Abstract: Cyclic hydrotreating of resids with low pressure, short term on-stream periods yields desirable products.

Abstract: A method is disclosed for converting an asphalt-free heavy hydrocarbon oil to high V.I. low pour point lube base stock and naphtha. The heavy oil is first catalytically dewaxed with a catalyst such as Ni-ZSM-5 and the dewaxed oil is then hydrocracked, or hydroconverted with a large pore zeolite catalyst such as dealuminized Y or ZSM-20 associated with palladium. The V.I. is controlled by the severity of the hydroconversion step.

Abstract: A method of denitrogenating viscous oils containing a relatively high content of nitrogenous compounds and of disposing of a resulting high nitrogen content oil stream, characterized by forming a raw oil stream and a first viscous bottoms stream that would not be operably pumpable to a partial oxidation unit without the inclusion of viscosity lowering constituents; extracting the nitrogenous compounds from the raw oil stream with an operable acid solvent to produce a raffinate oil of low nitrogen content oil and an extract stream of low viscosity, high nitrogen content oil; recovering the acid solvent from the extract stream, simultaneously producing a small volume stream of low viscosity, high nitrogen content oil; admixing the low viscosity high nitrogen content oil with the high viscosity bottoms stream to provide a pumpable mixed stream; sending the mixed stream to a partial oxidation unit to produce hydrogen; employing the produced hydrogen for hydrogenation of the raffinate oil at mild conditions; and r

Abstract: A mixture of heavy hydrocarbons, hydrogen and fresh catalyst comprising metals from the groups Vb, VIb, VIIb or VIII is passed first in a furnace for a limited heating time and then in a reactor where recycled catalyst is also added; the recycled catalyst is used in the form of a suspension recovered by fractionation of the reaction product.

Abstract: A lube oil feedstock is subjected to hydrotreating in the presence of hydrogen and a fluorine-promoted catalyst comprising nickel and molybdenum on a support wherein the nickel and fluorine are derived from an ammoniacal solution of nickel fluoride. The catalyst can be prepared by contacting the support with an alkaline impregnating solution consisting essentially of NH.sub.4.sup.+, Ni.sup.++, MO.sup.+VI and F.sup.-, said Ni.sup.++ and F.sup.- being supplied from nickel fluoride, in a single step employing the incipient wetness technique. The impregnated support is thereafter heated to drive off the alkaline component of the solution and thereby deposit the fluorine, nickel and molybdenum on the support.

Abstract: A method is described for the preparation of chalcogenides of ruthenium, rhodium, osmium and iridium transition metals of the Periodic Table of the Elements which comprises mixing in the absence of an aqueous solvent a Group VIII transition metal salt with a source of chalcogenide, said chalcogenide being selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, yielding a precipitate of the formula MX.sub.y wherein M is selected from the group consisting of ruthenium, rhodium, osmium and iridium, X is sulfur, selenium, tellurium and mixtures thereof and y is a number ranging from about 0.1 to about 3, preferably 0.1 to about 2.5. By the practice of the nonaqueous synthesis technique, Group VIII chalcogenides are prepared which are finely divided, have a high surface area, small particle size and small crystallite size which are also free of excess sulfur, water and/or hydrolysis products.

Abstract: Oxygen compounds are removed, e.g., by solvent extraction, from a shale oil prior to its hydrogenation. As a result, the amount of hydrogen consumed during subsequent hydrogenation to achieve a given level of nitrogen for the shale oil is less than that which would occur if the oxygen compounds were not removed from the shale oil. Removal of the nitrogen is necessary to avoid adverse effects on subsequent shale oil processing steps such as catalytic cracking.

Abstract: A method is disclosed for reducing the nitrogen content of shale oil using mild hydrogenation followed by liquid sulfur dioxide extraction of the hydrogenated shale oil. The mild hydrogenation is effective for increasing the fraction of shale oil that is insoluble in the liquid sulfur dioxide. The mild hydrogenation is sufficient for saturating unsaturated compounds present in the shale oil to the substantial exclusion of adding hydrogen to the nitrogen of the nitrogen-containing compounds. Following hydrogenation of the shale oil, it is extracted with liquid sulfur dioxide at a temperature from about 14.degree. F. to about 60.degree. F. forming two fractions, a liquid sulfur dioxide insoluble fraction containing a relatively low nitrogen content and a liquid sulfur dioxide soluble fraction containing a relatively high nitrogen content. The liquid sulfur dioxide fraction is separated from the insoluble shale oil fraction. The liquid sulfur dioxide can be recovered for recycling to another extraction step.

Abstract: Desulfurization, denitrogenation, deoxygenation and CCR reduction of highly aromatic petroleum and coal derived liquids are conducted with hydrogen and with a refractory base catalyst incorporating at least one Group VIA metal and at least one Group VIII metal. The catalyst has a surface area of between about 100 and 300 m.sup.2 /g and a total pore volume of between about 0.3 and 1.

Abstract: A method of denitrogenating an oil containing a relatively high concentration of nitrogenous compounds characterized by, first, extracting the nitrogenous compounds from the oil with an operable acid solvent to produce a raffinate of low nitrogen content oil and a bottoms of high nitrogen content oil; then recovering the acid solvent from the bottoms, simultaneously producing a small volumeteric flow rate stream of oil containing high content of nitrogenous compounds; depending upon the volumeteric rate of the high nitrogen content oil stream and upon demand, sending it to a hydrogen producing plant for supplying hydrogen for hydrogenation; and recycling the acid solvent. Preferred acid solvents comprise phosphoric acid, formic acid or the monoammonium salt of phosphoric acid. The recovery of the solvent may be by neutralization or by distillation.

Abstract: A hydrotreating catalyst comprises molybdenum, nickel, and phosphorus components supported on gamma alumina precalcined at a temperature of at least 1375.degree. F.

Abstract: Catalysts consisting of a base support having a strongly adherent outer coating of an active catalytic material have been found to give superior results in known hydrogen processing reactions wherein sulfur, nitrogen and the metal content of a hydrogen feedstock are reduced.

Abstract: An improved method for preparing a hydrocarbon hydrotreating catalyst containing a major amount of alumina and a minor amount of at least one Group VIB or Group VIII metal comprising:(1) contacting an aqueous mixture of hydrous alumina with at least one phosphorus-containing compound in an amount sufficient to increase the hydrocarbon hydrotreating activity of the final catalyst and forming a phosphorus-containing hydrous alumina;(2) calcining the phosphorus-containing hydrous alumina and forming a calcined alumina;(3) contacting the calcined alumina with at least one metal-containing compound and forming a metal-containing material, the metal being selected from the group consisting of Group VIB metal, Group VIII metal and mixtures thereof; and(4) calcining the metal-containing material and forming a catalyst having increased hydrocarbon hydrotreating activity.Improved hydrocarbon hydrotreating processes and catalysts are also disclosed.

Abstract: A process for upgrading crude shale oil containing nitrogen which comprises contacting crude shale oil in a hydrogenation zone with hydrogen in the presence of a hydrogenation catalyst to remove a selected portion of the nitrogen and then contacting the resulting product with an ion exchange resin to obtain a shale oil of substantially lower nitrogen content.

Abstract: Whole crude shale oil is contacted with a suitable catalyst, e.g., cobalt molybdate on alumina, and hydrogen within a temperature range of about 600.degree. F.-850.degree. F. and a pressure range of about 200 psig-5000 psig until a substantial amount of nitrogen compounds contained in the oil are converted to at least basic nitrogen compounds. Hydrogen consumption is high, about 700-3000 SCF/Bbl of fresh oil charged. The contacted oil, containing basic nitrogen compounds in the oil, formed by the hydrogen contacting, is reacted with dry HCl and resulting reaction product is removed from the oil. The reaction product can be converted into hydrogen and HCl for use in the process. As a result of the severe hydrogen contacting and the HCl treatment, a major amount of the whole crude shale oil can be converted to jet fuel.

Abstract: A process for hydrotreating a hydrocarbon stream such as petroleum distillate and similar hydrocarbon materials by contacting said stream with hydrogen and a catalyst comprising a porous refractory inorganic oxide support and deposited thereon hydrogenation components comprising chromium, molybdenum and at least one Group VIII metal. This process enables improved removal of nitrogen and sulfur, particularly from gas oils.

Abstract: Demetallized oils such as deasphalted or catalytically demetallized residua are upgraded as catalytic cracking feedstock by contact with a denitrogenation catalyst having at least 80 percent of its pore volume in pores less than 50 Angstroms in diameter.

Abstract: An improved method for preparing a hydrocarbon hydrotreating catalyst containing a major amount of alumina and a minor amount of at least one Group VIB or Group VIII metal comprising:(1) contacting an aqueous mixture of hydrous alumina with at least one phosphorus-containing compound in an amount sufficient to increase the hydrocarbon hydrotreating activity of the final catalyst and forming a phosphorus-containing hydrous alumina;(2) calcining the phosphorus-containing hydrous alumina and forming a calcined alumina;(3) contacting the calcined alumina with at least one metal-containing compound and forming a metal-containing material, the metal being selected from the group consisting of Group VIB metal, Group VIII metal and mixtures thereof; and(4) calcining the metal-containing material and forming a catalyst having increased hydrocarbon hydrotreating activity.Improved hydrocarbon hydrotreating processes and catalysts are also disclosed.

Abstract: In the hydroprocessing of blends of solvent refined coal and recycle solvent, small pore hydrotreating catalysts cause separation of a solid phase from treating blends containing high concentration of solvent refined coal.

Abstract: A non-stoichiometric vanadium sulfide catalyst utilized in a process for hydrorefining a hydrocarbon feed stock is prepared by (1) contacting vanadium oxide with ammonium sulfide to form an ammonium salt of vanadium sulfide and (2) the salt is neutralized with an acid in a non-oxidative atmosphere to form the vanadium sulfide catalyst. The acid used in the neutralizing step may be sulfuric acid or carbonic acid and the non-oxidative atmosphere may be hydrogen or nitrogen.

Abstract: A non-stoichiometric vanadium sulfide catalyst utilized in a hydrocarbon hydrorefining process is prepared by contacting a sulfur-bearing gas, such as H.sub.2 S, into an alkali metal hydroxide solution containing vanadium oxide to form a soluble alkali metal vanadium sulfide. The vanadium sulfide is precipitated from the soluble alkali metal vanadium sulfide with an acid, such as sulfuric acid or carbonic acid.

Abstract: A heavy hydrocarbon stream containing metals, asphaltenes, nitrogen compounds, and sulfur compounds is (a) contacted with hydrogen and a hydrotreating catalyst containing molybdenum and chromium, either as metals, as oxides, as sulfides, or mixtures thereof, deposed on a large-pore, catalytically active alumina to reduce the metals content in said stream, to convert the asphaltenes, nitrogen compounds, and sulphur compounds in said stream, the catalyst has a pore volume within the range of about 0.4 cc/gm to about 0.8 cc/gm, a surface area within the range of about 150 m.sup.2 /gm to about 300 m.sup.2 /gm, and an average pore diameter within the range of about 100 A (10 nm) to about 200 A (20 nm); and (b) at least a portion of the hydrotreated stream is cracked with a cracking catalyst to produce gasoline and distillates in improved yields. The catalyst in step (a) may also contain cobalt.

Abstract: The process comprises contacting a heavy hydrocarbon stream containing metals and asphaltenes to reduce the contents of nitrogen compounds, sulfur compounds, metals and asphaltenes in the hydrocarbon stream under suitable conditions and in the presence of hydrogen with a catalyst comprising a hydrogenating component consisting essentially of molybdenum and chromium, their oxides, their sulfides, or mixtures thereof on a large-pore, catalytically active alumina. The catalyst has a pore volume within the range of about 0.4 cc/gm to about 0.8 cc/gm, a surface area within the range of about 150 m.sup.2 /gm to about 300 m.sup.2 /gm, and an average pore diameter within the range of about 100 A to about 200 A.

Abstract: Highly active hydrofining catalysts are prepared by ion exchanging a silica-alumina hydrogel with an ammoniacal solution of a cobalt and/or nickel compound, and thereafter compositing the undried product with an alumina hydrogel and a molybdenum component, followed by drying and calcining. The resulting catalysts are particularly active for the denitrogenation of mineral oil feedstocks.

Abstract: The invention provides a titania-zirconia or a titania-zirconia-alumina catalyst base containing a system of metals, metal oxides or metal sulfides from Groups VIB, VIIB and VIII of the Periodic Table. Such catalyst are useful in the hydrodesulfurization and denitrogenation of hydrocarbon feed stocks and the saturation of aromatics contained therein.

Abstract: A method for reducing the nitrogen content of a feed stream derived from oil shale and/or coal comprising hydrodenitrogenating the feed stream, subjecting the hydrodenitrogenated feed stream to first flashing conditions to remove hydrogen, hydrogen sulfide, and ammonia, dehydrogenating the remainder of the feed stream, and subjecting the dehydrogenated feed stream to second flashing conditions to separate hydrogen from the process product.

Abstract: The process comprises contacting a heavy hydrocarbon stream under suitable conditions and in the presence of hydrogen with a catalyst comprising a hydrogenating component selected from the group consisting of (1) molybdenum, chromium, and a small amount of cobalt, (2) their oxides, (3) their sulfides, and (4) mixtures thereof deposed on a large-pore, catalytically active alumina. The molybdenum is present in an amount within the range of about 5 wt.% to about 15 wt.%, calculated as MoO.sub.3 and based upon total catalyst weight, the chromium is present in an amount within the range of about 5 wt.% to about 20 wt.%, calculated as Cr.sub.2 O.sub.3 and based upon the total catalyst weight, and the cobalt is present in an amount within the range of about 0.1 wt.% to about 5 wt.%, calculated as CoO and based upon the total catalyst weight. The catalyst possesses a pore volume within the range of about 0.4 cc/gm to about 0.8 cc/gm, a surface area within the range of about 150 m.sup.2 /gm to about 300 m.sup.

Abstract: Novel catalyst support, catalyst and process for hydrodemetalizing sulfur and metal-contaminated hydrocarbon oils such as residual petroleum fractions or whole crudes. The process may be used to prepare feedstocks suitable for fluid catalytic cracking. The novel catalyst support is alumina modified with rare earth oxide.

Abstract: The present invention relates to an improved method of catalyst presulfiding, wherein the catalyst is treated with elemental sulfur. The use of elemental sulfur as a catalyst presulfiding agent is a means of rapidly and reproducibly attaining a highly active catalyst.

Abstract: Middle distillate oil is produced with a minimum production of lighter hydrocarbons by (1) contacting hydrogen gas and a heavy distillate oil containing nitrogenous hydrocarbons with a catalyst in a first reaction zone under selected conditions, and (2) contacting hydrogen gas and at least a portion of the resulting effluent from the first zone with a catalyst in a second reaction zone under selected conditions. In each zone the catalyst is a composite of an amorphous silica-alumina carrier and a hydrogenation component wherein the silica and hydrogenation component are highly dispersed.

Abstract: A method for removing nitrogen from an essentially liquid syncrude feed obtained from at least one of oil shale, tar sands, and coal wherein the syncrude is mixed with an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, and combinations thereof, settling to form a first phase composed of syncrude low in nitrogen and a second phase composed of acid and syncrude high in nitrogen, separating the two phases, and catalytically hydrotreating the high nitrogen phase to reduce its nitrogen content.

Abstract: Hydrocarbonaceous material produced from pyrolysis of coal and shale is subjected to hydrogenation and fines removal by first passing it through an ebullating bed reactor in which the hydrocarbonaceous material is partially hydrogenated and partially vaporized. The vapor is then separated and further hydrogenated while the fines in the liquid portion are concentrated and removed as a slurry. The remaining liquid is vaporized, either by recycling it through the ebullating bed reactor or by flash evaporation, to rid it completely of fines. The thus vaporized remaining liquid is also subjected to further hydrogenation.

Abstract: Improved amphora aggregates having a substantially spherical shape, a void center and two cavities 180.degree. apart in the external surface communicating to the void center are useful in diffusion-limited reactions and/or reactions in which heat transfer is critical. Especially preferred is use of the amphora aggregates in the hydrotreating of light hydrocarbon fractions, catalytic reforming, and fixed-bed alkylation processes.

Abstract: Liquid products from retorting oil shale are upgraded to a total liquid suited to pipeline transport and containing increased amounts of the premium products gasoline through distillate fuel by hydrotreating to convert sulfur, oxygen, nitrogen and metal constituents and cascading the hydrotreater effluent through a hydrocracking reactor containing a catalyst which is characterized by a crystalline zeolite having a silica/alumina ratio greater than 12 and a constraint index of 1 to 12, for example zeolite ZSM-5.

Abstract: Highly active, acidic sulfactive metal hydrogenation catalysts comprising Mo and/or W plus Ni and/or Co are prepared by methods comprising as the essential novel feature impregnating gamma alumina particles with an aqueous solution having dissolved therein one or more fluosilicates of cobalt and/or nickel, followed by drying and calcining. The resulting compositions contain uniformly distributed fluorine and SiO.sub.2 as active acidic promoters, intimately associated with the sulfactive metal components.

Abstract: This invention relates to a catalyst for hydrotreatment of hydrocarbons comprising one or more of metals selected from the group consisting of transition metals and metals of group IIb of the periodic table supported on sepiolite. More particularly it relates to a catalyst effective in the selective demetallization treatment of hydrocarbons.

Abstract: A method is provided for avoiding feed-transfer-line plugging by a deposit comprising arsenic in hydroprocessing an oil containing an arsenic contaminant. In the method, a mixture of hydrogen gas and the oil is formed in situ in a bed of porous particulate contact material.

Abstract: Deposition of ammonium chloride from gaseous streams is prevented by maintaining the temperature of the gaseous stream above the deposition temperature for ammonium chloride at operating pressure. The invention is particularly useful in hydrocarbon hydrogen treating processes in which hydrogen recycle streams containing ammonium chloride or ammonium chloride-forming constituents must be recompressed before recycle to the hydrogen treating process.

Abstract: Desulfurization and hydrorefining of an asphaltene-containing black oil with hydrogen in contact with a colloidally dispersed vanadium catalyst in admixture with 2 weight percent to 30 weight percent water biased on the weight of the oil.

Abstract: A catalyst comprising (1) a subgroup of a certain class of nickel and/or cobalt-substituted semicrystalline aluminosilicates which are synthetic and which are predominantly ordered in two directions (laminar clay-like materials); (2) tungsten in the form of its oxide and/or sulfide; and (3) a crystalline zeolite which has an alpha value of at least 20, which is in particulate form, and which is dispersed through the layered aluminosilicate; and processes using this catalyst.

Abstract: Hydrofining of suitable sulfur and/or nitrogen containing organic feedstock is provided wherein such feedstock is subjected to hydrofining conditions in the presence of a catalytic amount of a solid containing, a synthetic amorphous solid prepared by hydrolyzing and polymerizing in the presence of water a silane having the formula R(Si)X.sub.3, wherein R is a nonhydrolyzable organic group, X is a hydrolyzable group and (Si) is selected from the group consisting of --Si-- and --Si(R).sub.2 --O --Si--, and calcining the polymerized product, said silane being admixed with a second compound, R'.sub.n MY.sub.m, wherein R' is selected from the group consisting of the same groups as R, Y is selected from the group consisting of the same groups as X and oxygen, M is at least one member selected from the group consisting of the elements of Groups IIIA, VIB, and VIII of the Periodic Table, m is any number greater than 0 and up to 8 and n is from 0 to any number less than 8.

Abstract: A method for processing shale oil to remove both nitrogen and impurities such as arsenic and/or selenium while minimizing such removal costs which comprises fractionating the shale oil feet to form a first naphtha cut which essentially boils at or below 350.degree. F and a gas oil cut which essentially boils above 350.degree. F, hydrotreating the first naphtha cut, separately removing a substantial amount of said impurity from the gas oil cut and then hydrotreating the gas oil cut. Thereafter the hydrotreated gas oil cut is fractionated to form a second naphtha cut which essentially boils above 380.degree. F and at or below 450.degree. F and has a high nitrogen content, and hydrotreating the second naphtha cut to reduce the nitrogen content.

Abstract: A process for hydrotreating petroleum fractions wherein a hydrogen-rich gas stream passed through the reaction zone on a once-through basis is obtained by passing a hydrogen-containing feed gas stream through an absorber which removes light paraffins. The gas separated from the reaction zone effluent by partial condensation is passed into a stripper as the stripping media used to remove these same light paraffins from the liquid used in the absorber.

Abstract: The invention provides a titania-zirconia or a titania-zirconia-alumina catalyst base containing a system of metals, metal oxides or metal sulfides from Groups VIB and VIII of the Periodic Table. Such catalysts are useful in the hydrodesulfurization and denitrogenation of hydrocarbon feed stocks and the saturation of aromatics contained therein.

Abstract: Carbonates and/or hydroxides of one or more of the Group VIII metals, cobalt and nickel, are reacted with molybdic acid in aqueous suspension to form a slurry of crystalline cobalt and/or nickel molybdate, which slurry is then reacted with gelatinous boehmite alumina, then extruded, dried and calcined. The method eliminates the use of ammoniacal solutions, washing and/or heating steps to remove undesired anions or cations, and requires but a single drying and calcination. The resulting catalysts are found to be very active for the desulfurization and denitrogenation of mineral oils.

Abstract: A carbonaceous feedstock, obtained from either a petroleum or coal source, is hydrodenitrified by the use of a supported sulfided catalyst containing nickel, molybdenum and iron, with the molybdenum being present in an amount of from about 10% to about 20%, by weight, calculated as MoO.sub.3, based on total weight of catalyst, the iron to molybdenum atomic ratio being from about 0.05 to about 0.5, and the nickel to molybdenum atomic ratio being from about 0.2 to about 0.6.The process effectively denitrifies high nitrogen content feeds.

Abstract: A particle pack composition comprising alumina having improved attrition resistance is produced by dry steaming a dough-like mixture of water, a hydrocolloid-forming compound and particles comprising alumina prior to calcining the mixture.

Abstract: A catalyst composition, a method for its preparation and a hydrotreating process using same. The catalyst comprises a rigidly interconnected pack of irregularly shaped particles having an average diameter below 0.15 mm. Among the particles and throughout the pack are access channels comprising interconnected macropores having diameters in the 0.1 to 15 micron range which contribute at least 5 percent of the pore volume. The particles comprise materials selected from the group consisting of at least one refractory oxide component and one hydrogenation component. For each 100 parts of the oxide component the composition contains, in parts by weight, an amount of the hydrogenating component, calculated as metal, in the range from 0.1 to 50 parts.

Abstract: A process for hydrotreating (hydroprocessing) hydrocarbons and mixtures of hydrocarbons utilizing a catalytic composite comprising a combination of a nickel component and a tungsten component with a silica-alumina carrier material wherein said carrier material is co-gelled silica-alumina consisting of from about 43 percent to about 57 percent by weight of alumina and from about 57 percent to 43 percent by weight silica and wherein said components are present in amounts sufficient to result in the composite containing, on an elemental basis, about 2 to about 10 percent by weight of the nickel component and about 8 to about 20 percent by weight of the tungsten component, in which process there is effected a chemical consumption of hydrogen. Key features of the subject composite are the criticality of the alumina content of the carrier material and the facility of using a co-gelled silica-alumina carrier material. The principal utility of the subject composite is in the hydrocracking of hydrocarbons.

Abstract: There is disclosed a hydrotreating process for petroleum distillate which comprises contacting the distillate with catalyst particles of special shape characteristics in the presence of hydrogen at elevated temperature and pressure.