1. www.sustoil.org 9 th June 2010 Title Optimisation of secondary processing (i.e biodiesel production) Speaker Zsanett Herseczki Institute UP

2. www.sustoil.org Introduction Recently Increases in crude oil prices Limited resources of fossil oil Environmental concerns renewed focus on vegetable oils and animal fats Glycerol formation Purification/cleaning of biodiesel

3. www.sustoil.org New types of biodiesel to make up the glycerol as a by- product, which increases the lubricant power of biofuel Increase in the yield of the process (10%) Biofuel can be used without further processing Cost of process Generation of waste water ECODIESEL DMC-BIOD ”GLIPEROL”

4. www.sustoil.org Oil/fats + ethanol (1:2) Tank reactor (immobilized Lipases) ECODIESEL “Ecodiesel”, is a biofuel patented by the UCO containing two moles of FAEE and one mole of Monoglycerides (MG), also incorporating the glycerine into the biofuels composition, and can only be obtained using enzymatic technology. 1,3 regioselective transesterification: ECODIESEL

5. www.sustoil.org DMC-BIOD ® is biofuel that integrates the glycerol in a process that can be developed by enzymatic technology Triglyceride Dimethyl carbonate Fatty acid glycerol carbonate monoester Fatty acid methyl esther (FAME) The Gliperol ® is a biofuel consisting of a mixture of three moles of FAME or FAEE and a mole of triacetin, obtained by the cross transesterification of ethyl or methyl acetate and the corresponding triglycerides in an enzymatic catalyzed process. Triglyceride Ethyl acetate Triacetin Fatty acid ethyl esther (FAEE)

6. www.sustoil.org Processing of oils and fats in the actual oil refining plants  Treatment of mixtures of vegetable oils and fractions of heavy oil vacuum (HVO), in flows of hydrogen and conventional catalysts (sulphured NiMo/Al 2 O 3 ) under standard conditions of temperature (300- 450 °C)  Reaction leads to a mixture of lower molecular weight alkanes Second-generation technology for the production of biodiesel  To convert cellulose waste into biodiesel  The biggest bottleneck of these technologies is its high cost oMicrodiesel: production of biofuels via microbial biotechnology o Fischer-Tropsch diesel oHTU biodiesel

7. www.sustoil.org Fischer-Tropsch technology Includes gasification of biomass raw materials, cleaning and packaging of synthesis gas and subsequent synthesis of liquid (or gas) biofuel Raw materials:  Wood  Grass  Agricultural residues  Forest  Main challenge is the production of synthesis gas  Biomass has different properties than coal several modifications in the conventional process are needed

8. www.sustoil.org HTU (Hydro Thermal Upgrading) biodiesel  Chemical and physical transformations in high-temperature (200– 600 °C), high-pressure (5–40 MPa) liquid or supercritical water  Liquefaction processes are generally lower temperature (200–400 °C) reactions which produce liquid products, often called bio-oil or bio-crude  Gasification processes generally take place at higher temperatures (400–700 °C) and can produce methane or hydrogen gases in high yields It requires pre-treatments to reduce the water content and increase the energy density (higher energy cost) Obstacle of high cost of biodiesel production from algae may be overcome

9. www.sustoil.org Glycerol from biodiesel production – Existing and new glycerol purification technologies 10 % Purity: 55-90 % In larger biodiesel plants 75-80 %

10. www.sustoil.org Crude glycerol glycerol fatty acid methyl ester methanol salt soaps water other impurities  Problems: foaming, high boiling point components (deep vacuum, high temperature)

11. www.sustoil.org Processes for refining glycerol The following technologies may be used to purify glycerol (after the soap splitting step) The glycerol soap splitting followed by a combination of methanol recovery/drying, fractional distillation, ion-exchange (zeolite or resins) and adsorption (active carbon powder) seems to be the most common purification pathway. fractional distillation ion-exchange adsorption precipitation extraction crystallisation dialysis

12. www.sustoil.org  Pretreatment - to remove colour and odour matters as well as any remaining fat components from crude glycerol (activated carbon )  Concentration step - removal of ionic substances using ion exclusion chromatography  Ion-exchangers – to remove inorganic salts, fat and soap components, colour and odour causing matters  Multiple vacuum flash evaporators - results in 90-95% concentration (10-15kPa vacuum) or  Thin film distillation - final concentration of glycerol to 99.5% is carried out in vacuum (0.5-1kPa) Conventional processes for glycerol purification

13. www.sustoil.org a) Feed heater; b) Evaporator; c) Separator with demister; d) Water Condenser; e) Glycerol heater; f) Glycerol heater/final product cooler; g) Falling film evaporator; h) Glycerol condenser Continuous glycerol Concentration – Multiple vacuum flash evaporators

14. www.sustoil.org a) Economizer; b) End heater; c) Thin-film distillation; d) Fractionating Column; e) Reboiler; f) Reflux Condenser; g) Glycerol condenser; h) Water condenser Continuous glycerol distillation - Thin film distillation

15. www.sustoil.org Recent development in glycerol purification processes (>99,5% glycerol)

16. www.sustoil.org Chromatography and regenerative column adsorption Activated carbon - The main components to separate are: Glycerol Water Ions (like K+) Saponification residues and Methanol traces Expensive regeneration High operational costs due to the high viscosity of the crude glycerol and the high pressure drop New developments on chromatography separation - some possible chromatography techniques : Gel permeation Ion exchange chromatography Hydrophobic interaction Reversed phase Affinity chromatography

17. www.sustoil.org Transformation of glycerol into high-quality products through green chemistry and biotechnology  Glycerol transforming processes  Valuable Chemicals from Glycerol

18. www.sustoil.org Glycerol transforming processes  Aqueous phase Reforming - Fischer-Tropsch  Selective reduction The main processes used to reduce glycerol to glycols are hydrogenolysis, dehydroxylation and bacteria  Halogenation 1,3-dichloro-2-propanol can be produced directly from glycerol using HCl as a catalyst  Dehydration The dehydration of glycerol can produce important chemicals such as acrolein, 3-hydroxypropionaldehyde and acrylic acid.  Etherification Glycerol alkyl ethers can be synthesised by etherification of alkenes such as isobutylene in the presence of an acid catalyst

19. www.sustoil.org  Esterification Reaction of glycerol with dimethyl carbonate produces a high yield of glycerol carbonate  Selective oxidation Oxidation products include glyceraldehydes, glyceric acid, glycolic acid, hydroxypyruvic acid, oxalic acid and tartronic acid  Pyrolysis Typical products include carbon monoxide, hydrogen, carbon dioxide, methane and ethane At lower temperatures (steam or supercritical water) longer molecules such as acrolein, formaldehyde and acetaldehyde are observed  Biotransformation

20. www.sustoil.org Derivatives of Glycerol

21. www.sustoil.org Application of glycerol  Personal/oral care products  Drugs /pharmaceuticals  Foods/beverages  Polyether polyols  Fuel additives  Plastics  Coatings  Adhesives

22. www.sustoil.org Application of glycerol in adhesives for wood panels Examples of various wood composite products plywood, OSB, particleboard, MDF and hardboard.  Formaldehyde based adhesive resins represent by far (>95%) the biggest volumes within the wood adhesives  Commonly used resin–binder systems include phenol-formaldehyde, urea- formaldehyde, melamine-formaldehyde, and isocyanate

23. www.sustoil.org Glycerol in aminoplastic resinsGlycerol in aminoplastic resins  Glycerol is used a) as flexibilizer into the stiff chain of aminoplastic resins b) to improve the hydrophobicity c) to decrease the curing time  Glycerol derivatives can also be used as "latent", acid liberating hardeners for curing melamine resins (3-Chloro-1,2-propanediol) Glycerol in impregnation resinsGlycerol in impregnation resins  Due to the comparatively high cost of glycerol; it is combined with other cheap substances Glycerol as formaldehyde catcherGlycerol as formaldehyde catcher  Glycerol reduces further the formaldehyde emissions by binding up remaining free volatiles into the polymer matrix Formaldehyde based adhesive resins and Glycerol

24. www.sustoil.org Soy flour (SF) resinsSoy flour (SF) resins  Glycerol has been reported to increase the flexibility and extensibility of soy protein plastics by reducing the interaction between protein molecules. Glyoxal/glycerol/ boric acidGlyoxal/glycerol/ boric acid  Interesting and environmentally friendly mixture suitable for wood dimensional stabilization. Natural tackifying resinNatural tackifying resin  A potential additive in natural wood adhesives could also be the glycerol ester of gum resin which is made from gum resin or refined gum resin through esterification with glycerol. Natural resins and Glycerol

25. www.sustoil.org Glycerol derivatives and wood adhesives

26. www.sustoil.org Triacetin – Properties, field of application Properties Field of application Food additive (e.g. butter) - E1518 Antifungal agent in external medicine Potential green solvent and fuel additive Molar mass218,2 g/mol Boiling point258-260 °C Melting point-78 °C Density1,16 g/ml at 25°C

27. www.sustoil.org Production of Triacetin  Triacetin is commonly prepared by Esterification of glycerol with acetic anhydride or acetic acid Reacting ketene with glycerol Oxidation of allyl acetate in the presence of acetic acid Ionic liquids as a catalyst and reaction media for triacetin synthesis was studied  Purification of crude triacetin - Crude triacetin typically contains acetic acid, acetic anhydride and smaller quantities of other impurities Acetic anhydride and acetic acid are usually removed by distillation Remaining triacetin is then usually distilled to remove nonvolatile impurities and to eliminate color and odor

28. www.sustoil.org Dilution, acid treatment Phase separation Decolorization Filtration Free fatty acid, salt Glycerol containing water, salt, methanol Crude glycerol Water, phosphoric acid Activated carbon Acetic acid Water, toluene Phase separation Toluene Esterification Water Filtration Salt Triacetin Triacetin, acetic acid, catalyst, salt Distillation Acetic acid Triacetin, catalyst, salt Methanol Neutralization NaOH solution Activated carbon Scheme for production of triacetin from crude glycerol

29. www.sustoil.org Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation Through a fermentation process glycerol can be converted into various more valuable products  H 2  Ethanol  Butanol  Acetone  2,3-butanediol  1,3-propanediol  Acetate  Propionate  Lactate and butyrate  Succinic acid  Formate

30. www.sustoil.org 1,3-propanediol (PDO)  PDO could not be produced from glucose fermentation (no natural microorganism)  Dilution of the crude glycerol is necessary because of the inhibition effect of impurities  The glycerol fermentation has been mostly studied under anaerobic conditions  Micro-aerobic or aerobic processes have also been reported on 1,3-PDO production by some species to simplify the process  The downstream processing of the alcohols from fermentation is costly owing to the low final product concentration and coexistence of by-products  Most separation methods are energy-consuming and expensive

31. www.sustoil.org Combined bioprocess of production biodiesel by lipase with microbial production of 1,3-propanediol by Klebsiella pneumoniae

32. www.sustoil.org Ethanol  Ethanol and succinate are the main products of glycerol fermentation by E.coli  E. aerogenes mainly produces ethanol and H 2  When glycerol is fermented by K. planticola, the formate and ethanol are the main products  Suitable dilution is necessary  When the crude glycerol like the glycerol-containing biodiesel waste is used, the excessive dilution of the raw material will increase the cost for product recovery and waste water treatment

33. www.sustoil.org Summary  Novel routes to biodiesel have been identified which do not produce any glycerol by-product and are currently being commercialised by some of the Sustoil partners (UCO&Seneca).  One of the major challenges the biodiesel industry faces is purifying raw glycerol to a standard which can be used as a reagent  Chemical industries need to be approached at a local, national and international level to determine their requirements and then research needs to be conducted on glycerol in association with biodiesel producers, chemists, biologists and engineers to provide a solution

34. www.sustoil.org Acknowledgments Prof. Gyula Marton† WP3 members University of Cordoba Seneca University of York Chimar Hellas Technical University of Denmark

35. www.sustoil.org Thank you for your attention!