Study on the Production of Gamma valerolactone from Hybrid Poplar

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1 Study on the Production of Gamma valerolactone from Hybrid Poplar Troy Runge, Chunhui Zhang March 16, 2011

2 Topics of my Talk Bioenergy Gamma valerolactone background Pentose & Hexose hydrolysis Levulinic acid production Gamma valerolactone production

3 US Renewable Energy

4 Bioenergy and Biobased Products Facilities

5 Gamma valerolactone GVL formed from catalytic hydrogenation of levulinic acid Herbal odor, it is used in the perfume and flavor Useful as a green solvent or biofuel blend Can be converted into fuels & chemicals Levulinic acid Gamma-valerolactone

6 Cellulose to GVL LA, FA, Humins GVL, Degradation Products Cellulose R 1 S 1 S 1 R 2 S 2 LA & FA GVL Humins Degradation products

7 GVL to Alkenes Butene, CO 2, H 2 O R 1 S 1 R 2 S 2 CO 2 Sequestration GVL/H 2 O Butene CO 2 H 2 O Oligomers Fuel, Chemicals Bond et al., Integrated Catalytic Conversion of γ- Valerolactone to Liquid Alkenes for Transportation Fuels, Science 26: February 2010.

8 Cellulose to Fuel Process Mild H 2 SO 4 Ru/Re/C catalyst Harsh H 2 SO 4 SiO 2 / Al 2 O 3 Amberlyst ZSM5

9 Economics of Process Cellulose is currently worth about the same as gasoline Back of the envelope calculation 1 kg of cellulose = $0.60 to $.90 (Assume $600 to $900/MT for pulp) 1 kg of fuel = $0.71 to 1.06 (Assume $2 to 3/gallon) Additionally best you can hope for is 60% conversion Must use cheap biomass

10 Using Biomass for the Process Biomass Wasted material Potentially hinder reactions

11 Process 2 2 Humins Biomass Extracted Biomass

12 Biomass to GVL Sugars, Cellulose, & Lignin Sugars, Humins, & Lignin R 1 S 1 R 2 S 2 R 3 S 3 GVL Cellulose & Lignin LA FA Biomass resources Sugars (pentoses) Humins & Lignin Degradation products

13 Hypotheses Hemicellulose extraction will not hinder the production of levulinic acid Utilization of extracted biomass instead of cellulose will not hinder the reaction of hexoses to GVL.

14 Experimental Characterize Biomass Extract pentoses (hemicellulose ) Produce & characterize LA & FA from extracted biomass Produce gamma valerolactone

Biomass Source Hybrid Poplar (Populus maximowiczii x nigra) Samples were manually debarked and chipped Samples were screened and dried (2mm to 8mm chips) Chemically characterized Arabinose Galactose

15 Biomass Source Hybrid Poplar (Populus maximowiczii x nigra) Samples were manually debarked and chipped Samples were screened and dried (2mm to 8mm chips) Chemically characterized Arabinose Galactose Glucose Xylose Mannose Total 0.30% 0.50% 40.70% 13.30% 3.00% 57.80% Acetic acid Lev. Acid HMF Furfural Total 3.70% 0.40% 0.50% 1.10% 5.70% Ash ASL Klason lignin Total 0.20% 3.60% 22.20% 26.00% 89.50%

16 Sugar Analysis Degradation Products Measured Cellulose Hexose Glucose Glucose Galactose Mannose Hydroxymethylfurfural (HMF) Levulinic Acid Formic Acid Hemicellulose Pentose Xylose Arabionose Furfural Acetic Acid Sugars Measured

17 Pentose Hydrolysis Pentosics Concentration (g/l) C, 0.7% H2SO4 140C, 0.9% H2SO4 150C, 0.5% H2SO4 150C, 0.7% H2SO4 Pentosics Concentration (g/l) C, 0.3% H2SO4 160C, 0.5% H2SO4 170C, 0.1% H2SO4 170C, 0.3% H2SO Time (min) Time (min)

18 Hexose Hydrolysis Hexosics Concentration (g/l) C, 0.7% H2SO4 140C, 0.9% H2SO4 150C, 0.5% H2SO4 150C, 0.7% H2SO Time (min) Hexosics Concentration (g/l) C, 0.3% H2SO4 160C, 0.5% H2SO4 170C, 0.1% H2SO4 170C, 0.3% H2SO Time (min)

Hydrolysis Kinetics Ki is the reaction rate ki is the

acid, Ei is the activation energy C A is the concentration

temperature Kpentose = 51840 [Ca] 0.728 exp (-59.

32/RT) m hexose < m pentose lower reaction order E hexose

19 Hydrolysis Kinetics Ki is the reaction rate ki is the frequency factor, mi is the reaction order in sulfuric acid, Ei is the activation energy C A is the concentration of acid R is the ideal gas constant T is the reaction temperature Kpentose = [Ca] exp (-59.06/RT) Khexose= 92 [Ca] exp (-40.32/RT) m hexose < m pentose lower reaction order E hexose < E pentose lower activation energy k hexose <<< k pentose much lower frequency due to accessibility

20 Extraction Step Results Best conditions 160C, 60min, 1.0%wt H 2 SO 4, 6:1 ratio Under the best conditions 90% of pentoses could be extracted 90% of hexoses retained in the solid Hexoses can then used for LA production in next step

21 Hexose Hydrolysis / Dehydration Harsh H 2 SO 4 rxn Factorial Temp (170C, 180C, 190C) Acid (1%, 3%, 5%) Ratio (6:1, 8:1, 10:1) Time (20min, 35min, 50min) Stepwise AOV Model Higher on each variable increased yield One significant interaction (negative) Intercept Coefficient Std. Error P value Constant Temp Acid Conc Time Ratio Temp. x Acid Conc

22 Dehydration Step Results Best conditions 190C, 60min, 5.0%wt H 2 SO 4, 10:1 ratio Under the best conditions 18% original wood mass converted to levulinic acid 61 % theoretic yield fairly high Similar yield (18%) of unextracted wood LA / FA can then used for GVL production in next step

23 GVL Batch Reaction Reactants Ru/Re/C catalyst: 1.03 g (Re/Ru = 1.3) LA sample: (90mL, 6.80 wt% levulinic acid, 1.75wt% formic acid, 0.5 M H 2 SO 4 ) Reactor Purged with helium Pressurized with hydrogen (35 bar) at ambient temperature. Heated to 423 K and then held constant for 4 h. Samples (~1 ml) were collected during reaction No GVL formed

24 GVL Flow Reaction Reactants Ru/Re/C catalyst: 1.5 g (Re/Ru = 1.3) Sample: (0.42M levulinic acid, 0.44 M formic acid, 0.35 M H2SO4 ) Reactor Initially purged with helium Pressurized with hydrogen (300 psi) Heated to 150C Varied flow rate GVL formed at low flow rate Also hydrogenated Phenol 4 OH benzoic acid

25 Conclusions LA can be produced in good yield using a 2 step acid process Mild hydrolysis extract pentoses Harsh conditions convert hexoses to LA/FA When using biomass acid soluble lignin products present interfere with GVL catalyst 4 OH Benzoic acid Phenol New processes needed to use biomass

26 University of Wisconsin Jim Dumesic Jesse Bond Stephanie Sorenson Pamella Wipperfurth Acknowledgements Forest Products Lab Junyong Zhu Carl Houtmann Funding UW Superior / Department of Defense Wisconsin Bioenergy Initiative Troy Runge trunge@wbi.wisc.edu

University of Groningen. Levulinic acid from lignocellulosic biomass Girisuta, Buana

University of Groningen. Levulinic acid from lignocellulosic biomass Girisuta, Buana University of Groningen Levulinic acid from lignocellulosic biomass Girisuta, Buana IMPRTANT NTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please