ET Process® and Beyond George Chou Sunho Biodiesel Corporation Presented in the Symposium of Biomass Energy Society of China Taipei, Taiwan December 2011 Why ET Process® ? -Sustainable -Fast -Profitable SBC (2011) Biodiesel and/or Fatty Acid Alkyl Ester Plant oil or animal fat + Alcohol Biodiesel + Glycerol Oil source : edible / nonedible oil fresh oils / waste greases crude / refined oils high / low FFA oils Alcohol : prime ( e.g., methanol, ethanol ) or secondary alcohol ( e.g., isopropanol, isobutanol ) Biodiesel : Fatty acid monoalkyl ester ( RCOOR’ ) SBC (2011) Technology Overview Transesterification Esterification : Oil + Alcohol : FFAs + Alcohol Biodiesel + Glycerol Biodiesel + H2O Disadvantages Chemical Approach ‧ Base Catalyst Liquid Solid ‧ Acid Catalyst Liquid Solid ‧ Supercritical Process Limits transesterification ‧Restrictions on level of H2O and FFA allowable in feedstock ‧Neutralization & washing required ‧Low quality glycerol co-product ‧Extremely high temp. and pressure required ‧Restriction on level of H2O and FFA allowable in feedstock ‧Decomposes glycerol due to high temp. ‧Impurities ( e.g., polymers ) due to thermogenetic reactions ‧Catalyst deactivation due to impurities Limits esterification ‧Restriction on level of H2O and FFA in feedstock ‧Equipment corrosion ‧Lengthy reaction time ‧Neutralization & washing required ‧Excess alcohol required ‧High temp. and pressure required ‧Excess alcohol required ‧Lengthy reaction time Not suitable for mass production Uniqueness Factor: ET Process® Role of Inert Solvent Disadvantages Enzymatic Approach Simultaneous transesterification & esterification ‧ Without inert solvent ‧Lengthy reaction time ‧Can only be done by batch operation ‧Deactivation of biocatalyst due to glycerol or water ‧High operating cost due to lipase consumption ‧Unstable product quality ‧ With inert solvent ET Process® ‧Totally green process ‧Long lipase life span ‧Room temp. and pressure operation ‧Automatic continuous, integrated state-of-the-art fully developed process (Patented worldwide) SBC (2011) Biotechnology Process® Methanol recycling Inert solvent recycling H2O discharge Methanol Vegetable oil Methanol make up Inert solvent make up Inert solvent Biodiesel Glycerol Simplified flowsheet of ET Process , Sunho Biodiesel (US 7473539, US 7666666) SBC (2011) The most wanted SBC (2011) Biodiesel Feedstocks Dec. 2008 FFA wt% Rapeseed oil 640 € / t 2% Soybean oil 610 € / t 2% Crude palm oil 470 € / t ~8% Yellow grease 240 € / t 15 - 20 % Edible tallow 350 € / t 15 - 20 % PFAD 250 € / t ~ 100 % Jatropha 300 € / t 10 % * PFAD: Palm Fatty Acid Distillate Source: www.bayertechnology.com SBC (2011) Cost savings by ET Process® Basis : CPO , 8 % FFA 470 € / t ( Dec. 2008 ) USD 681.5 / t Saving in feedstock USD 129.8 / ton biodiesel Profit from glycerol USD 75.0 / ton biodiesel Saving in operating cost USD 46.9 / ton biodiesel Total savings USD 251.7 / ton biodiesel i.e. , USD 0.251 / Kg biodiesel Basis : 1 € = 1.45 USD SBC (2011) Advantages With the ET Process®, government subsidy is not necessary for business sustainability. Biodiesel price can be lower than diesel, still with significant profit Payback : far less than 1 year SBC (2011) Further Potential Not just a biofuel technology, but also a production process for biobased chemicals used in biolube, biosurfactant, biosolvent, cosmetic, biotechnology and specific chemicals (fine chemicals), etc. SBC (2011) Applications for Biodiesel and Beyond Biodiesel or Fatty Acid Alkyl Esters ® ETProcess Process ® ET Oil ((Core Core technology technology)) Esterification Esterification& & transesterification transesterification Monoglycerides Glycerol (widely used and can be a high value-added material ) SBC (2011) Fatty Acid Alkyl Esters Tallow + IPA Fatty acid isopropyl ester + Glycerol High-Value End Products: High•Isopropyl myristate •Isopropyl palmitate •Glycerol monostearate •Isopropyl oleate and/or isopropyl linoleate SBC (2011) Applications of the ET Process® ‧ Starting with fatty acid + Lauryl alcohol Lauric acid Stearic acid + n-butanol or iso-butanol Lauryl Laurate + H2O n-butyl stearate or iso-butyl stearate + H2O ‧ Starting with oil Oil + n-butanol or iso-butanol Fatty acid n-butyl ester or + Glycerol Fatty acid iso-butyl ester SBC (2011) Derivatives of Monoglycerides Conventional manufacturing methods •Citric acid ester of MG •Distilled glycerol monostearate •Glyceryl laureate Sulfated MG 1. Reacted with SO3 gas; 2. NaOH Hydrogenated MG Heated oil + bubbled with H2 Direct Esterification Free FA Natural MG Monoglyceride Acrylated products FA + glycidyl methacrylate OR acrylic copolymer + MG OR glycerine + polyacrylic acid Epoxidized MG 1. MG + acetic anhydride 2. Peracetic acid in acetic acid Glycerol Monoglyceride Alkyd Resin MG + phthalic anhydride Oil Interesterification or Glycerolysis + Diglyceride Acetylated MG Acetic anhydride + MG Polymerized Epoxidation Reaction with diisocyanate Reaction with polyhydroxy acid (e.g., lactic acid) •Cocomonoglyceride sulfate •Food, Food preservative, Food packaging •Cosmetics, Detergent •Pharmaceutical •Plastic additives, Anti-static •Drug delivery •Fire retardant hydraulic fluid •Cosmetics, Detergent, e.g., Plantapon® CMGS •Sodium hydrogenated palm kernel fatty MG sulfate •Sodium hydrogenated palm fatty MG sulfate •Sodium hydrogenated tallow fatty MG sulfate •Glyceryl polymethacrylate •Methacrylated fatty acid monomer (e.g., oleic acid) •Epoxidized MG diacetate •Long or short alkyds; e.g., from rubber seed oil, palm, Parkia Biglobosa, etc. •Acetylated glycerol monostearate or stearodiacetin •Monoacetin •Acetylated castor oil MG •Polyurethane •Alkyd resin •Soybean oil MG, Linseed oil MG polymers or co-polymers •Polyurethane elastomer •Copolyester elastomer •Urethane methacrylate oligomer •Rapeseed monooleate-rich lactic resin •Detergent •Cosmetics (stabilizes emulsions, enhances viscosity, strong hydrating power, film former) •Pharmaceuticals •Plastic additives •Alkyd resin •Bioplastics •Additive for PVC •Bioplastic (commonly, epoxidation is applied for oils to make bioplastics) •Paint, Coating, Primer •Baked finishes on automobiles, refrigerators, stoves, washing machine •Printing Ink •Enamels (long alkyds) •Food packaging (block moisture transport) •Wax and plastic additive •Food dye solvent •Cosmetics •Foaming agent •Thermoset polymers (for PU) Coating, foam, insulating foams for buildings, carpets, adhesives, metal/plastic coatings, shoes Thermoplastic / Elastomer Others Glyptal = terephthalic acid + glycerine •Vinyl ester MG / Acrylated MG •Uralkyd (elastomer)-PMMA IPN •Glyptal polyester (crosslinked) •Liquid molding resin •Plastic Additive: IPN to add toughness to PMMA •Adhesive or coating What’s Next ? Lipid--based Biorefinery Society Lipid ‧ Biofuel ‧ Renewal Raw Materials SBC (2011)