Low temperature hydrogenation of pyrolytic lignin over Ru/TiO<sub>2</sub>: 2D HSQC and <sup>13</sup>C NMR study of reactants and products

Chen, Wen; McClelland, Daniel J.; Azarpira, Ali; Ralph, John; Luo, Zhongyang; Huber, George W.

doi:10.1039/c5gc02286j

Cited by 71 publications

(56 citation statements)

References 68 publications

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“…Solubility tests indicated that 51 % of the carbon (C %) making up the bio‐oil was pyrolytic lignin. Carbon derived from the pyrolytic lignin was undetectable in GC and HPLC due to their high boiling point, which is consistent with other studies . The summation of the carbon detected by HPLC, GC, and solubility tests was 102 C %, indicating that our characterization methods were able to detect all the carbon present in the bio‐oil with slight calibration errors.…”

Section: Resultssupporting

confidence: 90%

“…The remaining ≈50 % of carbon in the bio‐oil is detected as high molecular weight (MW) pyrolytic lignin with a carbon number greater than 7. Pyrolytic lignin consists of phenolic oligomers that can range anywhere from 50 to 3000 Da but that have an average MW between 400 and 1300 Da …”

Section: Resultsmentioning

confidence: 99%

“…Formation of network polymers derived from these keto groups is thought to be a main mechanism for coking . Pyrolytic lignin even forms coke on the catalyst surface at temperatures as low as 25 °C …”

Section: Introductionmentioning

confidence: 99%

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Hydrodeoxygenation of Pyrolysis Oils

2016

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The hydrodeoxygenation (HDO) of bio‐oil derived from white oak wood using non‐sulfided catalysts was studied in a two zone continuous flow trickle bed reactor system. The major organic components of the pyrolysis oil were pyrolytic lignin (large phenolic polymers), xylose, levoglucosan, organic acids (primarily acetic acid), and hydroxyacetaldehyde. The first zone was a low temperature zone (130 °C) that contained a Ru/C catalyst. In this zone, carbonyl groups were hydrogenated, producing propylene glycol (from hydroxyacetone), ethylene glycol (from hydroxyacetaldehyde), and sorbitol (from levoglucosan). A more severe hydrotreatment was performed in a second zone containing a bifunctional Pt/ZrP catalyst at a temperature between 300 and 400 °C. In the two‐stage HDO, an organic phase was produced that consisted of a distribution of hydrocarbons that were primarily cyclic alkanes (naphthenes) ranging from C7 to C24. The organic phase carbon yield decreased with increasing reaction temperature in the second zone. Catalyst deactivation and reactor plugging by coking occurred under all reaction conditions after 55–72 h time on stream (TOS). After ≈55 h TOS, more than 25 % of the carbon in the original bio‐oil was accumulated as coke, with increasing amounts for higher temperatures in the second zone. Hydrotreatment gave rise to >C5 hydrocarbon (gasoline and distillate‐range fuel) overall yields between ≈30 and 47 carbon % for all experiments compared to the 79.5 % theoretical yield calculated for the bio‐oil feedstock. Coke formation and undesired cracking to C1–C4 hydrocarbon gases were the main causes of lower fuel carbon yields.

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Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 99%

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Hydrodeoxygenation of Pyrolysis Oils

2016

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“…The ability to identify and assess the reactivity of the different structural units within this biopolymer is a fundamental aspect of understanding lignin's structure and advancing methods for its selective depolymerisation to generate renewable chemical feedstocks. [1][2][3][4][5][6][7][8][9] Recently, interest has increased in protocols that liberate lignin from biomass without causing large structural changes to the lignin (e.g. mild organosolv methods).…”

Section: Introductionmentioning

confidence: 99%

The synthesis and analysis of lignin-bound Hibbert ketone structures in technical lignins

et al. 2016

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Understanding the structure of technical lignins resulting from acid-catalysed treatment of lignocellulosic biomass is important for their future applications. Here we report an investigation into the fate of lignin under acidic aqueous organosolv conditions. In particular we examine in detail the formation and reactivity of non-native Hibbert ketone structures found in isolated organosolv lignins from both Douglas fir and beech woods. Through the use of model compounds combined with HSQC, HMBC and HSQC-TOCSY NMR experiments we demonstrate that, depending on the lignin source, both S and G lignin-bound Hibbert ketone units can be present. We also show that these units can serve as a source of novel mono-aromatic compounds following an additional lignin depolymerisation reaction.

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“…Thermochemical processes mainly include pyrolysis, [21][22][23] gasification, [24][25][26] oxidation, 27,28 hydrogenation, [29][30][31][32] etc. Thermochemical processes mainly include pyrolysis, [21][22][23] gasification, [24][25][26] oxidation, 27,28 hydrogenation, [29][30][31][32] etc.…”

mentioning

confidence: 99%

Biotransformation of lignin: Mechanisms, applications and future work

Zheng

2019

Biotechnology Progress

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As one of the most abundant polymers in biosphere, lignin has attracted extensive attention as a kind of promising feedstock for biofuel and bio-based products. However, the utilization of lignin presents various challenges in that its complex composition and structure and high resistance to degradation. Lignin conversion through biological platform harnesses the catalytic power of microorganisms to decompose complex lignin molecules and obtain value-added products through biosynthesis.Given the heterogeneity of lignin, various microbial metabolic pathways are involved in lignin bioconversion processes, which has been characterized in extensive research work. With different types of lignin substrates (e.g., model compounds, technical lignin, and lignocellulosic biomass), several bacterial and fungal species have been proved to own lignin-degrading abilities and accumulate microbial products (e.g., lipid

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Low temperature hydrogenation of pyrolytic lignin over Ru/TiO₂: 2D HSQC and ¹³C NMR study of reactants and products

Abstract: The low temperature hydrogenation of pyrolytic lignin over Ru/TiO2 was studied and characterized with quantitative 13C and 2D 1H–13C HSQC NMR to determine the changes in carbon functionality.

Cited by 71 publications

References 68 publications

Hydrodeoxygenation of Pyrolysis Oils

Hydrodeoxygenation of Pyrolysis Oils

The synthesis and analysis of lignin-bound Hibbert ketone structures in technical lignins

Biotransformation of lignin: Mechanisms, applications and future work

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Low temperature hydrogenation of pyrolytic lignin over Ru/TiO2: 2D HSQC and 13C NMR study of reactants and products

Abstract: The low temperature hydrogenation of pyrolytic lignin over Ru/TiO2 was studied and characterized with quantitative 13C and 2D 1H–13C HSQC NMR to determine the changes in carbon functionality.

Cited by 71 publications

References 68 publications

Hydrodeoxygenation of Pyrolysis Oils

Hydrodeoxygenation of Pyrolysis Oils

The synthesis and analysis of lignin-bound Hibbert ketone structures in technical lignins

Biotransformation of lignin: Mechanisms, applications and future work

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Product

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Low temperature hydrogenation of pyrolytic lignin over Ru/TiO₂: 2D HSQC and ¹³C NMR study of reactants and products