Abstract: The variation and thermal stability of hydrogen bonds (HBS) in Huolinhe lignite before and after O-methylation treatment were studied by in-situ diffuse reflectance FTIR(DRIFT). The pyrolysis behavior of the raw and treated coal was investigated by TG. A new calibration method using the band of kaolinite and illite near 3690cm－1 as the basis was suggested to compare the spectrum of the raw and treated coal. The results show that the amount of HBS greatly decreased after O-methylation, but it could not be eliminated completely. The decrease extent of HBS depends on the kinds of HBS. The weaker the HBS are the less the regulation extent will be. The thermal stability of HBS in coal after O-methylation increased at high temperature. During pyrolysis the O-methylated coal has greater conversion, lower initial decomposition temperature, wider pyrolysis temperature range and higher weight loss rate than the raw coal.
Abstract: The rheological behavior of 182 CWS samples was studied using 14 Chinese coals with 12 dispersants. The results show that the CWS rheology of low rank or high ash coal is mainly due to the physical and chemical properties as well as surface structure characteristics of coal. The CWS rheology of high rank coal depends mainly on the structure and property of the dispersants. Generally, when the molecular structure unit of dispersant has large space effect, its hydrophilic and hydrophobic groups are space alternate distribution, it results easily in CWS to exhibit pseudo-plastic behavior. When the dispersant is a length chain polymer, its hydrophilic and hydrophobic groups are linear alternate distribution, it results easily in CWS to exhibit dilatant behavior. Furthermore, the effect of interaction among complex coal particles on CWS rheological behavior has been discussed.
Abstract: The Conradson Carbon Residue(CCR) reaction was carried on the 200 mL Xytel pilot plant by hydrotreatment. According to the experimental results, a kinetic model of first-order and three-lump for the removal of CCR has been proposed based on the structural composition of carbon residue and the mechanism of the removal of CCR. Three-lump reaction kinetic model was compared with one-lump and two-lump models. The result shows that the one-lump reaction kinetic model can't describe the reaction satisfactorily. The predicted error of the two-lump and three-lump reaction kinetic models shows that there is no difference between them when we use the resins and asphaltenes as one lump. When the content of asphaltenes in the residue is low, there is no difference between the results of the two-lump and three-lump models. As we use the three-lump model for the removal of CCR to predict the result, the mean absolute error of the removal of CCR is 0.0056 and the average relative error of the CCR in the product is 1.01％. The three-lump reaction kinetic model can give better precision than the one-lump and the two-lump reaction kinetic models.
Abstract: The surface complex support ZrO2-SiO2 (ZrSiO) was prepared by surface reaction modification, and Ni-Cu/ZrSiO bimetallic catalyst was prepared by isovolumic impregnation. Adsorption and reaction of CH4 with H2O and O2 on the catalyst were characterized by IR, TPD, TPSR and microreactor techniques. The results showed that there exist three kinds of active sites on the catalyst: metal site M, Lewis acid site Znn+ and Lewis basic site Zr-O－. With the cooperation of metal site M, Lewis acid site Znn+ and Lewis basic site Zr-O－, CH4 was activated and dissociated into CO and H2, H2O was dissociated into H2 and O on the catalyst. Under condition of reaction temperature 450 ℃, n(CH4)∶ n(O2)∶ n(H2O)=1∶0.5∶2.5 and methane space velocity (SVCH4)＝1200h－1, the main reaction products on Ni-Cu/ZrSiO catalyst are H2 and CO2, with a selectivity over 95%.
Abstract: Using a fixed-bed pyrolysis reactor, the formation of Tar-N, HCN, NH3 and Char-N out of four kinds of blind coal from different producing areas,as well as the characteristics of released N on the fuel nitrogen,were studied between 400 ℃～1 200 ℃ under an Ar atmosphere. It was shown that HCN yield increased with increasing temperature from 400 ℃ to 1 200 ℃, while the yield of NH3 increased to its maximum at 1 000 ℃, followed by a slight decreasing. In contrast, Char-N yield decreased with increasing temperature. At≥1 000 ℃, the yield of NH3-N and NH3-N +HCN-N decreased as the volatiles of parent coal increased. Tar-N yield was little and almost had no change in all temperature range for all coals.
Abstract: β-Mo2N0.78 was synthesized using the reaction of molybdloum oxide with N2-H2 via temperature-programmed reaction. Thiophen hydrodesulfurization(HDS) overβ-Mo2N0.78 was carried out at atmosphere pressure. The results showed that the HDS activity increased with increasing reaction temperature, and pre-reduction could deactivate the catalytic activityβ-Mo2N0.78 also had a resistance to sulfurization. The bulk structure of catalysts did not change after long time HDS reaction. Influence of the synthesis factors including nitriding temperature, nitriding time, N2-H2 ratio and temperature program of nitriding reaction on HDS activity of β-Mo2N0.78 was investigated in detail: (1) the catalytic activity of catalyst decreased with the increasing of nitriding final temperature; (2) the catalyst which was nitrided for a long time at final temperature has low HDS activity; (3) a suitable N2-H2 ratio and a temperature program of nitriding reaction to synthesize catalyst with high HDS activity were determined. It was found that small crystallites of molybdenum nitride had high catalytic activity.
Abstract: The influence of metal copper and cupric oxide additive on Polycyclic Aromatic Hydrocarbons (PAHs) emissions during combustion of bituminous coal was investigated in experimental tube furnace. GC was adopted to analyze PAHs. The results indicate that copper and cupric oxide additive promote PAHs formation, especially for MMW-PAHs (moderate molecular weight PAHs) and HMW-PAHs (high molecular weight PAHs). This phenomenon can be explained by that copper additive offers a lot of active reaction centers for PAHs' synthesis. Because of the dual catalysis of cupric oxide additive, MMW-PAHs emissions remarkably increase. The TEQ (toxicity equivalence quantity) of PAHs emissions is decreased by copper and cupric oxide additive below 800 ℃. Above 900 ℃, the TEQ of PAHs emissions is increased by copper additive. The similar phenomenon has occurred when cupric oxide is added.
Abstract: The stability of CaCl2 in dry and moist air at elevated temperatures were studied by direct absorption of gaseous chlorides and mercury thiocyanate measurements technique supplemented by chemical analysis (pyrohydrolysis- mercury thiocyanate method) and flame atomic absorption spectrometer (FAAS). The principal reaction is shown to be hydrolysis of CaCl2 at high temperature and CaCl2 is actually hydrolyzed appreciably at about 700 ℃ in moist atmospheres. Kinetics calculation has shown that hydrolysis is two order reaction and the activation energy for the hydrolysis is 37.82 kJ/mol and 18.13 kJ/mol, over the range 700 ℃～1 000 ℃ and 1000℃～1300℃. The results will be of significance for chloride pollution control during coal combustion.
Abstract: In this paper, supported Au/α-Fe2O3 catalyst for low-temperature water-gas shift reaction(WGSR) was prepared through co-precipitation method. The reduction procedure was optimized to activate the category of gold catalysts, which involves rhombization of reduction conditions, i.e. reductive gas composition, reduction temperature, and reduction time, using 8.00%Au/α-Fe2O3 catalyst as sample. It was found that the sample, pre-reduced under 150 ℃ for 9 h in reductive gas flow (10% -H2/N2) , exhibits the higher activity. Then the influence of gold loading on the ultimately WGSR activity of Au/α-Fe2O3 catalyst was investigated due to the precious cost of gold, wherein its loading was controlled through adjusting the atomic ratio Au/Fe. The 8.00% Au/α-Fe2O3 catalyst shows the highest activity. The structure of Au/α-Fe2O3 catalysts with different gold loadings were studied by BET, XRD, XRF, UV-VIS, H2-TPR and O2-TPO characterization techniques. The introduction of gold during co-precipitation may suppress catalyst sintering during WGS reaction. During the preparation, the loss of gold will occur; the loss becomes more serious if the designed gold amount is increased. Moreover it will lead to the aggregation of gold particle, which was revealed by XRD and UV-VIS results. The Au/α-Fe2O3 catalysts with optimal Au loading (8.00%) shows the highest activity owing to the present of moderate Au0 particle and theα-Fe2O3 support holding susceptible reduction but resistant to oxidation, revealed by the TPR-TPO results. Therefore, the high catalytic activity of the investigated catalyst was attributed to the synergism between Au0 and Fe3O4.
Abstract: The physical features of nanosized combined support and CoMo supported catalysts with different nanosized scales were summarized. NH3-TPD was used to determine the acidic features of nanosized TiO2/Al2O3 composites and CoMo supported catalysts. The results showed that the supported nanosized TiO2 and the matrix γ-Al2O3 interacted with each other. When a small quantity of TiO2 was carried on the matrix, the total amount of acid sites increased with TiO2 content, and the composites had larger acid amount than matrix. The CoMo catalysts had much larger acid amount. From the shape of the TPD traces of the composites, we reached the conclusion that nanosized TiO2 is prior to support on the strong acid sites of the matrix. The crystalline size of TiO2 had more influence on acid amount than on acid distribution. The novel CoMo supported catalysts possesse suitable aperture properties and high hydrogenation activity for oil refining.
Abstract: The ultra activated carbon with a surface area of more than 3 000 m2/g was obtained from Daqing petroleum coke by KOH activation. The effects of the ratio of alkali to carbon, the activation temperature and the activation time on the adsorption properties were investigated, and the preparation parameters were optionized (KOH∶C=4∶1,activation temperature:800 ℃,activation time:2 h). A carbon molecular sieve with a mesopore ratio>85% and SBET>1 500 m2/g was then obtained from the UAC through heat-treatment; HNO3 oxidization was employed to make CMS with acid strength distribution on the surface being appropriate (150 ℃～240 ℃ weakly acid, 240 ℃～340 ℃ middle strong acid, 340 ℃～450 ℃ strong acid). This novel CMS with wider distribution in acidity is of potential in catalyst. Because better acidities distribution can intensify the strength between supports and metal ions and increase the loadings, CMS post oxidation is more suitable for being catalyst supports.
Abstract: The heavy oil upgrading technology with alternative hydrogen is very attractive for the heavy oil processing. The catalytic hydrocracking of Gudao residue with different catalysts precursors using water-syngas as alternative hydrogen was investigated, which provides hydrogen in-situ for hydrocracking through the water-gas shift reaction(WGSR). The results show that catalysts play a very important role in catalytic hydrocracking of Gudao residue using water-syngas as alternative hydrogen. Addition of catalysts to residue was found to improve the distribution of cracking products and inhibit the asphaltene or TI formation.
Abstract: Effects of chlorine on heavy metals distribution at different temperatures are studied with mixed wastes incinerated in a quartz tube by adding organic chlorine (PVC) and inorganic chlorine (NaCl). The results indicate that the chlorine content in wastes has no influences on heavy metals distribution at lower temperature. Only at higher temperature the influences can be detected. When chlorine is contained in wastes incineration, heavy metals will transfer to fly ash or flue gas more easily. The organic chlorine has more impacts on heavy metals transfer characteristics than inorganic chlorine. The chlorine can obviously alter distribution characteristics of the heavy metals that disperse between fly ash and flue gas or between bottom ash and fly ash.
Abstract: Incineration has been widely applied over the past decade for disposal of municipal solid wastes (MSWs) in China. However, high chlorine content in MSW results in two major problems: high temperature corrosion and the emission of dioxins. In this paper, thermodynamic equilibrium calculations were performed to reveal the formation and transformation of chlorine-containing compounds during thermal conversion process of PVC and MSWs under different conditions. Calculations were also applied to the reactions between Ca-based sorbents and chlorine-containing compounds. The results showed that HCl was the main chlorine containing product for PVC. For MSWs, organic and inorganic chlorine can transform into HCl gas completely when temperature was over 600 ℃. Ca-based sorbents was effective on the HCl removal for PVC but ineffective for MSWs at the temperature of normal incineration conditions. Therefore, a new chlorine-removal process was proposed, which can remove chlorine and restrain dioxin emission simultaneously.
Abstract: Scrap tires were pyrolysed in a pilot-scale kiln reactor at 450 ℃～650 ℃ and properties of the derived oil were investigated. The oil yield reached a maximum of 45.1% at 500 ℃ and then decreased with increasing pyrolytic temperature. A distillation was carried out and complete distillation curves were acquired. It was shown that the weight percentage of the fraction below 200 ℃ amounted to as much as 33%～40% and the increasing of pyrolytic temperature help raise the amount of light fraction. The pyrolytic oil and the oil fractions were subjected to FT-IR analysis, and it was shown that higher pyrolytic temperature resulted in higher aromaticity of the oil. This could be explained by the Diels-Alder route of the primary oil vapor to secondary aromatic compounds. Several aromatics, such as benzene, naphthalene and their alkyl derivatives, could be discriminated from the FT-IR spectra.
Abstract: In the present work, hydrogen production from wood sawdust in supercritical water is investigated using a batch reactor. CaO was added to produce a clean gas free of environmentally unfriendly gases. The effects of CaO and reaction conditions on both yield and composition of the products are investigated. When Ca/C molar ratio is increased from 0 to 0.48, the yield of hydrogen increases from 3.2 mmol/g to 6.5 mmol/g. The results indicate that the key factor that affects the conversion of wood sawdust is the reaction temperature. The conversion of carbon to gas increases from 47% to 76% and the yield of hydrogen is increased from 4.5 mmol/g to 6.5 mmol/g with an increase of temperature from 773 K to 873 K. Compared with temperature, the influence of both residence time and pressure is less significant.
Abstract: Fe－Mo－O catalysts were prepared by the Sol-Gel method. The surface composition, reducibility, ethane chemisorption and reactivity of the catalysts were systematically studied by using the techniques of XRD, IR, TPR, TPD and micro-reactor. The results showed that the catalyst calcined at 450 ℃ was ultrafine particles with BET surface area of 48.1 m2/g. There existed both Lewis acid sites(Fe3+,Mo6+) and Lewis base sites(oxygen of Mo=O and Mo-O-Fe bond) on the surface of the catalysts. Ethane can be chemisorbed on surface terminal oxygen of Lewis base sites Mo=O bonds by one H atom in -CH3 to form molecular adsorption states, and the adsorption ability increases with the rising of the temperature. Moreover, the ultrafine particles have higher lattice oxygen activity, and the adsorption amount and intensity of ethane on the ultrafine particles is greater than that on the bigger particles. Reaction products of partial oxidation of C2H6 on the Fe－Mo－O catalyst are mainly C2H4 and a little CH3CHO.
Abstract: A honeycomb Pt/Al2O3 catalyst was prepared by multi-coating and wet-impregnation method. The catalytic performance and comparison of integral reactor and circulating reactor for selective catalytic reduction of NO over the catalyst have been studied. Based on Langmuir-Hinshelwood method and experimental results the mechanism of NO reduction by C3H6 was proposed. The mathematical expression for reaction rate of NO and C3H6 has also been established. The calculation result is consistent with the experimental data, and the result shows that the decomposition of NO on the catalyst surface is inhibited by superfluous O2 at higher temperature.
Abstract: The precursors of methanol synthesis catalyst have been prepared using different coprecipitation method, and the catalytic activity and stability were tested using differential fixed-bed reactor. The pH values of the precursors of methanol synthesis catalyst in the period of ageing , especially around the colour-turning point have been studied. At the same time the effect of reaction temperature and reaction pH on the time of colour-turning of precursors and catalytic activity have been investigated as well. It is shown that the pH values of the precursors of methanol synthesis catalyst in the period of ageing changes continuously, the pH values appear a minimum in the vicinity of colour-turning point, at the same time the activity of the catalyst has a sharp increase after the colour-turning point. It is predicted that the composition and structure of the precursors altered obviously after the colour-turning point. It is shown that from the test result increasing reaction temperature favors structure adjustment of precursors; while increasing reaction pH restrain the structure adjustment of precursors. The experimental results showed that co-current feed method was the best method. The activity and stability of the catalyst prepared from co-current method was higher than those prepared by other methods. The optimum pH range of precursor was 7.5～8.5 and the temperature should be higher than 80 ℃.
Abstract: Volumetric mass transfer coefficient of hydrogen in pine gum and rosin which is very necessary to provide the important basic data for studies on reaction kinetics of catalytic hydrogenation of pine gum and rosin have been measured at various pressure (2.0 MPa～10.0 MPa), temperature (373 K～573 K), and 600 r/min stirring speed in a high-pressure agitated autoclave. According to the pressure change during the pure gas dissolution in solvent, volumetric mass transfer coefficients of H2 in pine gum and rosin were calculated. The result shows that volumetric mass transfer coefficient of hydrogen increased with temperature and pressure, and the relationship among them have also been correlated. During the calculation of volumetric mass transfer coefficient, the comparison of the results between integral method and differential method was also made, and the average absolute deviation is 4.74×10－4 for pine gum and 1.21×10－4 for rosin.
Abstract: The synthesis principal of NiMgAl hydrotalcite-like compounds by co-precipitation was studied in the system of Ni(NO3) 2-Mg(NO3) 2-Al(NO3) 3-NaOH. The effect of pH Ni/Mg ratios, co-preciptation temperature, time and temperature of hydrothermal treatment on the synthesis of NiMgAl-HTLCs were also investigated. The synthesized samples were characterized by using XRD, ICP, and FT-IR. Experimental results showed that unique NiMgAl-HTLcs with high crystallinity can be prepared by precipitation of solutions with M2+/M3+=2.0 and Ni/Mg=2.0～4.0 at pH=5.5～7.0, 100 ℃，7 h hydrothermal treatment. Study on the thermal stability of NiMgAl-HTLcs showed that the structure started to be destroyed at 3 00 ℃.
Abstract: Acylation of toluene to methylacetophenone with acetic anhydride（AA） over Hβzeolite was investigated. The effects of various factors such as reaction temperature, selection of solvent, amounts of catalysts and solvents, and the ratio of toluene to acetic anhydride (AA) on the yield and selectivity of para-methylacetophenone were examined. The suitable reaction conditions were optimized as 130 ℃, a toluene/acetic-anhydride (AA) mole ratio of 20, catalyst/ acetic-anhydride (AA) ratio (weight) of 0.8. Polar solvent (e.g., nitrobenzene ) enhances the acylation of toluene with acetic anhydride (AA), but the selectivity of para-methylacetophenone is reduced. Correspondingly, non-polar solvent (e.g., CO2) help restrain the deactivation of the catalyst.
Abstract: A new deacid refined method of distillate oil, microwave irradiation, was put forward. The optimum conditions of the refined process are investigated. The volume ratio of solvent to oil is (0.20～0.25)∶1, the pressure is0.04 MPa～0.06 MPa, the radiant time is 6 min under the constant pressure, microwave power is 375W, settled for 25 min the acidity will be reduced from 170.4 mg/100 mL to 8.35 mg/100 mL, which is good enough to meet the best specification of GB, and the refined process has no effect on the quality of the distillate oil. The oil used in this study is common cut 2 distillate from Liaohe oil field. The recovery ratio can reach 99.3%.
Abstract: A new mechanism of saving energy and reducing pollution is brought forward by analyzing water characters and all factors which bring saving energy and reducing pollution in the combustion process of emulsification oil. The theory shows that the reason of saving energy and reducing pollution is that emulsification oil can reduce surplus air ratio effectively. By this new theory, the reason of saving energy and reducing pollution in the combustion process of emulsification gasoline, emulsification diesel oil and emulsification heavy oil of W/O or O/W can be well explained, especially for that in a boiler with favorable combustion state. According to the theory, a good performace of the high soften-point pitch-water slurry combustion is gained.
Abstract: Critical temperature and pressure of 24 wide and narrow fractions from Talimu crude were determined with the semi-sealed tube apparatus. Based on these experimental data, the applicability of six empirical correlations for calculating critical properties of Talimu oil fractions were investigated. The average relative error is 1.35%～2.09% for critical temperature and 7.06%～9.96% for critical pressure. Among these correlations, Sim-Daubert and Lee-Kesler correlations are better for critical temperature calculation and better result for critical pressure calculation was obtained by Sim-Daubert correlation, while others are not satisfactory.
Abstract: The intrinsic kinetics of propylene epoxidation with H2O2 over TS-1 in t-butyl alcohol/water system was investigated. The reaction was carried out at T=303.15 K～323.15 K, p=0.3 MPa～0.6 Mpa. Based on the proposed reaction mechanism and adsorption characteristics, the kinetic model was established as follows:based on the experimental data, the model parameters were estimated. The results showed that the Eley-Rideal model could fit precisely with the experimental data, and the reaction takes place between H2O2 adsorbed on Ti active sites and propylene in free state.
Supervisor：Chinese Academy of Sciences
Sponsors by：Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Chinese Chemical Society
