Advanced biofuels: an overview Rob Bakker Projectleader Biofuels Wageningen URBiobased products [email protected] Overview lecture 2 nd generation biofuels Developments Technology Case study Questions Gasoline/E85 pump
Advanced biofuels: an overview
Rob Bakker Projectleader Biofuels
Wageningen UR�Biobased products
Overview lecture
� 2nd generation biofuels
� Developments
� Technology
� Case study
� Questions
Gasoline/E85 pump
Biofuels: characteristics
� Current technology (“1st generation”)� Production at large scale
� Limitations:• “Food vs. fuel”
• Productioncosts of biofuels are high in comparison with fuels of fossil origin (exception: sugar cane ethanol)
• Limited potential for greenhouse gas reduction
� Advanced biofuels (“2nd generation”)� Not yet implemented on industrial/commercial scale
� Capital intensive
� Need Economies of scale
First versus second generation biofuelsCurrent biofuels Advanced biofuels
FeedstocksSugar cane, wheat, corn, barley, sugarbeet Lignocellulosic biomass
Ethanol by fermentation of starch or sugars (sugar beet, sugar cane)
Ethanol or butanol by fermentation of sugars derived from cellulose and hemicellulose hydrolysis (lignocellulosic biomass)
Biodiesel derived by transesterification of plant oils; FAME MethanolBiodiesel derived from waste fats Fischer-Tropsch gasoline and dieselPure plant oils; SVO Dimethyl-ether; DME
Land-use efficiency Low (exception: ethanol from sugar cane) High
Industrial implementation Proven at commercial scale Pilot-plant scale
Capital investment needed per unit of production Lower Higher
Feedstock cost per unit of production High Low
Potential for replacing fossil fuels
Modest (exception: ethanol from sugar cane) High
Potential for reducing greenhouse gas emissions
Modest (exception: ethanol from sugar cane) High
Main fuels
2nd Generation?
� No clear definition for 2nd generation Biofuels
� Current definitions based on:
� Type of feedstock (raw material) used
� Type of conversion technology used
� Sustainability, no competition with food production etc.
� In general, 2nd generation biofuels:
� Can be produced out of a larger diversity of feedstocks and at lower cost;
� Will lead to higher Carbon benefits/Greenhouse gas emissions reduction
� Will lead to a diversity of fuels, and other (bio�based) products
� Will lead to less competition with food production
Yield of biofuel per ha of land
Bron: Unctad, 2008
Pathways for production of biofuels
Source: Unctad, 2008
In Red: first generation; In black: 2nd generation
Advanced Biofuels
� On endproduct:� Gasoline replacement fuels
� Diesel replacement fuels
� LPG vervangers
� On process:� Thermochemical: cracking, gasification, hydrothermal
� Biochemical: enzymatic, fermentation
� Combinaties thereof
� Op feedstock:� Lignocellulose, algae, waste streams, et.c
Overview advanced Biofuels
oils/fats cellulose / hemicellulose lignine starchprotein minerals
biodiesel ‘green diesel’ dimethylether (DME) ethanol, butanol
methanol
Esterification‘hydro-treating’
Gasification toto ‘syngas’
Fischer-Tropschsynthesis
Pre-
treatment
fermentation
sugars
hydrolysis
‘lignocellulose’
= conventional (‘1ste generation’)
pyrolysis
refinery
Diesel-replacements Gasoline-replacements
BIOMASS
FAME
Hydro-carbons
‘bio-oil’
Bioethanol from lignocellulose
Lignocellulosicbiomass
Enzymatic hydrolysis
Physical & chemical pretreatment
Fermentation
lignin
Combustionin
CHP
Heat back to processes (fermentation, destillation, etc)
Electricity to process and the grid
Minerals (ashes): building mateiral, fertilizer ?
SugarsEthanol99,7 vol%
enzymes
DestillationDehydration
Pretreatment of lignocellulose
Bron: Michael R. Ladisch, Nathan Mosier, Gary Welch, Bruce Dien, Andy Aden, Phil Shane, Purdue University
What is lignocellulose?
� All plant materials containing fibrous material e.g.
� Hardwood, softwood, grasses, straw, bagasse, leaves, etc.
� Lignocellulose = source of fermentable sugars and renewable energy
� cellulose: polymer of glucose
� hemi�cellulose: polymers of xylose and other sugars
� lignin: source of process heat and electricity
� minerals: fertilization, building materials
� Key: Lignocellulosic Biomass needs to undergo more intensive processing to release fermentable sugars for fermentation
Fibres in straw (1000X)
Ethanol from lignocellulose
� Challenges
� Development of cost�effective enzymes and robust microorganisms
� Process�integration; factory design
� Current production costs are not yet competitive
� Future: to 400 L ethanol per ton biomass
� Developments
� In various stages of development; pilot plants; demonstration plants
When will 2nd generation biofuels come on the market?
� Industry is taking more and more initiatives for pilot plants.
� 2012 seems when several industries will go for full�scale or demonstration scale upscaling.
� “Despite significant unknowns the assumed share of the contribution is assumed to be 30% of domestic needs by 2020.” (DG AGRI, 2007)
Ethanol�lignocellulose: developments
Sources:www.sekab.se; Abengoa,
www.iogen.ca
Sekab, Zweden
Abengoa, Spanje
Iogen, Canada
Inbicon 1,5 MGYStrawOperational
TMO 1 MGYDDGS/Wheat strawOperational
Royal Nedalco
Imecal 0,2 MGYMSW, operational
SEKAB 0,04 MGYWood, bagasseOperational
Futurol/Procethol 5 MGY
M&G 0,1 MGYOperationalM&G 12 MGY (FP7)
DesmetBallestra 0,2 MGYOperational
Abengoa Salamanca 1,4 MGYWheat straw Completed 2009 Lacq, France
ST1 Biofuels Oy (small demo)Food waste
Operational
Linde AG + Süd Chemie (Pilot) Straw
Operational
Biogasol 1,3 MGY
Ethanol uit lignocellulose projecten in EU
Bron: PGG; 2010
Advanced Biofuels: demarcation
� Ethanol from lignocellulose
� Butanol
� Biomass�to�Liquids (BtL)
� Pyrolysis, HTU
� Others:� Jatropha
� Hydrogenation of fats and oils
Ethanol fermentor
Butanol
� Butanol: � Higher energy content in comparison with ethanol
� Better properties for blending with fossil fuels
� Challenges:� Improving productivity of the fermentation
� Separation of end�products
� Use of lignocellulose as raw material
� Developments:� Commercial productionplants in Brazil, China on basis of
sugar/starch feedstocks
� Current Production of butanol for use as platformchemical (no use of biofuel, as yet)
Biomass�to�Liquids (BtL)
� Production on basis of gasification of biomass
� More flexibility in feedstocks
� Larger diversity in endproducts; e.g. Fischer�Tropsch diesel, DME, alcohols
� Production needs dry biomass; large scale production
Gasification Fischer-Tropsch Synthesis
wood(Biomass)
1 tonwood
~260 LFT waxbiosyngas
electricity from off-gas
~210 Lgreen diesel
lightFT pro duct
Source: ECN
BtL: developments
� Challenges� Cleaning of syngas from biomass; feeding of biomass to
entrained�flow gasifiers
� Biomass supply for very large scale (> 650 MW) plants
� Syngas fermentation (ethanol, ABE)
� Developments:� Current FT production on basis of natural gas/ coal
• E.g. Qatar, Nigeria, Colombia, Malaysia, China
� Co�gasification coal with biomass for production of conditionen syngas as feed for conventional FT�technology (large scale)
� Choren: Freiburg demonstration plant (15 kton/j)
BtL: developments
� Voorbeeld pilot plant Choren
Bron: www.choren.de
Pyrolysis, HTU
� Process� Heating up biomass without supply of oxygen
� Production of pyrolysis�oil or Biocrude from lignocellulose
� Both products could be used by a conventional refinery
� Challenges� Modification of process for various biomass types
� Yield of Oil per ton of biomass; Oil quality
� Developments� Production of pyrolysis�oil/Biocrude from biomassa at
pilot�scale
� Production of transportation fuels from pyrolysis oil/Biocrude potentially via hydrogenation
Other biofuel production routes
� Jatropha� Biofuelproduction on basis of new feedstock
� R&D is focused on agronomy, improvement of oil extraction, beneficial use of byproducts (presscake)
� Conversion can be done on relatively small scale
� Hydrogenation of fats and oils (Neste Oil)� Feedstocks: plant oils, (waste) fats
� Investments in Rotterdam, Singapore
� Future: only use of non�edible fats and oils
� Algae
Potential in relation to status technology
� Lignocellulosic ethanol� Pilotplant stage; demonstration plants in development
� Butanol� Production on basis of 1st generation: industrial scale
� Production on basis of lignocellulose: R&D stage
� BtL, other syngas routes� Pilotplant stadium; demo plants in development
� Pyrolyse�HTU� Conversion to Pyrolysisoil/Biocrude: Pilotplant and demo plant
� “ “ Biocrude to transportfuel: R&D stage
� Other source:� Jatropha: demonstration scale
� Hydrogenation of fats/oils: commercial scale
Source: Galagher review, 2008
Potential advanced biofuels for the EU
� 2nd generation can reduce requirement for land for biofuelproduction considerably
� Estimates: reduction of 30 M ha to less than 15 M ha (at 10% blending of biofuels in fossils)
� Speed of implementation partly dependent on investments in R&D, and capital investments in new processes
� Future: biorefinery of biomass: integrated production of chemicals, biofuels and energy
Future: integrated Biorefinery
� BioSynergy
� Production of chemicals, bioethanol and secondary energcarriers on basis of lignocellulosic�ethanol productionplant
Source: Reith et al, 2008; Kamm & Kamm, 2006
www.biosynergy.eu
Cellulose‘biotech./chemical’
Fuels,Chemicals,
Polymers andMaterials
LigninRaw material
Hemicelluloses(Polyoses)
‘biotech./chemical’
Lignin‘chemical’
LignocellulosesLignocellulosic
Feedstock (LCF)
Sugar Raw material
CogenerationHeat and Power,
Extract ives
Residues
Residues
Biosynergy movie
� http://www.surfmedia.nl/app/video/CYU8QEQcouScg1ZQdC4NHIAf/play?format_id=YfWDa76yPNija3wcDHJI1wsQ&mode=object
Biosynergy presentation on pretreatment
� http://www.biosynergy.eu/publications/biosynergy�workshop�ecbe/
Potential of 2nd generation for the Netherlands
� Ports (Rotterdam, Amsterdam, Delfzijl)
� Well�developed supply routes
� Availability of process heat from surrounding industry
� Biofuel industry is growing
� By� and coproducts
� Food� and agri industry
� “Biomass from nature”: many cellulosic biomass not used
� Primary production of biomass
� Integration of bioethanol�biogas�beneficial CO2 use
New products/chemicals from lignocellulose
Product Substrate Microorganism
Ethanol Lignocellulose Saccharomyces cerevisiae
Lactic Lignocellulose Rhizopus oryzae
Acid
Butanol Lignocellulose Clostridium beijerinckii
Hydrogen Lignocellulose Caldicellulosiruptor saccharolyticus
Objectives of pretreatment research at WUR
� Study effects of physical/chemical pretreatment on lignocellulosic biomass
� Variety of feedstocks
� Evaluate degradability and fermentability of alkaline�pretreated biomass substrates
� Variety of end�products: ethanol, hydrogen, lactic acid, butanol/ABE
� Integrate pretreatment with enzymatic and fermentative processes
Case: Bioethanol from lignocellulose
� “Co�productie van hernieuwbare transportbrandstoffen, groene chemicalien, electriciteit en warmte uit biomassa(rest)stromen”
� EET programme
� 2002�2006
� Participants� Private sector: Nedalco, Purac, Shell
� Institutes: A&F, ECN, TNO
� University: Wageningen U
Stro�oogst voor EET K01116
Food & Bioprocess Engineering
Key technologies needed for industrial implementation
� Pretreatment
� Make cellulose + hemicellulose fractions (more) accessible for enzymatic hydrolysis
� Enzymatic hydrolysis
� Cost effectieve use of enzymes in the process
� Fermentation
� Improve fermentation kinetics
� Conversion of all sugars (C5 and C6) during fermentation
� System integration
Example: Alkaline pretreatment of lignocellulose
� Goal: Study the effect of alkaline pretreatment on:
� Structural components of biomass
� Enzymatic degradability
� Fermentation inhibitor formation
� Ethanol fermentationWheat straw harvest ( NE Netherlands)
Methods (pretreatment)
� Feedstock
� Wheat straw
� Pretreatment
� Bench�scale, pilot�scale
� 85°C; atmospheric pressure
� varying alkali: biomass ratio
� 10 � 20% solids loading
� Enzymatic hydrolysis� lab�scale and bench�scale
� commercially available enzymesPulp reactor used for alkaline pretreatment
Movie on lignocellulosic biomass pretreatment
� DVD
Bench�scale fermentation with on�line CO2 monitoring
Methods (fermentation)
� Fermentation� fermentation following
hydrolysis
� Saccharomyces cerevisiae
� 37°C
� not�buffered
� CO2 monitoring
Results: lime pretreatment
Arabinan
Xylan
Mannan
Galactan
Glucan
Lignin
Ash Arabinan
Xylan
Mannan
Galactan
Glucan
Lignin
Ash
Wheat straw, untreated Lime�pretreated wheat straw
Effect of alkaline pretreatment on enzymatic
degradability
0
20
40
60
80
100
0 0,075 0,1 0,15
Ca(OH)2 (g/g dm straw)
Xyl
an a
nd g
luca
n co
nver
sion
(%
)
0
10
20
30
40
50
60
Tot
al c
onve
rsio
n (%
)A
0
20
40
60
80
100
0 0,075 0,1 0,15
Ca(OH)2 (g/g dm straw)
Xyl
an a
nd g
luca
n co
nver
sion
(%
)
0
10
20
30
40
50
60
Tot
al c
onve
rsio
n (%
)B
Figure 1. Effect of Ca(OH)2 loading rate (g/g dm straw) on enzymatic hydrolysis of xylan to xylose (▨)
and glucan to glucose (□) in lime pretreated wheat straw (washed insoluble fraction). Enzyme loading rate was 116 IFPU/g dm for GC220 (A) and 56 IFPU/g dm for Cellubrix (B)
Source: Bakker et al, 2007
Effect of pretreatment on ethanol fermentation
0
100
200
300
400
500
0 100 200 300Time (min)
CO
2 pr
oduc
tion
(ml)
A
pH 4
pH 5
pH 4.5
Production of CO2 (as equimolar of ethanol) during fermentation of lime�pretreated wheat straw by S. cerevisiae at 32°C and pH 4, 4.5 and 5.
Source: Bakker et al, 2007
Operational challenges (bench�scale hydrolysis)
Reactor during enzymatic hydrolysis at t = 0, 0.5, 2 and 24 h after adding enzymes
t = 0 h t = 0.5 h
t = 2.0h t = 24h
SSF�ethanol
T = 85°C
pH 10
T = 50°C
pH 5.0
T 32°C
pH 3.5 � 5
Wheat strawMechanicaltreatment
Limetreatment
Enzymatic treatment
Fermentation Ethanol
T = 85°C
pH 10
T = 37°C
pH 4.5�5.0
Wheat straw Mechanicaltreatment
Limetreatment
Enzymatic treatment
Fermentation Ethanol
Simultaneous Saccharification and Fermentation (SSF)
Separate Hydrolysis and Fermentation
Why SSF ?
Separate Hydrolysis and Fermentation
Simultaneous Saccharification and Fermentation (SSF)
+ • Optimal reaction conditions
• No product inhibition
• One reactor required
• No sugar inhibition
• Lower risk contamination
� • Two reactors required
• Sugar inhibition
• Risk for contamination
• Sub�optimal reaction conditions
• Substrate viscosity
Upscaling�100L
Capital charge33%
Glucose (Enzymes)
10%
Water treatment1%
Chemicals4%
Maintenance15%
Labour costs2%
Other10%
Straw25%
Bioethanol: prospective production cost
High Capital Charges:0.18 Euro/litreEthanol
Glucose for enzyme production: 0.05 Euro/litreEthanol
Straw feedstock Costs: 0.14 Euro/litreEthanol
Total Production Costs: ~ 0.52 Euro/litreEthanol (IRR 3.3%)Minimum selling price (IRR 15%) ~ 0.75 Euro/litreEthanol
Net electricity revenue (0,04 Euro/L Ethanol) subtracted
Current R&D
High solids processing
Extrusion
Refining
� Technology development
� Mild�temperature techniques; enzymatic hydrolysis
� Pretreatment with organic acids (in place of H2SO4)
� Small�scale processing/pretreatment routes for wet biomass; high solids; continuous
� Validation of pretreatment routes
� Integration of pretreatment with fermentation
� ABE, bioHydrogen, lactic acid, etc.
� Characterisation of lignocellulosic biomass
� Effect of pretreatment of structural components
Hydrogen
C. saccharolyticus growing
on sucrose
PEM fuel cell
Electricity from fermentation
HYVOLUTION movie (DVD)
HYVOLUTION
1 jan 2006 � 1 jan 2011
11 EU countries, Turkey, Russia and South Africa
Universities, research institutes & industries
Budget: 14 MEuro
EU grant: 10 Meuro
www.hyvolution.nl
Development of a 2�stage bioprocess and construction of prototype modules
Example 2: NaOH pretreatment of Miscanthus
� NaOH pretreatment
� Feedstock: Miscanthus
� Pretreatment followed by washing to remove lignin
� Enzymatic digestibility tests
� Hydrogen fermentation tests
Miscanthus
Enzymatic hydrolysis pretreated Miscanthus
t = 0 h t = 24 h
Optimization of NaOH pretreatment
Potato steam peels as bioresidue
� Starch�rich feedstock
� Hydrolysates made by enzymatic treatment (amylase and glucoamylase)
� >95% mobilisation efficiency
Trends in technology development:
� Improvements in 1st generation technology� O.a. optimalisatie gebruik van co�producten (DDGS, CO2)
� Further development and implementation of 2nd generation biofuel technology
� Integration of ethanol production with other forms of bioenergy� E.g. production of biogas, heat, electricity from non�fermentable residues
� Biorefinery� Integration of ethanolproduction in biorefinery
Stimulating measures Advanced Biofuels
� Excise tax exemption
� Investment subsidies for new facilities
� Netherlands: double counting
� Using waste, residues, and lignocellulose will count double towards mandatory blending percentage
� Schatting: fraction of advanced biofuels in total biofuels in 2020 = 1/3 of total biofuelproduction� Land use for biofuel production can thereby by
significantly reduced
� Future: biorefinery of biomass: integrated producion of chemicals, biofuels and energy
Looking to the future…
Questions? Comments?
© Wageningen UR
Carbonbalance consists of 3 parts:1. Greenhousegas balance of the
production (field up to utilisation)
2. Greenhouse effect of direct land use changes (what crops were replaced?)
3. Indirect landuse change
JRC, 2006. Availability and Cost of Biomass for Road Fuels in EU
D =
Carbon Debt
A x B/100
C
� A = ‘carbon debt’by LUC
� B = biofuel share(compared toco�products)
� C = annual CO2
repayment
� D = time to repaycarbon debt
Fargione et al., 2008
This methodology emphasizes the effect of indirect land use change
Indirect effects on land use Brazil
Cerrado
Amazon
Wood/CharcoalGrassland
Soybean
Sugarcaneloss 30 – 110 Mg C.ha–1
loss 10 – 50 Mg C.ha–1
loss 200 – 300 Mg C.ha–1
Avoided emissions: 2–2.7 Mg C.ha–1 y �1 =10 Mg CO2
15 (Cerrado) � 100 (Amazon) years to make up for losses(sugarcane)
Bindraban et at., 2008
Example: sugarcane to ethanol 1st and 2nd generation
� 1st generatie improvement: Cane Yield from77 (2007) to 100 ton per ha (2020): � Ethanol yield from 6.545 (2007) to 8.500 liter
(2020) per ha
� Bagasse is underutilisated and – “Trash” is not used�burnt in the field
� 2nd generation technology. Use of Bagasse and Trash� Ethanol yield from 8.500 naar 17.500 liter ethanol
per ha
� Per ha 2,6 x more ethanol in 2020� This can save 25 tons of CO2 per ha per year
� “Carbon debt” is payed off 6.5 times faster (6,5 y)