Abstract: Model compound pyridine was added to diesel oil to simulate the existence of coal-N. A laboratory opposed multi-burner (OMB) gasifier was used to investigate the axial and radial concentration distribution of HCN, NH3, NO and N2. The maximum concentrations of nitrogen pollutants (HCN, NH3 and NO) are produced at the nozzle plane and these concentrations decrease away from the plane. Moreover, N2 participates in gasification and the order of concentrations of nitrogen compounds in exit is N2>HCN>NH3>NO. NO and N2 increase as O2/fuel ratio increases. HCN and NH3 reach maximum when O2/fuel ratio is 1.3, but largely decrease at 1.7 and 0.9. Flow field distribution make radial concentration profiles uniform toward the exit region and low near the side-wall in other axial position. The steam addition leads to increased formation of HCN and NH3, whereas decreased formation of NO.
Abstract: Borax fluxing agent was added to four kinds of coal ash in terms of different quality ratios. The ash fusion test (AFT) of the mixtures of coal ash plus borax fluxing agent was carried out and the reactivity of mullite in coal ash was calculated by the density functional theory (DFT). The space group of the mullite is Pbam, belonging to the orthorhombic system. The results suggest that mullite is likely to combine with electron acceptor rather than with electron donor. The activity of Si is higher than that of Al when mullite combines with the electron donor. When borax is added into mullite, Na+ as the electron acceptor easily enters into the lattice of mullite, causing a transition from mullite to nepheline. The calculation results agreed well with the AFT results under reducing atmosphere.
Abstract: Effect of modified lignin series and naphthalene series dispersants on the stability of coal water slurry (CWS) and sedimentation behavior of coal particles were investigated using Turbiscan Lab dispersionstability analyzer. The results indicate that the sedimentation behavior of coal particles of CWS belongs to differential sedimentation and there is a conglobation between coal particles in CWS preparation. Stability of CWS prepared with lignin series dispersants is better than that prepared with naphthalene series, and the height and mean sedimentation rate of clarifying zone is about 68% of that of FDN when the dosage of additives is 1.0%. The Turbiscan Lab dispersionstability analyzer can analyze the stability of CWS and also can be useful to investigate the stability mechanism of CWS.
Abstract: The gasification reactivity of two anthracite chars with different coal rank and one demineralized anthracite char was determined at atmospheric pressure using fixed bed reactor. The microstructural characteristics of the initial anthracite chars were measured using N2 and CO2 as adsorbate. The variations of microstructure during gasification were measured using CO2 as adsorbate. The effect of mineral matter in anthracite on the variation of microstructure was investigated. The results show that both steam and CO2 play a role in opening micropores and enlarging them. The anthracite char steam gasification reactivity is proportional to its microporous surface area. However, there is no correlation exists between anthracite char CO2 gasification reactivity and its microporous surface area. The mineral matter in anthracite has no influence on the variation of microstructure during gasification.
Abstract: It is necessary to learn the thermodynamic properties of coalliquefaction oil (CLO) for the liquefaction process design and operation. The software package Aspen Plus was employed to calculate the eight fractions collected at different distillation temperatures lower than 300℃ from Shenhua coal liquefaction oil by the coalliquid module. Meanwhile, the Group Contribution Method (MXXC) was used as a comparable method to acquire the critical data that are validated by the GCMS data. The Aspen Plus calculation results show that the fraction's critical temperature increases with the increasing of the distillation temperature. And the critical pressure grows in the light molecular parts of CLO and then has an inflexion point at 180℃ ~ 200℃. On this turning point it has a great amount of polar compounds detected by GCMS. To assess the consistency of these two methods, the nonparametric test, Smirnove test, was applied to evaluate the cumulative distribution function. The statistic result indicates that the two methods have a same distribution function in the range of 95 percent confidence interval. This means that the critical data calculated from Aspen software could substitute the Group Contribution Method in computing the critical properties of the CLO fractions.
Abstract: Coal, slag, and fly ashes were sampled from a 410t/h utility boiler with the equipment of NID (Novel Integrated Desulfurization) system and mercury concentrations of these samples were determined. OntarioHydro method was applied to determine mercury speciation in flue gas before NID and after ESP. The experimental data indicate that the majority of mercury goes into fly ash. The ratio of mercury quantity in fly ash to total combustion product is about 90%, while that in flue gas is about 10%. The results also show that before NID and after ESP, the gaseous mercury concentration in the flue gas is about 21.3μg/m3~22.4μg/m3 and 1.93μg/m3~3.67μg/m3 respectively, indicating that the NID system has quite high mercury removal efficiency up to 83.6%~90.9%. The percentage of Hg2+ which is the main mercury speciation in flue gas before NID is about 67%. The percentage of Hg2+ in flue gas after ESP is about 71.8%~85.1%, while the content of Hg0 is zero, indicating that some chemical reactions have been happened to Hg0 when it passes by NID system. Hg0 becomes Hg2+ and is then adsorbed and removed.
Abstract: The tests of cocombustion of the blends of coal, coal gangue and sewage sludge were carried out in a thermogravimetric analyzer，model STA 409 PC，in which DSCTGA signals are simultaneously registered and both heat flow and weight loss profiles are obtained. The results indicate that the DTG curves of single coal and coal gangue only have one obvious peak of mass loss, but the DTG curve of sewage sludge has two obvious peaks of mass loss. Also, the DTG curves of the blends have two peaks of mass loss. It is found that the temperature corresponding to the maximum weight loss rate peak lowers with increasing the proportion of coal in the blends. The ignition temperature reduces with increasing the sewage sludge in the blends. When the sewage sludge ratio reaches 70%, the ignition point of the blends of sewage sludge and coal is very close to that of the sewage sludge.
Abstract: NO reduction through coal reburning can be conducted in two ways: homogeneous reduction by volatile matters and heterogeneous reduction by char. Experiments were undertaken in a 1D entrained flow reactor (EFR). The effects of the ignition including volatile homogeneous ignition (GI) and carbon heterogeneous ignition (HI) on the reburning process were studied. The results indicate that with increasing the concentration of O2, GI occurs and NO reduction efficiency decreases sharply. At the beginning of HI, the reduction efficiency increases in a narrow span of lower O2 concentration, and with the O2 concentration increasing the reduction efficiency will fall due to the overmuch oxygen. Higher reburning zone temperature can promote NO reduction reactions but also improve the ignition reaction under lower O2 condition. The effect of particle sizes on coal ignition and NO reduction process is more complicated. When the coal size is greater than 40μm, the reduction efficiency will decrease with the particle size increasing.
Abstract: The single-component and bi-component adsorption properties of Cd2+ and Ni2+ ions in coal fly ash particles were investigated. The results showed that coal fly ash was very effective for the removal of Cd2+ and Ni2+ ions from aqueous solutions; the removal percent of metal ions increases with the solution pH value. The adsorption equilibrium is achieved in about 60min; the adsorption capacity of Ni2+ is higher than that of Cd2+. The single-component adsorption corresponds with the Freundlich and RedlichPeterson (RP) isotherms. A significant competitive adsorption effect was found between Cd2+ and Ni2+ ions in the bicomponent adsorption; this competitive effect increased with increasing the concentrations of interfering ions. Equilibrium isotherms for the bicomponent adsorption of Cd2+ and Ni2+ ions have been analyzed by different isotherm models, which suggested that the bicomponent adsorption equilibrium data can be fitted well by the Freundlich competitive adsorption model. The results of desorption tests revealed that Cd2+ desorption from ash was easier than Ni2+ desorption. The solutions of 0.1mol/L HCl, 0.1mol/L HNO3 and 0.05mol/L H2SO4 exhibit similar efficiencies for the desorption Cd2+ and Ni2+ from ash; the desorption rates are > 60% for Cd2+ and > 35% for Ni2+.
Abstract: High-pressure liquefaction of a sawdust in syngas and hydrogen with tetralin as solvent was performed in an autoclave, and the effects of temperature, reaction time and initial reaction pressure on the sawdust high-pressure liquefaction were studied by testing the distribution and characteristic of liquefaction products. The effects of atmosphere on the products distribution and characteristic of sawdust liquefaction were also compared. The results show that the oil yield increases with increasing temperature, reaction time and pressure, while the effects of operating parameters on the oil yield are different: the temperature has a bigger effect than the reaction time and pressure. Under same conditions, the yield and characteristic of liquefaction products in hydrogen and syngas are almost the same, so it is possible to use syngas to replace hydrogen during biomass highpressure liquefaction. The optimal liquefaction conditions of the sawdust in tetralin at syngas atmosphere is 300℃, 2MPa pressure and reaction time of 30min with the conversion of 75.1% and the oil yield of 48.4%.
Abstract: Six kinds of bio-diesels were prepared with different oil materials, and some important characteristics such as the fatty acid composition, solidifying point and pour point were determined. The rheological properties and influencing factor of bio-diesels were studied systematically with AR-500 rheometers. The results show that the solidifying point and pour point of bio-diesel are affected by the fatty acid composition. The rheological data indicate that the biodiesels display a nonnewtonian flow shear-thinning behavior at low shear rate, and the rheological behaviors are influenced by temperature and shear rate. There is little difference in viscosity for bio-diesels when the temperature is higher than the phase change temperature of biodiesel. It is suggested that the fatty acid composition of biodiesel has no notable influence on viscosity. When the temperature is close to the phase change temperature, the viscosity of bio-diesel will increase greatly and the temperature is higher than the pour point of biodiesel.
Abstract: The thermogravimetric analysis of the rice husk bio-oil under the air atmosphere was performed. The activation energies for the volatilization, decomposition and char combustion of bio-oil are obtained to be 63.11kJ/mol, 81.01kJ/mol and 161.29kJ/mol, respectively. The experiments for the bio-oil combustion were carried out in a small kiln to focus on the ignition and pollutant emission characteristics. With the modification of the nozzle and the adjustment of the spray velocity, the bio-oil can be ignited successfully by using a pilot flame to preheat the kiln chamber. Bio-oil combustion has the tendency to form CO, which can be effectively reduced with a higher excess air ratio, but the formation of NOx will be increased. By adding methanol or ethanol into bio-oil, the ignition of bio-oil becomes easy, the temperature of combustion is increased, and the formation of CO and NOx is decreased.
Abstract: A series of experiments were conducted in a multiplefunctional combustion test bed with several kinds of biomass as reburning fuel to reduce NOx. The character and experimental parameters are emphasized to examine the influences on NOx reduction. The results show that biomass could get about 55% to 70% NOx reduction. Within a certain range of the parameters tested, NOx reduction increases with the increasing temperature of reburning zone and initial concentration of NO, and with decreasing excess air ratio and diameter of fuel particle. Under the same test conditions, cornstalk gets the highest NOx reduction and wheat straw, peanut shell，wood ship follow in turn.
Abstract: The oily substances in the water produced by polymer flooding in Gudao, Shengli Oilfield were extracted by petroleum ether and trichloromethane and two fractions (marked as F1 and F2) were obtained. The acidic components from fraction F2 were separated by alkaline extraction and esterified by methanol. The methyl esters products were separated into three fractions I, II and III by silica gel column chromatography. The oily substances and the acidic components were characterized using elementary analysis, IR spectral analyses and acidimetry. The structures and compositions of the methyl ester fractions (fraction I) were identified using GCMS technology. The results showed that the acidic emulsifying active substances in the produced water by polymer flooding were gathered in CHCl3 extracted fraction F2, and degradation products of hydrolyzed polyacrylamide (HPAM) constitute the major part of the acidic components. The compositions of fraction I and II were mainly petroleum acid methyl esters and aliphatic acid methyl esters with amide groups. The fraction III was mainly composed of aliphatic acid methyl esters with more amide groups and some strong polarity compounds containing SO group. The light petroleum acids in water produced by polymer flooding in Gudao Oilfield were mainly composed of C16~18 aliphatic acids, C14~18 naphthenic acids and C18~21 tetracyclic naphthenic acids, and the amount of naphthenic acids were more compared with the aliphatic acids.
Abstract: Room temperature acidic ionic liquids were synthesized with AlCl3 to Et3NHCl; their acidity and catalytic performance in normal hexane isomerization were investigated. The effects of reaction time, reaction temperature and catalyst-to-oil volume ratio on n-hexane isomerization were examined. The results show that the acidity of ionic liquids increases with the mole ratio of AlCl3 to Et3NHCl for the synthesis. The ionic liquid 2AlCl3/Et3NHCl exhibits excellent catalytic performance in the isomerization of n-hexane. The reaction conditions have significant influence on the conversion of nhexane and the yields of isoparaffins and total liquid components; however, the selectivity of isoparaffins varies slightly with any change in the reaction conditions. The optimal reaction conditions are 50℃, reaction time of 45min and catalyst-to-oil volume ratio of 1∶1.
Abstract: With acidic ionic liquid as a catalyst and hydrogen peroxide as an oxidant, the deep desulfurization of hydrotreated diesel was conducted by oxidizing thiophenic sulfur into sulfone, which was then extracted by NMP. Effects of reaction temperature, reaction time and amount of catalyst on the reaction of oxidative desulfurization were also investigated. The optimal reaction conditions are as follows: 3mL oil sample (200×10-6 sulfur content), 1.5g acidic ionic liquid, 0.3mL hydrogen peroxide, reaction temperature of 25℃, reaction time of 3.5h and VNMP/Vdiesel of 1∶1. Under these conditions, good desulfurization ratio (86.7%) and lower sulfur content in diesel (25×10-6) were obtained. After the reaction, diesel oil and catalyst can be separated by simple decantation, and the activity of catalysts would not change obviously after recycling for 5 times.
Abstract: Y zeolites prepared by different modification methods were compared and characterized by N2 sorption isotherms, XRD, Py-IR, and TEM techniques. Catalysts of W-Ni supported on the modified Y zeolites with or without acid treatment were prepared by impregnation method, and the hydrocracking of vacuum gasoil (VGO) was performed on these catalysts. The results show that addition of acid treatment process after the Y zeolites modified procedure can increase the surface area, mesopore volume, and optimize acid sites of the modified Y zeolite. The catalyst using modified Y zeolites with acid treatment process exhibits better catalytic performance, higher yield and selectivity of middle distillates than the others.
Abstract: Different SAPO-11 have been synthesized hydrothermally using the mixed template of di-n-propylamine (DPA) and di-iso-propylamine (DIPA) by varying the template content or the ratio of DPA/DIPA. Products were characterized using X-ray diffraction (XRD), N2 adsorption, NH3temperatureprogramed desorption (TPD) and 29Si MAS NMR, and evaluated towards n-tetradecane skeletal isomerization. The results indicated that the template had strong influence on the crystallinity, the Si distribution and thus the acidity of SAPO11. The sample prepared at template content of 1.5 and w (DPA) of 66% possessed small silicon domains and large amount of Si(n Al)(0 < n < 4) sites, and the catalyst obtained with this method performed highest catalytic activity in the hydroisomerization of n-tetradecane due to the high acidity.
Abstract: Low temperature selective catalytic reduction of NO by NH3 over V2O5-CeO2/TiO2 was investigated with or without H2O and SO2. Results show that 5V30Ce/TiO2 prepared at 400℃ has high reaction activity, and its NO conversion is 99.2% under the conditions of 10000h-1 and 165℃. When the calcination temperature is below 500℃, Ce does not interact with V and CeO2 is the major existence form at the catalyst surface, which can increase the catalyst surface area and V2O5 dispersion to enhance the catalytic activity. Above 500℃, CeVO4 can be formed and it can decrease the activity. The performance of V2O5-CeO2/TiO2 is superior to resist water poisoning, and the deactivation degree under SO2 is more serious than that under SO2 and H2O.
Abstract: Hβ/MCM-41 composite molecular sieves with different Si/Al ratios were synthesized by using β zeolites as the silicaalumina source of mesoporous phases. The catalytic performance of the as-synthesized composite molecular sieves in the acylation of anisole with acetic anhydride was evaluated and compared with that of mesoporous MCM-41 and microporous Hβ zeolites. The composite molecular sieve exhibits much higher stability than MCM-41 and Hβ. UVVis spectra and elementary analysis of the spent catalysts suggested that with the composite Hβ/MCM-41 as catalyst, the amounts of coke deposited during the reaction and C/H mol ratio of the deposited coke was much lower than that with Hβ as catalyst. The composite Hβ/MCM-41 is provided with both the strong acidity of microporous Hβ and the large pore of mesoporous MCM-41; the large pores in Hβ/MCM-41 facilitated the evacuation of heavier products from active sites of the molecular sieve and therefore preserve its catalytic activity provided by the strong acidity.
Abstract: The kinetics of the water gas shift (WGS) reaction has been studied over a large range of operation conditions in a differential reactor on the monolithic Re/Pt/Ce0.8Zr0.2O2/cordierite catalyst，which is very active and stable for low-temperature WGS reaction. The experiments were designed by means of orthogonal design, and the model parameters in kinetic equation were estimated using least square nonlinear regression analysis. Correlation coefficient examination and Fexamination show that the kinetics equation established is statistically indistinguishable, and the calculated data agrees well with the kinetics data. WGS reaction orders for CO, H2O, H2 and CO2 are 0.09， 0.88， -0.54 and -0.11, respectively, which are significantly different from those over the traditional Cubased catalysts. It suggests that lowtemperature WGS reaction may occur through different mechanisms over two catalysts.
Abstract: The coupling process of the cyclohexanol dehydrogenation and the furfural hydrogenation on precipitated Cu-Mn-Si catalysts was carried out at atmospheric pressure in gas phase. The effects of pH value and calcination temperature on the performance of catalysts were studied in detail. There was no observable difference in furfural hydrogenation reaction over the catalysts precipitated at different values of pH. However, pH value had significant influence on the selectivity of cyclohexanone. The catalysts precipitated at the pH values range of 7.5 to 10.0 showed good performance for the coupling process. The increase of calcination temperature decreased the surface area and copper surface area and increased the average pore size, leading to a difficult reduction of the active phase. The calcination temperature had no significant effect on the cyclohexanol dehydrogenation to cyclohexanone, whereas the conversion of furfural and the selectivity of 2methylfuran declined with the increase of calcination temperature.
Abstract: The influence of Sn promoter on the catalytic performance of Pt/ZSM-5 in propane dehydrogenation was investigated by using microreactor tests combined with thermogravimetry (TG), H2 chemisorption and temperatureprogrammed reduction (TPR)．It has been shown that addition of tin component to the supported Pt/ZSM-5 catalyst can improve the catalytic selectivity and stability in propane dehydrogenation, and the catalytic activity and selectivity both increase with increasing Sn loading. When the Sn/Pt molar ratio of PtSn/ZSM-5 catalyst was larger than 6.5, the catalytic activity and H2 uptake remarkably decreased. This might be correlated to the deep reduction of tin oxide to its metallic state as a result of weakening the interaction of excessive tin oxide with ZSM-5 support. For the supported PtSn/ZSM-5 catalyst (0.5% Pt, SiO2/Al2O3 mol ratio is 108), the optimum Sn/Pt mol ratio is 3.0 ~ 6.0.
Supervisor：Chinese Academy of Sciences
Sponsors by：Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Chinese Chemical Society
