Dr. Donncha Haverty, University of Limerick, Ireland, Dibanet Networking event, 31 October 2013, CERTH, Thessaloniki, Greece. Further info and videos: http://www.dibanet.org/networking_day_greece.php

1. WP 3
Advanced Biomass
Conversion
Levulinic Acid production from lignocellulose
biomass: comparison of the DIBANET
proposed design with the Biofine process for
the acid hydrolysis route to Levulinic Acid
Donncha Haverty, Karla Dussan, Dr. Anna V. Piterina, Dr. Buana Girisuta,
Dr. D. Hayes, Dr. J. Leahy, Prof. M. Hayes

2. Overview
• Capabilities developed at Carbolea during DIBANET
• Context
– Limiting factors in LA production
– Existing chemical processes for levulinic acid production
• DIBANET pretreatment as the basis of an improved acid
hydrolysis process
• The design
• Comparison with Biofine

3. Processing capacity
• Lab scale
– 0.1 Lt – 8Lt
– Atmosphere – 50 Bar
– In line sampling
• Pilot scale
– 100 Sq m
– Continuous system
– Up to 1Lt/min
throughput

6. Desirable series of reactions
•Lignin interference
•Recalcitrance
•Physical state (Mass transfer)
•Reactive intermediates
•Optimum kinetics/yields/process
engineering
•Selectivity highly T dependent
•Practicalities: T, P [Acid]
Y 
S =  LA max  = 0.2785.e −0.0099.T ( ACW + 283.1)
 YHU 6 max 

7. Originally DIBANET based on
Biofine

8. Areas for improvement
• Hydrolysis of Cellulose limiting (high energy input)
• Multiple components
• Acid effect on process equipment
• Desirable products not stable under process conditions
• Low through put (95% water)
• Energy intensive
• Post processing complicated by the sulphuric acid
• Scalability (high pressure CSTR)

9. The Context
• Is there a process to :
– Reduce Mechanical energy inputs (Grinding, Chopping)
– Reduce Energy inputs (heat)
– Increase LA Yields
– Environmentally sustainable
– Cost effective
• Capital, energy, rendering of output streams
– Encompasses the best attributes of different approaches:
fractionation, reduced recalcitrance etc

10. Pretreatment
• Feasible means of fractionating the biomass
• Renders the cellulose to a high surface area form.
• From 5 to 7.5% peroxide and high mass loadings
– > 90% lignin removal in 5 min
– > 85 % Hemicellulose converted to monomeric sugars in the
liquor in 5 min
– > Homogeneous cellulosic feedstock for hydrolysis
• The system is auto-thermal: temperatures of 110oC
without external heat
• Resultant cellulose is 10-12 times more digestible

11. Raw material 150 C 1% Acid
Pre-treated 150 C 1% Acid
Raw material 175 C 1% Acid
Pre-treated 150 C 5% Acid

12. Enzymatic Digestion
of Pretreated Miscanthus
1.3
Substrate type
1.2
1.1
m 1
e n
s 0 0.9
a 4 Avicel
e
l 5 0.8
e ,
)
r y 0.7
e a Pre-treated biomass
s s
s
o 0.6 FA/H2O2 -(7.5%)
c a
u
l S 0.5
G Pre-treated biomass
N
D
( 0.4 FA/H2O2 -(5%)
0.3
0.2
0.1 Raw (non-treated)
biomass)
0
0 0.45 1.5 7 24 48 72
Duration of the enzymatic hydrolysis (hrs)
Profile of glucose release during enzymatic digestion of Avicel (microcrystalline cellulose), raw and
pretreated Miscanthus (5.0% and 7.5% H2O2) at 45 oC with a commercial cellulase enzyme mix.

13. Design Proposal Basis
• Pre-treatment to yield two streams
- > Cellulose rich sludge
- > FA liquor with dissolved C5 sugars and Lignin
• Liquor is fed to CSTR for conversion of C5 to furfural
- > [FA] affects conversion
• The mixture is cleaned of humins and silicates
• Various evaporation and water addition steps are used to
precipitate the lignin
• A liquid stream containing FA, Furfural and Water is sent
for product recovery and recycling (largely determines the
feasibility)
• Cellulose sent for conventional hydrolysis at 150 C in a
series of CSTR’s

14. Pre-treatment and furfural
production

15. Levulinic Acid Production

16. Furfural recovery and FA recycle

17. LA Production: BIOFINE

18. Comparison of DIBANET and
BIOFINE Yields
DIBANET BIOFINE
In Kg/hr Yield In Kg/hr Yield Improvement
Biomass 100.00 100.00
H2O2 55.00 0.00
H2SO4 0.60 1.35
MTHF 0.20 0.40
CaO 0.50 1.00
Out Out
LA 19.45 70.00 16.45 57.00 22%
FURFURAL 15.10 69.20 8.95 41.02 69%
FA (80%) 6.45 45.00 7.42 52.20 -16%
Lignin 22.50 75.00 0.00 0.00 -
AHR 23.41 57.39

19. Comparison of DIBANET and
BIOFINE: Energy
Duty (kW)
Stage
Dibanet Biofine
LA production + Recovery 171.1 543.6
Furfural +FA Recovery 284.5 258.6
Total 456 802

20. Comparison of DIBANET and
BIOFINE: Product value
Dibanet Biofine
In In
Kg/hr or KWhr Unit cost/kg Sub cost/hr Kg/hr or KWhr cost/kg Sub cost'/hr
Biomass 100.00 0.10 10.00 100.00 0.10 10.00
H2O2 55.00 0.30 16.50 0.00 0.30 0.00
H2SO4 0.60 0.30 0.18 1.35 0.30 0.41
MTHF 0.20 1.00 0.20 0.40 1.00 0.40
CaO 0.50 0.30 0.15 1.00 0.30 0.30
Energy 662.00 0.01 6.62 805.00 0.01 8.05
Sub Total Cost/hr 33.65 19.16
Out Out
LA 19.45 2.00 38.90 16.45 2.00 32.90
FURFURAL 15.10 2.00 30.20 8.95 2.00 17.90
FA (80%) 6.45 0.30 1.94 7.42 0.30 2.23
Lignin 22.50 0.50 11.25 0.00 0.50 0.00
Subtotal Product per hr 82.29 53.03
Gross Margin/hr 48.64 33.87

21. Moving Biomass into the
pre-treatment reactor at scale
• Solid dosing pumps
– Several Manufacturers
• Pultzmeister
• Weir
– High solids loading 65% sludge
– Large particles (no requirement for milling)
– Exit to DN200
– Flow rates to 60 M 3/hr
– Pressures to >150 bar
– Range of feeders and augers

22. Pre-treatment reactor

23. Thank You
• Acknowledgements
– K Dussan
– Dr B Giristuta
– Dr D Hayes
– Dr A. Piterina
– Prof M Hayes
– Dr J. J Leahy
• Questions?

24. Biofine paper sludge
(cellulose only)