Exxon Research and Engineering Company

Glen P Hamner

Carl W Hudson

William F Arey, Jr

Willard H Sawyer

Ian A Cody

Roby Bearden, Jr

Donald T Eadie

William J Mattox

John M MacDonald

Alexis Voorhies, Jr

A method is described for rendering total liquid product hydroisomerates daylight stable and improving their oxidation stability, which method involves treating the hydroisomerate total liquid product with a Group VIII metal on refractory metal oxide catalyst or Group VIII metal on halogenated refractory metal oxide catalyst under mild conditions, which conditions are a temperature in the range of 170.degree. to 270.degree. C., a pressure in the range of 300 to 1500 psi H.sub.2, 0.25 to 10 v/v/hr and 500 to 10,000 SCF/B,H.sub.2.

Method for stabilizing hydroisomerates

A novel zeolite hydrocracking catalyst which contains NH.sub.4.sup.+ sites, at ambient temperatures, and surface sites constituted of a chemisorbed silica-containing species, and process for producing said catalyst. The process for preparation of the catalyst includes a series of steps: an initial step wherein an acid zeolite, or acid zeolite hydrocracking catalyst, is treated with an agent, e.g., a nitrogen-containing compound, suitably ammonia, to convert the H.sup.+ sites throughout said zeolite framework to NH.sub.4.sup.+ sites, and a subsequent post treatment of said NH.sub.4.sup.+ zeolite with an organosilane to silylate, modify and form on the surface of said zeolite a chemisorbed silica species, e.g., --O--Si(CH.sub.3).sub.3. The surface silylated catalyst is useful for the production of high octane gasoline. When employed at elevated temperatures in a hydrocracking operation the catalyst will evolve ammonia and convert to a surface silylated H.sup.+ zeolite catalyst to produce a high octane gasoline, at low hydrogen consumption.

Surface silylated zeolite cataysts, and processes for the preparation,

A process for the conversion of a feed rich in fused two-ring aromatic and fused two-ring hydroaromatic hydrocarbons, notably light cat cycle oil, furnance oils, coal liquids, tar sands liquids, shale oil liquids, and the like to high density jet fuels. Sulfur or nitrogen, or both are removed from said feed and a hydrodesulfurized/hydrodenitrogenated liquid product separated therefrom is hydrotreated in a second stage over a highly active fluorided Group VIII metal-on-alumina catalyst at conditions sufficient to selectively hydrogenate and saturate the fused two-ring aromatics and/or partially saturated fused two-ring hydroaromatics at high selectivity to naphthenes without any significant conversion thereof to lower molecular weight hydrocarbons. High density jet fuels having an API gravity ranging from about 25 to about 35, with a total aromatic content well below about 50 percent, preferably 5 percent to about 30 percent, are produced.

Process for the production of high density jet fuel from fused

A process for producing a pumpable syncrude from a Fischer-Tropsch wax by fractionating the wax into relatively low boiling fraction containing oxygenate compounds and a relatively high boiling fraction which is substantially free of oxygenate compounds and thereafter isomerizing/hydrocracking the low boiling fraction in the presence of hydrogen and a fluorided Group VIII metal-on-alumina catalyst. The preferred Group VIII metal is platinum. The pumpable syncrude is thereafter fractionated to produce a low boiling fraction which is thereafter isomerized/hydrocracked in the presence of hydrogen and a fluorided Group VIII metal-on-alumina catalyst to produce upgraded middle distillate fuel products. The preferred catalyst for middle distillate production is a fluorided platinum-on-alumina catalyst where a major portion of the fluoride within the catalyst is present as aluminum fluoride hydroxide hydrate.

Process for the hydroisomerization and hydrocracking of Fisher-Tropsch

A process for improving the color and oxidation stability of feed characterized as an admixture of liquid hydrocarbon compounds, inclusive of fused multi-ring aromatic and hydroaromatic hydrocarbons. This feed, which boils within a range of from about 224.degree. C. to about 538.degree. C. and contains moderate to high concentrations of organic sulfur and organic nitrogen compounds, is (1) hydrotreated over a hydrotreating catalyst at hydrotreating conditions, or (2) hydrotreated over a hydrotreating catalyst at hydrotreating conditions and the high boiling product therefrom hydrocracked over a hydrocracking catalyst at hydrocracking conditions, to obtain a low sulfur, low nitrogen product which is contacted as a feed in the presence of hydrogen, over a catalyst comprised of elemental iron and one or more alkali or alkaline-earth metals components at hydrogen partial pressure and temperature sufficient to improve product color, or stablize the product against light and oxygen degradation, or both.

Process for improving the color and oxidation stability of hydrocarbon

A process for the conversion of fused two-ring aromatic and fused two-ring hydroaromatic hydrocarbons into lower boiling aromatics, particularly alkylbenzenes of higher octane values. Such feeds are contacted in the presence of hydrogen over an iron catalyst at temperature sufficient to selectively hydrogenate and hydrocrack said fused two-ring aromatic hydrocarbon compound, or fused two-ring hydroaromatic hydrocarbon compounds, or both, to produce lower molecular weight, higher octane components suitable for direct blending with gasoline.

Process for improving octane by the conversion of fused multi-ring

A process for hydrocracking a hydrocarbon feedstock having a propensity to form polynuclear aromatic hydrocarbon compounds to suppress fouling the processing unit. The hydrocracking method includes contacting the hydrocarbon feedstock with a crystalline zeolite hydrocracking catalyst, contacting at least a portion of the resulting unconverted hydrocarbon oil containing polynuclear aromatic compounds with an iron catalyst in the presence of hydrogen to hydrogenate and hydrocrack the polynuclear aromatic hydrocarbon compounds, and recycling unconverted hydrocarbon oil having a reduced concentration of polynuclear aromatic compounds to the hydrocracking zone.

Hydrocracking process

A process wherein a feed comprising an admixture of liquid hydrocarbon compounds which includes a polynuclear aromatic hydrocarbon compound, or compounds (PNA's) is contacted in the presence of hydrogen over an iron catalyst at temperature sufficient to selectively hydrogenate and hydrocrack, or destroy the PNA's of the admixture without excessively hydrogenating and hydrocracking the non-PNA's of said feed. The process is particularly applicable for the removal of PNA's from reformates, processed naphthas, and other hydroprocessed streams or the like to achieve a lower and more favorable distribution of PNA's in a motor gasoline pool, and further to remove PNA's from prime fuels and heavier hydrocarbon mixtures.

Process for the removal of polynuclear aromatic hydrocarbon compounds

A process for the production of jet fuels, diesel fuels, multi-purpose fuels meeting the specifications for both high grade jet fuels and diesel fuels, and high quality blending components useful for the production of such fuels; and the compositions produced thereby. In accordance with the process, a multi-reactor system, inclusive of a first reactor and a second reactor are connected through a first distillation column which separates the product of the first reactor into two or more fractions to provide a heavy feed fraction which is charged to the second reactor, wherein the heavy feed is hydroselectively cracked. The product from the second reactor is fractionated to produce high quality jet and diesel fuels, multi-purpose jet and diesel fuels, or provide a major blending component for the production of such fuels, or fuel components.

Production of jet and diesel fuels

A catalyst support is prepared by grinding a calcined alumina to a powder, compacting the powder at an elevated pressure, recracking the compressed powder to a predetermined size particle and acid extracting the particle. The support can be composited with catalytic components such as hydrogenation components and/or zeolites and used in a variety of hydrocarbon treating processes, such as hydrorefining, hydrodesulfurization, hydroconversion, reforming, and catalytic cracking.

Method of preparing an alumina catalyst support and catalyst comprising

A process for the production of low sulfur, low nitrogen fuels at low hydrogen consumption by splitting a feed into two components, a high boiling component, suitably a 1050.degree. F.+ fraction, and a low boiling component, suitably a 1050.degree. F.- fraction, and processing the two different components over two different types of catalysts, at different severities. Suitably, on the one hand, the high boiling component is treated over a large pore metal hydrogenation catalyst at severity sufficient to convert at least 30 percent, preferably at least 50 percent of the feed, based on the weight of the feed, to a 1050.degree. F.- product. The 1050.degree. F.- product from the conversion over the large pore metal hydrogenation catalyst is then blended with the low boiling component split from the original feed, and the blended low boiling material is then treated at low severity over a small pore metal hydrogenation catalyst to hydrodesulfurize and hydrodenitrogenate said low boiling components. The product of the hydrodesulfurization, hydrodenitrogenation reaction constitutes a suitable feed for hydrocracking, or for use as a catalytic cracker feed.

Process for the hydroconversion and hydrodesulfurization of heavy feeds

A hydrodesulfurization process (and catalyst) wherein a sulfur-containing hydrocarbon feed is contacted, in the presence of hydrogen, with a catalyst having greater than 50 percent of its total pore volume of absolute diameter ranging from about 70A to about 160A. Preferably, the total pore volume of the catalyst contains greater than 70 percent of its total pore volume within the 70A to 160A pore diameter range, and more preferably greater than 90 percent of its total pore volume is within the 70A to 160A pore diameter range, with pore diameters below 70A and above 160A being minimized. The pore volume of such catalysts range between about 0.3 cc/g and 1.0 cc/g (B.E.T.), and preferably from about 0.4 cc/g to about 0.8 cc/g. The surface area of such catalysts range between about 150 m.sup.2 /g and 450 m.sup.2 /g, preferably from about 200 m.sup.2 /g to about 400 m.sup.2 /g.

Hydrodesulfurization of hydrocarbon feed utilizing a silica stabilized

This invention relates to novel catalysts, of two distinct types, useful for the catalytic hydroconversion of the 1050.degree. F.+ hydrocarbon materials 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 selectively 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 the use of such catalysts. One of the catalysts, i.e., one having properties inclusive of a large number of pores in the 100-275A pore size diameter range, is particularly suitable as a first stage catalyst and the other, which has properties inclusive of a large number of pores in the 100-200A pore size diameter, is especially suitable as a second stage catalyst for use in processing the effluent of said first stage.

Heavy crude conversion catalyst

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., one having properties inclusive of a large number of pores in the 100-275A pore size diameter range, is particularly suitable as a first stage catalyst and the other, which has properties inclusive of a large number of pores in the 100-200A pore size diameter, is especially suitable as a second stage catalyst for use in processing the effluent of said first stage.

Process for preparing a heavy crude conversion catalyst

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., one having properties inclusive of a large number of pores in the 100-275A pore size diameter range, is particularly suitable as a first stage catalyst and the other, which has properties inclusive of a large number of pores in the 100-200A pore size diameter, is especially suitable as a second stage catalyst for use in processing the effluent of said first stage.

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Baton Rouge, LA, United States of America

Glen P Hamner