Biofuels in Perspective

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6 Bio-based Fischer-Tropsch Diesel Production Technologies Robin Zwart Energy Research Centre of the Netherlands Biomass, Coal and Environmental Research Petten, The Netherlands RenévanRee Wageningen University and Research Centre, Wageningen, The Netherlands 6.1 Introduction Bio-based transportation fuels are expected to contribute significantly to the future transportation fuel portfolio both on national, EC and global levels. Bio-based transportation fuels that are currently produced and used are so called first generation biofuels. Examples are: pure vegetable plant oils, biodiesel produced from the seeds of oil-rich crops and from waste vegetable oils and animal fats, conventional bioethanol/ETBE produced from sugar and starch crops, and upgraded biogas produced from the digestion of organic residues. An advantage of these first generation biofuels is that production technologies are commercially available and that these fuels are already being produced for, and applied mainly as blending agents in, the current transportation fuel market. Disadvantages are (1) that the overall CO2-reduction potential of these fuels compared to their fossil alternatives, taking into account the whole biomass–fuel application chain, is generally reported to be less than 50 %, and (2) that the production processes are relatively raw material specific, decreasing the overall market application potential. Currently, technologies are being developed for the production of so called one-anda-half generation biofuels, which have better properties. Examples are: the upgrading Biofuels. Edited by Wim Soetaert, Erick J. Vandamme. © 2009 John Wiley & Sons Ltd. ISBN: 978-0-470-02674-8
96 Biofuels (hydrogenation) of biodiesel to a higher-quality bio-based diesel, the production of higher alcohols (i.e. biobutanol) from sugar and starch crops, and the production of bioethanol or biobutanol from a wider range more difficult to convert raw materials. Considering the European Policy goals on the implementation of biofuels, i.e. 2 % and 5.75 % fossil fuel substitution on energy basis in 2005 and 2010, these have to be met fully by the implementation of additional first and one-and-a-half generation biofuel production capacity. To meet to the longer-term market demands, for example the 25 % fossil fuel substitution directive for 2030, as mentioned in the Vision document of the European Technology Platform on Biofuels, and to gradually shift to biofuels with a better overall CO2-reduction potential, the introduction of so called second generation biofuels is a necessity. Examples are: bioethanol or biobutanol produced from lignocellulosic-rich raw materials and Biomass-to-Liquids (BtL) products, like Fischer-Tropsch (FT) diesel, dimethylether (DME), bioSNG, bioCNG and biomethanol. This chapter will fully concentrate on the current technological status and market perspectives for the production of FT-diesel from lignocellulosic-rich raw materials (wood, straw, etc.). Aspects that will be described in more detail are: the theoretical background of catalytic FT-diesel synthesis and the techno-economic aspects of biomass-based integrated gasification-based FT-diesel production concepts considered in some major demonstration projects. 6.2 Theoretical Background Catalytic FT-Diesel Synthesis Process The Fischer-Tropsch (FT) synthesis was discovered in 1923 by the German scientists F. Fischer and H. Tropsch at the Kaiser Wilhelm Institute for Coal Research in Mülheim, Germany. In the synthesis hydrocarbons are produced from syngas, viz. a mixture of the gases CO and H2. Historically, FT-processes have been operated on a large industrial scale to produce synthetic fuels as alternative for non-available fossil fuels (i.e. in Germany in the 1930s and 1940s, and in South Africa during the oil boycott). To date, the FT-process receives much attention because the hydrocarbon products are ‘ultra-clean’ due to the nature of the synthesis process, i.e. they are essentially free of sulphur and aromatics. Shell Gas-to-Liquids (GtL) derived FT-diesel blended with fossil diesel (i.e., V-power) is available to reduce local soot and SO2 emissions. 6.2.1 Chemistry 6.2.1.1 Synthesis In the catalytic FT-synthesis one mole of CO reacts with two moles of H2 to form mainly paraffin straight-chain hydrocarbons (CxH2x), with minor amounts of branched and unsaturated hydrocarbons (i.e. 2-methyl paraffins and a-olefins), and primary alcohols. Typical operation conditions for FT-synthesis are temperatures of 200–250 ◦ C and pressures between 25 and 60 bar. 1 In the exothermic FT-reaction about 20 % of the chemical energy is released as heat: CO + 2H2 ⇒−(CH2)−+H2O
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Biofuels Biofuels. Edited by Wim So
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Biofuels Edited by WIM SOETAERT Ghe
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Contents Series Preface ix Preface
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Contents vii 6.3 Biomass Gasificati
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Series Preface Renewable resources,
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Preface This volume on Biofuels fit
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Editors List of Contributors Wim So
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1 Biofuels in Perspective W. Soetae
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Table 1.1 Approximate average world
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Table 1.3 Energy yields of bio-ener
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Biofuels in Perspective 7 is burnt
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2 Sustainable Production of Cellulo
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Sustainable Production of Cellulosi
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Figure 2.9 2004 US adoption rates o
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3 Bio-Ethanol Development in the US
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Bio-Ethanol Development in the USA
Page 58 and 59: Biorefineries in Production (115) B
Page 60 and 61: Bio-Ethanol Development in the USA
Page 66 and 67: Cost of Cellulosic Ethanol, $ per g
Page 70 and 71: 4 Bio-Ethanol Development(s) in Bra
Page 72 and 73: Bio-Ethanol Development(s) in Brazi
Page 74 and 75: Share of energy consumption 100% 90
Page 80 and 81: Table 4.2 Main technological improv
Page 84 and 85: 4.7.4 Use of Fertilizers and Pestic
Page 90: Bio-Ethanol Development(s) in Brazi
Page 93 and 94: 78 Biofuels Table 5.1 Biodiesel pro
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Page 97 and 98: 82 Biofuels short reaction times. 9
Page 99 and 100: 84 Biofuels Table 5.4 Overview on h
Page 101 and 102: 86 Biofuels Table 5.5 Critical cond
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Page 105 and 106: 90 Biofuels KOH Methano Oil/Fat Aci
Page 107 and 108: 92 Biofuels 16. J. Graille, P. Loza
Page 112 and 113: 6.2.1.2 Catalysts Bio-based Fischer
Page 114 and 115: Bio-based Fischer-Tropsch Diesel Pr
Page 132 and 133: 7 Plant Oil Biofuel: Rationale, Pro
Page 134 and 135: Table 7.1 Market milestones for pla
Page 136 and 137: Water CO 2 Figure 7.1 Closed CO 2 l
Page 138 and 139: Plant Oil Biofuel: Rationale, Produ
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Page 147 and 148: 132 Biofuels Table 8.1 Enzymatic tr
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Page 155 and 156: 140 Biofuels Ratio of initial react
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144 Biofuels preparation of whole-c
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ability to reduce flocculation (% o
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148 Biofuels 5. R. C. Strayer, J. A
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150 Biofuels 46. H. Fukuda, Immobil
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9 Production of Biodiesel from Wast
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Production of Biodiesel from Waste
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9.3.2 Processing of Crude and Waste
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Heavy layer from alkaline neutralis
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CPO I 1 1 Heating 60°C Reaction st
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References Production of Biodiesel
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10 Biomass Digestion to Methane in
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Cow manure Pig manure Yard manure B
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Number of plants 3000 2500 2000 150
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Biomass Digestion to Methane in Agr
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Table 10.4 Alternative forms of ene
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Wet fermentation 3 - 10% TS applica
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Rel. Frequency [%] 35 30 25 20 15 1
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Steam 2 1 Energy crops (& manure) D
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198 Biofuels 11.1 Introduction Hydr
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200 Biofuels lactate 6 glucose 1 GA
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Table 11.2 Continued Organism Domai
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204 Biofuels NADH is that the react
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206 Biofuels Clostridium thermocell
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208 Biofuels in particular in Cl. p
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210 Biofuels ferredoxin-dependent m
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212 Biofuels Concentration (mM) 45
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214 Biofuels genes of the glycolysi
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216 Biofuels 11. S. Tanisho and Y.
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218 Biofuels 49. M. J. Axley, D. A.
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220 Biofuels 83. P. J. Silva, E. C.
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12 Improving Sustainability of the
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Table 12.1 Corn ethanol dry mill: e
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Table 12.2 Atmospheric CO2 (equival
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Table 12.3 Incremental CO2 equivale
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Improving Sustainability of the Cor
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Improving Sustainability of the Cor
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Index italic entries indicate refer
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iorefineries 3, 10, 11, 41 and corn
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policy (official) 59-61 production
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NADH 200-6, 207, 210 natural gas 1
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