FERMENTABLE SUGARS FOR BIOFUELS Donal F. Day Audubon Sugar Institute UNO Sept. 2014 Target: regionally appropriate biomass feedstocks The deep south states can to produce 50% of the biofuels in the future because they have the most available land with adequate water and sun. Questions to be Answered Agricultural Are these crops suitable for production in underutilized agricultural areas (Cold tolerance)? Industrial Are the products (syrups) suitable for use by industrial partners? Financial-Environmental What is the financial baseline for producing biofuels from these crops and what are the environmental costs associated with the production? CROP CHOICES (POTENTIAL YIELDS) Energycane Sweet Sorghum Wet ton/acre 40.5 Wet ton/acre 24.3 lbs simple Sugar/acre 123.6 lbs simple Sugar/acre 184.1 lbs complex Sugar/acre 362.3 lbs complex Sugar/acre 186.4 Total lbs Sugar/acre 19,679 Total lbs Sugar/acre 9,003 TASKS Approaches Feedstock Development Sustainable Production Logistics and processing Conversion and Refining Crops with staggered harvests that will grow across desired range (and not compete with food crops) Low input, sustainable production Harvest, transport, effective range Conversion to sugars (syrups) suitable for jet fuel production Economics, Markets and Distribution Establishment, market, selling costs Education Training of potential workers for new industry Extension Bringing stakeholders on-board Developing Process Sustainable Production Feedstock development Sustainability Harvest analyze Deliver Technology development Sugar Cane Gasoline ZSM-5 Biomass APR Kerosene Jet Fuel Condensation Corn Starch Hydrotreating Diesel Conversion to Fuel Value to Consumer Intermediate Product Process Economic feasibility Process Indeterminate Technology development Biomass * Primary processing plants supplying centralized biorefineries Storable syrups as feedstocks Primary plants drawing on local acreage * Staggered Harvest, Complementary Crops, producing both fermentable sugars and biomass. Sweet Sorghum July - September Energycane October -March Bagasse, syrup, woodchips, molasses, etc. April - June SUSTAINABLE PRODUCTION EXPERIMENTAL SITES Sites were established in Louisiana in different soil types and climatic zones for growing energycane and sweet sorghum. FEEDSTOCK DEVELOPMENT Energy cane- seven molecular markers have been found, four for leaf greenness and three for regrowth damage. Genetic variability was created by cross hybridization between a set of distinct species Cross pollination between sugarcane and miscanthus, F1 in field tests across Louisiana Cold tolerance testing of Energy cane in North Louisiana location Low input testing in North Louisiana One semi-commercial variety released sugarcane Energycane St. Gabriel (early June 2013) Breeding for Cold Tolerance Molecular markers developed for cold tolerance Energycane grows faster Than commercial varieties ENERGYCANE – YEAR 3 (N. LOUISIANA June 2014 SWEET SORGHUM Annual crop Contains, a sugar containing juice, starch containing seed heads and fiber 90-120 day crop cycle, can be grown across target region Gross structure similar to sugarcane Can be widely grown across Southern US SWEET SORGHUM PRODUCTION FOLLOWING LEGUME INCORPORATION IN THE SOIL (LOW INPUT TESTING) HARVESTING Sweet Sorghum Weight loss- 6-7% over 72 hr. period on harvesting 3 trials, one acre lots (about 18 rows) 8 inch billets, 3 different fan speeds evaluated Energy cane 7-9% weight loss over a 72 hr. period. Same design. Harvesting in October TOTAL FOSSIL ENERGY USE (LCA) Brazilian sugar cane Biofuel Feedstock Production Feasibility Index Crop Energy cane Corn Cotton Sorghum Rice Soybeans Sugarcane Market Price Crop Yield Variable Cost $75/ton 10 dry ton/A $500/A $5.00/bu. $0.80/lb. $8.00/bu. $16.00/cwt. $14.00/bu. $0.23/lb. 160 bu./A 1,200 lb./A 90 bu./A 70 cwt./A 45 bu./A 7,500 lbs./A $530/A $600/A $310/A $660/A $340/A $530/A Energy Cane Production Feasibility Scale 5 (75% - 100%) 4 (50% - 74%) 3 (25% - 49%) 2 (1% - 24%) 1 (no change) Feedstock Breakeven Economic Analysis PROCESSING- DEMONSTRATE SCALABILITY PRODUCE PRODUCTS FOR INDUSTRIAL TESTING Flexible Pilot Plant: Education, Extension and Training Facility Plant operational- initial process run July 2013 PILOT PLANT MILLING Sweet Sorghum Three runs of 5 ton lots. For two runs the whole plant was harvested, for one the seed heads and leaves were removed. Feed rate low. It was not possible to mill the clean billets because of choking (not enough fiber). Energy Cane Feed rate dependent on variety. Leaf removal necessary to improve efficiency. Increased power requirement due to high fiber content. POWER REQUIREMENTS- MILLING (CROP DEPENDENT) Sweet sorghum and energycane fall at different ends for fiber. Sugarcane Energy Cane Sweet Sorghum Eiland and Clarke, 2008 ASSCT, Panama City, Florida COMPOSITION SORGHUM SYRUP 27.1 % Water 72.9 % Dissolved Solids 0.1 % S 0.1 % P 0.25 % N 3.5 % Potassium 46 % Sucrose 1.1 % Chloride 13.2 % Glucose 11.2 % Fructose 8.4 % Ash 0.7 % Nitrate 0.4 % Calcium 0.3 % Sulfate 0.2 % Sodium 0.2 % Magnesium 0.1 % Phosphate 0.1 % Ammonium FUELS PRODUCTION -VIRENT ENERGY SYSTEMS Sugar Cane Gasoline ZSM-5 Biomass APR Kerosene Jet Fuel Condensation Corn Starch Hydrotreating Diesel COMPOSITION SORGHUM SYRUP 27.1 % Water 72.9 % Dissolved Solids 0.1 % S 0.1 % P 0.25 % N Removal of potassium and chloride requires advanced separation 46 % Sucrose techniques such as 3.5 % Potassium • Ion exchange • Electrodialysis 13.2 % Glucose • Nanofiltration 1.1 % Chloride 11.2 % Fructose 8.4 % Ash 0.7 % Nitrate 0.4 % Calcium 0.3 % Sulfate 0.2 % Sodium 0.2 % Magnesium 0.1 % Phosphate 0.1 % Ammonium LIGNOCELLULOSIC UTILIZATION CO-GENERATION Model developed in SUGARSTM Extraction by diffusion Diluted acid pretreatment for lignocellulosic conversion Annual production of fermentable sugars, excess bagasse, electric power and syrup Scenario 1 Excess bagasse used for electric power generation Feedstock Energy cane Sweet Sorghum Facility total Primary Excess Power sugars, million bagasse, million export, kg t million kWh 99.8 600.8 268 Scenario 2 Excess bagasse used for lignocellulosic sugars production 99.8 Excess bagasse, million t 330.2 Lignocellulosi c sugars, million kg 85.8 Syrup, K-m3 Primary sugars, million kg 50.5 Syrup, K-m3 94.1 49.6 164.2 119.9 24.9 49.6 147.4 38.9 44.5 149.4 765.0 387.9 75.4 149.4 477.6 124.7 138.6 LIGNOCELLULOSIC LOGISTICS AND Fragmentation patterns on milling PRE-PROCESSING (the lower the fiber the less fragmentation) Storage Pile storage best for short-term biomass storage Particle size effects pretreatment rates SURPLUS SUGARS PER DAY (10,000 T/D) Power Bagasse can be fluidized for steam drying, increasing energy value. Fiber Composition: 40% Cellulose (C6-Glucose) & 25% Hemicellulose (C5-Xylose) Grinding Rate : 10,000 tons/day , Bagasse Production : 3000 tons/day SUGARS FROM LIGNOCELLULOSE Unlike starch (corn), lignocellulose is made of tightly bonded sugars (cellulose, hemicellulose) and lignin The primary technical problem is economic access to the carbohydrates in this matrix. IDEALIZED PROCESS Sugar Cane Pretreatment Gasoline ZSM-5 Biomass APR Syrup Kerosene Jet Fuel Condensation Corn Starch Hydrotreating Diesel PRETREATMENT TECHNOLOGIES Treatment Temperature oC Pressure (atm) Time (min) acid 190-200 3-15 2-30 water 160-190 6-14 10-30 ammonia 150-170 9-17 30-60 lime 70-130 1-6 60-360 oxidizers 20-100 1 3-60 As yet there is no low cost ideal pretreatment Pretreated Post -hydrolysis Pretreatment Dilute Ammonia (DA) Pretreatment Sugarcane bagasse A Energy cane bagasse C E B D F Sorghum bagasse Untreated Treated SEM Images of Untreated and Treated Sugarcane, Energy Cane and Sorghum Bagasse Salvi, D., Aita, G., et al. 2010. "Dilute ammonia pretreatment of sorghum and its effectiveness on enzyme hydrolysis and ethanol fermentation." Applied Biochemistry and Biotechnology, 161 (1-8): 67-74. Aita, G., Salvi, D., Walker, M. 2011. "Enzyme hydrolysis and ethanol fermentation of dilute ammonia pretreated energy cane." Bioresource Technology, 102 (6): 4444-4448. ENZYMATIC SUGAR PRODUCTION Start 6 hours 3 hours sugar yield - 70-90% of cellulose in biomass converted to fermentable sugars 40 hrs IMMOBILIZED CELL COLUMNS Laboratory Small Scale-up BUTANOL PRODUCTION COMPARISON Batch Fermentation with 4% glucose Continuous Culture (0.6 ml/min) with 4% glucose 0.42% butanol 0.61% butanol 0.60% solvents 0.99% solvents Anoxic conditions needed Anoxic conditions maintained 1.5 L media used (5 days) 4.32 L media used (5 days) 3 L reaction vessel 400 ml reaction vessel 0.6 g solvents/L/day 21.384 g solvents/L/day Research financed by Optinol LLC (GLUCOSE TO BUTANOL) Scale-up Simplified Plant Design tentative Product Concentration ACONITIC ACID IS AN ABUNDANT ORGANIC ACID IN SUGARCANE, ENERGYCANE AND SWEET SORGHUM. Aconitic acid ~1% on Brix solids Found in molasses at 3-5% Used as flavor ingredient and adjuvant (up to 300 ppm) Similar to citric acid “Green Plastic” Aconitic acid 36 Biodegradable photolithotrophic plastics from sugarcane materials POLYESTER FROM ORGANIC ACID. Trans-Aconitic Acid Formulation The trans-aconitic acid is darker in color and contributes to the polymer color. Cis-Aconitic Acid Formulation The cis-aconitic acid is darker in color and contributes to the polymer color. Citric Acid Formulation The citric acid is a white crystalline powder forming a clear polymer with some bubbles. THANK YOU Always thinking outside the box This work supported by a USDA AFRI-Cap grant (Award No. 2011-69005-30515)