Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review

As the oil reserves are depleting the need of an alternative fuel source is becoming increasingly apparent. One prospective method for producing fuels in the future is conversion of biomass into bio-oil and then upgrading the bio-oil over a catalyst, this method is the focus of this review article. Bio-oil production can be facilitated through flash pyrolysis, which has been identified as one of the most feasible routes. The bio-oil has a high oxygen content and therefore low stability over time and a low heating value. Upgrading is desirable to remove the oxygen and in this way make it resemble crude oil. Two general routes for bio-oil upgrading have been considered: hydrodeoxygenation (HDO) and zeolite cracking. HDO is a high pressure operation where hydrogen is used to exclude oxygen from the bio-oil, giving a high grade oil product equivalent to crude oil. Catalysts for the reaction are traditional hydrodesulphurization (HDS) catalysts, such as Co–MoS2/Al2O3, or metal catalysts, as for example Pd/C. However, catalyst lifetimes of much more than 200 h have not been achieved with any current catalyst due to carbon deposition. Zeolite cracking is an alternative path, where zeolites, e.g. HZSM-5, are used as catalysts for the deoxygenation reaction. In these systems hydrogen is not a requirement, so operation is performed at atmospheric pressure. However, extensive carbon deposition results in very short catalyst lifetimes. Furthermore a general restriction in the hydrogen content of the bio-oil results in a low H/C ratio of the oil product as no additional hydrogen is supplied. Overall, oil from zeolite cracking is of a low grade, with heating values approximately 25% lower than that of crude oil. Of the two mentioned routes, HDO appears to have the best potential, as zeolite cracking cannot produce fuels of acceptable grade for the current infrastructure. HDO is evaluated as being a path to fuels in a grade and at a price equivalent to present fossil fuels, but several tasks still have to be addressed within this process. Catalyst development, understanding of the carbon forming mechanisms, understanding of the kinetics, elucidation of sulphur as a source of deactivation, evaluation of the requirement for high pressure, and sustainable sources for hydrogen are all areas which have to be elucidated before commercialisation of the process.

A review of catalytic upgrading of bio-oil to engine fuels

The incentive for use of renewable resources to replace fossil sources is motivating extensive research on new and alternative fuels derived from biomass. Bio-oils derived from cellulosic biomass offer the prospect of becoming a major feedstock for production of fuels and chemicals, and lignin is a plentiful, underutilized component of cellulosic biomass. Lignin conversion requires depolymerization and removal of oxygen. Likely processes for lignin conversion involve depolymerization (e.g., by pyrolysis) and catalytic upgrading of the resultant bio-oils. A major goal of the upgrading is catalytic hydrodeoxygenation (HDO), which involves reactions with hydrogen that produce hydrocarbons and water. The aim of this review is to present a critical introduction to HDO chemistry focused on compounds derived from lignin, including a summary of HDO reactions and those that accompany them, with a comparison of catalysts addressing their activities, selectivities, and stabilities. The reactions are evaluated in terms of reaction pathways of compounds representative of lignin-derived bio-oils, including anisole, guaiacol, and phenol. The review includes recommendations for further research and an attempt to place HDO in a context of options for renewable fuels and chemicals, but it does not provide an economic assessment.

Upgrading of lignin-derived bio-oils by catalytic hydrodeoxygenation

In this review, a comprehensive and illustrious survey is made of the applied aspects of microbial lipases in modern biotechnological practices. Lipases are the most versatile biocatalyst and bring about a range of bioconversion reactions such as hydrolysis, interesterification, esterification, alcoholysis, acidolysis and aminolysis. After a brief description of the microbial sources of lipases, the pivotal role of lipases in the processes and products of the food and flavourings industry is illustrated. An illustration is presented of biomedical applications. The panorama of lipases in the manufacture of fine chemicals is depicted with special emphasis on pharmaceuticals, pesticides, cosmetics, biosensors and detergents. Widening applications such as those in waste management and improved tanning techniques are other novel aspects of lipase utilization that are discussed in this review.

The realm of microbial lipases in biotechnology

Hydrothermal processing is an important thermochemical conversion process that is used to convert biomass into valuable products or biofuel. The process is usually performed in water at 250–374 °C under pressures of 4–22 MPa. The biomass is degraded into small components in water. Based on the target products, i.e., bio-oil, bio-gas or bio-carbon, the process conditions (temperature, pressure and time) are chosen. There has been significant effort in evaluating various biomass resources for hydrothermal processing because the process is suitable for any type of biomass including the co-utilization of biomass with waste materials. Additionally, because most biomass resources have high moisture contents, the most efficient way to process them is through hydrothermal processing. To understand hydrothermal biomass processing and the degradation pathway of biomass, it is necessary to understand the properties of water under hydrothermal conditions (i.e., subcritical and supercritical). In this respect, the physicochemical properties of water under subcritical and supercritical conditions and the interactions of water with biomass are discussed in the present paper. This review focuses on the hydrothermal processing of biomass and identifies the characteristics of various types of hydrothermal processing products. Additionally, this review provides an overview of the available biomass, the use of biomass as an energy source and related conversion technologies.

A review of hydrothermal biomass processing

Biomass to fuels: The role of zeolite and mesoporous materials☆

Solid wastes of organic origins are potential feedstocks for the production of liquid biofuels, which could be suitable alternatives to fossil fuels for the transport and heating sectors, as well as for industrial use. By hydrothermal liquefaction, the wet biomass is partially transformed into a water-immiscible, oil-like organic matter called bio-oil. In this study, an integrated NMR spectroscopy/mass spectrometry approach has been developed for the characterization of the hydrothermal liquefaction of bio-oil at the molecular level. 1H and 13C NMR spectroscopy were used for the identification of functional groups and gauging the aromatic carbon content in the mixture. GC–MS analysis revealed that the volatile fraction was rich in fatty acids, as well as in amides and esters. High-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) has been applied in a systematic way to fully categorize the bio-oil in terms of different classes of components, according to their molecular formulas. Most importantly, for the first time, by using this technique, and for the liquefaction bio-oil characterization in particular, FT-MS data have been used to develop a methodology for the determination of the aromatic versus aliphatic carbon and nitrogen content. It is well known that, because they resist hydrogenation and represent sources of polluting species, both aromatic molecules and nitrogen-containing species raise concerns for subsequent upgrading of bio-oil into a diesel-like fuel.

Characterization of bio-oil from hydrothermal liquefaction of organic waste by NMR spectroscopy and FTICR mass spectrometry.

The use of zeolite catalysts for the production of biofuels from biomass is reviewed. Zeolites as such or modified by the addition of other active phases are used in several processes for the transformation of the biomass and for the upgrading of the bio-oils deriving from its primary treatment. For each of the different processes, the most relevant results reported in the literature are provided together with some considerations on the effective or potential industrial applicability of the technologies.

Zeolite Materials for Biomass Conversion to Biofuel

Among biofuels, the bio-oil produced by hydrothermal liquefaction of waste biomass can be considered an alternative to fossil fuels in industry as well as transport and heating compartments. The bio-oil complex composition is directly dependent upon the specific biomass used as feedstock and the process used for the chemical conversion. The coexistence of proteins and lipids can explain, in principle, the high percentage of fatty acid amides found in the produced bio-oil. In the present study, the amides in a sample of bio-oil have been separated by gas chromatography and identified at first on the basis of their electron impact (EI) mass spectra. To distinguish between N-alkyl isomers, standard amides have been synthesized and analyzed. Because the most reasonable origin of fatty acid amides in hydrothermal bio-oils is the condensation reaction between fatty acids and the decarboxylation products of amino acids, a series of model experiments have been carried out by reacting hexadecanoic acid, at high te...

Amides in Bio-oil by Hydrothermal Liquefaction of Organic Wastes: A Mass Spectrometric Study of the Thermochemical Reaction Products of Binary Mixtures of Amino Acids and Fatty Acids

Enzymatic resolution of 1,2-diols : preparation of optically pure dropropizine

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