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1.
Hydrogen production from glycerol reforming in liquid (aqueous phase reforming, APR) and vapor (steam reforming SR) phase over alumina-supported nickel catalysts modified with Ce, Mg, Zr and La was studied. Characterization of catalysts by temperature programmed reduction and XPS analyses revealed important structural effects: (i) the intercalation of Mg between nickel and alumina that inhibited the alumina incorporation to nickel phases, (ii) the close contact between Ni and Zr phases and, (iii) the close surface interaction of La and Ce ions with NiO phases. The catalytic activity of the samples studied in this work clearly indicated the different catalyst functionalities necessary to carry out aqueous-phase and vapor-phase steam reforming of glycerol. For aqueous phase reforming of glycerol, the addition of Ce, La and Zr to Ni/Al2O3 improves the initial glycerol conversions obtained over the Ni/Al2O3 supported catalyst. It is suggested that the differences in catalytic activities are related with geometric effects caused by the decoration of Ni phases by Ce and La or by the close interaction between Ni and Zr. In spite that nickel catalysts showed high APR activities at initial times on stream, all samples showed, independently of support, important deactivation rates that deactivate the catalysts after few hours under operation. Catalysts characterization after APR showed the oxidation of the active metallic Ni during reaction as the main cause of the observed deactivation. In the case of the glycerol steam reforming in vapor phase, the use of Ce, La, Mg and Zr as promoters of Ni based catalysts increases the hydrogen selectivity. Differences in activity were explained in terms of enhancement in: surface nickel concentration (Mg), capacity to activate steam (Zr) and stability of nickel phases under reaction conditions (Ce and La).  相似文献   

2.
Hydrogen production from steam reforming of acetic acid was investigated over Ni/La2O3-ZrO2 catalyst. A series of Ni/La2O3-ZrO2 catalysts were synthesized by sol-gel method coupled with wet impregnation, which was characterized by XRD, BET, TEM, EDS, TG, SEM and TPR. Catalytic activity of Ni/La2O3-ZrO2 was evaluated by steam reforming of acetic acid at the temperature range of 550-750 °C. The tetragonal phase La0.1Zr0.9O1.95 is formed through the doping of La2O3 into the ZrO2 lattice and nickel species are highly dispersed on the support with high specific surface area. H2 yield and CO2 yield of Ni/La2O3-ZrO2 catalyst with 15%wt Ni reaches 89.27% and 80.41% at 600 °C, respectively, which is attributed to high BET surface area and sufficient Ni active sites in strong interaction with the support. 15%wt Ni supported on La2O3-ZrO2 catalyst maintains relatively stable catalytic activities for a period of 20 h.  相似文献   

3.
An Al2O3-ZrO2 support was prepared by grafting a zirconium precursor onto the surface of commercial γ-Al2O3. A physical mixture of Al2O3-ZrO2 was also prepared for the purpose of comparison. Ni/Al2O3-ZrO2 catalysts were then prepared by an impregnation method, and were applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). The effect ZrO2 and preparation method of Al2O3-ZrO2 on the performance of supported nickel catalysts in the steam reforming of LNG was investigated. The Al2O3-ZrO2 prepared by a grafting method was more efficient as a support for nickel catalyst than the physical mixture of Al2O3-ZrO2 in the hydrogen production by steam reforming of LNG. The well-developed tetragonal phase of ZrO2 and the high dispersion of ZrO2 on the surface of γ-Al2O3 were responsible for the enhanced catalytic performance of Ni/Al2O3-ZrO2 prepared by way of a grafting method.  相似文献   

4.
The catalytic behavior of Ni/Ce-ZrO2/θ-Al2O3 has been investigated in the partial oxidation of methane (POM) toward synthesis gas. The catalyst showed high activity and selectivity due to the heat treatment of the support and the promotional effect of Ce-ZrO2. It is suggested that the support was stabilized through the heat treatment of γ-Al2O3 and the precoating of Ce-ZrO2, on which a protective layer was formed. Moreover, sintering of the catalyst was greatly suppressed for 24 h test. Pulse experiments of CH4, O2 and/or CH4/O2 with a molar ratio of 2 were systematically performed over fresh, partially reduced and well reduced catalyst. Results indicate that CH4 can be partially oxidized to CO and H2 by the reactive oxygen in complex NiOx species existing over the fresh catalyst. It is demonstrated that POM over Ni/Ce-ZrO2/θ-Al2O3 follows the pyrolysis mechanism, and both the carbonaceous materials from CH4 decomposition over metallic nickel and the reactive oxygen species present on NiOx and Ce-ZrO2 are intermediates for POM.  相似文献   

5.
CO2 reforming of CH4 was performed using Ni catalyst supported on La-hexaaluminate which has been an well-known material for high-temperature combustion. La-hexaaluminate was synthesized by sol-gel method at various conditions where different amount of Ni (5–20 wt%) was loaded. Ni/La-hexaaluminate experienced 72 h reaction and its catalytic activity was compared with that of Ni/Al2O3, Ni/La-hexaaluminate shows higher reforming activity and resistance to coke deposition compared to the Ni/Al2O3 model catalyst. Coke deposition increases proportionally to Ni content. Consequently, Ni(5)/La-hexaaluminate(700) is the most efficient catalyst among various Ni/La-hexaaluminate catalysts regarding the cost of Ni in Ni(X)/La-hexaaluminate catalysts. BET surface area, XRD, EA, TGA and TPO were performed for surface characterization. This work was presented at the 6 th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.  相似文献   

6.
A mesoporous Ni-Al2O3 composite catalyst (Ni-A-NS) was prepared by a single-step non-ionic surfactant-templating method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel catalyst supported on mesoporous alumina (Ni/A-NS) was also prepared by an impregnation method. The effect of physicochemical properties on the performance of Ni-A-NS catalyst in the steam reforming of LNG was investigated. Ni-A-NS catalyst retained superior textural properties compared to Ni/A-NS catalyst. Nickel oxide species were highly dispersed on the surface of both Ni/A-NS and Ni-A-NS catalysts through the formation of surface nickel aluminate phase. Although both Ni/A-NS and Ni-A-NS catalysts exhibited a stable catalytic performance, Ni-A-NS catalyst showed a better catalytic performance than Ni/A-NS catalyst in the steam reforming of LNG. High nickel surface area and high nickel dispersion of Ni-A-NS catalyst played an important role in enhancing the dehydrogenation reaction of hydrocarbon species and the gasification reaction of adsorbed carbon species in the steam reforming of LNG. High reducibility of Ni-A-NS catalyst was also responsible for its high catalytic performance.  相似文献   

7.
The maximization of the total surface area of Pt-SnO2/Al2O3 catalyst was studied by using the Taguchi method of experimental design. The catalysts were prepared by sol-gel method. The effects of HNO3, H2O and aluminum nitrate concentrations and the stirring rate on the total surface area were studied at three levels of each. L9 orthogonal array leading nine experiments was used in the experimental design. The parameter levels that give maximum total surface area were determined and experimentally verified. In the range of conditions studied it was found that, medium levels of HNO3 and H2O concentration and lower levels of aluminum nitrate concentration and stirring rate maximize the total surface area.  相似文献   

8.
Pb, Sb, Bi and Te doped Ni catalysts were prepared and used for methane reforming with CO2 in order to diminish coke deposition. It was found that small amounts of Pb doped Ni catalysts exhibited excellent coke resistance ability with minor loss of the reforming activity. As the added amount of Pb increased from 0 to 0.015 (mole ratio between Pb/Ni), coke formation rate decreased from 166.7 mg-coke/g-cat h (on Ni/SiO2) to 0, while the reforming activity decreased slightly from 73.2% to 63.3% (conversion of CO2) at 800 °C, 60,000 ml(STP)/g-cat·h (CH4 CO2=1:1, no dilution gas in feed). Higher amounts of Pb and Sb, Bi, Te made Ni catalyst deactivated for methane reforming with CO2.  相似文献   

9.

Abstract  

The catalytic performance during combined steam and carbon dioxide reforming of methane (SCR) was investigated on Ni/MgAl2O4 catalyst promoted with CeO2. The SCR catalyst was prepared by co-impregnation method using nickel and cerium metal precursors on hydrotalcite-like MgAl2O4 support. In terms of catalytic activity and stability, CeO2-promoted Ni/MgAl2O4 catalyst is superior to Ni–CeO2/Al2O3 or Ni/MgAl2O4 catalysts because of high resistance to coke formation and suppressed aggregation of nickel particles. The role of CeO2 on Ni/MgAl2O4 catalyst was elucidated by carrying out the various characterization methods in the viewpoint of the aggregation of nickel particles and metal-support interactions. The observed superior catalytic performance on CeO2-promoted Ni/MgAl2O4 catalyst at the weight ratio of MgO/Al2O3 of 3/7 seems to be closely related to high dispersion and low aggregation of active metals due to their strong interaction with the MgAl2O4 support and the adjacent contact of Ni and CeO2 species. The CeO2 promoter also plays an important role to suppress particle aggregation by forming an appropriate interaction of NiO–CeO2 as well as Ni–MgAl2O4 with the concomitant enhancement of mobile oxygen content.  相似文献   

10.
Two types of CeO2-modified Ni/Al2O3 catalysts were prepared by a consecutive impregnation method with different sequences in the impregnation of Ni and CeO2, and their performance in autothermal reforming (ATR) of isooctane was investigated. Catalysts prepared by adding CeO2 prior to the addition of Ni, Ni/CeO2-Al2O3, produced larger amounts of hydrogen than those obtained using catalysts prepared by adding the two components in an opposite sequence, Ni-CeO2/Al2O3. The results of H2 chemisorption and temperature-programmed reduction revealed that added CeO2 increased the dispersion of the Ni species on Al2O3 and suppressed the formation of NiAl2O4 in the catalyst such that large amounts of Ni species were present as NiO, the active species for the ATR. The elemental and thermogravimetric analyses of deactivated catalysts indicated that Ni/CeO2-Al2O3, which showed a longer lifetime than Ni-CeO2/Al2O3, contained lesser amounts and different types of coke on the surface.  相似文献   

11.
Unsupported MoS2 particles, which were produced in the preparation of MoS2/Al2O3 using a sonochemical method, were successfully separated from the prepared sample catalyst by adding oleylamine as an agent for dispersing the unsupported particles. The fraction of the unsupported MoS2, which was estimated based on Mo balance, varied between 0.03 and 0.4, independent of the Mo loading levels investigated (6–54 wt% of Mo). The activity of the unsupported MoS2 for the hydrodesulfurization of dibenzothiophene was nearly the same as that of the Al2O3-supported MoS2, indicating that the activity of the prepared catalyst was not affected by the presence of the unsupported MoS2 particles.  相似文献   

12.
Ni(x)/Al2O3 (x=wt%) catalysts with Ni loadings of 5–25 wt% were prepared via a wet impregnation method on an γ-Al2O3 support and subsequently applied in the reductive amination of ethanol to ethylamines. Among the various catalysts prepared, Ni(10)/Al2O3 exhibited the highest metal dispersion and the smallest Ni particle size, resulting in the highest catalytic performance. To reveal the effects of reaction parameters, a reductive amination process was performed by varying the reaction temperature (T), weight hourly space velocity (WHSV), and NH3 and H2 partial pressures in the reactions. In addition, on/off experiments for NH3 and H2 were also carried out. In the absence of NH3 in the reactant stream, the ethanol conversion and selectivities towards the different ethylamine products were significantly reduced, while the selectivity to ethylene was dominant due to the dehydration of ethanol. In contrast, in the absence of H2, the selectivity to acetonitrile significantly increased due to dehydrogenation of the imine intermediate. Although a small amount of catalyst deactivation was observed in the conversion of ethanol up to 10 h on stream due to the formation of nickel nitride, the Ni(10)/Al2O3 catalyst exhibited stable catalytic performance over 90 h under the optimized reaction conditions (i.e., T=190 °C, WHSV=0.9 h?1, and EtOH/NH3/H2 molar ratio=1/1/6).  相似文献   

13.
A series of Mn-promoted 15 wt-% Ni/Al2O3 catalysts were prepared by an incipient wetness impregnation method. The effect of the Mn content on the activity of the Ni/Al2O3 catalysts for CO2 methanation and the comethanation of CO and CO2 in a fixed-bed reactor was investigated. The catalysts were characterized by N2 physisorption, hydrogen temperature-programmed reduction and desorption, carbon dioxide temperature-programmed desorption, X-ray diffraction and highresolution transmission electron microscopy. The presence of Mn increased the number of CO2 adsorption sites and inhibited Ni particle agglomeration due to improved Ni dispersion and weakened interactions between the nickel species and the support. The Mn-promoted 15 wt-% Ni/Al2O3 catalysts had improved CO2 methanation activity especially at low temperatures (250 to 400 °C). The Mn content was varied from 0.86% to 2.54% and the best CO2 conversion was achieved with the 1.71Mn-Ni/Al2O3 catalyst. The co-methanation tests on the 1.71Mn-Ni/Al2O3 catalyst indicated that adding Mn markedly enhanced the CO2 methanation activity especially at low temperatures but it had little influence on the CO methanation performance. CO2 methanation was more sensitive to the reaction temperature and the space velocity than the CO methanation in the co-methanation process.
  相似文献   

14.
Catalytic steam reforming of bio-oil was investigated in a fixed bed tubular reactor for production of hydrogen. Two series of nickel/alumina (Ni/Al2O3) supported catalysts promoted with ruthenium (Ru) and magnesium (Mg) were prepared. Each catalyst of the first series (Ru–Ni/Al2O3) was prepared by co-impregnation of nickel and ruthenium on alumina. They were examined to investigate the effect of adding ruthenium on the performance of the catalysts for hydrogen production. The effect of the temperature, the most effective parameter in the steam reforming of bio-oil, on the activity of the catalysts was also investigated. Each catalyst of the second series (Ni–MgO/Al2O3) was prepared by consecutive impregnation using various preparation procedures. They were tested to determine the effect of adding magnesium as well as the effect of the preparation procedure on the outlet gas concentrations. It was shown that in both series, the catalysts were more efficient in hydrogen production as well as carbon conversion than Ni/Al2O3 catalysts. The highest hydrogen yield was 85% which was achieved over Ru–Ni/Al2O3 at 950 °C. It was also found that the effect of adding a small amount of ruthenium was superior to that of nickel on the yield of hydrogen when the nickel content was equal to or greater than 10.7%.  相似文献   

15.
A series of Zr-doped ordered mesoporous Al2O3 with various Zr contents were synthesized by evaporation-induced self-assembly strategy and the Ni-based catalysts supported on these Al2O3 materials were prepared by impregnation method. These catalysts with large specific surface area, big pore volume, uniform pore size possess excellent catalytic performance for the low-temperature carbon dioxide reforming of methane. The activities of these catalysts were tested in carbon dioxide reforming of methane reaction with temperature increasing from 500 to 650?°C and the stabilities of these catalysts were evaluated for long time reaction at 650?°C. It was found that when Zr/(Zr?+?Al) molar ratio?=?0.5%, the Ni/0.5ZrO2–Al2O3 catalyst showed the highest activity, and exhibited superior stabilization compared to the Ni-based catalyst supported on traditional ordered mesoporous Al2O3. The “confinement effect” from mesoporous channels of alumina matrix is helpful to stabilize the Ni nanoparticles. As a promoter, Zr could stabilize the ordered mesoporous framework by reacting with Al2O3 to form ZrO2–Al2O3 solid solution. Since ZrO2 enhances the dissociation of carbon dioxide, more oxygen intermediates are given to remove the carbon formed during the reaction.  相似文献   

16.
Mesoporous Ni-Al2O3 (XNiAl) catalysts with different Ni/Al atomic ratio (X) were prepared by a co-precipitation method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of Ni/Al atomic ratio of mesoporous XNiAl catalysts on their physicochemical properties and catalytic activity for steam reforming of LNG was investigated. Physical properties of XNiAl catalysts did not show a consistent trend with respect to Ni/Al atomic ratio, while chemical properties of XNiAl catalysts strongly influenced by Ni/Al atomic ratio. Nickel species were highly dispersed on the surface of XNiAl catalysts through the formation of nickel aluminate phase or solid solution of nickel oxide and nickel aluminate phase. In the steam reforming of LNG, both LNG conversion and hydrogen composition in dry gas showed volcano-shaped curves with respect to Ni/Al atomic ratio. Nickel surface area of XNiAl catalysts was well correlated with LNG conversion and hydrogen composition over the catalysts. Among the catalysts tested, 0.8NiAl (Ni/Al = 0.8) catalyst with the highest nickel surface area showed the best catalytic performance.  相似文献   

17.
CO impedes the low temperature (<170 °C) oxidation of C3H6 on supported Pt. Supported Au catalysts are very effective in the removal of CO by oxidation, although it has little propene oxidation activity under these conditions. Addition of Au/TiO2 to Pt/Al2O3 either as a physical mixture or as a pre-catalyst removes the CO and lowers the light-off temperature (T 50) for C3H6 oxidation compared with Pt catalyst alone by ~54 °C in a feed of 1% CO, 400 ppm C3H6, 14% O2, 2% H2O.  相似文献   

18.
A series of V2O5-TiO2 aerogel catalysts were prepared by the sol-gel method with subsequent supercritical drying with CO2. The main variables in the sol-gel method were the amounts of V2O5 and when the vanadium precursor was introduced. V2O5-TiO2 xerogel and V2O5/TiO2 (P-25) were also prepared for comparison. The V2O5-TiO2 aerogel catalysts showed much higher surface areas and total pore volumes than V2O5-TiO2 xerogel and impregnated V2O5/TiO2 (P-25) catalysts. The catalysts were characterized by N2 physisorption, X-ray diffraction (XRD), FT-Raman spectroscopy, temperature-programmed reduction with H2 (H2-TPR), and temperature-programmed desorption of ammonia (NH3-TPD). The selective catalytic reduction of NOx with ammonia in the presence of excess O2 was studied over these catalysts. Among various V2O5-TiO2 catalysts, V2O5 supported on aerogel TiO2 showed a wide temperature window exhibiting high NOx conversions. This superior catalytic activity is closely related to the large amounts of strong acidic sites as well as the surface vanadium species with characteristics such as easy reducibility and monomeric and polymeric vanadia surface species. This work was presented at the 7 th Korea-China Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.  相似文献   

19.
This work investigates the improvement of Ni/Al2O3 catalyst stability by ZrO2 addition for H2 gas production from CH4/CO2 reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO2 loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH4:CO2 ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al2O3 was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO2, as it enhances dissociation of CO2 forming oxygen intermediates near the contact between ZrO2 and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO2–Al2O3 composite and the plugging of Al2O3 pore by ZrO2. The 15% Ni/10% ZrO2/Al2O3 co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.  相似文献   

20.
Nickel doped manganese oxide supported on titania materials were investigated for the low-temperature NH3-SCR. For this purpose, a series of Ni modified Mn/TiO2 catalysts were prepared and evaluated for the low-temperature SCR of NO with ammonia in the presence of excess oxygen. The catalytic performance of these materials was compared with respect to the nickel weight percentage in order to examine the correlation between physicochemical characteristics and reactivity of optimized materials. It was found that the 5% Mn–2% Ni/TiO2 catalyst showed the highest activity and yielded 100% NO conversion at 200 °C. XRD results reveal highly dispersed manganese–nickel species on TiO2 support for the Mn–Ni/TiO2 catalysts. Our TPR data results suggested an increase in reducibility of manganese species in Mn–Ni/TiO2 catalysts. The absence of the high-temperature (736 K) peak indicates that the dominant phase is MnO2. This increase of reducibility and dominant MnO2 phase seems to be the reason for the enhanced activity and time on stream patterns of nickel-promoted titania-supported manganese catalysts. BET results illustrate that the high NO conversion is strongly dependant on the specific surface area and pore volume of this catalyst. All the physicochemical techniques we used suggested that the composition of manganese and nickel oxides on the support surface is playing an important role for the enhancement of NO conversion and the prominent time on stream stability.  相似文献   

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