1.0. Introduction 4044 2.0. Biomass Chemistry and Growth Rates 4047 2.1. Lignocellulose and Starch-Based Plants 4047 2.2. Triglyceride-Producing Plants 4049 2.3. Algae 4050 2.4. Terpenes and Rubber-Producing Plants 4052 3.0. Biomass Gasification 4052 3.1. Gasification Chemistry 4052 3.2. Gasification Reactors 4054 3.3. Supercritical Gasification 4054 3.4. Solar Gasification 4055 3.5. Gas Conditioning 4055 4.0. Syn-Gas Utilization 4056 4.1. Hydrogen Production by Water−Gas Shift Reaction 4056

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Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering.

Biomass is an important feedstock for the renewable production of fuels, chemicals, and energy. As of 2005, over 3% of the total energy consumption in the United States was supplied by biomass, and it recently surpassed hydroelectric energy as the largest domestic source of renewable energy. Similarly, the European Union received 66.1% of its renewable energy from biomass, which thus surpassed the total combined contribution from hydropower, wind power, geothermal energy, and solar power. In addition to energy, the production of chemicals from biomass is also essential; indeed, the only renewable source of liquid transportation fuels is currently obtained from biomass.

The Catalytic Valorization of Lignin for the Production of Renewable Chemicals

Progress and recent trends in biodiesel fuels

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

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

Review of biomass pyrolysis oil properties and upgrading research

Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part I: Conversion over various catalysts

Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part II: Comparative catalyst performance and reaction pathways

Catalytic conversion of a biofuel to hydrocarbons: effect of mixtures of HZSM-5 and silica-alumina catalysts on product distribution

The catalytic conversion of canola oil to fuels and chemicals was studied over HZSM-5, H-mordenite, H-Y, silicalite, aluminum-pillared clay (AL-PILC) and silica-alumina catalysts in a fixed bed micro-reactor. The reactor was operated at atmospheric pressure, a temperature range of 375−500°C and weight hourly space velocity (WHSV) of 1.8 and 3.6 h−1. An organic liquid product (OLP), light hydrocarbon gases and water were the major products. The objective was to maximize the amount of OLP and its hydrocarbon content as well as optimize the selectivity for gas phase olefinic hydrocarbons. In addition, the performance of each catalyst in terms of minimizing the coke formation was examined. Among the six catalysts, HZSM-5 gave the highest amount of OLP of 63 mass% at 1.8 WHSV and 400°C. The hydrocarbon content of this OLP product was 83.8 mass%. With the exception of silica-alumina and aluminum-pillared clay catalysts, the other catalysts gave high concentrations of aromatic hydrocarbons which ranged between 23.1–95.6 mass% of OLP. The gas products consisted mostly C3 and C4 hydrocarbons. Ethylene, propylene and butanes were some of the valuable hydrocarbon gases. The olefin/paraffin ratio of the gas products was highest for AL-PILC catalysts but it never exceeded unity. The results showed that it was possible to significantly alter the yield and selectivity for the different hydrocarbon products by using different catalysts or changing the catalyst functionality such as acidity, pore size and crystallinity. Reaction pathways based on these results are proposed for the conversion of canola oil



La conversion catalytique d'huile de canola en combustibles et produits chimiques a ete etudiee sur des catalyseurs HZSM-5, H-mordenite, H-Y, silicalite, argile renforce d'aluminium (AL-PILC) et silice-alumine dans un micro-reacteur a lit fixe. Le reacteur a fonctionne a la pression atmospherique, dans une gamme de temperatures entre 375 et 500°C et a un volume par volume par heure (VVH) de 1,8 et 3,6 h−1. Les principaux produits sont un produit organique liquide (POL), des gaz d'hydrocarbures legers et de l'eau. L'objectif etait de maximiser la quantite de POL et sa teneur en hydrocarbures et egalement d'optimiser la selectivite pour les hydrocarbures olefiniques de la phase gazeuse. Par ailleurs, la performance de chaque catalyseur a ete examinee par rapport a la capacite de minimiser la formation de coke. Parmi les six catalyseurs, le HZSM-5 a donne la plus forte quantite de POL (63% en masse a un VVH de 1,8 et a 400°C). La teneur en hydrocarbures de ce produit organique liquide est de 83,8% en masse. A l'exception des catalyseurs de silice-alumine et d'argile renforce d'aluminium, les catalyseurs ont donne de fortes concentrations d'hydrocarbures aromatiques dont le pourcentage en masse du POL est compris entre 23,1 et 95,6. Les produits gazeux sont essentiellement des hydrocarbures C3 et C4. L'ethylene, le propylene et les butanes sont quelques-uns des gaz d'hydrocarbures interessants. Le rapport olefine/parafine des produits gazeux est plus grand pour les catalyseurs AL-PILC mais n'a jamais excede l'unite. Les resultats montrent qu'il est possible d'alterer considerablement le rendement et la selectivite pour les differents produits d'hydrocarbures en utilisant differents catalyseurs ou en modifiant la fonctionnalite des catalyseurs, telles l'acidite, la taille des pores et la cristalinite. Des voies reactives basees sur ces resultats sont proposees pour la conversion de l'huile de canola.

Catalytic conversion of canola oil to fuels and chemicals over various cracking catalysts

The influence of catalyst acidity, reaction temperature, and canola oil space velocity on the conversion of canola oil was evaluated using a fixed-bed microreactor at atmospheric pressure at reaction temperatures and space velocities (WHSV) in the ranges 400−500 °C and 1.8−3.6 h-1, respectively, over potassium-impregnated HZSM-5 catalysts. These catalysts were thoroughly characterized using XRD, N2 adsorption measurements, 1H NMR, TPD of NH3, FT-IR, and model compound reactions. Also, conditions for the production of the maximum yield of C2−C4 olefins from canola oil were determined. The incorporation of potassium into HZSM-5 catalyst resulted in both the dilution and poisoning of Bronsted and total acid sites. These acidity changes only severely affected the acid catalyzed reactions, such as oligomerization and aromatization, and resulted in drastic modifications in product distribution. The maximum C2−C4 olefin yield of 25.8 wt % was obtained at 500 °C and 1.8 h-1 space velocity with catalyst K1 of rela...

John Adjaye

Papers

Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part I: Conversion over various catalysts

Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part II: Comparative catalyst performance and reaction pathways

Catalytic conversion of a biofuel to hydrocarbons: effect of mixtures of HZSM-5 and silica-alumina catalysts on product distribution

Catalytic conversion of canola oil to fuels and chemicals over various cracking catalysts

Catalytic Conversion of Canola Oil over Potassium-Impregnated HZSM-5 Catalysts: C2−C4 Olefin Production and Model Reaction Studies