Abstract: In an improved method for converting methane to at least one higher hydrocarbon product and coproduct water which comprises contacting a gas comprising methane and at least one added gaseous oxidant with nonacidic solid, the improvement comprising conducting at least a portion of said contacting in the presence of added water.

Abstract: Methane is converted to higher hydrocarbons by contact with a catalyst comprised of a reducible metal oxide which had previously been treated with a reducing agent such as hydrogen to improve characteristics of the catalyst.

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 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: 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: 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 process for making hydrocarbons of at least two carbon atoms from methane is disclosed. In this process methane and a source of oxygen are introduced into a molten salt, maintained at a temperature in the range of between about 660.degree. C. and about 800.degree. C., comprising at least one metal iodide, the metal of which is selected from the group consisting of alkali metals, alkaline earth metals and mixtures thereof and a catalyst comprising at least one metal selected from the group consisting of metals of Group IB and Group VIII of the Periodic Table of the Elements. The methane and oxygen source are introduced into the mixture such that they do not contact each other.

Abstract: A class of mixed oxide catalysts comprising at least one reducible metal oxide, which oxide produces higher hydrocarbons and water when contacted with a hydrocarbon at synthesizing conditions, at least one oxide of zirconium, and at least one oxide of yttrium. The compositions are useful for hydrocarbon conversion, methane conversion, and oxidative dehydrogenation processes characterized by the formation of coproduct water.

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 Ti, mixed oxides of Ti and Si, and mixed oxides of Ti and at least one alkaline earth metal. In the more preferred embodiments, the third component serves as a carrier for the Mn and alkali 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: 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: A method is disclosed in which a first gas is contacted with a solid at an elevated reaction temperature to produce a gaseous product, the solid being deactivated during said contact and further, being exothermically reactivated by a second gas, the improvement which comprises providing the solids in at least three reactor zones and sequantically operating each reactor according to the cycle: reaction/reactant preheat/solids reativation. Preferaly the reactors are operated concurrently such that, at any time, at least one reactor is producing product and at least one reactor is preheating reactant to reaction temperature.

Abstract: A method is disclosed in which a first gas is contacted with a solid at an elevated reaction temperature to produce a gaseous product, the solid being deactivated during said contact and exothermically reactivated by a second gas and again contacted with the first gas, the improvement includes the steps of:(a) providing a quantity of the solids in relatively equal amounts to at least these fixed bed reactors;(b) sequentially operating each fixed bed reactor according to the cycle comprising: (1) preheating introducing the first gas into a first end of the reactor and withdrawing gaseous product from a second end of the reactor; (2) preheating the first gas to reaction temperature by introducing the first gas into the fixed bed of solids at a plurality of points along the length of the reactor and withdrawing the preheated gas from the second end of the reactor; and (3) reactivating the deactivated solids by introducing the second gas into the fixed bed of solids at a plurality of points along the length of th

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 higher molecular weight hydrocarbons which are then oxidatively dehydrogenated to form unsaturated aliphatic hydrocarbons is disclosed.

Abstract: Saturated hydrocarbon is transformed catalytically into olefinic hydrocarbon of corresponding skeletal configuration by reacting the saturated hydrocarbon with a suitable alkene cyclopentadienyl or alkene arene transition metal molecular complex, such as bis(ethylene)pentamethylcyclopentadienyliridium, bis(ethylene)pentamethylcyclopentadienylrhodium and bis(ethylene)hexamethylbenzene osmium in the presence of free alkene as hydrogen acceptor. The reaction may be performed photochemically under irradiation with ultraviolet light or it may be performed thermolytically under application of heat. The catalyst may be charged to the reaction as a preformed alkene cyclopentadienyl or alkene arene transition metal molecular complex or the catalyst may be formed in situ in the reaction mixture via displacement of ligand from a suitable transition metal complex containing the displaceable ligand, such as dicarbonylpentamethylcyclopentadienyliridium or cyclooctadienepentamethylcyclopentadienyliridium.

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: 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: In a continuous catalytic process for the production of higher molecular weight hydrocarbons from lower molecular weight hydrocarbons in which a lower molecular weight hydrocarbon containing reaction gas is contacted in a reaction zone with a higher molecular weight hydrocarbon synthesis catalyst under C.sub.2 + hydrocarbon synthesis conditions, the improvement comprising increasing the production of higher molecular weight hydrocarbons by the addition of an effective amount of aluminum metal vapor to the reaction gas, said synthesis conditions including a temperature greater than 1000.degree. C. and a gas hourly space velocity of greater than 3200 hr.sup.-1.

Abstract: Isobutene is produced by contacting isobutane with a sulfided, type L zeolitic catalyst containing platinum, tin, barium, and an inorganic binder. The isobutane is contacted with the catalyst in the presence of a sulfur-containing gas at a temperature of from 850.degree. F. to 1250.degree. F., a pressure of less than 20 psig, a liquid hourly space velocity of below 40, and an H.sub.2 /HC of less than 10. Preferably, the catalyst comprises: (1) a sulfided, type L zeolite containing from 8% to 10% by weight barium, from 0.6% to 1.0% by weight platinum, and tin at an atom ratio with the platinum of about 1:1; and (2) an inorganic binder of either silica, alumina, or aluminosilicates.

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 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: The invention relates to a process for converting light hydrocarbon feedstocks such as methane, ethane and/or natural gas, to higher molecular weight hydrocarbon products that are more readily handleable and transportable. The process comprises heating a gaseous mixture comprising said light hydrocarbon feedstocks and at least one oxide initiator selected from the group consisting of nitrogen oxides, sulfur trioxide and mixtures thereof at a temperature of at least about 600.degree. C. for a period of time effective to provide said higher molecular weight hydrocarbon product. In one embodiment, the invention provides for a process for converting the feedstocks, to unsaturated compounds such as ethylene. The invention also relates to the higher molecular weight products obtained by the process of the invention.

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: A transhydrogenation process for the conversion of alkanes to alkenes with high yields and extended catalyst life between regenerations comprises the pssing of an alkane combined with a suitable hydrogen acceptor over a catalyst bed, subject to the conditions that(a) the pressure is from 0-4 atmospheres (gauge);(b) the hydrogen acceptor is present to the extent of from 5-30% by volume;(c) the temperature of the catalyst is from 400.degree.-600.degree. C.; and(d) the temperature of the catalyst is raised during the process at a rate of from 1-15 deg. C/hr.The catalyst is preferably a chromia on alumina type.

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 process using hydrogen dissolving metals, alloys and intermetallic compounds to drive otherwise thermodynamically unfavorable dehydrogenation reactions is disclosed. The process comprises the steps of selecting an organic reactant comprising carbon and hydrogen, and exposing the organic reactant to a material at a temperature and pressure sufficient to remove at least one hydrogen from one said organic reactant and to form a material hydride, the material being selected from the group of metals, alloys and intermetallic compounds having a negative standard free energy of formation for a hydrided product MH.sub.y, where M is the material, H is hydrogen and y is a non-zero number between 0 and about 4 and represents the total hydrogen to material atom ratio wherein the standard free energy change for the reaction of the organic rectant in the present of the material to remove at least one hydrogen atom therefrom and from the material hydride is negative.

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: Saturated hydrocarbon is transformed catalytically into olefinic hydrocarbon of corresponding skeletal configuration by reacting the saturated hydrocarbon with a suitable alkene cyclopentadienyl or alkene arene transition metal molecular complex, such as bis(ethylene)pentamethylcyclopentadienyliridium, in the presence of free alkene as hydrogen acceptor. The reaction may be performed photochemically under irradiation with ultraviolet light or it may be performed thermolytically under application of heat. The catalyst may be charged to the reaction as a preformed alkene cyclopentadienyl or alkene arene transition metal molecular complex or the catalyst may be formed in situ in the reaction mixture via displacement of ligand from a suitable transition metal complex containing the displaceable ligand, such as dicarbonylpentamethylcyclopentadienyliridium or cyclooctadienepentamethylcyclopentadienyliridium.

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 continuous method for synthesizing hydrocarbons from a methane source which comprises contacting methane with moving beds of particles comprising an oxidative synthesizing agent under synthesis conditions wherein particles recirculate between two physically separate zones: a methane contact zone and an oxygen contact zone.

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 dehydrogenating dehydrogenatable hydrocarbons is disclosed in which a heat providing stream is utilized to supply a portion of the endothermic heat requirement of the reaction zone feed thereby decreasing the temperature drop of the dehydrogenation zone material. As a result, the amount of deleterious side reactions such as thermal cracking is reduced, and an increase in conversion of the dehydrogenatable hydrocarbons is realized.

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: 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: 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: 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: 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: 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: 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 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: 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 continuous method for synthesizing hydrocarbons from a methane source which comprises contacting methane with particles comprising an oxidative synthesizing agent under synthesis conditions wherein particles recirculate between two physically separate zones: a methane contact zone and an oxygen contact zone. Preferably, particles are maintained in each of the two zones as fluidized beds of solids. 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: 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 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.

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: A method is disclosed for converting methane to higher hydrocarbon product by contacting methane with a solid which comprises a reducible metal oxide which when contacted with methane at a temperature within the range of about 500.degree. to 1000.degree. C. is reduced and produces higher hydrocarbon products and a promoting amount of at least one chalcogen component. The preferred chalcogen components are selected from a group consisting of sulfur, selenium, tellurium, and compounds thereof.

Abstract: A method of synthesizing hydrocarbons from a methane source which includes the steps of separating a mixture of lower alkanes to form a first fraction containing predominately methane and at least one second fraction containing predominately C.sub.2 + alkanes; dehydrogenating the second C.sub.2 + fraction to form an effluent comprising C.sub.2 + olefins; contacting the methane fraction with an oxide of a metal which oxide when contacted with methane at between about 500.degree. and 1000.degree. C. is reduced and produces higher hydrocarbon products and water; and oligomerizing the C.sub.2 + olefin fraction and the methane contacting effluent to produce higher hydrocarbon products.