Reciclatori di Residui: una panoramica globale sul primo anello del riciclaggio
Produzione di biocarburanti da residui agricoli e forestali
Transcript of Produzione di biocarburanti da residui agricoli e forestali
WORKSHOP LIFE ECOREMED, 11/10/2013
Produzione di biocarburanti da residui agricoli e forestali
Domenico Pirozzi
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione (DICMAPI) Università “Federico II", Napoli, Italia
Biofuel Classification
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
– Enzymatic hydrolysis à Fermentation • Thermochemical fuels (most made via “gasification”)
– Fischer-Tropsch liquids (FTL) – Methanol, MTBE, gasoline – Dimethyl ether (DME) – Mixed alcohols – Green diesel
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Bioethanol
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Mixture of sugars
Lignocellulosic materials
hydrolysis BIOETHANOL
alcoholic fermentation
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BIODIESEL + Glycerol
TRIGLYCERIDES
VEGETABLE OILS ? ? ?
OLEAGINOUS MICROORGNISMS - microalgae
VEGETABLE OILS
• food or fuel?
• social cost
• deforestation
- bacteria, yeasts
OLEAGINOUS YEASTS
• significant fraction of lipids
• reduced cultural requirements • C/N ratio
• waste organic matters
• urban/industrial wastewaters
• lignocellulosic materials
MICROALGAE • promising results
• affected of CO2, light
• Reduced costs. • Environmental benefits
BIODIESEL
• Non toxic, biodegradable
• Reduced combustion emissions
• Reduced CO2 addition to atmosphere
LIGNOCELLULOSIC MATERIALS
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Mixed cultures of Algae (photoautotroph) + Yeasts (chemoheterotroph)
CO2 + water + light (+ nutrients) Algae + O2
O2 + Nutrients Yeasts + CO2
Process layout
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Mixture of sugars
Oleaginous biomass
oleag . yeasts culture
Triglycerides extraction BIODIESEL alcoholysis
methanol glycerol
Lignocellulosic materials
hydrolysis BIOETHANOL
alcoholic fermentation
BIOPLASTICS
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• high biomass productivity
• adaptability to different climatic and soil conditions – marginal lands: polluted soils, salinized soils
• phytoremediation • protection of hilly soils subjected to erosion
CROP: Arundo donax (Giant reed)
• from soil / ensilage
• significant amounts of microbial oils • little reutilisation of the stored lipids
YEAST: Lipomyces starkeyi
Biomass and lipid concentrations
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Biomass conc. g/L
Lipid fraction, %
Lipid conc. g/L
9.99 19.7 197
7.81 19.5 152
7.50 16.7 125
site water temp.
A Torre Lama irrigated high
B Torre Lama rainfed high
C Centro Rotary rainfed low
Distribution of fatty acids
Agronomic treatment
Hydrolysate mixture
Fatty acid
A
ADH 50%
B
ADH 50%
C
ADH 50%
A
ADH 100% (sorption with act. carbon)
A
ADH 100% (with adapted
L. starkeyi)
Myristic acid C14:0 2 1.8 1.9 1.7 1.9 Palmitic acid C16:0 23.7 24.1 23.8 22.3 22.7 Palmitoleic acid C16:1 <1 <1 <1 <1 <1 Stearic acid C18:0 16.3 16.2 16.3 15.8 16 Oleic acid C18:1 46.5 45.8 46 49.5 48.7 Linoleic acid C18:2 6.5 6.7 6.6 6.3 6.4 Linolenic acid C18:3 1.6 1.8 1.8 1.5 1.5 Arachidonic acid C20:4 <1 <1 <1 <1 <1
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Inhibitors in the hydrolysates of A. donax
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Acetic acid 6.22 7,22 7.10 Levulinic acid 1,44 1,21 1,23 Formic acid 1,67 1,80 1,88 Furfural 0,1 0,38 0,35 5-HMF 0,73 1,06 1,13 vanillin 0,035 0,041 0,055 hydroxybenzaldeyde 0,056 0,101 0,088
site water temp.
A Torre Lama irrigated high
B Torre Lama rainfed high
C Centro Rotary rainfed low
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Effect of contaminants
• Dispersion in the environment (contaminated biofuels or 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, process, microorganism is required
Fate of heavy metals
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methanol
Root Absorption
lignocellulosic materials
Hydrolysis lignin
mixture of sugars
Fermentation spent medium
oleaginous biomass
Triglyceride extraction
non-lipidic components
triglycerides
Alcoholysis
glycerol
BIOPLASTICS BIODIESEL
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KEY ASPECTS
• COMPARTIMENTALIZATION
• SELECTION OF THE PROCESS – Contamination of final products
• SELECTION OF PLANTS
– Chelating agents
• SELECTION OF MICROORGANISMS
– Bioaccumulation, Toxicity
THE END
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C/N ratio Lipid concentration after 10 days, %
(untreated cells) 9,3
14,5 12,1
29 19,3
58 24,0
116 24,1
174 25,3
LIPID DETERMINATION • cell disruption • lipid extraction • solvent removal • gravimetric measurement
The role of biotechnology Biotechnology is not a source of energy, but a scientific method that
provides tools to produce energy
• Biotechnology permits the modification/selection of plants to enhance their conversion to fuels • Biotechnology can be used for yield increase, better biomass quality, disease resistance
Biotechnology can be used to facilitate the manufacturing process (from biomass to
biofuels)
Concerns related to environment/biodiversity
protection
More acceptable for consumers
Second Generation Biofuels • Made from lignocellulosic materials
– Biomass that is generally not edible – Larger fraction of the plant is converted to fuel – Plants can be bred for energy characteristics (high yield, low
inputs) • Two generic processing routes: biological or thermochemical • Can blend with petroleum fuels in most cases • Substantial energy/environment benefits compared with most 1st
generation biofuels due primarily to greater biomass usability per unit land area
• Greater capital-intensity than 1st generation biofuels, but lower feedstock costs à higher cost-scale sensitivity à larger scale facilities needed for optimum economics
Thermochemical Transformation of Lignocellulosic Biomass
Ø Traditional paths entail high temperatures and suffer from carbon
Ø CPOX forms no carbon
Biomass
Pyrolysis High T
Oil Char Tar
Fuel Cat. upgrade
Syngas Char Gasification Methanol
Synfuel
CPOX Syngas Very high T
Sorbitol
HOO
HO OHOH
OH
Glucose Mannitol
Hydrolysis
isomerization
H2
Hydrogenation
OH
OH
Ethylene glycol
+other
polyols
OH
HOO
O
HO OH
O
OH
n
Cellulose
OH2O
Fructose
CH2OH
OCH2OH
OH
OH
HO
H2
Hydrogenation
OHOH
OH
OH OH
OH
OHOH
OH
OH OH
OH
-H2ODehydration
H2
Hydrogenation
H2
HydrogenolysisLight alkanes
CO2, etc.
H+
C-C cleavage+oxdationOrganic acids (unidentified)
OOH O
OOH OH
HMF DHM-THF
OH
Catalytic Conversion of Cellulose to Chemicals
Conversion of cellulose to ethylene glycol on Ni-WC & Ni-W2C: Na et al. Angew. Chem. Int. Ed. (2008); Catalysis Today (2009)
Biofuel value chain and UNIDO radius of attention
Oil bearing plants
Agricultural crops and residues
Woody biomass
Industrial and
municipal waste
Biomass resources
Harvesting,
collection,
handling,
and storage
Supply systems Conversion
Biochemical (fermentation)
Thermochemical (gasification)
Chemical (transesterification)
End products
Transportation fuels (biodiesel, bioethanol)
Heat Electricity
Solid fuels (wood pellets, charcoal)
High added-value chemicals
(pharmaceuticals, polymers)
Physical chemical (extraction)
byproducts
UNIDO (ICS-UNIDO expertise)
UNIDO and FAO FAO UNIDO and UNCTAD
Biofuel type Specific name Feedstock Conversion Technologies
Pure vegetable oil Pure plant oil (PPO), Straight vegetable oil (SVO)
Oil crops (e.g. rapeseed, oil palm, soy, canola, jatropha, castor, …)
Cold pressing extraction
Biodiesel - Biodiesel from energy crops: methyl and ethyl esters of fatty acids - Biodiesel from waste
- Oil crops (e.g. rapeseed, oil palm, soy, canola, jatropha, castor, …) - Waste cooking/frying oil
- Cold and warm pressing extraction, purification, and transesterification - Hydrogenation
Bioethanol Conventional bio-ethanol
Sugar beet, sugar cane, grain Hydrolysis and fermentation
Biogas Upgraded biogas Biomass (wet) Anaerobic digestion
Bio-ETBE Bioethanol Chemical Synthesis
Overview of Biofuel Production Technologies First Generation of Biofuels
Techn . Effort a Overall efficiency c
[%] Expected plant capacity b
[ MW bf ] Current stage of
development
a regarding system complexity (+ less promising… .++++ very promising ) b related to biomass feedstock c according state of development ( many different concepts ) only theoretical values d suitability for current distribution and use (+ less promising… .++++ very promising )
Distri - bution d Use d
Comparison of technologies Technology aspects
Biofuel option 2nd generation
LiquidBioethanol
FT-Fuels
Methanol
GaseousBiogas
Bio-SNG
Dimethylether
Hydrogen
Concept/ Lab
Pilot/Demo
+++
+++++++(+)
++++
++
10.......................1,000 0................................80
++++++
+++
++
++++++
+++
++
+ +
+++ +++
+++ +++
Many different concepts for biofuel options of the 2nd generation; associated with
appropriate benefits and bottlenecks along the pathway.
Source: IEE Leipzig, 2007
Biofuel type Specific name Feedstock Conversion Technologies
Bioethanol Cellulosic bioethanol Lignocellulosic biomass and biowaste
Advanced hydrolysis & fermentaion
Biogas SNG (Synthetic Natural Gas) Lignocellulosic biomass and residues
Pyrolysis/Gasification
Biodiesel Biomass to Liquid (BTL), Fischer-Tropsch (FT) diesel, synthetic (bio)diesel
Lignocellulosic biomass and residues
Pyrolysis/Gasification & synthesis
Other biofuels Biomethanol, heavier (mixed) alcohols, biodimethylether (Bio-DME)
Lignocellulosic biomass and residues
Gasification & synthesis
Biohydrogen Lignocellulosic biomass and biowaste
Gasification & synthesis or biological process
Overview of Biofuel Production Technologies Second/Third* Generation Biofuels
*Use GMO as a feedstock to facilitate hydrolysis / technologies for hydrogen production
Overall biorefinery concept - a new chemical industry sector
- equivalent to the petrochemistry concept
Comparison of technologies Economic versus environmental aspects
Source: IEE Leipzig, 2007
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• higher yield of triglycerides per unit area
• agro-forestal products and desidues
• non-food crops for contaminated soils
• non-food crops for partially-fertile soils – switchgrass, jatropha, miscantus, etc.
Exploitation of lignocellulosic biomasses
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WHY RENEWABLE FUELS?
• Higher costs of traditional fuels
• Reliance on imported oil
• Planetary warming
BIODIESEL
• Non toxic, biodegradable
• No CO2 added to atmosphere
• Reduced combustion emissions
A. donax: cultivation under different agronomic conditions
site water temp.
A Torre Lama irrigated high
B Torre Lama rainfed high
C Centro Rotary rainfed low
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Plant biomass yield, t/ha
48,7
50,8
42,7
Cellulose, % Hemicell., % Lignin, %
46,2 23,2 16,2
43,8 23,5 18,9
42,6 22,8 18,7
Good adaptability to the drought and to the temperature
Inhibitors in the hydrolysates of A. donax
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Acetic acid 6.22 7,22 7.10 Levulinic acid 1,44 1,21 1,23 Formic acid 1,67 1,80 1,88 Furfural 0,1 0,38 0,35 5-HMF 0,73 1,06 1,13 vanillin 0,035 0,041 0,055 hydroxybenzaldeyde 0,056 0,101 0,088
site water temp.
A Torre Lama irrigated high
B Torre Lama rainfed high
C Centro Rotary rainfed low
Pretreatments of hydrolysates to remove inhibitors
• overliming treatment with concentrated Ca(OH)2 • neutralization with NaOH + adsorption on active carbons • overliming followed by neutralization + adsorption.
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0
1
2
3
4
5
0 50 100 150 200 250 300
no treatmentoverlimingactive carbonoverliming + active carbon
time, h
dry
cell
biom
ass,
g/L
The L. starkeyi were able to grow in the presence of the pre-treated hydrolysate
Biomass and lipid concentrations (pre-treated hydrolysates)
Biomass conc. g/L Lipid fraction, % Lipid conc. g/L
Agronomic treatment AC OL AC+OL AC OL AC+OL AC OL AC+OL
A 4.04 1.51 3.78 19.9 19.7 19.8 80.4 29.7 74.8
B 3.56 1.45 3.60 19.6 19.8 19.5 69.8 28.7 70.2
C 3.27 1.56 3.18 16.8 16.6 16.6 54.9 25.9 52.8
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• AC = adsorption on active carbons • OL = overliming
Adaptation of L. starkeyi
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0
2
4
6
8
10
0 50 100 150 200 250
Ist cycle: 50% ADHIInd cycle: 75% ADHIIIrd cycle: 100% ADH
time, h
dry
cell
biom
ass,
g/L
50% ADH 75% ADH 100% ADH
Lipomyces
ADH = hydrolysate of Arundo donax
The adapted L. starkeyi were able to grow in the presence of the raw hydrolysate
Biomass and lipid concentrations (adapted yeasts)
Biomass conc. g/L Lipid fraction, % Lipid conc. g/L
Agronomic treatment I II III I II III I II III
A 9.31 6.21 5.34 19.7 19.9 19.9 183 124 106
B 9.11 5.94 5.20 19.5 19.8 19.9 178 118 103
C 8.99 5.97 5.03 16.7 16.8 17.1 150 100 86.0
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