Metal dispersion and catalytic activity of trimetallic Pt-Re-Sn/Al2O3 naphtha reforming catalysts

Abstract The chemisorption of CO over mono-, bi- and trimetallic naphtha reforming catalysts containing Pt, Re and Sn in the metallic function was studied. The temperature-programmed reduction (TPR) results show that there are important interactions among the metals. The CO chemisorption experiments were performed in a pulse equipment. Pulses of the adsorbate (CO) were successively injected to the system until saturation and the exposed Pt was determined from the amount of adsorbate irreversibly adsorbed. The exposed or accessible Pt obtained was compared with that one determined by the classical static method and it was also correlated with the results of catalytic activity of the metal function (cyclohexane dehydrogenation at 400 °C, 0.1 MPa, H 2 /CH = 30). The CO chemisorption results indicate that it is possible to determine in an easy way the metallic dispersion of Pt/Al 2 O 3 monometallic catalysts and that the same method can be applied to measure the exposed Pt on bimetallic Pt-Re and Pt-Sn catalysts and trimetallic Pt-Re-Sn catalysts. The values obtained from CO adsorption have very good repeatability and are proportional to the dehydrogenating activity of the catalyst. The latter correlation has a few outliners which were attributed to the electronic effects exerted by Sn and Re over Pt that modify differently the metal activity and the capacity to chemisorb CO.

[1]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[2]  W. Sachtler,et al.  On the mechanism for the platinum-catalyzed reduction of rhenium in PtReγ-Al2O3 , 1989 .

[3]  M. C. Rangel,et al.  n‐octane reforming over alumina‐supported Pt, Pt–Sn and Pt–W catalysts , 2000 .

[4]  Luciene Santos Carvalho,et al.  Trimetallic naphtha reforming catalysts , 2004 .

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

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

[7]  B. Hoffman,et al.  Characterization and catalytic function of Re0 and Re4+ in Re/Al2O3 and PtRe/Al2O3 catalysts , 1987 .

[8]  R. Fréty,et al.  Platinum-rhenium-alumina catalysts: III. Catalytic properties , 1976 .

[9]  I. Schifter,et al.  Pt-Sn/Al2O3 sol-gel catalysts: Metallic phase characterization , 1993 .

[10]  A. Webb Reducibility of supported rhenium , 1975 .

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

[12]  G. Corro,et al.  PROMOTIONAL EFFECT OF Sn ON NO OXIDATION OVER Pt/Al2O3 AS PROMISING GAS EXHAUST CATALYTIC CONVERTER. SELECTIVE Pt AND Sn DISPERSION DETERMINATION , 2002 .

[13]  Geoffrey I. Webb,et al.  Transmission electron microscopy and energy dispersive X-ray spectroscopy studies of Pt-Re/γ-Al2O3 catalysts , 1994 .

[14]  R. Fréty,et al.  Platinum-rhenium-alumina catalysts: II. Study of the metallic phase after reduction , 1976 .

[15]  R. Prins,et al.  Alloy formation and metal oxide segregation in PtRe/γ-AlO catalysts as investigated by temperature-programmed reduction , 1979 .

[16]  Andrew G. Glen,et al.  APPL , 2001 .

[17]  J. Sinfelt,et al.  KINETICS OF METHYLCYCLOHEXANE DEHYDROGENATION OVER PT—Al2O3 , 1960 .

[18]  F. Lónyi,et al.  New approaches to prepare supported Sn−Pt bimetallic catalysts , 1999 .

[19]  D. Stirling,et al.  Transmission Electron Microscopy, Energy Dispersive X-Ray Spectroscopy, and Chemisorption Studies of Pt–Ge/γ-Al2O3Reforming Catalysts , 1998 .

[20]  D. Gokak,et al.  Method for Metal Dispersion Measurements in Bimetallic Pt-Sn/Al2O3 Catalysts , 1994 .

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

[22]  D. Rawat,et al.  The determination of accessible Pt metal fraction in Pt–Sn/Al2O3 reforming catalyst , 1998 .

[23]  J. Barbier,et al.  Determination of metallic surface areas of platinum - rhenium catalysts , 1981 .

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

[25]  Luciene Santos Carvalho,et al.  Trimetallic naphtha reforming catalysts. I. Properties of the metal function and influence of the order of addition of the metal precursors on Pt–Re–Sn/γ-Al2O3–Cl , 2004 .