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2nd Generation biomass conversion
• 2nd Generation; new sustainable indigenous industry based on carbohydrate biomass of which a major component is lignocellulosic biomass
• Nonfood biomass transport fuel, fuel additives, chemicals (plastics, food ingredients, medical products)
1st Generation biomass conversion
• Vegetable oils biodiesel
• Biomass starch ethanol
Biomass
Sugar/starchcrops
LignocellulosicBiomass
Oil plants
extraction
Vegetable oil
hydrolysis
sugar
fermentation
Bio-ethanol
pyrolysis gasification Anaerobicdigestion
hydrolysis
refining
Catalyticupgrading
syngas
Catalytic reforming
Bio-oil
Motor fuels & Chemicals
biogas
methane
sugar
fermentation
esterify
biodiesel
Bioalcohol
Biofuels: a significant opportunity for Ireland
• Resources: grass, biomass, agricultural residues
• Global Biofuels Market: $160b in 2012 - growth of 13.0% p/a to 2017
• Global Biorefining Market: multi-sectorial, e.g. 20% of sales in global chemical industry = $250b, c. 400,000 jobs.
• Need to integrate Ireland into EU strategy and maximize business opportunities
Technologies, feedstock prices and policy framework
Ireland’s response• Policy: Cleantech focus by Agencies
• IDA/EI: Competence Centre for Biorefining and Bioenergy
– Grass and algae (desk studies) as feedstock, ethanol as primary fuel target. Near to market or technology importation to establish Irish-based activity
• need to develop strategic research base focused on
next generation technologies, to attract key industrial players and to position Ireland for success
1
Gasification Pyrolysis
Feedstock selection
Biosyn gas Char Bio oil
Biochar Activated carbon
Catalytic Upgrading
Diesel Miscible Biofuels
Gas cleaning & conditioning
Residue
Potential of microalgae (desktop)
Feedstocks 1. Grass (conserved & fresh) 2. Miscanthus
Primary Conversion Enzymatic Hydrolysis Pyrolysis & Gasification
An
alysis of Feedstocks &
products
Secondary Conversion Chemical (catalytic) Enzymatic Microbial
Biopolymers e.g PHA
Platform Chemicals Oils, Sugars.
Proteins, Phenols, Lignins,
Bioactives
Liquid Transport Fuels
Fermentation Optimisation
Catalysis (incl. enzymatic)
Enzymatic Hydrolysis
Fine chemicals Pharma
compounds
Competence Centre for Biorefinery and Bioenergy (CCBB) Initial Research Phase Overview
Next Steps• Address strategic gaps: field to wheel• Engage key industrial players through cutting edge
research• Exploit competitive advantages:
– Future feedstock development
– Future transport usage
– Novel, high-value co-products
– Sustainable procesess
• Education sector - Graduates, IP, leveraged funding,
Significant economic and commercial impacts
Need to select “good” varieties of plants?Novel varieties of Ryegrass, Miscanthus and
Sweet Sorghum easier to bioprocess
Smarter biofuels - Butanol: major advantages– production?Biogas methane: flexible fuel but production efficiency low?
Processes based on novel enzyme technologies or chemical routes (catalysis)
Demonstration-scale production
New Irish businesses: 2nd and 3rd G biogas and butanol technologies
Co-products and residues
Bioenergy alone not sustainable – dependent on nature &value of co-products
Residues minimized, converted to added value products
D-xylose (C5) conversion to bioplasticBiochar production process from residues
Novel non-GM protein supplement for animal
nutrition
University of Limerick Biorefining research
• Thermochemical processing of biomass through pyrolysis and thermal gasification to 2nd generation biofuels and biochar
• Chemical hydrolysis of lignocellulosic biomass to levulinic acid
University of Limerick
Catalytic Conversion
• Nonfood biomass levulinic acid fuel additives, chemicals
• Biomass derived bio-oil fuels, chemicals, hydrogen
• Biomass derived chemicals (by-products) fuels, hydrogen
• Vegetable oils biodiesel
• Biomass ethanol
Carbolea• Research group comprised mainly of chemists, chemical
engineers;• Group consist of 2 professors 2 Senior faculty, 2 CPI
research fellows; 5 post-docs & 10 PhD students• Research goes from field to engine & back to field• Extensive involvement in 1st generation biofuels
– 3 EU; several national programs; currently involved with ESB on fleet trials
– Waste cooking oil & tallow feedstocks– Modifying the low temperature behaviour of Biodiesel– Effect of biofuel deployment on fleet management.
• 2nd Generation; new sustainable indigenous industry based on carbohydrate biomass of which a major component is lignocellulosic biomass
Thermochemical-pyrolysis
NONFOOD BIOMASS (grasses or residue from fermentation, etc)
lignin (15-30%), cellulose (35-50%), hemicellulose (15-25%)
Pyrolysis
Gases,Char,Bio-oil
T=450-550oC,Residence time <2s,
Heating rates 103-104 K/s
70-80% yield
Bio-oil Properties
Mixture >300 compounds acetic acid 1-32%, formic acid 1-20%, phenols,
aromatics, water, etc.
Advantages: transportable, storable, much higher energy density than biomass and cleaner
Disadvantages: corrosive (pH=2.5), unstable, immiscible with petrofuels, low heating values
Bio-oil vs Transport Fuels
Bio-oil Gasoline DieselCarbon chainlength up to 100 5-10 12-
20 branched alkanes, linear
alkanes aromaticsH/C ratio ~1.3 1-2
~2
O/C ratio 0.5 0 0
Upgrading of bio-oil is necessary
Hydrodeoxygenation of Bio-oil
Bio-oil
Hydrocarbons(naphtha equivalent)
Diesel
Refining,catalysts
Hydrodeoxygenation,Mesoporous silica supported catalysts
Bio-oil + H2 Hydrocarbons + H2O
350-400oC
Bio-oil + R-OH Upgraded Bio-oil + H2O
Esterification
R1COOH + R-OH <-> R1COOR + H2O
AcetalizationAcid catalysts
Acid catalysts, 50-80oC
Acid catalysts
Esterification
R1CHO + 2 R-OH <-> R1CH(OR)2 + H2O
Gasification pyrolysis
Feedstock analysis
Feedstock selection& optimisation
Biosyn gas
Alcoholsynthesis
Bioethanol higher alcohols
Catalytic upgrading
Liquid hydrocarbon fuels
Char Bio oil
Biochar Activatedcarbon
CatalyticUpgrading
Diesel MiscibleBiofuels
Platform Chemicals
Gas cleaning & conditioning
ChemicalHydrolysis (Solid Acid Catalysts)
Pretreatment(Ionic Liquids)
Platform Chemicals
& optimisati
on
Lignin Residue
Sugars
Liquid Transport Fuels
Alternatives to Petrol-Derived Products
Fermentation
Catalysis
Gasification
TemperatureFluidising velocity
Inert material CharacteristicsResidence time
Particle sizeMoisture
Mineral contentFixed carbon
volatiles
Feedstock parameters Process variables
Gas quality
Gasification of Bio-oil
Bio-oil
Steam and autothermal reforming, >700oCSupported metals
Fischer-TropschProcess (FT), supported Co or Fe catalysts
MethanolMethanol to gaso-line process (MTG)
Diesel
CO + H2
Gasoline
Cu/Zn/Al2O3 catalysts,
high pressure
Bio-oil + H2O (+ O2) CO + H2 Hydrocarbons + H2O
Dimethyl ether(diesel substitute)
zeolites
synthesis gas
HydrogenClean fuel
Present industrial production:
coal natural gas (CH4, C2H6, etc) + H2O H2 + CO, steam-reforming
naphtha
CO + H2O CO2 + H2, water-gas shift reaction
50 million tons per year
Hydrogen from Bio-oil
Water soluble Bio-oil
Steam and autothermal reforming, supported metals,
>600oC
H2 + CO2 + some COPreferential oxidation
process (PROX),supported metals
H2 + CO2
Energy
Low temperaturefuel cell
Bio-oil + H2O (+ O2) CO2 + H2
YIELDS – up to 90%
Bio-oilH2O
extraction
Hydrogen production from bio-oil looks attractive
Hydrogen from Chemicals Derived from Biomass
Steam reforming over supported metals and oxides as catalysts
H2 + CO2
Formic acid, HCOOH
Ethanol, C2H5OH
Glycerol
Levulinic acid –platform chemical & primary goal of DIBANET (UL led FP7)
CROPS
ARGICULTURAL
RESIDUES
CELLULOSIC
SLUDGES
WOOD
STARCH
WASTE
PAPER
MOLASSES
THE
BIOFINE
PROCESS
LEVULINIC
ACID
FORMIC
ACID
FURFURAL
LIGNEOUS
CHAR
DOWNSTREAM
CONVERSION
SPECIALTY
CHEMICALS
COMMODITY
CHEMICALS
HERBICIDES
PESTICIDES
ENERGY
FUELS
AUTOMOTIVE
FUELS
FEEDSTOCKS
“BIOMASS”
PRODUCTS
Cellulose
Sugars
Intermediates I
HMF
Intermediates II
Levulinic Acid (50wt %)
First Stage
Plug Flow
Reactor
Second Stage
Back Mixed
Reactor
Chemical hydrolysis of cellulose to LA
Fast Reaction
(Seconds)
Slow Reaction
(Minutes)
Tars (30 wt%)
Formic Acid (20 wt %)
OCH2OHOHC
BIOREFINERY YIELDS
TYPICAL MOLAR YIELDS
(OF THEORETICAL)
TYPICAL MASS YIELDS
(PER TONNE OF FEED)
LEVULINIC ACID
FORMIC ACID
FURFURAL
LIGNEOUS CHAR
70%
70%
70%
100% (MASS)
0.25
0.10
0.15 (VARIES)
0.45
50% Cellulose
30% Hemicellulose
20% Lignin
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