Exxon Research and Engineering Company

LeRoy R Clavenna

Stephen M Davis

Geoffrey R Say

Rocco A Fiato

John M Longo

James H Taylor, Jr

James M Eakman

Frank Hershkowitz

Harry William Deckman

Roby Bearden, Jr

Martin Leo Gorbaty

Nicholas Charles Nahas

Leo D Brown

Michael C Kerby

Robert P Reynolds

Leonard Schoenman

Harold S Horowitz

Constantine P Gonatas

Charles A Euker, Jr

Jack I Ito

John W Fulton

Mark Leland Tiller

Brent England Beasley

David W Sharp

Nikos J Maris

Gerald A Wilcox

Robert H Shabaker

Joe M Tsou

A novel injector/reactor apparatus and an efficient process for the partial oxidation of light hydrocarbon gases, such as methane, to convert such gases to useful synthesis gas for recovery and/or subsequent hydrocarbon synthesis. Sources of a light hydrocarbon gas, such as methane, and oxygen or an oxygen-containing gas are preheated and pressurized and injected through an injector means at high velocity into admixture with each other in the desired proportions, at a plurality of mixing nozzles which are open to the catalytic partial oxidation reaction zone of a reactor and are uniformly-spaced over the face of the injector, to form a reactant gaseous premix having a pressure drop through the injector. The gaseous premix is injected in a time period which is less than 5 milliseconds, at a velocity between about 25 to 1000 feet/second, into a reaction zone comprising a catalytic partial oxidation zone so that the gaseous premix reacts in the presence of the fixed catalyst arrangement to reduce the amounts of CO.sub.2, H.sub.2 O and heat produced by the partial oxidation reaction and form, cool and recover a useful syngas.

Rapid injection catalytic partial oxidation process and apparatus for

The present invention relates to an integrated fluid coking/hydrogen production process. The fluid coking unit is comprised of a fluid coker reactor, a heater, and a gasifier. Solids from the fluidized beds are recycled between the coking zone and the heater and between the heater and the gasifier. A separate stream of hot solids from the gasifier is passed to the scrubbing zone of the reactor. Methane and steam are introduced into the stream of hot solids passing from the gasifier to the scrubbing zone. The hot particles act to catalyze the conversion of methane to carbon monoxide and hydrogen in the presence of steam.

Production of hydrogen from a fluid coking process using steam reforming

High surface purity heat transfer solids are formed, suitably by washing and treating particulate refractory inorganic solids, notably alumina, which contains as impurities up to about 0.5 wt. % silicon and/or up to about 500 wppm boron, with an acid, or dilute acid solution sufficient to reduce the concentration of silicon and boron in the outer peripheral surface layer of the particles, e.g., as measured inwardly toward the center of a particle to a depth of about 50 .ANG. using X-ray photoelectron spectroscopy, to no greater than about 5 atom percent silicon and boron, preferably about 2 atom percent silicon and boron, based on the total number of cations within said outer peripheral surface layer, thereby reducing the tendency of said particles to sinter and agglomerate in the conversion of said hydrocarbon to hydrogen and carbon monoxide in a fluidized bed synthesis gas operation vis-a-vis particles otherwise similar except that the particles are not treated with the acid. The tendency of the particles to sinter and agglomerate is further reduced by the additional removal of sodium, iron, calcium, and titanium impurities from the outer peripheral surface layer of the particles. Preferably the latter named impurities, or impurities other than silicon and boron, are reduced to a concentration below about 20 atom %, more preferably to a concentration below about 15 atom %, in the outer surface layer of the particles.

High surface purity heat transfer solids for high temperature fluidized

A particulate, precalcined low silica content zirconia, especially one stabilizer with yttria, is useful as a catalyst support or as a heat transfer solids component for conducting chemical reactions at high temperature, in oxidizing, reducing or hydrothermal conditions, especially in syn gas operations. An admixture of precalcined particulate low silica content zirconia, particularly a low silica content yttria-stabilized zirconia, is employed in a preferred embodiment as a heat transfer solid, in concentrations ranging generally from about 10 wt. % to about 99.9 wt. % with a particulate catalyst notably a nickel-on-alumina catalyst, in concentration ranging generally from about 0. 1 wt. % to about 90 wt. %. Such an admixture provides a particularly useful catalytic contact mass in high temperature oxidizing, reducing and hydrothermal environments, notably in conducting synthesis gas generation operations. This type of bed promotes continuous, highly efficient heat and mass transfer within the reacting gas phase. The presence of the heat transfer solid as a bed component maintains excellent bed fluidization characteristics, suppressing the normal tendency of the catalyst to sinter or agglomerate; tendencies which promote defluidization of the bed. Moreover, the heat transfer particles of the bed are highly attrition resistant, and are chemically compatible with the catalyst particles of the admixture.

Particulate solids for catalyst supports and heat transfer materials

A process for the in situ attrition and break up of an agglomerating, or agglomerated catalyst to maintain and control the fluidization characteristics of a bed wherein low molecular weight hydrocarbons, oxygen and steam are contacted with the bed to produce hydrogen and carbon monoxide via both partial oxidation and steam reforming reactions. The feeds are injected into the reaction zone with mechanical energy input sufficient to balance the intrinsic rate of agglomeration by fracturing and breaking apart in situ the agglomerated catalyst to maintain the fluidization characteristics of the bed throughout the cycle of operation.

High energy level in situ attrition and break up of catalyst to maintain

A process for the production of syn gas (hydrogen and carbon monoxide) by reaction at high temperature between low molecular weight hydrocarbons, steam and oxygen in an impurities-containing refractory lined reaction zone. The lined reaction zone is pretreated with steam, or with steam and a reducing gas, e.g. a mixture of steam and hydrogen to leach out, react with, and transport the impurities, i.e., the reaction products of silica, or silica plus phosphorus or sulfur, or silica plus phosphorus and sulfur, from the reaction zone. Steam alone may be used to leach out, convert the silica to gaseous silicic acid, and remove same from the reaction zone; and then the hydrocarbons, steam and oxygen feeds are introduced into the reaction zone to produce syn gas.

Process for the elimination of silica and other impurities in fluidized

A particulate, precalcined low silica content zirconia, especially one stabilized with yttria, is useful as a catalyst support or as a heat transfer solids component for conducting chemical reactions at high temperature, in oxidizing, reducing or hydrothermal conditions, especially in syn gas operations. An admixture of precalcined particulate low silica content zirconia, particularly a low silica content yttria-stabilized zirconia, is employed in a preferred embodiment as a heat transfer solid, in concentrations ranging generally from about 10 wt. % to about 99.9 wt. %, with a particulate catalyst, notably a nickel-on-alumina catalyst, in concentration ranging generally from about 0.1 wt. % to about 90 wt. %. Such an admixture provides a particularly useful catalytic contact mass in high temperature oxidizing, reducing and hydrothermal environments, notably in conducting synthesis gas generation operations. This type of bed promotes continuous, highly efficient heat and mass transfer within the reacting gas phase. The presence of the heat transfer solid as a bed component maintains excellent bed fluidization characteristics, suppressing the normal tendency of the catalyst to sinter or agglomerate; tendencies which promote defluidization of the bed. Moreover, the heat transfer particles of the bed are highly attrition resistant, and are chemically compatible with the catalyst particles of the admixture.

A structurally modified alumina useful as a catalyst support, or heat transfer solid for fluidized bed synthesis gas processing. A Group IIA metal, or metals, particularly magnesium and barium, is composited with a particulate alumina to provide a catalyst support, or alumina heat transfer solid, having increased resistance to sintering and agglomeration; properties which promote defluidization of the bed in conducting fluidized bed reactions at high temperatures. The particles of preference are represented by formulas (1) and (2), a composite particle being represented by formula (1), as follows:

Structurally modified alumina supports, and heat transfer solids for

Alumina heat transfer solids are admixed with a catalyst, or catalysts, and used in conducting high temperature fluidized bed reactions, particularly in a process for the production of hydrogen and carbon monoxide from a low molecular weight hydrocarbon by contact with a fluidized bed of catalyst and said heat transfer solids at high temperature in the presence of oxygen, or steam, or both oxygen and steam. The particulate heat transfer solids are characterized as having a performance index, PI, greater than 20, preferably greater than 40, as characterized by the formula PI=[(i).times.(ii).times.(iii).times.(iv)].sup.-1 where (i) the peripheral outer surface of the particle contains &lt;5 atom % (Si+B) as impurities, and (ii) &lt;20 atom % Na, Fe, Ca and Ti as impurities, where the bulk concentrations of the (Si+B) is sufficient to migrate into and contaminate the outer surface layer of the particles at process conditions. Moreover the (iii) tapped bulk density of the particles range from about 1.2 g/cc to about 2.5 g/cc, and (iv) the Davison Attrition Index of the particles is no greater than about 12.

High performance alumina heat transfer solids for high temperature

A process for the reactivation, or rejuvenation of a nickel-alumina catalyst employed in the production of a gas comprised of an admixture of hydrogen and carbon monoxide, or synthesis gas, by the conversion, in a reactor, or reaction zone, of light hydrocarbons in a fluidized bed of the catalyst at elevated temperature, in the presence of steam and oxygen. Catalyst reactivation is accomplished by withdrawing a portion of the catalyst from the fluidized bed of the reactor and treating the catalyst in an oxidation zone at temperature sufficient to oxidize and convert the nickel component of the catalyst to nickel aluminate and disperse said nickel aluminate within the alumina support, and then recycling the treated catalyst to the reactor, or reaction zone, to reactivate and increase the activity of the catalyst. The catalyst, on reduction in the reactor, or reaction zone, is provided an additional boost in activity by washing, treating or contacting the catalyst from the elevated temperature oxidation zone with an acid sufficient to remove trace impurities without removing any substantial amount of the nickel aluminate, and without forming a residue on the catalyst surface. The normal tendency of the catalyst to agglomerate at reaction conditions is also reduced by the acid treatment.

Process for the reactivation of nickel-alumina catalysts

A process utilizing a particulate catalyst, or particulate catalyst admixed with particulate heat transfer solids for conducting high temperature fluidized bed syn gas operations. Hydrogen and carbon monoxide are produced from a low molecular weight hydrocarbon by contact thereof, at high temperature in the presence of oxygen, or steam and oxygen, with a fluidized bed comprising said particulate solids. In one of its forms, barium hexaluminate is employed as a heat transfer solid, in concentrations ranging generally from about 10 wt. % to about 99.9 wt. %, in admixture with a particulate catalyst containing a metal, or metals, component catalytic for the production of hydrogen and carbon monoxide from low molecular weight hydrocarbons contacted with a fluidized bed of the catalyst at high temperature hydrothermal conditions. The catalyst, suitably one having a barium hexaluminate carrier component, is employed in concentration ranging generally from about 0.1 wt. % to about 90 wt. %. Such an admixture provides a particularly useful catalytic contact mass for conducting fluidized bed synthesis gas generation operations. This type of bed promotes continuous, highly efficient heat and mass transfer within the reacting gas phase. The presence of the catalyst having a barium hexaluminate carrier component, or barium hexaluminate heat transfer solid as a bed component maintains excellent bed fluidization characteristics, suppressing the normal tendency of the catalyst to sinter or agglomerate; tendencies which promote defluidization of the bed. Moreover, the heat transfer particles of the bed are highly attrition resistant, and are chemically compatible with the catalyst particles of the admixture.

Synthesis gas from particulate catalysts, and admixtures of particulate

Cement is produced by feeding residue solids containing carbonaceous material and ash constituents obtained from converting a carbonaceous feed material into liquids and/or gases into a cement-making zone and burning the carbon in the residue solids to supply at least a portion of the energy required to convert the solids into cement.

Cement production from coal conversion residues

In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

Alkali metal recovery from carbonaceous material conversion process

In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by treating them with a calcium or magnesium-containing compound in the presence of water. The treating process is carried out under conditions such that the calcium or magnesium-containing compound reacts with water insoluble constituents of the alkali metal residues such as alkali metal aluminosilicates to produce an aqueous solution containing water soluble alkali metal constituents. The aqueous solution is recycled to the gasification process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. The process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

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Baton Rouge, LA, United States of America

LeRoy R Clavenna