Lean NOx catalysis over alumina‐supported catalysts

aluminasupported catalysts show promise as lean NO_x catalysts. The role of alumina in influencing the structural and chemical properties of the active phase supported on it is discussed using some effective aluminabased lean NO_x catalysts. These include Ag/Al₂O₃, CoO_x/Al₂O₃ and SnO₂/Al₂O₃. Alumina plays an important role in stabilizing Ag in the oxidic phase and cobalt in the 2+ oxidation state. For SnO₂/Al₂O₃, alumina increases the SnO₂ surface area. On both Ag/Al₂O₃ and SnO₂/Al₂O₃, alumina also participates actively in the NO_x reduction reaction. An active organic intermediate is formed on Ag or Sn oxide which reacts with NO_x subsequently on alumina to form N₂.     

High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

High‐activity catalyst of SO 4 2− /ZrO2 supported on γ‐Al2O3 for n‐butane isomerization

A series of Al₂O₃supported SO ₄ ^2– /ZrO₂ superacid catalysts (named SZ/Al₂O₃) were prepared by a precipitation method and their catalytic behavior for nbutane isomerization at low temperature in the absence of H₂ and at high temperature in the presence of H₂ was studied in this paper. The catalytic activities of some of these catalysts were enhanced significantly at both low and high temperatures. At 250°C after 6 h on stream, the steady activity of the most active sample, 60%SZ/Al₂O₃, is about two times higher than that of conventional SZ. The texture properties of catalysts were studied by the methods of XRD and the adsorption of N₂. Experimental evidence of IR of adsorbed pyridine indicates that the significant activity enhancements of SZ/Al₂O₃ catalysts are caused by the increasing of the amount of strong acid sites.     

A study of the acidic and catalytic properties of pure and sulfated zirconia–titania and zirconia–silica mixed oxides

Protonated pyridine (PyH⁺) was not found on ZrO₂ (Z) or ZrO₂–TiO₂ (ZT), but was detected on sulfated oxides (ZS, ZTS) by IR spectroscopy. In contrast, ZrO₂–SiO₂ samples containing about 30–80 mol% ZrO₂ showed Brønsted acidity both in nonsulfated (ZS) and sulfated (ZSS) forms. The total acidity was determined by NH₃TPD. Introduction of sulfate ions increased the sitespecific catalytic activity (TOF) in the conversion of cyclopropane or nhexane. The effect of sulfate ions was more significant on samples rich in zirconia. Results suggest that Zr is homogeneously distributed in ZS samples rich in silica. Zirconiabound dimeric sulfate, generating strong acidity, could not be formed in these preparations due to the absence of fairly large ZrO₂ domains.     

Formation and reactions of isocyanic acid during the catalytic reduction of nitrogen oxides

Reactions which can produce and consume isocyanic acid (HNCO) over two types of catalysts active for the reduction of nitrogen oxides have been investigated. More than 1000 ppm HNCO can be produced by the reduction of 3000 ppm NO with H₂/CO mixtures over a Pt/SiO₂ catalyst. Complete hydrolysis of HNCO to ammonia and carbon dioxide occurs if even weakly catalytic materials, such as CeO₂/SiO₂ and BaO/SiO₂, are placed downstream. Isocyanic acid is also involved as an intermediate in the reaction of nitromethane over CoZSM5 and CuZSM5 under the conditions of hydrocarbon SCR. In the initial stages of reaction there is complete conversion through to N₂ with CuZSM5 but the process stops at ammonia with CoZSM5 at temperatures below 350°C. In both cases, but especially with CoZSM5, isocyanic acid becomes observable as the catalyst deactivates during continuous exposure at temperatures below about 290°C. In situ FTIR measurements indicate that deactivation is due to a reaction between isocyanic acid and ammonia which generates cyclic striazine compounds.     

Catalytic behaviour and characterisation of CuO1−z(La2O3)z/2 based catalysts deposited on γ-Al2O3 and prepared in situ with 0.0 ⩽z⩽1.00, without and with addition of Pd

(CuO)_1–z(La₂O₃)_z/2 based catalysts with 0.0z1.0 supported on -Al₂O₃ have been prepared in situ and the phases formed have been identified by XRD, SEM and TEM/EDS studies. The catalyst with z=0.5 exhibited the best catalytic activity for oxidation of CO (T ₅₀=295 and 390C with degrees of conversions of 93 and 92% at 450C under rich and lean conditions, respectively) and C₃H₆ (291 and 414C; 93 and 83%) and reduction of NO (405C; 60 and 0%). This catalyst contained appreciable amounts of the perovskite phase LaAl_1–xCu_xO₃ and the enhanced catalytic properties are ascribed to the presence of this phase. Addition of Pd to this catalyst implied that the degree of conversion of NO increased and that the light-off temperatures for all involved gas species decreased. Ageing experiments revealed that LaAl_1–xCu_xO₃ decomposed and that Cu containing Pd particles were formed during this procedure which in turn deteriorated the catalytic properties of the catalyst.     

Catalytic properties of SrSn1−xSbxO3 in methanol oxidation

Ceramic model catalyst materials of general formula SrSn_1–x Sb _x O₃ are synthesised by solid state reaction. X-ray diffraction shows the materials to be single phase over the composition range 0 x0.085, with a second phase, identified as SrSb₂O₅, being produced at higher antimony doping levels. XPS, Auger electron spectroscopy and valence band photoemission show strong segregation of Sb to the surface of the material even within the single phase regime. The catalytic properties of the materials are examined using methanol oxidation as a test reaction. The activity and selectivity to formaldehyde production shown by these materials is found to be strongly correlated with the attainment of the bulk solubility limit of Sb in the SrSnO₃ perovskite host.     

Investigation of CH4 Reforming with CO2 on Meso-Porous Al2O3-Supported Ni Catalyst

Meso-porous Al₂O₃-supported Ni catalysts exhibited the highest activity, stability and excellent coke-resistance ability for CH₄ reforming with CO₂ among several oxide-supported Ni catalysts (meso-porous Al₂O₃ (Yas1-2, Yas3-8), -Al₂O₃, -Al₂O₃, SiO₂, MgO, La₂O₃, CeO₂ and ZrO₂). The properties of deposited carbons depended on the properties of the supports, and on the meso-porous Al₂O₃-supported Ni catalyst, only the intermediate carbon of the reforming reaction formed. XRD and H₂-TPR analysis found that mainly spinel NiAl₂O₄ formed in meso-porous Al₂O₃ and -Al₂O₃-supported catalysts, while only NiO was detected in -Al₂O₃, SiO₂, CeO₂, La₂O₃ and ZrO₂ supports. The strong interaction between Ni and meso-porous Al₂O₃ improved the dispersion of Ni, retarded its sintering and improved the activated adsorption of CO₂. The coking reaction via CH₄ temperature-programed decomposition indicated that meso-porous Al₂O₃-supported Ni catalysts were less active for carbon formation by CH₄ decomposition than Ni/-Al₂O₃ and Ni/-Al₂O₃.     

An XRD, FTIR and TPD Investigation of NO2 Surface Adsorption Sites of δ, γ Al2O3 and Barium Supported δ, γ Al2O3

In this paper an XRD, FTIR and TPD investigation of NO₂ surface adsorption sites of , Al₂O₃ and barium supported , Al₂O₃ is reported. Aim of this study is to bring additional light on the surface structures involved in NOx adsorption. Two samples of barium supported aluminas have been prepared and aged at 800 °C. These samples were characterised in comparison with the relative alumina support. The XRD characterisation of these samples shows the presence of barium carbonate and barium aluminate supported on alumina. The comparison of the FTIR spectra, before and after NO₂ adsorption, has revealed the formation, upon NO₂ contact, of a complex variety of nitrate and nitrite groups. The thermal desorption of nitrate and nitrite species has been simultaneously studied by means of FTIR spectroscopy and by TPD technique. By comparing the structural, adsorptive and spectroscopic results obtained on alumina and on barium supported alumina samples, a hypothesis on the basic sites active in NO₂ adsorption and of the possible decomposition paths induced by thermal heating are proposed.     

31-P NMR study study of acidic sites on Al2O3 and Al2O3-SnO2 after reaction with CCl2F2/H2

The surface acidic properties of two series of samples,-Al₂O₃ and-Al₂O₃-SnO₂ after reaction with CCl₂F₂/H₂ (CFC12/H₂), have been investigated by solid state high resolution CP/MAS 31-PNMR, using trimethylphosphine (TMP) as a probe molecule. It was found after reaction, that Brønsted acid sites were formed on the-Al₂O₃ surface. The longer the reaction time, the more rigidly TMP bonded to the acid sites. For the-Al₂O₃-SnO₂ system, Brønsted acid sites were also found on both the Al₂O₃ and SnO₂ surfaces after reaction of the-Al₂O₃-SnO₂ system with CFC12/H₂. The signal intensity relevant to these sites, indicates that the SnO₂ component is attached to, and therefore covers Brønsted sites of-Al₂O₃. Two types of Lewis acid site initially present on SnO₂ were not observed after reaction with CFC12/H₂.     

Catalysts for the selective dehydrogenation of high molecular weight paraffins

Selective dehydrogenation of high molecular weight linear paraffins is an important process step for the production of biodegradable detergents. Pt, PtSn, PtGe and PtPb supported on -A1₂O₃ doped with alkaline metals were characterized and tested in then-decane dehydrogenation reaction. When alkaline metals are added to Pt/Al₂O₃ a promoting effect on the selectivity to olefins in then-decane dehydrogenation is observed. Regarding PtSn/Al₂O₃ -doped catalysts their performance depends on the alkaline metal used as dopant, the Sn content and the preparation method. Moreover these bimetallic catalysts show a better olefin yield and a lower selectivity to gases and aromatics than the monometallic platinum catalysts. PtGe and PtPb based catalysts have an analogous behavior to the PtSn one but its selectivity to olefins is lower.     

Trends for mono‐aromatic compounds hydrogenation over sulfided Ni, Mo and NiMo hydrotreating catalysts

The relative hydrogenation activity in typical hydrotreating conditions of toluene, mxylene, 1,3,5trimethylbenzene and 1,2,4,5tetramethylbenzene was unexpectedly found to decrease over a sulfided NiMo/Al₂O₃ catalyst and to increase over sulfided Ni/Al₂O₃ and Mo/Al₂O₃ catalysts. This change of activity trend is tentatively interpreted by the formation of a mixed NiMoS phase with a different electronic state compared to Ni or Mo sulfide phases. The nature of the aromatic compound influences strongly the magnitude of the promotion effect of Ni on the activity of the Mo in the sulfided NiMo/Al₂O₃ catalyst.     

Preparation and Characterization of Copper Catalysts Supported on Mesoporous Al2O3 Nanofibers for N2O Reduction to N2

The gas-phase hydrogenation of benzene to cyclohexane over Ce_{1 - x} Pt _x O_{2 -} (x = 0.01, 0.02) catalyst was investigated in the temperature range 80-200 °C. A 42% conversion of benzene to cyclohexane with 100% specificity was observed at 100 °C over Ce_0.98Pt_0.02O_{2 -} with a catalyst residence time of 1.22 × 10⁴ g s/mol of benzene. The activity of the catalyst was compared with those of Pt metal, combustion-synthesized Pt/-Al₂O₃ and Pt/-Al₂O₃. The turnover frequency value of Ce_0.98Pt_0.02O_{2 -} is 0.292, which is an order of magnitude higher than those of the other Pt catalysts investigated. The kinetics of reaction and the deactivation behavior of the catalyst were studied and a regeneration methodology was suggested. The deactivation kinetics and structural evidence from XRD, XPS, TGA and H₂ uptake studies suggest that the oxidized Pt in Ce_0.98Pt_0.02O_{2 -} is responsible for the high catalytic activity towards benzene hydrogenation.     

31P and119Sn high resolution solid state CP/MAS NMR study of Al2O3-SnO2 systems

A series of Al₂O₃-SnO₂ catalysts with the mole ratio of Al₂O₃ to SnO₂ equal to 1:1, 1 0.5, 1 0.1, 1 0.05 and 1 0.01 were characterized by³¹P NMR of adsorbed trimethyl phosphine (TMP) and¹¹⁹Sn MAS NMR spectroscopy. It was found from³¹P NMR that no Brønsted acid sites exist in these samples. Pure SnO₂ shows two different types of Lewis acid sites; in the mixed oxide samples a Lewis peak characteristic of pure Al₂O₃ is always seen, together with either one or two other Lewis peaks, depending on the Sn concentration.¹¹⁹Sn CP/MAS NMR spectra of the highest Sn-content sample show one narrow line at –603 ppm superimposed on a very broad line, indicating a strong interaction between Al and Sn oxides.     

The effect of steam treatment on MeO/Al2O3 model catalysts (Me = Ni,Co, Cu,Fe)

To study the influence of steam on the solid state reaction between MeO (Me = Ni, Co, Cu or Fe) and Al₂O3, MeO/-Al₂O₃ and MeO/-Al₂O₃ model catalysts were kept in either N₂/20% O₂ or N₂/O₂/30% H₂O at 500–1000°C. The samples were subsequently analyzed with RBS and FTIR. Surprisingly, nickel, cobalt and copper volatilized when MeO/-Al₂O₃ or MeAl₂U₄/-Al₂O₃ samples were annealed in the presence of 0.3 atm steam at 1000°C. Especially copper was found to volatilize very rapidly in the presence of steam, even at a temperature as low as 800°C. FTIR spectra of steam-treated NiO/-Al₂O₃ samples showed the incorporation of hydroxyl groups in the nickel oxide layer. This observation and an excellent agreement with thermochemical calculations support our conclusion that the volatile species are metal hydroxides. The solid state reaction of MeO with-Al₂O₃ was found to proceed at a much higher rate in the presence of 0.3 atm steam at 500–800°C, presumably as a result of an enhanced surface mobility of Me and Al ions along the grain boundaries and the surfaces of the internal pores of the-Al₂O₃ support, when steam is present.     

The CH4/NO/O2 “Lean-deNOx” Reaction on Mesoporous Mn-Based Mixed Oxides

High surface area Mn-based porous oxides (MANPO) containing additives like Ce, Sr and La were found to be very active and selective materials under 0.67% CH₄/0.2% NO/5% O₂ lean-deNO _x conditions in the 200–300°C low-temperature range. These materials perform also impressively in the presence of 4% H₂O in the feed stream, where a N₂ selectivity of 98% and an excellent stability over 24 h on stream have been observed. The MANPO materials can be considered serious competitors of noble metals for low-temperature lean-deNO _x applications.     

Acid‐catalyzed isobutane–isobutylene alkylation in liquid carbon dioxide solution

Liquid carbon dioxide was studied as a solvent for the isobutane–isobutylene alkylation. The acid catalysts in the reaction were anhydrous HF (AHF), pyridinium–poly(hydrogen fluoride) complex (PPHF), concentrated sulfuric acid and trifluoromethanesulfonic acid (TFSA). The effect of the acid–hydrocarbon volume ratio, temperature and residence time on the alkylate quality were studied over the temperature range of 50 T 0 °C. Carbon dioxide as a competing weak base decreases the acidity of the system which parallels the alkylate quality. In the case of HF and TFSA catalysts, solvent CO₂ increased the octane number of the alkylate product (RON 95.6 for HF and 88.0 for TFSAcatalyzed alkylation with CO₂ solvent).     

Supported Cu Catalysts with Yttria-Doped Ceria for Steam Reforming of Methanol

The steam reforming of methanol was studied over Cu/Al₂O₃ catalysts with the addition of yttria-doped ceria (YDC). The YDC-modified catalysts were prepared by impregnating a -Al₂O₃ support with Y and Ce then with Cu. The addition of YDC drastically enhanced the activity of Cu/Al₂O₃ in the methanol reforming reaction. The enhanced activity was attributed to the increase of Cu⁺ species by YDC in the methanol reforming environment. However, the addition of YDC decreased the copper dispersion. The Cu dispersion could be enhanced by adding chromium oxide. The addition of YDC and Cr where Al₂O₃ was first impregnated with Cr then with YDC showed the most pronounced enhancement of the catalyst activity. At reaction temperatures of 200250 °C, the CO concentration in the products was smaller than 0.1%.     

Investigation of the Intrinsic Activity of ZrxCe1−xO2 Mixed Oxides in the CO + NO Reactions: Influence of Pd Incorporation

The intrinsic activity of various Zr _x Ce_1–x O₂ mixed oxides and after a Pd deposition has been investigated in the CO + NO reactions from temperature-programmed experiments performed under stoichiometric conditions. It has been found that the activity of Zr _x Ce_1–x O₂ depends on either the specific surface area or the number of Ce cations and their intrinsic activity, Zr_0.5Ce_0.5O₂ being the most active support. The addition of palladium strongly enhances the catalytic activity of the supports probably due to a synergistic effect between CeO₂ and the metal since the initial activity of palladium-based catalysts is directly related to their Ce content. Such a catalytic enhancement has been explained by a bifunctional mechanism involving active sites probably composed of Pd and ceria. A strong deactivation operates leading to the disappearance of the beneficial effect of ceria. Such a deactivation seems to be dependent on the support composition, Pd supported Zr_0.25Ce_0.75O₂ being the most resistant to deactivation.     

Characterization of the Li1−x H x AlO2 system; 0.00 ⩽x ⩽ 0.90

The mechanism of cation replacement in the Li_1–x H _x AlO₂; 0.00 x 0.90 system was investigated with XRD. Examination of the peak position and intensity associated with the 018 and 110 Bragg reflections in a series of partially replaced samples showed that the cation replacement process proceeded by a two phase mechanism. Catalytic characterization of LiAlO₂ with the 2-propanol probe reaction revealed the formation of the condensation products methyl-cyclopentene, 4-methyl-2-pentanone, and 4-methyl-2-pentanol. These products were seen in addition to propylene and acetone. Catalytic characterization of Li_1–x H _x AlO₂;x = 0.90 with 2-propanol showed a significant decrease in condensation activity and no change in the propylene/acetone ratio relative to LiAlO₂. This suggests that the decrease in the amount of lithium eliminated the basic sites necessary for the condensation reactions.