Dehydrocyclization of Alkanes Over Zeolite-Supported Metal Catalysts: Monofunctional or Bifunctional Route

The direct catalytic conversion of alkanes into aromatics has found potentially important industrial applications. Initially only alkanes with 6 and more carbon atoms in the chain were concerned. Supported platinum catalysts were found active for the aromatization of alkanes; the drawbacks of these catalysts were their deactivation with time on stream and the existence of simultaneous parallel reactions. Much discussion has been published on the aromatization of C₆₊ alkanes. A bifunctional mechanism which involves both the metal and the acid sites of the support and a monofunctional mechanism involving only the metallic sites operate over, respectively, Pt supported on acidic support and Pt supported on nonacidic support. In the present review the mechanisms proposed for the aromatization of alkanes are described. Over monofunctional Pt catalysts two possible mechanisms prevail: 1,6 ring closure on the Pt surface involving primary and secondary C-H bond rupture, followed by dehydrogenation of the cycloalkanes into aromatics (1,5 ring closure to a lesser extent also contributes to aromatic production); or dehydrogenation of the alkanes into olefins, dienes, and trienes followed by thermal ring closure. Zeolites were found most suitable as support for preparing catalysts more active and more selective in the alkane aromatization. In addition catalysts based on noble metals supported on zeolite appeared more resistant against deactivation by coke. In this review the aromatization of hexane, heptane, and octane over Pt-zeolite catalysts is discussed in detail. Comparisons between different zeolite structures and different dehydrogenation sites are given. In particular a critical analysis of the results and interpretation concerning Pt-KL catalysts strongly suggests that the exceptional high selectivity towards aromatization of n-hexane exhibited by Pt-KL could not be explained by only the nest or constraint effect exerted by the channel dimension and morphology, not by only the terminal cracking properties, not by only the partial electron transfer from the zeolite support to the Pt particles, and not by only the Pt particle size. Zeolite structure also affects the aromatic product distribution, in particular when the alkane contains more than 7 carbon atoms. It is shown how Pt on medium-pore zeolites such as In-ZSM-5, silicalites will favor the aromatization of C₈ alkane isomers into ethylbenzene-styrene with respect to other C₈ aromatics. Aromatization of light alkanes, C₂-C₅, requires the increase of the hydrocarbon chain length up to 6 carbon atoms and higher, followed by cyclization reaction. Recently new processes to convert C₂-C₅ alkanes into aromatics have been disclosed, M2-forming from Mobil, Cyclar from BP-UOP, and Aroforming from IFP-Saluted. In general these processes use bifunctional catalysts possessing a dehydrogenating and an acid function. The catalysts consist of a metal ion or metal oxide supported on a microporous acid solid. In this review we analyze the results concerning mainly platinum supported on pentasil-type zeolite. It is shown that althoug Pt has better dehydrogenating properties as compared with gallium and zinc, the efficiency of catalysts based on Pt-ZSM-5 for light alkane aromatization is less because undersirable reactions such as hydrogenolysis and ethene (olefins) hydrogenation occur on the platinum surface, resulting in the production of unreactive alkanes, CH₂, C₂H₆. These drawbacks could be partially suppressed by alloying Pt and by increasing the reaction temperature.     

n-Octane aromatization on Pt-containing non-acidic large pore zeolite catalysts

Platinum catalysts supported on the potassium-form of different large-pore zeolites (i.e. K-LTL, K-BEA, K-MAZ, and K-FAU) have been tested for n-octane aromatization at 500 °C. All catalysts were prepared by the vapor phase impregnation (VPI) method. It was found that the Pt/K-LTL catalyst exhibit a better aromatization performance than the other zeolite catalysts. However, due to secondary hydrogenolysis, the C8 aromatics produced inside the zeolite are converted to benzene and toluene. By contrast, a non-microporous Pt/SiO₂ catalyst did not present the secondary hydrogenolysis. Therefore, despite a lower initial aromatization activity, Pt/SiO₂ results in higher selectivity to C8 aromatics than any of the other zeolite catalysts. All fresh catalysts were characterized by hydrogen chemisorption and FT-IR of adsorbed CO. In addition, the residual acidity of the supports was analyzed by temperature programmed desorption (TPD) of ammonia. In agreement with previous studies, it was found that after reduction at either 350 or 500 °C, the Pt/K-LTL showed much higher Pt dispersion than other catalysts. It is known that the structure of L zeolite can stabilize the small Pt clusters inside the zeolite channel. By contrast, FT-IR indicated that a large fraction of platinum clusters were located outside the zeolite channels in the case of Pt/K-BEA and Pt/K-MAZ catalysts.     

Propane transformation over H-ZSM5 zeolite modified with germanium

The propane aromatization was studied over H-ZSM5 zeolite modified by Ge, Pt and Pt-Ge. The aromatization was performed in a micro-reactor at 773K and at atmospheric pressure. The addition of germanium on H-ZSM5 increases the activity for propane transformation but decreases the selectivity toward aromatic compounds. The transformation of propane on Pt/H-ZSM5 indicates a significant increase in the activity and a decrease in the selectivity toward aromatics, while on the bimetallic Pt-Ge/H-ZSM5 catalyst both the activity and the selectivity toward aromatics increase. The dehydrogenation of propane over GeO₂/SiO₂ at 773 K and the n-heptane transformation overH-ZSM5 and Ge/H-ZSM5 at 673 K were performed. Results confirm the dehydrogenation capacity of GeO₂ and show similar activity and selectivity for n-heptane conversion on H-ZSM5 and Ge/H-ZSM5. The acidic properties of the catalysts were determined by TPD/NH₃ and IR/Pyanalyses. Results show that both the total and strong acidity decrease with the addition of germanium. Therefore, it seems that germanium affects the activity of propane conversion due to the dehydrogenation capacity of GeO₂,while the selectivity toward aromatics decreases due to the lower capacity of cyclization, by decreasing the acidity and the number of strong acid sites. In contrast, the Pt-Ge/H-ZSM5 catalyst presents the highest selectivity toward aromatics (53.4%) which is attributed to the decrease in hydrogenolysis capacity of platinum. The TPR results of the Pt-Ge/H-ZSM5 catalyst indicate interaction of Pt-Ge, and from the hydrogen consumption it was seen that Ge⁴⁺ is partially reduced to Ge²⁺, which is attributed to the presence of metallic platinum. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Product distribution in the aromatization of dilute ethene over H-GaAlMFI zeolite: effect of space velocity

Influence of space velocity on the aromatization of dilute ethene (5 mol% in N₂) over H-GaAlMFI zeolite catalyst, having high acidity (0.46 mmol g⁻¹, measured in terms of the pyridine chemisorbed at 400 °C) and high concentration of non-framework Ga-oxide species (0.32 mmol g⁻¹), at atmospheric pressure covering a wide temperature range (300–500 °C) has been thoroughly investigated. The selectivity of aromatics, propene, propane and C₄ hydrocarbons and alkane/aromatics and H₂/aromatics mole ratios are strongly influenced by the space velocity. The results indicate that the aromatization involves H₂ transfer reactions predominantly at the lower temperatures and/or higher space velocities whereas dehydrogenation reactions become predominant at higher temperatures and/or lower space velocities. The distribution of aromatics and C₈-aromatic isomers depends strongly upon the amount (i.e. yield) of aromatics and C₈-aromatics, respectively, formed in the process. The primary aromatics produced in the process are found to be mainly p- and o-xylenes. The aromatics distribution is, however, controlled by the aromatics inter-transformation (viz. isomerization, alkylation/dealkylation and disproportionation) reactions. The p-xylene/m-xylene ratio is decreased as expected, but the p-xylene/o-xylene ratio is increased with increasing both the space velocity and temperature. The increase of p-xylene/o-xylene ratio is found to be unusual, much above the equilibrium value.     

粘合剂和钡对Pt/L催化剂性能的影响

L分子筛芳构化催化剂与传统的双功能重整催化剂相比,链烷烃芳构化活性和选择性高得多。粘合剂影响L分子筛催化剂的强度、芳构化活性和选择性。Pt/K BaL催化剂比Pt/KL催化剂的芳构化活性和选择性高。钡含量影响Pt/K BaL催化剂的芳构化活性和选择性。微反结果表明,自制的Pt/KL和Pt/K BaL催化剂比文献报导的载铂L分子筛催化剂的芳构化活性和选择性高,100mL装置评价结果也证明两种自制催化剂具有很高的芳构化活性和选择性。     

Differences between ZSM-5 and ZSM-11 zeolite catalysts in 1-hexene aromatization and isomerization

ZSM-5 and ZSM-11 zeolites with high crystallinity are synthesized and tested in the aromatization and isomerization reactions of 1-hexene at 370 °C in a continuous flow fixed bed. The results indicate that ZSM-5 and ZSM-11 zeolites possess similar acid site amount and strength, and most of the acid sites belong to Brønsted acid. When the ZSM-5 and ZSM-11 zeolites were used as catalysts, the aromatics selectivity over ZSM-11 catalyst was higher than that over ZSM-5 catalyst in contrast to i-paraffins selectivity, maybe attributed to that the C₇ and C₈ aromatics have an easier exit from the ZSM-11 zeolite. Moreover, the decrease of particle size can present superior aromatics selectivity and less i-paraffins selectivity in the aromatization and isomerization of 1-hexene over the ZSM-11 catalyst.     

Octane number enhancement studies of naphtha over noble metal loaded zeolite catalysts

An Indian industrial naphtha containing mixture of various hydrocarbons belong to n-paraffins, isoparaffins, naphthenes and aromatics falling in C₅ to C₉ carbon range has been studied for its octane boosting through the production of isoparaffins over various Pt loaded zeolite catalysts possessing different acidity and porosity properties. Optimum balance of acid and metal functionalities in 0.6 wt.% Pt loaded on BEA zeolite helped in achieving highest increase in research octane number (RON) from 44 to 80, suitable for gasoline applications, through the production of lower isoparaffins (iC₄-iC₆) along with C₇+ isoparaffins.     

FTIR and XPS study of supported PtSn catalysts used for light paraffins dehydrogenation

A comparison between the characteristics of the metallic phase (studied by FTIR and XPS) of Pt and PtSn catalysts supported on Al₂O₃, K-doped Al₂O₃ and MgO (used for light paraffins dehydrogenation reactions) is reported in this paper. The beneficial effects produced by tin addition to platinum, both in the increase of the selectivity to propene and the low coke formation, would be related with the possible electronic modifications of Pt by Sn, with probable formation of alloys, mainly for Al₂O₃ and MgO supported bimetallic catalysts. On the other hand, the modification of the electronic state of Pt by Sn addition appears to be of a minor importance in bimetallic catalysts supported on K-doped Al₂O₃.     

Aromatization activity of gallium containing MFI and TON zeolite catalysts in n-butane conversion: Effects of gallium and reaction conditions

A kinetic study of n-butane conversion over acidic and gallium (Ga) containing MFI and TON zeolites has revealed that Ga active sites create a new pathway for aromatics formation via dehydrogenation reaction steps. This pathway does not involve bulky bimolecular hydrogen transfer steps of the aromatization process over acidic zeolites, and, as a consequence, leads to considerably higher enhancement of the aromatization activity of the one-dimensional TON catalyst when compared to the three-dimensional MFI catalyst. This finding highlights fundamentally different spatial requirements for alkane aromatization over acidic and Ga containing zeolites and indicates that the zeolites with severe spatial constraints could become very selective catalysts for alkane aromatization after their modification with Ga. It is anticipated that these results will initiate the search for new, highly selective aromatization catalysts based on zeolites with different structures. The second important finding of this work is the evolution of the aromatization activity of GaH-TON and GaH-MFI catalysts during n-butane reaction that is likely associated with formation of catalytically active Ga⁺ ions. In our study, this process was completed in about 15 min, i.e. much faster then similar processes that were reported earlier in the literature for the GaH-MFI catalysts. To the best of our knowledge, no data on the evolution of the aromatization activity was reported up to day for the one-dimensional GaH-TON catalysts.     

Bifunctional Catalysis of Mo/HZSM-5 in the Dehydroaromatization of Methane to Benzene and Naphthalene XAFS/TG/DTA/MASS/FTIR Characterization and Supporting Effects

The direct conversion of methane to aromatics such as benzene and naphthalene has been studied on a series of Mo-supported catalysts using HZSM-5, FSM-16, mordenite, USY, SiO₂, and Al₂O₃as the supporting materials. Among all the supports used, the HZSM-5-supported Mo catalysts exhibit the highest yield of aromatic products, achieving over 70% total selectivity of the hydrocarbons on a carbon basis at 5–12% methane conversion at 973 K and 1 atm. By contrast, less than 20% of the converted methane is transformed to hydrocarbon products on the other Mo-supported catalysts, which are drastically deactivated, owing to serious coke formation. The XANES/EXAFS and TG/DTA/mass studies reveal that the zeolite-supported Mo oxide is endothermally converted with methane around 955 K to molybdenum carbide (Mo₂C) cluster (Mo-C, C.N.=1,R=2.09 Å; Mo-Mo, C.N.=2.3–3.5;R=2.98 Å), which initiates the methane aromatization yielding benzene and naphthalene at 873–1023 K. Although both Mo₂C and HZSM-5 support alone have a very low activity for the reaction, physically mixed hybrid catalysts consisting of 3 wt% Mo/SiO₂+HZSM-5 and Mo₂C+HZSM-5 exhibited a remarkable promotion to enhance the yields of benzene and naphthalene over 100–300 times more than either component alone. On the other hand, it was demonstrated by the IR measurement in pyridine adsorption that the Mo/HZSM-5 catalysts having the optimum SiO₂/Al₂O₃ratios, around 40, show maximum Brönsted acidity among the catalysts with SiO₂/Al₂O₃ratios of 20–1900. There is a close correlation between the activity of benzene formation in methane aromatization and the Brönsted acidity of Mo/HZSM-5, but not Lewis aciditiy. It was found that maximum benzene formation was obtained on the Moz/HZSM-5 having SiO₂/Al₂O₃ratios of 20–49, but substantially poor activities on those with SiO₂/Al₂O₃ratios smaller and higher than 40. The results suggest that methane is dissociated on the molybdenum carbide cluster supported on HZSM-5 having optimum Brönsted acidity to form CH_x(x>1) and C₂-species as the primary intermediates which are oligomerized subsequently to aromatics such as benzene and naphthalene at the interface of Mo₂C and HZSM-5 zeolite having the optimum Brönsted acidity. The bifunctional catalysis of Mo/HZSM for methane conversion towards aromatics is discussed by analogy with the promotion mechanism on the Pt/Al₂O₃catalyst for the dehydro-aromatization of alkanes.     

Hydrothermal study of Pt–Sn-based SAPO-34 supported novel catalyst used for selective propane dehydrogenation to propylene

Catalyst's regeneration is unavoidable part during dehydrogenation. The hydrothermal treatment influence on the performance of Pt–Sn-based SAPO-34 supported novel catalyst, used for propane dehydrogenation to propylene is investigated in this study. The catalyst shows excellent stability for mild steaming (nitrogen mixed steam), during four consecutive runs (reaction–regeneration mode). On the other hand, Pt–Sn/ZSM-5 was largely affected on mild steaming due to severe dealumination. In order to get into mechanistic understanding, severe hydrothermal treatment was carried our using pure steam. The substation loss in catalyst activity was noted. Both fresh and severe hydrotreated catalysts were characterized by XRD, XRF, O₂-pulse analysis of coke, NH₃-TPD, IR spectrum of adsorbed ammonia, H₂-TPR, HR-TEM and XPS, to explore reasons for change in catalytic properties. The texture/topology is found stable. Changes in surface ensembles occur due to the loss of Sn, Al, formation of SnO_x species and in particular Pt sintering. This leads Pt active sites (zeolite–SnO–Pt) to inactive sites (zeolite–Pt, zeolite–PtO–Sn, Pt–Sn alloy, etc.) formation and reduced catalyst activity. TEM micrographs and H₂-chemisorption analysis confirms Pt particles agglomeration and/or sintering. About 98% catalyst activity is recovered by re-dispersed Pt using chlorination technique and credit goes to hydrothermally stable support (SAPO-34).     

Catalysts based on zeolite ZSM-23 for isodewaxing of a lubricant stock

Granular Pt/(ZSM-23-γ-Al₂O₃) catalysts with different platinum and zeolite contents have been synthesized with the aim of developing efficient isodewaxing catalysts for lowering the pour point of lubricants and diesel fuels. Their physicochemical properties have been studied by X-ray diffraction, temperature-programmed desorption of ammonia, and low-temperature nitrogen adsorption/desorption. The effects of catalyst composition and process conditions (1.0–3.0 MPa, 220–400°C) on the outcomes of the isodewaxing of the 280°C-EBP lubricant fraction isolated from the hydrocracking product of vacuum gas oil have been investigated. The highest yields of products with the same pour points have been obtained with a 0.30 wt % platinum catalyst supported on the 20 wt % zeolite ZSM-23 + 80 wt % γ-Al₂O₃ material. An analysis of the basic performance characteristics of the isodewaxing catalysts based on zeolite ZSM-23 and dewaxing catalysts based on zeolite ZSM-5 has demonstrated that the catalysts based on ZSM-23 ensure higher yields of dew-axed products than the laboratory and commercial catalysts based on ZSM-5.     

Aromatization of propane over GaHMFI catalysts. Reaction scheme, nature of the dehydrogenating species and mode of coke formation

The kinetic modelling of propane aromatization over a Ga/HMFI catalyst and the comparison of Ga₂O₃-HMFI mixtures with different compositions has allowed us to specify the respective roles of dehydrogenating species and of protonic sites. Propane aromatization over Ga/HMFI catalyst occurs mainly through a conventional bifunctional reaction scheme (with desorbed intermediates) in which the dehydrogenating gallium species are responsible for dehydrogenation of propane, of oligomers and of cyclic olefins and diolefins while protonic sites are responsible for oligomerization, cyclization and cracking. This bifunctional transformation is kinetically limited by propane dehydrogenation. Unfortunately, gallium species also catalyze alkane cracking and hydrogenolysis as well as alkene hydrogenation with formation of the undesired products methane and ethane. From the comparison of the catalytic properties of MFI gallosilicates calcined under air flow at various temperatures, it can be concluded that tetrahedral gallium is inactive in dehydrogenation reactions. Dehydrogenation occurs through a bifunctional mechanism involving the joint participation of gallium oxide (extra framework species) and of protonic sites. Coke formed during propane aromatization causes a blockage of the access to the protonic sites of the zeolite which is responsible for deactivation. Ga decreases the coking/aromatization rate ratio of HMFI and facilitates the coke removal through oxidative treatment, both effects being more pronounced after Ga/HMFI pretreatment at high temperature under hydrogen because of the better dispersion of the Ga species.     

Effect of Si/Al ratio on performance of Pt–Sn-based catalyst supported on ZSM-5 zeolite for n-butane conversion to light olefins

The performance of Pt–Sn-based catalyst, supported on ZSM-5 of different Si/Al ratios were investigated for simultaneous dehydrogenation and cracking of n-butane to produce light olefins. The catalysts were characterized by number of physio-chemical techniques including XRF, TEM, IR spectra, NH₃-TPD and O₂-pulse analysis. Increase in Si/Al ratio of zeolite support ZSM-5 significantly increased light olefin's selectivity, while feed conversion decreases due to lower acidity of support. The results indicated that both the n-butane cracking and dehydrogenation activity to light olefin's over Pt–Sn/ZSM-5 samples with increasing Si/Al ratios greatly enhanced catalytic performance. The catalysts were deactivated with time-on-stream due to the formation of carbon-containing deposits. A coke deposition was significantly related to catalyst activity, while at higher Si/Al ratio catalyst the coke precursors were depressed. These results suggested that the Pt–Sn/ZSM-5 catalyst of Si/Al ratio 300 is superior in achieving high total olefins selectivity (above 90 wt.%). The Pt–Sn/ZSM-5 also demonstrates resistance towards hydrothermal treatment, as analyzed through the three successive reaction-regeneration cycles.     

Comparison of Ethylene Glycol Steam Reforming Over Pt and NiPt Catalysts on Various Supports

Steam reforming of ethylene glycol (EG) was studied on Pt and NiPt catalysts supported on γ-Al₂O₃, TiO₂, and carbon. On all supports bimetallic NiPt catalysts show higher activity for H₂ production than the corresponding Pt catalysts as predicted from model surface science studies. The kinetic trends are similar for all catalysts (Pt and NiPt) with the H₂ production rate being zero-order and fractional order with respect to water and ethylene glycol, respectively. Slight differences in selectivity to minor products are observed depending both on active metal and support. On γ-Al₂O₃, NiPt shows higher H₂ and less alkane formation than Pt. TiO₂ supported catalysts show increased water-gas shift activity but also increased selectivity to alkane precursors. NiPt/C is identified as an active and selective catalyst for EG reforming.     

Modification of the catalytic properties of supported noble metal catalysts by carrier doping

The influence of altervalent cation doping of TiO₂ carriers on the chemisorptive and catalytic properties of supported Pt and Rh crystallites has been investigated. It was observed that doping of the carrier with higher valence cations leads to suppression of the H₂ and CO chemisorption capacity of Pt catalysts, while their activity in hydrogenation and oxidation reactions is significantly reduced. The opposite effects were observed in the case of Rh catalysts supported on higher valence doped TiO₂. These catalysts were found to possess higher activity in CO and CO₂ hydrogenation, in aromatics hydrogenation and in CO and C₂H₄ oxidation. Their stability characteristics were also found to be superior to those of the undoped Rh/TiO₂ catalyst. These effects are believed to originate from an electronic type interaction at the metal-support interface, induced by doping, which results in electron transfer from the support to the metal crystallites.     

XPS and EXAFS study of supported PtSn catalysts obtained by surface organometallic chemistry on metals: Application to the isobutane dehydrogenation

In this work, well defined alumina and silica supported Pt and PtSn catalysts were prepared by surface organometallic reactions and were characterized by TEM, XPS and EXAFS. These catalysts were tested in the catalytic dehydrogenation of isobutane. XPS results show that tin is found under the form of Sn(0) and Sn(II,IV), being the percentage of Sn(0) lower for alumina supported than for silica supported catalysts. Tin modified platinum catalysts, always show a decrease of approximately 1 eV in the BE of Pt, what would be indicative of an electron charge transfer from tin to platinum. When the concentration of Sn(0) is high enough, in our case Sn(0)/Pt ∼ 0.3, EXAFS experiments demonstrated the existence of a PtSn alloy diluting metallic Pt atoms, for both PtSn/γ-Al₂O₃ and PtSn/SiO₂. This PtSn alloy seems to be not active in the dehydrogenation reaction; however, it is very important for selectivity and stability, inhibiting cracking and coke formation reactions. The ensemble of our catalytic, XPS and EXAFS results, show that bimetallic PtSn/γ-Al₂O₃ catalysts, prepared via SOMC/M techniques, can be submitted to several sequential reaction–regeneration cycles, recovering the same level of initial activity each time and that the nature of the catalytic surface remains practically without modifications.     

Entropy considerations in monomolecular cracking of alkanes on acidic zeolites

Compensation between adsorption entropies and enthalpies results in less than a two-fold variation in adsorption equilibrium constants for C₃–C₆ alkanes at temperatures relevant for monomolecular cracking; the size-independent activation energy for CC bond activation in C₃–C₆ alkanes indicates that the marked increase in monomolecular cracking turnover rates observed with alkane chain size reflects a concurrent increase in activation entropies. Thermodynamic treatments for non-ideal systems rigorously describe confinement effects within zeolite channels and show that pre-exponential factors depend on solvation effects of the zeolite-host environment through variations in the thermodynamic activity of the zeolitic proton. Observed differences in rates and selectivities of monomolecular alkane activation with zeolite structure, after normalization to intrazeolitic concentrations, reflect differences in intrinsic rate constants.     

Catalytic activity of Pt‐Re‐Pb/Al2O3 naphtha reforming catalysts

BACKGROUND: The main purpose of the naphtha reforming process is to obtain high octane naphtha, aromatic compounds and hydrogen. The catalysts are bifunctional in nature, having both acid and metal sites. The metal function is supplied by metal particles (Pt with other promoters like Re, Ge, Sn, etc.) deposited on the support. The influence of the addition of Pb to Pt‐Re/Al₂O₃ naphtha reforming catalysts was studied in this work. The catalysts were prepared by co‐impregnation and they were characterized by means of temperature programmed reduction, thermal programmed desorption of pyridine and several test reactions such as cyclohexane dehydrogenation, cyclopentane hydrogenolysis and n‐heptane reforming. RESULTS: It was found that Pb interacts strongly with the (Pt‐Re) active phase producing decay in the metal function activity. Hydrogenolysis is more affected than dehydrogenation. Part of the Pb is deposited over the support decreasing the acidity and the strength of the most acidic sites. CONCLUSION: The n‐heptane reforming reaction shows that Pb modifies the stability and selectivity of the Pt‐Re catalysts. Small Pb additions increase the stability and greatly improve the selectivity to C₇ isomers and aromatics while they decrease the formation of low value products such as methane and gases. Copyright © 2011 Society of Chemical Industry