Presentation of Henrique M. Baudel for the Workshop on Hydrolysis Route for Cellulosic Ethanol from Sugarcane. Apresentação de Henrique M. Baudel 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. Catalytic Processes Laboratories
Biomass Conversion Group
UFPE
Development of hydrolysis route
for cellulosic ethanol
from sugarcane biomass
Henrique M. Baudel

2. ACKNOWLEDGEMENTS
- MCT, CNPq, CAPES, FINEP, FACEPE (Brazil)
STINT (Sweden), EULA-ALFA (European community), MES (Cuba)
- Cesar Abreu, Mario T. Kato, A.M.Souto-Maior (UFPE)
- Guido Zacchi, Gunnar Lidén, Bärbel Hahn-Hagerdal, Mats Galbe
Marie Linde; P. Sassner; C. Roslander (Lund University, Sweden)
- Silvia Nebra (NIPE/UNICAMP; FINEP-BIOETANOL)
- Claudio Z.Zaror, Oscar Parra (Univ. de Concepción, Chile)
- Carlos Martín (UMCC, Cuba)
- George J.M. Rocha, Adilson Gonçalves (EEL/USP)
- Aldo J.P. Dillon; M.Camassola (UCS); Alexandra Salgueiro (UNICAP)
- C. E. Vaz Rossel (CTBE), Luiz P. Ramos (UFPR), E.M.P. Bon (UFRJ)
- CTC colleagues and associates
- Students: J. Augusto Tomé, Isaías B. Soares, M.R. Tavares (UFPE)
Khalil Bensalem, Benjamin Bois (Univ. Lyon, France)
J. Sendelius, Cristhian Carrasco (Lund University, Sweden)
- Benjamin Knudsen, E.M. Bordin, Frank Haagensen (Novozymes)
- Carlos F. Chagas (Bioenzima); Antenor Dvorak (REGMED)

3. Frequently Asked Questions (FAQ)
• Why to produce Ethanol from Cane Biomass ?
• Fuel or Chemical Ethanol ?
• Holocellulosic or Cellulosic Ethanol ?
• Chemical or Enzymatic Processes ?

4. Why to produce Ethanol from Cane Biomass ?
• Cellulosic Ethanol Claimed by the Market
• Urged Profitable Eco-Friendly Depletion of Surplus Biomass
Ethanol from Surplus Cane Biomass = Opportunity
Possibilities
- more product (ethanol) using the same feedstock (sugarcane)
- complimentary with current plant activities
- getting best using (as much as possible) AMAP conventional technologies
- simpler process configuration
- easy and fast to implement (turn key)
- no major environmental issues
No competition
- profitable, low investment with food!
- self-sufficiency on energy

5. Bagasse or Straw?
Preliminary Issues
• Bagasse more suitable to burn ?
• Straw less recalcitrant to hydrolysis ?
• Bagasse available in-house
• Straw to be collected and transported ?
• Bagasse naturally comminuted
• Straw to be milled ?

6. Holocellulosic or Cellulosic Ethanol ?
1985 2000 2005 2015 ?
Chemical
Cellulosic ??????
Bagasse Straw
Chemical or Enzymatic
Enzymatic Bagasse Straw
Processes ? Cellulosic Holocellulosic
Once made feasible, Thermo-Chemical
enzymatic will be Thermo-Biochemical ??????
unrivalled in the
medium-long term!
Fuel or Chemical Ethanol ? BOTH!

7. Cellulosic Ethanol from Sugarcane Biomass
Enzymatic Hydrolysis of Bagasse

8. Feedstock Sugar Ethanol
Production Production Production
Preparation Saccharification Fermentation
and
Pretreatment Hydrolysis Purification
Residue Processing

9. Industrial R&D approach
Pretreatment
Feedstock Hydrolysis
Economic
Assessment
Residue
Processing Fermentation
per ton dry biomass
Litres of Ethanol per ton cane
per hectare

10. A Practical and Pragmatic Approach
Integration with existing 1st Generation Ethanol plants
- Capital cost, energy efficiency, emissions, transportation costs
Molasses boosting / Mixing with dilute hydrolysates
- No concentration required = energy savings / lower degradation
- Moderate cellulose conversions = cheaper enzyme cocktails
- Simpler fermentation
Combustion of the residual cellulignin / mixing with bagasse
- Use of existing boilers / steam generators
- Deliver of additional bagasse for ethanol production
- No recovery systems or conditioning required
Separate Hydrolysis and Fermentation (SHF)
- Simpler equipments and configurations = lower capital costs
- Use of existing fermentation equipments
- Processable solid LC residue = eco-efficiency
- Easy yeast recovery

11. Process Development Concept
Biomass
Pretreatment
Cellulosic
Slurry
Ethanol
Separation Prehydrolysate
LC Pulp
Enzymes Enzymatic cane juice /
Hydrolysis molasses
Slurry
Yeast
Hydrolysate C6 Recovery and
Separation Fermentation Distillation
LC Solid
Stillage Surplus
Surplus Biomass
Yeast
Burning
Treatment
and Disposal
Heat / Power

12. Process Development Concept
Biomass
Pretreatment
Cellulosic
Slurry
Ethanol
Separation Prehydrolysate
LC Pulp
Enzymes Enzymatic cane juice /
Hydrolysis molasses
Slurry
Attractive in the short-term.
Separation
Hydrolysate C6
Yeast
Recovery and
Fermentation Distillation
Competitive in the medium-term.
LC Solid
Best for the long-term ?
Surplus Biomass Stillage Surplus
Yeast
Burning
Treatment
and Disposal
Heat / Power

13. Pretreatment
• Do minor differences among feedstocks result in significant
differences performance?
• Washed or unwashed incoming biomass?
• Mill or Diffuser ?
• Single-step or two steps?
Over 1200 pretreatment runs performed at Lab/Bench,
PDU and Industrial scales during 2002-08!

14. Pretreatment
LAB / Bench Scale
PARR Batch Stirred 1-L Reactor POP Batch 1.5 L-Reactor
Acidic and Alkaline Pretreatments Acidic and Alkaline Pretreatments
(without explosion): (with/without explosion):
- Dilute Acid, (C)LHW - (C)WEX, Dilute acid,(C)LHW
- Lime / Soda ; (C)WAO, WPO - (L)AFEX, Lime / Soda ; WPO

15. Pretreatment
PDU Scale
Steam Explosion. Process Development Unit (PDU) Lund University, Sweden.

16. Pretreatment
PDU Scale
HB-21 polyvalent batch rotary
23-L reactor. REGMED, Brazil
- Dual-Chamber (1L and 20 L)
- Electrically Heated
- Gas Inlet (O2, CO2, NH3)
- Rapid Discharge Valve
- Adaptable to Cyclone / Flash Tank
Acidic and Alkaline Pretreatments
- Dilute Acid, (C)LHW, (C) WEX, (C)STEX
- Lime / Soda ; (C)WAO, WPO, AFEX

17. Pretreatment
Industrial Scale
2000 L batch reactor
Feeding system (O2, catalysts, NH3)
Controllable biomass loading
Controllable heating profile
Controllable pressure profile
Controllable discharge valve
Steam flow meter
Cyclone / flash tank
Polyvalent Steam Treatment Unit. CTC associate mills. Brazil.

18. Pretreatment
Similar bagasse compositions result in different PT performances.
100
86
82
80 75 74
Xylan
60 Glucan
43 43 Lignin
38 39
40 Others
Fiber reactivity
20
0
A B C D E F
Unwashed bagasse. 200ºC, 5 min, no catalyst.
24-h enzymatic hydrolysis, 2% WIS, pH 4.8, 15 FPU/g.
(The use of catalysts on STEX tends to reduce such differences)

19. Pretreatment
Bagasse originated from diffusers tends to be less recalcitrant than
the ones proceeding from mill/crushers, notably with uncatalysed
STEX (Steam Explosion) processes and rigid cane varieties.
Soft
100
Rigid
Holocelulose removal
90
80
70
C: Catalysed
C
NC
C
NC
C
NC
C
NC
C
NC
C
NC
C
NC
C
NC
C
NC
NC: Uncatalysed
(normalized)
M MD D M MD D M MD D M: Mill
D: Diffuser
180ºC 190ºC 200ºC MD: Mixed
Soft cane varieties are well processed in simpler equipments,
under milder operational conditions.

20. Pretreatment
Pre-washed bagasse tend to pretreat better, notably with
uncatalysed STEX (Steam Explosion) processes.
Pre-washed
Fiber Reactivity HC Removal Unwashed
100 100
85 85
70 70
55 55
40 40
180ºC 190ºC 200ºC 180ºC 190ºC 200ºC 180ºC 190ºC 200ºC 180ºC 190ºC 200ºC
Uncatalysed Catalysed Uncatalysed Catalysed
(normalized)
Fiber reactivity may be influenced, although not exclusively related to
hemicellulose removal.

21. Pretreatment
Global efficiency tends to be more favoured by hemicellulose
removal than by delignification
100
90 Higher Xylan
Removal
Glucan recovery
80
De
70 lign
ific
60 atio
De n
50 sac
40 et y
lati
30
on
20
Higher Lignin
10 Removal
0
0,4 0,5 0,6 0,7 0,8 0,9 1,0
(xylan+lignin) / glucan
glucan / (xylan + lignin)
Delignification of ST bagasse does NOT necessarily
improve process efficiency

22. Pretreatment
Two-step pretreatment tends to render more reactive fibers for
uncatalysed STEX (Steam Explosion) processes.
Unwashed bagasse
100
Single step
Fiber reactivity
80 Two steps
60
40
20
0
180ºC 190ºC 200ºC 180ºC 190ºC 200ºC
Catalysed Uncatalysed
(normalized)
(The use of catalysts on STEX tends to reduce such differences)

23. Small differences among PT bagasses result in significantly different
fiber reactivity levels and cellulose conversions
crystallization
EHHC/HHHC
Crystallinity
Converted cellulose
EHHC: Easy to Hydrolyse
Hemicelluloses
HHHC: Hard to Hydrolyse
Hemicelluloses
Washed uncatalysed ST bagasse. 180-200ºC , 5-10 min.
8-10%Hemicelluloses; 58-62%Cellulose; 25-28% Lignin.
24-h enzymatic hydrolysis; 2% WIS; 15 FPU/g.
HC ratio (EHHC/HHHC) defines pretreatment severity levels
for optimal HC removal from a given biomass

24. Still to Investigate
100
Fiber reactivity 80
60
40
?????? Uncatalysed
Catalysed
20
0
PCS1 PCS2 PCS3 PCS1 PCS2 PCS3 PSC: Physico-Chemical Severity
PSC = f (T, t, P, H2O, additives)
Pore Size Crystallinity
How to address the influence of the lignin removal on fiber reactivity ?
How do catalysts alter LCC structure while removing HC and/or lignin ?
How do HC and lignin behave after fragmentation and removal ?
Is delignification really necessary ?

25. " The challenges we face are real.
They are serious and they are many.
They will not be met easily...
... or in a short span of time
But know this: - They WILL be met!"
Barack Houssein Obama