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1.
A mesoporous Ni–Al2O3–ZrO2 aerogel (Ni–AZ) catalyst was prepared by a single-step epoxide-driven sol–gel method and a subsequent supercritical CO2 drying method. For comparison, a mesoporous Al2O3–ZrO2 aerogel (AZ) support was prepared by a single-step epoxide-driven sol–gel method, and subsequently, a mesoporous Ni/Al2O3–ZrO2 aerogel (Ni/AZ) catalyst was prepared by an incipient wetness impregnation method. The effect of preparation method on the physicochemical properties and catalytic activities of Ni–AZ and Ni/AZ catalysts was investigated. Although both catalysts retained a mesoporous structure, Ni/AZ catalyst showed lower surface area than Ni–AZ catalyst. From TPR, XRD, and H2–TPD results, it was revealed that Ni–AZ catalyst retained higher reducibility and higher nickel dispersion than Ni/AZ catalyst. In the hydrogen production by steam reforming of ethanol, both catalysts showed a stable catalytic performance with complete conversion of ethanol. However, Ni–AZ catalyst showed higher hydrogen yield than Ni/AZ catalyst. Superior textural properties, high reducibility, and high nickel surface area of Ni–AZ catalyst were responsible for its enhanced catalytic performance in the steam reforming of ethanol.  相似文献   

2.
A type of Yb2O3 doped Ni–ZrO2 catalyst for ethanol steam reforming was developed, and displayed excellent catalyzing performance for the selective formation of H2 and CO2. Over a Ni1.25Zr1Yb0.8 catalyst, STY(H2) can maintain stable at the level of 0.396 mol h−1 g−1 (data taken 120 h after the reaction started) under the reaction conditions of 0.5 MPa and 723 K, which was 1.6 times that (0.247 mol h−1 g−1) of the Yb-free counterpart Ni1.25Zr1. Characterization of the catalyst revealed that dissolution of an appropriate amount of Yb3+ ions in the zirconia host resulted in the formation of the Zr–Yb composite oxide with cubic-ZrO2 structure, c-(Zr–Yb)Oz, which inhibited effectively the transformation of c-ZrO2 to thermodynamically more stable m-ZrO2, thus avoiding sintering of the (Zr–Yb)Oz composite. It was demonstrated that the doping of Yb2O3 to Ni–ZrO2 changed also the valence states or the micro-environments of the Ni-species at the quasi-active surface of the tested catalyst, which was conducive to inhibiting agglomeration of the Nix0–Nin+ species active catalytically, with resulting in maintaining the high metallic nickel dispersion and inhibiting coking. The aforementioned two factors both contributed to improving the activity and operating stability as well as heat-resistant quality of the catalyst.  相似文献   

3.
The surfactant-assisted Ni–Al2O3 catalysts are prepared by the homogeneous precipitation method with a surfactant/Al molar ratio ranging from 0.0 to 2.0. It has been investigated the effects of the surfactant on the physicochemical properties and the catalytic activities of the Ni–Al2O3 catalysts. The BET surface area of the catalysts decreases with increasing the surfactant content. The pore volume and pore size of the catalysts increase with increasing the surfactant content. XRD results indicate that all of the catalysts exhibit strong diffraction peaks corresponding to NiO and weak peaks corresponding to NiAl2O4. In the TPR results, the reduction peaks which indicates that the Ni particles strongly interacted with the support are present at between 668 and 688 °C. The activities of the prepared catalysts for methane steam reforming increase with increasing surfactant content in fresh and poisoned state due to an increase of pore volume and pore size.  相似文献   

4.
A series of ZnO–Al2O3 catalysts with various ZnO/(ZnO + Al2O3) molar ratios have been developed for hydrogen production by dimethyl ether (DME) steam reforming within microchannel reactor. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction and temperature programmed desorption of NH3. It was found that the catalytic activity was strongly dependent on the catalyst composition. The overall DME reforming rate was maximized over the catalyst with ZnO/(ZnO + Al2O3) molar ratio of 0.4, and the highest H2 space time yield was 315 mol h−1·kgcat−1 at 460 °C. A bi-functional mechanism involving catalytic active site coupling has been proposed to account for the phenomena observed. An optimized bi-functional DME reforming catalyst should accommodate the acid sites and methanol steam reforming sites with a proper balance to promote DME steam reforming, whereas all undesired reactions should be impeded without sacrificing activity. This work suggests that an appropriate catalyst composition is mandatory for preparing good-performance and inexpensive ZnO–Al2O3 catalysts for the sustainable conversion of DME into H2-rich reformate.  相似文献   

5.
Ni catalyst supported on MgO–Al2O3 (Ni/MgO–Al2O3) prepared from hydrotalcite, and Ni–Mg–O catalyst are studied in regard to their activity in the CO2 reforming of methane at high temperatures in order to develop a catalytically activated foam receiver–absorber for use in solar reforming. First, the activity of their powder catalysts is examined. Ni/MgO–Al2O3 powder catalyst exhibits a remarkable degree of high activity and thermal stability as compared with Ni–Mg–O powder catalyst. Secondly, a new type of catalytically activated ceramic foam absorber – Ni/MgO–Al2O3/SiC – and Ni–Mg–O catalyzed SiC foam absorber are prepared and their activity is evaluated using a laboratory-scale receiver–reactor with a transparent quartz window and a sun-simulator. The present Ni-based catalytic absorbers are more cost effective than conventional Rh/γ-Al2O3 catalyzed alumina and SiC foam absorbers and the alternative Ru/γ-Al2O3 catalyzed SiC foam absorbers. Ni/MgO–Al2O3 catalyzed SiC foam absorber, in particular, exhibits superior reforming performance that provides results comparable to that of Rh/γ-Al2O3 catalyzed alumina foam absorber under a high flux condition or at high temperatures above 1000 °C. Ni/MgO–Al2O3 catalyzed SiC foam absorber will be desirable for use in solar receiver–reactor systems to convert concentrated high solar fluxes to chemical fuels via endothermic natural-gas reforming at high temperatures.  相似文献   

6.
Pristine Ni/γ–Al2O3 and CeO2–Ni/γ–Al2O3 catalysts were prepared by co-impregnation technique for dry reforming of propane. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) were used to examine the structure and morphology of the catalysts before and after the reforming reactions. The excellent interaction between catalyst active phases was observed in both CeO2–Ni/γ–Al2O3 and Ni/γ–Al2O3 stabilized with polyethelene glycol (Ni/γ–Al2O3–PEG). Towards C3H8 and CO2 conversion, the CeO2–Ni/γ–Al2O3 and Ni/γ–Al2O3–PEG showed improved catalytic activity when compared to the pristine Ni/γ–Al2O3 catalyst. Interestingly, high H2 concentration was achieved with the CeO2–Ni/γ–Al2O3 and high CO concentration with the Ni/γ–Al2O3–PEG, which is due to the nanoconfinement of nickel particles within the support and favorable metal-support interaction as a result of plasma reduction. The CeO2–Ni/γ–Al2O3 catalyst exhibited better stability for anti-sintering and coke resistance, thus exhibiting high reactivity and durability in the dry reforming.  相似文献   

7.
In this study, methane and methanol steam reforming reactions over commercial Ni/Al2O3, commercial Cu/ZnO/Al2O3 and prepared Ni–Cu/Al2O3 catalysts were investigated. Methane and methanol steam reforming reactions catalysts were characterized using various techniques. The results of characterization showed that Cu particles increase the active particle size of Ni (19.3 nm) in Ni–Cu/Al2O3 catalyst with respect to the commercial Ni/Al2O3 (17.9). On the other hand, Ni improves Cu dispersion in the same catalyst (1.74%) in comparison with commercial Cu/ZnO/Al2O3 (0.21%). A comprehensive comparison between these two fuels is established in terms of reaction conditions, fuel conversion, H2 selectivity, CO2 and CO selectivity. The prepared catalyst showed low selectivity for CO in both fuels and it was more selective to H2, with H2 selectivities of 99% in methane and 89% in methanol reforming reactions. A significant objective is to develop catalysts which can operate at lower temperatures and resist deactivation. Methanol steam reforming is carried out at a much lower temperature than methane steam reforming in prepared and commercial catalyst (275–325 °C). However, methane steam reforming can be carried out at a relatively low temperature on Ni–Cu catalyst (600–650 °C) and at higher temperature in commercial methane reforming catalyst (700–800 °C). Commercial Ni/Al2O3 catalyst resulted in high coke formation (28.3% loss in mass) compared to prepared Ni–Cu/Al2O3 (8.9%) and commercial Cu/ZnO/Al2O3 catalysts (3.5%).  相似文献   

8.
Ni (2.5 wt%) and Co (2.5 wt%) supported over ZrO2/Al2O3 were prepared by following a hydrolytic co-precipitation method. The synthesized catalysts were further promoted by Rh incorporation (0.01–1.00 wt%) and tested for their catalytic performance for dry CO2 reforming, combined steam–CO2 reforming and oxy–CO2 reforming of methane for production of syngas. The catalysts were characterized by using N2 physical adsorption, XRD, H2–TPR, SEM, CO2–TPD, NH3–TPD, TEM and TGA. The results revealed that ZrO2 phase was in crystalline form in the catalysts along with amorphous Al oxides. Ni and Co were confirmed to be in their respective spinel phases that were reducible to metallic form at 800 °C under H2. Ni and Co were well dispersed with their nano-crystalline nature. The catalyst with 0.2% loading of Rh showed superior performance in the studied reactions for reforming of methane. This catalyst also showed good coke resistance ability for dry CO2 reforming reaction with 3.8 wt% of carbon formation during the reaction as compared to 11.6 wt% carbon formation over the catalyst without Rh. The catalyst performance was stable throughout the reaction time for CH4 conversions, irrespective of carbon formation with slight decline (~1%) in CO2 conversion. For dry CO2 reforming reaction, this catalyst showed good conversion for both CH4 and CO2 (67.6% and 71.8% respectively) with a H2/CO ratio of 0.84, while for the Oxy-CO2 reforming reaction, the activity was superior with CH4 and CO2 conversions (73.7% and 83.8% respectively) and H2/CO ratio of 1.05.  相似文献   

9.
A 1:1 propane–butane mixture was used to study the effect of promoting 15 wt.% Ni/Al2O3 (15Ni) catalyst with small amounts of Mo (0.05, 0.1, 0.3, and 0.5 wt.%) for H2 production during LPG oxidative steam reforming. Stability tests at 450 °C showed that lower Mo loadings (0.1 and 0.05 wt.%) had higher conversions and H2 production rates than the non-promoted catalyst and a stable performance for the whole 18-h test period. TPO results showed that slightly more Ni sites were available for whisker formation over the Mo catalyst with 0.1 wt.% loading, the types of carbon resulting from cracking were the same on both promoted and non-promoted catalysts. Higher Mo loaded catalysts (0.3 and 0.5 wt.%) showed higher H2 yields than the non-promoted catalysts, but lower feed-fuel conversions. XRD revealed that the loss in activity was due to oxidation of active Ni species to inactive Ni and Ni–Mo.  相似文献   

10.
Catalysts with high nickel concentrations 75%Ni–12%Cu/Al2O3, 70%Ni–10%Cu–10%Fe/Al2O3 were prepared by mechanochemical activation and their catalytic properties were studied in methane decomposition. It was shown that modification of the 75%Ni–12%Cu/Al2O3 catalyst with iron made it possible to increase optimal operating temperatures to 700–750 °C while maintaining excellent catalyst stability. The formation of finely dispersed Ni–Cu–Fe alloy particles makes the catalysts stable and capable of operating at 700–750 °C in methane decomposition to hydrogen and carbon nanofibers. The yield of carbon nanofibers on the modified 70%Ni–10%Cu–10%Fe/Al2O3 catalyst at 700–750 °C was 150–160 g/g. The developed hydrogen production method is also efficient when natural gas is used as the feedstock. An installation with a rotating reactor was developed for production of hydrogen and carbon nanofibers from natural gas. It was shown that the 70%Ni–10%Cu–10%Fe/Al2O3 catalyst could operate in this installation for a prolonged period of time. The hydrogen concentration at the reactor outlet exceeded 70 mol%.  相似文献   

11.
Methane reforming in steam (SR), auto-thermal (ATR) and partial oxidation (POX) conditions over Ni/Ba–Ce0.9–Y0.1 catalyst was investigated in the temperature range 500–700 °C. Catalyst presents a satisfying activity in POX condition only. BCY carrier was not stable in the presence of CO2 and, irrespective of reaction conditions, it reacts with CO2 giving rise to the formation of BaCO3 and CeO2. The very low activity observed in SR conditions was due to the negative role exerted by water strongly absorbed on catalyst surface, limiting so the accessibility and reduction state of Ni active sites. In POX condition catalyst is active and satisfying H2 yield can be reached by operating at T = 700 °C. A significant reduction of coke formation was observed by operating in POX at 700 °C. On the contrary, in ATR condition at the same reaction temperature huge amount of filamentous coke was observed.  相似文献   

12.
The catalytic activity of Ni/CeO2–Al2O3 catalysts modified with noble metals (Pt, Ir, Pd and Ru) was investigated for the steam reform of ethanol and glycerol. The catalysts were characterized by the following techniques: Energy-dispersive X-ray, BET, X-ray diffraction, temperature-programmed reduction, UV–vis diffuse reflectance spectroscopy and X-ray absorption near edge structure (XANES). The results showed that the formation of inactive nickel aluminate was prevented by the presence of CeO2 dispersed on alumina. The promoting effect of noble metals included a decrease in the reduction temperatures of NiO species interacting with the support, due to the hydrogen spillover effect. It was seen that the addition of noble metal stabilized the Ni sites in the reduced state along the reforming reaction, increasing the ethanol and glycerol conversions and decreasing the coke formation. The higher catalytic performance for the ethanol steam reforming at 600 °C and glycerol steam reforming was obtained for the NiPd and NiPt catalysts, respectively, which presented an effluent gaseous mixture with the highest H2 yield with reasonably low amounts of CO.  相似文献   

13.
In order to syngas formation, combined steam and carbon dioxide reforming of methane (CSCRM) used in the presence of Ni–Pd/Al2O3 catalysts, which were synthesized by the sol-gel method. Al2O3 supported Ni–Pd catalyst exhibited the appropriate surface area of 176.2 m2/g and high dispersion of NiO phase with an average crystallite size of 11 nm, which was detected on catalyst surface utilizing transmission electron microscopy (TEM). The influence of three independent operating parameters including reaction temperature in the range of 500–1000 °C; (CO2 + H2O)/CH4 ratio, in the range of 1–3 and CO2/H2O ratio; in the range of 1–3, were investigated on the responses (i.e., CH4 conversion, H2 yield, CO yield, amount of coke formation on the catalyst surface and H2/CO ratio) in CSCRM by using response surface methodology–central composite design (RSM-CCD) method. The obtained results from ANOVA and the proposed quadratic models could fine forecast the responses. It was seen that the total methane conversion and CO yield was almost accessible at temperatures higher than 850 °C. Moreover, the CO2/H2O ratio exhibited no significant effect on the CH4 conversion, H2 yield and CO yield of Ni–Pd/Al2O3 catalysts in CSCRM reaction. However, the high CO2/H2O ratio in inlet feed led to the syngas formation with a low H2/CO ratio. The results revealed that lower CO2/H2O ratio and higher temperature as well as higher (CO2 + H2O)/CH4 ratio help to decrease the coke formation.  相似文献   

14.
A series of mesoporous Ni–Al2O3–ZrO2 xerogel (denoted as X-NAZ) catalysts were prepared by a P123-assisted epoxide-driven sol–gel method under different P123 concentration (X, mM), and they were applied to the hydrogen production by steam reforming of ethanol. The effect of P123 concentration on the physicochemical properties and catalytic activities of X-NAZ catalysts was investigated. All the catalysts retained a mesoporous structure. Pore volume of the catalysts increased with increasing P123 concentration. Ni surface area and ethanol adsorption capacity of X-NAZ catalysts exhibited volcano-shaped trends with respect to P123 concentration. The trend of hydrogen yield was well matched with the trend of Ni surface area and ethanol adsorption capacity. Thus, Ni surface area and ethanol adsorption capacity of the catalysts served as important factors determining the catalytic performance. Among the catalysts tested, 12-NAZ catalyst with the highest Ni surface area and the largest ethanol adsorption capacity showed the best catalytic performance in the steam reforming of ethanol. In conclusion, an optimal P123 concentration was required for maximum production of hydrogen in the steam reforming of ethanol over X-NAZ catalysts.  相似文献   

15.
Oxidative steam reforming of ethanol at low oxygen to ethanol ratios was investigated over nickel catalysts on Al2O3 supports that were either unpromoted or promoted with CeO2, ZrO2 and CeO2–ZrO2. The promoted catalysts showed greater activity and a higher hydrogen yield than the unpromoted catalyst. The characterization of the Ni-based catalysts promoted with CeO2 and/or ZrO2 showed that the variations induced in the Al2O3 by the addition of CeO2 and/or ZrO2 alter the catalyst's properties by enhancing Ni dispersion and reducing Ni particle size. The promoters, especially CeO2–ZrO2, improved catalytic activity by increasing the H2 yield and the CO2/CO and the H2/CO values while decreasing coke formation. This results from the addition of ZrO2 into CeO2. This promoter highlights the advantages of oxygen storage capacity and of mobile oxygen vacancies that increase the number of surface oxygen species. The addition of oxygen facilitates the reaction by regenerating the surface oxygenation of the promoters and by oxidizing surface carbon species and carbon-containing products.  相似文献   

16.
Bimetallic 5%Ni–10%Co/Al2O3 catalyst was synthesized using impregnation method and evaluated for methane dry reforming reaction at different reaction temperatures. NiO, Co3O4 and spinal metal aluminates, namely, CoAl2O4 and NiAl2O4 phases were formed on γ-Al2O3 support surface during calcination process. 5%Ni–10%Co/Al2O3 catalyst exhibited reasonable surface area of 86.93 m2 g?1 with small crystallite dimension of less than 10 nm suggesting that both Co3O4 and NiO phases were finely dispersed on the surface of support in agreement with results from scanning electron microscopy (SEM) measurement. Temperature-programmed calcination measurement indicates the complete thermal decomposition and oxidation of metal precursors, viz. Ni(NO3)2 and Co(NO3)2 to metal oxides and metal aluminates at below 700 K. Both CH4 and CO2 conversions were stable over a period of 4 h on-stream and attained an optimum at about 67% and 71%, respectively at 973 K whilst H2 selectivity and yield were higher than 49%. The ratio of H2/CO was always less than unity for all runs indicating the presence of reverse water–gas shift reaction. The activation energy for CH4 and CO2 consumption was computed as 55.60 and 40.25 kJ mol?1, correspondingly. SEM micrograph of spent catalyst detected the formation of whisker-like carbon on catalyst surface whilst D and G bands characteristic for the appearance of amorphous and graphitic carbons in this order were observed on surface of used catalyst by Raman spectroscopy analysis. Additionally, the percentage of filamentous carbon was greater than that of graphitic carbon.  相似文献   

17.
The SiO2 and Ni–SiO2 were synthesized via the complex-decomposition method by using different organic acids as the complexing agent and fuel. The Ni-supported SiO2 from different sources was prepared by the incipient impregnation method. The Ni–SiO2 and Ni/SiO2 were comparatively evaluated for carbon dioxide reforming of methane (CDR) under severe conditions of CH4/CO2 = 1.0, T = 750 °C, GHSV = 53200 mL g−1 h−1, and P = 0.1–1.0 MPa. The materials were fully characterized by XRD, XPS, TEM, TG-DSC, H2-TPR, and N2 adsorption-desorption at −196 °C. It was found that the complexing agent and preparation method of the catalyst significantly affected its surface area, the size and dispersion of Ni, the reduction behavior, and the coking and sintering properties, which determine the activity and stability of the catalyst for CDR. As a result, a highly active and stable Ni–SiO2 for pressurized CDR was obtained by optimizing the complexing agent.  相似文献   

18.
This paper reports on the steam reforming, in continuous regime, of the aqueous fraction of bio-oil obtained by flash pyrolysis of lignocellulosic biomass (sawdust). The reaction system is provided with two steps in series: i) thermal step at 200 °C, for the pyrolytic lignin retention, and ii) reforming in-line of the treated bio-oil in a fluidized bed reactor, in the range 600–800 °C, with space-time between 0.10 and 0.45 gcatalyst h (gbio-oil)−1. The benefits of incorporating La2O3 to the Ni/α-Al2O3 catalyst on the kinetic behavior (bio-oil conversion, yield and selectivity of hydrogen) and deactivation were determined. The significant role of temperature in gasifying coke precursors was also analyzed. Complete conversion of bio-oil is achieved with the Ni/La2O3-αAl2O3 catalyst, at 700 °C and space-time of 0.22 gcatalyst h (gbio-oil)−1. The catalyst deactivation is low and the hydrogen yield and selectivity achieved are 96% and 70%, respectively.  相似文献   

19.
Ni/Al2O3 catalysts containing 5 wt% of Ni and modified by addition of CaO (0–5 wt%) were tested in ethanol steam reforming reaction in order to reduce the dehydration ethanol reaction, which produces ethylene that may polymerize and produce coke. The catalysts were prepared by impregnation (I) and co-precipitation (C) methods. All catalysts were investigated for ethanol steam reforming and the catalytic performance was compared in terms of additive addition. The catalysts 5Ni–5Ca/Al (I) and 5Ni–5Ca/Al (C) were less selective to ethylene production and therefore were characterized by the following techniques: energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), temperature programmed reduction (TPR), X-ray absorption near edge structure (XANES), specific surface area by the BET method, scanning electron microcopy (SEM) and isopropanol decomposition reaction. By comparing the catalysts, the 5Ni–5Ca/Al (I) catalyst presented the lowest acidity and carbon deposition, and also presented no deactivation in 24 h of catalytic test.  相似文献   

20.
Ni/SiO2 and Ni–Al2O3/SiO2 catalysts were prepared by incipient wetness impregnation using citrate and nitrate precursors and tested with a reaction of combination of CO2 reforming and partial oxidation of methane to produce syngas (H2/CO). The catalytic activity of Ni/SiO2 and Ni–Al2O3/SiO2 greatly depended on interaction between NiO and support. NiO strongly interacted with support formed small nickel particles (about 4 nm for NiSC which is abbreviation of Ni/SiO2 prepared with Nickel citrate precursor) after reduction. The small nickel particles over NiSC catalysts exhibited a good catalytic performance.  相似文献   

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