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Biodiesel Production From Oils and Fats PDF
Biodiesel Production From Oils and Fats PDF
ABSTRACT. Biodiesel is an alternative fuel for diesel engines consisting of the alkyl monoesters of fatty acids from vegetable
oils or animal fats. Most of the biodiesel that is currently made uses soybean oil, methanol, and an alkaline catalyst. The high
value of soybean oil as a food product makes production of a costeffective fuel very challenging. However, there are large
amounts of lowcost oils and fats such as restaurant waste and animal fats that could be converted to biodiesel. The problem
with processing these low cost oils and fats is that they often contain large amounts of free fatty acids (FFA) that cannot be
converted to biodiesel using an alkaline catalyst. In this study, a technique is described to reduce the free fatty acids content
of these feedstocks using an acidcatalyzed pretreatment to esterify the free fatty acids before transesterifying the triglycerides
with an alkaline catalyst to complete the reaction. Initial process development was performed with synthetic mixtures
containing 20% and 40% free fatty acids, prepared using palmitic acid. Process parameters such as the molar ratio of alcohol,
type of alcohol, acid catalyst amount, reaction time, and free fatty acids level were investigated to determine the best strategy
for converting the free fatty acids to usable esters. The work showed that the acid level of the high free fatty acids feedstocks
could be reduced to less than 1% with a 2step pretreatment reaction. The reaction mixture was allowed to settle between
steps so that the watercontaining alcohol phase could be removed. The 2step pretreatment reaction was demonstrated with
actual feedstocks, including yellow grease with 12% free fatty acids and brown grease with 33% free fatty acids. After reducing
the acid levels of these feedstocks to less than 1%, the transesterification reaction was completed with an alkaline catalyst
to produce fuelgrade biodiesel.
Keywords. Alternative fuel, Biodiesel, Diesel, High free fatty acid, Rendered animal fat, Waste restaurant oil.
T
hroughout its history, the diesel engine has been the for diesel engines can cause numerous enginerelated prob-
subject of a great deal of research and development. lems (Korus et al., 1982; Van der Walt and Hugo, 1982). The
This work has focused on improving emissions and increased viscosity and low volatility of vegetable oils lead
fuel economy and, more recently, on finding an to severe engine deposits, injector coking, and piston ring
appropriate fuel. For many years, the ready availability of sticking (Vellguth, 1983; Clark et al., 1984; Pestes and Sta-
inexpensive middledistillate petroleum fuels provided little nislao, 1984; Perkins and Peterson, 1991). However, these ef-
incentive for experimenting with alternative, renewable fuels fects can be reduced or eliminated through transesterification
for diesel engines. However, since the oil crisis of the 1970s, of vegetable oil to form methyl esters, commonly known as
research interest has expanded in the area of alternative fuels. biodiesel (Zhang et al., 1988; Perkins and Peterson, 1991).
Many proposals have been made regarding the availability Transesterification provides a fuel viscosity that is close to
and practicality of an environmentally sound fuel that could that of No. 2 diesel fuel.
be domestically sourced. Methanol, ethanol, compressed Biodiesel is receiving increased attention as an alterna-
natural gas (CNG), liquefied petroleum gas (LPG), liquefied tive, nontoxic, biodegradable, and renewable diesel fuel. Its
natural gas (LNG), vegetable oils, reformulated gasoline, and properties vary somewhat depending on the oil feedstock and
reformulated diesel fuel have all been considered as alcohol used but it can always be used as a direct substitute
alternative fuels. Of these alternative fuels, only ethanol and for diesel fuel (Mittelbach et al., 1992; Peterson et al., 1992;
vegetable oils are nonfossil fuels. Peterson et al., 1994). Biodiesel has a higher cetane number
Many researchers have concluded that vegetable oils hold than diesel fuel, no aromatics, almost no sulfur, and contains
promise as alternative fuels for diesel engines (Goering et al., 10% to 11% oxygen by weight. These characteristics of bio-
1982; Bagby et al., 1987). However, using raw vegetable oils diesel reduce the emissions of carbon monoxide (CO), hydro-
carbon (HC), and particulate matter (PM) in the exhaust gas
compared to petroleumbased diesel fuel. In spite of its desir-
Article was submitted for review in August 2001; approved for able properties as a diesel fuel substitute, biodiesel from
publication by the Soil & Water Division of ASAE in September foodgrade oils is not economically competitive with petro-
2001. leumbased diesel fuel. Lowercost feedstocks are needed.
The authors are Mustafa Canakci, Kocaeli University, Izmit, Turkey; The objective of this study was to develop a process for pro-
and Jon Van Gerpen, ASAE Member Engineer, Professor, Department of
Mechanical Engineering, Iowa State University, Ames, Iowa. ducing fuel quality biodiesel from lowcost feedstocks with
Corresponding author: Jon Van Gerpen, Iowa State University, Dept. of high FFAs. The process development is described in this ar-
Mechanical Engineering, 2022 Black Engineering Building, Ames, IA ticle and the implementation of the process on a pilot plant
50011; phone: 5152945563, fax: 5152943261, email: jvg@iastate scale is described in a second article (Canakci and Van Ger-
.edu.
2.5
Run time Catalyst amount Catalyst amount
(hours) 5% 15% 25% 5% 15% 25% 2.0
0 hours 0.10 0.10 0.10 0.10 0.10 0.10
1.5
0 hours (after
palmitic acid
1.0
addition) 41.33 41.33 41.33 91.73 91.73 91.73
One minute 0.5
after catalyst
addition 4.14 4.19 3.35 8.96 6.92 7.80 0.0
0.25 4.17 3.58 2.46 9.18 7.15 5.35 0 5 10 15 20 25 30 35 40
Second Step Molar Ratio
0.50 3.79 3.50 2.73 8.89 5.49 6.61
Figure 2. Effect of molar ratio on the acid value of the mixture in 2nd step
1.00 3.63 3.57 3.00 8.09 5.60 6.45 for 1 h reaction time.
[a] 9:1 molar ratio of ethanol to FFA; catalyst: H2SO4.
Free, and Combined Glycerol (IodometricPeriodic Acid) after the main transesterification. The interphase material
Method (AOCS, 1991). This total glycerin amount was too will be discussed in a later section.
high to meet the total glycerin specification. A series of tests The reason for the differences between the simulated feed-
conducted with various FFA levels found that with KOH as stock and the yellow grease is still under investigation. Even
the catalyst, the FFA level must be less than 1 mg KOH/g in though the recipes for the pretreatment that were developed
order to produce ester with less than 0.24% total glycerin. using the synthetic feedstock needed to be changed, the para-
The results of other researchers (Feuge and Gros, 1949; metric studies were still considered to be useful since they
Freedman et al., 1984) confirm these results. Results to be re- identified the effects of the variables and made the required
ported later show that sodium methoxide is more tolerant of changes in the process easy to predict.
FFAs than KOH. Previous experience had shown that to get the FFA below
1 mg KOH/g after the second pretreatment step, the first step
PREPARATION OF METHYL ESTERS FROM YELLOW AND needed to get the FFA level to approximately 5 mg KOH/g.
BROWN GREASE Therefore, the first step was repeated with the molar ratio in-
To determine whether the process developed using the creased to 20:1 and the reaction time increased to 1 h. At this
synthetic high FFA feedstock could be extended to actual time, the acid value of the oil mixture was measured to be
feedstocks, methyl esters of yellow and brown grease were 5.22 mg KOH/g after the first step reaction.
prepared. The yellow grease was obtained from the Simonsen Using the material from the first pretreatment step, the
rendering plant in Quimby, Iowa. Rendering plant greases reaction was continued for the second step at three different
typically have a FFA level between 5% and 25% depending molar ratios with 5% sulfuric acid for 1 h. The changes in the
on the time of year. The specific fat analyzed for this project acid value of the mixture are shown in Table 5. The acid value
had an acid value of 25.15 mg KOH/g, which corresponds to of the mixture decreased to as low as 0.74 mg KOH/g with a
a FFA level of about 12%. The fatty acid distribution of the 40:1 molar ratio of methanol to FFA.
yellow grease is shown in table 4 compared to soybean oil. To investigate the useful range of the process developed
As would be expected from yellow grease derived primarily for yellow grease biodiesel production, the pretreatment
from animal fat, the fat was solid at room temperature. technique was applied to brown grease with an acid value of
66.08 mg KOH/g, which corresponds to a FFA level of about
Pretreatment of Yellow and Brown Grease 33%. The fatty acid composition of the brown grease was not
After filtering the yellow grease at 5560C using a 105 available. Initial tests showed that a twostep pretreatment
mm mesh polypropylene filter, a 5% sulfuric acid solution reaction with 20:1 molar ratio and 5% H2SO4 catalyst did not
with a 7.4:1 molar ratio of methanol to FFA, was added. The reduce the FFA to less than 2 mg KOH/g. A third step was
reaction was continued for 30 minutes at 60C. After settling needed with a 40:1 molar ratio. Three steps of pretreatment
overnight and separating the methanolwater mixture from were considered to be undesirable because the extra step of
the top, the acid value of the fatester mixture was measured pretreatment requires more time, more alcohol, and as will be
to be 14.63 mg KOH/g. This value was much higher than was shown later, reduces the yield. When the sulfuric acid catalyst
expected based on the work described earlier with the syn- amount was increased to 10%, the acid values after the first
thetic high FFA mixtures. The acid value change of the syn- and second steps were reduced to around 5 mg KOH/g and 2
thetic mixture with 20% palmitic acid decreased from 41.33 mg KOH/g, respectively. Therefore, the final recipe for the
mg KOH/g to 8.31 mg KOH/g with an 7.4:1 molar ratio while high FFA pretreatment consisted of a 1h reaction time, 10%
the yellow grease which started at 25.15 mg KOH/g only de- sulfuric acid amount, and 20:1 molar ratio for the first step,
creased to 14.63 mg KOH/g. A number of possible reasons and a 40:1 molar ratio for the second step. The changes in the
for the difference were proposed. Initially, it was thought that
Table 5. Effect of molar ratio on acid value in second step
the water in the yellow grease could be inhibiting the reac- at 5% catalyst amount.
tion. However, the water formed in the pretreatment reaction Reaction time Acid value
and that initially in the yellow grease were about 0.9% and Methanol molar ratio (hours) (mg KOH/g)
0.2%, respectively. So, the initial water amount was actually Before test 5.22
quite small compared to that produced by the reaction. In
20:1 1.0 1.64
addition, the total water amount produced in the pretreatment
30:1 1.0 1.19
reaction of the 20% palmitic acid mixture was about 1.3% 40:1 1.0 0.74
water. The initial water level of 0.2% does not seem to be
large enough to explain the difference in the extent of reac- Table 6. Effect of 10% catalyst amount on the acid value
tion. Yellow grease generally contains some unsaponifiable in 2 steps pretreatment reaction.
material and this may also affect the pretreatment reaction. Methanol molar ratio Run 1 Run 2
This material is almost certainly the cause of the interphase Before test 66.08 66.08
material that accumulated between the ester and wash water 1st step (20:1) 5.20 5.10
2nd step (40:1) 2.08 1.98
Temperature ( C)
turned to the process to maximize the yield. In recognition of
o
30
the losses when the methanolwater mixture is removed, it
was decided that the methanolwater mixture would not be 20
removed after the last step of pretreatment. The small amount 10
of water present in the mixture at this point does not seem to
affect the reaction. 0
Upper Phase (Yellow Grease 9% FFA) Lower Phase (Yellow Grease 9% FFA)
The catalyst amount used in transesterification was anoth- 10
Upper Phase (Brown Grease 33% FFA)
Upper Phase (Soybean Oil)
Lower Phase (Brown Grease 33% FFA)
Lower Phase (Soybean Oil)
er factor that affected the yield. When excess alkaline cata- Upper Phase (Lard)
Upper Phase (YGME)
Lower Phase (Lard)
Lower Phase (YGME)
lyst was used in the transesterification, it increased the soap 20
0 20 40 60 80 100
amount and the interphase. Interphase was the name given to % Methanol
a middle phase that appeared during the washing process be- Figure 3. Solubility of soybean oil, lard, YGME, yellow grease, and brown
tween the animal fat ester and the wash water. The composi- grease in methanol.
tion of the interphase has not been determined but it is
insoluble in both the ester and water. Interphase was never feedstocks were processed. At the higher FFA levels, the
observed when processing soybean oil, lard, tallow, or the methanolwater mixture removed during pretreatment was
synthetic high FFA feedstock. It apparently originates from carrying a greater amount of methyl ester and unreacted fat.
unsaponifiable material in the yellow and brown grease and This problem can be addressed by separating the methanol
may be calcium based since it was found only in animal fat and water from the material removed during pretreatment
greases. After the 4th washing step, the interphase was sepa- and returning the residue to the process stream.
rated from the ester. During the separation, some ester was
unavoidably removed with the interphase. The amount of in-
terphase decreased when the number of pretreatment steps CONCLUSIONS
was decreased from three to two. The objective of this study was to investigate the use of
lowcost, high FFA feedstocks to produce fuelquality bio-
The Effect of Solubility of Methanol in the Oils and diesel. It was determined that feedstocks with high FFAs
Methyl Ester could not be transesterified with the traditional alkaline cata-
To understand the losses of ester and fat in the pretreat- lysts that have been used with good success for vegetable oils.
ment process, the solubility of the reactants with methanol Alkaline catalysts form soap when they react with the FFAs.
was studied as a function of temperature. Soybean oil, lard, Soap removes the catalyst from the reaction and prevents the
yellow grease methyl ester (YGME), yellow grease, and separation of the glycerin and the ester.
brown grease were mixed with equal volumes of methanol at A process was developed to use acid catalysts to pretreat
60C for 1 h. No catalyst was added so chemical reaction was the high FFA feedstocks until their FFA level was below 1%,
assumed to be negligible. Table 2 shows that some reaction allowing the subsequent use of alkaline catalysts to convert
can occur between FFAs and methanol even without catalyst. the triglycerides. The effects of the methanol molar ratio,
In addition, the catalyst may affect the solubility of methanol acid catalyst amount, and reaction time on the reduction of
in the yellow grease. For these reasons, the data presented FFA level were studied with a simulated high FFA feedstock
here should not be taken as representative of actual reaction consisting of 20% palmitic acid in soybean oil. This part of
conditions. However, they do explain the processes that oc- the study showed that the FFA level of the feedstocks could
cur during the pretreatment process. be reduced to less than 1% with a 2step process of acidcata-
After mixing, the mixture was placed in a constant tem- lyzed pretreatment. Extension of the process to yellow and
perature bath. Each hour the temperature was reduced in brown grease showed that higher levels of acid catalyst and
10C decrements starting with 60C. At each temperature, methanol were required.
two samples were drawn from the upper and lower phases of The following specific conclusions are based on the pro-
the mixture and the samples were heated on a hot plate to cess development portion of this project.
evaporate the methanol. After evaporation, the percentages 1. The acidcatalyzed pretreatment reaction decreased the
of methanol in the lower phase and the upper phase were cal- acid value of the synthetic mixture to less than 2 mg
culated. Figure 3 shows the solubility of the reactants in KOH/g with a 2step process. Using the 2step acid
methanol at the different temperatures. The solubility of catalyzed pretreatment followed by an alkalicatalyzed
methanol in soybean oil and lard was low and about the same final reaction, the transesterification reaction was
for both compounds. This indicates that the solubility is not completed in much less time than would be possible with
affected by the saturation of the oil or fat. However, the solu- acidcatalyzed transesterification alone.
bility of the oil was strongly related to its FFA level and ester 2. Increasing the acid catalyst amount is very effective in
amount. When the two greases with different FFA levels (9% decreasing the acid value of the mixture. In the first
and 33%) are compared, it can be seen that the methanol solu- pretreatment step, using a 10:1 molar ratio and 30 min of
bility increases with higher FFA. The solubility of the metha- reaction time, the acid value of the simulated high FFA
nol in YGME was the highest among the samples. The feedstock was reduced from 41.33 mg KOH/g to 1.37 mg
YGME formed a single phase with methanol at 40C. These KOH/g using 15% acid catalyst.
data show why the yield decreased when the higher FFA 3. Ethanol decreased the FFA level of the synthetic mixture
faster than methanol.