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Recovery of Organic Acids From Fermentation Broths Southern Bio-Products Conference March 4-6, 2004 Beau Rivage Resort Biloxi, MS Tim Eggeman, Ph.D., P.E. Dan Verser, Ph.D. ZeaChem Inc. Organic Acids - Today. Points of View. Sugars: Inexpensive Under-Utilized More Sustainable
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Recovery of Organic Acids From Fermentation Broths Southern Bio-Products Conference March 4-6, 2004 Beau Rivage Resort Biloxi, MS Tim Eggeman, Ph.D., P.E. Dan Verser, Ph.D. ZeaChem Inc.
Points of View • Sugars: • Inexpensive • Under-Utilized • More Sustainable • Synthetic Routes will Eventually be Displaced • Platform Viewpoint is Under-Utilized Biology plus = Better Technology and Chemistry Market Diversification
Issues in Recovery • pH of Broth • Unreactive Species at Near Neutral pH • Commodity Scale Production is Constrained by Need to Avoid Salt Coproduction • Dilute Broths • Evaporating Water is Expensive • Prefer Selective Methods for Removing Organic Acids from Water
pH Options • Low pH Fermentation • Neutral pH Fermentation • Direct Acidification • Amine Complex Formation • Other • Bipolar Electrodialysis • Esterases
Lactic Acid - Traditional Alcohol Water Hydrolysis Sulfuric Acid Ester Lime Lactic Acid Direct Acidification Fermentation Esterification Sugars Water Gypsum
Direct Acidification US Demand for Lactic Acid = 176 MM lb/yr, Gypsum Coproduct = 252 MM lb/yr !!!
Lactic Acid – Amine Extraction (From: Baniel, A.M. et. al., US Pat. 5,510,526)
Citric Acid – Lime/Acid Lime Sugars Fermentation Precipitation Residue Sulfuric Acid Water Calcium Citrate Acidification Crystallization Citric Acid Gypsum
Citric Acid – Amine Extraction Water Forward Extraction Water Back Extraction Sugars Fermentation Crystallization Citric Acid Residue
Formic Acid Water Formic Acid CO Carbonylation Methyl Formate Hydrolysis Methanol Methanol
Some Common Themes • Eliminating Salt Coproduction is Difficult • Microbiology • Careful Selection of Cations and Recovery Scheme • Common Purification Methods • Amine Extraction • Esterification
Lab Status - Fermentation • Lab Scale Fermentation • Strain: Moorella Thermoacetica ATCC 39073 • Media: Glucose+Corn Steep Liquor • Batch Results • First Run: 28 g/l acetate • Goal: 35-50 g/l acetate, yield = 85+% of theoretical
Lab Status - Recovery • Lab Scale • Amine Complex Formation w/ CaCO3 Precipitation • Extraction of Amine Complex • Esterification • Results to Date • 97+% CaCO3 Recovery • Excellent Extraction (KD > 2) • Ester Yield: 75% of Theoretical
Conclusions • Technical Issues • pH and Avoidance of Salt Coproduction • Dilute Broths • Advantages of Platform Viewpoint • New Routes Based on Biology and Chemistry • Market Diversification
Acknowledgements • US Department of Energy - Inventions and Innovation Program (Grant Number DE-FG36-03GO13010) • Support by US DOE Does Not Constitute an Endorsement by US DOE of the Views Expressed in this Presentation