Exxon Research and Engineering Company

Lonnie W Vernon

Peter S Maa

Karl W Plumlee

William E Winter, Jr

Nicholas Charles Nahas

Lavanga R Veluswamy

Robert E Pennington

Fritz E Jacobs

Kwang K Koh

Martin Leo Gorbaty

Claude C Culross

Gopal H Singhal

Robert J Lang

Richard Frank Bauman

Robert B Long

Charles A Euker, Jr

Charles A Mims

A catalyst composition prepared by depositing a metal or metal compound onto a preformed carbon support and thereafter converting said metal or metal compounds to an oxide or sulfide having hydrogenation activity. The metal is selected from the group of metals consisting of Groups II-B, IV-B, IV-A, V-A, VI-A, VII-A and VIII-A metals of the Periodic Table of the Elements. The catalyst compositions are useful in hydroconversion and hydrotreating processes.

Catalyst composition prepared by vapor depositing onto a carbon support

An improved process for hydroconverting carbonaceous material wherein the hydroconversion is accomplished in the presence of a sulfide of tin or tin and at least one metal selected from the Group of metals consisting of the Groups IV-B, V-A, VI-A, VII-A and Group VIII-A metals of the Periodic Table of the Elements and in the presence of iodine. The tin and any other metal may be added directly as the sulfide or as a soluble precursor that will either decompose or be converted to the sulfide. The iodine may be added directly as iodine, hydrogen iodine or as a precursor which will decompose to yield either iodine or hydrogen iodide. The hydroconversion is also accomplished in the presence of hydrogen. The tin sulfide when used either alone or in combination with a sulfide of at least one other metal selected from the Group of metals consisting of Groups IV-B, V-A, VI-A, VII-A and VIII-A of the Periodic Table of the Elements when used with iodine surprisingly increases the yield of gasoline boiling range product from the hydroconversion or liquefaction process. When tin sulfide is used in combination with at least one other metal sulfide, the increase in the yield of gasoline boiling range product is even more surprising.

Coal liquefaction process with metal/iodine cocatalyst

An improved liquefaction process for solid carbonaceous materials wherein at least a portion of the liquefaction is accomplished in the presence of an added hydrogenation catalyst and a solvent containing at least 1.25 wt % donatable hydrogen and in the presence of partially liquefied, solid carbonaceous material at liquefaction conditions. In a preferred embodiment, the liquefaction is accomplished in a plurality of stages and a solvent containing at least 1.25 wt % donatable hydrogen is used in at least one stage, most preferably in the second stage. The partially liquefied solid carbonaceous material may be taken from the bottoms fraction of the effluent from any of the liquefaction stages.

Liquefaction process

An improved process for hydrocracking petroleum residuals wherein total conversion and the yield of lower boiling range products are increased. The hydrocracking is accomplished in the presence of a hydrogen donor solvent and molecular hydrogen. The conversion is accomplished at a pressure within the range from about 1500 to about 2500 psig and at a temperature within the range from about 800.degree.to about 850.degree. F. Operation at these conditions is essential to achieving the increased conversion and the increased yield of lower boiling liquid products. While the present invention has been described and illustrated by reference to particular embodiments thereof, it will be appreciated by those of ordinary skill in the art that the same lends itself to variations not necessarily illustrated herein. For this reason, then, references should be made solely to the appended claims for purposes of determining the true scope of the present invention.

Process for converting petroleum residuals

An improved process for hydrocracking petroleum residuals wherein total conversion and the yield of lower boiling range products are increased. The hydrocracking is accomplished in the presence of a hydrogen donor solvent comprising substantially all of the liquid product having an initial boiling point substantially equal to the final boiling point of the liquid product recovered from the hydrocracked product and, generally, within the range from about 600.degree. F. to about 750.degree. F. and molecular hydrogen. The conversion is accomplished at a pressure within the range from about 1500 to about 2500 psig and at a temperature within the range from about 800.degree. to about 880.degree. F. Operation at these conditions is essential to achieving the increased conversion and the increased yield of lower boiling liquid products.

Coal or a similar solid carbonaceous feed material is converted into lower molecular weight liquid hydrocarbons by contacting the feed material with a hydrogen-donor solvent containing above about 0.6 weight percent donatable hydrogen and molecular hydrogen in a liquefaction zone or a series of two or more liquefaction zones under liquefaction conditions in the presence of an added carbon-alkali metal catalyst comprising a carbon-alkali metal reaction product prepared by heating an intimate mixture of carbonaceous solids and an alkali metal constituent to a temperature above about 800.degree. F. in a reaction zone external to the liquefaction zone.

Catalytic hydrogen-donor liquefaction process

An improved process for liquefying coal and similar solid carbonaceous materials wherein the liquefaction is accomplished in a plurality of zones or stages and wherein the temperature is increased either linearly or nonlinearly in the first zone or stage, aromatics which are produced, liberated or contained in the solvent are separated after the first zone or stage and the liquefaction is continued in at least one other stage, at a temperature at least as high as the final temperature in the first zone or stage. In a preferred embodiment, the temperature in the first stage will be increased at least 50.degree. F. The improved process results in a higher conversion of carbon contained in the coal or similar solid carbonaceous material to liquid products.

Multiple-stage hydrogen-donor coal liquefaction

An increased yield of hydrogenated liquid product is obtained from coal by contacting the feed coal with a hydrogen-donor solvent and a hydrogen-containing gas in a series of two or more liquefaction zones arranged in series and operated in such a manner that the temperature in each zone increases from the initial to the final zone. The effluent from each liquefaction zone is passed to the next succeeding higher temperature zone in the series. Liquid hydrocarbonaceous products are recovered from the effluent withdrawn from the last zone. Hydrogen-donor solvent may be produced in the process by catalytically hydrogenating at least a portion of the liquid product from the last liquefaction zone, recovering a liquid fraction from the product of the catalytic hydrogenation and separating a hydrogen-donor solvent from the liquid fraction.

Staged temperature hydrogen-donor coal liquefaction process

Particulate coal is contacted with a vapor phase hydrogen donor solvent to swell the coal particles and, thereafter, the swollen coal particles are subjected to coal liquefaction conditions in the presence of a liquid phase solvent.

Coal liquefaction process

A process for hydrotreating a petroleum hydrocarbon feed comprising admixing a quinone compound, or compounds, with said hydrocarbon feed, and contacting said admixture with hydrogen at elevated temperature, suitably at temperatures ranging from about 500.degree. F. to about 1050.degree. F., preferably from about 750.degree. F. to about 900.degree. F. The petroleum hydrocarbon feed is characterized generally as comprised of a full boiling range crude, an atmospheric or vacuum residum, an unconventional whole heavy crude, or fractions boiling within the gasoline and mid-distillate ranges.

Hydrogenation of petroleum liquids using quinone catalysts

An increased yield of hydrogenated liquid product is obtained from coal by treating the feed coal with a hydrogen-donor solvent and hydrogen-containing gas in a first coal liquefaction reactor to produce a liquefaction effluent; separating the liquefaction effluent into a vaporous stream and a liquid stream, the liquid stream consisting of a low molecular weight liquid fraction and a high molecular weight liquid fraction; removing a sufficient amount of the low molecular weight liquid fraction from the high molecular weight liquid fraction to form a heavy bottoms stream containing less than about 50 weight percent of the low molecular weight liquid fraction based on the weight of the high molecular weight liquid fraction; treating the heavy bottoms stream with additional fresh hydrogen-donor solvent and hydrogen-containing gas in a second coal liquefaction reactor; separating the second liquefaction reactor product into a vaporous fraction and a liquid fraction, and recovering hydrogenated liquid products from the vaporous and liquid fractions. If desired the high molecular weight constituents in the liquid fraction from the second liquefaction reactor may be further treated with fresh hydrogen-donor solvent and hydrogen-containing gas in a third coal liquefaction reactor. Hydrogen-donor solvent may be preduced in the process by catalytically hydrogenating at least a portion of the liquid product from each liquefaction reactor, recovering a liquid fraction from the products of the catalytic hydrogenation, and separating a hydrogen-donor solvent from the liquid fraction.

Multiple-stage hydrogen-donor coal liquefaction process

Methane and carbon dioxide are produced by reacting steam with a carbonaceous feed material at a reaction temperature between about 1000.degree. F. and about 1500.degree. F. and a reaction pressure in excess of about 100 psia in the presence of a carbon-alkali metal catalyst and equilibrium quantities of added hydrogen and carbon monoxide. The raw product gas withdrawn from the reaction zone is treated for removal of the carbon dioxide, product methane is recovered from the treated gas, and the remaining hydrogen and carbon monoxide can be recycled to supply the added hydrogen and carbon monoxide needed in the reaction zone.

Integrated catalytic gasification process

A process for liquefying a particulate coal feed to produce useful petroleum-like liquid products by steps which include: (a) contacting, in a liquefaction zone, said coal feed with a hydrogen donor solvent at temperature and pressure sufficient to hydroconvert and liquefy the coal, (b) separating the product from the liquefaction zone by distillation into fractions inclusive of a liquid solvent fraction which contains at least 30 weight percent, and preferably at least 50 weight percent hydrogen donor compounds, particularly those fractions boiling within about the 350.degree.-850.degree. F. range, and preferably within about the 400.degree.-700.degree. F. range, (c) hydrotreating said liquid solvent fraction in a hydrogenation zone in the presence of a quinone catalyst, and (d) recycling the hydrogenated liquid solvent mixture to said coal liquefaction zone.

A process for liquefying a particulate coal feed to produce useful petroleum-like liquid products by steps which include: (a) admixing said coal feed, a solvent, particularly a non-donor solvent, and an ortho-quinone compound, to form a coal liquid slurry, and then (b) contacting said coal liquid slurry with molecular hydrogen in a liquefaction zone at temperature and pressure sufficient to hydroconvert and liquefy the coal. In accordance with a preferred embodiment, the product from the liquefaction zone is separated by distillation into fractions inclusive of fractions boiling within about the 350.degree.-850.degree. F. range, and preferably within about the 400.degree.-700.degree. F. range, which can be recycled to the coal liquefaction zone for use in slurrying the coal. The ortho-quinone compound acts as a hydrogenation catalyst, causing adequate hydrogenation of the coal within the coal liquefaction zone in the presence of the molecular hydrogen without any necessity of employing a hydrogen donor solvent, and hence there is no necessity for hydrogenation of the solvent in a separate hydrogenation zone.

A process for liquefying a particulate coal feed to produce useful petroleum-like liquid products by steps which include: (a) admixing said coal feed, a solvent, particularly a non-donor solvent, and a quinone compound, or admixture of quinone compounds, to form a coal liquid slurry, and then (b) contacting said coal liquid slurry with molecular hydrogen in a liquefaction zone at temperature and pressure sufficient to hydroconvert and liquefy the coal. In accordance with a preferred embodiment, the product from the liquefaction zone is separated by distillation into fractions inclusive of fractions boiling within about the 350.degree.-850.degree. F. range, and preferably within about the 400.degree.-700.degree. F. range, which can be recycled to the coal liquefaction zone for use in slurrying the coal. A feature of this invention is that the quinone compound acts as a hydrogenation catalyst, causing adequate hydrogenation of the coal within the coal liquefaction zone in the presence of the molecular hydrogen without any necessity of employing a hydrogen donor solvent, and hence there is no need for hydrogenation of the solvent in a separate hydrogenation zone.

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Baytown, TX, United States of America

Lonnie W Vernon