Exxon Research and Engineering Company

Exxonmobil Research and Engineering Company

Exxonmobile Research and Engineering Company

Charles H Mauldin

William C Baird, Jr

William C Behrmann

Kym B Arcuri

Larry E Pedrick

Stephen M Davis

Paul E Eberly

Kenneth L Riley

Claude C Culross

Stanislaw Plecha

Louis F Burns

Virgil L Payne

William A Wachter

Hyung Suk Woo

Gregg Johnston Howsmon

Leroy Russell Clavenna

Dave H Shaw

Michel A Daage

Robert J Wittenbrink

Russell John Koveal

Geoffrey R Say

Christine Esther Kliewer

Janet Renee Clark

Jeffrey T Elks

Mordechay Herskowitz

The present invention provides a catalyst comprising a catalytic metal, preferably cobalt, rhenium or mixtures thereof. The catalytic metal is supported on a support comprising a major amount of titania and a minor amount of cobalt aluminate derived from anatase titania. The support also includes a minor amount of titania derived from a titanium chelate.

Cobalt catalyst with improved activity maintenance

A method is provided for recovering rhenium from a titania-supported, rhenium-containing catalyst by treating the catalyst in the reduced form with an acid in an amount and for a time sufficient to dissolve the rhenium without dissolving the support.

Metal recovery

Supports for Fischer-Tropsch catalysts are formed by forming a particulate material from titania, alumina and optionally silica. A cobalt compound is incorporated into the particulate material which then is calcined to convert at least part of the alumina to cobalt aluminate.

Preparation of titania and cobalt aluminate catalyst supports and their use in Fischer-Tropsch synthesis

A process for enhancing metal catalysts for carbon monoxide hydrogenation comprising reducing the catalyst so that at least a portion is in the metallic state, impregnating under a non-oxidative atmosphere with a solution of a salt of at least one metal, optionally in combination with at least one of an ammonium salt, an alkyl ammonium salt, a weak organic acid and ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, and reducing to form an active catalyst. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operations. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.

Catalyst enhancement

A hydrocarbon wax product from a HCS slurry comprising liquid synthesis product and catalyst particles is purified by circulating the slurry from a synthesis zone with a first temperature through a treatment zone with a second temperature in which a hydrogen-containing treatment gas contacts the slurry. The gas treatment removes impurities from the hydrocarbon wax product and also removes catalyst de-activating species which may be present in the slurry. Purified wax product is separated and removed from the treated slurry via wax withdrawal means. This avoids or minimizes the need for further treating the wax product. Remaining treated slurry may be returned to the synthesis zone.

Temperature controlled in situ wax purification

A process for increasing the hydrogenation activity, particularly the carbon monoxide hydrogenation activity, of a catalyst or catalyst precursor comprised of a particulate solids support component and a catalytic metal, or metals component, preferably cobalt; cobalt alone or cobalt and an additional metal, or metals added to promote or modify the reaction produced by the cobalt. Treatment of the catalyst, or catalyst precursor is conducted at low temperature ranging from ambient to about 275&deg; C. sufficient to form on the surface of a catalyst precursor, e.g., a cobalt catalyst precursor, a cobalt metal hydroxide, low valence cobalt metal oxide, or mixture of cobalt metal hydroxide and low valence cobalt metal oxide. Sometimes also metallic metal, e.g., cobalt, is also formed, and dispersed on the surface of the support. On reduction, as may be produced by contact and treatment of the catalyst or catalyst precursor with hydrogen, the oxidized metal, or metals component of the catalyst or catalyst precursor is reduced to elemental or metallic metal, and the activity of the catalyst thereby increased. A catalyst, activated or produced in this manner, is a useful composition of matter, the catalyst being particularly useful for efficiently conducting carbon monoxide hydrogenation reactions, especially F-T synthesis reactions, to provide a variety of useful products.

Process for increasing carbon monoxide hydrogenation activity of catalysts via low temperature oxidation with water, steam or mixture thereof

A catalyst precursor comprising a composite of a solids support, or powder component, and a compound or salt of a metal, or metals component, inclusive of cobalt, is upon reduction rendered catalytically active for conducting hydrogenation reactions, especially carbon monoxide hydrogenation reactions by contact at low temperature with liquid water, or steam, or a mixture of liquid water and steam, sufficient to oxidize and convert the metal, or metals component of the catalyst precursor to a metal hydroxide, low oxygen-containing metal oxide, or mixture of metal hydroxide and low oxygen-containing metal oxide. On reduction, as may be produced by contact and treatment of the oxidized catalyst precursor with hydrogen, the now well dispersed oxide or hydroxylated catalytic metal, or metals component of the catalyst, is reduced to metallic metal, e.g., Co, and the catalyst thereby activated.

Cobalt catalyst compositions useful for conducting carbon monoxide hydrogenation reactions

A process for the preparation of a catalyst useful for conducting carbon monoxide conversion reactions, especially a Fischer-Tropsch catalyst, use of the catalyst for conducting such reactions, especially Fischer-Tropsch reactions, and the composition produced by said process. In the preparation of the catalyst, a solution of a polyol is employed to impregnate and disperse a compound or salt of a catalytic metal, or metals, e.g., copper or an Iron Group metal such as iron, cobalt, or nickel, or in a preferred embodiment both a compound or salt of rhenium and a compound or salt of a catalytic metal, or metals, e.g., copper or an Iron Group metal such as iron, cobalt, or nickel onto a refractory inorganic oxide support, e.g., titania. The rhenium, when present only in small amount permits full and complete reduction of the catalytic metal, or metals, dispersed by the polyol. Higher catalyst activities with lower rhenium loadings are thus achieved than in previous preparations where higher concentrations of rhenium were required to both effectively disperse, and reduce the catalytic metal, or metals, during the preparation. Surprisingly, as little as about {fraction (1/10)} of the rhenium is required to accomplish the reduction promotion where the dispersion is effected with the polyol.

Preparation of high activity catalysts; the catalysts and their use

A method for hydrocarbon synthesis reactions from carbon monoxide and hydrogen using a catalyst pellet which includes a solid core and a coated layer of porous support impregnated with a catalyst which optimizes the CO conversion.

Method for hydrocarbon synthesis reactions

A supported particulate cobalt catalyst is formed by dispersing cobalt, alone or with a metal promoter, particularly rhenium, as a thin catalytically active film upon a particulate support, especially a silica or titania support. This catalyst can be used to convert an admixture of carbon monoxide and hydrogen to a distillate fuel constituted principally of an admixture of linear paraffins and olefins, particularly a C distillate, at high productivity, with low methane selectivity. A process is also disclosed for the preparation of these catalysts.

Surface supported cobalt catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas and process for the preparation of said catalysts

The operation of a hydrocarbon synthesis reactor and catalyst distributed in the reaction slurry therein are improved by the presence in said reactor of one or more vertical downcomers open at both ends with gas disengaging areas located at their top end. The downcomer which circulates catalyst from the top of the reaction slurry to the bottom of said slurry is fully immersed in the reaction slurry and preferably extends from just above the bottom of the reaction zone of the reaction vessel to just below the top surface of the reaction slurry. The bottom end of said downcomer is shielded from intrusion of rising synthesis gas by the placement of a baffle which blocks rising gas entry but facilitates the exit of catalyst and liquid from the bottom of said downcomer and distributes them radially throughout the adjacent reactor slurry.

Hydrocarbon synthesis reactor employing vertical downcomer with gas disengaging means

A process for the preparation of a catalyst useful for conducting carbon monoxide conversion reactions, especially a Fischer-Tropsch catalyst, use of the catalyst for conducting such reactions, especially Fischer-Tropsch reactions, and the composition produced by said process. In the preparation of the catalyst, a solution of a carbohydrate, or sugar, notably a monosaccharide or disaccharide, particularly sucrose, is employed to impregnate and disperse a compound or salt of a catalytic metal, or metals, e.g., copper or an Iron Group metal such as iron, cobalt, or nickel, or in a preferred embodiment both a compound or salt of rhenium and a compound or salt of a catalytic metal, or metals, e.g., copper or an Iron Group metal such as iron, cobalt, or nickel, onto a refractory inorganic oxide support, e.g., titania. The rhenium, when present only in small amount permits full and complete reduction of the catalytic metal, or metals, dispersed by the carbohydrate. Higher catalyst activities with lower rhenium loadings are thus achieved than in previous preparations where higher concentrations of rhenium were required to both effectively disperse, and reduce the catalytic metal, or metals, during the preparation. Surprisingly, as little as about 1/10 of the rhenium is required to accomplish the reduction promotion where the dispersion is effected with the carbohydrate.

Supports for Fischer-Tropsch catalysts with increased strength and attrition resistance are formed by incorporating both silica and alumina into a support comprised primarily of titania; whereupon Fischer-Tropsch active metals can be composited with the support; the catalysts being particularly useful in slurry reactions.

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Baton Rouge, LA, United States of America

Charles H Mauldin