Production of α,ω diols from Biomass

Transcription

1 Production of α,ω diols from Biomass Thermal and Catalytic Sciences 216 November 3, 216 Jiayue He, Kefeng Huang, Pranav Karanjkar, Kevin J Barnett, Zachary Brentzal, Theodore Walker, Siddarth H Krishna, Sam Burt, Ive Hermans, Christos Maravelias, James A Dumesic, George W. Huber University of Wisconsin-Madison Department of Chemical & Biological Engineering 1

2 Catalytic Processes for Production of α,ω-diols from Lignocellulosic Biomass Support from Bioenergy Technology Office (BETO) Chris Marshall Michael Tspastsis, Ilja Siepmann

3 Price ($/MT) Price ($/MMBTU) High value infrastructure compatible commodity chemicals from biomass 1,6-Hexanediol (~13, MT/yr) ,6-hexanediol ($4,4/ton) 3 2 Gasoline ($2.5/gal) Volume (Million MT/yr.) 1 Source: ICIS, IEA Crude oil ($5/bbl) Biomass ($8/ton) Natural gas Source: Lux Research, Bio-based Materials and Chemical Intelligence Service, 3

4 There are several (aqueous-phase) acid catalyzed reactions in biomass conversion Hydrolysis Isomerization 1 Dehydration 2 Rehydration 1) Y. Roman-Leshkov, M. Moliner, J.A. Labinger, and M.E. Davis, Angewandte Chemie International Edition 49 (21) ) Y. Roman-Leshkov, J.N. Chheda, and J.A. Dumesic, Science 312 (26)

5 Low product selectivity is a key challenge in biomass conversion 5

6 Proposed reaction scheme 6

7 2 Activity of Acid sites are influenced by Solvent due to Solvation Effects Based on total detectable products Based on HMF Turnover frequency / hr T=17 C P=1 psig Cellulose=5wt% Acid= 5 mm H 2 SO 4 Solvent = THF Initial water content in solvent / vol % R. Weingarten, A Rodriguez-Beuerman, F Cai, JS Luterbacher, DM Alonso, JA Dumesic, GW Huber, Selective Conversion of Cellulose to Hydroxymethylfurfural in Polar Aprotic Solvents; ChemCatChem; (214)

8 HMF carbon yield (%) High HMF yields are obtained in Water THF GVL Ethyl Acetate Acetone Ethanol polar aprotic solvents Polar aprotic solvents T=17 C P=1 psig Cellulose=3 gr Acid=5 mm H 2 SO 4 Reaction vol.=6 ml time (min.) R. Weingarten, A Rodriguez-Beuerman, F Cai, JS Luterbacher, DM Alonso, JA Dumesic, GW Huber, Selective Conversion of Cellulose to Hydroxymethylfurfural in Polar Aprotic Solvents; ChemCatChem; (214) M A Mellmer, C Sener, JMR Gallo, JS Luterbachher, DM Alonso, JA Dumesic, Solvent Effects in Acid Catalyzed Biomass Conversion Reactions,, Ang Chemie (214)

9 Presence of water changes the product distribution SOLVENT: 11.6% water, bal. THF 2.7% water, bal. THF Pure THF 4 2 Yield (% Carbon) LGA Yield (% Carbon) Glucose Time (min) Time (min) Yield (% Carbon) LGO Yield (% Carbon) HMF Time (min) Time (min) Reaction Conditions: 1 wt% cellulose, 7.5 mm H 2 SO 4, 19 C 1 psig He, 6 ml total volume Source: Cao, F.; Schwartz, T. J.; McClelland, D. J.; Krishna, S. H.; Dumesic, J. A.; Huber, G. W., Dehydration of cellulose to levoglucosenone using polar aprotic solvents Energy & Environmental Science 215, 8 (6),

10 Levoglucosenone (LGO) Chiral carbon Sometimes referred to as the next HMF F Cao, TJ Schwartz, D McClelland, S Krishna, JA Dumesic, GW Huber, Dehydration of Cellulose to Levoglucosenone using Polar Aprotic Solvents, EES, (215)

11 Levoglucosenone (LGO) Chiral carbon Double bond conjugated with a ketone Sometimes referred to as the next HMF F Cao, TJ Schwartz, D McClelland, S Krishna, JA Dumesic, GW Huber, Dehydration of Cellulose to Levoglucosenone using Polar Aprotic Solvents, EES, (215)

12 Levoglucosenone (LGO) Chiral carbon Double bond conjugated with a ketone Protected aldehyde Sometimes referred to as the next HMF F Cao, TJ Schwartz, D McClelland, S Krishna, JA Dumesic, GW Huber, Dehydration of Cellulose to Levoglucosenone using Polar Aprotic Solvents, EES, (215)

13 Levoglucosenone (LGO) Chiral carbon Double bond conjugated with a ketone Protected aldehyde Two protected hydroxyl groups Sometimes referred to as the next HMF F Cao, TJ Schwartz, D McClelland, S Krishna, JA Dumesic, GW Huber, Dehydration of Cellulose to Levoglucosenone using Polar Aprotic Solvents, EES, (215)

14 Reaction Pathway for Dehydration of Cellulose in Polar Aprotic Solvents 14

15 LGO is hydrogenated to levoglucosanol over a metal catalyst (Pd/Al 2 O 3 ) High yields of Cyrene or Lgol achievable using monometallic catalysts Excess of exo-lgol produced over endo-lgol S.H. Krishna, D.J. McClelland, Q.R. Rashke, J.A. Dumesic, G.W. Huber, Catalytic hydrogenation of levoglucosenone to value-added chemicals. Submitted.

16 Selective Hydrogenolysis of Cyclic Ethers: Literature Bifunctional catalyst with a reducible metal and an oxophilic promoter; Low temperatures Reactant Transition state Product Proposed reaction pathway in literature with a RhRe/C catalyst through formation of a stable oxocarbenium ion [1] Tetrahydrofurfuryl alcohol Hydride transfer creates a stable oxocarbenium ion 97% selectivity to α,ω-diols Proposed reaction scheme for THP-2M hydrogenolysis with a IrRe/SiO 2 catalyst [2] THP-2M 1,6-HDO (>95% selectivity) 1,2-HDO 1-hexanol 2-hexanol 2-methyltetrahydropyran (2-MTHP) C-C cracking products Sources: [1] Chia et al., Journal of the American Chemical Society, 211, 133, [2] Chen et al., ChemCatChem, 21, 2,

17 Synergy between the reducible metal and oxophilic promoter is important Batch reactor activity data by Chia et al. [1] : THP-2M 1,6-HDO Catalyst Conversion (%) Rate (μmol g -1 min -1 ) 1,6-HDO selectivity (%) Byproducts selectivity (%) Rh/VXC (4 wt% Rh) ,2-hexanediol (11%), 1-hexanol (3%), others (42%) Re/VXC (3.6 wt% Re) RhRe/VXC (4 wt% Rh, 3.6 wt% Re) No reaction hexanols (3%), VXC = Vulcan XC-72, a carbon black by Cabot Corporation other products include over-hydrogenolysis and C-C cracking products Additional reaction conditions and details: Feedstock: 5% aq. THP-2M feedstock, Catalyst:Feedstock (g/g) = 2:7, Temperature = 12 o C, Pressure = 34 bar H 2, Time = 4 h Source: [1] Chia et al., Journal of the American Chemical Society, 211, 133,

18 High selectivity to 1,6-HDO is achievable using RhRe/VXC bifunctional catalysts separator THP-2M conversion (%) 1,6-HDO selectivity (%) To back-pressure regulator Reactor Gas-Liquid Hydrogen THP-2M solution through HPLC pump Time (h) Byproducts include small amounts of 1-hexanol, 2-MTHP, 1-pentanol Reaction conditions for continuous reaction: 5% aq. THP-2M, catalyst: RhRe/VXC, WHSV = 1.44 h -1, 12 o C, 34 bar H 2, 4 sccm H 2 Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2- methanol RSC Catalysis Science and Technology, in press. 18

19 High selectivity to 1,6-HDO is achievable using RhRe/VXC bifunctional catalysts THP-2M conversion (%) 1,6-HDO selectivity (%) RhRe/VXC RhRe/NDC Time (h) 2 Byproducts include small amounts of 1-hexanol, 2-MTHP, 1-pentanol with RhRe/VXC catalyst Reaction conditions: 5% aq. THP-2M (initial reaction volume = 5 ml), catalyst: RhRe/VXC, catalyst:feedstock (g/g) = 1:7, 12 o C, 34 bar H 2. Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2- methanol RSC Catalysis Science and Technology, in press. 19

20 Carbon Blacks vs. Activated Carbons Formation of carbon blacks (vapor phase) Hydrocarbons Gas-phase pyrolysis Formation of activated carbons (solid phase) Low-rank coals, wood, thermosetting polymers Thermal decomposition by charring Carbon black Glassy carbon Activation Activated carbons (chars) 1. Selective gasification 2. Chemical treatment 3. Carbon supports discussed here: Vulcan XC-72, Cabot Corp., carbon black VXC Source: L. R. Radovic, in Carbon Materials for Catalysis, John Wiley & Sons, Inc., 28, pp & Norit Darco 12X4, Cabot Corp., activated carbon NDC 2

21 Quantity adsorbed (cm 3 g -1 ) Pore volume (cm 3 g -1 Å -1 ) Characterization of Carbon Supports Carbon support NDC VXC Type of carbon support Activated (acid washed) Carbon black BET surface area (m 2 g -1 ) Quantity adsorbed (cm 3 g -1 STP) Nitrogen adsorption isotherm Adsorption Desorption NDC VXC Relative pressure (P/P o ) o ) Pore volume (cm 3 g -1 Å -1 ) VXC NDC Pore size distribution Pore width (Å) Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2- methanol RSC Catalysis Science and Technology, in press. 21

22 Quantity adsorbed (mmol g -1 ) Quantity adsorbed (mmol g -1 ) NDC has more surface oxygen present XPS analysis of carbon supports Surface elemental composition (mol %) Carbon C O S Si Na Al VXC NDC Adsorption Desorption NDC 4 3 Water vapor adsorption isotherm Water adsorption capacity of VXC = 1.2 mmol g Water adsorption capacity of NDC = 17.5 mmol g VXC Relative pressure (P/P o ) Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2- methanol RSC Catalysis Science and Technology, in press. 22

23 Signal (a.u.) Higher density of oxidized species on NDC than VXC more sites for interaction with metal and metal precursors Support characterization with DRIFTS NDC Band Position (cm -1 ) Assignment C-CO deformation of cyclic ketone C-O-C stretch of aromatic cyclic anhydride or O-H bend of carboxylic acid Acid Anhydride C-O-C stretch Relative abundance NDC VXC Phenol O-H bend Ether C-O-C stretch Phenol C-OH stretch.8.42 VXC 1215 Lactone C=O stretch Carb. Acid C=O stretch Carboxyl Carbonate C=O stretch Wavenumber (cm -1 ) C=C stretch (conjugated aromatic) O-H stretch of water or Sources: [1] Figueiredo et.al., Carbon, 1999, 37, carboxylic acid [2] Fanning et al., Carbon, 1993, 31, Abundance shown is relative to C=C stretch (the only signal due to [3] Collins et al., Carbon, 213, 57, a non-oxygenated bond) 23 Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-

24 Characterization of Bimetallic Catalysts Catalyst Rh/NDC RhRe/NDC Rh/VXC RhRe/VXC Rh loading (wt%) Rh:Re atomic ratio - 1:.5-1:.5 Rh atom density (atoms/nm 2 ) CO uptake (μmol/g) CO:Rh (mol:mol) Rate of THP-2M [ ] hydrogenolysis (μmol/g/min) 1 76 Reaction conditions for batch reactions: 12 o C, 34 bar H 2, 5% aq. THP-2M (Initial reaction volume = 25 ml), catalyst: RhRe/C, catalyst:feedstock (g/g) = 1:7, Reaction time = 4 h Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2- methanol RSC Catalysis Science and Technology, in press. 24

25 Normalized absorption Normalized absorption X-ray Absorption Near Edge Structure Re catalysts RhRe catalysts Re 2 O 7 ReO 2 Re/NDC reduced at 2 o C Re/VXC reduced at 2 o C 3 ReO 2 Re 2 O 7 RhRe/NDC reduced at 2 o C RhRe/VXC reduced at 2 o C Re foil 1 Re foil Energy (kev) Energy (kev) Catalyst Treatment prior to scan in He XANES fit for Re edge Re(VII) Re(IV) Re() Catalyst Treatment prior to scan in He XANES fit for Re edge Re(VII) Re(IV) Re() Re/NDC 2 C reduction RhRe/NDC 2 C reduction Re/VXC 2 C reduction RhRe/VXC 2 C reduction Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2- methanol RSC Catalysis Science and Technology, in press. 25

26 Fraction Fraction Scanning Transmission Electron Microscopy (STEM) 1..8 Average = 1.61±.61 nm 868 particles analyzed RhRe/NDC Particle size (nm).5.4 Average = 1.98±.73 nm 793 particles analyzed RhRe/VXC Particle size (nm) Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2- methanol RSC Catalysis Science and Technology, in press. 26

27 STEM-EDS images for catalyst nanoparticles Rh Map RhRe/NDC Avg. particle size : 1.61±.61 nm Drift ref. Re Rh RhRe/VXC Avg. particle size : 1.98±.73 nm Map Re Drift ref. Karanjkar et al.; Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2- methanol RSC Catalysis Science and Technology, in press. 27

28 Number of particles Number of particles STEM-EDS indicates segregation of Re species in NDC atomic% Re Re content (atomic %) RhRe/NDC Re content (% atomic) Rh:Re (mol:mol) Theoretical ICP EDS 33.3% 35.5% 61.3% 1:.5 1:.55 1: atomic% Re RhRe/VXC Theoretical ICP EDS Re content (atomic %) Re content (% atomic) Rh:Re (mol:mol) Note: The distribution considers composition of ~6 particles analyzed with EDS 33.3% 33.8% 36.7% 1:.5 1:.51 1:.58 28

29 Tiny Rh particles (<1 nm) Note: Schematic is for visualization purposes only! 1% Re 65% Re ~33% Re RhRe/NDC RhRe/VXC Nanoparticles with segrated particle composition Many small particles (<1 nm) rich in Rh are present that evade detection in STEM Many Re only particles also present and larger particles are rich in Re Higher surface oxygen content may restrict mobility of metals/metalprecursors resulting in segregation of Rh and Re Nanoparticles with relatively uniform composition Anchoring of metals/metal-precursors is relatively absent because of low surface oxygen Formation of small Rh particles (<1 nm) may be avoided because of smaller surface area of support 29

30 Conclusion New pathways for production of high value oxygenated commodity chemicals from biomass Cellulose can be converted into LGO and HMF in high yields in polar aprotic solvents LGO is a promising platform molecule LGO and HMF hydrogenated into THFDM which then undergoes hydrogenolysis into 1,6 hexanediol 1,5 pentanediol can be produced from biomass without expensive RhRe catalysts 3

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