Fast Pyrolysis Of Woody Biomass Research Articles

Comparing Life-Cycle Emissions of Biofuels for Marine Applications: Hydrothermal Liquefaction of Wet Wastes, Pyrolysis of Wood, Fischer-Tropsch Synthesis of Landfill Gas, and Solvolysis of Wood.

Recent restrictions on marine fuel sulfur content and a heightened regulatory focus on maritime decarbonization are driving the deployment of low-carbon and low-sulfur alternative fuels for maritime transport. In this study, we quantified the life-cycle greenhouse gas and sulfur oxide emissions of several novel marine biofuel candidates and benchmarked the results against the emissions reduction targets set by the International Maritime Organization. A total of 11 biofuel pathways via four conversion processes are considered, including (1) biocrudes derived from hydrothermal liquefaction of wastewater sludge and manure, (2) bio-oils from catalytic fast pyrolysis of woody biomass, (3) diesel via Fischer-Tropsch synthesis of landfill gas, and (4) lignin ethanol oil from reductive catalytic fractionation of poplar. Our analysis reveals that marine biofuels' life-cycle greenhouse gas emissions range from -60 to 56 gCO2e MJ-1, representing a 41-163% reduction compared with conventional low-sulfur fuel oil, thus demonstrating a considerable potential for decarbonizing the maritime sector. Due to the net-negative carbon emissions from their life cycles, all waste-based pathways showed over 100% greenhouse gas reduction potential with respect to low-sulfur fuel oil. However, while most biofuel feedstocks have a naturally occurring low-sulfur content, the waste feedstocks considered here have higher sulfur content, requiring hydrotreating prior to use as a marine fuel. Combining the break-even price estimates from a published techno-economic analysis, which was performed concurrently with this study, the marginal greenhouse gas abatement cost was estimated to range from -$120 to $370 tCO2e-1 across the pathways considered. Lower marginal greenhouse gas abatement costs were associated with waste-based pathways, while higher marginal greenhouse gas abatement costs were associated with the other biomass-based pathways. Except for lignin ethanol oil, all candidates show the potential to be competitive with a carbon credit of $200 tCO2e-1 in 2016 dollars, which is within the range of prices recently received in connection with California's low-carbon fuel standard.

Techno-economic Analysis of Sustainable Biofuels for Marine Transportation.

Renewable, low-carbon biofuels offer the potential opportunity to decarbonize marine transportation. This paper presents a comparative techno-economic analysis and process sustainability assessment of four conversion pathways: (1) hydrothermal liquefaction (HTL) of wet wastes such as sewage sludge and manure; (2) fast pyrolysis of woody biomass; (3) landfill gas Fischer-Tropsch synthesis; and (4) lignin-ethanol oil from the lignocellulosic ethanol biorefinery utilizing reductive catalytic fractionation. These alternative marine biofuels have a modeled minimum fuel selling price between $1.68 and $3.98 per heavy fuel oil gallon equivalent in 2016 U.S. dollars based on a mature plant assessment. The selected pathways also exhibit good process sustainability performance in terms of water intensity compared to the petroleum refineries. Further, the O and S contents of the biofuels vary widely. While the non-HTL biofuels exhibit negligible S content, the raw biocrudes via HTL pathways from sludge and manure show relatively high S contents (>0.5 wt %). Partial or full hydrotreatment can effectively lower the biocrude S content. Additionally, co-feeding with other low-sulfur wet wastes such as food waste can provide another option to produce raw biocrude with lower S content to meet the target with further hydrotreatment. This study indicates that biofuels could be a cost-effective fuel option for the marine sector. Marine biofuels derived from various feedstocks and conversion technologies could mitigate marine biofuel adoption risk in terms of feedstock availability and biorefinery economics.

Experimental and modeling approach for the optimization of oily water recovered from fast pyrolysis of woody biomass

Woody biomass consists of wood chips, leaves, branches, stems etc. They contain highest weight percentage of oily water compared to any other biomass. On woody biomass’ fast pyrolysis, high percentage of FPBO is obtained with char/ash, pyrolytic gases and oily water in considerable amount. The focus of this research is to obtain an optimized temperature at which the oily water recovered from biomass after fast pyrolysis is highest without much affecting the generation of bio-oil. The weight percentage of oily water recovery is affected by several factors- vapor residence time, condensation temperature, operating temperature and moisture content. The weight percentage of oily water is approximately 10.62% with 56.41% of bio-oil generation. The result is obtained at a temperature of 550 °C, further to which increase in oily water content started decreasing the bio-oil generation with very fast rate. This experimental result is analyzed, a surrogate mixture on various assumptions is prepared and a model is prepared using UNIFAC. There is a slight difference in weight percentage of oily water on experimental and modeling approach due to the ageing of surrogate mixture and assumptions in modeling.

Selectively Producing Acetic Acid via Boric Acid-Catalyzed Fast Pyrolysis of Woody Biomass

Boric acid is recently proved to be a good substitute for conventional acidic catalytic materials. However, few studies used boric acid as a catalyst in biomass pyrolysis. This study focused on the catalytic effects of boric acid (BA) on pyrolysis behaviors of woody biomass. The birch wood flour (WF) was used as feedstock and treated by impregnation of boric acid solution. Both untreated and boric acid-treated samples (BW) were characterized by FTIR and SEM. Thermogravimetry (TG) and pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS) techniques were used for studying mass loss, composition, and distribution of evolved volatiles formed from pyrolysis process. Additionally, a small fixed-bed pyrolyzer with an amplificated loading amount was used to prepare liquid products, and further, GC/MS were used to analyze the composition of these liquid products. Different pyrolysis temperatures and boric acid/wood flour mass ratios were also studied. The main results are as follows. Boric acid infiltrated into both cell cavity and cell wall through impregnation treatment. FTIR analysis showed that boric acid reacted with wood flour to form B-O-C bond during the treatment. After the treatment of boric acid, the initial degradation temperatures and residual carbon contents were increased, while the maximum weight loss rates were decreased. Boric acid significantly altered the composition and distribution of volatile pyrolysis products of wood flour. It significantly increased the contents of small molecule compounds such as acetic acid and furfural but, decreased the contents of phenol derivatives with high molecular weights. And these changes became more pronounced as the temperature increased. When mass ratio of boric acid (BA) to wood flour (WF) was 2, the acetic acid accounted for 91.28% of the total product in the pyrolysis liquid, which was 14 times higher than that of untreated wood flour. Boric acid effectively catalyzed fast pyrolysis of woody biomass to selectively produce acetic acid

Hydrodeoxygenation of crude bio-oil with various metal catalysts in a continuous-flow reactor and evaluation of emulsion properties of upgraded bio-oil with petroleum fuel

Abstract Crude bio-oil produced from fast pyrolysis of woody biomass was subjected to catalytic hydrodeoxygenation reaction with various metal catalysts (Ni/C, Ni/SBA-15, Ni/Al-SBA-15, NiMn/SBA-15, Pt/C) using for continuous-flow reaction system at 300 °C under H2 pressure. Gas, immiscible liquid phases (light oil and heavy oil), and char was obtained as the primary products. Heavy oil yield was in the range 27.9–42.3 wt%, while char production was 2.3–11.0 wt%, both less than the corresponding figures for batch processing. Hydrodeoxygenation enhanced the fuel properties of bio-oil, yielding higher HHV (32.8–38.0 MJ/kg) than bio-oil (15.7 MJ/kg) and heavy oil produced in a batch type reactor (24.4–34.5 MJ/kg). Additionally, Miscibility of crude bio-oil and upgraded heavy oils with gasoline and diesel were also evaluated with three emulsifiers (Span60, Brij58, or IGEPAL CO-520). Crude bio-oil was hardly emulsified, whereas upgraded heavy oil was well emulsified with Span60. Increasing Span60 concentration also enhance the miscibility of heavy oil and diesel. An emulsion of heavy oil and diesel was stable for 6 months, suggesting that the heavy oil produced might have potential use in blends with diesel.

Pretreatment of bio-oil with ion exchange resin to improve fuel quality and reduce char during hydrodeoxygenation upgrading with Pt/C

ABSTRACT To obtain high-quality biofuel, bio-oil obtained from fast pyrolysis of woody biomass was pretreated with ion exchange resin (amberlyst 36) at 50°C, 100°C, and 150°C, and then the recovered liquid product was upgraded using hydrodeoxygenation (HDO) with Pt/C at 300°C. After the two-stage upgrading, 4 types of products (gas, light oil, heavy oil, and char) were obtained. Two-immiscible liquid products were consisted of organic heavy oil, derived from bio-oil, and aqueous light oil, based on the ethanol. The mass balances of the HDO products were influenced by the pretreatment temperature. Ion exchange pretreatment of bio-oil was effective in reducing the char formation during the hydrodeoxygenation (HDO) process. The pretreatment also improved the following heavy oil properties: the water content, heating value, viscosity, acidity, and oxygen level. As a parameter used to indicate the biofuel acidity, the total acid number (TAN) value, was clearly reduced from 114.5 (bio-oil) to 34.1–78.2 (heavy oils). Furthermore, the water and oxygen contents of bio-oil (21.1 and 52.6 wt%, respectively) declined after the pretreatment followed by HDO (ranged 5.1–6.9 and 19.0–25.5 wt%, respectively), thereby improving its higher heating value (HHV) from 17.2 MJ/kg (bio-oil) to 26.2–28.1 MJ/kg (heavy oils). The degree of deoxygenation (DOD) increased as the pretreatment temperature decreased, and the highest energy efficiency (79.8%) was observed after pretreatment at 100°C. In terms of catalyst deactivation during the reaction, both carbon deposition and surface cracking intensified with increasing pretreatment temperatures.

Mathematical description of the process of condensation of pyrolysis fuel during fast pyrolysis of woody biomass

ABSTRACTA mathematical model of the pyrolysis fuel condensation process in the fast pyrolysis of woody biomass is presented. The model allows determining the effect of the regime parameters of the condensation process on the yield of liquid thermal decomposition products of wood and the condensation efficiency, and hence the efficiency of the entire process of thermal processing of biomass.

Efficient upgrading of pyrolysis bio-oil over Ni-based catalysts in supercritical ethanol

An efficient method to upgrade bio-oil derived from fast pyrolysis of woody biomass was investigated in supercritical ethanol without external hydrogen supply. A set of Ni-based catalysts (Ni, Ni-Mo, and Mg-Ni-Mo) supported on activated charcoal (AC) was tested to understand their catalytic effect on the yield and the quality of upgraded liquid fuel in supercritical ethanol. Mg-Ni-Mo/AC was found to be the most effective catalyst among the tested Ni-based catalysts; the liquid product obtained at 350 °C showed the highest yield (70.5 wt%) and the lowest oxygen-to-carbon (O/C) molar ratio (0.19). The catalyst also formed the lowest amount of solid product (9.8 wt%) at 350 °C by suppressing coke formation. At 350 °C, a higher quality liquid product with a total acid number (TAN) value of 6.2 mgKOHg−1 and a higher heating value (HHV) of 33.4 MJkg−1 was obtained compared with bio-oil feed (TAN: 48.0 mgKOHg−1 and HHV: 19.5 MJkg−1). A gas chromatography–mass spectrometer (GC–MS) analysis of the liquid product demonstrated that major oxygenated components in the bio-oil feed such as acids, aldehydes, and levoglucosan were effectively destroyed through hydrogenation, esterification, and deoxygenation reactions in the catalytic upgrading process.

Assessing deployment pathways for greenhouse gas emissions reductions in an industrial plant – A case study for a complex oil refinery

This study developed an integrated method to identify deployment pathways for greenhouse gas emissions reductions in an industrial plant. The approach distinguishes itself by assessing the techno-economic performance of combinations of mitigation options at the level of core processes of an industrial plant. Thus, synergies between mitigation options like economies of scale and negative interactions, such as overlap in emission reduction potential, are incorporated, resulting in more realistic insights into costs and associated risks. The method was successfully applied to a large petroleum refinery (∼4.1 MtCO2/y) in northwest Europe. The studied mitigation routes are: energy efficiency measures, carbon capture and storage, fast pyrolysis of woody biomass to produce infrastructure-ready transportation fuels, and gasification of torrefied wood pellets to produce electricity, hydrogen and/or Fischer-Tropsch fuels. Four deployment pathways were examined, all starting with energy efficiency measures and followed by (1) oxyfuel combustion capture, (2) post-combustion capture, (3) biomass gasification, or (4) biomass gasification with carbon capture and storage. Pathway 4 is most cost-effective under medium assumptions, regardless of the emissions reduction target, and allows for deep emissions reductions (6.3 MtCO2-eq/y; 154% reduction compared to the 2012 base case). For a 75% emissions reduction target, the average avoidance cost of pathway 4 is around −25 €2012/tCO2-eq. In comparison, the second most cost-effective pathway (1) was evaluated at average avoidance cost of −5 €2012/tCO2-eq. However, the ranking of the pathways in terms of avoidance cost depends heavily on future energy prices.

3-P92-1 木質バイオマスの急速熱分解による液体バイオ燃料の製造(液体燃料化,Session 3 バイオマス等,ポスターセッション)

3-P92-1 木質バイオマスの急速熱分解による液体バイオ燃料の製造(液体燃料化,Session 3 バイオマス等,ポスターセッション)

Fast pyrolysis of coffee ground in a tilted‐slide reactor and characteristics of biocrude oil

Coffee grounds are considered to be a promising biomass resource due to the growth of coffee consumption and their high calorific value. In this study, we produced biocrude oil from coffee grounds in a tilted‐slide reactor, which has been previously used for the fast pyrolysis of woody biomass. Various pyrolysis temperatures were tested and the maximum biocrude oil yield was 59% at the pyrolysis temperature of 550°C with a feeding rate of coffee grounds at 17.7 kg/h. In a multistage condenser, the biocrude oil yields and properties were different in each condenser stage. The higher heating value of the biocrude oil from the primary condenser was 7,157 kcal/kg, which was about 60% higher than that from woody biomass. A phase separation was observed when the biocrude oil was stored at the atmospheric condition, and the biocrude oil viscosity became quite larger than that from woody biomass, which could even impede its flow. The viscosity decreased with increasing temperature and was more sensitive to temperature variations at lower temperatures. Mixing of ethanol also significantly improved viscosity characteristics. © 2017 American Institute of Chemical Engineers Environ Prog, 36: 655–661, 2017

Characteristics of flame stability and gaseous emission of biocrude-oil/ethanol blends in a pilot-scale spray burner

A burner system with capacity of 30,000 kcal/h was designed for the combustion of biocrude-oil and ethanol blends. An air atomizing spray nozzle with larger fuel orifice was adopted to prevent nozzle clogging, with swirl flow introduced to the combustion air for flame stabilization. Biocrude-oil was prepared from the fast pyrolysis of woody biomass and was blended with ethanol to improve flame stability and ignition characteristics. At various mixing ratios of biocrude-oil and ethanol, flame stability was determined, and gaseous emissions of CO and NO were measured. It was found that stable combustion could be achieved with up to 90 vol% of biocrude-oil. CO emissions of biocrude-oil/ethanol blends were smaller than those of pure ethanol, whereas CO concentration increased significantly in case of pure biocrude-oil due to incomplete combustion. Pollutant NO emission increased slightly with the biocrude-oil mixing ratio. The biocrude-oil burner in this study could provide a design database for industrial burner development.

Norms, Standards, and Legislation for Fast Pyrolysis Bio-oils from Lignocellulosic Biomass

Fast pyrolysis of woody biomass is close to full maturity, with first-of-its-kind commercial size installations for fuel production being commissioned in Finland (Fortum) and in The Netherlands (Empyro), and in the design phase in Brazil (Ensyn). In the industrial-scale combustion tests, the use of fast pyrolysis bio-oil (FPBO) has been demonstrated to be a viable option to replace heavy fuel oil in district heating applications. Commercially usable district heating boilers and burners suitable for FPBO are available. There is research on diesel-engine and gas-turbine applications but, so far, no proven demonstrations. FPBO is completely different from mineral oils; hence, standards are needed. Analytical methods have been systematically validated and modifications to the standards as well as completely new methods have been made. Two ASTM burner fuel standards already exist and European boiler fuel grades are being developed under CEN. The focus on CEN standardization is on boiler use, because of its com...

Kinetic modeling of non-catalytic partial oxidation of nascent volatiles derived from fast pyrolysis of woody biomass with detailed chemistry

The gas-phase partial oxidation (POx) of nascent volatiles (NV) derived from the fast pyrolysis of cedar sawdust at 700 and 800°C was studied both numerically and experimentally. A detailed chemical kinetic model (DCKM) was applied to simulate the POx in a two-stage reactor: the first stage was designed for fast biomass pyrolysis and the second effected the POx of the NV. Analytical pyrolysis experiments were also conducted to approximate the molecular composition of the NV, which is required input for computations using DCKM. The DCKM was modified by an empirical kinetic model for the decomposition of an ill-defined portion of the NV. The kinetic model coupled with a plug-flow reactor model reproduced the observed trends in the product yields with respect to both temperature and oxygen-to-fuel ratio, for not only the major products, but also minor products such as aromatic hydrocarbons which are typically found in the refractory post-gasification tar.

Fast Pyrolysis of Wood for Biofuels: Spatiotemporally Resolved Diffuse Reflectance In situ Spectroscopy of Particles.

Fast pyrolysis of woody biomass is a promising process capable of producing renewable transportation fuels to replace gasoline, diesel, and chemicals currently derived from nonrenewable sources. However, biomass pyrolysis is not yet economically viable and requires significant optimization before it can contribute to the existing oil-based transportation system. One method of optimization uses detailed kinetic models for predicting the products of biomass fast pyrolysis, which serve as the basis for the design of pyrolysis reactors capable of producing the highest value products. The goal of this work is to improve upon current pyrolysis models, usually derived from experiments with low heating rates and temperatures, by developing models that account for both transport and pyrolysis decomposition kinetics at high heating rates and high temperatures (>400 °C). A new experimental technique is proposed herein: spatiotemporally resolved diffuse reflectance in situ spectroscopy of particles (STR-DRiSP), which is capable of measuring biomass composition during fast pyrolysis with high spatial (10 μm) and temporal (1 ms) resolution. Compositional data were compared with a comprehensive 2D single-particle model, which incorporated a multistep, semiglobal reaction mechanism, prescribed particle shrinkage, and thermophysical properties that varied with temperature, composition, and orientation. The STR-DRiSP technique can be used to determine the transport-limited kinetic parameters of biomass decomposition for a wide variety of biomass feedstocks.

The Feasibility of Using Raw Liquids from Fast Pyrolysis of Woody Biomass as Fuels for Compression-Ignition Engines: A Literature Review

The Feasibility of Using Raw Liquids from Fast Pyrolysis of Woody Biomass as Fuels for Compression-Ignition Engines: A Literature Review

Biochar-based catalyst for simultaneous reactions of esterification and transesterification

Biochar, a by-product of fast pyrolysis of woody biomass, was developed as a renewable catalyst for simultaneous transesterification and esterification of canola oil and fatty acid (oleic acid) mixture at 150°C under 1.52MPa. Surface area and porosity of biochar were increased significantly from negligible to 990m2/g, and 0.9 cm3/g through chemical activation method with KOH. The resultant biochar was sulfonated with fuming sulfuric acid to produce the biochar-based catalyst with high surface area and porosity (949m2/g and 0.85cm3/g). The ester formation yield was investigated based on the molar ratios of alcohol to canola oil (A:O), alcohol to oleic acid (A:FFA), or at constant mass ratio of alcohol to the mixture of oil and oleic acid. Increasing the FFA concentration from 15, 30 to 50wt.% (at constant A:O molar ratio) resulted in slight increase of reaction yields from 27.9, 35.1, to 36.7%, respectively. Results also revealed a continuous increase in reaction yield from 38.0 to 48.1% as increasing A:FFA molar ratio (from 10:1 to 30:1) at constant A:O. However, increasing A:O ratio (from 10:1 to 30:1) at constant A:FFA resulted in an unexpected decrease in the reaction yield from 48.1 to 28.8%. The biochar based catalyst showed promising catalytic activity (48% yield in 3h) for the combination of transesterification and esterification reactions in a mixture of canola oil and oleic acid for biodiesel production. Reaction yield decreased by ∼8% upon reusing the catalyst.

Investigation of physicochemical properties of biooils produced from yellow poplar wood ( Liriodendron tulipifera) at various temperatures and residence times

Fast pyrolysis of yellow poplar wood ( Liriodendron tulipifera) was performed under different temperature ranges and residence times in a fluidized bed reactor to maximize the yield of biooil. In this study, the pyrolysis temperature ranged from 400 °C to 550 °C, and the residence time of pyrolysis products was controlled between 1.2 and 7.7 s by inert nitrogen gas flow. The results revealed that the distribution of thermal degradation products (biooil, biochar, and gas) from the woody biomass was heavily influenced by pyrolysis temperature, as well as residence time. The highest yield of biooil was approximately 68.5 wt% (wet basis), with pyrolysis conditions of 500 °C and 1.9 s of residence time. Water content of the biooils produced at different temperatures was 25–30 wt%, and their higher heating values were estimated to be between 15 MJ/kg and 17 MJ/kg. Using GC/MS analysis, 30 chemical components were identified from the biooil, which were classified into 5 main groups: organic acids, aldehydes, ketones, alcohols, and phenols. In addition, biochar was produced as a co-product of fast pyrolysis of woody biomass, approximately 10 wt%, at temperatures between 450 °C and 550 °C. The physicochemical features of the biochar, including elemental analysis, higher heating values, and morphological properties by SEM, were also determined.

The influence of fast pyrolysis condition on biocrude-oil yield and homogeneity

The characteristics of biocrude-oil yield and quality have been investigated by changing fast pyrolysis condition for woody biomass. For the fast pyrolysis of woody biomass, a bubbling fluidized bed reactor having cylindrical shape was devised and a commonly used spiral quenching system was applied to the condensation of volatile gases from the reactor. Biomass feeding rate, nitrogen flow rate, pyrolysis temperature and particle size of woody biomass were changed to study the characteristics of volatile generation, its condensation and the homogeneity of the condensed biocrude-oil. In particular, the microscopic visualization of the collected biocrude-oil and its evaluation method by image processing technique were made for quantifying the homogeneity of the oil. From the results, the effects of heating and fluidization condition on the biocrude-oil yield and the homogeneity were fully scrutinized in a bubbling fluidized bed reactor. Also, the physical and chemical characteristics of the collected biocrude-oil were determined through various analysis techniques.

Numerical study of fast pyrolysis of woody biomass in a gravity‐driven reactor

AbstractIn the present study, computational fluid dynamics is applied to investigate fast pyrolysis characteristics of woody biomass in a gravity‐driven reactor. A Eulerian‐Eulerian approach is adopted, including three gas species and three solid phases, for multiphase reacting flow fields between solid and gas. Two‐stage semiglobal reaction kinetics considering the secondary tar cracking mechanism is used for simulation of the pyrolysis reaction. The flow and pyrolysisreaction characteristics of the reactor are investigated, and the reaction rates of woody biomass pyrolysis are evaluated for streamwise locations in the reactor. Also, the inlet condition and inclination angle are changed to study their effects on the reaction. From the predicted results, it is seen that the heat transfer to biomass is governed mainly by mixing of particles, and this influences the final pyrolysis reaction. © 2009 American Institute of Chemical Engineers Environ Prog, 2009