Oil shortage Greenhouse Effect

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Lynette Atkins
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1 Setting the Stage Oil shortage Greenhouse Effect M. King Hubbert ( ) American geophysicist Shell Oil research laboratory Houston, TX Production (billion bbl/yr) US Oil Production Hubbert s Prediction (1956) Actual 1.5 Predicted Production (billion bbl/yr) World Oil Production Deffeyes Prediction (2001) Source: Deffeyes, Hubbert s Peak (2001) Year Source: Deffeyes, Hubbert s Peak (2001) Year Where will we get our energy? Study by Shell Group Planning Georges Dupont-Roc Alexon Khor Chris Anastasi The Evolution of the World s Energy Systems 1996

2 Setting the Stage Greenhouse Effect Oil shortage Greenhouse Effect Infrared Visible Greenhouse Gases Recent CO 2 Concentration Greenhouse Gases CH 4 CFC NO x CO 2 Visible CO 2 Concentration (ppm) Mauna Loa Observatory Year Historical CO 2 Concentration Temperature Change Carbon Dioxide Concentration (ppm) Time Before Present (00 years) Time Before Present (00 years) Temperature Change from Present ( o C)

3 Combined Correlation Carbon Dioxide Concentration (ppm) Time Before Present (00 years) Temperature Change from Present ( o C) Hypothesis Independent Dependent 1 Temp CO 2 2 CO 2 Temp Carbon Emissions Recent Correlation 7 } 6 5 Rest of World Developed 1 World } (US, Canada, Western Europe) Year CO 2 Emissions (billion tonnes per year) Average Global Temperature ( o C) CO 2 Temp Year CO 2 Concentration (ppm) Conclusion Hypothesis Independent Dependent 1 Temp CO 2 2 CO 2 Temp Average Global Temperature ( o C) Princeton Model Model Data Year Model Includes: CO 2 Aerosols Solar Radiation

4 Potential Negative Effects rapid extinctions tropical diseases moving north Grain Belt becomes Dust Belt more insects rising ocean levels increased heat-related deaths Gulf Stream shuts down, chilling Europe increased storms/floods/hurricanes droughts and floods more common more forest fires due to drought weakened coral reefs Exacerbating Effects extended thaw in tundra polar ice caps melt methane clathrates melt Sustainable Energy and Transportation CO 2 Researchers Faculty Mark Holtzapple Richard Davison Post Docs Praveen Vadlani Vincent Chang Xu Li Masters Murlidahar Nagwani Chang Ming Lee Champion Lee Seth Adleson Robert Rapier William Kaar David Gaskin Hiroshi Shirage Wilbelto Adorno -Gomez Shelly Williamson Maria Almendarez Ramasubramania Narayan Patricia O'Dowd Hung -Wen Yeh Manohar Vishwanathappa PhD Nan Sheng Chang Shushien Chang Mitch Loescher Kyle Ross Susan Domke Salvador Aldrett-Lee Cateryna Aiello-Mazzarri Wenning Chan Piyarat Thanakoses Xu Li Cesar Granda Guillermo Coward -Kelly Li Zhu Se Hoon Kim Frank Agbogbo Zihong Fu Jonathan O'Dwyer Research Statistics You can t have it all! Year started = early 1991 Time spent = 12 years Labor = ~7 person years Total funding = $2.1 mill Cheap} University { Industry Good Fast

5 Examples of What is lignocellulose? trees grass agricultural residues energy crops Most of these are lignocellulose. Chemicals municipal solid waste sewage sludge animal manure Cellulose Hemicellulose Lignin - glucose polymer - xylosepolymer - aromatic polymer U.S. Biodegradable Wastes MixAlco Process Waste Amount (million tonne/year) Potential (billion gal/year) Municipal Solid Waste Sewage Sludge Industrial Biosludge Recycled Paper Fines Agricultural Residues Forestry Residues Manure Total 1, U.S. Gasoline Consumption = 130 billion gal/year U.S. Diesel Consumption = 40 billion gal/year Carboxylate Salts ate Patents 5,865,898 5,693,296 5,962,307 5,874,263 5,986,133 5,969,189 6,262,313 ate 6,043,392 6,395,926

tea bag Place tea bags in porous sack Place porous sacks in cattle rumen Incubate Remove porous sack Wash tea bags Dry Weigh

6 ment Treatment Carboxylate Salts ate T = 0 o C t = 1 h loading = 0.1 g Ca(OH) 2 /g biomass Water loading = 5 to 15 g H 2 O/g biomass In situ Digestion Weigh ~ 2 g of biomass Place biomass in tea bag Place tea bags in porous sack Place porous sacks in cattle rumen Incubate Remove porous sack Wash tea bags Dry Weigh residue In-Situ Digestion ment Vessels 48-h Digestion (g digested/g fed) Sugar- African cane millet bagasse straw Sorghum Tobacco straw stalks Untreated -treated

7 Advanced Treatment Lignin Removal Air + Gravel Lignin Content (g lignin/0 g bagasse) Lignin (g lignin/0 Content g in treated Treated bagasse) Bagasse No Air 25 o C Time(days) Time (days) Lignin Content (g lignin/0 g bagasse) Lignin Content in Treated Bagasse (g lignin/0 g of bagasse) o C o C 25 o C 55 Air 57 o C 50 o C Time 150 (days) Time (days) ation Environments where organic acids naturally form Carboxylate Salts ate animal rumen - cattle - sheep - deer - elephants anaerobic sewage digestors swamps termite guts Why are organic acids favored? Typical Product Spectrum at Different Culture Temperatures C 6 H 12 O 6 2 C 2 H 5 OH + 2 CO 2 G G = kcal/mol glucose ethanol C 6 H 12 O 6 3 C 2 H 3 OOH G G = kcal/mol glucose acetic acid The actual stoichiometry is more complex 5 C 6 H 12 O acetate + 2 propionate + butyrate + 5 CO CH H 2 O (67 mol%) (22 mol%) (11 mol%) 40 o C 55 o C C2 Acetic 41 wt % 80 wt % C3 Propionic 15 wt % 4 wt % C4 Butyric 21 wt % 15 wt % C5 Valeric 8 wt % <1 wt % C6 Caproic 12 wt % <1 wt % C7 Heptanoic 3 wt % <1 wt % 0 wt % 0 wt %

Marine Inoculum Total acid concentration

Inoculum No Air VSLR (g/(l d)) 18 14 Marine

8 Marine Inoculum Total acid concentration (g/l) Terrestrial Inoculum No Air VSLR (g/(l d)) Marine Inoculum Air LRT (days) Storage + ment + ation ing Air Tarp Cover + + Carboxylate Salts ate Gravel

Jet Ejector ing Jet Ejector High-Pressure Steam Distilled Water Salt Crystals Filter Salt Solution (or Broth) Heat Requirements Btu lb water removed Single-effect effect evaporator 00 Triple-effect

9 Jet Ejector ing Jet Ejector High-Pressure Steam Distilled Water Salt Crystals Filter Salt Solution (or Broth) Heat Requirements Btu lb water removed Single-effect effect evaporator 00 Triple-effect effect evaporator 333 Jet ejector dewatering -effect 0 20-effect effect 33 Carboxylate Salts ate O Stoichiometry O H 3 CCOCaOCCH 3 Η 3 CCCH 3 Calcium Acetate O Acetone + CaCO 3 O O O H 3 CCH 2 COCaOCCH 2 CH 3 Η 3 CCH 2 CCH 2 CH 3 + CaCO 3 Calcium Propionate Diethyl Ketone O O O H 3 CCH 2 CH 2 COCaOCCH 2 CH 2 CH 3 Η 3 CCH 2 CH 2 CCH 2 CH 2 CH 3 + CaCO 3 Calcium Butyrate Dipropyl Ketone Kinetics t (min) T ( C) (%)

Catalyst = 200 g/l Raney nickel Temperature = 130 o C Time = 35 min (@ P = 15 atm) Advantages of MixAlco Approach nonsterile fermentation no

10 ation Carboxylate Salts ate Ketone ation Stoichiometry Ketone ation O OH H 3 CCCH 3 + H 2 H 3 CCCH 3 H Acetone Isopropanol O OH H 3 CCCH 2 CH 3 + H 2 H 3 CCCH 2 CH 3 H Methyl Ethyl Ketone 2-Butanol O OH H 3 CCH 2 CCH 2 CH 3 + H 2 H 3 CCH 2 CCH 2 CH 3 H Diethyl Ketone 3-Pentanol Liquid H 2 Catalyst = 200 g/l Raney nickel Temperature = 130 o C Time = 35 min (@ P = 15 atm) Advantages of MixAlco Approach nonsterile fermentation no spoiled batches inexpensive tanks robust plant operation adaptable microorganisms stable microorganisms microorganisms self-generate no enzyme addition

Economics Base Case Plant Capacity Plant Capacity City Population (tonne/h) (mill gal/yr) 2 1.5 40,000 7.6 200,000 40 30.3 800,000 160 121.2 3,200,000 800 606.

11 Economics Base Case Plant Capacity Plant Capacity City Population (tonne/h) (mill gal/yr) , , , ,200, ,000,000 Capital Cost of Each Section (mill $) (40 tonne/h) Effect of Feedstock Cost ( 40 tonne/h, 15% ROI).6 Total = $20 mill Selling Price ($/gal) g/l, -effect 50 g/l, 20-effect 70 g/l, 30-effect / Conv Cost ($/tonne) and Sugar from Energy Cane Productivity in Puerto Rico (dry ton/(acre yr)) 30 60% 40% Fiber Sugar Conventional Sugarcane Energy Cane Source: Alex Alexander, The Energy Cane Alternative, Sugar Series 6, Elsevier % 30%

Energy Cane Processing from Energy Cane (no sugar credit) Energy Cane Sugar Fiber Extract Sugar Mill MixAlco Process Residue (Boiler Fuel) Sugar Fuel Required Area Centralized Processing Scale = 800

12 Energy Cane Processing from Energy Cane (no sugar credit) Energy Cane Sugar Fiber Extract Sugar Mill MixAlco Process Residue (Boiler Fuel) Sugar Fuel Required Area Centralized Processing Scale = 800 tonne/h Feedstock yield = 30 ton/(acre yr) 800tonne 8000h 1.1 ton acre yr Area = = 235,000acre h yr tonne 30 = 366 mi mi 50% of area planted Supply US Gasoline Consumption Effect of Automotive Efficiency gal gas 1.2 gal alc plant yr Plants= = 248plants yr gal gas gal alc 366mi 2 Area = 248plants = 90,900mi 2 plant 1 better (Current) 2 better 302 mi 213 mi 0% planted 302 mi 3 better 174 mi

13 Land required in Brazil Sweet Sorghum Grows in ~35 US states Yield = dry ton/(acre yr) % planted 345 mi William Rooney, Soil and Crop Sciences, Texas A&M University Land Area in United States 1 2 3

MixAlco Process. Cesar Granda, Ph.D. Department of Chemical Engineering Texas A&M University College Station, TX

MixAlco Process. Cesar Granda, Ph.D. Department of Chemical Engineering Texas A&M University College Station, TX MixAlco Process Cesar Granda, Ph.D. Department of Chemical Engineering Texas A&M University College Station, TX Oil Refinery Crude Oil $431/ton $66/bbl $1.57/gal Oil Refinery Chemicals Fuels Polymers $566/ton