Influence of hydrogen on n-butane isomerization over sulfated zirconia catalysts

This work investigates the influence of hydrogen on the catalytic activity of Fe- and Mn-promoted sulfated zirconia catalysts. It was found that the effect of hydrogen on the activity of Fe-promoted SZ in n-butane isomerization significantly depended on the Fe content of the catalyst. It was also discovered that the negative effect of hydrogen is more significant at lower temperatures. The reason for the decreased activity in hydrogen is thought to be due to the interaction of hydrogen with reaction intermediates.     

n-butane isomerization on sulfated zirconia. Deactivation and regeneration as studied by Raman,UV-VIS diffuse reflectance and ESR spectroscopy

n-butane isomerization on sulfated zirconia was studied in the temperature range 393–473 K. Rapid deactivation occurs, when the reaction is carried out in He carrier gas. In contrast, stable stationary activity was observed in H₂ carrier gas. In situ Raman and UV-VIS diffuse reflectance spectroscopy and ESR showed that the deactivation is caused by the formation of allylic and polyenylic cations and polycyclic aromatic compounds, the formation of which is largely prevented in the presence of H₂. Deactivated catalysts can be fully regenerated by treatment at 723–753 K in flowing O₂. The regeneration process was also followed by in situ spectroscopies.     

Promotive effect of isopentane on cyclohexane isomerization catalyzed by sulfated zirconia

Cyclohexane isomerization to methylcyclopentane over sulfated zirconia is markedly enhanced in the presence of isopentane which acts as a hydride transfer agent to facilitate the slow step of hydride transfer from cyclohexane to isopropyl cation. This was revealed by deuterium tracer studies. This revised version was published online in July 2006 with corrections to the Cover Date.     

Optimization of synthesis variables in the preparation of active sulfated zirconia catalysts

The synthesis of a series of sulfated zirconia catalysts was optimized using the isomerization of n-butane as a reaction probe. The normality of the H₂SO₄ solution used in the sulfation step was found to be the most important variable. A systematic change in the concentration of the H₂SO₄ solution showed that the optimum acid concentration was 0.25 N. When a catalyst prepared with this acid concentration was used, the conversion of n-butane at 200 °C was 35% at 5 min t-o-s. This was close to the thermodynamic equilibrium value of 56% conversion. This maximum was coincident with a catalyst with the highest specific surface area. An increase in the concentration of the H₂SO₄ solution above 0.25 N resulted in a decrease in both surface area and zirconia crystallinity. XPS studies showed a linear relationship between the H₂SO₄ solution concentration and the surface sulfur concentration. Bulk concentrations were determined by elemental analysis. The surface area increased to a maximum for a H₂SO₄ concentration of 0.25 N, while the concentration of bulk sulfur continued to increase when the acid concentration was progressively increased to 2.00 N. The use of a mordenite trap in the reactant stream resulted in an increase in n-butane conversion and a decrease in the rate of catalyst deactivation. XPS studies showed that the sulfur was present as sulfate species and that the oxidation state was not affected by the reaction.     

n-pentane isomerization and disproportionation catalyzed by promoted and unpromoted sulfated zirconia

Isomerization and disproportionation of n-pentane were catalyzed by sulfated zirconia, Fe- and Mn-promoted sulfated zirconia, and Pt-, Fe-, and Mn-promoted sulfated zirconia in a flow reactor at temperatures of −25 to 50°C and n-pentane partial pressures of 0.005–0.01 atm. Incorporation of the Fe and Mn promoters increased the activity of the sulfated zirconia by two orders of magnitude at 50°C; addition of Pt to the latter catalyst increased the activity only slightly. The primary reactions, disproportionation (to give butanes and hexanes) and isomerization, occurred in parallel; secondary disproportionation reactions gave heptanes, propane, butanes, and pentanes. The data are consistent with acid-base catalysis and carbenium ion intermediates, and the isomerization is inferred to proceed both by unimolecular and bimolecular mechanisms. H₂ in the feed stream and Pt in the catalyst both led to reductions in the rate of catalyst deactivation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Characterization of palladium supported on sulfated zirconia catalysts by DRIFTS, XAS and n-butane isomerization reaction in the presence of hydrogen

Palladium supported on sulfated zirconia (PdSZ) has been characterized by the n-butane isomerization reaction in the presence of hydrogen, X-ray absorption spectroscopy (XAS) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) of adsorbed carbon monoxide. Catalyst calcination at 873 K followed by hydrogen reduction at 513 K results in the formation of 30–40 Å Pd metal clusters, but the surface can only weakly adsorb CO, though stronger than Pd-free, sulfated zirconia catalysts. In the presence of hydrogen, PdSZ has a lower n-butane isomerization activity than SZ, and the Pd function cannot stabilize the reaction at low H₂/n-butane ratios.     

Alkane isomerization over sulfated zirconia and other solid acids

Some solid acids, including sulfated zirconia and certain industrial isomerization catalysts, catalyze two types of n-butane isomerizations, avoiding primary carbenium ions or carbonium ions: (1) an internal rearrangement of the C atoms in n-butane and (2) skeletal isomerization of n-butane to iso-butane. No superacid sites are required for these reactions. The skeletal isomerization is an intermolecular reaction, involving a C₈ intermediate. Easily accessible Brønsted acid sites and small amounts of olefin are crucial. Spectroscopic examination of the acid sites on sulfated zirconia shows that they are not stronger than the acid sites in zeolites such as HY. The butane isomerization rate is suppressed by CO, even when no CO is adsorbed on Lewis sites; formation of oxocarbenium ions is likely. The decisive role of Brønsted acid sites is demonstrated by results on deuterated catalysts.     

IR characterization of sulfated zirconia derived from zirconium sulfate

Surface characterization of a sulfate-derived zirconia sample containing approximately 1 wt% S was performed by IR spectroscopy. Several types of sulfate groups were detected which are resistant to heating in vacuo up to 973 K. By using CO as a spectroscopic probe, two kinds of Lewis acid sites were identified which were assigned to surface Zr⁴⁺ ions in different environments. Comparison with corresponding data for a nearly sulfate-free zirconia sample showed that sulfated zirconia has an enhanced Lewis acidity.     

Active sites on Pt containing sulfated zirconia

The influence of the Pt and sulfate concentration on the activity of Pt containing sulfated zirconia for n-heptane conversion was investigated. Pt was deposited on the support by impregnation and by photocatalytic deposition. The amount deposited was 2.5 and 0.4 wt% respectively. For comparison a hybrid catalyst consisting of sulfated zirconia and Pt on SiO₂ was prepared. As supports a commercial sulfated zirconia with a fixed sulfate concentration, a commercial and self synthesized Zr(OH)₄ were used. The sulfate content varied between 20 and 60% of a monolayer. The shifts to higher frequency in the IR spectra of CO adsorbed on Pt correlate with the increasing amounts of sulfates on zirconia and are attributable to the changes in the electron density of the supported metal, i.e. the electron deficiency of Pt increases with increasing concentration of acid sites. After activation in air and reduction in hydrogen two SO₂ peaks were detected by a temperature programmed heating procedure (TPE—temperature programmed evolution). The lower the desorption temperature of the first SO₂ peak, the higher the activity. The shift to lower temperature is connected with a higher Pt and sulfate concentration, furthermore with the proximity of the metal to acid sites. The catalysts with a low sulfate concentration possess only Lewis acid sites and are inactive for n-heptane conversion. At higher sulfate concentration, Br?nsted acid sites are present and the catalysts are active. The concentration of these acid sites is related to the concentration of sulfates, which desorb at lower temperature. Dedicated to Professor Konrad Hayek.     

Competitive mechanisms ofn-butane isomerization on sulfated zirconia catalysts

Isotopic analysis ofn-butane isomerization over sulfated zirconium oxide, using double¹³C-labelledn-butane, shows that at low temperature this isomerization is an inter-molecular process. Probably, a C₈ surface intermediate is formed which isomerizes and undergoes -fission; the iso-C₄ fragments are desorbed asi-butane. Previously, the same mechanism was indicated for Fe, Mn promoted catalysts. The isomerization rate at 130°C is drastically lowered by gaseous H₂, because the concentration of the unsaturated species, required for the formation of the C₈ intermediate, is low under such conditions. Whereas₁₃C-scrambledi-butane is a true primary product, isotopic scrambling ofn-butane continues after chemical equilibrium betweenn-butane andi-butane has almost been reached; i.e.¹³C scrambledn-butane is a secondary product. Intra-molecular rearrangement of carbon atoms inn-butane precedes intermolecular scrambling. The similarity of the isomerization mechanism over unpromoted sulfated zirconia and Fe, Mn promoted sulfated zirconia is paralleled by an equal strength of the acid sites in both catalysts. The shift in the FTIR band of CO adsorbed on the Lewis sites indicates that these sites, presumably surface Zr⁴⁺ ions, are weaker acids than A1³⁺ in dehydrated alumina.     

Characterization and selective poisoning of acid sites on sulfated zirconia

Microcalorimetric measurements and infrared spectroscopy of ammonia adsorption were used to characterize the acidic properties of sulfated zirconia catalysts. Reaction kinetic measurements forn-butane isomerization were conducted over catalysts that were selectively poisoned with controlled amounts of ammonia. Initial heats of ammonia adsorption on the strong acid sites of sulfated zirconia were 150–165 kJ/mol, and these sites contain Brønsted acid and possibly Lewis acid centers. Sulfated zirconia samples that show high activity for the isomerization ofn-butane possess Bransted acid sites of intermediate strength, with differential heats of ammonia adsorption between 125 and 140 kJ/mol. The results of selective poisoning of sulfated zirconia with ammonia confirm that Bransted acid sites of intermediate strength are active forn-butane isomerization at 423 K while not discounting a possible role of the stronger acid sites.     

Infrared spectroscopy and microcalorimetry studies of CO adsorption on sulfated zirconia supported platinum catalysts

Carbon monoxide adsorption has been investigated on Pt particles supported on a high surface area zirconia and sulfated zirconias. The accessibility of the Pt surface determined from the comparison of H₂ chemisorption and transmission electron microscopy depends on two parameters: the temperature of treatment in air used to dehydroxylate sulfated zirconia, and the temperature of reduction. An oxidative pretreatment at 823 K yields a poor accessibility of Pt (0.03 < H/Pt < 0.05) whatever the temperature of reduction, whereas a Pt dispersion of 0.6 can be obtained by oxidation at 673 K followed by a mild reduction at 473 K. FTIR spectroscopy of adsorbed CO on Pt/ZrO₂ shows besides the normal linear species at 2065 cm^–1, a band at 1650 cm^–1 which is attributed to CO bridged between Pt and Zr atoms. On Pt/ZrO₂-SO ₄ ^2– , all bridged species tend to disappear, as well as the dipole-dipole coupling andv _CO is shifted by 57 cm^–1 to higher frequencies. These results are attributed to sulfur adsorption on Pt which decreases the electron back-donation from Pt to the 2 ^* antibonding orbital of CO. The lower initial heat of CO adsorption observed on Pt/ZrO₂-SO^4/2– supports this proposal.     

Pentane isomerization and disproportionation catalyzed by sulfated zirconia promoted with iron and manganese

Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion ofn-pentane in a flow reactor at temperatures in the range of –25 to 40C andn-pentane partial pressures in the range of 0.005 to 0.01 atm. The rates of reaction increased with time on stream during an induction period and then decreased rapidly. The predominant reaction at –25C and short times on stream was isomerization to give isopentane; no dibranched products were observed. The selectivity for isomerization decreased and that for disproportionation increased with increasing temperature, with disproportionation becoming predominant at 40C; the principal product was then isobutane. The product distribution data are consistent with acid-base catalysis and carbocation intermediates. However, there appears to be more to the reaction mechanism than acid-base chemistry, and the roles of the iron and manganese promoters are not yet explained.     

Surface characterization and catalytic activity of sulfated-hafnia promoted zirconia catalysts for n-butane isomerization

Sulfated-hafnia promoted zirconia containing various compositions of hafnia (1-10 wt.%) were prepared by precipitation method in an attempt to ultimately carry n-butane isomerization reaction. The catalyst samples were calcined under dry air flow at 600 °C. The structural and crystal changes were monitored by FTIR and XRD whereas the textural changes were estimated by low temperature N₂ adsorption. FTIR spectroscopy has been used to characterize the hydroxyl groups and to determine the concentration of Brönsted and Lewis acid sites from pyridine adsorption. The catalytic activity, stability and selectivity of the catalyst samples were tested for n-butane isomerization at 250 °C. The results reveal that the existence of a small content of hafnia increases the surface sulfate density, stabilizes the tetragonal phase of zirconia, increases the amount and strength of Brönsted acid sites and enhances the initial catalytic activity of the samples. Increasing hafnia content to 5 and 10 wt.% is accompanied with the formation of hafnia monoclinic phase which causes a drastic decrease in the amount of Brönsted acid sites and the initial activity of the catalyst. The isomerization of n-butane occurred through bimolecular pathway with the formation of iso-butane, propane and pentanes as primary products. In spite of the high activity of the samples, the catalyst deactivates rapidly during the first hour of the reaction due to coke formation, retreating the catalyst at 450 °C in the presence of dry air before the catalytic reaction lead to regeneration of the initial catalytic activity of the catalyst which implies that the coke formation is the main source for catalyst deactivation.     

A comparison of cesium-containing heteropolyacid and sulfated zirconia catalysts for isomerization of light alkanes

The heteropolyacid H₃PW₁₂O₄₀ and its cesium salts Cs_xH_3-x PW₁₂O₄₀ (x = 1, 2, 2.5, 3) were synthesized, characterized and tested as catalysts for hydrocarbon reactions. All samples were characterized by a variety of techniques including elemental analysis, X-ray diffraction, dinitrogen adsorption, thermal gravimetric analysis and ammonia sorption. Results from these methods confirmed that pure cesium salts were prepared without significant contamination by amorphous oxide phases. Incorporation of cesium into the heteropolyacid decreased the acidic protons available for catalysis, increased the specific surface area, and increased the thermal stability. The heteropolyacids were tested as catalysts for butane skeletal isomerization, pentane skeletal isomerization and 1-butene double bond isomerization. For comparison, the activity of sulfated zirconia, a well-studied strong acid catalyst, was also evaluated for the three probe reactions. On a per gram basis, the Cs₂HPW₁₂O₄₀ sample was the most active heteropolyacid, presumably due to its high surface area. This sample was more active than sulfated zirconia for pentane skeletal isomerization and 1-butene double bond isomerization. However, sulfated zirconia was more effective for butane skeletal isomerization. Since the pentane and 1-butene reactions were monomolecular in nature, whereas butane isomerization was bimolecular, restrictions inside the micropores of the heteropolyacid may inhibit the formation of long chain intermediates. Interestingly, trace butenes were required to initiate butane isomerization reactions on sulfated zirconia, whereas heteropolyacids catalyzed the reaction in the absence of butenes. This revised version was published online in June 2006 with corrections to the Cover Date.     

Isomerization of n-butane by sulfated zirconia: the effect of calcination temperature and characterization of its surface acidity

The distributions of Brønsted and Lewis acid sites of different acid strengths on sulfated zirconia calcined at 450–650°C were measured by IR of adsorbed pyridine to elucidate the active sites for butane isomerization. The total numbers of Brønsted acid sites were largest when the catalyst was calcined at 500°C. The total numbers of Lewis acid sites increased with increasing calcination temperature to a maximum at 650°C. The catalytic activity in skeletal isomerization of butane correlated well with the number of Brønsted acid sites but not with the number of Lewis acid sites. The active sites were completely blocked by pyridine irreversibly absorbed at 350°C. We suggest that the strong Brønsted acid sites, which are able to retain pyridine against evacuation at 350°C, act as active sites for butane isomerization on sulfated zirconia.     

n-Butane isomerization over transition metal-promoted sulfated zirconia catalysts: effect of metal and sulfate content

n-Butane isomerization has been investigated over transition metal-promoted sulfated zirconia catalysts. Fe alone was a more efficient promoter than Mn and Cr, and mixtures of Fe–Mn, Fe–Cr, and Fe–V. Promotion of a commercial sulfated zirconia (4.8% sulfate) with iron amounts in excess of 2% depressed the conversion and increased the deactivation rate. Increasing reaction temperatures improved the conversion and decreased the induction period. At 70°C and above, the induction period was suppressed. The influence of activation temperature was studied over a Fe-sulfated zirconia catalyst (with 2% Fe and 4.8% SO₄²⁻ pre-calcined at 600°C). The best conversion was achieved when the catalyst was activated at 350°C in air. This temperature was apparently sufficient to generate the redox sites active at low reaction temperature. Activation in flowing helium depressed the catalytic activity and increased the induction period. The sulfate content had a significant effect on the catalyst performance. For 2% Fe-promoted zirconia, a maximum conversion was found for 7.5% SO₄²⁻, probably related with a better balance (or synergism) of the redox and acid sites involved in a bimolecular mechanism. The time required to reach a maximum of conversion (induction period) decreased with increasing total acidity, i.e. with sulfate content. The series of catalysts with different amounts of sulfate has been characterized by X-ray diffraction, nitrogen adsorption–desorption isotherms, TGA, ammonia-TPD, DRIFT, Raman, and X-ray photoelectron spectroscopy.     

Formation of tetramethylethylene radical cations after pentane adsorption on sulfated zirconia

Tetramethylethylene radical cations have been registered by ESR after pentane adsorption on sulfated zirconia. The radical cations proved to be not stable in the presence of oxygen, only molecular oxygen radical anions being registered. Tetramethylethylene formation and pentane disproportionation are shown to occur under illumination within the same spectral region proving that the former is formed as a by-product of pentane transformations.     

Transformation of propane,n-butane and n-hexane over H3PW12O40 and cesium salts. Comparison to sulfated zirconia and mordenite catalysts

Over H₃PW₁₂O₄₀ and its acidic cesium salts at 250°C, alkane transformations occur through the mechanisms previously proposed for sulfated zirconia and mordenite catalysts: propane is mainly transformed into butanes through a trimerization–isomerization–cracking process, n-butane into isobutane, propane and pentanes through a dimerization–isomerization–cracking process, n-hexane into methylpentanes and 2,3-dimethylbutane through a monomolecular mechanism. With all the samples, n-butane transformation is initially much faster than propane transformation, the difference in rate increasing significantly with the Cs content: from 25 times with H₃PW₁₂O₄₀ to 350 times with Cs_2.4H_0.6PW₁₂O₄₀. On the other hand, n-hexane transformation is 2.3 to 7 times faster than n-butane transformation. A decrease in acid strength and in acid site density with Cs introduction is proposed to explain the increase in the rate ratios. For all the reactions, sulfated zirconia pretreated at 600°C is 2–3 times more active than the heteropolycompounds. HMOR10 which is the most active catalyst for n-hexane transformation is the least active for n-butane and especially propane transformation. This very low activity of mordenite for these bimolecular processes can be related to particularities of its pore system: bimolecular reactions are strongly unfavoured in the narrow non-interconnected channels of this zeolite. This revised version was published online in August 2006 with corrections to the Cover Date.     

Isomerization ofn-butane on sulfated zirconia: Evidence for the dominant role of Lewis acidity on the catalytic activity

The catalytic activity of a ZrO₂/SO₄ catalyst in the isomerization ofn-butane at 423 K is reversibly suppressed by addition of CO. IR analysis of the adsorption of CO indicates that the only -coordination of CO onto coordinatively unsaturated surface Zr⁴⁺ cations occurs in the 300–473 K interval.