www.sustoil.org
9th June 2010
Title
• Optimisation of secondary processing (i.e biodiesel
production)
Speaker
• Zsanett Herseczki
Institute
• UP
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
www.sustoil.org
New types of biodiesel to make up the glycerol as a byproduct, 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”
www.sustoil.org
1,3 regioselective transesterification: 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.
Oil/fats
+
ethanol
(1:2)
Tank reactor
(immobilized
Lipases)
H2C-OOCR
HC-OOCR + 2 CH3-CH20H
ECODIESEL
PPL
H2C-OH
HC-OOCR
+
H2C-OOCR
H2C-OH
TRIGLYCERIDE
MONOGLYCERIDE
2 RCOOCH2CH3
FATTY ACID ETHYL
ESTER (FAEE)
ECODIESEL
www.sustoil.org
DMC-BIOD ® is biofuel that integrates the glycerol in a process that
can be developed by enzymatic technology
H2C-OOCR
O
HC-OOCR + CH3O-C-OCH3
H2C-O
C=O
HC-O
+
2 RCOOCH3
H2C-OOCR
H2C-OOCR
Fatty acid glycerol
Fatty acid methyl
Triglyceride Dimethyl carbonate carbonate monoester 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.
H2C-OOCR
HC-OOCR + 3 CH3-COOCH2CH3
CH3COO-CH + 3 RCOOCH2CH3
CH3COO-CH2
H2C-OOCR
Triglyceride
Lipase
CH3COO-CH2
Ethyl acetate
Triacetin
Fatty acid ethyl
esther (FAEE)
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/Al2O3) under standard conditions of temperature (300450 °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
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
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
It requires pre-treatments to reduce the water
processes generally content and increase the energy density (higher
take place at higher energy cost)
temperatures
(400–700 °C) and Obstacle of high cost of biodiesel production
can
produce from algae may be overcome
methane
or
hydrogen gases in
high yields
www.sustoil.org
Glycerol from biodiesel production – Existing and new
glycerol purification technologies
10 %
Purity: 55-90 %
In larger biodiesel plants 75-80 %
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)
www.sustoil.org
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.
www.sustoil.org
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)
www.sustoil.org
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
www.sustoil.org
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
www.sustoil.org
Recent development in glycerol purification processes (>99,5%
glycerol)
www.sustoil.org
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
www.sustoil.org
Transformation of glycerol into high-quality products
through green chemistry and biotechnology
Glycerol transforming processes
Valuable Chemicals from Glycerol
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
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
www.sustoil.org
Derivatives of Glycerol
www.sustoil.org
Application of glycerol
Personal/oral care products
Drugs /pharmaceuticals
Foods/beverages
Polyether polyols
Fuel additives
Plastics
Coatings
Adhesives
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, ureaformaldehyde, melamine-formaldehyde, and isocyanate
www.sustoil.org
Formaldehyde based adhesive resins and Glycerol
•Glycerol 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 resins
Due to the comparatively high cost of glycerol; it is combined with other cheap
substances
•Glycerol as formaldehyde catcher
Glycerol reduces further the formaldehyde emissions by binding up remaining
free volatiles into the polymer matrix
www.sustoil.org
Natural resins and Glycerol
•Soy 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 acid
Interesting and environmentally friendly mixture suitable for wood dimensional
stabilization.
•Natural 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.
www.sustoil.org
Glycerol derivatives and wood adhesives
www.sustoil.org
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
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
www.sustoil.org
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
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
H2
Acetate
Ethanol
Propionate
Butanol
Lactate and butyrate
Acetone
Succinic acid
 2,3-butanediol
Formate
1,3-propanediol
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
www.sustoil.org
Combined bioprocess of production biodiesel by lipase with
microbial production of 1,3-propanediol by Klebsiella pneumoniae
www.sustoil.org
Ethanol
Ethanol and succinate are the main products of glycerol
fermentation by E.coli
E. aerogenes mainly produces ethanol and H2
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
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
www.sustoil.org
Acknowledgments
Prof. Gyula Marton†
WP3 members
University of Cordoba
Seneca
University of York
Chimar Hellas
Technical University of Denmark
www.sustoil.org
Thank you for your attention!