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The Suitability of Algae Protein Residue as an Effective Biofuel

Research Report Alexis Barragan Academy for Math, Engineering and Science (AMES) Mentor: Ashley Budd

Table of Contents

Abstract Introduction Question and Hypothesis Materials and Methods

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TGA Data Calorimeter Data Elemental Composition Data

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Analysis Conclusion and Acknowledgments References

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Abstract The dependency on non-renewable resources for fuel and energy is harmful and unreliable. Resources such as fossil fuels are in a finite amount as well as damaging to the environment. Biofuels are an excellent source for renewable resources. Algae are aquatic plants that are used for lipid extraction and then for production of ethanol. Algae has a wide range of areas to grow in and it cleanses waste water. After lipid extraction, protein residue can be used for further energy production through pyrolysis. Through the use of a TGA, dehydrated algae samples were tested to measure the change in weight in relation to change in temperature The algae were left with a remaining mass percentage after TGA. Data is significant in that other commonly used feed for pyrolysis, such as rice straw or wood chips, have no mass remaining (when left untreated) at lower temperatures. The focus of algae production for biofuels can be algae extraction and pyrolysis of protein residue as well.

Introduction The United States Department of Energy (U.S. DOE) and Environmental Protection Agency (EPA) has concluded that the dependence on oil is harmful and costly (EPA, 2011). The vehicles driven in the United States release over 1.7 billion tons of CO2 into the atmosphere each year, contributing to the global climate change (U.S. DOE). Vehicles, as well as other equipment, run off of energy that comes from fossil fuels. Because non-renewable sources, such as oil, will not last forever. Existing fields of oil production are now running at 6.7 percent a year compared to the 3.7 percent decline estimated in 2007 by the International Energy Agency (Connor, 2009). It is necessary that renewable resources be used as a source of fuel. An increase in energy sustainability is vital (EPA, 2011). It is clear that there is a need to search for renewable fuel sources.

A non-renewable resource is a material that is used for fuel that is found within finite amounts (within human time scale) on Earth. Non-renewable resources include fossil fuels such as coal, petroleum, and natural gas. Along with being non-renewable, fossil fuels are harmful to the environment. According to a 2011 World Energy Consumption and Economic Outlook Report, 176.4 quadrillion Btu (British thermal units) of liquids such as petroleum and oils are used around the world and 150.0 quadrillion Btu of coal are consumed in the world while only 57.8 quadrillion Btu of renewable resources are consumed worldwide (EIA, 2011). The majority of 176.4 quadrillion Btu of liquids are non-renewable. A renewable resource, in contrast, is a material that when harvested with sustainability can be grown and resupplied within human time scale. These resources, such as solar power and geothermal power, are much more

environmentally friendly. Plants are considered to be a renewable source of energy because of their ability to be resupplied within human time scale.

A carbon footprint is a form of carbon calculation that measures the amount of carbon dioxide equivalent that a country, business, industry, or individual produces or is responsible for ("Climate change- glossary," 2008). With an efficient and renewable source of energy, vehicles and other machines will have decreased emissions and a diminished carbon footprint. Nevertheless, renewable energy technologies are still being researched and innovated. Renewable fuels such as biodiesel and ethanol decrease our need for petroleum in automobiles (EPA, 2011). Biodiesels are the monoalkyl esters of long chain fatty acids derived from plant or animal matter that meet the registration requirements for fuels and fuel additives established by the federal environmental protection agency (Brady, Ellis, Kimura, Lyons, Sinks & Stephens, 2007). Biofuels are synthesized with renewable resources such as forest and agriculture waste.

Algae are aquatic protists that have many advantages to being a potential renewable biofuel. The advantages include being able to grow practically anywhere: salt water, contaminated water, non-arable land, freshwater, arable land, etc. (Cannon, 2008). Algae also have been seen to grow better with waste water such as sewage and under concentration of CO2, a major greenhouse gas. It cleans and purifies the water which helps the sanitation department. It also decreases CO2 concentration in the atmosphere which is a major greenhouse gas helping out the environmental department (Cannon, 2008). As part of the photosynthesis process, algae produces oil and can generate 15 times more oil per acre than other plants used for biofuels, such as corn and switchgrass (Cannon, 2008).

Research on algae is being performed with the goal of producing biodiesel from the oils contained within the algae plant. However, the Society for Biological Engineering says that if the algae-to-biofuels process is carried out on a scale that addresses the quantity needed for the fuel markets, there will likely be an extreme overabundance of algal proteins (SEB, 2011). These leftovers of biomass could also potentially be used to convert to biofuels. A Thermogravimetric Analyzer (TGA) is an instrument that measures the change in weight in relation to the change in temperature over time of a sample. A bomb calorimeter measures how much energy is contained in a sample by the combustion of the compound. When both the TGA and calorimeter are used, along with the chemical composition analysis, the data can be compared to the data of similar tests done to commonly used feedstock in pyrolysis. This can then aid in discovering if algae protein residue is a competitive source of energy.

Question & Hypothesis Question: Can the protein residue found after algae lipid extraction be used as a fuel source? Hypothesis: Algal protein residue will be found to be a viable fuel source when compared to other known fuel sources.

Materials and Methods

Materials Crushed and dried algae with lipids Crushed and dried algae without lipids Thermogravimetric Analyzer (TGA) Bomb calorimeter Electronic scale Oxygen tank Latex gloves Safety glasses Pellet press 20 cm of iron wire 4 L of water stopwatch

Methods A TGA was used to find the change in weight in relation to the change in temperature of a sample. The TGA used in this study includes two arms with a pan at the end of each. One pan contained the sample that was to be tested while the other pan remains empty as a control. In this study, a sample of algae with lipids and a sample of the same species of algae without lipids were tested using the TGA. The dehydrated algae with lipids sample was tested first. Approximately 2 grams of the sample was placed in the testing pan of the TGA and a routine of commands was programmed into the TGA. The sample, along with the control, was inserted into a controlled environment (part of the TGA) to be put through the method as programmed: 7

1. External event ON 2. Data Storage ON 3. Select Gas 1 (UHP Nitrogen) 4. Flow rate 100 mL/min 5. Equilibrate at 60.00C 6. Isothermal for 5.00 minutes 7. Ramp 10.000C to 110.00C 8. Isothermal for 10.00 minutes 9. Ramp 10.000C/min to 1000.00C 10. Isothermal for 5.00 minutes 11. Data Storage OFF The sample was set to stay isothermal at certain temperatures to vaporize any water possibly remaining in the sample as well as help create a smooth line on the TGA graph. The sample was originally set to end at a temperature of 1000.00C but the graph showed a continuation in mass loss past that point so the method was changed mid-testing to:

7. Ramp 10.000C/min to 1200.00C The same method was used on the second sample, dehydrated algae without lipid, except it was preprogrammed to raise the temperature to 1200.00C.

A bomb calorimeter was used to find the energy contained within the algae samples. 0.0922 g of the algae with lipids sample was compressed with a pellet press and placed within the crucible. 0.0150 g of iron connector wire was connected to the sample and ignition wire. The crucible was placed within the bomb. The bomb was filled with oxygen and aired out a few times so as to limit the gasses inside the bomb to mostly oxygen. The bucket within the calorimeter was filled with 2 L of water at temperature of approximately 25.5C. The bomb was placed inside the bucket, connected to the igniter leads and the calorimeter was sealed. The thermometers were lowered into the bucket through the calorimeter. The initial temperature of the water was measured. After approximately 3 minutes we ignited the sample and recorded the temperature change of the water every 30 seconds for 10 minutes. The same process was repeated with the algae without lipids sample. Specific Heat calculations are done after each test to find the total energy of the algae samples.

Results
TGA Data

Figure 3: TGA graph of algae with lipids.

Figure 4: TGA graph of algae without lipids

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Calorimeter Data

Test 1 Time (mins and secs) Temperature (C)

Test 2 Time (mins and secs) Temperature (C)

0:00 0:30 1:00 1:30 2:00 2:30 3:00 3:30 4:00 4:30 5:00 5:30 6:00 6:30 7:00 7:30 8:00 8:30 9:00 9:30 10:00
Fig 7: Calorimeter data of algae with lipids. The total change in temperature was 0.03C

25.25 25.24 25.22 25.21 25.2 25.2 25.2 25.2 25.25 25.28 25.3 25.3 25.3 25.3 25.3 25.31 25.31 25.3 25.29 25.29 25.28

0:00 0:30 1:00 1:30 2:00 2:30 3:00 3:30 4:00 4:30 5:00 5:30 6:00 6:30 7:00 7:30 8:00 8:30 9:00 9:30 10:00
Fig 8: Calorimeter data of algae without lipids. The total change in temperature was 0.17C

24.9 25.05 25.05 25.05 25.04 25.03 25.03 25.03 25.04 25.07 25.08 25.09 25.1 25.1 25.1 25.1 25.1 25.09 25.09 25.08 25.07

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Additional Data
Elemental Composition

Nitrogen: 5.40%

Ash: 13.00% Carbon Carbon: 39.60% Oxygen: 35.90% Hyrdogen Oxygen Nitrogen Ash

Hydrogen: 6.10%

Figure 5: The elemental chemical composition of the algae with lipids sample

Nitrogen: 5.50%

Ash: 18.40% Carbon: 33.00% Carbon Hyrdogen Oxygen Nitrogen Oxygen: 37.10% Hydrogen: 5.90% Ash

Figure 6: The elemental chemical composition of the algae sample with the lipids extracted.

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Analysis The TGA measures the change in weight in relation to the change in temperature and the graphs represent this relationship. As time continues and the temperature increases, the weight decreases due to decomposition of organic compounds found within the sample. The first major dip in fig. 3 and fig. 4 occurs at between the temperature of 30-40C.They indicate the evaporation of water. The next dip at temperatures around 90-100C seems to have occurred based upon the sudden rise in temperature. The loss of the majority of the samples mass begins at approximately 150C. At 1200C the algae samples still had 20% mass left after pyrolysis. This is important in that other currently used sources for pyrolysis (i.e. wood chips, rice straw) had 0% mass left (when left untreated) at temperatures such as 500-600C when the graphs were compared qualitatively. Algae can burn longer during the pyrolysis process than other commonly used biomass sources. The difference between both samples is also significant in that there is little difference. The ending value is still approximately 20% at the same temperature of 1200C. Lipid extraction does not affect the remaining mass percentage. Both lipid extraction and pyrolysis can both be accomplished with essentially the same results as doing it separately. With lipid extraction being the major reason for algae growth and production, algae pyrolysis can become of more significance in its production, but more data must be acquired in order to better compare algae to other sources.

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Conclusion Algae have been observed to be a possible competitive source for pyrolysis compared to other currently used feedstock. The whole algae plant could be effectively used to produce energy with both the lipid extraction and pyrolysis of the protein residue. However more information is necessary to determine that. Similar data of other known sources for biofuels needs to be acquired in order to compare them. With new renewable energy technology algae growth and production is increasing dramatically due to its lipid-to-fuel potential. Pyrolysis could be an increasingly more significant reason to produce algae alongside lipid extraction.

Acknowledgements I want to thank all those who have helped me with my project. The AMES Science Research students who gave me ideas and feedback, my teachers and mentor Tara Wion and Ashley Budd, The University of Utah Chemical Engineering Department, Dr. Whitty who is of that department, and Alonzo Martinez. They have guided me with support, knowledge, and experience.

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Appendix 1: TGA thermogram for decomposition temperature of crosslinked RSPE at various VTMO concentration. (S0) 2.0 phr, (S4) 3.0 phr.1 The majority of the mass of the rice straw burns between temperatures 400C and 500C. Compared to the algae samples, it burns less completely and at higher temperatures.

Appendix 2: TGA curves of sugarcane bagasse (line 1), unbleached pulp (line 2), bleached pulp (line 3), NMMO (line 4), film 1 with 1.5 h of treatment (line 5), film 2 with 2.5 h of treatment (line 6), film 3 with 1.5 h of treatment without bath (line 7), and film 4 with 2.5 h of treatment without bath (line 8).2 The majority of the mass of the untreated bagasse burned off at temperatures between 300C and 400C. The algae samples burns at about the same temperatures.

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Appendix 3: Effect of heating rates on TGA plot of corn stover in a nitrogen atmosphere.3 Like the algae samples, the majority of the mass burned off between 200C and 400C.

Appendix 4: TGA curves of wood shavings (1), chicken litter (2) and char (3) recorded in nitrogen. The majority of the mass burns between 200C and 400C.4 When compared to the algae samples, the majority of the mass of the algae burns at about the same temperatures.

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References Brady, M., Ellis, T., Kimura, K., Lyons, J., Sinks, H., & Stephens, J. Washington State Department of Agriculture, Renewable diesel subcommittee. (2007). Renewable diesel technology. Retrieved from website: http://agr.wa.gov/bioenergy/docs/RenewableDieselWhitePaperFINAL.pdf Cannon, B. (2008, August 06). Algae: Biofuel of the future. Retrieved from http://www.virginia.edu/uvatoday/newsRelease.php?id=5985 Connor, S. (2009, August 03). Warning: Oil supplies are running out fast The Independent, Retrieved from http://www.independent.co.uk/news/science/warning-oil-supplies-arerunning-out-fast-1766585.html Environmental Protection Agency, (2008). Climate change- glossary of key terms. Retrieved from website: http://www.epa.vic.gov.au/climate-change/glossary.asp Knoshaug, E. (2011, March). Algal biofuels: The process. 37-47. Retrieved from http://www.aiche.org/uploadedFiles/SBE/Restricted/SBEOnlyNew/031137(1).pdf U.S Department of Energy, U.S. Environmental Protection Agency. (2011). Why is fuel economy important? Retrieved from http://www.fueleconomy.gov/feg/why.shtml U.S Department of Energy, U.S. Environmental Protection Agency. (2011). Reduce oil dependence cost Retrieved from http://www.fueleconomy.gov/feg/oildep.shtml U.S Department of Energy, U.S. Environmental Protection Agency. (2011). Increase energy sustainability. Retrieved from http://www.fueleconomy.gov/feg/consres.shtml U.S Department of Energy, U.S Energy Information Administration. (2011).International energy outlook 2011. Retrieved from http://205.254.135.24/forecasts/ieo/world.cfm

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