Fuel Processing Technology 86 (2005) 1097 – 1107

www.elsevier.com/locate/fuproc

Biodiesel processing and production

Jon Van Gerpen*
University of Idaho, Moscow, ID 83844, USA

Abstract

Biodiesel is an alternative diesel fuel that is produced from vegetable oils and animal fats. It
consists of the monoalkyl esters formed by a catalyzed reaction of the triglycerides in the oil or fat
with a simple monohydric alcohol. The reaction conditions generally involve a trade-off between
reaction time and temperature as reaction completeness is the most critical fuel quality parameter.
Much of the process complexity originates from contaminants in the feedstock, such as water and
free fatty acids, or impurities in the final product, such as methanol, free glycerol, and soap.
Processes have been developed to produce biodiesel from high free fatty acid feedstocks, such as
recycled restaurant grease, animal fats, and soapstock.
D 2004 Elsevier B.V. All rights reserved.

Keyword: Biodiesel

1. Introduction

Biodiesel is an alternative fuel for diesel engines that is produced by chemically

reacting a vegetable oil or animal fat with an alcohol such as methanol. The reaction
requires a catalyst, usually a strong base, such as sodium or potassium hydroxide, and
produces new chemical compounds called methyl esters. It is these esters that have come
to be known as biodiesel.

* Tel.: +1 208 885 7891; fax: +1 208 885 7908.

E-mail address: jonvg@uidaho.edu.

0378-3820/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2004.11.005
1098 J.Van Gerpen / Fuel Processing Technology 86 (2005) 1097–1107

Because its primary feedstock is a vegetable oil or animal fat, biodiesel is

generally considered to be renewable. Since the carbon in the oil or fat
originated mostly from carbon dioxide in the air, biodiesel is considered to
contribute much less to global warming than fossil fuels. Diesel engines operated
on biodiesel have lower emissions of carbon monoxide, unburned hydrocarbons,
particulate matter, and air toxics than when operated on petroleum-based diesel
fuel.
The objective of this paper is to describe the processing and production of
biodiesel. The emphasis will be on processing as it is conducted in the United
States, where most biodiesel is produced by reacting soybean oil or used cooking
oils with methanol.

2. Background

At current production levels, biodiesel requires a subsidy to compete directly

with petroleum-based fuels. However, federal and state governments are providing
incentives that encourage the rapid growth of the biodiesel industry. Current
production levels are 20–25 million gallons/year, but achieving current European
levels of 500 million to 1 billion gallons/year should be feasible.
The combined vegetable oil and animal fat production in the United States
totals about 35.3 billion pounds per year [1]. This production could provide 4.6
billion gallons of biodiesel. However, the annual consumption of on-highway
diesel fuel in the United States is about 33 billion gallons. If all of the vegetable
oil and animal fat produced in the U.S. were available to produce biodiesel, it
would only displace about 14% of the current demand for on-highway diesel
fuel.
Although biodiesel cannot entirely replace petroleum-based diesel fuel, there are at
least five reasons that justify its development.

1. It provides a market for excess production of vegetable oils and animal fats.
2. It decreases, although will not eliminate, the country’s dependence on imported
petroleum.
3. Biodiesel is renewable and does not contribute to global warming due to its
closed carbon cycle. A life cycle analysis of biodiesel showed that overall CO 2
emissions were reduced by 78% compared with petroleum-based diesel fuel [2].
4. The exhaust emissions of carbon monoxide, unburned hydrocarbons, and
particulate emissions from biodiesel are lower than with regular diesel fuel.
Unfortunately, most emissions tests have shown a slight increase in oxides of
nitrogen (NOx).
5. When added to regular diesel fuel in an amount equal to 1–2%, it can convert
fuel with poor lubricating properties, such as modern ultra-low-sulfur diesel fuel,
into an acceptable fuel.
 Biodiesel is produced through a process known as transesterification, as shown in the
equation below,

where R1, R2, and R3 are long hydrocarbon chains, sometimes called fatty acid chains.
There are only five chains that are most common in soybean oil and animal fats (others
are present in small amounts).
Although the research did not anticipate the production of alkyl esters for fuel, most
of the processes for biodiesel production were developed in the early 1940s and are
described in a series of patents by researchers from E.I. duPont and Colgate–Palmolive–
Peet [3–12]. The original objective of this work was to develop a simplified method for
extracting glycerol during soap production. The glycerol was needed for war-time
explosives production. By chemically converting oils and fats to methyl esters, the
glycerol could be separated because it is insoluble in the esters. The glycerol has a much
higher density so it is easily removed by settling or centrifuge. The glycerol-free methyl
esters were then reacted with alkali to form soap. Bradshaw [3–5] received a patent for a
process that added about 1.6 times the theoretical amount of an alcohol, such as
methanol, which contained 0.1 to 0.5% sodium or potassium hydroxide, to an oil or fat.
When performed at 80 8C, this process provided 98% conversion to alkyl esters and
high-quality glycerol. These patents contain the following observations about the
transesterification process:

! Excess alcohol of more than 1.6 times the stoichiometric amount is required for
complete reaction.
! The amount of alcohol used can be reduced by conducting the reaction in steps, where
part of the alcohol and catalyst are added at the start of each step, and the glycerol is
removed at the end of each step.
! Besides methanol, other alcohols can be used including ethanol, propanol,
isopropanol, butanol, and pentanol.
! Water and free fatty acids inhibit the reaction. Higher alcohols are particularly
sensitive to water contamination.
110 J.Van Gerpen / Fuel Processing Technology 86 (2005) 1097–1107
0

Fig. 1. Effect of alcohol to oil ratio on product composition for transesterification [19].

! Free fatty acids in the oils or fats can be converted to alkyl esters with an acid catalyst.
This can be followed by a standard alkali-catalyzed transesterification to convert the
triglycerides.
! Acid catalysts can be used for the transesterification of oils to alkyl esters, but they are
much slower than alkali catalysts.

Knothe [13] has described how ethyl esters were proposed as diesel fuel substitutes as
early as 1937 in the Belgian Congo. Widespread investigation of these esters did not
occur until the late 1970s and early 1980s when high petroleum prices inspired extensive
research into alternative fuels. Vegetable oils were proposed as diesel fuels but were
found to be problematic due mostly to their greater viscosity [14–18]. Problems were
 J.Van Gerpen / Fuel Processing Technology 86 (2005) 1097–1107 110
found with piston and injector deposits and crankcase oil dilution and resultant 1 oil
thickening. Conversion of the oils to their alkyl esters reduced the viscosity to near
diesel fuel levels and produced a fuel with properties that were similar to petroleum-
based diesel fuel and which could be used in existing engines without modifications.
Freedman et al. [19] presented the results of a parametric study of the trans-
esterification reaction variables that included temperature, molar ratio of alcohol to oil,
type of catalyst, and the degree of refinement of the oil. They observed that the reaction
proceeded to completion in 1 h at 60 8C but took 4 h at 32 8C. Fig. 1, from that work,
shows how the degree of reaction depends on the alcohol-to-oil ratio. Significant
amounts of partially reacted mono- and diglycerides will be present when the alcohol-to-
oil ratio is too low. The figure shows that an alcohol-to-oil ratio of 6:1 is necessary for a
complete single-step reaction. Mono- and diglycerides of saturated fatty acids crystallize
easily from the biodiesel fuel and can cause fuel filter plugging and other performance
problems.
Freedman compared both crude and refined vegetable oils as feedstocks and found
that the yield of methyl esters was reduced from 93% to 98% for the refined oil to 67%
to 86% for the crude oil. This was attributed mostly to the presence of up to 6.66% free
fatty acids in the crude oil, although phospholipids were also suggested as a source of
catalyst destruction. In a study of the effects of phospholipids on biodiesel production,
Van Gerpen and Dvorak [20] found that phosphorus compounds in the oil did not carry
over into the methyl esters, and while yield was reduced by 3–5% for phosphorus levels
above 50 ppm, this was due mostly to added difficulty separating the glycerol from the
esters.

Fig. 2. Process flow schematic for biodiesel production.

 While virtually all commercial biodiesel producers use an alkali-catalyzed process
for the transesterification process, other approaches have been proposed, including acid
catalysis [21] and enzymes [22–25]. The use of acid catalysts has been found to be
useful for pretreating high free fatty acid feedstocks to convert the FFAs to esters but the
reaction rates for converting triglycerides to methyl esters are too slow. Enzymes have
shown good tolerance for the free fatty acid level of the feedstock, but the enzymes are
expensive and unable to provide the degree of reaction completion required to meet the
ASTM fuel specification [26]. Immobilization of the enzyme and use of multiple
enzymes in sequence may provide future opportunities in this area [23–25].
Fig. 2 shows a schematic diagram of the processes involved in biodiesel production.
Alcohol, catalyst, and oil are combined in a reactor and agitated for approximately 1 h at
60 8C. Smaller plants often use batch reactors [27], but most larger plants (N4 million
liters/year) use continuous flow processes involving continuous stirred-tank reactors
(CSTR) or plug flow reactors [28]. The reaction is sometimes done in two steps (as
suggested by the patent literature discussed earlier). In this system, approximately 80%
of the alcohol and catalyst is added to the oil in a first stage CSTR. Then the reacted
stream from this reactor goes through a glycerol removal step before entering a second
CSTR. The remaining 20% of the alcohol and catalyst are added in this reactor. This
system provides a very complete reaction with the potential of using less alcohol than
single-step systems.
Following the reaction, the glycerol is removed from the methyl esters. Due to the low
solubility of glycerol in the esters, this separation generally occurs quickly and may be
accomplished with either a settling tank or a centrifuge. The excess methanol tends to act
as a solubilizer and can slow the separation. However, this excess methanol is usually not
removed from the reaction stream until after the glycerol and methyl esters are separated
due to concern about reversing the transesterification reaction. Water may be added to the
reaction mixture after the transesterification is complete to improve the separation of
glycerol [27,29].
Saka and Kusiana [30–34] claim that it is possible to react the oil and methanol
without a catalyst, which eliminates the need for the water washing step. However,
temperatures of 300 8C–350 8C and methanol to oil molar ratios of 42:1 are required.
While the reaction only requires 120 s, the purity of the final product needs to be fully
characterized, and formation of nonmethyl ester compounds in significant amounts is
possible.
Dasari et al. [33] measured reaction rates without catalysts at temperatures of 120 8C to
180 8C. They noted the difficulty of reproducing reaction kinetics results of other
researchers [31,35] and attributed it to catalytic effects at the surfaces of the reaction
vessels and noted these effects would be exacerbated at higher temperatures. Not
including the effect of surface reactions could cause difficulties when scaling up reactors
due to the decrease in the ratio of reactor surface area to volume [33].
Kreutzer [36] has described how higher pressures and temperatures (90 bar, 240 8C)
can transesterify the fats without prior removal or conversion of the free fatty acids.
However, most biodiesel plants use lower temperatures, near atmospheric pressure, and
longer reaction times to reduce equipment costs.
 Boocock et al. [37–39] have developed a novel technique for accelerating the
transesterification reaction rate. During its early stages, the transesterification reaction
is limited by the low solubility of the alcohol, especially methanol, in the oil.
Boocock proposed the addition of a cosolvent to create a single phase, and this greatly
accelerates the reaction so that it reaches substantial completion in a few minutes. The
technique is applicable for use with other alcohols and for acid-catalyzed pretreatment
of high free fatty acid feed stocks. The primary concerns with this method are the
additional complexity of recovering and recycling the cosolvent although this can be
simplified by choosing a cosolvent with a boiling point near that of the alcohol being
used. Additional concerns have been raised about the hazard level associated with
the cosolvents most commonly proposed, tetrahydrofuran and methyl tertiary butyl
ether.
Returning to Fig. 2, after separation from the glycerol, the methyl esters enter a
neutralization step and then pass through a methanol stripper, usually a vacuum flash
process or a falling film evaporator, before water washing. Acid is added to the
biodiesel to neutralize any residual catalyst and to split any soap that may have formed
during the reaction. Soaps will react with the acid to form water soluble salts and free
fatty acids. The salts will be removed during the water washing step, and the free fatty
acids will stay in the biodiesel. The water washing step is intended to remove any
remaining catalyst, soap, salts, methanol, or free glycerol from the biodiesel.
Neutralization before washing reduces the water required and minimizes the potential
for emulsions to form when the wash water is added to the biodiesel. Following the
wash process, any remaining water is removed from the biodiesel by a vacuum flash
process.
The glycerol stream leaving the separator is only about 50% glycerol. It contains some
of the excess methanol and most of the catalyst and soap. In this form, the glycerol has
little value and disposal may be difficult. The methanol content requires the glycerol to
be treated as hazardous waste. The first step in refining the glycerol is usually to add acid
to split the soaps into free fatty acids and salts. The free fatty acids are not soluble in the
glycerol and will rise to the top where they can be removed and recycled. The salts
remain with the glycerol although depending on the chemical compounds present, some
may precipitate out. Mittelbach describes a process for esterifying these free fatty acids
and then returning them to the transesterification reaction stream [40]. One frequently
touted option is to use potassium hydroxide as the reaction catalyst and phosphoric acid
for neutralization so that the salt formed is potassium phosphate, which can be used for
fertilizer. After acidulation and separation of the free fatty acids, the methanol in the
glycerol is removed by a vacuum flash process or another type of evaporator. At this
point, the glycerol should have a purity of approximately 85% and is typically sold to a
glycerol refiner. The glycerol refining process takes the purity up to 99.5% to 99.7%
using vacuum distillation or ion exchange processes.
The methanol that is removed from the methyl ester and glycerol streams will tend to
collect any water that may have entered the process. This water should be removed in a
distillation column before the methanol is returned to the process. This step is more
difficult if an alcohol such as ethanol or isopropanol is used that forms an azeotrope with
water. Then a molecular sieve is used to remove the water.
 Special processes are required if the oil or fat contains significant amounts of free
fatty acids (FFAs). Used cooking oils typically contain 2–7% FFAs, and animal fats
contain from 5% to 30% FFAs. Some very low quality feedstocks, such as trap grease,
can approach 100% FFAs. When an alkali catalyst is added to these feedstocks, the free
fatty acids react with the catalyst to form soap and water, as shown in the reaction
below:

Up to about 5% FFAs, the reaction can still be catalyzed with an alkali catalyst, but
additional catalyst must be added to compensate for the catalyst lost to soap. The soap
that is created during the reaction is either removed with the glycerol or is washed out
during the water wash. When the FFA level is above 5%, the soap inhibits separation of
the methyl esters and glycerol and contributes to emulsion formation during the water
wash. For these cases, an acid catalyst, such as sulfuric acid, can be used to esterify the
free fatty acids to methyl esters, as shown in the following reaction:

This process can be used as a pretreatment to convert the FFAs in high FFA
feedstocks to methyl esters and thereby reduce the FFA level. Then the low FFA
pretreated oil can be transesterified with an alkali catalyst to convert the triglycerides
to methyl esters. Keim [9] describes using this approach to convert palm oil
containing 50.8% free fatty acids to methyl esters. Methanol (77% of the weight of
oil) and sulfuric acid (0.75% of the weight of oil) were added to the oil while
stirring at 69 8C for 1 h. After neutralization, 1.25% sodium methoxide was added,
and the mixture was stirred for an additional hour at 50 8C. Analysis showed a yield
of 97% but a residual acid value equivalent to about 5% palmitic acid. The
incomplete reaction was probably due to water in the reactant mixture. As shown in
the reaction, water is formed, and if it accumulates, it can stop the reaction well
before completion. Kawahara and Ono [42] propose allowing the alcohol to separate
from the pretreated oil or fat following the reaction. Removal of this alcohol also
removes the water formed by the esterification reaction and allows for a second step
of esterification or proceeding directly to alkali-catalyzed transesterification. Jeromin
et al. [41] has described using acidic ion exchange resins in a packed bed for the
pretreatment.
Haas et al. [43,44] have shown that acid-catalyzed esterification can be used to
produce biodiesel from low-grade by-products of the oil refining industry, such as
soapstock. Soapstock, a mixture of water, soaps, and oil, is dried, saponified, and then
esterified with
methanol or some other simple alcohol using an inorganic acid as a catalyst. The
procedure relies on a large excess of alcohol, and the cost of recovering this alcohol
determines the feasibility of the process.
Zhang et al. [45,46] have reviewed the commonly used procedures for producing
biodiesel, including a process simulation using the commercial software package
HYSYS. Their economic assessment indicated that use of waste cooking oil feedstocks
provided a higher rate of return than refined vegetable oils even after including the
additional capital and operating costs of acid-catalyzed pretreatment.
The primary criterion for biodiesel quality is adherence to the appropriate standard. In
the United States, this standard is ASTM D 6751-02. This standard gives the required
extent of reaction through specifications for the total glycerol remaining in the fuel. The
total glycerol is defined as the sum of the free and bound glycerol, and the bound
glycerol is equal to the glycerol portion of the residual mono-, di-, and triglycerides. The
amount of residual methanol, catalyst, soap, and glycerol is controlled by limits on the
fuel’s flashpoint, ash level, and free glycerol. When these limits are met, the biodiesel
can be used in most modern engines without modifications while maintaining the
engine’s durability and reliability.

3. Conclusions

Biodiesel is an important new alternative transportation fuel. It can be produced from

many vegetable oil or animal fat feedstocks. Conventional processing involves an alkali-
catalyzed process, but this is unsatisfactory for lower cost high free fatty acid feedstocks
due to soap formation. Pretreatment processes using strong acid catalysts have been
shown to provide good conversion yields and high-quality final products. These
techniques have even been extended to allow biodiesel production from feedstocks like
soapstock that are often considered to be waste.

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