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WP-3 Optimisation of secondary processing (i

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

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 Zsanett Herseczki, Gyula Marton
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)  , Sándor Ember 2657 TOLMÁCS, Arany J.u.2. Tel: (35) , , Fax:(35) ,

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

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 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. ion-exchange precipitation extraction adsorption dialysis fractional distillation crystallisation

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 Continuous glycerol Concentration – Multiple vacuum flash evaporators
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

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

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
Glycerol ~45% Water, methanol ~10-15% Salt Soaps ~30% G-phases obtianed from Hungarian biodiesel factories contain Refining process Acid treatment (H3PO4 ), 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 Ca3PO4 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)  , Sándor Ember 2657 TOLMÁCS, Arany J.u.2. Tel: (35) , , Fax:(35) ,

18 Triacetin – Properties, field of application
Food additive (e.g. butter) - E1518 Antifungal agent in external medicine Potential green solvent and fuel additive Molar mass 218,2 g/mol Boiling point °C Melting point -78 °C Density 1,16 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
Azeotropic distillation Cat. + 3 H2O Used in excess Entraining solvents n-Hexane MIBK Toluene Raw material Partly purified glycerol Used catalysts H2SO4 H3PO4 Ion exchange resins – Amberlyst type (Amberlyst 15 and Amberlyst 36)

22 Production of triacetin from partly purified glycerol
Best catalyst: H2SO4 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!

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

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

26 Transformation of glycerol into high-quality products through green chemistry and biotechnology
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

27 Glycerol transforming processes
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

28 Glycerol transforming processes
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

29 Glycerol transforming processes
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 )

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

31 Future vision 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

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

34 Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation 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.

35 Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation 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 m3 and 1 m3, respectively It is worth attention that the increasing volumetric scale-up factor resulted in the decrease of final PDO concentration.

36 Assessment of various methods of pre-treatment, fermentation and downstream processing of alcohol production from glycerol fermentation 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.

37 Discussion!


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