ABSTRACT
Currently, biomethane obtained from coal resources, such as lignite and peat, serves as a sustainable biofuel urgently needed by the energy economy. To improve biomethane yield from lignite, the effects of different concentrations of benzyl alcohol, a degraded product of humic acid, on a biomethanation fermentation system were analyzed. The total biomethane yield, daily biomethane yield, coenzyme F420, VFA (volatile fatty acids) concentration, alkalinity, and pH were used to determine the optimal benzyl alcohol concentration. The biomethanation fermentation system with 2000 mg/L benzyl alcohol produced up to 4.03 mL/g of biomethane, which was 1.15 times that produced from the control group. The coenzyme F420, VFA, alkalinity, and pH of the system after adding 2000 mg/L benzyl alcohol were more preferable after adding other concentrations during the lignite biomethanation process. In summary, 2000 mg/L benzyl alcohol had a significantly positive effect on the lignite biomethanation fermentation system. When benzyl alcohol is added to the fermentation system, it accelerates the tricarboxylic acid cycle, which in turn produces more biomethane. Additionally, the self-supply of lignite microbial transformation nutrients from the perspective of chemical composition was explored as a novel approach in solving the common problem of low biomethane yield from a single lignite raw material. This also laid a foundation for subsequent steps through the adjustment of pretreatment conditions to ensure that the lignite pretreatment liquid contained increased benzyl alcohol, and a greater yield of biomethane can be produced after activated sludge addition.
ABSTRACT
Fulvic acid (FA) is a complex organic mixture composed of small molecules. The structure and composition of FA vary greatly because of the different raw materials used for preparing FA. In this work, FA was extracted from shallow low-rank lignite by hydrogen peroxide (H2O2) in a microwave field, and the functional groups of FA were characterized. The optimal extraction process was determined, with the H2O2 concentration being the key factor affecting the yield of FA. Thermogravimetric analysis showed that FA was mainly composed of low molecular weight and readily pyrolyzed compounds. As shown by Fourier transform infrared spectroscopy, in the process of FA extraction by H2O2 oxidation of lignite, the content of -COOH increased, long-chain aliphatic compounds decreased, stretching vibrations of aromatic ring skeletons disappeared, and aromatic ring substitution became mainly tri- or disubstitution. Fluorescence spectroscopy indicated that FA had a low degree of aromaticity. X-ray photoelectron spectroscopy qualitatively and quantitatively revealed that the main modes of carbon-oxygen bonding in FA were C-O-, COO-, and C=O. Thus, this study not only lays a foundation for studying the composition and structure of coal-based FA but also opens a new avenue for a clean and efficient utilization of lignite.
ABSTRACT
Fulvic acid (FA) has important properties and is used widely in agriculture, industry, medicine, and other fields. However, there is a lack of environmentally friendly and efficient extraction methods for coal-based FA and its molecular structural characterization. In this study, FA was extracted cleanly and efficiently from low-rank lignite via the innovative method of microwave combined with hydrogen peroxide and glacial acetic acid, followed by purification by the sulfuric acid-acetone method. The molecular structures of FA were precisely characterized by UV-vis spectroscopy, infrared (IR) spectroscopy, 1H nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry (GC-MS). The results showed that the microwave combined with hydrogen peroxide-glacial acetic acid method had stronger oxidative degradation ability compared with the conventional method. Under optimized conditions, the yield of FA reached 60.97%. During the oxidation process, the macromolecular network structure of coal was destroyed, resulting in the production of many oxygen-containing functional groups. According to the IR and UV-vis spectra, there were abundant oxygen-containing functional groups such as hydroxyl, carboxyl, carbonyl, and quinone groups in the molecular structure of FA. Determination of the total acid group content in the oxygen-containing functional groups of FA showed that the content of carboxyl groups was much higher than that of phenolic hydroxyl groups. The 1H NMR showed that there were hydrogen atoms present as part of carboxyl, aromatic, phenolic hydroxyl, and aliphatic groups in FA. The (GC-MS) results suggested that FA is a mixture of dozens of complex compounds, including alkanes, alcohols, esters, etc.
ABSTRACT
Fulvic acid (FA) is important in modern agriculture, ecological restoration, life science, and medicine. The precise characterization of the composition and molecular structure of FA has become a key scientific issue in both basic and applied research. In this study, coal-based FA was separated by microwave-assisted oxygenation from lignite originating from Inner Mongolia in China. Through elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, classical quantitative titration experiments, and quantum chemistry combined with software analysis, the representative microscopic molecular structure of FA was determined. The results show that coal-based FA mainly contains three kinds of benzene ring substituents, ether bonds, hydrogen bonds, carbonyl groups, hydroxyl groups, carboxyl groups, phenolic hydroxyl groups, and semiquinonyl groups. The oxygen content is high, the carbon-to-oxygen ratio is less than 1, and the hydrogen-to-carbon ratio is 1.09. The ratio of aromatic carbon to total carbon is approximately 0.6, and benzene rings are connected to each other by an ether-oxygen bridge. The fat chain length of FA is approximately 0.47. FA has a small molecular structure with many acidic groups, primarily carboxyl groups and phenolic hydroxyl groups. The two-dimensional planar molecular structure of FA was established; the chemical formula is C38H32NO24, and the relative molecular mass is 886. The lowest-energy, structurally optimized three-dimensional characteristic ball-and-stick and stick models were also constructed. The calculated infrared spectrum of the molecular structure matches well with the experimental spectrum of FA, and the types and distributions of functional groups agree with the findings of previous studies. The quantum chemical data confirm that the proposed molecular structure is reasonable. The findings provide a scientific reference for applied research on FA in the future.
