Selective catalytic transformation of lignin with guaiacol as the only liquid product.
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ABSTRACT:
SUBMITTER: Shen X
PROVIDER: S-EPMC8148073 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Lignin, a major component of lignocellulosic biomass, is a valuable source of phenolic and aromatic compounds. It is, therefore, vital to develop strategies to selectively deconstruct lignin to valuable chemicals. This study focuses on the kinetics of depolymerization of lignin and the production of phenols via a microwave-assisted catalytic process at mild conditions of 80 °C in dimethyl sulfoxide/water medium. Four different catalysts used in this study, viz., Fe2O3, LaFeO3, ZrO2, and zeolite-Y hydrogen (ZYH), were characterized for structure, specific surface area, and surface morphology. The molecular weight reduction of lignin and the evolution of phenolic monomers and oligomers were monitored using various techniques, and the rate constants of lignin degradation in the presence of different catalysts were determined using a continuous distribution kinetics model, assuming scission of the lignin macromolecule at any random position. The rate constants (min-1) followed the trend: ZYH (26 × 10-4) ≈ LaFeO3 (25 × 10-4) > ZrO2 (22 × 10-4) > Fe2O3 ≈ no catalyst (16 × 10-4). Vanillic acid (15 mg g-1) and methyl phenol (17 mg g-1) were the major phenolics obtained with LaFeO3, whereas coniferaldehyde (13 mg g-1) was the major phenolic compound with Fe2O3. Vanillin was produced at ca. 11 mg g-1 with both Fe2O3 and ZYH. LaFeO3 is shown to be a promising catalyst for both molecular weight reduction of lignin and the production of monomeric phenols, whereas the use of Fe2O3 results in the formation of only phenols, possibly via specific end-chain depolymerization. The selectivities of the monomeric phenols were higher with these two catalysts, whereas with ZYH and ZrO2, the selectivities of the oligomers were better. The reusability of the catalysts and the effect of catalyst loading on kinetics of lignin depolymerization were also evaluated.
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Project description:Transition metal salts were employed as the catalysts to improve the selective degradation of the α-O-4 lignin model compound (benzyl phenyl ether (BPE)) in the solvothermal system. The results concluded that most of the transition metal salts could enhance BPE degradation. Among which, NiSO4·6H2O exhibited the highest performance on BPE degradation (90.8%) for 5 h and phenol selectivity (53%) for 4 h at 200 °C. In addition, the GC-MS analysis indicated that the intermediates during BPE degradation included a series of aromatic compounds, such as phenol, benzyl methyl ether and benzyl alcohol. Furthermore, the mechanisms for BPE degradation and phenol selectivity in the NiSO4·6H2O system involved the synergetic effects between the acid catalysis and coordination catalysis, which caused the effective and selective cleavage of the C-O bonds.
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Project description:Herein, cobalt-reduced graphene oxide (rGO) catalyst was synthesized with a practical impregnation-calcination approach for the selective hydrodeoxygenation (HDO) of guaiacol to cyclohexanol. The synthesized Co/rGO was characterized by transmission electron microscopy (TEM), high-angle annular dark-field scanning TEM (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, X-ray diffraction (XRD), and H2 temperature-programmed reduction (H2-TPR) analysis. According to the comprehensive characterization results, the catalyst contains single Co atoms in the graphene matrix and Co oxide nanoparticles (CoOx) on the graphene surface. The isolated Co atoms embedded in the rGO matrix form stable metal carbides (CoCx), which constitute catalytically active sites for hydrogenation. The rGO material with proper amounts of N heteroatoms and lattice defects becomes a suitable graphene material for fabricating the catalyst. The Co/rGO catalyst without prereduction treatment leads to the complete conversion of guaiacol with 93.2% selectivity to cyclohexanol under mild conditions. The remarkable HDO capability of the Co/rGO catalyst is attributed to the unique metal-acid synergy between the CoCx sites and the acid sites of the CoOx nanoparticles. The CoCx sites provide H while the acid sites of CoOx nanoparticles bind the C-O group of reactants to the surface, allowing easier C-O scission. The reaction pathways were characterized based on the observed reaction-product distributions. The effects of the process parameters on catalyst preparation and the HDO reaction, as well as the reusability of the catalyst, were systematically investigated.
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Project description:Phenol is an important commodity chemical in the industry, which is currently produced using fossil feedstocks. Here, we report a strategy to produce phenol from lignin by directly deconstructing Csp2-Csp3 and C-O bonds under mild conditions. It was found that zeolite catalyst could efficiently catalyze both the direct Csp2-Csp3 bond breakage to remove propyl structure and aliphatic β carbon-oxygen (Cβ-O) bond hydrolysis to form OH group on the aromatic ring. The yield of phenol could reach 10.9 weight % with a selectivity of 91.8%. In this unique route, water was the only reactant besides lignin. A scale-up experiment showed that 4.1 g of pure phenol could be obtained from 50.0 g of lignin. The reaction pathway was proposed by a combination of control experiments and density functional theory studies. This work opens the way for producing phenol from lignin by direct transformation of Csp2-Csp3 and C-O bonds in lignin.
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Project description:The photocatalytic conversion of lignin to aromatic compounds in aqueous solutions is a promising approach. We herein report a crystalline carbon nitride prepared by high-temperature thermal polymerization and alkali-metal molten salt treatment, which was then applied in the selective conversion of lignin to aromatic compounds. The results showed that the tri-s-tri-C3N4 presented a relatively high activity and selectivity for the conversion of lignin in aqueous solutions. In a 95% water-acetonitrile solution, it achieved a relatively high conversation rate of lignin, reaching 62.00%, and the selectivity of the C-C bond cleavage was high, at 86.8%. The characterization results obtained by TEM, UV-vis/DRS, PL, and transient photocurrent response showed that the ultra-high activity of tri-s-tri-C3N4 was mainly due to the improvements in crystallinity and light absorption. Mechanism studies showed that the dispersion of the catalyst and the combination of lignin and catalyst in aqueous solvents with different acetonitrile ratios were the main factors affecting lignin conversion. As the water content in the solutions increased, the primary active sites were converted from h+ to ·O2-. This study revealed the interactions between lignin, photocatalysts, and reaction solutions, providing a theoretical basis for the photocatalytic conversion of lignin in aqueous solutions.
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Project description:Engineering the microbial transformation of lignocellulosic biomass is essential to developing modern biorefining processes that alleviate reliance on petroleum-derived energy and chemicals. Many current bioprocess streams depend on the genetic tractability of Escherichia coli with a primary emphasis on engineering cellulose/hemicellulose catabolism, small molecule production, and resistance to product inhibition. Conversely, bioprocess streams for lignin transformation remain embryonic, with relatively few environmental strains or enzymes implicated. Here we develop a biosensor responsive to monoaromatic lignin transformation products compatible with functional screening in E. coli. We use this biosensor to retrieve metagenomic scaffolds sourced from coal bed bacterial communities conferring an array of lignin transformation phenotypes that synergize in combination. Transposon mutagenesis and comparative sequence analysis of active clones identified genes encoding six functional classes mediating lignin transformation phenotypes that appear to be rearrayed in nature via horizontal gene transfer. Lignin transformation activity was then demonstrated for one of the predicted gene products encoding a multicopper oxidase to validate the screen. These results illuminate cellular and community-wide networks acting on aromatic polymers and expand the toolkit for engineering recombinant lignin transformation based on ecological design principles.
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Project description:The oxidative degradation of lignin into a variety of valuable products has been under investigation since the first half of the last century. Especially, the chance to claim this cheap, abundant and renewable source for the production of the important aroma chemical vanillin (1) was one of the major driving forces of lignin research. So far most of the developed methods fail in technical application since no viable concept for work-up is included. This work represents a combined approach of electrochemical conversion of Kraft lignin and product recovery by adsorption on a strongly basic anion exchange resin. Electrolysis conditions are optimized regarding reaction temperatures below 100 °C allowing operation of aqueous electrolytes in simple experimental set-up. Employing ion exchange resins gives rise to a selective removal of low molecular weight phenols from the strongly alkaline electrolyte without acidification and precipitation of remaining lignin. The latter represents a significant advantage compared with conventional work-up protocols of lignin solutions.
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Project description:The current work studies the reductive catalytic depolymerization (RCD) of lignin from a novel semi-industrial process. The aim was to obtain aromatic mono-, di-, tri-, and tetramers for further valorization. The substrate and products were characterized by multiple analytical methods, including high pressure size-exclusion chromatography (HPSEC), gas chromatography-mass spectrometry, GC-flame ionization detector (FID), GC-FID/thermal conductivity detector (TCD), and NMR. The RCD was studied by exploring the influence of different parameters, such as lignin solubility, reaction time, hydrogen pressure, reaction temperature, pH, type and loading of the catalyst, as well as type and composition of the organic/aqueous solvent. The results show that an elevated temperature, a redox catalyst, and a hydrogen atmosphere are essential for the depolymerization and stability of the products, while the reaction medium also plays an important role. The highest obtained mono- to tetramers yield was 98% and mono- to dimers yield over 85% in the liquid phase products. The reaction mechanisms influenced the structure of the aliphatic chain in the monomers, but left the phenolic structure along with the methoxy groups largely unaltered. The current work contributes to the development and debottlenecking of the novel and sustainable overall process, which utilizes efficiently all the fractions of wood, in line with the principles of green engineering and chemistry.
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