US3891539A - Hydrocracking process for converting heavy hydrocarbon into low sulfur gasoline - Google Patents

Hydrocracking process for converting heavy hydrocarbon into low sulfur gasoline Download PDF

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US3891539A
US3891539A US445365A US44536574A US3891539A US 3891539 A US3891539 A US 3891539A US 445365 A US445365 A US 445365A US 44536574 A US44536574 A US 44536574A US 3891539 A US3891539 A US 3891539A
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oil
fraction
hydrocracking
gas
gasoline
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Gerald Verdell Nelson
Glenn Cooper Wray
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Texaco Inc
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Texaco Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S208/00—Mineral oils: processes and products
    • Y10S208/02—Molecular sieve

Definitions

  • ABSTRACT A hydrocracking process wherein heavy hydrocarbon oils having from about 10 to 50 percent boiling above 1,000F. and containing appreciable amounts of su1- fur. nitrogen, and metal-containing compounds as well as asphaltenes are converted into a minor fraction of low sulfur residual fuel oil and a major fraction of low sulfur gasoline.
  • the process comprises hydrocracking the heavy oil with molecular hydrogen. at a temperature of about 700-850F. in the presence of a sulfur and nitrogen resistant hydrocracking catalyst comprising a hydrogenating component supported upon an amorphous inorganic oxide cracking base to convert the heavy hydrocarbon oil into a gas-oil fraction and a low sulfur residual fraction; separating the gas-oil fraction from the residual fraction; hydrocracking the gasoil fraction with molecular hydrogen.
  • a sulfur and nitrogen resistant hydrocracking catalyst comprising a hydrogenation component supported upon a cation exchanged crystalline silica-alumina zeolitic molecular sieve cracking base to yield low sulfur. low nitrogen gasoline.
  • This invention relates to the hydrocracking of heavy hydrocarbon oils. Particularly, it relates to hydrocracking heavy hydrocarbon oils having from about 10 to 50 volume percent boiling above IOF. and containing appreciable amounts of sulfur, nitrogen, and metalcontaining compounds as well as asphaltenes and other coke forming hydrocarbons.
  • Such heavy hydrocarbon oils are converted into a minor fraction of heavy residual fuel oil and a major fraction of low sulfur gasoline.
  • Such gasoline product is suitable for further processing, such as catalytic reforming or the like, to upgrade the quality and octane number.
  • the process comprises a two-stage catalytic hydrocracking process wherein heavy oil charge is contacted with molecular hydrogen in a first reaction zone in the presence of a hydrocrack ing catalyst comprising a hydrogenation component selected from the group consisting of Group VI metals, Group VIII metals, their oxides, their sulfides, and combinations thereof supported upon an amorphous refractory oxide cracking base, at a temperature in the range of 700-850F., for conversion of from 50 to 90 volume percent of the heavy hydrocarbon oil into a sulfur and nitrogen containing gas-oil having very low metals content without any substantial production of gasoline; separating the effluent from the first hydrocracking zone into a gas-oil fraction and a residual fuel fraction; and hydrocracking the gas-oil fraction in a second hydrocracking zone with molecular hydrogen in the presence of a catalyst comprising a hydrogenation component selected from the group consisting of Group VI metals, Group VIII metals, their oxides, their sulfides, and combinations thereof supported upon
  • gas-oil fraction is meant to include hydrocarbon fractions derived from crude petroleum, shale oil and the like, or from a hydrocarbon conversion process such as hydrocracking; catalytic cracking, thermal cracking, coking, etc., which fraction boils within the range of from about 430F. to about 1000F.
  • gas-oil as used herein is meant to include the light, medium, and heavy gas-oils as those terms are commonly employed in the art.
  • gasoline is meant to include the hydrocarbon fraction boiling in the range of from about 55F. to 430F., or, as it is sometimes expressed, C /430F.”.
  • dry gas refers to a fraction comprising methane, ethane, and propane when such fraction is separated from normally liquid, higher boiling hydrocarbons.
  • Hydrocracking processes for the conversion of heavy hydrocarbon oils into lower boiling fractions are well known. Examples of such hydrocracking processes may be found in such sources as US. Pat. Nos. 3,640,817; 3,617,50l; 3,583,902; 3,562,144; 3,551,323; 3,540,997; 3,360,457; and 3,254,017.
  • hydrocracking processes it is recognized that when a heavy hydrocarbon oil with a substantial volume boiling above IOOOF., and containing substantial amounts of asphaltenes, sulfur, nitrogen, and metal-containing organic compounds, is treated in the presence ofa hydrocracking catalyst, such compounds act as catalyst poisons.
  • U.S. Pat. No. 3,254,017 describes a hydrocracking process wherein a heavy hydrocarbon oil is sequentially treated in two hydrocracking zones. In the first hydrocracking zone, the heavy hydrocarbon oil is partially hydrocracked to gas-oil and is partially desulfurized and denitrogenated with molecular hydrogen in the presence of a selected catalyst.
  • the catalyst selected for the first hydrocracking zone comprises a hydrogenation component selected from Group VI metals, Group VIII metals, their oxides, their sulfides and mixtures thereof supported upon an amorphous refractory oxide cracking base having large pore openings in the range of at least 20 up to 200 angstrom units and preferably larger, such base being selected from alumina, silica-alumina, zirconia, titania, etc.
  • a large pore, amorphous cracking base has a capacity for adsorbing or otherwise collecting substantial quantities of ash and metals such as vanadium, nickel, iron and copper without destroying the hydrocracking activity of such catalyst.
  • Effluent from such a first hydrocracking zone comprising a gasoil fraction and unconverted residual fraction
  • a second hydrocracking zone under conditions such that a substantial portion of the gas-oil fraction is hydrocracked into lower boiling fractions such as gasoline but with a limitation upon operating conditions such that not more than a strict upper limit of 30 volume percent of the unconverted residual fraction is hydrocracked into lower boiling fractions.
  • a second selected hydrocracking catalyst is employed in the second hydrocracking zone.
  • Such second catalyst comprises a hydrogenation component selected from Group V] metals, Group VIII metals, their oxides, their sulfides, and mixtures thereof, supported upon a cracking base comprising a cation exchanged crystalline silica-alumina zeolite containing cations selected from hydrogen, ammonia, divalent metals such as calcium, magnesium and zinc, and rare earth metals, and containing less than about 5 percent sodium.
  • a cracking base comprising a cation exchanged crystalline silica-alumina zeolite containing cations selected from hydrogen, ammonia, divalent metals such as calcium, magnesium and zinc, and rare earth metals, and containing less than about 5 percent sodium.
  • Such second selected catalyst has uniform pore openings in the limited range of 5-20 angstroms such that hydrocarbon molecules contained in the residual fraction will not enter the catalyst pores to be hydrocracked. By limiting the access of the residual fraction hydrocarbons, the
  • reaction conditions in the first reaction zone must be sufficiently severe to remove a substantial portion of the sulfur and nitrogen contained in the hydrocarbon oil charge. No account is taken, in US. Pat. No. 3,562,144, of the effect of metals and ash upon the activity of the catalyst in the first hydrocracking zone. Metals and ash deposited upon the catalyst cause increased production of coke, and under the severe reaction conditions of the first hydrocracking zone coke production is substantial, causing rapid catalyst deactivation.
  • a combined hydretreating-hydrocracking process for whole crude oil is disclosed in US. Pat. No. 3,6l7,50l.
  • whole crude oil is hydrotreated for removal of sulfur and nitrogen compounds in a hydrotreating zone; hydrotreating effluent is fractionated into light product fractions, a heavy gas oil fraction and, a low sulfur fuel oil fraction; and the heavy gas oil is hydrocracked into additional light products.
  • a very substantial portion of the gas-oil component of the crude oil can be converted to gasoline, however the residual fraction of the crude oil, boiling above lOF. remains substantially unconverted, and is recovered from the process as a low value fuel oil product.
  • cffluent from the first hydrocracking zone may be separated into a relatively low sulfur residual fraction and a sulfur and nitrogen containing gas-oil fraction.
  • Substantial amounts of metals are removed in the first hydrocracking zone, such that the gas-oil fraction contains only minor amounts of metals even though the residual fraction may still contain an appreciable concentration of metals. If the entire liquid effluent from a first hydrocracking zone is passed into a second hydrocracking zone, the metals, ash, coke, asphaltenes, etc. contained in the residual fraction will accumulate upon the second reaction zone catalyst thereby requiring increased temperatures to maintain the desired hydrocracking activity for the conversion of gas-oil.
  • the reaction temperature exceeds about 790F.
  • the desulfurization and denitrogenation activity of hydrocracking catalyst declines very rapidly, without a concomitant decline in the hydrocracking activity of such catalyst. Consequently, even though a relatively efficient conversion of heavy hydrocarbon oils into gasoline may be obtained by employing two hydrocracking zones in sequential alignment, the gasoline product from such a process may contain substantial amounts of sulfur and nitrogen compounds, particularly when the catalyst has been in service for a period such that the reaction temperature of the second hydrocracking zone has been increased to a temperature above about 790F. in order to maintain the hydrocracking activity of the second hydrocracking catalyst.
  • hydrocracking conditions wherein no more than percent of the hydrocarbon oil charge residual fraction boiling above l000F. is converted to gas-oil and wherein 5 percent or less hydrocracked gasoline is produced; and wherein the gas-oil fraction is hydrocracked in a second hydrocracking zone with molecular hydrogen at a temperature of from about 700-780F. in the presence of a sulfur and nitrogen resistant hydrocracking catalyst to yield low sulfur, low nitrogen content gasoline.
  • Catalyst selected for the first hydrocracking zone comprises a hydrogenation component selected from Group VI metals, Group VIII metals, their oxides, their sulfides, and mixtures thereof supported upon an amorphous inorganic oxide cracking base.
  • Such cracking base is selected such that it has pore openings of from at least about to 200 angstroms and preferably larger. so a substantial portion of metal contaminants which may be present in the heavy hydrocarbon oil charge, may be adsorbed within such cracking base without severely affecting the hydrocracking activity of the first hydrocracking catalyst.
  • a portion of the residual oil may be recirculated to the first reaction zone for conversion into additional gas-oil fraction.
  • the conversion of heavy hydrocarbon oil charge residual fraction boiling above IOOOF. into gas-oil fraction boiling below 1000F. should be limited to a maximum of about 90 volume percent, and preferably no more than 80 volume percent.
  • asphaltenes and other heavy hydrocarbon materials contained in the hydrocarbon oil charge tend to precipitate onto the first cracking catalyst, thereby preventing access of convertible hydrocarbons to the active catalytic sites.
  • hydrocracking severity in the first hydrocracking zone improves desulfurization of residual fuel oil, lengthens catalyst life, and reduces the rate of coke deposition upon the first zone hydrocracking catalyst.
  • any gasoline produced in the first hydrocracking zone will contain substantial amounts of undesirable nitrogen and sulfur compounds such that reduction of gasoline production from the first hydrocracking zone substantially improves the quality of gasoline recovered from this process.
  • Such second hydrocracking catalyst is comprised of a hydrogenation component selected from the Group V] metals, Group VIII metals, their oxides, their sulfides, and mixtures thereof, supported upon a refractory metal oxide cracking base.
  • the cracking base may be in the amorphous form, such as alumina, silica-alumina, zirconia, silica-zirconia, silica-titania, etc., or the cracking base may comprise a crystalline silica-alumina zeolite wherein the sodium cations have been exchanged for cations selected from hydrogen, ammonia, calcium, magnesium, zinc, etc.
  • the gas-oil fraction may be hydrocracked into gasoline and simultaneously desulfurized and denitrogenated. At temperatures above about 780F., the desulfurization and denitrogenation activity of the preferred second hydrocracking catalyst declines rapidly.
  • a heavy hydrocarbon oil containing sulfur, nitrogen, and metal compounds may be converted into gasoline which is low in sulfur and nitrogen content and which is essentially free of metal contaminants.
  • Such gasoline is suitable for further treatment, such as in a catalytic reforming unit, to improve the quality and octane number thereof.
  • Heavy hydrocarbon oil charge stocks within the contemplation of the present invention include those hydrocarbon oils comprising from [0 to 50 volume percent of a residual fraction boiling above 1,000F. and containing at least about I weight percent Conradson Carbon, from 0.1 to 8 percent sulfur, and from 100 to 1000 ppm or more nitrogen.
  • Examples of such heavy hydrocarbon oils include total crudes, atmospheric and vacuum residuum, shale oils, tar sand oils, petroleum residues, coal tar, heavy coker distillates, heavy catalytically cracked recycle stocks, etc.
  • Such hydrocarbon oils may contain substantial amounts, from 50 to 1000 ppm and more, metal compounds such as organometallic compounds of vanadium, nickel, iron, copper, etc.
  • Such heavy hydrocarbon oils may also contain substantial amounts of refractory hydrocarbons such as asphaltenes and other high molecular weight hydrocarbons which may lead to the deposition of coke upon the hydrocracking catalyst.
  • the hydrogen which is employed with such heavy hydrocarbon oils in the first hydrocracking zone and the gas-oil fraction in the second hydrocracking zone need not be I00 percent pure. Conveniently, hydrogen from the reaction zones is recirculated within the process to conserve the consumption of hydrogen, and only sufficient fresh hydrogen is vented from the process to maintain hydrogen purity in the range of about percent or higher. Sources of hydrogen commonly available within a refinery such as catalytic reformer hydrogen with a purity of about percent or higher are suitable as sources of makeup hydrogen for the process to replace the hydrogen consumed in the reactions and that which is vented.
  • a major portion of the heavy hydrocarbon charge is hydrocracked into a gas-oil fraction without substantial production of lighter hydrocarbons such as gasoline and dry gas.
  • An effective temperature range for this conversion is from about 700F. to about 850F.
  • the desired hydrogen partial pressure may be maintained by utilizing hydrogen to hydrocarbon ratios in the range of from about L000 to about 15,000 standard cubic feed per barrel and operating pressures of from about 500 to about 3,000 psig.
  • Liquid hourly space velocity expressed as volumes of oil per hour per volume of catalyst (Vo/Hr/Vc) of from about 0.1 to about l may be utilized.
  • LHSVs in the range of 0.3 to 5.0 are employed to obtain a relatively long reac tion period before the catalyst must be regenerated.
  • Hydrocracking catalysts which may be employed in the first hydrocracking zone comprise those hydrocracking catalysts which are sulfur and nitrogen resistant, and which can maintain hydrocracking activity in the presence of relatively large amounts of metal compounds such as are commonly found in heavy hydrocarbon oils.
  • a first hydrocracking catalyst comprises a hydrogenation component supported upon a refractory metal oxide cracking base.
  • the hydrogenation component may be selected from Group Vl metals, Group VIII metals, their oxides, their sulfides, and
  • the hydrogenation component comprises a Group Vl metal oxide or sulfide in combination with a Group VIII metal oxide or sulfide.
  • particularly preferred hydrogenation components include cobalt-molybdenum sulfide mixtures, nickel-cobalt-molybdenum sulfide mixtures, and nickel-molybdenum sulfide mixtures.
  • other combinations which may be effectively employed include nickel-cobalt mixtures, nickel oxide-cobalt oxide mixtures, nickel oxide-cobalt oxide-molybdenum oxide mixtures, and nickel cobalt-molybdenum mixtures.
  • a Group V] metal or its oxide or sulfide is employed as a hydrogenation component, it is preferable that such metal be present in an amount of from about 5.0 to about 25.0 weight percent of the total catalyst.
  • a Group VIII metal, or its oxide or sulfide is employed as the hydrogenation component, it is preferable that such metal be present in an amount from about 0.3 to about 8.0 weight percent of the total catalyst.
  • the Group V! metal be present in an amount from about 5.0 to about 25.0 weight percent and the Group Vlll metal be present in an amount from about 1.0 to about 8.0 weight percent of the total catalyst.
  • the refractory metal oxide cracking bases which may be employed in the first hydrocracking zone include those amorphous oxides having cracking activity and which have relatively large pore openings in the range of to 200 angstroms and larger suitable for adsorption of substantial amounts of metal compounds and coke from the hydrocarbon charge oil without substantially affecting the hydrocracking activity.
  • amorphous cracking bases include alumina, silicaalumina, silica-zirconia, silica-titania, mixtures thereof, etc.
  • amorphous cracking bases having good cracking activity are useful for converting a major portion of the hydrocarbon oil charge boiling above about 1000F. into gas-oil boiling in the range of 430F.-l000F. without substantial production of gasoline and dry gas. Under such operating conditions, coke production is substantially decreased over more severe conditions, thus extending the useful life of the first hy drocracking catalyst.
  • the gas-oil conversion product of the heavy hydrocarbon charge is substantially demetalized.
  • desulfurization and denitrogenation activity of the first selected hydrocracking catalyst decreases rapidly. It has been noted that such decline in desulfurization activity is proportionally greater for oils boiling in the gas-oil range than for residual fractions.
  • the residual fraction effluent from the first hydrocracking reaction zone is still substantially desulfurized and may be recovered, if desired, as a relatively low sulfur content heavy fuel oil containing from about 1 percent or less sulfur.
  • Hydrocracking reaction temperatures below 700F. are not preferred, as conversion of heavy hydrocarbon oils into the desired gas-oil fraction is not substantial, thus requiring recycle of large volumes of unconverted residual fraction to the first reaction zone.
  • Reaction temperatures above about 850F. are not desirable because, at these temperatures, substantial amounts of the heavy hydrocarbon oil are converted into low quality sulfur containing gasoline and dry gas.
  • a portion of the unconverted residual recycle fraction boiling above I000F. may be withdrawn from the process to maintain conversion of the heavy hydrocarbon charge within the desired range.
  • Such residual recycle fractions may be employed as a heavy fuel oil, and since the desulfurization activity of the first hydrocracking catalyst remains more effective for the recycle fraction than for the gas-oil fraction at temperatures above 790F., the residual recycle fraction which is yielded from the process is relatively low in sulfur content, containing about one percent or less sulfur.
  • Efi'luent from the first hydrocracking zone may be separated, in a high pressure separation zone, into a first gas fraction comprising hydrogen and a liquid fraction.
  • the hydrogen containing gas fraction may be recirculated to the inlet of the first hydrocracking reaction zone for contact with additional amounts of heavy hydrocarbon oil charge.
  • a portion of the recycle gas may be vented to remove hydrogen sulfide, ammonia, and low boiling hydrocarbons in order to maintain the recycle gas hydrogen concentration at the desired value of about percent or higher. Additional hydrogen may be added to the recycle gas to replace that consumed in the reaction and that vented from the process.
  • Liquid from the first high pressure separator comprising residual fraction, gas-oil fraction, and a small amount of gasoline and dry gas is passed into a fractionation zone.
  • the fractionation zone the residual frac' tion, the gas-oil fraction, the gasoline and dry gas are separated.
  • a portion of the residual fraction may be recycled from the fractionation zone to the inlet of the first hydrocracking zone for conversion into additional amounts of gas-oil fraction.
  • An amount of the residual oil fraction is recovered from the fractionation zone such that the conversion of the residual fraction of the heavy hydrocarbon oil charge to gas-oil fraction boiling below l000F. is not greater than about 90 volume percent, and preferably not greater than about 80 volume percent.
  • the gas-oil fraction from the fractionation zone contains substantial amounts of sulfur and nitrogen compounds and only very small or trace amounts of metal contaminants.
  • Such gas-oil fraction is passed from the fractionation zone to the second hydrocracking zone for conversion into gasoline.
  • the heavy hydrocarbon charge oil is particularly heavy, containing from about 30 to about 50 percent residual hydrocarbons boiling above lO0F.
  • Such gas-oil fraction used as viscosity cutting oil in the first reaction zone serves also as a wash oil, and helps prevent accumulation of coke, tar and other high molecular weight hydrocarbons upon the surface of the first hydrocracking catalyst.
  • the gas-oil fraction is treated with molecular hydrogen in a hydrogen to hydrocarbon ratio of from about 1,000 to about 10,000 standard cubic feet per barrel (scf/b) at a temperature of from about 700780F., a pressure of from about 500 to about 2,500 psig, in the presence ofa sulfur resistant hydrocracking catalyst at a liquid hourly space velocity of from about 0.5 to about 8.0 Vo/Hr/Vc for conversion of said gas-oil fraction into a desulfurized and denitrogenated gasoline fraction boiling in the range of 55F. to 430F.
  • a hydrogen to hydrocarbon ratio of from about 1,000 to about 10,000 standard cubic feet per barrel (scf/b) at a temperature of from about 700780F., a pressure of from about 500 to about 2,500 psig, in the presence of a sulfur resistant hydrocracking catalyst at a liquid hourly space velocity of from about 0.5 to about 8.0 Vo/Hr/Vc for conversion of said gas-oil fraction into a desulfurized and denitrogenated gasoline fraction
  • Temperatures in the range of from about 700-780F. are preferred in the gas-oil hydrocracking reaction because at temperatures below about 700F. the rate of hydrocracking and desulfurization of the gas-oil fraction is too low to be economical and at temperatures of about 790F. and higher the desulfurization and denitrogenation activity of hydrocracking catalysts declines rapidly.
  • the hydrogen to hydrocarbon ratio and pressure are maintained within the described limits in order to provide a hydrogen partial pressure sufficient to promote hydrogenation of cracked hydrocarbons and promote desulfurization and denitrogenation of the gasoline fraction.
  • Catalysts useful within the second hydrocracking zone have hydrocracking activity and are resistant to sulfur and nitrogen poisoning.
  • Such hydrocracking catalysts comprise a hydrogenation component selected from Group V! metals, Group VIII metals, their oxides, their sulfides, and mixtures thereof.
  • Group Vl metals, their oxides or their sulfides are employed, such metals are preferably present in an amount from about 5.0 to about 25.0 weight percent of the total catalyst.
  • Group VIII metals are employed as hydrogenation components, such metals are preferably present in an amount from about 0.3 to about 8.0 weight percent of the total catalyst.
  • Group Vl metals are preferably present from about 5.0 to 25.0 weight percent of the catalyst and Group VIII metals are present in an amount of from about 1.0 to 8.0 weight percent of the catalyst.
  • hydrogenation components which are effective in the second hydrocracking zone include a nickel-tungsten combination, a nickel-oxide-tungsten oxide combination, a nickel-sulfide-tungsten sulfide combination, a cobalt sulfide-molybdenum sulfide combination, and a nickel sulfide-cobalt sulfide-molybdenum sulfide combination.
  • Such hydrogenation components are supported upon a refractory metal oxide cracking base.
  • Such cracking base may be selected from amorphous metal oxides such as alumina, silica-alumina, silica-zirconia, silica-titania, etc.; from cation exchanged crystalline silica-alumina, zeolitic molecular sieves; and from mixtures thereof.
  • amorphous metal oxides such as alumina, silica-alumina, silica-zirconia, silica-titania, etc.
  • cation exchanged crystalline silica-alumina zeolitic molecular sieves
  • zeolitic molecular sieves cations such as hydrogen, ammonia, calcium, magnesium, zinc, etc. have been exchanged therein until the sodium ion content is less than 5 percent and preferably less than I percent.
  • a particularly effective hydrogenation component for the second hydrocracking catalyst comprises a mixture of about 4.0-8.0 weight percent nickel sulfide and about 9.0-25.0 weight percent tungsten sulfide supported upon a cracking base.
  • a particularly effective cracking base comprises 40 to 85 percent amorphous silica-alumina having a silica/alumina ratio of from about 2:1 to about 9: l and about [5 to 60 percent ofa hydrogen or amm onia exchanged, type Y crystalline silica-alumina zeolitic molecular sieve having uniform pore openings in the range of from about 5 to about 20 angstrom units, and having less than 1 percent sodium content.
  • Effluent from the second hydrocracking zone is separated into a second gas fraction comprising hydrogen and a liquid fraction in a second high pressure separation zone.
  • the second gas fraction may be recycled to the inlet of the second hydrocracking zone in order to conserve hydrogen.
  • a portion may be vented to remove hydrogen sulfide, ammonia, and low molecular weight hydrocarbons from the system thereby maintaining hydrogen purity within the desired range of about percent or higher.
  • Makeup hydrogen may be added to the recycle gas to replace hydrogen consumed in the second hydrocracking zone and that vented.
  • the liquid component of the second hydrocracking reaction zone effluent comprises unreacted gas-oil fraction, gasoline and dry gas.
  • the gasoline is desulfurized and denitrogenated and is suitable for further processing, such as catalytic reforming, to improve the quality and octane number thereof.
  • the gasoline is separated from the liquid fraction and unconverted gas-oil may then be recycled to the second hydrocracking zone, along with gas-oil fraction from the first hydrocracking zone, for conversion into additional amounts of gasoline. It is contemplated that the unconverted gas-oil fraction may be recycled to the second hydrocracking zone to extinction, such that the entire gas-oil fraction charged from the first hydrocracking zone to the second hydrocracking zone is completely converted into gasoline and dry gas.
  • liquid effluent from the second hydro cracking zone may be charged to the fractionation zone for separation into its component fractions.
  • liquid effluent from the first hydrocracking zone and liquid effluent from the second hydrocracking zone are charged to the fractionation zone wherein they are separated into a residual fraction, a gasoil fraction, dry gas and gasoline.
  • a portion of the residual fraction is yielded to limit conversion of heavy hydrocarbon charge to 90 volume percent or less, and the remaining residual fraction may be recycled to the first hydrocracking zone for conversion into additional gas-oil fraction.
  • the gas-oil fraction from the fractionation zone is charged to the second hydrocracking zone.
  • the gasoline and dry gas are recovered as products from the fractionation zone.
  • a residuum hydrocarbon containing up to about weight percent sulfur, 1 weight percent nitrogen, 600 ppm vanadium, 100 ppm nickel and 200 ppm iron, charged at a rate of about 1000 barrels per hour (B/H) in Line 1 is mixed with 400 B/H of residual fraction recycle from Line 2, a gasoil fraction wash stream from Line 3 and a recirculating hydrogen gas stream from Line 4 to form a first reaction mixture, at a pressure of about 2,000 psig, a hydrogen to hydrocarbon ratio of about 10,000 scf/b, and a temperature of about 780F., which is contacted with a first hydrocracking catalyst comprising about 2.0 weight percent cobalt and about 10.0 weight percent molybdenum supported upon an amorphous silicaalumina base having pore openings of from about to about 1,000 angstroms.
  • the reaction mixture contacts the hydrocracking catalyst at a LHSV of about 0.5 vo/hr/vc.
  • an effluent stream is withdrawn via line 6 and passes into a first high pressure separation zone 7 wherein a first gas fraction comprising hydrogen is separated from a first liquid fraction.
  • a portion of the first gas fraction is vented from the first high pressure separation zone via line 8 to maintain the concentration of hydrogen within the first gas fraction at about 75 volume percent or higher.
  • the remainder of the first gas fraction passes from the high pressure separator 7 via line 9 to compressor 10.
  • the first gas fraction is recycled via line 4 for combination with additional amounts of residuum charge to form a reaction mixture for charge to the first hydrocracking zone 5, as hereinabove described.
  • Makeup hydrogen of about 85 percent purity or higher is added to the recycle gas in line 4 via line 11 to make up for the amount of hydrogen consumed in the first hydrocracking zone and for the amount of hydrogen vented via line 8.
  • a first liquid fraction is transferred via line 12 and is combined with a second hydrocracking zone liquid effluent (as will hereinafter be further described) from line 13.
  • the combined hydrocracking zone liquid effluents pass via line 14 into fractionation zone 15 wherein they are separated into a residual fraction, a gas-oil fraction, gasoline and dry gas.
  • residual fraction is withdrawn via line 16 and a portion of the residual fraction, at a rate of about 400 B/H is recycled via line 2 for combination with additional amounts of residuum as hereinbefore described.
  • the remainder of the residual fraction at a rate of about 200 B/H is withdrawn from the process via line 17 as a heavy fuel oil, containing about 1.0 weight percent sulfur.
  • Such residual fraction is withdrawn as fuel oil at such a rate to maintain the overall conversion of hydrocarbon oil charge boiling above I000F. into gasoil boiling below 1000F. to about volume percent or less.
  • the gas-oil fraction containing about 0.5 weight percent sulfur and about ppm nitrogen, is withdrawn from fractionator 15 via line 18.
  • a small portion ofgasoil fraction at a rate of about 50 B/H is transferred from line 18 via line 3 to the inlet of the first hydrocracking zone as a wash-oil stream as has hereinabove been described.
  • the remainder of the gas-oil fraction is mixed with the second recirculating gas stream from line 19 to form a second reaction mixture and is passed into second hydrocracking zone 20.
  • the second reaction mixture at a temperature of about 750F., a pressure of about 1,500 psig, a hydrogen to hydrocarbon ratio of about 7,500 scf/b contacts a second hydrocracking catalyst comprising about 6.0 weight percent nickel sulfide and about 19 weight percent tungsten sulfide hydrogenation component supported upon a hydrogen exchanged crystalline silica-alumina zeolitic molecular sieve having pore openings of from about 5 to about 20 angstrom units, at an LHSV of about 1.5 vo/hr/vc to desulfurize, denitrogenate, and convert said gas-oil fraction into gasoline.
  • a second hydrocracking catalyst comprising about 6.0 weight percent nickel sulfide and about 19 weight percent tungsten sulfide hydrogenation component supported upon a hydrogen exchanged crystalline silica-alumina zeolitic molecular sieve having pore openings of from about 5 to about 20 angstrom units, at an LHSV of about 1.5 vo/hr/vc
  • Effluent from the second hydrogenation zone 20 is passed via line 21 into a second high pressure separator 22 wherein the effluent is separated into a second gaseous fraction and a second liquid fraction.
  • a portion of the second gaseous fraction is vented via line 23 to remove hydrogen sulfide, ammonia, and low boiling hydrocarbons from the system and the remainder of the second gaseous fraction passes via line 24 into compressor 25.
  • compressor 25 From compressor 25 the second gaseous fraction passes as second recycle gas into line 19 for combination with additional gas-oil fraction as hereinabove described.
  • Makeup hydrogen to replace the hydrogen consumed in the second hydrocracking zone and the hydrogen vented via line 23 is added via line 26 to the second recycle gas stream in line 19.
  • Liquid component of the second hydrocracking zone effluent passes from the second high pressure separator 22 via line 13 for admixture with first hydrocracking zone liquid effluent in line 14 as hereinabove described.
  • a dry gas comprising methane, ethane, and propane is separated and removed at a rate of about 250,000 scf/h via line 27.
  • a gasoline stream is separated in fractionation zone 15 for recovery as a product.
  • Such gasoline at a rate of 825 Elf! and containing about 20 ppm sulfur and 2 ppm nitrogen, is recovered via line 28.
  • the gasoline product has an octane rating of 65 research octane clear, and is suitable for use as a charge stock to an octane improving process such as, for example, catalytic reforming.
  • the present invention provides a novel method for treating a hydrocarbon oil, containing substantial amounts of sulfur, nitrogen, and metal compounds, to produce a low sulfur gasoline product and a low sulfur heavy fuel oil product.
  • a hydrocracking process wherein heavy hydrocarbon oil charge containing 0.1 to 8 percent sulfur, l to 1000 ppm and more nitrogen, and I00 ppm and more compounds of nickel, vanadium, iron, and copper, and comprising from about 10 to 50 volume percent residual fraction boiling above l000F. are converted into a major portion of gasoline containing less than 100 ppm sulfur and nitrogen, and a minor portion of residual fuel oil containing about 1 percent or less sulfur; which process comprises:
  • hydrocracking heavy hydrocarbon oil charge in a first hydrocracking zone, with molecular hydrogen at a temperature in the range of from about 700850F. in the presence of a sulfur and nitrogen resistant hydrocracking catalyst comprising a hydrogenation component supported upon a cracking base consisting of an amorphous inorganic oxide having pore size distribution in the range of at least 20-200 angstrom units for conversion of said heavy hydrocarbon oil charge into not more than about percent gasoline fraction, a major portion of gas-oil fraction boiling in the range of 430l000F., and at least about percent residual oil fraction boiling above l00OF. containing about 1 percent or less sulfur;
  • liquid effluent from the second hydrocracking zone comprising gasoline, dry gas and unconverted gas-oil fraction is charged along with liquid effluent from the first hydrocracking zone comprising gas-oil fraction, residual fraction, and a small amount of gasoline and dry gas, to
  • the separation zone wherein said first and second hydrocracking zone liquid effluent is separated into a dry gas fraction, gasoline, a gas-oil fraction, and a residual fraction.
  • the hydrocracking catalyst in the first hydrocracking zone comprises a sulfur and nitrogen resistant hydrogenation component selected from the group consisting of Group Vl metals, Group Vlll metals, their oxides, their sulfides, and mixtures thereof, supported upon an amorphous metal oxide cracking base selected from the group consisting of alumina, silica-alumina, silica-zirconia, silica-titania, and mixtures thereof.
  • the hydrocracking catalyst employed in the second hydrocracking zone comprises a hydrogenation component selected from the group consisting of Group Vl metals, Group VIII metals, their oxides, their sulfides, and mixtures thereof, and an inorganic oxide cracking base selected from the group consisting of alumina, silica-alumina, silica-zirconia, silica-titania, a cation exchanged crystalline silica-alumina zeolitic molecular sieve having uniform pore openings in the range of from about 5 angstroms to about 20 angstroms, and mixtures thereof.
  • a hydrogenation component selected from the group consisting of Group Vl metals, Group VIII metals, their oxides, their sulfides, and mixtures thereof
  • an inorganic oxide cracking base selected from the group consisting of alumina, silica-alumina, silica-zirconia, silica-titania, a cation exchanged crystalline silica-alumina zeoli
  • the hydrocracking catalyst contained in the first hydrocracking zone comprises a hydrogenation component selected from the group consisting of a cobalt-molybdenum mixture, a cobalt oxide-molybdenum oxide mixture, a cobalt sulfide-molybdenum sulfide mixture, a nickel-cobaltmolybdenum mixture, a nickel oxide-cobalt oxidemolybdenum oxide mixture, and a nickel sulfide-cobalt sulfide-molybdenum sulfide mixture, and wherein the amorphous metal oxide cracking base is selected from the group consisting of alumina and silica-alumina.
  • the hydrogenation component of the hydrocracking catalyst contained in the second hydrocracking zone is selected from the group consisting of a nickel-tungsten mixture, a nickel oxide-tungsten oxide mixture, a nickel sulfide-tungsten sulfide mixture, a cobalt sulfide-molybdenum sulfide mixture, and a nickel sulfide-cobalt sulfidemolybdenum sulfide mixture and wherein the inorganic oxide cracking base is selected from the group consisting of alumina, silica-alumina, and a cation exchanged crystalline silica-alumina zeolitic molecular sieve having uniform pore openings in the range of from about 5 angstroms to about 20 angstroms, and mixtures thereof.
  • a hydrocracking catalyst consisting of a hydrogenation component selected from the group consisting of cobalt, molybdenum, nickel, their oxides, their sulfides, and mixtures thereof, and an amorphous metal oxide cracking base selected from the group consisting of alumina, silica-alumina, silicazirconia, silica-titania, and mixtures thereof, to partially convert said heavy hydrocarbon oil into 0-5 percent gasoline boiling in the range 55-430F;
  • cobalt oxide-molybdenum oxide mixture a cobalt sulfide-molybdenum sulfide mixture, a nickel sulfide-tungsten sulfide mixture, a nickel oxidetungsten oxide mixture, and a nickel-tungsten mixture
  • an inorganic cracking base selected from the group consisting of alumina, silicaalumina, a cation exchanged crystalline silica-alumina zeolitic molecular sieve having uniform pore openings in the range of from about 5 to about 20 angstrom units, and mixtures thereof, to convert said separated gas-oil fraction into gasoline containing
US445365A 1971-12-27 1974-02-25 Hydrocracking process for converting heavy hydrocarbon into low sulfur gasoline Expired - Lifetime US3891539A (en)

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US4519900A (en) * 1982-12-28 1985-05-28 Mobil Oil Corporation Zeolite containing catalyst support for denitrogenation of oil feedstocks
US4648959A (en) * 1986-07-31 1987-03-10 Uop Inc. Hydrogenation method for adsorptive separation process feedstreams
US4681674A (en) * 1985-11-07 1987-07-21 Mobil Oil Corporation Fixed bed catalytic reactor system with improved liquid distribution
US4698145A (en) * 1984-12-28 1987-10-06 Exxon Research And Engineering Company Supported transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing
US4713167A (en) * 1986-06-20 1987-12-15 Uop Inc. Multiple single-stage hydrocracking process
EP0310164A1 (fr) * 1987-09-29 1989-04-05 Shell Internationale Researchmaatschappij B.V. Procédé de conversion de matière première contenant des hydrocarbures
US4902405A (en) * 1988-01-13 1990-02-20 Atlantic Richfield Company Fixed bed hydrocracking process
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US5007998A (en) * 1990-03-26 1991-04-16 Uop Process for refractory compound conversion in a hydrocracker recycle liquid
US20030221990A1 (en) * 2002-06-04 2003-12-04 Yoon H. Alex Multi-stage hydrocracker with kerosene recycle
EP1487941A1 (fr) * 2002-03-21 2004-12-22 Chevron U.S.A. Inc. Nouveau procede d'hydrocraquage pour la production de distillats de haute qualite a partir de gazoles lourds
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US20140262956A1 (en) * 2013-03-15 2014-09-18 Advanced Refining Technologies Llc Novel resid hydrotreating catalyst
WO2015000849A1 (fr) * 2013-07-02 2015-01-08 Saudi Basic Industries Corporation Processus et installation pour transformer du pétrole brut en produits pétrochimiques à rendement en éthylène amélioré
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WO2015000841A1 (fr) 2013-07-02 2015-01-08 Saudi Basic Industries Corporation Procédé d'enrichissement de résidus lourds de raffinerie en produits pétrochimiques
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FR3030564A1 (fr) * 2014-12-22 2016-06-24 Axens Procede et dispositif pour la reduction des composes aromatiques polycycliques lourds dans les unites d'hydrocraquage
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US4255251A (en) * 1979-07-30 1981-03-10 Texaco Inc. Hydrocracking process and catalyst
US4519900A (en) * 1982-12-28 1985-05-28 Mobil Oil Corporation Zeolite containing catalyst support for denitrogenation of oil feedstocks
US4698145A (en) * 1984-12-28 1987-10-06 Exxon Research And Engineering Company Supported transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing
US4681674A (en) * 1985-11-07 1987-07-21 Mobil Oil Corporation Fixed bed catalytic reactor system with improved liquid distribution
US4713167A (en) * 1986-06-20 1987-12-15 Uop Inc. Multiple single-stage hydrocracking process
US4648959A (en) * 1986-07-31 1987-03-10 Uop Inc. Hydrogenation method for adsorptive separation process feedstreams
AU601871B2 (en) * 1987-09-29 1990-09-20 Shell Internationale Research Maatschappij B.V. Process for converting a hydrocarbonaceous feedstock
EP0310164A1 (fr) * 1987-09-29 1989-04-05 Shell Internationale Researchmaatschappij B.V. Procédé de conversion de matière première contenant des hydrocarbures
US4902405A (en) * 1988-01-13 1990-02-20 Atlantic Richfield Company Fixed bed hydrocracking process
US4950384A (en) * 1988-08-11 1990-08-21 Shell Oil Company Process for the hydrocracking of a hydrocarbonaceous feedstock
US4921595A (en) * 1989-04-24 1990-05-01 Uop Process for refractory compound conversion in a hydrocracker recycle liquid
US5007998A (en) * 1990-03-26 1991-04-16 Uop Process for refractory compound conversion in a hydrocracker recycle liquid
EP1487941A1 (fr) * 2002-03-21 2004-12-22 Chevron U.S.A. Inc. Nouveau procede d'hydrocraquage pour la production de distillats de haute qualite a partir de gazoles lourds
EP1487941A4 (fr) * 2002-03-21 2010-11-24 Chevron Usa Inc Nouveau procede d'hydrocraquage pour la production de distillats de haute qualite a partir de gazoles lourds
WO2003104358A1 (fr) * 2002-06-04 2003-12-18 Chevron U.S.A. Inc. Hydrocraqueur a etages multiples avec recyclage de kerosene
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US7951290B2 (en) * 2006-12-29 2011-05-31 Uop Llc Hydrocarbon conversion process
US20140262956A1 (en) * 2013-03-15 2014-09-18 Advanced Refining Technologies Llc Novel resid hydrotreating catalyst
WO2014151653A1 (fr) * 2013-03-15 2014-09-25 Advanced Refining Technologies Llc Nouveau catalyseur d'hydrotraitement de résidu
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IT972915B (it) 1974-05-31
JPS5139882B2 (fr) 1976-10-30
BE793384A (fr) 1973-06-27
JPS4880603A (fr) 1973-10-29
DE2255321A1 (de) 1973-07-12
GB1378829A (en) 1974-12-27
CA984324A (en) 1976-02-24

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