能源化学(英文版)

Select

Direct conversion of natural gas to higher hydrocarbons: A review

Sachchit Majhi, Pravakar Mohanty, Hui Wang, K. K. Pant

2013, 22(4): 543-554.

摘要 ( 6983 )

Direct conversion of methane to higher hydrocarbons is an effective process to solve the problem of natural gas utilization. Although remarkable progress has been achieved on the dehydro-aromatization of methane (DAM), low conversion caused by severe thermodynamic limitations, coke formation, and catalysis deactivation remain important drawbacks to the direct conversion process. Molybdenum catalysts supported on HZSM-5 type zeolite support are among the most promising catalysts. This review focuses on the aspects of direct methane conversion, in terms of catalysts containing metal and support, reaction conditions, and conversion in different types of reactors. The reaction mechanism for this catalytic process is also discussed.

Select

LSM-infiltrated LSCF cathodes for solid oxide fuel cells

Ze Liu, Mingfei Liu, Lei Yang, Meilin Liu

2013, 22(4): 555-559.

摘要 ( 7149 )

Mixed ionic-electronic conductors in the family of La_xSr_1-xCo_yFe_1-yO_3-δ have been widely studied as cathode materials for solid oxide fuel cells (SOFCs). However, the long-term stability was a concern. Here we report our findings on the effect of a thin film coating of La_0.85Sr_0.15MnO_3-δ (LSM) on the performance of a porous La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) cathode. When the thicknesses of the LSM coatings are appropriate, an LSM-coated LSCF electrode showed better stability and lower polarization (or higher activity) than the blank LSCF cathode without LSM infiltration. An anode-supported cell with an LSM-infiltrated LSCF cathode demonstrated at 825 ℃ a peak power density of ～1.07 W/cm², about 24% higher than that of the same cell without LSM infiltration (～0.86 W/cm²). Further, the LSM coating enhanced the stability of the electrode; there was little degradation in performance for the cell with an LSM-infiltrated LSCF cathode during 100 h operation.

Select

Catalytic properties of Ru nanoparticles embedded on ordered mesoporous carbon with different pore size in Fischer-Tropsch synthesis

Kun Xiong, Yuhua Zhang, Jinlin Li, Kongyong Liew

2013, 22(4): 560-566.

摘要 ( 9718 )

A series of 3 wt% Ru embedded on ordered mesoporous carbon (OMC) catalysts with different pore sizes were prepared by autoreduction between ruthenium precursors and carbon sources at 1123 K. Ru nanoparticles were embedded on the carbon walls of OMC. Characterization technologies including power X-ray diffraction (XRD), nitrogen adsorption-desorption, transmission electron microscopy (TEM), and hydrogen temperature-programmed reduction (H₂-TPR) were used to scrutinize the catalysts. The catalyst activity for Fischer-Tropsch synthesis (FTS) was measured in a fixed bed reactor. It was revealed that 3 wt% Ru-OMC catalysts exhibited highly ordered mesoporous structure and large surface area. Compared with the catalysts with smaller pores, the catalysts with larger pores were inclined to form larger Ru particles. These 3 wt% Ru-OMC catalysts with different pore sizes were more stable than 3 wt% Ru/AC catalyst during the FTS reactions because Ru particles were embedded on the carbon walls, suppressing particles aggregation, movement and oxidation. The catalytic activity and C₅₊ selectivity were found to increase with the increasing pore size, however, CH₄ selectivity showed the opposite trend. These changes may be explained in terms of the special environment of the active Ru sites and the diffusion of products in the pores of the catalysts, suggesting that the activity and hydrocarbon selectivity are more dependent on the pore size of OMC than on the Ru particle size.

Select

Highly selective synthesis of single-walled carbon nanotubes from methane in a coupled Downer-turbulent fluidized-bed reactor

Song Yun, Weizhong Qian, Chaojie Cui, Yuntao Yu, Chao Zheng, Yi Liu, Qiang Zhang, Fei Wei

2013, 22(4): 567-572.

摘要 ( 7104 )

For the synthesis of single-walled carbon nanotubes (SWCNTs) from CH₄ over a Fe/MgO catalyst, we proposed a coupled Downer-turbulent fluidized-bed (TFB) reactor to enhance the selectivity and yield (or production rate) of SWCNTs. By controlling a very short catalyst residence time (1-3 s) in the Downer, only part of Fe oxides can be reduced to form Fe nano particles (NPs) available for the growth of SWCNTs. The percentage of unreduced Fe oxides increased and the yield of SWCNTs decreased accordingly with the increase of catalyst feeding rate in Downer. SWCNTs were preferentially grown on the catalyst surface and inhibited the sintering of the Fe crystallites which would be formed thereafter in the downstream TFB, evidenced by TEM, Raman and TGA. The coupled Downer-turbulent fluidized-bed reactor technology allowed higher selectivity and higher production rate of SWCNTs as compared to TFB alone.

Select

Comprehensive study of nanostructured supports with high surface area for Fischer-Tropsch synthesis

Somayeh Farzad, Ali Haghtalab, Alimorad Rashidi

2013, 22(4): 573-581.

摘要 ( 7388 )

An extensive study of Fischer-Tropsch synthesis on nanostructure supports with high surface area such as nanostructure γ-alumina, single wall carbon nanotubes (SWNTs), and the hybrid of SWNTs/nanostructure γ-alumina has been investigated. The nanostructure γ-alumina was promoted with lanthanum to obtain better performance of catalyst and 15 wt% cobalt loading was the basis of our investigation. Fischer-Tropsch synthesis was performed in a fixed bed reactor under different reaction conditions (220-240 ℃, 15-25 bar, H₂/CO ratio of 2, GHSV of 900-1400) in order to study the effects of temperature, pressure and gas hourly space velocity (GHSV) changes on hydrocarbon selectivity and catalyst activity. The catalysts were extensively characterized by different methods including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma (ICP), hydrogen (H₂) chemisorption and temperature-programmed reduction (TPR). The results showed that the yield of hybrid supported catalyst (55.4%) is higher than that of nanostructure γ-alumina supported catalyst (55.0%) and lower than that of SWNTs supported cobalt catalyst (71.0%). The hybrid supported catalyst showed higher reduction degree and dispersion of cobalt particles. The temperature, pressure and GHSV effects on hybrid supported catalyst were studied and results showed that higher pressure favors the chain growth and temperature increase leads to the increases in methane selectivity and CO conversion. Higher hydrocarbon selectivity and CO conversion showed positive relationship with increasing GHSV while lower hydrocarbon selectivity diminishes.

Select

Synthesis and characterization of multiwall carbon nanotubes/alumina nanohybrid-supported cobalt catalyst in Fischer-Tropsch synthesis

Ali Karimi, Bahram Nasernejad, Ali Morad Rashidi

2013, 22(4): 582-590.

摘要 ( 8443 )

Multiwall carbon nanotubes (MWNTs) and alumina are combined to give a new type of nanohybrid for Fisher-Tropsch synthesis (FTS) catalyst support. Alumina nano-particles (10 wt%) were introduced directly on functionalized MWNTs by a modified sol-gel method. Microstructure observations show that alumina particles were homogeneously dispersed on the inside and outside of modified MWNTs surfaces. 15 wt% cobalt loading catalysts were prepared with this nanohybrid and γ-alumina as a reference, using a sol-gel technique and wet impregnation method respectively. These catalysts were characterized by TEM, XRD, N₂-adsorption, H₂ chemisorption and TPR. The deposition of cobalt nanoparticles synthesized by sol-gel technique on the MWNTs nanohybrid shift the reduction peaks to a low temperature, indicating higher reducibility for uniform cobalt particles. Nanohybrid also aided in high dispersion of metal clusters and high stability and performance of catalyst. The proposed MWNTs nanohybrid-supported cobalt catalysts showed the improved FTS rate (g_HC/(g_cat·min)), CO conversion (%), and water gas shift rate (WGS)(g_CO₂/(g_cat·h)) of 0.012, 52, and 30E-3, respectively, as compared to those of 0.007, 25, and 18E-3, respectively, on the γ-alumina-supported cobalt catalysts with the same Co loading.

Select

Promotion effect of adsorbed water/OH on the catalytic performance of Ag/activated carbon catalysts for CO preferential oxidation in excess H₂

Yuanyuan Guo, Limin Chen, Ding Ma, Daiqi Ye, Bichun Huang

2013, 22(4): 591-598.

摘要 ( 6311 )

Activated carbon (AC) supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation (PROX) in excess H₂ was evaluated. Ag/AC catalysts, after reduction in H₂ at low temperatures (≤200 ℃) following heat treatment in He at 200 ℃ (He200H200), exhibited the best catalytic properties. Temperature-programmed desorption (TPD), X-ray diffraction (XRD) and temperature-programmed reduction (TPR) results indicated that silver oxides were produced during heat treatment in He at 200 ℃ which were reduced to metal silver nanoparticles in H₂ at low temperatures (≤200 ℃), simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 ℃. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H200 treatment displayed similar PROX of CO reaction properties to Ag/SiO₂. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.

Select

Effect of solvent on catalytic performance of anhydrous catalyst in acetylene dimerization to monovinylacetylene

Jianguo Liu, Minghan Han, Zhanwen Wang

2013, 22(4): 599-604.

摘要 ( 6195 )

The production of monovinylacetylene (MVA) through Cu(I)-catalyzed acetylene dimerization reaction was performed in different reaction media. Based on the analyses of crystals precipitated from the catalyst solution and UV-Vis spectra of the catalysts, the reaction mechanism and solvent dependence were studied. The highest yield of MVA can be obtained when dimethylformamide is used as solvent because of its strong coordination ability to Cu(I). The activation of C≡C bond is presumed to be improved when the catalytic metal ion is coordinated by a solvent with less steric hindrance and electron-rich coordination atom. The results of the present study provide a possible way to accelerate the metal-catalyzed homogeneous reaction of alkyne substrates through careful selection of a solvent.

Select

Preparation of modified Ce-SAPO-34 catalysts and their catalytic performances of methanol to olefins

Shuxun Tian, Shengfu Ji, Dandan Lü, Bingyang Bai, Qi Sun

2013, 22(4): 605-609.

摘要 ( 5876 )

The modified Ce-SAPO-34 catalysts were prepared with three methods, i.e., the liquid ion exchange with air calcination, impregnation with air calcination and impregnation with steam calcination methods. The catalytic performances of the catalysts for methanol to olefins were investigated. The properties of the catalysts were characterized using XRD, BET, XRF, FT-IR and NH₃-TPD. The results indicated that compared to the SAPO-34 catalyst the catalyst prepared with the impregnation and air calcination prolonged the lifetime by 40 min and improved the selectivity to ethylene by 5% (mol) and the catalyst prepared with the impregnation and steam calcination showed the best modification effect, prolonging the lifetime by 70 min and improving the ethylene selectivity by 10% (mol). The catalyst prepared with the liquid ion exchange showed similar behaviour as the SAPO-34 catalyst. It was verified that the porous structure and surface acidity of these catalysts determined their catalytic behaviors.

Select

A novel PdNi/Al₂O₃ catalyst prepared by galvanic deposition for low temperature methane combustion

Xiqiang Pan, Yibo Zhang, Zhenzhen Miao, Xiangguang Yang

2013, 22(4): 610-616.

摘要 ( 6466 )

Galvanic deposition method was used to prepare the Pd/Ni-Al₂O₃-GD catalyst for the combustion of methane under lean conditions. The new catalyst and compared catalysts (Pd/Al₂O₃-IW, Pd-Ni/Al₂O₃-IW, Pd/Ni-Al₂O₃-IW) prepared by incipient wetness impregnation were characterized by N₂-physisorption, XRD and TEM to clarify particle size and size distribution of palladium species. Combined O₂-TPD and XPS results with the catalytic data, it shows that the surface palladium species with low valence exhibits better combustion performance due to their stronger interaction with support. The results indicate that the galvanic deposition method is an effective route to prepare efficient catalyst for methane combustion, and it also provides useful information for improving the present commercial catalyst.

Select

Influence of chromium modification on the properties of MnO_x-FeO_x catalysts for the low-temperature selective catalytic reduction of NO by NH₃

Kai Shen, Yaping Zhang, Xiaolei Wang, Haitao Xu, Keqin Sun, Changcheng Zhou

2013, 22(4): 617-623.

摘要 ( 6281 )

Catalytic properties of MnO_x-FeO_x complex oxide (hereafter denoted as Mn-Fe) catalysts modified with different loadings of chromium oxide were investigated by using the combination of physico-chemical techniques, such as N₂ physisorption, X-ray diffraction (XRD), high-resolution transmission electron microscope (HRTEM), in situ Fourier transform infrared spectroscopy (in situ FT-IR) and temperature-programmed reduction (TPR) and their catalytic activities were evaluated with the selective catalytic reduction (SCR) of NO_x by NH₃. It was found that with the addition of Cr, more NO could be removed in the low-temperature window (below 120 ℃). Among the tested catalysts, Mn-Fe-Cr (2 : 2 : 1) catalyst exhibited the best catalytic performance at 80 ℃ with the NO conversion higher than 90%. The combination of the reaction and characterization results indicated that (1) the strong interaction among tertiary metal oxides existed in the catalysts when Cr was appropriately added, which made the active components better dispersed with less agglomeration and sintering and the largest BET specific surface area could be obtained; (2) Cr improved the low-temperature reducibility of the catalyst and promoted the formation of the active intermediate (—NH₃⁺), which favored the low-temperature SCR reaction.

Select

Effect of manganese on the catalytic performance of an iron-manganese bimetallic catalyst for light olefin synthesis

Tingzhen Li, Hulin Wang, Yong Yang, Hongwei Xiang, Yongwang Li

2013, 22(4): 624-632.

摘要 ( 6802 )

A systematic study was carried out to investigate the promotion effect of manganese on the performance of a coprecipitated iron-manganese bimetallic catalyst for the light olefins synthesis from syngas. The catalyst samples were characterized by N₂ physisorption, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), Mössbauer spectroscopy, H₂-differential thermogravimetric analysis (H₂-DTG), CO temperature-programmed reduction (CO-TPR) and CO₂ temperature-programmed desorption (CO₂-TPD). The Fischer-Tropsch synthesis (FTS) performance of the catalyst was measured at 1.5 MPa, 250 ℃ and syngas with H₂/CO ratio of 2.0. The characterization results indicated that the addition of manganese decreases the catalyst crystallite size, and improves the catalyst BET surface area and pore volume. The presence of manganese suppresses the catalyst reduction and carburization in H₂, CO and syngas, respectively. The addition of manganese improves the catalytic activity of water-gas shift reaction and suppresses the oxidation of iron carbides in the FTS reaction. The incorporation of manganese improves the catalyst surface basicity and results in a significant improvement in the selectivities to light olefins and heavy hydrocarbons (C₅₊), and furthermore an inhibition of methane formation in FTS. The pure iron catalyst (Mn-00) has the highest initial FTS catalytic activity (65%) and the lowest selectivity (17.35 wt%) to light olefins (C₂⁼—C₄⁼). The addition of an appropriate amount of manganese can improve the catalyst FTS activity.

Select

Optimal operating conditions of radial flow moving-bed reactors for isobutane dehydrogenation

M. Farsi, A. Jahanmiri, M. R. Rahimpour

2013, 22(4): 633-638.

摘要 ( 7151 )

In this study, radial flow moving bed reactors for isobutane dehydrogenation have been modeled and simulated heterogeneously based on mass and energy conservation laws. The considered reaction networks in the model are isobutene dehydrogenation as main reaction, and hydrogenolysis, propane dehydrogenation as well as coke formation as side reactions that all occur on the catalyst surface. Then, the process condition has been optimized to produce more isobutene under steady state condition. To prove the accuracy of the considered mathematical model and assumptions, simulation results are compared with the plant data. As a powerful method in the global optimization, the genetic algorithm has been used to optimize the considered objective function. The isobutane conversion and isobutene selectivity under optimal conditions are about 40.1% and 91%, respectively.

Select

Production of hydrogen and syngas via pyrolysis of bagasse in a dual bed reactor

Morteza Shoja, Mokhtar Akhond Babatabar, Ahmad Tavasoli, Abtin Ataei

2013, 22(4): 639-644.

摘要 ( 6545 )

Pyrolysis of bagasse followed by thermal cracking of tar was carried out at atmospheric pressure using a dual bed reactor. The first bed was used for the pyrolysis and the second bed was used for thermal cracking of tar. Iron fillings were used as the packed bed material in the second bed. The effects of reaction time (20 to 40 min), reactor temperature (600 to 900 ℃) and packed bed height (40-100 mm) on the product (char, tar and gas) yield and gas (H₂, CO, CO₂, CH₄, C_nH_m) composition were studied. Over the ranges of the experimental conditions used, the operating conditions were optimized for pyrolysis temperature around 850 ℃, a reaction time of 30 min and packed bed height of 100 mm, thus we could obtain a gas richer in hydrogen and carbon monoxide and poorer in carbon dioxide and hydrocarbons. It was observed that compared with single bed process, dual bed process increased the gas yield from 0.397 to 0.750 m³/kg and decreased the tar yield from 0.445 to 0.268 g/g while the heating value of the product gas remained almost constant (10—11 MJ/m³).

Select

TiO₂ supported cobalt-manganese nano catalysts for light olefins production from syngas

Mostafa Feyzi, Asadollah Hassankhani

2013, 22(4): 645-652.

摘要 ( 8849 )

Cobalt-manganese nano catalysts were prepared by sol-gel method. This research investigated the effects of different cobalt-manganese (Co/Mn = 1/1) loading, pH and calcination conditions on the catalytic performance of Co-Mn/TiO₂ catalysts for Fischer-Tropsch synthesis (FTS) in a fixed bed reactor. It was found that the catalyst containing 30wt%(Co-Mn)/TiO₂ was an optimal catalyst for the conversion of synthesis gas to light olefins especially propylene. The activity and selectivity of optimal catalyst were studied under different operational conditions. The results showed that the best operational conditions were H₂/CO = 1/1 molar feed ratio at 250 ℃ and GHSV = 1300 h^-1 under atmospheric pressure. Characterization of catalysts was carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption measurements.

Select

Effect of methane co-feeding on the selectivity of ethylene produced from oxidative dehydrogenation of ethane with CO₂ over a Ni-La/SiO₂ catalyst

Xiaoxi Peng, Jianqiang Zhu, Lu Yao, Changwei Hu

2013, 22(4): 653-658.

摘要 ( 6342 )

A Ni-La/SiO₂ catalyst was prepared through the incipient wetness impregnation method and tested in the oxidative dehydrogenation of ethane (ODHE) with CO₂. The fresh and used catalysts were characterized by XRD and SEM techniques. The Ni-La/SiO₂ catalyst exhibited catalytic activity for the oxidative dehydrogenation of ethane, but with low ethylene selectivity in the absence of methane. The selectivity to ethylene increased with increasing molar ratio of methane in the feed. The carbon deposited on the catalyst surface in the sole ODHE with CO₂ was mainly inert carbon, while much more filamentous carbon was formed in the presence of methane. The filamentous carbon was easy to be removed by CO₂, which might play a role in improving the conversion of ethane to ethylene. The introduction of methane might affect the equilibrium of the CO₂ reforming of ethane and the ODHE with CO₂. As a consequence, the synthesis gas produced from CO₂ reforming of methane partly inhibited the reaction of ethane and promoted the ODHE with CO₂, thus increasing the selectivity of ethylene.

Select

Sulfonated carbon catalyzed oxidation of aldehydes to carboxylic acids by hydrogen peroxide

Lipeng Zhou, Beibei Dong, Si Tang, Hong Ma, Chen Chen, Xiaomei Yang, Jie Xu

2013, 22(4): 659-664.

摘要 ( 9071 )

Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N₂ physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H₂O₂ as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.

Select

Hydrogen production by glycerol reforming in supercritical water over Ni/MgO-ZrO₂ catalyst

Qihai Liu, Liewen Liao, Zili Liu, Xinfa Dong

2013, 22(4): 665-670.

摘要 ( 6580 )

Nano ZrO₂ and MgO-ZrO₂ were prepared by a self-assembly route and were employed as the support for Ni catalysts used in hydrogen production from glycerol reforming in supercritical water (SCW). The reforming experiments were conducted in a tubular fixed-bed flow reactor over a temperature range of 600-800 ℃. The influences of process variables such as temperature, contact time, and water to glycerol ratio on hydrogen yield were investigated and the catalysts were charactered by ICP, BET, XRD and SEM. The results showed that high hydrogen yield was obtained from glycerol by reforming in supercritical water over the Ni/MgO-ZrO₂ catalysts in a short contact time. The MgO in the catalyst showed significant promotion effect for hydrogen production likely due to the formation of the alkaline active site. Even when the glycerol feed concentration was up to 45 wt%, glycerol was completely gasified and transfered to the gas products containing hydrogen, carbon dioxide, and methane along with small amounts of carbon monoxide. At a diluted feed concentration of 5 wt%, near theoretical yield of 7 mole of H₂/mol of glycerol could be obtained.

Select

Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces

Bin Xing, Zizhang Wei, Guichang Wang

2013, 22(4): 671-679.

摘要 ( 6244 )

Vinyl acetate (VA) synthesis on Pd/Au(111) and Pd/Au(100) surfaces has been systematically investigated through first-principles density functional theory (DFT) calculations. The DFT results showed that for VA synthesis, the ‘Samanos’ reaction mechanism (i.e., direct coupling of coadsorbed ethylene and acetate species and subsequent β-hydride elimination to form VA) is more favorable than the ‘Moiseev’ mechanism (i.e., ethylene first dehydrogenates to form vinyl species which then couple with the coadsorbed acetate species to form VA). More importantly, it was found the surface coverage of acetate has a significant effect on the reactivity of VA synthesis, and the activation energy of the rate-controlling step on Pd/Au(100) surface is smaller than that on Pd/Au(111) surface (0.88 vs. 0.95 eV), indicating the former is more active than the latter.

过刊目录