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Liquid Products from the Continuous Flash Pyrolysis of Biomass
Abstract
A bench-scale continuous flash pyrolysis unit using a fluidized bed at atmospheric pressure has been employed to investigate conditions for maximum organic liquid yields from various biomass materials. Liquid yields for poplar-aspen were reported previously, and this work describes results for the flash pyrolysis of maple, poplar bark, bagasse, peat, wheat straw, corn stover, and a crude commercial cellulose. Organic liquid yields of 60-70% mf can be obtained from hardwoods and bagasse, and 40-50% from agricultural residues. Peat and bark with lower cellulose content give lower yields. The effects of the addition of lime and of a nickel catalyst to the fluid bed are reported also. A rough correlation exists between has content and maximum organic liquid yield, but the liquid yield correlates better with the alpha-cellulose content of the biomass. General relationships valid over all reaction conditions appear to exist among the ratios of final decomposition products also, and this correlation is demonstrated for the yields of methane and carbon monoxide.
... After drying, the moisture content of poplar bark was 7.0 ± 0.5%, which is slightly lower than that reported in previous studies by Scott et al., who reported moisture contents of around 7.55%. [35]. The ash content was 5.8 ± 0.5%, much higher than that reported in the literature for poplar wood, which is usually in the 1.0-4.5% range [19,[35][36][37], but in the 5-10% range for different species of poplar bark, as reported in the literature [38]. ...
... [35]. The ash content was 5.8 ± 0.5%, much higher than that reported in the literature for poplar wood, which is usually in the 1.0-4.5% range [19,[35][36][37], but in the 5-10% range for different species of poplar bark, as reported in the literature [38]. ...
Lignocellulosic residues have the potential for obtaining high value-added products that could be better valorized if biorefinery strategies are adopted. The debarking of short-rotation crops yields important amounts of residues that are currently underexploited as low-grade fuel and could be a renewable source of phenolic compounds and other important phytochemicals. The isolation of these compounds can be carried out by different methods, but for attaining an integral valorization of barks, a preliminary extraction step for phytochemicals should be included. Using optimized extraction methods based on Soxhlet extraction can be effective for the isolation of phenolic compounds with antioxidant properties. In this study, poplar bark (Populus salicaceae) was used to obtain a series of extracts using five different solvents in a sequential extraction of 24 h each in a Soxhlet extractor. Selected solvents were put in contact with the bark sample raffinate following an increasing order of polarity: n-hexane, dichloromethane, ethyl acetate, methanol, and water. The oily residues of the extracts obtained after each extraction were further subjected to flash chromatography, and the fractions obtained were characterized by gas chromatography coupled with mass spectrometry (GC–MS). The total phenolic content (TPC) was determined using the Folin–Ciocalteu method, and the antioxidant activity (AOA) of the samples was evaluated in their reaction with the free radical 2,2-Diphenyl-picrylhydrazyl (DPPH method). Polar solvents allowed for higher individual extraction yields, with overall extraction yields at around 23% (dry, ash-free basis). Different compounds were identified, including hydrolyzable tannins, phenolic monomers such as catechol and vanillin, pentoses and hexoses, and other organic compounds such as long-chain alkanes, alcohols, and carboxylic acids, among others. An excellent correlation was found between TPC and antioxidant activity for the samples analyzed. The fractions obtained using methanol showed the highest phenolic content (608 μg of gallic acid equivalent (GAE)/mg) and the greatest antioxidant activity.
... The flash pyrolysis of biomass gives a maximum yield of liquid product. Furthermore, a medium heating value gas is generated and minor amounts of a reactive char, both of which are available as good-quality fuels [13]. In fast pyrolysis, biomass decomposes extremely quickly to produce mostly vapor and gas and some char. ...
... Cellulose is the principal source of carbohydrates and phenols are the basis of the bio-oil from lignin, while the bio-oil from hemicellulose mainly consists of acids, ketones, and aldehydes [22]. This study finds that date stones have a higher carbon and hydrogen content than peach stones [13]. In contrast, date stones have a lower oxygen content than peach stones. ...
Flash and fast pyrolysis of date palm stones (Phoenix dactylifera L.) was carried out in two different well-swept fixed-bed reactors under a nitrogen atmosphere and the effect of pyrolysis temperature (400–700 °C) and retention time on the product yields and compositions was investigated. The results show that fast or flash pyrolysis of date palm stones yields more bio-oil than char or non-condensable gases, especially at moderate temperatures. A maximum bio-oil yield was obtained at a pyrolysis temperature of 500 °C as 40.4% and 38.3% via the flash and fast pyrolysis methods, respectively. The functional groups, morphology, surface areas, and the C, H, N, and O and ash, moisture, volatile matter, and fixed carbon content of the chars were examined using Fourier transform infrared spectroscopy, scanning electron microscopy, Brunauer-Emmett-Teller, ultimate analysis devices, and proximate analysis, respectively. Chars with a maximum surface area were used for the adsorption of dyes from aqueous solutions and the adsorption capacity and the kinetics of the chars were determined. Bio-oil composition was investigated using gas chromatography/mass spectrometry and the content of C, H, N, and O was determined by ultimate analysis. The results show that the saturation adsorption capacities of char from flash pyrolysis are 100 and 70.9 mg/g for Methylene Blue and Acid Red 111, and that these values from fast pyrolysis are 105.2 and 97.1 mg/g for Methylene Blue and Acid Red 111, respectively. The bio-oils contain higher levels of oxygen than the chars. The heating values vary from 27.5 to 31.3 MJ/kg and from 24.9 to 28.2 MJ/kg for bio-oils and chars, respectively. In addition, the bio-oil products from the pyrolysis of date palm stones are predominantly fatty acids. The results indicate that the bio-oil products obtained by the pyrolysis of date palm stone may be used as fuel or for the production of chemicals, and the solid products used as fuel or adsorbents.
... To our best knowledge, only some papers [5][6][7][8][9][10][11][12][13] studied the properties and compositions of bio-oils from more than one different biomass type prepared using the same pyrolysis process to be able to reliably discuss the differences caused by biomass type exclusively. Just four of them analysed the individual volatile compounds in the prepared bio-oils by GC-MS; however, only two of them presented real quantitative results based on a proper calibration which is crucial for the drawing reliable conclusions [14]. ...
... cal wood bio-oil. Nevertheless, all the previously mentioned researchers [5][6][7][8][9][10][11][12][13] used pyrolysis units that are not suitable for mobile applications (fixed bed, fluidized bed and rotating cone) as they require fluidization and/or heat carrier medium. Moreover, all the mentioned pyrolysis units require energy-demanding grinding of biomass into small particles usually below 1 mm. ...
One of the easiest ways to minimize the overall costs of bio-oil production is to minimize biomass transportation and, thus, pyrolysis should be performed at or close to the biomass original location. Thus, we applied ablative fast pyrolysis (AFP), as the only potentially mobile pyrolysis unit, to convert residual lignocellulosic biomass into bio-oil. Four different biomass types were converted to bio-oils: beech and poplar wood, straw and miscanthus. To study reliably the influence of biomass type on bio-oil yields, physicochemical properties and composition, pyrolysis was carried out at a constant temperature of 550 °C. Titrations and spectroscopic methods were used for the characterization of the main oxygenate groups. GC-MS was used for the quantification of more than 120 volatile compounds. Such a thorough analytical study of AFP bio-oils, heretofore missing in scientific literature, allowed us to reliably discuss the differences in bio-oils´ relative to the knowledge of biomass composition. Significant differences between the bio-oils were observed, with the lowest content of carboxylic and carbonyl groups in the straw bio-oil. The amount of carboxylic and phenolic groups in all the bio-oils was in the typical range observed for bio-oils unlike the carbonyls´ and levoglucosan content, which was lower than typical for bio-oils from other pyrolysis units.
... In addition the product distribution (char, liquids and noncondensable gases) depend on pyrolysis type and operating conditions [4] as depicted in Table 1. As mentioned above, in most cases the desired product is bio-oil since production of combustible gases is more efficient via gasification and if char is to be combusted then it is preferable to burn directly the entire biomass [5]. Thus, in this study the fast pyrolysis of bagasse was considered and examined. ...
... Over the past two decades, numerous reactor technologies have been examined and many processes have been tested and explored under different operating conditions. Scott et al. [5] have conducted a comprehensive study on pyrolysis reactor systems and concluded that 1) the bio-oil cooling demand will be minimum if the gas to feed ratio is minimized, 2) the reactor's temperature should remain as low as possible and 3) the pyrolyser should operate effectively on a small scale and at the same time have the potential to scale up easily. The bubbling fluidized bed (BFB) reactor appears to satisfy these criteria best and its construction and operation are now well established. ...
This study deals with the comprehensive design and simulation of a biomass fast pyrolysis polygeneration plant by using Aspen plus software. The system generates bio-oil, hydrogen and electricity. A bubbling fluidising bed (BFB) reactor was considered to model the pyrolyser. The reactor model was developed in Matlab environment due to the insufficient kinetic options provided directly in the simulator. Overall, the process consists of five main steps, namely pretreatment unit, pyrolysis reactor, biooil recovery, hydrogen plant and char combustion. In effect, this study exhaustively incorporates the basic mass, energy and economic calculations of a second generation biorefinery. The solid lignocellulosic waste of sugarcane industries, bagasse, was considered as feedstock as it is a relatively abundant agricultural residue and does not provide competition with food and land. Bio-oil is produced at a rate of 650 kg per metric tonne of dry bagasse and at a production cost of 0.8 $/L. An excess of electricity of 15MW can be sold to the grid while A detailed kinetic model was developed in order to simulate the behaviour of the pyrolyser and the kinetic parameters of bagasse pyrolysis were determined by fitting the model to appropriate experimental data. Subsequently, energy balances were applied in order to calculate the necessary heat of pyrolysis. This is 1.4 MJ/kg of bagasse that is in accordance with relevant literature data. The model was, also, validated with respective experimental data and thereby it can be effectively used to simulate the performance of similar fast pyrolysis systems at various process conditions. Finally, the study concludes with the estimation of the capital and labour costs associated with the reactor and bio-oil storage units. In effect, this study exhaustively incorporates the basic mass, energy and economic calculations of the core unit of a fast pyrolysis plant. The latter will be fully designed in the near future as an expansion of the current model. Overall, the current research suggests and investigates the utilisation of a relatively abundant agricultural residue via fast pyrolysis for the production of bio-oil. The conditions that maximise the liquids yield is 525°C and residence time of 0.5s.
... Since in the DFB gasifier at TU Wien, the pyrolysis happens in less than few seconds, only the correlations for the fast pyrolysis are considered. According to this research, there are correlations expressing: the yields of CH 4 and CO as reported in the work of Di Blasi et al. [30], or Scott et al. [31]; the yields of H 2 and CO; the yield of H 2 as a function of pyrolysis peak temperature [32], or the relation between the volatile products [33]; the yield of Char and its elemental composition as a function of pyrolysis peak temperature [34], also for secondary biomass [35] and dedicated cultivation [36]; the elemental composition of the Tars [37], and the thermal cracking [38] as well as the lower heating value in the function of temperature [39]. For the mentioned empirical correlations, the coefficient of the determination "R 2 " is always high enough to be taken as a reference for the further calculations. ...
... The same type of correlation exists also for the CHO content in the tar [31]. There is a weak relationship between the elemental composition of tar and pyrolysis temperature. ...
... Some gases are flammable and can be reused as fuel to generate heat. For this reason, many researchers have used NGC to generate heat in the reactor in order to reduce the production costs and to reduce emissions of NGC to the environment [44][45][46]. ...
... Firstly, the cost of producing heat with LPG was lower than using electric energy. Secondly, there was a greater heating power and higher stability to combust as compared to using charcoal & NCG [44][45][46] and charcoal [47,48]. Thirdly, the hot gas from combustion by LPG had a low oxygen composition in the flue gas, which can be directly used for the reactor in the pyrolysis process. ...
This article presents a design study and the development of a low-cost production process for obtaining bio-oil from sugarcane bagasse by using a Circulating Fluidized Bed reactor (CFBr). The reactor had a diameter of 4 in. and a height of 4.5 m. In addition, sand with a diameter of 249 μm was used as the bed material. Sugarcane bagasse was used as the raw material for the bio-oil production. This bio-oil production system had a feed rate of between 18 and 45 kg/h. The outstanding design of this system consisted of the production of a bio-oil with high efficiency by using the following: (1) a gas combustor used in gas turbine engine, (2) a non-condensable gas recovery for use in the process, and (3) a feeder and pre-heat exchanger before condenser unit. The experiment was performed at a superficial velocity of between 5 and 7 m/s, with a bed temperature ranging from 440 to 520 °C, and with a bed inventory at 0.5 and 4.5 kg. From the experiment, it was found that this system could produce a maximum yield of bio-oil of 78.07 wt% at the bed temperature of at 480 °C. In addition, the superficial velocity, the bed inventory, and feed rate were 7 m/s, 4.5 kg, and 30 kg/h, respectively. The properties of the bio-oil, such as its heating value, viscosity, density, and pH were measured at 18,483 kJ/kg, 24.54 cSt, 1274 kg/m³, and 2.4, respectively. The chemical components of bio-oil were also investigated by GC–MS. In this system, the cold efficiency and total energy conversion to bio-oil production were 46.06% and 32.94%, respectively. From a cost analysis of bio-oil production, the results showed that the cost production was 0.353 $/l. In addition, the results revealed that the bed temperature, the solid re-circulating rate, and the suspension density had significantly and directly affected the yield of bio-oil production. Furthermore, the oxygen in the exhaust gas from the combustion system and the non-condensable gas from the process had been shown to have a direct effect upon the properties of the bio-oil.
... Concurrently, elevated microwave heating power expedited the heating rate and reduced the duration of pyrolysis, thereby facilitating the formation of volatile products. However, when the microwave heating power continued to increase, the secondary pyrolysis of tar and other macromolecular substances led to a decline in the tar yield [39], while the pyrolysis gas yield increased rapidly, which was in accordance with the observations of Fagbemi et al. [40,41]. Figure 4 illustrates the variations in pyrolysis gas components under different microwave heating powers. ...
The rapid expansion of the scale of wind power has led to a wave of efforts to decommission wind turbine blades. The pyrolysis of decommissioned wind turbine blades (DWTBs) is a promising technological solution. Microwave pyrolysis offers the benefits of fast heating rates and uniform heat transfer, making it a widely used method in various heating applications. However, there are few studies on the microwave pyrolysis of DWTBs, and pyrolysis characteristics under different boundary conditions remain unclear. In this paper, we investigate the pyrolysis characteristics of DWTBs by utilizing silicon carbide (SiC) particles as a microwave absorbent. The results demonstrated that, when the microwave heating power increased from 400 W to 600 W, the heating rate and pyrolysis final temperature of the material increased, resulting in a reduction in pyrolysis residual solid yield from 88.30% to 84.40%. At 600 W, pyrolysis gas components included C2H4, CH4, and CO, while the tar components included phenol and toluene. The highest degree of pyrolysis was achieved under the condition of an SiC particle size of 0.85 mm, with better heating performance, and the calorific value of the pyrolysis gas generated was 36.95 MJ/Nm3. The DWTBs did not undergo pyrolysis when SiC was not added. However, when the mass ratio of SiC to DWTBs was 4, the tar yield was 4.7% and the pyrolysis gas yield was 17.0%, resulting in a faster heating rate and the highest degree of pyrolysis. Based on this, an optimal process for the microwave pyrolysis of DWTBs was proposed, providing a reference for its industrial application.
... It is important to regulate the hydrodynamics of the two materials effectively. The early, groundbreaking research on rapid pyrolysis was done by Scott and colleagues [18][19] at the University of Waterloo. ...
It is widely acknowledged that biofuels, whether usage of fluid, or hard fuel, electrical energy, have the potential to provide the bulk, anticipated renewable energy supply for future. The fundamental processes i.e., thermal, biological, and physical change can be used to create biofuels. These techniques makes various configurations or designs for chemical reactors. The focus of analysis is on thermo chemical change due to their superior efficiencies, lower costs, and more adaptability to extensive variety of energy, fuel, and biochemical alternatives. Quick pyrolysis and gasification methods are detailed, as well as the reactors that have been created the ideal circumstances for presentation. Characterized together with the minor products or, fluid, sizable amount of chemicals are fundamental crops.
... The reason for this difference is that in Model c1-4, tar breakdown reaction is taken into account and as a result of this reaction, tar is consumed downstream of the leaf whereas it is not in Model c1-3. It is noted that tar decomposition to the primary light gases takes place at high temperatures and sufficiently long residence times [28,29]. Temperature downstream of the leaf was sufficiently high mostly due to convective heating source temperature of 1000 • C. ...
Leaf-scale flames play a pivotal role in fire spread within the same crown fuel and from one shrub or tree to another. In the present work, pyrolysis and combustion of a solid fuel element representing a manzanita leaf were computationally investigated in a configuration where the fuel was subject to an upward stream of hot gases. The configuration resembled an experimental setup where vertically oriented manzanita leaves were burned. The composition of the pyrolysis gas released from the leaf and the reaction kinetics describing chemical evolution of the pyrolysis gas are two important aspects affecting the modeling outcome. To investigate this, four different scenarios were considered: (i) only CH 4 with CH 4 oxidation reaction; (ii) only CO with CO oxidation reaction; (iii) a mixture of CH 4 , CO and CO 2 with oxidation reactions for CH 4 and CO the same as (i) and (ii), and the corresponding reverse reaction of CO oxidation reaction; and (iv) the same as (iii) with an additional reaction representing tar breakdown. Time history of the computed leaf normalized mass and the leaf average surface temperature were compared against the corresponding experimental data. Case (iii) exhibited a better match with the experimental data followed by cases (iv) and (ii). On the other hand, case (i) showed the most deviation from the experimental data. It was also shown that the inclusion of tar breakdown in the kinetic scheme remarkably affected gas species distribution.
... In recent years the consumption of energy has increased and due to what conventional fossil fuels have been depleted with the increase of populations and economy, it is necessary to explore renewable energies and ensure sustainable development. In this sense, biomass seems to be a clean option, since it contains small amounts of sulfur, nitrogen and ash, which generate less emissions of SO 2 , NO x and soot than conventional fossil fuels (Bridgwater and Peacocke 2000;Czernik and Bridgwater 2004;Scott et al. 1985;Zhang et al. 2007). ...
The biomass conversion technologies, especially different types of pyrolysis, have been intensively studied to improve biomass energy transformation suggesting a low impact on the environment. In particular, fast pyrolysis of biomass is considered to be a thermal process in which the starting material is converted to bio-oil, char and gas products. In this work, volatile organic compounds (VOCs) of the gaseous fraction of peanut shells fast pyrolysis were collected and identified at atmospheric pressure. Aromatic compounds, hydrocarbons, furans and other oxygenated compounds were identified using solid phase microextraction (SPME) and gas chromatography coupled to mass spectrometry (CG-MS) as a detection system. The composition of volatiles was analyzed and compared with the constituents of liquid fraction for comparative purposes. Atmospheric implications of the main compounds identified in the gases fraction were assessed by determining tropospheric lifetimes of the VOCs identified and its impact on environment at the local, regional or global scale.
... The predicted yields of acetate acid in the volatile product for different biomasses at different pyrolysis temperature are shown in Figure 9 using the model equation in Eq. (19) with the NCT function in Eq. (15), the volatile enhancement model equation in Eq. (16) and the pseudo kinetic parameters above. The other two biomasses added here are rice straw from Sonabe & Worasuwannarak [27] with NCT at 6.46, and corn stover from Scott, et al. [28] with NCT at 15.18. The effect of these biomass types on the yield of acetate acid in the volatile product clearly exists, as shown in Figure 9. ...
Volatile state mathematical models for quantifying the chemical components in volatile biomass pyrolysis products were developed. The component mass yield Yi rate depends linearly on its pseudo kinetic constant and the remaining mass yield. The mass fraction rate of each component was modeled from the derivation of its mass yield rate equation. A new mathematical model equation was successfully developed. The involved variables are: biomass number, temperature, heating rate, pre-exponential factor, and pseudo activation energy related to each component. The component mass fraction yi and the mass yield were predicted using this model within a temperature range. Available experimental pyrolysis data for beechwood and rice husk biomass were used to confirm the developed model. The volatile products were separated into bio-pyrolysis gas (BPG) and a bio-pyrolysis oil (BPO). Five components in the BPG and forty in the BPO were quantified. The pseudo activation energy for each pseudo chemical reaction for a specific component was modeled as a polynomial function of temperature. The component mass fraction and yield are quantifiable using this developed mathematical model equation within a temperature range. The predicted component mass fractions and yields agreed excellently with the available experimental data.
... According to statistics of availability of biomass waste, India have huge-amount of waste biomass that it can reduce the dependence of India on fossil fuel if properly processed, in addition to improving the economy of the country. Moreover, it helps to reduce CO 2 and other harmful emission in environment by maintaining the carbon neutrality or even carbon negativity [4][5][6][7]. In general, any lignocellulosic biomass consists of structures of lignin, cellulose and hemicellulose as the name lignocellulosic indicates though there may other components such as starch, proteins, etc. ...
Non-catalytic co-pyrolysis of Delonix Regia (DR) wood and Polyalthia Longifolia (PL) leaves and varying fractions of polypropylene (PP) has been carried out at 600 °C in a tubular reactor. The fractions of PP varied in order to have 0 wt%, 10 wt%, 30 wt% and 50 wt% of it in the feed while the composition of DR and PL maintained constant and equal to each other so that to study the effect of PP on co-pyrolysis of two lignocellulosic biomass waste materials. The feed materials, along with the products (bio-oil and bio-char) have been extensively characterized for their physicochemical and fuel properties. In addition, extensive advanced material characterization techniques such as Fourier transmission Infrared Spectroscope (FTIR), proton nuclear magnetic resonance (¹H NMR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), etc. have been utilized for analysis purposes. The properties of bio-oil reported in this work are of the organic phase only of the liquid product. The average calorific value of organic fraction of bio-oil is increasing from 22.556 MJ/kg to 34.06 MJ/kg with increasing wt.% of polypropylene (PP) in co-feed from 0 wt% to 50 wt% respectively, while the calorific value of bio-char is showing mixed trend. Density of organic phase decreases from 973 kg/m³ to 816 kg/m³ with increasing the fraction of PP, while pH display opposite trends i.e., increasing from 4.31 to 4.97 which are close to commercial fuel properties. FTIR confirm the presence of functional groups of alkanes, aromatics, alcohols, phenols, aliphatic, ketone, ethers, etc. in organic fraction of bio-oil; and also confirmed by proton NMR. Further it is also confirmed that fraction of alkanes and aliphatic in bio-oil samples increases with PP fraction in the co-feed. The main finding of this work indicates that the fraction of PP in co-feed improved the physicochemical, chemical and fuel potential of the organic phase of liquid product. However, the trend of yield of organic fraction of liquid is not as expected and the reason could be the presence of leaves of PL because often the yield of liquid product is very low when leafy biomass used as feed.
... , magnesium carbonate (MgCO3), dolomite (CaCO3·MgCO3), and olivine are abundant and of low cost. Their calcined versions have high catalytic activities for tar elimination and catalytic upgrading[225,[325][326][327][328][329]. Alkaline-earth metal oxides such as MgO and MgO-based mixed oxides are among the most promising solid base catalysts[159,292,317,325,330,331]. ...
Direct catalytic upgrading of biomass-derived fast pyrolysis vapors can occur in different process configurations, under either inert or hydrogen-containing atmospheres. This review summarizes the myriad of different catalysts studied, and benchmarks their deoxygenation performance by also taking into account the resulting decrease in bio-oil yield compared to a thermal pyrolysis oil. Generally, catalyst modifications aim at either improving the initial selectivity of the catalyst to more desirable oxygen-free hydrocarbons, and/or to improve the catalysts’ stability against deactivation by coking. Optimizing pore structure and acid site density/distribution of solid acid catalysts can slow down deactivation and prolong activity. Basic catalysts such as MgO and Na2O/gamma-Al2O3 are excellent ketonization catalysts favoring oxygen removal via decarboxylation, whereas solid acid catalysts such as zeolites primarily favor decarbonylation and dehydration. Basic catalysts can therefore produce bio-oils with higher H/C ratios. However, since their coke formation per surface area is higher, compared to microporous HZSM-5 zeolite, pre-coking (or imperfect regeneration) of these basic catalysts and operating for longer time-on-stream can be approaches to improve the oil yield. In-line vapor-phase upgrading with a dual bed comprising a solid acid catalyst followed by a basic catalyst active in ketonization and aldol condensation further improves deoxygenation, while maintaining high bio-oil carbon recovery. Also low-cost catalysts such as iron-rich red mud have deoxygenation activity. An improved bio-oil carbon recovery— compared at similar level of oxygen removal—can be obtained when changing from an inert atmosphere to a hydrogen-containing atmosphere and using an effective hydrodeoxygenation (HDO) catalyst. To keep costs low, this can be conducted at near-atmospheric pressure conditions. Pt/TiO2 and MoO3/TiO2 showed high activity and reduced coke formation. Stable performance has been demonstrated using Pt/TiO2 for 100+ reaction/regeneration cycles with woody biomass feedstock. If future works can demonstrate the same durability for lower cost biomass containing higher contents of ash, N, and S, this would considerably boost the commercial viability of near atmospheric pressure HDO. Further research should be directed into testing the durability of lower cost HDO catalysts such as MoO3/TiO2 and further improving the activity and stability of lower cost catalysts.
... Dry biomass (Durian lai peel waste) was carbonized using slow pyrolysis. This method has been developed by some investigators [7][8][9]. Dry biomass was placed in electrically heated furnace at temperature of 400 o C for 30 min as shown in the Figure 2. After 30 min, the furnace was cooled down to room temperature, and then the particle size of the charcoal is reduced by mortar, we selected particle size of 2.00 mm as optimum value (obtained from the preliminary study). ...
Briquettes are widely used as a renewable energy to solve the problems of excessive use of wood as fuel. However, the performance of briquettes depends on the types of pyrolysis and the nature of binders used during the preparation. Their performances are related to problems such as low yield and energy content, but can be significantly improved with the use of adhesives in the right compositions. In this work, we investigated the effect starch binders compositions on the quality of briquettes from the pyrolysis of Durian lai peel (Durio kutejensis Becc). The briquettes were prepared from Durian peel charcoal by adding starch as a binder at various concentrations of 3%, 4%,5%, and 6% (w/w). Subsequently, analysis of moisture content, volatile matter ash content, and calorific value were found that the best quality obtained was form the briquette with binder concentration of 3 % (w/w).
... 74 However, the detailed chemistry of the reaction mechanism is not considered in global kinetic models as they contain only primary reactions. Therefore, the kinetic models were modified to consider secondary reactions also 79 which include gas formation from tar decomposition and tar polymerization reactions to give char as a byproduct. 80 Another model is a multireaction model or competing and parallel reaction model. ...
Biomass pyrolysis is a thermochemical conversion process that undergoes a complex set of concurrent and competitive reactions in oxygen-depleted conditions. A considerable amount of the literature uses lumped kinetic approaches to predict pyrolysis products. Despite the prolonged studies, the science of pyrolysis chemistry and models' capability to simulate the exact conversion phenomenon has unraveled yet. In this review, an initiative was made by compiling existing mathematical models for biomass pyrolysis viz., lumped and distributed kinetic models, particle, and reactor models. An absolute analysis of computational fluid dynamics (CFD), artificial neural network (ANN), and ASPEN Plus models was also conducted. It was observed that the coupling of distributed kinetic models with CFD provides a better understanding of the hydrodynamic reaction of particles under reactive flow with the influence on reactor performance and predicts exact product yield. Furthermore, the pros and cons of each modeling technique are also highlighted individually. Finally, considering the future perspective of biomass pyrolysis with respect to the modeling approach, suggestions have been incorporated.
... As a result, it is imperative to search for models that could predict product distribution, including primary and secondary biomass pyrolysis processes. Researchers formulated models to include the primary' reactions products as secondary reactions to produces materials similar to the direct products, i.e., gas, tar, and char, through cracking and polymerization reactions (Thurner, 1981;Bradbury, et al., 1979;Scott, et al., 1985;Agrawal, 1988). Several kinetic schemes have been proposed for combining primary degradation of biomass and secondary decomposition of volatile products (higher molecular weight hydrocarbons). ...
Modeling of biomass pyrolysis kinetics is an essential step towards reactors design for energy production. Determination of the activation energy, frequency factor, and order of the reaction is necessary for the design procedure. Coats and Redfern's work using the TGA data to estimate these parameters was the cornerstone for modeling. There are two significant problems with biomass modeling, the first is the determination of the kinetic triplet (Activation energy, Frequency factor, and the order of reaction), and the second is the quantitative analysis of products distribution. Methods used in modeling are either One-step or Multistep methods. The one-step techniques allow the determination of kinetic triplet but fail to predict the product distribution, whereas multistep processes indicate the product's distribution but challenging to estimate the parameters. Kissinger, Coats, and Redfern, KAS, FWO, Friedman are one-step methods that have been used to estimate the kinetic parameters. In this work, after testing more than 500 data points accessed from different literature sources for coal, oil shale, solid materials, and biomass pyrolysis using one-step global method, it was found that the activation energy generated by KAS or FWO methods are related as in the following equations: 𝐸𝐾𝐴𝑆 = 0.9629 ∗ 𝐸𝐹𝑊𝑂 + 8.85, with R² =0.9945 or 𝐸𝐹𝑊𝑂 = 1.0328 ∗ 𝐸𝐾𝐴𝑆 − 8.0969 with R2= 0.9945. The multistep kinetic models employed the Distributed Activation Energy Model (DAEM) using Gaussian distribution, which suffers from symmetry, other distributions such as Weibull, and logistic has been used. These multistep kinetic models account for parallel/series and complex, primary and secondary biomass reactions by force-fitting the activation energy values. The frequency factor is assumed constant for the whole range of activation energy. Network models have been used to account for heat and mass transfer (diffusional effects), where the one-step and multistep could not account for these limitations. Three network models are available, the Bio-CPD (Chemical Percolation Devolatilization) model, Bio-FLASHCHAIN, and the Bio-FGDVC (Functional Group Depolymerization Vaporization Crosslinking models). These models tried to predict the product distributions of the biomass pyrolysis process
... The very first biomass pyrolysis was initially developed by the laboratory to process unit scale production in Canada and the United States during the 1980s [24][25][26]. Since then the technology has proved to be a promising alternative biofuel [27][28][29]. ...
Bio-oils produced by biomass pyrolysis are substantially different from those produced by petroleum-based fuels and biodiesel. However, they could serve as valuable alternatives to fossil fuels to achieve carbon neutral future. The literature review indicates that the current use of bio-oils in gas turbines and compression-ignition (diesel) engines is limited due to problems associated with atomisation and combustion. The review also identifies the progress made in pyrolysis bio-oil spray combustion via standardisation of fuel properties, optimising atomisation and combustion, and understanding long-term reliability of engines. The key strategies that need to be adapted to efficiently atomise and combust bio-oils include, efficient atomisation techniques such as twin fluid atomisation, pressure atomisation and more advanced and novel effervescent atomisation, fuel and air preheating, flame stabilization using swrilers, and filtering the solid content from the pyrolysis oils. Once these strategies are implemented, bio-oils can enhance combustion efficiency and reduce greenhouse gas (GHG) emission. Overall, this study clearly indicates that pyrolysis bio-oils have the ability to substitute fossil fuels, but fuel injection problems need to be tackled in order to insure proper atomisation and combustion of the fuel.
... As observed by Raveendran et al., AAEM species influenced both the pyrolysis behaviors and the product yields strongly [9]. Scott et al. first conducted research into the effect of lime (CaO) on liquid products of biomass pyrolysis [11]. Nowakowski et al. suggested that the presence of potassium made the char yields increase from the short rotation willow coppice pyrolysis [12]. ...
The effects of potassium chloride (KCl) on the pyrolysis of medium density fiberboard (MDF) were investigated by using thermogravimetry/Fourier-transfer infrared spectroscopy (TG-FTIR). Five MDF samples treated with different KCl concentrations (0%, 0.5%, 1%, 2% and 3%) were heated with a heating rate of 20 °C/min. The thermogravimetry (TG) results showed that KCl caused the primary pyrolysis stage towards lower temperatures. The FTIR results indicated that with the concentrations of KCl, the formation of CH4 and C=O functional groups decreased while the formation of CO2 and CO increased. To figure out the reason for the observed phenomena, the kinetic parameters in primary pyrolysis and the secondary charring reaction were estimated by a differential evolution (DE) optimization algorithm. The prediction indicated that KCl shifted the initial degradation temperature of each component of MDF towards a lower temperature. Char and gas yields increased with the concentration of KCl, whereas the tar yield reduced. The changes in activation energies revealed that KCl played a catalyst role in the reaction of resin, hemicellulose and cellulose in primary pyrolysis. For lignin, KCl had little effect. In the secondary charring reaction, KCl apparently promoted the reaction of tar. The catalytic effect of KCl on MDF pyrolysis was the combination of primary pyrolysis and the secondary charring reaction. Finally, the optimal catalytic concentration for KCl on MDF pyrolysis was analyzed.
... FasP is the process with thermal decomposition under a moderate temperature of 300 -700 in the reaction zone without oxygen (Bridgwater and Peacocke, 1999;Scott and Piskorz, 1984). The reactor configurations include bubbling fluid beds (Robson, 2001;Scott et al., 1985), circulating and transported beds (Graham et al., 1988;Wegenaar et al., 2000), cyclonic reactors (Czernik et al., 1995;Diebold and Scahill, 1988), and ablative reactors (Peacocke and Bridgwater, 1996), which play an important role in this process to ensure the production. The FasP process is showed in Fig. 2. FasP is applied to decompose the waste into bio-oil. ...
The objective of this paper is to establish the state of knowledge on fast pyrolysis of bio-oil and bio-asphalt binder and to facilitate efforts in improving the overall performance of bio-asphalt and maximizing its road application. On the basis of reviewing the relevant literature recently, the fast pyrolysis (FasP) preparation process of bio-oil and its main properties, the preparation process of bio-asphalt and its performance and the application of bio-asphalt have been summarized. Due to the variations in raw materials, the adopted methods of FasP to prepare bio-oil could be different, and the properties of bio-oil from different sources are also different. At present, the plant-based bio-oil (mainly derived from wood waste and sawdust) has been widely used to prepare the bio-asphalt. Research on the low-temperature flexibility, high-temperature rheology, workability and other performance of biological asphalt showed that the workability and high-temperature performance of most asphalt are improved after adding bio-oil. However, the low-temperature performance is found to relatively reduce. Also, with regards to its application as a rejuvenator, bio-oil can considerably rejuvenate the aged asphalt’s mixture performance. By far, most of research on bio-asphalt is still focused on the performance of bio-asphalt binder in the laboratory; its application in practical road engineering is still to be examined. This review also provides an outlook for the future, for example, establishing an integrated preparation process from bio-oil to bio-asphalt, and evaluating the properties of bio-asphalt by new standards.
... One promising strategy is to produce transportation fuels from lignin biomass waste. [2][3][4][5] Converting the oxygenated aromatic compounds in water that come from fast pyrolysis of lignin (i.e., bio-oil) to transportation fuels or chemical precursors requires aqueous-phase catalytic or electrocatalytic hydrogenation and hydrodeoxygenation, 6 typically rate-limited on metals by surface reactions. To improve the kinetics of these and other aqueousphase catalytic reactions, an understanding of the effect of water (or solvent) on organic adsorption is critical, because adsorption energies can determine coverages and alter activation barriers. ...
Accurately predicting adsorption energies of oxygenated aromatic and organic molecules on metal catalysts in the aqueous phase is challenging despite its relevance to many catalytic reactions such as biomass hydrogenation and hydrodeoxygenation. Here we report the aqueous-phase adsorption enthalpies and free energies of phenol, benzaldehyde, furfural, benzyl alcohol, and cyclohexanol on polycrystalline Pt and Rh determined via experimental isotherms and density functional theory modeling. The experimental aqueous heats of adsorption for all organics are ~50-250 kJ mol −1 lower than calculated gas-phase heats of adsorption, with a larger decrease for Rh compared with Pt. Unlike in gas phase, phenol and other aromatic organics adsorb with similar strength on Pt and Rh in aqueous phase. The similar aqueous adsorption strength of phenol and benzaldehyde on Pt and Rh explains their comparable aqueous-phase hydrogenation activities, which are rate limited by a Langmuir-Hinshelwood surface reaction. A widely used implicit solvation model largely overpredicts the heats of adsorption for all organics compared with experimental measurements. However, accounting for the enthalpic penalty of displacing multiple water molecules upon organic adsorption using a bond-additivity model gives much closer agreement between experimental measurements and predicted heats of adsorption. This bond-additivity model explains that the similar adsorption strength of organics on Pt and Rh in aqueous phase is due to the stronger adhesion of water to Rh than Pt, which offsets the stronger gas-phase organic adsorption energy on Rh. The data reported herein also provides a valuable resource for benchmarking methods for predicting aqueous-phase adsorption energies of C5/C6 organics on metal surfaces.
... Modern technology for processing and burning solid fuels opens up wide prospects for its effective use in various fields of industry, energy generation, and agriculture. Along with traditional grate firing [1], widespread are the methods of arranging the combustion process in a fluidized bed [2], pulverized burning in order to study kinetic parameters [3][4][5], in laminar [6,7] and turbulent [8,9] jets; the methods of gasification [10,11], pyrolysis [12,13], and creating water-coal fuel [14][15][16][17] are being used extensively. ...
Bidirectional (or countercurrent) vortex combustors are some of the most promising vortex-flow devices in terms of the fuel and oxidizer mixing efficiency, the combustion efficiency, the emission characteristics, and the combustion stability. This paper suggests a new arrangement principle for combustion of solid pulverized peat in conditions of vortex countercurrent flow which has never been studied earlier; we developed a combustion unit implementing this principle and carried out a numerical analysis of the combustion process with various operating parameters. The calculation results confirmed the possibility of combustion within a wide range of parameters and showed that varying the air-fuel equivalence ratio from λ = 0.5 to λ = 5.05 results in significant change in both the structure of the limited vortex flow and the distribution of total pressure and temperature, as well as the averaged volume concentration of fuel particles. We calculated the boundaries of lean and rich flame blowouts where the gas-dynamic flow loses its stability and the toroidal vortex is disrupted. At the same time, secondary vortex structures are formed throughout the combustor volume.
... Therefore, in order to facilitate methane production from aqueous phase of pyrolysis oil during anaerobic digestion process, the amount of Hydroxyacetaldehyde (HAA) should be minimized. The pretreatment methods can not only reduce the formation of HAA but can also increase the overall yield of bio-oil [21,22]. HAA is a common low molecular weight organic compound produced from fragmentation of cellulose during pyrolysis, which has been identified as one of the most toxic compounds for fermentation micro-organisms found in bio-oils [20,23]. ...
The aim of this work was to evaluate biomethane production by anaerobic digestion using aqueous phase from Fast Pyrolysis of Douglas Fir Wood as substrate. The effect of biomass acid treatment and condensation temperature on the bio-oil chemical composition and aqueous phase separation with a fractional condensation system coupled to Auger reactor during pyrolysis at 500 °C was reported. As the first condenser temperature was augmented from 40 and 80 °C, the bio-oil yield obtained decreased from 30 to 16 wt% and the aqueous phase yield in the second condenser (kept at 25 °C) increased from 27 till 37 wt%. When the untreated biomass was pyrolyzed, the aqueous phase collected in the second condenser (at the first condenser operated at 80 °C) was anaerobically digested at 100 ppm for 400 h results in 31.3 NmL of CH4/batch. However, the best result was attained after washed biomass with acetic acid (10%) previously to fast pyrolysis, obtaining 86.8 NmL of CH4/batch using just 10 ppm, perhaps due to halved of formed hydroxyacetaldehyde and estimated levoglucosan content increases by more than three times at this condition. Thus, the attained results confirmed the viability of the adopted strategy to improve the anaerobic digestion of the aqueous phase obtained by fractional condensation systems for biomethane production.
... Flash pyrolysis process is essential to know the devolatilization characteristics and to maximize the evolved volatile gases in high heating rate with shorter duration. The process was previously studied in several works [26][27][28] in different reaction furnaces to be probably reproduced the reaction conditions closer to those encountered as one of the processes in practical fluidized bed gasification. Fluidized bed gasification could be attributed a co-relationship between (1) flash pyrolysis and (2) pyrolysis gas partial combustion as it is generally known that the gasification reaction in FBG is completed immediately. ...
Fluidized bed gasifiers (FBGs) and gas engines (GEs) could be available as waste-to-energy technology, because most small- and medium-scale municipal solid waste treatment plants have low electricity generation efficiencies. As feedstock composition vary widely based on regional characteristics, clarifying the relationship between gas and tar generation behaviors and feedstock is useful for the design of the GE generation process to predict gas and tar yields and compositions. To understand the synergistic effect of feedstock characteristics in fluidized bed gasification, flash pyrolysis of wood pellet, polyethylene, and polypropylene at 900 °C was conducted. Yields and compositions of gasses and tar from single and co-pyrolysis were investigated. The results reveal that co-pyrolysis increases the gas yield because of oxygenates and moisture present in the wood pellet. Tar yields found to decrease while polycyclic aromatic hydrocarbons (PAHs) are not reduced even during co-pyrolysis. That is because most chain hydrocarbons of tar are converted to CmHn gases and PAHs.
... The nonprioritization of hemicellulose is because of the fact that its degradation causes the formation of by-products which are inhibitory in nature to the hydrolytic enzymes. The production of bioethanol from lignocellulosic Scott et al. (1985) biomass can be divided into three basic furcation, that is, pretreatment, enzymatic hydrolysis, and fermentation. ...
... It contains mostly C (85-95%) with a small amount of H and O. Therefore, to overcome the cited limitation of ASPEN plus, it was decided to model the Char as pure carbon (homogeneous compound) instead of a heterogeneous nonconventional compound in the simulation (see the modelling assumptions cited before). The same type of correlation exists also for the CHO content in the tar [17,18]. Contrasting with the behaviour of char, there is a weak relationship between the elemental composition of tar and pyrolysis temperature. ...
Biomass energy conversion is a reliable way to produce energy and chemical products if compared with other renewable sources such as wind, solar and wave which have intermittent nature. Amongst different methods of converting biomass to energy, the thermo-chemical process of steam gasification is an outstanding way, since it enables a subsequent poly-generation process that can lead to production of heat, electricity, synthetic natural gas and synthetic chemicals such as methanol, Fischer-Tropsch diesel, gasoline and kerosene. The modelling of biomass gasification enables the optimization of the process designs, but it is a challenge due to its high complexity. Here, a new approach is used to simulate a 100 kW dual fluidized bed gasifier. Detailed pyrolysis modelling is a key factor of this approach and enables more accurate results. The results have been validated by experiments conducted with softwood pellets as fuel and fresh olivine sand as bed material. The impact of the gasifier temperature variation on the final product gas composition is measured in the experiments and implemented in the simulation to have a better insight on the pyrolysis process, the char heterogeneous reactions as well as the deviation from equilibrium of the water gas-shift reaction.
... Canada started the initial research on bubbling fluid reactor[242][243][244]. Dynamotive built a pilot plant with a capacity of 75 kg/h and 400 kg/h[245]. ...
Lignocellulosic biomass can be convert to a condensable liquid named bio-oil, a solid product named as char and a mixture of gaseous products comprising CO 2 , CO, H 2 , CH 4 , etc. In recent years, much effort has been made on the investigation of conversion of biomass through pyrolysis. However, commercialisation of the biomass pyrolysis technology is still challenging due to various issues such as the deleterious properties of bio-oil including the low heating value and the high instability at elevated temperatures. To overcome such issues, many processes, reactors and catalysts have been developed for pyrolysis and catalytic pyrolysis of biomass. A state to the art of pyrolysis or catalytic pyrolysis of biomass need to be summarised to have an overall evaluation of the technologies, in order to provide a useful reference for the further development of pyrolysis technology. This study reviews the various pyrolysis process, especially focus on the effects of essential parameters, the process design, the reactors and the catalysts on the pyrolysis process. In addition, progress in commercialisation of pyrolysis technology was also reviewed and the remaining issues in the process of commercialisation were discussed. © 2019 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences
... This pilot plant was designed to produce a low cost production for obtaining pyrolysis oil. The process of production line was modified to a new schematic process from many previous literatures which it was not duplicate with other systems (Onay et al., 2001;Onay, 2007;Sensoz and Angin, 2008;Jung et al., 2008;Duanguppama et al., 2016;Stamatov et al., 2006;Morales et al., 2014;Treedet and Suntivarakorn, 2011;Asadullah et al., 2008;Cai and Liu, 2016;Cai et al., 2018;Akarregi et al., 2013;Boukis et al., 2001;Antonelli, 1989;Trebbi et al., 1997;Dai et al., 2001;Scott et al., 1985;McAllister, 1997;Lappas et al., 2002;Maniatis et al., 1993;Knight et al., 1982;Cuevas et al., 1994). The features of this particular pilot plant was that the CFBr was heated using the exhaust gas from a can combustor and that LPG was used as the fuel to generate the heat. ...
This article focused on production cost of pyrolysis oil production of Napier Grass in Circulating Fluidized Bed Reactor (CFBr) which sand was used as bed material. The Napier grass was converted to pyrolysis oil by using fast pyrolysis process. The reactor temperature, superficial velocity (Uf) and feed rate of feedstock were adjusted in order to find the best condition of this experiment, and the Quadratic Response Model was used to predict the yield of pyrolysis oil and the optimum condition coupled with the experiment. From a results of this experiment, it was found that the maximum pyrolysis oil production was 36.93 wt% at 480 ºC of bed temperature, 7 m/s of superficial velocity and 60 kg/hr of feed rate, while the result from the Quadratic Response Model indicated that the maximum pyrolysis oil production was 32.97 wt%. From the analysis of properties of pyrolysis oil, results showed that heating value, density, viscosity, pH and water content were 19.79 MJ/kg, 1,274 kg/m 2.32 cSt, 2.3 and 48.15 wt%, respectively, and the ultimate analysis was also determined. From the analysis of the efficiency of energy conversion, it was concluded that the value of cold efficiency and total energy conversion to pyrolysis oil in this system were 24.88% and 19.77%, respectively. The greatest energy consumption in this system was made by the energy from the heating process. Furthermore, from the calculation result of production cost in this study, it was concluded that a production cost of pyrolysis oil was 0.481 /GJ at the 75 kg/hr of feed rate. Keywords: Napier grass, Fast pyrolysis, Pyrolysis oil, CFBr
... Depending on the selected pyrolysis temperature, the nature and composition of products may be changed. Most of the early studies were focused on flash pyrolysis at medium temperature to maximize bio-oil production (Scott et al., 1985;Piskorz et al., 1986;Yaman, 2004;Dominguez et al., 2005;Fonts et al., 2009;Zaimes et al., 2015). Aside the temperature, there are many parameters such as particle size, heating rate, residence time, and rotation speed in case of using a rotating reactor, which would affect the yield of the ultimate products along the process (Basu, 2010). ...
This study explored the potential of high temperature pyrolysis for energy recovery from domestic sewage. It mainly defines optimum operating conditions to maximize syngas generation. A pyrolysis unit was operated in batch mode, at temperatures of 450, 600 and 850 °C, rotation speeds of 10, 40 and 60 Hz. The sludge had 6% moisture content; it contained 65% organic matter and involved a low calorific value of 13.535 kJ/kg dry matter. Pyrolysis at 850 °C and high rotation speed of 60 Hz yielded the highest conversion of sludge to syngas, with an average of 59% of the organic matter as syngas, 29% as tar and 12% as biochar. Pyrolysis enabled 74% of the energy recovery as syngas and tar. Continuous full-scale pyrolysis systems would further increase the syngas by recovering condensable gaseous products and/or recycling tar back into the pyrolysis unit. A unified approach for energy recovery management should equally consider what fraction of the energy contained in the wastewater was consumed and wasted before generating the sludge. Therefore, the adopted management scheme should also cover all design and operation parameters of the treatment plant, because this is how the energy is best conserved even before the sludge is generated.
Focusing on a critical aspect of the future clean energy system - renewable fuels - this book will be your complete guide on how these fuels are manufactured, the considerations associated with utilising them, and their real-world applications. Written by experts across the field, the book presents many professional perspectives, providing an in-depth understanding of this crucial topic. Clearly explained and organised into four key parts, this book explores the technical aspects written in an accessible way. First, it discusses the dominant energy conversion approaches and the impact that fuel properties have on system operability. Part II outlines the chemical carrier options available for these conversion devices, including gaseous, liquid, and solid fuels. In the third part, it describes the physics and chemistry of combustion, revealing the issues associated with utilizing these fuels. Finally, Part IV presents real-world case studies, demonstrating the successful pathways towards a net-zero carbon future.
With pyrolytic bio-oil as raw material, an efficient bio-oil-based dispersant (BOBD) applied to coal water slurry (CWS) has been synthesized successfully by grafting polymerization of the organic fractions from the bio-oil and acrylic acid (AA) in the mild condition. As a comparison, two commercial dispersants, namely poly (styrene sulfonic acid) sodium (PSS) and sodium lignosulfonate (SL) were employed. The structures and properties of the synthesized BOBD were characterized by using FTIR, ¹H NMR, GC/MS, GPC, zeta potential, contact angle, and surface tension. The results showed the molecular weight of the BOBD was concentrated at 832 g/mol and 1954 g/mol. The surface tension and contact angle of BOBD aqueous solution were 47.71 mN/m⁻¹ and 60.8° respectively. The zeta potential of the suspension prepared from BOBD-water-coal was −67.1 mV. Using BOBD as a dispersant, the apparent viscosity of CWS loading 66 wt% coal dropped to 288 mPa·s at 0.3 wt% BOBD, and the maximum coal content reached 72 wt%. BOBD exhibited better viscosity reduction and stability enhancement capabilities than PSS and SL. The excellent dispersion performance of BOBD was due to the large electrostatic repulsion and steric hindrance derived from the grafted acrylic polymer, which effectively dispersed the coal particles uniformly. The rheological behavior of CWS with BOBD belonged to pseudoplastic fluid. The synthesized BOBD not only had an excellent dispersion performance but also could overcome the shortcomings of secondary pollution caused by PSS and SL containing element sulfur as dispersants in combustion. In addition, the synthetic route possessed simple, environmentally friendly and sustainable characteristics. The research opened up a new way for the utilization of bio-oil.
The pyrolysis process has opened the doors for biomass utilization effectively and sustainably. It is the one of the most efficient processes to valorize biomass into bio-oil, bio-char, and gaseous products, which can be further upgraded depending on the targeted applications. To understand the mechanism involved and the technical aspects, many efforts have been undertaken in the past. Yet, commercialization of pyrolysis process on a large scale still remains elusive and is faced by a lot of challenges. This might be attributed to the lack of detailed understanding of the pyrolysis process, for which comprehensive models for biomass pyrolysis need to be developed using evolving techniques like machine learning and artificial intelligence. The significance of pyro probe gas chromatography-mass spectrometry as an analytical tool for flash pyrolysis of biomass feedstock also helps in getting deeper mechanistic insights into pyrolysis. This article aims to discuss the recent studies carried out to understand pyrolysis process and its advancements by adopting machine learning/artificial intelligence techniques. Researchers will also be able to understand the application of various statistical methods to determine the most influential factor contributing to the quality/quantity of the pyrolysis products.
The impact of pyrolysis gas composition and the underlying reaction kinetics on the burning characteristics of a leaf was computationally investigated. The computational configuration resembled a previous experimental setup where vertically oriented manzanita (Arctostaphylos glandulosa) leaves were burned. Different compositions and reaction kinetics for the pyrolysis gas released during the leaf thermal decomposition were examined. The most detailed composition included CH4, CO, CO2, and H2, which was suggested by the previous experimental study of pyrolysis products of different plant species. The least involved compositions only included either CH4 or CO. In all considered compositions, in addition to pyrolysis gas, the release of the heavy gas, i.e. tar, was accounted for. Tar breakdown was represented by a single-step reaction with the light gases above and soot as the products where the stoichiometric coefficients were determined by an optimization technique for consistency with the measurements for the tar molecule. The burning simulation results agreed best with the previous experimental data when a mixture of CH4, CO, CO2 was used. The least agreement was noted when pyrolysis gas was represented by only CH4. Inclusion of tar breakdown reaction appreciably increased the overall heat release due to combustion of its products above the leaf.
In order to predict the pyrolysis mechanisms of four different biomasses (Asbos-Psilocaulon utile, Kraalbos-Galenia africane, Scholtzbos-Pteronia pallens, and Palm shell) were investigated by a novel method called Kalman filter and the results compared with the regression analysis. Both analyses were applied to five different generalised biomass pyrolysis models consisting of parallel and series irreversible-reversible reaction steps. The models consisting of reversible reactions in addition to parallel pyrolysis steps demonstrated a better fit with the experimental results. The pyrolysis step from biomass → bio-oil has the highest reaction rates (3.9*10−3, 8.2*10−3, 9.3*10−3, and 13.5*10−3 min−1) compared with the other pyrolysis steps defined in the models. Kalman filter is, therefore, defined as one of the promising filtering and prediction methods for the estimation of detailed pyrolysis mechanisms and model parameters using minimum experimental data.
In the modern world, the aviation sector plays a vital role in human life in terms of public transport and freighting of goods. Depletion of fossil resources and concerns of their effect to global warming is encouraging researchers to search for alternative options. The current work emphasizes the updated thermochemical process technologies over different heterogeneous catalysts with different feedstocks. The main parameters are availability of feedstock, challenges in the use of feedstock and process details. Besides environmental influence, also development status of bio-jet fuels will be presented.
Various phytoremediation residues (PMRs), including Brassica napus L. (BN), Pennisetum sinese (PS) and Lolium perenne L.(LP), were pyrolyzed at 400, 500, 600 and 700 °C, respectively. A series of sequential and single extractions were employed to analyze the chemical speciation and potential environmental risk of Cadmium (Cd) in different phytoremediation residues-derived biochars (PMBs). The results showed that the exchangeable Cd fraction decreased but the residual Cd fraction increased, indicating the inhibition of bioavailability of Cd and low potential ecological risk index of PMBs. When the temperature was over 600 °C, the Cd in biochar was acceptable to the environment and the leaching concentration of Cd extracted by the three extraction methods (distilled water, SPLP and TCLP) were all under the standard limit. Findings from this study illustrated that the treatment of pyrolysis was feasible for the three kinds of PMRs at 600 °C with acceptable environment risk.
The expected growth of the world’s population and the consequent increase in the global energy demand, together with the volatility of the energy market, results in specific uncertainties in the future world economy, which are reflected in the range of oil price projections both in the short and long term. Cuba is an island that lacks sufficient proven fossil energy resources to be able to have an advance in long-term sustainable economic and social development. However, the largest source of domestic energy production comes from imported oil. Hence the importance of the promotion and development of renewable sources of energy. In this sense, sugar cane bagasse (SCB) and trash (SCT) are the main residues derived from the production of sugar from cane which accounted for 3.3% of the total electricity production in the country, albeit the trash not being valorized to a significant extent.
Fast pyrolysis is an attractive alternative technology to process sugar cane residues, whereby solid biomass is converted mainly to bio-oil. The bio-oil has the potential for use as a fuel or as a feedstock for the extraction and/or synthesis of more valuable chemical compounds. However, the high heterogeneity and poor fuel quality of crude bio-oil (i.e. high oxygen and water fraction, high acidity, and high viscosity) impose the need for upgrading processes. Nowadays, research efforts have been conducted in pretreatment to address problems associated with the presence of naturally occurring alkali and alkaline earth metals (AAEMs) in biomass. In terms of specific elements, Si, Na, K, Mg and Ca are generally the major inorganic components in sugar cane. These elements have been demonstrated to act as catalysts during fast pyrolysis. Also, they possess large potential to reduce the yield and the bio-oil’s stability, and to alter the resulting bio-oil composition in a negative way. Most notably, AAEMs appear to suppress and/or suppress the pyrolytic production of levoglucosan out of cellulose and favor the production of lighter oxygenates instead.
This thesis focuses on the pretreatment of sugar cane residues prior to fast pyrolysis (500 °C) to produce bio-oils to be considered as a fuel or as a chemical platform. First study is centered on the effect of citric acid (CA) pretreatment for removing AAEMs from SCB and SCT and to compare its effectiveness to that of other well-known leaching agents such as demineralized water, HCl and H2SO4. Both raw and pretreated materials structure, thermal behavior and chemical composition are analyzed based on compositional analyses, Fourier transform infrared spectroscopy (FTIR-ATR) and thermogravimetric analysis (TGA). The influence of leaching temperature (T = 25 – 50 °C) and contact time (t = 1 – 12 h) on the removed ash fraction was assessed by using the nonparametric bifactorial analysis of variance proposed by Sokal and Rohlf. It was found that the mass fraction of ash removed (i.e. by leaching with CA and the reference leaching solutions) was in a narrow range (between 38.9 and 54.1%) regardless of biomass type and leaching conditions tested. The nonparametric bifactorial analysis of the results revealed that the nature of the leaching solution and its interaction with contact time are of major significance when demineralizing both SCT and SCB but no significance of temperature and its interaction with contact time was found. The FTIR-ATR revealed a modification of the xylan fraction and the reduction of CO by OH groups, caused by hydrolysis, demonstrating to be important for subsequent thermal degradation.
The biomass samples derived from the previous experimental design were then used to evaluate the effect of SCT and SCB leaching by CA (compared with well-known leaching agents including H2SO4, HCl and water) on the chemical composition of the pyrolysis vapors, viz. by applying micro-pyrolysis (Py-GC/MS) at 500 °C. As a result, the yields of levoglucosan in the pyrolysis vapors increased by 5–8 fold when sugar cane biomasses were leached with acids (i.e. CA or well-known inorganic acids). Differences in the range of leaching conditions tested had only minor influence on the composition of the pyrolysis vapors derived from CA pretreated sugar cane residues. CA treatment generally favored the reduction in the total production of ketones and furans independently of temperature and leaching time.
Experiments in a bench-scale pyrolysis reactor were conducted to see whether the results obtained in Py-GC/MS can be scaled to an actual fast pyrolysis reactor. The effects of leaching (25 °C and 1 h) sugar cane trash and sugar cane bagasse with CA on the yields and quality of fast pyrolysis bio-oils were studied, a comparison was made with commonly used leaching agents such as water or solutions of HCl and H2SO4. The quality of the obtained bio-oils was assessed by elemental analysis, total acid number (TAN) and water content determinations, combustion calorimetry and gas chromatography-mass spectrometry (GC/MS) analysis. Results from the fast pyrolysis of SCT or SCB pretreated with acids revealed higher yields on raw-feedstock basis (38–45 wt.%) of the organic bio-oil fraction than those from raw and water–leached feedstock, but lower yields of water and char. The most important observations related to bio-oils chemical composition from leaching with CA are a significant increase of the relative abundance of sugars from 15.1% in raw SCT to 44.7% in CA–leached SCT, as well as a decrease in carboxylic acids, ketones, furans and phenols with respect to the raw biomasses. Also, the bio-oils from the pyrolysis of CA–leached SCT and SCB have slightly higher HHVs than those obtained from reference leaching solutions (HCl and H2SO4).
The economic viability of pretreatment will depend on the minimization of CA consumption. In this sense, the effect of CA concentration used in pretreatment on the demineralization of SCT and SCB was studied. A comparison was made with H2SO4 as well-known leaching agent. An additional aim was to identify the optimal acid pretreatment concentration and its influence on the chemical characteristics of leached biomass and on the chemical composition of pyrolysis vapors, viz. by applying micro-pyrolysis. In general, the ash removal was found to decrease in both sugar cane residues upon a decrease in the concentration of the leaching solution. Small differences in total mass loss were associated with the type of biomass and the leaching agent used. The HHV of all pretreated samples had negligible differences, although at higher acid concentrations, a small reduction was observed. The proximate and ultimate analysis of leached SCT and SCB showed similar results for all H2SO4 or CA concentrations tested. Py-GC/MS studies at 500 °C of pretreated SCT and SCB showed an increase in the production of levoglucosan with respect to the raw feedstock. However, ketones production decreased by half or more compared to the raw materials irrespective of the acid concentration in pretreatment and the phenols didn’t follow any trend. The nonparametric analysis of results revealed that the pretreatment with lowest concentrations for CA (0.096 kgdm−3) and 0.251 kgdm−3 for H2SO4 have similar influence on the production of levoglucosan than higher concentrations tested. When comparing both biomasses, the nonparametric analysis demonstrated better results in SCB than in SCT with respect to the leaching solution concentration as dependent variable.
Raw sugar cane bagasse and trash were pretreated with CA having a concentration of 0.096 kgdm−3. The pretreatments were performed on a 10 dm3 scale and compared to the previous results at 0.25 dm3. The suitability of the pretreatment parameters established for scale up at 10 dm3 were verified by comparing the compositional characteristics of the treated biomasses and its products distribution in the vapor phase (by Py-GC/MS analysis) with previous results at 0.25 dm3 scale. Bio-oil samples were then obtained on a continuous auger pyrolysis reactor. Physicochemical characterization of the bio-oil included GC/MS, elemental composition, higher heating value, water and solids content and pH. Additionally, dynamic viscosity and stability (ageing) of the bio-oils were assessed. The average bio-oil yield on raw-feedstock basis revealed differences below 5% between SCT and SCB for both raw and leached with CA. The most important observations related to the effect of leaching with CA on the bio-oil’s chemical composition are a significant increase of the sugars, as well as a decrease of the carboxylic acids and phenols. From the analysis of the properties of bio-oils from pyrolysis of sugar cane residues, it is concluded that bio-oil samples from both raw or CA–leached SCT and SCB may not be suitable for direct use as a fuel but could be valuable as a chemical platform. The poor quality of bio-oils obtained from the pyrolysis of raw SCT or SCB makes them difficult to be considered as fuel nor for the production of chemical platform molecules.
A preliminary economic and environmental analysis associated with the installation and operation of a 2.5 t∙h−1 pyrolysis plant was carried out. The plant was designed for processing sugar cane residues raw (SCT and SCB) or pretreated (L-SCT and L-SCB). The analyses are based on comprehensive mathematical models and experimental data derived from a bench scale pyrolysis reactor using the auger technology. The models were implemented in Aspen One v10.0 and describe the heat, momentum and mass balances involved in both the pretreatment and pyrolysis stages presented as four scenarios. These models allow gathering basic engineering data; and provide the possibility to identify major issues and bottlenecks during the pyrolysis of raw and pretreated feedstock. Additionally, a preliminary cost analysis on the process to foresee its potential application at industrial scale is presented. Finally, an environmental impact study was performed using Life Cycle Assessment (LCA) methodology and extending the system boundaries to agriculture and sugar cane industry stages. The scenarios that use raw biomass are preferred to those that use pretreatment when economic (as well as environmental) aspects are taken into account. Although, the lower quality of bio-oils from raw SCT and SCB allows only using it as a low quality fuel. On the other hand, the investment costs for installing the L-SCT plant are in the same order, with the remarkable difference in the quality of the bio-oil. This last option could attract the attention as a way to valorize the non-edible and usually wasted SCT.
Pyrolysis is considered as a promising method to dispose polymer waste. To provide guidance for pyrolysis recycling of representative non-charring polymer namely poly(methyl methacrylate) (PMMA) waste with micron particle size, the pyrolysis kinetics and reaction mechanism of micron PMMA waste in nitrogen are studied in the present study. Thermogravimetric analyses at 5, 10, 20, 30 and 40 K/min coupled with two model-free methods including Senum-Yang and advanced Vyazovkin method as well as one model-fitting method namely Coats-Redfern method are employed. Results indicate that the micron PMMA waste pyrolysis may be nominally considered as one-step reaction. The reaction model and mechanism in charge of the micron PMMA waste pyrolysis may be g(α)=(1-α)-1/2-1 and chemical reaction, respectively. The average values of the activation energy and pre-exponential factor are 243.69 kJ/mol and 1.19×1019 min-1, respectively, which are both larger than those of traditional PMMA with particle size in millimeter or larger level. Based upon the one-step reaction model and the obtained kinetic parameters, the predicted thermogravimetric data agree well with the experimental results not only at heating rates of 5, 10 and 20 K/min which are employed to calculate the kinetic parameters, but also at heating rates of 30 and 40 K/min beyond those used to calculate the kinetic parameters.
Concerns over climate change coupled with the desire to develop an economy based on renewable and sustainable feedstocks have catalyzed interest in developing pathways and technologies for production of bio-based energy and bio-based products. Biomass utilization plays an important role in this picture since biomass is the only renewable energy source that can offer a direct (e.g., drop-in) replacement for fossil-based transportation fuels in the near to mid term. The United States alone has the capacity to produce more than one billion tons of sustainable biomass, which can be used to produce transportation fuels with dramatically reduced carbon footprints, bio-based chemicals to replace petroleum-derived analogs, and renewable electrical power. A bio-based economy can serve to create new economic opportunities and jobs while simultaneously reducing future climate impacts.
Pyrolysis converts biomass into liquid, gaseous and solid fuels. This work reviews the existing models for biomass pyrolysis, including kinetic, network and mechanistic models. The kinetic models are based on the global reaction mechanisms and have been extensively used for a wide range of biomass under various operating conditions. Major emphases have been on the network models as these models predict the structural changes during biomass pyrolysis. Key aspects of various network models include reaction schemes, structural characteristics and applications to CFD simulations. Recent advances in understanding reaction mechanisms using mechanistic models have been summarized. Importance of inherent inorganic species in biomass pyrolysis is also critically analysed. Future studies of biomass pyrolysis modelling should focus on developing multiscale models considering reactions of all biomass components (i.e., cellulose, hemicellulose, lignin, inorganic species and extractives) and potential interactions.
This review covers the characteristics of pyrolysis and catalytic pyrolysis bio‐oils by focusing on the fundamental factors that determine bio‐oil upgradability. The abundant works on the subject of bio‐oil production from lignocellulosic biomass were studied to establish the essential attributes of the bio‐oils for assessment of the oil stability and upgradability. Bio‐oils from catalytic pyrolysis processes relating to catalysts of different compositions and structures are discussed. A general relationship between the higher heating value and the oxygen content in the catalytic pyrolysis oils exists, but this relationship does not apply to the thermal pyrolysis oil. Reporting bio‐oil yield is meaningful only when the oxygen content of the oil is measured because the pyrolytic oil stability is mainly determined by the oxygen content. Isoenergy plot that associates bio‐oil yield with oxygen content is presented and discussed.
Energy derived from biomass provides a promising alternative source that reduces dependence on fossil fuels along with the emission of greenhouse gases (GHG). The production of heat, electricity, power, fuels, and various chemicals from the biomass can be achieved via thermochemical conversion technologies. This chapter summarizes the techno-economic analysis and life-cycle assessment of lignocellulosic biomass via thermochemical conversion routes such as combustion, pyrolysis, gasification, liquefaction, (hydrothermal). and co-firing. Specific indicators such as production costs, techno-economic analysis, functional units, and environmental impacts in a life-cycle analysis for different techniques were compared. Finally, the research lacunae and possible future trends in biomass conversion via thermochemical conversion techniques have been discussed, which may positively impact the future of research related to techno-economic and environmental benefits of bioenergy.
Sawdust is one of alternative energy sources to substitute the fossil fuels. The utilization of sawdust to produce
energy can be done through different types of technologies. Gasification is one of techonology that can be used to
convert sawdust into energy. Sawdust has the characteristics of small bulk density and bind to one another. The
gasifier type corresponding to these properties is an open top throatless downdraft gasifier. The prediction of
producer gas composition can be done through a simulation. This study was conducted to obtain the distribution of
combustible gas, tar concentration and temperature at the inside of gasifier on different variations of equivalence
ratio by using 2D of computational fluid dynamic. Simulation was performed on the variation of equivalence ratio of
0.2, 0.3 and 0.4. The simulation results showed that the increase of equivalence ratio tend to decrease of CO, H2, CH4
and tar followed by increasing of temperature at the inside of the gasifier.
This review presents and discusses the progress in combining fast pyrolysis and catalytic hydrodeoxygenation (HDO) to produce liquid fuel from solid, lignocellulosic biomass. Fast pyrolysis of biomass is a well-developed technology for bio-oil production at mass yields up to ∼75%, but a high oxygen content of 35–50 wt% strongly limits its potential as transportation fuel. Catalytic HDO can be used to upgrade fast pyrolysis bio-oil, as oxygenates react with hydrogen to produce a stable hydrocarbon fuel and water, which is removed by separation. Research on HDO has been carried out for more than 30 years with increasing intensity over the past decades. Several catalytic systems have been tested, and we conclude that single stage HDO of condensed bio-oil is unsuited for commercial scale bio-oil upgrading, as the coking and polymerization, which occurs upon re-heating of the bio-oil, rapidly deactivates the catalyst and plugs the reactor. Dual or multiple stage HDO has shown more promising results, as the most reactive oxygenates can be stabilized at low temperature prior to deep HDO for full deoxygenation. Catalytic fast hydropyrolysis, which combines fast pyrolysis with catalytic HDO in a single reactor, eliminates the need for reheating condensed bio-oil, lowers side reactions, and produces a stable oil with oxygen content, H/C ratio, and heating value comparable to fossil fuels. We address several challenges, which must be overcome for continuous catalytic fast hydropyrolysis to become commercially viable, with the most urgent issues being: (i) optimization of operating conditions (temperature, H2 pressure, and residence time) and catalyst formulation to maximize oil yield and minimize cracking, coke formation, and catalyst deactivation, (ii) development of an improved process design and reactor configuration to allow for continuous operation including pressurized biomass feeding, fast entrainment and collection of char, which is catalytically active for side reactions, efficient condensation of the produced oil, and utilization and/or integration of by-products (non-condensable gasses and char), and (iii) long-term tests with respect to catalyst stability and possible pathways for regeneration. By reviewing past and current research from fast pyrolysis and catalytic HDO, we target a discussion of the combined processes, including direct catalytic fast hydropyrolysis. By critically evaluating their potential and challenges, we finally conclude, which future steps are necessary for these processes to become industrially feasible.
Pyrolysis of poplar bark is investigated in the temperature range of 573–1023 K. The effect of temperature on the gas production rate, gas yield and composition calorific value of gaseous products and carbon conversion is reported. Production of CO, CH4 and CO2 can be predicted by a model based on the assumption that reaction is the rate controlling step.
The devolatilization behaviour of finely-ground (< 0.2 mm) Loy Yang brown coal was investigated under rapid heating conditions using a small-scale fluidized-bed pyrolyser. The pyrolyser operated continuously, coal being fed at rates of 1–3 g/h directly into a bed of sand fluidized by nitrogen. Particle heating rates probably exceeded 104 °C/s. The yields of tar, C1-C3 hydrocarbons and total volatile matter are reported for a pyrolyser-temperature range of 435 to 900 °C. A maximum tar yield of 23% w/w (dry ash-free coal), 60% more than the Fischer assay, was obtained at 580 °C. Yields of C1-C3 hydrocarbons increased with increasing temperature, reaching 8% at 900 °C. Elemental analyses showed that the composition of the tar and char products was strongly dependent on pyrolysis temperature. The effects on the devolatilization behaviour of the coal produced by the moisture associated with the coal, by hydrogen, and by the replacement of the sand by a fluidized bed of petroleum coke were investigated.
Systematic studies of the independent effects of temperature (300-1100°C), solids residence time (0-30 s), and heating rate (less than equivalent to 100-15000°C/s) on the yields, compositions, and rates of formation of products from the rapid pyrolysis of 0.0101 cm thick sheets of cellulose under 5 psig pressure of helium have been performed. The experiments mainly probe the primary decomposition of the cellulose, with contributions from post-pyrolysis reactions being confined to those occuring within and closely proximate to the sample. Temperature and sample residence time are the most important reaction conditions in determining the pyrolysis behavior, while heating rate effects are explicable in terms of their influence on these two parameters. A heavy liquid product of complex molecular composition accounted for 40 to 83 wt % of the volatiles above 400°C. Secondary cracking of this material increased with increasing residence time or temperature and was a significant pathway for producing several light gases. 9 refs.
A process has been investigated for the saccharification of wood, involving prehydrolysis, lignocellulose pyrolysis, and tar hydrolysis. In this process, ground wood was first prehydrolyzed to remove the more readily hydrolyzable hemicelluloses. The residual lignocellulose was then pyrolyzed rapidly to provide a tar containing levoglucosan and its condensation products. The tar was hydrolyzed to convert these products to glucose. Laboratory experiments have shown that this process can convert a common softwood such as Douglas-fir to 14% char and 42% hexoses. This amounts to a 59% recovery of the hexoses: 32% from prehydrolysis and 27% from pyrolysis. The prehydrolysis served not only to remove hemicelluloses, but also to increase the yield of glucose from pyrolysis and subsequent tar hydrolysis. It has been shown that this enhancement is due to the removal of inorganic ash and the catalytic effect of trace amounts of acid remaining in the lignocellulose.
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