Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
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.
for diesel engines can cause numerous enginerelated problems (Korus et al., 1982; Van der Walt and Hugo, 1982). The
increased viscosity and low volatility of vegetable oils lead
to severe engine deposits, injector coking, and piston ring
sticking (Vellguth, 1983; Clark et al., 1984; Pestes and Stanislao, 1984; Perkins and Peterson, 1991). However, these effects can be reduced or eliminated through transesterification
of vegetable oil to form methyl esters, commonly known as
biodiesel (Zhang et al., 1988; Perkins and Peterson, 1991).
Transesterification provides a fuel viscosity that is close to
that of No. 2 diesel fuel.
Biodiesel is receiving increased attention as an alternative, nontoxic, biodegradable, and renewable diesel fuel. Its
properties vary somewhat depending on the oil feedstock and
alcohol used but it can always be used as a direct substitute
for diesel fuel (Mittelbach et al., 1992; Peterson et al., 1992;
Peterson et al., 1994). Biodiesel has a higher cetane number
than diesel fuel, no aromatics, almost no sulfur, and contains
10% to 11% oxygen by weight. These characteristics of biodiesel reduce the emissions of carbon monoxide (CO), hydrocarbon (HC), and particulate matter (PM) in the exhaust gas
compared to petroleumbased diesel fuel. In spite of its desirable properties as a diesel fuel substitute, biodiesel from
foodgrade oils is not economically competitive with petroleumbased diesel fuel. Lowercost feedstocks are needed.
The objective of this study was to develop a process for producing fuel quality biodiesel from lowcost feedstocks with
high FFAs. The process development is described in this article and the implementation of the process on a pilot plant
scale is described in a second article (Canakci and Van Ger-
1429
Product
Rapeseed oil
Sunflower oil
Safflower oil
Soybean oil
Lard
Tallow
Yellow grease
Brown grease
[a]
C14:0
12
36
2.43
1.66
Table 1. Fatty acid distribution of some vegetable oils and animal fats.
Fatty acid distribution (% by weight)
Saturation
C16:0
C16:1
C18:0
C18:1
C18:2
C18:3
level (%)
3.49
0.85
64.40
22.30
8.23
4.34
6.08
3.26
16.93
73.73
9.34
8.60
1.93
11.58
77.89
10.53
10.58
4.76
22.52
52.34
8.19
15.34
2830
1218
4050
713
4150
2432
2025
3743
23
4763
23.24
3.79
12.96
44.32
6.97
0.67
38.63
22.83
3.13
12.54
42.36
12.09
0.82
37.03
Reference
Goering, 1982
Goering, 1982
Goering, 1982
[a]
Linstromberg, 1970
Linstromberg, 1970
[a]
[a]
1430
100
EXPERIMENTAL METHODS
Test Conditions:
90
80
Ester Conversion (%)
70
60
Ester Conversion (%)
(with water from
reaction of palmitic
acid)
50
40
30
20
10
0
0
2
3
4
Water% of Weight of Oil
1431
Table 2. Effect of catalyst amount and reaction time on the acid value
of soybean oil containing 20% and 40% palmitic acid[a].
Acid value (mg KOH/g)
20% FFA
40% FFA
Run time
(hours)
0 hours
Catalyst amount
0%
5%
15% 25%
Catalyst amount
5%
15% 25%
0.10
0.10
0.10
0 hours (after
palmitic acid
addition)
41.33
One minute
after catalyst
addition
38.19
0.25
37.07
5.80
2.86
4.30
0.50
35.73
3.83
1.15
0.92
1.00
33.38
1.77
0.67
0.54
18.82
[a]
0.10
0.10
0.10
8.09
0.10
6.25
25%, based on the FFA weight in the mixture, for a 1h reaction time. The test results are shown in table 3. The minimum
acid value for the 20% FFA case, after 1 h, was measured to
be 3.00 mg KOH/g with 25% sulfuric acid. While the final
acid values for the 20% FFA case were higher for ethanol than
for methanol, the rate of the reaction was faster for ethanol.
This may be due to the higher reaction temperature or ethanols higher solubility in oils and esters. The final acid values
for ethanol reacting with the 40% FFA feedstock were lower
than with methanol. Another observation was that the samples taken in the tests with ethanol did not freeze while being
stored in the refrigerator, as was observed for the tests with
methanol.
DEVELOPMENT OF 2STEP PRETREATMENT PROCESS
The tests described above show that the FFA level of the
20% FFA synthetic mixture can be decreased to below the target of 1% (2 mg KOH/g). However, the amounts of catalyst
and methanol were considered to be quite high, and FFA levels of 40% could not be processed. A method that would be
sufficiently robust to process 40% FFA mixtures while using
reasonable amounts of methanol and acid was needed. Since
water formation when the FFAs are converted to esters inhibits the reaction, the water must be removed to complete the
reaction. Hammond (1998) suggested that this could be
0 hours (after
palmitic acid
addition)
20% FFA
40% FFA
Catalyst amount
5%
15%
25%
Catalyst amount
5%
15%
25%
0.10
0.10
41.33
0.10
41.33
0.10
41.33
91.73
0.10
91.73
0.10
91.73
One minute
after catalyst
addition
4.14
4.19
3.35
8.96
6.92
7.80
0.25
4.17
3.58
2.46
9.18
7.15
5.35
0.50
3.79
3.50
2.73
8.89
5.49
6.61
1.00
3.63
3.57
3.00
8.09
5.60
6.45
[a]
Test Condition:
Sulfuric Acid Amount: 5%
Reaction Temperature: 60oC
Reaction Time: 1 Hour each
for 1st and 2nd Steps
3.0
Acid Value (mg KOH/g)
Run time
(hours)
0 hours
3.5
Acid value (mg KOH/g) after 10:1
molar ratio and 1 hour reaction
Recommended maximum acid value
for transesterification
2.5
2.0
1.5
1.0
0.5
0.0
0
10
15
20
25
Second Step Molar Ratio
30
35
40
Figure 2. Effect of molar ratio on the acid value of the mixture in 2nd step
for 1 h reaction time.
1432
Table 4. Fatty acid composition of the yellow grease and soybean oil.
Carbon chain (% by wt.)[a]
Product
Soybean oil
Yellow grease
[a]
C14:0
C15:0
C16:0
C16:1
C17:0
C18:0
C18:1
C18:2
C18:3
C20:0
1.73
0.23
10.29
21.75
4.45
0.11
0.56
4.28
12.05
21.55
40.61
53.68
11.03
8.16
1.38
0.34
0.19
Unknown
Sat.
components (% by wt.)
0.91
15.22
1.39
36.51
1.0
1.0
1.0
5.22
1.64
1.19
0.74
66.08
5.20
2.08
66.08
5.10
1.98
1433
3.5 g (1%)
0.7% K
0.23
0.014
74.8
0.35% K
0.23
0.016
74.3
0.35% Na
0.23
0.017
81.2
0.35% Na
0.20
0.011
80.5
1.75 g (0.5%)
2.13 g (0.61%)
2.87 g (0.82%)
Na
1.22 g (0.35%)
0.20
0.013
82.2
1.91
56.4
KOH
0.50 g (0.25%)
9.22
NaOCH3
0.82 g (0.41%)
0.19
0.004
67.0
0.18
0.002
75.1
0.42 g (0.21%)
1.0 g (to neutralize)
[a]
0.35% Na
1.01 g (0.5%)
KOH
6
7
Run
No.
After the pretreatment reactions with 20:1 and 40:1 molar ratios in
the 1st and 2nd step reactions, respectively, and 5% sulfuric acid
catalyst.
[b] The catalyst amounts were calculated based on 0.74 mg KOH/g acid
value of the 400 g yellow grease, which initially had 12% FFA.
Catalyst[a]
%
0.82 NaOCH3
0.41 NaOCH3
0.21 NaOCH3
0.10 NaOCH3
0.05 NaOCH3
0.5 KOH
0.25 KOH
0.41 NaOCH3
0.21 NaOCH3
3.53
1.82
1.42
1.20
1.10
1.61
1.11
1.82
1.42
Feedstock
(g)
400
300
300
300
300
300
300
300
300
Ester
(g)
151.83
164.95
161.94
162.58
163.57
47.21
200.90
225.36
Yield
(%)
51.91
56.39
55.36
55.58
56.40
66.97
75.12
Interphase
(g)
326.18
91.24
84.21
85.96
93.20
100.83
218.80
60.40
37.12
2nd step
3rd step
38.26
26.07
26.07
24.96
24.96
31.94
31.94
31.11
31.11
20.63
16.87
16.87
18.09
18.09
4.74
4.74
5.23
5.23
9.85
8.67
8.67
5.75
5.75
The catalyst amounts were calculated based on 2.03 mg KOH/g acid value of the brown grease, which initially had 33% FFA.
1434
60
50
40
o
Temperature ( C)
The fat and ester amounts are shown in Table 9. When the
number of steps was reduced from three to two, the yield was
increased because less of the fat and ester were removed. In
commercial production, this material would probably be returned to the process to maximize the yield. In recognition of
the losses when the methanolwater mixture is removed, it
was decided that the methanolwater mixture would not be
removed after the last step of pretreatment. The small amount
of water present in the mixture at this point does not seem to
affect the reaction.
The catalyst amount used in transesterification was another factor that affected the yield. When excess alkaline catalyst was used in the transesterification, it increased the soap
amount and the interphase. Interphase was the name given to
a middle phase that appeared during the washing process between the animal fat ester and the wash water. The composition of the interphase has not been determined but it is
insoluble in both the ester and water. Interphase was never
observed when processing soybean oil, lard, tallow, or the
synthetic high FFA feedstock. It apparently originates from
unsaponifiable material in the yellow and brown grease and
may be calcium based since it was found only in animal fat
greases. After the 4th washing step, the interphase was separated from the ester. During the separation, some ester was
unavoidably removed with the interphase. The amount of interphase decreased when the number of pretreatment steps
was decreased from three to two.
30
20
10
0
Upper Phase (Yellow Grease 9% FFA)
Upper Phase (Brown Grease 33% FFA)
Upper Phase (Soybean Oil)
Upper Phase (Lard)
Upper Phase (YGME)
10
20
0
20
40
60
% Methanol
80
100
Figure 3. Solubility of soybean oil, lard, YGME, yellow grease, and brown
grease in methanol.
CONCLUSIONS
The objective of this study was to investigate the use of
lowcost, high FFA feedstocks to produce fuelquality biodiesel. It was determined that feedstocks with high FFAs
could not be transesterified with the traditional alkaline catalysts that have been used with good success for vegetable oils.
Alkaline catalysts form soap when they react with the FFAs.
Soap removes the catalyst from the reaction and prevents the
separation of the glycerin and the ester.
A process was developed to use acid catalysts to pretreat
the high FFA feedstocks until their FFA level was below 1%,
allowing the subsequent use of alkaline catalysts to convert
the triglycerides. The effects of the methanol molar ratio,
acid catalyst amount, and reaction time on the reduction of
FFA level were studied with a simulated high FFA feedstock
consisting of 20% palmitic acid in soybean oil. This part of
the study showed that the FFA level of the feedstocks could
be reduced to less than 1% with a 2step process of acidcatalyzed pretreatment. Extension of the process to yellow and
brown grease showed that higher levels of acid catalyst and
methanol were required.
The following specific conclusions are based on the process development portion of this project.
1. The acidcatalyzed pretreatment reaction decreased the
acid value of the synthetic mixture to less than 2 mg
KOH/g with a 2step process. Using the 2step acid
catalyzed pretreatment followed by an alkalicatalyzed
final reaction, the transesterification reaction was
completed in much less time than would be possible with
acidcatalyzed transesterification alone.
2. Increasing the acid catalyst amount is very effective in
decreasing the acid value of the mixture. In the first
pretreatment step, using a 10:1 molar ratio and 30 min of
reaction time, the acid value of the simulated high FFA
feedstock was reduced from 41.33 mg KOH/g to 1.37 mg
KOH/g using 15% acid catalyst.
3. Ethanol decreased the FFA level of the synthetic mixture
faster than methanol.
1435
4.
5.
6.
ACKNOWLEDGEMENTS
This research was funded by a grant from the Iowa Energy
Center.
REFERENCES
Aksoy, H. A., I. Kahraman, F. Karaosmanoglu, and H. Civelekoglu.
1988. Evaluation of Turkish sulphur olive oil as an alternative
diesel fuel. JAOCS 65(6): 936938.
AOCS. 1991. Official Test Method Ca 1456 for total, free, and
combined glycerol (iodometricperiodic acid method). In
Official Methods and Recommended Practices of the American
Oil Chemists Society. Champaign, Ill.: AOCS.
_____. 1998. Official Test Method Cd 3a63 for acid value. In
Official Methods and Recommended Practices of the American
Oil Chemists Society. Champaign, Ill.: AOCS.
Bagby, M. O., B. Freedman, and A. W. Schwab. 1987. Seed oils for
diesel fuels: Sources and properties. ASAE Paper No. 871583.
St. Joseph, Mich.: ASAE.
Canakci, M., and J. Van Gerpen. 1999. Biodiesel production via
acid catalysis. Trans. ASAE 42(5): 12031210.
_______. 2001. A pilot plant to produce biodiesel from high free
fatty acid feedstocks. ASAE Paper No. 016049. St. Joseph,
Mich.: ASAE.
Clark, S. J., L. Wagner, M. D. Schrock, and P. G. Piennaar. 1984.
Methyl and ethyl soybean esters as renewable fuels for diesel
engines. JAOCS 61(10): 16321638.
Feuge, R. O., and A. T. Gros. 1949. Modification of vegetable oils:
VII. Alkali catalyzed interesterification of peanut oil with
ethanol. JAOCS 26(3): 97102.
Feuge, R. O., E. A. Kraemer, and A. E. Bailey. 1945. Modification
of vegetable oils: IV. Reesterification of fatty acids with glycerol.
Oil and Soap 22(8): 202207.
Freedman, B., and E. H. Pryde. 1982. Fatty esters from vegetable
oils for use as a diesel fuel. In Vegetable Oils Fuels: Proc. of the
Intl. Conf. on Plant and Vegetable Oils as Fuels, 117122. St.
Joseph, Mich.: ASAE.
Freedman, B., E. H. Pryde, and T. L. Mounts. 1984. Variables
affecting the yields of fatty esters from transesterified vegetable
oils. JAOCS 61(10): 16381643.
Goering, C. E., A. W. Schwab, M. J. Dangherty, E. H. Pryde, and A.
J. Heakin. 1982. Fuel properties of eleven vegetable oils. Trans.
ASAE 25(6): 14721477.
Hammond, E. G. Personal communication. Dept. of Food Science,
Iowa State Univ., Ames, Iowa, 16 September 1998.
Haumann, B. F. 1990. Renderers give new life to waste restaurant
fats. Inform 1(8): 722725.
Howell, S. 1997. U.S. biodiesel standards: An update of current
activities. SAE Paper No. 971687. Warrendale, Pa.: SAE.
1436
TRANSACTIONS OF THE ASAE
All in-text references underlined in blue are linked to publications on ResearchGate, letting you access and read them immediately.