Sterol Molecular Fingerprinting for High-value co-product Synthesis

Transcription

1 Sterol Molecular Fingerprinting for High-value co-product Synthesis Oliver Palardy, Stefanie Van Wychen, Paris Spinelli, Gina Fiorini, Tao Dong, Philip Pienkos, Lieve Laurens Algae Biomass Summit October 24, 2016

2 Algae-derived Commercial Products Reduce cost of algal biofuels: Harness unique position of algae as highly efficient photosynthetic cell factories Identify key targets to contribute to lowering the overall cost of algal biofuels production Quantify impact of major components supporting a multi-product algal biorefinery model Analogous to replacing the whole barrel paradigm; low volume product streams can provide large fraction of value Integrate biomass composition with cultivation and conversion performance 2

3 Algae as Photosynthetic Chemical Factories Co-product criteria for commercial success: 1. Identical to an existing chemical 2. Functionally identical 3. New material with unique functional performance Biomass components Polyunsaturated fatty acids Phytol Triglycerides Glycerol Carbohydrate monomers Antioxidants Whole biomass Biomass production cost: $491/ton* Product Epoxies, polyols, nutraceuticals Surfactants, fuel additive Biopolymers, coatings, Rubber Di-acids / nylon production Fermentation products (including ethanol and di-acids) Health food additives Food/feed markets EPA C20:5n3 fatty acid C14.0 C16.0 C16.1n7 C18.0 C18.1n9 C18.2n6 C18.3n3 C18.3n6 C20.4n6 C20.5n3 + Co-products biomass value $500-$800/ton *Davis et al 2016: 3

4 5 Potential Options for co-products 4 U.S. Department of Energy National Algal Biofuels Technology Review. Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office.

5 Algae Biorefinery Potential high volume products Biomass components wt % Product Market* (ton/yr) Fatty acids Hydrocarbon fuel products (U.S. consumption) 16,000,000 Omega-3-fatty acids 3-10 Polyols epoxy resin polyurethane 8,000,000 11,000, Nutraceuticals 22,000 Hydroxy-, branched-, fatty acids/alcohols ~1 Surfactants, fuel additives 3,500,000 Sterols 2-4 Surfactants 6,400, Phytosterol nutra-/pharmaceuticals 25, Emulsifiers N/A Phytol 3-4 Raw material for vitamin E, fragrance, soaps Surfactants, fuel additives 3,500,000 Polar lipids Ethanolamine 600, Phosphatidylcholine, phosphoinositol and phosphatidyl ethanolamine (lecithin ) 20,000-30,000 Glycerol 2-6 Di-acids for nylon production 2,500,000 * Market size estimated based on displacement volumes based on sorbitol market size 2-6 Feed, pharmaceuticals 25,000 Fermentable sugars (glucose, mannose) Polylactic acid (PLA) polymers 300, Di-acids (e.g. succinic, muconic, adipic acid) 2,500, Ethanol 60,000,000 Mannitol 3-6 Polyether polyols 2,300,000 Alginate ~3-5 Alginate additives N/A Starch 5-40 Polysaccharide-derived bioplastics 2,000,000 Protein Thermoplastics 5,000,000 Amino acids/peptides Polyurethane 11,000,000 Amino acids/peptides Biobutanol, mixed alcohol fuels 740,000 Whole biomass 100 Animal/Fish feed 16,000, ,000,000 5

6 Need for Bio-Derived Surfactants 6 Non-ionic surfactant markets growing exponentially ~ 6,400,000 ton/yr Large market for petrochemical-derived ethoxylated non-ionic surfactants using toxic synthesis route with ethylene oxide o e.g. alkylphenols used as antioxidants, lubricating oil additivies, detergents, emulsifiers, paints (market = 346,000 ton/yr) Demand increasing for bio-derived and bio-degradable emulsifiers OH Nonyl-phenol [KOH] OH Nonyl-phenol ethoxylates

7 Sterol Diversity in Scenedesmus acutus 7 Cholesterol Desmosterol 12 IS Fucosterol Early mid Late harvest Ergosterol

8 Sterol/Phytol purification from complex oils Phytol and Cholesterol separated from the oils as unsaponifiable lipids % sterols % Phytol Scenedesmus CAP oil Unsaponifiable lipids in algae (non-fatty acids) 4-7% of the extractable oils Fractionation of sterols/phytol in isolated unsaponifiables yield separate product streams and allow for tailoring surfactant properties Enrichment (-fold) Phytol Cholesterol Fraction Fraction Fraction Phytol (predominant branched hydrocarbon in Scenedesmus oils ) Ergosterol (predominant sterol in Scenedesmus oils) 8

9 Non-toxic Synthesis of Surfactants Phytol & Cholesterol-PEG surfactants PEG Da Succinic Anhydride Da Cholesterol 386 Da PEG$1000$ Phytol,SA,PEG$ Cholesterol,SA,PEG$ Algae,sterols,SA,PEG$ Synthesis of water-soluble PEG-succinic acid-ester of algae sterol - functional surfactant 9

10 10 MALDI-Mass Spectrometry Analysis of Synthesis products PEG 1000 Phytol-SA-PEG (PEG Da) Cholesterol-SA-PEG (PEG Da) Algae sterol/phytol-sa-peg (PEG Da, 494 Da, 484 Da)

11 Value Proposition Focus on co-products IHS Chemical Economics Handbook, Epoxy Resins, May 2014 & Surfactants, Household Detergents and their raw materials, June 2013 *Based on mid-harvest Scenedesmus biomass and demonstrated composition R. Davis (NREL) preliminary unpublished report 11

12 Summary 12 Inclusion of co-products in algal biorefinery processes improves overall economics Novel bio-derived surfactants synthesized, via non-toxic synthesis route from algae-based sterols and phytol Large biochemical diversity opens up routes for unique properties from separate product streams Future R&D to support advanced algal systems economics with isolation and commercial harnessing of high-value, large market bioproducts

13 Thank You!