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Biodiesel - Weeenmodels

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Il Modello EcoRemed: impiego di
biomasse agricole da suoli contaminati
per la produzione di biodiesel
Domenico Pirozzi
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione (DICMAPI)
Università “Federico II", Napoli, Italia
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Phytoremediation
•
advantages over traditional technologies (ex situ - in situ)
–
–
•
disadvantages
–
•
lower costs
safeguard of soil properties
long-term treatment
commercial exploitation: biofuels?
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Bioethanol
WORLDWIDE PRODUCTION
•
•
•
•
•
COMMERCIAL APPLICATIONS
alcoholic beverages
solvent/reagent for chemical syntheses
medical
cosmetics
automotive fuel (USA: E10, E15 –
Brazil: E100, blends)
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Bioethanol
Starch
seeds,
tubers, etc.
enzymatic
hydrolysis
sugar
crops
Mixture
of sugars
alcoholic
fermentation
BIOETHANOL
FERMENTATIVE METHOD
Ascomycetes:
Sacch. cerevisiae
Basidiomycetes:
Candida utilis
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Bioethanol and Biodiesel
Starch
seeds,
tubers, etc.
enzymatic
hydrolysis
Mixture
of sugars
alcoholic
fermentation
BIOETHANOL
sugar
crops
residual
oils
plants for
unfertile soils
oleaginous
crops
Triglycerides
alcoholysis
methanol
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
BIODIESEL
glycerol
Classification of Biofuels
First Generation (from sugars, grains, or seeds)
• Bioethanol
–
–
•
from sugar crops: sugar beets, sugarcane
from grains or seeds: corn, wheat, potato
Biodiesel
–
from rapeseed, soybeans, sunflowers, jatropha, coconut, palm, recycled cooking oil
Bottlenecks of the first generation biodiesel
• fertile soils not available
• social problems
• deforestation
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Classification of Biofuels
First Generation (from sugars, grains, or seeds)
• Biodiesel
–
•
rapeseed, soybeans, sunflowers, jatropha, coconut, palm, recycled cooking oil
Ethanol
–
–
From grains or seeds: corn, wheat, potato
From sugar crops: sugar beets, sugarcane
Second Generation (from lignocellulose: crop residues, grasses, woody crops)
• Biological fuels
–
•
Hydrolysis  Fermentation
Thermochemical fuels (most made via “gasification”)
–
–
–
–
–
Fischer-Tropsch liquids (FTL)
Methanol, MTBE, gasoline
Dimethyl ether (DME)
Mixed alcohols
Green diesel
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Second-generation bioethanol
Lignocellulosic
materials
hydrolysis
Mixture
of sugars
alcoholic
fermentation
BIOETHANOL
Triglycerides
alcoholysis
methanol
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
BIODIESEL
glycerol
Lignocellulosic materials
40-50%
cellulases
fermentable
sugars
25-35%
hemicellulases
15-20%
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Pre-treatment
cellulose encapsulated in the
lignin-hemicellulose matrix
Steam explosion
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Industrial application
Mossi & Ghisolfi - Crescentino (Vercelli)
PROESA technology
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Second-generation biodiesel
Lignocellulosic
materials
hydrolysis
Mixture
of sugars
alcoholic
fermentation
BIOETHANOL
growth of
oleag . yeasts
Oleaginous
biomass
extraction
Triglycerides
alcoholysis
methanol
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
BIODIESEL
glycerol
Oleaginous microorganisms
• waste organic matters
• urban/industrial wastewaters
• lignocellulosic materials
Lipid droplets within
the microorganisms
MICROALGAE
OLEAGINOUS YEAST
photoautotroph
chemoheterotroph
CO2 + water + light (+ nutrients)
O2 + Nutrients
Algae + O2
Yeasts + CO2
Possible synergistic application
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Further improvements
Recycle of glycerol
Bioplastics
Lignocellulosic
materials
hydrolysis
Mixture
of sugars
alcoholic
fermentation
BIOETHANOL
oleag . yeasts
culture
Oleaginous
biomass
extraction
BIOPLASTICS
Triglycerides
alcoholysis
methanol
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
BIODIESEL
glycerol
Distribution of fatty acids
Agronomic treatment
A
B
C
A
A
Hydrolysate mixture
ADH 50%
ADH 50%
ADH 50%
ADH 100%
(sorption with
act. carbon)
ADH 100%
(with adapted
L. starkeyi)
2
23.7
<1
16.3
46.5
6.5
1.6
<1
1.8
24.1
<1
16.2
45.8
6.7
1.8
<1
1.9
23.8
<1
16.3
46
6.6
1.8
<1
1.7
22.3
<1
15.8
49.5
6.3
1.5
<1
1.9
22.7
<1
16
48.7
6.4
1.5
<1
Fatty acid
Myristic acid C14:0
Palmitic acid C16:0
Palmitoleic acid C16:1
Stearic acid C18:0
Oleic acid C18:1
Linoleic acid C18:2
Linolenic acid C18:3
Arachidonic acid C20:4
•
Reduced tendency to oxidation
•
Satisfactory cold performance
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Effect of soil pollutants
•
Contamination of biofuels/wastes
•
Poor performance of microorganisms (reduced
biofuel yield)
–
–
–
–
Oxidative stress
Enzyme inhibition
Disruption of regulatory proteins
Reduced repair of DNA Impairment
A suitable choice of plants, microorganism, process is
required
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
Fate of heavy metals in biodiesel process
HEAVY
METALS
Root
Absorption
lignocellulosic
materials
lignin
Hydrolysis
mixture of
sugars
TRIGLYCERIDE EXTRACTION
• HM in non-lipidic components?
• bi- or tri-insaturated fatty acids
ROOT ABSORPTION
ALCOHOLYSIS
• reduced uptake
•FERMENTATION
HM
in glycerol?
storage
•• oxidative-stress
defense
Biosorption mechanisms:
binding, transmembrane
transport
Fermentation
spent medium
HYDROLYSIS
• HM in the aqueous
misture of sugars?
• chelating groups of lignin
oleaginous
biomass
Triglyceride
extraction
non-lipidic components
triglycerides
BIOPLASTICS
BIODIESEL
Alcoholysis
methanol
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
glycerol
Fate of heavy metals (bioethanol process)
HEAVY
METALS
Root
Absorption
lignocellulosic
materials
Hydrolysis
Lignin (chelation?)
mixture of
sugars
ROOT ABSORPTION
• reduced uptake
• storage
HYDROLYSIS
• oxidative-stress defense
• HM in the aqueous
misture of sugars?
•FERMENTATION
chelating groups of lignin
•
Biosorption mechanisms:
binding, transmembrane
transport
Alcoholic
fermentation
ethanol
solution
bioethanol
Distillation
water
biomass
DISTILLATION
• EtOH: logP = -0,58
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
KEY ASPECTS
•
SELECTION OF PLANTS
–
•
SELECTION OF MICROORGANISMS
–
–
•
Compartimentalization
Bioaccumulation
Resistance to toxic pollutants
SELECTION OF THE PROCESS
–
–
Hydrophilic pollutants: oleaginous fermentation to be preferred
Hydrophobic pollutants: alcoholi fermentation to be preferred
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
THE END
IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
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