Elucidation of the effect of fast pyrolysis and hydrothermal liquefaction on the physico-chemical properties of bio-oil from southern yellow pine biomass as a chemical feedstock (original) (raw)
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Bio-oil is a major product of biomass pyrolysis that could potentially be used in motor engines, boilers, furnaces and turbines for heat and power. Upon catalytic upgrading, bio-oils can be used as transportation fuels due to enhancement of their fuel properties. In this study, bio-oils produced from lignocellulosic biomasses such as wheat straw, timothy grass and pinewood were estimated through slow and high heating rate pyrolysis at 450 °C. The slow heating rate (2 °C/min) pyrolysis resulted in low bio-oil yields and high amount of biochars, whereas the high heating rate (450 °C/min) pyrolysis produced significant amount of bio-oils with reduced biochar yields. The physico-chemical and compositional analyses of bio-oils were achieved through carbon-hydrogen-nitrogen-sulfur (CHNS) studies, calorific value, Fourier transform-infra red (FT-IR) spectroscopy, gas chromatography-mass spectrometry (GC-MS), electrospray ionization-mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) spectroscopy. The yields of bio-oils produced from the three biomasses were 40-48 wt.% through high heating rate pyrolysis and 18-24 wt.% through slow heating rate pyrolysis. The chemical components identified in bio-oils were classified into five major groups such as organic acids, aldehydes, ketones, alcohols and phenols. The percent intensities of hydrogen and carbon containing species were calculated from 1 H and 13 C-NMR. The study on bio-oils from herbaceous and woody biomasses revealed their potentials for fossil fuel substitution and bio-chemical production.
Hydrothermal processing of pine wood: effect of process variables on bio-oil quality and yield
E3S Web of Conferences
Hydrothermal liquefaction processes (HTL) comprise complex chemical and physical transformations of biomass under the conditions of high temperature and pressure, commonly near- or supercritical water. During this processes, the components of biomass undergo various complicated chemical reactions strongly influenced by process variables. In this study, lignocellulosic biomass (pine wood) has been converted via liquefaction in subcritical water to bio-oil, water-soluble organics, gas and solid products. The process parameters (i.e. temperature and time processing) affecting the bio-oil yields and composition were comparatively studied. The chemical composition of resulting bio-oils was analyzed by means of mid-infrared spectroscopy, gel permeation chromatography, gas chromatography coupled to mass spectrometry and elemental analysis. The maximum bio-oil yield (38.35 wt.%) was obtained at 350 ºC for 10 min. The HHV of the obtained resultant bio-oils varied in the range of 24-28 MJ kg-...
2014
Bio-oil is a liquid fuel that can be produced from various lignocellulosic feedstocks via fast pyrolysis. It is a complex mixture comprised of hundreds of highly oxygenated organic compounds originating from lignin and carbohydrates and is recognized as a clean renewable bio-fuel, an attractive alternative to fossil fuels. It can be easily transported and used directly in boilers and modified turbines or upgraded/fractionated for drop in fuels or chemical production. Proper bio-oil characterization is important in optimizing the pyrolysis process, bio-oil upgrading and utilization, and its stabilization for long-term storage. With this in mind, research has been undertaken to develop better techniques to rapidly profile the composition of whole bio-oil samples, and an accelerated aging study performed to determine why bio-oil is unstable upon storage. Pyrolysis-GC/MS and TLC-FID were used as tools to differentiate bio-oils of different lignocellulosic biomasses, and among thermal-cracking (upgrading) fractions. Results showed that birch bio-oil had high syringol derivatives compared to pine and barley straw bio-oils which had higher guaiacol and non-methoxy-phenolic compounds, respectively, compared with birch bio-oil. TLC-FID was successful in bio-oil differentiation, showing diagnostic chromatographic profile differences. Direct infusion-ESI-ion trap MS and ESI-ion trap MS 2 were successfully used in the analysis of forest-residue bio-oil and reference bio-oils from cellulose and hardwood lignin dissolved in methanol:water. NH4Cl can be used as a dopant to distinguish carbohydrate-derived products from other bio-oil components. NaOH and NaCl dopants resulted in the highest intensity peaks in negative ion mode and positive mode, respectively. Tandem MS, that is, ESI-Ion Trap MS 2 was a successful tool for the confirmation of iii individual target ions such as levoglucosan and cellobiosan and for structural insight into lignin products. In accelerated aging (at 80 °C for 1, 3 and 7 days) studies, the physical and chemical properties of bio-oil from ash wood (produced from a pilot-scale auger pyrolyzer) and birch wood (lab-scale pyrolyzer) were monitored in order to identify the factors responsible for bio-oil instability. Water content, viscosity, and decomposition temperature (by TGA) increased for both bio-oil samples with aging. Chemical analysis showed reduction in amount of most of the bio-oil components as aging progressed, typically for are olefins and aldehydes. The oils remained a single phase throughout until the 7th day. viii 2.4. Conclusion 65 2.5. References 66 Chapter 3: Direct infusion mass spectrometric analysis of bio-oil using ESI-Ion Trap MS 69
Characterization of Fast Pyrolysis Bio-oils Produced from Pretreated Pine Wood
Applied Biochemistry and Biotechnology, 2009
The pretreatment of biomass prior to the fast pyrolysis process has been shown to alter the structure and chemical composition of biomass feed stocks leading to a change in the mechanism of biomass thermal decomposition. Pretreatment of feed stocks prior to fast pyrolysis provides an opportunity to produce bio-oils with varied chemical composition and physical properties. This provides the potential to vary bio-oil chemical and physical properties for specific applications. To determine the influence of biomass pretreatments on bio-oil produced during fast pyrolysis, we applied six chemical pretreatments: dilute phosphoric acid, dilute sulfuric acid, sodium hydroxide, calcium hydroxide, ammonium hydroxide, and hydrogen peroxide. Bio-oils were produced from untreated and pretreated 10-year old pine wood feed stocks in an auger reactor at 450°C. The bio-oils' physical properties of pH, water content, acid value, density, viscosity, and heating value were measured. Mean molecular weights and polydispersity were determined by gel permeation chromatography. Chemical characteristics of the bio-oils were determined by gas chromatography-mass spectrometry and Fourier transform infrared techniques. Results showed that the physical and chemical characteristics of the bio-oils produced from pretreated pine wood feed stocks were influenced by the biomass pretreatments applied. These physical and chemical changes are compared and discussed in detail in the paper.
ACS Sustainable Chemistry & Engineering, 2016
Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13 C nuclear magnetic resonance (13 C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13 C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cakebased bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.
Energy & Fuels, 2011
Bio-oil produced from pinewood by fast pyrolysis has the potential to be a valuable substitute for fossil fuels. Pretreatment prior to the fast pyrolysis process has been shown to alter the structure and chemical composition of biomass. To determine the influence of biomass pretreatments on bio-oil produced during fast pyrolysis, we tested three pretreatment methods: dilute acid, dilute alkali, and steam explosion. Bio-oils were produced from untreated and pretreated pinewood feedstocks in an auger reactor at 450°C. The bio-oils' physical properties including pH, water content, acid value, density, viscosity, and heating value were measured. Chemical characteristics of the bio-oils were determined by gas chromatographyÀmass spectrometry. Results showed that bio-oil yield and composition were influenced by biomass pretreatment. Of the three pretreatment methods, 1% H 2 SO 4 pretreatment resulted in the highest bio-oil yield and best bio-oil quality.
Energy & Fuels, 2012
A red pine fast pyrolysis bio-oil was subjected to sequential solvent fractionation into n-hexane soluble (HS), ether soluble (ES), ether insoluble (EIS), dichloromethane soluble (DS), and methanol soluble (MeS) fractions. The volatile components of bio-oil were analyzed by gas chromatography−mass spectrometry (GC−MS), indicating the presence of acids, aldehydes, ketones, alcohols, phenols, and anhydromonosaccharides, which consisted of methoxy, hydroxy, and carbonyl functional groups. These results imply that the bio-oil was similar to the most reported fast pyrolysis bio-oil samples in molecular composition. The bio-oil and its five subfractions were analyzed by negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The predominant compounds in bio-oil were O 2 −O 17 class species with 1−22 double-bond equivalent (DBE) values and 4−39 carbon numbers. The most abundant class species in biocrude oil, HS, ES, EIS, DS, and MeS subfractions were O 7 , O 6 , O 8 , O 10 , O 7 , and O 8 class species, respectively. The predominant EIS subfraction presented an obvious relative low DBE value, sustaining the tentative identification as "sugar fraction". The predominant compounds in DS subfraction were likely lignin dimers, whereas those in MeS subfraction should be lignin dimers and trimers. The number of oxygen atoms of the bio-oil compounds was negatively correlated with the average DBE value, indicating that oxygen atoms were present in various functional groups of the bio-oil compounds. The N 1 O x class species were also identified, which contained 1−16 DBE and 6−30 carbon numbers.
EXPLORING RESOURCES, PROCESS AND DESIGN FOR SUSTAINABLE URBAN DEVELOPMENT: Proceedings of the 5th International Conference on Engineering, Technology, and Industrial Application (ICETIA) 2018, 2019
Bio-oil was formed through pyrolysis process with the catalyst zeolite/pine fruit mass ratio of 5 g/200 g; 10 g/200 g; 15 g/200 g; 20 g/200 g; and 25 g/200 g, and several temperatures of 300, 360, 400, 460, and 500 o C. Pine fruit served as the biomass. It was selected because it has been underutilized and considered as plantation waste. From the present study, it was found that the highest yield of 8.1% was achieved at 500 0 C and the catalyst zeolite to pine fruit mass ratio of 25 g/200 g. The bio-oil calorific value of 31.256 J/g was achieved at a pyrolysis temperature of 500 0 C and the catalyst zeolite to pine fruit mass ratio of 25 g/200 g. Bio-oil with the highest yield has the density of 1.006 g/mL, the viscosity of 65.84 cSt, the heating value of 31.256 J/g, the water content of 2.88 %, and the flash point of 128 0 C. The biooil from pyrolysis of pine fruit can be concluded to have identical in density, flash point. Meanwhile, the heating value of bio-oil from pine fruit is greater than the standard , and the water content of bio-oil from pine fruit is lower than the standard .
Physico-Chemical Properties of Bio-Oil from the Pyrolysis of Pinus caribea (Morelet) Needles 1 2 1 1
2019
Biomass is a renewable natural resource per excellence for the present and the future as well and it appears to have formidable positive eco-friendly properties. The high regenerative ability and decay resistance of pine needles has influenced its continual relegation as an unimportant forest product. There is need to transform these species residues (needles) into forms that will make their combustion easier and more efficient. In this study, the physical and chemical properties of Bio-oil from Pinus caribea Needles were investigated. Pine needles were collected from felled tree in the Department of Zoology (University of Ibadan) and grounded to 6 mm particle size to yield sufficiently small particles. Approximately 4.92kg of pine needles was oven dried at 100±3⁰C until constant weight to determine the moisture content. 820g of shredded pine needles was loaded into the vacuum pyrolysis chamber reactor at 600˚C and 700˚C in triplicates. Physico-chemical and compositional analyses of the bio-oil were achieved through carbon-hydrogen-nitrogen-sulphur (CHNS) studies, Calorific Value, Fourier transform-infrared (FT-IR) spectroscopy and Gas chromatography-mass spectrometry (GC-MS) through standard procedures (American Standard for Testing and Materials). Data were analysed using t-test at α0.05. The pyrolytic product at 700˚C had higher bio-oil yield, Density, Moisture content and pH of 10%, 1.0975kg/dm3, 4.76% and 6.635 respectively. Ultimate analysis for the following elements C, H, O ranged from (83.97-85.43%), (13.29-14.23%) and (0.40-0.53%) for 600˚C and 700˚ respectively, while Sulphur and Nitrogen were available in trace amounts at both temperature regime. The proximate analysis was favourable at 700˚C with lower Ash content and higher heating value of 0.67% and 48.96±0.1825Mj/Kg1 respectively. The functional groups with FT-IR analysis include alcohols, esters, alkynes with most of the compounds characterized by saturated bonds. GC-MS of the bio-oil showed mostly hydrocarbons including aromatic compounds (phenols and alkenes) and some aliphatic compounds. The result of this study is an indication that bio-oil of Pinus caribea needles revealed its potential for fossil fuel substitution and biochemical production.