Modification of alumina support with TiO2-P25 in CO2 reforming of CH4

Catalyst activity and stability for CO₂ reforming of CH₄ depends specifically upon the support and the active metal. A side reaction of dry reforming of methane is the decomposition to carbon that covers the Ni particles causing catalyst deactivation. Hence, an appropriate combination of Ni with support is needed to allow for long term stable operation. In this paper, CO₂ reforming of CH₄ is studied by investigating the effect of addition of TiO₂-P25 separately to γ-Al₂O₃ and α-Al₂O₃ supports used for nickel based catalyst. The reforming reactions are performed using (CO₂:CH₄) feed ratio of 1:1 and reaction temperature range of 500–800 °C. Both fresh and used catalysts are characterized by SEM and TGA techniques. It is found when α-Al₂O₃ support is modified with 20 wt% TiO₂-P25, the catalyst activity and stability is enhanced. The conversion rates of CH₄ and CO₂ without and with 20 wt% TiO₂-P25, respectively, are changed from 72.3% to 76.7% and 73.3% to 81.2%, respectively, and, most importantly, carbon formation is reduced from 28.1 to 12.8, respectively. However, when γ-Al₂O₃ support is modified with TiO₂-P25, the catalyst activity is enhanced with simultaneous increase in carbon formation.     

Catalytic CO2 reforming of methane over Ir/Ce0.9Gd0.1O2−x

CO₂ reforming of methane over Ir loaded Ce_0.9Gd_0.1O_2−x (Ir/CGO) has been studied between 600 and 800 °C and for CH₄/CO₂ ratios between 2 and 0.66 in order to evaluate its potential use as an anode material for direct conversion of biogas at moderate temperatures in solid oxide fuel cells. The catalyst exhibited a superior catalytic activity compared to the support alone and other Ir based catalysts. High CH₄/CO₂ ratios and temperatures were required to obtain the maximum H₂/CO ratio, which could never exceed unity. Long-term experiments were carried out, showing the excellent stability of the catalyst with time on stream. Carbon formation was totally inhibited (in most experimental conditions) or very limited in the most severe conditions of the study (800 °C, CH₄/CO₂ = 2). This carbon was found to be highly reactive towards O₂ upon TPO experiments.     

Low-temperature continuous wet oxidation of trichloroethylene over CoOx/TiO2 catalysts

TiO₂-supported metal oxides such as CoO_x, CuO_x, NiO_x and FeO_x have been used for catalytic wet oxidation of trichloroethylene (TCE) in a continuous flow type fixed-bed reactor system, and the most promising catalyst for this wet catalysis has been characterized using XPS and XRD techniques. All the supported catalysts gave relatively low conversions for the wet oxidation at 36 °C, except for 5 wt% CoO_x/TiO₂ which exhibited a steady-state conversion of 45% via a transient activity behavior up to 1 h on stream. XPS measurements yielded that a Co 2p_3/2 main peak at 779.8 eV appeared with the 5 wt% CoO_x/TiO₂ catalyst after the continuous wet TCE oxidation at 36 °C for ca. 6 h (spent catalyst) and this binding energy value was equal to that of Co₃O₄ among reference Co compounds used here, while the catalyst calcined at 570 °C (fresh catalyst) possessed a main peak at 781.3 eV, very similar to that for CoTiO_x species such as CoTiO₃ and Co₂TiO₄. Only characteristic reflections for Co₃O₄ were indicated upon XRD measurements even with the fresh catalyst sample. The simplest model, based on these XPS and XRD results, for nanosized Co₃O₄ particles existing with the fresh catalyst could reasonably explain the transient activity behavior observed upon the wet TCE oxidation.     

Dry reforming of methane over LaNi1−yByO3±δ (B = Mg,Co) perovskites used as catalyst precursor

Perovskites LaNiO₃, LaNi_1−xMg_xO_3−δ and LaNi_1−xCo_xO_3−δ were synthesized by auto combustion method. TPR analysis reveled that Mg or Co substituted perovskites were more difficult to reduce. The perovskites were evaluated as catalyst precursors in the dry reforming of methane. Catalysts obtained by reduction of LaNiO₃ and LaNi_1−xMg_xO_3−δ perovskite had the highest catalytic activity for CO₂ reforming of CH₄ at 700 °C using drastic reaction conditions (10 mg of catalyst, a mixture of CH₄/CO₂ without dilution gas). Methane and carbon dioxide conversions were 57% and 67%, respectively, with a H₂/CO ratio equal to 0.47.The presence of cobalt leads to a decrease of the catalytic activity. This decreasing of activity may be attributed to the Co–Ni alloy formation. Computational calculations revealed that Ni atom cleaves the C–H atom while Co is not able to activate the CH₄ molecule. The interaction energy of CH₄ with the Ni and CO atom was 18 kcal/mol and 0.7 kcal/mol, respectively.The catalysts were characterized by TPR, TEM and in situ XRD.     

Methanation of carbon dioxide over mesoporous Ni–Fe–Ru–Al2O3 xerogel catalysts: Effect of ruthenium content

Mesoporous nickel (35 wt%)–iron (5 wt%)–ruthenium (x wt%)–alumina xerogel (denoted as 35Ni5FexRuAX) catalysts with different ruthenium contents (x = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) were prepared by a single-step sol–gel method for use in the methane production from CO₂ and H₂. Conversion of CO₂, yield for CH₄, metal surface area, and the amount of desorbed carbon dioxide of the catalysts showed volcano-shaped trends with respect to ruthenium content. Experimental results revealed that metal surface area and the amount of desorbed carbon dioxide of 35Ni5FexRu catalysts were well correlated with conversion of CO₂ and yield for CH₄.     

Impact of support oxide and Ba loading on the NOx storage properties of Pt/Ba/support catalysts: CO2 and H2O effects

A series of 1 wt.%Pt/_xBa/Support (Support = Al₂O₃, SiO₂, Al₂O₃-5.5 wt.%SiO₂ and Ce_0.7Zr_0.3O₂, x = 5–30 wt.% BaO) catalysts was investigated regarding the influence of the support oxide on Ba properties for the rapid NO_x trapping (100 s). Catalysts were treated at 700 °C under wet oxidizing atmosphere. The nature of the support oxide and the Ba loading influenced the Pt–Ba proximity, the Ba dispersion and then the surface basicity of the catalysts estimated by CO₂-TPD. At high temperature (400 °C) in the absence of CO₂ and H₂O, the NO_x storage capacity increased with the catalyst basicity: Pt/20Ba/Si < Pt/20Ba/Al5.5Si < Pt/10Ba/Al < Pt/5Ba/CeZr < Pt/30Ba/Al5.5Si < Pt/20Ba/Al < Pt/10BaCeZr. Addition of CO₂ decreased catalyst performances. The inhibiting effect of CO₂ on the NO_x uptake increased generally with both the catalyst basicity and the storage temperature. Water negatively affected the NO_x storage capacity, this effect being higher on alumina containing catalysts than on ceria–zirconia samples. When both CO₂ and H₂O were present in the inlet gas, a cumulative effect was observed at low temperatures (200 °C and 300 °C) whereas mainly CO₂ was responsible for the loss of NO_x storage capacity at 400 °C. Finally, under realistic conditions (H₂O and CO₂) the Pt/20Ba/Al5.5Si catalyst showed the best performances for the rapid NO_x uptake in the 200–400 °C temperature range. It resulted mainly from: (i) enhanced dispersions of platinum and barium on the alumina–silica support, (ii) a high Pt–Ba proximity and (iii) a low basicity of the catalyst which limits the CO₂ competition for the storage sites.     

Syngas production via CO2 reforming of methane using Co-Sr-Al catalyst

The effect of addition of strontium in Co based catalysts during CO₂ reforming of methane was investigated in the temperature range 500–700 °C. The Co/γ-Al₂O₃ supported catalysts with strontium as a promoter (0–2.25 wt%) were prepared by incipient wet impregnation method. Numerous techniques such as N₂ adsorption–desorption isotherm, H₂ temperature-programmed reduction (TPR), temperature-programmed desorption (TPD), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Transmission Electron Microscopy (TEM), pulse chemisorption and temperature-programmed oxidation (TPO) were applied for characterization of fresh and spent catalysts. The results of characterizations and catalyst activity test revealed that introduction of Sr in Co/γ-Al₂O₃ catalyst had significant effect on stability and coke suppression. The Sr addition improves the metal–support interaction as well as enhances the Lewis basicity of the catalyst. The improvement in basicity helps the chemisorption and dissociation of CO₂ over the catalyst which in turn reduces carbon deposition.     

Comparative study between fluidized bed and fixed bed reactors in methane reforming combined with methane combustion for the internal heat supply under pressurized condition

The effect of catalyst fluidization on the conversion of methane to syngas in methane reforming with CO₂ and H₂O in the presence of O₂ under pressurized conditions was investigated over Ni and Pt catalysts. Methane and CO₂ conversion in the fluidized bed reactor was higher than those in the fixed bed reactor over Ni_0.15Mg_0.85O catalyst under 1.0 MPa. This reactor effect was dependent on the catalyst properties. Conversion levels in the fluidized and fixed bed reactor were almost the same over MgO-supported Ni and Pt catalysts. It is suggested that this phenomenon is related to the catalyst reducibility. On a catalyst with suitable reducibility, the oxidized catalyst can be reduced with the produced syngas and the reforming activity regenerates in the fluidized bed reactor. Although serious carbon deposition was observed on Ni_0.15Mg_0.85O in the fixed bed reactor, it was inhibited in the fluidized bed reactor.     

Synthesis of ordered mesoporous manganese titanium composite oxide catalyst for catalytic ozonation

In this account, highly ordered mesoporous MnO_x/TiO₂ composite catalysts with efficient catalytic ozonation of phenol degradation were synthesized by the sol–gel method. The surface morphology and properties of the catalysts were characterized by several analytical methods, including SEM, TEM, BET, XRD, FTIR, and XPS. Interestingly, Mn doping was found to improve the degree of order, and the ordered mesoporous structure was optimized at 3% doping. Meanwhile, MnO_x was highly dispersed in the ordered mesoporous materials to yield good catalytic ozonation performance. Phenol could completely be degraded in 20 min and mineralized at 79% in 60 min. Thus, the catalyst greatly improved the efficiency of degradation and mineralization of phenol when compared to single O₃ or O₃ + TiO₂. Finally, the reaction mechanism of the catalyst was discussed and found to conform to pseudo-first-order reaction dynamics.     

Modulation of selective sites by introduction of N2O,CO2 and H2 as gaseous promoters into the feed during oxidation reactions

Results obtained by adding gaseous promoters (CO₂, N₂O and H₂) into the reaction feed are presented for two different reactions: (i) oxidative dehydrogenation of propane (ODP), and (ii) catalytic combustion of methane (CCM). The ODP is performed on a mixture of NiMoO₄ and CeO₂, by adding 3 vol.% CO₂ into the feed, and on a NiMoO₄/[Si,V]-MCM-41 mesoporous catalyst, in the presence of 1 or 5 vol.% N₂O in the feed. The CCM is carried out (i) on Pd(2 wt.%)/Ce_xZr_1−xO₂ and Pd(2 wt.%)/γ-Al₂O₃ catalysts, on pure CeO₂ and on a mixture of Pd(2 wt.%)/γ-Al₂O₃ and CeO₂ powders, by adding 3 vol.% CO₂ into the feed, and (ii) on a Pd(2 wt.%)/γ-Al₂O₃ catalyst, in the presence of various amounts of H₂ in the feed. It is shown, through all these various examples, that the activity and/or the selectivity of catalysts can be improved by tuning, in a very controlled manner, the oxidation state of active sites via the use of these gaseous promoters.     

Complementary effect of plasma–catalysis hybrid system on methane complete oxidation over non-PGM catalysts

Methane complete oxidation reaction was carried out in a non-thermal plasma (dielectric barrier discharge) quartz tube reactor where both plasma and catalyst were combined into one in-plasma catalysis system. In plasma only condition, the CO selectivity was maintained at high value (~ 50%) until the temperature reached about 200 °C. In the presence of both plasma and catalyst, however, methane was oxidized even at room temperature mostly to CO₂ with low CO selectivity over certain non-PGM catalyst like Co₁Ni₁O_x. Hence, methane complete oxidation reaction proceeded at much lower temperature similar to PGM catalyst such as Pd/Al₂O₃, while maintaining low CO selectivity.     

Bi-Co3O4 catalyzing N2O decomposition with strong resistance to CO2

Bi added to Co₃O₄ by coprecipitation method significantly decreased the average crystalline size of Co₃O₄ and increased the surface area and the active sites of the catalyst in population for catalyzing the N₂O decomposition. Over Bi_0.02Co that was the optimized from the Bi_xCo catalysts, 2000 ppm of N₂O in pure Ar was completely decomposed at 400 °C in GHSV of 20,000 h^− 1. Outstandingly, the catalyst exhibited a strong resistance to CO₂, stable N₂O conversion larger than 95% was obtained over the catalyst in the presence of 10% CO₂ at the reaction temperature.     

Transient study of the dry reforming of methane over Pt supported on different γ-Al2O3

CO₂ reforming of methane has been studied over Pt/Al₂O₃ model catalysts in a temperature range of 600–800 °C using steady-state and transient methods (Transient Response Method (TRM) and DRIFT-MS). Pt-supported catalysts were prepared using two different alumina (γ-Al₂O₃(S) Sasol-Puralox and a synthesized γ-Al₂O₃(N) with nanofibrous structure). Catalysts and supports were characterized by conventional methods (XRD, TEM, A_BET, XPS) before and after reaction. Pt⁰ species are present in the catalysts, with a higher relative contribution for the catalyst that has a nanostructured support. Pt/γ-Al₂O₃(N) catalyst presented the best performance in reactivity and showed a low rate of carbon formation and a minimal water production. From TRM and DRIFT-MS results it can be concluded that, when CO₂ and CH₄ are fed separately into the reaction system, they are activated over the catalytic surface. Besides, when both reactants are fed contemporaneously the presence of CH_X species promotes the CO₂ activation that is responsible for the reforming reaction.     

Enhanced activity of MnxW0.05Ti0.95 − xO2 − δ for selective catalytic reduction of NOx with ammonia by self-propagating high-temperature synthesis

A series of TiO₂ supported MnWO_x catalysts Mn_xW_0.05Ti_0.95 − xO_2 − δ (x = 0.05, 0.1, 0.15) were synthesized by solution combustion method. The Mn_0.10W_0.05Ti_0.85O_2 − δ catalyst showed highest activity in NH₃-SCR reaction within a broad temperature range of 200 °C–400 °C. XRD and TEM results indicate that the active Mn and W species are highly dispersed over TiO₂ support in the form of nanoparticles (4–7 nm). The TEM and H₂-TPR results also suggest that a MnWO_x phase has been formed on the TiO₂, which is beneficial for the activity of the Mn_xW_0.05Ti_0.95 − xO_2 − δ catalysts in the high temperature range of 280 °C–400 °C.     

Highly efficient non-noble metal based nanostructured catalysts for selective CO methanation

Highly efficient non-noble metal based catalysts (Zr_1 − xNi_xO₂) showed outstanding catalytic performance at lower temperature for selective CO methanation. The characterization techniques revealed that Zr_1 − xNi_xO₂ catalyst contained uniformly dispersed Ni particles with strong interaction between Ni and ZrO₂.     

Surface modification of Ni catalysts with trace Pt for oxidative steam reforming of methane

Hysteresis of catalytic performance with respect to temperature increasing and decreasing in oxidative steam reforming of methane (CH₄/H₂O/O₂/Ar = 40/30/20/10) over the monometallic Ni catalysts disappeared by the modification with Pt, and the additive effect of Pt by the sequential impregnation method (Pt/Ni) was much more significant than that by the co-impregnation method (Pt + Ni) in terms of catalytic performance and catalyst bed temperature profile. Characterization results by means of TEM, TPR, EXAFS, and FTIR suggest that the Pt atoms on the Pt/Ni catalysts were located more preferably on the surface to form a PtNi alloy than those on the Pt + Ni catalysts. The modification of Ni with Pt suppressed the oxidation of Ni species near the bed inlet in the oxidative steam reforming of methane at 1123 K, although the species on the monometallic Ni catalysts were oxidized under similar conditions. This can be due to the decreased oxidation rate of the species and the increased reduction rate caused by the surface modification of Ni with Pt. Consequently, the PtNi species can be maintained in the metallic state near the bed inlet, and the species can be the active site for the reforming reaction as well as the combustion reaction, which this leads to a lower bed temperature and smaller temperature gradient than those seen for the monometallic Ni catalysts.     

Plasma catalysis over lanthanum substituted perovskites

The removal of CH₄ (3600 ppm) with O₂ (3 × 10⁴ ppm) in mixtures with Ar or N₂ as carrier gas has been studied in a plasma-catalyst system. The plasma yields CO plus H₂O as majority products. A small extra oxidation to CO₂ is found at 338 K when a catalyst (SiO₂ or La_1−xSr_xCoO_3−d (x = 0.5) perovskite) is placed in the glow zone of the plasma. With the perovskite, the oxidation efficiency to CO₂ increased with temperature up to 90% at 453 K. This result supports that this lanthanum substituted cobaltite further activates the plasma species producing a synergetic effect where the specific surface area is not a critical factor as previously reported in the literature.     

Catalytic oxidation of benzene with ozone over Mn ion-exchanged zeolites

Catalytic oxidation of benzene with ozone was carried out over Mn ion-exchanged zeolites at 343 K. Benzene was oxidized on Mn-Y to form CO_x without the release of organic byproducts, whereas formic acid was formed with supported manganese oxide catalysts, Mn/SiO₂ and Mn/SiO₂–Al₂O₃. Mn-Y showed higher activity and selectivity to CO₂ than other zeolite catalysts, Mn-β, Mn-MOR, and Mn-ZSM-5. Linear relationship was observed between benzene consumption, CO_x formation and ozone consumption. Formic acid adsorbed on Mn-Y catalyst was completely oxidized to CO₂ with ozone at around 343 K.     

Mesoporous CuO/TixZr1 − xO2 catalysts for low-temperature CO oxidation

Mesoporous CuO/Ti_xZr_1 − xO₂ catalysts were prepared by a surfactant-assisted method, and characterized by N₂ adsorption/desorption, TEM, XPS, in-situ FTIR and H₂-TPR. The catalysts exhibited high specific surface area (S_BET = 241 m²/g) and uniform pore size distribution. XPS and in-situ FTIR displayed that Cu⁺ and Cu²⁺ species coexisted in the catalysts. The CuO/Ti_xZr_1 − xO₂ catalysts presented obviously higher activity in CO oxidation reaction than the CuO/TiO₂ and CuO/ZrO₂ catalysts. Effect of molar ratios of Ti to Zr and calcination temperature on catalytic activity was investigated. The CuO/Ti_0.6Zr_0.4O₂ catalyst calcined at 400 °C exhibited excellent activity with 100% CO conversion at 140 °C.     

Effects of preparation methods on the properties of cobalt/carbon catalyst for methane reforming with carbon dioxide to syngas

The effect of different preparation methods on the physicochemical property, reforming reactivity, stability and carbon deposition resistance of cobalt/carbon catalyst was investigated through fixed bed flow reaction. The catalysts were prepared by the impregnation and characterized by the XRD and scanning electron microscopy (SEM). The result indicated that the active components of cobalt/carbon catalyst prepared by using ultrasonic wave distributed evenly, activity was high and the loading time was short. The Co/Carbon catalyst prepared by incipient-wetness impregnation, 10 wt% loading and 300 °C calcination, achieved the best activity. Furthermore, the effect of reaction temperature, air speed and CH₄/CO₂ ratio on the catalyst activity and CO/H₂ ratio in products was investigated. It was found that the conversion of CO₂ and CH₄ increased with the increasing of reaction temperature. However, the conversion of CO₂ and CH₄ increased first and then decreased with the increasing of air speed. With the increasing of CH₄/CO₂ in feed gas, both the catalyst activity and the CO/H₂ ratio in products decreased.