+

US20080023372A1 - Hydrocracking Process - Google Patents

Hydrocracking Process Download PDF

Info

Publication number
US20080023372A1
US20080023372A1 US11/460,307 US46030706A US2008023372A1 US 20080023372 A1 US20080023372 A1 US 20080023372A1 US 46030706 A US46030706 A US 46030706A US 2008023372 A1 US2008023372 A1 US 2008023372A1
Authority
US
United States
Prior art keywords
zone
hydrocarbonaceous
hydrocracking
liquid phase
hydrocarbonaceous feedstock
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/460,307
Other languages
English (en)
Inventor
Laura E. Leonard
Peter Kokayeff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Priority to US11/460,307 priority Critical patent/US20080023372A1/en
Assigned to UOP LLC reassignment UOP LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KOKAYEFF, PETER, LEONARD, LAURA E
Priority to RU2009106855/04A priority patent/RU2405024C2/ru
Priority to DE112007001743T priority patent/DE112007001743T5/de
Priority to BRPI0715107-1A priority patent/BRPI0715107A2/pt
Priority to CN2007800358490A priority patent/CN101517042B/zh
Priority to MX2009000941A priority patent/MX2009000941A/es
Priority to PCT/US2007/073708 priority patent/WO2008014150A2/fr
Publication of US20080023372A1 publication Critical patent/US20080023372A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the field of art to which this invention pertains is the catalytic conversion of hydrocarbons to useful hydrocarbon products. More particularly, the invention relates to catalytic hydrocracking.
  • the present invention pertains to the hydrocracking of a hydro-carbonaceous feedstock.
  • Petroleum refiners often produce desirable products such as turbine fuel, diesel fuel and other products known as middle distillates as well as lower boiling hydrocarbonaceous liquids such as naphtha and gasoline by hydrocracking a hydrocarbon feedstock derived from crude oil or heavy fractions thereof.
  • Feedstocks most often subjected to hydrocracking are gas oils and heavy gas oils recovered from crude oil by distillation.
  • a typical heavy gas oil comprises a substantial portion of hydrocarbon components boiling above about 371° C. (700° F.), usually at least about 50 percent by weight boiling above 371° C. (700° F.).
  • a typical vacuum gas oil normally has a boiling point range between about 315° C. (600° F.) and about 565° C. (1050° F.).
  • Hydrocracking is generally accomplished by contacting in a hydro-cracking reaction vessel or zone the gas oil or other feedstock to be treated with a suitable hydrocracking catalyst under conditions of elevated temperature and pressure in the presence of hydrogen as a separate phase in a two-phase reaction zone so as to yield a product containing a distribution of hydrocarbon products desired by the refiner.
  • the operating conditions and the hydrocracking catalysts within a hydrocracking reactor influence the yield of the hydrocracked products.
  • the fresh feedstock for a hydrocracking process is first introduced into a denitrification and desulfurization zone having hydrogen in a gaseous phase and particularly suited for the removal of sulfur and nitrogen contaminants and subsequently introduced into a hydrocracking zone containing hydrocracking catalyst and having hydrogen in a gaseous phase.
  • Another method of hydrocracking a fresh feedstock is to introduce the fresh feedstock and the effluent from the hydrocracking zone into the denitrification and desulfurization zone.
  • the resulting effluent from the hydrocracking zone is separated to produce desired hydrocracked products and unconverted feedstock which is then introduced into the hydrocracking zone.
  • at least a major portion of the hydrogen present in reaction zones was present in a gaseous phase. This method or technique is commonly referred to as “trickle bed” wherein the continuous phase is gaseous and not liquid.
  • U.S. Pat. No. 5,720,872 B1 discloses a process for hydroprocessing liquid feedstocks in two or more hydroprocessing stages which are in separate reaction vessels and wherein each reaction stage contains a bed of hydroprocessing catalyst.
  • the liquid product from the first reaction stage is sent to a low pressure stripping stage and stripped of hydrogen sulfide, ammonia and other dissolved gases.
  • the stripped product stream is then sent to the next downstream reaction stage, the product from which is also stripped of dissolved gases and sent to the next downstream reaction stage until the last reaction stage, the liquid product of which is stripped of dissolved gases and collected or passed on for further processing.
  • the flow of treat gas is in a direction opposite the direction in which the reaction stages are staged for the flow of liquid.
  • Each stripping stage is a separate stage, but all stages are contained in the same stripper vessel.
  • U.S. Pat. No. 3,328,290 B1 discloses a two-stage process for the hydrocracking of hydrocarbons in which the feed is pretreated in the first stage.
  • U.S. Pat. No. 5,403,469 B1 discloses a parallel hydrotreating and hydrocracking process. Effluent from the two processes are combined in the same separation vessel and separated into a vapor comprising hydrogen and a hydrocarbon-containing liquid. The hydrogen is shown to be supplied as part of the feed streams to both the hydrocracking and the hydrotreater.
  • U.S. Pat. No. 5,980,729 discloses a hydrocracking process wherein a hydrocarbonaceous feedstock and a hot hydrocracking zone effluent containing hydrogen is passed to a denitrification and desulfurization reaction zone to produce hydrogen sulfide and ammonia to thereby clean up the fresh feedstock.
  • the resulting hot, uncooled effluent from the denitrification and desulfurization zone is hydrogen stripped in a stripping zone maintained at essentially the same pressure as the preceding reaction zone with a hydrogen-rich gaseous stream to produce a vapor stream comprising hydrogen, hydrocarbonaceous compounds boiling at a temperature below the boiling range of the fresh feedstock, hydrogen sulfide and ammonia, and a liquid hydro-carbonaceous stream containing unconverted feedstock.
  • This liquid hydrocarbonaceous stream is introduced into a hydrocracking zone to produce a hydrocracking zone effluent which then joins the fresh feedstock as described hereinabove and is subsequently introduced into the denitrification and desulfurization zone.
  • U.S. Pat. No. 6,106,694 discloses a hydrocracking process wherein a hydrocarbonaceous feedstock and a hot hydrocracking zone effluent is passed to a denitrification and desulfurization reaction zone to produce hydrogen sulfide and ammonia to thereby clean up the fresh feedstock.
  • the resulting hot, uncooled effluent from the denitrification and desulfurization zone is hydrogen stripped in a stripping zone maintained at essentially the same pressure as the preceding reaction zone with a hydrogen-rich gaseous stream to produce a vapor stream comprising hydrogen, hydrocarbonaceous compounds boiling at a temperature below the boiling range of the fresh feedstock, hydrogen sulfide and ammonia, and a liquid hydrocarbonaceous stream containing unconverted feedstock.
  • This liquid hydrocarbonaceous stream is subsequently introduced into the hydrocracking zone to produce an effluent which is subsequently introduced into the denitrification and desulfurization reaction zone as described hereinabove.
  • the present invention is a catalytic hydrocracking process, in one embodiment, wherein a liquid phase stream comprising a hydrocarbonaceous feedstock, a liquid phase effluent from a hydrocracking zone, and a sufficiently low hydrogen concentration to maintain a liquid phase continuous system is fed into a hydrotreating zone to produce hydrogen sulfide and ammonia and provide a first hydrocarbonaceous stream comprising hydrocarbons having a reduced level of sulfur and nitrogen.
  • the hydrocarbons having a reduced level of sulfur and nitrogen are introduced into a hydrocracking zone with a sufficiently low hydrogen concentration to maintain a liquid phase continuous system to produce a hydrocracking zone effluent which provides lower boiling range hydrocarbons.
  • the first hydrocarbonaceous stream comprising hydrocarbons having a reduced level of sulfur and nitrogen is separated in a high pressure product stripper or by conventional distillation to provide the hydrocarbons having a reduced level of sulfur and nitrogen which are subsequently introduced into the hydrocracking zone.
  • the present invention is a catalytic hydrocracking process wherein a liquid phase stream comprising a hydrocarbonaceous feedstock, a liquid phase effluent from a hydrocracking zone, and a sufficiently low hydrogen concentration to maintain a liquid phase continuous system is fed into a hydrotreating zone to produce hydrogen sulfide and ammonia, and provide a first hydrocarbonaceous stream comprising hydrocarbons having a reduced level of sulfur and nitrogen.
  • the first hydrocarbonaceous stream comprising hydrocarbons having a reduced level of sulfur and nitrogen is introduced into a hydrocracking zone with a sufficiently low hydrogen concentration to maintain a liquid phase continuous system to produce a hydrocracking zone effluent.
  • the hydrocracking zone effluent is introduced into a separation zone which in one embodiment is preferably a high pressure product stripper to produce a second hydrocarbonaceous stream containing lower boiling hydrocarbons and a liquid phase hydrocarbonaceous stream comprising unconverted hydrocarbons which is introduced into the hydrotreating zone as hereinabove described. Hydrocracked hydrocarbons boiling at a temperature range lower than the hydrocarbonaceous feedstock are recovered.
  • a liquid phase continuous system would exist at one extreme with only sufficient hydrogen to fully saturate the hydrocarbon feedstock and at the other extreme where sufficient hydrogen is added to transition to a gas phase continuous system.
  • the amount of hydrogen that is added between these two extremes is dictated by economic considerations. Operation with a liquid phase continuous system avoids the high costs associated with a recycle gas compressor.
  • the process of the present invention is particularly useful for hydrocracking a hydrocarbon oil containing hydrocarbons and/or other organic materials to produce a product containing hydrocarbons and/or other organic materials of lower average boiling point and lower average molecular weight.
  • the hydrocarbon feedstocks that may be subjected to hydrocracking by the method of the invention include all mineral oils and synthetic oils (e.g., shale oil, tar sand products, etc.) and fractions thereof.
  • Illustrative hydrocarbon feedstocks include those containing components boiling above 288° C.
  • a preferred hydrocracking feedstock is a gas oil or other hydrocarbon fraction having at least 50% by weight, and most usually at least 75% by weight, of its components boiling at a temperature above about 371° C. (700° F.).
  • One of the most preferred gas oil feedstocks will contain hydrocarbon components which boil above 288° C. (550° F.) with best results being achieved with feeds containing at least 25 percent by volume of the components boiling between 315° C. (600° F.) and 565° C. (1050° F.).
  • the selected hydrocarbonaceous feedstock and hydrogen are introduced into a hydrotreating reaction zone at hydrotreating reaction conditions.
  • the resulting effluent from a hereinafter described hydrocracking reaction zone is also introduced into the hydrotreating reaction zone.
  • Preferred hydrotreating reaction conditions include a temperature from about 204° C. (400° F.) to about 482° C. (900° F.), a pressure from about 3.5 MPa (500 psig) to about 17.3 MPa (2500 psig), a liquid hourly space velocity of the fresh hydrocarbonaceous feedstock from about 0.1 hr ⁇ 1 to about 10 hr ⁇ 1 with a hydrotreating catalyst or a combination of hydrotreating catalysts.
  • Only enough hydrogen is introduced into the hydrotreating reaction zone to maintain a liquid phase continuous system. This means that in contrast to conventional hydroprocessing processes which operate in trickle bed mode in which it is the gas phase that is continuous, the present invention operates in a liquid phase continuous system.
  • hydrotreating refers to a process wherein a hydrogen-containing treat gas absorbed in the liquid hydrocarbon is used in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur and nitrogen from the hydrocarbon feedstock.
  • suitable hydrotreating catalysts for use in the present invention are any known conventional hydrotreating catalysts and include those which are comprised of at least one Group VIII metal, preferably iron, cobalt and nickel, more preferably cobalt and/or nickel and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina.
  • hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum. It is within the scope of the present invention that more than one type of hydrotreating catalyst be used in the same reaction vessel.
  • the Group VIII metal is typically present in an amount ranging from about 2 to about 20 weight percent, preferably from about 4 to about 12 weight percent.
  • the Group VI metal will typically be present in an amount ranging from about 1 to about 25 weight percent, preferably from about 2 to about 25 weight percent.
  • the resulting effluent from the hydrotreating reaction zone is directly introduced into a hydrocracking reaction zone to provide lower boiling hydrocarbons.
  • the resulting effluent is introduced into a separation zone which is preferably a high pressure product stripper or a conventional fractionation zone to recover lower boiling hydrocarbons and to provide a hydrocarbonaceous stream containing hydrocarbons boiling in the range of the fresh feedstock which is subsequently introduced into a hydrocracking zone.
  • the high pressure product stripper is preferably operated at a temperature from about 204° C. (400° F.) to about 482° C. (900° F.) and a pressure from about 3.5 MPa (500 psig) to about 17.3 MPa (2500 psig).
  • the effluent from the hydrocracking reaction zone is preferably introduced into a high pressure stripper preferably operated at a temperature from about 204° C. (400° F.) to about 482° C. (900° F.) and a pressure from about 3.5 MPa (500 psig) to about 17.3 MPa (2500 psig) to produce a vaporous hydrocarbonaceous stream and a liquid hydrocarbonaceous stream containing hydrocarbons boiling in the range of the fresh feedstock which is introduced into the hydrotreating zone.
  • the hydrotreating zone effluent is separated between the hydrotreating zone and the hydrocracking zone, the effluent from the hydrocracking zone is directly introduced into the hydrotreating zone.
  • the feed is introduced into the hydrocracking zone along with the added hydrogen in an amount sufficiently low to maintain a liquid phase continuous system.
  • the hydrocracking zone may contain one or more beds of the same or different catalyst.
  • the preferred hydrocracking catalysts utilize amorphous bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components.
  • the hydrocracking zone contains a catalyst which comprises, in general, any crystalline zeolite cracking base upon which is deposited a minor proportion of a Group VIII metal hydrogenating component. Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base.
  • the zeolite cracking bases are sometimes referred to in the art as molecular sieves and are usually composed of silica, alumina and one or more exchangeable cations such as sodium, magnesium, calcium, rare earth metals, etc. They are further characterized by crystal pores of relatively uniform diameter between about 4 and 14 Angstroms (10 ⁇ 10 meters). It is preferred to employ zeolites having a relatively high silica/alumina mole ratio between about 3 and 12. Suitable zeolites found in nature include, for example, mordenite, stilbite, heulandite, ferrierite, dachiardite, chabazite, erionite and faujasite.
  • Suitable synthetic zeolites include, for example, the B, X, Y and L crystal types, e.g., synthetic faujasite and mordenite.
  • the preferred zeolites are those having crystal pore diameters between about 8-12 Angstroms (10 ⁇ 10 meters), wherein the silica/alumina mole ratio is about 4 to 6.
  • a prime example of a zeolite falling in the preferred group is synthetic Y molecular sieve.
  • the natural occurring zeolites are normally found in a sodium form, an alkaline earth metal form, or mixed forms.
  • the synthetic zeolites are nearly always prepared first in the sodium form.
  • Hydrogen or “decationized” Y zeolites of this nature are more particularly described in U.S. Pat. No. 3,130,006 B1.
  • Mixed polyvalent metal-hydrogen zeolites may be prepared by ion-exchanging first with an ammonium salt, then partially back exchanging with a polyvalent metal salt and then calcining.
  • the hydrogen forms can be prepared by direct acid treatment of the alkali metal zeolites.
  • the preferred cracking bases are those which are at least about 10 percent, and preferably at least 20 percent, metal-cation-deficient, based on the initial ion-exchange capacity.
  • a specifically desirable and stable class of zeolites are those wherein at least about 20 percent of the ion exchange capacity is satisfied by hydrogen ions.
  • the active metals employed in the preferred hydrocracking catalysts of the present invention as hydrogenation components are those of Group VIII, i.e., iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. In addition to these metals, other promoters may also be employed in conjunction therewith, including the metals of Group VIB, e.g., molybdenum and tungsten.
  • the amount of hydrogenating metal in the catalyst can vary within wide ranges. Broadly speaking, any amount between about 0.05 percent and 30 percent by weight may be used. In the case of the noble metals, it is normally preferred to use about 0.05 to about 2 weight percent.
  • the preferred method for incorporating the hydrogenating metal is to contact the zeolite base material with an aqueous solution of a suitable compound of the desired metal wherein the metal is present in a cationic form.
  • the resulting catalyst powder is then filtered, dried, pelleted with added lubricants, binders or the like if desired, and calcined in air at temperatures of, e.g., 371°-648° C. (700°-1200° F.) in order to activate the catalyst and decompose ammonium ions.
  • the zeolite component may first be pelleted, followed by the addition of the hydrogenating component and activation by calcining.
  • the foregoing catalysts may be employed in undiluted form, or the powdered zeolite catalyst may be mixed and copelleted with other relatively less active catalysts, diluents or binders such as alumina, silica gel, silica-alumina cogels, activated clays and the like in proportions ranging between 5 and 90 weight percent.
  • diluents may be employed as such or they may contain a minor proportion of an added hydrogenating metal such as a Group VIB and/or Group VIII metal.
  • Additional metal promoted hydrocracking catalysts may also be utilized in the process of the present invention which comprises, for example, aluminophosphate molecular sieves, crystalline chromosilicates and other crystalline silicates. Crystalline chromosilicates are more fully described in U.S. Pat. No. 4,363,718 B1 (Klotz).
  • the hydrocracking of the hydrocarbonaceous feedstock in contact with a hydrocracking catalyst is conducted in the presence of sufficiently low concentrations of hydrogen to maintain a liquid phase continuous system and preferably at hydrocracking reactor conditions which include a temperature from about 232° C. (450° F.) to about 468° C. (875° F.), a pressure from about 3.5 MPa (500 psig) to about 17.3 MPa (2500 psig) and a liquid hourly space velocity (LHSV) from about 0.1 to about 30 hr ⁇ 1 .
  • the term “substantial conversion to lower boiling products” is meant to connote the conversion of at least 5 volume percent of the fresh feedstock to products having a lower boiling point than the hydrocarbonaceous feedstock.
  • the per pass conversion in the hydrocracking zone is in the range from about 15% to about 75%. More preferably the per pass conversion is in the range from about 20% to about 60%. Then the ratio of unconverted hydrocarbons boiling in the range of the hydrocarbonaceous feedstock to the hydrocarbonaceous feedstock is from about 1:5 to about 3:5.
  • the present invention is suitable for the production of naphtha, diesel or any other desired lower boiling hydrocarbons.
  • hydrogen is necessarily consumed and must be replaced by one or more hydrogen inlet points located in the reaction zones.
  • the amount of hydrogen added at these locations is controlled to ensure that the system operates as a liquid phase continuous system.
  • the limiting amount of hydrogen that is added is that amount which causes a transition from a liquid phase continuous system to a vapor phase continuous system.
  • the relative amount of hydrogen required to maintain a liquid phase continuous system in both the hydrotreating and the hydrocracking zones is dependent upon the specific composition of the hydrocarbonaceous feedstock, the level or amount of conversion to lower boiling hydrocarbon compounds, the composition and quantity of the lower boiling hydrocarbons and the reaction zone temperature and pressure. Artisans skilled in the conversion and hydrocracking of hydrocarbons will readily be able to determine the appropriate amount of hydrogen to provide a liquid phase continuous system once all of the above-mentioned variables have been selected.
  • a feedstream comprising vacuum gas oil is introduced into the process via line 1 and admixed with a hereinafter described hydrocracking zone effluent transported via line 16 .
  • a hydrogen-rich gaseous stream is introduced via line 2 and also joins the feedstream and the resulting admixture is transported via line 3 and introduced into hydrotreating zone 4 .
  • Additional hydrogen-rich gas is introduced via lines 5 and 6 into hydrotreating zone 4 in order to supplement the required hydrogen which is consumed in hydrotreating zone 4 .
  • the amount of hydrogen present in hydrotreating zone 4 is sufficiently low to maintain a liquid phase continuous system.
  • the resulting effluent from hydrotreating zone 4 is carried via line 7 and introduced into high pressure product stripper 8 .
  • a hydrocarbonaceous vaporous stream comprising hydrogen sulfide, ammonia and hydrocarbons boiling in the range lower than the feedstock is removed from high pressure product stripper 8 via line 9 and recovered.
  • a liquid hydrocarbonaceous stream containing hydrocarbon compounds boiling in the range of the feedstock is removed from high pressure product stripper 8 via line 10 and is joined with a hydrogen-rich stream provided via line 11 and the resulting admixture is transported via line 12 and introduced into hydrocracking zone 13 .
  • Additional hydrogen is provided via lines 14 and 15 to hydrocracking zone 13 .
  • the hydrogen provided to hydrocracking zone 13 is in an amount sufficiently low to maintain a liquid phase continuous system therein.
  • a resulting hydrocracking zone effluent is removed from hydrocracking zone 13 via line 16 and joins the fresh feedstock provided via line 1 as hereinabove described.
  • a feedstream comprising vacuum gas oil is introduced into the process via line 1 and admixed with a hereinafter described hydrocracking zone effluent transported via line 16 .
  • a hydrogen-rich gaseous stream is provided via line 2 and also joins the feedstream and the resulting admixture is transported via line 3 and introduced into hydrotreating zone 4 .
  • Additional hydrogen is introduced into hydrotreating zone 4 via lines 5 and 6 .
  • the total supply of hydrogen to hydrotreating zone 4 is sufficiently low to maintain a liquid phase continuous system.
  • a resulting effluent stream is removed from hydrotreating zone 4 via line 7 and is joined with a hydrogen-rich gaseous stream provided via line 8 in an amount sufficiently low to maintain a liquid phase continuous system and the resulting admixture is transported via line 9 and introduced into hydrocracking zone 10 .
  • Additional hydrogen is provided to hydrocracking zone 10 via lines 11 and 12 in an amount sufficiently low to maintain a liquid phase continuous system therein.
  • a resulting effluent stream is removed from hydrocracking zone 10 via line 11 and is joined with a hydrogen-rich gaseous stream provided via line 12 and the resulting admixture is transported via line 13 and introduced into high pressure product stripper 14 .
  • a hydrocarbonaceous vaporous stream containing hydrocarbons boiling in a range below the feed is removed from high pressure product stripper 14 via line 15 and recovered.
  • a liquid stream containing unconverted hydrocarbons is removed from high pressure product stripper via line 16 and joins the feedstream provided via line 1 as hereinabove described.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US11/460,307 2006-07-27 2006-07-27 Hydrocracking Process Abandoned US20080023372A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US11/460,307 US20080023372A1 (en) 2006-07-27 2006-07-27 Hydrocracking Process
RU2009106855/04A RU2405024C2 (ru) 2006-07-27 2007-07-17 Способ гидрокрекинга
DE112007001743T DE112007001743T5 (de) 2006-07-27 2007-07-17 Hydrocracking-Verfahren
BRPI0715107-1A BRPI0715107A2 (pt) 2006-07-27 2007-07-17 processo para hidrocraqueamento de uma carga de alimentaÇço hidrocarbonÁcea
CN2007800358490A CN101517042B (zh) 2006-07-27 2007-07-17 加氢裂化方法
MX2009000941A MX2009000941A (es) 2006-07-27 2007-07-17 Proceso de hidrodesintegracion.
PCT/US2007/073708 WO2008014150A2 (fr) 2006-07-27 2007-07-17 Procédé d'hydrocraquage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/460,307 US20080023372A1 (en) 2006-07-27 2006-07-27 Hydrocracking Process

Publications (1)

Publication Number Publication Date
US20080023372A1 true US20080023372A1 (en) 2008-01-31

Family

ID=38982215

Family Applications (1)

Application Number Title Priority Date Filing Date
US11/460,307 Abandoned US20080023372A1 (en) 2006-07-27 2006-07-27 Hydrocracking Process

Country Status (7)

Country Link
US (1) US20080023372A1 (fr)
CN (1) CN101517042B (fr)
BR (1) BRPI0715107A2 (fr)
DE (1) DE112007001743T5 (fr)
MX (1) MX2009000941A (fr)
RU (1) RU2405024C2 (fr)
WO (1) WO2008014150A2 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090321310A1 (en) * 2008-06-30 2009-12-31 Peter Kokayeff Three-Phase Hydroprocessing Without A Recycle Gas Compressor
US20090326289A1 (en) * 2008-06-30 2009-12-31 John Anthony Petri Liquid Phase Hydroprocessing With Temperature Management
US20090321319A1 (en) * 2008-06-30 2009-12-31 Peter Kokayeff Multi-Staged Hydroprocessing Process And System
US20100155294A1 (en) * 2006-12-29 2010-06-24 Uop Llc Hydrocarbon conversion process
US20100329942A1 (en) * 2009-06-30 2010-12-30 Petri John A Apparatus for multi-staged hydroprocessing
US20100326884A1 (en) * 2009-06-30 2010-12-30 Petri John A Method for multi-staged hydroprocessing
US20110064909A1 (en) * 2006-05-24 2011-03-17 Auxetic Technologies Limited composite material
US20130098802A1 (en) * 2011-07-29 2013-04-25 Omer Refa Koseoglu Hydrocracking process with interstage steam stripping
US10988421B2 (en) 2013-12-06 2021-04-27 Exxonmobil Chemical Patents Inc. Removal of bromine index-reactive compounds

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102029128B (zh) * 2009-09-28 2012-06-27 中国石油化工股份有限公司 一种产物循环的加氢处理方法
US20120074038A1 (en) * 2010-09-27 2012-03-29 Uop Llc Liquid phase hydroprocessing with low pressure drop
US9365781B2 (en) 2012-05-25 2016-06-14 E I Du Pont De Nemours And Company Process for direct hydrogen injection in liquid full hydroprocessing reactors
RU2593262C1 (ru) * 2015-05-05 2016-08-10 Дмитрий Львович Астановский Способ гидрогенизационной обработки нефтяного сырья
EP3516014A4 (fr) 2016-09-21 2020-04-22 Hindustan Petroleum Corporation Limited Procédé de conversion d'hydrocarbures

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328290A (en) * 1965-03-30 1967-06-27 Standard Oil Co Two-stage process for the hydrocracking of hydrocarbon oils in which the feed oil ispretreated in the first stage
US5403469A (en) * 1993-11-01 1995-04-04 Union Oil Company Of California Process for producing FCC feed and middle distillate
US5720872A (en) * 1996-12-31 1998-02-24 Exxon Research And Engineering Company Multi-stage hydroprocessing with multi-stage stripping in a single stripper vessel
US5904835A (en) * 1996-12-23 1999-05-18 Uop Llc Dual feed reactor hydrocracking process
US5980729A (en) * 1998-09-29 1999-11-09 Uop Llc Hydrocracking process
US6106694A (en) * 1998-09-29 2000-08-22 Uop Llc Hydrocracking process
US6123835A (en) * 1997-06-24 2000-09-26 Process Dynamics, Inc. Two phase hydroprocessing
US20050082202A1 (en) * 1997-06-24 2005-04-21 Process Dynamics, Inc. Two phase hydroprocessing
US20060144756A1 (en) * 1997-06-24 2006-07-06 Ackerson Michael D Control system method and apparatus for two phase hydroprocessing

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT642040A (fr) 1959-12-30 1900-01-01
US3238290A (en) 1963-03-13 1966-03-01 Charles A Ruple Dead end anchor for high voltage cables
US4363718A (en) 1979-08-23 1982-12-14 Standard Oil Company (Indiana) Crystalline chromosilicates and process uses
AU658131B2 (en) * 1990-11-07 1995-04-06 Davy Process Technology Limited Hydrodesulphurisation process

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328290A (en) * 1965-03-30 1967-06-27 Standard Oil Co Two-stage process for the hydrocracking of hydrocarbon oils in which the feed oil ispretreated in the first stage
US5403469A (en) * 1993-11-01 1995-04-04 Union Oil Company Of California Process for producing FCC feed and middle distillate
US5904835A (en) * 1996-12-23 1999-05-18 Uop Llc Dual feed reactor hydrocracking process
US5720872A (en) * 1996-12-31 1998-02-24 Exxon Research And Engineering Company Multi-stage hydroprocessing with multi-stage stripping in a single stripper vessel
US6123835A (en) * 1997-06-24 2000-09-26 Process Dynamics, Inc. Two phase hydroprocessing
US6428686B1 (en) * 1997-06-24 2002-08-06 Process Dynamics, Inc. Two phase hydroprocessing
US20050082202A1 (en) * 1997-06-24 2005-04-21 Process Dynamics, Inc. Two phase hydroprocessing
US20060144756A1 (en) * 1997-06-24 2006-07-06 Ackerson Michael D Control system method and apparatus for two phase hydroprocessing
US5980729A (en) * 1998-09-29 1999-11-09 Uop Llc Hydrocracking process
US6106694A (en) * 1998-09-29 2000-08-22 Uop Llc Hydrocracking process

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110064909A1 (en) * 2006-05-24 2011-03-17 Auxetic Technologies Limited composite material
US7989057B2 (en) * 2006-05-24 2011-08-02 Auxetic Technologies Limited Composite material
US20100155294A1 (en) * 2006-12-29 2010-06-24 Uop Llc Hydrocarbon conversion process
US7906013B2 (en) 2006-12-29 2011-03-15 Uop Llc Hydrocarbon conversion process
US8999141B2 (en) 2008-06-30 2015-04-07 Uop Llc Three-phase hydroprocessing without a recycle gas compressor
US20090326289A1 (en) * 2008-06-30 2009-12-31 John Anthony Petri Liquid Phase Hydroprocessing With Temperature Management
US20090321319A1 (en) * 2008-06-30 2009-12-31 Peter Kokayeff Multi-Staged Hydroprocessing Process And System
US20090321310A1 (en) * 2008-06-30 2009-12-31 Peter Kokayeff Three-Phase Hydroprocessing Without A Recycle Gas Compressor
US9279087B2 (en) 2008-06-30 2016-03-08 Uop Llc Multi-staged hydroprocessing process and system
US8008534B2 (en) 2008-06-30 2011-08-30 Uop Llc Liquid phase hydroprocessing with temperature management
US20100329942A1 (en) * 2009-06-30 2010-12-30 Petri John A Apparatus for multi-staged hydroprocessing
US8518241B2 (en) 2009-06-30 2013-08-27 Uop Llc Method for multi-staged hydroprocessing
US8221706B2 (en) 2009-06-30 2012-07-17 Uop Llc Apparatus for multi-staged hydroprocessing
US20100326884A1 (en) * 2009-06-30 2010-12-30 Petri John A Method for multi-staged hydroprocessing
US20130098802A1 (en) * 2011-07-29 2013-04-25 Omer Refa Koseoglu Hydrocracking process with interstage steam stripping
US9803148B2 (en) * 2011-07-29 2017-10-31 Saudi Arabian Oil Company Hydrocracking process with interstage steam stripping
US10988421B2 (en) 2013-12-06 2021-04-27 Exxonmobil Chemical Patents Inc. Removal of bromine index-reactive compounds

Also Published As

Publication number Publication date
DE112007001743T5 (de) 2009-06-18
MX2009000941A (es) 2009-02-05
WO2008014150A2 (fr) 2008-01-31
CN101517042B (zh) 2013-04-10
WO2008014150A3 (fr) 2008-10-16
BRPI0715107A2 (pt) 2013-03-26
RU2009106855A (ru) 2010-09-10
CN101517042A (zh) 2009-08-26
RU2405024C2 (ru) 2010-11-27

Similar Documents

Publication Publication Date Title
US20080023372A1 (en) Hydrocracking Process
US5980729A (en) Hydrocracking process
CA2344953C (fr) Procede d'hydrocraquage ameliore
US8999141B2 (en) Three-phase hydroprocessing without a recycle gas compressor
US6379532B1 (en) Hydrocracking process
EP1103592B1 (fr) Procédé d'hydrocraquage
US6623623B2 (en) Simultaneous hydroprocessing of two feedstocks
US7906013B2 (en) Hydrocarbon conversion process
US20080159928A1 (en) Hydrocarbon Conversion Process
US6638418B1 (en) Dual recycle hydrocracking process
US20060118464A1 (en) Hydrocarbon conversion process
US7108779B1 (en) Hydrocarbon desulfurization process
EP1270705B1 (fr) Procédé d'hydrogénation simultanée de deux charges
US7041211B2 (en) Hydrocracking process
US7470357B1 (en) Hydrocarbon conversion process
WO2008010799A1 (fr) Procédé de désulfurisation d'hydrocarbures
US7842180B1 (en) Hydrocracking process
CA2423946A1 (fr) Processus d'hydrocraquage
CA2491012C (fr) Procede d'hydrocraquage ameliore
EP1752511B1 (fr) Procédé d'hydrocraquage pour la production de diesel à teneur en soufre ultra-faible
CA2525650C (fr) Methode d'hydrocraquage pour la production de carburant diesel a tres basse teneur en soufre
AU5394101A (en) Simultaneous hydroprocessing of two feedstocks
CA2552275A1 (fr) Processus integre de production de diesel a tres faible teneur en soufre et de mazout a faible teneur en soufre

Legal Events

Date Code Title Description
AS Assignment

Owner name: UOP LLC, ILLINOIS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LEONARD, LAURA E;KOKAYEFF, PETER;REEL/FRAME:018010/0954

Effective date: 20060726

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载