Co-processing of pyrolisis bio oils and gas oil for new generation of bio-fuels: Hydrodeoxygenation of guaïacol and SRGO mixed feed (original) (raw)
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Production of advanced biofuels: Coprocessing of upgraded pyrolysis oil in standard refinery units
Applied Catalysis B-environmental, 2010
One of the possible process options for the production of advanced biofuels is the coprocessing of upgraded pyrolysis oil in standard refineries. The applicability of hydrodeoxygenation (HDO) was studied as a pyrolysis oil upgrading step to allow FCC co-processing in standard refineries. Different HDO reaction end temperatures (230-340 °C) were evaluated in a 5 L autoclave, keeping the other process conditions constant (total 290 bar, 5 wt. % Ru/C catalyst), in order to find the required oil product properties necessary for successful FCC co-processing (miscibility with FCC feed and good yield structure: little gas/coke make and good boiling range liquid products). After HDO, the upgraded pyrolysis oil undergoes phase separation resulting in an aqueous phase, some gases (mainly CO 2 and CH 4 ), and an oil phase that was further processed in a Micro Activity Test (MAT) reactor (simulated FCC reactor). Although the oil and aqueous phase yields remained approximately constant when the HDO reaction temperature was increased, a net transfer of organic components (probably hydrodeoxygenated sugars) from the aqueous phase to the oil phase was observed, increasing the carbon recovery in the oil product (up to 70 wt. % of the carbon in pyrolysis oil).
Upgrading of Pyrolysis Oils Review.docx
A review on upgrading of pyrolysis oil from biomass was presented. Effects of greenhouse gas emissions on the environment and the role of biomass in reducing greenhouse gas emissions were discussed. Biomass processing through to production of bio-oils through fast pyrolysis was reviewed and the significance of pyrolysis oil upgrading pointed out. The physical and chemical properties of pyrolysis oils from various feedstocks (pine, birch, poplar) were discussed. Key process parameters and the importance of the mechanism of oxygen removal (deoxygenation) were also discussed. The importance of oxygen in the bio-oil and the various methods for upgrading pyrolysis oils including zeolite cracking to hydro-deoxygenation were reviewed. A review was also carried out on modern developments in bio-oil upgrading such as the BIOCOUP Project- Co-processing of upgraded bio-oils with fossil fuels in standard refinery units. It was noted that modern approaches such as hydrodeoxygenation showed promising results for cofeeding/co-processing with fossil fuels in a petroleum refinery.
Upgrading of Pyrolysis Bio-oil: A Review
2019
The increase in the population of the planet and the rapid economic growth and, consequently, the high consumption of energy has created many environmental problems in the globe. Due to these reasons and the lack of renewability of these fossil fuels, there has been a steep trend towards the production of renewable fuels from natural sources, one of which is the production of energy from biomass. In this study, biofuel production from biomass has been investigated using thermochemical methods and precisely "pyrolysis method", a method that reduces the production of oil from millions of years to a few seconds, and is the most industrialized thermochemical method for producing fuel from biomass. This research focuses on thermochemical processes, pyrolysis principles, hydrothermal methods and specifications, chemical composition and applications of biofuels, and the devices and equipment needed for it. This research is the start of research and study on bio-refineries in the ...
Challenges and Opportunities for Bio-oil Refining: A Review
Energy & Fuels, 2019
Bio-oil derived from fast pyrolysis of lignocellulosic materials is among the most complex and inexpensive raw oils that can be produced today. Although commercial or demonstration scale fast pyrolysis units can readily produce this oil, this industry has not grown to significant commercial impact due to the lack of bio-oil market pull. This paper is a review of the challenges and opportunities for bio-oil upgrading and refining. Pyrolysis oil consists of six major fractions. (water 15-30 wt.%, light oxygenates, 8-26 wt. %, mono-phenols, 2-7 wt.%, water insoluble oligomers derived from lignin 15-25wt.%, and water soluble havey molecules 10-30 wt.%). The composition of water soluble oligomers is relatively poorly studied. In the 1880s bio-oil refining (formally known as wood distillation) targeted the separation and commercialization of C1-C4 light oxygenated compounds to produce methanol, acetic acid and acetone with the commercialization of the lignin derived water insoluble fraction for preserving purification techniques. Strategies for biofuels production are discussed in section four. Bio-oil derived products are discussed in the last section. 2. Bio-oil Composition The study of bio-oil chemical composition has been the subject of active research in the last twenty years 2,24-35. Pyrolysis oil contains numerous oxygenated compounds, which include carboxylic acids, water, alcohols, esthers, anhydrosugars, furanics, phenolics, aldehydes, and ketones covering a wide range of molecular weights and functionalities 2,24,29,30,36-41. The specific composition is directly related to the feedstock and the conditions used in their production 42-44. Water is typically quantified by Karl Fischer titration 2 and is the most abundant bio-oil compound accounting between 15 and 30 wt. % 2 (See Figure 1). Water forms mostly from dehydration reactions of carbohydrate depolymerized products in the liquid intermediate 44. Gas Chromatography/Mass Spectroscopy (GC/MS) is by far the most common technique for the quantification of the pyrolysis oil organic volatile fraction 2,24,27,45. GC/MS detectable compounds typically account for between 30 and 40 wt. % 2. Table 2 shows the range of compounds quantified by GC/MS reported in the literature. Only four molecules (glycoaldehyde, acetic acid, acetol and levoglucosan) are found in quantities sufficiently high (>5 wt. %) to justify their separation and commercialization as chemicals. Methanol can also be produced in quantities justifying its commercialization but hardwood has to be used as feedstock. The remainder of the oil if refined is likely to be commercialized as fractions (mono-phenols, pyrolytic lignin, anhydrosugars, pyrolytic humins, and hybrid oligomers). Because bio-oil consists of hundreds of compounds with concentrations below 0.5 wt. % it is desirable to express their chemical composition in terms of few chemical groups or families 24. This idea was first proposed by Hallet and Clark 46. The authors 46 modeled bio-oil evaporation rates using a model based on this characterization scheme 46. In DTG-FTIR studies with bio-oils doped with pure compounds (butyric acid, syringol, syringaldehyde, levoglucosan), Stankovikj et al. 29 observed that the compound vapor pressures were depressed in pyrolysis oils. The authors described bio-oil composition in several families based on their chemical composition and thermal behavior (see Figure 1). The first family is the C2-C4 compounds (mainly hydroxyacetaldehyde, acetol and acetic acid) typically quantified by GC/MS 2,42,47-49 (see Table Table 1. Main pyrolysis oil compounds identified and quantified by GC/MS (wt. %) 2, 43 No. Compound Range C2-C4 molecules 1 Glycolaldehyde 1.0-13.7 2 Acetic acid 2.5-8.7 3 Acetol 2.6-8.6 5 Propanoic acid 0.2-2.8 Mono-phenols and mono-furans 7 2-cyclopenten-1-one 0.
Critical Analysis of Process Parameters for Bio-oil Production via Pyrolysis of Biomass: A Review
Recent Patents on Engineering
Since recent past the research on biodiesel production and processing has got high momentum as evidenced from the large number of publications and patents on the subject. Many novel and improved protocols based on chemical, physical, and biological approaches have been reported that addresses the critical issues related to biodiesel production, recovery, purification, and associated recovery of high valued secondary products. Biodiesel typically comprises lower alkyl fatty acid (chain length C 14-C 22) esters of short-chain alcohols, primarily, methanol or ethanol. Various methods, such as pyrolysis, micro-emulsification, ozonization, ultrasonication, and transesterification have been reported for the production of biodiesel from vegetable oil. Among these, transesterification is appeared as attractive and widely accepted technique. This transesterification is mostly done chemically or enzymatically using lipase as biocatalyst. Lipase catalysis has received increasing attention due to its certain advantages over the conventional chemical catalysis. However, poor operational stability and low focus on the application of lipase for the biodiesel production are some of the important obstructing factors that impede the progress of the enzyme-based process. In addition to the transesterification step, separation of the ester from the reaction mixture, purification of the ester and glycerol, maintenances of appropriate fuel quality standards of the biodiesel (or blend stocks) as per specification for the particular nation, storage and stabilization are ascribed as the critical steps having immense effect on the successful implementation of biodiesel production and processing. In this review, the authors emphasise the important patents developed in the last few years that contribute to mitigate the major technological challenges on biodiesel production and processing.
Development of the Basis for an Analytical Protocol for Feeds and Products of Bio-oil Hydrotreatment
Energy & Fuels, 2012
Methods for easily following the main changes in the composition, stability, and acidity of bio-oil as a result of hydrotreatment are presented in this paper. The methods provide the basis for the development of an analytical protocol, which can be used for bio-oil, as well as the hydrotreated products from bio-oil. The correlation to more conventional methods is provided; however, the use of these methods for the upgrading products is different than previously recognized. The differences in the properties of bio-oil and the hydrotreated products will also create challenges for the analytical protocol. Polar pyrolysis liquids and their hydrotreated products can be divided into five main groups with solvent fractionation, and the change in the proportions of the groups as a result of handling or processing is easy to follow. Over the past 10 years, this method has been successfully used for comparison of fast pyrolysis bio-oil quality and the changes during handling and storage and provides the basis of the analytical protocol presented in this paper. This paper describes the use of the method for characterization of bio-oil hydrotreatment products. A discussion of the use of gas chromatographic and spectroscopic methods is also included. In addition, fuel oil analyses suitable for fast pyrolysis bio-oils and hydrotreatment products are discussed.
Quality Control in Fast Pyrolysis Bio-Oil Production and Use
Environmental Progress & Sustainable Energy, 2009
Introducing a new fuel, fast pyrolysis bio-oil, into the market is not without its challenges. Fast pyrolysis bio-oil is different from conventional liquid fuels, and therefore must overcome both technical and marketing hurdles. To standardize the bio-oil quality on the market, specifications are needed and in order to promote its acceptance as a fuel, the methodology should be as similar to that for mineral oils as possible. In the EU a new chemical regulation system is being implemented. The regulation applies to substances manufactured in or imported to the EU in annual quantities of one tonne or more per company.This article will focus on norms and standards for fast pyrolysis bio-oils. It will include the present status and address what still has to be done on bio-oil specifications and relevant test methods. The article will address industrial needs in commercialization of the fuel oil use of bio-oil, including the registration application to the REACH program, as well as development of a standard within ASTM. The article will discuss the most important properties of bio-oil and the variation in these properties. It will address the issue of quality follow-up in bio-oil production, including the properties to be followed and the laboratory and on-line monitoring methods. The article will provide a state of the art of fuel oil specifications, test methods, and testing procedures as they are applied to bio-oil. It will review the effort in support of the implementation of an ASTM standard including the methods validation work. © 2009 American Institute of Chemical Engineers Environ Prog, 2009
The development and optimisation of a fast pyrolysis process for bio-oil production
2011
Abba Sani Kalgo asserts his moral right to be identified as the author of this thesis This copy of the thesis has been supplied on condition that anyone who consults it is understood to recognise that its copyright rests with its author and that no quotation from the thesis and no information derived from it may be published without proper acknowledgement.
Bio-oil, solid and gaseous biofuels from biomass pyrolysis processes-An overview
International Journal of Energy Research, 2011
As the global demand for energy rapidly increases and fossil fuels will be soon exhausted, bio-energy has become one of the key options for shorter and medium term substitution for fossil fuels and the mitigation of greenhouse gas emissions. Biomass currently supplies 14% of the world's energy needs. Biomass pyrolysis has a long history and substantial future potential-driven by increased interest in renewable energy. This article presents the stateof-the-art of biomass pyrolysis systems, which have been-or are expected to be-commercialized. Performance levels, technological status, market penetration of new technologies and the costs of modern forms of biomass energy are discussed.
Smart Grid and Renewable Energy, 2010
Oil hydrotreating units in refineries are aimed at reducing the sulfur content of fuels to accomplish standard particular specifications. However, this process is currently one of the best available technologies to produce biofuels from vegetable oil in a refinery. Vegetable oils can be processed or co-processed in these units if several adaptations are performed, so some properties could be improved in comparison with conventional fuel such as density and cetane number. This study highlights the theoretical greenhouse gases (GHG) emissions (using a life cycle assessment-LCA-approach) of a hydrotreated vegetable oil (HVO) from bibliographical data. Results were compared with other biofuel production processes, such as those obtained by transesterification of vegetable oil (FAME, fatty acid methyl ester). It has also been included the comparison with conventional fossil diesel as a benchmark in order to assess the theoretical compliance with GHG savings proposed in European Directive 2009/28/EC. Finally, ongoing projects and future perspectives in Spain are mentioned.