Catalytic Steam Reforming

The steam reforming process converts hydrocarbons into mixtures of hydrogen, carbon monoxide, carbon dioxide, and methane $$C_n H_m + nH_2 O \to nCO + \left( {n + \frac{m}{2}} \right)H_2 \left( { - \Delta H_{298}^0 < 0} \right) $$ (1) $$ CO + H_2 O \rightleftarrows CO_2 + H_2 \left( { - \Delta H_{298}^0 = 41.2kJ\,mol^{ - 1} } \right) $$ (2) $$ CO + 3H_2 \rightleftarrows CH_4 + H_2 O\left( { - \Delta H_{298}^0 = 206.2kJ\,mol^{ - 1} } \right) $$ (3) The expression reforming is misleading since it is used also for the well-knowm process for improvement of the octane number of gasoline [1]. In the gas industry, reforming has generally been used for “the changing by heat treatment of a hydrocarbon with high heating value into a gaseous mixture of lower heating value” [2].

[1]  E. R. Gerhard,et al.  Kinetics of the Methane-Steam Reaction , 1975 .

[2]  R. Moss,et al.  Field-emission studies on nickel. Part 1 .—Adsorption and interaction of ethylene and hydrogen , 1970 .

[3]  J. Lahaye,et al.  Mechanism of carbon formation during steamcracking of hydrocarbons , 1977 .

[4]  W. Akers,et al.  Kinetics of the methane‐steam reaction , 1955 .

[5]  P. Delescluse,et al.  Diffuse scattering in RHEED induced by linear disorders of sulphur segregated on nickel (111) surface , 1980 .

[6]  P. Wynblatt,et al.  Crystallite Sintering and Growth in Supported Catalysts , 1975 .

[7]  A. Frennet,et al.  CORRELATION BETWEEN THE CATALYTIC ACTIVITY OF METALS AND THE SURFACE STATES RESULTING FROM THE REACTION OF THE GASEOUS REACTANTS AND THE METAL. , 1969 .

[8]  L. L. V. Reijen,et al.  Coprecipitated nickel–alumina catalysts for methanation at high temperature. Part 1.—Chemical composition and structure of the precipitates , 1981 .

[9]  K. Sjöström.  Steam Reforming of n-Heptane at Low Concentration for Hydrogen Injection into Internal Combustion Engines , 1980 .

[10]  A. W. Ritchie,et al.  The effect of crystal parameter on hydrogenation and dehydrogenation , 1950 .

[11]  J. Rostrup-Nielsen.  Equilibria of decomposition reactions of carbon monoxide and methane over nickel catalysts , 1972 .

[12]  J. Anderson,et al.  The adsorption of CH4, C2H6 and neo-C5H12 on (111), (100) and (110) faces of nickel observed by l. e. e. d. and by photoelectric work-function measurement , 1970, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[13]  F. C. Roesler.  Theory of radiative heat transfer in co-current tube furnaces , 1967 .

[14]  R. P. Eischens.  Classical Methods in Catalysis Research , 1975 .

[15]  David J. Smith,et al.  Direct lattice imaging of small metal particles , 1981 .

[16]  G. Butler,et al.  Sintering of nickel-alumina catalysts , 1972 .

[17]  B. Höhlein,et al.  Experiments for combining nuclear heat with the methane steam-reforming process , 1975 .

[18]  J. A. Pask,et al.  Diffusion of Iron and Nickel in Magnesium Oxide Single Crystals , 1969 .

[19]  Sydney P. S. Andrew,et al.  Catalysts and Catalytic Processes in The Steam Reforming of Naphtha , 1969 .

[20]  David L. Trimm,et al.  The Formation and Removal of Coke from Nickel Catalyst , 1977 .

[21]  Lars J. Christiansen,et al.  40 Transient profiles in sulphur poisoning of steam performers , 1980 .

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

[23]  Y. Ogino,et al.  Studies on Catalysts for Low-Temperature Steam-Reforming of Hydrocarbons (IV) , 1971 .

[24]  J. Nørskov.  Calculated Binding Properties of Hydrogen on Nickel Surfaces , 1982 .

[25]  C. Mirodatos,et al.  Chemistry of silica-supported catalysts: preparation activation and reduction , 1981 .

[26]  E. Ruckenstein,et al.  Effect of the pore size on the aging of supported metals , 1975 .

[27]  H. Grabke,et al.  Kinetics of the Steam Reforming of Methane on Iron as a Catalyst , 1980 .

[28]  M. Boudart.  Two‐step catalytic reactions , 1972 .

[29]  M. W. Roberts,et al.  Interaction of hydrogen sulphide with nickel, tungsten and silver films , 1961 .

[30]  C. R. Schnell.  Reaction mechanism of steam re-forming , 1970 .

[31]  E. Plummer,et al.  New evidence for multiple binding sites for sulfur at the Ni(100)-vacuum interface , 1977 .

[32]  C. Kemball.  The Structure and Stability of Hydrocarbon Intermediates on the Surface of Catalysts , 1972 .

[33]  D. Trimm,et al.  Carbon formation from light hydrocarbons on nickel , 1973 .

[34]  T. Borowiecki,et al.  Promotion of nickel catalysts for the steam reforming of methane , 1976 .

[35]  D. Goodman,et al.  A surface science investigation of the role of potassium promoters in nickel catalysts for CO hydrogenation , 1982 .

[36]  M. Perdereau.  Emploi quantitatif de la spectroscopie Auger; Étalonnage de la méthode , 1971 .

[37]  J. Rostrup-Nielsen.  Chemisorption of hydrogen sulfide on a supported nickel catalyst , 1968 .

[38]  G. Froment,et al.  Simulation of Thermal Cracking Furnaces , 1978 .

[39]  F. Shephard.  Activity and properties of nickel catalysts in the hydrogenolysis of propane , 1969 .

[40]  Y. Yoneda,et al.  Nature of catalytically active sites over solid acids. I. Selective poisoning of Lewis acid sites on silica-alumina with pyridine and its application to olefin polymerization. , 1976 .

[41]  J. Oudar.  Sulfur Adsorption and Poisoning of Metallic Catalysts , 1980 .

[42]  P. W. Selwood,et al.  The Mechanism of Chemisorption: Hydrogen on Nickel at Elevated Pressures , 1958 .

[43]  R. E. Cunningham,et al.  5 The Reaction of Hydrogen and Ethylene on Several Faces of a Single Crystal of Nickel , 1957 .

[44]  E. Sickafus.  Sulfur and carbon on the (110) surface of nickel , 1970 .

[45]  G. Rhead.  Diffusion on surfaces , 1975 .

[46]  J. Coad,et al.  Auger spectroscopy of carbon on nickel , 1971 .

[47]  G. Martin.  The kinetics of the catalytic hydrogenolysis of ethane over Ni/SiO2 , 1979 .

[48]  J. Rostrup-Nielsen.  Criteria for Carbon Formation , 1982 .

[49]  M. Saito,et al.  Studies on the Reaction of n-Butane, Ethylene and 1-Butene with Steam on Silica-Supported Nickel Catalyst , 1970 .

[50]  M. Jacono,et al.  Structural, magnetic, and optical properties of nickel oxide supported on .eta.- and .gamma.-aluminas , 1971 .

[51]  R. Baker,et al.  Catalytic gasification of graphite by nickel in various gaseous environments , 1981 .

[52]  T. Edmonds,et al.  Surface Structures Formed during the Interaction of Sulphur Compounds with the (111) Face of Nickel , 1971 .

[53]  Geoffrey A. Manley,et al.  A Review of the Auditory Physiology of the Reptiles , 1981 .

[54]  C. H. Bartholomew,et al.  The stoichiometry and poisoning by sulfur of hydrogen, oxygen and carbon monoxide chemisorption on unsupported nickel , 1977 .

[55]  46 Two dimensional model for the simulation of tubular reactors for thermal cracking , 1980 .

[56]  H. Ibach,et al.  Decomposition of hydrocarbons on flat and stepped Ni(111) surfaces , 1979 .

[57]  C. Adams,et al.  Adsorption of H2S on alumina at low coverages , 1962 .

[58]  H. Liander.  The utilisation of natural gases for the ammonia process , 1929 .

[59]  P. B. Tottrup,et al.  Kinetics of decomposition of carbon monoxide on a supported nickel catalyst. [Effects of temperature, water, and hydrogen; competition for methanation] , 1976 .

[60]  G. Ghiotti,et al.  The chemisorption of carbon monoxide on various transition aluminas , 1976 .

[61]  Jens R. Rostrup-Nielsen,et al.  Activity of nickel catalysts for steam reforming of hydrocarbons , 1973 .

[62]  M. Boudart,et al.  ETHANE HYDROGENATION-CRACKING ON IRON CATALYSTS WITH AND WITHOUT ALKALI , 1954 .

[63]  Gilbert F. Froment,et al.  FIXED BED CATALYTIC REACTORS—CURRENT DESIGN STATUS , 1967 .

[64]  H. Davy.  VIII. Some new experiments and observations on the combustion of gaseous mixtures, with an account of a method of preserving a continued light in mixtures of inflammable gases and air without flame , 1817, Philosophical Transactions of the Royal Society of London.

[65]  L. L. V. Reijen,et al.  Coprecipitated nickel–alumina catalysts for methanation at high temperature. Part 2.—Variation of total and metallic areas as a function of sample composition and method of pretreatment , 1981 .

[66]  J. Rostrup-Nielsen.  Coking on nickel catalysts for steam reforming of hydrocarbons , 1974 .

[67]  R. L. Gorring,et al.  Gas diffusion in porous catalysts. Diffusion-controlled elution of physically adsorbed hydrocarbons , 1964 .

[68]  Max Leva,et al.  Cooling of Gases through Packed Tubes , 1948 .

[69]  J. Ross,et al.  Mechanism of the steam reforming of methane over a coprecipitated nickel-alumina catalyst , 1973 .

[70]  R. J. Waite,et al.  Formation of filamentous carbon from iron, cobalt and chromium catalyzed decomposition of acetylene , 1973 .

[71]  C. H. Bartholomew.  Carbon Deposition in Steam Reforming and Methanation , 1982 .

[72]  J. J. Lander,et al.  Solubility and Diffusion Coefficient of Carbon in Nickel: Reaction Rates of Nickel‐Carbon Alloys with Barium Oxide , 1952 .

[73]  G. Ertl,et al.  The role of potassium in the catalytic synthesis of ammonia , 1979 .

[74]  J. Demuth,et al.  Crystallographic Dependence of Chemisorption Bonding for Sulfur on (001), (110), and (111) Nickel , 1974 .

[75]  J. Domínguez,et al.  The effect of shape and crystal structure of small particles on their catalytic activity , 1981 .

[76]  E. W. Plummer,et al.  Bonding of H to Ni, Pd, and Pt Surfaces , 1981 .

[77]  P. W. Selwood,et al.  THE CHEMISORPTION OF HYDROGEN SULFIDE, METHYL SULFIDE, AND CYCLOHEXENE ON SUPPORTED NICKEL CATALYSTS , 1962 .

[78]  L. Hofer,et al.  Structure of Carbon Deposited from Carbon Monoxide on Iron, Cobalt and Nickel , 1955 .

[79]  H. Wise,et al.  Thermodynamics of sulfur chemisorption on metals. III. Iron and cobalt , 1982 .

[80]  Eli Ruckenstein,et al.  Kinetics of crystallite sintering during heat treatment of supported metal catalysts , 1973 .

[81]  D. Trimm,et al.  Structural factors in the deposition of carbon on nickel , 1976 .

[82]  J. Sinfelt.  Catalytic Hydrogenolysis over Supported Metals , 1970 .

[83]  P. Walker,et al.  Growth of single-crystal graphite by pyrolysis of acetylene over metals , 1969 .

[84]  C. Mirodatos,et al.  The exchange of methane, ethane, and propane with deuterium on silica-supported nickel catalyst , 1980 .

[85]  B. Imelik,et al.  Metal-support and metal-additive effects in catalysis : proceedings of an international symposium , 1982 .

[86]  P. W. Selwood.  The chemisorptive bonding of hydrogen on nickel , 1976 .

[87]  O. Hougen,et al.  Kinetics of the reduction of nickel oxide by hydrogen , 1962 .

[88]  T. Massaro,et al.  Bulk Diffusion of Carbon‐14 through Polycrystalline Nickel Foil between 350 and 700°C , 1971 .

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

[90]  J. P. Hook.  Methane-steam reforming , 1980 .

[91]  D. Trimm,et al.  The kinetics of gasification of carbon deposited on nickel catalysts , 1979 .

[92]  D. Saraf,et al.  Simulation of Side Fired Steam-Hydrocarbon Reformers , 1979 .

[93]  J. Rostrup-Nielsen.  Some principles relating to the regeneration of sulfur-poisoned nickel catalyst , 1971 .

[94]  H. Wise,et al.  Thermodynamics of sulfur chemisorption on metals. I. Alumina‐supported nickel , 1980 .

[95]  J. Blakely,et al.  Carbon interaction with nickel surfaces: Monolayer formation and structural stability , 1979 .

[96]  Gerald G. Johnson,et al.  A COMPUTERIZED POWDER DIFFRACTION IDENTIFICATION SYSTEM , 1967 .

[97]  T. Baird,et al.  Carbon formation on iron and nickel foils by hydrocarbon pyrolysis—reactions at 700°C , 1974 .

[98]  M. Vannice.  Catalytic Activation of Carbon Monoxide on Metal Surfaces , 1982 .

[99]  C. H. Bartholomew.  Chemistry of nickel-alumina catalysts , 1976 .

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

[101]  Jens R. Rostrup-Nielsen,et al.  High temperature hydrogen sulfide chemisorption on nickel catalysts , 1981 .

[102]  W. Sachtler,et al.  The Nature of Weak Adsorption on Transition Metals , 1974 .

[103]  Charles N. Satterfield,et al.  Mass transfer in heterogeneous catalysis , 1969 .

[104]  J. Ross,et al.  Evidence for the participation of surface nickel aluminate sites in the steam reforming of methane over nickel/alumina catalysts , 1978 .

[105]  A. Holmen,et al.  Coke formation during cracking of hydrocarbons. I. The effect of pre-sulphiding on coke formation on a nickel-chromium-iron alloy under steam cracking conditions: Coke formation during cracking of hydrocarbons , 1981 .

[106]  F. Tompkins,et al.  Chemisorption of gases on nickel films. Part 2.—Equilibrium studies , 1957 .

[107]  J. Chipman,et al.  Thermodynamics of the Fcc Fe−Ni−C and Ni−C alloys , 1971 .

[108]  D. Grenoble.  The chemistry and catalysis of the water/toluene reaction: 1. The specific activities and selectivities of the Group VIII metals supported on Al2O3 , 1978 .

[109]  E. J. Gohr,et al.  Recent Progress in Hydrogenation of Petroleum , 1932 .

[110]  E. Nowak,et al.  Activation of supported nickel oxide by platinum and palladium , 1967 .

[111]  S. Engels,et al.  Feststoffreaktionen in Katalysatoren und Katalysatorkomponenten. I. Feststoffreaktionen in Katalysatoren zur autothermen Methankonvertierung , 1974 .

[112]  M. Vannice,et al.  Characterization of Ni/TiO2 catalysts by TEM, X-ray diffraction, and chemisorption techniques , 1981 .

[113]  J. Lapujoulade,et al.  Hydrogen adsorption on Ni (100) , 1973 .

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

[115]  Peter B. Tøttrup,et al.  Evaluation of intrinsic steam reforming kinetic parameters from rate measurements on full particle size , 1982 .

[116]  A. Ovenston,et al.  Internal carbon deposition resulting from a redistribution of gaseous species under combined diffusion and steam reforming reactions in a catalyst pellet , 1982 .

[117]  Calvin H. Bartholomew,et al.  Sulfur poisoning of nickel methanation catalysts: I. in situ deactivation by H2S of nickel and nickel bimetallics☆ , 1979 .

[118]  G. Somorjai,et al.  Potassium catalyzed methane production from graphite at low temperatures (473–673 K)☆ , 1981 .

[119]  R. J. Bratton,et al.  Kinetics of vapour phase hydration of magnesium oxide. Part 2.—Dependence on temperature and water vapour pressure , 1965 .

[120]  R. J. Waite,et al.  Nucleation and growth of carbon deposits from the nickel catalyzed decomposition of acetylene , 1972 .

[121]  R. Stephens,et al.  The poisoning of a steam hydrocarbon gasification catalyst , 1972 .

[122]  P. Schoubye.  Methanation of CO on some Ni catalysts , 1969 .

[123]  J. Figueiredo,et al.  Gasification of carbon deposits on nickel catalysts , 1975 .

[124]  Yoshihiro Yamazaki,et al.  Steam Reforming of Hydrocarbons on Noble Metal Catalysts (Part 1) , 1974 .

[125]  W. Hahn,et al.  Activity measurements in oxide solid solutions: The systems NiO-MgO and NiO-MnO in the temperature interval 1100–1300°C , 1961 .

[126]  E. Kikuchi,et al.  The reaction of n-heptane on rhodium catalysts in the presence of steam , 1977 .

[127]  J. Demuth,et al.  Chemisorption on (001), (110) and (111) Nickel Surfaces , 1974 .

[128]  O. Beeck.  Catalysis and the Adsorption of Hydrogen on Metal Catalysts , 1950 .

[129]  W. Erley,et al.  Absolute CO coverage: Direct comparison between the (111) and (110) faces of Ni, Pd, and Pt at 300 K , 1980 .

[130]  G. Dixon,et al.  Role of Urania and Alumina as Supports in the Steam Reforming of n-Butane at Pressure over Nickel-containing Catalysts , 1969 .

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

[132]  G. Martin,et al.  Adsorption of hydrocarbons and various gases on Ni-SiO2 catalysts studied by high field magnetic methods , 1974 .

[133]  Michel Boudart,et al.  Kinetics of Heterogeneous Catalytic Reactions , 1984 .

[134]  G. Martin,et al.  Mise en évidence de deux états de chimisorption de H2 sur certains catalyseurs de nickel supporté, par mesure d’aimantation à saturation , 1973 .

[135]  T. R. Phillips,et al.  The kinetics and mechanism of the reaction between steam and hydrocarbons over nickel catalysts in the temperature range 350–500 °C, part 1 , 1969 .

[136]  Anders Nielsen,et al.  Revamp of ammonia plants , 1982 .

[137]  G. Froment.  Thermal cracking for olefins production. Fundamentals and their application to industrial problems , 1981 .

[138]  Calvin H. Bartholomew,et al.  The stoichiometry of hydrogen and carbon monoxide chemisorption on alumina- and silica-supported nickel , 1980 .

[139]  K. M. Sundaram,et al.  Kinetics of coke deposition in the thermal cracking of propane , 1979 .

[140]  C. H. Bartholomew,et al.  Chemisorption of hydrogen sulfide on nickel and ruthenium catalysts: I. Desorption isotherms , 1978 .

[141]  M. W. Roberts,et al.  Surface and defect properties of solids , 1974 .

[142]  O. Gijzeman,et al.  Interaction of methane with Ni(111) and Ni(100); diffusion of carbon into nickel through the (100) surface; An aes-leed study , 1979 .

[143]  Y. Nishiyama,et al.  Carbon formation on copper-nickel alloys from benzene , 1974 .

[144]  S. D. Robertson.  Carbon formation from methane pyrolysis over some transition metal surfaces—I. Nature and properties of the carbons formed , 1970 .

[145]  G. Webb,et al.  Carbonaceous deposition associated with the catalytic steam-reforming of hydrocarbons over nickel alumina catalysts , 1981 .

[146]  R. Anderson,et al.  Hydrogenolysis of 2,2-dimethylbutane and n-hexane over supported ruthenium, nickel, cobalt, and iron , 1979 .

[147]  H. Grabke,et al.  Einfluß von Schwefel auf die Aufkohlung einer CrNiFe‐Legierung bei hohen Temperaturen , 1979 .

[148]  W. Pies,et al.  I. Barin, O. Knacke, O. Kubaschewski: Thermochemical Properties of Inorganic Substances — Supplement. Springer‐Verlag, Berlin‐Heidelberg‐New York; Verlag Stahleisen, Düsseldorf 1977. 861 Seiten, Preis: DM 170,– , 1978 .

[149]  D. Ollis,et al.  The chemistry and catalysis of the water gas shift reaction: 1. The kinetics over supported metal catalysts , 1981 .

[150]  G. Froment,et al.  Chemical Reactor Analysis and Design , 1979 .

[151]  Clarence Dayton Chang,et al.  Hydrocarbons from Methanol , 1983 .

[152]  H. C. Hottel,et al.  Radiant heat exchange in a gas-filled enclosure: Allowance for nonuniformity of gas temperature , 1958 .

[153]  O. Fraser.  Nickel as a Catalyst , 1937 .

[154]  W. G. McNaught,et al.  Some catalytic exchange reactions with deuterium oxide on evaporated metal films , 1974 .

[155]  J. Rostrup-Nielsen.  Mechanisms of carbon formation on nickel-containing catalysts , 1977 .

[156]  F. Pettit,et al.  Formation of NiAl2O4 by Solid State Reaction , 1966 .