Synthetic natural gas from CO hydrogenation over silicon carbide supported nickel catalysts

Silicon carbide supported nickel catalysts for CO methanation were prepared by impregnation method. The activity of the catalysts was tested in a fixed-bed reactor with a stream of H₂/CO = 3 without diluent gas. The results show that 15 wt.% Ni/SiC catalyst calcined at 550 °C exhibits excellent catalytic activity. As compared with 15 wt.% Ni/TiO₂ catalyst, the Ni/SiC catalyst shows higher activity and stability in the methanation reaction. The characterization results from X-ray diffraction and transmission electron microscopy suggest that no obvious catalyst sintering has occurred in the Ni/SiC catalyst due to the excellent thermal stability and high heat conductivity of SiC.     

Characterization of aerogel Ni/Al2O3 catalysts and investigation on their stability for CH4-CO2 reforming in a fluidized bed

The CH₄-CO₂ reforming was investigated in a fluidized bed reactor using nano-sized aerogel Ni/Al₂O₃ catalysts, which were prepared via a sol–gel method combined with a supercritical drying process. The catalysts were characterized with BET, XRD, H₂-TPR and H₂-TPD techniques. Compared with the impregnation catalyst, aerogel catalysts exhibited higher specific surface areas, lower bulk density, smaller Ni particle sizes, stronger metal-support interaction and higher Ni dispersion degrees. All tested aerogel catalysts showed better catalytic activities and stability than the impregnation catalyst. Their catalytic stability tested during 48 h reforming was dependent on their Ni loadings. Characterizations of spent catalysts indicated that only limited graphitic carbon formed on the aerogel catalyst, while massive graphitic carbon with filamentous morphology was observed for the impregnation catalyst, leading to significant catalytic activity degradation. An aerogel catalyst containing 10% Ni showed the best catalytic stability and the lowest rate of carbon deposition among the aerogel catalysts due to its small Ni particle size and strong metal-support interaction.     

Catalytic filamentous carbon as supports for nickel catalysts

Ni catalysts supported on catalytic filamentous carbon (CFC) were studied in the model reaction of methane decomposition at 525 °C. The supports (CFC) were synthesized by decomposition of methane over metal catalysts (Ni, Ni-Cu, Co and Fe-Co-alumina) at 500-675 °C. The yield of secondary carbon was shown to reach 224 g/g_Ni on the Ni/CFC (Ni-Cu, 625 °C) catalyst. The stability and activity of the Ni/CFC catalysts for deposition of the secondary carbon at 525 °C depend both on textural properties of the support and on the surface structure of the CFC filaments. It seems that highly porous carbon supports are more suitable for development of Ni/CFC catalyst for methane decomposition. The catalytic properties of the supported Ni/CFC systems may be accounted for by generation of weak dispersive interactions between specifically shaped Ni crystallites 30-70 nm in size and basal planes on the surface of the carbon filament.     

MCM-41 supported PdNi catalysts for dry reforming of methane

A series of bimetallic PdNi catalysts supported on mesoporous MCM-41 with different Ni content (Ni/Si ratio of 0.2–0.4) was synthesized. The effect of Pd addition to Ni-containing catalysts as well as the effect of the Ni content on the surface and catalytic properties of the catalysts was studied. The samples were characterized using various techniques, such as energy-dispersive X-ray spectroscopy, N₂ adsorption–desorption isotherms, X-ray diffraction, thermogravimetric and differential analyses, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy and temperature-programmed reduction. Reforming of methane with carbon dioxide was used as a test reaction. The results indicated that the addition of a small amount of Pd (0.5%) to Ni-containing catalysts leads to formation of small nano-sized, easy reducible NiO particles. Agglomeration of NiO as well as of metallic nickel phase over PdNi samples increased with increasing the Ni content. Formation of filamentous carbon over surface of spent monometallic Ni and bimetallic PdNi catalyst was observed. In spite of filamentous carbon deposition, the catalytic activity and stability of bimetallic PdNi catalysts are higher than those of monometallic Ni one. Within bimetallic system, the PdNi catalyst with Ni/Si ratio of 0.3 revealed the best performance and stability caused by presence of small nickel particles well dispersed on the catalyst surface.     

Production of synthesis gas by autothermal reforming of iso-octane and toluene over metal modified Ni-based catalyst

The reforming process of gasoline is an attractive technique for fuel processor or hydrogen station applications. We investigated catalytic autothermal reforming (ATR) of iso-octane and toluene over transition metal supported catalysts. The catalysts were prepared by an incipient wetness impregnation method and characterized by N₂ physisorption, XRD, and TEM techniques before and after the reaction. Many of the tested catalysts displayed reasonably good activity towards the reforming reactions of iso-octane. Especially, Ni/Fe/MgO/Al₂O₃ catalyst showed more activity than the other catalysts tested in this study including commercial HT catalyst. Ni/Fe/MgO/Al₂O₃ catalyst showed good stability for 700 h in the ATR of iso-octane. No major change was observed in catalytic activity in ATR of iso-octane or in the structure of catalyst. Since iso-octane, toluene are surrogates of gasoline, Ni/Fe/MgO/Al₂O₃ catalyst can be considered as ATR catalyst for gasoline fuel processor and hydrogen station systems.     

Investigation of alumina-supported Ni and Ni-Pd catalysts by partial oxidation and steam reforming of n-octane

Aseries of nickel and nickel-palladium supported upon alumina catalysts were prepared in order to obtain a suitable catalyst that could be used in the process of producing hydrogen by partial oxidation and steam reforming of n-octane. Hydrogen production by partial oxidation and steam reforming (POSR) of n-octane was investigated over alumina-supported Ni and Ni-Pd catalysts. The process occurred by a combination of exothermic partial oxidation and endothermic steam reforming of n-octane. It was found that Ni/Al₂O₃ catalyst activity was high at high temperatures and increased with the Ni loadings. Its activity, however, was not obviously increased when Ni loadings were over 5.0 wt%. Compared with nickel catalyst, the bimetallic catalyst of Ni-Pd/A1₂O₃ showed markedly increased activity and hydrogen selectivity at experimental conditions. The catalytic performance also became more stable when the palladium was added, which indicated that palladium plays an essential role in the catalytic action. The used catalysts of Ni-Pd/A1₂O₃ were regenerated three times by using air at space velocity of 2,000 h⁻¹ to obtain a long duration catalyst. Also, the typical catalyst was characterized by using SEM, BET, TG and ICP methods in detail.     

Hydrodeoxygenation of stearic acid using Mo modified Ni and Co/alumina catalysts: Effect of calcination temperature

Abstract

The calcination temperature (Cal-Temp) plays a vital role in the performance of supported metal catalysts. In this work, the alumina supported Ni, NiMo, Co, and CoMo catalysts were prepared at different Cal-Temp. The catalysts were characterized by various techniques to identify the catalytically active different surface species to correlate their role in the hydrodeoxygenation of stearic acid. With increasing Cal-Temp, the metal dispersion was increased for Ni, NiMo, and CoMo catalyst (up to 973 K) and decreased for Co catalyst. With increasing Cal-Temp, the catalytic activity was thus increased for Ni and NiMo catalyst and decreased for Co catalyst. The activity of CoMo catalyst was, however, enhanced with rising Cal-Temp up to 973 K and declined slightly after that. The optimum Cal-Temp for Ni, NiMo, Co, and CoMo catalyst was found to be 1023 K, 973 K, 773 K, and 973 K. The reaction followed the decarbonylation route over active metallic centers (Ni and Co) and the HDO route over oxophilic M²⁺?MoO₂ (M = Ni/Co) and reducible cobalt oxide species. The C₁₇ alkane was thus the principal product over Ni catalyst, whereas C₁₈ alkane was the primary product over CoMo and NiMo catalyst. In contrast, both C₁₇ and C₁₈ alkanes were significant over Co catalyst.     

Addition effect of ruthenium on nickel steam reforming catalysts

Several Ni-based catalysts supported on a mixture of MgO, La₂O₃, and Al₂O₃ were prepared. The catalytic performance in the steam reforming of m-cresol was evaluated. In the investigation of the effect of Ru loading added to the Ni-catalyst, it was found that the presence of Ru strongly enhances the catalytic performance of the Ni-based catalyst when increasing Ru loading up to 2 wt%. Effect of Ni loading to the Ru-based catalyst system was also investigated. It was found that the addition of nickel to the Ru-based catalyst up to 15 wt% enhanced significantly the catalytic activity of the catalyst. The lifetime of the Ru–Ni catalysts in the reforming of m-cresol was further tested at 750 °C. In agreement with general observations of the use of Ni monometallic catalyst, deactivation of the catalyst due to the carbon deposition reaction already occurred in the reforming of the oxygenated compound. On the other hand, a reasonable high resistant on the carbon deposition in the reforming of m-cresol was given by the 2 wt% Ru–15 wt% Ni catalyst system. An effort in improving the strength of the catalyst support with this catalyst system was also conducted, and the catalyst showed significant increase in the stability of the reforming of oxygenated aromatic compound.     

The role of nickel in pyridine hydrodenitrogenation over NiMo/Al2O3

Al₂O₃ supported Mo, Ni, and NiMo/Al₂O₃ catalysts with various Ni contents were prepared to investigate the role of Ni as a promoter in a NiMo bimetallic catalyst system. The hydrodenitrogenation (HDN) reaction of pyridine as a catalytic probe was conducted over these catalysts under the same reaction conditions and the catalysts were characterized using BET surface area measurement, infrared spectroscopy, temperature programmed reduction, DRS and ESR. According to the results of reaction experiments, the NiMo/Al₂O₃ catalyst showed higher activity than Mo/Al₂O₃ catalyst in the HDN reaction and particularly the one with atomic ratio [Ni/(Ni+Mo)]=0.3 showed the best activity for the HDN of pyridine. The findings of this study lead us to suggest that the enhancement in the HDN activity with nickel addition could be attributed to the improvement in the reducibility of molybdenum and the formation of Ni-Mo-O phase.     

Ni-Mo双金属催化剂的甲烷化性能与耐硫稳定性

采用沉淀-浸渍法合成一系列Ni-Mo基双金属催化剂,在固定床反应器中对其催化活性和耐硫性能进行评价,并辅以不同的表征手段阐释其作用机理。实验结果表明,以MCM-41分子筛为载体的催化剂活性和稳定性优于以NaY、γ-Al₂O₃和拟薄水铝石（PB）为载体的催化剂;反应前后催化剂的表征结果则说明Ni-Mo分子间适宜的相互作用是决定催化剂性能的关键。MCM-41载体催化剂中适宜的Ni-Mo分子间相互作用使得此催化剂中活性组分与载体间的相互作用适中,还原后的活性金属Ni能够均匀分散在载体表面,从而提高了催化剂的耐硫稳定性和抗积炭能力。不同Ni-Mo比同样会影响Ni-Mo分子间的相互作用,通过考察确定20Ni-10Mo/MCM-41的活性和稳定性最优。     

载体对Ni基催化剂催化蒽醌加氢活性的影响

研究了载体对Ni基催化剂用于蒽醌法制备H₂O₂加氢活性的影响,同时对比了骨架镍的催化活性,考察Ni负载量对催化剂活性的影响。结果表明,负载在SiO₂上的催化剂比负载在γ-Al₂O₃上的催化活性高,对于Ni/SiO₂催化剂,Ni负载质量分数28.57%～50%时,加氢活性较高,按单位质量纯Ni上H₂O₂产量计算,Ni/SiO₂优于骨架镍催化剂,Ni负载量过高时,加氢活性降低。2-乙基蒽醌在Ni/SiO₂催化剂上的加氢为结构敏感型反应,当Ni在SiO₂的分散度达到约18%时,催化活性较佳。     

Preparation of highly active nickel catalysts supported on mesoporous nanocrystalline γ-Al2O3 for CO2 methanation

In this study, a group of Ni catalysts supported on mesoporous nanocrystalline γ-Al₂O₃ with high surface area and with different Ni contents was prepared and employed in carbon dioxide methanation reaction. The obtained results showed increasing in nickel content from 10 to 25 wt.% decreased the specific surface area of catalysts from 177 to 130 m²/g and increased the nickel crystallite size from 12 to 24 nm. In addition, increasing in nickel content increased the reducibility of catalyst. The catalytic results revealed that the catalyst with 20 wt.% of Ni possessed high activity and stability in CO₂ methanation reaction.     

基于MCM-41的镍基甲烷化催化剂活性与稳定性

采用浸渍法分别以MCM-41,Al₂O₃和SiO₂ 为载体制备了不同镍负载量的甲烷化催化剂,并在连续流动固定床反应装置上对其甲烷化催化活性进行了评价。研究结果表明,与Ni/Al₂O₃和Ni/SiO₂相比,相同镍负载量的Ni/MCM-41催化剂具有更好的催化活性。同时研究了Ni含量对于Ni/MCM-41催化剂催化活性的影响,发现随着Ni含量的增加,CO转化率和CH₄收率逐渐升高,并且在Ni含量大于10%（质量分数）以后趋于稳定。在n（H₂）：n（CO）=3：1、反应压力1.5 MPa、反应温度350℃及质量空速12000 ml·h^-1·g^-1的反应条件下,10%Ni/MCM-41催化剂CH₄选择性达到94.9%,CO转化率接近100%。在100 h催化活性稳定性试验中,10%Ni/MCM-41催化活性无明显下降,表现出良好的催化活性稳定性。采用X射线衍射（XRD）、氮气物理吸附（BET）、热重分析（TG）及氢气程序升温还原（H₂-TPR）等技术手段对催化剂进行了表征,结果表明Ni颗粒大小是影响Ni/MCM-41催化剂催化活性的主要因素。     

载体对镍基催化剂顺酐液相加氢性能的影响

分别以ZrO₂、SiO₂与Al₂O₃为载体,采用等体积浸渍法制备了Ni质量分数为15%的催化剂,考察了其催化顺酐液相加氢性能,并利用BET、XRD、H₂-TPR以及TPO-MS等表征手段对催化剂进行了详细表征。结果表明,随载体不同各催化剂的加氢活性及选择性存在较大差异,Ni/Al₂O₃催化剂的C=C键加氢活性最高,但其几乎没有C=O加氢活性,催化顺酐加氢主产物为丁二酸酐。Ni/ZrO₂催化剂具有最高的C=O加氢活性,催化顺酐加氢主产物为γ-丁内酯,在反应温度为483 K,氢气压力为5 MPa的条件下反应8 h时,Ni/ZrO₂催化剂的γ-丁内酯选择性达79.20%。催化剂的套用实验表明,Ni/ZrO₂与Ni/SiO₂催化剂具有高的使用稳定性,Ni/Al₂O₃催化剂则在套用过程中快速失活。顺酐加氢至γ-丁内酯的中间产物--丁二酸酐与催化剂间的相互作用是影响催化剂加氢选择性及使用稳定性的主要原因。     

载体二氧化钛的晶型对对硝基苯酚加氢催化剂Ni/TiO2的影响

The catalytic hydrogenation ofp-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma （ICP）, X-ray powder diffraction （XRD）, transmission electron microscopy （TEM）, X-ray photoelectron spectra （XPS） and temperature-programmed reduction （TPR）. Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2（A） is higher than that of rutile titania supported nickel catalyst Ni/TiO2（R）, possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2（A） is easier than that for Ni/TiO2（R） at similar reaction conditions.     

Hydrogen production from steam reforming of kerosene over Ni–La and Ni–La–K/cordierite catalysts

Ni–La and Ni–La–K catalysts supported on cordierite were prepared for steam reforming of kerosene to produce hydrogen. All these catalysts were tested in a fixed-bed reactor under different conditions. The catalysts obtained under different calcination temperatures and different reaction temperatures were characterized by TG–DTG and XRD techniques respectively. The influence of NiO and La₂O₃ contents on the activity of catalysts for steam reforming of kerosene to produce hydrogen was also investigated in our experiments. The experimental results indicate that the calcination temperature has much more influence on catalyst activity. The catalyst supported the promoter 5 wt% K₂O, 25 wt% NiO and 10 wt% La₂O₃, is the optimal catalyst under 773 K of reaction temperature and 2300 h⁻¹ of space velocity. Composition of Ni is highly dispersed on the catalyst surface. And through the duration test, the catalyst activity and stability are very satisfactory at 873 K of the reaction temperature.     

Structured silicalite-1 encapsulated Ni catalyst supported on SiC foam for dry reforming of methane

Structured silicalite-1 zeolite encapsulated Ni catalyst supported on silicon carbide foam (i.e., Ni@S1-SiC) was prepared using a new yet simple one-pot method, showing the significantly improved anti-sintering and anti-coking performance in comparison with the conventional supported and encapsulated Ni catalysts (i.e., Ni/S1, Ni/S1-SiC, and Ni@S1), in catalytic dry reforming of methane (DRM). The developed Ni_0.08@S1-SiC catalyst showed high CO₂/CH₄ conversions of >85% and H₂/CO molar ratio of >0.85 at 700°C, outperforming other control catalysts under investigation. Additionally, the Ni_0.08@S1-SiC catalyst demonstrated high turnover frequency (TOF) values of ~5.6 and ~2.1/s regarding to CO₂/CH₄ conversions at 400°C, exhibiting excellent stability and low pressure-drop during 100 hr on stream evaluation. Post-reaction characterization of the used catalysts demonstrated that the combination of zeolite encapsulated Ni catalysts and SiC foam enabled well-dispersed and ultrafine Ni nanoparticles, low pressure drop and intensified transfer steps, presented excellent anti-sintering and anti-coking abilities.     

Effect of Nickel as Dopant in Mn/TiO<Subscript>2</Subscript> Catalysts for the Low-Temperature Selective Reduction of NO with NH<Subscript>3</Subscript>

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.     

Suppression of carbon deposition in CO2-reforming of methane on metal sulfide catalysts

The catalytic performance of metal sulfides of Mo and W was studied for the CO₂-reforming of methane by comparing with that of Ni/SiO₂. The sulfide catalysts have lower activity than the Ni/SiO₂ catalyst for this reaction, however, no deactivation due to carbon deposition was observed on the sulfide catalysts. The activity for direct decomposition of CH₄ was much smaller on the sulfides than on supported Ni. The rate equation suggested that, during steady-state reaction, the surface was abundant in adsorbed CO₂ on sulfides, by which direct decomposition of CH₄ should be retarded in addition to their lower activity for this reaction.     

HI decomposition over active carbon supported binary Ni–Pd catalysts prepared by electroless plating

A series of binary Ni–Pd catalysts supported on active carbon was prepared by electroless plating method. For comparison, active carbon supported monometallic Pd and Ni catalysts were also prepared by liquid-phase reduction. Among the Pd, Ni and binary Ni–Pd catalysts, the catalyst of 1%Ni–1%Pd/C showed the best catalytic performance for the decomposition of HI. Furthermore, characterizations by BET and XRD revealed that the binary Ni–Pd catalyst had the higher stability in specific surface area and structure than monometallic Pd catalyst during HI decomposition.