones(Demirbas, 2001).Medicina: Se utiliza para tratar intoxicaciones y en algunos casos para eliminar toxinas del cuerpo(Brown y Holcombe, 1967).Industria alimentaria: Se utiliza para decolorar y puricar aceites, bebidas y otros productos alimenticios(Faix y Fortmann, 1991).Cosmética: Se utiliza en la elaboración de algunos productos cosméticos, como cremas dentales y jabones.Según las pruebas de la Universidad Popular del Cesar (UPC), a partir de distintos tipos de carbón es posible activarlo por medio de diversos procesos ...
... Esto se puede hacer mediante diferentes métodos, como:Activación física: Se trata de calentar el material precursor a altas temperaturas en presencia de un gas oxidante, como el vapor de agua o el dióxido de carbono(Bridgwater, 2012a).Activación química: Se trata de impregnar el material precursor con un agente químico, como el ácido clorhídrico o el hidróxido de potasio, y luego calentarlo(Demirbas, 2001).2.4.2. Aplicaciones del carbón activadoEl carbón activado tiene una amplia gama de aplicaciones, incluyendo:Puricación de agua: Se utiliza para eliminar impurezas, contaminantes y malos olores del agua(Faix y Fortmann, 1991).Puricación de gases: Se utiliza para eliminar gases contaminantes del aire(Crittenden et al. 2018).Decoloración: Se utiliza para eliminar colorantes de líquidos y soluciones(Bridgwater, 2012a).Extracción: Se utiliza para extraer sustancias de líquidos y soluciones(Demirbas, 2001).Medicina: Se utiliza para tratar intoxicaciones y en algunos casos para eliminar toxinas del cuerpo(Brown y Holcombe, 1967).Industria alimentaria: Se utiliza para decolorar y puricar aceites, bebidas y otros productos alimenticios(Faix y Fortmann, 1991).Cosmética: Se utiliza en la elaboración de algunos productos cosméticos, como cremas dentales y jabones.Según las pruebas de la Universidad Popular del Cesar (UPC), a partir de distintos tipos de carbón es posible activarlo por medio de diversos procesos ...
This project documents the first stage of the manufacturing and implementation process of a pyrolysis reactor for the Technological University of Uruguay (UTEC). The reactor will support research and development efforts at the Physics and Materials Science Laboratory of the Regional Technological Institute North (ITRN) of UTEC, located in Rivera.
The first stage encompasses the design and simulation testing of the internal (hot) section of the pyrolysis reactor. The reactor is primarily designed for pyrolysis and the production of activated carbon using pine and eucalyptus sawdust as feedstock.
... The estimated moisture content for these residues was considered ideal, as pyrolysis typically requires dry biomass with a moisture content below 10% to ensure process quality and facilitate heat transfer, as well as the processing and storage of resulting products. 41 Moreover, a low ash content is equally beneficial in pyrolysis processes because it reduces the likelihood of ash accumulation and fouling, as well as minimizes corrosion on furnace surfaces and also contributes to the production of biochar with better micropore surface areas. 24,40 The analyzed biomasses showed high volatile matter contents (84.81% for BH, 79.73% for CH, and 86.18% for PS), indicating ease of decomposition during the process. ...
... The presence of high lignin content may favor the production of biochar with greater surface area and porosity. 41,45,46 Analysis of products obtained by pyrolysis ...
The Legal Amazon Region has numerous lignocellulosic biomasses with unknown technological properties, contrasting with an urgent demand for energy transition towards a more sustainable economy. This study analyzed the biomasses of baru husk (BH), cupuaçu husk (CH), and pequi seed (PS) through slow pyrolysis at 650 °C to assess the suitability of the bio-oils and biochars as potential biorefinery bioproducts. The physicochemical characterizations showed that all residues are potential candidates for bioproduct production, with CH biomass obtaining the best results for biochar production due to its high carbon content (80.65%) and surface area of 298.0491 m2 g-1, while BH and PS are more suitable for bio-oil production due to their high volatile matter content (> 84%). The main compounds in the bio-oil identified by gas chromatography-mass spectrometry (GC-MS) were phenolic (48.5, 56.7, and 60.36% for BH, CH, and PS, respectively) and furanic (22, 12.17, and 10.28% for BH, CH, and PS, respectively). Finally, it is concluded that based on the physicochemical and morphological characteristics obtained in this study, the pyrolysis products have potential for future investigation in various processes such as adsorption, carbon sequestration, and obtaining valuable chemical compounds, contributing to the promotion of the bioeconomy through sustainable waste management.
... This process can use several types of feedstocks, such as wood fines [21], however the use of Eucalyptus urograndis is particularly interesting since its remarkable features, such as bulky density and high calorific power [4]. FP submits the biomass to high temperature (≈500 °C) during short residence times (≈2 s) under an inert atmosphere, characterizing it as a high severity process [22,23]. ...
The correct application of lignin is directly related to its structure which is strongly affected by the extraction method. In this work, three technical lignins were obtained from Eucalyptus urograndis by Kraft, fast pyrolysis (FP), and microwave-assisted organosolv delignification (MWAOD), and their structural and antioxidant properties were evaluated and compared to those of milled wood lignin (MWL). The samples were characterized by FTIR, 2D and ³¹P NMR, GPC, TGA, DSC and DPPH. assay. The technical lignins were obtained with elevated yields (33 – 68.5%) and high purities (76 – 93%). The combination of different analytical techniques showed that the higher the severity the lower the molecular weights (657 – 1959 g mol⁻¹), the higher the quantity of condensed structures (β-5’ and β-β’), and the higher the concentration of phenolic hydroxyls. During MWAOD process, partial acetylation of aliphatic hydroxyls of organosolv lignin (OL) occurred under mild conditions. The thermal stability and the molecular mobility of lignins were also affected by the nature of the extraction method. The DPPH. assay showed that the structural features of lignins also affected their antioxidant activities, since the IC50 values varied from 13.2 to 19.3 µg mL⁻¹. Therefore, three technical lignins with different structural features were obtained from the same biomass through distinct processes, offering different possibilities for their valorization.
... Pyrolysis is a thermal decomposition process that involves heating waste in the absence of oxygen to produce a mixture of gases, liquids known as pyrolysis oil, and solid char. The pyrolysis oil can be used as a fuel, and the gases can be combusted for energy generation [23]. Gasification is a highly efficient thermochemical WTE process that converts carbon-rich waste materials into a gaseous fuel called syngas (synthetic gas) in the presence of controlled amounts of oxygen and/or steam. ...
Waste management has become a big concern globally, affecting countries from lower-income to lower-middle-income and even mostly developed ones. Urban areas are the hub of solid waste generation and house a significant portion of the world's population, with a much higher population density than rural areas. Municipal solid waste (MSW) generation is expected to increase substantially in the coming years with the increasing population growth rate. Developed countries, while advancing in waste management and trying to make use of this waste by recycling or harnessing energy in various established and emerging technologies, developing and underdeveloped countries are still struggling to manage waste and largely rely on landfills. Managing these wastes in alternative ways is an environmental demand, as landfills can never be a long-term waste management solution, and harvesting energy from these wastes can add to the economies of these countries. This paper reviews the different available and emerging technologies to generate energy from waste and aims to find out the prospects of these technologies, particularly for underdeveloped nations. Our results show that potential power outputs from incineration are 415 MW in Bangladesh, 2 MW in Ethiopia, 110 MW in Sudan, 48 MW in Senegal, 92 MW in Nepal, and 389 MW in Cambodia, while for anaerobic digestion, energy can be generated at 681 MW, 3 MW, 93 MW, 35 MW, 41 MW, and 255 MW, respectively. Additionally, the study has compared the carbon emissions of these waste-to-energy (WTE) technologies with those of traditional power plants on a per-unit-of-power-produced basis. This work has proposed a viable model for implementing these technologies, addressing the barriers that currently hinder their adoption. The goal of this work is to explore how these technologies can reduce environmental impacts, promote economic development through sustainable practices, and create job potential for the respective countries.
... Pyrolysis involves the thermal decomposition of biomass in an oxygen-free environment at high temperatures, yielding a complex mixture of several hundred oxygenated compounds. The composition of the produced bio-oil, which typically varies in oxygen content from 20 to 50 wt.%, is highly dependent on the biomass source and pyrolysis conditions [4,7,8]. Such variability not only highlights the complex nature of bio-oil but also presents analytical challenges in consistently assessing its quality and composition before and after upgrading processes. ...
The analytical characterization of pyrolysis bio-oil represents a formidable challenge, attributed to its complex composition and inherent corrosive properties. Addressing this, we introduce an improved version of Effective Carbon Number (ECN) model, a novel predictive framework designed to accurately estimate the Flame Ionization Detector (FID) response factors of oxygenated compounds within bio-oil based solely on their molecular structures. The ECN model, underpinned by an analysis of over 150 compounds, leverages the structural attributes of molecules to ascertain their respective response factors, thereby facilitating precise concentration measurements. Central to our findings is the model’s ability to correlate FID detector responses directly with two critical parameters: the total number of carbon atoms within the molecule, and the degree of oxidation of each carbon atom. Additionally, we have compiled a comprehensive table delineating response factors across various oxygenated functionalities, a resource that significantly expedites the analysis process of complex bio-oil mixtures.
... Co-pyrolysis is known to enhance the quality and calorific value of bio-oil while reducing its oxygen content [32][33][34][35]. Compared to enriching bio-oils with hydrogen at high pressure, co-pyrolysis is a safer and easier way to produce quality bio-oil [36][37][38][39]. ...
This study examined the catalytic fast co-pyrolysis of hemp stalk and glycerol using HZSM-5 and dolomite catalysts to produce diesel-range hydrocarbons. The co-pyrolysis method was used to produce aromatic and aliphatic hydrocarbons (C9–C20) in the diesel fuel range and a high amount of organic phase bio-oil. A bubbling fluidized bed reactor was used for this purpose. The yields and contents of derived bio-oils at different mixing ratios with glycerol (10, 15, and 20 wt.%), different catalysts (HZSM-5 and dolomite), and pyrolysis temperatures (350, 400, 450, 500, and 550 °C) were investigated. The co-pyrolysis results showed that the bio-oil yield improved with glycerol. The highest bio-oil yield (46.82%wt.) was achieved through in situ catalytic co-pyrolysis with glycerol (15%wt.) and dolomite at 550 °C. In addition, in situ catalytic co-pyrolysis with glycerol and dolomite caused a decrease of 48.84% (GC–MS peak area) in oxygenated compounds compared to direct pyrolysis of hemp stalk. The content of catalytic co-pyrolysis bio-oil mainly consisted of aliphatic hydrocarbons in the C12–C20 carbon range, and it also contains a significant amount of ketones, phenols, and alcoholic compounds. In addition, co-pyrolysis with the use of dolomite in the reactor, mostly methyl elaidate, methyl palmitate, 9-octadecene, and (E)- and 8-heptadecene structures were found in the bio-oil. Moreover, the findings presented in this paper can lead to the development of basic, cheap, and sustainable new methods for integrating pyrolysis oil into existing refinery infrastructure.
... To convert waste plastic into fuel, "pyrolysis" is suitable option. It is one of the best techniques for mass to energy conversion with liquid and gaseous products having high calorifc values [22]. Pyrolysis is defned as thermal cracking of long-chain polymer molecules into smaller and less complex molecules. ...
Plastics are basically long-chain hydrocarbon compound synthesizes from nonrenewable liquid petroleum products. Since plastics have special and variety of features such as easy availability and handling, light weight, energy efficiency, nondegradable nature, cheap, faster production, and design flexibility, it has gained wide popularity in short time period and has become indispensable part of day-to-day life. The increasing usage and production of plastic with exponential rate have resulted in increasing plastic waste disposal problems which may cause adverse effect on environment and human health. Moreover, fast exhaustion of nonrenewable fossil fuel has also become a major problem. To encounter both the problem at a same time, plastic waste conversion method has come into picture. Several plastic waste conversion methods such as landfills, plastic incineration, and recycling are available out of which recycling has gained a lot of interest. One of the important recycling methods is pyrolysis, which is referred as most suitable method due to its advantages such as flexible, easy in handling, less intense sorting, less labor intensive, and high-quality liquid oil extraction. The gaseous by-product also has high calorific value. In the present study, an attempt has been made to produce alternative fuel from waste polypropylene plastic. The study further aims to compare the properties of the obtained WPPO with diesel and blend of WPPO and diesel to ascertain its feasibility for engine runs.
... Fast pyrolysis involves the thermal decomposition of organic material in the absence of oxygen, yielding liquid bio-oil as a primary product. This bio-oil, with its high energy density, has potential as a renewable substitute for petroleum-derived fuels [3,4]. The economic feasibility of bio-oil production and its use as a fuel have been extensively analyzed, highlighting its promise as a costcompetitive and environmentally friendly solution [5,6]. ...
This study investigated the fast pyrolysis of biomass in fluidized-bed reactors using computational fluid dynamics (CFD) with an Eulerian multifluid approach. A detailed analysis was conducted on the influence of various modeling parameters, including hydrodynamic models, heat transfer correlations, and chemical kinetics, on the product yield. The simulation framework integrated 2D and 3D geometrical setups, with numerical experiments performed using OpenFOAM v11 and ANSYS Fluent v18.1 for cross-validation. While yield predictions exhibited limited sensitivity to drag and thermal models (with differences of less than 3% across configurations and computational codes), the results underline the paramount role of chemical kinetics in determining the distribution of bio-oil (TAR), biochar (CHAR), and syngas (GAS). Simplified kinetic schemes consistently underestimated TAR yields by up to 20% and overestimated CHAR and GAS yields compared to experimental data (which is shown for different biomass compositions and different operating conditions) and can be significantly improved by redefining the reaction scheme. Refined kinetic parameters improved TAR yield predictions to within 5% of experimental values while reducing discrepancies in GAS and CHAR outputs. These findings underscore the necessity of precise kinetic modeling to enhance the predictive accuracy of pyrolysis simulations.
... wt.%) in the ash of raw palm shells. The soils with fertilizer are also affected due to the high oxide compounds in the raw palm shells [39]. After palm shells were converted into palm char, it was found that the palm char contained inorganic matter in form of oxides with 35.93 wt.% of Fe 2 o 3 and also 37.90 wt.% of sio 2 (TABlE 3). ...
To identify the mineral grade ore, two distinct Malaysian ilmenite ores (FeTiO3) from different placers deposits were examined. The sources of ilmenite ore were the Kinta Valley in Perak and the Langkawi Black Sand Beach in Kedah. Both of the ores were reduced by palm char as a sustainable carbon reductant. The study examined carbon characteristics and phase transitions following carbothermal reduction at 1550°C. Prior to the studies, the reductant palm char was characterized by XRF, BET surface area measurement, SEM, and ultimate with proximate analyses. It is shown that the palm char had low moisture (4.10 wt.%) and high fixed carbon (75.40 wt.%). The high carbon content, volatile matter, and porous structure of palm char played a significant role in the gas generated during the carbothermal reduction of ilmenite ores. Carbothermal reduction of both ilmenite ores with palm char-produced rutile, iron, titanium carbide, and pseudobrookite. The XRF analysis exhibits the existence of 18.41 and 35.76 wt.% of Fe and TiO2 respectively in Perak ilmenite ore. While Langkawi ilmenite ore shows 9.28 and 22.72 wt.% of Fe and TiO2 respectively.
... In the field of solar thermal energy or geothermal systems, in solar concentrating systems, the number is relevant for the design of heat exchangers and heat transfer fluid systems [331,332]. In biomass processing and biofuel production, Re is relevant for the design of reactors and mixing systems [333]. In the design of devices to harness wave energy, Re is important to optimize the interaction between the device and the fluid [334]. ...
The Reynolds number (Re), introduced in the late 19th century, has become a fundamental parameter in a lot of scientific fields—the main one being fluid mechanics—as it allows for the determination of flow characteristics by distinguishing between laminar and turbulent regimes, or some intermediate stage. Reynolds’ 1895 paper, which decomposed velocity into average and fluctuating components, laid the foundation for modern turbulence modeling. Since then, the concept has been applied to various fields, including external flows—the science that studies friction—as well as wear, lubrication, and heat transfer. Literature research in recent times has explored new interpretations of Re, and despite its apparent simplicity, the precise prediction of Reynolds numbers remains a computational challenge, especially under conditions such as the study of multiphase flows, non-Newtonian fluids, highly turbulent flow conditions, flows on very small scales or nanofluids, flows with complex geometries, transient or non-stationary flows, and flows of fluids with variable properties. Reynolds’ work, which encompasses both scientific and engineering contributions, continues to influence research and applications in fluid dynamics.
... Catalytic fast pyrolysis (CFP) is a viable thermochemical conversion route for producing fuels from biomass. [1][2][3] One approach to obtaining stable bio-oils is through ex situ CFP, which involves sending pyrolysis vapors to a downstream reactor where oxygen functionalities are removed (deoxygenation) through the use of multifunctional catalysts. [4][5] The development of more active selective, inexpensive, and recyclable catalysts for ex situ CFP can improve the yield and properties of upgraded bio-oils. ...
Molybdenum carbide (Mo2C) nanoparticles and thin films are particularly suitable catalysts for catalytic fast pyrolysis (CFP) as they are effective for deoxygenation and can catalyze certain reactions that typically occur on noble metals. Oxygen deposited during deoxygenation reactions may alter the carbide structure leading to the formation of oxycarbides, which can determine changes in catalytic activity or selectivity. Despite emerging spectroscopic evidence of bulk oxycarbides, so far there have been no reports of their precise atomic structure or their relative stability with respect to orthorhombic Mo2C. This knowledge is essential for assessing the catalytic properties of molybdenum (oxy)carbides for CFP. In this article, we use density functional theory (DFT) calculations to (a) describe the thermodynamic stability of surface and subsurface configurations of oxygen and carbon atoms for a commonly studied Mo-terminated surface of orthorhombic Mo2C, and (b) determine atomic structures for oxycarbides with a Mo:C ratio of 2:1. The surface calculations suggest that oxygen atoms are not stable under the top Mo layer of the Mo2C(100) surface. Coupling DFT calculations with a polymorph sampling method, we determine (Mo2C)xOy oxycarbide structures for a wide range of oxygen compositions. Oxycarbides with lower oxygen content (y/x <=2) adopt layered structures reminiscent of the parent carbide phase, with flat Mo layers separated by layers of oxygen and carbon; for higher oxygen content, our results suggest the formation of amorphous phases, as the atomic layers lose their planarity with increasing oxygen content.
... Another thermochemical process is the pyrolysis, which needs pre-treatments of the feedstock such as grinding and drying, to ensure rapid reaction that rapidly heated the biomass in absence of oxygen, at different temperatures ranging from 400 to 800 °C, and times residence (1-60 min) [24]. At lower process temperatures (~ 290 °C), and longer vapor residence times (~ 10-60 min) is favoured the production of char. ...
A wide variety of eco-friendly and at zero waste techniques are developed for biomass conversion and valorization of its residues and by-products such as water fraction and organic residues which could be further utilized. The wastewater reuse is one of the best strategies for water security, sustainability, and resilience. To date, the municipal wastewater was the most widely used, nowadays the innovative technologies for biomass conversion and energy production allow the recovery of wastewater with better and safer features than the municipal effluents. Depending on the moisture content of the starting feedstock, the hydrothermal liquefaction process (HTL) generates also up to 95% of wastewater (HTL–WW) generally rich in nitrogen, phosphorus, and sulfate as well as micronutrients and minerals. Although it is currently recycled through various biological systems such as microalgae cultivation and anaerobic digestion, the possibility of using the wastewater from HTL process as irrigation water for agricultural purpose is discussed representing a source of crop nutrients for the high amount of organic and inorganic compounds and a new approach in contributing to reduce the increasing pressure on freshwater resources.
Graphical abstract
Residual Macadamia F.Muell nutshell gasification assisted by CO2 was studied in this work. Monometallic Co, Na, and K and bimetallic CoNa and CoK catalysts were prepared and tested in the catalytic process. The idea of this research was to try to find any synergism between already known catalytically active components and to investigate possible ways to use mixed materials. All the materials under investigation were examined by SEM-EDX and XRD. The DTA-TG of the initial fresh macadamia nutshell was presented in this work. The synergism between the Co and K components was revealed in the CO2-assisted gasification process. The found optimal catalyst was 1.5 wt%K-1.5 wt% Co/PMNS.
Asphalt binder replacement with bio-materials (bio-asphalt) has recently gained significant attention. Bio-asphalt serves as a sustainable avenue and is currently being researched for reducing the dependency on asphalt binder. This work is aimed towards understanding the thermal, morphological, chemical, and rheological behaviour of asphalt binder partially replaced with sugarcane molasses (SM). The optimum dosage for partial replacement was arrived as 30% (by weight of asphalt binder). Two base binders (VG 40 and VG 30) along with five SM sources were used to prepare the bio-asphalts. The thermal stability evaluated using thermogravimetric analysis revealed that bio-asphalts have acceptable thermal resistance withstanding temperature up to 200 °C. Fluorescence microscopy exhibited that SM particles were uniformly dispersed in the base binder, rendering a stable structure. Through chemical analysis (asphaltene–maltene ratio) it was found that the asphaltene percentage marginally increases after the addition of SM. Rheological characterization comprised of multiple stress creep recovery and linear amplitude sweep tests. Test results indicated that incorporation of SM resulted in lower non-recoverable creep compliance (Jnr), decreased permanent strain, and similar/slightly higher percent recovery (% R). The fatigue life of bio-asphalts improved due to the formulation of compounds capable of imparting elasticity to the bio-asphalts.
The molecular form of hydrogen can be extracted from a wide variety of resources, which include water, biomass, and fossil fuels among others [1]. In order to obtain hydrogen from these various sources, there needs to be an abundant supply of readily available energy in a nonstop state of availability. Therefore, sustainable hydrogen could be created by utilizing technologies that tap into the potential of renewable energy, such as the sun, wave sea, wind, etc. [2–4]. The pathway to the generation of environmentally friendly hydrogen is depicted in Fig. 2.1. This chapter focuses mainly on environmentally friendly methods of producing hydrogen. In the future, the primary technologies utilized to produce hydrogen will be determined by the type of raw material that is put into production: renewable resources or fossil fuels.
Sustainable agriculture addresses the environmental, economic, and social issues related to agricultural systems. In general, the objectives of sustainable agriculture are intended (1) to improve the entire food and agricultural system. (2) To ensure that arable land is protected and (3) to preserve the vitality of family-owned farms and rural communities. With the development of sustainable agriculture, it might increase high-yield polyculture, organic fertilizers, biological pest control, irrigation efficiency, perennial crops and crop rotation. Green solutions should be developed to overcome the issues, i.e. environmental sustainability and food security and safety achieving sustainable agriculture. Integrated management concerning water resource management, soil management, fertilizers and pesticides management, integrated farming system, and climate-smart agro-foresty management (CSAFM) should be established. In addition, the developed innovation technologies should be focused on renewable energy (biogas), soil conservation (biochar), water quality/wetlands, agricultural drip irrigation, and AIoT technologies for precision agriculture. The critical connection of water resource, energy efficiency and food production could be affected in green agriculture. The implementation of Green Chemistry Principles (GCP) with green process engineering could enhance energy-resource efficiency, water reclamation effectiveness and food-security assurance by forming water–Energy–Food (WEF) nexus. Therefore, construction of decarbonizing supply chains for carbon neutrality in agriculture industries should be developed in the future.
Plant life has dominated this planet from the beginning of time. With over 82% of biomass (BM) coming from plants, primarily trees, plants are the dominant form of life on Earth. BM represents a readily available, ecologically favorable, and renewable low‐cost carbon source. Its rational disposal has emerged as a critical challenge in modern times due to its widespread generation from farming, manufacturing, and forestry activities. Nanotechnology (NT) has enormous potential for a wide range of BM‐related applications, including BM development, processing technique, modification, and utilization. Richard Feynman, a physicist who later won the Nobel Prize in Physics, presented a discussion in 1959 titled “There's Plenty of Room at the Bottom.” This address was the beginning of the New Theory of Physics, which is NT, where he discusses the potential of NT for manipulating matter at the atomic level. In recent years, there has been a significant surge in interest surrounding carbon nanomaterials (CNMs), specifically carbon nanotubes (CNTs) and graphene. These materials have captured the interest of researchers due to their extraordinary characteristics and widespread applications. Utilizing BM as a source shows great potential in creating functional carbon materials (CMs) due to its sustainability, affordability, and high carbon content. Nowadays, CNMs derived from BM have been a popular area of study. Various structures, synthesis techniques, and widespread applications of CNMs have been documented. Thus, this review provides a detailed overview that outlines the latest technological advancements in the fabrication of BM‐derived CMs. It also studies the production of high‐value‐added CNMs from BM and delves into the utilization of BM‐based CNMs as a precursor for textile wastewater treatment. Furthermore, this study also outlines the progress of BM‐derived CNMs in supercapacitors (SCs), sensors, battery electrode materials, fuel cells (FCs), and E‐textiles, showcasing their pivotal role in advancing sustainable technologies for the future.
A obra “Indicadores de Qualidade Ambiental: Uma Perspectiva a partir da Zona de Transição Amazônica-Cerrado-Pesquisa em saúde e meio ambiente” explora as interações entre o meio ambiente e a saúde Cultura e Sociedade, com foco nas dinâmicas da transição ecológica entre dois dos biomas mais ricos e ameaçados do planeta: Amazônia e Cerrado. A degradação ambiental nesses ecossistemas não afeta apenas a biodiversidade, mas também a qualidade de vida das populações locais, causando doenças respiratórias, dermatológicas e alimentares, além de comprometer os recursos naturais essenciais para a subsistência. A fronteira entre a Amazônia e o Cerrado é uma região única, onde se encontram duas dos mais importantes biomas do planeta. No entanto, essa região enfrenta desafios significativos relacionados à sustentabilidade, saúde, cultura e sociedade. Este livro apresenta uma abordagem integrada para entender esses desafios e propor soluções inovadoras. Este livro é uma leitura essencial para aqueles que buscam compreender como os ecossistemas e a saúde humana estão intrinsecamente conectados e como o futuro depende de soluções integradas que combinem sustentabilidade, ciência e políticas públicas inovadoras.
The widespread use of PFAS in nonstick cookware, hydrophobic textiles, stain‐resistant fabrics, cosmetics, and floor coverings has led to their persistent presence in wastewater streams, posing significant human health and ecological risks. Exposure to PFAS is linked to adverse reproductive outcomes and elevated blood pressure in pregnant individuals, and it negatively impacts aquatic ecosystems, particularly algal populations and microbial communities. This evaluation focuses on biochar's efficacy and cost‐efficiency in removing PFAS from water, highlighting its potential as a sustainable remediation method. Biochar's high microporous volumes (0.1–1.0 cm³/g), aromaticity, and surface oxygen‐containing functional groups make it effective for PFAS adsorption. Various biochar production methods, such as pyrolysis of biomass waste, and innovative modification techniques like acid treatment, ball milling, and metal nanoparticle incorporation are explored to enhance PFAS adsorption capacity. The mechanisms, kinetics, and thermodynamics of PFAS adsorption onto biochar are examined, providing insights into molecular‐level interactions and adsorption isotherms. Furthermore, machine learning models are utilized to understand the impact of processing parameters on PFAS removal efficiency. The review also presents toxicological studies on the harmful effects of PFAS exposure on organisms and humans, emphasizing the urgent need for effective remediation strategies. Ultimately, the potential of biochar‐based approaches in treating PFAS‐contaminated water is underscored by optimizing its physicochemical properties through innovative production and modification methods, along with predictive modeling of adsorption behavior.
Resumo
O objetivo desta revisão é identificar lacunas de conhecimento e necessidades de pesquisa relacionadas à utilização de biochar e nano-biochar para remediação ambiental sustentável. Osnanocompósitos Biochar oferecem uma alternativa promissora para lidar com a poluição de águas residuais, esgotos e efluentes industriais, imobilizando ou removendo poluentes e patógenos. Além disso, o biochar serve como material de eletrodo em baterias de íons de lítio devido à sua alta área superficial e condutividade elétrica. A biorremediação usando aplicações de biochar pode fornecer soluções inovadoras para solos contaminados resultantes de resíduos de petróleo, derramamentos de óleo de hidrocarbonetos e outros compostos perigosos. Biochar aumenta a retenção de água no solo, a isponibilidade de nutrientes, a capacidade de troca catiônica e o pH do solo, criando condições
favoráveis para o crescimento das culturas. Pode até absorver o metano produzido nas entranhas dos animais. O biocarvão derivado do bagaço de cana-de-açúcar, tratado com grupos funcionais ativados, é particularmente eficaz na remediação de poluentes ambientais, especialmente no Brasil. Além da sua utilização como combustível alternativo, o biochar e o nanobiochar do bagaço contribuem para um
ambiente mais limpo, promovendo o sequestro de carbono, melhorando a fertilidade do solo, apoiando a biorremediação e permitindo a reciclagem de resíduos grícolas. O biochar é obtido como substrato sólido rico em carbono através da pirólise do bagaço de cana-de-açúcar em temperaturas acima de 300 °C em ambiente livre de oxigênio. Nano-biochar, um composto inovador de tamanho nanométrico, é
preparado a partir de biochar a granel usando abordagens de cima para baixo, como moagem de bolas, centrifugação, sonicação e síntese hidrotérmica. Comparado ao biochar a granel normal, o Nanobiochar apresenta vantagens significativas em termos de área de superfície, tamanho de poro, volume
total de poro e funcionalidades de superfície. No geral, as funções e propriedades biocatalíticas do nanobiochar têm amplas aplicações em sensores, imobilização de enzimas e produção de polímeros.
Palavras-chave:
Bagaço de Cana; Nano-biocatalisador; Biorremediação de resíduos de petróleo; Economia circular
New York State (NYS) is actively promoting the transition to a bioeconomy to address climate change, reduce greenhouse gas (GHG) emissions, and foster sustainable development. This study aims to evaluate the potential of NYS's bioeconomy, as outlined in the scoping plan guided by the Climate Leadership and Community Protection Act (CLCPA), in achieving net-zero emissions by 2050. The primary objectives are to assess the bioeconomy's role in meeting climate targets by quantifying its contributions to GHG mitigation and renewable energy integration and to propose a robust monitoring framework for tracking progress. The study also examines the socioeconomic benefits of bioeconomy initiatives, particularly for disadvantaged communities (DACs), and identifies key dimensions and indicators for sustainability monitoring. The hypothesis tested posits that an integrated bioeconomy strategy can simultaneously address environmental, social, and economic goals. Findings reveal that while biomass resources offer significant opportunities for GHG mitigation and economic growth, challenges remain in feedstock estimation, deployment readiness, and stakeholder coordination. A comprehensive monitoring framework is proposed to guide policy decisions and ensure alignment with sustainability objectives. This research provides actionable insights to advance NYS's bioeconomy, emphasizing inclusivity, environmental stewardship, and resilience.
Lignin is the only naturally occurring, renewable biopolymer and an alternative for the production of six-membered aromatic chemicals. The utilization of lignin can increase the additional revenue of biorefineries and reduce the dependence on crude oil for the production of aromatic chemicals. Therefore, the development of technologies for the production of valuable chemicals from lignin waste in biorefineries is of great importance. Catalytic hydrotreatment of lignin is considered one of the most promising technologies for the production of biobased aromatic chemicals and fuels. Among the various hydrotreatment routes, the solvent-free hydrotreatment approach is advantageous because this process reduces production costs and is similar to petroleum refinery processes such as cracking and heteroatom removal. This review addresses recent developments in solvent-free catalytic hydrotreatment of various lignins such as sulfur-containing, sulfur-free, and pyrolytic lignins to produce low oxygen-containing aromatics such as alkylphenolics in batch, semicontinuous, and continuous reactors. Special emphasis is given to the various noble and non-noble metal catalysts, the best route between single and two-stage processing, key factors in solvent-free depolymerization of lignin, techno-economic evaluation, crude oil vs lignin oil refining, challenges and future prospects, etc.
Plastic is a threat to the environment since it does not biodegrade, but it also has the potential to become a substantial resource to produce alternative energy sources, creating a multibillion-dollar untapped market. Every year, millions of tons of plastic are produced, resulting in a significant rise in plastic waste, which causes ecological and environmental problems. According to estimates, only around 10% of this waste plastic is now recycled. Plastic waste may be handled in two ways: recycling or converting it into energy. The first alternative, recycling, has several challenges, including the need for labor-intensive processes and concerns about water pollution, which may threaten its long-term sustainability. As a result, the second technique for turning waste plastic into energy has been developed, enhanced, and extensively researched. Pyrolysis is a technique that involves heating plastics at temperatures ranging from 455–700 °C without oxygen. This process yields high-calorific fuel that can be utilized as an alternative fuel. This study explores the thermal and catalytic cracking processes involved in waste plastic pyrolysis, focusing on crucial factors such as temperature, time, feedstock, reactor type, and catalyst that impact results such as oil production, gases, and heat. Furthermore, the study investigates the properties of the liquid oil produced and offers suggestions for enhancing the liquid fuel yield for each kind of plastic.
As the consumption of fossil fuels increases, the demand for alternative energy sources is growing. Current research focuses on alternative energy sources. Significant importance is given on renewable energy sources, such as waste biomass of agricultural origin, which is thermally processed through pyrolysis, producing products that can have further applications. Serbia, an agricultural country with great potential for using waste biomass as energy, such as corn, could significantly reduce environmental pollution by managing agricultural waste and decreasing greenhouse gas emissions from the combustion of fossil fuels through the utilization of pyrolysis technology. While biomass in its raw form may not be suitable for energy production due to its high oxygen and moisture content and lower calorific value, the process of pyrolysis emerges as a pivotal solution. This thermal processing method transforms biomass into solid, liquid, and gaseous products, the quality of which is determined by the initial biomass and process parameters. The critical aspect is that optimizing these pyrolysis conditions can significantly improve the quality of the products, thereby increasing their potential for energy applications. This study investigated two types of corn and their liquid and solid pyrolysis products obtained at a temperature of 400 ℃. The following parameters were compared between the initial biomass and the liquid and solid products: calorific value, pH, moisture content, ash content, and metal ions affecting energy efficiency, such as K, S, Mg, and Al. Based on the obtained results, it can be concluded that the liquid and solid pyrolysis products hold potential as energy sources. However, certain modifications are necessary to enhance their energy potential. For instance, increasing the calorific value can be achieved by increasing the carbon and hydrogen content. This can be done by adding materials abundant in these elements, such as plastic waste. Consideration should also be given to the quality of the products and their subsequent applications, both for energy purposes and other uses such as chemical production (from the liquid fraction) or use as adsorbents or fertilizers (solid fraction).
Meeting the needs of a growing population calls for a change from linear production systems that exacerbate the depletion of finite natural resources and the emission of environmental pollutants. These linear production systems have resulted in the human-driven perturbation of the Earth’s natural biogeochemical cycles and the transgression of environmentally safe operating limits. One solution that can help alleviate the environmental issues associated both with resource stress and harmful emissions is resource recovery from waste. In this review, we address the recovery of resources from food and beverage processing wastewater (FPWW), which offers a synergistic solution to some of the environmental issues with traditional food production. Research on resource recovery from FPWW typically focuses on technologies to recover specific resources without considering integrative process systems to recover multiple resources while simultaneously satisfying regulations on final effluent quality. Process Systems Engineering (PSE) offers methodologies able to address this holistic process design problem, including modelling the trade-offs between competing objectives. Optimisation of FPWW treatment and resource recovery has significant scope to reduce the environmental impacts of food production systems. There is significant potential to recover carbon, nitrogen, and phosphorus resources while respecting effluent quality limits, even when the significant uncertainties inherent to wastewater systems are considered. This review article gives an overview of the environmental challenges we face, discussed within the framework of the planetary boundary, and highlights the impacts caused by the agri-food sector. This paper also presents a comprehensive review of the characteristics of FPWW and available technologies to recover carbon and nutrient resources from wastewater streams with a particular focus on bioprocesses. PSE research and modelling advances are discussed in this review. Based on this discussion, we conclude the article with future research directions.
Biomass fast pyrolysis liquid is being developed for fuel and chemical applications. As these developments proceed, the liquid product is increasingly being transported by air, water, rail and road to satisfy user demands for products. This paper addresses the legislative requirements and regulations for the safe transport of this liquid. As biomass derived fast pyrolysis liquid is not on the UN approved carriage lists; its own classification has been determined from the UN manual as:
UN 1993 Flammable Liquid [Fast Pyrolysis Liquid], n.o.s., 3, 1º(a), 2º(a), 1
This classification should be used on all packages containing biomass fast pyrolysis liquid. Protocols for the labelling of packages and containers of all sizes are given with the aim of compliance with transport regulations in the EU, Canada and the USA. In conjunction with the requirements for packaging and labelling, guidance on the details to be enclosed on the transportation documents are given, with appropriate MSDS for the liquids. Guidance on the handling of fast pyrolysis liquid and its storage are given with procedures for treatment of spills.
The disclosure encompasses in-line reactive condensation processes via vapor phase esterification of bio-oil to decease reactive species concentration and water content in the oily phase of a two-phase oil, thereby increasing storage stability and heating value. Esterification of the bio-oil vapor occurs via the vapor phase contact and subsequent reaction of organic acids with ethanol during condensation results in the production of water and esters. The pyrolysis oil product can have an increased ester content and an increased stability when compared to a condensed pyrolysis oil product not treated with an atomized alcohol.
This publication is an updated version of a study on testing and modifying standard fuel oil analyses (Oasmaa et al. 1997, Oasmaa & Peacocke 2001). Additional data have been included to address the wide spectrum of properties that may be required in different applications and to assist in the design of process equipment and power generation systems. In addition, information on specifications and registration is provided. Physical property data on a range of pyrolysis liquids from published sources have been added to provide a more comprehensive guide for users.
The objective of this paper is to present a design evaluation and techno-economic assessment of two technologies being developed within an EU supported contract by Wellman Process Engineering Ltd. and the Biomass Technology Group b.v.. The work produced capital cost estimates and production cost estimates for liquids from both processes and electricity production costs, at a range of scales from 0.25 t/h dry wood input to 10 t/h dry wood input [to the pyrolysis reactor]. The overall system covered from received chipped at site wood to product liquids, or electricity, as generated by a dual fuel diesel engine.
Capital and operating costs have been derived for the production of pyrolysis liquids using standard cost estimation techniques to provide a consistent methodology and avoid concerns over release of confidential information.
Pyrolysis liquid production costs ranged from 9.5 €/GJ at 2 dry t/h feed rate for the Wellman process and 8.0 €/GJ at 2 dry t/h feed rate for the BTG process at 2 t/h federate at zero feedstock cost. Electricity production costs for the pyrolysis processes are relatively high – ranging from 12 €cents/kWh at 10 t/h [net electrical output 13.3 MWe to over 40 €cents/kWh at 0.25 t/h [~0.33 MWe output]. The mean EU price to industrial users for electricity is 4 €cents/kWh. The potential markets for pyrolysis liquids may initially be in selected European countries as a domestic heating fuel, with electricity production as a longer-term aim.
There is increasing recognition that low-cost, high capacity processes for the conversion of biomass into fuels and chemicals are essential for expanding the utilization of carbon neutral processes, reducing dependency on fossil fuel resources, and increasing rural income. While much attention has focused on the use of biomass to produce ethanol via fermentation, high capacity processes are also required for the production of hydrocarbon fuels and chemicals from lignocellulosic biomass. In this context, this book provides an up-to-date overview of the thermochemical methods available for biomass conversion to liquid fuels and chemicals. In addition to traditional conversion technologies such as fast pyrolysis, new developments are considered, including catalytic routes for the production of liquid fuels from carbohydrates and the use of ionic liquids for lignocellulose utilization. The individual chapters, written by experts in the field, provide an introduction to each topic, as well as describing recent research developments.
Bio-oils produced from fast pyrolysis of biomass are chemically complex compounds. As fuels they have a number of negative properties such as high acidity, water content, variable viscosity and heating values about half that of petroleum fuel. These negative properties are related to the oxygenated compounds contained in bio-oils that result in a 45% oxygen content. For production of a viable fuel the raw bio-oils must be upgraded. The bio-oil hydrotreating process has been approached by applying hydrogenation catalysts under heat and pressure. Researchers have reported application of a successful two-stage catalytic hydrodeoxygenation (HDO) process. We have recently developed a two-stage HDO catalysis as well. The upgraded bio-oil contains hydrocarbons very similar to petroleum fuels. Yields of the upgraded bio-oils are more than 70% by energy capture. Future research on the upgraded product will focus on distillation and introduction into petroleum refineries and investigating the potential for direct blending with current petroleum fuels.
Experimental results and a process design will be presented for an integrated process which uses hydropyrolysis plus hydroconversion to convert biomass into gasoline and diesel. The hydrogen needed for the hydropyrolysis and hydroconversion process is produced by reforming the light gases so that no external H2 is required. Finished hydrocarbon products with less than 2% oxygen are produced using this processing approach.
This design solves many of the problems associated with pyrolysis and subsequent upgrading. By having an integrated process, a fungible finished product is produced which has the oxygen removed and is ready for use. This eliminates the need for transporting high TAN, unstable, low BTU content pyrolysis oils. An integrated process also eliminates the problems associated with upgrading pyrolysis oils which were created in a hydrogen starved environment and therefore include high olefinic, polynuclear aromatics and free radicals which were not present in the original biomass. Pyrolysis oils require high pressure to convert because of the condensed ring aromatic structures present. Hydropyrolysis oils can be converted at moderate pressure. The initial hydropyrolysis step is done at moderate pressure and then feeds directly into the hydroconversion step run at almost the same pressure. The light gases from the hydroconversion then go to a small steam reformer where the H2 is made and the CO2 rejected. The H2 produced is recycled back to the hydropyrolysis step.
Initial data which shows the yields and product properties from experiments in pilot scale equipment will be presented and compared to results for traditional pyrolysis. Some economic analysis will also be done to show the advantages of integrated balanced hydropyrolysis + hydroconversion compared to traditional approaches.
In order to gain insight into the fast pyrolysis mechanism of biomass and the relationship between bio-oil composition and pyrolysis reaction conditions, to assess the possibility for the raw bio-oil to be used as fuel, and to evaluate the concept of spout-fluidized bed reactor as the reactor for fast pyrolysis of biomass to prepare fuel oil, the composition and combustion characteristics of bio-oil prepared in a spout-fluidized bed reactor with a designed maximum capacity 5 kg/h of sawdust as feeding material, were investigated by GC-MS and thermogravimetry. 14 aromatic series chemicals were identified. The thermogravimetric analysis indicated that the bio-oil was liable to combustion, the combustion temperature increased with the heating rate, and only minute ash was generated when it burned. The kinetics of the combustion reaction was studied and the kinetic parameters were calculated by both Ozawa-Flynn-Wall and Popsecu methods. The results agree well with each other. The most probable combustion mechanism functions determined by Popescu method are f(a)=k(1-a)2 (400-406°C), f(a)=1/2k(1-a)3 (406-416°C) and f(a)=2k(1-a)3/2 (416-430°C) respectively.
This book is for chemical engineers, fuel technologists, agricultural engineers and chemists in the world-wide energy industry and in academic, research and government institutions. It provides a thorough review of, and entry to, the primary and review literature surrounding the subject. The authors are internationally recognised experts in their field and combine to provide both commercial relevance and academic rigour. Contributions are based on papers delivered to the Fifth International Conference sponsored by the IEA Bioenergy Agreement.
IntroductionMaterials and Methods
ResultsMaximis Ation Function of CarbonizationPyrolytic Carbon DepositionConclusion
References
IntroductionMaterials and Methods
Results and DiscussionConclusion
AcknowledgmentReferences
IntroductionExperimentalResults and DiscussionConclusion
AcknowledgementsReferences
IntroductionExperimentalResults and DiscussionConclusions
References
IntroductionRating Index (RI)Step Wise Procedure to Calculate Rating IndicesBiomass Characterisation Based on NriConclusions
References
Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor. Influential factors including temperature, weight hourly space velocity (WHSV) of bio-oil, mass ratio of steam to bio-oil (S/B) as well as catalyst type on hydrogen selectivity and other desirable gas products were investigated. Based on hydrogen in stoichiometric potential and carbon balance in gaseous phase and feed, hydrogen yield and carbon selectivity were examined. The experimental results show that higher temperature favors the hydrogen selectivity by H2 mole fraction in gaseous products stream and it plays an important role in hydrogen yield and carbon selectivity. Higher hydrogen selectivity and yield, and carbon selectivity were obtained at lower bio-oil WHSV. In catalytic steam reforming system a maximum steam concentration value exists, at which hydrogen selectivity and yield, and carbon selectivity keep constant. Through experiments, preferential operation conditions were obtained as follows: temperature 800-850°C, bio-oil WHSV below 3.0 h-1, and mass ratio of steam to bio-oil 10-12. The performance tests indicate that Ni-based catalysts are optional, especially Ni/a-Al2O3 effective in the steam reforming process.
Fractional catalytic pyrolysis is a process selectively targeting individual biopolymer components of the biomass to produce specific product slates. This method was used to screen several biomass feedstocks (switchgrass, corn stover, pinewood, hybrid poplar wood, oakwood) for adhesives production. Pyrolysis experiments were conducted at 400 to 450 °C and pyrolysis oil yields ranged from 30-50 wt%. The oils had very low molecular weight, low viscosity and pH of 3-4. The oils were used as substitutes for phenol in phenol /formaldehyde reactions. Both Novolac and Resol resins were prepared from the oils. For these reactions, there was no need for any pretreatments such as extractions, filtrations or neutralization (they were used as received). Excellent polymerization results were obtained and up to 95 wt% of the phenol could be replaced by the oils. The results were similar for all feedstocks except switchgrass oils which did not form good resins. All the oils were rich in both hydrocarbons and phenolics. However, the switchgrass oil had the highest hydrocarbon fraction.
Within the framework of the applied research carried out by ENEL, aimed at utilising non-traditional fuels derived from the renewable resources of the territory, the Thermal Research Centre of Pisa has realized a R&D plant for bio-oil production, through a flash pyrolysis process of vegetable biomass. The Project, that is being carried out in close collaboration with the Umbria Region, is partially financed by EU. The plant has been erected at the ENEL thermoelectric power plant of Bastardo (Perugia). The process unit (RTP-Rapid Thermal Processing) has been developed by the Canadian Ensyn Company, whereas ENEL has designed and constructed the auxiliary facilities. The plant, with a capacity of processing 15 tonnes/day of dry feedstock and capable of producing around 10 tonnes/day of liquid fuel, is the largest plant of this type in Europe. The paper describes the technical characteristics of the plant and the aims of the tests that will be performed with hardwood sawdust and other sorts of feedstocks. The tests are finalized to assess the technical-economic fesibility of the flash-pyrolysis process, a step necessary for the commercialisation of the technology.
Many plant materials contain minor amounts, often only in the 100 ppm range, of complex compounds which may have a considerable present or potential application in biological or pharmaceutical areas. Extraction and concentration of these specialty chemicals by conventional technology can be a laborious and costly process.
Examples are given in which fast fluid bed pyrolysis has been used in our research to obtain pyrolysis liquids considerably enriched in such compounds, even when they have very low volatilities. One example involves the recovery of an alkaloid from plant leaves. Another feedstock gives complex terpene-based compounds (taxanes) which can be precursors for synthesis of new antitumor agents, or that can be used as a potential plant fungicide. Additional examples of complex compounds obtained in significant yields in fast pyrolysis oils can be found in the high molecular weight lignin fragments, largely aromatic in character, which are a part of the “pyrolytic lignin” fraction of a pyrolysis oil; and in the anhydrosugar monomers, dimers and oligomers obtained from the carbohydrate fraction of biomass on fast pyrolysis.
Some unique features, and some speculations on mechanisms, of such specialized pyrolytic processes are discussed.
This paper presents the results obtained during the commissioning and first series of experiments of the EGEMIN entrained bed flash pyrolysis process. The feedstock used was as-received wood waste and at an average reactor temperature of about 510 °C. A bio-oil yield of 40% was obtained on a moisture-free basis. The charcoal and gas yields were 29 and 16% respectively while the balance was water. Elemental analysis of the products indicates the incomplete conversion of the char as well as a relatively high oxygen content in the bio-oil.
IntroductionExpefumentalResults And DiscussionAcknowledgementReferences
IntroductionTechnical ApproachExperimentalResultsConclusions
AcknowledgementsReferences
This paper presents the results obtained in the characterization of two different pyrolysis oils, the first one produced by carbonization and the second by flash pyrolysis. Chemical and physical properties such as density, viscosity, elemental composition, char content, water content, solubility and heating value were first determined, then an in-depth chemical characterization was carried out by liquid-liquid fractionation. We present a diagram indicating the separation procedure to provide four fractions (acids, bases, polars and hydrocarbons). We also recuperated very polar molecules which were retained in the aqueous layer (“aqueous” fraction). Each fraction was subsequently analyzed by GC-MS and FTIR.
The acidic fraction is the most abundant and contains essentially phenolic structure, nevertheless phenols are differently substituted in the two oils: alkyl and methoxy groups in the carbonization oil, methoxy, acidic, aldehydic and ketonic functions in the flash pyrolysis oil. The other fractions present a similar composition for the two oils. Basic fraction is always very small, some aromaticN-containing compounds were identified. The “polar” neutral fraction is also small and its characterization is very difficult. The hydrocarbon fraction is especially constituted of aromatics and cyclics, some aliphatics were also identified. The “aqueous” fraction contains mainly carboxylic esters, alcohols and ethers.
Highly oxygenated, biomass-derived oils can be upgraded to high quality hydrocarbon fuels by catalytic hydrotreating. Pacific Northwest Laboratory has successfully converted both high-pressure liquefaction oils and low-pressure pyrolysis oils to a highly aromatic, gasoline boiling range fuel. These studies were conducted in a 1-liter, continuous-flow reactor system. Six different biomass-derived oils and one peat-derived oil have been tested.
A handicap facing both the producer and the user of fast-pyrolysis oils is the lack of a description of these oils that is adequate for commercial applications. These oils are highly oxygenated and are relatively immiscible with petroleum oils. Under the current IEA Biomass Energy Agreement, the new Pyrolysis Activity (PYRA) has taken on the task of establishing a useful description of a series of pyrolysis oils. This series roughly parallels that of petroleum fuel oils already described, so that with as few changes as possible to the users’ equipment, a bio-oil could be used in place of the equivalent petroleum-derived oil. The specifications for biomass pyrolysis oils differ in the density, heating value, water content, and corrosiveness. These proposed specifications are presented for discussion by the biomass conversion community and feedback to the Pyrolysis Activity.
The Liquefaction Group of the lEA Biomass Agreement has carefully studied and analyzed a thermochemical conversion process under development at the National Renewable Energy Laboratory (NREL, formerly the Solar Energy Research Institute). This process converts biomass to an aromatic gasoline product. Biomass is subjected to very rapid pyrolysis in a vortex reactor to maximize the formation of oil vapors. After the char is removed from the process stream, the oil vapors are immediately sent to a catalytic cracking reactor with ZSM-5 zeolite catalyst to form a mixture of aromatic gasoline and gaseous olefins. Subsequent processing recovers byproduct gaseous olefms and converts them to aromatic gasoline. The small amount of toxic benzene formed as an intermediate compound is alkylated to extinction to form relatively benign compounds with a higher octane, such as cumene. The narrow boiling range desired for tomorrow’s reformulated gasolines is maintained by recycling both the volatile light ends and the difficult-to-bum heavy ends to extinction. A gasoline with a very high blending octane is the primary product. It is expected that this product will command a premium price. The process features state-of-the-art energy-saving and waste-management techniques. Using a consistent and well documented approach, the technoeconomics of this process were determined for both a “present” case and a “potential” case. The difference between the product costs for these two cases serves as an incentive for further research and development (R&D).
The bio-oil obtained from the fast pyrolysis of biomass has a high oxygen content. Ketones and aldehydes, carboxylic acids and esters, aliphatic and aromatic alcohols, and ethers have been detected in significant quantities. Because of the reactivity of oxygenated groups, the main problems of the oil are instability. Therefore study of the deoxygenation of bio-oil is needed. In the present work the mechanism of hydrodeoxygenation (HDO) of bio-oil in the presence of a cobalt molybdate catalyst was studied. Particularly, the effects of reaction time, temperature, and hydrogen pressure on the HDO activity were examined. On the experimental results, a kinetic model for HDO of bio-oil was proposed.
In the context of alternative sources of energy, many routes have been explored for using biomass. Direct combustion remains the most energy efficient use of biomass but liquids, rather than solids or gases, are preferred. Liquids have many advantages: high energy density, easy storage, handling and transportation and flexibility of use. Nevertheless, these liquids present some unwanted characteristics such as high viscosity, acidity, particulates content and chemical instability. Some upgrading is necessary before utilisation, specially for feeding turbines or internal combustion engines. Three different types of upgrading can be envisioned: physical, chemical/catalytic and the recovery of chemicals. Physical methods such as those to improve viscosity, offer potentially low cost steps which can be applied when the oil is used as soon as produced. The more expensive chemical/catalytic processes offer long term stabilisation and a range of improvement extending to high quality products. This paper reviews the main characteristics of the flash pyrolysis oils, their influence during the utilisation step and the possible solution to overcome this situation. The most important upgrading methods, both physical and chemical/catalytic, are summarised.
Preliminary experimentation passing fresh softwood pyrolysis vapors over a ZSM-5 containing catalyst has shown promise for the production of a gasoline consisting primarily of high octane, methylated benzenes. Stoichiometric considerations show that the upper limit on the gasoline yield is about 63 gallons per ton of dry feedstock, if the coke by-product yield is only 5% and the phenolic by-product yield is only 3%. This gasoline yield would represent 48% of the energy in the biomass feedstock.
In the reported experiments, a continuous fluidized bed bench scale flash pyrolysis unit operating at atmospheric pressure and feed rates of about 15 g/h has been successfully designed and operated. A unique solids feeder capable of delivering constant low rates of biomass has been developed. Extensive pyrolysis tests with hybrid aspen-poplar sawdust (105-250 mu m) have been carried out to investigate the effects of temperature, particle size, pyrolysis atmosphere and wood pretreatment on yields of tar, organic liquids, gases and char. At optimum pyrolysis conditions high tar yields of up to 65% of the dry wood weight fuel are possible at residence times of less than one second. Refs.
IntroductionMaterials and Methods
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The theoretical yield of charcoal from biomass lies in the range 50-80% on a dry weight basis. In spite of the fact that mankind has been manufacturing charcoal for about 6000 years, traditional methods for charcoal production in developing countries realize yields of 20% or less, and modern industrial technology offers yields of only 25-37%. Moreover, reaction times for the batch process in an industrial kiln are typically 8 days. In this article we describe a practical method for manufacturing high-quality charcoal from biomass that realizes near-theoretical yields of 42-62% with a reaction time of about 15 min to 2 h, depending on the moisture content of the feed. Because of its high efficiency, this technology can help to reduce worldwide deforestation and pollution, while providing greater amounts of a desirable, renewable fuel and chemical resource to mankind.
The conversion of biomass into bio-oil using fast pyrolysis technology is one of the most promising alternatives to convert biomass into liquid products. However, substituting bio-oil for conventional petroleum fuels directly may be problematic because of the high viscosity, high oxygen content, and strong thermal instability of bio-oil. The focus of the current research is decreasing the oxygen and polymerization precursor content of the obtained bio-oil to improve its thermal stability and heating value. Catalytic fast pyrolysis of corncob with different percentages (5, 10, 20, and 30% by volume) of fresh fluidized catalytic cracking (FCC) catalyst (FC) and spent FCC catalyst (SC) in bed materials was conducted in a fluidized bed. The effects of the catalysts on the pyrolysis product yields and chemical composition of the bio-oil were investigated. A greater catalyst percentage lead to a lower bio-oil yield, while a lower catalyst percentage lead to little change of the composition of the bio-oil. The best percentages of FC and SC were 10 and 20%, respectively. FC showed more catalytic activation in converting oxygen into CO, CO2, and H2O than SC, but the oil fraction yield with FC was remarkably lower than that with SC because of more coke formation. The gas chromatography/mass spectrometry (GC/MS) analysis of the collected liquid in the second condenser showed that the most likely polymerization precursors, such as 2-methoxy-phenol, 2-methoxy-4-methyl-phenol, 4-ethyl-2-methoxy-phenol, 2-methoxy-4-vinylphenol, and 2,6-dimethoxy-phenol decreased, while monofunctional phenols, ketones, and furans increased compared to that in the noncatalytic experiment. The hydrocarbons increased with the increase of the catalyst percentages, and this contributed to the decrease of the oxygen content of the bio-oil. Multi-stage condensation achieved a good separation of the oil fraction and water.
Economical utilization of renewable energy sources is one of the viable solutions to reducing our dependency on fossil-based energy. Biomass is the only renewable energy source that can provide liquid fuels. In general, liquid fuels are obtained from biomass using either thermochemical or biochemical conversion method. Fast pyrolysis, a thermochemical process, is getting a lot of attention because all the three products (char, bio-oil and gas) have high potential as biomass energy feedstocks. Fast pyrolysis is a high temperature process in which biomass is thermally cracked into smaller compounds in an inert atmosphere at high heating rate. The vapor from this process is quickly condensed to liquid, which is called pyrolysis oil or bio-oil. The favorable conditions for maximum yield of oil are in the range of 400-600 oC and residence time of a few seconds and particle size less than 2 mm. Bio-oil is a chemically complex mixture of more than 300 compounds. Heating value of bio-oil is comparable with the heating value of other conventional liquid fuels evidence that it can be used as a transportation fuel. The possible utilization of bio-oil are however limited because of some negative attributes such as low pH, low heating value, high oxygen content, and high viscosity.
Gravity can be used to separate bio-oil into two phases - top aqueous phase and lower viscous tar phase. The aqueous phase contains mainly water and carbohydrates and the tar phase contains primarily lignin derived compounds. An aqueous phase reforming (APR) is a process in which hydrogen is produced from carbohydrate solutions. The uniqueness of the APR is that the reforming occurs at liquid state without volatilizing water. Hence, the energy requirement for the APR is lesser than the conventional steam reforming. In addition, the APR occurs at a low temperature and high pressure (200-300 oC and 10-90 bar) which favors water-gas shift reaction. There are a number of physical and chemical techniques to upgrade tar portion of bio-oil to a high quality fuel such as emulsification, solvent addition, hydro treatment and catalytic cracking. Hydrodeoxygenation (HDO) is one of the promising techniques for bio-oil to improve its heating content. The HDO is a process in which high pressure hydrogen is added into bio-oil in the presence of catalyst. Hydrogen reacts with oxygenated components to produce hydrocarbons and water. The operating conditions of HDO are around 250-450 oC and 150 bar. This study will explore the possibility of simultaneous reforming and hydrodeoxygenation of bio-oil.
Since the composition of bio-oil will be different for different feedstocks, four types of feedstocks have been selected for bio-oil production. The study of simultaneous APR and HDO of bio-oil will be carried out at different temperature, pressure and different types of catalyst. The challenging part for this study is the selection of the best catalyst which favors both the reactions with high conversion and stability. Effect of pressure, temperature and residence time on the quality of bio-oil over different catalysts will be reported. The best catalyst will be selected and the operating parameters will be optimized. This study will be carried out in a high pressure batch reactor. The chemical and physical analysis of bio-oil will be quantified before and after the reaction. Product gas analysis also will be carried out using GC coupled with thermal conductivity detector.