Exxon Research and Engineering Company

Exxonmobil Research and Engineering Company

Claude C Culross

William E Winter, Jr

Steve D Reynolds

Charles H Mauldin

Gordon Frederick Stuntz

Gregg Johnston Howsmon

Stephen Neil Vaughn

Robert J Wittenbrink

Leroy Russell Clavenna

Stephen D Reynolds

Louis F Burns

Michael Siskin

Michel A Daage

Glen Barry Brons

Stephen M Davis

Alan Roy Katritzky

Russell John Koveal

William A Wachter

Gopal H Singhal

Peter S Maa

Christine Esther Kliewer

Lonnie W Vernon

Robert J Lang

Jeffrey T Elks

David C Long

Hyung Suk Woo

Joanne K Pabst

James Dirickson Mumford

Michael Y Wen

John W Larsen

Dan R Neskora

Steve J Hsia

Stephen D LeViness

Trikur Anantharaman Ramanarayaman

Steve N Reynolds

Steve C LeViness

A process for rejuvenating reversibly deactivated catalyst particles in a three-phase slurry body of gas bubbles and catalyst particles in a slurry liquid, includes passing slurry from the top down to the bottom of the body through a slurry catalyst rejuvenating means. The slurry is sequentially passed through a first gas bubble reducing zone, a catalyst rejuvenating gas contacting zone, a second gas bubble reducing zone and then a downcomer transfer zone. The gas bubble reducing, contacting and at least a portion of transfer occur in slurry body. At least part of the means is in the slurry body.

Slurry catalyst rejuvenation in-situ in slurry reactor

A method is disclosed for renewing the activity of a Dispersed Active Metal (DAM) catalyst during operation of a reactor wherein the hydrogenation of carbon monoxide to produce a mixture of hydrocarbons is being carried out comprising withdrawing a mixture of hydrocarbons and a portion of the DAM catalyst, reducing the hydrocarbon content thereof, heating the mixture above the melting temperature of at least one of the metals of the DAM to form a melt, removing any slag that forms on the melt, cooling the melt to form a solid, reducing the particle size thereof to form a renewed particulate DAM catalyst, which is then returned to the reactor. Wherein the DAM catalyst is a Raney catalyst, a leachable metal is added to the reduced hydrocarbon mixture or the melt under non-oxidizing conditions and, after the solid is reduced to a fine particle size, extracting the leachable metal with caustic. The activity of the DAM may be modified or enhanced during the process by the addition of promoter metals, or prior to being returned to the reactor, by slurry low temperature oxidation followed by reduction at elevated temperature, and may further be enhanced by being passivated prior to being returned to the reactor. The catalyst may be withdrawn and replaced periodically or continuously during the operation of the reactor.

Carbon monoxide hydrogenation process

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 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.

Preparation of high activity catalysts; the catalysts and their use

A process for the preparation of a catalyst which is highly active for the synthesis of hydrocarbons from mixtures of hydrogen and carbon monoxide. A silica or silica-containing support is treated with a solution containing both an Iron Group metal, or metals, and nitrous acid, nitric acid, or a nitro-containing organo, or nitro-containing hydrocarbyl compound, or compounds, sufficient to hydroxylate the surface thereof and increase the number of hydroxyl groups on the surface of the support such that the metal component will be highly dispersed, this increasing the activity of the catalyst in a hydrocarbon synthesis reaction as contrasted with that of a catalyst of similar composition, similarly prepared except that the support component of the catalyst was not contacted and simultaneously treated with both the Iron Group metal and the acid.

Process for the preparation of high activity hydrocarbon synthesis

Small particle size catalysts having an average particle size of less than 20 or 10 microns, which agglomerate when contacted with a hydrocarbon liquid, are easily dispersed in the hydrocarbon liquid by first forming a mixture comprising the catalyst particles and one or more non-acidic, liquid polar oxygenates, such as an alcohol, ketone, ester, ether or mixture thereof. The mixture is contacted with the hydrocarbon liquid in which the particles then readily disperse. This process is useful for adding fresh or regenerated small particle size catalyst to catalytic hydroprocessing process slurries, including a reactive Fischer-Tropsch hydrocarbon synthesis slurry. One to four carbon atom alcohols are preferred oxygenates for use with a Fischer-Tropsch slurry.

Small catalyst particle addition to slurry reactor (Law749)

Small catalyst particle addition to slurry reactor

A process for the preparation of a novel highly active, highly selective catalyst useful for conducting carbon monoxide hydrogenation reactions, particularly Fischer-Tropsch reactions, the catalyst per se, and process for use of such catalyst in conducting carbon monoxide hydrogenation reactions, particularly Fischer-Tropsch synthesis reactions. The catalyst is prepared by contacting together, preferably by dispersing in a liquid, a preformed, particulate refractory inorganic oxide support, preferably a fumed silica support, compound or salt of a catalytic metal, or metals, i.e., a metal selected from Groups IB, IIB, VIIB or VIII of the Periodic Table, preferably cobalt, an oxidizable alcohol, oxidizable aldehyde, or oxidizable ketone promoter, suitably glyoxal, and an oxidant sufficient to react with the promoter and convert the metal, or metals, to an insoluble highly dispersed metal carboxylate which is deposited and supported on the support. The solids are recovered, and heated at an elevated temperature to reduce the catalytic metal, or metals, to the zero-valent state and form the catalyst composite. This catalyst in its reduced form is very active, and selective, in conducting carbon monoxide hydrogenation reactions, particularly in converting a mixture of hydrogen and carbon monoxide to C.sub.5 + hydrocarbons, on contact of the gaseous mixture with the catalyst at reaction conditions.

Process for the preparation of high activity carbon monoxide

A continuous impregnation process for the preparation of a heterogeneous catalyst. A catalytic metal, or metals, is composited with a porous solids support component via the steps of: (i) forming a slurry of porous, particulate solids dispersed in an organic, or hydrocarbon solvent, preferably all organic, or hydrocarbon solvent which forms an azeotrope with water, (ii) adding, in aqueous solution, preferably continuously, one or more of a salt, acid, or compound of the catalytic metal, or metals, which is insoluble in the organic, or hydrocarbon solvent to which it is added; the aqueous solution contacting the porous, particulate support solids wicking into the pores to disperse the salt, acid or compound of the catalytic metal, or metals, therein, (iii) stirring, preferably vigorously and continuously, the slurry containing the porous, particulate solids, water, and salt, acid, or compound of the catalytic metal, or metals, and (iv) distilling at a temperature sufficient to vaporize and remove the water from the support component, and slurry, to leave the catalytic metal, or metals, component deposited within the pores of the support component of the catalyst. The catalyst is next recovered, and calcined.

Heterogeneous catalysts via impregnation process

A method for converting solid carbonaceous materials to liquid products. The solid carbonaceous material is first treated with a aqueous composition of a metal carbonate or bicarbonate. This results in the metal being atomically dispersed in the carbonaceous material. The treated solid carbonaceous material is then subjected to liquefaction conditions. The preferred metal is iron.

Coal liquefaction using atomically dispersed metals

A process for the atomic dispersion of metals into support materials, preferably silica, alumina, and amorphous and zeolitic alumino-silicates. The support material is contacted with an aqueous composition of a metal carbonate, or bicarbonate. This results in the metal being atomically dispersed in the support material.

Method for atomically dispersing catalytic metals into support materials

The present invention relates to a catalytic process for converting a solid carbonaceous material, such as coal, to a liquid product in the presence of hydrogen. More particularly, this invention relates to a coal liquefaction process wherein a mixture of coal, bottoms, solvent and a sulfiding agent is subjected to liquefaction conditions in the presence of a catalyst precursor. This catalyst or catalyst precursor is comprised of a thermally decomposable compound of Groups IIB, IVB, VB, VIB, VIIB, and VIII of the Periodic Table of the Elements such as molybdenum.

Liquefaction process

This invention is directed to a staged process for producing liquids from coal or similar carbonaceous feeds combining a pretreatment stage and a liquefaction stage. In the process, the feed is reacted with carbon monoxide and water at an elevated temperature and pressure. The so pretreated coal is sent to a liquefaction reactor, wherein the coal is reacted at a somewhat higher temperature in the presence of hydrogen and catalyst to produce valuable liquid fuels or feedstocks.

Liquefaction of coal with aqueous carbon monoxide pretreatment

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Baton Rouge, LA, United States of America

Claude C Culross