The role of the oxidic support on the deactivation of Pt catalysts during the CO2 reforming of methane

Pt supported on γ-Al₂O₃, TiO₂ and ZrO₂ are active catalysts for the CO₂ reforming of methane to synthesis gas. The stability of the catalysts increased in the order Pt/γ-A1₂O₃ < Pt/TiO₂ < Pt/ZrO₂. For all catalysts, the decrease in activity with time on stream is caused by carbon formation, which blocks the active metal sites for reaction. With Pt/TiO₂ and Pt/ZrO₂, deactivation started immediately after the start of the reaction, while the Pt/γ-A1₂O₃ catalyst showed an induction period during which carbon was accumulated without affecting the catalytic activity.     

Catalyst deactivation and engineering control for steam reforming of higher hydrocarbons in a novel membrane reformer

The catalyst deactivation and reformer performance in a novel circulating fluidized bed membrane reformer (CFBMR) for steam reforming of higher hydrocarbons are investigated using mathematical models. A catalyst deactivation model is developed based on a random carbon deposition mechanism over nickel reforming catalyst. The results show that the reformer has a strong tendency for carbon formation and catalyst deactivation at low steam to carbon feed ratios for high reaction temperatures and high pressures . The trend is similar for the cases without and with hydrogen selective membranes. Based on this preliminary investigation, an engineering control approach, i.e., in-site control with a concept of critical/minimum steam to carbon feed ratio, is proposed and used to determine the carbon deposition free regions for both cases without and with hydrogen membranes. The comparison between the reported data and model simulation shows that the critical steam to carbon feed ratio predicted by the model agrees well with the reported industrial/experimental operating data.     

Yolk-shell structured Pt-CeO2@Ni-SiO2 as an efficient catalyst for enhanced hydrogen production from ethanol steam reforming

A novel Pt-CeO₂@Ni-SiO₂ yolk-shell catalyst was fabricated through modified Stöber method and was applied to the ethanol steam reforming reaction. The catalyst structure was characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, nitrogen adsorption-desorption and X-ray photoelectron spectroscopy. Compared with the mechanically mixed catalyst, the yolk-shell catalyst exhibited excellent catalytic performance and stability in ethanol steam reforming. The selection of hydrogen reached as high as 66%, and the conversion reached nearly 100% at 400 °C for 28 h.     

Reduction behaviors and catalytic properties for methanol steam reforming of Cu-based spinel compounds CuX2O4 (X=Fe,Mn, Al,La)

In this study, various Cu-based spinel compounds, i.e., CuFe₂O₄, CuMn₂O₄, CuAl₂O₄ and CuLa₂O₄, were fabricated by a solid-state reaction method. Reduction behaviors and morphological changes of these materials have been characterized by H₂ temperature-programmed reduction (H₂-TPR), X-ray diffraction (XRD), Scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Moreover, the catalytic properties for steam reforming of methanol (SRM) of these Cu-based spinel compounds were investigated. H₂-TPR results indicated that the reducibility of Cu-based spinel compounds was strongly dependent on the B-site component while the CuFe₂O₄ catalyst revealed the lowest reduction temperature (190 °C), followed respectively by CuAl₂O₄ (267 °C), CuMn₂O₄ (270 °C), and CuLa₂O₄ (326 °C). The reduced CuAl₂O₄ catalyst demonstrated the best performance in terms of catalytic activity. Based on the SEM and XRD results, pulverization of the CuAl₂O₄ particles due to gas evolution and a high concentration of nanosized Cu particles (≈50.9 nm) precipitated on the surfaces of the Al₂O₃ support were observed after reduction at 360 °C in H₂. The BET surface area of the CuAl₂O₄ catalyst escalated from 5.5 to 13.2 m²/g. Reduction of Cu-based spinel ferrites appear to be a potential synthesis route for preparing a catalyst with high catalytic activity and thermal stability. The catalytic performance of these copper-oxide composites was superior to those of conventional copper catalysts.     

甘油水蒸汽重整制氢Ni/Ce0.9Gd0.1O1.95催化剂的研究

采用浸渍法和共沉淀法制备了Ni质量分数10%的10%Ni/Ce_0.9Gd_0.1O_1.95催化剂,通过X射线衍射、N₂物理吸附与H₂脉冲化学吸附、H₂程序升温还原等技术表征了催化剂的结构和性质,并考察了其催化甘油水蒸汽重整制氢反应性能。结果表明,浸渍法制备的10%Ni/Ce_0.9Gd_0.1O_1.95-S催化剂的活性最佳,该催化剂上Ni晶粒小、分散度高,形成氧空穴使得催化剂抗积炭能力大大提高,所以活性、氢气选择性较高,稳定性也较好。同时考察了水与甘油物质的量比和泵流速对甘油重整反应性能的影响,发现在水与甘油物质的量比为24:1,泵流速为0.06 mL·min^-1的条件下,甘油几乎完全转化,氢气选择性也非常高,而且反应10 h没有失活。     

Z417/Z418蒸汽转化催化剂的应用及积炭中毒失活原因分析

对中国石油西安石化分公司新建制氢装置蒸汽转化催化剂的使用进行了总结，剖析转化催化剂积炭和中毒失活的原因，提出了防止积炭和中毒失活的预防措施及保证装置长周期运行的方法。     

汽油氧化重整制氢反应催化剂失活因素研究

对汽油氧化重整制氢反应催化剂失活因素进行了理论分析与实验研究 ,研究结果表明 :在进行反应中 ,催化剂表面积碳是造成催化剂失活的原因 ,为避免催化剂表面积碳 ,反应的最小水碳比应大于理论计算的最小水碳比。计算了在不同反应温度条件下的最小理论水碳比     

Mixtures of carbon and Ni/Al2O3 as catalysts for the microwave-assisted CO2 reforming of CH4

In this work, the microwave-assisted CO₂ reforming of CH₄ over mixtures of carbonaceous materials and an in-lab prepared Ni/Al₂O₃ was studied. Ni/Al₂O₃ is not heated by microwave radiation, and for this reason, microwave receptors, such as carbonaceous materials, must be mixed with this catalyst. In order to evaluate the role of the carbonaceous component of the blend, two different carbonaceous materials were used: an activated carbon, FY5, and a metallurgical coke, CQ. The carbonaceous component acted not only as microwave receptor but also as catalyst and, consequently, it influenced the catalytic activity of the mixture. FY5 + Ni/Al₂O₃ was found to be a better catalyst than CQ + Ni/Al₂O₃, since FY5 on its own showed a better catalytic activity than CQ. Ni/FY5, which consists of Ni impregnated directly onto the microwave receptor, was also evaluated as a catalyst. It was found that the catalytic activity of the mixture FY5 + Ni/Al₂O₃ was better than that of Ni/FY5. Finally, the influence of the heating device on the catalytic activity of FY5 + Ni/Al₂O₃ was studied. Conversions over FY5 + Ni/Al₂O₃ and microwave heating were found to be similar to conversions over Ni/Al₂O₃ and conventional heating.     

H2 production through steam reforming of ethanol over Pt/ZrO2, Pt/CeO2 and Pt/CeZrO2 catalysts

The effect of the support nature and metal dispersion on the performance of Pt catalysts during steam reforming of ethanol was studied. H₂ and CO production was facilitated over Pt/CeO₂ and Pt/CeZrO₂, whereas the acetaldehyde and ethene formation was favored on Pt/ZrO₂. According to the reaction mechanism, determined by temperature-programmed desorption (TPD) and Diffuse Reflectance Infrared Spectroscopy (DRIFTS) analysis, some reaction pathways are favored depending on the support nature, which can explain the differences observed on the resulting product distribution.     

Effective supports to moderate H2S inhibition on cobalt and nickel molybdenum sulfide catalysts in deep desulfurization of gas oil

Deep desulfurization of gas oil was attempted in the presence of H₂S over commercially available catalysts. Hydrotreated gas oil containing 340 ppm of sulfur (ppmS) was successfully desulfurized to less than 10 ppmS under the presence of 1.67% H₂S over CoMoS and NiMoS supported on acidic supports. Such supports are believed to enhance the sulfur release from active sites and the hydrogenation of refractory sulfur species to accelerate their deep desulfurization.     

Pt/TiO_2催化二甲醚部分氧化重整制氢

二甲醚是一种理想的氢载体,可用于解决氢的储存和运输。以Pt/TiO_2为部分氧化催化剂,结合Ni/Al_2O_3重整催化剂,考察钛前驱体和焙烧温度对二甲醚部分氧化重整制氢反应的影响。结果表明,以Ti(C4H9O)4为原料制备的TiO_2为金红石相,Ti(SO4)2或Ti O(OH)2为原料制备的TiO_2为锐钛矿相;以Ti(C4H9O)4为原料制备的Pt/TiO_2-E催化剂催化性能略好,转化率接近100%,H2收率约90%,表明金红石相TiO_2负载的Pt催化剂略佳;以Ti(SO4)2为原料制备的Pt/TiO_2-S催化剂500℃焙烧可获得金红石相TiO_2。与Pt/Al_2O_3催化剂相比,Pt/TiO_2催化剂具有更好的催化性能,H2收率超过90%,而Pt/Al_2O_3催化剂H2收率约80%。     

Ethanol steam reforming over Ni/La–Al2O3 catalysts: Influence of lanthanum loading

Hydrogen production from ethanol reforming over nickel catalysts supported on lanthanum loaded Al₂O₃ substrates was studied. Activity results revealed the enhancement in the reforming stability of the Ni catalysts with the increase in the lanthanum loading on Al₂O₃ substrates. Catalytic behavior of Ni/La–Al₂O₃ catalysts in the ethanol steam reforming was found to be the contribution of the activity of the La–Al₂O₃ supports for the ethanol dehydration reaction and the activity of the nickel metallic phase that catalyzes both dehydrogenation and CC bond rupture. Physicochemical characterization of catalysts revealed that acidity, nickel dispersion and nickel-support interaction depend on the La-loading on Al₂O₃. The better reforming stability of catalysts with the increase in La content was explained in terms of the ability of nickel surface and/or La–Ni interactions to prevent the formation of carbon filaments.     

Effects of small MoO3 additions on the properties of nickel catalysts for the steam reforming of hydrocarbons: II. Ni---Mo/Al2O3 catalysts in reforming, hydrogenolysis and cracking of n-butane

Addition of molybdenum to nickel catalysts has a favourable effect on their properties in the steam reforming of hydrocarbons. Some attempts were made to explain the mechanism of promoter action by determining the properties of such catalysts in hydrogenolysis and cracking reactions. With small amounts of promoter (≤0.5 wt.%) advantageneous changes in selectivity of steam reforming and disadvantageneous changes in n-butane hydrogenolysis were observed. The promoter does not affect practically the catalyst properties in n-butane cracking. The effect of molybdenum was compared with that of potassium promoter applied in the industry.     

Ni-Mg-Al催化剂M2+/M3+比对CH4-CO2重整制合成气的影响

考察了Ni-Mg-Al催化剂中M²⁺/M³⁺比的不同对CH₄-CO₂重整制合成气反应性能的影响。在质量空速12000mL/(g_cat·h)、800℃条件下进行催化反应,并用X射线衍射、电子透射电镜等手段对催化剂进行了表征和分析。分析结果表明催化剂中单质与载体有很强的相互作用力并且在载体上均匀分布,同时反应过程中催化剂从单一的固溶体结构转变为固溶体-尖晶石共存结构,这有利于催化性能的提升。催化剂孔结构在反应前后也稳定存在,未发生坍塌。实验发现随着M²⁺/M³⁺比的不同,催化剂碱性强弱对其催化稳定性起着决定性作用,M²⁺/M³⁺比为3时,催化剂碱性最强,同时具有优良的抗积炭和抗烧结能力,是最佳M²⁺/M³⁺比。     

Preparation of Ni/MgO catalyst for CO2 reforming of methane by dielectric-barrier discharge plasma

A novel plasma-treated Ni/MgO catalyst was prepared by treating coprecipitated NiCO₃–MgCO₃ with dielectric-barrier discharge plasma. The results by XRD, TEM and N₂ adsorption analyses showed that the plasma-prepared Ni/MgO catalyst possessed smaller particle size, enhanced nickel dispersion, and higher specific surface area than a conventionally reduced Ni/MgO catalyst. The plasma-prepared Ni/MgO catalyst also exhibited better catalytic activity for carbon dioxide reforming of methane. More than 20% higher conversions of methane and carbon dioxide were obtained than those over the conventional Ni/MgO catalyst at 700 °C and a space velocity of 96,000 mL/(h?g_cat).     

Structure and reactivity of plasma treated Ni/Al2O3 catalyst for CO2 reforming of methane

The glow discharge plasma treated Ni/Al₂O₃ catalyst showed an excellent anti-coke property for CO₂ reforming of methane. Characterizations using X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR), transmission electron microscopy (TEM), and CO adsorbed infrared spectroscopy (IR) were conducted to investigate the structure and reactivity of the plasma treated Ni/Al₂O₃ catalyst for CO₂ reforming of methane. It confirms that the plasma treatment of Ni precursor at room temperature followed by calcination thermally has a significant influence on the surface characteristics of the active phase. The plasma treated catalyst contains high concentration of close packed plane with improved Ni dispersion and enhanced Ni-alumina interaction, which lead to high catalytic activity and excellent resistance to formations of filamentous carbon and encapsulating carbon.     

Effects of La addition to Ni/Al2O3 catalysts on rates and carbon deposition during steam reforming of n-dodecane

Steam reforming of n-dodecane on La-Ni/γ-Al₂O₃ catalysts was investigated at a relatively low temperature (773 K) to elucidate the catalytic behavior at the inlet of a practical reformer. The addition of lanthanum to the Ni/γ-Al₂O₃ formulation completely suppressed carbon deposition, which otherwise occurs to a significant extent on unmodified Ni/γ-Al₂O₃. Modification with La also enhanced the initial turnover rates of hydrogen formation. The La-Ni/γ-Al₂O₃ catalysts, however, deactivated with increased time-on-stream at a high steam-to-carbon ratio of 3.5, because of oxidation of the active Ni metal. Reduction at 873 K almost fully regenerated the catalytic activity, indicating that the deactivation was not primarily a result of sintering or carbon deposition, but was due to the oxidation of active Ni metal.     

Development of new nickel based catalyst for biomass tar steam reforming producing H2-rich syngas

Mayenite (Ca₁₂Al₁₄O₃₃ or 12CaO.7Al₂O₃) was previously developed and applied as Ni support for biomass tar steam reforming in the absence and presence of H₂S by our group because of its high oxygen restoring property in the structure [C. Li et al., Appl. Catal., B. 2008]. In this study, catalyst Ni/mayenite (mayenite as support) was prepared by impregnation method with nickel nitrate hexahydrate. Experiments were tested in a fixed-bed reactor, toluene as a tar model compound. The influence of the catalyst preparation and operating parameters (reaction temperature, steam to carbon ratio and space time) on catalyst activity and products selectivity were studied, and a long-time evaluation (more than 76 h) also exhibited excellent resistance to coking. These results were compared to these obtained by commercial-like catalysts: Ni/CaO_x/MgO_1−x and our previous NiO/mayenite, showing that Ni/mayenite exhibited excellent property for biomass tar reforming, with higher H₂ yield than that of Ni/CaO_x/MgO_1−x, and higher CO selectivity than that of NiO/mayenite. For kinetic model, the first order reaction used for toluene with activation energy of 80.24 kJ.mol^− 1 was coincident with literature data.