Levulinic Acid Reactor and Process Development
3 likes2,376 views
The document discusses the advanced biomass conversion for levulinic acid production from lignocellulose biomass, comparing the proposed dibanet design with the biofine process. It highlights improvements in efficiency and yields achieved through a new pretreatment strategy that enhances cellulose digestibility and reduces energy inputs. Additionally, it presents a detailed analysis of product yields, energy duties, and cost-effectiveness of the dibanet process versus the biofine approach.
![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 ](https://image.slidesharecdn.com/dibanetdonnchahavertylevulinicacidproduction-130109094636-phpapp02/85/Levulinic-Acid-Reactor-and-Process-Development-6-320.jpg)
![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](https://image.slidesharecdn.com/dibanetdonnchahavertylevulinicacidproduction-130109094636-phpapp02/85/Levulinic-Acid-Reactor-and-Process-Development-13-320.jpg)
Levulinic Acid Reactor and Process Development
- 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
- 16. Furfural recovery and FA recycle
- 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
- 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)