The New Generation of Biofuels:

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1 The New Generation of Biofuels: How Europe and Latin America can Work Together Daniel Hayes Carbolea Research Group University of Limerick, Ireland LLSCIL LUIMNIGH UNIVERSITY F LIMERICK

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3 University of Limerick

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5 The Status Quo is Not Sustainable The hydrocarbon economy has satisfied out needs. However. nly recently have externalities been considered. Mostly sourced abroad. Global warming greenhouse gas emissions Kyoto Global warming C2 is responsible for ~57% of Kyoto agreement commitments and Kyoto successor likely to include further reductions.

6 5% 100% Mix: Std. Engines 10% Modified 85% Sugar beet Wheat Corn Rapeseed Soybean Sunflower Current focus is on 1st Generation Feedstocks Biodiesel Liquid Biofuels Ethanol What Biofuels are Currently Used?

7 Sucrose Foods Are Ideal Chemically Sucrose STARCH Amylopectin

8 Fats/ils are Also Easy!

9 Problems with 1 st Gen Feedstocks High establishment, maintenance costs. Poor energy ratios. High greenhouse gas emissions. Food versus fuel. Most of crop is not utilised.

10 Ethanol from Sugarcane is the Exception!! We are still not using all the plant!! 42m dry tonnes of bagasse in Brazil

11 How Can We Produce Sustainable, Economic Biofuels?

12 Utilise Cheap Biomass! Lower cost: waste/residues Sustainable energy crops, marginal land. Biomass where most of crop can be utilised. Such biomass tends to be lignocellulosic (cellulose, hemicellulose, lignin). Typical grasses/woods 45% cellulose, 25% hemicellulose, 25% lignin

13 Intra-Molecular Hydrogen Bonds HH 2 C H 1 H 4 H H 1 6 HH HC 2 C 4 HH H 2 C 2 H 1 1 H H H 4 H H 1 HH HC 2 C Cellulose 4 H 2 H 1 H Inter-Molecular Hydrogen Bond HH 2 C 4 5 H H 1 HH 2 C 4 H (a) Amylose Starch H 1 HH 2 C 4 H H HH 2 C 4 5 H 3 6 HH 2 C 4 H 2 H 1 4 H H H 2 C 1 6 (b) Amylopectin H branching point 1 HH 2 C 4 H H

14 Lignin

15 Lignocellulosic Feedstocks Require Advanced Technologies to Produce Biofuels/Chemicals SECND GENERATIN BIFUEL TECHNLGIES or BIREFINERIES

16 Biorefineries Analogous to oil refineries. btain saleable products from the chemical constituents of biomass. Biomass ideally low value, abundant and composed mainly of lignocellulose (carbohydrate and lignin).

17 Biomass Pre-treatment Size Reduction Steam Explosion Liquid Hot Water Dilute Acid Alkaline ther Solvents Pre-treatment Size Reduction Washing Drying Torrefaction Soil Enhancement Hydrolysis Processes PRDUCTS Acid Hydrolysis Dilute Concentrated Ethanol Sugars Fermentation Butanol Enzymatic Hydrolysis SHF SSF SSCF CBP DIBANET Levulinic Acid Thermochemical Processes Lignin Residue Electricity Pyrolysis Bio-oil Diesel Upgrading Hydrogen Gasification Biochar Syngas

18 Ethanol or Something Else? Many hydrolysis technologies focus on ethanol production. Yields from glucose not optimised. May not allow efficient utilisation of C5 sugars. Maximum Maximum theoretical yields of ethanol is approximately 50% of mass of carbohydrate. Fermentation may result in saleable mass halving. The production of value The production of value-added added products without biotic activity would be desirable.

19 Carbolea Biomass Research Group

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21 Feedstock Chemical Evaluation Important chemical characteristics: C6 Sugars: Glucose, Galactose, Mannose C5 Sugars: Arabinose, Xylose Cellulose Cellulose crystallinity Lignin content Lignin content Extractives WSC Ash. Elemental analysis.

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24 Picture of Elementar

25 Biomass Evaluation - NIR Develop NIR as a primary analytical tool. Target for all lignocellulosic components and for undried, heterogeneous biomass. Vastly reduces cost and time of analysis. Great utility in biorefining schemes. Technique widespread in feed industry and developing in sugar industry.

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27 Wet, Unground Dry, Unground Dry, ground

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29 No Pretreatment Detrend, SNV, 1D

30 Carbolea Research Interests: 2.Pyrolysis and Gasification Pyrolysis heating of biomass in absence of oxygen bio-oil, oil, biogas, biochar Gasification limited supply of oxyegn, higher temperatures more biogas. 10kg/hr pyrolysis/gasification unit operational shortly. Evaluation of Irish waste and energy crops as feedstocks.

31 UL Gasifier

32 UL Gasifier

33 Carbolea Research Interests: 3. Biochar Maximal char yields under slow-pyrolysis conditions. Huge interest in biochar as a soil amender: Carbon abatement strategy. Pollution remediation. Improved biomass yields: Particular ultrastructure of biochars arbuscular arbuscular micchorizal fungi (AMF). Greater moisture and nutrient retention.

34 Carbolea Research Interests: 3. Biochar (Cont d) Biochar interest stems from Terra Preta soils in Amazonian region of Brazil. Work at Carbolea focused on biochar analysis and performance evaluations: Porosity/surface area, scanning electron microscopy, cation exchange capacity, TGA, NMR Effects of varying pyrolysis conditions. Methods for improving char quality e.g. oxidised Plant-growth trials, AMF monitoring. Target is a Terra Preta analogue.

35 DIBANET Project The Production of Sustainable Diesel-Miscible Miscible-Biofuels from the Residues and Wastes of Europe and Latin America 3.7m project under FP7 Energy 2008 call: Co-operation operation between Europe and Latin America in the field of second generation biofuels. 13 partners, 7 from LA (4 Brazil, 2 Argentina, 1 Chile) and 6 from Europe (Ireland, UK, Greece, Hungary, Denmark). Project developed with key strategic needs of Europe and Latin America. How can we work together for sustainable biofuels?

36 Shared Needs in EU and LA Increasing reliance on imported diesel fuels. Increases in quantities of organic wastes. DIBANET - Diesel compatible fuels from wastes Biological technologies (e.g. enzymatic hydrolysis) not suitable chemical hydrolysis techniques. Important to use all of the feedstock and minimise process wastes.

37 DIBANET Process Chain Levulinic Acid Furfural C H

38 Synergistic EU-LA Relationship EU - Levulinic acid from wastes LA - Produce sustainable ethanol (export) Current EU policy on diversification of energy supply (An Energy Policy for Europe, CM(2007) 1)

39 EU and LA Working Together Ireland can, with practical levels of wastes, achieve over 8% biofuels. 5% from the levulinic acid produced from these wastes and 3% from the energy of the imported ethanol from LA. If DIBANET research improves the yield of levulinic acid by 25% then the EU 10% biofuels mandate can be met.

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