Abstract: In a method for converting methane into higher hydrocarbon products and coproduct water which comprises contacting a gas comprising methane and a contact solid comprising at least one reducible metal oxide in the substantial absence of added gaseous oxidant, the improvement comprising conducting at least a portion of the contacting in the presence of added water.

Abstract: A novel process is disclosed for the steam dehydrogenation of dehydrogenatable hydrocarbons in the vapor phase in conjunction with oxidative reheating of the intermediate products. The process utilizes a single catalyst to perform both the selective oxidation and steam dehydrogenation functions. The particular catalyst employed comprises a Group VIII noble metal component, a Group IA and/or a Group IIA component and may contain among other modifiers a Group IIIA or IVA metal, and a halogen component. The catalytic components are supported on an inorganic substrate such as alumina.

Abstract: A process for the preparation of ethane and ethylene by oxidation of methane with oxygen at a temperature of 600.degree. to 900.degree. C., in which lead (II) oxide is used as catalyst (a) dispersed on a carrier of pumice, silicon carbide, zinc oxide, zirconium dioxide, and/or oxides of alkaline-earth elements, or (b) in a mixture with manganese (II) oxide dispersed on a carrier of pumice, silicon carbide, silicon dioxide, titanium dioxide, zirconium dioxide, zinc oxide, and/or oxides of alkaline-earth elements, or (c) without a carrier in a mixture with sodium silicate alone or in combination with silicon dioxide, titanium dioxide, zirconium dioxide, manganese (II) oxide, zinc oxide, and/or oxides of alkaline-earth elements. Ethane and ethylene are obtained with this process in high selectivities with good catalyst activities.

Abstract: More efficient mixing, more complete hydrogen consumption, and more thorough cooling of a dehydrogenation zone effluent is obtained by educting a portion of the dehydrogenation effluent from the reaction and externally cooling the withdrawn effluent in a heat exchanger and externally admixing the withdrawn effluent with an oxygen-containing stream. Eduction of the hydrogenation effluent by the oxygen-containing stream provides the necessary pressure drop for passing the dehydrogenation effluent through the heat exchanger and then admixing the effluent and oxygen-containing stream.

Abstract: Compositions comprising boron-promoted reducible metal oxides (especially reducible oxides of Mn) and optionally containing alkali and alkaline earth metal components are disclosed, as well as use thereof for hydrocarbon conversions characterized by formation of byproduct water. Particular processes comprise the conversion of methane to higher hydrocarbons and the dehydrogenation of dehydrogenatable hydrocarbons, e.g., dehydrogenation of C.sub.2 -C.sub.5 alkanes to form the corresponding olefins.

Abstract: Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

Abstract: Method and apparatus for partial oxidation of hydrocarbonaceous gases, wherein a hydrocarbonaceous gas is preheated, reacted with oxygen, and quenched by means of a rotating matrix comprising glassy ceramic fibers. Such a rotating matrix may be constructed and compartmented by a method and apparatus which utilizes the inherent tensile strength properties of the fibers to provide strength to the compartment walls. Such partial oxidation method and apparatus is especially useful in a direct, integrated process for the production of tert-butyl ethers, wherein the product of partially oxidizing methane and isobutane are caused to be methanol and isobutylene, which intermediates are directly recovered and combined to form methyl tert-butyl ether by method and apparatus of the invention. Furthermore, by-products of such partial oxidation may also be converted to useful tert-butyl ethers.

Abstract: The catalyzed oxidative coupling of a lower molecular weight alkane to higher molecular weight hydrocarbons which are then oligomerized to form aromatic hydrocarbons is disclosed.

Abstract: The catalyzed oxidative coupling of a lower molecular weight alkane to move valuable, higher molecular weight hydrocarbons is disclosed.

Abstract: In a process for dehydrogenating paraffins having from 2-12 carbon atoms per molecule (preferably propane and/or n-butane) to olefins, in the presence of free oxygen, steam and a catalyst comprising Ni, P, Sn, O and, optionally alkali metal, the improvement comprises having ammonia present at a NH.sub.3 :paraffin mole ratio of at least about 1:100.

Abstract: The catalyzed oxidative coupling of a lower molecular weight alkane to higher molecular weight hydrocarbons which are then oxidatively dehydrogenated to form unsaturated aliphatic hydrocarbons is disclosed.

Abstract: A method for dehydrogenating dehydrogenatable hydrocarbons which comprises contacting said hydrocarbons with an oxide of Pr having combined therewith an amount of alkali and/or alkaline earth metal which is sufficient to improve the selectivity to dehydrogenated hydrocarbon products. The oxide is reduced by the contact which is carried at about 500.degree. to 1000.degree. C. Reducible oxides of Pr are regenerated by oxidizing the reduced composition with oxygen. Solids prepared from the oxide Pr.sub.6 O.sub.11 are particularly effective in the process.

Abstract: Ethane is catalytically dehydrogenated in a reaction zone comprising at least two separate beds of dehydrogenation catalyst. The reactants are reheated and hydrogen is consumed through use of an intermediate bed of hydrogen selective oxidation catalyst. The amount of hydrogen consumed in the combustion step is increased by cooling the effluent of the first dehydrogenation catalyst bed by direct or indirect heat exchange.

Abstract: A method for dehydrogenating dehydrogenatable hydrocarbons which comprises contacting said hydrocarbons with a solid comprising at least one reducible oxide of at least one metal which oxides when contacted with hydrocarbons at the temperature are reduced and produce dehydrogenated hydrocarbon products and water, the solid being associated with a silica support. The oxide is reduced by the contact which is carried at about 500.degree. to 100.degree. C. The reducible metal oxides are regenerated by oxidizing the reduced composition with oxygen.

Abstract: A method for synthesizing hydrocarbons from a methane source which comprises contacting methane with a reducible oxide of Tb. The Tb oxide is preferably combined with an amount of alkali and/or alkaline earth metal which is sufficient to improve the selectivity to higher hydrocarbon products. The oxide is reduced by the contact which is carried at about 500.degree. to 1000.degree. C. Reducible oxides of Tb are regenerated by oxidizing the reduced composition with molecular oxygen. The oxide Tb.sub.4 O.sub.7 is particularly effective in the process.

Abstract: A method for synthesizing hydrocarbons from a methane source which comprises contacting methane with an oxide of Pr. The oxide is reduced by the contact which is carried at about 500.degree. to 1000.degree. C. Reducible oxides of Pr are regenerated by oxidizing the reduced composition with oxygen. The oxide Pr.sub.6 O.sub.11 is particularly effective in the process.

Abstract: A method for synthesizing hydrocarbons from a methane source which comprises contacting methane with a reducible oxide of Fe. The iron oxide is preferably combined with an amount of alkali and/or alkaline earth metal which is sufficient to improve the selectively to higher hydrocarbon products. The oxide is reduced by the contact which is carried at about 500.degree. to 1000.degree. C. Reducible oxides of Fe are regenerated by oxidizing the reduced composition with oxygen. The oxide Fe.sub.3 O.sub.4 is particularly effective in the process. Bulk iron oxides promoted by sodium and/or compounds thereof are particularly preferred contact solids.

Abstract: Dehydrogenatable hydrocarbons may be subjected to a dehydrogenation reaction in which the hydrocarbons are treated with a dehydrogenation catalyst comprising a modified iron catalyst in the presence of steam in a multicatalyst bed system. The reaction mixture containing unconverted hydrocarbons, dehydrogenated hydrocarbons, hydrogen and steam is then contacted with an oxidation catalyst whereby hydrogen is selectively oxidized. The selective oxidation catalyst which is used will comprise a noble metal of Group VIII of the Periodic Table, a metal of Group IVA and, if so desired, a metal of Group IA or IIA composited on a porous inorganic support. The inorganic support will comprise an alumina precursor which possesses and ABD less than about 0.6 g/cc, a pore volume greater than about 0.5 cc/g, and a pore distribution such that between 10% and 70% of the pore volume is present as pores whose diameters are greater than about 300 Angstroms. After peptizing and calcination at a temperature of about 900.degree.

Abstract: A catalyst is disclosed which comprises a molybdenum-tungsten-containing complex represented by the formulaMo.sub.a W.sub.b M.sub.c A.sub.d O.sub.

Abstract: Methane is converted into higher hydrocarbons by a process wherein a gas comprising methane and molecular oxygen is contacted at elevated temperatures with a molten salt mixture containing at least one reducible metal oxide.

Abstract: A solid composition of matter consisting essentially of:(a) a component comprising: (1) at least one metal selected from the group consisting of Group IA metals and compounds containing said metals and (2), optionally, at least one material selected from the group consisting of tin, compounds containing tin, chloride ions and compounds containing said chloride ions and(b) a component comprising at least one metal selected from the group consisting of Group IIA metals and compounds containing said metals.The composition is particularly useful as a contact material for the oxidative conversion of less valuable organic compounds to more valuable organic compounds, particularly in the presence of a free oxygen containing gas.

Abstract: An improved method for converting methane to higher hydrocarbon products by contacting a hydrocarbon gas comprising methane, an oxygen-containing gas and a reducible metal oxide under conditions effective to produce higher hydrocarbon products and water, the improvement which comprises conducting the contacting in the presence of at least one stabilizer selected from the group consisting of chalcogens and compounds thereof.

Abstract: A process is disclosed for converting methane to a higher order hydrocarbon comprising contacting a gaseous reactant comprising methane with a phosphate-containing catalyst for a sufficient period of time and at an effective temperature to provide said higher order hydrocarbon, said catalyst being represented by the formulaM.sub.x PO.sub.ywhereinM is selected from the group consisting of Pb, Bi, Sb, Sn, Tl, In, Mn, Cd, Ge or a mixture of two or more thereof,x is from about 0.1 to about 10, andy is the number of oxygens needed to fulfill the valence requirements of the other elements.

Abstract: A process for converting low molecular weight gases such as methane and natural gas to higher hydrocarbons by means of a molten salt containing a synthesizing contact agent. The gas is contacted with a molten salt containing a metal, the oxide of which is reduced when contacted with methane at a temperature in the range of 500.degree. to 1000.degree. C. to produce higher hydrocarbons and water. The reduced metal oxide/salt mixture may be regenerated to the active state by contacting the molten salt mixture with an oxygen-containing gas.

Abstract: A catalyst for removing acetylenic impurities from gaseous organic product streams, comprising at least Fe and Ni, other elements from Groups 8, 1b, 2b, 4b, 6b and 7b of the Periodic Table, an alkaline earth metal and an alkali metal.

Abstract: A solid composition of matter is disclosed consisting essentially of sodium, potassium, a Group IA metal or a Group IA metal and a Group IIA metal, titanium, oxygen and, optionally, at least one of a halogen and tin, in which at least one of the sodium, the potassium, the Group IA metal or the Group IIA metal is present in an amount in excess of any amount present in electrically neutral compounds of the metal, the titanium and oxygen.The above compositions are particularly useful as solid contact materials for the oxidative conversion of feed organic compounds to product organic compounds, particularly in the presence of a free oxygen containing gas. A method for such conversion is also disclosed.

Abstract: A solid composition of matter selected from the group consisting of:(a) a component comprising: (1) at least one material selected from the group consisting of Group IA metals and compounds containing said metals, a component comprising: (2) at least one material selected from the group consisting of zinc and compounds containing zinc, and a component comprising: (3) at least one material selected from the group consisting of chloride ions, compounds containing chloride ions; tin and compounds containing tin; and(b) a component comprising: (1) at least one material selected from the group consisting of Group IA metals and compounds containing said metals, a component comprising: (2) zinc oxide, and, optionally, a component comprising: (3) at least one material selected from the group consisting of chloride ions, compounds containing chloride ions tin and compounds containing tin.

Abstract: Oxidative dehydrogenation of organic compounds in vapor phase with catalysts comprising crystalline compositions of iron, oxygen and at least one other metallic element. Preferred catalysts are ferrites.

Abstract: Compositions comprising Mn-containing oxides, alkali metals or compounds thereof and barium carbonate. The composition preferably comprises a major amount of the barium carbonate and minor amounts of the other components. The compositions are useful for hydrocarbon conversion, methane conversion, and oxidative dehydrogenation processes characterized by formation of coproduct water.

Abstract: Methane is converted to higher hydrocarbons, paticularly ethylene and ethane, and most desirably ethylene, by:contacting a feed comprising methane, such as natural gas, and a free oxygen containing gas, such as oxygen or air, with a solid contact material, comprising:(a) a component comprising: at least one metal selected from the group consisting of Group IA and Group IIA metals;(b) a component comprising: at least one material selected from the group consisting of phosphate radicals and compounds containing phosphate radicals; and(c), optionally, at least one material selected from the group consisting of halogen ions and compounds containing halogen ions,under oxidative conversion conditions sufficient to convert the methane to the higher hydrocarbons.

Abstract: Unsaturated hydrocarbons may be prepared by subjecting dehydrogenatable hydrocarbon to dehydrogenation in the presence of a dehydrogenation catalyst. The effluent stream from this step, comprising unconverted hydrocarbons, dehydrogenated hydrocarbons, hydrogen and steam, may then be passed to a selective oxidation step in which the hydrogen is selectively oxidized in the presence of an oxygen-containing gas to the substantial exclusion of the oxidation of the hydrocarbons. The oxidation catalyst which is employed will comprise a Group VIII noble metal, a Group IVA metal and a Group IA or IIA metal composited on a metal oxide support. The metal oxide support such as alumina will possess a particular configuration such as a polylobular particle containing from 3 to about 8 lobes and having a ratio of exterior surface to catalyst volume greater than [4D+2L] in which D is the largest representative diameter and L is the length of the particle.

Abstract: A class of mixed oxide catalysts comprising Mn-containing oxides, alkali metals or compounds thereof, and at least one member of the group consisting of oxides of Zr, mixed oxides of Zr and Si, and mixed oxides of Zr and at least one alkaline earth metal. In the more preferred embodiments, the third component serves as a carrier for the Mn and alkaline metal components. The composition preferably comprises a major amount of the carrier material and minor amounts of the other components. The compositions are useful for hydrocarbon conversion, methane conversion, and oxidative dehydrogenation processes characterized by formation of coproduct water.

Abstract: A catalyst for removing acetylenic impurities from gaseous organic product streams, comprising at least Fe and Ni, other elements from Groups 8, 1b, 2b, 4b, 6b and 7b of the Periodic Table, an alkaline earth metal and an alkali metal.

Abstract: An improved method for dehydrogenating dehydrogenatable hydrocarbons by contacting a gas comprising said hydrocarbons and an oxidative dehydrogenation agent at dehydrogenation conditions, the improvement which comprises contacting the hydrocarbon with an oxidative dehydrogenation agent containing a promoting amount of alkali metal and/or compounds thereof and associated with a support selected from the group consisting of alkaline earth metals and compounds thereof.

Abstract: An improved method for converting methane to higher hydrocarbon products by contacting a hydrocarbon gas comprising methane, an oxygen-containing gas and a reducible metal oxide under conditions effective to produce higher hydrocarbon products and water, the improvement which comprises conducting the contacting in the presence of at least one promoter selected from the group consisting of halogens and compounds thereof.

Abstract: A method for the oxidative conversion of a feed material comprising methane, such as natural gas, to higher hydrocarbons, particularly ethylene and ethane and desirably ethylene, in which feed is contacted with a solid contact material comprising cobalt; at least one metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth, preferably, zirconium; phosphorous; at least one Group IA metal; and oxygen under oxidative conversion conditions sufficient to convert the methane to the higher hydrocarbons. Substantial improvement in the conversion of methane and selectivity to ethylene and ethane is obtained by adding chlorine to the contact material. The further addition of sulfur to the contact material also improves the conversion and selectivity and permits the method to be carried out in an essentially continuous manner in the presence of a free oxygen containing gas.

Abstract: An improved method for converting methane to higher hydrocarbon products by contacting at a selected temperature at least one reducible oxide of at least one metal, associated with a hydroxylated magnesia support (that is, magnesia derived from magnesium hydroxide or a magnesium-containing component contacted with hydroxyl-containing material).

Abstract: Process and device for the production of ethane and/or ethylene by heterogeneous catalytic reaction of methane and oxygen using a catalyst suitable for the formation of C.sub.2 hydrocarbons at increased temperatures, whereby in continuous operation a mixture of methane and oxygen is reacted at temperatures between 500.degree. and 900.degree. C. and at an oxygen partial pressure of less than 0.5 bar at the reactor entrance, while the ratio of the methane partial pressure to the oxygen partial pressure is greater than 1.The conversion reaction takes place with or without gas recycling in a reactor containing a bed of solid catalyst or by the use of a fluidized bed of fluidized catalyst particles, or in a cross-flow reactor with distributed input of oxygen.

Abstract: Hydrocarbons are catalytically dehydrogenated in a reaction zone comprising at least two separate beds of dehydrogenation catalyst. The reactants are reheated and hydrogen is consumed through use of an intermediate bed of hydrogen selective oxidation catalyst. The amount of hydrogen consumed in the combustion step is increased by cooling the effluent of the first dehydrogenation catalyst bed by direct or indirect heat exchange.

Abstract: A process for low temperature oxydehydrogenation of ethane to ethylene uses an improved supported catalyst produced by impregnating the support with the soluble portion of a precursor catalyst solution and then activating the impregnated support. The activated impregnated support provides good selectivity to ethylene and avoids the problems which can arise from impregnation of the support with the soluble and insoluble portions of a precursor catalyst solution.

Abstract: A method for synthesizing hydrocarbons from a methane source which comprises contacting methane with an oxide of Ru. The oxide is reduced by the contact which is carried at about 500.degree. to 1000.degree. C. Reducible oxides of Ru are regenerated by oxidizing the reduced composition with oxygen.

Abstract: A method for reheating of a catalytic reactor by successive oxidations and reductions of a multiple oxidation state catalyst.Heat is added to the catalyst bed by a series of successive oxidation and reduction reactions occurring on the catalyst. Both catalyst oxidation and catalyst reduction are exothermic reactions, and both reactions generate heat to increase the temperature of the catalyst bed.

Abstract: An improved support for a contact agent, useful for converting methane to higher hydrocarbon products by contacting a gas comprising methane with a contact agent at a selected temperature, is formed by sintering the surface of the support.

Abstract: A process for the low temperature oxydehydrogenation of ethane to ethylene uses a calcined oxide catalyst containing Mo, V, Nb, and Sb.

Abstract: A method for dehydrogenating dehydrogenatable hydrocarbons which comprises contacting said hydrocarbon with an oxide of Ru having combined therewith an amount of alkali and/or alkaline earth metal which is sufficient to improve the selectivity to dehydrogenated hydrocarbon products. The oxide is reduced by the contact which is preferably carried at about 500.degree. to 1000.degree. C. Reducible oxides of Ru are regenerated by oxidizing the reduced composition wth oxygen. Bulk ruthenium oxides promoted by sodium and/or compounds thereof are particularly preferred contact solids.

Abstract: A method for dehydrogenating dehydrogenatable hydrocarbons which comprises contacting said hydrocarbon with an oxide of Ce having combined therewith an amount of alkali and/or alkaline earth metal which is sufficient to improve the selectivity to dehydrogenated hydrocarbon products. The oxide is reduced by the contact which is carried at about 500.degree. to 1000.degree. C. Reducible oxides of Ce are regenerated by oxidizing the reduced composition with molecular oxygen. The oxide CeO.sub.2 is particularly effective in the process.

Abstract: A method for synthesizing hydrocarbons from a methane source which comprises contacting methane with an oxidative synthesizing agent under elevated pressures, preferably at pressures within the range of about 5 to 30 atmospheres. Particularly effective oxidative synthesizing agents are reducible oxides of metals selected from the group consisting of Mn,Sn,In,Ge,Pb,Sb, and Bi.

Abstract: An improved method for converting methane to higher hydrocarbon products by contacting a gas comprising methane with a contact agent at a selected temperature, the agent comprising a reducible metal oxide, a support of at least two oxides, and an alkali metal.

Abstract: An improved method for converting methane to higher hydrocarbon products by contacting a gas comprising methane and a reducible metal oxide under synthesis conditions, the improvement which comprises performing the contacting in the presence of oxides of nitrogen. Nitrous oxide is a preferred nitrogen oxide.

Abstract: An improved method for converting methane to higher hydrocarbon products by contacting a gas comprising methane and an oxidative synthesizing agent at synthesizing conditions, the improvement which comprises contacting methane with a solid comprising a promoting amount of alkali metal and/or compounds thereof, said solid being associated with a support selected from the group consisting of alkaline earth metals and compounds thereof. Magnesia is a particularly preferred support.