Abstract: CuO/γ-Al2O3 was used to remove SO2 from flue gas. The effects of catalyst preparation parameters and reaction conditions on sulfur removal activity were investigated. The characterization of the CuO/γ-Al2O3 desulphurizer with different Cu loading has been carried out by XRD. The CuO/γ-Al2O3 desulphurizer with 8%～10% Cu loading shows the highest activity for SO2 removal. The decrease of sulfur removal activity of CuO/γ-Al2O3 with Cu loading higher than 10% may be due to segregation of CuO on the surface of Al2O3. At temperatures of 350℃～500℃ and GHSV of 3 000 L/kg·h～56 000 L/kg·h, the CuO/γ-Al2O3 desulphurizer shows high sulfur removal activity which is greatly promoted by presence of oxygen in the simulated flue gas.
Abstract: The optimum condition was determined for organic sulfur removal from coal by copper chloride oxidation and tetrachloroethylene extration through orthogonal testing. The effect of desulfurization conditions on organic sulfur removal was studied. At the same time, the influence of this desulfurization method on the quality of coal was inquired into. The results showed that this method was good and reaction condition was very mild. And the best desulfurization condition was that PCE as organic solvent, the size of coal was 0.076 mm, the concentration of coal was 0.067 g/mL, reaction time was 120 min and reaction temperature was 120 ℃. Under this condition, the highest organic sulfur removal reached 43%. It was obvious that the organic sulfur removal increased with the decrease in size of coal and it increased at first, and then changed little, even decreased with increasing reaction time, temperature and concentration of coal. The analysis of IR spectrum showed that the structure of coal wasn't destroyed. The loss of heating value of coal was less.
Abstract: Yunnan lignite and Nantong bituminous coal were extracted with a carbon disulfide-N-methyl-2-pyrrolidinone (CS2-NMP) mixed solvent, actone and pyridine at room temperature in turn,and the solid powders were gained after removal of the solvent. Adsorption behaviors of nitrogen by the coal, its extract fractions and residuals were investigated using Accelerated Surface Area and Porosimetry (ASAP) 2010 apparatus, and the experimental data were fitted by BET equation and y=kx+b. Results showed that solvent extraction can increase the porosity for the coal with high extraction yield, and the nitrogen adsorption behaviors of coal complied with the Henry law.This demonstrated that, at the saturated temperature of nitrogen (77 ),an exact nitrogen adsorption isotherm can be obtained from few data values of adsorption volumes
Abstract: Vapor-phase fluorine emission characteristics during coal combustion have been studied by means of fixed bed tube furnaces. And the kinetics model of vapor-phase fluorine emission during coal combustion have been established successfully through the experimental data for constant temperature kinetics. The results indicated that fluorine emission tends to increase with increasing combustion temperature, fluorine emission starts at 300 ℃～400 ℃, 500 ℃～1 100 ℃ is the main fluorine emission temperature range. Fluorine emission increases with increasing retention period, the initial 5 min is the main fluorine emission period. Fluorine emission can be affected by reductive combustion atmosphere to some extent, and has relationship with mode of occurrence and content of fluorine in coal. Kinetics calculation has shown that fluorine emission during coal combustion can be described by first order reaction kinetics model, and activation energy and frequency factor depend on the mode of occurrence of fluorine and the thermal stability of fluorine-bearing minerals in coal. The activation energy is between 28.0kJ·mol－1 and 65.1 kJ·mol－1 and the frequency factor is between 12.5 min－1 and 46.0min－1 for experimental coals.
Abstract: The influence of regeneration temperatures in range of 400 ℃～700 ℃ and the regeneration atmosphere composed of O2 and N2 in varying proportions on regeneration conversion and the following sulfidation reactivity were investigated in a fixed bed reactor at atmospheric pressure. In addition, the influence of deposited dust adhered to the surface of sorbents on regeneration were studied, which can be encountered in the combined process of simultaneous removal of dust and sulfur. The characterization of regenerated samples was undertaken by XRD and BET techniques. The results showed that increasing temperature had a negative effect on first-cycle regeneration conversion, but little effect on regeneration conversion and sulfidation reactivity in the following cycle. Meanwhile regeneration atmosphere studied has very little effect on the regeneration conversion and the following sulfidation reactivity. Furthermore, the addition of dust into the sorbent would decrease the regeneration conversion, but had no noticeable influence on the following sulfidation reactivity.
Abstract: By adding the catalytic promoters of Ni and Co with the liquid co-deposition method, we have developed a new kind of electrocatalyst for PEMFC. Activity improvement of the electro-catalyst was confirmed by oxygen electrode polarization measurements. When the contents of Ni and Co were 0.8% and 1% (based on carbon) respectively, the electro-catalyst exhibited better performance. SEM and TEM showed that the Pt/C electro-catalysts were in high dispersion state, due to the existence of Ni and Co. After 96 h test, no obvious deactivation was observed.
Abstract: The macerals of 24 Chinese coals with different coal ranks were characterized and their effects on the properties of coal water slurry (CWS) were investigated. The results indicated that high content of vitrinite and low content of inertinite in coal with similar ash content are beneficial to the slurryability, static stability and rheological behavior of CWS. From the results of plurality fit linear, both vitrinite and inertinite showed the remarkable effects on the properties of CWS, while the exinite had less effect. The inertinite content in coal shows significant effects on the static stability of CWS. The soft sediment is normally formed after 15 days when inertinite content in coal is lower then 30%. Fit exponential analysis indicated that the maximum reflectivity of vitrinite had a good correlation with the slurryability of CWS, the slurryability increases with increasing maximum reflectivity, which can be used as a parameter to estimate the slurryability of CWS.
Abstract: The compound with low molecular weight is thought to play a key role in the structure of coals and has a significant effect on the process of coal pyrolysis. The purpose of this paper is to describe the characteristic of pyrolytic process of extract. The sample was obtained from vitrain extracted by tetrahydrofuran. The thermal decomposition behavior of vitrain and its extract were investigated by TG and Py-FTIR, the latter can continuously obtain IR spectra of the volatiles as the sample is heated. The TG and DTG curves of extract are different from those of vitrain. The rate of weight loss of extract is higher than that of vitrain. Two peaks in DTG curve of extract were observed at 190 ℃ and 452 ℃ individually, while no peak was observed at 190 ℃ for vitrain. The maximum peak in DTG curve moves towards low temperature compared with vitrain. The results of Py-FTIR shows that the amounts of aliphatics evolution of extract is higher than those of vitrain, the evolution profile indicates the evolution of aliphatic compounds is fast. The amounts of methane and CO2 evolution from extract were lower than those of vitrain, no CO was produced from extract.
Abstract: The hydrogenation of carbon dioxide over Fe-Zn-M/HY (M=Cr, Al) composite catalysts at 340 ℃, 5.0 MPa was studied. Effects of Fe content of Fe-Zn-M catalysts on the conversion of carbon dioxide, the selectivity of hydrocarbon products were investigated. The adsorption performance of carbon dioxide and the reductive performance of Fe-Zn-M (M=Cr, Al) catalysts were studied by means of carbon dioxide Temperature-Programmed-Desorption (TPD) and H2 Temperature-Programmed-Reduction (TPR). The results indicated that the activity of the composite catalysts was improved with the increase of Fe content of Fe-Zn-M catalysts while the selectivity to hydrocarbons was decreased. Furthermore, the fraction of iso-alkanes in hydrocarbons produce decreased with the increase of the Fe content. CO2-TPD and H2-TPR study showed that the higher Fe content could result in more adsorption of carbon dioxide and easier reduction of the catalysts.
Abstract: The change of viscosity and average molecular weight of heavy oil from Liaohe oilfield with temperature and reaction time are investigated in the paper. The effect of metal salts and reservoir minerals on the aquathermolysis of the heavy oil are also studied. The results show that Liaohe heavy oil can undergo aquathermolysis in steam injection process. It is found that the metal salts can accelerate the aquathermolysis of heavy oil and lead the viscosity and average molecular weight decrease further. The reservoir minerals have the synergetic effects on the aquathermolysis of the heavy oil. The results provide a theoretical basis for down-hole catalytic upgrading of heavy oil.
Abstract: Water soluble bimetallic catalysts, derived from FeSO4·7H2O and ammonium heptamolybdate(AHM), were used for upgrading Kelamayi AR at an initial H2 pressure of 7.0MPa, 436 ℃, for 1 h. No coking (toluene insolubles <1%), and high yield of the distillates (<450 ℃, about 60%) show that the catalyst has a high activity in inhibiting coking and hydrocracking. To treat Kelamayi AR, the best concentrations of Mo and Fe are 15 μg/g～25 μg/g and 1100μg/g～1300μg/g in the studied range. The catalysts were characterized by XPS, XRD and TEM and it was confirmed that metals are present as metallic sulfides. Molybdenum is more difficult in sulfuration reaction than iron, thus the sulfuration conversion of Molybdenum is less than 50%. The nature of reciprocity between components of the bimetallic catalysts is “physiochemical-dispersion”, which can inhibit the crystal growing up each other. Compared with oil-soluble catalysts, the grain of water-soluble catalysts (100 nm) after sulfuration reaction is large, but smaller than monometal catalyst. As may be the result of inhibiting the crystal growing.
Abstract: WP/γ-Al2O3 catalyst whios active component is tungsten phosphide was prepared by mechanical mixing, co-impregnation and stepwise-impregnation methods, respectively from the tungsten phosphate precursor by means of temperature-programmed reduction in highly-pure flowing hydrogen. The HDS activity of thiophene over these catalysts was examined. The result revealed that the methods used for catalyst preparation had some effect on the catalyst structure and activity to HDS of thiophent especially for the lower temperature reaction. With mechanical mixing method, the HDS activity of the catalyst prepared by mixing then reduction is higher than that prepared by reduction then mixing. With co-impregnation and stepwise-impregnation methods, the HDS activity of the catalyst prepared by calcination is higher than that without calcination or close to each other, respectively. Catalysts prepared by impregnation had higher HDS activity than that prepared by mechanical mixing.
Abstract: A series of CuO-ZnO-Al2O3/HZSM-5 composed catalysts were prepared with different precipitation agents, such as aqueous solution of ammonia, sodium hydroxide, sodium oxalate and sodium carbonate. Their catalytic performance for hydrogenation of CO2 was evaluated. The physical-chemical properties of the catalysts were also studied by means of H2-TPR, XRD, BET, CO2-TPD and H2-TPD. The result showed that precipitation agents had obvious effect on the activity, structure of crystal phases, reduction property, as well as absorption properties to CO2 and H2 of catalyst. There existed two kinds of adsorption center on the catalyst. Their activity and selectivity were in close relationship with the adsorption property. The mechanism of CO2 hydrogenated directly to methanol and DME were proposed based on the study.
Abstract: The n-alkane content is one of the most important aspects to relate the cryogenic properties of the diesel oil. We can accord to the n-alkane content to design the pour point depressant for diesel oil. On the basis of the mathematical model of the relationship between the n-alkane content and the cryogenic properties of the diesel oil, by selecting the functional group of the diesel oil pour point depressant, the molecule design model of the new-type depressant is obtained. The ratio of different length carbon chains can be calculated by the program developed in our laboratory. According to the designed model, a series of diesel oil pour point depressants with different carbon chains are synthesized. As a result, we can prepared different pour point depressants for different diesel oil. By evaluating the performance of polyacrylate as pour point depressant, the designed model is verified.
Abstract: Mesoporemicrospore composite molecular sieves were synthesized under hydrothermal conditions by use of cetyltrimethylammonium-bromide(CTMAB) and tetramethylammonium (TMAOH) as the templates. The as-synthesized composite molecular sieves showed diffraction peaks at small and large angle regions in their XRD patterns, which correspond to the mesopore and microspore structures. IR spectra showed that the as-synthesized sample had characteristic absorption bands of mesoporous MCM-41 and microporous ZSM-3 molecular sieves, and their IR spectra are clear different between composite molecular sieves and mechanical mixture. The N2 absorption and desorption isotherms of the as-synthesized samples showed that the sample was a composite molecular sieve, and the corresponding BJH pore size distribution of the material indicated that there were two kinds of pores mainly located at 0.7 nm and 3.3 nm. The SEM images of composite molecular sieves is different from the mechanical mixture's, the former is that the ZSM-3 overgrowth on MCM-41 or MCM-41 re-crystal, the latter is evenly scatter and not re-crystal images.
Abstract: Al-MCM-41 mesoporous molecular sieves with high specific surface area have been hydrothermally synthesized with Shenghua Refinery's FCC decant oil dissolved in toluene as additive, using cationic surfactant of cetyl trimethyl ammonium bromide as template, tetraethyl orthosilicate as silica source and aluminum sulfate as aluminum source in this article. XRD, SEM, nitrogen adsorption and TG-DTA have been used to characterize pore structures of these synthesized samples. Effects of additive on synthetic conditions have been investigated and longer time for blending colloidal solution has been taken. Emphasis has been put on changes of structure properties such as crystallization, crystal cell parameter, BET surface area, average pore diameter and pore volume with addition amount of FCC decant oil under conditions that the ratios of toluene to FCC decant oil are 1∶1 and 2∶1 respectively. Explanations of these varieties have been supported from synthetic mechanism. Results of N2 adsorption reveal that BET surface area and pore volume of molecular sieves synthesized are respectively up to 1163.7m2·g－1 and 134cm3·g－1, and average pore diameter is 4.34 nm. TG-DTA profiles show that for the molecular sieves added by FCC decant oil there existed two clear exothermic phases, which are respectively resulted from the removals of surfactant and FCC decant oil from pores. In addition, DTA profile shows that exothermic peak for removal of the template of the sample added by FCC decant oil is inclined to shift to higher temperature, which explains that decomposition temperature of template molecules bonded with Si-O-Al group is increased with addition of SC- SEM photos show that crystal particles become smaller, more disperse and still look like the shape of bars.
Abstract: Compared with concentrated sulfur acid, ionic liquids synthesized by friethylamine hydrochloride and anhydrous AlCl3 were not excellent catalysts for the alkylation of isobutane with butene for the low selectivity of C8 in alkylate and low octane number of alkylate. Different ions of transition metals such as copper, iron and zinc were dissolved in ionic liquids, in order to improve the catalytic properties of ionic liquids. The experiments results indicated that, after dissolution of Cu2+ and Cu+, the catalytic properties of ionic liquids were greatly improved. When the mol quantity of Cu2+ dissolved was 5% of those of AlCl3 in ionic liquids, alkylation results from ionic liquids is comparable with those obtained with concentrated sulfur acid: the yield of alkylate reaching 178% of the volume of butene inputted, the selectivity of C8 reaching 75% and the octane number of alkylate reaching 92.2(RON). Moreover, ionic liquids could be reused.
Abstract: The catalytic decomposition of methane as an alternative process for the production of hydrogen from natural gas has been studied. The results show that a 15% Ni/SiO2 catalyst has good activity for decomposition of methane to hydrogen and carbon deposit. The capacity of methane decomposition is 4.5 g CH4/g catalyst at reaction temperature range of 550 ℃～600 ℃. It means that the Ni/SiO2 catalyst is still active during deposition of several thousands carbon atoms on a Ni0 atom. It can be reasonably explained by the mechanism of carbon filament formation. The catalytic activity can be fully regenerated by either air oxidation or steam gasification and the catalyst is stable after 10 successive decomposition/regeneration cycles. XRD analyses indicate that no apparent increase in the amount of carbon remaining on the catalyst after successive regenerations and no structural changes in the nickel particles.
Abstract: On the basis of total survey on the composition of municipal solid waste (MSW) in China, a formulation was determined for preparation of an artificial refuse derived fuel (aRDF) with the aim both to represent the typical specifications of MSW and to reproduce it easily. Hence, when the aRDF was used in some investigations, the results would be of significance and comparability. An aRDF was synthesized in this way in this paper. Then it was investigated by proximate/ultimate analysis and by TG-FTIR techniques. It is demonstrated that the aRDF well “duplicates” the typical composition and characterization of MSW in China. The results show that during pyrolysis under controlled condition the HCl evolves and aromatic compounds occur at different temperature ranges, which strongly suggests that the formation of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) be partly or even completely prevented when gases from different temperature zones in heat treatment apparatus are separately utilized. It is obvious that only Cl source and dioxin precursors (mainly aromatic compounds) appear simultaneously can PCDD/Fs be synthesized. Besides, aRDF pyrolysis can be described as the first order reaction and their activation energies calculated by Freeman-Carroll method fall into the range of 64.6 kJ/mol～136 kJ/mol.
Abstract: Plasma pyrolysis of polypropylene has been tested for the propose of converting waste plastic into gaseous fuel and useful chemicals.The plasma reactor has a D.C. arc nitrogen plasma generator with maximum input electric power of 55 kW and a reaction chamber of 50 mm inner diameter and 1 000 mm height. The results of a series of experiments show that under our optimum experimental conditions of power input 35.2 kW, feed rate 60 g/min, the concentration of H2 and C2H2 at the exit of the chamber can be as high as 18% and 5% respectively. The steam injection is introduced for improving the gaseous product quality. With water steam injection, the sum of H2, CO in the gas products can reach to 40% while the decrease of C2H2 concentration is slight. Meanwhile 96% of solid conversion and gas productivity of 2 160 mL/g are achieved. The results indicate that plasma assisted thermal decomposition of polypropylene may be a useful way for recovering energy and useful chemicals from waste plastic.
Abstract: Because LPG generally is a multi-component mixture of propane, propylene, butane and butylene etc, the mass ratio of each component for gas phase or liquid phase varies during the spontaneous vaporization. The mass or volume fraction of each component can be determined by the empirical formula or experimental data only for two component LPG mixture of propane and butane, the variation of other LPG composed with multi-component must be determined by chromatographic analysis. In this paper a model is established to simulate the LPG component mass ratio change during the spontaneous vaporization according to the theory of chemical phase equilibrium, principle of mass conservation and equation of state of real gas. Because the model is differential and algebra equations set, a difference equation set is presented. Based on the solution the curves are given for the mass fraction variation of each component of any multi-component LPG mixture in the spontaneous vaporization process and can be used to actual engineering. At the same time the analyses are made on the changes of saturation pressure, Warburg's number and combustion potential of LPG caused by the mass ratio change of each component during the spontaneous vaporization.
Abstract: Lead oxide was used as additive in coking coal to investigate homogeneous desulfurization behavior during coking process. Result shows that in plastic stage, lead oxide additive was sulfided and the release of sulfur in coal was suppressed. The amount of sulfur absorbed by lead oxide increased with the increase of added amount of lead oxide, however, this tendency almost disappeared when the additive amount reaches 0.6% of coal. In contract stage, lead sulfide decomposed under hydrogen-rich atmosphere and some elemental lead vaporized. Homogenous reaction between hydrogen sulfide and elemental lead vapor removes hydrogen sulfide efficiently as the hot coal gas left the carbonizer. Elemental analysis on the coke product shows that more than 50% of lead in coke could be removed. It's suggested that lead oxide additive could remove hydrogen sulfide homogeneously during coking process and is little deleterious on coke quality.
Abstract: The catalytic activities of CuO supported on three kinds of TiO2 were investigated with a microreactor-GC NO+CO reaction system. The results showed that the catalytic activity of CuO/TiO2 catalysts for NO+CO reaction decrease in the order: Cu6-Ti(T)> Cu6-Ti(S)>Cu6-Ti(nm), and the specific surface and the crystallite transformation didn't show negative influence on catalytic activities. TPR profiles indicated that Cu6-Ti had three or four TPR peaks, indicating the existence of several kinds of Cu species. By comparing the results of TPR and catalytic activities, it could be concluded that besides highly dispersed CuO, the CuO crystallite also plays an important role in NO+CO reaction. The results of H2-TPR of pre-treated Cu6-Ti showed that in the processing of reaction, Cu species exists in several valency. Using NO-TPD, we presumed that the catalytic activity has a close relationship with NO dissociation, but not with the amount of adsorbed NO.
Abstract: Terephthalic acid can be obtained in the presence of a catalyst CdCO3 by isomerization of potassium salt of coal acid (water-soluble acids, WSA) produced from coal oxidation. Effects of the amount of catalyst, initial pressure of CO2, reaction temperature and reaction time were investigated. It was confirmed that WSA can be converted to terephthalic acid in the presence of a catalyst. In case of isomerizing the potassium salt of coal acids alone, the optimum conditions of isomerization were found to be: temperature 430 ℃～450 ℃, initial pressure of CO2 4.0 MPa, catalyst CdCO3 4% and reaction time 2 h. Such optimum conditions were similar to those of the isomerization by a mixture of potassium coal acids (WSA) and potassium benzoic acid (BA). The yield of crude TPA by isomerization of potassium salt of coal acid was about 34%, which was equivalent to 75% of BPCA(theoretical yield), and was the effective composition of WSA. It has shown that the selectivity was good. The yield of crude TPA was about 68% if isomerization was carried out with a mixture of potassium salts of coal acid and benzoic acid at its optimum conditions. The yield of TPA was as high as 70% after being deducted from the theoretical yield of BA dismutation, and about two times of WSA isomerization alone.The purity of the refined TPA was ≥ 99%.
Abstract: Several deasphalted oil samples were obtained from vacuum residuum and FCC slurry oil deasphalted at continuous propane deasaphalting pilot equipment. Their catalytic cracking performances were investigated using a heavy oil micro-reaction apparatus at the condition of reaction temperature: 510 ℃, catalyst to oil ratio: 5.5 and space velocity: 15 h－1. The experimental results showed that the product distribution and selectivity of the deasphalted oil from vacuum residuum was better than that from gasoline while the deasphalted oil from FCC slurry oil was worse than gasoline. Meanwhile it was found that the catalytic cracking property of the deasphalted oil from vacuum residuum became worse with increasing its yield.
Abstract: Photocatalytic oxidation of phenol in water was studied in a shallow pond reactor using TiO2 immobilized onto activated carbon fiber as photocatalyst. A 300 W high pressure Hg-lamp(365 nm) was used as light source. The influences of light intensity, light filter as well as different light sources on the photocatalytic process were investigated, and the comparison of photolysis, adsorption and photocatalysis was also conducted. The results showed that there was almost no oxidation of phenol in photolysis process, the ratio of the photocatalytic degradation rate constant and adsorption rate constant of phenol over TiO2 /ACF was 3.35/1; increasing Hg-lamp light intensity can improve the rate of oxidation; there was an apparent improvement of the photocatalytic rate under the irradiation of the high pressure Hg-lamp without filter, while the photocatalytic rate could be still described in terms of pseudo first order kinetics; the oxidation rate of high pressure Hg-lamp with a filter was lower than that of a UV germicidal lamp.
Abstract: Nanchuan lean coal in which inorganic sulphur had been removed was used to investigate the effect of electrolysis conditions on organic sulphur removal from coal. The results indicated that the amount of sulfur removed in creases with time, but the removal rate becomes slower. When the concentration of HCl is lower than 3.2 M, the sulfur removal changes little; when it is 3.2 M～4.8 M, the sulfur removal is improved significantly. The higher concentration of coal slurry, the lower the sulfur removal rate. The desulfrization of organic sulphur is 18% for 0.05g/mL coal slurry in 10 h in acidic medium. Therefore, organic sulphur is more difficult to be removed than inorganic sulphur by electrolysis.
Supervisor：Chinese Academy of Sciences
Sponsors by：Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Chinese Chemical Society
