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WP-3 Optimisation of secondary processing (i.e biodiesel production) Coordinator – Prof. Gyula Marton Deputy coordinator – Zsanett Herseczki University.

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Presentation on theme: "WP-3 Optimisation of secondary processing (i.e biodiesel production) Coordinator – Prof. Gyula Marton Deputy coordinator – Zsanett Herseczki University."— Presentation transcript:

1 WP-3 Optimisation of secondary processing (i.e biodiesel production) Coordinator – Prof. Gyula Marton Deputy coordinator – Zsanett Herseczki University of Pannonia - UP Foggia, 24.04.2009

2 Objectives and Tasks To review novel routes to biodiesel (e.g. heterogeneous catalysis, biocatalysis, etc.) by UCO and SENECA (Task 1) To review and assess the different technologies available to refine and purify glycerol by UP and NEC (Task 2)

3 Objectives and Tasks To develop a portfolio of most promising speciality (among chemicals and adhesives through green chemistry) can be obtained from crude glycerol as a platform chemical by UoY and CHIMAR Task 3 and Task 4

4 Objectives and Tasks To carry out a technical-economic assessment of the production of triacetin from crude glycerol by UP and NEC (Task 5) To develop methods of pretreatment, hydrolysis and fermentation of glycerol for ethanol production by DTU (Task 6)

5 Program 1. Novel routes to biodiesel that incorporate glycerol – Rafael Loque – University of Cordoba (Spain) 2. Glycerol from biodiesel production – Existing and new glycerol purification - Zsanett Herseczki- UP 3. Production of Triacetin from crude glycerol – Zsanett Herseczki- UP 4. Application of glycerol in adhesives for wood panels – Dr. Katsampas Ilias – CHIMAR HELLAS (Greece) 5. Transformation of glycerol into high-quality products through green chemistry and biotechnology – Abbas Kazmi – UoY (UK) (presented by Zsanett Herseczki) 6. Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation – John Woodley DTU (Denmark) (presented by Zsanett Herseczki)

6 Glycerol from biodiesel production – Existing and new glycerol purification technologies Zsanett Herseczki, Gyula Marton University of Pannonia, Cooperative Research Centre for Environmental and Information Technology, H-8200 Veszprem, POB 158, Hungary Phone/Fax: +36-(88) 624-986, e-mail: hzsanett@almos.uni-pannon.huhzsanett@almos.uni-pannon.hu Sándor Ember 2657 TOLMÁCS, Arany J.u.2. Tel: (35)-550-153, 550-038, 350-089 Fax:(35)-550-154, 350-190 e-mail: nek@wnet.hunek@wnet.hu

7 Introduction Recently Increases in crude oil prices Limited resources of fossil oil Environmental concerns renewed focus on vegetable oils and animal fats 10 % Problem?

8 Crude glycerol glycerol fatty acid methyl ester methanol salt soaps water other impurities Problems: foaming, high boiling point components (deep vacuum, high temperature)

9 Crude glycerol G-phases obtianed from Hungarian biodiesel factories contain Glycerol~45% Water, methanol~10-15% Salt~10-15% Soaps~30% Poor quality Requires expensive refining Current technologies require significant economies of scale to be economical

10 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

11 Conventional processes for glycerol purification 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)

12 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

13 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

14 Recent development in glycerol purification processes (>99,5% glycerol)

15 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

16 Partly purified G-phase G-phases obtianed from Hungarian biodiesel factories contain Glycerol~45% Water, methanol ~10-15% Salt~10-15% Soaps~30% Refining process Acid treatment (H 3 PO 4 ), pH~3, stirring at 80°C, 1 hour Neutralization of excess acid, (Ca(OH) 2 ), pH~4,8 Distillation to remove water, methanol (under vacuum) Free fatty acids Crude glycerol Ca 3 PO 4 Crude glycerol Water, methanol Glycerol containing salt

17 Glycerol alkyl esters – Production of Triacetin from crude glycerol Zsanett Herseczki, Gyula Marton University of Pannonia, Cooperative Research Centre for Environmental and Information Technology, H-8200 Veszprem, POB 158, Hungary Phone/Fax: +36-(88) 624-986, e-mail: hzsanett@almos.uni-pannon.huhzsanett@almos.uni-pannon.hu Sándor Ember 2657 TOLMÁCS, Arany J.u.2. Tel: (35)-550-153, 550-038, 350-089 Fax:(35)-550-154, 350-190 e-mail: nek@wnet.hunek@wnet.hu

18 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

19 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 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

20 Ionic liquid as a green catalytic reaction medium for triacetin synthesis Esterification of carboxylic acids with alcohols in room temperature ionic liquids as a catalyst and reaction media was studied Molar ratio of aluminium chloride/butylpyridine chloride is less than 1.0 (Lewis basic) - the mechanism of esterification in ionic liquid may be different from that in sulfuric acid Selectivity of triacetin was ~ 3,6-26% (conversion ~100%) Outstanding advantage: resultant esters may not dissolved in the ionic liquid and therefore they could be isolated easily The ionic liquid is suitable to those esterifications between aliphatic acids and alcohols at mild reaction conditions (30-75°C)

21 Production of triacetin from partly purified glycerol + 3 + 3 H 2 O Azeotropic distillation Used in excess Cat. Used catalysts H 2 SO 4 H 3 PO 4 Ion exchange resins – Amberlyst type (Amberlyst 15 and Amberlyst 36) Entraining solvents n-Hexane MIBK Toluene Raw material Partly purified glycerol

22 Best catalyst: H 2 SO 4 Best entraining solvent: toluene Product purification: removal of excess acetic acid by distillation removal of salt by filtration Purity >96% Color: pale yellow Distillation of glycerol, triacetin is not necessary! Production of triacetin from partly purified glycerol

23 Scheme for production of triacetin from crude glycerol 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

24 Program 1. Novel routes to biodiesel that incorporate glycerol – Rafael Loque – University of Cordoba (Spain) 2. Glycerol from biodiesel production – Existing and new glycerol purification - Zsanett Herseczki- UP 3. Production of Triacetin from crude glycerol – Zsanett Herseczki- UP 4. Application of glycerol in adhesives for wood panels – Dr. Katsampas Ilias – CHIMAR HELLAS (Greece) 5. Transformation of glycerol into high-quality products through green chemistry and biotechnology – Abbas Kazmi – UoY (UK) (presented by Zsanett Herseczki) 6. Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation – John Woodley DTU (Denmark) (presented by Zsanett Herseczki)

25 Dr. Abbas Kazmi Green Chemistry Centre of Excellence, University of York, York, UK Transformation of glycerol into high- quality products through green chemistry and biotechnology

26 The biodiesel industry currently regards glycerol as a waste by-product however with novel methods glycerol has the potential to be converted into high value products Glycerol transforming processes Valuable Chemicals from Glycerol Transformation of glycerol into high- quality products through green chemistry and biotechnology

27 Aqueous phase Reforming - Fischer-Tropsch Conversion of glycerol to hydrogen and carbon monoxide (Synthesis Gas) The process conditions are 250˘C using a Pt-Re catalyst in a single reactor The synthesis gas can be used as a building block for chemicals and fuels using the Fischer-Tropsch reaction 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 and subsequent dehydrochlorination using NaOH to generate epichlorohydrin and NaCl Glycerol transforming processes

28 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 at temperatures from 50°C-150°C. Esterification Glycerol can be esterified with carboxylic acids or via carboxylation and nitration and reaction of glycerol with dimethyl carbonate produces a high yield of glycerol carbonate Glycerol transforming processes

29 Selective oxidation Oxidation products include glyceraldehydes, glyceric acid, glycolic acid, hydroxypyruvic acid, oxalic acid and tartronic acid The oxidation of glycerol can be catalysed using highly active aerobic catalysts such as platinum and palladium 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 Glycerol can be converted to a very large number of chemicals using micro-organisms and enzymes (e.g. 3-hydroxypropionaldehyde ) Glycerol transforming processes

30 Hydrogen Succinic acid Ethanol Propylene glycol Dihydroxyacetone Acrolein Glycerol Tertiary Butyl Ether (GTBE) Mono- and Di-acylglycerol (DAG) Citric acid Valuable Chemicals from Glycerol

31 Market for glycerol is likely to remain volatile in the near future 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 Future vision

32 Program 1. Novel routes to biodiesel that incorporate glycerol – Rafael Loque – University of Cordoba (Spain) 2. Glycerol from biodiesel production – Existing and new glycerol purification - Zsanett Herseczki- UP 3. Production of Triacetin from crude glycerol – Zsanett Herseczki- UP 4. Application of glycerol in adhesives for wood panels – Dr. Katsampas Ilias – CHIMAR HELLAS (Greece) 5. Transformation of glycerol into high-quality products through green chemistry and biotechnology – Abbas Kazmi – UoY (UK) (presented by Zsanett Herseczki) 6. Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation – John Woodley DTU (Denmark) (presented by Zsanett Herseczki)

33 Yuan Xu (DTU) Denmark Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation

34 The fermentation production of value-added alcohols from glycerol offers an attractive opportunity of stimulating the biofuel industry due to the relatively low price of glycerol and some advantages over glucose fermentation, such as the production of 1,3-propanediol (PDO), which could not be produced from glucose fermentation. Dilution of the crude glycerol is necessary because of the inhibition effect of impurities and high substrate concentration on some species, like the ethanol producing strain Enterobacter aerogenes. It has little effect on 1,3-PDO producing species Clostridium butyricum and Klebsiella pneumoniae. Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation

35 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 Fed batch fermentation could result in high product concentration up to 70 g/L of 1,3-PDO Continuous fermentation and immobilized cell fermentation could enhance the productivity over 8 g/L h of 1,3-PDO. The scale-up production of 1,3-PDO has been found both in anaerobic and microaerobic operations up to 2 m 3 and 1 m 3, respectively It is worth attention that the increasing volumetric scale-up factor resulted in the decrease of final PDO concentration. Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation

36 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 in use are energy-consuming and expensive. To increase the economic viability of industrial application, the metabolic engineering technology could be adopted on the microorganisms to increase their product specificity or improve their tolerance to the impurities and high substrate concentration of the crude glycerol. Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation

37 Discussion!


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