Presentation of Richard Murphy for the Workshop on Hydrolysis Route for Cellulosic Ethanol from Sugarcane. Apresentação de Richard Murphy realizada no "Workshop on Hydrolysis Route for Cellulosic Ethanol from Sugarcane" Date / Data : February 10 - 11th 2009/ 10 e 11 de fevereiro de 2009 Place / Local: Unicamp, Campinas, Brazil Event Website / Website do evento: http://www.bioetanol.org.br/workshop1

1. Biofuels and biomaterial
research in the Porter Alliance
Dr Richard Murphy
Imperial College London
Commercial in confidence – Imperial College London 2008

2. Structure
• Introduction to the Porter Alliance
• Biomass yield
• Biomass ‘quality’
• Sustainability and policy
• Closing remarks
Commercial in confidence – Imperial College London 2008

3. The alliance
with colleagues at Southampton University,
York University and University of Cambridge
Over 130 scientists, engineers,
economists and policy experts.

4. Mission
Devise economically, socially and
environmentally sustainable routes to the
production of energy and materials from
plants with a positive impact on climate
change and energy security.

5. Challenges
• Increase biomass yields
• Reduce threats to and from biomass
• Increase processable biomass
• Create optimised processing
• Create flexible, modular biorefining
• Create integrated delivery pipelines

6. The integrated biorefinery
Ragauskas et
al. Science 311
(2006)

7. Backing ligno-cellulosics
• 80% of biomass is in lignin and cellulose
• Perennial crops have low inputs and can
support higher levels of biodiversity
• If we could get at the sugar locked up in
cellulose, the current world motor fuel
energy consumption (1020 J/yr) might be
met from 125 M ha (10% of global arable
land)

8. The integrated biorefinery
Chain
Photosynthetic
Solar radiation Efficiency Useful energy
Efficiency
100 Wm-2 ~ (25%) 0.25 Wm-2
~ (1 %)
Scope for 2-fold Scope for 3-fold
Improvement improvement
Dunnett and Overall: scope for 6-fold improvement!
Shah J.
Biobased
Mater. Bio. 1
(2007)

9. Consider the whole process chain
BM 1
FEP 1 SC 1
BM 2 PC 1
FEP 2 SC 2
BM 3 PC 2
FEP 3 SC 3
BM 4 PC 3
FEP 4 SC 4
BM 5 PC 4
FEP 5 SC 5
BM 6
LEARNING
Biomass Front-end Primary Secondary
Classes Processes Conversions Conversions

10. Costs will improve with R&D and
commercialisation
From: The Royal Society report - Sustainable biofuels 2008

11. The essential messages
• There is a lot of headroom to make truly
sustainable lignocellulosic biofuel
• You must look at integrated processes to
achieve this
• We need to generate knowledge that will
guide us in choosing the best processes

12. Why the optimism ?
1. Tractable R&D challenges and
opportunities
2. Significant reductions in GHG emissions
are possible
3. Assuring sustainable land use
4. Many countries/regions can participate

13. Structure
• Introduction to the Porter Alliance
• Biomass yield
• Biomass ‘quality’
• Sustainability and policy
• Closing remarks

14. Biofuel crops and biomass sources
are diverse
Recognized interest
Wheat (grain and straw) Willows (SRC)
Oil seed Rape Poplars (SRC)
Sugar Beet Miscanthus
Sugar cane Biomass forestry
Sweet sorghum
Cassava Forestry/ processing residues
Jatropha Post-consumer ‘waste’ biomass
Future potential
Bamboo Coconut Algae
‘Novel’ (previously uncultivated) species

15. Approaches to achieving
higher yields
Development pipeline for biofuel crops
Increase yield Combat risks & limits
• Growth & architecture • Marginal land
• Duration of production • Resources
• Selection & breeding • Climate change
• Novel crops • Pests
• Carbon capture • Diseases
Integrated with sustainability and processing knowledge

16. Generating more mass –
Willow as an example
Realistic UK target
Angela Karp

17. Accelerating biomass yield in
Willow
VIc
0.0 Ea taM aa g2 4
5.1 MAX1
MnHt03LARS
MxDia03LARS
MnHt05RRes
MxDia06LARS
1 8.9 MAX4
2 4.3 W 11 47
2 4.4 W 98 8
Many thin stems Fewer thick stems 4 3.4 fEa c tM a ac 1 0 4
5 0.5 VI_ 5c
5 8.4 fEa tc M a at_ 20 9
The more axillary branching (max) mutants in
Arabidopsis have altered branching. Corresponding
genes map to yield QTL in willow.

18. Unique well established germplasm collections
1,300 accessions of willow (incl. 100 pure species) at Rothamsted Research
500 diverse poplars capturing wide natural diversity
Extensive
perennial grass
collections
including
800 accessions
of Miscanthus @
Rothamsted and
IBERS

19. Yield projections and modelling
Example data on poplar locations/yield - TSEC-Biosys Project
from:- Matt Ayott, Gail Taylor
Southampton University
Productivity map of Populus EC FP7 Project
trichocarpa genotype ‘trichobel’,
second rotation

20. Model plants & systems biology
Arabidopsis Targets for QTL
genomics Knowledge base
Poplar proteomics
Gene
discovery
metabolomics Data integration
Maize
high resolution Prediction tools
sampling
Targets for
Brachypodium molecular breeding

21. New leads for improving
biomass yield
knockout
Thorsten Hamann
knockout wT wT
The mutated gene is implicated The mutated gene
in response to pathogen infection encodes a UDP
glycosyl transferase

22. Structure
• Introduction to the Porter Alliance
• Biomass yield
• Biomass ‘quality’ and conversion
• Sustainability and policy
• Closing remarks

23. More quantity is only part of the solution
 Increased and sustainable yield
• Optimise cell wall composition
– Systems biology approach
– High throughput analytics
– Regulating cell wall phenolics
– Self-processing plants ?
Increased and sustainable yield + optimised processability

24. and… big does not necessarily
mean sweet
with Rothamsted Research
Nick Brereton
Total Glucose Yield (g) / Oven Dry Weight (g)
- enzymatic hydrolysis, no pre-treatment
25.00%
20.00%
15.00%
10.00%
5.00%
An example in Willows 0.00%
Miscanthus 7 month Tora 2yr old Bowles Hybrid 3yr old
old
Bowles hybrid releases its glucan
High Biomass Medium Biomass
much more readily than other Yielding Willow Yielding Willow
varieties, even though it does not
produce the greatest mass

25. Willows contd.
Natural variation is large in saccharification and ethanol potential yield.
0 Ethanol ltr ha-1 without Pretreatment
J 1
orr
0 NOTE:
No pre-treatment,
Calculated ethanol yield
J 9
orr
0
the ‘inherent’
0
Bowles Hybrid enzymatic sugar
release is being
0
investigated here
0
0
Willow genotype

26. Miscanthus giganteus
a b
July to
December
c d
e f
During its annual growth there are large
developmental changes in Miscanthus .
How do these relate to saccharification ?
g h
by Muhammad Umer Ijaz PhD student,
with Rothamsted Research
Pl

27. Miscanthus giganteus contd.
Also:-
• variation
with internode
• fluctuation in
Starch content
Saccharification potential (no pre-treatment) changes substantially over the
development cycle
Harvesting time influences ease of enzymatic hydrolysis
Harvesting time is dictated by many constraints

28. Microbes that release sugar
from cell walls – pre-treatment
with
Mike Ray, Porter
Institute Research Fellow
and David Leak
and Pietro Spanu
We use fungi that
depolymerise the wood
cell wall

29. Microbial pre-treatment contd.
from pine sapwood
• Up to 70% of glucan becomes
available for enzymatic hydrolysis
• Ferments to ethanol without
inhibition
• No harmful waste streams
• Low energy inputs
• Little GHG emission

30. Experimental issues – Particle size
Effect of particle size on glucose yield
45
Glucose yield/ % ODW
40
35 >2000 µM
30 850-2000 µM
25
420-850 µM
20
15 250-420 µM
10
180-250 µM
5
0 100-180 µM
with Dr Mike Ray, Porter
Institute Research Fellow

31. Experimental – Enzymatic hydrolysis
• NREL recommends 96-168 hours
• Most papers promoting high-throughput
suggest 24 hours as sufficient
with Dr Mike Ray, Porter
Institute Research Fellow

32. Experimental – Enzymatic hydrolysis
Effect of incubation time on sugar yield
25
Glucose yield/ % ODW
20 Pine
Spruce
15
Willow O
10
96 144 168
5 72
6 24
0 1
0 50 100 150
Time/ hours with Dr Mike Ray, Porter
Institute Research Fellow

33. Structure
• Introduction to the Porter Alliance
• Biomass yield
• Biomass ‘quality’
• Sustainability and policy
• Closing remarks

34. Positively influencing GHG
and soil carbon balances
Understanding ‘Direct’ & ‘Indirect Effects’
– Read (2007)
Not all land use
– Searchinger et al + Fargione et al (2008)
change has to be
– Galbraith (2005)
‘negative’
from Dr Jem Woods, Porter Institute

35. Land availability
Country Population Total Land Arable land Land Considered Suitable % Suitable % of
for Crop Growth suitable
used
(2001-2005) - no - with
constraints - constraints -
2005
(people) (1000 ha) (1000 ha) (1000 ha) (1000 ha) (%) (%)
Brazil 186,831 853,363 58969 239,573 614,064 28% 25%
China 1,312,979 934,949 142265 178,228 756,722 19% 80%
India 1,134,403 306,140 159712 139,357 166,783 46% 115%
Southern Africa
Tanzania 38,478 93,819 9118 35,964 57,855 38% 25%
South Africa 47,939 122,300 14753 31,154 91,075 25% 47%
Mozambique 20,533 79,854 4270 48,043 31,811 60% 9%
Zambia 11,478 74,837 5260 22,304 52,533 30% 24%
Angola 16,095 123,776 3200 40,383 83,313 33% 8%
UK 60,245 24,418 5728 9,888 14,530 40% 58%
South East Asia
Indonesia 226,063 189,220 22600 79,444 109,776 42% 28%
Malaysia 25,653 33,300 1800 16,495 16,805 50% 11%
Total 3,080,697 2,835,976 427,675 840,833 1,995,267 30% 51%
World 6,515,000 12,976,000 3,500,000
from Dr Jem Woods, Porter Institute

36. Use of LCA in Porter Alliance Biofuels
R&D
Sustainability and life
Sustainability and life
cycle analysis
cycle analysis
Fungi
Fungi Butanologenic
Butanologenic
• Complexity of R&D
Rumen microbes
Rumen microbes
recombinant
recombinant
bacteria
bacteria opportunities and
Miscanthus
Miscanthus
Willow
Willow
Ionic liquids
Ionic liquids Long chain alkane //
Long chain alkane
alkanol producing
alkanol producing
possibilities – use process
Switchgrass
Switchgrass
Developmental front
Developmental front
end processes
end processes
organisms
organisms
systems engineering and
Poplar
Poplar Direct fermentation
Direct fermentation
sustainability modelling
Dilute acid // alkaline
Dilute acid alkaline of oligosaccharides
of oligosaccharides
Sugar cane bagasse
Sugar cane bagasse
Forest residues
Forest residues
Mild thermal
Mild thermal Developmental
Developmental
microbial
microbial
• LCA (+ other tools) to
find the most
Hydrothermal
Hydrothermal ethanologens
ethanologens
Crop residues
Crop residues
Steam
Steam
Thermochemical
Thermochemical
Proprietary
Proprietary
microbial
microbial
ethanologens
ethanologens
environmentally
sustainable routes
ENERGY CROPS
ENERGY CROPS FRONT END
FRONT END PRIMARY
PRIMARY
PROCESSES
PROCESSES CONVERSION
CONVERSION
Optimising yield
Optimising yield
Optimising
Optimising Optimising
Optimising
accessible carbon
accessible carbon conversion to
conversion to
biofuel
biofuel

37. Uses of LCA in policy – UK RTFO
• The UK Renewable Transport Fuels Obligation
(RTFO) provides a mechanism to support the
use of sustainable biofuels in the UK market
• It assesses greenhouse gas emissions and other
sustainability-linked criteria in an LCA context
• The first Quarterly Report on this by the
Renewable Fuels Agency was published in
October 2008
see http://www.renewablefuelsagency.org/

38. Supply chains and boundaries in the UK RTFO
process
Alternative Assessed ex post by
land use RTFO Administrator
Boundary for monthly
Previous Cultivation & carbon intensity calculation
land use harvest
Feedstock Biofuel Biofuel
Biofuel use
transport production transport
Waste
material
Excludes minor sources, from:
Alternative • Manufacture of machinery or
waste equipment
management • PFCs, HFCs, SF6
Assessed separately
Fossil fuel reference system
E4TECH, 2007

39. UK RTFO 1st quarterly report
• Biodiesel dominates Data here are for whole blended fuel
• Major biodiesel suppliers USA, UK &
Germany
• Major bioethanol suppliers Brazil, UK
Note: data is for obligation year to date based on submitted monthly returns to the
RFA. Final audit of this data occurs annually and revisions to the data may occur
at any point up to that time. RFA will publish a comprehensive end of year dataset

40. UK RTFO 1st quarterly report
The methodology is indicating differential savings in GHGs –
this is expected on the basis of LCA studies
Note: data is for obligation year to date based on submitted monthly returns to the
RFA. Final audit of this data occurs annually and revisions to the data may occur
at any point up to that time. RFA will publish a comprehensive end of year dataset

41. UK RTFO 1st quarterly report
Overall GHG savings were 44% vs a target of 40%
Note: data is for obligation year to date based on submitted monthly returns to the
RFA. Final audit of this data occurs annually and revisions to the data may occur
at any point up to that time. RFA will publish a comprehensive end of year dataset

42. UK RTFO 1st quarterly report
A ‘qualifying environmental standard’ is an existing certification scheme
that meets an acceptable number of the seven RTFO sustainability
principles (fuels from ‘wastes’ automatically comply)
Note: data is for obligation year to date based on submitted monthly returns to the
RFA. Final audit of this data occurs annually and revisions to the data may occur
at any point up to that time. RFA will publish a comprehensive end of year dataset

43. Structure
• Introduction to the Porter Alliance
• Biomass yield
• Biomass ‘quality’
• Sustainability and policy
• Closing remarks

44. We also regard Integration as
essential to progress
Platform tools &
Unique resources Systems Biology technologies
Sustainability
Processing
Bio energy crops Knowledge base evaluation
Integrated Biofuels
Refinery
Optimised bioenergy
crops

45. Integration – people, interests,
skills, challenges

46. Thank you - see more of us at
• www.porteralliance.org.uk