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1.
Plasma-enhanced catalytic biogas reforming for hydrogen-rich syngas production over a Ni–K/Al2O3 catalyst was investigated using a tabular dielectric barrier discharge non-thermal plasma reactor. To better understand the plasma catalysis synergy at elevated temperatures, we compared different reaction modes: plasma catalysis, plasma alone, and catalysis alone in a reaction temperature range of 160–400 °C. The combination of Ni–K/Al2O3 and plasma produced synergistic effects. Notably, the plasma-catalytic synergy was temperature-dependent and varied at different reaction temperatures. Using plasma catalysis, the maximum conversion of CH4 and CO2 (31.6% and 22.8%, respectively) was attained over Ni–K/Al2O3 at 160 °C, while increasing the reaction temperature to 340 °C noticeably enhanced the H2/CO ratio to 2.71. Moreover, compared to plasma-catalytic biogas reforming at 160 °C, increasing the reaction temperature to 400 °C suppressed biogas conversion with dramatically reduced coke formation on the Ni–K/Al2O3 surface from 6.81 wt% to 3.37 wt%.  相似文献   

2.
CO methanation has attracted much attention because it transforms CO in syngas and coke oven gas into CH4. Here, porous Al2O3 microspheres were successfully used as catalyst supports meanwhile the Mn was used as a promoter of Ni/Al2O3 catalysts. The as-obtained Ni/Al2O3 and Mn–Ni/Al2O3 samples display a micro-spherical morphology with a center diameter near 10 μm. Versus the Ni/Al2O3 catalyst, the 10Mn–Ni/Al2O3 catalyst exhibits a high specific surface area of 92.5 m2/g with an average pore size of 7.0 nm. The 10Mn–Ni/Al2O3 catalyst has the best performance along with can achieve a CO conversion of 100% and a CH4 selectivity of 90.7% at 300 °C. Even at 130 °C, the 10Mn–Ni/Al2O3 catalyst shows a CO conversion of 44.0% and a CH4 selectivity of 84.1%. The higher low-temperature catalytic activity may be since the catalyst surface contains more CO adsorption sites and thus has a stronger adsorption performance for CO. Density functional theory (DFT) calculations confirm that the Mn additive enhances the adsorption of CO, especially for the 10Mn–Ni/Al2O3 catalyst with the strongest adsorption energy.  相似文献   

3.
Thermocatalytic decomposition of methane is proposed to be an economical and green method to produce COx-free hydrogen and carbon nanomaterial. In present work, 60 wt% Ni/Al2O3 catalysts with different additives (Cu, Mn, Pd, Co, Zn, Fe, Mg) were prepared by co-impregnation method to investigate promotional effects of these metal additives on the activity and stability of 60 wt% Ni/Al2O3 and find out a really effective promoter for decomposition of methane. The catalyst was characterized by N2 adsorption/desorption, X-ray diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometer and hydrogen temperature programmed reduction. While metal additives (5 wt%) were added into 60 wt% Ni/Al2O3, the activity stability of 60 wt% Ni/Al2O3 was improved and the CH4 conversion of 60 wt% Ni/Al2O3 was also improved except Zn addition. Mn addition was found to improve the catalytic activity of 60 wt% Ni/Al2O3 significantly and the CH4 conversion of 5 wt% Mn-60 wt% Ni/Al2O3 was ∼80%. Cu addition was found to remarkably improve the catalytic stability of 60 wt% Ni/Al2O3 and the CH4 conversion of 5 wt% Cu-60 wt% Ni/Al2O3 decreased from 61% to 45% after 250 min of reaction time. Carbon nanomaterials formed in the thermocatalytic decomposition process were characterized by X-ray diffraction, scanning electron microscopy, thermal gravimetric analyzer and Raman spectroscopy. Carbon deposits consist of amorphous carbon and carbon nanofibers.  相似文献   

4.
Today, bi - reforming of methane is considered as an emerging replacement for the generation of high-grade synthesis gas (H2:CO = 2.0), and also as an encouraging renewable energy substitute for fossil fuel resources. For achieving high conversion levels of CH4, H2O, and CO2 in this process, appropriate operation variables such as pressure, temperature and molar feed constitution are prerequisites for the high yield of synthesis gas. One of the biggest stumbling blocks for the methane reforming reaction is the sudden deactivation of catalysts, which is attributed to the sintering and coke formation on active sites. Consequently, it is worthwhile to choose promising catalysts that demonstrate excellent stability, high activity and selectivity during the production of syngas. This review describes the characterisation and synthesis of various catalysts used in the bi-reforming process, such as Ni-based catalysts with MgO, MgO–Al2O3, ZrO2, CeO2, SiO2 as catalytic supports. In summary, the addition of a Ni/SBA-15 catalyst showed greater catalytic reactivity than nickel celites; however, both samples deactivated strongly on stream. Ce-promoted catalysts were more found to more favourable than Ni/MgAl2O4 catalyst alone in the bi-reforming reaction due to their inherent capability of removing amorphous coke from the catalyst surface. Also, Lanthanum promoted catalysts exhibited greater nickel dispersion than Ni/MgAl2O4 catalyst due to enhanced interaction between the metal and support. Furthermore, La2O3 addition was found to improve the selectivity, activity, sintering and coking resistance of Ni implanted within SiO2. Non-noble metal-based carbide catalysts were considered to be active and stable catalysts for bi-reforming reactions. Interestingly, a five-fold increase in the coking resistance of the nickel catalyst with Al2O3 support was observed with incorporation of Cr, La2O3 and Ba for a continuous reaction time of 140 h. Bi-reforming for 200 h with Ni-γAl2O3 catalyst promoted 98.3% conversion of CH4 and CO2 conversion of around 82.4%. Addition of MgO to the Ni catalyst formed stable MgAl2O4 spinel phase at high temperatures and was quite effective in preventing coke formation due to enhancement in the basicity on the surface of catalyst. Additionally, the distribution of perovskite oxides over 20 wt % silicon carbide-modified with aluminium oxide supports promoted catalytic activity. NdCOO3 catalysts were found to be promising candidates for longer bi-reforming operations.  相似文献   

5.
In this study, a simple solid-state synthesis method was employed for the preparation of the Ni–Co–Al2O3 catalysts with various Co loadings, and the prepared catalysts were used in CO2 methanation reaction. The results demonstrated that the incorporation of cobalt in nickel-based catalysts enhanced the activity of the catalyst. The results showed that the 15 wt%Ni-12.5 wt%Co–Al2O3 sample with a specific surface area of 129.96 m2/g possessed the highest catalytic performance in CO2 methanation (76.2% CO2 conversion and 96.39% CH4 selectivity at 400 °C) and this catalyst presented high stability over 10 h time-on-stream. Also, CO methanation was investigated and the results showed a complete CO conversion at 300 °C.  相似文献   

6.
CoNi/Al2O3 and MgCoNi/Al2O3 catalysts are investigated for hydrogen production from CO2 reforming of CH4 reaction at the gas hourly space velocity of 40,000 mL g−1 h−1. The MgO promoted CoNi/Al2O3 catalyst shows much higher conversions (97% for CO2 and 95% for CH4 at 850 °C) than the CoNi/Al2O3 catalyst. In addition, the stability is maintained for 200 h in CO2 reforming of CH4. The outstanding catalytic activity and stability of the MgO promoted CoNi/Al2O3 catalyst is mainly due to the basic nature of MgO, an intimate interaction between Ni and the support, and rapid decomposition/dissociation of CH4 and CO2, resulting in preventing coke formation in CO2 reforming of CH4.  相似文献   

7.
Biogas, a mixture of CO2/CH4, is reasonable for conversion to syngas (H2/CO) by dry methane reforming (DMR) reaction. The modification of Ni/SBA-16 with a lanthanum promoter using the co-impregnation technique is investigated in this study. The temperature of reaction (600–750 °C), La loading (3.85–11.56 wt%), and Ni loading (10–30 wt%) are the parameters that are varied for maximizing reaction conversions. The synthesized catalysts and SBA-16 supporting material were characterized by several methods before and after reaction. According to the analysis, the existence of La2O3 particles on the catalyst's surface has decreased the particle sizes, as well as enhanced their dispersion. Therefore, the maximum CH4 conversion of 94.21%, CO2 conversion of 90.12%, H2 yield of 90.53%, and H2/CO molar ratio of 2.03 are achieved using 20Ni-5.78La/SBA16 at 700 °C. Besides, this catalyst showed lower deposited coke and higher stability compared with other synthesized catalysts.  相似文献   

8.
Ni, Co and Ni–Co bimetallic catalysts of different ratios were synthesized by the Incipient Wetness Impregnation Method (IWI) over Magnesium Aluminate support, keeping the total metal loading 15 wt.%, characterized and tested for the reforming of methane with carbon dioxide at 873 K and 1 atm pressure. Magnesium Aluminate supported catalysts were also compared with Al2O3 supported Ni catalysts with similar metal loading. The results obtained revealed that MgAl2O4 exhibited excellent thermal stability as compared to Al2O3 as support at higher temperatures. Ni–Co catalyst, with an explicit Ni:Co (3:1) ratio for the 75Ni25Co/MgAl2O4 provided the highest CH4 conversion and was about 1.82 times that of the 100Ni/MgAl2O4; CO2 conversion also followed similar trends. Co-existence of Ni and Co with synergic effect in an explicit Ni:Co (3:1) ratio reduced the reduction temperature and increased the amount of metal in 75Ni25Co/MgAl2O4. CH4 and CO2 conversions, TOFDRM, H2: CO ratios and catalyst deactivations were related to the concentrations of the Ni–Co and particularly an explicit ratio of 3:1 for the Ni:Co in 75Ni25Co/MgAl2O4 catalyst provided the best initial & final conversions, TOFDRM and H2:CO ratio. Detail carbon analysis suggested that the type of coke deposited on 75Ni25Co/MgAl2O4 after the DRM reaction is of the same nature and are originating from the CH4 cracking reaction and are of reactive type.  相似文献   

9.
A series of La2O3–NiO–Al2O3 catalysts promoted by different loading of lanthanum were prepared via the hydrolysis-deposition method to improve the catalytic performance of nickel-based catalyst for CO2–CH4 reforming. The catalysts were characterized by N2 adsorption - desorption, XRD, H2-TPR, TG-DTG, TEM, Raman and TPH techniques. Results showed that the precursor of active component was mainly in the form of NiAl2O4 spinel, which almost disappeared after reduction process from XRD characterization, suggesting well reduction performance. The catalyst with La loading of 0.95 wt% (La–Ni-1) presented a small average Ni grain size of 7.71 nm and exhibited well catalytic performance at 800 °C, with CH4 conversion of 94.37%, CO2 conversion of 97.15%, H2 selectivity of 75.01% and H2/CO ratio of 0.92. The Ni grain size of La–Ni-1 increased only 5.84% to 8.16 nm after performance test, which was lower than that of others and indicated a well structure stability. Additionally, the strong carbon diffraction peak over La–Ni-0.5 and La–Ni-2 catalysts suggested the presence of crystalline carbon species accumulated on the catalysts, while there was no carbon peak over La–Ni-1 sample. A 150 h stability test for La–Ni-1 demonstrated that the conversion of CH4 was around 95%, higher than that of La–Ni-0 (without lanthanum addition) and La–Ni-4 (with La content of 3.82 wt%). The carbon deposition rate of La–Ni-1 was only 1.63 mg/(gcat·h), lower than that of La–Ni-4 (2.20 mg/(gcat·h)), showing both high activity and well stability. Therefore, the “confinement effect” of La2O3 to Ni crystalline grain would inhibit the sintering of active component, prevent the carbon deposition, and improve the catalytic reforming performance.  相似文献   

10.
Ce-promoted Ni/Al2O3 catalysts with Ce contents of 0, 5, 10, 15, and 20 wt% were investigated for CO2 methanation. Ni/15Ce/Al2O3 showed good selectivity and catalytic performance in CO2 methanation and remained stable at 350 °C for 80 h with minor fluctuations. Interactions between Ni and the Ce/Al2O3 support was characterized using X-ray diffraction, temperature-programmed reduction of H2, temperature-programmed desorption of CO2, X-ray photoelectron spectroscopy, Raman spectroscopy, and thermogravimetric analysis. Addition of Ce did not increase the catalytic surface area, which can significantly enhance the heterogeneous catalytic activity. However, XPS analysis showed that the Ce on the Ni/Al2O3 catalyst changed the surface electron states of Ni, Ce, and O. Additionally, CO2 adsorption/desorption was confirmed to be related to the amount of Ce present on Ni/Al2O3 by TGA and CO2-TPD. The Ce addition thus played an important role in determining the CO2 adsorption, desorption, and conversion.  相似文献   

11.
The valorization of cow manure (CM), as bio-waste, under a CO2 atmosphere could be an attractive strategy for tackling the environmental problems related to waste management and CO2 emission and producing valuable syngas. For this purpose, highly loaded Ni–Al2O3 catalysts with alkaline-earth metals (Mg and Sr) were synthesized and applied to the gasification of CM under CO2. The lowest yields of bio-oil (16.98 wt %) and coke (0.34 wt %) and the highest yield of syngas (55.09 wt %) were obtained from the catalytic decomposition of hydrocarbons when Sr was incorporated into Ni/Al2O3 (SN-AO). The highest selectivity for H2 (34.23 vol %) and CO (37.16 vol %) were obtained applying SN-AO followed by Mg-promoted Ni/Al2O3 (MN-AO) and Ni/Al2O3 (N-AO) catalysts. With increasing gasification temperature from 750 °C to 850 °C, the syngas yield (from 55.09 to 70.17 wt %) and H2 concentration (from 34.23 to 38.03 vol %) increased considerably because of the endothermic gasification process. The yield and selectivity of syngas (H2 and CO) increased under CO2 compared to those obtained under N2, indicating the high potential of CO2 for the thermal decomposition and dehydrogenation of the volatile matter.  相似文献   

12.
Ethanol steam reforming (ESR) is one of the most promising reliable and recyclable technologies for hydrogen production. However, the development of robust, efficient Ni-based catalysts that minimize metal sintering and carbon deposition remains a key challenge. The influence of cobalt loading and ESR conditions on H2 selectivity and catalytic stability is the focus of this study. Ni–Co/Al2O3 catalysts with various Co percentages were prepared by the co-impregnation method and complementary characterization tests were performed. Among the catalysts tested, Ni–Co/Al2O3 (5 wt% Co) exhibited the smallest metal crystallite size, the highest surface area, and the best catalytic performance. Thereafter, the effects of temperature, LHSV and S:C molar ratio were studied. 100% ethanol conversion and maximum H2 selectivity (95.14%) were reached at 600 °C, 0.05 L/gcat.h and S:C molar ratio of 12:1. Furthermore, ethanol turnover frequency (TOF) was computed for each catalyst. TOF results showed that the Ni–Co interaction had an impact on the catalytic activity. Finally, Ni2CoAl was subjected to 50-h stability test and only 6.12 mgcarbon/gcat.h coke deposition was observed.  相似文献   

13.
In the present study, Ni-M-Tb/Al2O3 (M: Mg, Ca, Sr and Ba) nanostructured catalysts with different ratios of the alkali metals were synthesized by the ultrasonic-assisted one-pot method. The catalytic performance was investigated in terms of CO2 conversion, CH4 selectivity, and stability via the H2-TPR analysis. The structural properties were delineated using XRD, SEM, TEM and BET equation. The results showed that the 2Ni-5Mg-5Tb/Al2O3 catalyst with a maximum CO2 conversion of 75.37% and CH4 selectivity of 100%, at the operating temperature of 400 °C in the molar ratio of H2:CO2:3.5 for 100 h, had the best performance. This could benefit from the particular electronic structure of Tb in combination with Mg and Ni, reducing agglomeration, as demonstrated by the SEM and BET results. Based on the current findings, novel catalysts with high conversion efficiency of CO2 to CH4 might be achieved by tuning a decent combination of alkaline and rear earth elements as the promoters of Ni-based catalysts.  相似文献   

14.
In this paper, the effects of strong base (KOH) addition on the catalytic performances of Ni/Al2O3 catalysts in acetic acid steam reforming for hydrogen generation was investigated. The addition of KOH drastically changed the physiochemical property and catalytic performances of the nickel–based catalysts. KOH reacted with γ–Al2O3 during calcination, forming ɑ–Al2O3 with Al(OH)3 as a reaction intermediate, which led to reconstruction of the porous structure, merge of small pores, decreased specific area and sintering of nickel. Most importantly, the catalytic activity of nickel–based catalysts were significantly enhanced by the addition KOH, especially the ones with low nickel loading. There are almost no active of 1 wt% Ni/Al2O3 catalyst for steam reforming of acetic acid, while, with adding 5 wt % KOH, activity of the catalyst matched that of 20 wt% Ni/Al2O3. In–situ DRIFTS study showed the involvement of the reactive intermediates including CH3, CH2, CO, COO, COC, CC and absorbed CO2 in acetic acid steam reforming. The Ni/Al2O3 catalyst with low nickel loading had insufficient metallic nickel to gasify these reactive intermediates. The presence KOH effectively aided gasification of the reactive intermediates, and thus significantly promoted the catalytic activity. In addition, the KOH with varied loading significantly affect formation of catalytic coke and polymeric coke formed during the reforming reaction.  相似文献   

15.
Ni/xY2O3–Al2O3 (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al2O3 catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H2-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH4 conversion increased with elevating levels of Y2O3 from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY2O3–Al2O3 catalysts maintained high activity after 24 h on stream, while Ni/Al2O3 had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.  相似文献   

16.
Oxidative dry reforming of methane has been performed for 100 h on stream using Ni supported on MgAl2O4 spinel at different loadings at 500–700 °C, CO2/CH4 molar ratio of 0.76, and variable O2/CH4 molar ratio (0.12–0.47). Syngas with an H2/CO ratio of 1.5–2.1 has been produced by manipulating reforming feed composition and temperature. The developed oxidative dry reforming process allowed high CH4 conversion at all conditions, while CO2 conversion decreased significantly with the lowering of the reforming temperature and increasing O2 concentration. When considering both greenhouse gas conversions and H2/CO ratio enhancement, the optimal reforming condition should be assigned to 550 °C and O2/CH4 molar ratio of 0.47, which delivered syngas with H2/CO ratio of 1.5. Coke-free operation was also achieved, due to the combustion of surface carbon species by oxygen. The 3.4 wt% Ni/MgAl2O4 catalyst with a mean Ni nanoparticle diameter of 9.8 nm showed stable performance during oxidative dry reforming for 100 h on stream without deactivation by sintering or coke deposition. The superior activity and stability of MgAl2O4 supported Ni catalyst shown during reaction trials is consistent with characterization results from XRD, TPR, STEM, HR-STEM, XPS, and CHNS analysis.  相似文献   

17.
A green template-free method is proposed for the synthesis of mesoporous Ni–Cu/Al2O4 catalyst in sub-kilogram scale. In the convenient synthetic method, an intermediate is formed via electrostatic forces and hydrogen bonding interactions between the aluminate ions and the metal ions and/or metal hydroxides under suitable pH conditions. The desired Ni–Cu/Al2O4 composites, with Ni/Cu molar ratios of 10%, 20% and 30% of Cu at Cu/Al molar ratio of 10.0%, respectively, are then obtained from calcination. The nitrogen adsorption-desorption isotherms show that the Ni–Cu/Al2O4 composites have specific surface areas of 136–170 m2g-1. The Ni–Cu/Al2O4 products are used as catalyst materials in the methanol steam reforming (MSR) of hydrogen and are shown to have a high conversion efficiency (>99%), a low methane concentration, good stability, and a high hydrogen yield (H2/methanol molar ratio ≈ 3.0) at low reaction temperatures in the range of 200–300 °C. In addition, the coke formation on the catalyst surface is less than 1.0 wt% even after a reaction time of 30 h. Notably, the Ni–Cu/Al2O4 catalyst can be regenerated by calcination at 800 °C and retains a high methanol conversion efficiency of close to >99% when reused in MSR.  相似文献   

18.
《能源学会志》2020,93(6):2544-2549
Hydrogen-rich syngas was successfully produced from catalytic steam gasification of petroleum coke. This work studied the steam gasification of petroleum coke over KOH, K2CO3, KNO3, CaO, Fe2O3, K2CO3–CaO and K2CO3–Fe2O3 in a pressurized fixed bed. KOH and K2CO3 demonstrated good catalytic activity compared with other catalysts. The carbon conversion efficiency (CCE) increased from 14.7 wt% to 61.4 wt% and 87.9 wt% after adding 10 wt% K2CO3 and 10 wt% KOH, respectively, and H2 content increased from 60.9 vol% to 66.7 vol% and 64.2 vol%. The increase of gasification temperature and pressure resulted in the increase of CCE. However, raising temperature was beneficial to the increase of H2 and CO contents, while the elevated pressure was in favor of the formation of CH4. In addition, the K-catalytic steam gasification of petroleum coke accorded with the oxygen transfer and intermediate hybrid mechanism.  相似文献   

19.
The effect of CeO2 loading amount of Ru/CeO2/Al2O3 on CO2 methanation activity and CH4 selectivity was studied. The CO2 reaction rate was increased by adding CeO2 to Ru/Al2O3, and the order of CO2 reaction rate at 250 °C is Ru/30%CeO2/Al2O3 > Ru/60%CeO2/Al2O3 > Ru/CeO2 > Ru/Al2O3. With a decrease in CeO2 loading of Ru/CeO2/Al2O3 from 98% to 30%, partial reduction of CeO2 surface was promoted and the specific surface area was enlarged. Furthermore, it was observed using FTIR technique that intermediates of CO2 methanation, such as formate and carbonate species, reacted with H2 faster over Ru/30%CeO2/Al2O3 and Ru/CeO2 than over Ru/Al2O3. These could result in the high CO2 reaction rate over CeO2-containing catalysts. As for the selectivity to CH4, Ru/30%CeO2/Al2O3 exhibited high CH4 selectivity compared with Ru/CeO2, due to prompt CO conversion into CH4 over Ru/30%CeO2/Al2O3.  相似文献   

20.
Hydrogen is an ideal energy carrier and can play a very important role in the energy system. The present study investigated the enhancement of hydrogen production from catalytic dry reforming process. Two catalysts namely Ni/γ-Al2O3 and Co/γ-Al2O3 promoted with different amounts of strontium were used to explore selectivity and yield of hydrogen production. Spent and fresh catalysts were characterized using techniques such as BET, XRD, H2-TPR, CO2-TPD, TGA and O2-TPO. The catalyst activity and characterization results displayed stability improvement due to addition of Sr promoter. The least coke formations i.e. 3.8 wt% and 5.1 wt% were obtained using 0.75 wt% Sr doped in Ni/γ-Al2O3 and 0.5 wt% Sr doped in Co/γ-Al2O3 catalysts respectively. Time on stream tests of promoted catalysts for about six hours at 700 °C showed stable hydrogen selectivity. Moreover, the hydrogen selectivity was significantly improved by the addition of Sr in Ni and Co based catalysts. For instance the hydrogen selectivity increased from 45.9% to 47.8% for Ni/γ-Al2O3 and from 48% to 50.9% for Co/γ-Al2O3 catalyst by the addition of 0.75 wt% Sr in Ni/γ-Al2O3 and 0.5 wt% Sr in Co/γ-Al2O3 catalyst respectively.  相似文献   

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