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


Bioethanol


Mixture of sugars

Lignocellulosic materials

hydrolysis BIOETHANOL

alcoholic fermentation


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


Mixed cultures of Algae (photoautotroph) + Yeasts (chemoheterotroph)

CO2 + water + light (+ nutrients) Algae + O2

O2 + Nutrients Yeasts + CO2

Process layout


Mixture of sugars

Oleaginous biomass

oleag . yeasts culture

Triglycerides extraction BIODIESEL alcoholysis

methanol glycerol

Lignocellulosic materials

hydrolysis BIOETHANOL

alcoholic fermentation

BIOPLASTICS


•  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


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


Inhibitors in the hydrolysates of A. donax


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.





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


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


KEY ASPECTS

•  COMPARTIMENTALIZATION

•  SELECTION OF THE PROCESS –  Contamination of final products

•  SELECTION OF PLANTS

–  Chelating agents

•  SELECTION OF MICROORGANISMS

–  Bioaccumulation, Toxicity

THE END



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


•  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


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.





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


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.




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.


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


•  AC = adsorption on active carbons •  OL = overliming

Adaptation of L. starkeyi


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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Produzione di biocarburanti da residui agricoli e forestali