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

Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited

Renewable Resources Robert-Jan van Putten,†,‡ Jan C. van der Waal,† Ed de Jong,*,† Carolus B. Rasrendra,‡,⊥ Hero J. Heeres,*,‡ and Johannes G. de Vries* †Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam, the Netherlands ‡Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands DSM Innovative Synthesis BV, P.O. Box 18, 6160 MD Geleen, the Netherlands Department of Chemical Engineering, Institut Teknologi Bandung, Ganesha 10, Bandung 40132, Indonesia

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources

Furfural offers a promising, rich platform for lignocellulosic biofuels. These include methylfuran and methyltetrahydrofuran, valerate esters, ethylfurfuryl and ethyltetrahydrofurfuryl ethers as well as various C(10)-C(15) coupling products. The various production routes are critically reviewed, and the needs for improvements are identified. Their relative industrial potential is analysed by defining an investment index and CO(2) emissions as well as determining the fuel properties for the resulting products. Finally, the most promising candidate, 2-methylfuran, was subjected to a road trial of 90,000 km in a gasoline blend. Importantly, the potential of the furfural platform relies heavily on the cost-competitive production of furfural from lignocellulosic feedstock. Conventional standalone and emerging coproduct processes-for example, as a coproduct of cellulosic ethanol, levulinic acid or hydroxymethyl furfural-are expensive and energetically demanding. Challenges and areas that need improvement are highlighted. In addition to providing a critical review of the literature, this paper also presents new results and analysis in this area.

Furfural—A Promising Platform for Lignocellulosic Biofuels

Biomass can be utilized to produce bio-oil, a promising alternative energy source for the limited crude oil. There are mainly two processes involved in the conversion of biomass to bio-oil: flash pyrolysis and hydrothermal liquefaction. The cost of bio-oil production from biomass is relatively high based on current technologies, and the main challenges are the low yield and poor bio-oil quality. Considerable research efforts have been made to improve the bio-oil production from biomass. Scientific and technical developments towards improving bio-oil yield and quality to date are reviewed, with an emphasis on bio-oil upgrading research. Furthermore, the article covers some major issues that associated with bio-oil from biomass, which includes bio-oil basics (e.g., characteristics, chemistry), application, environmental and economic assessment. It also points out barriers to achieving improvements in the future.

Bio-oil production and upgrading research: A review

Optimization of mechanical oil extraction from Jatropha curcas L. kernel using response surface method

Mechanical extraction of oil from Jatropha curcas L. kernel: Effect of processing parameters

The synthesis of fatty acid ethyl esters (FAEE) from Jatropha curcas L oil was studied in a batch reactor and a continuous centrifugal contactor separator (CCCS) using sodium ethoxide as the catalyst The effect of relevant process variables like rotational speed, temperature, catalyst concentration, and molar ratio of ethanol to oil was investigated Maximum yield of FAEE was 98?mol% for both the batch (70 degrees C, 600?rpm, 08% w/w of sodium ethoxide) and CCCS reactor configuration (60 degrees C, 2100?rpm, 1% w/w of sodium ethoxide, oil feed 28?mL/min) The volumetric production rate of FAEE in the CCCS at optimum conditions was 112?kgFAEE/m3liquid??min Practical applications: The Jatropha curcas L shrub produces a non-edible oil in yields up to 15?ton/(ha?y), which is known to be suitable for biodiesel synthesis We here report an experimental study on the synthesis of jatropha biodiesel using ethanol instead of methanol as the alcohol source Ethanol is accessible from biomass by fermentation and as such a green alternative for methanol In addition, it is more readily available in developing countries than methanol Biodiesel synthesis was performed in a CSSS, a continuous device that integrates reaction and separation The device has potential to be applied in small scale mobile biodiesel technology due to its compact size, robustness, flexibility in operation, and high volumetric productivities

Biodiesel synthesis from Jatropha curcas L. oil and ethanol in a continuous centrifugal contactor separator

The synthesis and properties of a number of novel branched Jatropha curcas L. oil (JO) derivatives containing vicinal di-ester units in the fatty acid chains are reported. Both the length (acetyl vs. hexanoyl) and the stereochemistry of the vicinal di-ester units (cis vs. trans) were varied. The compounds were prepared by two different synthetic approaches using catalytic chemistry. The first approach involves epoxidation of JO using a Sharpless epoxidation with methyltrioxorhenium as the catalyst to give epoxidized JO (1), followed by an esterification reaction with the corresponding anhydrides using ammonium-12-molybdophosphate (AMP) as catalyst to give trans-di-esters of JO (4a, 4b). The second approach is based on the dihydroxylation of JO using either the Prilezhaev method, resulting in trans-diols of JO (2), or the Upjohn method using osmium tetroxide as catalyst to give cis-diols of JO (3). In subsequent steps, the diols were esterified with acetic- or hexanoic anhydride using dimethylaminopyridine as catalyst to produce the corresponding cis- and trans-di-esters of JO (5a, 5b, 6). The best cold flow properties (lowest pour- and cloud point, crystallization and melting temperature) were obtained for JO with hexanoyl branches in a trans orientation (5b, pour point of � 148C, melting point of � 58C, and crystallization temperature of � 258C) and these values are considerably better than for the JO source. Practical applications: Jatropha curcas L. oil (JO) is a toxic oil with potential applications not only as a greenbiodiesel but alsoas a feedstock for theoleochemical industry. The toxicityprohibits theusein food products but does not interfere with technical applications. Here we report studies on the synthesis of interesting JO derivatives (epoxidized, dihydroxylated, and branched compounds) that could be useful starting materials for a range of derivatives with a broad application perspective. The branched JO derivatives with vicinal di-ester units in the fatty acid chains have cold flow properties (pour- and cloud point, melting point and crystallization temperature) considerably better than the original JO. In addition, the oxidative stability was also improved significantly. These novel branched JO derivatives may have interesting applications as cold-flow improvers for biodiesel or as biolubricants.

Synthesis and properties of highly branched Jatropha curcas L. oil derivatives

This paper describes a systematic study on the synthesis of higher fatty esters of corn starch (starch laurate and starch stearate) by using the corresponding vinyl esters. The reactions were carried out in DMSO using basic catalysts (Na(2)HPO(4), K(2)CO(3), and Na-acetate). The effect of the process variables (vinyl ester to starch ratio, catalyst intake, reaction temperature and type of the catalyst) on the degree of substitution (DS) of the starch laurate and starch stearate esters was determined by performing a total of 54 experiments. The results were adequately modeled using a non-linear multivariable regression model (R(2)>= 0.96). The basicity of the catalyst and the reaction temperature have the highest impact on the product DS. The thermal and mechanical properties of some representative product samples were determined. High-DS products (DS = 2.26-2.39) are totally amorphous whereas the low-DS ones (DS = 1.45-1.75) are still partially crystalline. The thermal stability of the esterified products is higher than that of native starch. Mechanical tests show that the products have a tensile strength (stress at break) between 2.7-3.5 MPa, elongation at break of 3-26%, and modulus of elasticity of 46-113 MPa.

Robert Manurung

Papers

Optimization of mechanical oil extraction from Jatropha curcas L. kernel using response surface method

Mechanical extraction of oil from Jatropha curcas L. kernel: Effect of processing parameters

Biodiesel synthesis from Jatropha curcas L. oil and ethanol in a continuous centrifugal contactor separator

Synthesis and properties of highly branched Jatropha curcas L. oil derivatives

Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch