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A hierarchical porous zeolite Y (HPZY) supported Ni–Co catalyst was prepared by pyrolyzing nickel tetracarbonyl and using modified deposition-precipitation to highly disperse Ni–Co nanoparticles onto HPZY. Hecaogou subbituminous coal was effectively ethanolyzed to obtain ethanol-soluble portion (ESPE) in a high yield (21.2%). Sequentially, ESPE was subjected to the deep hydroconversion (DHC) over prepared Ni10%-Co3%/HPZY at 150 °C under 4 MPa of initial hydrogen pressure for 24 h in n-heptane to produce deeply hydroconverted ethanol-soluble portion (ESPDHC). All the group components in ESPE, including arenes (53.3%), oxygen-containing organic compounds (24.4%), and nitrogen-containing aromatics (2.3%) were completely converted to chain alkanes (CAs, 36.8%), cyclanes (39.2%), and hydroarenes (24.0%). In addition, the hydroisomerization of CAs and hydroreforming of aromatic rings (ARs) in ESPDHC are predominant over Ni10%-Co3%/HPZY with more accessibility of active sites under mild conditions. Ni10%-Co3%/HPZY with suitable acidity and highly dispersed Ni–Co nanoparticles can effectively activate H2 to H⋯H and further heterogeneously split H⋯H to H+ and H−. H⋯H and H+ transfer plays crucial roles in the DHC of ESPE. Correspondingly, the related mechanisms are evidenced by the DHC of 2,2′-oxydinaphthalene (ODN) over Ni–Co/HPZY. Ni10%-Co3%/HPZY maintains high activity for the DHC of ODN under mild conditions after 4 recycles.

A supported nickle catalyst was prepared by loading ca. 11% of nickel nanoparticles (NNPs) on mesoporous zeolite Y (MZY) and denoted as Ni11%/MZY. A straw was methanolyzed at 300 °C to obtain methanol-soluble portion as a straw-derived bio-oil (SDBO) in the yield of 19.3%. According to the analysis with a gas chromatograph/mass spectrometer, SDBO consists of arenes (7.8%), oxygen-containing organic compounds (82.8%), nitrogen-containing organic compounds (6.3%), and sulfur-containing organic compounds (3.1%). It was subjected to catalytic hydroconversion (CHC) over Ni11%/MZY in n-hexane under 5 MPa of initial hydrogen pressure (IHP) at 160 °C for 16 h. As a result, all the compounds in SDBO were converted to chain alkanes (60.1%) and cyclanes (39.9%). In Ni11%/MZY, uniformly dispersed NNPs and strong Lewis acid sites in the defective crystal texture of MYZ play crucial roles in hydrogenating aromatic rings and removing heteroatoms (HAs), respectively. Benzyloxybenzene (BOB) was used as a lignin-related model compound. The main product from the CHC of BOB over Ni11%/MZY in n-hexane under 5 MPa of IHP at 160 °C for 2 h is methylcyclohexane in the yield of 90.9%, indicating that both hydrogenation of benzene rings and deoxygenation significantly proceeded. After being recycled 4 times, Ni11%/MZY is still active for the CHC of BOB.

An extraction-column chromatography system was designed to enrich and purify condensed arenes (CAs) from a high-temperature coal tar (HTCT). Pyrene, fluoranthene, phenanthrene, anthracene, and naph...

Hanglaiwan subbituminous coal (HSBC) was subjected to solvent extraction (SE) with an isometric carbon disulfide/acetone mixed solvent (IMCDSAMS) to obtain a residue (RSE). Thermal dissolution (TD)...

The occurrence forms of organic nitrogen in Xianfeng lignite (XL), Xiaolongtan lignite (XLT) and Shengli lignite (SL) as well as their extraction residues were characterized by X-ray photoelectron spectroscopy (XPS). The results show that the content distributions of organic nitrogen in the three extraction residues are different, but all are mainly dominated by pyrrolic nitrogen. The NaOH-catalyzed supercritical methanolysis of lignite extraction residues at 300°C was then investigated, which indicates that the yields of petroleum ether soluble portions from supercritical methanolysis of extraction residues derived from XL, XLT and SL are 46.0%, 43.8%, and 47.6%, respectively. The characterization of nitrogen-containing compounds (NCCs) in petroleum ether soluble portions by Fourier transform ion cyclotron resonance mass spectrometry (FTICR/MS) indicates that NCCs are mainly composed of N1, N1O1-N1O5, N2, N2O1-N2O4, N3O2 and N5O2-N5O4 class species. The molecular structural characteristics of NCCs were speculated according to the distributions of double bond equivalent values and carbon numbers, which shows that most of NCCs contain oxygen-functional groups like hydroxyl and carboxyl groups, and the nitrogen atoms are mainly present in aromatic structures (mainly 1–3 aromatic rings) in the forms of pyrrolic, pyridinic and amino groups. The cleavage of C-O bridged bonds in lignite is an important pathway for producing NCCs.

An effective deep eutectic solvent (DES) combined with column chromatography was designed for separating nitrogen-containing aromatics (NCAs) from the light portion (LP, which is petroleum-ether-ex...

We reports the preparation of hierarchical activated carbon (HAC) obtained by CO2 activation of coal gasification residue (CGR) produced from two-stage acid leaching (TSAL). The performance of HAC on removing methylene blue (MB) from aqueous solution was investigated. The obtained HAC was characterized by N2 adsorption-desorption isotherm, Fourier transform infrared spectroscopy (FTIRS), and scanning electron microscopy (SEM). The results show that HAC exhibits hierarchical pore structure with high BET surface area (SBET = 862.76 m2 g-1) and total volume (Vtotal = 0.684 cm3 g-1). SEM images indicated a hierarchical pore texture, and FTIRS results reveal the presence of abundant organic functional groups. Adsorption studies were carried out and experimental data were fitted to 4 non-linear isotherm models and 4 kinetic models. The adsorption experimental equilibrium data of MB onto HAC were best fitted to the Redlich-Peterson (R-P). The kinetic data show that the pseudo-first-order (PFO) model is more suitable at low MB concentration, while the advantages of the pseudo-second-order (PSO) model and the Elovich model are more obvious as the concentration increases. Furthermore, according to the thermodynamic parameters, the HAC-MB adsorption process is spontaneous and endothermic.

Low-temperature coal tar (LTCT) is a sticky liquid mixture produced mainly from coal pyrolysis, which contains various value-added chemicals (VACs). Liquid-liquid extraction is considered as one of the green and effective ways to explore the organic composition and separate the VACs from LTCT. Herein, petroleum ether, methanol, and carbon disulfide were used to extract arenols from a LTCT. As a result, the relative content and absolute content of arenols extracted from the LTCT are ca. 96.3% and 85.9%, respectively. Among them, p-cresol is predominant, accounting for 22.2%. The isolated contents of arenols are up to 84.6%. Moreover, a kilogram-scale operation was carried out under the same conditions, which offers a potential application in industrial production.

A biochar (BC)-supported non-noble metal catalyst CoMoSxOy@BC was prepared by in-situ co-pyrolysis and ex-situ sulfurization, and a two-step conversion (TSC) strategy, including H2-controlled catal...

Spent auricularia auricular substrate (SAAS) was oxidatively degraded with aqueous hydrogen peroxide (AHPO)/acetic anhydride (AAH) to produce carboxylic acids (CAs) under mild conditions. The results show that up to 53.6% of the organic matter in SAAS was converted to the soluble species (SSs). In total 122 CAs were detected in the SSs by the analysis with a gas chromatograph/mass spectrometer, which can be classified into 29 group components, mainly being aliphatic acids and along with small amount of aromatic acids. Among the aliphatic acids, normal alkanedioic acids are the most abundant. The detected aromatic acids include benzoic acids, phthalic acids, trimellitic acids, pyromellitic acids, and their derivatives. The synergistic oxidation and the released OH, CH3COO , and HOO induced by AHPO/AAH play crucial roles in oxidatively degrading SAAS.

Two attapulgite powder (AP)-supported nickel catalysts were prepared by thermally decomposing nickel tetracarbonyl onto AP in a laboratory (L-Ni/AP) and in a factory (F–Ni/AP). The Ni nanoparticles...

A novel and highly active zeolite Y/ZSM-5 composite zeolite (CZ)-supported nickel catalyst (Ni/CZ with 10% of Ni loading) was prepared by modified deposition–precipitation to uniformly disperse Ni ...

Ultrasonic-assisted extraction (UAE) combined with medium pressure liquid chromatography (MPLC) was designed for carbazole separation from anthracene slag (AS). The effects of liquid/solid ratio, temperature, and extraction times on carbazole separation were investigated. When using CCl4 and ethyl acetate as extraction solvents and combining with MPLC, carbazole recovery and purity are 75.1% and 95.4%, respectively. The mechanism for carbazole separation were presumed by examining intermolecular interactions such as N-H ⋯ π, π–π, and C-Cl ⋯ π interactions. These results demonstrate that UAE/MPLC has a considerable potential as a green and promising strategy for separating and purifying carbazole and other chemicals from AS.

Soluble portions (SPs) 1–4 (SP1–SP4) were afforded from sequentially dissolution and alkanolyses of Baiyinhua lignite (BL) in cyclohexane, CH3OH, CH3CH2OH, and (CH3)2CHOH at 300 °C. They were analyzed with a gas chromatograph/mass spectrometer and quadrupole exactive orbitrap mass spectrometer (QEOTMS) with an atmosphere pressure chemical ionization source in positive-ion mode, while BL was characterized with an X-ray photoelectron spectrometer (XRPES). The results show that the yields of SP2 and SP3 are much higher than those of SP1 and SP4, and the total SP yield is ca. 39.0%. According to the analysis with XRPES, pyrrolic nitrogen atoms are the most abundant nitrogen existing forms in BL. Thousands of nitrogen-containing aromatics (NCAs) were resolved with QEOTMS and their molecular masses are mainly in the range of 200–450 u. The main NCAs are N1O1 and N1O2 class species with double bond equivalent values of 4–18 and carbon numbers of 7–30. The nitrogen atoms appear in pyridines, quinolines, benzoquinolines or acridine, and dibenzoquinolines or naphthoquinolines, while the oxygen atoms exist in methoxy and furan rings.

Organic matter in Baiyinhua lignite (BL) was characterized by direct characterizations with solid-state 13C nuclear magnetic resonance spectrometer and X-ray photoelectron spectrometer, thermal approaches with thermogravimetric analyzer, Curie-point pyrolyzer-gas chromatograph/mass spectrometer, and sequential thermal dissolution (TD) followed by the analysis with a gas chromatograph/mass spectrometer. The results show that normal alkanes, alkylnaphthalenes, and oxygen-containing organic compounds with Ar–O– and –(C O)–O– moieties are predominant in BL. Aliphatic carbon atoms are dominated by methylene with the average carbon number of 2. The number of aromatic rings (ARs) and substituents attached on the ARs are 2 and 4, respectively. The most abundant organic oxygen species contain Ar–O– moieties. The cleavage of >Cal-Cal Car-Cal Car–O– bonds is the main reaction during the pyrolysis at 500 °C, which plays the most important role in devolatilizing organic species from BL. The products from the TD differ greatly due to the distinct pathways. When using methanol as the solvent, >C–O–C O)–O– is negligible, which is the main reaction of TD in ethanol.

Liuhuanggou bituminous coal (LBC) and its extraction residue (ER) were thermally dissolved sequentially in cyclohexane, toluene, and ethanol at 300 °C to obtain soluble portions (SPs) 1–3 (SP1-SP3) from the thermal dissolution (TD) In the total yield (TY) of 10.4% and SPs I-III (SPI-SPIII) from the TD in the TY of 4.9%, respectively. The SPs were analyzed by multiple analytical tools, including gas chromatograph/mass spectrometer (GC/MS), quadrupole exactive orbitrap mass spectrometer (QEOTMS), and Fourier transform infrared spectrometer. The analysis with GC/MS shows that normal alkanes are the most abundant in SPI, while arenes are predominant in SP1, SP2, and SPII. According to the analysis with QEOTMS, abundant heteroatom-containing organic species were concentrated into SP3 and SPIII with molecular masses of 150–750 u. The relative contents of N1 and N1O1 species are predominantly high in SPIII and SP3, respectively.

An environmentally benign and cost-effective method was designed for isolating and purifying condensed arenes from acetone-extractable portion (AEP) of a high-temperature coal tar through a high pressure preparative chromatograph (HPPC) with different packings, including silica gel, octadecyl silane, octyl bonded silica gel, and diol bonded silica gel. In total, 196 compounds were detected with a gas chromatograph/mass spectrometer from AEP and its eluates. From the eluates, naphthalene, anthracene, phenanthrene, fluoranthene, and pyrene were successfully isolated and purified, and their structures were confirmed by their 1H and 13C nuclear magnetic resonance spectra in addition to their mass spectra. Extraction-HPPC device and solvent recovery process were designed and developed, which can potentially be applied to industrial production because the process is easy-to-operate and ecofriendliness. In addition, the solvents used can be easily recovered and reused, and neither waste water nor other pollutions are emitted.

Light oil, phenol oil, naphthalene oil, washing oil, and anthracene oil separated from a high-temperature coal tar (HTCT) were extracted via a modified HCl/NaOH extraction method to obtain an acid-soluble portions (ASPs), a base-soluble portions (BSPs), and an acid/base-insoluble portions (ISPs), which were further analyzed with a gas chromatograph/mass spectrometer (GC/MS) to understand the composition of the HTCT. The results show that the recoveries of the 3 portions separated from each fraction decrease in the order of ISPs >> BSPs > ASPs. According to the analysis with GC/MS, a total of 403 compounds were detected from the 5 fractions and their separated portions. Noteworthily, nitrogen-containing organic compounds, oxygen-containing organic compounds, and arenes dominate BSPs, ASPs, and ISPs, respectively. Combined with the distribution of fragmental ions in the mass spectra, detailed pathways for fragmentating the major compounds in different fragmentation modes were proposed, which facilitates the...

The effect of pretreatment (PT) with Trichoderma sp. AH on the organooxygen compounds (OOCs) in methanol-soluble portions (MSPs) obtained from the methanolysis of raw and pretreated rice straw (RS) was investigated. According to the analyses with a gas chromatograph/mass spectrometer (GC/MS) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer, molecular masses (MMs) of the OOCs range from 100 to 500 u and are dominant from 300 to 450 u. The relative abundances of detected compounds with MMs from 300 to 350 u in MSP of pretreated RS are higher than those in MSP of raw RS. The predominant compounds in MSPs of raw and pretreated RSs are On (n = 1–10) with double bond equivalent (DBE) values of 1–28 and carbon atom numbers (CANs) of 4–35. The most abundant classes in MSPs of raw and pretreated RSs are O5 and O4, respectively. Besides, N1On (n = 0–9) classes with DBE values of 1–23 and CANs of 4–35 were also identified. These results facilitate understanding the effect of pretreatment with Trichoderma sp. AH on RS conversion and OOC selectivity from the methanolysis of RS and the application of MSP in producing transportation fuel.

Highly selective hydrogenation of furfural to furan-2-ylmethanol (FM) in isopropanol was achieved over a novel magnetic Cu–Co/C derived from zeolitic imidazolate frameworks prepared by galvanic replacement reaction. Furfural conversion and FM selectivity (FMS) are 100% and 97.2%, respectively, at 200 °C. FMS was held around 95% after 5-times recycle of the Cu–Co/C. In addition, cinnamaldehyde was completely converted with 96.8% of phenylpropanol selectivity over the Cu–Co/C at 150 °C.

A highly active difunctional Ni-Mg2Si/γ-Al2O3 was prepared by thermally decomposing nickel tetracarbonyl onto γ-Al2O3 impregnated with Mg2Si. The non-catalytic hydroconversion (NCHC) and catalytic hydroconversion (CHC) of the extract (E) and extraction residue (ER) from Yinggemajianfeng lignite were investigated over Ni-Mg2Si/γ-Al2O3 at 240 °C in n-hexane. Benzyloxybenzene and oxybis(methylene)dibenzene were used as lignite-related model compounds to speculate the possible mechanisms for the catalytic hydrocracking and hydrogenation over Ni-Mg2Si/γ-Al2O3. As a result, more organic matter in ER was converted to soluble portion (SP) by the CHC than by the NCHC. The main SP from the CHC are chain alkanes and cyclanes, while that from the NCHC is rich in arenes and oxygen-containing organic compounds. The results indicate that Ni-Mg2Si/γ-Al2O3 effectively catalyze the hydrocracking of >Calk–O– linkages and the hydrogenation of aromatic rings in E and ER.

Xilingol No. 6 lignite (XL) was subjected to thermal dissolution in methanol at 200 °C, 240 °C, 280 °C, and 320 °C, respectively. Each reaction mixture was sequentially extracted with methanol and isometric carbon disulfide/acetone mixed solvent in a modified Soxhlet extractor to afford extracts a and b, respectively. According to the analysis with a Curie-point pyrolyzer-gas chromatograph/mass spectrometer, the main products from the flash pyrolysis of Ea320, i.e., Ea obtained from XL methanolysis at 320 °C, are phenolic compounds. The analysis with a quadrupole-orbitrap mass spectrometer indicates that N3O2-N3O4 are predominant nitrogen- and oxygen-containing class species (NOCCSs) in Ea320. In the NOCCSs, nitrogen atoms mainly exist in the forms of pyridine, imidazole or pyrazole, and pyrazine or pyrimidine, while the main oxygen atoms exist in alkoxy, furan, ester or carbonyl group. In addition, possible pathways for the formation of the NOCCSs were speculated.

Zhaotong lignite-derived residue was inflicted to successive thermal dissolution and methanolysis (STD/M) in cyclohexane and CH3OH, respectively, at different temperatures. To investigate the variation of oxygen-functional moieties (OFMs), extraction residue (ER) and the residue (RSTD/M) from the STD/M were characterized with a X-ray photoelectron spectrometer, solid-state 13C nuclear magnetic resonance spectrometer, Fourier transform infrared spectrometer, and thermogravimetric analyzer. Meanwhile, the soluble portions from ZL methanolysis were identified by a Fourier transform ion cyclotron resonance mass spectrometer coupled with an electrospray ionization source. The results show that the cleavage of >Calkyl-O-, especially XnC6H5-nO−CH2CH2- linkages significantly proceeded during ER methanolysis. According to the Curie-point pyrolyzer-gas chromatography/mass spectrometric analysis, the number of compounds detected in the flash pyrolysis of ER is much more than that of RSTD/M. The investigation of organic oxygen transformation during ZL methanolysis will be beneficial to the utilization of oxygenated chemicals in lignite-derived liquids.

Converting lignite into soluble organic compounds (SOCs) under mild conditions is significant for both evaluating molecular structure and producing clean fuels/chemicals. A three-step dissociation, i.e., sequential extraction, sequential thermal dissolution (TD), and ruthenium-ion-catalyzed oxidation (RICO), was adopted to convert the organic matter (OM) in Xiaolongtan lignite (XL) into SOCs. The perspectives on chemicals, geochemical information, and structural characteristics of XL were evaluated based on the molecular compositions of SOCs. Much higher yields of SOCs were obtained from TD than from extraction, which could be attributed to the thermal dissociation of non-covalent interactions in XL. Normal alkanes, alkyl-substituted benzenes, alkyl-substituted phenols, ketones, and aliphatic esters are the main group components released from TD. A series of important biomarkers were released and their distributions and evolution pathways during XL-forming process imply that higher terrestrial plants could be the main input of the OM in XL. Benzenecarboxylic acids were produced from TD residue in high selectivity via the RICO. According to the results from the RICO, the insoluble macromolecular structures in XL are rich in peri-condensed aromatics along with some cata-condensed aromatics and polyaryls, and CH3 is the major alkyl side chain on the aromatic rings. Adjacent aromatic moieties are mainly connected each other directly by Car Car bridged bonds.

Heishan lignite (HL) was extracted with isometric acetone/carbon disulfide mixed solvent under ultrasonic irradiation. The extraction residue (ER) was subjected to thermal dissolution/methanolysis (TD/M) in methanol and catalytic hydroconversion (CHC) in cyclohexane (CH) at 300 °C under 1 MPa of N2 over a supported acid (SA). The methanol-soluble portion (MSP) from the TD/M and CH-soluble portion (CHSP) from the CHC were analyzed with a gas chromatograph/mass spectrometer (GC/MS) and Fourier transform infrared (FTIR) spectrometer, while ER and the residues from the TD/M (RTD/M) and CHC (RCHC) were characterized with the FTIR spectrometer and an X-ray photoelectron spectrometer (XRPES). The results show that the yields of MSP and CHSP are ca. 22.6% and 16.1%, respectively. According to the analysis with GC/MS, CHSP is rich in tetramethylbenzenes and dimethylnaphthalenes, while most of the GC/MS-detectable compounds in MSP are xylenols, trimethylphenols, and methyl normal alkanoates. During the TD/M, the cleavage of some C O bonds could be the main reaction, whereas the SA effectively catalyzed the cleavage of Car Calk bonds connecting some aromatic rings (ARs) and side chains on the ARs in ER. No significant difference in the distribution of functional groups was observed in FTIR spectra between HL and ER, while the distribution of functional groups in MSP is extraordinarily different from that in CHSP. According to the analysis with XRPES, RTD/M has higher carbon content but lower oxygen content.

Baiyinhua lignite (BL) was sequentially treated in cyclohexane, CH3OH, CH3CH2OH, and (CH3)2CHOH at 300 °C to afford soluble portions (SPs) 1–4 (SP1–SP4), which were analyzed with a Fourier transform infrared spectrometer, gas chromatograph/mass spectrometer (GC/MS), and quadrupole exactive orbitrap mass spectrometer (QEOTMS) with atmosphere pressure chemical ionization source in negative-ion mode. In addition, it was characterized with a solid-state 13C nuclear magnetic resonance and X-ray photoelectron spectrometer (XRPES). The results show that aliphatic and aromatic carbons, accounting for 37.1% and 59.2%, respectively, are dominated in BL. Each aromatic cluster contains 2 rings on average with 3 substituent groups on each ring. According to the analysis with XRPES, –OH group is the most abundant existing form of oxygen in BL. The analysis with GC/MS shows that the most abundant group components are arenols in SP1 and SP2, and alkanoates in SP3. Thousands of oxygen-containing aromatics (OCAs) were resolved with the QEOTMS and the molecular masses are mainly in the range of 250–400 μ. The main OCAs detected are O1–O6 class species, dominated by O2–O5 class species, which could be mainly assigned to acidic species, such as alkylarenediols, alkylarenetriols, and alkylarenoic acids.

Liquefaction residue (LRSFSBC) from Shenmu-Fugu subbituminous coal was ultrasonically extracted with petroleum ether, methanol, cyclohexane, ethyl acetate, acetone, carbon disulfide (CDS) and isometric CDS/acetone mixture (IMCDSAM), respectively. A number of alkanes, arenes, arenols, alkanols, alkenones, esters, and nitrogen-containing organic compounds were identified according to the analyses with Fourier transform infrared spectrometer, gas chromatograph/mass spectrometer, direct analysis in real-time ionization source coupled with ion trap mass spectrometer, and solid-state 13C nuclear magnetic resonance (SS 13C NMR). The tetra- and penta-substituted anthracene or phenanthrene unit could be the average structures in LRSFSBC by SS 13C NMR analysis. The main intermolecular interactions among the organic species in LRSFSBC are π–hydrogen bonds and π–π interactions. These interactions are also the cause for “capsule” formation. Stronger interactions between LRSFSBC and solvents, especially CDS and IMCDSAM, destroyed the interactions and thereby led to high extract yields.

Yinggemajianfeng lignite (YL) was subjected to thermal dissolution (TD) in a co-solvent of an ionic liquid (IL, 1-butyl-3-methyl-imidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate,...

The chemical structures of bagasse and residue (RBE) from bagasse ethanolysis (BE) were characterized with multiple direct tools. According to solid-state 13C nuclear magnetic resonance (SS 13C NMR) analysis, the aromatic carbon content in bagasse is 21.1%, while ‘Oxy-methylene’ (28.2%) and ‘Oxy-methine’ (45.7%) are the most abundant among the aliphatic carbons. X-ray photoelectron spectrometric analysis shows that the oxygen atoms mainly exist in >C-O- moieties of bagasse, which is consistent with SS 13C NMR, thermogravimetric, and Fourier transform infrared semi-quantitative analyses, while the >C-O- moieties in RBE are obviously reduced, indicating that the >C-O- bond cleavage should be the major reaction during BE. Based on the analysis with a gas chromatograph/mass spectrometer, a series of alkyl-substituted phenols & benzenepolyols (39.85%), alkoxybenzenes (ABs, 3.02%), alkoxyphenols (APs, 11.29%), ketones (12.66%), and ethyl alkanoates (13.64%) were detected in ethanol-soluble portion (ESP) from BE. Interestingly, in one-pot, the total relative content of cyclanols in the selective hydroconverted ESP is as high as 69.18% over Ru/lanthanum hydroxide (Ru/La(OH)3) in water, suggesting that ABs and APs are converted to cyclanols via highly selective demethoxylation over Ru/La(OH)3, while many -OH groups are retained. The high yields of cyclanols demonstrate the potential for the selective hydroconversion of bagasse-derived bio-oil to value-added cyclanols.

Trifluoromethanesulfonic acid supported on attapulgite powder (TFMSA/AP) and Mg2Si/γ-Al2O3 were facilely prepared by impregnating TFMSA onto AP and Mg2Si onto γ-Al2O3. The extraction residue from Yiwu lignite (YLER) was subjected to non-catalytic hydroconversion (NCHC) and catalytic hydroconversion (CHC) over TFMSA/AP and Mg2Si/γ-Al2O3, respectively. Detailed molecular compositions of the soluble portions from the NCHC (SPNCHC) and CHC over TFMSA/AP (SPCHC-A) and Mg2Si/γ-Al2O3 (SPCHC-B) were characterized with a gas chromatograph/mass spectrometer. As a result, the yields of SPCHC-A and SPCHC-B are 19.6% and 17.5%, respectively, which are much higher than that of SPNCHC (1.04%), suggesting that both TFMSA/AP and Mg2Si/γ-Al2O3 show excellent activity for the CHC of YLER. Arenes and arenols are predominant in SPCHC-A and SPCHC-B, respectively, while large amounts of alkanoates were detected in SPNCHC. The results indicate that TFMSA/AP effectively catalyzes the cleavage of Car–Calk and Calk–O bridged bonds (BBs) in YLER, while Mg2Si/γ-Al2O3 significantly promotes the cleavage of C–O BBs in YLER. Di(1-naphthyl)methane, 1-methylnaphthalene, oxydibenzene, and benzyloxybenzene were used as coal-related model compounds (CRMCs) for the CHC to further explore the catalysis of TFMSA/AP and Mg2Si/γ-Al2O3. The results show that TFMSA/AP not only releases mobile H+ but also heterolytically splits H2 to form an immobile H− and a mobile H+, leading to the cleavage of Calk–Car and Calk–O BBs in the CRMCs. In contrast, Mg2Si/γ-Al2O3 facilitates heterolytically splitting H2 to an immobile H+ and a mobile H−, resulting in the cleavage of C–O BBs in the CRMCs.

Lignites show great potential as feedstock for the production of valuable carboxylic acids by mild oxidation. In this study, valuable aromatic polycarboxylic acids were produced from Xianfeng lignite-derived residue (XLDR) through mild oxidation in green aqueous H2O2 solution. The results show that XLDR oxidation can produce benzene carboxylic acids (BCAs) and polycyclic aromatic carboxylic acids (PCACAs) in high selectivity. The BCAs are dominated by mellitic acid and benzenepentacarboxylic acid with 55.5% and 13.3% in the total yield of all group components based on the analysis with gas chromatography/mass spectrometer. Moreover, three series of PCACAs with an aliphatic ring were identified by direct analysis in a real-time ionization source coupled to a time-of-flight mass spectrometer. The BCAs and PCACAs could be generated from different kinds of aromatic structures via oxidation by OH produced from H2O2.

An active, low-cost, and recyclable catalyst was prepared by impregnating trifluoromethanesulfonic acid (TFMSA) onto metal-organic frameworks (MOFs)-derived N-doped carbon matrix nanoparticles. The residue (RTD) from thermal dissolution (TD) of Hefeng subbituminous coal in methanol was subjected to further TD and catalytic hydrocracking (CHC) over the catalyst, i.e., TFMSA/MOFs at 300 °C in cyclohexane. Detailed molecular compositions of the soluble portions from TD (SPTD) and CHC (SPCHC) were characterized with a Fourier transform infrared spectrometer, gas chromatograph/mass spectrometer (GC/MS), and positive-ion atmospheric pressure chemical ionization orbitrap mass spectrometer (PIAPCIORMS). The results show that 15.60% of organic matter in RTD was converted to a soluble portion by the CHC, whereas the yield of SPTD is only 1.04%. According to the analysis with GC/MS, SPCHC is rich in alkyl-substituted benzenes, while most of the GC/MS-detectable compounds in SPTD are alkyl-substituted arenols, alkyl-substituted cyclenones, and phenylalkanones in addition to alkyl-substituted benzenes. The analysis with PIAPCIORMS shows that both the number and yields of basic nitrogen-containing species were dramatically reduced after the CHC. These facts indicate that TFMSA/MOFs effectively catalyzed the cleavage of Car–Calk bridged bonds connecting some aromatic rings (ARs) and side chains on some ARs in RTD to obtain soluble compounds. Di(1-naphthyl)methane and 2-(benzyloxy)naphthalene were used as coal-related model compounds (CRMCs) and their CHCs were investigated to further explore the catalysis of TFMSA/MOFs in the CHC of RTD. As a result, TFMSA/MOFs effectively catalyzed the cleavage of Car-Calk and C-O bonds in the CRMCs under moderate conditions. TFMSA/MOFs can be easily separated by using an external magnetic field and the recovered TFMSA/MOFs is still highly active for the CHC of DNM.

Successful immunogene therapy depends not only on the therapeutic gene but also on the gene delivery vector. In this study, we synthesized a novel copolymer consisting of low-molecular-weight polyethylenimine (PEI) cross-linked by myo-inositol (INO) and conjugated with a galactose-grafted PEG chain, named LA-PegPI. We characterized the chemical structure and molecular weight of the copolymer and particle properties of LA-PegPI/pDNA. Furthermore, we showed that LA-PegPI/pDNA polyplexes possessed excellent stability in physiological salt solution, low cytotoxicity, and high transfection efficiency in the asialoglycoprotein receptor (ASGPR)-positive liver cells in vitro. Importantly, we also showed that through intraperitoneal injection of LA-PegPI/pDNA nanoparticles, the reporter gene was forcefully expressed in the liver hepatocytes of mice. Finally, we documented that intraperitoneal injection of LA-PegPI/pIL15 nanoparticles effectively suppressed tumor growth and prolonged survival time of tumor-bearing mice via activation of CD8+ T cells and NK cells and upregulation of the cytokines IFN-γ, TNF, and IL12 in an orthotopic hepatocellular carcinoma mouse model. Interestingly, LA-PegPI/pluc nanoparticles could effectively stimulate the proliferation of NK cells and inhibit tumor growth in this model. In summary, LA-PegPI is a useful gene vector for immunogene therapy of hepatocellular carcinoma, and its potential for clinical application warrants further study.

Carbazole and its derivates are important value-added chemicals (VACs) in anthracene oil (AO), which is one of the coal tar fractions. In this work, imidazolium-based ionic liquids (ILs) were used ...

Fushun oil shale (FOS) was subjected to thermal dissolution (TD) under different conditions. The results show that the optimal solvent, temperature, time, and ratio of solvent to FOS are ethanol, 300 °C, 2 h, and 5 ml·g− 1, respectively and the corresponding yield of the soluble portion (SP) is 32.2% (daf), which is much higher than the oil content of FOS (ca. 6%), suggesting that TD in ethanol is an excellent way to extract organics from FOS. According to 3 direct analyses, aliphatic moieties in FOS are the most abundant followed by C O-containing moieties and each cluster in FOS has 3 conjugated aromatic rings on average with fewer substituents. According to the analysis with a gas chromatograph/mass spectrometer, alkanes are predominant in all the SPs. A number of alkenes were identified in the SPs from the TD, while none of the alkenes were detected in acetone-SP obtained at room temperature, implying that the TD can destroy the π-π and intertwining interactions between alkenes and macromolecular structures in FOS. Moreover, a small amount of alkyl-substituted phenols and alkoxy-substituted phenols were detected in ethanol-SP from the TD, which could be the products from ethanolyzing the macromolecular moiety of FOS.

Oak wood sawdust (OWSD) was extracted under supercritical CO2 sequentially with petroleum, carbon disulfide (CDS), methanol, acetone, and isometric CDS/acetone mixture to afford extracts 1–5 (E1–E5), respectively. Then the extraction residue (RE) was subjected to sequential oxidation with aqueous hydrogen peroxide (AHPO)/acetic anhydride (AAH) at 65 °C to afford soluble portions 1–4 (SP1–SP4). In total, ca. 95.8% of organic matter in OWSD became soluble by the sequential extraction and oxidation. No significant difference in the distribution of functional groups was observed in Fourier transform infrared spectra of OWSD and RE, while the distribution of functional groups in the oxidation residue is significantly different from that in either OWSD or RE. In total, 117 and 168 compounds were detected in E1–E5 and SP1–SP4, respectively, with a gas chromatograph/mass spectrometer. E1–E5 are rich in esters, while carboxylic acids are abundant in SP1–SP4 in addition to esters. HO· released from AHPO/AAH played a crucial role in oxidatively degrading RE.

A novel magnetic Co-doped MoO 2 @C was prepared by in-situ co-pyrolysis and used for catalyzing hydrodeoxygenation (HDO) of bio-derived guaiacol to arenes or substituted phenols controlled by solvent type. Considering the variation of product distributions from the HDO of guaiacol using different solvents, the reaction intermediates of each stage were traced to explore its HDO pathways over Co-MoO 2 @C. The results show that guaiacol conversion to catechol via specific demethylation instead of direct demethoxygenation induces the entire reactions. Subsequently, catechol was converted to arenes or phenols by selective dehydroxylation or alkylation over Co-MoO 2 @C using different solvents. The synergy among Co, MoO 2 , and biochar plays a crucial role in activating H 2 and ethanol, which is the key to achieving high reactant conversion and product selectivities under relatively lower initial H 2 pressure (0.8 MPa). This solvent-controlled trend is also applicable to the catalytic HDO of the ethanol-soluble portion from bagasse. Furthermore, possible mechanisms for bimetallic synergic catalysis of the formation and transfer of active hydrogen atoms were proposed.

An active and recyclable supported Ni catalyst was developed by thermally decomposing nickel tetracarbonyl to highly dispersive nickel nanoparticles onto treated zeolite 5A (TZ5A) impregnated with trifluoromethanesulfonic acid (TFMSA). Oxybis(methylene)dibenzene (OBMDB) and benzyloxybenzene (BOB) were used as lignin-related model compounds (LRMCs) to evaluate Ni13%-TFMSA/TZ5A activity for the catalytic hydroconversion (CHC) of the LRMCs. The results show that Ni13%-TFMSA/TZ5A effectively induces the formation and transfer of H+ and biatomic active hydrogen, and thereby catalyzes the CHC of OBMDB and BOB to afford cyclohexane under mild conditions. The CHC includes the cleavage of C–O and C–C bridged bonds, the hydrogenation of benzene ring, and dehydroxygenation of the resulting phenylmethanol and cyclohexanol. Ni13%-TFMSA/TZ5A can be easily separated and still active for the CHC after 3-times recycle.

A highly active magnetic solid superbase (MSSB) was prepared by impregnating Mg2Si onto γ-Al2O3-coated ferroferric oxide nanoparticles via one-pot synthesis method and successfully applied in the catalytic hydroconversion (CHC) of the extraction residue (ER) from Naomaohu lignite. Large amounts of chain alkanes and arenes were detected in the soluble portion (SP) from the non-catalytic hydroconversion of the ER, while oxygen-containing organic compounds are predominant in the SP from the CHC of the ER, indicating that MSSB catalyzes the cleavage of C O bridged bonds in the ER. Oxybis(methylene)dibenzene was used as the lignite-related model compound to evaluate the catalytic activity of MSSB. The results show that MSSB facilitates heterolytically splitting H2 to release H− and subsequent H− transfer, leading to the cleavage of C O bridged bonds.

Yanshan petroleum coke (YPC) was subjected to oxidation with aqueous sodium hypochlorite under mild conditions followed by subsequent solvent extraction to afford various arenecarboxylic acids (ACAs). In total, 77 compounds were identified with a chromatograph/mass spectrometer, which can be classified into 14 group components. Among them, benzenepolycarboxylic acids (BPCAs) are the most abundant. The results indicate that YPC is rich in condensed aromatic moieties. The formation of O2− is vital to the decomposition of the condensed aromatic moieties in YPC to ACAs. Chlorine-containing BPCAs with more than 2 carboxylic groups were not detected, manifesting that ACA chlorination proceeded via Cl2 addition and subsequent HCl elimination rather than Cl substitution. BPCAs and heavier ACAs were produced from condensed aromatics and substituted arenes, respectively, in YPC. Benzenecarboxylic acids (BCAs) and their chlorides can be enriched into different fractions by solvent extraction, facilitating the YPC utilization as a chemical resource. Hence, this investigation provides a promising approach for obtaining BCAs, especially BPCAs, from YPC and for understanding aromatic structural features in organic matter of YPC.

Catalyst Ni/attapulgite powder (AP) was facilely prepared by thermally decomposing nickel tetracarbonyl onto AP. Anthracene was used as a condensed arenes (CAs)-related model compound to evaluate the catalytic activity and selectivity of Ni/AP for hydrogenating CAs. The results show that anthracene can be completely converted to perhydroanthracenes (PHAs) at 175 °C and selectively converted to 9,10-dihydroanthracene (DHA, ca. 86.4%) at 300 °C by catalytic hydrogenation over Ni/AP. Ni/AP effectively promotes the formation and transfer (F & T) of biatomic active hydrogen (H⋯H) at 175 °C, resulting in the complete hydrogenation of anthracene to PHAs. The mechanism for the F & T of H⋯H is consistent with the observation from the higher selectivities of cis-PHAs than that of trans-PHAs. At 300 °C, the catalytically produced H⋯H over Ni/AP tends to be homolytically spitted to hydrogen radical (H ), inducing the partial hydrogenation of anthracene to DHA. Quantum chemical calculations based on density functional theory further confirmed the temperature-controlled hydrogenation of anthracene over Ni/AP. This finding is a conclusive proof that the active hydrogen species is crucially important for affecting the product selectivities from the catalytic hydrogenation of anthracene over Ni/AP. Our research also offers a novel strategy for highly selective conversion of CAs to polycyclic alkanes or hydroarenes.

A novel and highly active magnetic solid superacid (MSSA) with extraordinary separable and recyclable properties was facilely developed by impregnating trifluoromethanesulfonic acid onto mesoporous zirconia coated ferroferric oxide nanoparticles. The extraction residue (ER) from Piliqing subbituminous coal was subjected to non-catalytic hydrocracking (NCHC) and catalytic hydrocracking (CHC) in cyclohexane over MSSA at 300 °C. Detailed molecular compositions of the soluble portions from NCHC (SPNCHC) and CHC (SPCHC) were characterized with a Fourier transform infrared spectrometer and gas chromatograph/mass spectrometer (GC/MS). As a result, the yield of SPCHC is remarkably higher than that of SPNCHC and most of the GC/MS-detectable compounds in SPCHC are arenes, while SPNCHC contains alkanes, arenes, arenols, and ketones, indicating that MSSA effectively catalyzed the cleavage of Car-Calk bridged bonds connecting some aromatic rings (ARs) and side chains on some ARs in the ER. Di(1-naphthyl)methane (DNM) and 9-benzylphenanthrene (9-BP) were used as coal-related model compounds (CRMCs) and their CHCs were investigated to further probe the catalysis of MSSA in the CHC of the ER. The result suggests that MSSA is highly active for cleaving the Car-Calk bond in the CRMCs and generating naphthalene and phenanthrene under mild conditions. Based on the exploration of controlling reactions, the catalytic mechanism was discussed. MSSA could be easily separated and still active for the CHC of DNM after 3-times recycle.

Catalysts C600, C700, and C800 prepared from Ca(CH3COO)2 calcination at 600, 700, and 800 °C, respectively, were characterized with an X-ray diffractometer, scanning electron microscope, and specific surface area analyzer. Over the catalysts, bio-oils (BOs) were obtained by the supercritical ethanolysis (SCE) of wheat stalk powder (WSP). Their yields, ultimate analyses, chemical composition and some fuel properties were investigated. WSP and the residues from the SCE of WSP were analyzed with a Fourier transform infrared spectrometer. The results show that C700 has a small particle size and large specific surface area, and can effectively catalyze the SCE of WSP. The BO yields from non-catalytic, C600 , C700 , and C800-catalyzed SCE of WSP are 30.1, 22.9, 70.7 and 34.4%, respectively. BO700 from C700-catalyzed SCE of WSP has relatively higher H/C and H/O ratios and calorific value but lower acidity, kinematic viscosity, and water content. The relative content of alcohols in the BO obviously increased, while the contents of carboxylic acids, ethyl esters, and anhydrides decreased over C700.

Zhaotong lignite (ZL) was sequentially extracted with cyclohexane, carbon disulfide, methanol, acetone, and isometric carbon disulfide/acetone mixed solvent to afford extracts 1–5 (E1–E5) under ultrasonic radiation at room temperature. In addition, ZL was characterized with solid-state 13C nuclear magnetic resonance (SS 13C NMR), Raman spectrometer and X-ray photoelectron spectrometer (XRPES), while the extracts were analyzed with a gas chromatograph/mass spectrometer along with a positive-ion (PI) and negative-ion (NI) electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer (ESIFTICRMS). According to the characterization with SS 13C NMR, aliphatic carbons count for 59.5% of all the organic carbons in ZL, and each aromatic cluster contains 2 or 3 aromatic rings on average. The pyrrolic nitrogen and sulfones are the most abundant nitrogen and sulfur forms, respectively, in ZL based on the analysis with XRPES. ESIFTICRMS resolved thousands of basic and non-basic species, and the molecular masses are mainly concentrated in the range of 350–600 and 300–500 u, respectively. Acidic S1O3 class species with double bond equivalent values of 3–8 and carbon numbers of 6–39 are dominant species and could be attributed to acidic group-substituted thiophenes. Main nitrogen-containing species detected in the PI mode are basic N1O0–3, N2S2, and N2O1–8S1–2. Most of the species were speculated to contain some core structures, such as pyridines, pyrimidines, or pyrazines.

Catalysts trifloromethanesulfonic acid (TFMSA)/treated attapulgite powder (TAP), Ni/TAP, and Ni-TFMSA/TAP with different Ni and TFMSA loadings were prepared. The typical catalysts were characterized with multiple instruments and used for catalyzing hydroconversion of di(1-naphthyl)methane (DNM), which was used as a coal-related model compound. The suitable loadings of Ni and TFMSA in Ni-TFMSA/TAP were determined to be 28.6% of Ni and 33% of TFMSA. Under optimal reaction conditions of 5 MPa of initial hydrogen pressure, 240 °C, and 4 h over Ni-TFMSA/TAP, DNM was completely converted, producing decalin and 1-methyldecalin as the main products. The result suggests that Ni-TFMSA/TAP is highly active for both cleaving the Car-Calk bond in DNM and hydrogenating the resulting naphthalene and 1-methylnaphthalene under mild conditions. Based on the identification of reaction products, the catalytic mechanism for DNM hydroconversion was discussed.

The extraction residue from Shengli lignite was sequentially dissolved in cyclohexane, benzene, methanol, ethanol, and isopropanol in an autoclave at 320 °C to afford soluble portions (SPs) 1–5 (SP1-SP5) and the final residue (FR). The total yield of SP1-SP5 is ca. 55.1%. The FR was subjected to ruthenium ion-catalyzed oxidation and the resulting products were isolated from the reaction mixture and esterified. Both the esterified products and SP1-SP5 were analyzed with a gas chromatograph/mass spectrometer. In total, 342 compounds were identified in SP1-SP5. They can be classified into normal alkanes, branched alkanes, alkenes, alkanedienes, arenes, alkanols, methylcycloalkanes, alkenols, alkylbenzenemethanols, arenols, anisol and substituted anisols, polymethyldihydrobenzofurans, arenofurans, dibenzofurans, ethoxymethylbenzenes, aldehydes, ketones, esters, nitrogen-containing organic compounds, sulfur-containing organic compounds, and other compounds. Among the compounds, arenols are predominant in SP1 and SP2 and the main compounds in SP3, while the main compounds in SP4 and SP5 are esters and arenes, respectively. According to the esterified products identified, the products from the FR oxidation can be grouped into non-benzene ring carboxylic acids (NBCAs) and benzenepolycarboxylic acids (BPCAs). The total yield of BPCAs is much higher than that of NBCAs, suggesting that the FR is rich in condensed aromatic moieties. Keywords: Lignite, Arenols, Esters, Arenes, Condensed aromatic moieties