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The reaction. Currently, the preferred alcohol is (R = CH3).

This article is by Gerhard Knothe of through a Chemical Abstracts search Historical the U.S. Department of ’s or are listed in a publication summariz- National Center for Agricultural ing literature prior to 1949 on fuels Utilization Research in Peoria, Illinois. from agricultural sources (1). After the perspectives 1940s, literature on vegetable -based , defined as monoalkyl esters diesel fuels is very sparse until the late on vegetable of vegetable oils or animal (Scheme 1970s. Although discussed later in this 1), is a promising for use article in more detail, two references in compression-ignition (diesel) engines (2,3) describing the first use of a -based and is being produced or used commer- meeting the current definition of cially in numerous countries around the biodiesel are worth close examination. diesel fuels world, including the , Austria, the Czech Republic, France, T HE ORIGINAL Germany, Italy, Malaysia, and Sweden. DEMONSTRATION It is generally known that vegetable A relatively common literature state- oils were tested as diesel fuels well ment on the early use of vegetable oils before the energy crises of the 1970s as diesel fuels is that , the and early 1980s generated renewed inventor of the engine that bears his interest in alternative fuels, but details name, tested “his” engine on on the first uses (until the early 1950s) at the 1900 World’s Fair in , the are often unclear or presented inconsis- Exposition Universalle. A biography of tently in the literature. Valuable insights Diesel by Nitske and Wilson (4) often is into the use of vegetable oils and their cited as a source. On page 139 of that derivatives as diesel fuels were achieved biography, the statement is made that during that time, only to be rediscov- “as the nineteenth century ended, it was ered beginning in the late 1970s. This obvious that the fate and scope of the article will discuss the history of internal- engine were depen- R. Diesel biodiesel or, more generally, that of veg- dent on its fuel or fuels. At the Paris etable oil-based diesel fuels and corre- exposition of 1900, a , late it with current use. Most literature built by the French Otto Company, ran references used here were found wholly on peanut oil. Apparently none

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of the onlookers was aware of this. The few years of his life, Diesel spent con- time, reliable figures obtained by tests: engine, built especially for that type of siderable time traveling to promote and Consumption of earth- oil, 240 fuel, operated exactly like those pow- to discuss his engine, according to the grammes (0.53 lb.) per brake horse- ered by other oils.” biography by Nitske and Wilson). In power-hour; calorific power of the oil, Unfortunately, the bibliography in any case, Diesel states in those papers 8600 calories (34,124 British thermal that biography (4) does not clarify that “at the Paris Exhibition in 1900 units) per kg, thus fully equal to oils; 11.8 per cent. This oil is almost as effective as the natural miner- al oils, and as it can also be used for In any case, they make it certain lubricating oil, the whole can be that motor-power can still be produced carried out with a single kind of oil pro- from the heat of the sun, duced directly on the spot. Thus this which is always available for agricultural purposes, engine becomes a really independent even when all our natural stores engine for the tropics.” of solid and fuels are exhausted. Diesel continued that (note the pre- —Diesel scient concluding statement) “similar successful experiments have also been made in St. Petersburg with ; and animal oils, such as train-oil, have where the authors obtained this infor- there was shown by the Otto Company been used with excellent results. The mation nor does it list references to cer- a small Diesel engine, which, at the fact that oils from vegetable sources tain articles by Diesel that will be dis- request of the French Government, ran can be used may seem insignificant to- cussed later in this paper. Thus, accord- on Arachide (earth-nut or pea-nut) oil, day, but such oils may perhaps become ing to Nitske and Wilson, the peanut and worked so smoothly that only very in course of time of the same impor- oil-powered diesel engine at the 1900 few people were aware of it. The engine tance as some natural oils and World’s Fair in Paris was built specifi- was constructed for using , the tar products are now. Twelve years cally to use that fuel, which is not con- and was then worked on ago, the latter were not more developed sistent with later statements by Diesel, without any alterations being made. than the fat oils are today, and yet how as discussed below. Furthermore, that The French Government at the time important they have since become. One biography implies that it was not neces- thought of testing the applicability to cannot predict what part these oils will sarily Diesel who conducted the demon- power production of the Arachide, or play in the Colonies in the future. In stration and that he was not the source earth-nut, which grows in considerable any case, they make it certain that of the idea of using vegetable oils as quantities in their African colonies, and motor-power can still be produced fuel. This interpretation is corroborated which can be easily cultivated there, from the heat of the sun, which is by Diesel’s later statements. The idea for because in this way the colonies could always available for agricultural pur- using peanut oil appears to have origi- be supplied with power and poses, even when all our natural stores nated instead within the French govern- from their own resources, without being of solid and liquid fuels are exhaust- ment, according to Diesel. However, compelled to buy and import or ed.” Diesel conducted related tests in later liquid fuel. Diesel also wrote the Die years. “This question has not been further Entstehung des Dieselmotors, published A Chemical Abstracts search yielded developed in France owing to changes by Verlag von Julius Spring, , in references to papers by Diesel in which in the Ministry, but the author resumed 1913, in which he referred to the use of he reflected on that event in 1900. Two the trials a few months ago. It has been peanut oil in a diesel engine at the Paris references (5,6) related to a presentation proved that Diesel engines can be World’s Fair in 1900. However, the Diesel made to the Institution of worked on earth-nut oil without any statements in that book are consider- Mechanical (of Great Britain) difficulty, and the author is in a position ably less detailed than those in the other in March 1912 (apparently in the last to publish, on this occasion for the first two references (5,6).

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B A CKGROUND AND SOURCES Concerns about the rising use of as well as nonvegetable sources such as The aforementioned background on fuels and the possibility of industrial (17) and even fish oils using vegetable oils to provide resultant fuel shortages in the United (18–21). Walton (22) summarized European tropical colonies, especially States in the years after World War II results on 20 vegetable oils (castor, those in Africa, with a certain degree of played a role in inspiring a “dual fuel” grapeseed, , camelina, pumpkin energy self-sufficiency can be found in project at The Ohio State , beechnut, , lupin, pea, the related literature throughout the (Columbus, Ohio), during which cot- poppyseed, groundnut, , linseed, 1940s. was often considered as tonseed oil (14) and (15), and chestnut, sunflower seed, palm, , a source of in the “historic” blends thereof with conventional diesel , , and shea ). studies, although the diversity of oils fuel, were investigated. He also pointed out (22) that “at the and fats as sources of diesel fuel, an Once again, energy per- moment the source of supply of fuels is important aspect again today, and striv- spectives have become a significant dri- in a few hands, the operator has little or ing for energy independence were ving force for the use of vegetable oil- no control over prices or qualities, and reflected in other “historic” investiga- based diesel fuels, although environ- it seems unfortunate that at this date, as tions. Belgium, France, and Italy partic- mental aspects (mainly reduction of with the petrol engine, the engine has to ularly appear to have been interested in exhaust emissions) play a role at least be designed to suit the fuel whereas, vegetable oil fuels at the time, although as important as energy security. For strictly speaking, the reverse should several British and German papers were example, in the United States, the obtain—the fuel should be refined to published. Reports from other countries Clean Air Act Amendments of 1990 meet the of an ideal engine.” also reflect a theme of energy indepen- and the Energy Policy Act of 1992 More insights can be gained by consult- dence. mandate the use of alternative, or ing the references listed in this article. Vegetable oils also were used as emer- “clean,” fuels in regulated truck and Although environmental aspects gency fuels and for other purposes dur- bus fleets. Amendments to the Energy played virtually no role in promoting ing World War II. For example, Policy Act enacted into law in 1998, the use of vegetable oils as fuel in “his- prohibited the export of which provide for biodiesel use toric” times and no emissions studies in order to substitute it for imported (also in blends with conventional diesel were conducted, it is still worthwhile to diesel fuel (7). Reduced imports of liquid fuel), are a major reason the use of note some allusions to this subject from fuel were also reported in , biodiesel in the United States is that time. necessitating the commercial exploita- increasing significantly. • “In case further development of tion of vegetable oils (8). pro- In modern times, biodiesel is derived, vegetable oils as fuel proves practicable, duced diesel fuel, lubricating oils, “gaso- or has been reported to be producible it will simplify the fuel problems of line,” and “,” the latter two by from, many different sources, including many tropical localities remote from a cracking process, from tung and other vegetable oils, animal fats, used mineral fuel, and where the use of wood vegetable oils (9,10). However, the exi- oils, and even soapstock. entails much extra labor and other diffi- gencies of the war caused hasty installa- Generally, factors such as geography, culties connected with the various heat- tion of cracking based on frag- climate, and economics determine ing capacities of the wood’s use, to say mentary data (9). Researchers in , which vegetable oil is of most interest nothing of the risk of indiscriminate prompted by the events of World War II, for potential use in biodiesel fuels. deforestation” (23). extended their investigations on ten veg- Thus, in the United States, • “It might be advisable to mention, etable oils for development as a domes- is considered as a prime feedstock; in at this juncture, that, owing to the tic fuel (11). Work on vegetable oils as Europe, it is rapeseed (canola) oil; and altered combustion characteristics, the diesel fuel ceased in India when petrole- in tropical countries, it is palm oil. As exhaust with all these oils is invariably um-based diesel fuel again became avail- noted above, different feedstocks were quite clean and the characteristic diesel able plentifully at low cost (12). The investigated in the “historic” times. knock is virtually eliminated” (22). Japanese battleship Yamato reportedly These included palm oil, soybean oil, • Observations by other authors used edible refined soybean oil as cottonseed oil, castor oil, and somewhat included: “invisible” or “slightly bunker fuel (13). less common oils, such as babassu (16), smoky” exhausts when running an

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engine on palm oil (24); clearer exhaust responding vegetable oil (usually The other approaches—microemulsi- gases (25); in the case of use of fish oils methyl) esters. Methyl esters are the fication and dilution with petrodiesel— as diesel fuels, the exhaust was most common form of biodiesel, largely appear to have received little or no described as colorless and practically due to methanol being the least expen- attention during the “historic” times of odorless (21). sive alcohol. studies on vegetable oils as diesel fuel. However, the use of blends of conven- tional diesel fuel with cottonseed oil Artificial “,” “kerosene,” and “diesel” (14), corn oil (15), and (18) were obtained in China from and other oils. has been described. Ilieff (37) used alco- hol (ethanol) for improving the atom- Other oils that were used in such an approach included ization and combustion of highly vis- fish oils, linseed oil, castor oil, palm oil, and cottonseed oil. cous castor oil. Various other technical aspects, the effect of different kinds of vegetable oils The visual observations of yesterday The high of vegetable oils relative to corrosion and lube oil dilu- have been confirmed in “modern” times as a major cause of poor fuel atomiza- tion and contamination, etc. have been for biodiesel fuel. Numerous recent tion resulting in operational problems studied (38). studies have shown that most exhaust such as engine deposits was recognized emissions are reduced when using early (24,26–28). Although engine T HE FIRST ‘ BIODIESEL’ biodiesel fuel. modifications such as higher injection Walton (22) recommended that “to get pressure were considered (27,29), the utmost value from vegetable oils as T ECHNICAL ASPECTS reduction of the high viscosity of veg- fuel it is academically necessary to split The kinematic viscosity of vegetable etable oils usually was achieved by heat- off the and to run on the oils is about an order of magnitude ing the (24,27). Often residual . Practical experi- greater than that of conventional, the engine was started on petrodiesel ments have not yet been carried out petroleum-derived diesel fuel. High vis- and, after a few minutes of operation, with this; the problems are likely to be cosity causes poor atomization of the was then switched to the vegetable oil much more difficult when using free fuel in the engine’s combustion cham- fuel, although a successful cold-start on fatty acids than when using the oils bers and ultimately results in opera- high-acidity peanut oil was reported straight from the crushing . It is tional problems, such as engine (30). Advanced injection timing was a obvious that the have no fuel deposits. Since the renewal of interest technique also employed (31). Seddon value and in addition are likely, if any- during the late 1970s in vegetable oil- (32) gives an interesting practical thing, to cause an excess of in derived fuels, four possible to account about a truck that operated comparison with gas oil.” the problem of high viscosity have been successfully on different vegetable oils Although Walton’s statement points investigated: transesterification, pyrol- using preheated fuel. in the direction of what is now termed ysis, dilution with conventional petro- Pyrolysis, cracking, or other methods biodiesel by recommending the elimina- leum-derived diesel fuel, and of decomposition of vegetable oils to tion of from the fuel, some microemulsification (26). yield fuels of varying nature is an remarkable work performed in Belgium Transesterification is the most com- approach that accounts for a significant and its former colony the Belgian Congo mon method and leads to monoalkyl amount of the literature in “historic” (known after its independence for a long esters of vegetable oils and fats, now times. Artificial “gasoline,” “kerosene,” time as Zaire) deserves more recognition called biodiesel when used for fuel pur- and “diesel” were obtained in China than it has received. Indeed, it appears poses. Briefly, it consists of reacting the from tung oil (9) and other oils (10). that Belgian patent 422,87, granted on vegetable oil feedstock with an alcohol, Other oils that were used in such an Aug. 31, 1937, to G. Chavanne (of the usually methanol, in the presence of a approach included fish oils (16–18), lin- University of Brussels), constitutes the catalyst, usually a base such as sodium (33), castor oil (34), palm oil first report on what is today known as or hydroxide, to give the cor- (35), and cottonseed oil (36). biodiesel. It describes the use of ethyl

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esters of palm oil (although other oils search engine with “biodiesel” as the Industrial Importance Particularly and methyl esters are mentioned) as key word) yielded first literature use of for Great Britain, Proc. Inst. Mech. diesel fuel. These esters were obtained the term biodiesel in a Chinese paper Eng.: 179–280 (1912). Chem. Abstr. by acid-catalyzed transesterification of published in 1988 (42). The next paper 7:1605 (1913). the oil (base is now more com- using that term appeared in 1991 (43) mon). This work has been described in and from then on the use of the term Nitske, W.R., and C.M. Wilson, Rudolf more detail (2). “biodiesel” in the literature has expand- Diesel, Pioneer of the Age of Power, Of particular interest is a related ed exponentially. University of Oklahoma Press, extensive report published in 1942 on Norman, Oklahoma, 1965. the production and use of palm oil ethyl Readers may contact the author ester as fuel (3). That work described at the USDA National Center Schwab, A.W., M.O. Bagby, and B. what was probably the first test of an for Agricultural Utilization Research, Freedman, Preparation and Properties urban bus operating on biodiesel. A bus 1815 N. University St., of Diesel Fuels from Vegetable Oils, fueled with palm oil ethyl ester served Peoria, IL 61604 (phone: Fuel 66:1372–1378 (1987). the commercial passenger line between 309-681-6112; fax: 309-681-6340; Brussels and Louvain (Leuven) in the e-: [email protected]). van den Abeele, M., L’Huile de Palme: summer of 1938. Performance of the Matière Première pour la bus operating on that fuel reportedly Préparation d’un Carburant Lourd was satisfactory. It was noted that the Bibliography Utilisable dans les Moteurs à viscosity difference between the esters Combustion Interne (Palm Oil as and conventional diesel fuel was consid- Bruwer, J.J., B. van D. Boshoff, F.J.C. for the Production of a erably less than that between the parent Hugo, L.M. du Plessis, J. Fuls, C. Heavy Motor Fuel), Bull. Agr. oil and conventional diesel fuel. Also, Hawkins, A.N. van der Walt, and A. Congo Belge 33:3–90 (1942). Chem. the article pointed out that the esters are Engelbrecht, Sunflower Seed Oil as Abstr. 38:2805 (1944). miscible with other fuels. That work an Extender for Diesel Fuel in also discussed what is probably the first Agricultural Tractors, Symposium of Walton, J., The Fuel Possibilities of cetane number (CN) testing (CN is a the South African Institute of Vegetable Oils, Gas Oil Power combustion-related diesel fuel quality Agricultural Engineers, 1980. 33:167–168 (1938). Chem. Abstr.. index) of a biodiesel fuel. On page 52 of 33:19396 (1939). that report, CN of palm oil ethyl ester Chavanne, C.G., Belgian Patent was reported as approximately 83 (rela- 422,877, Aug. 31, 1937; Chem. Abs. Wiebe, R., and J. Nowakowska, The tive to a high-quality standard with CN 32:4313 (1938). Technical Literature of Agricultural 70.5 and a low-quality standard of CN Motor Fuels, USDA Bibliographic 18 and diesel fuels with CN of 50 and Chavanne, G., Sur un Mode Bulletin No. 10, Washington, DC, 57.5). Thus, those results agree with d’Utilisation Possible de l’Huile de pp. 183–195 (1949). “modern” work reporting relatively Palme à la Fabrication d’un high CN for such biodiesel fuels. Carburant Lourd (A Method of The numbered references are available In more recent times, use of methyl Possible Utilization of Palm Oil for at the inform portion (netlink: esters of to reduce the vis- the Manufacture of a Heavy Fuel), www.aocs.org/press/inform.htm) of the cosity of vegetable oil was reported at Bull. Soc. Chim. 10: 52–58 (1943). AOCS page. Persons who have several technical conferences in 1980 Chem. Abstr. 38:2183 (1944). e-mail but do not have Internet access and 1981 (39–41) and marks the begin- should send a request for references to ning of the rediscovery and eventual Diesel, R., The Diesel Oil-Engine, [email protected]. References also will commercialization of biodiesel. 93:395–406 (1912). be sent by fax upon a request to inform A final thought should be given to Chem. Abstr. 6:1984 (1912). by fax (217-351-8091) or by mail the term “biodiesel” itself. A Chemical (inform, P.O. Box 3489, Champaign, IL Abstracts search (using the “SciFinder” Diesel, R., The Diesel Oil-Engine and Its 61821-3489).❏

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