Biodiesel Production from Alligator Fat: Sustainable Fuel Solution

 
Biodiesel from alligator fat using
supercritical methanol via a laboratory
scale flow reactor
 
 
August Gallo
Thomas Junk
University of  Louisiana at Lafayette
Department of Chemistry
 
UNIVERSITY OF LOUISIANA AT LAFAYETTE
RAY P. AUTHEMENT  COLLEGE OF SCIENCES
DEPARTMENT OF CHEMISTRY
 
Fossil fuels
 
According to the Energy Information Administration (EIA),
the world energy consumption is projected to increase by 33%
from 2007 to 2035
 
 In the year 2007 the United States alone consumed 21% of
the world’s energy
 
As of 2008, transportation share of the U.S. petroleum
consumption is 71%
 
The U.S transportation sector is 97 percent reliant on oil, with
60 percent of this oil imported
 
 
 
 
 
Biofuels
 
Energy security
Economic stability
Environmental gains
Dominant biofuels- biodiesel and bioethanol.
Food vs. biofuels
 
 
Alligator and its fats
 
In United States, Louisiana has the population of about 1.5
million alligators constituting 75% of the total population
Louisiana’s wild and farm raised alligator harvest is
approximately 275,000 per year
In the year 2008 the revenue generated
 
from wild and farm
raised alligators was ~ $70 million
15 million pounds of alligator fat is available annually in
Louisiana, which is currently being disposed as waste
 
The increasing popularity of alligator farming, coupled
with the high fat content of alligators, strongly supports
the use of waste alligator fat as a source for biodiesel fuel.
It stands to reason, however, that the methods presented
here are of general applicability for the conversion of
other animal fats (e.g., lard, chicken fat) to biodiesel.
 
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Biodiesel is increasingly used as a renewable
alternative to conventional diesel fuel. With
approximately 51 billion liters in 2010, the
United States is the largest producer of biofuels.
Biodiesel is prepared from vegetable or animal
fats, usually by transesterification with methanol
(Fig. 1)
 
An established procedure for the transesterification of fats with
methanol consists of stirring the respective fat with methanol and
a suitable catalyst, usually sodium hydroxide.
An alternative procedure is the rendering of oil prior to
transesterification, leaving a residue of nitrogen-rich material.  In
each case, solid byproducts and an emulsion are obtained, which
have to be separated by filtration and/or centrifugation and
generate a significant amount of caustic solid waste.  A typical
setup is shown in Fig. 2, the formation of solids in the product
mixture is evident by the turbid appearance of the fluid phase.
Optimized conditions consisted of heating the fat with methanol
in a 3:1 weight ratio for 2.5 hours at 65°C in the presence of 1%
of NaOH.
 
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p
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s
s
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n
g
 
Production of biodiesel
 
 
Fig. 2
 
Conversion using supercritical
methanol - rationale
 
We are developing an alternative procedure with several objectives
in mind: 1) the reduction of elimination of solid waste products, 2)
the avoidance of emulsions and caustic residues that require
additional separation steps, and 3) reduced reaction times.  The use
of supercritical methanol eliminates the need for a catalyst, promises
short reaction times, and produces product mixtures that are virtually
free of solid residues. Methanol has a critical temperature of approx.
240
°C
, as shown in the diagram below (Fig. 3)
 
Batch Process Equipment
 
Fatty acid profile of alligator fat
 
GC analysis
 
Main methyl ester after treatment in flow reactor
 
Conclusions – Batch process
 
The use of supercritical methanol in the conversion of waste
alligator fat to biodiesel was shown to be a viable alternative to
traditional transesterification.  Key advantages of this method
include: a) avoidance of caustic catalysts, b) the elimination of
solid byproducts posing disposal problems, and c) significant
simplification of the conversion process, no emulsions.  The
use of raw fat containing proteins resulted in the formation of
liquid amines and amides in the resulting product. These pose
no harm; in fact, the addition of amines to increase the thermal
stability of diesel fuels has been patented (USP 4,166,726).
Furthermore, it is common practice to co-inject solutions of
urea into diesel engines to reduce harmful NOX emissions.
Optimized batch conditions were achieved when 2 g of oil was
heated with 8 g of methanol to 300°C for 3 hours, resulting in
95.8 % of methyl esters and undetectable levels of  free acids.
 
Flow Reactor Study
Several inherent problems with the batch
process- temperature control after completion of
the reaction.
With a flow reactor, the reactants can enter and
leave the system under more controlled
conditions.
A simple system  was devised using an HPLC
pump, shut off valve, woods metal bath, heater,
digital thermometer, 6 ft. column, water cooled
jacket and a pressure valve to control the
pressure.
 
Flow Reactor
 
Flow Reactor Study-FAME analysis
 
Concentration of the main methyl ester as a function of
time, 1 mL/min
 
Flow Reactor Study-FAME analysis
 
Concentration of the main methyl ester as a function of
time, 0.2 mL/min
 
Flow Reactor Study-FAME analysis
 
Concentration of the main methyl ester as a function of
temperature - 1 mL/min
 
GC Analysis of FAME vs.Temperature
 
Conclusions – Flow Reactor
 
These graphs show the concentration of the esters increases
exponentially.
The highest concentration was reached at 400°C for the all
esters, then the concentrations decreased rapidly. For the
higher flow rate the exponential decrease was not observed.
A new run was carried at 300, 320, 340, 360, 380, 400, 420,
440, 460, 480°C and 500°C.  The number of samples was
increased in order to have more information about the ester
concentration especially between 400°C and 500°C.
These graphs show that the highest concentration was
reached at 460
°
C. In this case we observed, for the
unsaturated ester, a exponential decrease of the
concentration.
 
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n
 
The economics of the lipid production was investigated with the
following assumptions:
 
The cost of lipid source was assigned to be zero, since feed stock
was alligator fat waste that normally entails disposal costs for the
processing industry.
 
Byproduct glycerol was assumed to fetch a price of $ 0.22 per kg
(ICIS, 2010).
 
Cost of equipment were taken from SuperPro Designer and from
the equipment data of  Peters and Timmerhaus (Peter and
Timmerhaus, 1981).
 
Equipment cost
 
Utilities
 
Results (Economic analysis)
 
Fixed capital investment = 2.51 million dollars.
Total capital investment = 2.98 million dollars.
Raw material cost = 0.44 million dollars.
Labor cost (18 people) = 0.87 million dollars.
Utility costs = 0.125 million dollars.
Annual total product cost = 3.01 million dollars.
Average return on investment = 28.5% per year.
Payback period = 2.3 years.
 
Acknowledgements
 
I would like to thank the department of chemistry at UL
Lafayette and the following individuals who made this work
possible through support and guidance:
 
 Dr. Rakesh Bajpai, Professor of Chemical Engineering, UL
 Dean Mark Zappi, Dean of Engineering, UL
 Patrick Spiller, UL
 Kevin Martin, University of Poitiers, France
 Teddy Lacourcelle, University of Poitiers, france
 Dr. William Holmes, UL
 Dr. Yuemin Liu, UL
 
 
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Biodiesel production from waste alligator fat offers a sustainable solution for energy security and environmental benefits. Louisiana's abundant alligator population provides a source for biofuel production, reducing reliance on fossil fuels. The process involves converting animal fats into biodiesel using supercritical methanol. With the increasing popularity of biofuels, utilizing alligator fat presents a viable alternative fuel source, contributing to economic stability and reducing waste.


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  1. UNIVERSITY OF LOUISIANA AT LAFAYETTE RAY P. AUTHEMENT COLLEGE OF SCIENCES DEPARTMENT OF CHEMISTRY Biodiesel from alligator fat using supercritical methanol via a laboratory scale flow reactor August Gallo Thomas Junk University of Louisiana at Lafayette Department of Chemistry

  2. Fossil fuels According to the Energy Information Administration (EIA), the world energy consumption is projected to increase by 33% from 2007 to 2035 In the year 2007 the United States alone consumed 21% of the world s energy As of 2008, transportation share of the U.S. petroleum consumption is 71% The U.S transportation sector is 97 percent reliant on oil, with 60 percent of this oil imported

  3. Biofuels Energy security Economic stability Environmental gains Dominant biofuels- biodiesel and bioethanol. Food vs. biofuels

  4. Alligator and its fats In United States, Louisiana has the population of about 1.5 million alligators constituting 75% of the total population Louisiana s wild and farm raised alligator harvest is approximately 275,000 per year In the year 2008 the revenue generatedfrom wild and farm raised alligators was ~ $70 million 15 million pounds of alligator fat is available annually in Louisiana, which is currently being disposed as waste The increasing popularity of alligator farming, coupled with the high fat content of alligators, strongly supports the use of waste alligator fat as a source for biodiesel fuel. It stands to reason, however, that the methods presented here are of general applicability for the conversion of other animal fats (e.g., lard, chicken fat) to biodiesel.

  5. Current status Biodiesel is increasingly used as a renewable alternative to conventional diesel fuel. With approximately 51 billion liters in 2010, the United States is the largest producer of biofuels. Biodiesel is prepared from vegetable or animal fats, usually by transesterification with methanol (Fig. 1)

  6. Traditional processing An established procedure for the transesterification of fats with methanol consists of stirring the respective fat with methanol and a suitable catalyst, usually sodium hydroxide. An alternative procedure is the rendering of oil prior to transesterification, leaving a residue of nitrogen-rich material. In each case, solid byproducts and an emulsion are obtained, which have to be separated by filtration and/or centrifugation and generate a significant amount of caustic solid waste. A typical setup is shown in Fig. 2, the formation of solids in the product mixture is evident by the turbid appearance of the fluid phase. Optimized conditions consisted of heating the fat with methanol in a 3:1 weight ratio for 2.5 hours at 65 C in the presence of 1% of NaOH.

  7. Fig. 2

  8. Conversion methanol - rationale We are developing an alternative procedure with several objectives in mind: 1) the reduction of elimination of solid waste products, 2) the avoidance of emulsions and caustic residues that require additional separation steps, and 3) reduced reaction times. The use of supercritical methanol eliminates the need for a catalyst, promises short reaction times, and produces product mixtures that are virtually free of solid residues. Methanol has a critical temperature of approx. 240 C, as shown in the diagram below (Fig. 3) using supercritical

  9. Batch Process Equipment

  10. Fatty acid profile of alligator fat 1:4 MR 2 h % area (LSU) C14:0 0.69 C15:0 0.04 C16:0 15.04 C16:1 8.75 C17:0 0.08 C18:0 2.98 C18:1 30.37 C18:2 22.45 C18:3 1.92 C20:1 - C20:3 - C20:4 - C21:0 17.67 1:4 MR 2 h % area (ULL) 1.22 - 22.78 11.81 - 4.90 56.63 - - 1.56 0.58 0.53 - Fatty acids 1:4 MR 2 h % area (LSU) 1:4 MR 2 h % area (ULL) Fatty acids Unsaturated 63.5 78.11 Saturated 36.5 28.9

  11. GC analysis Main methyl ester after treatment in flow reactor

  12. Conclusions Batch process The use of supercritical methanol in the conversion of waste alligator fat to biodiesel was shown to be a viable alternative to traditional transesterification. Key advantages of this method include: a) avoidance of caustic catalysts, b) the elimination of solid byproducts posing disposal problems, and c) significant simplification of the conversion process, no emulsions. The use of raw fat containing proteins resulted in the formation of liquid amines and amides in the resulting product. These pose no harm; in fact, the addition of amines to increase the thermal stability of diesel fuels has been patented (USP 4,166,726). Furthermore, it is common practice to co-inject solutions of urea into diesel engines to reduce harmful NOX emissions. Optimized batch conditions were achieved when 2 g of oil was heated with 8 g of methanol to 300 C for 3 hours, resulting in 95.8 % of methyl esters and undetectable levels of free acids.

  13. Flow Reactor Study Several inherent problems with the batch process- temperature control after completion of the reaction. With a flow reactor, the reactants can enter and leave the system under more controlled conditions. A simple system was devised using an HPLC pump, shut off valve, woods metal bath, heater, digital thermometer, 6 ft. column, water cooled jacket and a pressure valve to control the pressure.

  14. Flow Reactor

  15. Flow Reactor Study-FAME analysis Concentration of the main methyl ester as a function of time, 1 mL/min

  16. Flow Reactor Study-FAME analysis Concentration of the main methyl ester as a function of time, 0.2 mL/min

  17. Flow Reactor Study-FAME analysis Concentration of the main methyl ester as a function of temperature - 1 mL/min

  18. GC Analysis of FAME vs.Temperature

  19. Conclusions Flow Reactor These graphs show the concentration of the esters increases exponentially. The highest concentration was reached at 400 C for the all esters, then the concentrations decreased rapidly. For the higher flow rate the exponential decrease was not observed. A new run was carried at 300, 320, 340, 360, 380, 400, 420, 440, 460, 480 C and 500 C. The number of samples was increased in order to have more information about the ester concentration especially between 400 C and 500 C. These graphs show that the highest concentration was reached at 460 C. In this case we observed, for the unsaturated ester, a exponential decrease of the concentration.

  20. Economicevaluation The economics of the lipid production was investigated with the following assumptions: The cost of lipid source was assigned to be zero, since feed stock was alligator fat waste that normally entails disposal costs for the processing industry. Byproduct glycerol was assumed to fetch a price of $ 0.22 per kg (ICIS, 2010). Cost of equipment were taken from SuperPro Designer and from the equipment data of Peters and Timmerhaus (Peter and Timmerhaus, 1981).

  21. Equipment cost No of equipments Name of equipment Total cost Grinder 1 73,000 Electric heater 2 63,000 Heat exchanger 1 1000 Nutsche filter 1 240,000 Storage tank 1 45,000 Vessel reactor 2 129,766.8 Distillation column 1 21,296.36 Cooling heat exchanger 1 1 1273.41 Cooling heat exchanger 2 1 1297.67 Total cost 575634.24

  22. Utilities Name of equipment Utilities Electricity KW h/y Grinder 650,240 Electric heater 1,504,512 Vessel reactor 7554.88 Cooling water/steam Cooling water 37547 m3/y Steam 581000 kg/y

  23. Results (Economic analysis) Fixed capital investment = 2.51 million dollars. Total capital investment = 2.98 million dollars. Raw material cost = 0.44 million dollars. Labor cost (18 people) = 0.87 million dollars. Utility costs = 0.125 million dollars. Annual total product cost = 3.01 million dollars. Average return on investment = 28.5% per year. Payback period = 2.3 years.

  24. Acknowledgements I would like to thank the department of chemistry at UL Lafayette and the following individuals who made this work possible through support and guidance: Dr. Rakesh Bajpai, Professor of Chemical Engineering, UL Dean Mark Zappi, Dean of Engineering, UL Patrick Spiller, UL Kevin Martin, University of Poitiers, France Teddy Lacourcelle, University of Poitiers, france Dr. William Holmes, UL Dr. Yuemin Liu, UL

  25. Questions?

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