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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

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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 (17621843) 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 (183291) 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 tienne Lenoir (18221900)
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 (18581913), 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 (183395), 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 [1012]. 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 5

doi:10.1016/B978-0-08-087872-0.00502-3

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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 (181980), 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 (186165) 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 fr 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 ethanolgasoline 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 alcoholgasoline 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 (18891944) and Charles Kettering (18761958) [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 ethanolgasoline 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 (18631947). This reemergence of ethanolgasoline 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

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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 Waltons 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

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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.

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