On-Line Mass Spectrometric Methods for the Determination of the Primary Products of Fast Pyrolysis of Carbohydrates and for Their Gas-Phase Manipulation

Hurt, Matthew; Degenstein, John C.; Gawecki, Piotr; Borton, David J.; Vinueza, Nelson R.; Yang, Linan; Agrawal, Rakesh; Delgass, W. Nicholas; Ribeiro, Fabio H.; Kenttämaa, Hilkka I.

doi:10.1021/ac402380h

Cited by 40 publications

(70 citation statements)

References 44 publications

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“…The cellulosic and hemi-cellulosic fraction of pyrolysis oil vapors and condensed bio-oil is largely responsible for many of its adverse fuel properties and the high propensity for coke formation [1]. Studies on pyrolysis of cellulose and sugar-derived oxygenates coupled with gas or liquid chromatography (GC or LC) and mass spectrometry (MS) have shown how the small oxygenates formed during pyrolysis can undergo secondary polymerization reactions, forming larger molecules and eventually coke [17,18]. The composition of pyrolysis vapor and condensed bio-oil is highly complex as highlighted in several reviews [1,19,20].…”

Section: Introductionmentioning

confidence: 99%

The Influence of Active Phase Loading on the Hydrodeoxygenation (HDO) of Ethylene Glycol over Promoted MoS2/MgAl2O4 Catalysts

et al. 2019

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The hydrodeoxygenation (HDO) of ethylene glycol over MgAl2O4 supported NiMo and CoMo catalysts with around 0.8 and 3 wt% Mo loading was studied in a continuous flow reactor setup operated at 27 bar H2 and 400 °C. A cofeed of H2S of typically 550 ppm was beneficial for both deoxygenation and hydrogenation and for enhancing catalyst stability. With 2.8-3.3 wt% Mo, a total carbon based gas yield of 80-100 % was obtained with an ethane yield of 36-50 % at up to 118 h on stream. No ethylene was detected. A moderate selectivity towards HDO was obtained, but cracking and HDO were generally catalyzed to the same extent by the active phase. Thus, the C2/C1 ratio of gaseous products was 1.1-1.5 for all prepared catalysts independent on Mo loading (0.8-3.3 wt%), but higher yields of C1-C3 gas products were obtained with higher loading catalysts. Similar activities were obtained from Ni and Co promoted catalysts. For the low loading catalysts (0.83-0.88 wt% Mo), a slightly higher hydrogenation activity was observed over NiMo compared to CoMo, giving a relatively higher yield of ethane compared to ethylene. Addition of 30 wt% water to the ethylene glycol feed did not result in significant deactivation. Instead, the main source of deactivation was carbon deposition, which was favored at limited hydrogenation activity and thus, was more severe for the low loading catalysts.

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Section: Introductionmentioning

confidence: 99%

The Influence of Active Phase Loading on the Hydrodeoxygenation (HDO) of Ethylene Glycol over Promoted MoS2/MgAl2O4 Catalysts

et al. 2019

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“…In order to overcome the aforementioned limitations, an on‐line mass spectrometric analysis method published recently was employed to detect the initial products (i. e., the first products leaving the hot pyrolysis surface) of fast pyrolysis of lignin model compounds ranging from trimers to a polymer. We believe that this is the first time that the fast pyrolysis behavior of pure, nonderivatized lignin oligomers (larger than dimers) has been examined and reported.…”

Section: Introductionmentioning

confidence: 99%

Initial Products and Reaction Mechanisms for Fast Pyrolysis of Synthetic G‐Lignin Oligomers with β‐O‐4 Linkages via On‐Line Mass Spectrometry and Quantum Chemical Calculations

et al. 2017

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The products of fast pyrolysis that first leave the hot pyrolysis surface were identified for three G‐lignin model compounds, a trimer, a tetramer and a synthetic polymer, all containing β‐O‐4 linkages, by using a very fast heating pyrolysis probe coupled with a linear quadrupole ion trap mass spectrometer or a linear quadrupole ion trap coupled with an orbitrap detector. High‐resolution measurements were used to determine the elemental compositions of the deprotonated pyrolysis products. Their structures were examined using collision‐activated dissociation experiments and via comparison to the dissociation reactions of ionized authentic compounds. The initial pyrolysis products for all model compounds range from monomers to tetramers. Even for the polymer, no products larger than tetramers were observed. None of the products were radicals. The observed trimers and tetramers were formed directly from the intact model compounds rather than from repolymerization of initially formed monomers. Both the observed product distributions and quantum chemical calculations suggest that the mechanism(s) of the major reactions occurring under the conditions employed here are Maccoll and/or retro‐ene eliminations rather than radical reactions. Based on a comparison of the behavior of the smaller β‐O‐4 model compounds to the synthetic β‐O‐4 lignin polymer, the smaller model compounds appear to be good surrogates for further studies of the mechanisms of fast pyrolysis of lignin.

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“…Dramatic difference in biopolymer behavior on heated, structured surfaces is integral to reactor design for utilization of natural resources such as biomass. Industrial scale pyrolysis reactions are commonly carried out in the presence of pressed silica and alumina based catalysts with macropores 27 28 , while the majority of fundamental pyrolysis studies are carried out on smooth metal surfaces 4 6 . The impact of porous structures and dramatic role of temperature on the de-wetting liftoff behavior of cellulose at high temperature allows for tuning to increase heat transfer and dramatically alter the throughput of biomass reactors, which are overall heat transfer limited systems.…”

Section: Resultsmentioning

confidence: 99%

“…When subjected to high temperatures (>400 °C), long chain biopolymers such as cellulose decompose into smaller, more valuable products used for renewable fuels and chemicals. The chemistry of cellulose decomposition is the subject of ongoing investigation 1 2 3 4 ; promotion of the desirable reaction pathways and/or variation of the heating rate can strongly alter product distribution consisting of hundreds of chemicals 5 6 . Recent work has shown that long chain, crystalline cellulose reacts to a short-lived liquid intermediate with millisecond lifetime comprised of molten oligomers before decomposing to vapors 7 8 9 .…”

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confidence: 99%

Reactive Liftoff of Crystalline Cellulose Particles

Teixeira

Krumm

Vinter

et al. 2015

Sci Rep

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The condition of heat transfer to lignocellulosic biomass particles during thermal processing at high temperature (>400 °C) dramatically alters the yield and quality of renewable energy and fuels. In this work, crystalline cellulose particles were discovered to lift off heated surfaces by high speed photography similar to the Leidenfrost effect in hot, volatile liquids. Order of magnitude variation in heat transfer rates and cellulose particle lifetimes was observed as intermediate liquid cellulose droplets transitioned from low temperature wetting (500–600 °C) to fully de-wetted, skittering droplets on polished surfaces (>700 °C). Introduction of macroporosity to the heated surface was shown to completely inhibit the cellulose Leidenfrost effect, providing a tunable design parameter to control particle heat transfer rates in industrial biomass reactors.

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On-Line Mass Spectrometric Methods for the Determination of the Primary Products of Fast Pyrolysis of Carbohydrates and for Their Gas-Phase Manipulation

Cited by 40 publications

References 44 publications

The Influence of Active Phase Loading on the Hydrodeoxygenation (HDO) of Ethylene Glycol over Promoted MoS2/MgAl2O4 Catalysts

The Influence of Active Phase Loading on the Hydrodeoxygenation (HDO) of Ethylene Glycol over Promoted MoS2/MgAl2O4 Catalysts

Initial Products and Reaction Mechanisms for Fast Pyrolysis of Synthetic G‐Lignin Oligomers with β‐O‐4 Linkages via On‐Line Mass Spectrometry and Quantum Chemical Calculations

Reactive Liftoff of Crystalline Cellulose Particles

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