This paper provides an updated review on fast pyrolysis of biomass for production of a liquid usually referred to as bio-oil. The technology of fast pyrolysis is described including the major reaction systems. The primary liquid product is characterised by reference to the many properties that impact on its use. These properties have caused increasingly extensive research to be undertaken to address properties that need modification and this area is reviewed in terms of physical, catalytic and chemical upgrading. Of particular note is the increasing diversity of methods and catalysts and particularly the complexity and sophistication of multi-functional catalyst systems. It is also important to see more companies involved in this technology area and increased take-up of evolving upgrading processes. © 2011 Elsevier Ltd.

Review of fast pyrolysis of biomass and product upgrading

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

Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple "upstream" (i.e., lignin bioengineering, lignin isolation and "early-stage catalytic conversion of lignin") and "downstream" (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a "beginning-to-end" analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on the improved understanding of lignin's biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis.

Pyrolysis is one of the thermochemical technologies for converting biomass into energy and chemical products consisting of liquid bio-oil, solid biochar, and pyrolytic gas. Depending on the heating rate and residence time, biomass pyrolysis can be divided into three main categories slow (conventional), fast and flash pyrolysis mainly aiming at maximising either the bio-oil or biochar yields. Synthesis gas or hydrogen-rich gas can also be the target of biomass pyrolysis. Maximised gas rates can be achieved through the catalytic pyrolysis process, which is now increasingly being developed. Biomass pyrolysis generally follows a three-step mechanism comprising of dehydration, primary and secondary reactions. Dehydrogenation, depolymerisation, and fragmentation are the main competitive reactions during the primary decomposition of biomass. A number of parameters affect the biomass pyrolysis process, yields and properties of products. These include the biomass type, biomass pretreatment (physical, chemical, and biological), reaction atmosphere, temperature, heating rate and vapour residence time. This manuscript gives a general summary of the properties of the pyrolytic products and their analysis methods. Also provided are a review of the parameters that affect biomass pyrolysis and a summary of the state of industrial pyrolysis technologies.

Lignocellulosic biomass pyrolysis: A review of product properties and effects of pyrolysis parameters

Fossil fuel consumption in transportation system and energy-intensive sectors as the principal pillar of civilization is associated with progressive release of greenhouse gases. Hydrogen as a promising energy carrier is a perfect candidate to supply the energy demand of the world and concomitantly reduce toxic emissions. This article gives an overview of the state-of-the-art hydrogen production technologies using renewable and sustainable energy resources. Hydrogen from supercritical water gasification (SCWG) of biomass is the most cost effective thermochemical process. Highly moisturized biomass is utilized directly in SCWG without any high cost drying process. In SCWG, hydrogen is produced at high pressure and small amount of energy is required to pressurize hydrogen in the storage tank. Tar and char formation decreases drastically in biomass SCWG. The low efficiency of solar to hydrogen system as well as expensive photovoltaic cell are the most important barriers for the widespread commercial development of solar-based hydrogen production. Since electricity costs play a crucial role on the final hydrogen price, to generate carbon free hydrogen from solar and wind energy at a competitive price with fossil fuels, the electrical energy cost should be four times less than commercial electricity prices.

Hydrogen production from renewable and sustainable energy resources: Promising green energy carrier for clean development

http://ehsan13967.persiangig.com/document/pyrolysis6.pdf

Review of biomass pyrolysis oil properties and upgrading research

http://ir.giec.ac.cn/bitstream/344007/8483/2/Aqueous-phase%20catalytic%20process%20for%20production%20of%20pentane%20from%20furfural%20over%20nickel-based%20catalysts.pdf

Aqueous-phase catalytic process for production of pentane from furfural over nickel-based catalysts

Upgrading of fast pyrolysis liquid fuel from biomass over Ru/γ-Al2O3 catalyst.

Copper-iron modified bimodal support (M) with different mass fractions of Cu and Fe elements were prepared by an ultrasonic impregnation method. The catalytic performance for higher alcohol syntheses (HAS) was investigated in a fixed-bed flow reactor. Several techniques, including N-2 physical adsorption, temperature-programmed reduction/desorption of hydrogen, (H-2-TPR/TPD) and X-ray diffraction (XRD) were used to characterize the catalysts. The results indicated that the bimodal pore support was formed by the addition of small-pore silica sol into the macroporous silica gel. Increased amounts of small pore silica sol caused a decrease in pore size in the bimodal carrier. An increase in the Fe/Cu molar ratio facilitated the dispersion of CuO, promoted the reduction of CuO and Fe2O3 on the surface layers, and enhanced the interaction between the copper and iron species as well as the bimodal support inside the large pores. The copper was well-dispersed on the catalyst and the amount of iron carbides formed was high in catalysts with a high Fe/Cu molar ratio. Increasing the Fe/Cu mass ratio promoted the catalytic activity and thus facilitated the synthesis of higher alcohols. When the Fe/Cu molar ratio was increased to 30/20, the CO conversion and the yield of higher alcohols increased to 46% and 0.21 g . mL(-1) . h(-1), respectively. At the same time, the mass ratio of C2+OH/CH3OH reached 1.96.

/pdf/structure-and-performance-of-cu-fe-bimodal-support-for-2rw1mrce8i.pdf

Wang Tiejun

Papers

Review of biomass pyrolysis oil properties and upgrading research

Aqueous-phase catalytic process for production of pentane from furfural over nickel-based catalysts

Upgrading of fast pyrolysis liquid fuel from biomass over Ru/γ-Al2O3 catalyst.

Structure and Performance of Cu-Fe Bimodal Support for Higher Alcohol Syntheses

Catalytic cracking mechanism of bio-oil model compounds.