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.     

Co/CeO2-ZrO2 catalysts prepared by impregnation and coprecipitation for ethanol steam reforming

Co/CeO₂-ZrO₂ catalysts for the ethanol steam reforming were prepared by wet incipient impregnation and coprecipitation methods. These catalysts were characterized by nitrogen adsorption, TEM-EDX, XRD, H₂-TPR, and CO chemisorption techniques. It was found that the catalyst reducibility was influenced by the preparation methods; catalysts with different reduction behaviors in the pre-reduction showed different catalytic activities toward hydrogen production. The H₂-TPR studies suggested the presence of metal–support interactions in Co/CeO₂-ZrO₂ catalysts during their hydrogen pre-reduction, a necessary treatment process for catalysts activation. These interactions were influenced by the preparation methods, and the impregnation method is a favorable method to induce a proper metal–support effect that allows only partial reduction of the cobalt species and leads to a superior catalytic activity for the hydrogen production through ethanol steam reforming. At 450 °C, the impregnated catalyst gives a hydrogen production rate of 147.3 mmol/g-s at a WHSV of 6.3 h⁻¹ (ethanol) and a steam-to-carbon ratio of 6.5.     

Sustainable H2 production from ethanol steam reforming over a macro-mesoporous Ni/Mg-Al-O catalytic monolith

A macro-meso-porous monolithic Ni-based catalyst was prepared via an impregnation route using polystyrene foam as the template and then used in the steam reforming of ethanol to produce a H₂-rich gas. The Ni/Mg-Al catalyst has a hierarchically macro-meso-porous structure as indicated by photographs and scanning electron microscopy (SEM). The surface area of the catalyst was 230 m²?g^-1 and the Ni dispersion was 5.62%. Compared to the pelletized sample that was prepared without a template, the macro-meso-porous Ni/Mg-Al monolith exhibited superior reactivity in terms of H₂ production and also had lower CH₄ yields at 700oC and 800oC. Furthermore, the monolithic catalyst maintained excellent activity and H₂ selectivity after 100-h on-stream at 700^oC, as well as good resistance to coking and metal sintering.     

Oxidative steam reforming of ethanol over PtRu/ZrO2 catalysts modified with sodium and magnesium

This paper reports the catalytic performance of a PtRu/ZrO₂ catalyst modified with Na and Mg in an oxidative steam reforming of ethanol (OSRE) reaction tested in the temperature range of 300–400 °C. The results show that the PtRuMg₁/ZrO₂ catalyst requires higher temperatures (T_R ~ 400 °C) to achieve complete conversion than either the PtRuNa₁/ZrO₂ or PtRu/ZrO₂ catalysts (T_R ~ 300 °C). Also, an apparent coke deposit is found on the PtRuMg₁/ZrO₂ catalyst. The preferential PtRuNa₁/ZrO₂ catalyst shows active at temperatures as low as 300 °C and produces less CO (< 0.2%) at temperatures lower than 340 °C.     

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.     

Steam reforming of ethanol over Co3O4/CeO2 catalysts prepared by different methods

In this paper, Co₃O₄/CeO₂ catalysts for steam reforming of ethanol (SRE) were prepared by co-precipitation and impregnation methods. The catalysts prepared by co-precipitation were very active and selective for SRE. Over 10%Co₃O₄/CeO₂ catalyst, ethanol conversion was close to 100% and hydrogen selectivity was about 70% at 450 °C. The catalysts were characterized by X-ray diffraction, temperature-programmed reduction (TPR) and BET surface area measurements. The preparation method influenced the interaction between cobalt and CeO₂ evidently. The incorporation of Co ions into CeO₂ crystal lattice resulted in weaker interaction between cobalt and ceria on catalyst surface. In comparison with catalysts prepared by impregnation, more cobalt ions entered into CeO₂ lattice, and resulted in weaker interaction between active phase and ceria on surface of Co₃O₄/CeO₂ prepared by co-precipitation. Thus, cobalt oxides was easier to be reduced to metal cobalt which was the key active component for SRE. Meanwhile, the incorporation of Co ions into CeO₂ crystal lattice was beneficial for resistance to carbon deposition.     

Synthesis gas production by steam reforming of ethanol

A two-layer fixed-bed catalytic reactor for syngas production by steam reforming of ethanol has been proposed. In the reactor, ethanol is first converted to a mixture of methane, carbon oxides and hydrogen over a Pd-based catalyst and then this mixture is converted to syngas over a Ni-based catalyst for methane steam reforming. It has been shown that the use of the two-layer fixed-bed reactor prevents coke formation and provides the syngas yield closed to equilibrium.     

Transient modeling of combined catalytic combustion/CH4 steam reforming

This paper presents an investigation into the complex interactions between catalytic combustion and CH₄ steam reforming in a co-flow heat exchanger where the surface combustion drives the endothermic steam reforming on opposite sides of separating plates in alternating channel flows. To this end, a simplified transient model was established to assess the stability of a system combining H₂ or CH₄ combustion over a supported Pd catalyst and CH₄ steam reforming over a supported Rh catalyst. The model uses previously reported detailed surface chemistry mechanisms, and results compared favorably with experiments using a flat-plate reactor with simultaneous H₂ combustion over a γ-Al₂O₃-supported Pd catalyst and CH₄ steam reforming over a γ-Al₂O₃-supported Rh catalyst. Results indicate that stable reactor operation is achievable at relatively low inlet temperatures (400 °C) with H₂ combustion. Model results for a reactor with CH₄ combustion indicated that stable reactor operation with reforming fuel conversion to H₂ requires higher inlet temperatures. The results indicate that slow transient decay of conversion, on the order of minutes, can arise due to loss of combustion activity from high-temperature reduction of the Pd catalyst near the reactor entrance. However, model results also show that under preferred conditions, the endothermic reforming can be sustained with adequate conversion to maintain combustion catalyst temperatures within the range where activity is high. A parametric study of combustion inlet stoichiometry, temperature, and velocity reveals that higher combustion fuel/air ratios are preferred with lower inlet temperatures (≤500 °C) while lower fuel/air ratios are necessary at higher inlet temperatures (600 °C).     

Co/ZrO2催化乙醇水蒸汽重整制氢反应的研究

采用浸渍-热分解-氢还原法制备Co/ZrO2催化剂,并用XRD、BET比表面、TPR、差热-热重等测试分析手段对该催化剂进行表征。采用固定床反应器考察了催化剂对乙醇水蒸汽重整制氢反应的催化性能。结果表明:700℃焙烧的ZrO2以单斜和四方相形式共存,负载Co后观察不到有四方相。3%Co/ZrO2催化剂对乙醇水蒸汽重整制氢反应表现出较高的活性。在500℃、水醇比为3∶1时,乙醇的转化率达到76.6%,H2的产率和选择性为0.57mol/mol和81.8%。反应温度升高,提高了乙醇的转化率和H2产率,同时也促进了催化剂表面的积炭。     

Preparation of MEMO silane-coated SiO2 nanoparticles under high pressure of carbon dioxide and ethanol

The objective of this study is to investigate and compare methods of nanosilica coating with γ-methacryloxypropyltrimethoxy (MEMO) silane using supercritical carbon dioxide and carbon dioxide-ethanol mixture. Characterization of grafted silane coupling agent on the nanosilica surface was performed by the infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The d₅₀ value and particle size distribution were determined by laser particle size analyzer (PSA). The operating parameters of silanization process at 40 °C, such as the silica/silane weight ratio, the presence of ethanol, and the pressure, were found to be important for the successful coating of silica particles with minimum agglomeration. The results indicate that presence of ethanol in high-pressure carbon dioxide plays an important role in achieving successful deagglomeration of coated nanoparticles. Dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM) revealed that dispersion of the silica particles in the PMMA matrix and interfacial adhesion between silica particles and polymer matrix were enhanced, when silica nanoparticles treated with silane under high pressure of carbon dioxide and ethanol were used for the nanocomposite preparation.     

Co/La2O3催化乙醇水蒸汽重整制氢反应的研究

采用浸渍、热分解、氢还原等步骤制备了一系列Co/La2O3,催化剂,并将其应用于乙醇水蒸汽重整制氢反应.采用固定床反应考察了温度和水醇比对催化剂性能的影响.用N2吸附、XRD、TPR等手段对催化剂进行了表征.结果表明:5%Co/La2O3,催化剂对乙醇水蒸汽重整制氢反应表现出最高的活性.在500℃、水醇比为3:1时,乙醇的转化率达可到64.8%,H2的产率和选择性分别为1.0 mol/mol和86.1%.另外,在反应温度低于450℃时,H2的选择性可达90%以上.     

负载型金属催化剂在乙醇水蒸气重整制氢中的应用

系统地阐述了近年来对乙醇水蒸气重整制氢催化剂的研究进展;对影响催化剂性能的因素及对策进行了分析与讨论;展望了乙醇水蒸气制氢催化剂的研究方向.     

Highly selective supported Pd catalysts for steam reforming of methanol

Steam reforming of methanol, CH₃OH + H₂O 3H₂ + CO₂, was carried out over various Pd catalysts (Pd/SiO₂, Pd/Al₂O₃, Pd/La₂O₃, Pd/Nb₂O₅, Pd/Nd₂O₃, Pd/ZrO₂, Pd/ZnO and unsupported Pd). The reaction was greatly affected by the kind of support. The selectivity for the steam reforming was anomalously high over Pd/ZnO catalysts.     

Production of hydrogen for fuel cells by steam reforming of ethanol over supported noble metal catalysts

The catalytic performance of supported noble metal catalysts for the steam reforming (SR) of ethanol has been investigated in the temperature range of 600–850 °C with respect to the nature of the active metallic phase (Rh, Ru, Pt, Pd), the nature of the support (Al₂O₃, MgO, TiO₂) and the metal loading (0–5 wt.%). It is found that for low-loaded catalysts, Rh is significantly more active and selective toward hydrogen formation compared to Ru, Pt and Pd, which show a similar behavior. The catalytic performance of Rh and, particularly, Ru is significantly improved with increasing metal loading, leading to higher ethanol conversions and hydrogen selectivities at given reaction temperatures. The catalytic activity and selectivity of high-loaded Ru catalysts is comparable to that of Rh and, therefore, ruthenium was further investigated as a less costly alternative. It was found that, under certain reaction conditions, the 5% Ru/Al₂O₃ catalyst is able to completely convert ethanol with selectivities toward hydrogen above 95%, the only byproduct being methane. Long-term tests conducted under severe conditions showed that the catalyst is acceptably stable and could be a good candidate for the production of hydrogen by steam reforming of ethanol for fuel cell applications.     

Ni nanoparticles supported on carbon as efficient catalysts for steam reforming of toluene (model tar)

This paper investigated the influences of surface properties of carbon support and nickel precursors (nickel nitrate,nickel chloride and nickel acetate) on Ni nanoparticle sizes and catalytic performances for steam reforming of toluene.Treatment with nitric acid helped to increase the amount of functional groups on the surface and hydrophilic nature of carbon support,leading to a homogeneous distribution of Ni nanoparticles.The thermal decomposition products of nickel precursor also played an important role,Ni nanoparticles supported on carbon treated with acid using nickel nitrate as the precursor exhibited the smallest mean diameter of 4.5 nm.With the loading amount increased from 6 wt％ to 18 wt％,the mean particle size of Ni nanoparticles varied from 4.5 nm to 9.1 nm.The as-prepared catalyst showed a high catalytic activity and a good stability for toluene steam reforming:98.1％ conversion of toluene was obtained with the Ni content of 12 wt％ and the S/C ratio of 3,and the conversion only decreased to 92.0％ after 700 min.Because of the high activity,good stability,and low cost,the as-prepared catalyst opens up new opportunities for tar removing.     

Catalytic steam reforming of methane over La0.8Sr0.2CrO3 based Ru catalysts

La_0.8Sr_0.2CrO₃ based Ru catalysts were studied as potential new anodic materials for Solid Oxide Fuel Cells directly fed with methane and operating at intermediate temperature under water deficient conditions. Two kinds of materials very close in composition were obtained following two different preparation procedures. Catalyst samples were characterized by physicochemical methods (XRD, SEM, BET and Chemical Analysis) and studied in methane steam reforming under water deficient conditions. Carbon formation during catalytic testing was studied by temperature programmed oxidation (TPO). Both types of catalysts were found very active and resistant to carbon formation. The unusual oscillatory behavior of the catalytic activity observed for one type of catalyst was discussed.     

Promotional role of MgO on sorption-enhanced steam reforming of ethanol over Ni/CaO catalysts

This article describes the design and synthesis of MgO-modified Ni/CaO catalysts for sorption-enhanced steam reforming of ethanol. The results show that the introduction of MgO effectively increases the dispersion of CaO via forming MgCa(CO₃)₂ precursor. In the prepared MgO-modified Ni/CaO catalysts, metallic Ni exists around MgO supported on CaO. Both 100% ethanol conversion and >96% hydrogen purity can be stabilized in 10 cycles over the catalyst containing 20 wt% MgO. The interaction between metallic Ni and MgO enhances the sintering resistance of the catalyst. More importantly, reaction pathway studies have confirmed that the formation of CaCO₃ hinders the activation of H₂O on the Ni/CaO catalyst surface, and thus inhibits the conversion of the reaction intermediates including HCO* and CH _x*. MgO can dissociate H₂O to form hydroxyl groups which participate in the conversion of the reaction intermediates, thereby the MgO-modified Ni/CaO catalysts have better catalytic performance and carbon deposition resistance.