Mn/Mg/Al-spinels as catalysts for SOx abatement: Influence of CeO2 incorporation and catalytic stability

Mg,Mn,Al-oxides with spinel structure, Al/(M²⁺ + Al) molar ratio of 0.25 and 0.50 and an Mn/Mg molar ratio of 0.30 have been evaluated as catalysts for SO_x removal under conditions similar to those found in FCC units. The best performance was that of the sample with the higher aluminium content. The incorporation of CeO₂ in this sample favored SO_x uptake for short reaction times as well as the reduction of the sulfated catalysts. When the regeneration was started at 530 °C, only H₂S was observed as reaction product, but when this step started at 650 °C, the release of SO₂ preceded that of H₂S, regardless of the chemical composition of the sample. As to the additive performance for successive reaction–regeneration cycles, the incorporation of CeO₂ produced a less efficient catalyst with regard to the removal of the SO₂ along the process, but with a higher regeneration efficiency and a lower formation of SO₂ as regeneration product.     

Metallic mixed oxides (Pt,Mn or Cr) as catalysts for the gas-phase toluene oxidation

The gas-phase toluene oxidation was studied over metal containing mixed oxides derived from hydrotalcite-like compounds with high specific surface area. Both the catalysts with platinum and manganese showed to be promising catalysts, due to its good activity and low light-off temperature. Special attention must be paid to the platinum catalyst, which showed a light-off at 460 K and complete toluene oxidation at 635 K. No other products besides CO₂, CO and H₂O were observed.     

Influence of the Chemical Composition of MgAlFeCu Mixed Oxides as Catalysts for SO2 Removal

A series of MgAlFeCu mixed oxides with different chemical compositions derived from hydrotalcite-like compounds were prepared by the NaAlO₂-coprecipitation method and characterized by XRF, XRD, and N₂ adsorption analysis. These sulfur-transfer catalysts were evaluated as SO_x removal catalysts under the conditions similar to those of FCC units. The results showed that the total SO₂ adsorption amounts increased with increasing magnesium content. And the redox properties of Fe₂O₃ enhanced significantly the adsorption-reduction capacities of the catalysts, while CuO can be used as an effective oxidation promoter. Furthermore, the catalyst LDOs-6 (Mg/Al = 6, Fe₂O₃% = 8% and CuO% = 1%) presented the excellent SO₂ removal capacity, its total amounts of adsorbed SO₂ reached 1.74 g /g in 7 min, which also remained constant after eight cycles. These results indicated that the performances of the catalysts were closely related to the chemical composition.     

Influence of the preparation process on the performance of three hydrotalcite-based De-SOx catalysts

In this study, three hydrotalcite-based De-SO_x catalysts were prepared using different approaches: impregnation, coprecipitation, and precipitation using the separate nucleation and aging steps (SNAS) method. The physicochemical properties of these catalysts were studied and their SO_x removal behaviors were characterized with a custom-built apparatus simulating the conditions in a fluid catalytic cracking (FCC) regenerator. The results showed that the catalyst prepared using the SNAS method had the highest SO_x adsorption rate, the largest SO_x pick-up capacity (1.31 g/g cat.) and the lowest onset reduction temperature (805 K), which makes it an excellent De-SO_x catalyst with promising applications in industry.     

Characterization of Zn–Ni–Fe hydrotalcite-derived oxides and their application in the hydrolysis of carbonyl sulfide

A series of Zn, Ni and Fe containing hydrotalcite-like compounds with various M²⁺/M³⁺ ratios were synthesized by co-precipitation method at pH = 10. The products were characterized by XRD, SEM, TG-DTA, FTIR, CO₂-TPD and N₂ adsorption/desorption techniques. The results showed that M²⁺/M³⁺ ratio affected the formation of hydrotalcite crystal seriously. The precursors with M²⁺/M³⁺ mole ratio of 2 and 3 showed pure hydrotalcite phase. After calcination at 250 °C, the derived oxides with larger surface area and more basic sites were obtained. Desulfurization tests showed that the Zn–Ni–Fe hydrotalcite-derived oxide exhibited an excellent activity in low temperature hydrolysis of COS. The optimum M²⁺/M³⁺ mole ratio was 3.     

Catalytic combustion of toluene over Fe–Mn mixed oxides supported on cordierite

The catalytic combustion of toluene over Fe–Mn mixed oxides supported on cordierite was investigated. The catalysts were synthesized by the impregnation method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and BET specific surface area measurement. The effects of the mole ratio of Fe to Mn, the loading of Fe–Mn mixed oxides on the catalyst support and the calcination temperature were all investigated. The results indicate that Fe–Mn/cordierite catalysts with a 4 mol ratio of Fe to Mn, used with 10 wt% loading, and calcined at 500 ^°C showed the highest catalytic activities as measured by the oxidation of toluene. Compared to unsupported powder catalysts of Fe–Mn mixed oxides, the Fe–Mn/cordierite catalyst showed higher activity for the catalytic combustion of toluene with less active component.     

Catalytic performance of LaCo0.5M0.5O3 (M = Mn,Cr, Fe,Ni, Cu) perovskite-type oxides and LaCo0.5Mn0.5O3 supported on cordierite for CO oxidation

Catalytic combustion of CO over perovskite-type oxides LaCo_0.5M_0.5O₃ (M = Mn, Cr, Fe, Ni, Cu) and LaCo_0.5Mn_0.5O₃ supported on cordierite were investigated. The catalysts were synthesized by impregnation method with citrate and characterized by XRD, SEM and TPR. The LaCo_0.5Mn_0.5O₃ catalyst showed much higher activity in CO oxidation compared with LaCo_0.5M_0.5O₃ (M = Cr, Fe, Ni, Cu) due to different kinds of valence state and lattice oxygen content. When LaCo_0.5Mn_0.5O₃ was supported on cordierite, the activity was improved significantly. However, calcining temperature and the presence of water vapor affected the catalytic activity due to sintering and competition of H₂O with CO for adsorption, respectively.     

Effects of Fe addition on the structure and catalytic performance of mesoporous Mn/Al–SBA-15 catalysts for the reduction of NO with ammonia

Mesoporous Al–SBA-15 has been synthesized by a hydrothermal method and used as a support for Mn/Al–SBA-15, Fe/Al–SBA-15, and Mn–Fe/Al–SBA-15 catalysts. XRD, N₂ sorption, XPS, H₂-TPR and activity tests have been used to assess the properties of catalysts. The Mn–Fe/Al–SBA-15 catalyst exhibited a higher SCR activity than Mn/Al–SBA-15 or Fe/Al–SBA-15 due to a synergistic effect between Mn and Fe. After the addition of Fe, the binding energy of Mn 2p_3/2 on Mn–Fe/Al–SBA-15(573) decreased by about 0.4 eV and the Mn^4 +/Mn^3 + ratio decreased to 1.10. The appropriate Mn^4 +/Mn^3 + ratio may have a great effect on the reduction of NO over Mn–Fe/Al–SBA-15(573) catalyst.     

Role of ceria in the improvement of SO2 resistance of LaxCe1 − xFeO3 catalysts for catalytic reduction of NO with CO

Perovskite-type catalysts with LaFeO₃ and substituted La_xCe_1 − xFeO₃ compositions were prepared by sol–gel method. These catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), CO temperature-programmed reduction (CO-TPR), and SO₂ temperature-programmed desorption (SO₂-TPD). Catalytic reaction for NO reduction with CO in the presence of SO₂ has been investigated in this study. LaFeO₃ exhibited an excellent catalytic activity without SO₂, but decreased sharply when SO₂ gas was added to the CO + NO reaction system. In order to inhibit the effect of SO₂, substitution of Ce in the structure of LaFeO₃ perovskite has been investigated. It was found that La_0.6Ce_0.4FeO₃ showed the maximum SO₂ resistance among a series of La_xCe_1 − xFeO3 composite oxides.     

Catalytic conversion of CO,NO and SO2 on the supported sulfide catalyst: I. Catalytic reduction of SO2 by CO

Catalytic reduction of SO₂ to elemental sulfur by CO has been systematically investigated over γ-Al₂O₃-supported sulfide catalysts of transition metals including Co, Mo, Fe, CoMo and FeMo with different loadings of the metals. The sulfided CoMo/Al₂O₃ exhibited outstanding activity: a complete conversion of SO₂ was achieved at a temperature of 300°C. The reaction proceeds catalytically and consistently over time and most efficiently at a molar feed ratio CO/SO₂ = 2. A precursor CoMo/Al₂O₃ oxide which experienced sulfurization through the CO–SO₂ reaction yielded a working sulfide catalyst having a yet lower activity than the CoMo catalyst sulfided before reaction (pre-sulfiding). The catalytic activity of various metal sulfides decreased in order of 4% Co 16% Mo > 4% Fe15% Mo > 16% Mo ≥ 25% Mo > 14% Co ≥ 4% Co > 4% Fe. A DRIFT study showed that CO adsorbs exclusively on CoMo phase and that SO₂ predominantly on γ-Al₂O₃. It is suggested that the Co–Mo–S structure is more adequate than the other metal-sulfur structures for the formation of a carbonyl sulfide (COS) intermediate because of the proper strength of metal–sulfur bond, and catalytically works with γ-Al₂O₃ for the COS–SO₂ reaction.     

Hydrogen production by aqueous-phase reforming of ethanol over nickel catalysts prepared from hydrotalcite precursors

Derived hydrotalcite catalysts, with different Ni loadings, were prepared and tested in aqueous-phase reforming of ethanol. Upon calcination of the hydrotalcite-like compounds, there was formation of MgO periclase-type phase, where both nickel and aluminum oxides are well dispersed. The mixed oxides showed only one reduction peak in temperature range of 900–1000 °C. The catalytic tests were carried out in a batch reactor with an aqueous solution of 1 wt.% ethanol at different temperatures (200, 230 and 250 °C). The derived hydrotalcite catalysts showed high activity, with 65% of ethanol conversion at 230 °C, high hydrogen selectivity and lower methane production than alumina supported nickel catalyst.     

Highly dispersed Mn–Ce mixed oxides supported on carbon nanotubes for low-temperature NO reduction with NH3

A series of Mn–Ce mixed-oxide catalysts supported on carbon nanotubes (CNTs) were prepared for the first time and used for the selective catalytic reduction of NO with NH₃. Mn(0.4)-Ce/CNTs catalysts with loading from 0.6% to 1.8% (molar ratio) in our tests showed more than 90% NO conversion at 120–180 °C at a high space velocity of 42,000 h^− 1. Transmission electron microscopy confirmed that the particle size of Mn–Ce mixed oxides supported on CNTs was 2 to 4 nm. BET result indicated Mn–Ce mixed-oxide catalysts obtained enlarged surface area and pore volume which was beneficial to the catalytic activity.     

Mercury oxidation by hydrochloric acid over TiO2 supported metal oxide catalysts in coal combustion flue gas

Mercury oxidation by hydrochloric acid over the metal oxides supported by anatase type TiO₂ catalysts, 1 wt.% MO_x/TiO₂ where M = V, Cr, Mn, Fe, Ni, Cu, and Mo, was investigated by the Hg⁰ oxidation and the NO reduction measurements both in the presence and absence of NH₃. The catalysts were characterized by BET surface area measurement and Raman spectroscopy. The metal oxides added to the catalyst were observed to disperse well on the TiO₂ surface. For all catalysts studied, the Hg⁰ oxidation by hydrochloric acid was confirmed to proceed. The activity of the catalysts was found to follow the trend MoO₃ ~ V₂O₅ > Cr₂O₃ > Mn₂O₃ > Fe₂O₃ > CuO > NiO. The Hg⁰ oxidation activity of all catalysts was depressed considerably by adding NH₃ to the reactant stream. This suggests that the metal oxide catalysts undergo the inhibition effect by NH₃. The activity trend of the Hg⁰ oxidation in the presence of NH₃ was different from that observed in its absence. A good correlation was found between the NO reduction and the Hg⁰ oxidation activities in the NH₃ present condition. The catalyst having high NO reduction activity such as V₂O₅/TiO₂ showed high Hg⁰ oxidation activity. The result obtained in this study suggests that the oxidation of Hg⁰ proceeds through the reaction mechanism, in which HCl competes for the active catalyst sites against NH₃. NH₃ adsorption may predominate over the adsorption of HCl in the presence of NH₃.     

Surfactant-assisted synthesis and catalytic activity for SOx abatement of high-surface-area CuMgAlCe mixed oxides

CuMgAlCe mixed oxides were prepared by a modified coprecipitation–calcination method using CTAB as surfactant template. All the precursors showed hydrotalcite-like layered structure and mixed oxides with mainly periclase phase were obtained after calcination. Catalytic activity for SO₂ removal of mixed oxides was examined through adsorption–reduction cycles under the conditions similar to those of FCC units. The results showed that incorporation of both Ce and Cu could improve SO_x oxidative chemisorption. CTAB/metal molar ratio during synthesis had a significant influence on the structural properties of mixed oxides. Sample CuMgAlCe-0.1 prepared by CTAB/metal molar ratio of 0.1 had the highest specific area 142.2 m²/g and also presented the best SO₂ adsorption rate and capacity. This behavior is mainly due to its exposed more adsorption sites provided by high specific surface area, facilitating SO₂ diffusion and contact with active components. It still possessed excellent cyclic stability that is beneficial for industrial application.     

Effect of Cu content on the bifunctional Fischer–Tropsch Fe–Cu–K/ZSM5 catalyst

A series of bifunctional 20Fe–Cu(x)–4K/ZSM5 (x = 0, 2, 4 and 6 wt.%) catalysts were prepared to elucidate the effect of Cu promoter on F–T synthesis functionality. The catalysts were characterized by nitrogen adsorption, X-ray diffraction, temperature-programmed reduction, thermal analysis and temperature-programmed desorption of NH₃. Although addition of Cu essentially increases the initial activity, its effect is not significant at steady-state reaction. At 2 wt.%Cu loading, the homogeneous mixing of Fe and Cu oxides results in iron carbide formation, however, beyond this loading phase segregation occurs and eventually decreases the reducibility and acid site density, as reflected in the activity and selectivity.     

SO42−–Mn–Co–Ce supported on TiO2/SiO2 with high sulfur durability for low-temperature SCR of NO with NH3

The catalysts SO₄^2 − Mn–Co–Ce/TiO₂/SiO₂ were investigated for the low-temperature SCR of NO with NH₃ in the presence of SO₂. An excellent SO₂ durability at low temperature was obtained with the catalyst used TiO₂/SiO₂ as support and modified with SO₄^2 −. The catalyst sulfated with 0.1 mol/L H₂SO₄ solution and then calcined at 300 °C exhibited the best NO_x conversion efficiency of 99.5% at 250 °C in the presence of 50 ppm SO₂. The conversion efficiency did not decrease after repeatedly used for 8 times.     

Thermodynamic calculation for the activity and mechanism of Mn/TiO2 catalyst doped transition metals for SCR at low temperature

The introduction of transition metals in Mn/TiO₂ catalysts played significant roles in oxidative abstraction of hydrogen from adsorbed ammonia during the selective catalytic reduction (SCR). Thermodynamic calculation studies showed that the SCR performance was in accordance with the ammonia oxidation with transition metals, and the reaction tendency for the ammonia oxidation was decreased in the following order: CuO > Co₃O₄ > NiO > Fe₂O₃ > Cr₂O₃ > ZnO > La₂O₃ > CeO₂ > ZrO₂. In addition, Mn/TiO₂ catalyst doped metal (Fe and Cu) oxides enhanced performance for NO_x conversion, being approximately 100% at 453 K.     

Bi-metallic catalysts of mesoporous Al2O3 supported on Fe,Ni and Mn for methane decomposition: Effect of activation temperature

Methane decomposition reaction has been studied at three different activation temperatures (500 °C, 800 °C and 950 °C) over mesoporous alumina supported Ni–Fe and Mn–Fe based bimetallic catalysts. On co-impregnation of Ni on Fe/Al₂O₃ the activity of the catalyst was retained even at the high activation temperature at 950 °C and up to 180 min. The Ni promotion enhanced the reducibility of Fe/Al₂O₃ oxides showing higher catalytic activity with a hydrogen yield of 69%. The reactivity of bimetallic Mn and Fe over Al₂O₃ catalyst decreased at 800 °C and 950 °C activation temperatures. Regeneration studies revealed that the catalyst could be effectively recycled up to 9 times. The addition of O₂ (1 ml, 2 ml, 4 ml) in the feed enhanced substantially CH₄ conversion, the yield of hydrogen and the stability of the catalyst.     

Catalytic performance of NO oxidation over LaMeO3 (Me = Mn,Fe, Co) perovskite prepared by the sol–gel method

The catalytic performance of LaMeO₃ (Me = Mn, Fe, Co) perovskite prepared by a sol–gel method was studied. These catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption (BET), H₂ temperature programmed reduction (TPR), NO temperature programmed desorption (TPD) and CO–O₂ pulse. LaCoO₃ exhibited the best activity than that of LaFeO₃ and LaMnO₃ even after hydrothermal ageing. The activity sequence is in accordance with the reducibility of the samples. The activated oxygen species and adsorbed NO play key roles in the NO oxidation reaction.     

Influence of SBA-15 support on CeO2–ZrO2 catalyst for the dehydrogenation of ethylbenzene to styrene with CO2

Pure oxides of ceria (CeO₂) and zirconia (ZrO₂) were prepared by precipitation method and a catalyst comprising of 25 mol% of CeO₂ and 75 mol% of ZrO₂ (25CZ) mixed metal oxide was prepared by co-precipitation method and also a catalyst with 25 wt% of 25CZ (25 mol% of CeO₂ and 75 mol% of ZrO₂) and 75 wt% SBA-15(25/25CZS) was prepared by precipitation–deposition method. Aqueous NH₃ solution was used as a hydrolyzing agent for all the precipitation reactions. These catalysts were characterized by X-ray diffraction and nitrogen adsorption–desorption techniques for the confirmation of SBA-15 structural intactness. All these catalysts were found to be effective for the oxidative dehydrogenation of ethylbenzene (ODHEB) to styrene in the presence of CO₂ and also it was observed that there was a sequential enhancement in the catalytic activity from individual oxides to mixed oxides followed by supported mixed oxide catalysts. Of the catalysts studied in this work, the supported 25/25CZS catalyst exhibited the superior activity, which was about 10–20 times higher than the activity of bulk single oxides in terms of turn over frequency.