Abstract: A process for hydrodesulfurizing a residual oil by passing the oil downwardly through a catalytic reaction zone at a hydrogen pressure which is sufficiently high that demetallization occurs rapidly so that at end-of-run the upstream catalyst region is more nearly metals-saturated than the downstream catalyst region. At the end of the catalyst cycle, the more nearly metals-saturated upstream portion of the catalyst is removed from the process while the less nearly metals-saturated downstream portion of the catalyst is passed to a guard chamber where during further operation of the process it approaches metals-saturation. In this manner, no portion of catalyst is removed from the process until it has an elevated metals content.

Abstract: A hydrodesulfurization process for vanadium-containing ols and certain hydrogenative metal-containing supported catalysts, wherein after deposition of certain amount of vanadium on the catalyst in the absence of added water vapor, water vapor is added to the reaction zone resulting in long-lived, low-cost desulfurization.

Abstract: A heavy hydrocarbonaceous oil is converted to lower boiling products by treatment with hydrogen in the presence of a particulate acidic copper chloride catalyst.

Abstract: An integrated process is described wherein a heavy oil catalytic cracking unit is integrated with a pretreating zone. In the pretreating zone, petroleum feedstock is contacted, in the presence of hydrogen, with used equilibrium catalyst purged from the cracking zone to reduce the metals, carbon residue, and sulfur content of the petroleum feedstock prior to charging the feedstock to the cracking zone of the heavy oil catalytic cracking unit.

Abstract: A process for removing arsenic from a mineral oil feedstock containing at least 2 ppmw arsenic comprises contacting said feedstock at elevated temperatures with a catalytic absorbent comprising a nickel sulfide and a molybdenum sulfide composited with a refractory oxide, said nickel sulfide and said refractory oxide each being present in relatively large proportions. Under preferred conditions a product oil stream containing less than 2 ppmw arsenic is continuously obtained from said contacting until a weight of arsenic at least equivalent to that of the nickel in the catalytic absorbent has been absorbed thereon.

Abstract: A novel process for the demetallization of petroleum feedstocks comprising contacting a petroleum feedstock at elevated pressures and temperatures, and preferably in the presence of hydrogen, with a catalyst comprising a manganese component composited with alumina, said catalyst having a surface area in excess of 175 m.sup.2 /gm and having at least 60% of its pore volume in pores having diameters between 50 and 200 A. Preferred catalysts comprise between about 2 and 15 weight-percent manganese. Removal of more than 25%, usually more than 50%, of the organometallic impurities can be achieved.

Abstract: A method of removing arsenic and selenium contaminants from a hydrocarbonaceous fluid, such as a synthetic crude oil and fractions thereof, is disclosed. In the disclosed method, the hydrocarbonaceous fluid, containing the contaminant is subjected to a heat treating step for a period of time sufficient to form a precipitate. The thus treated hydrocarbonaceous fluid can then be separated from the precipitate to recover a hydrocarbonaceous fluid having a reduced contaminant content.

Abstract: This invention is concerned with removing metal and sulfur contaminants from residual oil fractions by catalytic contact in a novel dual bed system. In this process the oil is first contacted with a catalyst comprising a Group VIB metal and an iron group metal oxide, such as a mixture of cobalt and molybdenum oxides, composited with an alumina support that contains delta or theta phase alumina, the catalyst having at least 60% of its pore volume in pores of 100A to 200A diameter, at least about 5% of its pore volume in pores having a diameter greater than 500A, and a surface area up to about 110m.sup.2 /g. The oil is then contacted with a second catalyst of the high surface-area, cobalt-molybdenum on alumina type. The second catalyst has a major fraction of its pores in the 30 to 100A diameter range.

Abstract: A hydro-refining catalyst comprising at least one hydrogenation metal component supported on an alumina or alumina-containing carrier containing from about 5 to about 25 wt. % silica, said catalyst having a specific surface area in the range of from about 250 to about 300 m.sup.2 /g and a pore volume distribution characterized in that (1) the volume of pores having a diameter of 60 to 150 A is at least about 80% of the volume of pores having a diameter of 0 to 150 A, (2) the volume of pores having a diameter of 150 to 300 A is less than about 20% of the volume of pores of 0 to 300 A, (3) the volume of pores having a diameter of 150 to 2,000 A is less than about 0.01 ml/g, (4) the volume of pores having a diameter of 0 to 600 A is in the range of from about 0.45 to about 0.60 ml/g. The catalyst is used in the hydro-refining of heavy hydrocarbon oils containing sulfur, nitrogen and metal contaminants.

Abstract: Sulfur-containing petroleum oil feedstocks which include heavy hydrocarbons constituents undergo simultaneous desulfurization and hydroconversion by contacting such feedstocks with sodamide in the presence of hydrogen and at elevated temperatures. The mixture of reaction products resulting from the above procedure can be separated to give sodium sulfur salts and a petroleum oil product which has been substantially desulfurized and demetallized and significantly upgraded as demonstrated by a reduced Conradson carbon content and an increased API gravity.

Abstract: Heavy petroleum oils, preferably whole crude or residua, are desulfurized and upgraded by contacting the petroleum oil with sodium oxide in the presence of hydrogen at elevated temperatures. The resulting mixture comprising desulfurized petroleum oil and a dispersion of sodium salts, primarily sodium sulfide and sodium hydroxide, is separated by conventional means and sodium oxide is regenerated from the salts.

Abstract: Heavy carbonaceous feeds, including various sulfur-containing heavy petroleum oils, are simultaneously desulfurized and subjected to hydroconversion by contacting these feedstocks with alkali metal oxides in a conversion zone maintained at elevated temperatures and in the presence of hydrogen. In this manner, the feeds are substantially desulfurized, and significant upgrading of the feedstocks is also obtained as demonstrated by decreased Conradson carbon, increased API gravity, and conversion of a substantial portion of the 1,050.degree. F+ portion of the feedstream. In addition, methods for the regeneration of the alkali metal oxides from the alkali metal sulfide salts produced in the reaction zone are disclosed.

Abstract: Metals are removed from metal- and asphaltene-containing petroleum oils by contacting the oil with pellets of sorptive type attapulgus clay which has been extruded and then dried at a temperature between about 100.degree. and 650.degree. C. to a volatile content of less than 20 weight %.

Abstract: Processes for the simultaneous desulfurization and hydroconversion of heavy carbonaceous feeds, including various sulfur-containing heavy petroleum oils, are disclosed. These feeds are contacted with alkali metal hydroxides in a conversion zone, in the presence of added hydrogen, and at elevated temperatures, whereby the feeds are substantially desulfurized, while at the same time significant upgrading of these feedstocks is obtained as demonstrated by decreased Conradson carbon, increased API gravity, and the conversion of a substantial portion of the 1,050.degree. F+ portion of the feedstream. In addition, methods for the regeneration of alkali metal hydroxides from the alkali metal salts produced in the conversion zone are disclosed.

Abstract: Sulfur and metal contaminants, such as nickel, vanadium and iron, are removed from hydrocarbon feedstocks, by contacting the feedstocks at an elevated temperature and pressure in the presence of hydrogen and a catalyst comprising a hydrogenation component and a support material comprised of phosphorus oxide and alumina. The hydrogenation component includes a Group VIB and/or Group VIII metal of the Periodic Table, particularly molybdenum or tungsten and cobalt or nickel. The presence of phosphorus oxide in the catalyst composition has been found to impart increased catalytic activity for demetallization of metal-contaminated hydrocarbon feedstocks such as heavy petroleum crudes and residua.

Abstract: Method of removing a contaminant, such as arsenic or selenium, from a synthetic hydrocarbonaceous fluid comprising providing a guard bed having a plurality of sections, a first section having from about 10 to about 75 percent of its volume occupied by a contaminant-removing material comprising, alone or on a carrier, either iron, cobalt, nickel, oxides or sulfides of these metals, or combinations thereof; the remainder being inert material. A second section of the guard bed has a major portion of its volume occupied by the contaminant-removing material. The feed oil, in the presence of hydrogen is contacted with the particles in the respective sections of the guard bed.

Abstract: Sulfur-containing petroleum oil feedstocks which include heavy constituents undergo both desulfurization and hydroconversion by contacting such feedstocks with sodium hydride in the presence of hydrogen, at elevated temperatures. The mixture of reaction products resulting from the above procedure can be separated to give a petroleum oil product which has been desulfurized and demetallized and has a reduced Conradson carbon content and an increased API gravity relative to the feedstock, and a by-product of sodium sulfide salt.

Abstract: The conversion of high metals containing feed stock is accomplished in the presence of a low molecular weight carbon-hydrogen fragment contributing material and an acid function crystalline zeolite catalyst to produce gasoline of high quality and yields superior to that obtained heretofore.

Abstract: A hydrotreating process, particularly a hydroconversion process, wherein a hydrogenation catalyst is contacted with a hydrocarbon or hydrocarbonaceous feed containing 1050.degree. F.+ materials at a preselected high initial temperature and maintained essentially at this temperature throughout an operating run. In accordance with such mode of operation certain advantages are obtained, these including: (1) greater overall conversion of 1050.degree. F.+ to 1050.degree. F.- hydrocarbon products at a given level of hydrodesulfurization, catalyst consumption rate, with the same reactor volume and pressure requirements; (2) greater overall reduction of Con carbon; and (3) improved overall feed metals reduction.

Abstract: An improved process for desulfurization of metals and sulfur containing petroleum oils, preferably those containing residua hydrocarbon components, comprising passing the sulfur containing petroleum oils through a bed of substantially aged desulfurization catalyst at a temperature not less than 770.degree.F preceeding conventional hydrodesulfurization treatment.

Abstract: Waste lube oil is refined by treating it with hydrogen in an ebullated bed of catalyst particles and subjecting the liquid effluent to vacuum distillation or other equivalent separation procedures to produce a clean and usable lubestock and a heavy residue which contains the sludge and metallic ingredients in the waste lube oil. This process finds its greatest utility in recovering usable lubricant from a waste product.

Abstract: This invention relates to novel catalysts, of two distinct types, useful for the catalytic hydroconversion of the 1050.degree.F.+ hydrocarbon material contained in heavy crudes and residua such that the resulting product will be suitable for further processing in conventional refinery operations allowing maximization of clean liquid products. Catalysts, which include Group VIB and Group VIII metals, preferably in admixture, and preferably including a Group IVA metal, notably germanium, having certain critical ranges of physical characteristics inclusive of large uniform pore sizes, are used for the conversion, these having been shown to possess improved catalytic activity and selectivity for the hydroconversion of the 1050.degree.F.+ materials of the heavy feeds and residua. Novel methods are described for the preparation of such catalysts, as well as for use of such catalysts. One of the catalysts, i.e.

Abstract: This invention relates to novel catalysts, of two distinct types, useful for the catalytic hydroconversion of the 1050.degree.F.+ hydrocarbon material contained in heavy crudes and residua such that the resulting product will be suitable for further processing in conventional refinery operations allowing maximization of clean liquid products. Catalysts, which include Group VIB and Group VIII metals, preferably in admixture, and preferably including a Group IVA metal, notably germanium, having certain critical ranges of physical characteristics inclusive of large uniform pore sizes, are used for the conversion, these having been shown to possess improved catalytic activity and selectivity for the hydroconversion of the 1050.degree.F.+ materials of the heavy feeds and residua. Novel methods are described for the preparation of such catalysts, as well as for use of such catalysts. One of the catalysts, i.e.

Abstract: 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.

Abstract: An asphaltene-containing oil hydrodesulfurization process employing stages in series with an interstage flashing step. The second stage catalyst comprises Group VI and Group VIII metals together with a promoting amount of Group IV-B metal. The coke level on the second stage catalyst is reduced by intermittent increase and decrease of the hydrogen pressure in the second stage.

Abstract: 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.

Abstract: A process for upgrading a hydrocarbon fraction and for generating hydrogen in situ by contacting the hydrocarbon fraction with a dense-water-containing fluid at a temperature in the range of from about 600.degree. to about 900.degree.F. in the absence of externally supplied hydrogen and of pretreatment of the hydrocarbon fraction and in the presence of a catalyst system containing a sulfur- and nitrogen-resistant catalyst.

Abstract: A method of removing a catalyst-poisoning contaminant, such as arsenic or selenium, from a hydrocarbonaceous fluid, such as a synthetic crude, characterized by a multi-step process as follows. First, at least two guard beds are prepared from a plurality of particles of material that is either iron, cobalt, nickel, oxides, or sulfides of these metals or mixtures thereof. Next, the synthetic crude oil is admixed with hydrogen at a superatmospheric pressure of at least 500 pounds per square inch gauge (psig) and flowed past the particles serially through the guard beds, contacting the particles in the first bed at a temperature in the range of from about 300.degree. to about 550.degree.F and contacting the particles in the second and subsequent guard beds at a temperature greater than said first bed and greater than 550.degree. and up to about 850.degree.F. Some reduction in the concentration of the contaminant is effected in the first, low temperature guard bed.

Abstract: Heavy hydrocarbon feedstocks, such as atmospheric and vacuum residua, heavy crude oils and the like, are converted to predominantly liquid hydrocarbon products by contacting said feedstocks in the presence of hydrogen with a regenerable alkali metal carbonate molten medium containing a glass-forming oxide, such as boron oxide, at a temperature in the range of from above about the melting point of said molten medium to about 1000.degree.F. and at elevated pressures. Preferably, the regenerable molten medium comprises an oxide of boron in combination with a mixture of sodium and lithium carbonate or a mixture of sodium carbonate, potassium carbonate and lithium carbonate. The carbonaceous materials (coke) which are formed in the molten medium during the above-described conversion process are gasified by contacting said carbonaceous materials with a gaseous stream containing oxygen, steam, or carbon dioxide at temperatures of from above about the melting point of said medium to about 2000.degree.F.

Abstract: A process for removing metalliferous contaminants from a hydrocarbon feedstock is disclosed, comprising contacting the feedstock in the presence of hydrogen with a solid, said solid consisting essentially of an inert particulate solid having an average pore size in the range of from 1,000 to 10,000 A, preferably 5,000 to 7,000, and a surface area in the range of from 1 to 20 m.sup.2 /gram, preferably 2 to 10 m.sup.2 /gram.

Abstract: A hydrocarbon oil, particularly a heavy hydrocarbon oil, containing vanadium, nickel, sulfur and asphaltenes is brought into contact with red mud at an elevated temperature in the presence of hydrogen. The treatment removes vanadium, nickel and asphaltenes from oil in high yields.

Abstract: A multiple stage hydrodesulfurization process is described for the catalytic hydrodesulfurization and hydrodemetallization of a residual petroleum oil boiling above the gasoline range to prepare a zeolite riser cracking feed. The product of the hydrodesulfurization section comprises essentially material boiling above the gasoline range and comprises little material boiling within the gasoline range in order to preserve the feed for subsequent cracking to gasoline without added hydrogen. The hydrodesulfurization-demetallization section comprises an initial stage involving relatively high hydrogen pressure in the presence of a catalyst comprising a relatively low proportion of catalytically active hydrogenation metals. The process employs a final stage in series employing a relatively lower hydrogen pressure and a catalyst comprising a relatively higher proportion of hydrogenation metals.

Abstract: A method for removing a contaminant comprising at least one of arsenic and selenium from a synthetic crude oil or fraction thereof characterized by mixing with the synthetic crude oil feed (1) particles of a material that is either iron, cobalt, nickel, oxides or sulfides of these metals, or a mixture thereof, and (2) hydrogen, and heating the mixture in a reaction zone to deposit said contaminant(s) on said particles. A liquid product stream comprising the synthetic crude oil without the contaminant(s) is recovered, leaving a thickened slurry. All or a portion of the thickened slurry can be withdrawn from the process and all or a part of the slurry can be mixed with fresh synthetic feed. Also disclosed are specific and preferred process details.