Abstract: Carbon disulfide (CDS), methanol, acetone and isometric carbon disulfide/acetone mixture (IMCDSAM) were used as solvents to sequentially extract Naomaohu lignite (NL) via ultrasonic-assisted extraction to obtain extracts (E1−E4) and final extraction residue (ER). Composition and structure of E1−E4 were analyzed by GC-MS. It is found that the main compounds in E1 are alkanes, aromatics, alcohols and esters. Alkanes, alcohols and esters are the main compounds in E2. Alcohols, phenolics and esters are the main components in E3, and esters are mainly phthalic diester compounds. Affected by synergistic effect of the two solvents CDS and acetone, the relative content of alkenes in E4 is relatively high. FT-IR was used to characterize functional groups in NL, E1−E4 and ER. The results show that the ultrasonic extraction process only extracts free small compounds from macromolecular skeleton of the NL and some other molecules, which connect the macromolecular skeleton by weak covalent bonds, and the process does not destroy the macromolecular skeleton structure. In addition, peak fitting results from FT-IR show that types of infrared absorption peaks in ER do not change after ultrasonic extraction, while intensity of the peaks varies. TG-DTG profiles of NL and ER indicate that after ultrasonic extraction weight loss of NL increases from 47.09% to 51.04%, and peak of the maximum weight loss rate is advanced from 450 to 430 ℃. Pyrolysis kinetic analyses of NL and ER based on Coats-Redfern model show that after ultrasonic extraction activation energy of ER in rapid pyrolysis stage is lower than that of NL, and the pyrolysis process is easier to proceed.
Abstract: A novel and highly active nitrogen-doped porous carbon-supported nickel catalyst Ni@N-PC was successfully developed by a thermolysis of nickel-based zeolitic imidazolate frameworks growing on both sides of graphitic carbon nitride and used for catalyzing hydroconversion of isopropanol soluble portion from ultrasonic extraction of high-temperature coal tar (ISPHTCT). The active nickel nanoparticles were mainly encapsulated on the top of carbon nanotubes and partially dispersed on the surface of carbon nanosheets. Naphthalen-1-ol was used as a model compound to investigate the catalytic hydroconversion activity under different reaction conditions and reveal the mechanism for catalytic hydroconversion. The ISPHTCT and catalytic hydroconversion products of ISPHTCT (ISPCHCP) were analyzed with gas chromatograph/mass spectrometer. The results show that 70% of naphthalen-1-ol was converted at 160 °C and completely converted at 200 °C for 120 min, and the ISPHTCT was greatly upgraded. A total of 180 organic compounds including 33 nitrogen-containing organic compounds, 11 sulfur-containing organic compounds and 39 oxygenates were identified in ISPHTCT, while no obvious nitrogen-containing organic compounds, sulfur-containing organic compounds and oxygenates were detected in ISPCHCP, indicating the excellent performance of Ni@N-PC for heteroatom removal. All the alkenes, cyclenes and alkynes were saturated and the majority of arenes were converted to cyclanes by catalytic hydroconversion over Ni@N-PC, which exhibited high catalytic hydrogenation activity.
Abstract: Mosaic coke is a kind of special artificial carbon material, which is usually used as the raw material to produce high-quality nuclear graphite. The quality of graphite has been usually focused on the properties of mosaic cokes. In order to investigate the influence of the quinoline insoluble (QI) content of heavy-phase pitch on the micro-structure and properties of mosaic coke, 9 kinds of heavy-phase pitches with varied QI contents were used as the raw materials to produce series of mosaic cokes in this study. Optical micro-scope, scanning electronic micro-scope, X-ray diffraction, Raman spectrum and curve-fitted methods were used to judge the micro-structure of 9 kinds of mosaic cokes. Also, the micro-strength of mosaic cokes was determined. The results show that the higher content of QI in heavy-phase pitch has the mosaic structure easier to be produced during the liquid-phase carbonization process. What’s more, with the increase of QI content, the content of regular carbon microcrystals decreases, but the content of amorphous carbon and micro-strength are improved. When the QI contents in the heavy-phase are higher than 7%, the derived mosaic cokes have the total contents of mosaic structure (the sum of fine mosaic structure, medium mosaic and coarse mosaic) higher than 82% and the micro-strength higher than 85%. In other words, the heavy-phase pitch with the content of QI higher than 7% is a promised raw material to produce high-quality mosaic coke.
Abstract: Recently, the disposal of waste by beneficial and environmentally friendly methods has attracted great attention. In this work, we have studied the production of high-value carbon nanotubes (CNTs) which have remarkable applications by catalytic pyrolysis of sugarcane bagasse (SCB) as an agricultural waste using a two-stage process. Various reaction factors including the effects of zeolite types (HZSM-5, HMOR, and HY), pyrolysis temperatures (450−700 °C), and SCB/ZSM-5 ratios (3−12) on SCB pyrolysis were investigated to generate CNTs from pyrolysis products. A Co-Mo/MgO catalyst was used for growing CNTs via the decomposition of pyrolysis products. The morphological structure and quality of CNTs were characterized using TEM and Raman spectroscopy, while the fresh Co-Mo/MgO catalyst was characterized by XRD and TPR analyses. The results showed that zeolite type, pyrolysis temperature, and SCB/ZSM-5 ratio had significant effects on the CNTs yield. The optimum carbon yield (24.9%) was achieved using the HZSM-5 catalyst at the pyrolysis temperature of 500 °C and with the SCB/ZSM-5 ratio of 6. TEM observations confirmed the growth of bamboo-like carbon nanotubes (BCNTs) and carbon nano-onions (CNOs) in different proportions according to the reaction parameters. Also, CNTs with the largest diameter distribution range (7−76 nm) were produced using the SCB/ZSM-5 ratio of 6. Raman spectra demonstrated the production of high-quality CNTs under all studied conditions.
Abstract: A molecular modeling based on the density functional theory (DFT) and the transition state theory (TST) was performed to investigate the influence of biomass gas CO on the N2O decomposition catalyzed by CaO during reburning in the circulating fluidized bed boiler. The model for N2O adsorption onto the CaO(100) surfaces were constructed; and the processes of the N2O decomposition on the CaO(100) surface and the surface recovery of CaO(100) were investigated. The results illustrate that the energy barrier of N2O decomposition on the CaO(100) surface is much lower than that in homogeneous case, and CaO is therefore able to catalyze the N2O decomposition. The atomic O from N2O decomposition can poison the active sites O atom on the CaO(100) surface, while biomass gas CO can promote the regeneration of the active sites on the surface of CaO(100), which is beneficial for CaO to catalyze the N2O removal.
Abstract: The dramatic increase in atmospheric CO2 concentrations has attracted people's attention, and many strategies have been developed to convert CO2 into high-value chemicals. Metal-organic frameworks (MOFs), as a class of versatile materials, can be used in the CO2 capture and conversion because of their unique porosity, large specific surface area, rich pore structure, multiple active centers, good stability and recyclability. Various functional nanomaterials have been designed and synthesized based on metal organic framework (MOF) of crystalline porous materials to meet these challenges. Herein, in this review, the latest processes of MOFs in field the of CO2 hydrogenation to carbon monoxide, methane, formic acid, methanol and olefins are summarized, and the synthesis methods of catalysts based on MOFs and the reasons for their high catalytic activity are analyzed. Besides, a brief introduction to improve the catalytic activity of the new MOF material and explore the feasible strategies for CO2 conversion are advised. Finally, the paper discusses the main challenges and opportunities of MOF-type catalysts in CO2 chemical conversion, and presents a brief outlook on further developments in this research area.
Abstract: Zn-doped and Zn-Al co-doped La2O3 catalysts were prepared by citric acid sol-gel method and characterized by a series of in situ technologies, to investigate the structure-activity relationship of La2O3-based catalysts in the oxidative coupling of methane (OCM). The in situ XRD results reveal a thermal expansion of the La2O3 crystal along the c-axis at high temperature. The H2-TPR results show two types of oxygen species on the La2O3-based catalysts, viz., the strong-binding oxygen species and weak-binding oxygen species; in addition, the XPS results indicate that the strong-binding oxygen species is probably attributed to anion radical O−. The doping with Zn can significantly increase the number of oxygen vacancies in the Zn-doped La2O3 catalysts, which can promote the activation of oxygen and generate more strong-binding oxygen species; as a result, the Zn-doped La2O3 catalyst shows better performance in OCM in comparison with the unmodified La2O3 catalyst. Moreover, the co-doping with Al can promote the dispersion of Zn in La2O3 and further raise the number of strong-binding oxygen species in the Zn-Al co-doped La2O3 catalysts, which is beneficial to enhance the selectivity to C2+ hydrocarbons in the OCM reaction
Abstract: Effects of calcium content on the performance of HZSM-5 nanoparticles of 150 nm with Si/Al ratio = 230 in the methanol to olefin conversion were investigated. The parent and modified catalysts showed their largest yields of ethylene and propylene at 490 °C and lower WHSV (= 3.3 h−1). The selectivity for propylene over HZSM-5 was 0.45 at 490 °C whereas it was promoted to 0.51 over Ca27-HZSM-5 (Ca/Al = 27). With decreasing temperature from 490 to 440, and 390 °C, the yield of propylene and ethylene remained nearly constant at 0.13−0.14 and 0.10−0.11 over Ca27-HZSM-5, respectively; more narrow than the corresponding range of yields for HZSM-5 (0.10−0.14 and 0.08−0.12). FT-IR results confirmed the formation of oxygenated and poly alkyl aromatic species in the carbon deposits. TG results indicated that oxygenate coke was formed and converted to heavier poly aromatic coke species with time. Increasing Ca in the porous structure of HZSM-5 may lead to heavier aromatic carbonaceous deposits. In general, Ca content positively affected activity through modification of the density, strength, and accessibility of Brønsted and Lewis acid sites. Long-term MTO activity test of HZSM-5 with Ca/Al = 27 showed stable performance over 100 h, although with an oscillatory feature.
Abstract: A new Mo-Sn catalyst prepared by hydrothermal method was used for the synthesis of dimethoxymethane (DMM) from methanol oxidation. The catalyst with low Mo content can achieve low-temperature oxidation of methanol to DMM with high selectivity. The influence of Mo content on the structure and the catalytic performance of the catalyst was investigated. It was found that Mo1Sn10 catalyst showed the best catalytic performance under the conditions of 140 °C and atmospheric pressure, the methanol conversion was 14.2%, and the selectivity of DMM reached 88.9% without the formation of COx during the reaction process. The catalysts were characterized by XRD, Raman, FT-IR, XPS, NH3-TPD and H2-TPR. The results showed that the catalysts with different Mo content had obvious differences in structure and performance. Lower Mo content was more conducive to the formation of Mo5+ and MoOx, and the resulting changes in acidity and redox properties were the important reasons for the excellent performance of the catalysts.
Abstract: A series of acid-activated montmorillonites (Acid-MMTs) were prepared via Na-montmorillonite treated with nitric acid solution at different treatment temperature and time. And the Acid-MMTs used as solid acid were physically mixed with commercial Cu/ZnO/Al2O3 to obtain bifunctional catalysts for steam reforming of dimethyl ether (SRD) reaction. The results showed that the structure, texture and acidity of Acid-MMTs were significantly changed compared with Na-MMT, which was dependent on the acid treatment conditions. The structure and acidity of Acid-MMTs obviously affected the SRD performance over bifunctional catalyst. The bifunctional catalyst composed of the Na-MMT activated in 20% nitric acid solution at 80 ℃ for 12 h (Acid-MMT-80/12) and Cu/ZnO/Al2O3 exhibited the best SRD performance, with the dimethyl ether conversion and H2 yield reaching 97% and 94% under the conditions of p =0.1 MPa, t =350 ℃, GHSV=3000 h−1, respectively, and DME conversion and H2 yield remained basically constant in 10 h, indicating that the catalyst had better stability.
Abstract: The effects of K, Ru or La promoters on the structure, surface area, crystal phase, and catalytic behavior during FT synthesis of carburized and uncarburized fused Fe catalysts were studied by XRD, XPS, TPD, N2-physisorption and catalytic reaction evaluation techniques. Addition of K improved selectivity of C5+ products for both the carburized and uncarburized catalysts. Addition of Ru suppressed catalytic activity of the carburized catalyst, but had little influence on the uncarburized one. Addition of La led to the encapsulation of the iron carbide, which consequently severely inhibited the carburization and decreased the activity. While Ru and La promote the formation of light components due to their ability to promote hydrogen adsorption. The performance of the reaction in the experiment indicated that the U-K catalyst had the best product distribution, in which the methane selectivity was 4.04%, and the C5+ selectivity was 75.84%.
Abstract: To obtain type II active phase with higher activity, MoS2-based catalysts were prepared by thermal decomposition of ammonium tetrathiomolybdate. The influence of Ni adding way and decomposition atmosphere on the microstructures of MoS2 slabs, chemical state of surface elements, as well as hydrodesulfurization and hydrodenitrogenation activities were investigated. Results indicated that simultaneous impregnation of Mo and Ni precursors caused in situ deposition of amorphous NiMoS4 over the support surface, which subsequently facilitated the substitution of Mo atoms by Ni atoms at MoS2 edges. Accordingly, these decorated catalysts exhibited higher dispersion of MoS2 slabs with more suitable slab length (3–5 nm) and stacking number (2–4), which attributed to larger numbers of rim and corner active sites exposed at the edges. These active sites were essential in hydrogenation and hydrogenolysis reactions. In comparison with N2 atmosphere, thermal decomposition in H2 atmosphere was more conducive to the substitution of Mo atoms by Ni atoms at MoS2 edges, which provided more active Ni-Mo-S structures for the adsorption, activation and hydrogenolysis of quinoline and dibenzothiophene molecules. The catalyst prepared by thermal decomposition of NiMoS4 in H2 atmosphere showed superior activities in the quinoline hydrodenitrogenation with 23.8% conversion and in the dibenzothiophene hydrodesulfurization with 93.3% conversion, under the conditions of 340 °C, 3 MPa, a weight hourly space velocity of 23.4 h–1, H2/oil volume ratio of 600 and 0.1 g of NMS-H2 catalysts.
Abstract: The n-hexane was used as a model compound to study the catalytic cracking behavior of light hydrocarbon in HZSM-5 zeolites, and the law of product selectivity of real acid-catalyzed reaction was investigated by analyzing the product distributions. The results showed that no pyrolysis reaction was found at 300 ℃. Only the acid catalytic reaction took place by the mechanism of carbocation, whose activity was positively correlated to the amount of Brønsted (B) acid sites. The selectivity of ethane, ethylene and propane was negatively correlated, while that of propylene was positively correlated with the Si/Al ratios and catalyst to oil ratios, suggesting that low acid density might be more favorable for monomolecular cracking reactions. It was worth nothing that the total selectivity of C4 products was much higher than that of C2 products. Combined with the quantum chemistry calculation results, it could be confirmed that the super-stability of ${{\rm{C}}_{{2}}}{\rm{H}}_{{5}}^ {{+}}$ carbenium ion from the monomolecular cracking of n-hexane made it difficult to produce ethylene and ethane through hydrogen transfer reaction. It’s easier to form a C8 carbenium ion (${{\rm{C}}_{{8}}}{\rm{H}}_{{{19}}}^ {{+}}$) with another n-hexane molecule, and then to generate more C4 products. These results revealed the nature of the low selectivity of ethylene in light hydrocarbon catalytic cracking products. It could be concluded that the product selectivity of catalytic cracking of light hydrocarbons could be modulated by controlling reaction paths depending on the catalyst acid properties and the catalyst to oil ratios. This work will provide important theoretical support for the catalyst design and process development of naphtha catalytic cracking.
Abstract: The adsorption behaviors of CO2, CH4 and N2 on MER zeolites were investigated by Grand Canonical Monte Carlo (GCMC) simulation method. The calculated pure gas uptake agreed well with the experimental data, which proved that the current simulation model and COMPASS force field are reliable. On this basis, molecular dynamics (MD) simulations were carried out for diffusion and separation of CO2, CH4 and N2 on K-MER zeolites, with the silicon MER zeolite as the reference. The results show that mean squared displacement (MSD) versus simulation time is sublinear. In MER zeolites, the configuration diffusion regime is dominant resulted from the tight fit of the gas molecules and the zeolite pore size. The diffusion of CO2, CH4 and N2 in MER zeolites with three-dimensional cage structures is anisotropic. The gas molecules diffuse preferentially along with the direction of x axis in K-MER zeolites. Extra-framework cations in zeolite plays important influence on the gas diffusion. In K-MER zeolites, the self-diffusion coefficients of CO2 and N2 are negative correlated with loading, whereas for the self-diffusion coefficient of CH4, it firstly increases and then decreases with the increase of loading. All of the self-diffusion coefficients of CO2, CH4 and N2 increase with the elevation of temperature. The order of diffusion activation energy is N2 (16.51 kJ/mol)﹥CH4 (8.39 kJ/mol)﹥CO2 (4.38 kJ/mol). K-MER zeolite membrane has good separation selectivity for gas mixture system of CO2/CH4, CO2/N2 and N2/CH4. The permeance of CO2 and N2 through K-MER zeolite membrane is as high as 104 GPU (1 GPU= 3.35×10−10 mol/(s·m2·Pa)).
Abstract: Pt/C, PtBi(95∶5)/C, Pd/C, and PdBi(95∶5)/C were synthesized by the sodium borohydride reducing method to produce metal nanoparticles with advanced electronic properties to enhance the ethanol oxidation reaction (EOR) mechanism. The Transmission Electron Microscopy (TEM) images and X-ray photoelectron spectroscopy (XPS) showed that a small Bi content does not affect the nanoparticle size PdBi/C; in contrast, it does affect the PtBi ones. The X-ray diffraction analysis revealed a lattice parameter modification by Bi dope in Pt crystalline structure. Furthermore, the ATR-FTIR results indicated the suppression of carbonate formation and increment in acetate production. The results of polarization and power density curves on DEFC, the material PtBi/C presented the more high power density, almost six times bigger than Pt/C. PtBi/C also has the highest current density (44 mW/cm2) and the lowest onset potential (−0.6 V) in linear sweep voltammetry experiments. It also has the highest final current density in current-time experiments. Hence, PtBi/C is a very promising electrocatalyst for DEFC.
Abstract: Zn-Co(OH)2 precursor was hydrothermally deposited on carbon paper at 120 ℃, using cobalt nitrate and zinc nitrate as raw materials. Then Zn-Co(OH)2 was etched and partially sulfided into CoSOH/Co(OH)2 with 5 mol/L NaOH and 1 mol/L Na2S aqueous solution at room temperature. The catalytic performance in oxygen evolution reaction (OER) was investigated. XRD, SEM, TEM, XPS were used to characterize the microstructure, physical and chemical properties of the catalyst. The results show that the used method can etch Zn atoms, create oxygen vacancies and dope sulfur. The oxygen vacancies and doped sulfur play a positive role in enhancing the OER performance. In addition, amorphous CoSOH also exhibited better OER activity. The synergy between CoSOH and Co(OH)2 finally induces the best catalytic properties (overpotential η=310 mV, Tafel slope b=90 mV/dec) and long-term electrochemical stability, that is CoSOH/Co(OH)2 possess superior electrocatalytic oxygen evolution performance.
Abstract: For the Fe-based catalysts in Fischer-Tropsch synthesis, the reduction and activation process of α-Fe2O3 precursor has a significant effect on the catalytic performance. As a crystalline material, the reduction and activation of α-Fe2O3 is assuredly influenced by the exposed crystal plane; however, there is a lack of necessary research in this regard. In this work, α-Fe2O3 nanocrystals of three different morphologies, viz., pseudo-cubic, hexagonal-plate and rhombohedra, were synthesized, which mainly expose the crystal planes of (102), (001) and (104), respectively. The evolution of α-Fe2O3 crystal structure was then investigated in CO atmosphere by using the Operando Raman spectroscopy (ORS). The results show that the α-Fe2O3 (001) plane has a better reductive activity in comparison to the (104) and (102) planes. The SEM, TEM, XPS and XRD characterization and DFT calculation results reveal that CO2 desorption is a decisive step for the reduction of α-Fe2O3; owing to the weak binding ability of (001) crystal plane to oxygen atoms, the desorption of CO2 on the (001) crystal plane is much easier, which can promote the reduction process.
Supervisor：Chinese Academy of Sciences
Sponsors by：Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Chinese Chemical Society
