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At least 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

On the Mechanism of Soot Nucleation. III. The Fate and Facility of the E-Bridge

Rotationally-excited dimerization of aromatic moieties is a mechanism proposed recently to explain the initial steps of soot particle inception in combustion and pyrolysis of hydrocarbons. The product of such dimerization, termed E-bridge, is an angled molecular structure composed of two aromatic rings sharing a common bond. The present study explores the immediate fate of the E-bridge. The performed theoretical analysis indicates that abstraction of a bridge H atom by a gaseous H leads to a rapid transformation of the angled to planar structure. The implications of this result is that the collisionally-activated E-bridge formation followed by its flattening effectively increases the size of “planar” aromatic precursors by combining two aromatic moieties with essentially collisional rates, instead of a slower “atom-by-atom” buildup. The faster growth speeds up PAH reaching a size when physical dimerization takes over. Furthermore, the dimerization can be further assisted by the biradicaloid valence structure of the flattened E-bridge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The Role of Protons and Hydrides in the Catalytic Hydrogenolysis of Guaiacol at the Ruthenium Nanoparticle-water Interface

The mechanistic roles of free hydronium ions, surface hydrides, and interfacial protons during guaiacol hydrodeoxygenation (HDO) on ruthenium nanoparticles are established. As guaiacol adsorbs on Ru, it loses its strong aromaticity and undergoes a rapid H-shift from its hydroxyl to meta carbons (in relation to its hydroxyl group), leading enol and keto surface isomers to exist in chemical equilibrium. HDO occurs via a hydridic H-adatom (H*) attack to the enol, followed by a kinetically relevant C-O bond rupture step, during which water shuttles the hydroxyl proton, enabling its intramolecular attack to the methoxy, evolving a high charged [Ru(s)-(C6H5O-)…(H+)…OCH3]† transition state. The competing HYD begins with a rapid H* attack to the keto, before a second, kinetically relevant H* attack, without proton involvement. Water, despite shifting the thermodynamics towards the more polar surface keto, promotes HDO to a much greater extent than HYD, because of its dual catalytic roles—it mobilizes hydroxyl proton (Brønsted acid) to cleave the strong C-O bond, synchronizing with the Ru metal surface (base) function that stabilizes the resulting [Ru(s)-(C6H5O-)…(H+)…OCH3]† transition state, and the water layers solvate this charged transition state, further reducing its free energy. Free hydronium ions do catalyze a separate homogeneous enol-keto isomerization, but this reaction is kinetically unrelated to HDO catalysis. This mechanistic picture explains the strong effects of polar protic solvent in hydrodeoxygenation, highlighting (i) the requirements of surface hydrides and interfacial protons acting in tandem to complete a HDO turnover and (ii) the cooperative role of protic solvent and metal surface in breaking the aromaticity and stabilizing charged reactive precursors and transition states.

Shangguan, Junnan↗
DOE OSTI2017

Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1 H, 2 H, and 13 C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sites and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13 C NMR results for isotopically labeled acetic acid ( 13 CH 3 COOH and CH 3 13 COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3 -TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.

09 BIOMASS FUELS↗
DOE OSTI2022

Latitude, Elevation, and Mean Annual Temperature Predict Peat Organic Matter Chemistry at a Global Scale

Peatlands contain a significant fraction of global soil carbon, but how these reservoirs will respond to the changing climate is still relatively unknown. A global picture of the variations in peat organic matter chemistry will aid our ability to gauge peatland soil response to climate. Here, the goal of this research is to test the hypotheses that (a) peat carbohydrate content, an indicator of soil organic matter reactivity, will increase with latitude and decrease with mean annual temperatures, (b) while peat aromatic content, an indicator of recalcitrance, will vary inversely, and (c) elevation will have a similar effect to latitude. We used Fourier Transform Infrared Spectroscopy to examine variations in the organic matter functional groups of 1034 peat samples collected from 10 to 20, 30–40, and 60–70 cm depths at 165 individual sites across a latitudinal gradient of 79°N–65°S and from elevations of 0–4,773 m. Carbohydrate contents of high latitude peat were significantly greater than peat originating near the equator, while aromatic content showed the opposite trend. For peat from similar latitudes but different elevations, the carbohydrate content was greater and aromatic content was lower at higher elevations. Higher carbohydrate content at higher latitudes indicates a greater potential for mineralization, whereas the chemical composition of low latitude peat is consistent with their apparent relative stability in the face of warmer temperatures. The combination of low carbohydrates and high aromatics at warmer locations near the equator suggests the mineralization of high latitude peat until reaching recalcitrance under a new temperature regime.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Cross-kingdom comparative genomics reveal the metabolic potential of fungi for lignin turnover in deadwood

Deadwood is a major carbon source in forests, and yet the fate of this carbon remains a gap in our understanding of global carbon cycling. Lignin, the most recalcitrant biopolymer in wood, is mainly decayed through extracellular enzymatic and chemical processes initiated by white-rot fungi. However, the intracellular conversion of lignin decay products has been overlooked in the fungal kingdom. Here we integrate comparative genomic and phylogenetic analyses to understand the distribution and evolution of enzymes responsible for modifying lignin-related aromatic compounds—such as decarboxylases, hydroxylases, dioxygenases and other downstream ring-cleavage enzymes—that funnel carbon to central metabolism across the bacterial and the fungal kingdoms. We demonstrate that specific fungal lineages conserve these enzyme families, and that the abilities to enzymatically depolymerize lignin and catabolize lignin-related aromatic compounds are not necessarily coupled. Our analyses also reveal an expanded substrate specificity of aromatic ring-cleavage enzymes during fungal evolution, as well as a clade of extracellular enzymes among them, broadening the spatial range of these biochemical capabilities. Together, our results highlight a large diversity of fungal enzymes and hosts that warrant further investigation for inclusion into carbon cycling models and biotechnological applications for the conversion of aromatic compounds.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Toward engineering E. coli with an autoregulatory system for lignin valorization

Significance Lignin valorization is critical for economic viability of future biorefineries but is hindered due to the challenges of engineered bio-chassis such as the slow kinetics of substrate uptake, aromatics toxicity, and cost. Here, an autoregulatory system involving a vanillin autoinducible promoter is demonstrated with an aromatics transporter in Escherichia coli that is induced by lignin-derived aromatics and simultaneously converted to value-added platform chemical with diverse applications. In addition to alleviating toxicity, the engineered E. coli strain eliminates the need for an external inducer such as isopropyl β- d -1-thiogalactopyranoside during fermentation, thereby significantly reducing the process cost. This study demonstrates an autoregulatory system for aromatics bioconversion and serves as a platform for future strain development for lignin valorization.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

GAS PHASE SYNTHESIS OF (ISO)QUINOLINE AND ITS ROLE IN THE FORMATION OF NUCLEOBASES IN THE INTERSTELLAR MEDIUM

Nitrogen-substituted polycyclic aromatic hydrocarbons (NPAHs) have been proposed to play a key role in the astrochemical evolution of the interstellar medium, yet the formation mechanisms of even their simplest prototypes—quinoline and isoquinoline—remain elusive. Here, we reveal a novel concept that under high temperature conditions representing circumstellar envelopes of carbon stars, (iso)quinoline can be synthesized via the reaction of pyridyl radicals with two acetylene molecules. The facile gas phase formation of (iso)quinoline in circumstellar envelopes defines a hitherto elusive reaction class synthesizing aromatic structures with embedded nitrogen atoms that are essential building blocks in contemporary biological-structural motifs. Once ejected from circumstellar shells and incorporated into icy interstellar grains in cold molecular clouds, these NPAHs can be functionalized by photo processing forming nucleobase-type structures as sampled in the Murchison meteorite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Phenolic compounds and black carbon feedback controls on peat decomposition and carbon accumulation in southeastern peatlands under regimes of seasonal drought, drainage and frequent fire

Peatlands store one-third of soil C in terrestrial ecosystems and have persisted through changing climate over millennia from the arctic to the tropics. Approximately one-third of peat stores are found in subtropical and tropical peatlands (STPs) formed from high-lignin woody biomass. In this project, our questions are: 1) why do these non-sphagnum peatlands (STPs) accumulate C under warmer-drier climates and 2) how might insights coming from studying control mechanisms in STPs improve the management and conservation of the vast C stores in boreal peatlands subject to increasing climate forcing. We hypothesized that a dual control or “latch mechanism” reduces decomposition in shrub/tree communities in STPs due to both (1) higher production of polyphenol and aromatic compounds in STPs than found in northern Sphagnum/Carex communities and (2) the buildup of recalcitrant organic matter produced by light fire-drought-warming-adapted communities, together leading to a reduction in the microbial decay rate of peat. After three-years of intensive biological and chemical analysis in a series of field and microcosm experiments along our north to south bog gradient from Minnesota to Peru, we show how previously unrecognized biotic factors, particularly dynamic interlinked above- and belowground attributes control C sequestration in peatlands. Our key findings include (1) phenolics-bridged plant-microbe symbioses, principally slow-growing microbes dominated in higher phenolic wooded STPs, preserving C in peatlands under climate change, 2) phenolics are the overarching factor controlling the relative abundance of slow-and fast-growing microbes, the slow-growing microbes in STPs metabolize C slowly and are inherently resistant to disturbance, 3) global data analysis shows that soil respiration does not increase exponentially from boreal to tropical peatlands, suggesting that slow-growing microbes may have become dominant in most non-boreal peatlands, 4) peat chemistry analysis from over 2000 samples show that across peatlands both from the arctic to tropics and from high to low elevation peatlands recalcitrance increases as aromatic content increases, and 5) peat affected by low-severity wildfires displays a similar pattern of higher aromatic content. Our findings all demonstrate links between peat recalcitrance and increased content of phenolics and other aromatic compounds in plants. Thus, linked plant–microbe symbiotic traits are a key to understanding ecological resilience and resistance developed in peatlands under disturbance. New trait-based approaches that can better link above-and below ground processes are needed to advance both the accuracy and precision of current abiotic-factor-based Earth system models in predicting future soil C responses to climate-change feedbacks.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Effect of Cation–π Interaction on Macroionic Self‐Assembly

Abstract A series of rod‐shaped polyoxometalates (POMs) [Bu 4 N] 7 [Mo 6 O 18 NC(CH 2 O) 3 MnMo 6 O 18 (OCH 2 ) 3 CNMo 6 O 18 ] and [Bu 4 N] 7 [ArNMo 6 O 17 NC(CH 2 O) 3 MnMo 6 O 18 (OCH 2 ) 3 CNMo 6 O 17 NAr] (Ar=2,6‐dimethylphenyl, naphthyl and 1‐methylnaphthyl) were chosen to study the effects of cation–π interaction on macroionic self‐assembly. Diffusion ordered spectroscopy (DOSY) and isothermal titration calorimetry (ITC) techniques show that the binding affinity between the POMs and Zn 2+ ions is enhanced significantly after grafting aromatic groups onto the clusters, leading to the effective replacement of tetrabutylammonium counterions (TBAs) upon the addition of ZnCl 2 . The incorporation of aromatic groups results in the significant contribution of cation–π interaction to the self‐assembly, as confirmed by the opposite trend of assembly size vs. ionic strength when compared with those without aromatic groups. The small difference between two aromatic groups toward the Zn 2+ ions is amplified after combining with the clusters, which consequently triggers the self‐recognition behavior between two highly similar macroanions.

Luo, Jiancheng↗
DOE OSTI2020

The Critical Role of Reductive Steps in the Nickel-Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C-O Bonds

Hydrogenolysis of the aromatic C-O bond in aryl ethers is catalyzed by Ni in decalin or water at 150 °C. Observations of a significant kinetic isotope effect (kH/kD = 5.7) for the reactions of diphenyl ether under H2 and D2 and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is the rate-limiting step rather than C-O scission. Hydrogen addition occurs on the metal before C-O bond scission. DFT calculations indicate that hydrogen atom addition to the ortho position followed by C-O scission is energetically more feasible than C-O scission followed by H addition to either phenoxyl or phenyl moieties. Hydrogenolysis initiated via H addition in water is more selective (~75 %) compared to reactions in decalin (~30 %). The high selectivity for hydrogenolysis is attributed to stabilization of polar transition state by water as a polar solvent.

Wang, Meng↗
DOE OSTI2018

Effect of Cation-π Interaction on Macroionic Self-Assembly

Here, a series of rod–shaped polyoxometalates (POMs) [Bu 4 N] 7 [Mo 6 O 18 NC(CH 2 O) 3 MnMo 6 O 18 (OCH 2 ) 3 CNMo 6 O 18 ] and [Bu 4 N] 7 [ArNMo 6 O 17 NC(CH 2 O) 3 MnMo 6 O 18 (OCH 2 ) 3 CNMo 6 O 17 NAr] (Ar=2,6–dimethylphenyl, naphthyl and 1–methylnaphthyl) were chosen to study the effects of cation–π interaction on macroionic self–assembly. Diffusion ordered spectroscopy (DOSY) and isothermal titration calorimetry (ITC) techniques show that the binding affinity between the POMs and Zn 2+ ions is enhanced significantly after grafting aromatic groups onto the clusters, leading to the effective replacement of tetrabutylammonium counterions (TBAs) upon the addition of ZnCl 2 . The incorporation of aromatic groups results in the significant contribution of cation–π interaction to the self–assembly, as confirmed by the opposite trend of assembly size vs. ionic strength when compared with those without aromatic groups. The small difference between two aromatic groups toward the Zn 2+ ions is amplified after combining with the clusters, which consequently triggers the self–recognition behavior between two highly similar macroanions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Cu‐Catalyzed Aerobic Oxidative C─C Cleavage in Lignin‐Derived Oligomers and Biological Funneling of the Monomeric Products

Existing methods for lignin deconstruction to aromatic monomers primarily cleave carbon–oxygen bonds within the polymer, resulting in sub-optimal monomer yields and formation of oligomers that retain intact carbon–carbon bonds. Here, we demonstrate that copper-catalyzed aerobic oxidation under aqueous alkaline conditions promotes oxidative cleavage of carbon–carbon bonds in lignin oligomers derived from reductive catalytic fractionation (RCF) of pine and poplar biomass. Fundamental insights are gained from reactions of model compounds that resemble subunits present in RCF oligomers. Optimal results are achieved in a flow reactor that provides precise control over O2 delivery, temperature, and reaction residence time. The Cu-catalyzed aerobic oxidation conditions access aromatic monomers in 19 and 34 wt% monomer yields, respectively, from pine- and poplar-derived RCF oligomers. Overall, the sequence consisting of biomass RCF into monomers and oligomers followed by oxidative deconstruction of the RCF oligomers generates substantially higher yields of aromatic monomers from lignin. Engineered strains of Pseudomonas putida support biological funneling of the oligomer-derived oxygenated aromatic compounds into cis,cis-muconic acid from pine or 2-pyrone-4,6-dicarboxylic acid from poplar.

09 BIOMASS FUELS↗
DOE OSTI2026

Dual Chemical Looping/Catalytic Process for Alkylation of Benzene With Ethane and Propane Yielding Ethylbenzene and Cumene Over Copper‐Containing Mordenite

Given the sustained demand for alkylated aromatics and the strained olefin market, there is an urgent need to develop efficient one‐step processes for the direct alkylation of aromatics using alkanes instead of olefins. Such technologies offer greater energy efficiency and sustainability by eliminating the need for separate, energy‐intensive alkane dehydrogenation steps. In this work, we report a dual chemical looping / catalytic process that couples alkane dehydrogenation with aromatic alkylation over a copper‐containing mordenite yielding up to 25% of alkylated aromatics with >97% selectivity per cycle. In situ MAS NMR and FTIR spectroscopies combined with DFT calculations showed that the alkylation of benzene with alkanes proceeds via a π‐bounded Cu(I)‐olefin intermediate, which subsequently interacts with benzene, catalyzed by Brønsted acid sites, leading to alkylated products that readily desorb from the active material into the gas phase. DFT calculations show that alkylation mediated solely by Cu(I) has prohibitively high barriers (>1.8 eV), whereas a bi‐functional pathway involving both Cu(I) and Brønsted acid sites can proceed with significantly lower barrier (0.8 eV) through a concerted C–C bond formation and proton transfer step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Selective Oxidation of Lignin Model Compounds

Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Finally, owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Reactivity of novel high-performance fuels on commercial three-way catalysts for control of emissions from spark-ignition engines

The Department of Energy “Co-Optimization of Fuels and Engines” initiative aims to simultaneously develop novel high-performance fuels with advanced engine designs to reduce petroleum consumption. To achieve commercialization, advanced engines running on alternative fuels still must meet emissions regulations. Warm three-way catalysts (TWC) are very effective at meeting the stringent emissions regulations on pollutants such as nitrogen oxides (NOx), non-methane organic gases (NMOG) and carbon monoxide (CO) from gasoline-fueled spark-ignition (SI) engines operating under stoichiometric conditions; thus, most SI engine emissions occur during cold-start, when the TWC has not yet achieved light-off. In the current study, the light-off behavior of novel high-performance fuel candidates has been investigated on a hydrothermally-aged commercial TWC using a synthetic engine-exhaust flow reactor system according to industry guidelines. Over 30 potential fuel components were examined in this study, including alkanes, alkenes, alcohols, ketones, esters, aromatic ethers, and non-oxygenated aromatic hydrocarbons. Short-chain acyclic oxygenates, including alcohols, ketones, and esters, tended to light off at relatively low temperatures, while alkenes, aromatics, and cyclic oxygenates tended to light off at relatively high temperatures. The light-off behavior of alkanes and alkenes depended strongly on their size and structure. In terms of the influence on CO light-off on the TWC, the fuels fell into two distinct categories: (i) non-inhibiting species including C 2 -C 3 alcohols, alkanes, acyclic ketones, and esters; and (ii) inhibiting species including alkenes, aromatic hydrocarbons, cyclic oxygenates, and C 4 alcohols.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2018

Catalytic fast pyrolysis of bamboo sawdust via a two-step bench scale bubbling fluidized bed/fixed bed reactor: Study on synergistic effect of alkali metal oxides and HZSM-5

Catalytic fast pyrolysis of bamboo sawdust was conducted by a tandem bubbling fluidized bed/fixed bed reactor. Effect of pyrolysis and catalyst temperatures on product yield was studied. In addition, synergistic effect of HZSM-5 and base catalysts (including CaO, MgO, and SrO) for the promotion of aromatic hydrocarbons was revealed. Experimental results illustrated that both pyrolytic and catalytic reactor temperatures played pivotal roles in the yield of bio-oil, and the optimal pyrolysis and catalytic reactor temperatures were 550 °C and 500 °C, respectively. Ex-situ catalytic trial decreased the yield of bio-oil compared to in-situ run, while it facilitated the formation of phenol and alkylphenols. Mixed catalytic upgrading modes exhibited more significant aromatization and deoxygenation activities than sequential ones. In particular, ex-situ run using CaO mixed with HZSM-5 increased the concentration of aromatic hydrocarbons to 31.34%, which was ~11.48% higher than that derived from CaO and HZSM-5 sequentially processed mode. The dominated products in alkylphenols were cresol isomers and ethylphenols, and compared to sequential cases, mixed catalytic upgrading trials promoted the relative selectivity of phenol. Synergistic effect of base catalysts and HZSM-5 contributed to the production of monocyclic aromatic hydrocarbons, and CaO mixed with HZSM-5 mode showed the most prominent synergistic effect for the enhanced relative selectivity to xylenes and toluene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Catalytic fast co-pyrolysis of bamboo sawdust and waste tire using a tandem reactor with cascade bubbling fluidized bed and fixed bed system

Catalytic fast co-pyrolysis (co-CFP) of bamboo sawdust and waste tire over HZSM-5 and MgO was conducted using a tandem pyrolysis and upgrading system which consists of a bubbling fluidized bed and a fixed bed reactor. HZSM-5 mixed and sequential with MgO modes were studied to explore the additive effect for the promotion of aromatic hydrocarbons. Experimental results indicated that co-CFP of bamboo sawdust with waste tire over pure HZSM-5 increased the yields of pyrolysis oil and char, while the gas yield decreased with the increasing of waste tire percentage in the feedstock blends. The product distribution of pyrolysis oil obtained from co-CFP of bamboo sawdust and waste tire over pure HZSM-5 was dominated by aromatic hydrocarbons, and the relative concentration increased from 26.71 to 71.50% as the waste tire percentage elevated from 0 to 60 wt%. Co-CFP of bamboo sawdust and waste tire using HZSM-5 mixed with MgO mode produced a higher yield of pyrolysis oil than the sequential mode when HZSM-5/MgO mass ratio was raised from 1:4 to 1:1. However, the sequential mode was proved to be more effective in the promotion of aromatic hydrocarbons than the mixed mode at a higher HZSM-5 proportion. A positive additive effect for alkylbenzenes was found when the sequential mode was used at varying HZSM-5/MgO mass ratios. Regarding the olefins, C10 olefins were main products, and limonene selectivity increased at first and then decreased with the highest selectivity of 38.87% occurring at HZSM-5/MgO of 2:3 in the mixed mode case. In conclusion, the additive effect of HZSM-5 and MgO indicated that both the mixed and sequential modes inhibited the formation of polycyclic aromatic hydrocarbons with the most significant additive effect obtained at HZSM-5/MgO mass ratio of 1:1 using the mixed mode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Structural elucidation of hydro-products from hydrothermal carbonization of loblolly pine at different temperatures using NMR techniques

Structural properties and functional groups variations of hydro-products from hydrothermal carbonization (HTC) of loblolly pine at 180, 200, 220, 240 and 260 °C were investigated in this paper. More than 50% fixed carbon content can be obtained in solid products, indicating HTC is a valued carbon sequestration method. The Higher Heating Value (HHV) of the solid residue from 260 °C reached 30.74 MJ/kg, nearly 1.53 times that of untreated pine. Higher temperature benefit for the generation of condensed aromatic structure especially at 240 °C, while 260 °C more conductive to etherification and aryl-condensation substitution reaction. Solid products from HTC were condensed carbon materials consist of lignin/pseudo-lignin and furfural structures with low carbonyl and carboxyl content, protonated carbon percentage in aromatic structure is higher than un-protonated carbon in aromatic structures, methoxy content reduced at higher temperature while aliphatic side-chains content increased; Liquid chemicals were water-soluble products consist of condensed polyaromatic structure with an elevated content of carbonyl and carboxyl groups, un-protonated carbon in aromatic structures show higher percentage, methoxy content increased at higher temperature while aliphatic side-chains content decreased, free phenol hydroxyl are richer than C 5 substituted condensed phenolic OH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗