Mark Holtzapple Department of Chemical Engineering Texas AM University

1. Mark Holtzapple Department of Chemical Engineering Texas A&M University This testimony will describe both biofuels and the StarRotor engine. Mark Holtzapple, the speaker, is a professor of chemical engineering at Texas A&M University. He may be contacted in the following ways: Mark Holtzapple Department of Chemical Engineering 3122 TAMU Texas A&M University College Station, TX 77843-3122 979-845-9708 (phone) 979-845-6446 (fax) 979-219-2599 (cell phone) m-holtzapple@tamu.eduThis testimony will describe both biofuels and the StarRotor engine. Mark Holtzapple, the speaker, is a professor of chemical engineering at Texas A&M University. He may be contacted in the following ways: Mark Holtzapple Department of Chemical Engineering 3122 TAMU Texas A&M University College Station, TX 77843-3122 979-845-9708 (phone) 979-845-6446 (fax) 979-219-2599 (cell phone) m-holtzapple@tamu.edu

2. Oil Refinery

3. Biomass Refinery

4. Chemicals: 1st Generation

5. Chemicals: 1st Generation

6. Chemicals: 1st Generation

7. Chemicals: 1st Generation

8. Chemicals: 2nd Generation

9. Chemicals: 2nd Generation

10. Chemicals: 3rd Generation

11. Chemical Flowchart

12. Carboxylic Acids

13. Ketones

14. Aldehydes

15. Secondary Alcohols

16. Primary Alcohols

17. Esters

18. Ethers

19. Chemicals: 3rd Generation

20. Chemicals: 3rd Generation

21. 1. Uses Multiple Feedstocks trees grass agricultural residues energy crops An ideal process should accept a wide variety of feedstocks, such as trees, grass, agricultural residues, energy crops, municipal solid waste, sewage sludge, and animal manure.An ideal process should accept a wide variety of feedstocks, such as trees, grass, agricultural residues, energy crops, municipal solid waste, sewage sludge, and animal manure.

22. Biomass wastes can produce up to 135 billion gallons of alcohol per year, which is a significant portion of our annual gasoline and diesel consumption.Biomass wastes can produce up to 135 billion gallons of alcohol per year, which is a significant portion of our annual gasoline and diesel consumption.

23. 2. Uses High-Productivity Feedstocks To minimize land area, high-productivity crops must be used. The corn yield assumes the US average [143 bushels/(acre·yr)] with 15% moisture. Sweet sorghum yields of 20 dry tons/(acre·yr) have been demonstrated in Texas test plots and energy cane yields of 30 dry tons/(acre·yr) have been demonstrated in Puerto Rico test plots.To minimize land area, high-productivity crops must be used. The corn yield assumes the US average [143 bushels/(acre·yr)] with 15% moisture. Sweet sorghum yields of 20 dry tons/(acre·yr) have been demonstrated in Texas test plots and energy cane yields of 30 dry tons/(acre·yr) have been demonstrated in Puerto Rico test plots.

24. Sweet Sorghum

25. Energy cane is a high-productivity variety of sugarcane that grows in the tropics and semi-tropics. These two full-grown men are standing next to one year’s growth of energy cane, which stands about 15 feet in height. This photograph was taken in Puerto Rico.Energy cane is a high-productivity variety of sugarcane that grows in the tropics and semi-tropics. These two full-grown men are standing next to one year’s growth of energy cane, which stands about 15 feet in height. This photograph was taken in Puerto Rico.

26. This photograph shows the length of the energy cane when cut.This photograph shows the length of the energy cane when cut.

27. Productivity in Puerto Rico(dry ton/(acre·yr))

28. Energy Cane Processing

29. Some Potential Commodity Products from Sugar Food acidulants Citric, gluconic, succinic acids Biodegradable polymers Polyhydroxyalcoanates Polylactic acid Synthetic rubber precursors 2,3-butanediol, a precursor to butadiene Fiber precursors 1,3-propanediol, a component of DuPont's Sorona

30. Aquatic Biomass – Water Hyacinth

31. Aquatic Biomass – Water Hyacinth

32. Aquatic vs Terrestrial Feedstocks To minimize land area, high-productivity crops must be used. The corn yield assumes the US average [143 bushels/(acre·yr)] with 15% moisture. Sweet sorghum yields of 20 dry tons/(acre·yr) have been demonstrated in Texas test plots and energy cane yields of 30 dry tons/(acre·yr) have been demonstrated in Puerto Rico test plots.To minimize land area, high-productivity crops must be used. The corn yield assumes the US average [143 bushels/(acre·yr)] with 15% moisture. Sweet sorghum yields of 20 dry tons/(acre·yr) have been demonstrated in Texas test plots and energy cane yields of 30 dry tons/(acre·yr) have been demonstrated in Puerto Rico test plots.

33. 3. Increases Agricultural Income Farmers can gross much more per acre by growing energy crops (e.g., sweet sorghum or energy cane) than by growing corn.Farmers can gross much more per acre by growing energy crops (e.g., sweet sorghum or energy cane) than by growing corn.

34. 4. Reduces Environmental Impact To grow biomass, there is an environmental cost (water, fertilizer, pesticides, herbicides, and eroded soil). Compared to corn, sweet sorghum and energy cane require less inputs per unit of biomass produced. To grow biomass, there is an environmental cost (water, fertilizer, pesticides, herbicides, and eroded soil). Compared to corn, sweet sorghum and energy cane require less inputs per unit of biomass produced.

35. 5. Desirable Process Properties The ideal properties of a process that converts biomass to fuels may be described as follows: Sterility – A process that requires sterility requires extra energy and capital inputs. Also, the plant operators must be sophisticated to maintain sterility. If sterility is violated, the product can spoil and become a disposal problem. Ideally, a process should not require sterility. Genetically modified organisms (GMO) – Genetically modified organisms are often unstable. Also, their disposal creates environmental challenges. Ideally, a process should not use genetically modified organisms. Adaptable –Preferred feedstocks may become scarce due to drought, insects, or other environmental problems. Ideally, the process should adapt to a variety of feedstocks so that replacements can be found during difficult times. Pure cultures – Pure cultures of organisms require sophisticated persons, such a microbiologists, to monitor the cultures and grow them from stock cultures. Ideally, the process should not require pure cultures. Capital – It will be expensive to install the infrastructure to use biomass feedstocks. Ideally, the process should be inexpensive so that capital is easy to raise and plants can be built quickly. Enzymes – Enzymes are expensive to manufacture. Ideally, the process should not require enzymes. Product yields – Biomass has many components (cellulose, hemicellulose, lignin, starch, pectin, lipids, proteins, etc.). Ideally, all of these components should be converted to product. Vitamins – Microorganisms require vitamins to grow. Typically, these can be supplied from corn steep liquor, but there is not enough available to service a large biofuel industry. Ideally, the process should not require vitamins. Co-Products – A process that requires valuable co-products (e.g., protein) to be economical will have limited applications. Once the co-product market is saturated, additional plants cannot be built. Ideally, the process should not require valuable co-products to make the economics work.The ideal properties of a process that converts biomass to fuels may be described as follows: Sterility – A process that requires sterility requires extra energy and capital inputs. Also, the plant operators must be sophisticated to maintain sterility. If sterility is violated, the product can spoil and become a disposal problem. Ideally, a process should not require sterility. Genetically modified organisms (GMO) – Genetically modified organisms are often unstable. Also, their disposal creates environmental challenges. Ideally, a process should not use genetically modified organisms. Adaptable –Preferred feedstocks may become scarce due to drought, insects, or other environmental problems. Ideally, the process should adapt to a variety of feedstocks so that replacements can be found during difficult times. Pure cultures – Pure cultures of organisms require sophisticated persons, such a microbiologists, to monitor the cultures and grow them from stock cultures. Ideally, the process should not require pure cultures. Capital – It will be expensive to install the infrastructure to use biomass feedstocks. Ideally, the process should be inexpensive so that capital is easy to raise and plants can be built quickly. Enzymes – Enzymes are expensive to manufacture. Ideally, the process should not require enzymes. Product yields – Biomass has many components (cellulose, hemicellulose, lignin, starch, pectin, lipids, proteins, etc.). Ideally, all of these components should be converted to product. Vitamins – Microorganisms require vitamins to grow. Typically, these can be supplied from corn steep liquor, but there is not enough available to service a large biofuel industry. Ideally, the process should not require vitamins. Co-Products – A process that requires valuable co-products (e.g., protein) to be economical will have limited applications. Once the co-product market is saturated, additional plants cannot be built. Ideally, the process should not require valuable co-products to make the economics work.

36. 6. Desirable Fuel Properties Lastly, let’s identify the ideal properties of the fuel.Lastly, let’s identify the ideal properties of the fuel.

37. Fuel Properties Key properties of fuel components are described below: Octane – A high octane rating is required to prevent internal combustion gasoline engines from knocking, which can cause damage. All the fuel components (ethanol, MTBE, and mixed alcohols) have a high octane rating. Volatility – Volatile emissions from the fuel tank cause air pollution. Ethanol is very polar, which raises the fuel volatility. In contrast, MTBE and mixed alcohols have a low volatility. Pipeline shipping – To lower costs, fuel components should be shipped through the pipelines. Ethanol is so polar, it absorbs water in the pipelines causing fuel problems. To prevent this problem, it is shipped by train or truck to the terminal where it is “splash blended,” an expensive proposition. In contrast, MTBE and mixed alcohols can be shipped through the pipelines. Energy content – The purpose of fuel is to store energy. Fuels with a high oxygen content, such as ethanol, have a low energy content whereas fuels with a lower oxygen content, such as MTBE and mixed alcohols, have a high energy content. Heat of vaporization – Ethanol requires a lot of energy to vaporize, which can cause engine starting problems. In contrast, MTBE and mixed alcohols have a lower heat of vaporization. Ground water damage – Fuel is stored in underground tanks, which tend to leak. MTBE contaminates ground water and is being banned. In contrast, the alcohols do not damage ground water.Key properties of fuel components are described below: Octane – A high octane rating is required to prevent internal combustion gasoline engines from knocking, which can cause damage. All the fuel components (ethanol, MTBE, and mixed alcohols) have a high octane rating. Volatility – Volatile emissions from the fuel tank cause air pollution. Ethanol is very polar, which raises the fuel volatility. In contrast, MTBE and mixed alcohols have a low volatility. Pipeline shipping – To lower costs, fuel components should be shipped through the pipelines. Ethanol is so polar, it absorbs water in the pipelines causing fuel problems. To prevent this problem, it is shipped by train or truck to the terminal where it is “splash blended,” an expensive proposition. In contrast, MTBE and mixed alcohols can be shipped through the pipelines. Energy content – The purpose of fuel is to store energy. Fuels with a high oxygen content, such as ethanol, have a low energy content whereas fuels with a lower oxygen content, such as MTBE and mixed alcohols, have a high energy content. Heat of vaporization – Ethanol requires a lot of energy to vaporize, which can cause engine starting problems. In contrast, MTBE and mixed alcohols have a lower heat of vaporization. Ground water damage – Fuel is stored in underground tanks, which tend to leak. MTBE contaminates ground water and is being banned. In contrast, the alcohols do not damage ground water.

38. Properties of Fuel Oxygenates

39. Energy Content

40. MixAlco Process The process economics are shown in the next few pages.The process economics are shown in the next few pages.

42. MixAlco Process – Version 1

44. Advanced Lime Treatment

45. Building the Pile

46. Building the Pile

47. Building the Pile

48. Lignin Removal

51. Environments where organic acids naturally form animal rumen - cattle - sheep - deer - elephants anaerobic sewage digestors swamps termite guts

52. Why are organic acids favored?

53. Typical Product Spectrumat Different Culture Temperatures

57. Marine Inoculum

58. Storage + Pretreatment + Fermentation

60. A compressor pulls a slight vacuum on the salt solution, causing water to boil. The compressor pressurizes the water allowing it to condense in a heat exchanger. The heat of condensation from the condensing steam provides the heat of evaporation needed by the boiling salt solution; thus, the heat is cycled. The small amount of work input to the compressor drives the cycle. The salt crystals are removed by filtration and sent for further processing. This process can also be used to desalinate seawater to make drinking water.A compressor pulls a slight vacuum on the salt solution, causing water to boil. The compressor pressurizes the water allowing it to condense in a heat exchanger. The heat of condensation from the condensing steam provides the heat of evaporation needed by the boiling salt solution; thus, the heat is cycled. The small amount of work input to the compressor drives the cycle. The salt crystals are removed by filtration and sent for further processing. This process can also be used to desalinate seawater to make drinking water.

62. Thermal Conversion Stoichiometry

63. Thermal Conversion Kinetics

66. Ketone Hydrogenation Stoichiometry

67. Ketone Hydrogenation

69. MixAlco Process – Version 2

70. Acid “Springing”

71. MixAlco Process – Version 2

72. Hydrogenation Stoichiometry

73. Hydrogenation

74. Economics

75. Capital and Feedstock Cost

76. Costs – Basic Assumptions

77. Costs – Basic Assumptions

78. Costs – Feedstock $/tonne $/gal $/yr Biomass ($60/tonne) 60.00 0.352 19,220,312 Lime, CaO ($100/tonne) 7.60 0.045 2,432,413 Inhibitor ($6/kg) 1.00 0.006 322,909 Hydrogen ($990/tonne) 40.89 0.239 13,203,753 109.49 0.642 35,179,387

79. Costs – Utilities $/tonne $/gal $/yr Electricity ($0.08/kWh) 2.96 0.017 955,810 Steam ($10/GJ) 14.18 0.083 4,578,851 Natural gas ($8/GJ) 7.20 0.042 2,324,945 Cooling water ($0.06/m3) 3.17 0.019 1,023,622 Solid fuel sales ($2.50/GJ) -9.25 -0.054 -2,986,909 18.26 0.107 5,896,319

80. Costs – Labor $/tonne $/gal $/yr Plant manager (1 @ $150,000/yr) 0.475 0.003 150,000 Supervisors (4 @ $80,000/yr) 1.003 0.006 320,000 Sales (1 @ $80,000/yr) 0.246 0.002 80,000 Clerical (3 @ $40,000) 0.377 0.002 120,000 Workers (20 @ $45,000/yr) 2.813 0.016 900,000 4.914 0.029 1,570,000

81. Costs – Fixed Charges $/tonne $/gal $/yr Depreciation (0.1 X FCI) 17.18 0.101 5,500,000 Local tax (0.03 X FCI ) 5.16 0.030 1,650,000 Insurance (0.007 X FCI ) 1.20 0.007 385,000 Maintenance (0.04 X FCI ) 6.94 0.041 2,220,000 30.48 0.179 9,755,000

82. Costs – Fixed Charges $/tonne $/gal $/yr Depreciation (0.1 X FCI) 34.36 0.202 11,000,000 Local tax (0.03 X FCI ) 10.32 0.060 3,300,000 Insurance (0.007 X FCI ) 2.40 0.014 770,000 Maintenance (0.04 X FCI ) 13.88 0.082 4,440,000 60.96 0.358 19,510,000

83. Costs – Summary $/tonne $/gal $/yr Feedstock 109.49 0.642 35,179,387 Utilities 18.26 0.107 5,896,319 Labor 4.91 0.029 1,570,000 Fixed Charges 30.48 0.179 9,755,000 162.42 0.957 52,400,706

84. Costs – Summary $/tonne $/gal $/yr Feedstock 109.49 0.642 35,179,387 Utilities 18.26 0.107 5,896,319 Labor 4.91 0.029 1,570,000 Fixed Charges 60.96 0.358 19,510,000 192.90 1.136 62,155,706

85. Ethanol Price History – 10 years

86. Ethanol Price History – 18 months

87. Profitability

88. Return on Investment ($1/annual gallon)

89. Profitability

90. Return on Investment ($2/annual gallon)

91. Issues

92. 1. Biomass Harvesting and Transport

98. Transportation Costs ($/(m3·1000 km))

99. Cost of Transporting Energy ($/(GJ·1000 km)

102. 2. Land Availability

103. Centralized Processing of Energy Cane

104. Centralized Processing of Energy Cane

105. Centralized Processing of Energy Cane

106. Supply US Gasoline Consumption

107. Effect of Automotive Efficiency

108. Energy Cane Land Required in Brazil

109. Sweet Sorghum Land Area in United States

110. 3. Energetics

111. MixAlco Fermentation

112. MixAlco Fermentation

115. Dewatering Energetics

116. 4. Environmentally Acceptable Hydrogen Sources

117. 4. Environmentally Acceptable Hydrogen Sources

118. 4. Environmentally Acceptable Hydrogen Sources

119. 4. Environmentally Acceptable Hydrogen Sources

120. 4. Environmentally Acceptable Hydrogen Sources

121. 4. Environmentally Acceptable Hydrogen Sources

122. 4. Environmentally Acceptable Hydrogen Sources

123. 5. Purification

124. Crystallization

125. Acid “Springing”

126. Distillation

127. RecentImprovements

128. Ammonium Bicarbonate Buffer

129. Ammonium Bicarbonate Buffer

130. Acid Production

131. Alcohol Production

132. Conclusions The technology is - “green” - profitable - world-wide - simple Many potential products - ketones - alcohols - organic acids

133. Conclusions Near-term applications - waste ® chemicals Mid-term applications - waste ® fuels Far-term applications - crops ® fuels