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
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)
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
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)
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)
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.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.hu
Introduction
Recently
•Increases in crude oil prices
renewed focus on vegetable
•Limited resources of fossil oil
oils and animal fats
•Environmental concerns
Problem?
10 %
Crude glycerol
•glycerol
•fatty acid methyl ester
•methanol
•salt
•soaps
•water
•other impurities
Problems: foaming, high boiling point
components (deep vacuum, high
temperature)
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
Processes for refining glycerol
•The following technologies may be used to purify glycerol (after the
soap splitting step)
extraction
ion-exchange
dialysis
fractional distillation
precipitation
adsorption
crystallisation
•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.
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)
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
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
Recent development in glycerol purification processes (>99,5%
glycerol)
Chromatography and regenerative column adsorption
•Activated carbon - The main components to separate are:
Glycerol
Water
Methanol traces
Ions (like K+)
Saponification residues and
•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
Partly purified G-phase
G-phases
obtianed
from
Hungarian biodiesel factories
contain
Glycerol
~45%
Water,
methanol
Salt
~10-15%
Soaps
~10-15%
~30%
Refining process
Acid treatment (H3PO4 ), pH~3, stirring at 80°C, 1 hour
Free fatty acids
Crude glycerol
Neutralization of excess acid, (Ca(OH)2), pH~4,8
Ca3PO4
Crude glycerol
Distillation to remove water, methanol (under vacuum)
Water, methanol
Glycerol
containing salt
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.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.hu
Triacetin – Properties, field of application
Properties
Molar mass
Boiling point
Melting point
218,2 g/mol
258-260 °C
-78 °C
Density
1,16 g/ml at 25°C
Field of application
•Food additive (e.g. butter) - E1518
•Antifungal agent in external medicine
•Potential green solvent and fuel additive
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
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)
Production of triacetin from partly purified
glycerol
O
OH
HO
O
OH
O
Cat.
O
+ 3 H3C
OH
O
Used in excess
Used catalysts
•H2SO4
•H3PO4
•Ion exchange resins –
Amberlyst type (Amberlyst 15
and Amberlyst 36)
Azeotropic
distillation
+
3 H2O
O
O
Entraining solvents
•n-Hexane
•MIBK
•Toluene
Raw material
•Partly purified glycerol
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!
Scheme for production of triacetin from
crude glycerol
Crude glycerol
Dilution,
acid
treatment
Phase
separation
Water,
phosphoric
acid
Filtration
Decolorization
Free fatty
acid, salt
Activated
carbon
Activated
carbon
Methanol
Esterification
Glycerol containing
water, salt, methanol
Water,
toluene
Phase
separation
Toluene
Water
Acetic acid
NaOH
solution
Triacetin,
acetic acid,
catalyst, salt
Neutralization
Acetic acid
Distillation
Filtration
Triacetin,
catalyst,
salt
Salt
Triacetin
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)
Transformation of glycerol into highquality products through green chemistry
and biotechnology
Dr. Abbas Kazmi
Green Chemistry Centre of Excellence, University of York,
York, UK
Transformation of glycerol into highquality 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
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
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
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 )
Valuable Chemicals from Glycerol
Hydrogen
Succinic acid
Ethanol
Propylene glycol
Dihydroxyacetone
Acrolein
Glycerol Tertiary Butyl Ether (GTBE)
Mono- and Di-acylglycerol (DAG)
Citric acid
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
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)
Assessment of various methods of pre-treatment,
fermentation and downstream processing of
alcohol production from glycerol fermentation
Yuan Xu
(DTU) Denmark
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 1,3propanediol (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
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.
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.
Discussion!