Abstract: Liquefaction experiment of Shendong coal was run with 0.1t/d PSU. The residues were analyzed by means of microscopy. It is found that coal macerals change significantly. Liptinite and vitrinite convert entirely and inertinite converts partly. Unconverted inertinite can be observed from residues. There are also some newly formed components such as mesophase and semicoke. Mineral matters accumulate and keep their petrological features in coal. The reflectance of unconverted inertinite in residue dissolved by THF ranges from 2.0% to 3.0%,which is a little higher than that of high reflectance inertinite in coal. The high reflectance inertinite in coal is the main source of unconverted inertinite in residue.
Abstract: 4 bituminous coals with different ranks were thermally and hydrothermally treated under different conditions, and the raw and treated coals were extracted with carbon disulfide/N2pyrrolidinone (CS2/NMP) mixed solvent (1∶1 by volume). It is found that the extraction yields of the thermal or hydrothermal treated coals at proper conditions increase in different extent. The increments of extraction yields for hydrothermal treated coals are higher than those of thermal treated coals. FTIR shows that the adsorption peaks at 3410 cm－1 attributed to OH group for the hydrothermal treated coals decrease, suggesting the dissociation of the coal aggregation structure due to the breakage of hydrogen bonds, resulting in the increase of extraction yields for the treated coals. For higher rank coal, the removal of minerals and the dissociation of π cation association after hydrothermal treatment of coal may be responsible for the increase of extraction yield. In addition, the mechanism of hydrothermal treatment of coal was discussed.
Abstract: Effects of hydrothermal treatment on swelling, extraction and liquefaction behavior of Shenhua coal were studied through analyses of element content, ash content, volatile content and IR spectrum of treated coal. The results indicate that hydrogenation of coal is distinctly carried out in the process of hydrothermal pretreatment and the hydrogen content of treated coal is more than that of raw coal. The contents of ash and volatile matters of treated coal are lower than those of raw coal. With the increase of treatment temperature the volatile content of the hydrothermal treated coal decreases and the ash content of treated coal increases. CO2 is main gas product and unvaries with the temperature changing, whereas CO and CH4 are formed when the temperature is above 250℃ and increase with the temperature during hydrothermal treatment. Hydrothermal treatment is not in favor of coal swelling and the swelling ratio of treated coal decreases with the increase of treatment temperature. The swelling ratio of extraction residue by CS2/NMP mixed solvent in NMP solvent is lower than that of the corresponding raw coal. The CS2/NMP mixed solvent extraction yields of coal treated at appropriate temperature are higher than that of raw coal, but the extraction yields of treated coal obtained by n-hexane, toluene and THF successive Soxhelt extraction are lower. Hydrothermal treatment at 250℃~300℃ can increase the conversion of treated coal in direct hydroliquefaction. The gas + oil yield of treated coal is lower than that of raw coal and the preasphaltene yield of treated coal is much higher. IR spectra of treated coals show that the forms of noncovalent bonds are changed by hydrothermal treatment, and the hydrolysis of ester and ether bonds and the pyrolysis of aromatic side chains also maybe occur at high treatment temperature.
Abstract: Using sodium carbonate as the catalyst, the carbon dioxide gasification kinetics of the four high rank anthracites （Vad=2.69%～4.35%）was investigated by isothermal thermogravimetric analysis under high pressure. The range of pressure from 0.101MPa to 3.0MPa was tested. The results show that when the pressure is higher than 2.0MPa, the increase of pressure has no effect on the reaction rate. The coal conversion as a function of reaction time was measured at the temperature from 750℃ to 950℃ and at 2.0MPa, which could be preferably correlated by the shrinkingcore model (SCM). According to the reaction rate constant determined by SCM, the reactivity order of the four anthracites is: Yongan Fengshai coal >Yongan Jiashai coal>Yongding coal >Shangjing coal. The activation energies, ranging from 157.21kJ/mol to 185.89kJ/mol, are obtained. The reaction rate constant, activation energy and preexponential factor under high pressure are larger than those of the gasification in CO2 at atmospheric pressure. At 850℃ the power of CO2 partial pressure for Yongan Jiashai coal is 0.34744, which agrees well with the literature.
Abstract: Light olefins, such as ethylene and propylene, are mostly used to produce plastics, fibers and other chemicals. In views of the supplement and demand contradiction of light olefins, and the utilizing problems of heavy oil in China, coke and heavy oil cogasifying process was proposed. The principle of the process was introduced in this paper. In a fixed bed reactor, coke and Shengli residue were mixed and tested. The results indicate that the contents of light olefins can be obtained in maximal value when the temperature is in 750℃~ 800℃ and the residence time is less than 0.5s. When the residue pyrolysis in the atmosphere of gasifying and pyrolysis zone with a temperature of 750℃, the contents of light olefins (C2H4+C3H6), alkanes (CH4+C2H6) and synthesis gas (H2+CO) are 20%, 28%, and 46%, respectively. The SEM images of produced coke were observed, and it shows that the produced coke can be consumed completely by blowing oxygen. The above results show that the coke and heavy oil cogasifying process to produce light olefins and synthesis gas together has no coking problem.
Abstract: The research on the influence of the ash from circulating fluidized bed (CFB) boiler on the desulfurization behavior of coal pyrolysis in the cogeneration process which combines coal pyrolysis with CFB combustion was carried out in a fixed bed reactor. The circulating ash with CaO from CFBC shows a significant action of sulfur retention in coal pyrolysis process. Compared with the coal pyrolysis with inert solid heat carrier, about 60%~70% sulfur in gas and tar is retained in the ash. It is revealed that the behavior of sulfur retention increases with the atomic ratio of Ca/S. Only 0.6% and 4.8% of the total sulfur enter in the gas phase and liquid phase respectively at Ca/S atomic ratio of 3.6. At the same time, CaO can reduce the yield of tar and the total sulfur content in the tar. It is predicted that CaO can play a positive role in the reduction of sulfur emission in the combination process of coal pyrolysis and CFB combustion.
Abstract: By using scanning electron microscope (SEM), energy dispersive Xray analysis (EDX) and Xray powder diffraction analysis (XRD), the microstructure, elemental and mineral components of interior parts of sintering deposit from the superheater surface of a fieldscale circulated fluidized bed(CFB) municipal solid waste(MSW) incinerator were studied. The results show that the deposit is rich in calcium and sulfur. The main mineral in the deposit is CaSO4. The structure of sintering deposit can be divided into root and growth part. Calcium and chlorine are higher in root than in growth part, while silicon and aluminium are much lower in the root. More alkali metals such as sodium and potassium are found in the inner layer of the root than in outer layers. Moreover, large amount of carbons present in the inner layer. The framework is more compact in root than in growth part. Vapor phase condensation and thermophoresis of submicrogranule are the leading mechanisms of the formation of inner layer of root. Transition layer and growth part are formed mainly by inertial impact of fly ashes and gassolid chemical reactions as well as high temperature sintering. The coeffect of fusion phase and chemical reactions is the primary growth motivity of the sintering deposit.
Abstract: The fly ashes melting was teased in a selfdeveloped swirling melting furnace system. The influences of calcium oxide, silicon dioxide, magnesia additives on the melting characteristics were studied during fly ashes melting process. When the amount of calcium oxide added is 5 percent, there is a effective control action on the melting point of fly ash. The amounts of crystals are lessened in the slag, and the stability of slag is enhanced. The meltingaid effect of calcium oxide can be appropriately adjusted based on the composition of fly ash. Adding silicon dioxide in the fly ash can redound to reducing the melting point of fly ash and promote the liquidity of sample. With the increasing of silicon dioxide added, the glassy amorphous materials in the melted sample are increased. The higher the adding amount of silicon dioxide, the better is the stability of melted slag. The netlike structures of silicates in the fly ash will be destroyed by adding the magnesia. The glutinosity of melted sample reduces with increasing the adding amount of magnesia. The glassy materials in the slag can be increased and the crystal phases transform can take place with adulterating magnesia. The crystals in the sample are enveloped by the amorphous slag. The sample would achieve the better melting effect when the adding amount is more than 5 percent in fly ash sample.
Abstract: The characteristics of mercury adsorption by Cabased sorbents were experimentally measured in a benchscale fixedbed mercury adsorption facility with a mercury permeation tube embedded in an isothermal water bath and simulated flue gas compositions. The adsorption performance of calciumbased sorbents including lime, hydrated lime and a mixture of fly ash and hydrated lime is better in the presence of SO2 . The presence of SO2 in the simulated flue gas can enhance the Hg0 capture efficiency from about 15% to 20%, and the adsorption capacity is increased more than 50% at 30min of exposure of sorbents to flue gas. It is found that there is a higher capture effect at higher temperature. It is supposed that heterogeneous reactions of Cabased sorbents and SO2 can increase Hg0 capture , the sites for Hg0 capture are influenced positively by the presence of SO2. The behavior can be correlated with the chemisorption mechanism. The potential of Cabased sorbents used to control Hg and SO2 emissions costeffectively is great.
Abstract: La modified Ni/γAl2O3 catalysts prepared by codeposition and impregnation methods for partial oxidation of methane (POM) were studied. Catalysts prepared by codeposition method show high activity and stability because of high dispersion. The CH4 conversion was close to 100% and H2 selectivity reached 99.8% over La modified Ni/γAl2O3 catalysts with co deposition method under the condition of space velocity=80000h-1 and CH4/O2/N2=14/7/79 (in vol) at 800℃. By BET，TPR and XRD， it was found that the addition of La enhanced the surface area of the catalysts, lowed reduction temperature of active component and improved the stability of the supports. Meanwhile, the catalysts prepared with codeposition inhibited the formation of granular NiAl2O4, thus it showed high activity for POM.
Abstract: Process for hydrogen production from methane decomposition in a fluidized bed and catalyst regeneration by air were studied. Two nickel catalysts, 25Ni/CuAl2O3 and 75Ni/CuAl2O3,were used in the process.Methane decomposition and catalyst reactivation reactions were conducted at the same temperature,500℃and 650℃ respectively. Gas volume was controlled in 370mL/min(STP). The results reveal that the catalytic stability of low nickel content catalyst excels that of high nickel content catalyst and its catalytic activity reduces with temperature increasing and operation cycles. But after 5 th operation cycle, methane conversion trends to be a constant value. At same time it is found that switch time affects the methane conversion, i.e. there is an optimal switch time of 5 min. The samples formed after methane decomposition are characterized by XRD and TEM. Finally the results were discussed.
Abstract: A series of supported Ni2P catalysts on HZSM-5 were prepared via the method of temperatureprogrammed reduction (TPR). The structure characteristics of samples have been characterized by means of N2BET, XRD, and SEM techniques. Thiophene hydrodesulfurization (HDS) was chosen as a model reaction to investigate the influences of Ni loading and initial Ni/P mol ratio. The results show that Ni2P phase is formed on the support of HZSM-5. Ni2P/HZSM-5 catalysts have high activity and excellent stability in thiophene HDS reaction. The preparation factors have great effects on the activity and stability of thiophene HDS reaction. With the increase of Ni2P loading and the initial P/Ni mol ratio, the activity and stability of the Ni2P/HZSM-5 catalyst increase firstly and then decrease. The influence of reaction conditions such as liquid space velocity, reaction temperature, reaction pressure, hydrogen to oil ratio on thiophene HDS performance were also studied. An optimum Ni2P/HZSM-5 catalyst was obtained from the precursor with initial phosphorus (Ni/P=1/3 mol ratio) at Ni loading of around 5%. It has substantially high thiophene HDS conversion (~100%) and stability (more than 100h) at the condition of 370℃, 2.0MPa, a VHSV of 3h-1 and a hydrogen to oil ratio (v/v) of 200.
Abstract: βMo2N0.78 as a hydrodesulfurization(HDS) catalyst shows high activity in HDS reaction of sulfurous model compounds, which was reported in previous works. Therefore, the changes of the catalyst composition and structure after HDS reaction and the influences of aftertreatment on HDS catalytic activity were studied in this paper. The XRD results indicate that the bulk structure of βMo2N0.78catalyst is kept unchanged, though the catalyst surface is sulfided and the oxynitride is consumed at HDS condition. And the hydrogen reduction treatment of βMo2N0.78 catalyst before and after HDS reaction can not improve the catalytic activity. Presulfided βMo2N0.78 has a similar HDS activity with that of passivated sample at its stable stage. Second passivation of the catalyst after HDS reaction can recovery the catalytic activity.
Abstract: A deasphalted oil (DAO) was hydroisomerized in a flow type fixedbed reactor over a commercial catalyst at 9.0MPa, 380℃ and LHSV 0.8h-1. The products were distilled and separated by true boiling point distillation method. Carbon number distribution and hydrocarbon type of various cuts were determined by normal or high temperature GC-MS. It was found that the viscosity and the yield increased with the increase of boiling point for the light cuts, while the contents of monocycloalkanes decreased sharply. As for the heavy cuts, their carbon number distributions became wide with the increase of boiling points. Variation of monocycloalkanes in heavy cuts had significant impact on the viscosity index (VI) and pour point of the base oil. VIs and low temperature properties of +380℃ heavy cuts could meet the specifications of API II higher grade lube base oil.
Abstract: In the petroleum refining industry， the process for alkylation of isobutane with butene is an important approach to produce a high octane gasoline blend stock. In published literature, however, it is difficult to find out all the thermodynamic data for the alkylation. In this paper, thermodynamic calculation and analysis on the alkylation has been carried out in detail. The thermodynamic data on the alkylation including enthalpy ΔHt, Gibbs energy ΔGt and equilibrium constant of reaction at different temperature have been calculated. The affection of temperature, pressure and inert material on the thermodynamic equilibrium of the reaction has been discussed.
Abstract: αMoC1－xpromoted by K2CO3, was studied as catalysts for carbon monoxide hydrogenation reactions under conditions of 573, 8.0MPa, GHSV=2000h-1,n(H2)/n(CO)=1.0. Unpromoted αMoC１－xproduced mainly CO2 and light hydrocarbons, addition of K2CO3 as a promoter, however, resulted in remarkable selectivity shift from hydrocarbons to alcohols. Moreover, the promoter of potassium enhanced the ability of chain propagation of αMoC１－xwith higher selectivity of C2+OH. The investigations of the effects of the loadings of K2CO3 in αMoC１－xrevealed that the maximum yield of alcohols was obtained at K/Mo (mol ratio) =0.1. However, there was no significant difference between αMoC１－xand K/αMoC１－xcatalysts in the distributions of alcohols and hydrocarbons; they both have similar linear A-S-F plots. Though, the promotion effects of potassium on the formation of higher alcohols could be attributed to the formation of "K-Mo-C" phase in K/αMoC１－xcatalysts, which was considered to be the active sites for the alcohols synthesis.
Abstract: A series of V-Cr/SBA-15 catalysts with different V and Cr contents were prepared by the incipient wetness impregnation method. The structure of the catalysts was characterized by XRD, BET and TPR technique. The catalytic activity of the catalysts for the propane oxidative dehydrogenation with CO2 to propene was evaluated using a fixed bed reactor. The results show that vanadium and chromium oxide were well dispersed on the surface of SBA-15 and the structure of the SBA-15 was not destroyed during the impregnation. The catalytic activity of the catalysts depended on the loading of vanadium and chromium. The V and Cr bimetallic catalysts had better performance than those of the single metallic catalysts. The TPR results showed that there was the strong interaction between the vanadium oxide and the chromium oxide in the V-Cr/SBA-15 catalysts. This interaction remarkably changed the redox properties of the catalysts.
Abstract: Diethyl carbonate(DEC) synthesis reaction by oxidative carbonylation of ethanol has been studied using vapor phase flow reaction system in the presence of Cubased catalyst prepared by the conventional impregnation method. The effect of various preparation parameters on the catalytic activities were intensively evaluated in terms of ethanol conversion and DEC selectivity. The results show that activated carbon and CuCl2 are better support and precursor respectively and their catalytic activity was improved when Pd(PPh3)2Cl2 was applied as the promoter. The catalyst had better activity when Cu and Pd loading are 9.0% and 0.5% respectively. The conversion of ethanol was over 30% and DEC selectivity was 95% under optimum preparation condition and the catalysts retained better catalytic activity in 100h continues reaction.
Abstract: The deactivation of catalyst in benzene alkylation with propene over H β zeolites under different conditions was investigated. The amounts and properties of coke deposited on the spent catalysts under various reaction conditions were determined. With the change of reaction temperature from 270℃to 320℃at 5.7MPa, the reacting mixture may either lie in a phase of liquid (L) or supercritical fluid (SCF), or endure a phase variance from SCF to L, which results in different catalyst lifetimes, coke amounts and coke properties. SCF with the liquidlike densities and enhanced transport properties is able to extract coke precursors in situ, thereby to prolong the catalyst life. Under the condition of 300℃and 5.7MPa, the reacting mixture was in a state of SCF or L near its critical point during the entire reaction process, and therefore the catalyst exhibits the longest life time and slowest coke deposition rate. The C/H mol ratio of the spent catalyst is related to the reaction temperature, while the burningup temperature of coke deposited in the spent catalyst increases with the prolonging of the catalyst lifetime.
Abstract: The hetero-atomic zeolite TiY was synthesized hydrothermally. The crystal structure, thermal stability, surface acidity and catalytic properties of TiY were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), pyridineIR and micro-reaction activity test (MAT). The results showed that titanium had not influence on the crystal form of Y, but the time of crystallization prolonged and the unit cell of zeolite TiY increased. TiY has higher thermal and hydrothermal stability than USY. Both the amount of Lewis acid sites and the strength of Bronsted acid sites of TiY increased. Comparing with USY, the activity of TiY for cracking reaction enhanced whereas the coke on the catalyst reduced distinctly.
Abstract: A wellordered mesoporous material P-SBA-15 functionalized with phosphoric acid group was prepared by postsynthetic method. Characterizations by power X-ray diffraction (XRD), infrared spectroscopy (IR), as well as nitrogen sorption（BET）were carried out to understand the physical properties of P-SBA-15. The results show that the structure of P-SBA-15 remains that of silica mesoporous material SBA-15, and the specific surface area and the mesopore size of P-SBA-15 are 605.45m2/g and 5.576nm ( np/n si =5% for example), respectively. Synthesis of iso-propyl undecylenate over the P-SBA-15 catalysts was studied in order to investigate the catalytic properties of mesoporous molecular sieve P-SBA-15. Compared with liquid acid and microporous zeolite catalysts, the P-SBA-15 is the best one among the solid acids for esterification reaction. Reuse of P-SBA-15 indicated this catalyst has high stability under esterification conditions.
Abstract: Through solidstate ionic exchange technique, a series of Cu(I), Ag(I) cation modified zeolite β sorbents were prepared on the base of preparation of Na β zeolite with different Si/Al ratio. The samples were characterized by XRD, FTIR and N2 adsorptiondesorption technique. Although the crystallicity and BET surface area of the sorbents are affected by exchanged metal cation in the framework, the XRD results show that asmade samples were kept framework structure integrity. The BET surface areas of asmade Na β samples decrease as the Si/Al ratio increase, and BET surface areas of Cu(I β , Ag(I)β sorbents decrease comparing with the same Si/Al ratio Na βzeolite. FTIR spectra of the samples show that the peak of framework vibration moves to low wave number as Cu(I), Ag(I) were inserted. Then the thiophene adsorption properties of Cu(I) β , Ag(I) β , Na β were evaluated at ambient conditions. Static state experimental results show that Cu(I)β exhibits stronger adsorption for thiophene. As the Si/Al mol ratio of zeolite β is 25 about 95% thiophene was adsorbed by Cu(I) β and 87% by Ag(I) β . Through dynamic adsorption experiments, the breakthrough capacities of the Cu(I)β and Ag(I) β sorbents are 0.144mmol/g and 0.132mmol/g, respectively.
Abstract: Oxidative deep desulfurization was considered as one of the most promising nonHDS process. In the present work, thiophene selective oxidation was studied over TS-1 using hydrogen peroxide as oxidant in model gasoline. The oxidation of thiophene was investigated in the presence of hydrocarbons. Effect of these typical hydrocarbons on selective oxidation of thiophene can be obtained: n-octane and cyclohexane have no effect on removal of thiophene from model gasoline. Benzene also has no effect on final thiophene removal from model gasoline, but has a little effect on initial removal rate of thiophene. n-Octene will seriously influence the removal of thiophene from model gasoline. Therefore further study is required to improve the selectivity of TS-1 in model gasoline containing alkene. Loading silver or copper on TS-1 will increase its selectivity in thiophene oxidative removal from model gasoline containing alkene. The best amount of silver or copper on TS-1 is 0.05% or 0.07%,respectively.
Abstract: The previous research proves that removal activity for H2S by solid base is high. The removal activity for organic sulfur compounds by solid base was studied. The results show that the solid base has a certain extent removal activity for these compounds. Mercaptans are removed easily. The stronger acidity and polarity of mercaptan, the more easily it is removed. Thiophenes are most difficult to be removed due to their weak polarity and large space obstruction. The order of removal efficiency of these compounds is approximately as follows: mercaptan＞carbonyl sulfide＞sulfide＞disulfide＞thiophenes.
Abstract: The methanol conversion over HY zeolite was studied at 1atm, 280℃~360℃. The effects of temperature, GHSV, and reaction time on the performance of reaction of methanol were discussed. The results showed that HY catalyst gave isoalkanes with high selectivity. Higher temperature(280℃~340℃) and lower GHSV decreased the selectivity to dimethyl ether and increased that to C2，C3，i-C4 ，i-C5. With the further increase of temperature, the selectivity of C2，C3 increased while that to i-C4 ，i-C5 decreased. The selectivity to isoalkanes decreased quickly with the reaction time.
Supervisor：Chinese Academy of Sciences
Sponsors by：Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Chinese Chemical Society
