Exxon Research and Engineering Company

Exxonmobil Research and Engineering Company

William C Baird, Jr

Charles H Mauldin

Roby Bearden, Jr

Gary Brice McVicker

Michele Sue Touvelle

Jingguang Chen

George A Swan, Iii

Edward Stanley Ellis

Michel A Daage

Paul E Eberly

James J Schorfheide

Darryl P Klein

Sylvain S Hantzer

Darryl Patrick Klein

David E W Vaughan

Daniel Paul Leta

Kenneth L Riley

Jonathan Martin McConnachie

Joseph P Boyle

Walter David Vann

David E Vaughan

Leo D Brown

Garland B Brignac

James Ronald Bielenberg

Jorge L Soto

Ehsan I Shoukry

Jingguang G Chen

Ralph Louis Bollinger, Jr

Robert J Wittenbrink

Clyde L Aldridge

Jack Wayne Johnson

Daniel Francis Ryan

Michael F Raterman

Geoffrey R Say

Lu Han

Carl W Hudson

Eduardo Mon

Mark Alan Greaney

Bruce R Cook

Thomas R Halbert

Richard A Demmin

Chris A Wright

Janet Renee Clark

Paul D Oldenburg

Robert C Schucker

Howard J Freund

James Ronald Rigby

Paul W Kamienski

Douglas Wayne Hissong

Thomas H Ledford

George J Balinsky

Brandon T Stone

Roby Beardon, Jr

Robert G Corry

Hydrocarbon feedstreams are desulfurized using an alkali metal reagent, optionally in the presence of hydrogen. Improved control over reaction conditions can be achieved in part by controlling the particle size of the alkali metal salt and by using multiple desulfurization reactors. The processes herein allow a simple and effective method for removing the majority of coke formed in the alkali metal reagent reactions with the hydrocarbon feedstreams. This makes it cost effective to run such processes at higher severities (which result in higher coke production) thereby resulting in increased amounts of valuable converted hydrocarbon product yields. The process improvements herein may also be used to increase total throughput through a unit due to the ability to effectively manage higher coke content in the reaction products.

Alkali metal hydroprocessing of heavy oils with enhanced removal of coke products

Hydrocarbon feedstreams are desulfurized using an alkali metal reagent, optionally in the presence of hydrogen. Improved control over reaction conditions can be achieved in part by controlling the particle size of the alkali metal salt and by using multiple desulfurization reactors. After separation of the spent alkali metal reagent, the resulting product can have suitable characteristics for pipeline transport and/or further refinery processing.

Desulfurization process using alkali metal reagent

The present invention relates to a process for regeneration of alkali metal salt reagent used in desulfurization of heavy oil feedstreams. In particular, the present invention relates to a process utilizing potassium hydroxide as an external supply reagent to a heavy oil conversion process and in-situ conversion of the spent reactants utilized in such process into a potassium sulfide reagent for reintroduction into the heavy oil conversion process.

Heavy oil conversion process with in-situ potassium sulfide generation

After desulfurizing a hydrocarbon feedstream using an alkali metal reagent, the hydrocarbon feedstream can include particles of spent alkali metal salts. The spent alkali metal salts can be separated from the hydrocarbon feedstream and regenerated to form an alkali metal reagent, such as a alkali hydroxide or alkali sulfide. The regeneration process can pass through an intermediate stage of forming an alkali carbonate by successive reactions with carbon dioxide and calcium oxide. The calcium oxide can also be regenerated.

Regeneration of alkali metal reagent

The hydrogenation activity of a heteroatom removal catalyst, having activity for both heteroatom removal and hydrogenation, is selectively suppressed by a treatment which comprises contacting the catalyst with (i) hydrogen, (ii) a selectively deactivating agent that suppresses the catalyst's hydrogenation activity, and (iii) a protective agent, such as CO, that preserves and protects the heteroatom removal activity during the treatment. This may be achieved in a reactor while it is on-line and removing heteroatoms from a hydrocarbon feed.

Selectively suppressed hydrogenation catalyst

Selectively suppressing catalytic hydrogenation

A process to regenerate iron-based hydrogen sulfide sorbents using steam. The steam is preferably mixed with hydrogen-containing gas and/or an inert gas, such as nitrogen. In a preferred embodiment, the sorbent is first exposed to the steam and then exposed to a hydrogen-containing gas at regeneration conditions.

Regeneration of iron-based hydrogen sulfide sorbents

Disclosed is a process for opening naphthenic rings of naphthenic ring-containing compounds, along with catalysts which can be used in that process. The ring opening is accomplished using a ring opening catalyst comprising Ir on a composite support of alumina and acidic silica-alumina molecular sieve. The ring opening activity is not significantly deactivated by exposure to oxygen at greater than about 250&deg; C.

Naphthene ring opening over an iridium ring opening catalyst

A process to regenerate metal oxide desulfurization sorbents using an oxidizing and reducing atmosphere. The sorbents may be mono- or multi-metallic in nature, and preferably comprise Cu, Ni and/or Co. If desired, secondary metals may be incorporated to increase regeneration efficiency and/or capacity. Other additives may be used to suppress hydrocarbon cracking. A sorbent containing Zn may be combined with an Fe, Co, Ni, Mo, or W catalyst or a noble metal catalyst and combinations thereof.

Regeneration of hydrogen sulfide sorbents

Disclosed is a process for opening naphthenic rings of naphthenic ring-containing compounds, along with catalysts which can be used in that process. The ring opening is accomplished using a ring opening catalyst system which combines an Ir ring opening catalyst with a Pt and Pd catalyst. The combination of the Pt and Pd-containing catalyst with an Ir-containing catalyst incorporates desirable isomerization activity and also results in substantial ring opening activity that enables Ir to be loaded at a level that is substantially below that of Ir-only ring opening processes.

Naphthene ring opening over a ring opening catalyst combination

Disclosed is a process for opening naphthenic rings of naphthenic ring-containing compounds, along with catalysts which can be used in that process. The naphthene ring opening catalyst is a catalyst which comprises at least one of a Group VIII metal selected from Ir, Pt, Pd, Rh, and Ru in an amount effective to ring open naphthene rings on naphthene ring-containing compounds, the metal being supported on a substrate comprising at least one Group IB, IIB, and IVA metal in an amount effective to moderate cracking of a naphthene ring-containing feed to form methane.

Naphthene ring opening over group VIII metal catalysts containing cracking moderators

Disclosed is a process for opening naphthenic rings of naphthenic ring-containing compounds, and catalysts which can be used in that process. The naphthene ring opening catalyst is a polymetallic catalyst comprising Group VIII metals. In a preferred embodiment the naphthene ring opening catalyst comprises Ir in combination with a Group VIII metal selected from at least one of Pt, Rh, and Ru, in an amount effective for opening a naphthene ring-containing compound at a tertiary carbon site.

Method and catalyst for opening naphthenic rings of naphthenic ring-containing compounds

A process for opening naphthenic rings of naphthenic ring-containing compounds, along with catalysts which can be used in that process. The naphthene ring opening catalyst is a catalyst comprising at least one Group VIII metal selected from Ir, Pt, Rh, and Ru, wherein these metals are supported on an alkali metal or alkaline-earth metal modified support in an amount effective for opening a naphthene ring-containing compound at a tertiary carbon site.

Ring opening with group VIII metal catalysts supported on modified substrate

Naphtha desulfurization with reduced product mercaptans is achieved by reacting a naphtha feed containing sulfur compounds and olefins with hydrogen in the presence of a hydrosesulfurization catalyst at reaction conditions including a temperature of from 290-425&deg; C., a pressure of from 60-150 psig, and a hydrogen gas ratio of from 2000-4000 scf/b. It has been found that desulfurizing within these narrow conditions permits deep desulfurization with reduced mercaptan reversion, to produce a naphtha product with low total sulfur and low mercaptan sulfur levels.

Naphtha desulfurization with reduced mercaptan formation

Electrochemical oxidation of sulfur compounds in naphtha using ionic liquids

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Baton Rouge, LA, United States of America

William C Baird, Jr