Hydrocarbon Research, Inc.

Hri, Inc.

Suntech, Inc.

Michael C Chervenak

Edwin S Johanson

Govanon Nongbri

Ronald H Wolk

Richard M Eccles

Paul Harriman Kydd

Alfred G Comolli

Seymour B Alpert

Peter Maruhnic

Allen S Li

Marvin S Rakow

Henry E Reif

John Shen

Susan M Brandt

George R DeVaux

Shyy-Jong D Lin

Virginia A Malik

An improved process for catalytic desulfurization of petroleum residua feedstocks to provide at least about 75% desulfurization of the liquid product while achieving low catalyst deactivation and increased catalyst age. In the process which uses an ebullated catalyst bed reactor, the reaction conditions are usually maintained at 790.degree.-860.degree. F. temperature, 1000-1800 psig hydrogen partial pressure, and 0.2-2.0 Vf/hr/Vr space velocity. To control carbon and metals deposition on the catalyst, used catalyst is withdrawn from the reactor, a minor portion of the catalyst is discarded to control metals deposition and maintain catalyst activity, and the remaining catalyst is regenerated to remove carbon by carbon burnoff and returned to the reactor for further use. If desired, the regenerated catalyst can be presulfided before returning it to the reactor. Following phase separation and distillation steps, the desulfurized hydrocarbon liquid products are withdrawn from the process. For feedstocks requiring higher desulfurization, two stages of catalytic reaction are provided in which the used catalyst is withdrawn from each stage reactor and regenerated to remove carbon and then returned to the same stage reactor. Alternatively, fresh catalyst is added to the second stage only, some used catalyst from the second stage reactor is transferred to the first stage reactor, and used catalyst is discarded from the first stage reactor.

Catalyst desulfurization of petroleum residua feedstocks

A process for high hydroconversion of petroleum residua containing at least about 25 V % material boiling above 975.degree. F. to produce lower boiling hydrocarbon liquid products and avoid undesirable precipitation of asphaltene compounds. In the process, the feedstock is at least about 80 percent catalytically hydroconverted to material boiling below 975.degree. F. and containing a mixture of gas and liquid fractions, after which the gas fraction is removed while maintaining the resulting liquid fractions temperature above about 730.degree. F. to avoid precipitation of asphaltene compounds which causes operations difficulties in the downstream equipment. Alternatively, the pressure-reduced liquid fraction can be stripped of material boiling below about 650.degree. F. before cooling the liquid to a temperature below about 730.degree. F. to prevent such precipitation of asphaltene compounds in the downstream equipment. The resulting liquid fraction is distilled to produce hydrocarbon liquid products, and a vacuum bottoms fraction is recycled to the catalytic reaction step to obtain increased percent conversion to lower boiling liquid products.

Sustained high hydroconversion of petroleum residua feedstocks

Activated bauxite particulate material having usual nominal particle size range of 20-50 mesh (U.S. Sieve Series) is treated by fluidization in an upflowing gas so as to attrite the particles and stabilize the particle shape and size, thereby making the catalyst more uniform in shape and resistent to attrition in subsequent ebullated bed reactor operations. The treated activated bauxite catalyst material is then rescreened to provide a narrower differential size range having a particle equivalent diameter ratio range for large to small particles of about 1.4-2.0, and a preferred 20-30 mesh (U.S. Sieve Series) particle size range. The selected pretreated catalyst is then introduced into the ebullated bed reactor of a hydrodemetallization process for hydrocarbon feedstocks containing high metals concentration. Use of such pretreated bauxite catalyst particles results in improved reactor fluidization operations and less catalyst loss by attrition and carryover of fines from the reactor, and achieves improved results of 60-70 W % demetallization and 50-55 V % hydroconversion of the 975.degree. F..sup.30 fraction to lower boiling hydrocarbon products in a single stage operation.

Frangible catalyst pretreatment method for use in hydrocarbon

A process for the catalytic hydroconversion of special petroleum feedstocks, containing 10-28 W % asphaltenes, and having Ramsbottom carbon residue of 12-35 W %, such as Cold Lake and Lloydminster crude and residua materials. In the process, high percentage conversion (65-80 V %) to lower boiling hydrocarbon products can be achieved by maintaining a narrow range of reaction conditions, preferably in an ebullated bed catalytic reactor. Reaction temperature is 780.degree.-835.degree. F., hydrogen partial pressure is 2000-3000 psig, and space velocity is 0.25-5.0 V.sub.f /hr/V.sub.r. Higher conversion of about 80 to 95 volume percent can be obtained with recycle of 975.degree. F..sup.+ vacuum bottoms fraction to the reactor. Useful catalysts have total pore volume of about 0.5-0.9 cc/gm and include cobalt-molybdenum and nickel-molybdenum on alumina support.

Selective operating conditions for high conversion of special petroleum

A process for converting coal and other hydrocarbonaceous materials into useful and more valuable liquid products. The process comprises: feeding coal and/or other hydrocarbonaceous materials with a hydrogen-containing gas into an ebullated catalyst bed reactor; passing the reaction products from the reactor to a hot separator where the vaporous and distillate products are separated from the residuals; introducing the vaporous and distillate products from the separator directly into a hydrotreater where they are further hydrogenated; passing the residuals from the separator successively through flash vessels at reduced pressures where distillates are flashed off and combined with the vaporous and distillate products to be hydrogenated; transferring the unseparated residuals to a solids concentrating and removal means to remove a substantial portion of solids therefrom and recycling the remaining residual oil to the reactor; and passing the hydrogenated vaporous and distillate products to an atmospheric fractionator where the combined products are fractionated into separate valuable liquid products. The hydrogen-containing gas is generated from sources within the process.

H-Coal process and plant design

Improved method for maximizing jet fuel from shale oil involves hydrotreating the treated oil at a temperature of about 600.degree.-650.degree. F. in the presence of a catalyst having a relatively low metal content and then hydrotreating the oil at a temperature in excess of about 800.degree. F. in the presence of a catalyst having a relatively high metal content. A 480.degree. F. minus boiling point fraction fractionated from the foregoing process can meet JP-4 jet fuel specifications. Hydrocracking the 480.degree. F. plus boiling point fraction results in substantial additional quantities of jet fuel.

Maximizing jet fuel from shale oil

A multiple-zone fluidized bed coal conversion process for producing fuel gas and distillate liquid products. The coal is fed into an upper fluidized bed maintained at 950.degree.-1500.degree. F. for devolatilization. The resulting coke and some tars are deposited on a particulate carrier material, which descends along with the larger particles of unreacted coal through a stripping zone into a lower fluidized bed gasification zone, which is maintained at 1700.degree.-2000.degree. F. by steam and O.sub.2 -containing gas introduced therein to gasify the coke and char. Fine particles of unreacted coal and carrier are passed with gas and distillate vapor through a cyclone gas-solids separation step located in the devolatilization zone, from which the solids are returned to the lower bed for further gasification. Ash produced in the lower bed along with the clean hot particulate carrier is transferred through an up-transport tube to the upper bed. The effluent from the devolatilization/hydrogenation zone passes through an external cyclone separator which removes the particles as a disposal stream. Alternatively, the effluent from the devolatilization zone may be passed through a third or uppermost bed of particulate carrier material for heat recovery and more complete removal of tars from the product gas.

Multi-zone coal conversion process using particulate carrier material

A continuous hydrogenation process and apparatus wherein liquids are contacted with hydrogen in an ebullated catalyst reaction zone with the liquids and gas flowing vertically upwardly through that zone into a second zone substantially free of catalyst particles and wherein the liquid and gases are directed against an upwardly inclining surface through which vertical conduits are placed having inlet ends at different levels in the liquid and having outlet ends at different levels above the inclined surface, such that vapor-rich liquid is collected and discharged through conduits terminating at a higher level above the inclined surface than the vapor-poor liquid which is collected and discharged at a level lower than the inclined surface.

Catalytic hydrogenation process and apparatus with improved vapor liquid

Coal is finely ground and cleaned so as to preferentially remove denser ash-containing particles along with some coal. The resulting cleaned coal portion having reduced ash content is then fed to a coal hydrogenation system for the production of desirable hydrocarbon gases and liquid products. The remaining ash-enriched coal portion is gasified to produce a synthesis gas, the ash is removed from the gasifier usually as slag, and the synthesis gas is shift converted with steam and purified to produce the high purity hydrogen needed in the coal hydrogenation system. This overall process increases the utilization of as-mined coal, reduces the problems associated with ash in the liquefaction-hydrogenation system, and permits a desirable simplification of a liquids-solids separation step otherwise required in the coal hydrogenation system.

Integrated coal cleaning, liquefaction, and gasification process

A process for the hydrogenation of coal at elevated temperature is disclosed, wherein particulate coal having an average particle size of less than 1000 microns is admixed with a liquid hydrocarbon to form a slurry containing about 30-50 weight percent solids, and the slurry is passed to an ebullated bed reactor wherein the coal is catalytically hydrogenated at reactor pressure of about 100 to 300 atmospheres to produce hydrocarbon products including a liquid residuum containing unconverted processed coal solids. The improved process includes the steps of removing the hydrocarbon products from the reactor; reducing the pressure of the hydrocarbon products not more than 10% below reactor pressure to separate the hydrocarbon products by phase separation of the gaseous components from the liquid component containing residuum and unconverted coal solids; dividing the liquid into a stream for liquid-solids separation and a bypass stream; passing a portion of the liquid residuum to a liquid-solids separator at substantially the same temperature as the phase separating step; recovering from the separator a purified liquid product stream containing a substantially reduced concentration of unconverted coal solids combining a sufficient amount of the bypass stream with the solids reduced stream to maintain the desired levels of solids and residuum in the reactor; recycling the purified liquid product stream to the ebullated bed reactor in a liquid handling system wherein the pressure throughout the process is maintained at least 90% of the reactor pressure; and recovering from the cyclonic separator a second liquid product stream containing 25 to 45 weight percent unconverted coal solids.

Reactor residuum concentration control in hydroconversion of coal

A pressure let-down valve assembly for handling pressurized liquids which contain abrasive solids including a valve adapted for handling such liquids and a flow reversal means for changing the direction of the flowing liquid. The flow reversal means contains a chamber having an outlet located at a point which permits a sufficient amount of liquid to accumulate therein to absorb at least a portion of the energy of the flowing solids in the liquid.

Pressure let-down valve assembly for handling abrasive liquids

The hydrogenation of low rank coal to produce hydrocarbon liquids and gases is conducted in a first stage reaction zone at elevated temperature and pressure and without catalyst, followed by further hydrogenation of the total effluent in a second stage ebullated bed catalytic reaction zone which is maintained at slightly lower temperature. The first stage may comprise an ebullated bed of high density non-catalytic contact material. However, the presence of such contact material is not required. Clarified hydrocarbon liquid streams are returned to the first stage reaction zone as the slurrying oil and to the second stage zone as recycle oil to maintain a significantly high percentage of unconverted coal solids in the first stage reaction zone than in the second stage zone. This two stage reaction arrangement produces a high percentage conversion of the low rank coal to liquid and gaseous products with good process operability.

Staged hydrogenation of low rank coal

A process is provided for the simultaneous conversion of coal and residuum oil to predominantly liquid products, employing ebullated bed techniques. A fluid blend of particulate coal admixed with crude oil comprising from about 20 to 100% by weight of residuum oil boiling above about 975.degree. F. is contacted with hydrogen in the presence of an ebullated bed of particulate hydrogenation catalyst to effect conversion of at least about 50% of the residuum oil component and up to about 94% of the m.a.f. coal. In an alternate embodiment the oil feed includes recycled oil from the product liquids.

Catalytic hydrogenation of blended coal and residual oil feeds

The removal of particulate solids containing iron sulfides from hydrogenated coal liquids by magnetic separation is improved by pretreatment of the liquid with a gas mixture containing hydrogen and hydrogen sulfide. The coal-derived liquid is contacted with the gas mixture containing at least about 2 vol. % hydrogen sulfide, with the remainder of the gas mixture comprising principally hydrogen. Residue time for the liquid-gas contact should be at least about two minutes and temperature should be less than about 650.degree.F. The treated liquid is then passed through a magnetic field having strength of at least about 3000 gauss to achieve substantial removal of sulfur-containing solids from the liquid. The magnetic solids are then removed from the separator unit, e.g., by flushing using a light solvent oil, and the remaining liquid fraction carrying less-magnetic solids is passed on to further processing.

Pretreatment of coal-derived liquid to improve magnetic separation of

A two-stage hydrodesulfurization process for a 65 to 80 percent desulfurization of a high metal content residuum, such as those obtained from Venezuela, in which the contact solids activity in both stages is maintained at an equilibrium level by constant replacement of the contact solids in both stages. The first stage contains a porous alumina solids contact material activated with at least one promoter oxide selected from Fe.sub.2 O.sub.3, TiO.sub.2 and SiO.sub.2, which has as its primary purpose the removal of vanadium and nickel from the feed material. However, the treatment of the feed in the first stage was found to improve the second stage performance by a factor greater than the amount of metals removed. The second stage contains a highly active desulfurization catalyst of limited porosity.

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Pennington, NJ, United States of America

Michael C Chervenak