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

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

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

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

Originally DIBANET based on Biofine

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)

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

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

Raw material Pre-treated Raw material Pre-treated

150 C 150 C 175 C 150 C

1% Acid 1% Acid 1% Acid 5% Acid

Enzymatic Digestion of Pretreated Miscanthus

1.3 1.2 1.1

Substrate type

e s a e l e r e s o c u l G

m n 0 4 5 , ) y a s s a S N D (

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

0 0.45 1.5 7 24 48 72

Avicel
Pre-treated biomass FA/H2O2 -(7.5%) Pre-treated biomass FA/H2O2 -(5%)

Raw (non-treated) biomass)

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.

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 CSTRs

Pre-treatment and furfural production

Levulinic Acid Production

Furfural recovery and FA recycle

LA Production: BIOFINE

Comparison of DIBANET and BIOFINE Yields

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

Comparison of DIBANET and BIOFINE: Energy

Duty (kW) Dibanet Biofine 171.1 543.6 284.5 258.6 456 802

Stage LA production + Recovery Furfural +FA Recovery Total

Comparison of DIBANET and BIOFINE: Product value

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

Biomass H2O2 H2SO4 MTHF CaO Energy Sub Total Cost/hr

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

Pre-treatment reactor

Thank You
Acknowledgements
K Dussan Dr B Giristuta Dr D Hayes Dr A. Piterina Prof M Hayes Dr J. J Leahy

Questions?

Biofine paper sludge (cellulose only)