Exxon Research and Engineering Company

Exxonmobil Research and Engineering Company

Roby Bearden, Jr

Clyde L Aldridge

William C Baird, Jr

Michael C Kerby

Gordon Frederick Stuntz

Stephen M Davis

William Ernest Lewis

William Neergaard Olmstead

Ronald Damian Myers

Daniel Paul Leta

Saul Charles Blum

Francis X Mayer

Walter David Vann

Clarence M Eidt, Jr

Mark Alan Greaney

Glen Barry Brons

Michael F Raterman

Jonathan Martin McConnachie

James Ronald Bielenberg

William J Metrailer

Ralph Louis Bollinger, Jr

Michael Siskin

Martin Leo Gorbaty

Lloyd A Pine

Zhiguo Hou

Rustom Merwan Billimoria

John P Greeley

Lu Han

James H Taylor, Jr

Manuel Anthony Francisco

Ramanathan Sundararaman

Thomas Francis Degnan, Jr

Jorge L Soto

Stuart Leon Soled

Sabato Miseo

Russell R Chianelli

Kenneth L Riley

David William Savage

William E Winter, Jr

David T Ferrughelli

Thomas R Halbert

Robert C Schucker

Willard H Sawyer

Leo D Brown

Paul Podsiadlo

Anjaneya Sarma Kovvali

Randolph John Smiley

Peter S Maa

Glen P Hamner

LeRoy R Clavenna

Richard A Demmin

Michael Charles Kerby

Chris A Wright

Paul D Oldenburg

Mainak Ghosh

Bruce M Sankey

Howard J Freund

Natalie Ann Fassbender

James Ronald Rigby

John Brenton MacLeod

Tan-Jen Chen

Winston K Robbins

Joseph K Mertzweiller

Thomas B Rauchfuss

Douglas Wayne Hissong

Martin C Poole

Thomas H Ledford

John G Matragrano

Stephen D Reynolds

Brandon T Stone

Rutton D Patel

Amitava Sarkar

Clyde L Aldrige

Ferrughelli Thomas David

Marty G Bienstock

Systems and methods are provided for slurry hydroconversion of a heavy oil feed, such as an atmospheric or vacuum resid. The systems and methods allow for slurry hydroconversion using catalysts with enhanced activity and/or catalysts that can be recycled as a side product from a complementary refinery process.

Slurry hydroconversion using enhanced slurry catalysts

Systems and methods are provided for slurry hydroconversion of a heavy oil feedstock, such as an atmospheric or vacuum resid, in the presence of an enhanced or promoted slurry hydroconversion catalyst system. The slurry hydroconversion catalyst system can be formed from a) a Group VIII non-noble metal catalyst precursor/concentrate (such as an iron-based catalyst precursor/concentrate) and b) a Group VI metal catalyst precursor/concentrate (such as a molybdenum-based catalyst precursor/concentrate) and/or a Group VI metal sulfided catalyst.

Slurry hydroconversion catalysts

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

The present invention relates to a process for desulfurizing heavy oil feedstreams with alkali metal compounds and improving the compatibility of the to stream components in either the feed stream, an intermediate product stream, and/or the reaction product stream in the desulfurization process. The present invention utilizes a high stability aromatic-containing stream that is preferably added to the heavy oil prior to reaction with the alkali metal compounds. The resulting stream resists precipitation of reaction solids in the desulfurization reactors. Even more preferably, the desulfurization system employs at least two desulfurization reactors in series flow wherein the high stability aromatic-containing stream is contacted with the reaction product from the first reactor prior to the second reactor, wherein the first reactor can be operated at a higher severity than without the use of the high stability aromatic-containing component stream.

Process for producing a high stability desulfurized heavy oils stream

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

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 present invention relates to a process for removing sulfur from sulfur-containing hydrocarbon streams utilizing a multi-ring aromatic hydrocarbon complex containing an alkali metal ion. Preferably, the sulfur-containing hydrocarbon stream is comprised of high molecular weight hydrocarbons, such as a low API gravity, high viscosity crude, tar sands bitumen, an oil derived from shale, or heavy refinery intermediate stocks such as atmospheric resids or vacuum resids which are typically difficult to desulfurize and contain relatively high amounts of sulfur. However, intermediate refinery streams and refinery product streams may also be treated by the process of the current invention to achieve very low sulfur concentrations to meet environmental specification for fuels sulfur content.

Desulfurization of petroleum streams utilizing a multi-ring aromatic alkali metal complex

The present invention relates to a process for desulfurizing bitumen and other heavy oils such as low API gravity, high viscosity crudes, tar sands bitumen, or shale oils with alkali metal compounds under conditions to promote in-situ regeneration of the alkali metal compounds. The present invention employs the use of superheated water and hydrogen under conditions to improve the desulfurization and alkali metal hydroxide regeneration kinetics at sub-critical temperatures.

Process for the desulfurization of heavy oils and bitumens

A slurry hydroprocessing process for upgrading a hydrocarbon feedstock containing nitrogen and sulfur using bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals wherein the ratio of Group VIB metal to Group VIII metal is about 10:1 to about 1:10.

Slurry hydroprocessing using bulk multimetallic catalysts

The invention described herein is directed to (a) slurry hydroprocessing (SHP) of a feed under SHP conditions; (b) deasphalting, under deasphalting conditions the product obtained from said step (a) and recovering a solvent deasphalted oil and solvent deasphalted rock; (c) calcining said solvent deasphalted rock at a temperature of &lE;about 1200&deg; F. to produce an ash catalyst precursor; (d) recycling said ash catalyst precursor to said step (a).

Combination slurry hydroconversion plus solvent deasphalting process for heavy oil upgrading wherein slurry catalyst is derived from solvent deasphalted rock

This invention relates to reducing the amount of thiols (mercaptans) in petroleum streams, specifically, mercaptans above the five carbon molecular weight range.

Mercaptan removal from petroleum streams (Law950)

Sulfur-containing petroleum feeds are desulfurized by contacting the feeds with staged addition of sodium metal at temperatures of at least about 250&deg; C. in the presence of excess hydrogen to sodium metal. The formation of Na,S is substantially suppressed and the formation of NaSH is promoted in the desulfurization process.

Process for desulfurization of petroleum feeds utilizing sodium metal

TAN containing oils, e.g., crudes, are treated by flashing to remove substantially all of the water therefrom, thermally treating the recovered liquid to reduce the naphthenic acid content thereof, and re-combining light gases recovered from the flashing step with the treated liquid.

Thermal process for reducing total acid number of crude oil

The invention relates to a process for demetallating a petroleum stream by contacting a metals-containing petroleum feed in the presence of a base selected from Group IA and IIA hydroxides and carbonates and ammonium hydroxide and carbonates and mixtures thereof an oxygen containing gas and a phase transfer agent at a temperature of up to 180.degree. C. for a time sufficient to produce a treated petroleum feed having a decreased metals content. The invention provides a method for enhancing the value of petroleum feeds that traditionally have limited use in refineries due to their metals, e.g., Ni and V content.

Method for decreasing the metals content of petroleum streams

The invention relates to an integrated, continuous process for the removal of organically bound sulfur (e.g., mercaptans, sulfides and thiophenes) comprising the steps of contacting a heavy oil, sodium hydroxide, hydrogen and water at a temperature of from about 380.degree. C. to 450.degree. C. to partially desulfurize the heavy oil and to form sodium sulfide, contacting said sodium sulfide via steam stripping to convert the sodium sulfide to sodium hydroxide and the sulfur recovered as hydrogen sulfide. The sodium hydroxide is recirculated for reuse. The partially desulfurized, dewatered heavy oil is treated with sodium metal under desulfurizing conditions, typically at a temperature of from about 340.degree. C. to about 450.degree. C., under a hydrogen pressure of at least about 50 psi to essentially desulfurize the oil, and form sodium sulfide. Optionally, the sodium salt generated can be regenerated to sodium metal using regeneration technology. The process advantageously produces essentially sulfur-free product oils having reduced nitrogen, oxygen and metals contents and reduced viscosity, density, molecular weight and heavy ends.

Continuous in-situ combination process for upgrading heavy oil

Growing community of inventors

Baton Rouge, LA, United States of America

Roby Bearden, Jr