Alumina-supported catalysts for propane oxidative dehydrogenation from mixed VXM(6−X)O19 (M=W, Mo) hexametalate precursors

γ-Al₂O₃ supported vanadium oxides were modified by tungsten and molybdenum oxides in order to improve dispersion and selectivity towards olefins in propane oxidative dehydrogenation (ODH). Both vanadium–tungsten and vanadium–molybdenum catalysts were obtained by adsorption of mixed isopolyanions (VW₅O₁₉⁵⁻, V₂W₄O₁₉⁴⁻, VMo₅O₁₉⁵⁻ and V₂Mo₄O₁₉⁴⁻) from aqueous solutions. The isopolyanion solutions were characterized by UV-Vis and ⁵¹V NMR spectroscopy. Vanadium, vanadium–tungsten and vanadium–molybdenum precursors and catalysts were also characterized by UV-Vis (diffuse reflectance) and solid state ⁵¹V NMR spectroscopy. An improved selectivity to propene in the presence of tungsten and molybdenum in VO_x/γ-Al₂O₃ was observed and attributed to dilution of vanadium by tungsten or molybdenum oxides on the γ-Al₂O₃ surface.     

Palladium–vanadium interaction in binary supported catalysts

We have studied the activity and selectivity of Pd/γ-Al₂O₃, VO_x/γ-Al₂O₃ and Pd–VO_x/γ-Al₂O₃ catalysts for the decomposition of NO and the reduction of NO with CO. Pd–VO_x/γ-Al₂O₃ catalysts were prepared by anchoring Pd(AcAc)₂ on VO_x/γ-Al₂O₃. Characterization of the binary samples by hydrogen chemisorption and TPR measurements indicated that the reduction of VO_x is enhanced by a close contact with palladium and that partially reduced vanadia decorate noble metal particles. This palladium–vanadium interaction alters the catalytic properties of palladium: the activity for NO decomposition is higher for the binary sample and, for the NO–CO reaction, both the activity and the selectivity to N₂ increase when vanadium is in contact with palladium.     

Oxides of copper, ceria promoted copper, manganese and copper manganese on Al2O3 for the combustion of CO, ethyl acetate and ethanol

Combustion of CO, ethyl acetate and ethanol was studied over CuO_x/Al₂O₃, CuO_x–CeO₂/Al₂O₃, CuMn₂O₄/Al₂O₃ and Mn₂O₃/Al₂O₃ catalysts. It was found that modification of the alumina with ceria before subsequent copper oxide deposition increases the activity for combustion of CO substantially, but the effect of ceria was small on the combustion of ethyl acetate and ethanol. The activity increases with the CuO_x loading until crystalline CuO particles are formed, which contribute little to the total active surface. The CuO_x–CeO₂/Al₂O₃ catalyst is more active than the CuMn₂O₄/Al₂O₃ catalyst for the oxidation of CO but the CuMn₂O₄/Al₂O₃ catalyst is more active for the combustion of ethyl acetate and ethanol.

Thermal ageing and water vapour in the feed caused a modest decrease in activity and did not affect the CuO_x–CeO₂/Al₂O₃ and CuMn₂O₄/Al₂O₃ catalysts differently. In addition, no difference in intermediates formed over the two catalysts was observed.

Characterisation with XRD, FT-Raman and TPR indicates that the copper oxide is present as a copper aluminate surface phase on alumina at low loading. At high loading, bulk CuO crystallites are present as well. Modification of the alumina with ceria before the copper oxide deposition gives well dispersed copper oxide species and bulk CuO crystallites associated to the ceria, in addition to the two copper oxide species on the bare alumina. The distribution of copper species depends on the ceria and copper oxide loading. The alumina supported copper manganese oxide and manganese oxide catalysts consist mainly of crystalline CuMn₂O₄ and Mn₂O₃, respectively, on Al₂O₃.     

Catalytic removal of perchloroethylene (PCE) over supported chromium oxide catalysts

The oxidation of perchloroethylene (PCE) was investigated over chromium oxide catalysts supported on SiO₂, SiO₂–Al₂O₃, activated carbon, mordenite type zeolites, MgO, TiO₂ and Al₂O₃. Supported chromium oxide catalysts were more active than any other metal oxide catalysts including noble metal examined in the present study. PCE removal activity of chromium oxide catalysts mainly depended on the type of supports and the content of metal loaded on the catalyst surface. TiO₂ and Al₂O₃ containing high surface areas were effective for the high performance of PCE removal, since the formation of well dispersed Cr(VI) active reaction sites for the present reaction system, was enhanced even for the high Cr loading on the catalyst surface. CrO_x catalysts supported on TiO₂ and Al₂O₃ also exhibited stable PCE removal activity at a low feed concentration of PCE of 30 ppm up to 100 h at 350°C. However, significant catalyst deactivation was observed at high PCE concentration of 10 000 ppm. CrO_x/TiO₂ revealed stronger water tolerance than CrO_x/Al₂O₃ due to the surface hydrophobicity.     

Selective oxidation of hydrogen sulfide over mixture catalysts of V–Sb–O and Bi2O3

The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over vanadium–antimony mixed oxide catalysts. The investigation was focused on the phase cooperation between V–Sb–O and Bi₂O₃ in this reaction. Strong synergistic phenomenon in catalytic activity was observed for the mechanically mixed catalysts of V–Sb–O and Bi₂O₃. Temperature-programmed reduction (TPR) and oxidation (TPO), two separated bed reaction tests, and XPS analyses were carried out to explain this synergistic effect by the reoxidation ability of Bi₂O₃.     

Reversible sorption–desorption of NOx by mixed oxides under various atmospheres

Characteristics of MnO_y–ZrO₂ and Pt–ZrO₂–Al₂O₃ as reversible sorbents of NO_x were investigated under dynamic changes in atmosphere. These sorbents can be used reversibly with a change of C₃H₈ concentration in the reaction gases. Catalytic reduction of NO occurred in the presence of propane, which was more pronounced on Pt–ZrO₂–Al₂O₃ than on MnO_y-ZrO₂ due to high activity of Pt surface for this reaction on MnO_y in MnO_y–ZrO₂. The sorption was observed as soon as the atmosphere changed from a reducing to an oxidizing one. This implies that a high equilibrium partial pressure of O₂ is necessary for NO uptake since the sorbed NO⁻₃ species becomes stable. The beginning of NO_x desorption atmospheres was somewhat dependent on the amount of stored NO_x. The presence of propane in the gas phase strongly affected the characteristic sorption and desorption properties of MnO_y–ZrO₂ and Pt–ZrO₂–Al₂O₃. The sorption and desorption properties are different for MnO_y–ZrO₂ and Pt–ZrO₂–Al₂O₃, since the noble metal or metal oxide possesses unique activity for the NO reaction with C₃H₈ and the amount of oxygen available for oxidative sorption of NO.     

Factors controlling the selectivity of V2O5 supported catalysts in the oxidative dehydrogenation of propane

The surface properties of a series of V₂O₅ catalysts supported on different oxides (Al₂O₃, H–Na/Y zeolite, MgO, SiO₂, TiO₂ and ZrO₂) were investigated by transmission electron microscopy and FTIR spectroscopy augmented by CO and NH₃ adsorption. In the case of the V₂O₅/SiO₂ system TEM images evidenced the presence of V₂O₅ crystallites, whereas such segregated phase was not observed for the other samples. VO_x species resulted widely spread on the surface of Al₂O₃, H–Na/Y zeolite, MgO and SiO₂, whereas on TiO₂ and ZrO₂ they are assembled in a layer covering almost completely the support. Furthermore, evidences for the presence in this layer of V–OH Brønsted acid sites close to the active centres were found. It is proposed that propene molecules primarily produced by oxydehydrogenation of propane can be adsorbed on this acid centres and then undergo an overoxidation by reaction with redox centres in the neighbourhood. This features could account for the low selectivity of V₂O₅/TiO₂ and V₂O₅/ZrO₂ catalysts.     

Oxidative dehydrogenation of propane over differently structured vanadia-based catalysts in the presence of O2 and N2O

The effect of the nature and distribution of VO_x species over amorphous and well-ordered (MCM-41) SiO₂ as well as over γ-Al₂O₃ on their performance in the oxidative dehydrogenation of propane with O₂ and N₂O was studied using in situ UV–vis, ex situ XRD and H₂-TPR analysis in combination with steady-state catalytic tests. As compared to the alumina support, differently structured SiO₂ supports stabilise highly dispersed surface VO_x species at higher vanadium loading. These species are more selective over the latter materials than over V/γ-Al₂O₃ catalysts. This finding was explained by the difference in acidic properties of silica- and alumina-based supports. C₃H₆ selectivity over V/γ-Al₂O₃ materials is improved by covering the support fully with well-dispersed VO_x species. Additionally, C₃H₆ selectivity over all materials studied can be tuned by using an alternative oxidising agent (N₂O). The improving effect of N₂O on C₃H₆ selectivity is related to the lower ability of N₂O for catalyst reoxidation resulting in an increase in the degree of catalyst reduction, i.e. spatial separation of active lattice oxygen in surface VO_x species. Such separation favours selective oxidation over CO_x formation.     

Synthesis of cyclic carbonates from epoxides: Use of reticular oxygen of Al2O3 or Al2O3-supported CeOx for the selective epoxidation of propene

Reticular oxygen of Al₂O₃ or CeO_x supported on Al₂O₃ was used for the epoxidation of propene without any double bond cleavage. In batch reaction, Al₂O₃ alone was able to convert propene into propene oxide (PO) with 100% selectivity and 2% conversion of propene with a close to 3:1 ratio with respect to the number of Al(III) reduced to elemental Al. When Ce₂O₃/Al₂O₃ or CeO₂/Al₂O₃ was used, Al remained in its +3 oxidation state, while the Ce oxide was the oxidant as demonstrated by XPS analyses. CeO_x/Al₂O₃ was more active (propene conversion yield of 4–5%) but the selectivity was lower (70%) as PO was isomerized into acetone and propionaldehyde.

Interestingly the use of reticular oxygen very much improves the selectivity with respect to the use of pure O₂. In fact, while propene was more efficiently oxidized (10%) with O₂ in presence of Al₂O₃ or CeO_x/Al₂O₃, the selectivity was as low as 40% because C1 and C2 products were formed. However, the use of reticular oxygen represents a selective two-step technique for the use of molecular oxygen as oxidant of propene. The used oxides can be re-oxidized and the whole process can be further improved towards higher yields.

PO is quantitatively converted into propene carbonate by reaction with CO₂ in presence of Nb₂O₅.     

Selective oxidation of propylene to acrolein over supported V2O5/Nb2O5 catalysts: An in situ Raman, IR, TPSR and kinetic study

The vapor-phase selective oxidation of propylene (H₂CCHCH₃) to acrolein (H₂CCHCHO) was investigated over supported V₂O₅/Nb₂O₅ catalysts. The catalysts were synthesized by incipient wetness impregnation of V-isopropoxide/isopropanol solutions and calcination at 450 °C. The catalytic active vanadia component was shown by in situ Raman spectroscopy to be 100% dispersed as surface VO_x species on the Nb₂O₅ support in the sub-monolayer region (<8.4 V/nm²). Surface allyl species (H₂CCHCH_2*) were observed with in situ FT-IR to be the most abundant reaction intermediates. The acrolein formation kinetics and selectivity were strongly dependent on the surface VO_x coverage. Two surface VO_x sites were found to participate in the selective oxidation of propylene to acrolein. The reaction kinetics followed a Langmuir–Hinshelwood mechanism with first-order in propylene and half-order in O₂ partial pressures. C₃H₆-TPSR spectroscopy studies also revealed that the lattice oxygen from the catalyst was not capable of selectively oxidizing propylene to acrolein and that the presence of gas phase molecular O₂ was critical for maintaining the surface VO_x species in the fully oxidized state. The catalytic active site for this selective oxidation reaction involves the bridging VONb support bond.     

Development of vanadium-based mixed oxide catalysts for selective oxidation of H2S to sulfur

Various vanadium-based binary and multi-metallic oxides were prepared and their catalytic activities for the selective oxidation of H₂S to elemental sulfur were tested. Because the deactivation of vanadium-based catalysts originated from a relatively slow rate of reoxidation of the reduced vanadium oxide [PhD thesis, Pohang University of Science and Technology, 2000], the focus was given to increase the redox ability, especially in the reoxidation step. Stable and improved activity was observed in BiVO_x, TiVO_x, and ZrV₂O₇ at 250°C, but TiVO_x was the only catalyst that could maintain its activity below 250°C. Much higher activity was observed when VO_x/TiO₂ became multi-metallic by the incorporation of Fe, Cr, and Mo. TPR–TPO, microbalance, and XPS techniques were used to explain the redox properties of VO_x/SiO₂, VO_x/TiO₂, and V-Fe-Cr-Mo-O_x/TiO₂ catalysts in the reoxidation step.     

Activity enhancement of SnO2-doped Ga2O3–Al2O3 catalysts by coexisting H2O for the selective reduction of NO with propene

Catalytic reduction of NO by propene in the presence of oxygen was studied over SnO₂-doped Ga₂O₃–Al₂O₃ prepared by sol–gel method. Although SnO₂-doped Ga₂O₃–Al₂O₃ gave lower NO conversion than Ga₂O₃–Al₂O₃ in the absence of H₂O, the activity was enhanced considerably by the presence of H₂O and much higher than that of Ga₂O₃–Al₂O₃. The presence of SnO₂ and Ga₂O₃–Al₂O₃ species having intimate Ga–O–Al bondings was found to be essential for the promotional effect of H₂O. The promotional effect of H₂O was interpreted by the following two reasons. The first one is the removal of carbonaceous materials deposited on the catalyst surface by H₂O. The other is the selective inhibition by H₂O of the reaction steps resulting in propene oxidation to CO_x without reducing NO.     

Effects of alumina incorporation in coprecipitated NiO–Al2O3 catalysts

The effect of Al₂O₃ levels on the properties of NiO in coprecipitated NiO–Al₂O₃ samples were investigated, using samples with up to 60.7 wt.% Al₂O₃ that had been calcined in the range 300–700°C. Characterization techniques included BET surface area of fresh and reduced catalysts, X-ray diffraction analysis of structure and crystallite size, magnetic susceptibility measurements, oxidizing power, and reducibility in H₂. Only NiO was detected in samples with up to 4.1 wt.% Al₂O₃ for all sample calcination temperatures. Surface areas were similar for all fresh samples but decreased rapidly after calcination at high temperatures. The surface area loss was less for the higher Al₂O₃-containing samples. Nickel oxide crystallite sizes increased at higher calcination temperatures, but remained approximately the same for each Al₂O₃ level.

The NiO was nonstoichiometric (NiO_1+x), with x decreasing at higher calcination temperatures and increasing with small amounts of added Al₂O₃ through a maximum at about 3 wt.% Al₂O₃. However, this did not correlate well with microstrain in the NiO crystallites nor with reducibility, which decreased with Al₂O₃ addition. At higher levels of Al₂O₃ (13.6 wt.% and above), surface areas increased with higher Al₂O₃ loadings, but NiO crystallite sizes remained approximately the same, independent of both Al₂O₃ content and calcination temperature. X-ray diffraction patterns were very diffuse, and it was not possible to rule out the presence of pseudo-spinel combinations of NiO and Al₂O₃. Reducibility was more difficult than with low Al₂O₃ levels, and nonstoichiometry was low and independent of Al₂O₃ content.

Reducibilities of all samples calcined at 300°C correlated well with the final BET surface area of the reduced samples, indicating that more dispersed NiO crystallites are more difficult to reduce, a conclusion that supports a model for reduction proposed previously.     

Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts for catalytic combustion of methane

A series of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H₂-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts the surface phase structure were the Ce_1−xCu_xO_2−x solid solution, -Al₂O₃ and γ-Al₂O₃. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce_1−xCu_xO_2−x solid solution. The Cu component of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce_1−xCu_xO_2−x solid solution and the Al₂O₃ washcoats and the FeCrAl support.     

A pilot plant study for catalytic decomposition of PCDDs/PCDFs over supported chromium oxide catalysts

Chromium oxide catalysts supported on TiO₂ and Al₂O₃ were examined in a fixed-bed flow reactor system for the removal of PCE (perchloroethylene), a simulant of 2,3,7,8-TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin), and in a pilot plant employing actual flue gas from a sintering plant for the removal of PCDDs/PCDFs (poly-chlorinated dibenzo-dioxin/poly-chlorinated dibenzo-furan). The 12.5 wt.% chromium oxides supported on TiO₂ and Al₂O₃ revealed excellent stability and performance of PCE removal in the feed gas stream containing water vapor. In a pilot plant study, the catalysts washcoated on the honeycomb reactor revealed 93–95% of PCDDs/PCDFs removal activity over CrO_x/Al₂O₃-HC20 (CrO_x/Al₂O₃ catalyst washcoated on 20 cell-honeycomb), and more than 99% of the decomposition activity over CrO_x/TiO₂-HC20 (CrO_x/TiO₂ catalyst washcoated on 20 cell-honeycomb) at 325 °C and 5000 h⁻¹ of reactor space velocity without the de novo synthesis of PCDDs/PCDFs. In particular, CrO_x/TiO₂-HC20 showed 94% of PCDDs/PCDFs decomposition activity even at 280 °C reaction temperature. The catalyst also exhibited significant NO removal activity. The chromium oxide seems to be a promising catalyst for the removal of PCDDs/PCDFs and NO_x contained in the flue gas.     

Hydrothermal synthesis of vanadium oxide nanotubes from V2O5 gels

Vanadium oxide nanotubes (VO_x-NT) have been synthesized in high yield by adding hexadecylamine to V₂O₅·nH₂O gels, followed by a hydrothermal treatment (150–180 °C, 2–7 days). Scanning electron microscopy (SEM) and X-ray diffraction analysis have been performed to optimize the temperature and reaction time required for formation of VO_x-NT and the morphology of the nanotubes investigated by transmission electron microscopy (TEM).     

Effect of hydrogen on reaction intermediates in the selective catalytic reduction of NOx by C3H6

Selective catalytic reduction of NO_x by C₃H₆ in the presence of H₂ over Ag/Al₂O₃ was investigated using in situ DRIFTS and GC–MS measurements. The addition of H₂ promoted the partial oxidation of C₃H₆ to enolic species, the formation of –NCO and the reactions of enolic species and –NCO with NO_x on Ag/Al₂O₃ surface at low temperatures. Based on the results, we proposed reaction mechanism to explain the promotional effect of H₂ on the SCR of NO_x by C₃H₆ over Ag/Al₂O₃ catalyst.     

MgO-modified VOx/SBA-15 as catalysts for the oxidative dehydrogenation of n-butane

VO_x catalysts supported on SBA-15 with and without MgO modification were prepared and characterized by N₂ adsorption–desorption, XRD, HRTEM, H₂-TPR, NH₃-TPD and XPS. Compared to the VO_x/SBA-15 catalyst, the VO_x/MgO/SBA-15 ones exhibit much higher C₄-olefins selectivity and yield in the oxidative dehydrogenation of n-butane. The enhanced performance can be attributed to the rise in VO_x reducibility as well as to the relatively lower acidity of the MgO-modified SBA-15 materials.     

Oxidative degradation properties of Co-based catalysts in the presence of ozone

Four series of cobalt-based catalysts, such as bare Co₃O₄ and CoO, CoO_x–CeO₂ mixed oxides, CoO_x supported over alumina and alumina–baria and CoMgAl and CoNiAl hydrotalcites have been synthesized and investigated for the oxidative degradation of phenol in the presence of ozone. Characterizations were obtained by several techniques in order to investigate the nature of cobalt species and their morphological properties, depending on the system. Analyses by XRD, BET, TPR, UV–visible diffuse reflectance spectroscopy and TG/DT were performed.

The CoNiAl hydrotalcite exhibits, after 4 h of reaction, the highest phenol ozonation activity followed by Co(3 wt%)/Al₂O₃–BaO and CoMgAl. The samples Co(1 wt%)/Al₂O₃–BaO and Co(1 and 3 wt%)/Al₂O₃ show a comparable medium activity, while the oxidation properties of bare oxides Co₃O₄, CoO and CoO_x–CeO₂ are really low. Leaching of cobalt ions in the water solution was detected during the reaction, the amount varied depending on the nature of catalysts. A massive release was observed for the CoMgAl and CoNiAl hydrotalcites, while cobalt catalysts over alumina and alumina–baria look much more stable. The recycle of CoO_x/Al₂O₃ and CoO_x/Al₂O₃–BaO was studied by performing three consecutive cycles in the phenol oxidation. Because of the potential interest of the cobalt-supported catalysts in the ozonation process, the oxidative degradation of naphtol blue black was also investigated.

On the basis of TPR and UV–visible results it appears that highly dispersed Co²⁺ ions especially present over Co(3 wt%)/Al₂O₃–BaO are the main active sites for phenol and naphtol blue black oxidative degradation by ozone.     

Pt–Ba–Al2O3 for NOx storage and reduction: Characterization of the dispersed species

Pt–Ba–Al₂O₃ active and selective for NO_x storage and selective reduction to N₂ has been prepared and tested. Characterization of the parent Al₂O₃, Pt–Al₂O₃ and Ba–Al₂O₃ materials, as well as of Pt–Ba–Al₂O₃ catalyst in the oxidized, reduced and sulphated state has been performed by FT-IR spectroscopy of low-temperature adsorbed carbon monoxide and of adsorbed acetonitrile. XRD, TEM and XPS analyses have also been performed. Evidence for the predominance of Ba species, which are highly dispersed on the alumina support surface, and may be carbonated or sulphated, has been provided. Competitive interaction of Pt and Ba species with the surface sites of alumina has also been found.