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Oxygenated polycyclic aromatic hydrocarbons (OPAHs) are an important group of components produced from the thermal conversion of cellulose. Through using gas chromatography mass spectrometry (GC–MS), Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) and ultraviolet fluorescence spectroscopy (UV-F), the information for the evolution of OPAHs is obtained in this study. The tar produced at low temperature mainly contains light components such as homologues of pyran and furan, while the components in the tars at 700 °C and 900 °C show high double bond equivalent (DBE) values, indicating the existence of large aromatic structures. High temperature promote condensation reactions during cellulose thermal conversion, thus leading to a higher percentage of OPAHs in the tar at higher temperature process. According to Density Functional Theory (DFT) calculation, the energy barrier of Diels-Alder reaction (302.65 kJ/mol) is lower than the dehydration (583.26 kJ/mol), which means that Diels-Alder reaction could be the main route for OPAH formation rather than dehydration reaction. High reaction temperature is calculated to be favorable for the formation of naphthol during the cellulose thermal conversion because of the high energy barrier of dehydration between phenol and furan. It is consistent with the ESI FT-ICR MS result that there is a higher content of naphthol in the tar at 700 °C than that at 500 °C.

The formation of resultant volatiles is closely related with chemical structure of char during the pyrolysis process. In this study, all-components, that are semi-char, tar and gas product obtained by Shenfu coal pyrolyzed under various residence time at 435 °C were comprehensively analyzed at molecular level, aiming to reveal the reaction pathways responsible for the evolution of chemical structure of coal/char. The results showed that CO2 and CO were the predominant pyrolysis gas product which inferred high content of organic oxygen species in low-rank Shenfu coal. At the initial stage of pyrolysis, cracking of bridged bonds, especially heteroatom bridged bonds, such as O, N and S, would produce relatively stable radicals in semi-char. Phase change of light components and decomposition of asphaltene in mobile phase can be strongly related with light tar aliphatic compounds formation. At the middle and later stage of pyrolysis, thermal cracking of polar radicals and decomposition of solvent extracted metaplast materials made predominant contribution to tar formation. In addition, the cracking of peripheral aromatic structures of coal/char skeleton structure, through which secondary reaction (such as methylation and dehydrogenation reaction) took place, would result in tar (light tar and heavy tar) and H2 formation.

Heavy components affect conversion behaviors of sludge-derived pyrolytic liquids during their utilization and contribute significantly to the formation of the notorious tar and soot during sludge gasification and combustion. Understanding the evolution of heavy components during pyrolysis is vital for developing a reliable sewage sludge utilization technology. This study investigates the compositions of oils from the pyrolysis of sewage sludge using an electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT ICR-MS). Hundreds of compounds with molecular mass higher than 400 Da were detected from the pyrolytic oil obtained at 450 and 650 °C. Higher pyrolysis temperatures promoted decomposition and polycondensation of large molecules and increased the amount of nitrogen-containing compounds in the liquid. Aromatic structured molecules consisting of carbon, hydrogen and nitrogen were the predominant compounds at 850 °C. From the results of this study, the evolution routes of heavy components in the pyrolytic liquid are proposed.

The structural evolution of coal during pyrolysis process has been studied for a long time but remains unclear, mainly due to the extraordinary complexity of coal structure. The present study aimed to further identify the chemical structural evolution of different parts in the semi-chars obtained by low-temperature pyrolysis of a Chinese low-rank coal (Shenfu coal). Semi-chars and their solvent extracted materials (oil, resin, asphaltene and preasphaltene) were analyzed by 13C nuclear magnetic resonance (NMR) mass spectrometry, diffuse reflectance Fourier transform-infrared spectroscopy (DRIFTs) and ultraviolet (UV) fluorescence spectroscopy, separately. The results showed that 23.8% weight loss occurred during the whole pyrolysis process at 435 °C and half of the weight loss was achieved in the initial five minutes. By contrast, amount of the extracts in semi-chars (solvent extracted metaplast materials) decreased more dramatically in the initial stage of the pyrolysis, and 51.8% of the extracts disappeared in the initial one minute. Oil and preasphaltene showed higher thermal sensitivity than asphaltene and resin. Considerable content of metaplast materials with 1–2 rings (especially in oil and/or asphaltene) were produced along with the pyrolysis process. Condensed aromatic structures in semi-chars were relatively stable and mainly decomposed in the initial stage of pyrolysis which could be attributed to the dramatically decomposition of some active aromatic structures with ≥ 4 rings (especially the components in extracts such as preasphaltene). The results provided a new insight into the structural evolution of coal during low-temperature pyrolysis process, which specially considered the detailed information of the solvent extractable metaplast materials in semi-chars.

Four types of biomass-derived organics (toluene/1-methylnaphthalene/phenol/ethanol) were catalytically decomposed and steam reformed over Ni/α-Al2O3 for co-production of hydrogen and carbon nanotubes (CNTs). In the decomposition reaction, the oxygen functional group in phenol and ethanol promoted the co-production of hydrogen and CNTs, while a small amount of toluene and 1-methylnaphthalene were cracked to hydrogen and amorphous carbon. In the reforming reaction, the yields of hydrogen and CNTs sharply increased. More than 2000 mmol/(g-cata∗h) of H2 and 260 mg/(g-cata∗h) of CNTs were produced after the reforming of toluene and ethanol. However, 1-methylnaphthalene was difficult to be reformed and small amount of CNTs were formed. The organics with low molecular weight and low degree of unsaturation conduced to the formation of hydrogen and CNTs. The growth of CNTs on Ni/α-Al2O3 mainly follows the tip-growth mechanism. The diameter distribution of CNTs is not only influenced by Ni particle size, but also related to the different organics and steam addition.

Microwave-assisted extractions (MAEs) were carried out on Shenfu (SF) low-rank coal using four types of solvent, namely tetrahydrofuran, methanol, dichloromethane and ethyl acetate. Comparison with the traditional thermal extractions (TEs) indicated that MAEs were much more efficient in extracting organic components of SF coal. A large amount of aromatic compounds with 2–3 rings and rich branched alkanes could be extracted from coal by MAE. The results also showed that solvent polarity and the interaction between solvent and functional groups abundant in the extracts were the two main factors leading to differences of their MAE. Among the studied solvents, tetrahydrofuran could extract much more amount of polar compounds and its solution was rich in highly-condensed polycyclic aromatic compounds (PACs) with ≥ 4 rings. And this feature had relationship with its strongest interaction with the C O bond. Ethyl acetate, in contrast, showed strong interaction with the C O bonds and had good potential for the extraction of low-polarity compounds especially PACs with two aromatic rings and aliphatic compounds with long alkane chains. And for methanol and dichloromethane, their solvent polarity played dominant roles during the MAE procedures. The results provided more detailed mechanistic influences of different solvents on MAE of coal, and would help for the identification of a suitable solvent for efficient detection of components in organic substances, especially the extraordinary complex compounds in coal.

Coal property and structures of 32 kinds of Chinese coals were investigated from the insights of second-order Raman spectrum using micro-Raman spectroscopy. A new deconvolution method for the second-order Raman spectrum of coal has been established, and the spectrum from 2100 to 3400 cm–1 was curve-fitted by eight Gaussian bands successfully. The results indicate that the bands at 3060 and 2810 cm–1 are sensitive to the volatiles content in coal and the bands at 2925, 2670, and 2480 cm–1 are related to the more ordered structures of coal. Reasonable correlations between the second-order Raman bands area ratios and coal property parameters have been found, and an effectively comprehensive method for evaluating the coal property based on a second-order Raman spectrum has been built. The results reveal that the C–H and amorphous carbon structures increase with the increase of volatile content in the coal but have no obvious relationship with the fixed carbon content. Besides, the order degree of coal structu...

This work aimed to evaluate the detailed chemical structures of the asphaltenes in the tetrahydrofuran-microwave-extracted portions from two Chinese coals, namely, Shenfu and Zhundong coal (SF, ZD) and to clarify their characteristics on chemical composition at molecular level. Based on the analyses of diffuse reflectance Fourier transform infrared spectroscopy (DRIFT) and Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), the detailed chemical structure of a series of basic and non-basic nitrogen- and oxygen-containing class species in the asphaltenes were clarified. The results revealed that condensed nitrogen-containing alkylaromatic structures with amidogens (1–3) were the main structure units in N 4 O y (y = 0–2) class species due to the high double bond equivalent (DBE) values for both the asphaltene from SF (A SF ) and the asphaltene from ZD (A ZD ). Acidic O 2 –O 7 class species with two or three aromatic rings were the main structure units, among which O 4 and O 2 class species had the highest relative abundances (RAs) in A SF and A ZD , respectively. Acidic oxygen-containing components in A ZD had narrower range of DBE and carbon number and mainly consisted of aromatic structure units with two rings. On the contrary, the average DBE values of O 4 –O 7 class species in A SF had positive relationship with oxygen atom number which could be attributed to the introduction of phenol groups. The results provided more detailed information on the structural characteristics of polar and aromatic-rich components of mobile phase in coal.

The existence form and structure properties of mobile phase (MP) in low-rank coals (LRCs) can significantly influence the initial stage of thermal conversion. In the present work, three Chinese LRCs, namely, Shenfu, Zhundong and Hongshaquan, were extracted with tetrahydrofuran using the microwave-assisted heating. The tetrahydrofuran-microwave-extracted (TME) portion as the representative of MP was further separated to four fractions defined as oil, resin, asphaltene and preasphaltene, respectively. Diffuse reflectance Fourier transform-infrared spectroscopy (DRIFT), gas chromatography/mass spectrometer (GC/MS), matrix-assisted laser desorption ionization time-of-flight mass spectrometer (MALDI-TOF-MS) and X-ray photoelectron spectroscopy (XPS) were used to comprehensively investigate the molecular characteristics of the derived materials. The results indicated that the studied TME portions were mainly consisted of asphaltenes and rich in highly branched aliphatic hydrocarbons due to the relatively low CH 2 /CH 3 and H ar /H al ratios. Para -alkyl substituted aromatic structures with 1–2 rings were the main aromatic structures in the TME portions. C O bonds were the main oxygen-containing structures in the TME portions and could be more likely seen in aliphatic compounds. Combining the MALDI-TOF-MS and DRIFT analyses, the ratio of aliphatic side chains and aromatic hydrogens (3000–2800 cm −1 /900–700 cm −1 , I 2 ) derived from IR spectra seemed to be a suitable parameter for assessing the average molecular weight (AMW) of the specific fraction in TME portion of LRCs when the ratio of C O/C O was at very low level. The results made a further explanation for the detailed chemical structure of mobile phase in coal and could be helpful for studying the formation mechanism of volatiles during pyrolysis process.

Using Fe2O3, Fe2O3/Al2O3, and Fe2O3–NiO/Al2O3 as oxygen carriers (OCs) on chemical looping combustion with CO was investigated in this study. All the modified iron-based OCs were prepared by sol–gel method, and the samples were characterized by X-ray diffraction (XRD), N2 adsorption/desorption, and scanning electron microscope/energy dispersive X-ray spectroscopy. The temperature-programmed reduction showed that loading on Al2O3 will promote the reduction of Fe2O3 to Fe3O4, but further reduction will be inhibited, and the addition of NiO can effectively reduce this inhibition. Thermogravimetric analysis also revealed that NiO addition can improve the maximum reaction rate of iron-based OCs in the oxidation stage. Mixing with NiO will also decrease the oxygen capacity of iron-based OCs. The XRD data of the reduced samples showed that both Al2O3 and NiO have an isomorphous replacement effect on Fe3O4. The isomorphous replacement effect of NiO is much stronger than that of Al2O3. Thus, NiO introduction can effectively inhibit the formation of FeAl2O4 and promote the further reduction of Fe-oxides to Fe. However, Ni2 + will replace part of the Fe2 + in Fe3O4 to form NiFe2O4 and slightly decrease the oxygen capacity of iron-based OCs.

Revealing the pyrolysis reaction pathway related to coal structure evolution under different temperatures is important for the industry to design reactors and process operations. In this study, all the pyrolysis products obtained under different pyrolysis temperatures were comprehensively analyzed by multiple techniques. The results showed that the aromatic nucleus were inclined to react with methyl radicals, forming char with abundant methyl substitution aromatic structure at low pyrolysis temperature. At medium pyrolysis temperature, dramatically condensation reaction occurred, resulting in the formation of aromatic protonated carbon and abundant polycyclic aromatic hydrocarbons (PAHs) containing benzenoid rings joined by a carbon‑carbon single bond remaining in char. The concentration of aliphatic hydrocarbons in light tar decreased dramatically and converted into light hydrocarbon gas compounds (especially H2 and CH4). At high pyrolysis temperature, severe carbonation of char led to the formation of abundant PAHs with reduced aliphatic side chain in light tar. Tar precursors preferred to form larger PAHs due to occurrence of drastic secondary reaction. The contents and diversity of oxygen−/nitrogen-containing heteroatom compounds in heavy tar were significantly reduced with the increase of temperature. Finally, the devolatilization mechanism responsible for the evolution of chemical structure of Shenfu coal pyrolyzed at elevated temperatures was proposed.