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R. E. Babcock, P. I.
E. C. Clausen, Co- P.I.
Michael Popp, Co-P.I.
Brian Mattingly, G. A.
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The contents of this report reflect the views of the authors, who are responsible for the facts and the
accuracy of the information presented herein. This document is disseminated under the sponsorship of the
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exchange. The U.S. Government assumes no liability for the contents or use thereof.
Biodiesel Production from Varying Grades of Beef Tallow and Chicken Fat
Introduction
As biodiesel becomes an increasingly important source of fuel in the
United States (Ginder and Paulson, 2006), investors in biodiesel production
facilities will continue to search for economically feasible sources of vegetable oil
and animal fats that can be used to produce biodiesel (Zhang et al., 2003). One
of these animal fats is poultry fat, a feedstock that is relatively inexpensive when
compared to other oil and fat sources such as soybean oil (Mattingly et al.,
2004). However, the free-fatty acid (FFA) content of poultry fat can vary greatly
depending on the fat profile of the bird which, in turn, can be affected by
seasonal feed ration changes as well as exposure of trimmings to ambient
temperatures during transport from slaughter to rendering facilities (Fox, 2004).
This is important, since the FFA content affects the biodiesel yield potential
(Canacki and van Gerpen, 2001; Haas et al., 2000) and thereby has a major
impact on the economic feasibility of this feedstock (Mattingly et al., 2004). High
FFA content, in combination with conventional base-catalyzed transesterification,
lowers the yield of biodiesel and produces by-products like soapstock and
glycerine.
The purpose of this research effort was to collect chemical reaction and
yield data and to analyze the economic feasibility of utilizing two different
alternatives for FFA removal during biodiesel production. This completion report
presents the laboratory results and the analysis of the impact of by-product and
poultry price changes on the economic feasibility of selecting among the
alternative technologies proposed for dealing with FFA in the untreated poultry
fat. Additional laboratory data relative to the cloud point of biodiesel using beef
tallow and coconut oil feedstock as compared to soybean oil is included in the
appendix of this report.
Background
The two methods for removing FFA at different stages of the biodiesel
production process are: i) what is commonly referred to as caustic stripping or
alkali refining (Wan, 1991) of untreated poultry fat, which creates soapstock as a
by-product and yields treated poultry fat that can now be easily transesterified to
biodiesel and glycerine (caustic pretreatment); and ii) a two-step process
(Canacki and van Gerpen, 2001) involving acid-catalyzed esterification followed
by base-catalyzed transesterification, where the FFA is converted to biodiesel
and subsequent transesterification yields additional biodiesel and glycerine (acid
pretreatment). The main tradeoff between caustic and acid pretreatment is that
the first processing technology involves caustic stripping (a proven technology)
but requires sale or marketing of the soapstock by-product, whereas the second
processing technology is less conventional, more catalyst intensive and yields no
soapstock.
Quantifying the differences in production costs between these two
pretreatments, where known, will allow for calculation of break-even investment
for added processing equipment needed for the acid pretreatment at a biodiesel
production facility under varying soapstock, poultry fat and initial FFA conditions.
While this paper focuses on poultry fat, the process evaluation can be applied to
other feedstocks with variable FFA content as well.
Transesterification
1 m triglycerides + 3 m MeOH ←⎯ ⎯→ 3 m Biodiesel + 1 m Glycerin
NaOH
(2)
In Equation (2), the triglycerides, aside from FFA, are the primary component of
untreated poultry fat (with the exception of the potential for some impurities),
MeOH is methanol which is generally added at a 6:1 molar ratio with the excess
recovered for subsequent use (Freedman et al., 1984), NaOH is sodium
hydroxide, the catalyst added by weight of triglyceride treated (0.25%, Mattingly,
2006), biodiesel or methyl ester is the desired end product and glycerine is a by-
product.
Esterification
1 m FFA + 1 m MeOH ←⎯ ⎯→ 1 m Biodiesel + 1 m H 2O
H 2SO 4
(3)
In Equation (3), H2SO4 is sulfuric acid that serves as the catalyst and was added
at 10% excess by weight of FFA (Canacki and van Gerpen, 2001) and H2O is
water generated in the process.
Acid Neutralization
1 m H 2SO 4 + 2 m NaOH ⎯
⎯→ 2m H 2O + 1m Na 2SO 4 (4)
In Equation (4), Na2SO4 is sodium sulfate, a by-product of the neutralization of
sulfuric acid with sodium hydroxide.
Tables 1 and 2 present a summary of the important results for the different
chemical techniques investigated, and the different reaction variables studied.
Detailed quantitative results can be found in the thesis of Brian Mattingly
(Mattingly, 2005).
Reaction
Results Comments
Variable
Temperatures for reactions
Increasing the reaction
conducted at atmospheric
Temperature temperature increases the rate
pressure are limited by the
of the reaction.
boiling point of the methanol.
Increasing the concentration of Increasing the base catalyst
Base catalyst
base catalyst increases the rate concentration promotes the
concentration
of the reaction formation of soaps.
After examining the different methods available for converting chicken fat into
biodiesel, several important conclusions can be made. First, chicken fat can be
successfully converted to biodiesel by using a single step, base catalyzed,
transesterification method. The amount of biodiesel yield lost to soap formation
during this process can be estimated based on the amount of sodium hydroxide
used. By titrating the fat, the least amount of NaOH necessary to catalyze the
reaction can be found, and the formation of soaps can be minimized. A 90% yield of
biodiesel can be generated from Clarksville Grade chicken fat (0.1% FFA), however,
when using Feed Grade chicken fat (2.3% FFA) the yield drops to less than 70%
due to the increased level of free fatty acids. The literature has indicated that the
FFA level in the Feed Grade chicken fat can be reduced by pre-treating the fat with
an acid catalyzed esterification process.
Second, soaps formed during base catalyzed transesterification can be
eliminated by applying sulfuric acid after the transesterification has been completed.
This also simplifies the separation of the product phases, and prevents the formation
of emulsions if a water wash procedure is used for the finished fuel.
Finally, the optimization data have shown that the transesterification reaction
can be accelerated by increasing the reaction temperature, and increasing the
amount of base catalyst. For reactions occurring at atmospheric pressure, the
temperature is limited by the boiling point of methanol (64.6°C), with the highest
temperature used in this study being 60°C. Increasing the amount of base catalyst
will increase soap formation, but as noted previously, these soaps can be eliminated
by using sulfuric acid in a second processing step.
The results of this research provide data that can be used to determine the
most effective conversion technique for each grade of fat. For Clarksville Grade
chicken fat a single step, base catalyzed, transesterification looks promising. By
using the minimum amount of NaOH, an extended reaction time, and a reaction
temperature of 55-60°C, the process generated a high yield of biodiesel that will
likely make further processing or pre-treatment unnecessary. Using a similar
technique for Feed Grade chicken fat, however, did not result in a favorable yield of
biodiesel due to excess soap formation, and further processing steps are necessary
to achieve a high yield. The research has shown that the use of sulfuric acid in a
second processing step is effective for eliminating soaps formed during
transesterification, and literature indicates that this can be effective for esterification
of the soapstock. Acid catalyzed esterification as a pre-treatment step is also an
option for reducing the FFA’s prior to the transesterification process. Any further
conclusions must take into consideration current economic data regarding the costs
and values associated with reagents, catalysts, products, and energy use. A single
step transesterification will require the lowest processing costs for biodiesel
production by using the least amount of energy and catalyst when compared to the
other methods investigated. However, any free fatty acids present in the feedstock
will be lost as soap, decreasing the overall yield. These losses can be reduced by
using an acid catalyzed esterification process to convert the free fatty acids to
biodiesel, but the increase in overall yield will be offset by additional processing
costs incurred through the additional requirements for catalyst and energy.
6
Table 4. Molecular Weights and Densities of Chemicals, Inputs and Outputs at
Room Temperature
Economic Results
Partial break-even prices of biodiesel using either caustic or acid pretreatment
were calculated assuming different levels of FFA content (0-10%) of the poultry fat,
different price levels of the by-product soapstock (0 and 4 ¢/lb) as well as different
observed price levels for the poultry fat (7, 13, and 20 ¢/lb). All other input and
output prices were held constant at their observed average price levels as reported
in Table 3 with the exception of glycerine (set to zero) to account for changes in
market conditions.
Table 5 shows several trends when comparing break-even prices of the two
technologies. First, the higher the price of poultry fat, the larger the potential
investment for acid pretreatment equipment. Second, the higher the FFA content,
the greater the potential for acid pretreatment equipment. Third, soapstock prices
have essentially no effect on break-even prices, since the alkali refining fee, ranging
from $0.03 to $0.05 on a sliding scale from 2 to 10% FFA content, makes up most of
the partial break-even price difference. Note that it takes ~ 7.2 lbs of poultry fat to
make one gallon of biodiesel. Fourth, the difference in break-even prices among the
two pretreatment options is shown on a $/gal of biodiesel basis and is deemed plant
scale independent. Investors can thus use these numbers to determine break-even
7
investment thresholds for equipment needed at prevailing expected price levels and
desired target output capacity. Fifth, if investing in acid pretreatment equipment
would not be feasible, the producer could decide how much of a premium he would
be willing to pay for lower levels of FFA content in poultry fat by following the partial
break-even price of biodiesel under the caustic pretreatment option down a price
column for different FFA levels. This pretty much turns out to be the alkali refining
fee as other input costs and by-product values are insignificant contributors to the
equation. Sixth, acid pretreatment essentially removes the impact of FFA content on
the breakeven price. Note the narrow range in price differences across FFA content.
Finally, changes in poultry fat prices have a large impact on partial break-even price,
as this input makes up a significant portion of the partial break-even cost per gallon.
8
Table 5. Impact of Pretreatment Choice on Investment Potential as a Result of Partial Biodiesel Break-even Price
($/gal) Differentials Using Different Soapstock and Poultry Fat Prices
a
This is the difference in the partial break even price of biodiesel between caustic pretreatment and acid pretreatment. It represents the most in $/gal
a producer could invest for acid pretreatment equipment to be on the same basis as buying poultry fat that has been pretreated using caustic stripping.
One other observation is worth noting. Glycerine prices have equal potential to reduce break-even
prices using either production method. At current price levels, glycerine prices are not expected
to play a large role in affecting break-even price levels.
Economic Conclusions
The potential for investment in acid pretreatment equipment by a biodiesel
producer as changes in FFA content affect biodiesel yield and thereby the cost of
production has been summarized. A comparison of two production technologies that
are different, primarily in how FFA is managed, revealed that the soapstock co-
product at current price levels is an insignificant factor in the feasibility of acid
pretreatment. In the unlikely event that soapstock prices rise above the price for
untreated poultry fat, this conclusion would no longer. Ignored in this analysis is the
impact of retail biodiesel prices, as the acid pretreatment method yields slightly
higher amounts of biodiesel per pound of untreated poultry fat the higher the amount
of FFA content in the untreated fat as caustic pretreatment removes the FFA as
soapstoack and acid pretreatment converts the FFA to biodiesel. At high biodiesel
prices and low soapstock prices this magnifies the impact of the soapstock co-
product implications.
References
Canakci, M., and J. Van Gerpen. 2001. Biodiesel Production from Oils and Fats
with High Free Fatty Acids. Transactions of the American Society of
Agricultural Engineers, 44(6): 1429-1436.
Chemical Market Reporter. Schnell Publishing Company, New York, NY. Various
Issues from 2001-2004.
Freedman, B., E.H. Pryde, and T.L. Mounts. 1984. Variables Affecting the Yields of
Fatty Esters from Transesterified Vegetable Oils. Journal of the American Oil
Chemists’ Society, 61(10):1638-1643.
Ginder, R and N. Paulson. 2006. The Growth and Direction of the Biodiesel Industry
in the U.S. Selected Paper. American Agricultural Economics Association
Meeetings, Long Beach, CA.
Kay, R. D., W. M. Edwards and P. A. Duffy. 2004. Farm Management, 5th Edition.
McGraw Hill. New York, NY.
Mattingly, B. 2005. Production of Biodiesel from Chicken Fat Containing Free Fatty
Acids. Unpublished Master’s Thesis, University of Arkansas, Department of
Chemical Engineering.
Wan, Peter J. 1991. Introduction to Fats and Oils Technology. American Oil
Chemists Society, Champion, IL.
Zhang, Y., M. Dubé, D. McLean and M. Kates. 2003. Biodiesel Production from
Waste Cooking Oil: 2. Economic assessment and sensitivity analysis.
Bioresource Technology 90:229-240.
11
Appendix
12
Biodiesel Cloud Point Analysis of Beef Tallow and Coconut Oils
prepared by Dr. Rahul Gangidi as a MBTC subcontract
Introduction
Biodiesel can be used as a diesel fuel with little to no modification of the
diesel engine (Kinset and Tyson, 2003). Biodiesel is made from renewable
resources that would not add additional greenhouse gases to the atmosphere, and
its burning results in a reduction in carbon monoxide and sulfur emissions (Ma and
Hanna, 1999). A number of feedstocks are currently used to produce biodiesel
including soybean oil, cottonseed oil, canola oil, chicken fat, pork tallow and beef
tallow.
Oils with a high lauric acid (C12:0) content have a low cloud point than beef
tallow. Lauric acid oils are mainly Cuphea species oils (Wilson et al., 1960) and
coconut oils. Cuphea is an herbaceous crop that is native to the U.S., while coconut
oils are native to tropical climates, such as the southern Pacific and southern Atlantic
coasts of the U.S. As is noted in Table 1, Cuphea plants have a higher lauric acid
content than coconut oils.
Table 1. Composition (wt. %) of the Fatty Acids in Coconut Oil, Beef Tallow and
Soybean Oil (Gunstone et al., 1994)
13
Mixtures of lauric acid oils and beef tallow could significantly decrease the
cloud point of the resulting mixture and encourage its use as a biodiesel feedstock.
In addition, the use of coconut oil as a supplement in biodiesel production may
encourage the planting of coconut palms on seashores. This planting could prevent
damage to coastal areas from hurricanes and tsunamis. However, the optimum
blend of lauric acid oils and beef tallow must be found. The objective of this study
was to determine the cloud point of the beef tallow, coconut oil and a blend of beef
tallow and coconut oils.
Methods
Base catalyzed transesterification of the oils
An oil layer (180-260 g) was added to the reactor vessel followed by 1% (w/w)
sodium hydroxide, as a catalyst. Theoretically, three moles of methanol are required
for the transesterification of one mole of triglyceride. Excess methanol is usually
added to the oil, which drives the reaction forward. The contents of the reactor
vessel were stirred for 15-60 min. Acid was added to the reactor to neutralize the
soaps formed in the vessel. Glycerol was removed from the oil using a separatory
funnel. The oil was washed four times to remove any residual soaps. The oil was
then dried over anhydrous Na2SO4 with stirring for 15 min, and then allowed to settle
before decanting. The methyl esters were centrifuged at least twice to remove any
moisture particles from the decanted layers. The ratio of the recovered methyl
esters to the oil was used to calculate the yield of biodiesel. The cloud point of the
oil was determined using a modified ASTM D2500 method.
14
Thermometer
Insulating
styrofoam
Results
The yields of biodiesel, when coconut oil was used as feedstock, were 88.44,
90.25 and 65.27% for the trials 1, 2 and 3, respectively. The yield of biodiesel when
beef tallow was used as substrate was 74.72%. Approximately 180 g of beef tallow
and 1.8 g of sodium hydroxide, or 257 g of coconut oil and 2.57 g of the sodium
hydroxide were used in biodiesel preparation.
The cloud points of the beef tallow, coconut oil (sample 1), coconut oil
(sample 2), and soybean oil were 12, -3, -2 and -2oC (Table 2). Haziness was
observed when the visibility of the biodiesel was reduced, but the biodiesel was
partially transparent. The haziness could have been due to the presence of
moisture in the biodiesel. Cloudiness was confirmed when a whitish and opaque
film formed on the surface of the glass cylinder close to the ice/salt mixture. Thus,
the cloud points of coconut oil and soybean oil appear to be quite similar. As
expected, the cloud point of coconut oil was significantly less than the cloud point of
beef tallow.
A blend of coconut oils and the beef tallow should have a cloud point between
12 and -2/-3°C. Fifty and 67% blends of coconut oil in beef tallow had measured
cloud points of 12 and 5°C (Table 3). The 50% blend of coconut oil in beef tallow
does not appear to appreciably decrease the cloud point, whereas a 33% blend
appears to have a significantly lower cloud point than 100% beef tallow. Further
15
Table 2. Cloud Points of Beef Tallow, Coconut Oils (Samples 1 and 2) and
Soybean Oil
Temperature (°C) Beef Tallow Coconut Oil Coconut Oil Soybean Oil
(Sample 1) (Sample 2)
20 Clear liquid No No No
19 Hazy No No No
18 Hazy No No No
17 Small clouds, No No No
partially
localized
16 Small clouds, No No No
partially
localized
15 Yes, slightly No No No
14 Yes, slightly No No No
13 Yes, slightly No No, No
hazy slightly
12 Yes, cloudy No No, No
11 No Hazy slightly No
10 No No, Hazy
9 No Hazy slightly Hazy
8 No No, Hazy
7 No, hazy Hazy slightly Hazy
6 No, hazy No, Hazy
5 No, hazy Hazy slightly Hazy
4 No, hazy Slightly whitish Hazy
film
3 No, hazy Slightly whitish Hazy
film
2 No, hazy Slightly cloudy Hazy
1 No, hazy Slightly cloudy Hazy
0 No, hazy Slightly cloudy Cloudy/hazy
-1 No, hazy Slightly cloudy Cloudy/hazy
-2 No, hazy Cloudy Cloudy
-3 Cloudy
studies need to be conducted to examine the cloud point reduction in beef tallow
with the addition of higher percentages of coconut oils in beef tallow. The cloud
point results could be slightly different if the actual ASTM D2500 method were used
in the cloud determination. Nevertheless, the current method shows the trend in
cloud points of beef tallow, coconut oils and blends of beef tallow in coconut oils.
16
Table 3. Cloud Points of Coconut Oil Blended in Beef Tallow
50 67
20 Clear liquid No
19 Hazy No
18 Hazy No
17 Small clouds, No
partially
localized
16 Small clouds, No
partially
localized
15 Yes, slightly No
14 Yes, slightly No
13 Yes, slightly No
12 Yes No
11 No
10 No
9 No
8 No
7 No, hazy
6 No, hazy
5 Cloudy
Coconut oil biodiesel could be blended into the beef tallow biodiesel to reduce
the cloud point of the 100% beef tallow biodiesel. Further studies must be conducted
with oils similar to coconut oils to positively optimize the reduction of the cloud point
of the beef tallow biodiesel.
Acknowledgements
I wish to thank Mr. Thang Ho (Department of Chemical Engineering,
University of Arkansas, Fayetteville) for the producing the biodiesel, and Mr. Brian
Mattingly (Department of Chemical Engineering, University of Arkansas, Fayetteville)
for guidance in the production of the biodiesel.
References
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17
Canakci, M.; Van-Gerpen, J. Biodiesel production from oils and fats with high free
fatty acids. Transactions of the ASAE 2001, 44, 1429–1436.
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Gasoline and diesel fuel update. Energy Information Administration. May 17, 2005.
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Golden Sachs: Oil could spike to $105. Energy Bulletin. March 30, 2005.
http://energybulletin.net/5017.html
Gunstone FD, Harwood JL, Padley FB. The Lipid Handbook, 2nd edn., Chapman and
Hall, London, 1994.
Kramer, J. K. G.; Fellner, V.; Dugan, M. E. R.; Sauer, F. D.; Mossoba, M. M.;
Yurawecz, M. P. Evaluating acid and base catalysts in the methylation of milk
and rumen fatty acids with special emphasis on conjugated dienes and total trans
fatty acids. Lipids 1997, 32, 1219-1228.
Ma, F.; Hanna, M. A. Biodiesel production: a review. Biores. Technol. 1999, 70, 1-
15.
McCormick, R. L.; Graboski, M. S.; Alleman, T. L.; Herring, A. M.; Tyson, K. S. 2001.
Impact of biodiesel source material and chemical structure on emissions of
criteria pollutants from a heavy-duty engine. Environ. Sci. Technol. 2001, 35,
1742-1747.
18
Tyson, K. S. Biodiesel, handling and use guidelines. NREL: Golden CO, September,
2001, p 22.
Srivastava, A.; Prasad, R. Triglycerides-based diesel fuels. Renewable Sustainable
Energy Rev. 2000, 4, 111-133.
Wilson, T. L.; Miwa, T. K.; Smith-Jr., C, R. Cuphea llavea seed oil, a good source of
capric acid. J. Amer. Oil Chem. Soc. 1960, 37, 67-76.
19