FAPC-150

Robert M. Kerr Food & Agricultural Products Center

f a p c
FOOD TECHNOLOGY
FACT SHEET
Adding Value to Oklahoma 405-744-6071 • www.fapc.biz

Biodiesel Production Techniques

Nurhan Turgut Dunford
FAPC Oilseed Chemist

Base Catalysis/Transesterification to 1.5 percent of the weight of the oil) is required when
Biodiesel production requires a feedstock (fat or NaOH or KOH is used. NaOH and KOH also lead to
oil) and an alcohol. In most cases, a catalyst also is water formation, which slows the reaction rate and causes
present. Figure 1 shows a schematic diagram of the unit soap formation.
operations involved in biodiesel production. Depend- Methanol is the most common alcohol used for con-
ing on the quality of the feedstock, either esterification version of fats and oils to biodiesel. Methanol is flam-
or transesterification reactions are used for biodiesel mable, so proper handling is required for safety. Detailed
production (see FAPC Fact Sheet FAPC-149 Biodiesel information on methanol and biodiesel handling can be
Glossary for definition of the terms). Most of the cur- found at www.biodieselcommunity.org/safety or www.
rent biodiesel production operations use base catalysis biodiesel.org/pdf_files/fuelfactsheets/MSDS.pdf.
(transesterification). This method works well if the free Transesterification is a reversible reaction. Thus, ex-
fatty acid, moisture and phosphorous contents of oil/ cess methanol is required to shift the equilibrium favor-
fat are less than 0.1 percent, less than 0.1 percent and ably. Table 1 shows approximate amounts of oil, alcohol
less than 10 ppm, respectively. Typical feedstocks for and catalyst required and the amount biodiesel and glyc-
biodiesel production are soybean, canola/rapeseed, sun- erine produced through transesterification. Theoretical
flower, cottonseed, palm seed and palm kernel, corn and biodiesel yields for biodiesel soybean and tallow are as
mustard seed oil. Pork, beef and poultry fat and grease follows: 1004.2 kg/1000 kg soybean and 998.1 kg/1000
also can be converted to biodiesel. Palm oil and animal kg tallow. The amount of methanol in Table 1 is based on
fat may have a high free fatty acid content, which causes 100 percent excess, and the data are for transesterification
soap formation that has adverse effects on downstream using sodium methoxide as a catalyst.
processing and leads to yield reduction.
Sodium hydroxide (NaOH), potassium hydroxide Table 1. Approximate reactant and product amounts for
transesterification reaction.
(KOH) and sodium methoxide (CH3ONa) are the most
common catalysts for transesterification. Sodium methy-
Chemicals/Feedstock/Product Amount (lbs)
late (sodium methoxide) is more effective than NaOH
Oil/fat 100
and KOH as a catalyst, but it is more expensive. Sodium
Methanol 22
methoxide is sold as a 30 percent solution in methanol
Catalyst 0.3 -­ 0.5
for easier handling. Base catalysts are very sensitive to
Biodiesel 100
the presence of water and free fatty acids. The amount
Glycerine 11
of sodium methoxide required is 0.3 to 0.5 percent of
Excess methanol 11
the weight of the oil. A higher amount of catalyst (0.5

Oklahoma Cooperative Extension Service • Division of Agricultural Sciences and Natural Resources
 Methanol and oil do not mix well, and poor contact Acid Catalysis
between the oil and methanol reactants means the reac- If the free fatty acid content of the feedstock is
tion rate is slow. Vigorous mixing at the beginning of the greater than 1 percent, base catalysis is not suitable.
reaction improves reaction rates. Near the end of the reac- There are two approaches for handling high free fatty
tion, reduced mixing helps the separation of glycerine, acid content feedstock.
and the reaction would proceed faster in the top layer, One way would be to refine the feedstock before base
which is oil and methanol. At ambient temperature (21 catalysis. Free fatty acids can be removed by chemical
degrees Celsius or 70 degrees Fahrenheit), the reaction neutralization or physical deacidification. Chemical
takes four to eight hours to complete. The reaction is neutralization involves treatment with caustic NaOH or
usually conducted below the boiling point of methanol KOH. Soap formed during this process is removed, and
(60 degrees Celsius or 140 degrees Fahrenheit). At this the remaining oil is ready for base catalysis. However,
temperature, the reaction time may vary between 20 some oil is lost during this process. Physical deacidifica-
minutes to one and a half hours. A higher temperature tion, or steam stripping, also removes free fatty acids. This
will decrease reaction times, but this requires use of a process is performed under vacuum and requires steam.
pressure vessel because the boiling point of methanol Fats and oils with high free fatty acid content can
is 65 degrees Celsius or 148 degrees Fahrenheit. The be converted to biodiesel using acid catalysis, which is
reactor is either sealed or equipped with a condenser the second approach for handling high free fatty acid
to minimize alcohol evaporation during the conversion content feedstock. This technique uses a strong acid.
process. Higher oil conversion rates can be achieved if Soap formation is not a problem because there are no
the production system is set up as a two-step process alkali metals in the reaction medium. Acid catalysts can
with two reactors. In such cases, glycerine formed in the be used for transesterification of the triglycerides, but the
first reactor is removed, and the reaction is completed in reaction might take several days to complete. This is too
the second reactor. slow for industrial processing.

Figure 1. Typical flow diagram for conversion of oil to biodiesel

Dryer
Biodiesel

Oil/fat Wash
Biodiesel
Column
Alcohol/ Reactor Separator
catalyst Water
Glycerine + Alcohol

Alcohol

Alcohol Glycerine + Water Glycerine

Recovery + Alcohol Recovery

Glycerine
Glycerine + Water

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 Acid catalysis also is used for direct esterification for re-use. There are also solid catalysts that can be used
of oils with high free fatty acid content or for making for biodiesel production. This process, which is referred
esters from soap stock, which is a byproduct of edible oil to as heterogeneous catalysis, utilizes fixed-bed reactors,
refining. The esterification of free fatty acids to alcohol and the catalyst stays in the reactor and is used for an
esters is relatively fast; it would take about one hour at extended time. Sulfonic resins such as Nafion® NR50,
60 degrees Celsius to complete the reaction. Water is sulphated zirconia (SZ) and tungstated zirconia (WZ)
formed during this reaction. To improve reaction rates, have sufficient acid site strength to catalyze biodiesel-
water needs to be removed from the reaction medium forming transesterification reactions as efficiently as
by phase separation. sulfuric acid. Alkaline earth metal oxides, various alka-
Acid catalysis requires a high alcohol to free fatty line metal compounds supported on alumina or zeolite
acid ratio (20:1 or 40:1 mole ratio) and large amount of can catalyze transesterification reactions. Information
catalyst (5-25 percent). Sulfuric acid and phosphoric about a commercial system that uses a solid catalyst can
acid are the most common acid catalysts. The feedstock be found at www.axens.net. In general, heterogeneous
is sometimes dried to 0.4 percent water and filtered be- catalysis systems are designed for continuous opera-
fore the reaction. Then, an acid and methanol mixture tion and produce high-purity glycerine (greater than 98
is added to the feedstock. Once the conversion of the percent). The product, fatty acid esters, does not require
fatty acids to methyl esters has reached equilibrium, the water washing, and yields are generally high. It also has
methanol, water and acid mixture is removed by settling been reported that catalyst requirements per ton of biod-
or centrifugation. Fresh methanol and base catalyst are iesel for heterogeneous catalysis are much lower than for
added into the remaining oil for transesterification. The other processes. However, these systems operate under
rest of the process is the same as base catalysis shown in high temperature and pressure.
Figure 1. Reaction times of 10 minutes to 2 hours have
been reported. Non-Catalytic Conversion Techniques
Both transesterification and esterification reactions Due to poor methanol and oil miscibility, conversion
can be operated either as a batch or continuous process. of oil to biodiesel is a very slow reaction. Use of a co-
A batch process is better suited to smaller plants that solvent that is soluble in both methanol and oil may im-
produce less than 1 million gallons per year and provide prove reaction rates. The BIOX Process (www.bioxcorp.
operation flexibility. Continuous processing allows use com) uses either tetrahydrofuran (THF) or MTBE-methyl
of high-volume separation systems, and therefore in- tert-butyl ether as a co-solvent to generate a one-phase
creases throughput. system. In the presence of a co-solvent, the reaction is 95
percent complete in 10 minutes at ambient temperatures
Enzymatic Conversion and does not require a catalyst. THF has a boiling point
There is interest in using lipases for enzymatic ca- very close to that of methanol. The excess methanol
talysis of oils for biodiesel production. The enzymes and co-solvent are recovered in a single step after the
can be used in solution or immobilized onto a support reaction is complete. Co-solvents that are subject to the
material, which allows the use of fixed-bed reactors. The hazardous and/or toxic air Environmental Protection
reaction can be performed at 35 to 45 degrees Celsius. Agency (EPA) list for air pollutants must be completely
However, the reaction is very slow, requiring from four removed from the biodiesel and its byproducts (glycerine
to 40 hours. Because of the high cost of the enzymes, and methanol). Emissions must be tightly controlled, and
this process is not economically feasible for biodiesel processing equipment must be “leak proof.”
production at this time. The second non-catalytic approach utilizes methanol
at very high temperature and pressure (350 to 400 degrees
Solid Catalyst Celsius and greater than 80 atm or 1200 psi) to convert
The processes discussed above, which also are re- oil to biodiesel. This process requires a high alcohol to
ferred to as homogeneous catalysis, involve utilization of oil ratio (42:1 mole ratio). The reaction is complete in
a catalyst that is soluble in alcohol. In these systems the about three to five minutes. The process requires high
catalyst ends up in the byproducts, and it is not recovered pressure vessels which can be quite expensive. The en-

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ergy consumption also is higher than the conventional to be minimized for good phase separation. Glycerine
processes. The reaction must be quenched very rapidly and methanol can be further purified by distillation.
so the products do not decompose. Resins or adsorbents have been used to purify biodiesel
to eliminate water wash. The residual methanol in biod-
Downstream Processing iesel still needs to be evaporated. Examples of some of
Biodiesel will be in a mixture of excess methanol, the commercial adsorbents and ion exchange resins can
catalyst and glycerine after the completion of the oil be found at www.dallasgrp.com/biodiesel.pdf or www.
conversion reaction. As a rule of thumb difference, in amberlyst.com/biodiesel_purification.
specific gravity of 0.1 in a mixture of compounds will
result in phase separation by gravity. As can be seen in Table 2. Specific gravity of the compounds used and
produced during biodiesel production.
Table 2, gravity separation is suitable to recover biodiesel
from the process byproducts (glycerine and methanol).
Compound Specific Gravity
However, impurities in the feedstock may cause emul-
Methanol .79
sion formation, which interferes with phase separation.
Biodiesel .88
Saturated salt (sodium chloride) or centrifugation breaks
Soybean oil .92
the emulsion and speeds up the phase separation.
Catalyst .97
A good conversion reaction will require excess
Glycerine 1.28
methanol, but the amount of methanol in the system has

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