Biogas reforming on La-promoted NiMgAl catalysts derived from hydrotalcite-like precursors

Hydrotalcite-like precursors have been synthesized in order to study the influence of lanthanum on the structure and the properties of the precursors, as well as on the catalytic activity and stability of their derived catalyst on biogas reforming. From XRD, and TPO characterization, we confirmed that hydrotalcite-like precursors where obtained. After calcination at 750 °C, Mg(Ni,Al)O solid solution was detected. High surface areas have been obtained finding the highest surface area on the catalyst without lanthanum. TPR experiments were performed in order to study the reducibility of the catalysts. One reduction peak was found in the catalyst without lanthanum while two peaks were observed in the catalysts with lanthanum. A reduction peak at 900 °C was observed over the sample without Ni and La. Catalytic tests, at 700 °C with a feed of CH₄:CO₂ 1:1, were performed after appropriate reduction during 50 h. While a decrease on catalytic activity was observed with the addition and the increase of La content, an enhancement in the stability was observed. No sign of deactivation of the catalyst and no carbon deposition were found on the catalysts doped with lanthanum.     

The promoting effect of La, Mg, Co and Zn on the activity and stability of Ni/SiO2 catalyst for CO2 reforming of methane

CO₂ reforming of methane into synthesis gas over Ni/SiO₂ catalysts promoted by La, Mg, Co and Zn was investigated. The catalysts were prepared by impregnation method and characterized by XRD, TPR, SEM and TG-DTA techniques. Ni-La/SiO₂ catalyst was found to exhibit high activity and excellent stability with the addition of suitable amount of La promoter, which increased the dispersion of NiO and the interaction between NiO and SiO₂. Two different types of carbon species, namely, easily oxidized carbonaceous species and inert carbon, were observed on the surface of the used catalysts. The inert carbon deposited on Ni-Mg/SiO₂ catalyst may be the main reason for its deactivation, while the principal reason for the deactivation of Ni-Co/SiO₂ catalyst might be the sintering of metallic Ni. The addition of La and Mg decreased the contribution of reverse water-gas shift reaction, leading to higher H₂ yield.     

Nickel‒cobalt bimetallic catalysts prepared from hydrotalcite-like compounds for dry reforming of methane

Ni–Co/Mg(Al)O alloy catalysts with different Co/Ni molar ratios have been prepared from Ni- and Co-substituted Mg–Al hydrotalcite-like compounds (HTlcs) as precursors and tested for dry reforming of methane. The XRD characterization shows that Ni–Co–Mg–Al HTlcs are decomposed by calcination into Mg(Ni,Co,Al)O solid solution, and by reduction finely dispersed alloy particles are formed. H₂-TPR indicates a strong interaction between nickel/cobalt oxides and magnesia, and the presence of cobalt in Mg(Ni,Co,Al)O enhances the metal-support interaction. STEM-EDX analysis reveals that nickel and cobalt cations are homogeneously distributed in the HTlcs precursor and in the derived solid solution, and by reduction the resulting Ni–Co alloy particles are composition-uniform. The Ni–Co/Mg(Al)O alloy catalysts exhibit relatively high activity and stability at severe conditions, i.e., a medium temperature of 600 °C and a high space velocity of 120000 mL g^?1 h^?1. In comparison to monometallic Ni catalyst, Ni–Co alloying effectively inhibits methane decomposition and coke deposition, leading to a marked enhancement of catalytic stability. From CO₂-TPD and TPSR, it is suggested that alloying Ni with Co favors the CO₂ adsorption/activation and promotes the elimination of carbon species, thus improving the coke resistance. Furthermore, a high and stable activity with low coking is demonstrated at 750 °C. The hydrotalcite-derived Ni–Co/Mg(Al)O catalysts show better catalytic performance than many of the reported Ni–Co catalysts, which can be attributed to the formation of Ni–Co alloy with uniform composition, proper size, and strong metal-support interaction as well as the presence of basic Mg(Al)O as support.     

H2-rich syngas production from biogas reforming: Overcoming coking and sintering using bimetallic Ni-based catalysts

Dry reforming of methane is a very appealing catalytic route biogas (mainly composed by greenhouse gases: carbon dioxide and methane) conversion into added value syngas, which could be further upgraded to produce liquid fuels and added value chemicals. However, the major culprits of this reaction are coking and active phase sintering that result in catalysts deactivation. Herein we have developed a highly stable bimetallic Ni–Rh catalyst supported on mixed CeO₂–Al₂O₃ oxide using low-noble metal loadings. The addition of small amounts of rhodium to nickel catalysts prevents coke formation and improves sintering resistance, achieving high conversions over extended reaction times hence resulting in promising catalysts for biogas upgrading.     

Stability of Ni and Rh–Ni catalysts derived from hydrotalcite-like precursors for the partial oxidation of methane

In this work, NiMgAl and RhNiMgAl catalysts prepared from HTLCs precursors were investigated for the Partial Oxidation of Methane (POM) at 550 and 750 °C. Samples have been characterized by XRD, TPR, H₂ chemisorption, TPSR analyses, XPS, field emission scanning electron microscopy and Raman spectroscopy. NiMgAl catalysts with high Ni content (40 and 16 wt%) showed high stability and high methane conversion for POM. On the other hand those with lower Ni content (NiHT15 and NiHT25, with 6 and 4 wt%) exhibited low catalytic activity with low H₂/CO ratio (<2) and fast deactivation. In RhNiHT25 (0.6 wt. % Rh), the Ni reducibility was improved, increasing the methane conversion and hydrogen selectivity. In addition, the noticeable increase in stability was related to the absence of carbon deposition after 30 h on stream at 550 °C. These results show that RhNiHT25 is promising for application in membrane reactors to produce high purity hydrogen.     

Influence of reduction temperature on Ni particle size and catalytic performance of Ni/Mg(Al)O catalyst for CO2 reforming of CH4

Hydrotalcite-derived Ni/Mg(Al)O is promising for CH₄–CO₂ reforming. However, the catalysts reported so far suffer from sever coking at low temperatures. In this work, we demonstrate that a significant improvement of coke-resistance of Ni/Mg(Al)O can be achieved by fine tuning the Ni particle size through adjusting the reduction condition of catalyst. Ni particles having average size within 4.0–7.1 nm are in situ generated by reducing the catalyst at a selected temperature within 923–1073 K. Controllability of Ni particle size is related to the formation of Mg(Ni,Al)O solid solution upon hydrotalcite decomposition. It is found that the catalyst reduced at 973 K exhibits high activity, stability, and coke-resistance even at reaction temperature as low as 773 K. In contrast, the catalyst reduced at 923 K has low activity and deactivates due to Ni oxidation, while those reduced at 1023 and 1073 K suffer from sintering and severe coking. STEM and O₂-TPO reveal that coke deposition is directly proportional to the Ni particle size but becomes negligible at a size below 6.2 nm. It is evidenced that a critical size of about 6 nm is required to inhibit coking effectively. CO₂ temperature-programmed surface reaction indicates that the deposited carbon on small Ni particles can be easily removed by the CO₂ activated at the Ni–Mg(Al)O interfaces, accounting for the better resistance to coking.     

La-doped supported Ni catalysts for steam reforming of methane

Ni-La/α-Al₂O₃ catalysts at different Ni/La ratio of respectively 7/3, 8/2 and 9/1 to obtain a material with total loading of 10 wt% as used in industrial methane steam reforming field are prepared with incipient wetness impregnation method. Various techniques including TGA-DTA, XRF, XRD, particles size, H₂-RTP and BET are used to characterize materials and their catalytic performance is evaluated during the steam reforming reaction at different temperatures ranging from 500 to 800 °C. Only NiO and α-Al₂O₃ phases are evidenced by DRX indicating probably the presence of small lanthanum crystallites in high dispersion state. Addition of La may cause strong change at the surface of NiO sites. Substitute Ni by La leads to smaller and well dispersed NiO particles sizes with strong metal support interaction (SMSI). TPR analysis reveals the reduction of Ni species with high Ni-La-Al interactions particularly well observed with 3 wt%La catalyst. The small Ni particles sizes highly dispersed on the support enhance the dissociative adsorption of CH_x species. The highest H₂ yield is obtained with 7Ni-3La/Al catalyst reaching 94% at 800 °C.     

Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2 reforming,steam–CO2 reforming and oxy–CO2 reforming of CH4

Ni (2.5 wt%) and Co (2.5 wt%) supported over ZrO₂/Al₂O₃ were prepared by following a hydrolytic co-precipitation method. The synthesized catalysts were further promoted by Rh incorporation (0.01–1.00 wt%) and tested for their catalytic performance for dry CO₂ reforming, combined steam–CO₂ reforming and oxy–CO₂ reforming of methane for production of syngas. The catalysts were characterized by using N₂ physical adsorption, XRD, H₂–TPR, SEM, CO₂–TPD, NH₃–TPD, TEM and TGA. The results revealed that ZrO₂ phase was in crystalline form in the catalysts along with amorphous Al oxides. Ni and Co were confirmed to be in their respective spinel phases that were reducible to metallic form at 800 °C under H₂. Ni and Co were well dispersed with their nano-crystalline nature. The catalyst with 0.2% loading of Rh showed superior performance in the studied reactions for reforming of methane. This catalyst also showed good coke resistance ability for dry CO₂ reforming reaction with 3.8 wt% of carbon formation during the reaction as compared to 11.6 wt% carbon formation over the catalyst without Rh. The catalyst performance was stable throughout the reaction time for CH₄ conversions, irrespective of carbon formation with slight decline (～1%) in CO₂ conversion. For dry CO₂ reforming reaction, this catalyst showed good conversion for both CH₄ and CO₂ (67.6% and 71.8% respectively) with a H₂/CO ratio of 0.84, while for the Oxy-CO₂ reforming reaction, the activity was superior with CH₄ and CO₂ conversions (73.7% and 83.8% respectively) and H₂/CO ratio of 1.05.     

Catalytic activity of SBA-15 supported Ni catalyst in CH4 dry reforming: Effect of Al,Zr, and Ti co-impregnation and Al incorporation to SBA-15

In this study, the catalytic activity of the mesoporous SBA-15 supported Ni–Al, Ni–Zr, and Ni–Ti catalysts prepared by an impregnation method were investigated in dry reforming of methane. In addition, Al incorporated SBA-15 (Al–SBA-15) materials used as catalyst support were synthesized following a one-pot hydrothermal route in three different conditions: synthesis in the presence of only HCl, only NaCl, and both HCl and NaCl (denoted as A, S, and B, respectively). All catalysts were characterized by XRD, N₂ adsorption-desorption isotherms, ICP-OES, DRIFTS, SEM, TEM-EDX and TGA techniques before and/or after reaction tests. Among Al, Zr, and Ti impregnated catalysts, Ni–Al impregnated catalyst showed the highest activity in dry reforming of methane. According to activity test results, Al–SBA-15 supported Ni catalyst prepared by the one-pot hydrothermal route in the presence of both HCl and NaCl showed the best catalytic activity with high methane (81%) and carbon dioxide conversion (88%) values at 750 °C. The highest H₂ and CO selectivity values were obtained with the same catalyst with an H₂/CO molar ratio of 0.80. Therefore, these results showed that partial Al (0.11%) incorporated into the structure of SBA-15 was sufficient to improve the catalytic activity of the catalyst in dry reforming of methane.     

Synthesis of Ni@Al2O3 nanocomposite with superior activity and stability for hydrogen production from plastic-derived syngas by CO2-sorption-enhanced reforming

Catalytic dry (CO₂) reforming of plastic-derived syngas is a promising method of producing hydrogen-rich syngas and reducing greenhouse gases. The development of catalysts with high activity and stability is critical for this reaction. In this study, we fabricated core-shell structured Ni@Al₂O₃ catalysts with different shell thicknesses using advanced polyol and sol-gel methods. The effects of different Al/Ni ratios on the activity and stability of the catalysts in the CO₂ reforming reaction were investigated. The main challenge for CO₂ reforming of methane is carbon deposition. In the developed catalysts, the mesoporous Al₂O₃ coating outside the Ni core enhances the stability. However, the interaction between the core and the shell strongly affects the catalyst activity and product selectivity in the reaction. The catalyst with an Al/Ni ratio of 2 exhibited the highest methane conversion of up to 88% and the lowest carbon deposition, compared to the congeners with Al/Ni ratios of 1 and 3.     

Pre-reforming of liquefied petroleum gas over nickel catalysts supported on magnesium aluminum mixed oxides

A series of Ni/Mg_xAl catalysts with different Mg/Al molar ratios were prepared by impregnating Mg-Al mixed oxides with nickel nitrate aqueous solution and used for the pre-reforming of LPG in the temperature range of 400-500 °C. XRD and H₂-TPR results showed that the Ni/Mg_xAl catalysts calcined at 800 °C mainly consisted of γ-Al₂O₃, Mg(Ni)Al₂O₄ and Mg(Ni)O phases varying with Mg/Al molar ratio without free NiO species observed. The effects of Mg/Al molar ratio, S/C molar ratio and reaction temperature on the catalytic behavior of the Ni/Mg_xAl catalysts were investigated in detail. The results revealed that the catalyst with Mg/Al molar ratio of 1.25 had the highest catalytic activity and stability. The increase in S/C molar ratio promoted both the steam reforming of LPG and the methanation of carbon oxides and hydrogen. The stability tests of 15%Ni/Mg_1.25Al catalyst showed that the catalyst was stable for the pre-reforming of LPG, and the stability decreased with elevating the reaction temperature due to more coke deposition.     

Preparation of nanocrystalline Zr,La and Mg-promoted 10% Ni/Ce0.95Mn0.05O2 catalysts for syngas production via dry reforming reaction

The influence of the various promoters (Zr, La and Mg) on the physicochemical and catalytic characteristics of the 10% Ni/Ce_0.95Mn_0.05O₂ solid solution catalyst were investigated in methane dry reforming at atmospheric pressure. The co-precipitation method was employed for the synthesis of the catalyst carrier. The catalysts were characterized by BET, XRD, H₂-TPR and TPO analyses. The obtained results revealed that the addition of the promoters increased the BET surface area and the highest BET surface area was related to the catalyst promoted by La (58.99 m²/gr). The results of the TPR analysis showed that the broad peak related to the reduction of NiO species was shifted to the higher temperature, indicating the enhancement of the interaction between NiO particles and the support due to the addition of the promoter. The obtained results indicated that the addition of Mg improved the activity (CH₄ conversion (%) = 67 at 700 °C) and stability and reduced the amount of deposited carbon. Furthermore smaller Ni crystalline size was related to the catalyst promoted by Mg (10.0 nm). The highest and the lowest amount of carbon deposition was observed on the 10Ni/Ce_0.95Mn₀.₀₅O₂ and 10Ni/Ce_0.85Zr_0.10Mn_0.05O₂ catalysts, respectively.     

Reaction mechanism of naphtha steam reforming on nickel-based catalysts,and FTIR spectroscopy with CO adsorption to elucidate real active sites

To improve the understanding of the hydrocarbon steam reforming reaction mechanism and the nature of the active sites, different nickel-based catalysts have been synthesized and studied under several reaction conditions. Catalysts from hydrotalcite precursors show better activity and higher coking resistance than traditionally prepared samples. Furthermore, introducing additives (Ce, Li or Co) in the hydrotalcite structure produces no blockage of the nickel active sites. Different structural and physical–chemical properties have been analyzed by XRD, TPR, BET and elemental analysis. FTIR spectroscopy with CO adsorption reveals interesting catalyst structure–catalytic behavior relationships; oxygen release through the catalyst surface is key parameter to improve steam reforming activity and coking resistance; and, highly unsaturated Ni surface atoms located on the metal–support interphase are relevant structures to the catalysis and most active sites for the steam reforming reaction. Steam reforming reaction proposed sequence involves: 1) hydrocarbon preferably activation on active Ni surface sites and steam preferred activation on basic support surface sites, 2) oxygen spill-over from the support to the metal phase, and 3) reaction between carbon and oxygen species occurring on the metal–support interphase.     

Cu,Mg and Co effect on nickel-ceria supported catalysts for ethanol steam reforming reaction

Ethanol steam reforming is a promising reaction which produces hydrogen from bio and synthetic ethanol. In this study, the nano-structured Ni-based bimetallic supported catalysts containing Cu, Co and Mg were synthesized through impregnation method and characterized by XRD, BET, SEM, TPR and TPD analysis. The prepared catalysts were tested in steam reforming of ethanol in the S/C = 6, GHSV of 20,000 mL/(g_cat h) at the temperature range of 450–600 °C. Among the xNi/CeO₂ (x = 10, 13, 15 wt%) catalyst, the sample containing 13 wt% Ni with surface area of 64 m²/g showed the best performance with 89% ethanol conversion and 71% H₂ selectivity as well as low CO selectivity of 8% at 600 °C and The addition of Cu, Mg, and Co to catalyst structure were evaluated and it was found that the nature of second metal has a strong influence on the catalyst selectivity for H₂ production. Considering to results of TPR analysis, the 13Ni–4Cu/CeO₂ catalyst showed proper reduction which caused in better activity. On the other side based on TPD analysis, the more basic property of 13Ni–4Mg/CeO₂ bimetallic catalyst provided a better condition to methane steam reforming, leading to lower CH₄ selectivity and consequently more H₂ production. The 13Ni–4Cu/CeO₂ exhibited the highest activity and lowest selectivity towards ethanol conversion and CO production about 99% and 4%, while the 13Ni–4Mg/CeO₂ catalyst possessed the highest H₂ selectivity and lowest CH₄ selectivity about 74% and 1% respectively at 600 °C. The Ni–Cu and Ni–Mg bimetallic catalysts shows good stability with time on stream.     

Activity and stability enhancement of Ni-MCM-41 catalysts by Rh incorporation for hydrogen from dry reforming of methane

Ni incorporated and Ni–Rh incorporated bimetallic MCM-41 like mesoporous catalysts, which were synthesized following a one-pot hydrothermal procedure, showed very high activity in dry reforming of methane. Among the Ni incorporated catalysts, Ni-MCM-41-V, with a Ni/Si ratio of 0.19, showed the best catalytic performance. Rh incorporation into this catalyst by the one-pot procedure improved both activity and time on stream stability of the catalyst. However, Rh incorporation by impregnation caused instabilities due to coke formation, after about 11 h of reaction time. Occurrence of reverse water gas shift reaction caused higher CO selectivity than H₂ selectivity, with the Ni incorporated catalysts. Rh incorporation into these catalysts decreased the relative significance of reverse water gas shift reaction, with respect to dry reforming reaction.     

Biogas reforming over bimetallic PdNi catalysts supported on phosphorus-modified alumina

A series of bimetallic PdNi catalysts supported on alumina modified with different amounts of phosphorus (0.5-5 wt%) were prepared. The effect of phosphorus content on the structure, surface properties and catalytic behavior of supported PdNi catalysts in biogas reforming was studied. The physicochemical properties of the samples were characterized by using different techniques: N₂ adsorption-desorption isotherms, X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), temperature-programmed desorption of ammonia (TPD), thermogravimetric and differential thermal analysis (TG/DTA) and scanning transmission electron microscopy (STEM). The catalytic properties of the catalysts were evaluated in the reaction of reforming of methane with CO₂. It was shown that increasing the P content (≥1 wt%) leads to agglomeration of the metal Ni particles, as well as to increase of the total acidity of the catalysts. Within bimetallic system, the PdNi catalyst with 0.5 wt% phosphorus showed the best performance and stability caused by the presence of highly dispersed nickel particles on the catalyst surface due to the strong interaction between supported species and alumina.     

Coke-resistance over Rh–Ni bimetallic catalyst for low temperature dry reforming of methane

Methane and carbon dioxide can be converted into syngas using the prospective dry reforming of methane technology. Carbon deposition is a major cause of catalyst deactivation in this reaction, especially at low temperature. The superior stability of bimetallic catalysts has made their development more and more appealing. Herein, a series of bimetallic RhNi supported on MgAl₂O₄ catalysts were synthesized and used for low temperature biogas dry reforming. The results demonstrate that the bimetallic RhNi catalyst can convert CH₄ and CO₂ by up to 43% and 52% over at low reaction temperature (600 °C). Moreover, the reaction rate of CH₄ and CO₂ of RhNi–MgAl₂O₄ remains stable during the 20 h long time stability test, most importantly, there was no obviously carbon deposition observed over the spent catalyst. The enhanced coking resistance should be attributed to the addition of a little amount of noble metal Rh can efficiently suppress dissociation of CH_X1 species into carbon, and the high surface areas of MgAl₂O₄ support can also promote the adsorption and activation of carbon dioxide to generate more O1 species. Balancing the rate of methane dissociation and carbon dioxide activation to inhibit the development of carbon deposition is a good strategy, which provides a guidance for design other high performance dry reforming of methane catalysts.     

The effect of La2O3 and CeO2 modifiers on properties of Ni–Al catalysts for LNG prereforming

Ni/La–Al₂O₃ and Ni/Ce–Al₂O₃ catalysts with a small amount of promoters intended for prereforming of LNG were characterized by XRF, N₂ adsorption-desorption, XRD, H₂ chemisorption, HRTEM and XPS. The catalytic activity was evaluated in methane steam reforming both in the kinetic and diffusion regime, at temperatures characteristic of pre-reforming. Carbonaceous deposit was analysed by TPO-MS method. The nature and location of the coke were studied by HRTEM.La or Ce addition into Ni–Al system causes the increase of the active surface area of Ni by enhancing its dispersion. Studies at kinetic regime have shown that the promoted catalysts have almost twice the activity than reference Ni–Al catalyst. This effect was not confirmed by measurements in the diffusion regime on whole catalyst tablets. Almost identical textural properties of catalysts and diffusive limitations related to them but not the catalytic properties of the material itself appeared to be crucial factors. The presence of La (but not Ce) causes a significant increase in resistance to coking.     

Modification of silica supported nickel catalysts with lanthanum for stability improvement in methane reforming with CO2

Dry reforming of methane (DRM) with excessive methane composition at CH₄/CO₂ = 1.2:1 was studied over lanthanum modified silica supported nickel catalysts (Ni-xLa-SiO₂, x: 1, 2, 4, and 6% in the target weight percent of La). The catalysts were prepared by ammonia evaporation method. Nickel phyllosilicate and La₂O₃ were the main phases in calcined catalysts. The modification of La enhanced the formation of 1:1 and Tran-2:1 nickel-phyllosilicate. There existed an optimum content of La loading at 1.50 wt% in Ni–2La–SiO₂ which resulted in its highest reduction degree (95.3%). The catalysts with appropriate amounts of La exhibited higher amount of CO₂ adsorption and created more medium and strong base centers. The sufficient number of exposed metallic nickel sites to catalyze the reforming reaction, as well as enough medium and strong basic sites in Ni–La–SiO₂ interface to accomplish the carbon removal were two important factors to attenuate catalyst deactivation. The catalyst stability evaluated at 750 °C for 10 h followed the order: Ni–2La–SiO₂ > Ni–4La–SiO₂ > Ni–1La–SiO₂ ≈ Ni–6La–SiO₂ > Ni–SiO₂. Ni–2La–SiO₂ catalyst possessed the lowest deactivation behavior, whose CH₄ conversion dropped from 60.2 to 55.9% after 30 h operation at 750 °C, indicating its high resistance against carbon deposition and sintering.     

Biogas dry reforming for hydrogen production over Ni-M-Al catalysts (M = Mg,Li, Ca,La, Cu,Co, Zn)

Biogas can be highlighted as a renewable raw material for the production of hydrogen. In this study, Ni-M-Al catalysts were evaluated to obtain hydrogen from the biogas reforming. The catalysts were synthesized by coprecipitation with Ni and Al with a molar percentage of 55 and 33%, respectively, varying the third component M = Mg, Li, Ca, La, Cu, Co, Zn, with a molar percentage of 11%. The reactions were carried out in a fixed bed tubular reactor using a synthetic biogas (70% of CH₄ and 30% of CO₂). The results showed that the CH₄ conversion increased with the temperature up to 700 °C for La11, Cu11, and Zn11 catalysts. CO₂ conversion increased for all catalysts in the range of 500–700 °C. The H₂/CO molar ratios observed in the reactions were higher than 1 due to the contribution of the CH₄ decomposition reaction. The catalyst containing La presented better stability in the reactions due to the stronger acid sites and high resistance to sintering. Carbon filaments were produced by all catalysts at 600 and 700 °C. Sintering was the main cause of deactivation of the catalysts, except for La11.