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1.
A mesoporous nickel–alumina aerogel catalyst (NiAE-SS) was prepared by a single-step sol–gel method and a subsequent CO2 supercritical drying method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel catalyst supported on alumina aerogel (Ni/AE-IP) was also prepared by an impregnation method. The effect of preparation method of supported nickel catalysts on their physicochemical properties and catalytic performance in the steam reforming of LNG was investigated. NiAE-SS catalyst retained superior textural properties compared to Ni/AE-IP catalyst. Nickel species were finely dispersed on the surface of both Ni/AE-IP and NiAE-SS catalysts through the formation of surface nickel aluminate phase. Although both Ni/AE-IP and NiAE-SS catalysts exhibited a stable catalytic performance, NiAE-SS catalyst showed a better catalytic performance than Ni/AE-IP catalyst in terms of LNG conversion and hydrogen yield. High nickel surface area, high nickel dispersion, and well-developed mesoporosity of NiAE-SS catalyst played an important role in enhancing the catalytic performance in the steam reforming of LNG. Uniformly distributed metallic nickel particles in the NiAE-SS catalyst were also responsible for its high catalytic performance.  相似文献   

2.
Mesoporous alumina xerogel (A-SG) is prepared by a sol–gel method for use as a support for a nickel catalyst. The Ni/A-SG catalyst is then prepared by an impregnation method, and is applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of the mesoporous alumina xerogel support on the catalytic performance of Ni/A-SG catalyst is investigated. For the purpose of comparison, a nickel catalyst supported on commercial alumina (A-C) is also prepared by an impregnation method (Ni/A-C). Both the hydroxyl-rich surface and the electron-deficient sites of the A-SG support enhance the dispersion of the nickel species on the support during the calcination step. The formation of the surface nickel aluminate phase in the Ni/A-SG catalyst remarkably increases the reducibility and stability of the catalyst. Furthermore, the high-surface area and the well-developed mesoporosity of the Ni/A-SG catalyst enhance the gasification of surface hydrocarbons that are adsorbed in the reaction. In the steam reforming of LNG, the Ni/A-SG catalyst exhibits a better catalytic performance than the Ni/A-C catalyst in terms of LNG conversion and hydrogen production. Moreover, the Ni/A-SG catalyst shows strong resistance toward catalyst deactivation.  相似文献   

3.
A mesoporous alumina (A-NS) support was prepared by a non-ionic surfactant-templating method. A nickel catalyst supported on mesoporous alumina (Ni/A-NS) was then prepared by an impregnation method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel catalyst supported on commercial alumina (Ni/A-C) was also prepared by an impregnation method. Well-developed mesoporosity of A-NS support and strong metal-support interaction of Ni/A-NS catalyst greatly enhanced the nickel dispersion and nickel surface area through the formation of surface nickel aluminate. In the steam reforming of LNG, Ni/A-NS catalyst showed a better catalytic performance than Ni/A-C catalyst. High nickel surface area, high nickel dispersion, and well-developed mesoporosity of Ni/A-NS catalyst not only provided a large number of active nickel sites, but also suppressed the carbon deposition and nickel sintering during the reaction. Furthermore, Ni/A-NS catalyst exhibited a better catalytic performance than nickel catalyst supported on mesoporous alumina prepared by either an anionic surfactant-templating method or a cationic surfactant-templating method.  相似文献   

4.
An ordered mesoporous nickel–alumina catalyst (denoted as OMNA) was prepared by a single-step evaporation-induced self-assembly method, and it was applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel catalyst supported on ordered mesoporous alumina support (denoted as Ni/OMA) was also prepared by an impregnation method. Although both Ni/OMA and OMNA catalysts retained unidimensionally ordered mesoporous structure, textural properties of the catalysts were significantly affected by the preparation method. Nickel species were finely dispersed in the OMNA catalyst as a form of surface nickel aluminate with a high degree of nickel-saturation. On the other hand, both bulk nickel oxide and surface nickel aluminate phases were formed in the network of Ni/OMA catalyst. Nickel species in the OMNA catalyst exhibited not only high reducibility but also strong resistance toward sintering during the reduction process, compared to those in the Ni/OMA catalyst. Both Ni/OMA and OMNA catalysts showed a stable catalytic performance without catalyst deactivation during the steam reforming of LNG due to the confinement effect derived from well-developed ordered mesoporous structure in the catalysts. However, OMNA catalyst with small crystallite size of metallic nickel exhibited higher LNG conversion and hydrogen yield than Ni/OMA catalyst. Furthermore, OMNA catalyst was more active in the steam reforming of LNG than non-ordered mesoporous nickel–alumina catalysts prepared by common surfactant-templating methods using cationic, anionic, and non-ionic surfactants.  相似文献   

5.
A series of Ni–Ce–Al composite oxides with various Ni molar contents were synthesized via the refluxed co-precipitation method and used for natural gas reforming of CO2 (NGRC) for syngas production. The effect of Ni molar content, reaction temperature, feed gas ratio and gas hourly space velocity (GHSV) on the Ni–Ce–Al catalytic performance was investigated. The Ni10CeAl catalyst was selected to undergo 30 h stability test and the conversion of CH4 and CO2 decreased by 2.8% and 2.6%, respectively. The characterization of the reduced and used Ni10CeAl catalyst was performed using BET, H2-TPR, in-situ XRD, TEM, and TGA-DTG techniques. The in-situ XRD results revealed that Ce2O3, CeO2 and CeAlO3 coexisted in the Ni10CeAl catalyst after reduction at 850 °C for 2 h. The results of the TEM analysis revealed that the Ni particle size increased after the NGRC reaction, which mainly caused the catalyst deactivation.  相似文献   

6.
Two types of mesoporous γ-aluminas (denoted as A-A and A-S) are prepared by a hydrothermal method under different basic conditions using cationic surfactant (cetyltrimethylammonium bromide, CTAB) as a templating agent. A-A and A-S are synthesized in a medium of ammonia solution and sodium hydroxide solution, respectively. Ni/γ-Al2O3 catalysts (Ni/A-A and Ni/A-S) are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of a mesoporous γ-Al2O3 support on the catalytic performance of Ni/γ-Al2O3 is investigated. The identity of basic solution strongly affects the physical properties of the A-A and A-S supports. The high surface-area of the mesoporous γ-aluminas and the strong metal–support interaction of supported catalysts greatly enhance the dispersion of nickel species on the catalyst surface. The well-developed mesopores of the Ni/A-A and Ni/A-S catalysts prohibit the polymerization of carbon species on the catalyst surface during the reaction. In the steam reforming of LNG, both Ni/A-A and Ni/A-S catalysts give better catalytic performance than the nickel catalyst supported on commercial γ-Al2O3 (Ni/A-C). In addition, the Ni/A-A catalyst is superior to the Ni/A-S catalyst. The relatively strong metal–support interaction of Ni/A-A catalyst effectively suppresses the sintering of metallic nickel and the carbon deposition in the steam reforming of LNG. The large pores of the Ni/A-A catalyst also play an important role in enhancing internal mass transfer during the reaction.  相似文献   

7.
The goal of this study was to investigate Cr-free, Fe/Ni, metal oxide catalysts for the high temperature shift (HTS) reaction of a fuel processor using liquefied natural gas (LNG). As hexavalent chromium (Cr6+) in commercial HTS catalyst is a hazardous material, we selected Ni as a substitute for chromium in the Fe-based HTS catalyst and investigated the HTS activities of these Cr-free, metal oxide catalysts under the LNG reformate condition. Cr-free, Fe/Ni-based catalysts containing Ni instead of Cr were prepared by coprecipitation and their performance was evaluated under a gas mixture condition (56.7% H2, 10% CO, 26.7% H2O, and 6.7% CO2) that simulated the gas composition from a steam methane reformer (SMR, at H2O/CH4 ratio = 3 with 100% CH4 conversion). Under this condition, the Fe/Ni catalysts showed higher CO removal activities than Fe-only and Cr-containing catalysts, but the methanation was promoted when the Ni content in the catalyst exceeded 50 wt%. Brunner-Emmett-Teller (BET), X-ray diffraction (XRD), inductively coupled plasma (ICP) and X-ray photoelectron spectroscopy (XPS) analyses were performed to explain the HTS activity of the Fe/Ni catalysts based on the catalyst structure.  相似文献   

8.
Mesoporous alumina xerogel (AX) supports prepared by a sol–gel method were calcined at various temperatures. Ni/mesoporous alumina xerogel (Ni/AX) 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 of calcination temperature of AX supports on the catalytic performance of Ni/AX catalysts in the steam reforming of LNG was investigated. Physical and chemical properties of AX supports and Ni/AX catalysts were strongly influenced by the calcination temperature of AX supports. Crystalline structure of AX supports was transformed in the sequence of γ-alumina → (γ + θ)-alumina → θ-alumina → (θ + α)-alumina with increasing calcination temperature from 700 to 1000 °C. Nickel species were strongly bonded to the divalent vacancy of γ-alumina, (γ + θ)-alumina, and θ-alumina through the formation of 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 calcination temperature of AX supports. Among the catalysts tested, Ni/AX-900 (nickel catalyst supported on AX that had been calcined at 900 °C) showed the best catalytic performance. The smallest nickel crystalline size and the strongest nickel–alumina interaction were responsible for high catalytic performance of Ni/AX-900 catalyst in the steam reforming of LNG.  相似文献   

9.
In this study, a group of Ni‐Co/Mg‐Al catalysts was prepared for hydrogen production via supercritical water gasification of lignin. The effects of different supports and preparation methods were examined. All catalysts were evaluated under the operation conditions of 650 °C, 26 MPa, and water to biomass mass ratio of 5 in a batch reactor. The Cop.2.6Ni‐5.2Co/2.6Mg‐Al catalyst showed the best performance with highest gas yield (12.9 wt%) and hydrogen yield (2.36 mmol·g?1). The results from catalyst characterization suggest that the properties of this type of catalyst are dependent on multiple factors including support Mg‐Al molar ratio and preparation method, and better coke resistance of the catalyst could be obtained by the preparation method of coprecipitation. Therefore, coprecipitation method should be applied for the preparation of Ni‐Co/Mg‐Al catalysts for hydrogen production via supercritical water gasification of lignin. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

10.
In this work, the co-pyrolysis of pine sawdust and low-density polyethylene (LDPE) was performed in a two-stage fixed-bed reactor to achieve hydrogen-rich syngas and to investigate the effect of the parameters on gas yield and composition. Gas chromatography was used to confirm the content of the gas products. The pyrolysis was supported with Ni (in 5-25 wt%) loaded on activated carbon (AC). The maximum hydrogen concentration was 392.8 mmol g−1 sample, which was achieved by the use of the 10% Ni-AC catalyst. The influence of Ni loading on supporter was investigated by scanning electron microscope and transmission electron microscope techniques besides the thermogravity analysis. The increasing size of the Ni particles can be observed as a function of the Ni concentration on the catalyst. Carbon deposition was detected and the amorphous carbon seems more dominant than filamentous form. In addition, the effect of fluid residence time (water inlet and purge gas) on syngas yield was studied. Three different fluid residence times were investigated, and among them, the highest hydrogen yield was 392.8 mmol g−1sample at 1.57 minutes residence time. Furthermore, the catalyst lifetime was studied using 10 wt% of Ni containing AC, and the average hydrogen concentration was 196.0 mmol g−1 sample over 15 cycles.  相似文献   

11.
The wet H2-rich gas was used as reducing gas instead of the H2/N2 gas in the reduction step of the catalyst preparation. It is found that the selectivity for CO methanation over the catalysts 0.4Ni/ZrO2 so-obtained was decreased in comparison to the case of the H2/N2 gas used as reducing gas. Even though, the samples with the different feed atomic ratios of Ni/Zr prepared by the impregnation method and the co-precipitation method, respectively, were evaluated with the wet H2-rich gas both as reducing gas and as reactant gas. The catalysts Ni/ZrO2-CP prepared by the co-precipitation method exhibited a high catalytic activity for CO removal at a lowered reaction temperature with increasing the Ni loading. Over the catalyst 3.0Ni/ZrO2-CP, CO in the reactant gas could be removed to below 10 ppm at reaction temperatures of 220–260 °C with the selectivity higher than 50%. And the selectivity was kept at 100% during the 100 h test at 220 °C. The catalysts were characterized by XRD, XPS, XRF and the adsorption isotherm measurement. In addition, effect of water vapor in reactant gas was studied over the catalysts 0.4Ni/ZrO2 with the wet H2-rich gas and the dry H2-rich gas as reactant gas, respectively, in the case of the H2/N2 gas fixed as reducing gas. It is seen that presence of water vapor in the reactant gas retarded methanation reactions of CO and CO2 on the catalysts.  相似文献   

12.
The effect of regeneration conditions on the cyclic sorption-enhanced steam reforming of ethanol (SESRE) in a fixed-bed reactor was investigated. Columnar Ni–Ca catalysts were used in the cyclic SESRE experiments. The effects of different parameters, including temperature, purge direction, and purge gas on the regeneration process were discussed. The experimental results reveal that the regeneration temperature strongly affected not only the CO2 desorption rate but also the durability of the CaO sorbent. The stability of the CaO sorbent within the Ni–Ca catalyst was improved owing to the formation of Ca12Al14O33. Moreover, the type of purge gas (N2 or air) for regeneration had negligible effect on the CO2 capture performance of the Ni–Ca catalyst. For regeneration by air purging, coke decomposition over the Ni–Ca catalyst was accompanied by a slight decline in the activity of the Ni catalyst, which was attributed to the cyclic Ni redox.  相似文献   

13.
Dewatered sewage sludge was treated with NaOH additive and Ni catalyst in supercritical water in a high-pressure autoclave to examine the effects of separate and combined NaOH additive and Ni catalyst on hydrogen generation. The effects of Ni/NaOH ratio on hydrogen production were also investigated to identify possible catalytic mechanism and interactions. NaOH and Ni, separately or in combination, improved the hydrogen production and hydrogen gasification efficiency. The addition of NaOH additive not only promoted the water–gas shift reaction, but also favored H2 generation of Ni catalyst by capturing CO2. The hydrogen yield of combined catalysts with different Ni/NaOH ratios was higher than the theoretical sum of hydrogen yield from the mixture by 10–33%. The largest hydrogen yield, of 4.8 mol per kilogram of organic matter, which was almost five times as much as without catalyst, was achieved with the addition of 3.33 wt% Ni and 1.67 wt% NaOH. The combined NaOH additive and Ni catalyst also improved the gasification of several other dewatered sewage sludges, increasing the hydrogen yield by four to twelve times that seen without catalyst. Combined NaOH additive and Ni catalyst are effective in dewatered sewage sludge gasification at low temperature.  相似文献   

14.
For the production of bio-SNG (substitute natural gas) from syngas of biomass steam gasification, trace amounts of sulfur and tar compounds in raw syngas must be removed. In present work, biomass gasification and in-bed raw gas upgrading have been performed in a decoupled dual loop gasifier (DDLG), with aggregation-resistant nickel supported on calcined olivine (Ni/olivine) as the upgrading catalyst for simultaneous desulfurization and tar elimination of biogenous syngas. The effects of catalyst preparation, upgrading temperature and steam content of raw syngas on sulfur removal were investigated and the catalytic tar reforming at different temperatures was evaluated as well. It was found that 850 °C calcined Ni/olivine was efficient for both inorganic-sulfur (H2S) and organic-sulfur (thiophene) removal at 600–680 °C and the excellent desulfurization performance was maintained with wide range H2O content (27.0–40.7%). Meanwhile, tar was mostly eliminated and H2 content increased much in the same temperature range. The favorable results indicate that biomass gasification in DDLG with Ni/olivine as the upgrading bed material could be a promising approach to produce qualified biogenous syngas for bio-SNG production and other syngas-derived applications in electric power, heat or fuels.  相似文献   

15.
Hydrogen production from the pyrolysis-gasification of waste tyres has been investigated with a Ni/CeO2/Al2O3 catalyst using a two-stage fixed bed reaction system. The conditions of catalyst preparation such as Ni and CeO2 content and calcination temperature were investigated in relation to product yield and composition. The fresh and reacted catalysts were analysed using thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The results showed that there were small changes in the gas and hydrogen yield by adding 5 wt.% of CeO2 into the Ni/CeO2/Al2O3 catalyst. The gas yield related to the mass of waste tyre and the amount of reacted water were increased with the increase of CeO2 content from 5 to 15 wt.%. However, with the further increase of CeO2 content to 30 wt.%, the gas yield related to the mass of tyre and the amount of reacted water was reduced. Increasing the Ni content of the catalyst showed a positive influence on the gas yield and hydrogen production. The investigation of the calcination temperature of the Ni/CeO2/Al2O3 catalyst showed that the oil yield related to the mass of tyre and reacted water decreased from 28.4 to 23.4 wt.% for the catalyst calcined at 500 °C, and decreased from 24.2 to 17.7 wt.% for the catalyst calcined at 750 °C. When the Ni content of the catalyst was increased from 5 to 20 wt.%. there were only small changes in total gas and hydrogen production from the pyrolysis-gasification of waste tyre. Lower coke deposition on the reacted catalyst was obtained for the Ni/CeO2/Al2O3 catalyst prepared at the calcination temperature of 750 °C compared with the 500 °C calcination temperature.  相似文献   

16.
Mesoporous Ni–Al2O3 (XNiAE) aerogel catalysts with different Ni/Al atomic ratio (X) were prepared by a single-step sol-gel method and a subsequent CO2 supercritical drying method. The effect of Ni/Al atomic ratio of mesoporous XNiAE aerogel catalysts on their physicochemical properties and catalytic activity for steam reforming of liquefied natural gas (LNG) was investigated. Textural properties and chemical properties of XNiAE catalysts were strongly influenced by Ni/Al atomic ratio. Nickel species were highly dispersed on the surface of XNiAE catalysts through the formation of surface nickel aluminate phase. In the steam reforming of LNG, both LNG conversion and hydrogen yield showed volcano-shaped curves with respect to Ni/Al atomic ratio. Average nickel diameter of XNiAl catalysts was well correlated with LNG conversion and hydrogen yield over the catalysts. Among the catalysts tested, 0.35NiAE (Ni/Al = 0.35) catalyst with the smallest average nickel diameter showed the best catalytic performance. The highest surface area, the largest pore volume, the largest average pore size, and the highest reducibility of 0.35NiAE catalyst were also partly responsible for its superior catalytic performance.  相似文献   

17.
Hydrogen production from the gasification of lignin with Ni/MgO catalysts in supercritical water was conducted using stainless steel tube bomb reactor. Ni/MgO catalysts were prepared by impregnation method and were calcined at 773–1173 K in air for 8 h. The results of characterization for reduced Ni/MgO catalysts showed that Ni metal and NiO–MgO phase are formed after the reduction of calcined catalyst by H2H2. Furthermore, Ni metal surface area, which was calculated by CO chemical adsorption technique, decreased with increase in calcination temperatures. It was found that the carbon yield of gas products was increased with increase in Ni metal surface area except 10 wt% Ni/MgO (773 K) catalyst. Thus, it can be supposed that there is an optimal Ni particle size for the gasification of lignin in supercritical water. It should be noted that 10 wt% Ni/MgO (873 K) catalyst showed the best catalytic performance (carbon yield 30%) under reaction condition tested. It was concluded that Ni/MgO catalyst is a promising system for the gasification of lignin in supercritical water.  相似文献   

18.
Ni and Co supported on SiO2 and Al2O3 silica cloth thin layer catalysts have been investigated in the catalytic decomposition of natural gas (CDNG) reaction. The influence of carrier nature and reaction temperature was evaluated with the aim to individuate the key factors affecting coke formation. Both Ni and Co silica supported catalysts, due to the low metal support interaction (MSI), promotes the formation of carbon filament with particles at tip. On the contrary, in case alumina was used as support, metals strongly interact with surface thus depressing both the metal sintering and the detachment of particles from catalyst surface. In such cases, carbon grows on metal particle with a “base mechanism” while particles remain well anchored on the catalyst surface. This allowed to realize a cyclic dual-step process based on methane decomposition and catalyst oxygen regeneration without deactivation of catalyst. Technological considerations have led to conclude that the implement of a process based on decomposition and regeneration of catalyst by oxidation requires the development of a robust catalytic system characterized by both a strong MSI and a well defined particle size distribution. In particular, the catalyst should be able to operate at high temperature, necessary to reach high methane conversion values (> 90%), avoiding at the same time the formation of both the carbon filaments with metal at tip or the encapsulating carbon which drastically deactivate the catalyst.  相似文献   

19.
The catalysis of methane steam reforming (MSR) by pure Ni honeycombs with high cell density of 2300 cells per square inch (cpsi) was investigated to develop efficient and inexpensive catalysts for hydrogen production. The Ni honeycomb catalyst was assembled using 30-μm-thick Ni foils, and showed much higher activity than that of a Ni honeycomb catalyst with cell density of 700 cpsi at a steam-to-carbon ratio of 1.36 and a gas hourly space velocity of 6400 h?1 in a temperature range of 873–1173 K. Notably, the activity increased approximately proportional to the increasing geometric specific surface area of the honeycombs. The turnover rate of the Ni honeycomb catalyst was higher than that of supported Ni catalysts. The changes in chemical state of the Ni catalyst during hydrogen reduction and MSR reaction were analyzed by in situ X-ray absorption fine structure spectroscopy, which revealed that deactivation was mainly due to oxidation of the surface Ni atoms. These results demonstrated that the high-cell-density Ni honeycomb catalyst exhibits good performance for MSR reaction, and easy regeneration of the deactivated Ni honeycomb catalyst is possible only via hydrogen reduction.  相似文献   

20.
In this study, the nickel boron (Ni–B) catalyst was studied in the microwave environment for hydrogen production from the hydrolysis of a sodium borohydride solution to release H2. The catalytic activity of the Ni–B catalyst was measured by hydrogen production from the hydrolysis of sodium borohydride. The catalytic properties of the Ni–B catalyst in the microwave medium were examined by considering parameters such as NaOH concentration, NaBH4 concentration, catalyst amount, temperature, and microwave power. Thus, the results obtained from the experiments carried out with Ni–B catalyst both in non-microwave and microwave media were compared. In the experiments, under microwave irradiation, the best result was the release of hydrogen gas from the Ni–B catalyst by applying 100 W of microwave energy at 40 °C. Activation energy values were calculated using the reaction rate constants obtained at different temperatures in the nth order kinetic model and the Langmuir - Hinshelwood model.  相似文献   

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