Abstract: A series of formed active cokes for SO2 removal in flue gas was prepared from fly char and its parent coal with two steps: the carbonization of raw briquette in N2 flow at different temperatures between 400 ℃ and 700 ℃ and the activation of the carbonized product at 900 ℃ in a stream of N2+H2O. The effects of carbonization temperature on pore properties (BET surface area, micropore area and volume, pore size distribution) and other physical and chemical properties (yield, mechanical strength, sulfur capacity and iodine value) were investigated. The results show that the carbonization temperature plays an important role in preparation process. Among those parameters, the mechanical strength is close related to carbonization temperature, which increases with increasing carbonization temperature, whereas there is little effect of temperature on gross yield. In addition, other parameters (BET area, sulfur capacity, etc.) decrease with increasing carbonization temperature with different degree. In the meantime, pore size distribution of active coke produced at lower carbonization temperature is relatively reasonable. The optimal carbonization temperature range is 600 ℃～700 ℃, under which the prepared active coke exhibits the properties comparable to those commercial ones and could meet the requirements for desulphurization.
Abstract: γ-Alumina supportedβ-Mo2N0.78 catalysts were synthesized via temperature-program-med nitriding reaction of MoO3 using N2-H2 mixture gas. The precursor of active phases was prepared by impregnation of γ-Alumina with aqueous solution of ammonium heptamolybdate((NH4)6Mo7O24·4H2O), followed by drying and calcination in air. The hydrodesulfurization(HDS) reaction of thiophene over these catalysts was performed in a fixed-bed reactor at atmosphere pressure. The influence of HDS reaction temperature, pre-reduction of H2 and the addition of Co and Ni on the activity of β-Mo2N0.78/γ-Al2O3 were studied. The results show that the HDS activity increases with increasing reaction temperature from 320 ℃ to 400 ℃. Pre-reduction can deactivate the activity of catalyst. The addition of Co and Ni can improve the catalytic activity ofβ-Mo2N0.78/γ-Al2O3 catalyst.
Abstract: Based on the model test, the regularity of Dongshan coal underground gasification was obtained. Air-blown gasification and oxygen-steam-blown gasification were conducted. The studies were focused on the influence of air blast on the gas composition, the influence of steam/oxygen ratio on the gas composition, gasification stability, and gasification rate. In the same time the mass balance of oxygen-steam gasification process was conducted. The results show that the underground gasification of Dongshan coal through blowing air can produce fuel gas with lower heat value, the composition of gas is influenced by the amount of air blast. Underground gasification of Dongshan coal with oxygen-steam as gasifying agent could produce synthetic gas for di-methyl ether synthesis, but moving the agent supply position is needed to keep the process going on according to the movement of fire face and change of gas composition. Mass balance can be used for prediction of gas composition. The ratio of steam to oxygen will affect gas quality and optimum steam/oxygen ratio is 1.8～2.2 for the model test. The gasification face development rate of the test coal changes gently in underground gasification process, which indicates that the underground gasification of lean coal has high stability.
Abstract: Nantong bituminous coal was extracted with carbon disulfide-N-methyl-2-pyrrolid-inone (CS2-NMP) mixed solvent, acetone and pyridine, and all the residue was gained. Sorption behaviors of nitrogen and granularity of the coal and extract residue, were tested using Accelerated Surface Area and Porosimetry (ASAP) 2010 apparatus and scanning electron microscope. The BET specific area of the samples, the distribution regulation of BJH pore volume and BJH pore area according to the pore radius, and the influence of the extraction behavior on the granularity were studied. The results showed that through “dissolving” the small molecule substance the solvent extraction will improve the adsorption ability, the specific area of the pore and the character of pore space, and decrease the granularity, but not break the basic structure unit of coal. The solvent extraction of coal belongs to physical behavior essentially. The specific area varies from 187 m2/g to 318 m2/g, and the pore volume varies from 0.175 m3/g to 0.535 m3/g. The most probable pore radius for the original coal and its solvent extract residua is all about 0.72 nm. According to the most probable pore radius, the diameter of basic structure unit of the coal was calculated for about 3.5 nm. The result approved the assumption on the colloidal group structure model of coal molecule.
Abstract: Thermogravimetric behavior and products distribution of the co-coking of coal from Shougang coking plant with waste plastics from municipal solid waste of Beijing were studied using thermal balance and 10 g fixed-bed reactor. The results showed that the temperature range of weight loss of Shougang blend coal was from 300 ℃ to 750 ℃, but for waste plastics it was from 300 ℃ to 550 ℃. Co-coking of blend coal and waste plastics made tar yield increase and water yield decrease in the overlapped decomposition temperature region for the synergism between them. Moreover, the new idea and formulas of synergism extent were proposed as and . Based on the formation, the conclusion was obtained that the maximum synergism occurred when the ratio of waste plastic added was 1%.
Abstract: Using 200 kg coking-oven, the quality of the coke from the co-coking of coal with PS (polystirene) and WMP (waste mixed plastics) was studied to provide fundamental data for further industrial application. The results showed that the yield of metallurgical coke decreased obviously and at the same time, the quality of coke also decreased with the increasing of percentages of waste plastics added. Though the yield of metallurgical coke was much lower for WMP addition, co-coking of coal with WMP got better coke quality indexes of M40, M10 and CSR than co-coking of coal with the same ratio of PS. It was proved that co-coking of coking coal only with waste plastics simply couldn't be applied in industry as a solution of “white pollution”.
Abstract: The effect of blending various coals on the properties of coal water slurry (CWS) was studied. Three Chinese coals with lower slurryability and static stability or poor rheological behaviour and two others with good properties of CWS as well as a lignite with better rheological behaviour but poor slurryability were selected in this study. The results showed that the addition of coals with higher slurryability and static stability to those with poor quality of CWS can improve the slurryability, stability and rheological behaviours, and forthemore, the viscosity of CWS decreases markedly. For the different blending propations, the coal content in the slurry can be increased by 2%～3% and the static stability enhances from 1 d to 10 d for the formation of soft sediment. The addition of lignite with poor slurryability can also remarkably improve the stability and rheological behaviour of CWS. It seems to be that blending the coal with greater difference in the surface properties including pore structure, contact angle and MHC can improve the properties of CWS.
Abstract: The catalysis effect of carbide lime, which is a residue in the ethyne production and has a good sulfur-retention property, on pulverized coal combustion has been studied on a thermogravimetric analyzer. It is found that when the carbide lime is added into Jincheng anthracite with a weight ratio of 0.5% in a slurrying process, the ignition temperature of coal is reduced from 582 ℃ to 576 ℃ and the burnout efficiency of fixed carbon is promoted from 91.11% to 92.75%. When the adding proportion of carbide lime is enhanced to 1.0%, the ignition temperature is further decreased to 570 ℃ and the burnout efficiency is increased to 94.39%. However, blending carbide lime with the coal in a dry process gives little catalysis on combustion parameters. In the three experimental coals, carbide lime with a weight ratio of 0.5% has the best catalysis effect on ignition temperature of Jincheng anthracite (maximum reduction by 6 ℃) and on burnout efficiency of Lu'an semi-anthracite (maximum promotion by 5.43%), but it has little effect on the properties of Changguang bituminous coal with a high ash content of 40%.
Abstract: Quinoline catalytic cracking was studied on a fixed-bed microactivity test unit by using toluene, cetane, and tetralin as solvent. Reaction temperature, catalyst to oil ratio, weight hourly space velocity and feedstock nitrogen content affected the nitrogen content of spent catalyst and the nitrogen distribution in products. Catalyst acidity and hydrogen donating abilities of hydrocarbon solvent had marked effect on quinoline cracking. The coke on spent catalyst can be divided into three types, hydrocarbons, adsorbed nitrogen compounds, and condensed nitrogen. The possible reaction pathway of quinoline catalytic cracking is put forward. Quinoline could adsorb on catalyst surface by physical or chemical adsorption, or be deposited as coke via dehydrogenation. Quinoline could be converted into alkylquinoline. Quinoline could be hydrogenated into tetrahydroquinoline, which would be cracked into pyridine, aniline and ammonia.
Abstract: An experimental test was carried out to study the NOx reduction efficiency using ammonia injection SNCR (selective non-catalytic reduction) technology. Chemical kinetics modeling was investigated simultaneously. Results show that higher temperature causes oxidization of ammonia while lower temperature decreases reduction efficiency. The optimal temperature range is about 850 ℃ to 1 100 ℃ in our test, highest NOx reduction about 82% is achieved. With the increasing of ammonia dosage chemical reaction slows especially at lower temperature. The time reaching chemical equilibrium dramatically increases when temperature is lower than 700 ℃. Therefore, the acceptable temperature with short time in the coal-fired boiler should be higher than 700 ℃. The risk of ammonia leakage is neglectable when temperature is higher than 950 ℃. It plays a key role in the whole reactions that competition between two chain-branching reactions of NH2. Lower temperature is beneficial for the first chain-branching reactions which are the DeNOx process, while the higher temperature is beneficial for the second chain-branching reactions which are the ammonia oxidization process. The homogeneous numerical simulation results show good agreement with the experimental data especially at higher temperature.
Abstract: The activation mechanism of petroleum coke with KOH at higher temperature was studied. Methods including SEM, XRD, pore structure analysis by adsorbing N2 and GC were employed during the study. The result showed that the petroleum coke was well activated at 750℃～800℃. The XRD result revealed that the product was mainly made of amorphous carbon partly graphited. The pore structure analysis showed that the products had a surface area of 2900m2/g－1 and the content of micropore over 90%. The CH4 volumetric adsorption was 115∶1. GC results showed that the gases produced during the activation were made up of H2, CO2, CO, CH4. According to the gas composition, the reactions probably taking place during the activation were put forward.
Abstract: PCDD/Fs in fly ash from bag filters of different type of incinerator were detected by high resolution gas chromatography coupled with low resolution mass spectrometry(HRGC/LRMS). The results show the types of fuel and chlorine content in fly ash have remarkable influence on concentration of PCDD/Fs in fly ash. There is a direct proportional correlation between PCDD/Fs and chlorine content in fly ash. Although large amounts of heavy metals are found in fly ash, they do not have a noticeable relationship with dioxins in fly ash. The congener profiles of dioxins in fly ash are different between the fluidized bed incinerator and stoke grate incinerator. The major homologue of PCDD/Fs is 1,2,3,4,6,7,8-HpCDD，1,2,3,4,6,7,8-HpCDF and OCDD. The TEQ of PCDFs is higher than that of PCDDs. The primary study shows that the concentration of dioxins in fly ash and toxic equivalent quantity(TEQ) from the stoke grate incinerator are higher than those of fly ash from the fluidized bed incineration.
Abstract: TCLP experiment has been performed to study the relationships between liquid-to-solid ratio (L/S), initial pH value, extraction time and leaching characteristics of heavy metals (Pb, Cr, Cd, Ni, Cu, Zn) in fly ash from a coal and MSW(municipal solid waste) co-firing fluidized bed incinerator. The results suggest that the leaching weight of heavy metals increases with the rise of L/S, in which the leaching weight of Cr and Cu increases in most cases, but the leaching weight of Cd, Ni and Zn changes slightly when L/S exceeds 20. The leaching behavior of Pb is special, for its leaching curve has obviously a wave crest and a wave hollow. The leaching concentration of heavy metals at initial pH≤2.90 is larger greatly than that at initial pH≥4.03. With the increase of extraction time, the leaching concentration of Pb, Cr and Zn decreases, but that of Cd and Ni increases in general. The leaching concentration of Cu increases first, and then reduces. Among the three factors which are L/S, initial pH and extraction time, the effect of initial pH on heavy metals leaching is the largest. Heavy metals leaching from fly ash is more easily in acidic liquor than in basic liquor.
Abstract: Ultrafine Mo-Co-K catalysts were characterized by BET,XPS and TPD techniques in this paper. By comparing the characterization results with the catalytic performance for higher alcohol synthesis of the catalysts,the role of Co in ultrafine Mo-Co-K catalysts for the synthesis of higher alcohols was studied. The addition of Co into ultrafine Mo-K catalyst enhanced the activity and selectivity to higher alcohols of the catalyst, on the other hand,the addition of Co enhanced the specific surface area of the catalyst and promoted the formation of smaller pores. The catalytic performance of the catalysts correlated with their texture very well, and the above two tendency showed an excellent corresponding relationship. The electron binding energy of lower valence Mo species which might act as the active sites of higher alcohol synthesis was affected by Co less obviously. The addition of Co into ultrafine Mo-K catalyst diminished the adsorption strength of H2 and CO on the strong adsorption sites of the catalyst,which might improve the reaction of higher alcohol synthesis. The results showed that Co acted only as a structure promoter in the catalysts and affected the catalytic performance by changing the texture and strong adsorption centers for H2 and CO of the catalysts.
Abstract: ZrO2-SiO2 (ZrSiO) supported Ni-Cu-La2O3 catalyst for CH4 partial oxidation to produce hydrogen was prepared by isovolumetric impregnation. By using TPR, XPS, IR, TPD and microreactor techniques, the effect of La2O3 on adsorption and reaction of CH4 with H2O and O2 on the catalyst were studied. The results showed that the addition of La2O3 has obvious influence on the electronic charge distribution of metal active sites Ni, Cu on Ni-Cu/ZrSiO catalyst, and increases the chemisorption intensity of CH4 and H2O. The main reaction products of CH4 partial oxidation with H2O and O2 on Ni-Cu-La2O3/ZrSiO catalyst are H2 and CO2. Under condition of 450 ℃, nCH4∶nO2∶nH2O＝1∶0-5∶2-5 and SV(CH4)=1 200 h－1, conversion of CH4 (xCH4) is greater than 90%, selectivity of H2 (SH2) is more than 99%, and SCO is merely 1.% on Ni-Cu-La2O3/MgSiO catalyst. Moreover, the catalysis mechanism of promoter La2O3 was discussed.
Abstract: Using cationic surfactant of cetyltrimethylammonium bromide as templating agent, silicasol as silica source and aluminum sulfate as aluminum source, and auxiliary organic amines and hexane as additives respectively, the mesoporous molecular sieves MCM-41 were synthesized by hydrothermal method in basic media. The synthesized samples were characterized by XRD, N2 adsorption-desorption, and SEM. The experimental results show that, with the exception of triethylamine, after adding tri-n-propylamine, diisobutylamine tri-n-butylamine, tri-n-octylamine to reaction system respectively, the mesoporous MCM-41 samples attained have larger pore diameter compared with MCM-41 prepared without additives and have higher BET surface area and larger pore volume. Using hexane as auxiliary additive also can enlarge the MCM-41 pore diameter, but the sample have lower BET surface area (887.3 m2/g) and pore volume (0.81 cm3/g).
Abstract: The phthalic anhydride-urea route was employed to in-situ synthesize CoPc in the supercages of zeolite Y. The prepared CoPcY was characterized by various physicochemical methods and catalytic reaction. The results show that the route is a simple and effective method for in-situ synthesis of CoPc complexes in the supercages of zeolite Y. In the route, the synthesis parameters (synthesis temperature, catalyst and salt used in ion exchange) have great influence on the properties of the prepared CoPcY, in which the optimum synthesis temperature for CoPc is 180℃ and a suitable salt for ion exchange is cobalt chloride. The CoPc in-situ synthesized in supercages of Zeolite Y by this route shows high catalytic activity for cyclohexane oxidation under mild reaction conditions, and TON is over 5 000 as H2O2 is used as oxidant, reaction temperature is 60 ℃ and reaction time is 10 h.
Abstract: In this parper, a series of P-Mo based multiple component catalysts, P1.33-dMo12VaCubSbcAsdK1.5Ox／SiC（0.0≤a，b，c，d≤0.50）, were prepared by co-precipitation method. The structure and properties of the catalysts were investigated by means of XRD，FTIR, DSC and ESR. The results of XRD and FTIR show that the catalyst is P-Mo heteropoly compound that possess Keggin heteropolyanion structure. The study of DSC and ESR indicate that the catalyst have good stability. The effect of content of catalyst on catalytic activity for isobutane oxidation was evaluated. It was found that the addition of V, Cu, Sb, As with appropriate amount can improve the selectivity of methacrylic acid and yield of MAA+MAL to some extent. For catalyst P1.13Mo12V0.25Cu0.25Sb0.25As0.2K1.5Ox／SiC, the conversion of isobutane is 10.7％, the yield of MAA+MAL is about 6.8％ under the reaction condition: 360 ℃, atmospheric pressure, feed composition: isobutane∶air=1∶2(mol), and GHSV=3 600 h－1.
Abstract: In this paper, CeO2 aerogel and Ce1-xMnxO2 aerogel (x=0.05, 0.10, 0.15,0.20) were prepared by sol-gel method and super critical fluid drying technology- Mn/CeO2 was prepared by impregnating CeO2 aerogel with the solution of manganese nitrate. The prepared aerogels were characterized by TEM, BET, CO oxidation reaction and H2-TPR. The experimental results of TEM and BET showed that with the increase of manganese content, the particle size of ceria aerogel decreased and the surface area increased. Reaction of CO oxidation showed that the oxidation activity was improved by adding Mn to the ceria aerogel. The best result was gained when the Mn content is 15 mol%. Ce1-xMnxO2 aerogel (x=0.05, 0.10, 0.15,0.20) and Mn/CeO2 show different carbon monoxide oxidation activities. Catalyst prepared by impregnation method (Mn/CeO2) shows lower catalyst activity than CeO2 and Ce1-xMnxO2(x=0.05, 0.10, 0.15,0.20) areogel. TPR experiment shows Mn species on ceria are also reduced through three steps as MnO2.
Abstract: Development of the catalysts with high activity and stability for the methane steam reforming has significant importance for the practical application of the process of nature gas steam reforming in fuel cell. The catalytic performances of Ni/ZrO2 in the steam reforming of methane were investigated in this paper. The influences of the reduction temperatures of the catalyst, calcination temperatures of ZrO2 support, reaction temperature, ratios of feed gas and space velocities on the catalytic performance of Ni/ZrO2 were examined. The structure of the catalyst was characterized by XRD, TEM, XPS and TPR. The experimental results indicate that Ni/ZrO2 catalyst had relatively high activity and stability in the steam reforming of methane. No significant influence was observed on the catalytic activity when the calcination temperatures of the support changed from 550 ℃ to 850 ℃. The catalyst reduced at 550 ℃ showed somewhat higher activity, but a little influence on CO selectivity in the range of reduction temperature from 450 ℃ to 750 ℃. The conversion of methane increased with an increase of H2O/CH4 ratio, while CO selectivity decreased. The conversion of methane and CO selectivity decreased with an increase of space velocity. The result of 85% methane conversion and 70% CO selectivity was obtained over 10% Ni/ZrO2 catalyst under the conditions of 650 ℃, 1.984×104 h－1 and H2O∶CH4∶N2=2∶1∶2.67.
Abstract: At room temperature and ambient atmosphere, the reactions of acenaphthene, anthracene, naphthalene, fluorine, 1-methylnaphthalene, 2,6-dimethylnaphthalene, phenol and α-naphthol with nitrobenzene over the high active catalyst of AlCl3 were investigated. The results show anthracene, naphthalene and phenol do not react with PhNO2, while acenaphthene, fluorine, 1-methylnaphthalene, 2,6-dimethylnaphthalene and α-naphthol could react with PhNO2 to give corresponding anilinoaromatics. The reaction activity sequence of acenaphthene > 1-MN > 2,6-DMN>fluorine, which deduced by GC/MS analysis, is reasonably explained according to ultra-conjugate effect. The reaction of acenaphthene and PhNO2 is carried out under different conditions, in which the molar ratio of AlCl3 to acenaphthene is 1.2 and 2.4, respectively. Pure biacenaphthenyls and 5-anilinoacenaphthene are prepared by recrystalling the reaction product. The structures of these compounds are identified by GC, GC/MS，FTIR and UV analyses.
Abstract: Solution of ferric nitrate was obtained from industrial iron based on the following equation Fe+4HNO3→Fe(NO3)3+NO+H2O and 2NO+O2→2NO2. Fe-Cu-K-Si catalysts were prepared in a continuous precipitation reactor. Performance of No.16 catalyst prepared from Q-235 carbon steel is the best among three industrial irons: iron sheet, iron powder and Q-235. In the range of 265 ℃～276 ℃, 1.5 MPa～1.6 MPa, H2/CO 0.68～1.0 and WHSV 3.6 L/g·h～4.2L/g·h, the mean values of xH2+CO and C5+ are 68.7% and 96.7 g·m－3 in the evaluation test of 432 h. Performance of No.16 catalyst being lower than that of No.9 catalyst is due to effect of poison of P,S contained in industrial iron Q-235.
Abstract: The TS-1 powder，which is synthesized using tetrapropylammonium bromide (TPABr) as template, was molded into catalyst by extruding. The prepared catalysts containing 30％, 50％, 60％ or 80％ TS-1 were used to catalyze the propylene epoxidation to produce PO in a fixed bed reactor. The results show that TS-1 is the active site of the catalyst. The catalyst with 80％ TS-1 has the highest activity and mechanical intensity. The selectivity of PO decreases and the utilization of hydrogen peroxide increases as TS-1 content increases in the catalyst. Both the selectivity of PO and the utilization of hydrogen peroxide increase as the WHSV of propylene increases from 0.30 h－1 to 0.70 h－1. The catalyst containing 80％ TS-1 exhibits 97.8% hydrogen peroxide conversion, 86.4% PO selectivity and 91.8% hydrogen peroxide utilization when the WHSV of propylene is 0.70 h－1.
Abstract: The research progress of heavy oil recovery by aquathermolysis is reviewed this paper, mainly from the aspects of aquathermolytic reactions, the catalytic reactions is the mechanism of these reactions, and the field application of recovering heavy oil by aquathermolysis. At the same time, the research results and the future of aquathermolysis are discussed. It is addressed that the aquathermolysis, a new method to recover heavy oil commercially and efficiently, has very high potential value. At present, the research in recovering heavy oil by aquathermolysis has been directed more towards study in investigating more characteristics and effects of high temperature water, examining the aquathermolytic behavior of special components of a wider range of heavy oil samples by choosing proper model compound or other methods, then establishing a protocol of thermodynamics and kinetics models of these components, so as to design the aquathermolytic reactions and screening crucial catalysts which can accelerate the visbreaking reactions to upgrade the heavy oil. The key research work is still developing a series cheaper catalysts with higher activity and selectivity, accordingly with lower sensitivity to the aquathermolytic conditions for different heavy oils, screening or developing some additives with good synergistic effects, eventually, projecting the field applied techniques.
Abstract: Photocatalytic process is an energy-saving and high efficiency technology in sewage disposal. The progress in the photocatalytic process over semiconductor materials are reviewed, based on the findings reported in literatures. The paper covers the current status of research on photocatalytic degradation, the mechanism of photocatalytic reaction, the advance of photocatalytic destruction of common organic pollutants, the approaches to improve activity of semiconductor and some problems existing in the progress of photocatalytic technology and so on.
Supervisor：Chinese Academy of Sciences
Sponsors by：Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Chinese Chemical Society
