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

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

2 Oil Refinery Crude Oil $431/ton $66/bbl $1.57/gal Oil Refinery Chemicals Fuels Polymers $566/ton $73/bbl $1.73/gal

3 Biomass Refinery Food Feed Biomass $40/ton $15/bbl* $0.36/gal* Biomass Refinery Chemicals Fuels Polymers $ /ton $50 75/bbl $ /gal * Equivalent energy basis Pharmaceuticals Fiber

4 Chemicals: Thermochemical platform Lignocellulose Gasify CO H 2 Catalyst (Syngas) Chemicals Fischer Tropsch fuels Methanol Mixed alcohols Ammonia

5 Chemicals: Thermochemical platform Lignocellulose Disadvantages Gasify CO H 2 Catalyst (Syngas) Chemicals Fischer Tropsch fuels Methanol Mixed alcohols Ammonia 30 40% biomass energy lost to heat Must couple to electricity markets Expensive gasifiers Complex downstream processing Difficult to supply enough biomass to achieve economy of scale

6 Chemicals: Sugar platform Corn Enzymes Sugars Microorganism Chemicals Squeeze Sugarcane Ethanol Butanol Acetone 2,3 Butanediol Glycerol Acetoin Acetic acid Lactic acid Propionic acid Succinic acid Butyric acid Citric acid

7 Chemicals: Sugar platform Corn Enzymes Disadvantages Sugars Sugarcane Limited availability Competition with food Requires sterility Difficult separations Squeeze Microorganism Chemicals Ethanol Butanol Acetone 2,3 Butanediol Glycerol Acetoin Acetic acid Lactic acid Propionic acid Succinic acid Butyric acid Citric acid

8 Chemicals: Sugar platform (2 nd Generation) Lignocellulose Enzymes Sugars Microorganism Chemicals Ethanol Butanol Acetone 2,3 Butanediol Glycerol Acetoin Acetic acid Lactic acid Propionic acid Succinic acid Butyric acid Citric acid

9 Chemicals: Sugar platform (2 nd Generation) Lignocellulose Enzymes Disadvantages Sugars Requires sterility Expensive enzymes Difficult to use all sugars Uses GMOs Lignin not converted to liquid fuels Extensive pretreatment required Difficult to supply enough biomass to achieve economy of scale Microorganism Chemicals Ethanol Butanol Acetone 2,3 Butanediol Glycerol Acetoin Acetic acid Lactic acid Propionic acid Succinic acid Butyric acid Citric acid

10 Chemicals: Mixed Acids platform Lignocellulose Mixed- Culture Microorganisms Carboxylic acids/salts Chemistry Chemicals Ketones Aldehydes Secondary mixed alcohols Primary mixed alcohols Carboxylic acids Esters Ethers

11 Chemical Flowchart Formic Acid Aldehyde Formic Acid Carboxylate Salt Ketone H 2 Carboxylic Acid H 2 Secondary Alcohol Ester Primary Alcohol Ether Ether

12 Anaerobic Digestion Biomass (cellulose, starch, proteins, fats) Mixed culture of microorganisms Hydrolysis (free sugars, amino acids, fatty acids) Carboxylic acids = Volatile fatty acids [VFAs[ VFAs] ] (e.g., acetic, propionic,, butyric,,, heptanoic acid) (C2 to C7) Acidogenesis Acetogenesis (Carboxylic acids, NH 3, CO 2, H 2 S) (Acetic Acid, CO 2, H 2 ) Methanogenesis (CH 4, CO 2 )

13 Desirable Process Properties No sterility No GMOs Adaptable No pure cultures Energy in lignin ends up in liquid fuel Low capital No enzymes High product yields No vitamin addition Co-products not required

14 Desirable Fuel Properties

15 Fuel Properties Ethanol MTBE Mixed Alcohols Octane high high high Volatility high low low Pipeline shipping no yes yes Energy content low high high Heat of vaporization high low low Ground water damage no yes no

16 Properties of Fuel Oxygenates Blending Reid Vapor o C (kpa( kpa) Alcohols Blending Octane (R + M)/2 214 Methanol (MeOH( MeOH) Ethanol (EtOH( EtOH) Isopropanol (IPA) tert-butanol (TBA) Isobutanol (IBA) 102 Ethers 55 Methy tertiary butyl ether (MTBE) Di-isopropyl isopropyl ether (DIPE) Isopropyl tertiary butyl ether (IPTBE) 113 Klass,, Biomass for Renewable Energy, Fuels, and Chemicals, Academic Press P (1998).

17 Energy Content Energy (MJ/L) (Btu/gal) Gasoline Mixed Alcohols Version 1 Mixed Alcohols Version 2 Ethanol , , , ,300

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20 MixAlco Process Version 1 Mixed Alcohol Fuels Biomass Pretreat Ferment Carboxylate Salts Dewater Thermal Conversion Mixed Ketones Hydrogenate Lime Lime Kiln Calcium Carbonate Hydrogen

21 Pretreatment Mixed Alcohol Fuels Biomass Pretreat Ferment Carboxylate Salts Dewater Thermal Conversion Mixed Ketones Hydrogenate Lime Lime Kiln Calcium Carbonate Hydrogen

22 Pretreatment is needed Source: Michael Ladisch, Purdue Univ.

23 Lime Treatment Biomass + Lime Gravel

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25 In-Situ Digestion 48-h h Digestion (g digested/g fed) Sugar- cane bagasse African millet straw Sorghum straw Tobacco stalks Untreated Lime-treated

26 Advanced Lime Treatment Air Biomass + Lime Gravel

27 Lignin Removal Lignin Removal Lignin Content in Treated Bagasse (g lignin/100 g of bagasse) Time(days) Time (days) Time 150 (days) Time (days) Lignin Content in Treated Bagasse (g lignin/100 g treated bagasse) No Air Air Lignin Content (g lignin/100 g bagasse) Lignin Content (g lignin/100 g bagasse) 25 o C 50 o C o C 25 o C 50 o C 57 o C

28 Mixed-Acid Fermentation Lime Treatment: 2 weeks, 25 o C Terrestrial Inoculum Total acid concentration (g/l) No Air Air Conversion 8 VSLR (g/(l d)) 4 2 LRT (days)

29 Building the Pile ~100 ft

30 Building the Pile

31 Building the Pile Crew directing the flow

32 Fermentation Mixed Alcohol Fuels Biomass Pretreat Ferment Carboxylate Salts Dewater Thermal Conversion Mixed Ketones Hydrogenate Lime Lime Kiln Calcium Carbonate Hydrogen

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

34 Why are organic acids favored? C 6 H 12 O 6 2 C 2 H 5 OH + 2 CO 2 ΔG G = kcal/mol glucose ethanol C 6 H 12 O 6 3 C 2 H 3 OOH ΔG G = kcal/mol glucose acetic acid The actual stoichiometry is more complex C 6 H 12 O 6 acetate + propionate + butyrate + CO 2 + CH 4 + H 2 O

35 Typical Product Spectrum at Different Culture Temperatures 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 % 100 wt % 100 wt %

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39 Storage + Pretreatment + Fermentation Tarp Cover Air Biomass + Lime + Calcium Carbonate Gravel

40 Technology Evolution Source of inoculum Type of buffer

41 Marine Inoculum Total acid concentration (g/l) Terrestrial Inoculum No Air VSLR (g/(l d)) Marine Inoculum Air Conversion LRT (days)

42 Ammonium Bicarbonate Buffer 40 o C Total acid concentration (g/l) CaCO3 NH4HCO3 step NH4HCO3 Total Ammonium Bicarbonate Calcium Carbonate Time (days)

43 Ammonium Bicarbonate Buffer o C 40 NH 4 HCO 3 35 step size addition Total Acid Concentration (g/l) CaCO 3 10 batch addition 5 batch addition NH 4 HCO Time (Days)

44 Dewatering Mixed Alcohol Fuels Biomass Pretreat Ferment Carboxylate Salts Dewater Thermal Conversion Mixed Ketones Hydrogenate Lime Lime Kiln Calcium Carbonate Hydrogen

45 Vapor-Compression Dewatering Compressor Work Distilled Water Salt Crystals Filter Salt Solution (Fermentor Broth)

46 Dewatering Energetics Ethanol Distillation (5% to 99.9%) kg steam MJ heat 3 = 8.4 = 28.5% of the combustion heat L ethanol kg ethanol Source: B.L. Maiorella, Ethanol, Comprehensive Biotechnology, Vol. 3, Pergamon Press (1985). MixAlco: Carboxylate Salt Vapor-Compression Dewatering (5% to 100%) 54.3 MJ heat 1000 kg water 95 kg water 5 kg acid = 1.03 MJ kg acid = 5.9% of the combustion heat Source: Jorge Lara, An Advanced Vapor-Compression Desalination System, PhD Dissertation, Texas A&M (2005).

47 Thermal Conversion Mixed Alcohol Fuels Biomass Pretreat Ferment Carboxylate Salts Dewater Thermal Conversion Mixed Ketones Hydrogenate Lime Lime Kiln Calcium Carbonate Hydrogen

48 Thermal Conversion Stoichiometry O O O H 3 CCOCaOCCH 3 Η 3 CCCH 3 Calcium Acetate 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

49 Thermal Conversion Stoichiometry Commonly known as dry distillation. Used before and during WWI to make acetone from calcium acetate

50 Thermal Conversion Kinetics t (min) T ( C) Conversion (%)

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52 Hydrogenation Mixed Alcohol Fuels Biomass Pretreat Ferment Carboxylate Salts Dewater Thermal Conversion Mixed Ketones Hydrogenate Lime Lime Kiln Calcium Carbonate Hydrogen

53 Ketone Hydrogenation Stoichiometry 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

54 Ketone Hydrogenation Liquid Ketones Catalyst = 200 g/l Raney nickel Temperature = 130 o C Time = 35 P = 15 atm (220 psi) H 2

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56 MixAlco Process Version 2 Mixed Alcohol Fuels Biomass Lime Pretreat Lime Kiln Ferment Carboxylate Salts Dewater Calcium Carbonate Acid Springing Mixed Acids Esterification Hydrogenolysis Hydrogen

57 Acid Springing Calcium Salts R 3 N HAc Ca(Ac) 2 R 3 NHAc H 2 O CO 2 CaCO 3 R = - CH 2 CH 3 R= - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 R 3 NHAc R 3 N

58 Acid Springing Ammonium Salts NH 3 HAc NH 4 Ac R= - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 R 3 NHAc R 3 N

59 MixAlco Process Version 2 Mixed Alcohol Fuels Biomass Lime Pretreat Lime Kiln Ferment Carboxylate Salts Dewater Calcium Carbonate Acid Springing Mixed Acids Esterification Hydrogenolysis Hydrogen

60 Hydrogenation Stoichiometry O H 3 CCOH + HOCH 2 CH 2 CH 2 CH 2 CH 3 Heavy Alcohol O H 3 CCOCH 2 CH 2 CH 2 CH 2 CH H 2 Ester O H 3 CCOCH 2 CH 2 CH 2 CH 2 CH 3 + H 2 O Ester H H 3 CCOH + HOCH 2 CH 2 CH 2 CH 2 CH 3 H Heavy Alcohol O H 3 CCOH + 2 H 2 Acetic Acid Ethanol H H 3 CCOH + H 2 O H

61 Esterification + Hydrogenolysis Water Mixed Alcohols Carboxylic Acids Esters Alcohols H 2 Heavy Alcohols

62 Esterification + Hydrogenolysis Water + NH 3 Mixed Alcohols NH 4 Carboxylate Salts Esters Alcohols H 2 Heavy Alcohols

63 MixAlco Process Version 2 Ammonium Salts CO 2 NH 4 HCO 3 NH 3 Esters Mixed Alcohol Fuels Biomass Pretreat Ferment Dewater Esterification Hydrogenolysis Lime Carboxylate Salts Hydrogen

64 Esterification Acid catalyzed (H 2 SO 4 ) or solids acid catalysts. Same reaction as free fatty acids esterification in biodiesel production.

65 Ester Hydrogenolysis Copper chromite high temperatures (> 200 o C ) high pressures (> 600 psi) widely used in industry (e.g., for making detergent alcohols from fatty acids) Reduced CuO-ZnO catalyst low temperature (~150 o C) low pressure (<350 psi) preferred

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67 Plant Capacity Plant Capacity (tonne/h)) (mill gal/yr) Version 1 Version 2 *City Population Base Case , , , ,200, ,000,000 * Feedstock = Municipal solid waste + Sewage sludge

68 Effect of Scale on Capital Cost Versions 1& Capital Cost (mill $) Capacity (tonne/h)

69 Mixed Ketone Selling Price Version 1 (15% ROI) Capacity (tonne/h) Ketone Selling Price ($/gal) Biomass Cost ($/tonne)

70 Mixed Alcohol Selling Price Version 1 (15% ROI) Alcohol Selling Price ($/gal) Capacity (tonne/h) Biomass Cost ($/tonne)

71 Mixed Secondary Alcohols (e.g., isopropanol) (Version 1) Secondary Alcohols Yield = ~ 86 gal/dry ton

72 Mixed Acid Selling Price Version 2 (15% ROI) Capacity (tonne/h) Acid Selling Price ($/lb) Biomass Cost ($/tonne)

73 Carboxylic Acids

74 Mixed Alcohol Selling Price Version 2 (15% ROI) Alcohol Selling Price ($/gal) Capacity (tonne/h) Biomass Cost ($/tonne)

75 Mixed Primary Alcohols (e.g., ethanol) (Version 2) Yield = ~ 130 gal/dry ton

76 Enzymatic route/ethanol fermentation Source: Yield = ~100 gal/dry ton for bagasse (90% of theoretical)

77 Energy Content Energy (MJ/L) (Btu/gal) Gasoline Mixed Alcohols Version 1 Mixed Alcohols Version 2 Ethanol , , , ,300

78 Yield on an ethanol equivalent basis 130 gal/ton 95,000/84,300 = 147 gal/ton ~50% more than enzymatic/ethanol fermentation route

79 Conclusions The technology is - green - profitable - world-wide wide - simple Many potential products - ketones - alcohols - organic acids

80 Conclusions Near-term applications - waste chemicals Mid-term applications - waste fuels Far-term applications - crops fuels

81 Thank you for your time and attention