Abstract: The metal contents of Nigerian coal minerals were analyzed using an atomic absorption spectrophotometer. Calcium, Na, and Fe occurred as the major elements with concentrations ranging from 9782g/gfor Ca to 432μg/g for Na whereas K, Mg, Mn, Ni, Cr, Zn, Pb, and Cu, which occurred at trace levels ranged from 673.73μg/g for Mg to 2.97μg/g for Mn. The results of the quantitative analysis of porphyrins extracted from the coal minerals showed that Onyeama coal has the highest amount of porphyrins (ca~0.96μg/g) while Okpara has the lowest (ca~0.30μg/g). The porphyrins were qualitatively characterized by a combination of thin layer chromatography (TLC), infrared, and ultravioletvisible spectrophotometers. The results of the mid infrared analysis (MIR) showed the presence of absorption bands at 3440cm-1~3450cm-1 and 1640cm-1~1680cm-1 , which are owing to the stretching vibrations of N ─ H and C=C of aromatics, with C─ H out of plane (oop) bending vibrations at wavenumbers less than 900cm-1, all of 〖JP3〗which are characteristic absorptions of porphyrin free base. The ultravioletvisible data showed prominent peaks at ~400 nm Soret band) and at wavelength ranges of 535nm~550 nm(β band) and 565nm~ 600nm(α band) for the coal porphyrins analyzed. The geochemical significance of the metals and porphyrins in coal minerals are discussed.
Abstract: Hydropyrolysis (HyPy) has been developed for the release and investigation of biomarker compounds in the covalentlybonded biomarkers. These biomarkers possess considerable significance to obtain the important information from original organic geochemistry. They can be widely used for the assessment of biogenic sources, maturity, and sedimentary environment as well as the oil/source correlation. Indeed, the considerable evidences indicate that distinct compositional fraction can exist between the bitumen “A” and kerogen from source rocks. The biomarker compounds from hydropyrolysis will provide considerably more information on geochemistry than those from bitumen “A”. The results showed that these primary components in the molecular skeleton of kerogen can be released rationally by catalytic hydropyrolysis. HyPy shows the advantages to maximize the yields of covalentlybounded biomarkers from kerogen, to minimize structural rearrangement of biomarker species, and to maintain the biologicallyinherited stereochemistry. The application of this method to the field of organic geochemistry will provide a new way for the investigation of sedimentary organic matter with higher evolution. It will have a significance and extensive foreground in geochemistry.
Abstract: The effects of hydrothermal treatment on the structure and hydroliquefaction property of Shenhua coal were studied by determination of maximum reflectivity of vitrinite and TG analysis of treated coal. In addition, TG/DTA and IR characterizations were also used to compare the structure of preasphaltenes obtained from liquefaction products of raw coal and hydrothermally treated coal. The results indicate that maximum reflectivity of vitrinite from treated coal is higher than that of raw coal and increases with the hydrothermal treatment temperature. For 250℃ hydrothermal treatment coal, the vitrinite maximum reflectivity is 0.774 % and the weight loss is higher than that of other treated coal. The effects of hydrothermal treatment on hydroliquefaction properties of treated coal are in accord with the influences on vitrinite maximum reflectivity and thermogravimetric property. Hydrothermal treatment of coal under optimal temperature can improve the pyrolysis and cyclization of aliphatic side chain in coal macromolecular, the ability of donation hydrogen, and increase the vitrinite maximum reflectivity so that the liquefaction reactivity of the treated coal is improved. In addition, the thermal stability of preasphaltene from liquefaction products of treated coal is also distinctly enhanced compared to that of raw coal.
Abstract: The effects of the heating rate of pyrolysis, the different reaction agents (steam and carbon dioxide) and temperature on the gasification of Shenfu coal char at ambient pressure and 850℃~1000℃ by TGA were investigated. The initial structure of coal char was analyzed by SEM and N2 physisorption apparatus. The pore volume of the pore size of 2nm~170nm accounts for above 90% of the total pore volume. The BET surface area of SP (slow pyrolyze char) is 1.0777m2·g-1, and the BET surface area of FP (fast pyrolyzed char) is 1.8939m2·g-1.The reactivity index of the fast pyrolyzed char gasification with steam is 4.16 times higher than that of slow pyrolyzed char, which is resulted from the destruction of the structure of pore and retarding of secondary reaction because of the higher escaping rate of volatile from fast pyrolysis . The gasification reactivity index of the SP char and the FP char with steam is 9.94 and 7.15 times higher than with carbon dioxide respectively, because steam can come into wider range of pores and be dissociated easier than carbon dioxide. The experimental data was fitted by the random pore model and the kinetic parameters were obtained. Gasification temperature has a similar effect on the gasification reaction rate of the SP char with steam and carbon dioxide and the FP char with steam, however, a smaller effect on the FP char gasification with CO2 is found.
Abstract: Chemical fundamentals and effectiveness of typical industrial hydrogen donors such as FCC decant oil and its subfractions during mild thermal cracking of a vacuum residue were revealed. Hydrogen donor abilities of the industrial donors were first analyzed, and the thermal cracking of a vacuum residue (VR) was then studied in an autoclave by blending with a hydrogen donor—a FCC decant oil (DO) or one of its subfractions (DO3). It is shown that while the addition of hydrogen donor increases, the yield of 180℃－ fraction decreases and the yields of both 180℃～350℃ fraction and of 350℃－ fraction increase. The viscosity of product residual fuel oil at 100℃ is reduced and its stability measured by spot test is improved with the addition of hydrogen donor. When hydrogen donor addition into feedstock is over 15%, the stability of residual fuel oil is qualified for marketing. It was found that it is the relative high hydrogen donor ability of industrial hydrogen donor employed that improves the products in both the stability of residual fuel oil and the yield of light fractions when vacuum residue is mildly thermal cracked in the presence of hydrogen donors. No correlation in this process exists between residual fuel oil′s group composition and stability. Further investigation through solubility / structural analysis revealed the chemical basis for the improved stability of residual fuel oil, i.e. addition of industrial hydrogen donor can effectively inhibit both preasphaltene formation and the deterioration of association index of the asphaltene when vacuum residue is processed by mild thermal cracking.
Abstract: The regeneration of large particle catalyst in FCC naphtha aromatization was studied in a fixed bed microreactor. CO2/CO mol ratio in product gas during the regeneration was analyzed and apparent kinetic equation for coke combustion was derived. The results showed that the cokeburning rate is in first order with respect to both carbon content and oxygen partial pressure. Because of the internal diffusion, the cokeburning rate for large particle catalyst is only about 60% of that for the small one. CO2/CO mol ratio decreases with the increase of regeneration temperature from 600℃ to 720℃; it increases greatly with the temperature when the regeneration temperature exceeds 720℃. The CO2/CO mol ratio increases linearly with the oxygen partial pressure.
Abstract: Based on the regular analytical data of the plant, the feedstocks of Deep Catalytic Cracking (DCC) on a molecular scale were simulated by the Monte Carlo method combined with Structural Oriented Lumping. The results show that Monte Carlo method can simulate the characters of the DCC feedstock on a molecular scale very well, and the predicted values of feedstock properties such as average molecular weight, saturated hydrocarbon content, aromatic content, resin content, asphaltene content, carbon content, hydrogen content, sulfur content and nitrogen content are in good agreement with the plant data during two operation states. Moreover, the molecular matrices formed in the process of Monte Carlo Simulation lay a foundation for modeling the reaction kinetics of DCC on a molecular scale.
Abstract: The properties of BiMo based catalysts with varied composition and structure for the direct selective oxidation of propane to acrolein were investigated. It has been seen by XRD, XPS, in situ FTLRS, and ESR that propane is selectively oxidized to acrolein via propylene intermediate species. The lattice oxygen of the catalysts is the active oxygen species for the selective oxidation of propane to acrolein via propylene; the selectivity and yield of acrolein associate closely with the redox properties of Mo=O species while the activity of Mo=O correlates tightly with its coordinated circumstance. The selective activity of Mo=O is improved in a sequence of locations as distorted octahedral MoO6, corner shared octahedral in koechlinite structure, edge shared octahedral and tetrahedral MoO4 in distorted scheelite structure. The selectivity and yield of acrolein approached 45% and 13.5%, respectively, and the amount of lattice oxygen with selective oxidative activity amounted to 258μmol/g on the optimum catalyst.
Abstract: Nickeliridium bimetallic catalysts with different iridium contents were prepared by the wet impregnation method. Their catalytic performances in ammonia decomposition were investigated. The results illustrated that the activity of nickel catalyst in ammonia decomposition at low temperature (300℃ to 450℃) was significantly enhanced by adding iridium to the catalyst. A maximum ammonia conversion was observed with the iridium content being 0.7%. At 400℃, the ammonia conversion over 10%Ni0.7%Ir/γ-Al2O3 catalyst was 43.55%, which was 40.0% higher than that on the corresponding catalyst without iridium. X-ray diffraction (XRD) suggested that the addition of iridium provided a better dispersion of active nickel species. Temperature programmed reduction (H2-TPR) profiles demonstrated that there was a synergetic effect between iridium and nickel, and adding iridium to the catalyst may reduce the interaction between the active species and support. Temperature programmed desorption (H2-TPD) indicated that 10%Ni0.7%Ir/γ-Al2O3 catalyst had more active sites than the corresponding 10%Ni/γ-Al2O3.
Abstract: A variety of CuO-ZnO-ZrO2 methanol catalysts with ZrO2 contents were prepared by coprecipitation. The catalytic activity and thermostability of catalysts for hydrogenation of synthesis gas to methanol were tested using a fixedbed reactor. The results showed that the catalyst containing 0.10 (atomic ratio) of ZrO2 performed the best catalytic behavior. The BET, XRD and TPR measurement revealed that the addition of ZrO2 increased the dispersion particle of catalysts, enlarge the surface areas , deduced the catalytic reduction temperature, prevented the catalysts from sintering at higher temperature and enhanced the reduction capability of the catalysts also.
Abstract: Different metallic acetates were used as the catalysts to synthesize cyclic carbonates from carbon dioxide and diols in the presence of acetonitrile. In the course of reaction, acetonitrile acted as not only the solvent but also the dehydrating reagent to eliminate the effect of the water produced from the reaction. Thus, the thermodynamic equilibrium was shifted and the yield of cyclic carbonates was improved. Using 1,2propylene glycol as the reactant to screen the catalysts, it was found that anhydrous zinc acetate possessed the highest catalytic activity. The reaction of carbon dioxide and diols was systemically studied over anhydrous zinc acetate. The results showed that the yields of fivemembered cyclic carbonates were obviously higher than that of sixmembered cyclic carbonates and the yield of 1,2propylene carbonate was the highest. Using 1,2propylene glycol as the reactant and anhydrous zinc acetate as the catalyst, the reaction conditions were optimized as 1,2propylene glycol 100mmol, acetonitrile 10mL, catalyst 2.5mmol, reaction pressure 10MPa, reaction temperature 170℃, and reaction time 12h. Under the optimal conditions, the yield of 1,2propylene carbonate was 24.2% and the conversion of 1,2propylene glycol was 38.9%.
Abstract: Mesoporous SiMCM-41 supported ZnCl2, ZnO, FeCl3 and Fe2O3 catalysts prepared through impregnation were characterized by 29SiNMR, ICP, XRD and UVRaman. Their behaviors on the synthesis of diphenyl carbonate (DPC) from phenol and CO2 in CCl4 were examined. The dispersion of active components, the interaction between metal and support, and changes in catalyst structure during reaction were investigated. The results proved that mesoporous SiMCM-41 was stable during reaction; when ZnCl2, ZnO, FeCl3 and Fe2O3 were loaded into SiMCM-41, the activated sites were bounded on the surface of support by the reaction with silanol groups of pore wall in the molecular sieves, which prevented them from leaching out of catalyst. Among the catalysts examined, ZnO/SiMCM-41 exhibited the highest yield and selectivity for DPC synthesis.
Abstract: Intercalation of PdCl42- in MgAlNO3 hydrotalcite was carried out by coprecipitation. The asprepared MgAl-PdCl4 hydrotalcite was characterized by XRD, IR, DTA and nitrogen sorption. The effects of palladium concentration in the intercalation solution, intercalation time, Mg/Al mol ratio and calcination temperature on the structure of asprepared hydrotalcite were investigated. The results illustrated that PdCl42- and NO3- coexist between layers and the intercalation of PdCl42- may reduce the interlayer spacing. Longer intercalation time is beneficial to the intercalation of PdCl42- and 8h is enough to forming MgAl-NO3HLTcs with good crystalline. MgAl-NO3HLTcs can be formed at Mg/Al = 2~4; the interlayer spacing decreases with the increase of the Mg/Al mol ratio. At high Pd content or high Mg/Al mol ratio, the decomposition temperatures for PdCl42- (to PdO) and NO3- is about 370℃ and 410℃, respectively; however, at low Pd content or low Mg/Al mol ratio, the decompositions of PdCl42- and NO3- change from a continuous process to a discrete one. The destruction of hydrotalcite structure to MgO-Al2O3PdO phase starts at 400℃ and is nearly completed at 600℃. The surface area of hydrotalcite increases with the calcination temperature at first, reaches a maximum at 600℃, and then decreases when further increase of the calcination temperature due to the aggregation of particles and formation of spinel MgAl-2O4.
Abstract: Four macrocyclic d-f heterodinuclear complexes \[M1M2L\](NO3)(H2O)n(L, ligand) were synthesized and characterized. The complexes with different valences were then immobilized on mesoporous SBA-15 synthesized by microwave heating. The samples are characterized by IR, UV-vis, XRD, ICP-AES, TG/DTA and used as catalysts in the oxidation of cyclohexane with H2O2 as an oxidant. The influences of solvent, reaction temperature, and time on the conversion of cyclohexane were examined. The complexes encapsulated in SBA15 exhibit excellent catalytic activity and stability in cyclohexane oxidation with H2O2.
Abstract: The polycyclic aromatic hydrocarbons (PAHs) in flue gas emitted from a coalfired power plant equipped with selective catalytic reduction (SCR) deNOx device were determined. The concentrations and distributions of phase and type of PAHs in the flue gas at the outlet and inlet of the SCR device were compared. The results show that the SCR deNOx device leads to the increase of concentrations and toxic equivalent of PAHs, especially the low rings of PAHs in the flue gas. However, the device has no significant influence on the PAHs partition between particle and the gas phase.
Abstract: In order to investigate the relationship between the composition and the activity of Mn-Ce-O composites, 7 samples with Mn/Ce molar ratios of 10/0, 8/2, 6/4, 5/5, 4/6, 2/8, 0/10 were prepared by coprecipitation. NH3 was selected as a model pollutant and H2O2 was used as oxidant. The oxidation reaction in supercritical water was carried out in a continuous flow packedbed reactor at th temperature of 450℃, the pressure of 25MPa, and the residence time of 1s with the oxidant addition of 2.94 times the stoichiometric amount. The catalytic activity is greatly influenced by the catalyst composition and the catalyst with Mn/Ce mol ratio of 5/5 is found to be the best one, on which the conversion of NH3 can reach to 99.7%. The catalysts were characterized by N2 adsorption, XRD and TPR. The results indicate that there exists an interaction between Mn and Ce oxides.
Abstract: The depolymerization of scrap tire or nature rubber in supercritical toluene was studied. Experiments were carried out under the conditions of 300℃~360℃, 3.7MPa~7.0MPa, 20min~90min, toluene/sample weight ratio 5.0~10.0, respectively. The study was focused on the relationship between depolymerization and the reaction conditions and the depolymerization products distribution. Liquid products were analyzed by a gas chromatography coupled with a mass spectrometer. The results show that most of liquid products are similar in different experiment samples containing alkyl aromatic species and alkene. Their molecular weights are below 300. Supercritical toluene plays an important role, which is not only to swell and dissolve experiment samples, but also to participate in the depolymerization. The results obtained may enforce the basic knowledge on selecting depolymerization fluids and operating parameters correctly.
Abstract: The chemical composition of 80 jet fuel samples was analysed by GC/MS, which is grouped into five categories of hydrocarbon compounds including n-paraffins, isoparaffins, cyclo paraffins, hydroaromatic and decalin. Several physical properties including density, flash point, freezing point, heating value and boiling range were measured by the standard ASTM methods. The database of compositionproperty relationship of the jet fuels was built up. The effect of chemical composition and boiling range on the physical properties was discussed. Combined with the Cookson′s models, 8 models were developed to predict the relationship of compositionproperties by multiple linear regressions (MLR), which gives a better prediction than the MLR correlations reported.
Abstract: The behavior of particles and bubbles in a twodimensional jetting fluidized bed included in a pressured vessel was investigated experimentally by using the CCD camera technology that can detailedly record the behavior of bubbles. EulerianEulerian model was used to simulate the hydrodynamics of a pressurized jetting fluidized bed with a central jet and Vshaped distributor. The influence of gas velocity on the size of bubble, bed expansion ratio and jet penetration height at higher pressure was studied. Both experimental and simulation l results clearly indicate that the jet height decreases and the bubbles become more round when the gasvelocity of distributor is increased at higher pressure. When the jetting gasvelocity is increased, the jet height increases and the bubbles become slender. It has been verified that the result from hydrodynamic model shows a good agreement with experimental data, which suggests that the model can be used to study the fluidization properties in the pressurized fluidized bed.
Abstract: The radial and axial gas holdups in the inner loop of an airlift reactor with a down tube and an annulus gas distributor are investigated under different superficial gas and external liquid circulation velocities. Experimental installation is made of plexiglass with an inner diameter of 0.284m and a height of 3.0m. Air and tap water were used as the gas and liquid phase, respectively. The experimental results show that the radial gas holdup within the inner loop increases with an increase of superficial gas or external liquid circulation velocity. These distribution characteristics at different axial locations are influenced obviously by the reactor structure. The axial profile of the sectionaveraged gas holdup firstly increases with axial height increasing, and then decreases slightly above the exit of the draft tube. Furthermore, the distributions of gas holdup are numerically computed by using an ANSYS CFX10.0 software package. The computational results indicate that the radial distributions of gas holdup are nonaxial symmetry in nature, which is caused by the nonaxial symmetry of the setup. The axial gas holdup increases dramatically above the gas distributor. There exists a minimal gas holdup below the exit of the down tube, which is resulted from the external liquid. The simulated data aforesaid can provide additional information for the experimental investigation. Therefore, it is suggested that the method combining experiment with simulation is suitable for the development of a new type of multiphase reactor.
Abstract: An apparatus for measuring coal slurry at coal liquefaction condition were made. A calculation method, power number method, which suits for this apparatus were developed. The measuring range is: Re＜300, during this range, the method works well. Glycerin was taken as a standard reagent to check the reliability of the apparatus and the power number method. The results of viscosity data of a Chinese brown coal slurry were presented using the apparatus and the power number method. The viscositytemperature curve was obtained. It was found that the curve is suitable for Vogel equation at 300℃.
Abstract: Sulfur, nitrogen and carbon residue in the feedstock and products obtained from fixedbed hydrotreating process were analyzed, and the content changes were investigated in this paper. The results showed that most of sulfur and nitrogen in residue feedstock were removed effectively in fixedbed hydrotreating and carbon residue of products decreased considerably. Therefore, the characteristics of the residue feedstock were improved greatly, and the products can be used as an ideal inputs of FCC. With the increase of the reaction temperature, the removal rates of sulfur and nitrogen increased, and a high temperature also helps to decrease the content of carbon residue.
Abstract: In this article, Ni/CNTs(carbon nanotubes) catalyst′s effect for methanol vaporphase carbonylation under atmospheric pressure were studied. The relations between the catalyst activity and drying condition, the temperature of thermal treatment(with N2) and reduction(with H2) were investigated. The catalyst showed high activity when catalyst were dried step by step. The optimal temperature for thermal treatment with N2 and reduction with H2 were 300℃ and 700℃respectively.
Abstract: A series of supported tungsten phosphide catalysts of 30% W (counted in WO3) supported over γ-Al2O3, TiO2, SiO2, γ-Al2O3/SiO2, γ-Al2O3/TiO2 and SiO2/TiO2, respectively, were prepared by temperatureprogrammed reduction of the corresponding phosphates. The samples were characterized by XRD, BET and TG analysis. The activity of these catalysts were determined in the hydrodesulfurization (HDS) of thiophene and simultaneous thiophene HDS and cyclohexene reducingolefin (HDY), respectively. The results showed that WP species could not be clearly detected in tungsten phosphide over the supports containing alumina, while species with a structure of Al-O-W-P was obviously formed. TiO2 could play a better role in restraining the generation of WP species on the surface of composite supports than that of SiO2. TG results indicated that the starting reaction temperature of phosphidingreduction of the supported tungsten phosphide precursor was probably determined by the structure of catalyst, while the extent of phosphidingreduction was probably related to the interaction between support and active species and between two supports. W species on the surface of catalysts over the support containing alumina could not be completely reduced to WP and some W species may be existed in the form of Al-O-W-P. Tungsten phosphide over different supports showed better cyclohexene HDY conversion than that of thiophene HDS conversion. The-Al-O-W-P species favor the thiophene HDS reaction and also favor the simultaneous thiophene HDS and cyclohexene HDY reactions. Besides of the TiO2, thiophene HDS activities of supported tungsten phosphide catalysts decreased to some extent by adding cyclohexene.
Abstract: Characteristics of the removal rate of sulfur and nitrogen by hydrofining for oil from pyrolysis of scrap tires in pilotscale rotary kiln was investigated．The effectw of reaction temperature (240℃~390℃), pressure (2.0MPa~3.0MPa), volume airspeed (1.0h-1~2.0h-1) and hydrogen oil volume ratio (800〖DK〗∶1~1200∶1) were examined. Reaction temperature has a remarkable influence on the removal rate of sulfur and nitrogen. Reaction pressure does not show obvious impact on the removal rate for light fraction pyrolytic oil. However, higher reaction pressure improves the removal rate for middle fraction pyrolytic oil, especially denitrogenation rate. Lower volume airspeed and higher hydrogen oil volume ratio increase the removal rate of both sulfur and nitrogen. The optimum condition is acquired for light fraction pyrolytic oil, that is 360℃, 3.0MPa，volume airspeed of 2.0h-1, and hydrogen oil volume ratio of 800∶1. The rate of desulfurization and denitrogenation are over 97%. Under this condition the mass content of sulfur after hydrofining is 0.025%, reaching national standard of automobile unleaded gasoline for sulfur which is lower than 0.1%. For middle fraction pyrolytic oil, when reaction temperature is 390℃ and other parameters just like light fraction oil, the removal rate of sulfur and nitrogen could reach 94% and 79%, respectively.
Supervisor：Chinese Academy of Sciences
Sponsors by：Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Chinese Chemical Society
