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过刊目录

    2008, Vol. 17, No. 2 Online: 2008-06-30
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    Articles
    Catalytic decomposition of CH4 over Ni-Al2O3-SiO2 catalysts: Influence of pretreatment conditions for the production of H2
    Jangam Ashok;Gangadhara Raju;Padigapati Shiva Reddy;Machiraju Subrahmanyam;Akula Venugopal*
    2008, 17(2): 113-119.  DOI:
    摘要 ( 10960 )   PDF  
    This article reports the production of COx free hydrogen and carbon nanofibers by the catalytic decomposition of methane over Ni-Al2O3-SiO2 catalysts. The influence of reaction temperature, pretreatment temperature, and effect of reductive pretreatment on the decomposition of methane activity is investigated. The physico-chemical characteristics of fresh and deactivated samples were characterized using BET-SA, XRD, TPR, SEM/TEM, CHNS analyses and correlated with the methane decomposition results obtained. The Ni-Al-Si (4 : 0.5 : 1.5) catalyst reduced with hydrazine hydrate produced better H2 yields of ca. 1815 mol H2/mol Ni than the catalyst reduced with 5% H2/N2.
    A silica-immobilized Pt2+catalyst for the selective, aerobic oxidation of methane via an electron-transfer chain
    Zengjian An;Xiulian Pan;Xiumei Liu;Xiuwen Han;Xinhe Bao*
    2008, 17(2): 120-124.  DOI:
    摘要 ( 10478 )   PDF  
    The combination of Pt2+, benzoquinone and NaNO2 forms an electron-transfer chain, which leads to the oxidation of methane by O2 in CF3COOH aqueous solution. The overall turnover number per hour (TOF) of methane at 120 oC is 0.5 h-1, however, only about one fourth (23%) of methane is converted to the desired product of methanol in the formation of CF3COOCH3. The over-oxidation of methane to CO2, over the catalyst with the Pt2+ species immobilized via 2, 2'-bipyridyl as a ligand on the silica substrate, is depressed distinctly. Under the same conditions, the conversion to methanol dominates, and no CO2 is observed, on account of the over-oxidation of methane, as confirmed by the isotope experiment.
    Influence of preparation methods on CuO-CeO2 catalysts in the preferential oxidation of CO in excess hydrogen
    Zhigang Liu;Renxian Zhou*;Xiaoming Zheng
    2008, 17(2): 125-129.  DOI:
    摘要 ( 10558 )   PDF  
    Influence of three different preparation methods, i.e. impregnation, coprecipitation, and inverse coprecipitation, on the preferential oxidation of CO in excess hydrogen (PROX) over CuO-CeO2 catalysts has been investigated and CuO-CeO2 catalysts are characterized using BET, XPS, XRD, UV Raman, and TPR techniques. The results show that the catalysts prepared by coprecipitation have smaller particle sizes, well-dispersed CuOx species, more oxygen vacancies, and are more active in the PROX than those prepared by the other methods. However, the inverse coprecipitation depresses the catalytic performance of CuO-CeO2 catalysts and causes the growth of CuO-CeO2 because of different pH value in the precipitation process.
    Effect of diluent and reaction parameter on selective oxidation of propane over MoVTeNb catalyst using nanoflow catalytic reactor
    Restu Kartiko Widi;*;Sharifah Bee Abdul Hamid;Robert Schloegl
    2008, 17(2): 130-134.  DOI:
    摘要 ( 10328 )   PDF  
    The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic reactor. The effects of catalyst dilution on the catalytic performance of the MoVTeNb mixed oxide catalyst in selective oxidation of propane to acrylic acid were also investigated. The effects of some reaction parameters, such as gas hourly space velocity (GHSV) and reaction temperature, for selective oxidation of propane to acrylic acid over diluted MoVTeNb catalyst have also been studied. The configuration of the nanoflow is shown to be suitable for screen catalytic performance, and its operating conditions were mimicked closely to conventional laboratory as well as to industrial conditions. The results obtained provided very good reproducibility and it showed that preparation methods as well as reaction parameters can play significant roles in catalytic performance of these catalysts.
    Evaluation of a mathematical model using experimental data and artificial neural network for prediction of gas separation
    M. Peer;M. Mahdyarfar;T. Mohammadi*
    2008, 17(2): 135-141.  DOI:
    摘要 ( 9627 )   PDF  
    In recent times, membranes have found wide applications in gas separation processes. As most of the industrial membrane separation units use hollow fiber modules, having a proper model for simulating this type of membrane module is very useful in achieving guidelines for design and characterization of membrane separation units. In this study, a model based on Coker, Freeman, and Fleming's study was used for estimating the required membrane area. This model could simulate a multicomponent gas mixture separation by solving the governing differential mass balance equations with numerical methods. Results of the model were validated using some binary and multicomponent experimental data from the literature. Also, the artificial neural network (ANN) technique was applied to predict membrane gas separation behavior and the results of the ANN simulation were compared with the simulation results of the model and the experimental data. Good consistency between these results shows that ANN method can be successfully used for prediction of the separation behavior after suitable training of the network.
    Catalytic activity of phosphorus and steam modified HZSM-5 and the theoretical selection of phosphorus grafting model
    Renqing Lü*;Zuogang Cao;Xinhai Liu
    2008, 17(2): 142-148.  DOI:
    摘要 ( 10676 )   PDF  
    The modification of HZSM-5 zeolite with phosphorus and steam has been studied. Results show that 1% phosphorus and steam modified HZSM-5 has the highest catalytic activity for n-heptane. Physicochemical and catalytic properties of 1% phosphorus and steam modified HZSM-5 zeolites have been investigated. The X-ray diffraction (XRD) results exhibit that there is considerable variation in the relative intensity of the individual diffraction peaks. The acidity of the samples decreases with an increase in the steaming temperature, which is determined by the IR of adsorbed pyridine and temperature programmed desorption (TPD) of ammonia. The oxidation state of phosphorus shown by XPS is +5, and a model for surface structure modification is proposed. The nitrogen adsorption isotherm for all samples is a combination of type I and type IV, all hysteresis loops resemble the H4-type. The density functional and cluster model methods have been invoked to select the phosphorus grafting model, and it was found that the phosphorus grafting model were more probable in the form of the terminal oxygen coordinating with aluminum.
    Acetalization of carbonyl compounds with 2, 2, 4-trimethyl-1, 3- pentanedio catalyzed by novel carbon based solid acid catalyst
    Ling Liu;Yuechang Zhao;Shan Gan;Xuezheng Liang;Jianguo Yang*;Mingyuan He
    2008, 17(2): 149-152.  DOI:
    摘要 ( 7994 )   PDF  
    The synthesis of 2, 4-diisopropyl-5, 5-dimethyl-1, 3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethyl-1, 3-pentanediol (TMPD) catalyzed by the novel carbon based acid was first carried out. High conversion (~98%) and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times. Moreover, the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.
    Influence of lanthanum on the performance of Zr-Co/activated carbon catalysts in Fischer-Tropsch synthesis
    Tao Wang;Yunjie Ding;*;Yuan Lü;Hejun Zhu;Liwu Lin;
    2008, 17(2): 153-158.  DOI:
    摘要 ( 11036 )   PDF  
    The influence of La loading on Zr-Co/activated carbon (AC) catalysts has been studied for Fischer-Tropsch synthesis. The catalyst samples were characterized by XRD, TPR, CO-TPD, and temperature programmed CO hydrogenation. The catalytic property was evaluated in a fixed bed reactor. The experimental results showed that CO conversion increased from 86.4% to 92.3% and the selectivity to methane decreased from 14.2% to 11.5% and C5+ selectivity increased from 71.0% to 74.7% when low La loading (La = 0.2wt%) was added into the Zr-Co/AC catalyst. However, high loadings of La (La = 0.3-1.0 wt%) would decrease catalyst activity as well as the C5+ selectivity and increase methane selectivity. XRD results displayed that La-modified Zr-Co/AC catalyst had little effect on the dispersion of Co catalyst. But, the results of TPR, CO-TPD, and temperature programmed CO hydrogenation techniques indicated that the extent of cobalt reduction was found to greatly influence the activity and selectivity of the catalyst. The addition of a small amount of La increased the reducibility of the Zr-Co/AC catalyst and restrained the formation of methane and improved the selectivity to long chain hydrocarbons. However, excess of La led to the decrease of the reducibility of Co catalyst thus resulted in higher methanation activity.
    Effects of carrier and Mn loading on supported manganese oxide catalysts for catalytic combustion of methane
    Jinyan Hu;Wei Chu*;Limin Shi
    2008, 17(2): 159-164.  DOI:
    摘要 ( 11954 )   PDF  
    Supported manganese oxide catalysts were prepared by incipient wetness impregnation method for methane catalytic combustion, and effects of the support (Al2O3, SiO2 and TiO2) and Mn loading were investigated. These catalysts were characterized with N2 adsorption, X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Methane conversion varied in a large range depending on supports or Mn loading. Al2O3 supported 15% Mn catalyst exhibited better activity toward methane catalytic oxidation. The manganese state and oxygen species played an important role in the catalytic performance.
    In situ FT-IR spectroscopy investigations of carbon nanotubes supported Co-Mo catalysts for selective hydrodesulfurization of FCC gasoline
    Jingcheng Zhang;Wenkun Yin;Hongyan Shang*;Chenguang Liu
    2008, 17(2): 165-170.  DOI:
    摘要 ( 11289 )   PDF  
    To better understand the nature of carbon nanotubes supported Co-Mo catalysts (Co-Mo/CNTs) for selective hydrodesulfurization (HDS) of fluid catalytic cracking (FCC) gasoline, studies are carried out using in situ Fourier transform infrared spectroscopy (FT-IR). The catalytic performances of Co-Mo/CNTs catalysts were evaluated with a mixture of cyclohexane, diisobutylene, cyclohexene, 1-octene (60 : 30 : 5 : 5, volume ratio) and thiophene (0.5%, ratio of total weight) as model compounds to simulate FCC gasoline. The HDS experimental results suggested that the HDS activity and selectivity of Co-Mo/CNTs catalysts were affected by Co/Mo ratio; the optimal Co/Mo atomic ratio is about 0.4, and the optimum reaction temperature is 260oC. The in situ FT-IR studies revealed that 1-octene can be completely saturated at 200oC. In the FT-IR spectra of diisobutylene, the characteristic absorption peak around 3081 cm-1 for the stretching vibration peak of =C--H bond was still clear at 320oC, indicating that diisobutylene is difficult to be hydrogenated. As for the thiophene, no characteristic absorption peak could be found around 3092 cm-1 and 835 cm-1 when the reaction temperature was raised to 280oC, indicating that thiophene had been completely hydrodesulfurized. On the basis of FT-IR results, it can be deduced that thiophene HDS reaction occurred mainly through direct hydrogenolysis route, whereas thiophene HDS and diisobutylene hydrogenation reaction over Co-Mo/CNTs catalysts might occur on two different kinds of active sites.
    Kinetics of methanol steam reforming over COPZr-2 catalyst
    Yongfeng Li*;Weiming Lin;Lin Yu;Zhifeng Hao;Rongjian Mai
    2008, 17(2): 171-174.  DOI:
    摘要 ( 10171 )   PDF  
    The COPZr-2 catalyst, which was prepared in our prophase research, showed good catalytic performance in methanol steam reforming reaction. In this article, the best one was chosen as an example to study the reaction kinetics of methanol steam reforming over this type of catalyst. First, the effects of methanol conversion to outlet CO2 and methanol conversion to outlet CO on methanol pseudo contact timeW/FMeOH were investigated. Then by applying the reaction route that methanol direct reforming (DR) and methanol decomposition (DE) were carried out in parallel, the reaction kinetic model with power function type was established. And the parameters for the model were estimated using a non-linear regression program which computed weighted least squares of the defined objects function. Finally, the kinetic model passed the correlation test and the F-test.
    Effect of operating conditions and potassium content on Fischer-Tropsch liquid products produced by potassium-promoted iron catalysts
    Francisco E. M. Farias;Fernando G. Sales;Fabiano A. N. Fernandes*
    2008, 17(2): 175-178.  DOI:
    摘要 ( 10197 )   PDF  
    The dependencies of Fischer-Tropsch synthesis liquid hydrocarbon product distribution on operating pressure and temperature have been studied over three potassium-promoted iron catalysts with increasing potassium molar content. The study followed an experimental planning and the results were analyzed based on surface response methodology. The effects of different operating conditions and potassium contents on the liquid product distribution were compared based on number average carbon number and dispersion. Results showed that high pressures (25 to 30 atm) favored the production of waxes that could be converted into liquid fuels through hydrocracking, while greater direct selectivity towards diesel was favored by low pressure (20 atm) using catalysts with low potassium to iron molar ratios. The liquid product distribution produced using an iron catalyst with high potassium content presented higher number-average number of carbons when compared to the distribution obtained using an iron catalyst with low potassium content.
    Effect of calcination temperature on structure and performance of Ni/TiO2-SiO2 catalyst for CO2 reforming of methane
    Sanbing Zhang;Jiankang Wang;Xiaolai Wang*
    2008, 17(2): 179-183.  DOI:
    摘要 ( 11038 )   PDF  
    The influence of calcination temperature on the structure and catalytic behavior of Ni/TiO2-SiO2 catalyst, for CO2 reforming of methane to synthesis gas under atmospheric pressure, was investigated. The results showed that the Ni/TiO2-SiO2 catalyst calcined at 700 ℃ had high and stable activity while the catalysts calcined at 550 and 850 ℃ had low and unstable activity. Depending on the calcination temperature, one, two, or three of the following Ni-containing species, NiO, Ni2.44Ti0.72Si0.07O4, and NiTiO3 were identified by combining the temperature programmed reduction (TPR) and X-ray diffraction (XRD) results. Their reducibility decreased in the sequence: NiO>Ni2.44Ti0.72Si0.07O4>NiTiO3. It suggests that high and stable activities observed over the Ni/TiO2-SiO2 catalyst calcined at 700 ℃ were induced by the formation of Ni2.44Ti0.72Si0.07O4 and smaller NiO species crystallite size.
    Direct gas-phase epoxidation of propylene to propylene oxide using air as oxidant on supported gold catalyst
    Zhanghuai Suo*;Mingshan Jin;Jiqing Lu;Zhaobin Wei;Can Li
    2008, 17(2): 184-190.  DOI:
    摘要 ( 10179 )   PDF  
    Gold catalysts supported on SiO2, TiO2, TiO2-SiO2, and ZrO2-SiO2 supports were prepared by impregnating each support with a basic solution of tetrachloroauric acid. X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) techniques were used to characterize their structure and surface composition. The results indicated that the size of gold particles could be controlled to below 10 nm by this method of preparation. Washing gold catalysts with water could markedly enhance the dispersion of metallic gold particles on the surface, but it could not completely remove the chloride ions left on the surface. The catalytic performance of direct vapor-phase epoxidation of propylene using air as an oxidant over these catalysts was evaluated at atmospheric pressure. The selectivity to propylene oxide (PO) was found to vary with reaction time on the stream. At the reaction conditions of atmosphere pressure, temperature 325oC, feed gas ratio V(C3H6)/V(O2) = 1/2, and GHSV = 6000 h-1, 17.9% PO selectivity with 0.9% propylene conversion were obtained at initial 10\, min for Au/SiO2 catalyst. After reacting 60 min only 8.9% PO selectivity were detected, but the propylene conversion rises to 1.4% and the main product is transferred to acrolein (72% selectivity). Washing Au/TiO2-SiO2 and Au/ZrO2-SiO2 samples with magnesium citrate solution could markedly enhance the activity and PO selectivity because smaller gold particles were obtained.
    Selective oxidation of propane to acrylic acid over mixed metal oxide catalysts
    Wei Zheng;*;Zhenxing Yu;Ping Zhang;Yuhang Zhang;Hongying Fu;Xiaoli Zhang;Qiquan Sun;Xinguo Hu
    2008, 17(2): 191-194.  DOI:
    摘要 ( 11455 )   PDF  
    The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 oC showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio (Mo1V0.31Te0.23Nb0.12). The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H8 : O2 : H2O : N2 = 4.4 : 12.8 : 15.3 : 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.
    Simulation and model design of pipe-shell reactor for the direct synthesis of dimethyl ether from syngas
    Yanfang Hu;Zhaoguang Nie*;Dingye Fang
    2008, 17(2): 195-200.  DOI:
    摘要 ( 10705 )   PDF  
    The simulation was made based on the model of pipe-shell reactor that was established by the model of global kinetics of synthesis of dimethyl ether from syngas over a bifunctional catalyst. The results of simulation showed that the selectivity for dimethyl ether (DME) and the conversion of CO were higher but the hot spot was kept below the temperature limit of the pipe-shell reactor. The suitable diameter of the pipe was φ38×2 mm, and the length of the pipe was 5.8 m. The optimal process conditions of the reactor were that the pressure was 5 MPa, the temperature of the cooling water was 240 oC, and the temperature of the raw gas at inlet of the reactor was 220 oC. The production of this reactor was 102800 t/y (ton per year) under these conditions.
    Autothermal reforming of methane over Ni catalysts supported over ZrO2-CeO2-Al2O3
    Xiulan Cai*;Yuanxing Cai;Weiming Lin
    2008, 17(2): 201-207.  DOI:
    摘要 ( 9774 )   PDF  
    Ni catalysts supported on Al2O3, ZrO2-Al2O3, CeO2-Al2O3 and ZrO2-CeO2-Al2O3 were prepared by co-precipitation method, and their catalytic performances for autothermal reforming of methane to hydrogen were investigated. The Ni-supported catalysts were characterized by XRD, TPR and XPS. The relationship between the structures and catalytic activities of the catalysts was discussed. The results showed that the catalytic activity and stability of the Ni/ZrO2-CeO2-Al2O3 catalyst was better than those of other catalysts with the highest CH4 conversion, H2/CO and H2/COx ratio at 750oC. The catalyst showed a little deactivation along the reaction time during its 72 h on stream with the mean deactivation rate of 0.08%/h. The catalytic performance of the Ni/ZrO2-CeO2-Al2O3 catalyst was also affected by reaction temperature, nO2 : nCH4 molar ratio and nH2O : nCH4 molar ratio. TPR, XRD and XPS measurements indicated that the formation of ZrO2-CeO2 solid solution could improve the dispersion of NiO, and inhibit the formation of NiAl2O4, and thus significantly promoted the catalytic activity of the Ni/ZrO2-CeO2-Al2O3 catalyst.
    Effect of pretreatment methods on the performance of Cu-Zr-Ce-O catalyst for CO selective oxidation
    Hanbo Zou*;Shengzhou Chen;Weiming Lin
    2008, 17(2): 208-211.  DOI:
    摘要 ( 9336 )   PDF  
    The Cu-Zr-Ce-O catalysts prepared using the coprecipitation method exhibited better catalytic performance for CO selective oxidation. The Cu-Zr-Ce-O catalysts pretreated with different methods were studied by CO-TPR and XPS techniques. The results showed that the Cu-Zr-Ce-O catalyst pretreated with oxygen exhibited the best catalytic performance and had the widest operating temperature window, with CO conversion above 99% from 160 to 200oC. The O2 pretreatment caused an enrichment of the oxygen storaged on the Cu active species and promoted the conversion of adsorbed oxygen into surface lattice oxygen. It also improved the amount of Cu+/Cu2+ ionic pair, and then facilitated the formation of CuO active species on the catalyst for selective CO oxidation.