1st European Summer School on Renewable Motor Fuels Birkenfeld, Germany, 29 31 August 2005

Bio-ethanol existing pathways

D. Schieder Technical university of Munich Monday, 29 August 2005, 14:40 15:20

Bio-ethanol existing pathways

Dr. Doris Schieder
Institute of Technology of Biogenic Resources Petersgasse 18 94315 Straubing Germany Phone +49 9421 187 108 Fax +49 9421 187 111 Email doris.schieder@wzw.tum.de

1. Bio-ethanol in the transportation sector Fuel ethanol for the transportation sector has been used as early as 1900. Famous forerunners in the automobile industry like Henry Ford strongly encouraged this option. However, the expansion of the petroleum industry in the early 20th century resulted in the preference for the less cost-intensive mineral oil. Today ethanol is a well-established transportation fuel. In 2004 around 32 billion litres of fuel ethanol were produced worldwide. The production has been increasing continuously since the eighties especially in the US and Canada (Figure 1). Up to now the main producers and consumers are Brazil and the US. This is the result of regulations in these countries which have been introduced to promote the home agricultural industry or the reduction of traffic emissions in conurbations (e. g. the proalcool-programme in Brazil in the early 1970s or the North-American clean-air-acts of the 1990s). It is because of the clean-air-act that as a matter of routine in many conurbations throughout the US up to 10% ethanol is added to gasoline fuels.
35 30
World Brazil US/Canada Europe

billion litres per year

25 20 15 10 5 0

1980 1985 1990 1995 2000 2001 2002 2003 2004

Figure 1: Production of fuel ethanol 1980-2004. Today there is a foreseeable shortage of mineral oil and simultaneously an increasing demand for energy in the industrial countries as well as in a growing number of fast developing countries. Even in Europe the requirements of a sustainable protection of the climate make bio-ethanol an important near-term option to gradually substitute renewable energy sources for fossil ones. The EU bio-fuels directive 2003/30/EG therefore promotes bio-fuels including fuel ethanol, if it is produced from biogenic resources (bio-ethanol). Bioethanol (water free fuel ethanol produced from biogenic resources) can be a substitute of prime importance in fuel blends with gasoline. To reach the EU-directives goal of a renewable bio-fuels share of 5.75%, around 12 billion litres of bio-ethanol will be needed in 2010. As a consequence, the bio-ethanol production in European countries (figure 1, table 2) is expected to increase significantly during the next years. 1

Positive effects of fuel blends of gasoline and ethanol are the substantial improvement in the antiknock resistance and the reduction of motor emissions mainly as far as particles, CO and NOx are concerned. In contrast to gasoline fuels, bio-ethanol contains neither sulfur nor aromatic compounds. The research octane number (RON) of ethanol is around 108. Compared to gasoline fuels (RON around 92-96) it enables a higher engine power whereas its energy content is around 30% lower (Table 1).
Bio-ethanol Heating value [MJ/kg] Heating value [MJ/l] Octane number (RON) Density at 15C [kg/l] Viscostiy at 20C [mm2/s] Oxygen content [%] Fuel equivalent to gasoline 26.8 21.3 108 0.79 1.5 35 0.66 ETBE 36.4 26.9 115-118 0.74 1.5 16 0.83 MTBE 35.0 25.9 113-120 0.74 0.7 18 0.80 Gasoline 42 32 92-96 0.76 0.6 0-2 1.0

Table 1:

Selected fuel properties of bio-ethanol, gasoline and butyl-ethers.

There are long years of experience on the use of bio-ethanol in the transportation sector, esp. in Brazil and in the US. Without technical modifications, gasoline engines can be operated up to blends of 10-20%v/v ethanol. The operation with higher blends or with pure, esp. with hydrous ethanol requires technically modified motors. Throughout the EU, the addition of ethanol to gasoline is limited to 5%v/v by the fuel standard DIN EN 228. Blends of 0 to 5%v/v ethanol, show a vapour pressure anomaly. Especially during the summer months the vapour pressure may exceed the limits of DIN EN 228 (60 kPa). The chemical reaction of ethanol with isobutene, a product of oil refineries, gives ETBE (ethyl-tertiary-butyl-ether). ETBE can be added to gasoline fuels up to 15%v/v according to DIN EN 228. It can be used to substitute MTBE (methyl-tertiary-butyl-ether) which is commonly used to improve the antiknock resistance of unleaded gasoline fuels. As MTBE is supposed to cause serious health risks, ETBE is regarded to be a less harmful substitute. Blends of ETBE and gasoline show no excessive vapour pressure (Table 1). In France, blends of ETBE from bio-ethanol now have been used in the transportation sector for more than 10 years. Since the early nineties, different producers offer flexible-fuel vehicles which can be operated with blends from pure gasoline up to 85% ethanol (E85). The vehicles are equipped with sensors which identify the blending grade of the fuel in order to control and adjust the critical motor operation parameters, like fuel injection, air supply or ignition. Flexible-fuel vehicles meanwhile are very well established in the US. E85 blends are offered at separate gasoline pumps. In Europe, Sweden is performing projects to promote flexible-fuel vehicles since 1995. Projects in other EU countries are on the launching pad, e.g. in Germany. However, the EU member states currently seem to prefer the blending with ETBE. Table 2 shows the typical use of bio-ethanol fuels in selected countries.

Typical fuel use Brazil US Canada France Spain Sweden Germany blends up to E26 E10 and E85 E10 ETBE ETBE E10, E85, E95 ETBE ?

Preferred feedstock sugar cane corn wheat sugar beet, wheat wheat, barley wheat wheat, rye

Estimated fuel ethanol production in 2003 [million litres] around 14 000 10 600 n.a. 125 225 50 startup of first plants in 2004

Table 2:

Use of ethanol based fuels and preferred feedstock crops in selected countries.

The blending of diesel fuels with bio-ethanol has not been commercially experienced in Europe. With an increasing number of diesel engines, this option is currently discussed again, e.g. in Germany. Blending of diesel is supposed to be possible at levels up to 15% with suitable additives. There have been recent commercial experiments in the US, Brazil, Australia, and Sweden, which indicate a reduction of motor emissions, esp. of particles and CO. However, the flashpoint reduction (from >50C to <20C) of these blends is crucial with respect to diesel fuel standards. 3. Feedstock and production pathways According to the state of the art, bio-ethanol is produced by microbiological fermentation of sugar or starch crops. In Brazil, the traditional feedstock is sugar cane, while in the US it is corn. Suitable feedstock crops in the European countries are wheat or sugar beet, but also other grains, like barley or rye. Lignocellulosic biomass can be an option to enlarge the feedstock array considerably. In addition, less costly lignocellulosic wastes from agriculture or forestry, like wood residues or straw can be used. The fermentation of grains offers annual bio-ethanol yields in the range of 1800-2500 litres per hectare. Corn provides up to 3800, while sugar cane and sugar beet provide up to 5600 and 7000 litres. From lignocellulosic feedstock up to 9000 litres can be expected depending on the feedstock type. Sugar crops like sugar cane or sugar beet just have to be crushed and to be extracted with hot water/steam to get aqueous sugar concentrates which can be fermented. Sugar beet or sugar cane based ethanol plants are often connected to sugar factories using molasses for fermentation. Starch crops like corn or various types of grains contain polymerized saccharides which have to be depolymerised by hydrolysis (saccharification) prior to fermentation. Modern ethanol technologies use enzymes for the saccharification. The raw material is prepared by wet or dry milling followed by mashing and cooking with hot water/steam, e.g. by jet cooking at 105150C. The enzymatic saccharification of starch commonly is performed by different amylases as a multi-stage process in the temperature range of about 85-55C. -amylases reduce the viscosity of the mash (liquefaction) while glucoamylases hydrolyse the starch to give fermentable glucose. The fermentation usually is performed by yeasts (Saccharomyces spec.). Yeasts show a high fermentation selectivity as well as a high ethanol tolerance. The main co-product of the fermentation is gaseous CO2 which is produced at equimolar amounts to ethanol. Some producers collect it to sell it for technical purposes. After fermentation, the ethanol is separated from the mash by distillation and rectification. The rectification provides ethanol of 3

about 92-96%v/v quality, which must be dehydrated by e.g. molecular sieves to give anhydrous bio-ethanol (min. 99%v/v). The fermentation residue contains not fermented feedstock material as well as yeasts. Fermentation residues of corn and grains like wheat or rye are called stillage. Stillages are valuable fermentation co-products which can be used as high protein animal feed. Industrial ethanol plants commonly evaporate and dry the stillage. According to its composition it is preferably sold as distillers dried grain (DDG) or distillers dried grain with solubles (DDGS). Alternatively, the stillage can be used to produce energy by the biogas pathway or by combustion of the DDGS. The production of ethanol from sugar and starch crops is technically proven and has been performed in an industrial scale for many years. The conversion of lignocellulosic feedstock, however, needs a distinct treatment in some aspects. Lignocellulose mainly consists of about 40-50% cellulose, 15-35% hemicellulose and 10-30% lignin. These components form a close, partially crystalline compound which is hardly accessible to microbiological degradation. Prior to ethanol fermentation this compound has to be disintegrated and the polysaccharides cellulose and hemicellulose have to be hydrolyzed to give fermentable sugars. Crucial steps are the technical performance of the disintegration and saccharification as well as the fermentation. Former technologies using acid percolation, e.g. the Scholler-process, are considered to be economical not feasible. Advanced technologies propose two staged processes for the feedstock disintegration and saccharification. At the first stage, the feedstock is crushed and the lignocellulosic compound is disintegrated by a chemical or physico-chemical treatment with acids, alkali and/or steam at 100-220C. The subsequent saccharification is performed using acids or enzymes which hydrolyse cellulose and/or hemicelluloses. The enzymatic saccharification is much more selective and less destructive towards the saccharides than the acidic saccharification. However, the saccharification of cellulose requires distinct enzyme types and higher amounts of enzymes than the conversion of starch. This makes the enzymatic hydrolysis of lignocellulose much more expensive. To improve the situation and reduce the costs, current research and development efforts are directed towards an improvement of the catalytic activity and towards less expensive enzyme production technologies. Classical fermentation yeasts are not very well suited for the conversion of lignocellulosic feedstock. Yeasts ferment glucose derived of cellulose but are not able to ferment the main saccharide components of hemicellulose, like xylose or arabinose. However, the fermentation of hemicellulose is important to achieve sufficiently high ethanol yields and good economical performances. During the past decades, biotechnological methods were used to reach this target. Genetically modified bacteria, e.g. E. Coli and Zymomonas mobilis, were successfully engineered which are able to ferment almost all types of saccharides in lignocellulosic feedstock with high yields and high selectivity. However, for a commercial application there are still some crucial hurdles left. The fermentation residues, which contain mainly lignin, can be used as burner fuels to cover the energy demand of the ethanol plant and even produce surplus heat and electricity. The production of bio-ethanol from lignocellulosic feedstock by the enzymatic pathway is now well developed but has not yet been commercially used. The Canadian enzyme producer Iogen Inc. runs a first technical-scaled demonstration plant since 2004. Further industrial scale pilot-plant projects using chemical or enzymatic saccharification are in preparation all over the world. As an alternative to the fermentation pathway, conversion technologies are developed which use thermo-chemical gasification. The product gas can be converted to e.g. methanol in the first stage. In a second step, methanol and the product gas give ethanol via homologation. The main benefit of the thermo-chemical pathway is the conversion of the entire biomass. Even lignin which is not accessible to microbiological fermentation can be converted. 4

However, the subsequent conversion steps require the purification of the raw gas and are affected by side-reactions which lower the product yields. Despite of the high feedstock conversion rate in the gasification step this reduces the overall energy efficiency and the economy of the process. Figure 2 reflects the most important bio-ethanol production pathways from different feedstock crops.

Feedstock
Sugar crops Sugar beet Sweet sorghum Sugar cane

Conversion Pathways and Ethanol Recovery

Crushing Sugar extraction with steam/hot water Rectification Ethanol purification

Co-products
Vinasse Animal feed Bagasse Heat, Electricity

Starch crops Corn Wheat Rye Barley

Wet or dry milling Mashing with hot water/steam

Enzymatic liquefaction and saccharification by amylases

Animal feed, e.g. DDGS (Heat Electricity)

Lignocellulosic feedstock Hardwood Softwood Miscanthus Switchgrass Straw Corn stover Wood residues Verge grass Cellulosic wastes

Crushing Pretreatment - Steam explosion - Acid hydrolysis - Alcaline hydrolysis - NH3 fiber explosion Crushing Themochemical gasification

Acidic saccharification

Fermentation

Lignin Heat , Electricity CaSO4 (Animal feed)

Enzymatic saccharification by cellulases

Production of Methanol

Homologation and ethanol recovery

Heat Electricity

Figure 2: Production pathways of bio-ethanol from various feedstock. Compared to the fermentation of starch and sugar crops, the conversion of lignocelluloses offers important benefits, esp. concerning the feedstock availability. On the other hand, the enzymatic as well as the thermo-chemical pathway require much more sophisticated conversion technologies than traditional sugar or starch fermentation pathways. 4. Energetic, economical and ecological aspects The fermentation pathways require thermal energy, esp. steam, for feedstock pre-treatment, rectification and for evaporation and drying of the fermentation residues. Modern conversion processes are highly optimized and their energy consumptions are minimized. Multi-staged evaporators and heat recovery systems serve to reduce the remaining need of energy. However, extensive heat recovery systems enhance the costs for investments and maintaining of the ethanol plant. Therefore, an individual balance has to be found between the costs of heat recovery and of energy consumption. The overall production chain also requires energy for the supply of the feedstock and for the distribution of the fuel ethanol. This means for cultivation, harvesting, transportation, and storage. The ratio between energy output (fuel ethanol) and fossil energy input of the overall process is reported to be in the range of 0.95-3.2 for advanced corn, grain, and sugar beet processing. The efficiency preferably depends on the feedstock type and on the assumptions of credits for co-products, e. g. stillage, of the conversion process. Without co-product credits, the ratio is in the range of 0.95-1.8 while it is around 1.2-3.2 including co-product credits. For gasoline it is around 0.79. For sugar cane processing in Brazil the input of fossil energy is considerably low, as usually bagasse is used to produce process heat and 5

electricity. Recent studies report energy efficiencies in the range of 8-10. The efficiency of corn or grain processing also could be improved significantly, if feedstock or fermentation residues were used to provide process heat and electricity by combustion or by biogas production. However, currently the production of animal feed from stillage is still of economical preference. The situation may change e.g. with raising costs for burner fuels and enhanced benefits for biomass derived electricity. Lignocellulosic ethanol engineering studies commonly assume the use of feedstock residues (lignin) and of biogas from internal waste water treatment to cover the energy demand of the ethanol plant. Therefore, fossil energy efficiencies in the range of Brazilian cane processing or even higher may be reached. The production costs of bio-ethanol mainly depend on the plant capacity, the type of feedstock used and on the location. As a consequence of the economy of scale, industrial fuel ethanol plants today are preferably designed for annual production capacities of more than 100 million litres. Table 3 shows an estimation of the average production costs of industrial scaled plants for Europe and the US. Estimations for industrial fuel ethanol plants in Europe given by different authors differ very much, as plant size, location properties, and feedstock costs also differ considerably.
Europe Feedstock Wheat Rye * (Germany) gas / coal 60-260 383 0.24-0.26 Sugar beet US Lignocellulosic feedstock** Corn near-term Poplar wood (NREL 1999) residue (lignin) 198 283 0.097 $ 0.282 $ 0.019 $ 0.36 $ 0.55 $ start up 2010 Corn stover (NREL 2002) residue (lignin) 262 318 0.088 $ 0.219 $ 0.025 $ 0.282 $ 0.43 $

Process energy supply Ethanol capacity [Million litres per year] Ethanol yield [litres per Mg feedstock] Feedstock costs per litre ethanol Operating costs per litre ethanol Co-product benefits per litre ethanol Total production costs per litre ethanol Total production costs per litre gasoline equivalent

gas / coal > 50 345-385 0.24-0.34 0.19-0.27

gas / coal > 50 100 0.20-0.44 0.20-0.24

gas / coal > 50 370-470 0.22 $ 0.17 $ 0.09 $ 0.30 $ 0.46 $

0.25-0.31 0.06 0.41-0.60 0.62-0.91 0.49-0.55 0.74-0.83 0.03-0.07 0.40-0.62 0.64-0.94

* Source: Schmitz, N., Bioethanol in Deutschland (2003) ** Source: International Energy Agency IEA (2004), US-National Renewable Energy Laboratory NREL (2002)

Table 3:

Average cost estimations for the production of fuel ethanol by the fermentation pathway in industrial scale plants (data of different studies).

The production from sugar or starch crops is strongly influenced by the feedstock costs, which make about 50-70% of the total costs at industrial scale plants. The operating costs are mainly dominated by capital and energy costs. Due to higher costs of feedstock, energy, and capital recovery, the production from grain in Europe is currently more expensive than from corn in the US. Co-product credits can be achieved by selling DDGS or surplus electricity generated by internal heat and power stations. The average conversion costs for sugar beet are somewhat lower than for grain, but the average feedstock costs are expected to be higher. Some amounts of low price beet may be supplied from surplus production for the sugar industries. Compared to the Europe and the US, ethanol can be produced at much lower costs (around 0.2 /l) from sugar cane in Brazil, due to extremely low feedstock and operation costs. The process energy is covered using the co-product bagasse as burner fuel. As a consequence, without import taxes the production of fuel ethanol in Europe could hardly compete with Brazilian ethanol. Actually the price of Brazilian ethanol in Europe is a result of the market price in Brazil, the additional cost for over seas transportation (around 0.05 /l) and the 6

import taxes (0.1 /l). In the recent years, the resulting price was fluctuating in the range of 0.340.42 /l. For the processing of lignocellulosic feedstock there are only estimations available derived from theoretical calculations mainly based on small scale pilot plants. The data presented in Table 3 refer to the fermentation pathway. They are derived from studies of the International Energy Agency and the US National Renewable Energy Laboratory NREL. The near term perspective of 1999 for the feedstock poplar wood estimates production costs in the US of about 0,36 $/l at plant capacities of about 200 million litres per year. The NREL study of 2002 refers to corn stover and to a further optimized plant design with reduced operating costs. Compared to the production from corn in the US, the operating costs for lignocellulosic biomass are supposed to be higher, due to the more complex conversion technology. In contrast, the feedstock costs are supposed to be much lower. This may be feasible, using residual material from agriculture or forestry. Similar to the sugar cane processing in Brazil, the energy demand of the ethanol plant is expected to be covered by the combustion of fermentation residues, and surplus electrical energy is supposed to be sold. The 2010 scenario assumes further improvements in the conversion technology and in the enzyme production, which lead to higher ethanol yields, reduced operating costs, and enhanced coproduct credits. It has to be pointed out, that these estimations still have not been proven on a technical scale. Cost assessments of NREL and IEA for the next decades even estimate production costs of less than 0,2 $/l, assuming cost reduction effects of commercialization (nth plant) and of further optimized conversion technologies. However, up to now it is still uncertain if the assumed costs of the near term scenarios actually can be realised. Per litre gasoline equivalent, the production costs of European grain or sugar beet ethanol are in the range of about 0.62-0.91 . Without taxation, bio-ethanol therefore can be supposed to be competitive to gasoline fuels. Well-to-wheel studies estimate the effects of renewable fuels on greenhouse gas reduction compared to fossil fuels. The studies reflect the net impact of greenhouse gases of the entire life cycle including feedstock and fuel production as well as fuel distribution and consumption per km of vehicle driven. Crucial points of bio-ethanol well-to-wheel studies are usually the consumption of fossil energy and the assumption of co-product credits, i.e. the greenhouse gas reduction potentials of co-products like animal feed. The greenhouse gases generally considered for the estimation of the global warming potential (GWP) are CO2, N2O and CH4.

Lignocellulosic feedstock Sugar beet Rye

min
Wheat Corn

max

0%

20%

40%

60%

80%

100%

120%

Reduction of global warming potential (CO2 equivalent) compared to gasoline

Figure 3: Well-to-wheel green house gas emissions of (fermentation) fuel ethanol from various feedstock crops: estimated reduction of global warming potential compared to gasoline fuels. The base line (0%) refers to gasoline.

The net emission of CO2 mainly depends on the amounts of fossil energy consumed for the feedstock and ethanol production as well as for the product distribution. Emissions of N2O are preferably emitted from the agricultural crop production and therefore are usually higher for fuels derived from agricultural feedstock than for fossil fuels. Other gases which are known to affect the climate are NOx, CO or non methane organic compounds. They are emitted from combustion processes, e.g. from the generation of process heat or from vehicle operation. Figure 3 shows the average net reduction potentials which are expected for fuel bio-ethanol from various feedstock crops. It indicates that fuel ethanol from biomass can provide a significant reduction of the global warming potential compared to gasoline. Fuel ethanol from sugar and starch crops, which is produced using fossil fuels (e.g. gas or coal) for the generation of process heat, is expected to provide a reduction of up to 65%. The fermentation of lignocellulosic biomass is assumed to provide a reduction potential of 50% to more than 100%, as the process heat and even surplus energy is supposed to be generated from fermentation residues. 5. Conclusion The use of bio-ethanol as a transportation fuel offers a significant reduction potential of green house gas emissions from the transportation sector. Fuel ethanol therefore can be a powerful near-term option to hit GWP-reduction targets. However, current production costs of bioethanol in Europe and in the US are still much higher than of (tax free) gasoline and tax breaks are required to make bio-ethanol able to compete on the fuel market. For the processing of corn, grain or sugar crops, no technical breakthroughs and therefore no significant cost reductions can be expected in the next couple of years. In addition, with an increasing global population, excessive agricultural production of grain or sugar crops for fuel may lead to future food or fuel conflicts. The processing of lignocellulose provides the option to enlarge the feedstock array and to reduce feedstock costs by processing agricultural and forestry wastes. Set aside land can also be used for dedicated cellulosic crop cultivation. First cellulosic ethanol pilot plants are now in operation and their actual performances have to be studied. Further technical and biotechnical improvements are to be expected or under development. On the long term, the success of bio-ethanol for transportation will depend on the economical competition with other bio-fuels as well as on future vehicle concepts. 6. References English Aden, A., et. al., Lignocellulosic Biomass to Ethanol Process Design and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic Hydrolysis for Corn Stover, National Renewable Energy Laboratory NREL, USA, Technical Report NREL/TP-510-32438 (2002) Badger, P. C., Ethanol from Cellulose: A General Review, in: Trends in New Crops and New Uses, Eds: J. Janick and A. Whipkey, ASHS Press, Alexandria, VA, (2002), 17 De Carvalho Macedo, I., et. al., Greenhouse Gas Emissions in the Production and Use of Ethanol in Brazil: Present Situation (2002), (2003) International Energy Agency, Biofuels for Transport - An International Perspective, Publication of the International Energy Agency IEA, Paris, (2004), ISBN 92 64 01 51 24 F.O. Lichts, World Ethanol and Fuels Report, (2003 and 2004) General Motors, et. al., GM Well-to-Wheel Analysis of Energy Use and Greenhouse Gas Emissions of Advanced Fuel/Vehicle Systems A European Study, (2002) 8

Kosaric, N., Duvnjak, Z., Ethanol; Ullmanns Encyclopedia of Industrial Chemistry, Vol. A9 McCormick, R., Parish, R., Milestone Report: Technical Barriers to the Use of Ethanol in Diesel Fuel, National Renewable Energy Laboratory NREL, USA, Milestone Report NREL/MP-540-32674 (2001) Roehr, M. (Ed.), The Biotechnology of Ethanol Classical and Future Applications, WileyVCH, Weinheim (2001), ISBN 3-527-30199-2 Shapouri, H., Duffield, J. A., Wang, M., The Energy Balance of Corn Ethanol: An Update, US Department of Agriculture, Agricultural Economic Report Number 813 (2002) Sheehan, J., Himmel, M., Enzymes, Energy and the Environment: A Strategic Perspective on the U.S. Department of Energys Research and Development Activities for Bioethanol, Biotechnol. Prog. 15 (1999), 817 Sheehan, J., et. al., Energy and Environmental Aspects of Using Corn Stover for Fuel Ethanol, Journal of Industrial Ecology, Vol. 7/3-4 (2004), 117 Ward, O. P., Singh, A., Bioethanol Technology: Developments and Perspectives, Advances in Applied Microbiology 51 (2002), 53 Wyman, C. E., Ethanol from Lignocellulosic Biomass: Technology, Economics, and Opportunities, Bioresource Technology 50 (1994) 3 Wyman, C. E., Twenty Years of Trials, Tribulations and Research Progress in Bioethanol Technology, Applied Biochemistry and Biotechnology 91-93 (2001), 5 Zaldivar, J., et. al., Fuel ethanol production from lignocellulose: a challenge for metabolic engineering and process integration, Appl. Microbiol. Biotechnol. 56 (2001), 17 German Hartmann, H., Kaltschmitt, M., Biomasse als erneuerbarer Energietrger, Schriftenreihen Nachwachsende Rohstoffe Bd.3, Landwirtschaftsverlag, Mnster, (2002), ISBN 3-78433197-1 Schmitz, N., Bioethanol in Deutschland, Schriftenreihe Nachwachsende Rohstoffe, Band 21, Landwirtschaftsverlag, Mnster, (2003) Schmitz, N., Innovationen bei der Bioethanolerzeugung, Schriftenreihe Nachwachsende Rohstoffe, Band 26, Landwirtschaftsverlag, Mnster, (2005) Wagner, U., Igelspacher, R., Ganzheitliche Systemanalyse zur Erzeugung und Anwendung von Bioethanol im Verkehrssektor, Landtechnische Berichte aus Forschung und Praxis Gelbes Heft 76, Bayerisches Staatsministerium fr Landwirtschaft und Forsten, Mnchen, (2003) Internet Alternative Fuels Data Center, website of the US-Department of Energy, www.eere.energy.gov/afdc/ Berg, C., World Fuel Ethanol Analysis and Outlook, (2004), www.distill.com/World-FuelEthanol-A&O-2004.html Website of the American Coalition for ethanol, (2005), www.ethanol.org Website of the BioAlcohol Fuel Foundation, rnskldsvik, Sweden, (2005), www.baff.info Website of the Iogen Corporation, Ottawa, Canada, (2005), www.iogen.ca