Advanced biofuels: an overview

Rob Bakker Projectleader Biofuels

Wageningen UR�Biobased products

robert.bakker@wur.nl

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)