Perspectives on Biobased Products & Production of Oxidized and Reduced Derivatives of 5-Hydroxymethylfurfural (HMF)

Transcription

1 Perspectives on Biobased Products & Production of xidized and Reduced Derivatives of 5-ydroxymethylfurfural (MF) Dr. Mike Lilga hemical and Biological Process Development Pacific Northwest National Laboratory Richland, WA Northwest Bioenergy Research Symposium Seattle, WA November 13, 2012

2 il Barrel Breakdown Fraction Volume % Value (billions) Fuel 70.6 $385 Petrochemicals 3.4 $375 J. Marshall New Scientist, 2007,

3 Petrochemical are Derived From Key Building Blocks Key Building Blocks Example Products figure from: Dr. arriëtte Bos, Wageningen UR-FBR Biorefining 2012, 31 ctober 2012 For the U.S. chemical industry, around 98% of all chemicals produced in excess of 4 million kg/yr are produced from petroleum and natural gas. J. Frost Industrial Biotechnology 3 1(1) 2005,

4 Possible Key Biorefinery Building Blocks Furans Levulinic acid ydroxy acids 6 Sugars Starch 5 Sugars Polyols Lactones Ethanol Diacids Sugars could be derived from any source: corn, sugar cane, cellulose, hemicellulose, etc sugars: Werpy et al., Top Value Added hemicals from Biomass Vol. I, U.S. DE, 2004 Bozell and Peterson, Green hem., 12, 2010, lignin: Bozell et al., Top Value Added hemicals from Biomass Vol. II, PNNL-16983,

5 Key Biomass Building Blocks are Platforms for Numerous Biobased Products Tetrahydrofuran 4 8MW = N 2-Pyrrolidone 4 7 NMW = g-butyrolactone MW = N NMP 1,4-Butanediol Succinic acid MW = Yield 4,4-Bionelle MW = (polyester) 3 2 N DBE 2 N N 2 1,4-Diaminobutane 4 12N 2 MW = MW = N 3 N 2 Succindiamide 4 8N 2 2 MW = N Succinonitrile 4 4N 2 MW = Levulinic acid MW = ydroxymethylfurfural 2,5-Furandicarbaldehyde MW = MW = N N 2 2,5-TF-dimethylamine 6 14N 2 MW = ,5-Furandimethoxy 2,5-TF-dimethoxy MW = Succinic acid MW = MW = ,5-Furandicarboxylic acid MW = Angelalactones MW = ,4-Pentanediol MW = R Various esters 3 g-valerolactone MW = Levulinic acid MW = Pentenoic acid MW = Methyl-TF 4 8MW = d-aminolevulinate 5 9N 3 MW = Diphenolic acid MW = N 2 6 Sugars 5 Sugars Starch 2 Glyceric acid MW = Glyceraldehyde MW = ,3-Propanediol 1,2-xo-3-propanol MW = MW = B B B Glycerol B Diglyceraldehyde MW = MW = Ac Ac Ac Glycerol triacetate MW = R 1 3 Propylene glycol MW = Propanol 3 8 MW = R 2 Mono-, di-, or triglycerate 5 R 3

6 Moving Biobased Products Forward Strengthen Technology Push Deconstruction of lignocellulosic biomass into sugars and lignin via thermal and/or biochemical routes Formation of key platform molecules and conversion to products (chemistry/biochemistry/catalysis/engineering) Separations Need to understand enabling synergies with fuel production 6

7 Moving Biobased Products Forward Strengthen Market Pull Determine end product properties/specifications define applications Being a renewable product may not be enough it has to outperform onduct techno-economic, lifecycle, and market analyses Any bio-based product with suitable properties whose cost is the cost of a petrochemical-based product has a high probability of commercialization 7

8 Propylene Glycol (PG) from renewable sources for clean production of chemicals DE-Energy Efficiency and Renewable Energy (EERE) DE-EERE, Industry Industry atalyst capabilities developed by the ffice of Science were leveraged in a series of EERE-funded RADA projects. EERE supported technology transfer to industry. Private funds were used to pilot and commercialize the technology. ADM licensed the patent portfolio and completed construction of a full-scale production facility in

9 Evolution of the Plastic Bottle 100% Petroleum Based poly(ethylene terephthalate) % Biobased poly(ethylene terephthalate) 100% Biobased poly(ethylene furanoate) (PEF) 9

10 PEF as Superior Properties Superior barrier properties: PEF oxygen barrier is 6 times better than PETE PEF carbon dioxide barrier is 3 times better than PETE PEF water barrier is 2 times better than PETE More attractive thermal properties: More heat resistant. The Tg of PEF is 86 compared to the Tg of PETE of 74 Lower processing temperature. The Tm of PEF is 235 compared to the Tm of PETE of

11 5-ydroxymethylfurfural Derivatives Levulinic acid 2 N N 2 2,5-TF-dimethylamine 3 5-ydroxymethylfurfural (MF) 2,5-TF-dimethanol (TFDM) 2,5-Furandicarboxylic acid (FDA) 2,5-Diformylfuran (DFF) 2,5-Furandimethanol (FDM) 11 11

12 MF and MF Derivatives are Potential Bio- Based Intermediates for a Variety of Products Polymers Polyesters Polyurethanes Polyamides Binders Adhesives oatings Foams Some leading references: J. Lewkowski, ARKIV (i) (2001) A. Gandini and M.N. Belgacem, Prog. Polym. Sci. 22 (1997) Moreau, M.N. Belgacem, and A. Gandini, Top. atal. 27 (2004)

13 xidation of MF ydroxymethyl Furfural xidation Methods M.A. Lilga, R.T. allen, J. u, J.F. White, and M.J. Gray, U.S. Patent No. 8,193,381 B2, June 5, ydroxymethyl Furfural xidation Methods M.A. Lilga, R.T. allen, J. u, J.F. White, and M.J. Gray, U.S. Patent No. 8,193,382 B2, June 5, ydroxymethyl Furfural xidation Methods, M.A. Lilga, R.T. allen, J. u, J.F. White, and M.J. Gray, U.S. Patent No. 7,700,788 B2, April 20,

14 % ompositon Batch xidation of 3 wt% MF at 60 and 150 psi 2 in Neutral Solution ver 9%Pt/ MF MF DFF FFA FDA FFA FDA 40 DFF Reaction Time (h) xidation is sequential and selectivity is difficult to control in batch mode 14

15 The Project an various oxidized MF derivatives be produced selectively in a flow reactor? ould selectivity and conversion be controlled by varying process conditions? onduct catalyst and process screening experiments Not in the scope: atalyst/process optimization Mechanistic studies 15

16 onv. and Sel., wt%. xidation of MF ver 5% Pt/Zr 2 Selectivity to FDA: 5% Pt/Zr 2 0.5% MF, 150 psig air, 100, FDA LSV = h -1, GSV = 300 h LSV = 7.5 h -1 LSV = 3 h MF onv, wt% Sel to FDA, wt% Sel to FFA Sel to DFF Sel to ther By- Products Time (min) 16

17 onv. and Sel., wt%. xidation of MF ver 5% Pt/Si 2 Selectivity to DFF: 5% Pt/Si 2 (PNNL) 1% MF, 150 psig air, , LSV = h -1, GSV = 261 h -1 DFF LSV = 13 h -1 T = 100 LSV = 19.6 h -1 T = 100 LSV = 13 h -1 T = 60 MF onv, wt% Sel to FDA Sel to FFA Sel to DFF 20 Sel to thers Time (min) 17

18 Reduction of MF MF FDM TFDM ydroxymethyl Furfural Reduction Methods and Methods of Producing Furandimethanol, M.A. Lilga, R.T. allen, J.F. White, and M.J. Gray, U.S. Patent No. 7,994,347 B2, August 9, ydroxymethyl Furfural Reduction Methods and Methods of Producing Furandimethanol, M.A. Lilga, R.T. allen, J.F. White, and M.J. Gray, Filed 6/2007, Pending. 18

19 ydrogenation of MF to FDM ver Pt/Al 2 3 onv. and Sel., wt%. Selectivity of MF to FDM: 5% Pt/Al 2 3 1% MF, 500 psi, 70, LSV = 15 h -1, GSV = 420 h onv, wt% Sel to FDM, wt% Sel to TFDM Sel to thers Time (min) 19

20 onv. and Sel., wt% FDM ydrogenation to TFDM over Ni/Si Selectivity of FDM to TFDM: Ni/Si 2 1% FDM, 500 psig, 70, LSV= 15h -1, GSV=210h -1, onv., wt% Sel to TFDM Sel to thers Time (min) 20

21 MF Reduction to TFDM ver a o/ni Staged atalyst Bed onv. and Sel., wt%. Selectivity of MF to TFDM: o/ni; o-0179 / Ni % MF, 500 psig 2, 70, LSV = h -1, GSV = h LSV = 2.7 h -1 LSV = 4.5 h Time (min) MF onv Sel to (not FDM) Sel to FDM Sel to Sel to Sel to TFDM Sel to In direct conversion, Ni was poisoned by MF, but the staged approach of o reduction to FDM followed by Ni reduction to TFDM worked well. 21

22 Summary Products add value to the biorefinery A broad range of biobased products are possible from key intermediates Technology advances are needed to selectively carry out conversions Drop-in products have established markets and uses, but new products will need performance testing and establishment of new markets FDA, FFA, DFF, FDM, and TFDM can be produced with good selectivities by controlling process conditions and selecting the appropriate catalyst(s) 22

23 Acknowledgments MF xidation and Reduction Rich allen Mike Gray Jim White John u Dani Muzatko Alan ooper Financial Support Archer Daniels Midland Battelle Memorial Institute 23

24 Types of Biobased Products Product Type Drop In Replacement Functional Equivalent New Functionality Upside Fully fungible Markets exist ost structure and growth potential known Market risk reduced Analogous markets and cost structures exist May offer improved function New market opportunities ften no competitive petrochemical routes Use inherent properties of biomass Downside ompetes against cost ompetes against depreciated capital Limited market differentiation ost competition Markets may not be clearly defined apital risk high Time to commercialization may be long apital risks often high Time to commercialization long Markets ill-defined Increasing Risk Decreasing Market Definition Decreasing ompetition Incr. Time To ommercialization Adapted from Gene Peterson, Perspectives on DE Biobased Products R&D U.S. Department of Energy Bioproducts from ellulosic Feedstock Workshop, December 4,

25 Evolution of the Plastic Bottle 25

26 Evolution of the Plastic Bottle biobased p-xylene from Virent, Gevo, others biobased FDA from YXY (Avantium) 26

27 ontinuous xidation Reactor for Flow Studies 3/8 SS tube reactor ~4 cc catalyst Gases and liquids were fed up flow GSV h -1 (20-40 ml/min) LSV 3-20 h -1 ( ml/min) Samples taken at pressure 27

28 onv. and Sel. (%) xidation to FFA is Facile at 30 Selectivity to FFA: 5% Pt/ 1% MF in 0.83% Na 2 3, 150 psig air, 30, LSV= h -1, GSV= h -1 FFA MF onv Sel to FDA LSV=7.5 h -1 Air GSV=300 h -1 LSV=4.5 h -1 Air GSV=300 h -1 LSV=4.5 h -1 Air GSV=600 h Time (min) Sel to FFA Sel to DFF Sel to thers 28