Volume 5 biomass and biofuel production 5 02 – historical perspectives on biofuels

Volume 5 biomass and biofuel production 5 02 – historical perspectives on biofuels Volume 5 biomass and biofuel production 5 02 – historical perspectives on biofuels Volume 5 biomass and biofuel production 5 02 – historical perspectives on biofuels Volume 5 biomass and biofuel production 5 02 – historical perspectives on biofuels Volume 5 biomass and biofuel production 5 02 – historical perspectives on biofuels Volume 5 biomass and biofuel production 5 02 – historical perspectives on biofuels Volume 5 biomass and biofuel production 5 02 – historical perspectives on biofuels

5.02 Historical Perspectives on Biofuels G Knothe, USDA Agricultural Research Service, Peoria, IL, USA Published by Elsevier Ltd 5.02.1 5.02.2 5.02.3 5.02.4 Conclusion References Introduction Early Engine Developments Ethanol Vegetable Oil-Based Fuels 11 11 11 12 13 14 5.02.1 Introduction The Industrial Revolution of the nineteenth century was to a significant degree enabled by the development of mechanized energy, that is, the development of engines that could perform work previously performed by human or animal labor, or, in some cases, replace a natural resource, for example, wind, to power ships A major use of these engines was in transportation, for the more efficient, that is, time- and labor-saving, overcoming of great distances While originally the steam engine was practically the only choice for the various applications, within a few decades other engines were developed The most salient was the internal-combustion engine, of which two major versions came to exist This chapter summarizes research results and commercial development of fuels derived from agricultural sources used to power these engines in ‘historical’ times up to around World War II It relies heavily on previously published accounts on the history of ethanol [1] and vegetable oil-based diesel fuels and biodiesel [2, 3] Many additional references and details are available by referring to these chapters A list of relevant technical chapters has also been compiled [4] Another account of ethanol and vegetable oil fuels is also available [5] 5.02.2 Early Engine Developments While experiments with what could be considered forerunners of the internal-combustion engine were already conducted in the sixteenth and seventeenth centuries, the first version of an internal-combustion engine was apparently developed by the American inventor Samuel Morey (1762–1843) and was discussed in several articles in the American Journal of Science [1] A few decades later, in the early 1860s, the four-stroke version of the internal-combustion engine was developed by the German inventor Nikolaus August Otto (1832–91) in collaboration with the mechanic Michael Joseph Zons [6, 7], giving rise to what is now termed the spark-ignition (or gasoline) engine (also called the Otto engine) The Otto engine was apparently the first practical four-stroke engine, while, for example, the internal-combustion engine developed in 1859 by the Belgian inventor Étienne Lenoir (1822–1900) was a two-stroke engine Another few decades later, another version of the internal-combustion engine, the compression-ignition engine, usually called the diesel engine after its inventor Rudolf Diesel (1858–1913), was developed Both the internal-combustion engines commonly utilize products derived from petroleum: the spark-ignition engine using gasoline (petrol) and the diesel engine using diesel fuel These are hydrocarbon fuels with the main differences to be found in the structure of the compounds comprising them Gasoline (petrol) preferably contains lighter branched compounds, exemplified by isooctane, the compound which gives the octane scale its name and is actually 2,2,4-trimethylpentane Diesel fuel, on the other hand, preferably consists of long, straight-chain hydrocarbons, exemplified by hexadecane, the trivial name of which is cetane, providing the name to the cetane scale used for rating the ignition quality of diesel fuel However, as discussed here, other fuels derived from a variety of biomass feedstocks are also suitable 5.02.3 Ethanol Thus, within a few years of their development, different kinds of fuels were being tested for both kinds of internal-combustion engines One of the fuels of prime interest from the early days of the spark-ignition engine was ethanol, derived from fermentation of various biomass materials This observation has an additional interesting aspect as Eugen Langen (1833–95), a German inventor and entrepreneur who partnered with Otto to find the first company commercializing the internal-combustion engine, also was involved with a sugar refinery owned by his family [8, 9] Otto apparently used alcohol as a fuel when first developing the engine [1] In the case of the diesel engine, Diesel himself discusses the variety of fuels tested in ‘his’ engine [10–12] The finite nature of petroleum-based fuels was already noted at that time and agriculturally derived fuels were recognized as renewable alternatives This observation served as an incentive to promote renewable fuels from agricultural feedstocks Accordingly, significant research efforts were devoted to alcohol fuels for spark-ignition engines and vegetable oil-based fuels for diesel engines in the years through World Comprehensive Renewable Energy, Volume doi:10.1016/B978-0-08-087872-0.00502-3 11 12 Biomass and Biofuels War II In the years after World War II, with petroleum available abundantly and cheaply, research on alternative fuels was largely dormant until the fuel crises of the 1970s and early 1980s rekindled interest in renewable fuels As mentioned above, Otto reportedly used ethanol as fuel to power ‘his’ engine This was probably straightforward as it appears that ethanol could not be considered an ‘alternative’ fuel [1] at that time Petroleum, which would become a major source of energy powering world economies in the decades to come, especially after the discovery in Pennsylvania in 1859 (although petroleum was known prior to this event) by Edwin Drake (1819–80), was emerging as an energy source, while ethanol as fuel, for example, for lighting purposes, was already well known, especially a mixture called ‘camphene’ consisting of ethanol with turpentine and a small amount of camphor oil [1] Such mixtures with ethanol had gradually replaced whale oil as lamp fluid In the United States, a heavy tax of $2.08 per gallon gradually imposed on ethanol during the American Civil War (1861–65) was apparently a major contributing factor to the rise of the petroleum industry, as the latter benefited from not being subject to this tax [1] This tax was abolished in 1906 In European countries, concerns about the security of the petroleum supply existed from the very beginning, which is why countries such as France, Germany, and Great Britain promoted the utilization of ethanol Engines were designed to run on both gasoline and ethanol and some engines were even designed to run on pure ethanol In Germany, tariffs were imposed on petroleum imports and a ‘Centrale für Spiritus-Verwerthung’ was in charge of regulating the ethanol market It has been stated that the adaptation of vehicles in Germany to run on ethanol may even have prolonged World War I [1] Most research regarding ethanol showed that it was a satisfactory fuel, often even stated to be superior to gasoline [1], and most certainly played a role in promoting its use Engine knock did not occur with ethanol or ethanol–gasoline blends as fuel Fuel economy could be improved by adjusting the compression ratio of the engine, largely overcoming the lower energy content of ethanol versus gasoline Overall, efficiency was stated to be equal or superior to gasoline It was also stated that the use of ethanol was cleaner than that of gasoline, with specific notice that the exhaust was clearer when operating an engine on ethanol instead of gasoline Some problems such as separation of ethanol and gasoline or cold start could be overcome by the use of ‘binders’ or starting assist agents such as ether Stability of alcohol–gasoline blends in the presence of water was noted but not seen as a major problem if tank cleanliness, and so on, was ensured The competition with petroleum, however, led interests related to this energy source to continuously state that ethanol was an inferior fuel [1] In the United States, however, the lifting of the aforementioned heavy tax on ethanol did not cause the expected revival of the fuel ethanol market Ethanol derived from feedstocks such as potatoes or grain was more expensive than gasoline as more petroleum fields were coming online in locations such as Texas On the other hand, alcohol from molasses was less expensive, with collusion between petroleum companies and the Caribbean alcohol market suspected by some contemporaries [1] The competition between alcohol and petroleum manifested itself in the following years in other respects While it was well known at the time that blending ethanol with gasoline alleviated engine knock, eventually the additive tetraethyl lead was used for this purpose in gasoline, largely due to a switching of positions around 1923 or 1924 of two researchers in industry, Thomas Midgley (1889–1944) and Charles Kettering (1876–1958) [1] The background for this was originally to provide a ‘bridge’ across the perceived gap between petroleum-based fuels becoming exhausted and renewable fuels becoming available in sufficient quantities Studies on the health effects of leaded gasoline were not discussed or were suppressed However, eventually due to health concerns, leaded gasoline was banned in the United States in 1986 With the exception of the United States, in the 1920s and 1930s ethanol was blended with gasoline in every industrialized nation [1] In European countries, ethanol was obtained from potatoes, grapes, and other crops, while elsewhere sugarcane and molasses served among the primary feedstocks The use of ethanol was promoted through mandatory blending or tax incentives in many countries In some locations, ethanol was less expensive than imported gasoline The aspect of energy security played a major role in these actions promoting the use of ethanol as did the issue of providing income to the agricultural sector by utilizing surplus crops However, in the years shortly before and during World War II, ethanol production decreased due to production changing to ammunition and vanishing crop surpluses Despite this development, some isolated efforts to commercialize ethanol–gasoline blends occurred in the United States in the 1930s, mainly in the Midwest [1] Legislative proposals to promote the cause of ethanol were unsuccessful This eventually merged in the farm chemurgy movement of the 1930s, the goal of which was to lead to industrial products from agricultural feedstocks and was supported by Henry Ford (1863–1947) This reemergence of ethanol–gasoline blends was met by opposition from the petroleum industry 5.02.4 Vegetable Oil-Based Fuels The competition mentioned above between a petroleum-derived fuel and a fuel derived from biomass appears to be less noticeable in the literature regarding diesel engines and diesel fuel It may be surmised that a major reason for this is the supply issue as considerably less vegetable oil was available for petrodiesel replacement and often vegetable oils were considered for more remote locations It may also be interesting to note that while Otto was inspired to work on what was to become the four-stroke internal-combustion engine by hearing about the work of Lenoir, Diesel was inspired to develop his engine as an efficient alternative to the steam engine originally through lectures in thermodynamics at what is now the Technical University of Munich In his book Die Entstehung des Dieselmotors [11], Diesel describes experiments with various liquid fuels, most of them petroleum-type or petroleum-derived fuels Interestingly, he also describes experiments conducted with alcohol Due to water Historical Perspectives on Biofuels 13 content and lower energy content, several adjustments were needed to have the engine run on 90% alcohol for an extended period of time with energy output identical to that of petroleum On the other hand, vegetable oils, the alkyl esters of which are now alternative fuels as biodiesel, were not originally investigated by Diesel Rather, on page 115 of his book [11], Diesel addresses the use of vegetable oils as a fuel (translated): For sake of completeness it needs to be mentioned that already in the year 1900 plant oils were used successfully in a diesel engine During the Paris Exposition in 1900, a small diesel engine was operated on a rachide (peanut) oil by the French Otto company It worked so well that only a few insiders knew about this inconspicuous circumstance The engine was built for petroleum and was used for the plant oil without any change In this case also, the consumption experiments resulted in heat utilization identical to petroleum Similar to the background for promoting the use of ethanol, the background in the papers by Diesel [10, 12] on using vegetable oils was to provide European tropical colonies, especially those in Africa, with a certain degree of energy self-sufficiency This pattern of energy independence can be found in the related literature throughout the 1940s Palm oil was often considered as a feedstock in historic times, although feedstock diversity was reflected in other historic investigations Vegetable oils were also used as emergency fuels and for other purposes during World War II in countries such as Argentina, Brazil, China, and India In the United States, some post-World War II research programs dealt with vegetable oil fuels, also inspired by concerns over the rising use of petroleum fuels and the possible resulting shortages Many different feedstocks were used in historic times as vegetable oil fuels Besides palm oil, these included soybean, cottonseed, castor, babassu, groundnut, and raisinseed oil, and many others as well as non-vegetable sources such as industrial tallow and even fish oils In modern times, biodiesel is derived or has been reported to be producible from many different sources including vegetable oils, animal fats, used frying oils, and even soapstock Generally, factors such as geography, climate, and economics determine which vegetable oil is of most interest for potential use in biodiesel fuels Thus, presently in the United States, soybean oil is considered as a prime feedstock; in Europe, it is rapeseed (canola) oil; and in tropical countries, it is palm oil In parallel to the present, many historic publications discuss the satisfactory performance of vegetable oils as fuels or fuel sources although it is often noted that their higher costs relative to petroleum-derived fuel would prevent widespread use The high viscosity of vegetable oils in comparison with petrodiesel was noted and the formation of engine deposits ascribed to this property Reducing the high viscosity of vegetable oils was usually achieved by heating the vegetable oil fuel Often the engine was started on petrodiesel and after a few minutes of operation switched to the vegetable oil fuel The performance of the vegetable oil fuels was generally satisfactory, but power output was reportedly slightly lower than with petroleum-based diesel fuel and fuel consumption was slightly higher, although engine load-dependent or opposite effects were reported It is mentioned in many publications that the diesel engines used operated more smoothly on vegetable oils than on petroleum-based diesel fuel Fuel quality issues were also addressed; for example, it was suggested to keep the acid content at a minimum and the effects of different kinds of vegetable oils on metal corrosion and lube oil dilution were studied Similar to the observations when running engines on ethanol, it was observed that the exhaust appeared cleaner when running an engine on vegetable oil instead of petrodiesel Pyrolysis, cracking, or other methods of decomposition of vegetable oils to yield fuels of varying nature account for a significant amount of the literature in historic times with artificial ‘gasoline’, ‘kerosene’, and ‘diesel’ being obtained from various oils such as tung oil, fish oils, and linseed, castor, palm, cottonseed, and olive oils The other approaches to reducing the high viscosity of vegetable oils [13] – dilution with petrodiesel and, especially, microemulsification – appear to have received little attention during the historic times In one case, ethanol was used for improving the atomization and combustion of highly viscous castor oil Besides powering vehicles, the use of vegetable oils for other related purposes found some attention These uses included lubricating oils and greases as well as heating and power purposes In 1938, it was recommended [14] that to obtain the best value from vegetable oil fuels it would be necessary to cleave the triglycerides and use residual fatty acid, but problems with free fatty acids as fuel were anticipated On the other hand, the glycerides were seen as not possessing fuel value, but rather causing excess deposits A step beyond Walton’s statement is the first reports on what is now termed biodiesel A Belgian patent, No 422,877, was granted on 31 August 1937 to C G Chavanne [15] and probably constitutes the first report on what is today known as biodiesel It describes the use of ethyl esters of palm oil (although other oils and methyl esters are mentioned) as diesel fuel These esters were produced by acid-catalyzed transester­ ification of the oil (base catalysis is now more common) The work conducted in Belgium and the Belgian Congo has been described in more detail [16, 17] It was mentioned that a bus fueled with palm oil ethyl ester served the commercial passenger line between Brussels and Louvain (Leuven) in the summer of 1938 It was noted that the viscosity difference between the esters and conventional diesel fuel was considerably less than that between the parent oil and conventional diesel fuel It was also pointed out that the esters are miscible with other fuels and probably the first cetane number testing of a biodiesel fuel was discussed Conclusion This chapter summarizes the history through the 1940s of biomass-derived fuels, particularly ethanol as replacement for gasoline and vegetable oil-derived diesel fuels, including biodiesel, as replacement for petroleum-derived diesel fuels In summary, ‘alter­ native’ fuels are not a new concept Many technical insights obtained in historic times on the properties of these fuels have been 14 Biomass and Biofuels proven to be correct The background issues for using these fuels, namely, obtaining them from renewable, domestic feedstocks to provide energy security as well as supporting the agricultural economy, are also more current than ever Disclaimer: Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the US Department of Agriculture (USDA) USDA is an equal opportunity provider and employer References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] Kovarik W (1998) Henry Ford, Charles Kettering and the “Fuel of the Future” Automotive History Review 32: 7–27 Knothe G (2001) Historical perspectives on vegetable oil-based diesel fuels Inform 12: 1103–1107 Knothe G (2010) The history of vegetable oil-based diesel fuels In: Knothe G, Van Gerpen J, Krahl J (eds.) The Biodiesel Handbook, 2nd edn Urbana, IL: AOCS Press Wiebe R and Nowakowska J (1949) The technical literature of agricultural motor fuels USDA Bibliographic Bulletin No 10 pp 183–195 Washington, DC: US Department of Agriculture Songstad DD, Lakshmanan P, Chen J, et al (2009) Historical perspective of biofuels: Learning from the past to rediscover the future In Vitro Cellular and Developmental Biology Plant 45: 189–192 Feldhaus FM (1906) Otto, Nicolaus August Allgemeine Deutsche Biographie 52: 734–735 Graf von Seherr-Thoß HC (1998) Otto, Nicolaus August Neue Deutsche Biographie 19: S700–S702 Feldhaus FM (1907) Langen, Eugen Allgemeine Deutsche Biographie 53: S769–S770 Goldbeck G and Reuß H-J (1982) Langen, Eugen Neue Deutsche Biographie 13: 571–573 Diesel R (1912) The diesel oil-engine Engineering 93: 395–406 Chemical Abstracts 6: 1984, 1912 Diesel R (1913) Die Entstehung des Dieselmotors Berlin, Germany: Verlag von Julius Springer Diesel R (1912) The diesel oil-engine and its industrial importance particularly for Great Britain Proceedings of the Institution of Mechanical Engineers 179–280 Chemical Abstracts 7: 1605, 1913 Schwab AW, Bagby MO, and Freedman B (1987) Preparation and properties of diesel fuels from vegetable oils Fuel 66: 1372–1378 Walton J (1938) The fuel possibilities of vegetable oils Gas Oil Power 33: 167–168 Chemical Abstracts 33: 8336, 1939 Chavanne CG Procédé de transformation d’huiles végétales en vue de leur utilisation comme carburants (Procedure for the transformation of vegetable oils for their uses as fuels) Belgian Patent 422,877, 31 August 1937 Chemical Abstracts 32: 43132, 1938 Chavanne G (1943) Sur un mode d’utilization possible de l’huile de palme la fabrication d’un carburant lourd (A method of possible utilization of palm oil for the manufacture of a heavy fuel) Bulletin des Sociétés Chimiques 10(52): 58 Chemical Abstracts 38: 21839, 1944 van den Abeele M (1942) L’huile de palme: Matière première pour la préparation d’un carburant lourd utilisable dans les moteurs combustion interne (Palm oil as raw material for the production of a heavy motor fuel) Bulletin of Agriculture Congo Belge 33(3): 90 Chemical Abstracts 38: 28051, 1944  ... describes experiments conducted with alcohol Due to water Historical Perspectives on Biofuels 13 content and lower energy content, several adjustments were needed to have the engine run on 90% alcohol... Biographie 52 : 73 4–7 35 Graf von Seherr-Thoß HC (1998) Otto, Nicolaus August Neue Deutsche Biographie 19: S700–S 702 Feldhaus FM (1907) Langen, Eugen Allgemeine Deutsche Biographie 53 : S769–S770 Goldbeck... feedstocks and was supported by Henry Ford (186 3–1 947) This reemergence of ethanol–gasoline blends was met by opposition from the petroleum industry 5. 02. 4 Vegetable Oil-Based Fuels The competition mentioned