Exhaustively separating organic matter (OM) from shale oil sludge (SOS) not only facilitates the value-added utilization of the OM, but also is capable of avoiding the pollution by discharging or combusting SOS. The OM in the SOS was sequentially extracted under ultrasonic irradiation using petroleum ether (PE), methanol, carbon disulfide (CDS), and isometric mixture (IMM) of acetone and carbon disulfide. As a result, over 99.8% of the OM in the SOS was extracted. According to the analysis with a gas chromatograph/mass spectrometer, the extracts primarily consist of alkanes, alkenes, and arenes. The interaction energies between model compounds (MCs, e.g., dodecane and naphthalene were used to represent alkanes and arenes, respectively) and a solvent were investigated via quantum chemical calculations. The results show that n-hexane exhibits the binding energy (BE) towards dodecane (-35.08 kJ mol-1) and naphthalene (-33.55 kJ mol-1). Methanol has significantly stronger BE towards naphthalene (-18.57 kJ mol-1) than towards dodecane (-14.91 kJ mol-1), while CDS shows near BEs for naphthalene (-16.71 kJ mol-1) and for dodecane (-15.93 kJ mol-1). As the weak intermolecular interaction, based on the Independent Gradient Model according to Hirshfeld Partition and Atoms in Molecules Theories, the alkane dissolution is primarily dominated by dispersion forces. For arenes, the enhanced adsorption occurs due to C-H … π interactions with the solvents. In the case of IMM, the synergic effect between acetone and CDS significantly increases the solubility of aromatics in the SOS. This is achieved through strong π-π interactions between > C=O in acetone and S=C=S in CDS. IMM proves to be very effective for extracting OM from SOS because of the synergic effect and the easy recovery of IMM due to its low boiling point.

NiCs/Al2O3 with medium-strong alkaline and the contents of Ni and Cs of 26.55 wt% and 0.02 wt%, respectively, was prepared by a three-step method and characterized with multiple tools. Oxydibenzene (ODB) and benzyloxybenzene (BOB) were used as low-rank coal-related model compounds and their catalytic hydroconversion (CHC) were investigated over NiCs/Al2O3. Under mild conditions (MCs), NiCs/Al2O3 can effectively activate H-2 to biatomic active hydrogen (HH) and part of HH can be effectively split to relative mobile H- and immobile H+ on the NiCs/Al2O3 surface. Both ODB and BOB can be completely converted and full hydrogenation (FH) of the benzene ring (BR) in -O-BR is the first step for the CHC of both ODB and BOB via HH transfer to the BR under MCs. Subsequently, H- transfer to an ipso-carbon (IC) in the resulting oxydicyclohexane from the FH of ODB cleaves an -O-CH< bond to produce cyclohexane (CHI) and cyclohexyloxy anion (CHOA), which abstracts H+ from HH to afford cyclohexanol (CHII) followed by H- transfer to the IC in CHII and subsequent HO- release to yield CHI. As a result, CHI is the only final product from the CHC of ODB. In contrast, H- transfer preferentially proceeds to the carbon atom in the -CH2- of the resulting benzyloxycyclohexane from the FH of the BR in -O-BR of BOB to produce toluene and CHOA followed by the FH of toluene to get methylcyclohexane and the H+ abstraction by CHOA from HH to obtain CHII. Moreover, NiCs/Al2O3 shows a distinguished recyclability and repeatability.

The efficient utilization of industrial solid waste not only reduces environmental pollution, but also increases economic benefit. In this study, a Ni-based ZSM-5 zeolite/porous carbon composite (Ni-10(%)@ZSM-5/PC) was prepared from coal gasification fine slag and used for upgrading petroleum ether-extractable portion (PEEP) from coal tar residue. PEEP yield is 70.1%. According to the detection with a gas chromatograph/mass spectrometer, PEEP consists of O-containing organic compounds (37.0%), arenes (32.0%), chain alkanes (27.2%), alkenes (1.8%), N-containing organic compounds (0.8%), and S-containing organic compounds (1.0%). The catalytic hydroconversion (CHC) of PEEP was carried out under 5 MPa initial hydrogen pressure at 160 degree celsius for 24 h . The hydroconverted PEEP is mainly composed of chain alkanes (45.1 %), cyclanes (33.7 %), hydroarenes (16.9 %), and alkenes (4.4 %). The strong Br & oslash;nsted acid sites and uniformly dispersed Ni nanoparticles (NNPs) in Ni-10(%)@ZSM-5/PC play important roles in aromatic ring (AR) hydrogenation and heteroatom removal. According to the CHC of benzyloxybenzene (BOB), Ni-10(%)@ZSM-5/PC could activate H-2 to diatomic active hydrogen (H center dot center dot center dot H)by NNPs and release H+, leading >C-O- cleavage and AR hydrogenation.

Tank bottom sludge (TBS), consisting of heavy oil (HO), sediment, and water, is one of liquid-solid wastes from petroleum production. Effective separation of HO from TBS and its isolation for value-added products are of great importance for avoiding the pollution from TBS and creating economic benefits. In this work, a two-step solvent extraction strategy is proposed to extract HO from TBS and enrich refined paraffin (RP) from HO. The effects of solvent type, extraction time, extraction times, and solvent volume on the HO extraction and RP enrichment were examined. The results show that more than 95% of HO was extracted using isometric carbon disulfide/acetone mixed solvent at room temperature and petroleum ether/acetonitrile (PE/AN) proved to be effective for enriching RP. The mechanism for the extraction with PE/AN is revealed by calculating the nonbonded interaction energy between PE/AN and selects model compounds at the molecular level. Independent gradient model isosurface and scatter plot prove the wide existence of van der Waals forces and X-H/Y & sdot;& sdot;& sdot;pi bonds (X represents >CH or -O and Y denotes a cation or anion) between PE/AN and a model compound through molecular dynamics simulation. This work presents an environmentally friendly and feasible strategy for the clean production of RP from TBS.

The catalytic hydroconversion (CHC) of benzyloxybenzene (BOB) and oxydibenzene (ODB), two typical lignite-related model compounds (LRMCs) representing alpha-0-4 and 4-O-5 model linkages, have been investigated using uniformly dispersed Ni-15/HY prepared by a three-step method. The cleavage of >CH-O- bridged bonds in BOB and partial hydrogenation of ODB are considered as a crucial first step, and the target reactions in this work are to produce complete hydrodeoxidized ring saturation products. Through the exploration of reaction mechanism, H+/H- and biatomic active hydrogen, as the main hydrogen species involved in the reaction, play an important role in the CHC of BOB and ODB. Herein, the synergic effect between the hydrogenation of nickel nanoparticles and the acidic function of Y-type zeolite improves the CHC performance, resulting in Ni-15/HY displaying proficient catalytic activity and selectivity for the CHC of BOB and ODB. Under the optimal reaction conditions, BOB and ODB can be completely converted to cyclanes over Ni-15/HY, and the main products are dicyclohexylmethane (57.6 %) and cyclohexane (92.4 %), respectively. The developed Ni-15/HY can not only promote the hydroconversion of BOB and ODB to produce ring-saturated products, but also undergo the rearrangement reaction to produce two- or three-ring cyclanes, which is desirable to upgrade LRMCs to high-density hydrocarbon fuels.

In this paper, the kinetic model under the influence of each factor is given by investigating the effects of distribution effect, external diffusion effect and internal diffusion effect on the immobilized pectinase reaction system. The magnetic chitosan microspheres were prepared by the reversed-phase suspension cross-linking method, and the effects of the type and amount of cross-linking agent and the ratio of chitosan to magnetic core incorporation on the performance of the magnetic spheres were investigated. Then, the immobilized pectinase was prepared by using cross-linked chitosan magnetic microspheres as a carrier, and an orthogonal test was used to determine the conditions of immobilized enzyme preparation and to study the enzymatic properties and operational stability of immobilized pectinase. The results showed that the transmittance of the magnetic microspheres of this test increased from 32% to 90.79% in 10 min in a magnetic field, but in a gravity field, the transmittance increased from 32.12% to 46.44% in 50 min. The experimentally prepared microspheres exhibit good magnetic responsiveness. The optimum temperature of immobilized pectinase was 50°C, and the remaining enzyme activity was still 61.24% after 6 repetitions. The immobilized pectinase made by crosslinking glutaraldehyde with chitosan magnetic microspheres has a high recovery of enzyme activity and good operational stability, as indicated by this.

MY zeolites with mesopores were prepared by hydrothermal method using functionalized SiO2 (F-SiO2) as a silica source, and hydrophobic bifunctional Ru/MY-O catalysts were obtained by deposition precipitation method and silylation treatment. This work aims at obtaining polycyclic alkane (PCA) based high-density hydrocarbon fuels (HDHFs). We focused on the catalytic hydroconversion (CHC) of 2-phenoxy-1-phenylethanol (PP-ol) and oxydibenzene (ODB), two typical lignin-related model compounds (LRMCs), over Ru/MY-O. The effects of different reaction conditions and catalysts on the product distribution in PP-ol and ODB were investigated. The partial hydrogenation of ODB was found to be a necessary step before achieving C-O ether bond cleavage and C-C bond coupling. The balance of metal/acidic sites is critical for maximizing PCA yields. Changes in the metal/acid ratio had a greater effect on PCA yield in PP-ol than in ODB. Poor stability of cycloalkyl cations and partial hydrogenation of ODB hinder the generation of C-C coupling products. The incorporation of mesopores and hydrophobic treatment were found to weaken the negative effects of C-C bond coupling products and water on the catalyst. The conversion of Ru3/MY-O was improved by nearly 10% compared to Ru3/Y in the fifth cycle reaction. This work provided a theoretical basis for the generation of HDHFs from lignin.

The production of alkyl-free phenols (AFPs) from lignin can reduce dependence on fossil sources. Depolymerization (C-alk-O bond cleavage) and dealkylation (C-ar-C-alpha bond cleavage) are two important steps from lignin to AFPs. Condensation of lignin fragments during depolymerization and harsh reaction conditions during dealkylation have been challenging. Here, we report a selective oxidation-hydrogenolysis-deacylation strategy. The C alpha H-OH in the beta-O-4 structure is oxidized to C-alpha & boxH;O by a preoxidation step, and then the phenolic monomers with acyl groups are obtained by hydrogenolysis over Ni-based catalysts and finally by acid-catalyzed deacylation to give AFPs. This strategy achieves effective cleavage of the C-ar-C-alpha bond under mild conditions while avoiding condensation. The AFP yield from beta-O-4-hydroxy polymers exceeds 87%. Compared to oxidized lignin, the AFP yield reaches 8.8 wt % under optimized conditions. The C-ar-C-alpha bond cleavage and condensation reaction pathways were proposed by a combination of controlled experiments and density functional theory studies. This work provides a new route and theoretical support for the conversion of lignin to AFPs.

Catalytic hydroconversion (CHC) of a lignin-derived soluble portion to value-added chemicals is of great significance. Ni/sepiolite was successfully prepared via a impregnation method and used for the CHC of a cotton stalk-derived soluble portion (CSDSP). Cyclanes and cyclohexanols are the main products with total relative content of 64.7% from the CHC of CSDSP over Ni/sepiolite. To better understand the reaction mechanism, the CHC of oxydibenzene (ODB), benzyloxybenzene (BOB), and guaiacol over Ni/sepiolite were investigated. They were completely converted at 240 degrees C under 4 MPa of initial hydrogen pressure. According to the resulting products, H...H and H+ are the main active hydrogen species in the CHC and H+ transfer induces the cleavage of -CH2-O-bond in BOB followed by hydrogenating benzene ring (BR), while the CHC of ODB and guaiacol proceeds via the hydrogenation of BR and subsequent cleavage of -CH2-O-bond.

Base soluble portions (BSPs) obtained by acid-base extraction of 5 high-temperature coal tar (HTCT) fractions were comprehensively analyzed with the gas chromatograph/mass spectrometer (GC/MS), Fourier transform infrared (FTIR) spectrometer, and quadrupole exactive orbitrap mass spectrometer (QPEOTMS) equipped with positive-ion atmospheric pressure chemical ionization. The relative content of nitrogen-containing aromatics (NCAs) in each fraction showed a decreasing trend in washing oil (97.5 %) > anthracene oil (95.8 %) > light oil (82.7 %) > naphthalene oil (76.4 %) > phenol oil (12.1 %). Among them, NCAs such as quinoline, acenaphtho[1,2-b]pyridine, benzo[f]quinoline, acridine, benzo[h]quinoline, and anthracene-9-carbonitrile were selectively enriched. The FTIR spectra of BSPs showed significant differences, mainly concentrated in the wavenumbers of 3655, 3520, 3444, 3316, 3051, 1629, 1397, 1131, and 749 cm(-)(1). Semi-quantitative characterization of the BSPs functional group distribution by FTIR spectra basically supports GC/MS analysis. The QPEOTMS analysis shows that NnOxSy (n = 1-4) class species with double bond equivalent (DBE) values of 4-28 and carbon number (CN) at 4-45 are the main basic compounds. N1OxSy species (50.2 %) with DBE = 7 are the most abundant in BSPLO, while the N-1 species with CN = 9 account for 27.2 % in BSPLO. Quinolines with DBE = 7 and CN = 9-11 are the main N-1 species in BSPLO. However, benzoquinolines or anthracene-9-carbonitrile account for a large share in BSPAO. Comprehensive evaluation of various instruments facilitates molecular identification of the detailed composition information of NCAs in HTCT fractions for cleaning and value-added utilization as nitrogen-containing chemicals.

Upgrading lignin derivatives (LDs) to cyclanes by catalytic hydroconversion facilitates the value-added utilizations. Ni-20%/beta(25) was prepared via a deposition-precipitation method and used for catalytically hydroconverting guaiacol and a poplar lignin derivate (PLD). Guaiacol was completely converted to cyclohexane (CH) as the main product in the yield of 93.3 mol% at 220 degrees C under initial hydrogen pressure of 4 MPa for 2 h, while the PLD was significantly converted to cyclanes over Ni-20%/beta(25) for 8 h. Density functional theory combined with experiments explained the related mechanisms, i.e., H-2 was activated to H center dot center dot center dot H, which was split to relatively mobile H+ and immobile H- over Ni-20%/beta(25). H.H transfer to benzene ring (BR) leads to BR hydrogenation and subsequent H+ transfer to the oxygen atom in -OCH3 and -OH connected to the hydrogenated BR induces the demethoxylation and dehydroxylation.

Lignite possesses abundant >CH-O-, >C=O, and -OH bonds, which can potentially obtain oxygen -containing compounds from lignites. Herein, a variety of nickel nanoparticles supported on modified Zeolite 4A (M) were prepared, which achieved cleave >CH-O- in lignite for producing oxygen -containing atomic compounds. About 92% of benzyloxybenzene (BOB) was cracked to toluene and phenol over Ni-10%/M under 320( degrees)C, 4 h, and 1 MPa H-2. H-2 and CH3OH can be activated over Ni-10%/M and spilled into H+, which attacks the oxygen atom in BOB, cleaving the >CH-O- bond and producing phenol and toluene. Furthermore, verifying the synergy effect of H-2 and CH3OH, methanol -d was added to catalytic hydroconversion of BOB. According to the pathways for producing molecular ion peak (m/z = 96) and isotopic ion peaks (m/z = 95 and m/z = 97) in the products, phenold2 was identified by the analysis with gas chromatograph/mass spectrometer, which verified the catalytic hydroconversion mechanism of BOB proposed in this paper. In catalytic hydroconversion of XilinGol League No. 6 lignite residue with Ni-10%/M under 320 C-degrees, 8 h, and 1 MPa H-2, 54.7 % of organic matter became methanolsoluble portion (MSP). The main group components detected in the MSP are n-alkanes, arenes, phenols, and ester, offering a potential way to obtain coal structure information and organic chemicals.

Catalytic hydroconversion (CHC) of lignin-derived compounds (LDCs) to cyclanes and cyclohexanol (CHII) promotes the value-added utilization of LDCs. Nevertheless, designing a highly active and selective catalyst for this purpose remains a challenge. Herein, Ni/hydroxyapatite (HAP) was fabricated by a slightly modified deposition-precipitation approach and employed for the CHC of benzyloxybenzene (BOB) and phenethoxybenzene (PEOB) under different conditions. Consequently, BOB was fully converted with CHII and methylcyclohexane (MCH) as the main products (MPs) in the yield of 94.8 and 100 % under the optimum conditions of 20 mg Ni-15/HAP, 140 degrees C, 4 MPa H-2, and 4 h, while complete conversion of PEOB to CHII and ethylcyclohexane (ECH) as MPs proceeded under initial hydrogen pressure of 4 MPa at 180 degrees C for 4 h. In addition, other lignin-related model compounds can also be selectively hydrogenated to cyclanes and CHII, suggesting the high activity and selectivity of Ni-15/HAP. Meanwhile, based on the product distribution and Ni-15/HAP characterization, relevant mechanisms were proposed. Specifically, BOB conversion to CHII and MCH via the >CH-O- bond cleavage induced by H- addition, abstraction of H+ by the resulting phenoxy anion from the catalyst surface, and benzene ring hydrogenation, whereas conversion of PEOB to CHII and ECH was similar to BOB. Furthermore, Ni-15/HAP displays an excellent reusability.

MY zeolites with mesopores were prepared by hydrothermal method using functionalized SiO2 (F-SiO2) as a silica source, and hydrophobic bifunctional Ru/MY-O catalysts were obtained by deposition precipitation method and silylation treatment. This work aims at obtaining polycyclic alkane (PCA) based high -density hydrocarbon fuels (HDHFs). We focused on the catalytic hydroconversion (CHC) of 2-phenoxy-1-phenylethanol (PP-ol) and oxydibenzene (ODB), two typical lignin -related model compounds (LRMCs), over Ru/MY-O. The effects of different reaction conditions and catalysts on the product distribution in PP-ol and ODB were investigated. The partial hydrogenation of ODB was found to be a necessary step before achieving C -O ether bond cleavage and C -C bond coupling. The balance of metal/acidic sites is critical for maximizing PCA yields. Changes in the metal/acid ratio had a greater effect on PCA yield in PP-ol than in ODB. Poor stability of cycloalkyl cations and partial hydrogenation of ODB hinder the generation of C -C coupling products. The incorporation of mesopores and hydrophobic treatment were found to weaken the negative effects of C -C bond coupling products and water on the catalyst. The conversion of Ru3/MY-O was improved by nearly 10% compared to Ru3/Y in the fifth cycle reaction. This work provided a theoretical basis for the generation of HDHFs from lignin.

The ethanolyzed soluble portion (SPE) prepared from the ethanolysis of Hanglaiwan long flame coal (HLFC) extraction residue was converted to catalytically hydroconverted SPE (CHSPE) by the catalytic hydroconversion (CHC) over Ni-10 %/SAPO-34 at 200 degrees C under an initial hydrogen pressure of 5 MPa for 24 h. The possible mechanisms for the origin and synergic effect of active hydrogen had been speculated according to the reactions of HLFC-related model compounds. H-2 can be activated by Ni-10 %/SAPO-34 to produce HH, H+, and H-, the synergic effect of which leads to cleaving >C-O- bonds. After the CHC, arenes and heteroatom-containing aromatic compounds in SPE are converted to cyclanes, indicating that aromatic ring hydrogenation and heteroatom removal occur simultaneously during the CHC of SPE. The relative abundance (RA) of CH-containing species in CHSPE is larger than that in SPE, while the RAs of oxygen- and nitrogen-containing species in CHSPE are smaller than those in SPE. In addition, Ni-10 %/SAPO-34 has excellent cyclability for the CHC of SPE, and the relative content of cyclanes decreases only by 17.4 % after five recycles. Undoubtedly, this investigation provides an effective strategy for directional upgrading of derived soluble portion from low metamorphic coals.

Nickel supported on a nitrogen-doped carbon material (NDCM) was successfully prepared and used for catalyzing the hydroconversion of benzyloxybenzene (BOB) and poplar lignin (PL). Over Ni/NDCM, BOB was completely converted to toluene and phenol in the yields of 75.5 and 73.1 mol%, respectively, under initial hydrogen pressure (IHP) of 2 MPa at 240 degrees C for 2 h. The adsorption energies (AEs) of different systems were calculated using the density functional theory. The AEs of H2 on Ni (111), Ni (200), and Ni (220) crystal planes are -1.26, -1.27, and - 1.28 eV, respectively, indicating that Ni (111) crystal plane is the most active for splitting H2 to mobile H+ and immobile H-, the higher absolute value of AE (-2.5 eV) of BOB on Ni/NDCM facilitates BOB hydrocracking. Moreover, Ni/NDCM could promote the cleavage of >CH-O- bonds in PL to produce more phenols.

The dynamic combined strategy consisting of extraction, column chromatography, and catalytic hydroconversion (CHC) was used to prepare cyclohexanol (CH) from crude phenols (CPs) derived from a low temperature coal tar (LTCT) and enrich condensed arenes from the dephenolized fraction. Fluoranthene, anthracene, and pyrene with purities of 92.2, 91.7, and 95.5 %, respectively, were enriched by a combination of extraction and gradient elution in medium pressure preparative liquid chromatograph (MPPLCI) and high pressure preparative liquid chromatograph. CPs obtained by extracting LTCT were catalytically hydroconverted over a nickel supported on a nitrogen-doped carbon material (NDCM) prepared with a nickel-organic framework as the precursor. The mechanism for the CHC of CPs was explored using phenol as the model compound. The results show that phenol was completely converted and the selectivity of CH is up to 99.9 % in n-hexane under initial hydrogen pressure of 3 MPa at 160 degrees C for 1 h. The characterization of Ni/NDCM and the distribution of the products from the CHC of phenol indicate that Ni/NDCM can strongly adsorb phenol and effectively activate H2 to H center dot center dot center dot H, which transfer plays a crucial role in hydrogenating the aromatic rings.

The catalytic hydroconversion (CHC) of heavy carbon organic species (HCOSs) to cycloalkanes represents an importantly used chemical industry process due to the wide applicability of the resulting products in energy and fine chemistry. Despite the existing conventional catalysts applied to the CHC of HCOSs, the development of highly active bifunctional Ni-based heterogeneous catalysts for this process is still a challenge. Therefore, we show that the modified deposition-precipitation of nickel (II) nitrate on hydrothermally synthesized mesoporous zeolite Beta (MZB) prepares a Ni/MZB catalyst with a through-crosslinking mesopore structure and uniformly disperse Ni nanoparticles (NPs) at rough MZB crystal surface. The 10%Ni/MZB (10% Ni loading), in the presence of exposing on amount of accessible Lewis acid sites (LASs) and attaching Ni NPs by chemical bonding from the silica matrix of MZB skeleton, exhibits excellent activity to promote the CHC of all kind of aromatic rings and heteroatom-containing species, including chain alkanes, arenes, oxygen-containing organic compounds (OCOCs), nitrogen-containing organic compounds (NCOCs), and sulfur-containing organic compounds (SCOCs), to produce cycloalkanes and hydroarenes under mild conditions. Interestingly, density functional theory (DFT) calculations indicate that the transfer of biatomic active hydrogen (H...H) and heterogenous H+ from 10%Ni/MZB plays important roles during the CHC of diphenoxybenzene (DPOB). After being recycled 4 times, 10%Ni/MZB is still maintains high activity for CHC of DPOB under mild conditions.

A low-temperature coal tar (LTCT) was separated by dual-solvent systems to realize its value-added utilization. Cumulative extract yield (CEY) versus time, extraction kinetics at different stages, extracted composition, and functional group distribution were intensively studied using nonlinear fitting, linear fitting, gas chromatograph/mass spectrometer (GC/MS), and Fourier transform infrared (FTIR) spectrometer, respectively. The relationship between CEY and time conformed to logistic model, and the determination coefficient is 0.97. Among the 3 extraction stages, the slope of the kinetic fitting curves in their extraction stage using petroleum ether (the first 3 runs) in the highest extract yield is 7.5 and 5 times that using methanol and carbon disulfide extraction stage, respectively. Alkanes, arenols, and arenes can be enriched into petroleum ether, methanol, and carbon disulfide, respectively. A total of 314 compounds detected in the LTCT and extracts with GC/MS were subdivided into 85 group components. The result of FTIR analysis is consistent with that of GC/MS. Separation mechanism was expounded by theory analysis and quantum chemistry from hydrogen bonds (O-H···O) and van der Waals force. Quantum chemical calculations show that the attraction of alkane, alkene, anthracene, and naphthalene with n-hexane or carbon disulfide is mainly dispersive interaction, while the attraction of methanol with phenols is mainly electrostatic interaction. Although the bond length of O-H···O formed between methanol and phenols is 2/3 of that of C-H···O, and the bond angle is ca. 45° larger, the binding energy is 9 times that of the latter, indicating that the main hydrogen bonds are O-H···O. In summary, dual-solvent extraction has considerable potential to separate alkanes, arenols, and arenes from the LTCT.