The role of deposited poisons and crystallite surface structure in the activity and selectivity of reforming catalysts

Abstract Over the past three decades catalytic reforming has evolved very rapidly to the point where it is now one of the most important industrial applications of catalysis [1]. The process was originally developed to produce gasoline components of high antiknock quality, in response to the fuel requirements of high compression ratio automobile engines. The objective of the process is to convert saturated hydrocarbons (alkanes and cyclo-alkanes) in petroleum naphtha fractions to aromatic hydrocarbons as selectively as possible, since the latter have excellent antiknock ratings. Naphtha fractions are composed of hydrocarbons having boiling points within the approximate range of 320–470 K. Reaction temperatures of 700–800 K and pressures of 10–35 atm are employed in the process. The catalysts employed commonly contain platinum or a combination of platinum and a second metallic element such as rhenium or iridium [2].

[1]  D. Do,et al.  Role of Sulphur in Catalytic Reforming of Hydrocarbons on Platinum/Alumina , 1988 .

[2]  D. Do,et al.  A unified theory of coking deactivation in a catalyst pellet , 1987 .

[3]  A. Sárkány,et al.  Hydrocarbon adsorption and coke formation on Pt/Al2O3 and Pt-Sn/Al2O3 catalysts , 1987 .

[4]  D. Do,et al.  The reformer lineout phenomenon and its fundamental importance tocatalyst deactivation , 1987 .

[5]  J. Barbier,et al.  Effect of presulfurization on the formation of coke on supported metal catalysts , 1986 .

[6]  C. L. Pieck,et al.  Influence of sulfurization on coke formation over catalysts for naphtha reforming , 1986 .

[7]  W. Sachtler,et al.  The effects of rhenium and sulfur on the maintenance of activity and selectivity of platinum/alumina hydrocarbon conversion catalysts. II: Experiments at elevated pressure , 1986 .

[8]  N. Fígoli,et al.  The role of Re and S in the Pt$z.sbnd;Re$z.sbnd;S/Al2O3 catalyst , 1986 .

[9]  M. R. Sad,et al.  Influence of chlorine content on the behavior of Pt-Re/Al2O3 catalyst for naphtha reforming , 1986 .

[10]  J. Dumesic,et al.  The effects of metal-oxygen bond strength on properties of oxides: II. Water-gas shift over bulk oxides , 1986 .

[11]  R. Burwell.  Supported platinum, palladium, and rhodium catalysts , 1986 .

[12]  R. Fréty,et al.  Thioresistance of supported metal catalysts: structure sensitivity of hydrogen sulphide adsorption on Pt/A1203, Ir/A1203 and Pt-Ir/A1203 catalysts , 1985 .

[13]  Role of rhenium in Pt-Re-Al2O3 reforming catalysis ― an integrated study , 1985 .

[14]  M. A. Pacheco,et al.  Reaction Kinetics of Methylcyclohexane Dehydrogenation over a Sulfided Pt + Re/ Al2O3 Reforming Catalyst. , 1985 .

[15]  W. Sachtler,et al.  The effects of rhenium and sulfur on the activity maintenance and selectivity of platinum/alumina hydrocarbon conversion catalysts , 1985 .

[16]  M. A. Pacheco,et al.  Effect of pretreatment on Pt/Al2O3 and Pt + Re/Al2O3 catalyst deactivation , 1985 .

[17]  L. Bencharif,et al.  Effect of sulphur on the properties of platinum catalysts as characterized by cyclic voltammetry , 1985 .

[18]  G. Corro,et al.  Structure sensitivity and coke formation on Pt/Al2O3 catalysts , 1985 .

[19]  G. Froment,et al.  Activities and selectivities for reforming reactions on unsulfided and sulfided commercial platinum and platinum-rhenium catalysts , 1985 .

[20]  H. Wise,et al.  Deactivation and Poisoning of Catalysts , 1985 .

[21]  V. Ponec,et al.  The influence of the metal particle size on the formation of multiple metal-carbon bonds , 1985 .

[22]  G. Bond.  The origins of particle size effects in heterogeneous catalysis , 1985 .

[23]  G. Corro,et al.  Coke formation on bimetallic platinum/rhenium and platinum/iridium catalysts , 1985 .

[24]  G. Corro,et al.  Coke formation on platinum-alumina catalyst of wide varying dispersion , 1985 .

[25]  Z. Paâl,et al.  Initial changes of the catalytic properties of platinum containing catalysts I. Transformations of mono- and bimetallic Pt/Al2O3 catalysts by carbonaceous deposits , 1984 .

[26]  A. Borgna,et al.  Sulfurization of PtAl2O3Cl catalysts: VI. Sulfur-platinum interaction studied by infrared spectroscopy , 1984 .

[27]  J. Dalmon,et al.  Exchange with deuterium of methane on nickel catalysts , 1984 .

[28]  Eric G. Deroulane.  Second european symposium on catalysis by metals. Multimetallic catalysts in synthesis and transformation of hydrocarbons: concluding remarks, critical issues and perspectives , 1984 .

[29]  R. Fréty,et al.  Activity and selectivity of Pt-Al2O3 in n-hexane conversion: effect of hydrogen pressure during precursor activation , 1984 .

[30]  L. Guczi.  Mechanism of reactions on multimetallic catalysts , 1984 .

[31]  W. Sachtler.  Selectivity and rate of activity decline of bimetallic catalysts , 1984 .

[32]  G. Bond,et al.  Silica-supported ruthenium-copper catalysts: structural studies and activities for n-butane hydrogenolysis , 1984 .

[33]  C. Apesteguía,et al.  Sulfurization of pt/al2o3-cl catalyst. v. pt particle-size effect on sulfur adsorption , 1984 .

[34]  P. Gallezot,et al.  Modifications of the atomic structure of Platinum aggregates induced by H2S, SO2, and elemental sulfur adsorption , 1984 .

[35]  M. Primet,et al.  Sulfurization and regeneration of platinum , 1984 .

[36]  V. Ponec.  Catalysis by Alloys in Hydrocarbon Reactions , 1984 .

[37]  J. Völter,et al.  Deactivation of supported pt and pt-sn catalysts in the conversion of methylcyclopentane , 1983 .

[38]  H. Wise,et al.  Thermodynamics of sulfur chemisorption on metals: V. Alumina-supported iridium , 1983 .

[39]  R. Burch,et al.  The role of tin and rhenium in bimetallic reforming catalysts , 1983 .

[40]  D. Trimm.  Catalyst design for reduced coking (review) , 1983 .

[41]  N. Fígoli,et al.  Operational conditions and coke formation on Pt-Al2O3 reforming catalyst , 1983 .

[42]  G. Bond,et al.  Catalysis, science and technology , 1983 .

[43]  M. Yacamán,et al.  The relation between dispersion and particle size on supported catalysts , 1983 .

[44]  E. M. Traffano,et al.  Hydrogen and Oxygen Spillover on Pt/Al2O3 During Naphtha Reforming , 1983 .

[45]  C. Apesteguía,et al.  The role of catalyst presulfurization in some reactions of catalytic reforming and hydrogenolysis , 1982 .

[46]  G. Somorjai,et al.  The reactivity and composition of strongly adsorbed carbonaceous deposits on platinum. Model of the working hydrocarbon conversion catalyst , 1982 .

[47]  J. Barbier,et al.  Sulfuration of Pt/Al2O3, Pt−Re/Al2O3 and Pt−Ir/Al2O3 catalysts , 1982 .

[48]  J. L. Carter,et al.  Bimetallic catalysts; application in catalytic reforming , 1982 .

[49]  E. Petersen,et al.  Fouling of a platinum-rhenium reforming catalyst using model reforming reactions , 1982 .

[50]  C. Apesteguía,et al.  Sulfurization of Pt/Al2O3−Cl catalysts. IV. Adsorption sites of H2S on Al2O3, Al2O3−Cl and Pt/Al2O3−Cl , 1982 .

[51]  E. Petersen,et al.  A novel reactor system that permits the direct determination of deactivation kinetics for a heterogeneous catalyst , 1982 .

[52]  G. Somorjai,et al.  Desorption, decomposition, and deuterium exchange reactions of unsaturated hydrocarbons (ethylene, acetylene, propylene, and butenes) on the platinum(111) crystal face , 1982 .

[53]  J. Figueiredo.  Progress in Catalyst Deactivation , 1982 .

[54]  G. Webb,et al.  Reactions of hydrocarbons on metallic catalysts , 1982 .

[55]  C. H. Bartholomew,et al.  Sulfur Poisoning of Metals , 1982 .

[56]  F. G. Gault.  Mechanisms of Skeletal Isomerization of Hydrocarbons on Metals , 1982 .

[57]  J. Katzer,et al.  X-ray absorption spectroscopy of Pt-ReAl2O3 catalysts , 1981 .

[58]  R. Burch.  Platinum-tin reforming catalysts: I. The oxidation state of tin and the interaction between platinum and tin , 1981 .

[59]  G. Leclercq,et al.  Catalytic hydrogenation of cyclohexene: 4. The effect of sulfur on supported platinum , 1981 .

[60]  E. Ruckenstein,et al.  Effects of chemisorption of electron acceptor elements on the stability of platinum clusters , 1981 .

[61]  C. Apesteguía,et al.  Sulfurization of Pt/Al2O3-Cl catalysts. II. Accessible metal fraction , 1981 .

[62]  G. Somorjai,et al.  THE STRUCTURE SENSITIVITY OF CYCLOHEXANE DEHYDROGENATION AND HYDROGENOLYSIS CATALYZED BY PLATINUM SINGLE CRYSTALS AT ATMOSPHERIC PRESSURE , 1981 .

[63]  P. Wells,et al.  Variation of catalyst selectivity by control of the environment of surface sites , 1981 .

[64]  V. Ponec,et al.  Selectivity of metals and alloys in hydrocarbon reactions , 1981 .

[65]  J. Oudar.  Sulfur Adsorption and Poisoning of Metallic Catalysts , 1981 .

[66]  T. Garetto,et al.  Sulfurization of Pt/Al2O3−Cl catalysts , 1980 .

[67]  M. R. Sad,et al.  Influence of the Chlorine Content on the Behavior of Catalysts for n-Heptane Reforming , 1980 .

[68]  H. J. Krebs,et al.  Hydrogenation kinetics of carbonaceous layers on polycrystalline iron , 1980 .

[69]  W. Sachtler,et al.  Conversion of n-hexane over monofunctional supported and unsupported PtSn catalysts , 1980 .

[70]  F. M. Dautzenberg,et al.  The role of rhenium and sulfur in platinum-based hydrocarbon-conversion catalysts , 1980 .

[71]  J. Oudar.  Sulphur-metal interactions , 1980 .

[72]  R. Prins,et al.  Chemistry and chemical engineering of catalytic processes , 1980 .

[73]  N. Fígoli,et al.  Optimum Chlorine on Naphtha Reforming Catalyst Regarding Deactivation by Coke Formation , 1980 .

[74]  J. Bernard,et al.  The Sulfur Poisoning of Pt Alkaline L Zeolites , 1980 .

[75]  B. Cooper,et al.  The Coking of Platinum/Alumina Reforming Catalysts , 1980 .

[76]  R. Prins,et al.  On the temperature-programmed reduction of PtIr/γ-AlO catalysts , 1979 .

[77]  M. Balooch,et al.  Platinum-catalyzed gasification of graphite by hydrogen , 1979 .

[78]  J. Anderson,et al.  Adsorption and temperature-programmed desorption of hydrogen with dispersed platinum and platinum-gold catalysts , 1979 .

[79]  R. Fréty,et al.  The state of Re in PtReγ-Al2O3 catalysts , 1979 .

[80]  B. Gates,et al.  Chemistry of catalytic processes , 1979 .

[81]  W. Goddard,et al.  Electronic properties of metal clusters (Ni13 to Ni87) and implications for chemisorption , 1978 .

[82]  J. Anderson,et al.  Reactions of neopentane and neohexane on platinum/Y-zeolite and platinum/silica catalysts , 1978 .

[83]  A. Frennet,et al.  Effect of multiple sites and competition in adsorption on the kinetics of reactions catalyzed by metals , 1978 .

[84]  T. Fischer,et al.  Model experiments on the poisoning of Pt catalysts by sulfur , 1978 .

[85]  M. Boudart.  Structure of metallic catalysts , 1978 .

[86]  J. Védrine,et al.  X-ray photoelectron spectroscopy study of Pd and Pt ions in type Y-zeolite. Electron transfer between metal aggregates and the support as evidenced by X-ray photoelectron spectroscopy and electron spin resonance , 1978 .

[87]  T. Fischer,et al.  The adsorption of sulfur on the platinum (100) surface , 1977 .

[88]  G. Somorjai,et al.  The stability and structure of high miller index platinum crystal surfaces in vacuum and in the presence of adsorbed carbon and oxygen , 1977 .

[89]  R. A. Santen,et al.  Surface Composition and Selectivity of Alloy Catalysts , 1977 .

[90]  B. D. Mcnicol.  The reducibility of rhenium in re on γ-alumina and ptre on γ-alumina catalysts , 1977 .

[91]  E. Wolf,et al.  Kinetics of deactivation of a reforming catalyst during methylcyclohexane dehydrogenation in a diffusion reactor , 1977 .

[92]  J. Brunelle,et al.  Active centers of platinum-silica catalysts in hydrogenolysis and isomerization of n-pentane , 1976 .

[93]  H. Verbeek,et al.  The study of the alloys of platinum and tin by chemisorption , 1976 .

[94]  J. Katzer,et al.  Platinum catalyst deactivation in low-temperature ammonia oxidation reactions: I. Oxidation of ammonia by molecular oxygen , 1976 .

[95]  G. Somorjai,et al.  Mechanism of catalysis of hydrocarbon reactions by platinum surfaces , 1975, Nature.

[96]  J. Clarke.  Selectivity in catalysis by alloys , 1975 .

[97]  J. Barbier,et al.  Activity of metallic catalysts: IV. Influence of the nature of the support and effect of sulfur-containing poisons on two examples of “demanding reactions” , 1975 .

[98]  M. Cini.  Ionization potentials and electron affinities of metal clusters , 1975 .

[99]  Marvin F. L. Johnson.  The state of rhenium in Pt/Re/alumina catalysts , 1974 .

[100]  Patricio Reyes,et al.  React. Kinet. Catal. Lett. , 1974 .

[101]  J. J. Burton.  STRUCTURE AND PROPERTIES OF MICROCRYSTALLINE CATALYSTS , 1974 .

[102]  J. Katzer,et al.  On subdivision of the classification of demanding reactions , 1974 .

[103]  J. Sinfelt.  Supported “bimetallic cluster” catalysts , 1973 .

[104]  T. Einstein,et al.  Indirect Interaction between Adatoms on a Tight-Binding Solid , 1973 .

[105]  P. G. Menon,et al.  Separate determination of Pt and Re in Pt$z.sbnd;Re$z.sbnd;Al2O3 reforming catalyst , 1973 .

[106]  J. Oudar,et al.  Étude par la diffraction des électrons lents et la spectroscopie auger de l'adsorption du soufre sur le platine , 1973 .

[107]  M. R. Hoare,et al.  Statistics and stability of small assemblies of atoms , 1972 .

[108]  G. Somorjai.  On the mechanism of sulfur poisoning of platinum catalysts , 1972 .

[109]  W. Sachtler,et al.  The reactions between cyclopentane and deuterium on nickel and nickel-copper alloys , 1972 .

[110]  J. Oudar,et al.  Structure, mécanisme de formation et stabilité de la couche d'adsorption du soufre sur le nickel , 1970 .

[111]  J. Wall,et al.  Galaxy identifications from the Parkes 2700 MHz survey: The selected regions and the ±4° declination zone , 1970 .

[112]  W. Sachtler,et al.  The role of individual surface atoms in chemisorption and catalysis by nickel-copper alloys , 1969 .

[113]  R. V. Hardeveld,et al.  The statistics of surface atoms and surface sites on metal crystals , 1969 .

[114]  J. E. Benson,et al.  On the specific activity of platinum catalysts , 1966 .

[115]  V. Nikolajenko,et al.  Investigation of properties of the metallic nickel surface in mixed NiMgO catalysts , 1963 .

[116]  P. B. Weisz,et al.  Aging of Platinum Reforming Catalysts , 1961 .

[117]  W. K. Meerbott,et al.  Aromatics Manufacture over Platforming Catalyst , 1954 .

[118]  D. Dowden.  56. Heterogeneous catalysis. Part I. Theoretical basis , 1950 .

[119]  G. Schwab.  Alloy catalysts in dehydrogenation , 1950 .