Gulf Research & Development Company

Joel D McKinney

Raynor T Sebulsky

John A Paraskos

James A Frayer

Henri K Lese

Francis Edmund Wynne, Jr

Kirk J Metzger

Thomas C Readal

Harry C Stauffer

Bruce R Mitchell

Joseph A Bludis

David Lyzinski

Robert A Titmus

Harold E Swift

Harold Beuther

Stephen J Yanik

Robert D Christman

Jaime Lopez

Eugene A Pasek

Alfred M Henke

Kirk J Metzer

Heavy or refractory oils are hydroprocessed in the presence of added water and added hydrogen sulfide with or without a slurry catalyst comprising molybdenum sulfide. The water and hydrogen sulfide may originate from the catalyst preparation procedure.

Heavy oil hydroprocessing

A process for the conversion of gas oil to a naphtha pyrolysis feedstock and needle coke comprising thermally cracking the gas oil to produce a product comprising cracked naphtha and aromatic tar oil, delay coking said aromatic tar oil to produce needle coke and coker naphtha, and hydrotreating said cracked naphtha and said coker naphtha at a temperature at least 50.degree. F. (28.degree. C.) lower than the temperature in the thermal cracking and coking zones to avoid hydrocarcking reactions and to produce a hydrogenated naphtha containing at least 10 volume percent of cycloparaffins. Said hydrogenated naphtha is thereupon passed through a pyrolysis zone without added molecular hydrogen and without a catalyst operated at a temperature between 1,300 and 2,300.degree. F. (704 and 1,260.degree. C.) and a residence between 0.05 and 2 seconds to produce a product containing ethylene. The ethylene yield can be increased by adding a sulfur compound to the hydrogenated naphtha stream flowing to the pyrolysis zone.

Process for conversion of gas oil to ethylene and needle coke

A catalyst having utility as a downstream catalyst in processes for hydrodesulfurization of asphaltene-containing petroleum oils, coal liquids, shale oils or oils from tar sands which employ both upstream and downstream catalysts in series. The downstream catalyst comprises supported Group VI and Group VIII metals together with a promoting amount of a Group IV-B metal. The particles of said promoted catalyst are elongated extrudates whose surface is provided with a plurality of alternating longitudinal grooves and protrusions. In processes using this catalyst, the upstream catalyst comprises Group VI and Group VIII metals without promotion with Group IV-B metal and the particles of the upstream catalyst may or may not have similar surface grooves. The adaptation of the grooved particle configuration to the promoted catalyst composition provided the early development of a plateau-like aging curve which was not achieved by the adaptation of the grooved shape to a non-promoted catalyst.

Hydrodesulfurization catalyst

An asphaltene-containing oil hydrodesulfurization process employing a guard reactor and a main reactor in series, with the diameter of the guard reactor being smaller than the diameter of the main reactor. The catalyst in the guard reactor comprises particles of supported Group VI and Group VIII metals in the form of elongated extrudates whose surface is provided with a plurality of alternating longitudinal grooves and protrusions. An advantageous mass velocity-related activity effect is demonstrated when catalyst particles having this shape are disposed in a guard reactor having a smaller diameter than the diameter of the main reactor with which it is associated.

Hydrodesulfurization process employing a guard reactor

An asphaltene-containing oil hydrodesulfurization process employing an upstream catalyst and a downstream catalyst in series. The downstream catalyst comprises supported Group VI and Group VIII metals together with a promoting amount of Group IV-B metal in the form of particles whose surface is shaped by multiple elongated alternating grooves and protrusions. The upstream catalyst comprises Group VI and Group VIII metals without promotion with Group IV-B metal in the form of particles which may or may not be similarly shaped. Beds of the downstream and upstream catalyst may be diposed in the same or in different reactors. The adaptation of the grooved particle configuration to the promoted catalyst composition provided the early development of a plateau-like aging curve which was not achieved by the adaptation of the grooved shape to a non-promoted catalyst.

Hydrodesulfurization process employing a promoted catalyst

A catalytic asphaltene-containing oil hydrodesulfurization process employing a fixed catalyst bed comprising particles of supported Group VI and Group VIII metals, preferably together with a separate and downstream fixed catalyst bed comprising particles of Group VI and Group VIII metals together with a promoting amount of Group IV-B metal. The catalyst particles in both beds are in the form of elongated extrudates whose surface is provided with a plurality of alternating longitudinal grooves and protrusions. An advantageous mass velocity-related catalyst activity effect is achieved by recycling a portion of the desulfurized liquid product.

Hydrodesulfurization process including product recycle

An asphaltene-containing oil hydrodesulfurization process employing upstream and downstream reactors in series with an interstage flashing step. The catalyst in the downstream reactor comprises supported Group VI and Group VIII metals together with a promoting amount of Group IV-B metal. The particles of the catalyst in the downstream reactor are in the form of extrudates whose surface is provided with a plurality of alternating longitudinal grooves and protrusions. The catalyst in the upstream reactor comprises Group VI and Group VIII metals without promotion with Group IV-B metal and is in the form of particles whose surface may or may not have a similar grooved form. An advantageous mass velocity-related activity effect has been found when the downstream reactor has a diameter which is smaller than the diameter of the upstream reactor. The reduced diameter provides a concomitant advantage related to hydrogen pressure since it is shown that the reduced diameter permits the downstream reactor to withstand enhanced pressures and it is also shown that the promoted catalyst is particularly susceptible to regeneration via increases in hydrogen pressure.

Multi-reactor hydrodesulfurization process

In a thermal cracking process employing inert hot solids as a heat source, the cracker effluent solids are passed to a burner for combustion of deposited and entrained coke. The liquid product of the thermal cracking process is distilled and the liquid residue comprises a low value solids-containing slurry which is used as a torch oil in the coke burner. The liquid residue from a catalytic cracking process also comprises a low value slurry since it contains particles of cracking catalyst and in the present process is used as auxiliary torch oil in the solids burner. The catalyst particles are rendered inert at the high temperature of the burner, thereby enhancing the quantity of inert solids circulating in the thermal cracking process. The use of a second slurry as torch oil reduces the quantity of thermally cracked liquid residue required as torch oil and enhances the quantity of more valuable solids-free distillate liquid recoverable from the thermal cracking process.

Method for enhancing distillate liquid yield from an ethylene cracking

A process for thermal cracking of petroleum light gas oil to produce a product including ethylene comprising passing said oil, a diluent gas and entrained hot solids through a cracking zone at a temperature between 1,300.degree. and 2,500.degree. F. at a relatively high cracking severity corresponding to a methane yield of at least 12 weight percent based on hydrocarbon feed oil and with a weight ratio of diluent gas to feed oil of at least 0.3. A naphtha feedstock can be separately cracked at a lower severity using a lower weight ratio of diluent gas to feed oil, with the inert solids from both cracking zones being sent to a common burner whose fuel comprises heavy oil product from both cracking zones.

Thermal cracking of light gas oil at high severity to ethylene

An improved catalytic cracking catalyst is obtained by a method which comprises incorporating into a crystalline aluminosilicate catalyst by ion exchange a substantial concentration of a metal selected from the group consisting of antimony, bismuth and manganese.

Method for preparing crystalline aluminosilicate cracking catalysts

A process for the non-catalytic riser cracking of shale oil to produce ethylene in the presence of entrained hot, inert solids.

Thermal cracking of shale oil

A process for the production of ethylene by the non-catalytic riser cracking of hydrodesulfurized residual petroleum oils in the presence of entrained hot, inert solids.

Thermal cracking of hydrodesulfurized residual petroleum oils

An improved hydrocarbon catalytic cracking process which comprises introducing tin into the cracking zone so as to maintain a volume ratio of carbon dioxide to carbon monoxide in the gaseous effluent from the catalyst regeneration zone of at least 3.0.

Hydrocarbon catalytic cracking process

An improved hydrocarbon catalytic cracking process which comprises determining the concentrations of carbon dioxide and carbon monoxide in the gaseous effluent from the catalyst regeneration zone and adjusting the rate of addition of a selective treating agent to the hydrocarbon feed to the cracking zone so as to maintain a volume ratio of carbon dioxide to carbon monoxide of at least 2.2 in said effluent.

A process for hydrodenitrogenation of shale oil comprising fractionating the shale oil into relatively light and heavy fractions, passing the relatively light fraction through a zone containing a catalyst comprising supported molybdenum and Group VIII metal and passing the relatively heavy fraction through a zone containing a catalyst comprising supported tungsten and Group VIII metal.

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Pittsburgh, PA, United States of America

Joel D McKinney