Biodiesel

from Oils
and Fats
B. Brian He
University of Idaho, USA

Scott W. Pryor
North Dakota State University, USA
https://​doi​.org/​10​.21061/​IntroBiosystemsEngineering/​Biodiesel

How to cite this chapter:

He, B. & Pryor, S. (2020). Biodiesel from Oils and Fats. In Holden, N. M., Wolfe, M. L., Ogejo, J. A., & Cummins, E. J. (Ed.),
Introduction to Biosystems Engineering. https://​doi​.org/​10​.21061/​IntroBiosystemsEngineering/​Biodiesel

This chapter is part of Introduction to Biosystems Engineering

International Standard Book Number (ISBN) (PDF): 978-­1-­949373-­97-­4
International Standard Book Number (ISBN) (Print): 978-­1-­949373-­93-­6
https://​doi​.org/​10​.21061/​IntroBiosystemsEngineering

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Biodiesel from Oils and Fats
B. Brian He Scott W. Pryor
Biological Engineering Agricultural and Biosystems Engineering and College of
University of Idaho Engineering
Moscow, ID, USA North Dakota State University, Fargo, ND, USA

KEY TERMS

Feedstocks Conversion process Properties

Chemistry Process configuration Storage and handling

Variables
Ci,FA = mass fraction of a particular fatty acid
MWave,FA = average molecular weight of fatty acids in the oil
MWave,FAME = average molecular weight of fatty acid methyl esters or
biodiesel
MWgly = molecular weight of glycerol (92.09 kg/kmol)
MWi,FA = molecular weight of a particular fatty acid
MWwater = molecular weight of water (18.02 kg/kmol)

Introduction
Biodiesel is the term given to a diesel-­like fuel made from biologically derived
lipid feedstocks, such as vegetable oils, animal fats, and their used derivatives
such as waste cooking oils. Biodiesel is a renewable fuel that can be made from
a diverse array of domestic feedstocks, has low safety concerns for use and
handling, and can have relatively low environmental impact from production
and use.
Biodiesel has several properties that make it a safer fuel than conventional
petroleum-­based diesel. While conventional diesel is categorized as a flammable
fuel, biodiesel is rated as combustible, which means it has a low vapor pressure,
is resistant to static sparks, and is much less likely to self-­ignite during stor-
age. During transportation, tankers carrying pure biodiesel are not required to
display warning signs in the United States.

1
 Biodiesel is especially of interest to farmers because of the potential for
on-­farm production using harvested crops. Oil can be extracted from oilseeds
relatively easily, and this oil can then be used to make biodiesel to run farm
machinery. It provides farmers an additional resource for economic welfare
and an additional choice for managing cropland. In addition, using biodiesel
from domestically grown feedstocks can decrease a country’s dependence on
imported oil, thus enhancing national energy security. On the other hand, con-
cerns are sometimes raised about converting oils and fats, which could serve
as food resources, into fuels (Prasad and Ingle, 2019).
Biodiesel is typically considered an environmentally friendly fuel. Production
and combustion of biodiesel results in less air pollution than using conventional
diesel. According to a study sponsored by the U.S. Department of Agriculture
and the Department of Energy, using biodiesel in urban buses can reduce total
particulate matter (PM), carbon monoxide (CO) and sulfur oxides (SOx) by 32%,
35% and 8%, respectively (Sheehan et al., 1998).
The diesel engine is named for Rudolf Diesel, who invented it in the 1890s.
Diesel’s engines could run on various fuels including vegetable oils. At the Paris
Exposition in 1900, Diesel demonstrated his engines running on peanut oil and
made this famous statement:

The use of vegetable oils for engine fuels may seem insignificant today. But such
oils may become in course of time as important as petroleum and the coal tar
products of the present time.

Diesel’s vision was valid in that vegetable oils can still be used directly as a
fuel for diesel engines. However, raw vegetable oils without pre-­processing
are not an ideal fuel for modern diesel engines due to their high viscosity and
other chemical properties. Burning raw vegetable oils in today’s diesel engines
results in heavy carbon deposits in the cylinders, which can stall the engine in
a short period of time.
To overcome this problem, research was conducted starting in the late 1930s
to chemically process vegetable oils into a mixture of short-­chained alkyl fatty
acid esters. This fuel has a much lower viscosity and is thus better suited for
use in diesel engines. During the petroleum crisis in the 1970s, the use of alkyl
fatty acid esters as a fuel for diesel engines became more popular. Two decades
later, in the 1990s, the name “biodiesel” was coined and gained popularity.
In the early 1980s, Mittelbach and his team at the Technical University of Graz
in Austria were the first to research biodiesel as a diesel fuel. The commercializa-
tion of biodiesel started with a pilot biodiesel production facility by an Austrian
company, Gaskoks, in 1987. The European Biodiesel Board (EBB), a non-­profit
organization promoting the use of biodiesel in Europe, was founded in 1997.
Biodiesel research and utilization in the U.S. started around the same time
as in Europe. Dr. Charles Peterson and his research team at the University of
Idaho conducted a series of research projects on the use of vegetable oil as
tractor fuel. The team worked on biodiesel production, engine testing, emis-
sion assessment, and field utilization. The National Biodiesel Board (NBB)
was founded in the U.S. in 1992 and has conducted health and environmental

2  •  Biodiesel from Oils and Fats

assessments on biodiesel utilization. The NBB also registered biodiesel with
the U.S. Environmental Protection Agency (USEPA) as a substitute fuel for
diesel engines. Supported by the NBB and the biodiesel research community,
biodiesel was established as an industry sector. Total biodiesel production
reached approximately 7.2  billion L in the USA in 2018 with an additional
39.4 billion L produced globally.
Although biodiesel can be used as a pure diesel-­replacement fuel called B100,
it is typically available as a diesel/ biodiesel blend at retail pumps. Biodiesel
blends are designated to indicate a volumetric mixture such as B5 or B20 for
5% or 20% biodiesel, respectively, in conventional diesel.

Outcomes
After reading this chapter, you should be able to:

• Describe the advantages and limitations of using biodiesel in diesel-­powered engines

• Describe biodiesel production processes

• Explain how biodiesel is similar to and different from conventional petroleum-­based diesel

• Describe how feedstock composition and properties affect biodiesel properties

• Explain the important unit operations commonly used for producing biodiesel

• Calculate proportions of vegetable oil, methanol, and catalyst needed to make a given quantity of biodiesel, and
the size of the reactor required for conversion

Concepts
Biodiesel Chemistry
To qualify as biodiesel in the U.S., a fuel must strictly comply with the ASTM
definition of a “fuel comprised of mono-­alkyl esters of long chain fatty acids
derived from vegetable oils or animal fats, designated B100” (ASTM, 2015). It must
also meet all of the quality parameters identified in that standard. In Europe,
the definition of biodiesel is covered by the European standard EN 14214 (CEN,
2013). The generic name for vegetable oils (more generally plant oils) or animal
fats issimply fat or lipid. The primary distinguishing factor between a fat and
an oil is that a fat is a solid at room temperature while an oil is a liquid. The
primary compounds in both oils and fats
are a group of chemicals called triglycer-
ides (figure 1a).
Glycerol (figure 1b), also known as glyc-
erin, is a poly-­hydric alcohol with three
alcoholic hydroxyl groups (-­OH). Pure
glycerol is colorless, odorless, and hygro-
scopic. Fatty acids (figure 1c) are a family Figure 1. Chemical structure of triglycerides, glycerol, and fatty acids. R, R1,
of carboxylic acids with relatively long R2, and R3 represent alkyl groups typically with carbon chain lengths of 15–­17
carbon chains. atoms.

Biodiesel from Oils and Fats  •  3

 Triglycerides, also called triacylglycerols, are the glycerol esters of fatty acids,
in which three fatty acids attach chemically to a glycerol carbon backbone
where the hydroxyl (OH) groups are attached. Triglycerides in oils and fats may
contain fatty acid chains of 10 to 24 carbons (C10-­C24) but are most commonly
16 to 18 carbons (C16-­C18) in length. The three fatty acids attached to the glycerol
molecule can be the same or different. The alkyl chain length of fatty acids, the
presence and number of double bonds contained in the fatty acid chains, and
the position and orientation of the double bonds collectively determine the
chemical and physical properties of the triglyceride. Some examples are pro-
vided in table 1.

Table 1. Fatty acids commonly seen in oils and fats.

Abbreviation Common Name Formula Chemical Structure MW [1]
C12:0[2] lauric acid C12H24O2 CH3(CH2)10COOH 200.3
C14:0 myristic acid C14H28O2 CH3(CH2)12COOH 228.4
C16:0 palmitic acid C16H32O2 CH3(CH2)14COOH 256.5
C18:0 stearic acid C18H36O2 CH3(CH2)16COOH 284.5
C18:1 oleic acid C18H34O2 CH3(CH2)7CH:CH(CH2)7COOH 282.5
C18:2 linoleic acid C18H32O2 CH3(CH2)3(CH2CH:CH)2(CH2)7COOH 280.5
C18:3 linolenic acid C18H30O2 CH3(CH2CH:CH)3(CH2)7COOH 278.5
C20:0 arachidic acid C20H40O2 CH3(CH2)18COOH 312.6
C20:1 eicosenoic acid C20H38O2 CH3(CH2)7CH:CH (CH2)9COOH 310.5
C20:5 eicosapentaenoic C20H30O2 CH3(CH2CH:CH)5(CH2)3COOH 302.5
C22:1 erucic acid C22H42O2 CH3(CH2)7CH:CH(CH2)12COOH 338.6
[1]
MW = molecular weight, g/mol
[2]
Cx:y stands for a chain of x carbon atoms with y double bonds in that chain.

Biodiesel Properties
Biodiesel is a commercialized biofuel used by consumers around the globe.
Several international standards have been developed and approved to assure
engine manufacturers and diesel engine customers that biodiesel meets speci-
fied fuel quality requirements. As a commercial product, biodiesel must comply
with the specifications defined by the ASTM Standard D6751 (ASTM, 2015) in
North America or EN14214 (CEN, 2013) in Europe. Several other countries have
also developed their own standards; in many cases, they are based on the ASTM
and EN standards. Table 2 summarizes the specifications for biodiesel fuel
according to these two standards.
Biodiesel properties are affected by both the feedstock and the conversion
process. Meeting specification for all parameters in the relevant standards must
be documented before a fuel can be marketed. However, some fuel proper-
ties are more critical than others in terms of use. In the USA, biodiesel sulfur
content must be no more than 15 ppm for Grade S15, and 500 ppm for Grade
S500, to qualify as an ultra-­low sulfur fuel. If virgin vegetable oils are used as
the feedstock, sulfur content in the biodiesel is typically very low. However, if

4  •  Biodiesel from Oils and Fats

Table 2. Major specifications for biodiesel (B100).
ASTM D6751[a]
Grade 1B Grade 2B
Property Units (S15) (S15) EN14214
Sulfur (15 ppm or lower level) (maximum) ppm 15 15 [b]

Cold soak filterability (maximum) Sec. 200 360 [b]

Mono-­glyceride (maximum) % mass 0.40 [b]

0.8
Calcium & magnesium combined (maximum) ppm (μg/g) 5 5
Flash point (closed cup) (minimum) °C 93 101
Alcohol control (one of the following shall be met)
a) Methanol content (maximum) mass % 0.2 0.2
b) Flash point (minimum temperature) °C 130 [b]

Water and sediment (maximum) % volume 0.050 0.005

Kinematic viscosity (40°C) mm /s2
1.9–­6.0 3.5–­5.0
Sulfated ash (maximum) % mass 0.02 0.02
Copper strip corrosion No. 3 No. 1
Cetane number (minimum) 47 51
Cloud point °C Must be reported [b]

Carbon residue (maximum) % mass 0.05 0.03

Acid number (maximum) mg KOH/g 0.50 0.5
Free glycerol (maximum) % mass 0.02 0.02
Total glycerol (maximum) % mass 0.24 0.25
Phosphorus content (maximum) % mass 0.001 0.001
Distillation temperature (90%) (maximum) °C 360 [b]

Sodium and potassium combined (maximum) ppm (μg/g) 5 5

Oxidation stability (minimum) hours 3 6
[a]
Grade refers to specification for monoglycerides and cold soak filterability. S15 indicates maximum sulphur content of 15 ppm.
[b]
Not specified in the standard

used cooking oils or animal fats are used, the sulfur content in biodiesel must
be carefully monitored to meet the required specification.
A liquid fuel’s flash point refers to the lowest temperature at which its vapor
will be combustible. Biodiesel has a high flash point, making it safe for handling
and storage. The flash point, however, may drop if the residual alcohol from
the biodiesel production process is inadequately removed. To maintain a high
flash point, biodiesel alcohol content cannot be more than 0.2%. Cloud point
and cold soak filterability are both properties relating to flowability at cold
temperatures and are important for biodiesel use in relatively low temperature
environments. Cloud point refers to the temperature at which dissolved solids
begin to precipitate and reduce clarity. Cold soak filterability refers to how
well biodiesel flows through a filter at a specified temperature (4.4°C). Biodiesel
is limited in its use in colder climates because it typically has a much higher
cloud point (−6°C to 0°C for rapeseed and soybean based biodiesel and up to
14°C for palm oil based biodiesel) than conventional No. 2 diesel (−28°C to −7°C).

Biodiesel from Oils and Fats  •  5

 Generally, methyl esters of long-­chain, saturated fatty acids have high cloud
points, especially in comparison to conventional diesel fuel. Although there
are commercial additives available for improving biodiesel cold flow proper-
ties, their effectiveness is limited. Cold flow properties can be a limiting factor
related to the biodiesel blend used (e.g., B2 vs. B10 or B20) in colder climates or
at colder times of the year.
The presence of monoglycerides in biodiesel is an indicator of incomplete
feedstock conversion and can adversely affect fuel combustion in an engine.
Monoglycerides also contribute to measurements of both total glycerine and
free glycerol. Total glycerol should be 0.24% or lower to avoid injector deposits
and fuel filter clogging problems in engine systems.
Biodiesel viscosity is significantly lower than that of vegetable oil but is higher
than conventional diesel in most cases. Biodiesel viscosity will vary based pri-
marily on the fatty acid carbon chain length and level of saturation in the feed-
stock. Although specified biodiesel viscosity levels range from 2.8 to 6.1 mm2/s
at 40°C, typical values are greater than 4 mm2/s at that temperature (Canackci
and Sanli, 2008), while No. 2 conventional diesel has a specified viscosity range
of 1.9–­4.1 mm2/s at 40°C with typical values less than 3.0 mm2/s (ASTM, 2019).
Most biodiesel fuels have a higher cetane number than conventional diesel.
Cetane number measures the ability of a fuel to ignite under pressure and a
high cetane number is generally advantageous for combustion in diesel engines.
Typical values are approximately 45–­55 for soybean-­based biodiesel and 49–­62
for rapeseed-­based biodiesel. The higher cetane number of biodiesel is largely
attributed to the long carbon chain and high degree of unsaturation in fatty acid
esters. Acid number of biodiesel fuel is an indication of free fatty acid content
in biodiesel, which affects the oxidative and thermal stabilities of the fuel. To
ensure biodiesel meets the specification of acid number, feedstocks with high
free fatty acid content must be thoroughly treated and the finished product
adequately washed.
Mineral ash contents of combined calcium and magnesium, combined sodium
and potassium, and carbon residue have a harmful effect on biodiesel quality
by leading to abrasive engine deposits. Phosphorus content is also regulated
closely because of its adverse impact on the catalytic converter. Good quality
control practices are vital in controlling residual mineral content in biodiesel.
Biodiesel instability can also be affected negatively by excess water and sedi-
ment because of inadequate refining, or from contamination during transport or
storage. Biodiesel tends to absorb moisture from the air, making it susceptible
to such contamination. It can absorb 15–­25 times more moisture than conven-
tional petroleum-­based diesel (He et al., 2007). Excess water can be controlled
by adequately drying the moisture from biodiesel after water washing, and
through proper handling and storage of the fuel.

Biodiesel Feedstocks
The primary feedstocks for making biodiesel are vegetable oils and animal fats.
Typical properties are given in table 3. The feedstocks for biodiesel production
can be any form of triglycerides. The most commonly used feedstocks include

6  •  Biodiesel from Oils and Fats

Table 3. Typical fatty acid composition of common oils and fats.[1]
Fatty Acid Profiles (% m/m)
Oils and Fats C12:0 C14:0 C16:0 C18:0 C18:1 C18:2 C18:3 C20:1
Plant Oils
Algae oil 12–­15 10–­20 4–­19 1–­2 5–­8 35–­48[2]
Camelina 12–­15 15–­20 30–­40 12–­15
Canola, general 1–­3 2–­3 50–­60 15–­25 8–­12
Canola, high oleic 1–­3 2–­3 70–­80 12–­15 1–­3
Coconut oil 45–­53 16–­21 7–­10 2–­4 5–­10 1–­2.5
Corn 1–­2 8–­16 1–­3 20–­45 34–­65 1–­2
Cottonseed 0–­2 20–­25 1–­2 23–­35 40–­50
Grape seed oil 5–­11 3–­6 12–­28 58–­78
Jatropha 11–­16 6–­15 34–­45 30–­50 3–­5[4]
Flax (linseed) oil 4–­7 2–­4 25–­40 35–­40 25–­60
Mustard seed oil 1–­2 8–­23 10–­24 6–­18 5–­13 &
20–­50[3]
Olive 9–­10 2–­3 72–­85 10–­12 0–­1
Palm oil 0.5–­2 39–­48 3–­6 36–­44 9–­12
Palm kernel oil 45–­55 14–­18 6–­10 1–­3 12–­19
Peanut 8–­9 2–­3 50–­65 20–­30
Rapeseed (high erucic/oriental) 1–­3 0–­1 10–­15 12–­15 8–­12 45–­60[3] &
7–­10[4]
Rapeseed (high oleic /canola) 1–­5 1–­2 60–­80 16–­23 10–­15
Safflower (high linoleic) 3–­6 1–­3 7–­10 80–­85
Safflower (high oleic) 1–­5 1–­2 70–­75 12–­18 0–­1
Sesame oil 8–­12 4–­7 35–­45 37–­48
Soybean oil 6–­10 2–­5 20–­30 50–­60 5–­11
Soybean (high oleic) 2–­3 2–­3 80–­85 3–­4 3–­5
Sunflower 5–­8 2–­6 15–­40 30–­70
Sunflower (high oleic) 0–­3 1–­3 80–­85 8–­10 0–­1
Tung oil 3–­4 0–­1 4–­15 75–­90
Animal Fats
Butter 7–­10 24–­26 10–­13 28–­31 1–­3 0–­1
Chicken fat
Lard 1–­2 25–­30 10–­20 40–­50 6–­12 0–­1
Tallow 3–­6 22–­32 10–­25 35–­45 1–­3
[1]
Compiled from various sources: Peterson et al., 1983; Peterson, 1986; Goodrum and Geller 2005; Dubois et al., 2007; Kostik et al., 2013; Knothe et al.,
2015.
[2]
C20:5
[3]
C22:1
[4]
C20:0

Biodiesel from Oils and Fats  •  7

 soybean oil, rapeseed/canola oil, and animal fats. Used cooking oils and/or
yellow/trap greases can also be used but may be better as supplements to a
feedstock supply with more consistent quality and quantity. Feedstock choice for
biodiesel production is generally based on local availability and price. Vegetable
oils and/or animal fats all have existing uses and markets. The availability of
each type of feedstock varies widely depending on current market conditions,
and changes almost on a yearly basis. Before a biodiesel production facility is
constructed, securing adequate feedstock supply is always the number one
priority. Based on their availability, soybean oil and corn oil are the major feed-
stocks in the U.S., while rapeseed/canola oil is the most common feedstock
used in Europe. Other major producing countries include Brazil and Indonesia
which rely on soybean oil and palm oil, respectively.
Compared to other oilseeds, soybeans have a relatively low oil content, typi-
cally 10–­20% of the seed mass. However, soybean yields are relatively high,
typically 2,500–­4,000 kg/ha (2,200–­3,600 lb/acre), and the U.S. and Brazil are
the two largest soybean producers in the world. Due to the large production
and trade of soybeans, approximately 11 million metric tons (24.6 billion lbs)
of soybean oil were on the market in the 2016–­2017 season; of that, 2.8 million
metric tons (6.2 billion lbs) were used for biodiesel production (USDA ERS, 2018a).
In recent years, corn oil has been used increasingly and has become the sec-
ond largest feedstock for making biodiesel in the U.S. Corn planted in the U.S. is
mainly used for animal feed, corn starch or sweeteners, and for ethanol produc-
tion. Corn oil can be extracted in a facility producing corn starch or sweeteners
and is also increasingly being extracted from different byproducts of the ethanol
industry. The total supply of corn oil in the U.S. was approximately 2.63 mil-
lion metric tons (5.795 billion lbs) in 2017 (USDA ERS, 2018b). The quantity of
corn oil used for biodiesel production was approximately 717,000 metric tons
(1.579 billion lb), or approximately 10% of the total biodiesel market. Canola oil
is the third largest feedstock with a use of approximately 659,000 metric tons
(1.452 billion lbs) in 2017 (USDA EIA, 2018).
Rapeseed belongs to the Brassica family of oilseed crops. Original rape-
seed, including the cultivars planted in China and India, contains very high
contents of erucic acid and glucosinolates, chemicals undesirable in animal
feed. Canola is a cultivar of rapeseed developed in Canada with very low
erucic acid and glucosinolates contents. While the oilseed crop planted in
Europe is still called rapeseed there, it is essentially the same plant called
canola in North America. The yield of rapeseed in Europe is high, in the range
of 2,000–­3,500 kg/ha (1,800–­3,100 lb/acre) and is planted almost exclusively
for biodiesel production.
Other plant oils, including palm and coconut oil, can also be used for pro-
ducing biodiesel and are especially popular in tropical nations due to very high
oil yields per acre. Plant species with high oil yields, requiring low agricultural
inputs and with the ability to grow on marginal lands, such as camelina and
jatropha, are of particular interest and have been researched for biodiesel pro-
duction. Oils from safflower, sunflower, and flaxseed can be used for making
biodiesel, but their high value in the food industry makes them uneconomical
for biodiesel production.

8  •  Biodiesel from Oils and Fats

 Some strains of microalgae have a high lipid content and are also widely
researched and used to produce algal oil as a biodiesel feedstock. They are
considered a promising feedstock because of their potential to be industrialized
or produced in an industrial facility rather than on agricultural land. Microalgae
can be cultivated in open ponds, but high-­oil strains may be better suited to
production in closed photo-­bioreactors. The potential yield of microalgal oil
per unit land can be as high as 6,000 L/ha/y (1600 gal/ac/y), more than 10
times that of canola or soybeans. Currently, however, microalgal lipids are not
used for industrial biodiesel production because of their high production cost.
Like plant oils, animal fats contain similar chemical components and can be used
directly for biodiesel production. In 2017, approximately 1.2 million metric tons
(2.6 billion lbs) of used cooking oils and animal fats were used for biodiesel produc-
tion in the U.S., accounting for 23% of the total used cooking oils and animal fats
in the U.S. market (Swisher, 2018) and less than 20% of U.S. biodiesel production.

Conversion Process
Biodiesel is made by reacting triglycerides (the chemicals in oils and fats) with
an alcohol. The chemical reaction is known as transesterification. In transesteri-
fication of oils and/or fats, which are the glycerol esters of fatty acids (figure 2),
the glycerol needs to be transesterified by another alcohol, most commonly
methanol. The three fatty acids (R1, R2, and R3) react with the alkyl groups of the
alcohol to produce fatty acid esters, or biodiesel. Those fatty acids from the
triglyceride are replaced by the hydroxyl groups from the alcohol to produce
glycerol, a by-­product. The glycerol can be separated from the biodiesel by
gravity, but the process is typically accelerated through a centrifugation step.
If methanol (CH3–­OH) is used as the alcohol for the transesterification reac-
tion, methyl groups attach to the liberated triglyceride fatty acids (Rx–­CH3), as
illustrated in figure 2. The resulting mixture after glycerol separation is referred
to as fatty acid methyl esters (or FAME as commonly called in Europe), and
biodiesel after further refining. Without the glycerol skeleton, the mixture of
FAME is much less viscous than the original vegetable oil or animal fat, and its
fuel properties are suitable for powering diesel engines.
The transesterification of oils and fats involves a series of three consecutive
reactions. Each fatty acid group is separated from the glycerol skeleton and
transesterified individually. The intermediate products are diglycerides (when
two fatty acid groups remain on the glyc-
erol backbone) and monoglycerides (when
one fatty acid group remains on the glyc-
erol backbone). Transesterification reac-
tions are also reversible. The diglyceride
and monoglyceride intermediate prod-
ucts can react with a free fatty acid and
reform triglycerides and diglycerides,
respectively, under certain conditions.
The degree of reverse reaction depends on Figure 2. Transesterification of triglycerides with methanol. R1, R2, and R3
the chemical kinetics of transesterification are alkyl groups in chain lengths of, most commonly, 15–­17 carbons.

Biodiesel from Oils and Fats  •  9

 and the reaction conditions. In practical application, approximately twice the
stoichiometric methanol requirement is added in order to drive the forward
reactions and to ensure more complete conversion of oils and fats into bio-
diesel. The excess methanol can be recovered and purified for reuse in the
system.
The density of vegetable oil at 25°C is in the range of 903–­918 kg/m3
(7.53–­7.65 lb/gal) depending on the specific feedstock (Forma et al., 1979). The
density of biodiesel is approximately 870–­880 kg/m3 (7.25–­7.34 lb/gal) (Pratas
et al., 2011). Comparison reveals that vegetable oil is approximately 4% heavier
than biodiesel. While planning for biodiesel production, it is an acceptable
assumption that each volume of biodiesel produced requires an equal volume
of vegetable oil.
To calculate the exact volume of chemicals (i.e., reactant methanol and cata-
lyst) needed for the transesterification, the molecular weight of the vegetable oil
is needed. However, as seen from table 3, vegetable oils vary in fatty acid com-
position depending on oil source and even on the specific plant cultivar. There
is no defined molecular weight for all vegetable oil, but an average molecular
weight is used for calculations. Based on the hydrolysis of fatty acid esters of
glycerol, the molecular weight of vegetable oil (a mixture of fatty acid glycerol
esters), MWave, can be calculated as:

MWave = MWgly –­3 MWwater + 3 MWave,FA (1)

where MWgly = molecular weight of glycerol = 92.09 kg/kmol

MWwater = molecular weight of water = 18.02 kg/kmol
MWave,FA = average molecular weight of fatty acids in the oil

The water is subtracted in the equation because three individual fatty acids are
joined to the single glycerol molecule in a condensation reaction that produces
three water molecules in the process. The opposite reaction, hydrolysis, would
split the fatty acid from the glycerol through incorporation of the water mol-
ecule ions into the products. The overall average molecular weight of vegetable
oil fatty acids is calculated as:

1 C
  i,FA (2)
MWave,FA MWi,FA

where Ci,FA = mass fraction of a particular fatty acid

MWi,FA = molecular weight of that particular fatty acid

The difference between the weight of the methyl group (–­CH3; 15 kg/kmol)
and that of the hydrogen atom (–­H; 1 kg/kmol) on the carboxyl group of fatty
acids is 14 atomic mass units. To find the average molecular weight of fatty acid
methyl esters (FAME) or biodiesel, MWave,FAME, the following formula can be used:

MWave,FAME = MWave,FA + 14 (3)

10  •  Biodiesel from Oils and Fats

Use of a Catalyst
The transesterification reaction will occur even at
room temperature if a vegetable oil is mixed with
methanol, but would take an extraordinarily long
Figure 3. Chemical reaction between methanol and potassium
time to approach equilibrium conditions. A catalyst
hydroxide to form potassium methoxide.
and elevated temperatures are typically used to
help the reaction move forward and dramatically
reduce the reaction time. The catalysts suitable for transesterification of oils and
fats are either strong acids or strong bases; the latter are most commonly used,
especially for virgin vegetable oils. Sodium hydroxide (NaOH) and potassium
hydroxide (KOH) are inexpensive choices for use as base catalysts; they are typically
available commercially as solid flakes or pellets. Before being used as a catalyst
for transesterification, the solid form of NaOH or KOH needs to be prepared by
reacting with methanol to form a homogenous solution. This dissolving process
is a chemical reaction to form soluble methoxide (–­OCH3), as shown in figure 3.
The methoxide is the active species for catalysis in the system. Therefore,
the solution of sodium methoxide (NaOCH3) or potassium methoxide (KOCH3)
in methanol are the preferred form of the catalysts for large continuous-­flow
biodiesel production. Solutions of NaOCH3 or KOCH3 in methanol are com-
mercially available in 25–­30% concentrations.

Other Factors Affecting Conversion

Note in figure 3 that one mole of water is formed per mole of KOH reacted. Water
in the transesterification of oils and/or fats is undesirable because it potentially
leads to the hydrolysis of triglycerides to free fatty acids, which in turn react with
the base catalyst, either KOH or KOCH3, to form soap. This soap-­making process is
called saponification (figure 4). Soap in the system will cause the reaction mixture
to form a uniform emulsion, making the separation of biodiesel from its by-­product
glycerol impossible. Therefore, special attention is needed to avoid significant soap
formation. Thus, prepared methoxide is preferred to hydroxide as the catalyst for
use in biodiesel production, so water can be minimized in the system.
Transesterification of oils and/or fats requires a catalyst for realistic conversion
rates, but the reaction will still take up to eight hours to complete if it is carried
out at room temperature. Therefore, the process temperature also plays a very
important role in the reaction rate, and higher reaction temperatures reduce the
required reaction time. When the reaction temperature is maintained at 40°C
(104°F), the time for complete transesterification can be shortened to 2–­4 hours. If
the reaction temperature is at 60°C (140°F), the time can be reduced even further to
1–­2 hours for a batch reactor. The highest reaction temperature that can be applied
under atmospheric pressure is limited by the boiling temperature of methanol,
64.5°C (148°F). Typical reaction temperatures for transesterification of oils and
fats in large batch operations are in the range of
55–­60°C (130–­140°F). Higher temperatures can be
used but require a closed system under pressure.
There are situations in which high amounts
of free fatty acids (higher than 3% on a mass Figure 4. Saponification between potassium hydroxide and a fatty
basis) exist naturally in feedstocks, such as used acid.

Biodiesel from Oils and Fats  •  11

 vegetable oils and microalgal lipids. To trans-
esterify feedstocks with high free fatty acid con-
tent, direct application of base catalysts, either
as hydroxide (–­OH) or methoxide (–­OCH3), is not
Figure 5. Esterification of a fatty acid reacting with methanol (in recommended because of the increased likeli-
the presence of an acid catalyst) to yield a methyl ester and water. hood of soap formation. Instead, a more com-
plicated two-­step transesterification process is
used. In the first step, a strong acid, such as sulfuric acid (H2SO4), is used as a
catalyst to convert most of the free fatty acids to biodiesel via a chemical pro-
cess called esterification (figure 5). In the second step, a base catalyst is used
to convert the remaining feedstock (mainly triglycerides) to biodiesel.

Safe Handling of Chemicals in Biodiesel Production

Conversion of oils and/or fats to biodiesel is a chemical reaction so a good under-
standing of the process chemistry, safe chemical processing practices, and all
regulations is necessary to ensure safe and efficient biodiesel production. First
aid stations must be in place in biodiesel laboratories and production facilities.
Although biodiesel itself is a safe product to handle, some of the components
involved in production can be hazardous. The chemicals in biodiesel production
can include methanol, sodium or potassium hydroxide, and sulfuric acid, all of
which have safety concerns related to storage and use. Extreme caution must
be practiced in handling these chemicals during the whole process of biodiesel
production. The appropriate Material Safety and Data Sheets for all chemicals used
should be reviewed and followed to maintain personal and environmental safety.

Applications
Biodiesel Production Systems
The fundamental unit operations for transesterification of a feedstock with
low free fatty acid content, such as virgin soybean or canola oil, using KOH as
catalyst are illustrated in figure 6. The catalyst solution is prepared by react-
ing it with methanol, in the case of hydroxide flakes, or by mixing it with a
measured amount of methanol, in the case of methoxide solution, in a mixer.
The prepared catalyst/methanol solution is added to the vegetable oil/fat in
the reactor under gentle agitation. The reactor may be an individual or a series
of stirred tanks, or some other reactor type. As discussed above, the trans-
esterification reaction typically takes place in 1–­2 hours at 55–­60°C (130–­140°F).
Crude glycerol is the term used for the glycerol fraction after initial separa-
tion. It contains some residual methanol, catalyst and a variety of other chemical
impurities in the triglyceride feedstock. Crude glycerol is either refined on site or
sold to a market for further processing. Although there are many uses of glycerol
in industries from food to cosmetics to pharmaceuticals, the economics of refining
severely limits its use. The grey water from biodiesel washing is a waste product
containing small quantities of methanol, glycerol, and catalyst. It needs adequate
treatment before it can be discharged to a municipal wastewater system.

12  •  Biodiesel from Oils and Fats

Process Configuration
Biodiesel can be produced in
a batch, semi-­continuous, or
continuous process. The eco-
nomics of process configura-
tion are largely dependent on
production capacity. Batch
processes require less capi-
tal investment and are easier
to build. A major advantage
of batch processing is the
flexibility to accommodate
variations in types and quan-
tities of feedstock. Challenges
of batch processing include
lower productivity, higher
labor needs, and inconsis- Figure 6. Schematic illustration of a biodiesel production system.
tent fuel quality. Continuous-­
flow biodiesel production
processes can be scaled more easily and are preferred by larger producers. In
continuous-­flow processes, fuel quality is typically very consistent. The higher
initial capital costs, including costs for complicated process control and process
monitoring, are mitigated in large operations by greater throughput and higher
quality product. As a result, the net capital and operating costs per unit product
is less than that of batch processes. The types of reactors for transesterification
can be simple stirred tanks for batch processes and continuously stirred tank
reactors (CSTR) for continuous-­flow processes.
Upon completion of the reaction, the product mixture passes to a separator,
which can be a decanter for a batch process or a centrifuge for the continuous-­
low system. The crude glycerol, which is denser than the biodiesel layer, is
removed. Any residual catalyst in the biodiesel layer is then neutralized by a
controlled addition of an acid solution. In the same unit, most of the excess
methanol and some residual glycerol is concentrated in the aqueous acid solu-
tion layer and withdrawn to a methanol recovery unit, where the methanol is
concentrated, purified, and recirculated for reuse.
The neutralized biodiesel layer is washed by gentle contact with softened
water to further remove residual methanol and glycerol. The washed biodiesel
layer is dried by heating to approximately 105°C (220°F) until all moisture is
volatized. The finished biodiesel after drying is tested for quality before being
transferred to storage tanks for end use or distribution.

Biodiesel Storage and Utilization

Biodiesel has relatively low thermal and oxidative stabilities. This is due to
the unsaturated double bonds contained in the oil and fat feedstocks. There-
fore, biodiesel should be stored in cool, light-­proof containers, preferably in

Biodiesel from Oils and Fats  •  13

 underground storage facilities. The storage containers should be semi-­sealed
to minimize air exchange with the environment, reducing the possibility of oxi-
dation and moisture absorption of biodiesel. Where permitted, the headspace
of the storage containers can be filled with nitrogen to prevent biodiesel from
coming into contact with oxygen. If biodiesel will be stored for longer than six
months before use, adding a biocide and a stability additive is necessary to
avoid microbial activity in the biodiesel. Biodiesel storage and transportation
containers should not be made of aluminum, bronze, copper, lead, tin, or zinc
because contact with these types of metals will accelerate degradation. Con-
tainers made of steel, fiberglass, fluorinated polyethylene, or Teflon can be used.
Biodiesel is a much stronger solvent than conventional diesel. Storage tanks
for conventional diesel may have organic sludge build-­up in them. If using such
tanks for biodiesel storage, they should be thoroughly cleaned and dried to
prevent the sludge from being dissolved by biodiesel and potentially causing
problems to fuel lines and fuel filters. Similar problems can occur when using
biodiesel in older engines with petroleum residues in fuel tanks or transfer lines.
For more information on handling and storing biodiesel, readers are recom-
mended to consult “Biodiesel Handling and Use Guide” (5th ed.) prepared by
the National Renewable Energy Laboratory of the U.S. Department of Energy
(Alleman et al., 2016).

Examples
Example 1: Volumes of soybean oil for biodiesel production
Problem:
Last year, a farmer used a total of 13,250 L of diesel fuel to run the farm’s
machinery and trucks. After attending a workshop on using biodiesel on farms
for both economic and environmental benefits, the farmer has decided to use
a B20 blend of biodiesel in all the farm’s vehicles. The average annual yield of
soybeans on the farm is 2,800 kg/ha. The soybeans contain 18.5% oil on a mass
basis, and the efficiency of soybean oil extraction through mechanical pressing
is approximately 80%. The density of soybean oil is 916 kg/m3.
Answer the following questions to help the farmer develop the details needed:

(a) How much pure biodiesel (B100) is needed to run the farm’s vehicles
using a B20 blend (i.e., a mixture of 20% biodiesel and 80% of conven-
tional diesel on a volume basis)?
(b) How much soybean oil is needed to produce sufficient B100 to blend with
conventional diesel?
(c) What field area will yield enough soybeans for the needed quantity of oil?

Solution:
(a) Given that the farmer uses 13,250 L of diesel fuel yearly, if 20% of the
quantity is replaced by biodiesel, the quantity of pure biodiesel must be:

13,250 L × 0.20 = 2,650 L

14  •  Biodiesel from Oils and Fats

 The farmer will still need to purchase conventional diesel fuel, which is
80% of the total consumption:

13,250 L × 0.80 = 10,600 L

Therefore, 2,650 L of pure biodiesel (B100) is needed to blend with

10,600 L of conventional diesel to make a total of 13,250 L of a B20 blend
for the farm’s vehicles.
(b) As an estimate of how much soybean oil (in kg) is needed, each volume of
biodiesel requires approximately one volume of soybean oil (or other oil)
to produce it, as noted in the Conversion Process section. Therefore, the
initial estimate for the quantity of soybean oil is the same as the required
quantity of pure biodiesel, i.e., 2,650 L of soybean oil.
Calculate the mass quantity of soybean oil by multiplying the volume
of soybean oil by the density of soybean oil (916 kg/m3 or 0.916 kg/L):

2,650 L × 0.916 kg/L = 2,427 kg

(c) The given soybean yield is 2,800 kg/ha, the oil content of soybean is
18.5%, and the oil extraction efficiency is 80%. Therefore, each ha planted
in soybean will yield:

(2800 kg) (0.185) (0.80) = 414.4 kg of soybean oil

The area of soybean field for produce the needed 2427 kg of soybean
oil is:

2,427 kg / 414.4 kg/ha = 5.86 ha

In summary, the farmer needs to plant at least 5.86 ha of soybeans to have

enough soybean oil to produce the biodiesel needed to run the farm’s vehicles.

Example 2: Average molecular weight of soybean oil

Problem:
The farmer had the farm’s soybean oil analyzed by a commercial laboratory via
a gas chromatographic analysis and obtained the following fatty acid profile
on a mass basis:

Palmitic Stearic Oleic Linoleic Linolenic

(C16:0) (C18:0) (C18:1) (C18:2) (C18:3)
Profile 9% 4% 22% 59% 6%
MWi,FA (kg/kmol) 256.5 284.5 282.5 280.5 278.5

( a) What is the average molecular weight of the soybean oil?

(b) What is the average molecular weight of biodiesel from this soybean oil?

Biodiesel from Oils and Fats  •  15

 Solution:
(a) First, calculate the average molecular weight of fatty acids (MWave,FA) in the
soybean oil using equation 2:

1 C
  i,FA (2)
MWave,FA MWi,FA

1 9% 4% 22% 59% 6%
    
MWave,FA 256.5 284.5 282.5 280.5 278.5

0.09 0.04 0.22 0.59 0.06

    
256.5 284.5 282.5 280.5 278.5

 0.003589 kmol/kg

Therefore, MWave,FA = 1 / 0.003589 = 278.6 kg/kmol.

Next, calculate the average molecular weight of the soybean oil using
equation 1:

MWave = MWgly –­3MWwater + 3MWave,FA (1)

= 92.09 –­(3×18.02) + (3×278.6) kg/kmol

Therefore, MWave= 873.7 kg/kmol.

(2) Calculate the average molecular weight of biodiesel using equation 3:

MWave,FAME = MWave,FA + 14 (3)

= 278.6 + 14 kg/kmol

Therefore, MWave,FAME = 292.6 kg/kmol.

In summary, the average molecular weights of the soybean oil and biodiesel
are 873.7 and 292.6 kg/kmol, respectively.

Example 3: Chemicals in converting soybean oil to biodiesel

Problem:
As determined in example 1, the farmer needs to produce 2,650 L of pure bio-
diesel (B100; molecular weight = 880 kg/kmol) to run the farm’s vehicles and
machinery with B20 blends. In converting soybean oil into biodiesel, the metha-
nol (CH3OH, molecular weight = 32.04 kg/kmol) application rate needs to be
100% more than the stoichiometrically required rate to ensure a complete reac-
tion. The application rate of the potassium hydroxide catalyst (KOH, molecular
weight = 56.11 kg/kmol) is 1% of the soybean oil on a mass basis. How much
methanol and potassium hydroxide, in kg, are needed to produce the required

16  •  Biodiesel from Oils and Fats

biodiesel? The average molecular weights of the soybean oil and biodiesel are
873.7 and 292.6 kg/kmol, respectively.

Solution:
First, write out the transesterification of soybean oil to biodiesel with known
molecular weights (MW) (similar to figure 2):

Next, convert the quantity of biodiesel from volume to mass by the biodiesel
density, 880 kg/m3 = 0.880 kg/L:

2,650 L × 0.880 kg/L = 2,332 kg

Next, calculate the amount of methanol from the stoichiometric ratio of the
transesterification reaction.
methanol : biodiesel

The stoichiometric mass ratio 3 × 32.04 : 3 × 292.6

The unknown mass ratio (kg) M : 2,332
Or (3 × 292.6) × M = (3 × 32.04) × 2,332

Therefore, the quantity of methanol is

M = (3 × 32.04) × 2,332 kg/ (3 × 292.6) = 255.5 kg

Next, calculate the total amount of methanol with 100% excess, as required:

M′ = 2M = 2 × 255.5 = 511 kg

Finally, calculate the quantity of catalyst KOH needed. Since the application
rate of the catalyst KOH is 1% of the soybean oil, before the quantity of KOH
can be calculated, the quantity of soybean oil must be obtained from the stoi-
chiometric ratio of the transesterification reaction.
soybean oil : biodiesel

The stoichiometric mass ratio 873.7 : 3 × 292.6

The unknown mass ratio (kg) S : 2,332
Or (3 × 292.6) × S = 873.7 × 2,332 kg

The quantity of soybean oil is, then:

S = 873.7 × 2,332 kg / (3 × 292.6) = 2,321 kg

Biodiesel from Oils and Fats  •  17

 Therefore, the quantity of catalyst KOH is calculated as 1% of the oil:

2,321 kg × 0.01 = 23.2 kg

In summary, the quantities of methanol and potassium hydroxide are 511 kg

and 23.2 kg, respectively.

Image Credits
Figure 1. He, B. (CC By 4.0). (2020). Chemical structure of triglycerides, glycerol, and fatty acids.
R, R1, R2, and R3 represent alkyl groups typically with carbon chain lengths of 15–­17 atoms.
Figure 2. He, B. (CC By 4.0). (2020). Transesterification of triglycerides with methanol. R1, R2,
and R3 are alkyl groups in chain lengths of, most commonly, 15–­17 carbons.
Figure 3. He, B. (CC By 4.0). (2020). Chemical reaction between methanol and potassium
hydroxide to form potassium methoxide.
Figure  4. He, B. (CC By 4.0). (2020). Saponification between potassium hydroxide and a
fatty acid.
Figure 5. He, B. (CC By 4.0). (2020). Esterification of a fatty acid reacting with methanol (in
the presence of an acid catalyst) to yield a methyl ester and water.
Figure 6. He, B. (CC By 4.0). (2020). Schematic illustration of a biodiesel production system.
The chemical formula in Example 3. He, B. (CC By 4.0). (2020).

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Biodiesel from Oils and Fats  •  19