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And Three-Carbon Monosaccharides to Understand Hemicellulose and Cellulose Pyrolysis

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And Three-Carbon Monosaccharides to Understand Hemicellulose and Cellulose Pyrolysis Pyrolysis of Two- and Three-Carbon Monosaccharides to Understand Hemicellulose and Cellulose Pyrolysis Phillip R. Westmoreland and Patrick J. Fahey [Presently post-doc at U.S. Naval Academy, Chemistry Dept] Dept of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh NC Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 Sugars, cellulose, & hemicelluloses have many OHs. Alcohol dehydrogenation and dehydration: Studied extensively in the aqueous phase and over metal-oxide and organic catalysts; However, less study of the gas-phase and melt-phase reactions. Experiments and calculations are used to probe the fates of the OH groups, including their influence on each other: Pyrolyses of simple alcohols with detailed GCxGC-TOFMS analysis. Observed products correspond to dehydrogenation, dehydration, and cyclic Grob fragmentation. Mechanistic steps are proposed, building on our prior work on cellulose and glucose pyrolysis. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 2 Use mono-, di-, tri-ols as biomass model compounds. Experiments in pulse-injected flow reactors show that gas-phase pyrolysis of alcohols makes a transition from: Dehydrogenation dominance for mono-alcohols … to … Dehydration and fragmentation for diols and a triol. These dehydration and dehydrogenation reactions are proposed to occur by unimolecular and bimolecular pericyclic reactions. (as has been used to explain glucose and cellulose pyrolysis by Seshadri and Westmoreland; Assary and Curtis, Mayes, Broadbelt, Vinu, et al.; and Auerbach et al.). V. Seshadri, P. R. Westmoreland, “Concerted reactions and mechanism of glucose pyrolysis and implications for cellulose kinetics,” J. Phys. Chem. A 116:49 (2012) 11997-20013. V. Seshadri, P. R. Westmoreland, “Roles of Hydroxyls in the Noncatalytic and Catalyzed Formation of Levoglucosan from Glucose," Catalysis Today 269 (2016) 110-121. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 3 Cellulose: Polymer of β-glucose (β-D-glucopyranose). β-D-glucopyranose unit Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 Hemicellulose is less ordered; here, xyloglucan. The heptamer block is shown (glucan 4-xylose 3). In blue, backbone β-D-glucans; in red, α-D-xylose; in black, α-D-galactose and in brown, α-L-fucose residues. M. Ochoa-Villarreal et al., “Ch. 4. Plant Cell Wall Polymers” in Polymerization (A. De Souza Gomes ed.), 2012. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 5 Our earlier finding: Cellulose forms levoglucosan end. Our flash pyrolysis with liquid chromatography / MS revealed cello-n-san’s early formation. Hypothesis: The polymer scission step is breaking the glycosidic bond and forming bicyclic LGA group. Y.-C. Lin, J. Cho, G. Tompsett, P. R. Westmoreland, G. Huber, J. Phys. Chem. C 113:46 (2009) 20097–20107. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 6 How? Pericyclic breaking of glycosidic C1-O bond. 6 1 Found and unimolecular bimolecular 6 transition 6 transition state 1 state (~235 kJ/mol (~180 kJ/mol 1 or or 56 kcal/mol) 43 kcal/mol) Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 7 Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 8 Pericyclic TSs for the other glucose reactions, too… Note how many poly-ols are present; How do they decompose? What are the multi-ol effects? Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 9 Pyrolyses with GCxGC-TOFMS give details. TGA/DSC Flash pyrolyzer Pulse-Injected Deactivated-SS or Quartz flow reactors TA Instruments, CDS Analytical, SDT Q600 Pyroprobe 5200 GCxGC/TOFMS LECO Corp., Pegasus 4D Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 10 Serial columns and TOF MS resolve close elutions. Here, analyzing t-butyl alcohol revealed butan-2-ol as an impurity in the feed. Pyrolysis at 400°C in the Pulse-Injected Deactivated-SS reactor implies: t-Butyl alcohol mainly dehydrates to isobutene (2-methylpropene). Butan-2-ol impurity mainly dehydrogenates to methylethyl ketone but also dehydrates to but-2-ene. Secondary: StabilWax®-DA with Carbowax-20M polyethylene glycol stationary phase (Restek Corp.) Primary: 30 m, 0.25 mm ID, Rtx-200 fused-silica capillary column with polytrifluoropropylmethylsiloxane stationary phase (Restek Corp.) Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 11 Mono-alcohols: methanol ethanol propanol 2-propanol (& d8 version) butan-2-ol t-butyl alcohol neopentyl alcohol 5-HDMF Diols: ethan-1,2-diol propan-1,2-diol propan-1,3-diol Triol: propan-1,2,3-triol Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 12 All but one of the saturated 1° and 2° mono- alcohols mainly underwent 1,2-dehydrogenation. Forms a carbonyl group in place of the alcohol’s C-OH. 1° alcohol aldehyde. (Methanol formed methanal, ethanol formed ethanol, propanol formed propanal). 2° alcohols ketone with no alteration of alkyl chains. (Propan-2-ol formed dimethylketone, butan-2-ol formed methyl ethyl ketone). Not radical chemistry: Mixture of propan-2-ol and propan-2-ol-d8 was pyrolyzed. No products of any H-D exchange. Any other products like alkenes created much smaller chromatographic peaks. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 13 The main exception was neopentyl alcohol. Dehydrogenated to 2,2-dimethylpropanal (CH3)3C-CH=O and dehydrated to 2- methylpropene (CH3)2C=CH2. Two other mono-alcohols were not 1° or 2° alkyl alcohols. Saturated tertiary mono-alcohol 2- methylpropan-2-ol (t-butyl alcohol) only dehydrated, forming 2-methylpropene, (CH3)2C=CH2. Phenol did not form any detectable reaction products at 400°C. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 14 Pericyclic decompositions will dominate at 400°C. Methanol provides illustrative examples, depending on [ROH]: “meta” “para” Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 15 Compare mono-ols: meta vs. para dehydrogenation. Meta molecular catalysis has lowest activation energies (kcal/mol). Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 16 Multiple types of reactions occur for diols (and triol). Symmetrical ethan-1,2-diol: Dehydrogenation product HO-CH2CH(=O) But also fragmentation to CH3CH=O and CH2=O. Compare to propandiols… Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 17 Multiple types of reactions for diols (2). Propan-1,2-diol: Dehydrogenated to single carbonyl at the internal C-OH position, HOCH2CH(=O)CH3, and to two carbonyls, O=CHCH(=O)CH3. Dehydrated at internal C-OH position to form CH3CH2CH=O . Fragmentation to CH3CH=O and CH2=O. Symmetrical propan-1,3-diol: Some 1,2-dehydration product CH2=CHCH2OH, but more CH2=CHCH=O . CH3CH2CH2OH and CH3CH2CH=O, implying either re-hydrogenation of the carbon-carbon double bond or displacement of the OH. Fragmentation to CH3CH=O and CH2=O. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 18 Multiple types of reactions for triol. Propan-1,2,3-triol: Forms products suggesting dehydration, dehydrogenation, and displacement or re- hydrogenation: CH2=CH-CH=O, CH3CH(=O)CH=O, CH3C(=O)CH2OH . Fragmentation to CH3CH=O and CH2=O. 13 13 Paine et al. pyrolyzed C1- and C2-labelled 1,2,3-triol; suggested cyclic 1,3-dehydration (naming it “cyclic Grob fragmentation”) to explain the labelling patterns in methanal and ethanal products. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 19 Extend with molecular-beam mass spectrometry. TOF-MS detection Electron-ionization MBMS system at NCSU VUV-Photoionization at Lawrence Berkeley Natl Lab Advanced Light Source Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 Thick-walled reactor has a slip-on, formed heater. section with ¼” thick sheath, 3.3 in. 0.5 1.0 in. in. total length to be heated, 6 in. http://www.thermocoax.com 21 Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 22 Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 To conclude: Experiments and calculations are used to probe the fates of the OH groups, including their influence on each other. Detailed speciation is provided by GCxGC-TOFMS and labelling. The results indicate the importance of pericyclic reactions in pyrolysis of OH groups in sugars and cellulosics. Continuing work computes rate coefficients for the steps and probes further with molecular-beam mass spectrometry. Results point to possible routes for radical influences – pertinent for lignin-hemicellulose interactions. Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, November 1-3, 2016 23 Grateful acknowledgements: Vikram Seshadri, Jordan Keith. US Department of Energy NABC program through a subaward
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