WO2012005861A1 - Procédé intégré de vapocraquage - Google Patents

Procédé intégré de vapocraquage Download PDF

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Publication number
WO2012005861A1
WO2012005861A1 PCT/US2011/039776 US2011039776W WO2012005861A1 WO 2012005861 A1 WO2012005861 A1 WO 2012005861A1 US 2011039776 W US2011039776 W US 2011039776W WO 2012005861 A1 WO2012005861 A1 WO 2012005861A1
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WO
WIPO (PCT)
Prior art keywords
vapor
resid
thermal conversion
liquid
steam
Prior art date
Application number
PCT/US2011/039776
Other languages
English (en)
Inventor
S. Mark Davis
Richard C. Stell
Jiunn-Shyan Liou
Stephen H. Brown
Paul F. Keusenkothen
Arthur R. Di Nicolantonio
Jason J. Waldrop
Original Assignee
Exxonmobil Chemical Patents Inc.
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
Priority claimed from US12/833,556 external-priority patent/US8399729B2/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to CN201180033756.0A priority Critical patent/CN103154203B/zh
Priority to SG2012088456A priority patent/SG186124A1/en
Publication of WO2012005861A1 publication Critical patent/WO2012005861A1/fr

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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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/005—Coking (in order to produce liquid products mainly)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
    • C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/007—Visbreaking
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • 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
    • C10G2300/30—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
    • C10G2300/70—Catalyst aspects
    • C10G2300/708—Coking aspect, coke content and composition of deposits
    • 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
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • C10G2300/807—Steam
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • the invention relates to a method of making olefins from a crude or resid- containing crude fraction in a steam cracking furnace or a pyrolysis furnace.
  • Thermal cracking of hydrocarbons is a petrochemical process that is widely used to produce olefins such as ethylene, propylene, butylenes, butadiene, and aromatics such as benzene, toluene, and xylenes.
  • olefins such as ethylene, propylene, butylenes, butadiene, and aromatics such as benzene, toluene, and xylenes.
  • the olefins may be oligomerized (e.g., to form lubricant basestocks), polymerized (e.g., to form polyethylene, polypropylene, and other plastics), and/or functionalized (e.g., to form acids, alcohols, aldehydes and the like), all of which have well- known intermediate and/or end uses.
  • Steam cracking also referred to as pyrolysis, has long been used to crack various hydrocarbon feedstocks into olefins, preferably light olefins such as ethylene, propylene, and butenes.
  • the feedstock for steam cracking is a hydrocarbon such as naphtha, gas oil, or other non-resid containing fractions of whole crude oil, which may be obtained, for instance, by distilling or otherwise fractionating whole crude oil.
  • Conventional steam cracking utilizes a steam cracking furnace which has two main sections: a convection section and a radiant section.
  • the hydrocarbon feedstock typically enters the convection section of the furnace as a liquid (except for light feedstocks which enter as a vapor) wherein it is typically heated and vaporized by indirect contact with hot flue gas from the radiant section and by direct contact with steam.
  • the vaporized feedstock (and optional steam) mixture is then conveyed into the radiant section where the cracking takes place.
  • the vaporized mixture is introduced through crossover piping into the radiant section where it is quickly heated, at pressures typically ranging from about 10 to about 50 psig (69 to 345 kPa), to a severe hydrocarbon cracking temperature, such as in the range of from about 1450°F (788°C) to about 1650°F (900°C), to provide thorough thermal cracking of the feedstream.
  • the resulting products, including olefins leave the steam cracking furnace for further downstream processing.
  • the effluent from the pyrolysis furnace contains a variety gaseous hydrocarbons, e.g., saturated, monounsaturated, and polyunsaturated, and can be aliphatic and/or aromatic, as well as significant amounts of molecular hydrogen.
  • the cracked product is then further processed such as in the olefin production plant to produce, as products of the plant, the various separate individual streams of high purity, i.e., hydrogen, the light olefins ethylene, propylene, butylenes, and aromatic compounds, as well as other products such as pyrolysis gasoline.
  • knock-out drums integrated with the steam cracking furnace has evolved as an important extension of this platform to enable processing of heavier feedstocks such as atmospheric resids.
  • the knock-out drum provides a means to separate the heaviest components from crackable gas oil molecules and prevent the heaviest, asphaltene-type molecule containing fractions from fouling the steam cracking furnace.
  • most of the heavy vacuum resid molecules, which are favored as feedstock due to lower cost remain in the liquid phase and are not converted in the radiant section of the steam cracking furnace.
  • This invention discloses a method for producing chemicals from heavy feedstocks in a manner where significant portions of the vacuum resid are converted to lighter molecules which can be more easily vaporized in the knock-out drum and subsequently converted to fuels and chemicals.
  • This invention relates to a process for cracking hydrocarbon feedstock containing resid comprising:
  • this invention relates to a process for cracking hydrocarbon feedstock containing resid comprising:
  • a vapor/liquid separator such as a knock-out drum
  • said separator being in fluid communication with (e.g., integrated into) a steam cracking furnace, to form a second vapor phase and second liquid phase;
  • the liquid phase exiting the first vapor/liquid separator is further heated to a temperature such as 1000 to 1200°F (538-649°C), typically in the lower coils of the convection section of a steam cracker, typically a portion of the heated material typically is visbroken, thereafter water (such as steam) is used to quench and vaporize the visbroken materials the reaction, the vaporized visbroken material is then passed to a second vapor/liquid separator where the visbroken material is separated into a liquid phase and a vapor phase.
  • a temperature such as 1000 to 1200°F (538-649°C)
  • water such as steam
  • the vapor phase is then introduced into a steam cracker (either in the convection section or the radiant section) and where at least 30 wt% olefins are recovered from the material exiting the radiant furnace (based upon the weight of the total hydrocarbon material exiting the radiant furnace).
  • the initial hydrocarbon feedstock typically contains between
  • the resid containing liquid from the second vapor/liquid separator is not processed further for producing chemicals. Instead this material is preferably used as a blendstock into fuel oil or for further refinery processing for producing fuels.
  • this invention relates to a process for cracking hydrocarbon feedstock containing vacuum resid comprising:
  • a first thermal conversion zone preferably containing coke particles, preferably the zone has a coke particle/fresh feed ratio(wt/wt) of at least 1 : 1 (preferably at least 3: 1, preferably at least 5: 1, alternately from 1 : 1 to 50: 1, preferably from 3: 1 to 30: 1), based on the weight of circulating coke solids and fresh feed entering the zone) to thermally convert at least a portion of said resid-containing liquid phase;
  • Figure 1 is a flow diagram of an embodiment of the present invention process.
  • Figure 2 is a flow diagram of an embodiment of the present invention process.
  • Figure 3 is a flow diagram of an embodiment of the present invention process.
  • Figure 4 is a flow diagram of an embodiment of the present invention process.
  • This invention involves integration of a heavy feed steam cracker including an integrated vacuum resid vapor/liquid separator (e.g., knock-out drum) with a thermal conversion unit, such as a delayed coker, fluid coker, FlexicokerTM, visbreaker, or catalytic hydrovisbreaker, where vacuum resid is converted to lighter components that are suitable for steam cracking.
  • a thermal conversion unit such as a delayed coker, fluid coker, FlexicokerTM, visbreaker, or catalytic hydrovisbreaker, where vacuum resid is converted to lighter components that are suitable for steam cracking.
  • Suitable for steam cracking means that the materials can be cracked in a steam cracker.
  • a steam cracking furnace (also referred to as a "steam cracker”) is a pyrolysis furnace that has two main sections or furnaces: a convection section and a radiant section, where hydrocarbon feedstock enters the less severe convection section of the furnace as a liquid (except for light feedstocks which enter as a vapor) and where the feedstock is heated and vaporized typically by indirect contact with hot flue gas from the radiant section and is optionally contacted with steam.
  • the vaporized feedstock and steam mixture is then conveyed into the radiant section where it is quickly heated, at pressures typically ranging from about 10 to about 50 psig (69 to 345 kPa-gauge), to a severe hydrocarbon cracking temperature, such as in the range of from about 1450°F (788°C) to about 1650°F (900°C), to provide thorough thermal cracking of the feedstream.
  • the resulting products typically comprise olefins, aromatics and dienes.
  • Resid as used herein refers to the complex mixture of heavy petroleum compounds otherwise known in the art as residuum or residual.
  • Atmospheric resid is the bottoms product produced in atmospheric distillation when the endpoint of the heaviest distilled product is nominally 650°F (343°C), and is referred to as 650°F + (343°C + ) resid.
  • Vacuum resid is the bottoms product from a column under vacuum when the heaviest distilled product is nominally 1050°F (566°C), and is referred to as 1050°F + (566°C + ) resid.
  • At least a portion of the 650°F + resid, up to at least the 1050°F + boiling point fraction, is vaporized, such as when combined with steam, and/or when the pressure is reduced or flashed in the knock-out drum of the steam cracker.
  • vacuum resid containing hydrocarbon feedstock means that the identified resid is present at at least 0.1 wt%, based upon the weight of the hydrocarbon feedstock (preferably at least 1 wt%, preferably at least 10 wt%, preferably at least 15 wt%, preferably at least 20 wt%).
  • flash drum flash pot
  • knock-out drum knock-out pot
  • flash drum means generally to effect a phase change for at least a portion of the material in the vessel from liquid to vapor, via a reduction in pressure and/or an increase in temperature.
  • An integrated knock-out drum is a vapor/liquid separator that is in fluid communication with a steam cracker.
  • the integrated knock-out drum is in fluid communication with the convection section of a steam cracker, where feedstock is heated (optionally mixed with superheated steam) and transferred to said knock-out drum operating as a vapor/liquid separator, thereafter the vapors from the knock-out drum are returned to the steam cracker, preferably either to the convection or radiant section, or both.
  • the addition of steam may further assist flash separation by reducing the hydrocarbon partial pressure, assist in conversion and vaporization of the 750°F + (399°C ) to 1050°F + (566°C ) (preferably even a substantial portion of the 1100°F + (593°C + )) resid fractions, and prevent fouling.
  • the vapor/liquid separator operates at a temperature and pressure where those portions of the feed material that cause coking are kept in a liquid state, preferably operates at a temperature of between about 375 to 525°C, preferably from 400 to 500°C, preferably from 800°F (about 425°C) and about 870°F (about 465°C), but also typically not over about 900°F (about 482°C).
  • a crude oil or fraction thereof containing resid is utilized as a feedstock for a steam cracking furnace.
  • Suitable lower value feeds may typically include heavier crudes, defined as those hydrocarbon feedstocks that have a low API gravity as a result of high concentrations of 650°F + (343°C + ) resid, high sulfur, high Total Acid Number (TAN), high naphthenes, high aromatics, and/or low hydrogen content.
  • Crude as used herein, means whole crude oil as it issues from a wellhead, production field facility, transportation facility, or other initial field processing facility, optionally including crude that has been processed by a step of desalting, treating, and/or other steps as may be necessary to render it acceptable for conventional distillation in a refinery. Crude as used herein is presumed to contain resid.
  • Crude fractions are typically obtained from the refinery pipestill. Although any crude fraction obtained from the refinery pipestill may be useful in the present invention, a significant advantage offered by the present invention is that crude or crude fractions still containing all or a portion of the original 1050°F + (566°C ) resid present in the whole crude obtained from the wellhead may be used as feed for a steam cracker.
  • the crude or other feedstock to the present system may comprise at least about 1 wt% 1050°F + (566°C ) resid, preferably at least about 5 wt% 1050°F (566°C ) resid, and more preferably at least about 10 wt% 1050°F + (566°C + ) resid up to about 50 wt% 1050°F + (566°C + ) resid.
  • Resid typically contains a high proportion of undesirable impurities such as metals, sulfur, and nitrogen, as well as high molecular weight (Ci 2 + ) naphthenic acids (measured in terms of TAN according to ASTM D-664, TAN refers to a total acid number expressed as milligrams ("mg") of KOH per gram ("g") of sample).
  • TAN high molecular weight naphthenic acids
  • this invention can be practiced on 566°C + resid having: one or more (preferably two, three, four, five, six or seven) of the following properties: 1) 50 ppm of Ni or more, alternately 100 ppm or more, alternately 125 ppm or more, based upon the weight of the 566°C + resid; and/or 2) 200 ppm vanadium or more, alternately 500 ppm or more, alternately 900 ppm or more, based upon the weight of the 566°C + resid; and/or 3) 4 wt% sulfur or more, alternately 5 wt% or more, alternately 6 wt% or more, based upon the weight of the 566°C + resid; and/or 4) a TAN of at least 0.1, alternately at least 0.3, alternately from about 0.1 to about 20, about 0.3 to about 10, or about 0.4 to about 5; and/or 5) an API gravity of 19 or less (AST)
  • Example resids that can be used herein are the 566°C + resids obtained from crudes including, but not limited to, crudes from of the following regions of the world: U.S. Gulf Coast, southern California, north slope of Alaska, Canada tar sands, Canadian Alberta region, Mexico Bay of Campeche, Argentinean San Jorge basin, Brazilian Santos and Campos basins, Egyptian Gulf of Suez, Chad, United Kingdom North Sea, Angola Offshore, China Bohai Bay, China Karamay, Iraq Zagros, Ukraine Caspian, Nigeria Offshore, Madagascar northwest, Oman, Netherlands Schoonebek, Venezuelan Zulia, Malaysia, and Indonesia Sumatra.
  • Additional resids useful herein include 566 + °C + resids obtained from crude oils described as "disadvantaged" in US 7,678,264, incorporated by reference herein.
  • the feed comprises crude or atmospheric resid that contain appreciable amounts of 1050°F + (566°C + ) resid, e.g., 10 wt% or more of 1050°F + (566°C + ) resid, or 20 wt% or more of 1050°F + (566°C + ) resid, or 30 wt% or more of 1050°F + (566°C + ) resid, or 40 wt% or more of 1050°F + (566°C + ) resid, or even up to 50 wt% of 1050°F + (566°C + ) resid
  • the resid-containing feed is passed into a first steam cracking furnace with integrated knock-out drum.
  • a thermal conversion unit such as a delayed coker, fluid coker, FlexicokerTM, visbreaker or catalytic hydro visbreaker, where it is heated and at least 30 wt% (based upon the weight of the feed) of the vacuum resid is converted to a 1050°F " (566°C ⁇ ) cut.
  • a 1050°F " (566°C ) cut is defined to be hydrocarbons normally boiling below 1050°F " (566°C ⁇ ).
  • the thermally converted resid is introduced to a knock-out drum, said drum being integrated into a steam cracking furnace, to form an overhead vapor phase and liquid bottoms phase.
  • Said vapor phase is passed to the radiant furnace in said steam cracking furnace. At least 30 wt% olefins are recovered from the material exiting the radiant furnace (based upon the weight of the total hydrocarbon material exiting the radiant furnace).
  • the addition of steam may further assist flash separation by reducing the hydrocarbon partial pressure, assist in conversion and vaporization of the 750°F + (399°C + ) to 1150°F + (621°C + ) resid fractions, and prevent fouling.
  • the fluid coker preferably includes an integrated air gasifier (or partial oxidation reactor) which is used to convert coke to fuel gas by steam/air gasification and combustion at between about 1400-1800°F (760-982°C).
  • This gasification can be facilitated by cofeeding oxygen or by using oxygen enriched air.
  • Hot, partially gasified coke from this gasification reaction is continuously withdrawn from the gasifier and fed to one or more solids transfer lines where it is contacted with the bottoms material recovered from one or more steam cracking furnaces equipped with integrated vapor/liquid separators (such as knock-out drums).
  • This residual oil fraction is converted at 1300-1800°F (704-982°C) to a mixture of lighter hydrocarbons containing high concentrations of ethylene and propylene.
  • the transfer line reactors can be configured in several ways, a preferred configuration is similar to that used in fluid catalytic cracking units; e.g., the transfer line is operated as a vertical riser reactor where the hot solids are contacted with feed near the bottom of the riser, the solids and vapor are transported upward along the riser, and the solids and vapor are separated using one or more cyclones in series.
  • the transfer line can be operated as "downer" or downflow reactor. Irrespective of the specific configuration, the transfer line reactor is highly effective for contacting hot coke with the residual oil.
  • vacuum resid from a refinery can be passed directly into the resid conversion unit and then used as feedstock for a steam cracking furnace equipped with an integrated knock-out drum.
  • the flash drum preferably operates at a temperature of from about 800°F (about 425°C) and about 870°F (about 465°C), but also typically not over about 900°F (about 482°C). Flashing material through the flash drum to obtain an overhead vapor and liquid bottoms further facilitates vaporization of the 650°F + (343°C ) resids.
  • Liquid products produced in resid thermal cracking can produce high yields of chemicals in the steam cracker and show reduced tendency (versus the 1050°F + (566°C + ) resid) for fouling the steam cracking furnace.
  • This invention further relates to a process for producing chemicals from heavy feedstocks in a manner where more of the vacuum resid is largely converted to fuels and chemicals.
  • the process involves integration of a heavy feed steam cracker including an integrated vacuum resid knock-out drum with a secondary thermal conversion reactor where vacuum resid is converted to lighter components that are suitable for steam cracking.
  • the secondary thermal conversion reactor is normally operated in a similar time/temperature window as conventional visbreaking and coking processes, although it can be advantageous to operate at somewhat milder conditions than are normally employed for producing fuels.
  • the thermal conversion reactor operates at 25°C or more (alternately 50°C or more, alternately 75°C or more) below the operating temperature of the furnace section of the steam cracker following the thermal conversion reactor. In some embodiments it is preferable to cascade the lighter liquids and gases through the radiant section of the steam cracker without condensation. By closely integrating the two conversion processes, one operating at milder severity and one operating at high severity, the process is able to convert a much wider range of heavy feeds to high value chemicals. (When a reactor or reaction zone is stated to be "operating at" a certain temperature it means that material in the reactor or zone has been heated to that temperature.)
  • knock-out drum may be taken to generally refer to any vapor/liquid separator device.
  • FIG. 1 A basic flow scheme for the process of the invention is shown in Figure 1, where a hydrocarbon feedstock (containing atmospheric resid) 100 is introduced to a first thermal conversion reactor 600 where at least 30 wt% (preferably at least 50%, preferably at least 70%, preferably about 90%) of the resid is converted to a 1050°F (566°C ) cut and/or petroleum coke.
  • a hydrocarbon feedstock (containing atmospheric resid) 100 is introduced to a first thermal conversion reactor 600 where at least 30 wt% (preferably at least 50%, preferably at least 70%, preferably about 90%) of the resid is converted to a 1050°F (566°C ) cut and/or petroleum coke.
  • the whole liquid and vapor product is then introduced (207) to a knock-out drum 205 (typically operating at 800 to 900°F (423 to 482°C)), said drum being in fluid communication with (e.g., integrated into) a steam cracking furnace 200 (having a convection furnace 206 and a radiant furnace 250) to form an overhead vapor phase 210 and liquid bottoms phase 220.
  • a knock-out drum 205 typically operating at 800 to 900°F (423 to 482°C)
  • a steam cracking furnace 200 having a convection furnace 206 and a radiant furnace 250
  • the vapor phase 210 is then passed to the radiant furnace 250 in said steam cracking furnace 200, either directly or via a heater, such a transfer line heater or a convection section 206 of the steam cracker 200, where the radiant section is typically operating at 750 to 900°C, and at least 30 wt% (preferably 40% or more) of the radiant section feed is converted to light olefins (e.g., C 2 , C 3 C 4 ) which are recovered from the material exiting the radiant furnace 221 (based upon the weight of the total hydrocarbon material exiting the radiant furnace).
  • a heater such a transfer line heater or a convection section 206 of the steam cracker 200
  • the radiant section is typically operating at 750 to 900°C, and at least 30 wt% (preferably 40% or more) of the radiant section feed is converted to light olefins (e.g., C 2 , C 3 C 4 ) which are recovered from the material exiting the radiant furnace 221 (based upon the weight of the total hydrocarbon
  • FIG. 2 Another basic flow scheme for the process of the invention is shown in Figure 2, where a resid containing hydrocarbon feedstock 100 is heated (typically in the convection furnace 206 of a steam cracker furnace) and, preferably, at least 10 wt% (preferably at least 20 wt%, preferably at least 25 wt%, alternately from about 20-30%) of the vacuum resid is converted to a 1050°F " (566°C ⁇ ) cut. The whole feed is heated to about 750-850°F (399- 454°C). The heated feedstock is then passed 207 to a knock-out drum 205 (preferably integrated into a steam cracker furnace), typically operating at 800 to 900°F (423 to 482°C).
  • a knock-out drum 205 preferably integrated into a steam cracker furnace
  • the heated feedstock is then separated (typically in the flash drum by centrifugal forces and gravity settling of coalesced liquid droplets) to form an overhead vapor phase 210 and a liquid bottoms phase 220 containing said resid.
  • the liquid bottoms phase 220 is then passed to a thermal conversion reactor 300, optionally containing coke particles, where it is more highly converted into lighter molecules 223 boiling below 1050°F (566°C).
  • the lighter molecules 223 are then passed to a knock-out drum 205* (typically operating at 800 to 900°C), said drum preferably being integrated into a steam cracking furnace, to form a second overhead vapor phase 210* and second liquid bottoms phase 220*.
  • the overhead vapor phase 210* is then passed to the radiant furnace 250* (typically operating at 750 to 900°C), in a steam cracking furnace, preferably the steam cracking furnace that the knock-out drum 205* is integrated with. Thereafter at least 30 wt% (preferably at least 40% light olefins (e.g., C 2 , C 3 , C 4 olefins) are recovered from the material exiting the radiant furnace 225 (based upon the weight of the total hydrocarbon material exiting the radiant furnace).
  • a steam cracking furnace typically operating at 750 to 900°C
  • at least 30 wt% preferably at least 40% light olefins (e.g., C 2 , C 3 , C 4 olefins) are recovered from the material exiting the radiant furnace 225 (based upon the weight of the total hydrocarbon material exiting the radiant furnace).
  • FIG. 3 Another basic flow scheme for the process of the invention is shown in Figure 3.
  • a heavy feedstock crude or vacuum resid 101 (preferably containing about 10 to 50% molecules boiling in the vac resid range (1050°F + (566°C + )) 100 is fed to a first steam cracking furnace 200 which includes an integrated knock-out drum 205.
  • the whole feed is heated to about 750-850°F (399-455°C) in the convection section 206 of the furnace.
  • the whole feed passes 207 into the knock-out drum separation device 205 where molecules boiling below about 1000-1100°F (538-593°C) are vaporized (or remain vaporized) and are separated from heavier compounds which remain in the liquid phase.
  • Material typically enters the drum at a temperature of about 800-850°F (427-454°C) and vaporization is facilitated by the use of steam stripping or stripping with light hydrocarbons.
  • the vapors pass overhead 210 into the radiant section 250 of the first steam cracking furnace, whereas the heavy liquids are withdrawn from the bottom of the knock-out drum 220.
  • the heavy liquid molecules are then directed to a secondary conversion reactor 300 where the heavy liquids are thermally cracked into lighter molecules.
  • the light molecules then pass 221 to a drum separation device 400 integrated in a steam cracker furnace (not shown) where molecules boiling below about 538-593°C are vaporized (or remain vaporized) and are separated from heavier compounds which remain in the liquid phase.
  • Material typically enters the drum at a temperature of about 427-470°C and vaporization is facilitated by the use of steam stripping or stripping with light hydrocarbons.
  • the vapors pass overhead through line 410 into the radiant section (not shown) of a steam cracking furnace, whereas the bottoms are withdrawn from the bottom of the knock-out drum through line 420.
  • Steam may be introduced into the steam cracking furnace (not shown).
  • Bottoms 420 from the knock-out drum may be used for fuel oil, among other things.
  • the material exiting the thermal conversion reactor is not reintroduced into the first steam cracker.
  • the secondary conversion reactor can be directly coupled with the steam cracking furnace and can take the form of a delayed coker drum, a fluid coker, a flexicoker, a visbreaker, a catalytic hydrovisbreaker, or other suitable conversion reactor designs.
  • the feed can be further preheated to about 800-900°F (427-482°C) before entering the coking reactor by reheating in a reboiler or furnace or by contacting with a hot gas such as steam or hydrogen.
  • a high fraction of the vacuum resid molecules (e.g., above about 50%) are thermally cracked into lighter molecules which boil below 1050°F (566°C).
  • resid molecules are normally in the range of 30-60% in visbreaking or up to 95% or more in once through catalytic hydrovisbreaking or coking. This is accomplished by balancing the reaction temperature and residence time with stripping of lighter liquid products in the conversion vessel which is operated adiabatically.
  • a significant fraction of the heavy vacuum resid molecules are converted to a solid coke product with low hydrogen content or to heavier tar-like bottoms fractions.
  • a catalytic hydrovisbreaker in addition to producing a heavier, tar-like bottoms fraction with low hydrogen content, hydrogen is added to feed heteroatoms to produce H 2 S, NH 3 , and H 2 0 and to cracked olefmic fragments to prevent coking.
  • the reaction is continued until the drum gradually fills with solid coke.
  • the feed is then switched to a second drum, while coke is removed from the first drum, and the process is continued in a cyclic manner.
  • vapor and liquid product from the coking reaction are fed to a second steam cracking furnace incorporating an integrated knock-out drum.
  • This furnace may be operated with a slightly lower knock-out drum temperature or cut point as compared to the first furnace (or group of furnaces used to supply the coker feed), preferably the second knock-out drum operates at 25°C or more (preferably 50°C or more, preferably 75°C or more) below the operating temperature of the first knock-out drum.
  • Lighter molecules generated in the coking (or secondary conversion) reactor remain vaporized and pass into the radiant section of the steam cracker, whereas the heavier vacuum gas oil (VGO) molecules and material that was not converted in the coker are withdrawn from the bottom of the second knock-out drum.
  • these molecules are disposed by other means, for example blending into fuel oil, and are not recycled back to the coker as is normally practiced in fuels coking processes.
  • hot vapor overhead from the coker can be partially quenched using a cooler VGO or distillate stream between the outlet of the coker and the inlet of the knock-out drum in order to promote further condensation of heavier VGO components with lower hydrogen content.
  • Fuel cokers are normally equipped with a large primary fractionator which is used to preheat fresh feed by mixing with coker products and to scrub the coker vapor of entrained liquid droplets by mixing coker feedstock with the coker drum vapor stream. Bottoms reenter the reactor with this fresh feed. In the integrated steam cracking process, this primary fractionator is eliminated.
  • the integrated knock-out drum is particularly efficient and effective with regards to the operation of heavy feed steam cracking and coking processes without fouling, as it allows cut points between the vapor and heavy liquids to be easily varied consistent with the properties of the feedstock.
  • a particularly preferred configuration is the direct integration of a thermal cracking process with a steam cracker.
  • direct integration is meant that that the steam cracker convection section heats the feed to the thermal conversion device and the effluent of the thermal conversion device passes directly to the knock-out drum and then to the radiant section without passing through any intermediate heat exchangers.
  • Preferred thermal conversion reactors for use herein include delayed cokers, fluid cokers, FlexicokersTM, visbreakers and catalytic hydrovisbreakers.
  • a preferred basic configuration for the thermal conversion reactor is similar to a delayed coker. Specifically the process: i) operates at a slightly lower severity (e.g., from 800 to 900°F (427-482°C), preferably 800 to 850°F (427-454°C), ii) uses about 0.1 to 1.0 kg of steam per kg of resid feedstock, iii) operates coke drums at lower hydrocarbon vapor partial pressures and/or shorter vapor residence times, iv) separates coking vapors from entrained heavy liquids in an integrated knock-out drum device, and v) preferably operates once through without bottoms recycle. Delayed coking is described in an article by P.J. Ellis and C.A.
  • the preheated liquid feed exiting the bottom of the drum serving as a distillation tower and heat exchanger is typically at 360 to 400°C.
  • This hot liquid is passed through a pump which raises the liquid pressure to 300 to 600 psig (2.1 to 4.1 MPa).
  • the hot pressurized feed flows through the coker furnace where it is heated to close to 500°C.
  • the furnace effluent close to 500°C and 60 psig (414 kPa) flows into the coke drum which separates solid coke from vapors and entrained liquid droplets.
  • the volatile components can then be removed and passed to steam cracker (preferably a steam cracker having an integrated knock-out drum), leaving coke behind.
  • the material passed to the steam cracker is then converted into olefins.
  • the liquid phase from the first vapor/liquid separator is heated in a heating zone (such as a delayed coker) to coking temperatures (such as up to 649°C) and is then conducted to a coking zone wherein volatiles are collected overhead and coke is formed.
  • a heating zone such as a delayed coker
  • coking temperatures such as up to 649°C
  • the liquid phase from the first vapor/liquid separator is subjected to delayed coking which involves the thermal decomposition of petroleum resid to produce gas, liquid streams of various boiling ranges, and coke.
  • the liquid phase from the first vapor/liquid separator is rapidly heated in a fired heater or tubular furnace, then the heated liquid phase from the first vapor/liquid separator is then passed to a coking drum that is maintained at conditions under which coking occurs, generally at temperatures above about 400°C under super-atmospheric pressures.
  • the heated feed in the coker drum also forms volatile components that are removed and passed to steam cracker (preferably a steam cracker having an integrated knock-out drum), leaving coke behind.
  • steam cracker preferably a steam cracker having an integrated knock-out drum
  • a catalytic hydrovisbreaking reactor is used as the thermal conversion reactor 300, the heavy oil is mixed with catalyst (such as a metal sulfide) and a molecular hydrogen- containing gas (e.g., H 2 , syngas, fuel gas) and a high fraction of the vacuum resid molecules, such as at least about 60%, even between about 60-80%, or even up to 95%, are converted into lighter molecules which boil below 1050°F (566°C).
  • catalyst such as a metal sulfide
  • a molecular hydrogen- containing gas e.g., H 2 , syngas, fuel gas
  • Typical operating conditions include temperatures of 785-900°F (418-482°C), residence times of 2-100 minutes (0.1 to 5 LHSV (Liquid Hourly Space Velocity)), hydrogen treat rates of 500-5000 SCF/B, and operating pressures of 100-3000 psig (0.689-20.7 MPa). Preferred conditions are about 785- 860°F (418-460°C), 10-40 min (0.2 to 2 LHSV), 1000-2500 SCF/B, and 500-1500 psig (3.45-17.2 MPa).
  • Typical reactor designs include a coil reactor, a coil reactor combined with a pumparound soaker, or a slurry bubble column with liquids recirculation, although other designs are possible.
  • reaction conditions are optimized to match feed quality; e.g., lower quality feeds may require more severe conditions to achieve high conversions in the range of 50-95%, preferably about 60-80%.
  • Conventional facilities high and low pressure separators
  • Catalysts used in the catalytic hydro visbreaking process are normally based on sulfided transition metals. The most common metals are Mo, Ni, and Co.
  • catalysts are normally based on micrometer or sub micrometer sized metal sulfide particles dispersed in a carbonaceous matrix (a.k.a Microcat®).
  • the Microcat® can be based on molybdenum sulfide; other transition metal sulfides such as those produced from tungsten, vanadium, iron, nickel, and cobalt; or molybdenum sulfide in combination with one or more of these alternative transition metal sulfides, or combinations of the alternative transition metal sulfides. While molybdenum alone provides satisfactory operations for many feeds, use of other metals or multimetallic catalyst systems can provide improved performance for resid conversion, hydrogen addition, and desulfurization, e.g., higher catalytic activity.
  • Fresh catalyst is typically formed by mixing a heavy VGO cut with a low cost catalyst precursor such as ammonium heptamolybdate or phosphomolybdic acid and heating to 600-800°F (316-427°C) for 10-60 minutes.
  • Catalyst pre-forming is preferably carried out in the presence of hydrogen and H 2 S or elemental sulfur.
  • the Microcat® produced in this manner is stable over many cycles of conversion, filtration, and reuse. However, the catalyst can deactivate over long times. For this reason, it may be advantageous to remove a small purge stream from the process.
  • This "spent" catalyst can be regenerated in separate facilities or reformulated into fresh catalyst precursor.
  • the liquid phase exiting the first vapor/liquid separator is further heated to a temperature such as 1000 to 1200°F (538 to 649°C), preferably 1100 to 1200°F (593 to 649°C), preferably about 1125 to 1190°F (607 to 643°C), typically in the lower coils of the convection section of a steam cracker, where typically a portion of the heated material typically is visbroken, thereafter water (such as steam) is used to quench and vaporize the visbroken materials.
  • the vaporized visbroken material is then passed to a second vapor/liquid separator where the visbroken material is separated into a second liquid phase and a second vapor phase.
  • the second vapor phase is then introduced into a steam cracker (either in the convection section or the radiant section, or both) and at least 30 wt% olefins (preferably 40% or more, preferably 50 wt% or more) are recovered from the material exiting the radiant furnace (based upon the weight of the total hydrocarbon material exiting the radiant furnace).
  • a steam cracker either in the convection section or the radiant section, or both
  • at least 30 wt% olefins preferably 40% or more, preferably 50 wt% or more
  • the bottoms from the first knock-out drum are heated to 1000-1200°F (538 to 649°C) (preferably from 1100 to to 1200°F (593 to 649°C), preferably to about 1200°F (649 °C)) rapidly in the lower convection section where flue heat continually replaces endothermic heat losses.
  • 1000-1200°F 538 to 649°C
  • 1100 to to 1200°F 593 to 649°C
  • 649 °C preferably to about 1200°F (649 °C)
  • the bottoms are heated in only one pass so that the high velocity of the resid continually washes coke precursors off of the internal surfaces. If some coking does occur, periodic steam/air decoking will burn/spall it off the tubes.
  • the convection tubes can be porous sintered metal surrounded by a solid outside tube where steam is in the annulus.
  • the steam pressure is higher than the process pressure causing steam to seep though the sintered inner tube preventing coke laydown.
  • the visbroken bottoms (e.g., 1000-1200°F (538 to 649°C)) are then quenched rapidly upon exiting the convection section otherwise the extra residence time may cause excessive coking.
  • Steam and/or water are excellent quench mediums because they reduce the hydrocarbon partial pressure vaporizing a significant fraction of the newly formed light hydrocarbons. Note, during this quenching operation ample liquid is present, which prevents coking. In the vapor phase, two-molecule coking reactions are not favored (than the liquid phase) because the hydrocarbon concentration is low. In a preferred embodiment, any fouling that may still occur in the vapor phase is prevented by quenching to ⁇ 840°F (449° C). In an optional embodiment, a portion of the bottoms from the primary knock-out drum can aid in the quenching operations.
  • a small second knock-out drum separates visbroken light- hydrocarbons from remaining resid.
  • the piping to the second drum coalesces the remaining liquid, which then separates from the hydrocarbon vapor/steam mixture in the drum.
  • the second drum By operating the second drum at ⁇ 840°F(449°C) fouling in the vapor phase will be low.
  • the vapor can be conveyed either to the first knock-out drum or to the first drum's overhead piping.
  • the vapor/liquid from the quench can be directed to the piping upstream of the first knock-out drum eliminating the need for a second knock-out drum.
  • a dual knock-out drum design allows the bottoms from the first knock-out drum to be severely visbroken just once, reducing the likelihood of severe coking.
  • the secondary knock-out drum temperature is not so high (nor the hydrocarbon partial pressure so low) that the bottoms will not flow and/or can not be fluxed.
  • a preferred embodiment of the present invention is to prevent liquid deposition by steam tracing with superheated steam all vessels and lines downstream of the vapor/liquid separations.
  • the tracing steam which is significantly hotter than the process vapor, eliminates cold spots that may exist if these lines are only insulated. Even hotter steam can be used to superheat the vapor to a limited extent. If necessary, some of the tracing steam can be injected directly into the vapor to providing further superheating.
  • a significant advantage of the present invention is high utilization of heavy feeds without excessive coking.
  • a heavy feedstock crude or resid 101 (preferably containing about 10 to 50% molecules boiling in the vac resid range (1050°F + (566°C )) is fed to a first steam cracking furnace 200 which includes an integrated knock-out drum 205. The whole feed is heated to about 800 to 900°F (427 to 482°C) in the convection section 206 of the furnace.
  • the whole preheated feed 207 passes into the knock-out drum separation device 205 where molecules boiling below about 1000-1100°F (538-593°C) are vaporized (or remain vaporized) and are separated from heavier compounds which remain in the liquid phase. Material typically enters the drum at a temperature of about 800-850°F (427-454°C) and vaporization is facilitated by the use of steam stripping or stripping with light hydrocarbons.
  • the vapors pass 210 into the radiant section 250 of the first steam cracking furnace, whereas the heavy liquids are withdrawn from the bottom of the knock-out drum 220.
  • the heavy liquid molecules are then directed to the convection section 206 of the furnace (either by mixing with fresh feed or passing into a separate heating coil zone) where the heavy liquids are visbroken into lighter molecules.
  • Water or steam 227 is introduced to vaporize the lighter molecules (typically outside the convection section).
  • the visbroken light molecules then pass 221 to a knock-out drum separation device 400 integrated in a steam cracker furnace (not shown) where molecules boiling below about 538-593°C are vaporized (or remain vaporized) and are separated from heavier compounds which remain in the liquid phase.
  • the vapors pass 410 into the radiant section (not shown) of a steam cracking furnace, whereas the bottoms are withdrawn from the bottom of the knock-out drum through line 420.
  • Steam may be introduced into the steam cracking furnace (not shown). Bottoms 420 from the knock-out drum may be used for fuel oil, among other things.
  • the material exiting the thermal conversion reactor is not reintroduced into the first steam cracker.
  • the residual vacuum resid material remaining after primary conversion and separation in the knock-out drum is not recycled for additional conversion to chemicals.
  • This residual material contains highly refractory compounds, such as heptane insoluble polynuclear aromatics hydrocarbons, which are not preferred for chemical feeds. These residual molecules are better utilized by blending into fuel oil or optionally by converting in separate refinery resid conversion equipment to produce fuels.
  • the vacuum resid feed converted in this invention contains greater than 10.0 wt% hydrogen, preferably greater than 11.0 wt%.
  • the feed into the thermal conversion reaction (such as a coker or delayed coker) contains greater than 10.0 wt% hydrogen, preferably greater than 11.0 wt%, preferably greater than 11.5 wt%, based upon the weight of the feed.
  • the temperature of the gas exiting the thermal conversion reactor is 750 to 900°F (399 to 482°C), preferably 780 to 860°F (416 to 460°C), preferably 800 to 850°F (427 to 454°C).
  • the pressure in the thermal conversion reactor is up to 30 psig (207kPa), preferably up to 25 psig (172 kPa), preferably from 1 to 20 psig (138kPa).
  • the hydrocarbon feedstock is not cooled when passing from the convection section of the first steam cracking furnace to the integrated first knockout drum.
  • not cooled is meant that the mixed flow of feedstock liquid and vapor preferably does not drop in temperature by more than 30°C (alternately by not more than 50°C, alternately by not more than 100°C).
  • the hydrocarbon feedstock is not cooled when passing from the convection section of the second steam cracking furnace to the integrated second knock-out drum.
  • the thermally converted material (such as resid or liquid bottoms phase) is passed to the convection section of a steam cracker prior to entering the integrated knock-out drum.
  • molecular hydrogen (typically a molecular hydrogen containing gas) is added to the heated feedstock at any point in the process.
  • steam can be added to the heated feedstock at any point in the process. This can be especially useful to assist vaporization in the integrated knock-out drum zones.
  • the thermal conversion reactor operates at 649°C or less, preferably 640°C or less, preferably 630°C or less.
  • the thermal conversion reactor is a delayed coker operating with low severity conditions (e.g., temperature less than 860°F (460°C) and pressure of 30 kPa or less) and the output from the delayed coker is transferred directly into a knock-out drum, preferably the output from the delayed coker is transferred to a knock-out drum integrated into a steam cracker (the output from the delayed coker may be put through the convection section of the steam cracker before it is transferred to the integrated knock-out drum).
  • the feed to the delayed coker is heated in the convection section of the steam cracker and the effluent from the delayed coker drum flows directly in the knock-out pot that is integrated with the steam cracker radiant section.
  • a given coke drum can be integrated to supply feed to one or more steam cracker furnaces equipped with integrated knock-out drums. Integration of a multiple coke drums with one or more furnaces and knock-out pots is also possible. Instead of one drum, there could be two or three drums in parallel. One drum would be on stream and the others would be being emptied of coke.
  • vacuum resid is passed into a steam cracker convection section, then passed to a vapor/liquid separator (where the vapor/liquid separator is in fluid communication with the steam cracker, particularly the convection section of the steam cracker), thereafter the resid is converted into a vapor phase and a liquid phase.
  • the vapor phase is passed into the same or different steam cracker in the radiant or convection section, or both.
  • the liquid phase is passed to a thermal conversion zone, such as a coker, delayed coker, flexicoker, catalytic visbreaker or a catalytic hydrovisbreaker, where it is converted into a vapor or liquid stream and coke.
  • the vapor or liquid stream then passed into the convection section of a steam cracker (preferably a steam cracker different from the first steam cracker) and thereafter passed to a vapor/liquid separator (where the vapor/liquid separator is in fluid communication with the steam cracker, particularly the convection section of the steam cracker), and thereafter the heated vapor or liquid stream is converted into a vapor phase and a liquid phase and said vapor phase is passed into the same or different steam cracker in the radiant or convection section, or both.
  • a steam cracker preferably a steam cracker different from the first steam cracker
  • a vapor/liquid separator where the vapor/liquid separator is in fluid communication with the steam cracker, particularly the convection section of the steam cracker
  • this invention relates to:
  • a process for cracking hydrocarbon feedstock containing vacuum resid comprising:
  • step (b) is brought (e.g. heated or cooled) to a temperature of 538 to 649°C (alternately, less than 649°C) to visbreak at least a portion of the liquid bottoms phase; thereafter the visbroken liquid bottoms phase is quenched and subsequently passed to a second vapor/liquid separator, where the visbroken liquid bottoms phase is separated into a second liquid phase and a second vapor phase; thereafter the second vapor phase is then introduced into the steam cracking furnace of step (c).
  • a temperature of 538 to 649°C alternatively, less than 649°C
  • a process for cracking hydrocarbon feedstock containing vacuum resid comprising:
  • step (c) is heated to a temperature of 538 to 649°C to visbreak at least a portion of the liquid phase; thereafter the visbroken liquid phase is quenched and subsequently passed to a another vapor/liquid separator, where the visbroken liquid phase is separated into a visbroken liquid phase and a visbroken vapor phase; thereafter the visbroken vapor phase is then introduced into the thermal conversion zone of step (d).
  • the thermal conversion zone contains coke particles, where the zone has a coke particle/fresh feed ratio (wt/wt) of at least 1 : 1 (preferably at least 3: 1, preferably at least 5: 1, alternately from 1 : 1 to 50: 1, preferably from 3:1 to 30: 1), based on the weight of circulating coke solids and fresh feed entering the zone.
  • the thermal conversion zone is a delayed coker, a fluid coker, a FlexicokerTM, a visbreaker or a catalytic hydrovisbreaker.
  • a system for cracking hydrocarbon feedstock containing vacuum resid comprising: a) a first thermal conversion zone operating at a temperature of less than 649°C selected from the group consisting of: a delayed coker, a fluid coker, a FlexicokerTM, a visbreaker or a catalytic hydrovisbreaker, said first thermal conversion zone in fluid communication with b) a steam cracking furnace having a vapor/liquid separator in fluid communication with said furnace.
  • a transfer line reactor comprising a hydrocarbon feed inlet in fluid communication with a lower portion of said separator, and a pyrolysis product outlet line
  • At least one cyclone separator having an inlet connected to said pyrolysis product outlet line, a cracked product outlet at a top portion of said cyclone separator, and a solids outlet at the bottom of said cyclone separator.
  • said fluidized coker further comprises a fluidized bed heater vessel, having recirculating solids conduits connecting lower portions of said heater vessel and said gasifier, and at least one gas conduit connected between an upper portion of said gasifier and the lower portion of said heater vessel.
  • this invention relates to:
  • a process for cracking hydrocarbon feedstock containing vacuum resid comprising:
  • thermo conversion zone is a delayed coker, a fluid coker, a FlexicokerTM, a visbreaker or a catalytic hydrovisbreaker.
  • a process for cracking hydrocarbon feedstock containing vacuum resid comprising:
  • thermo conversion zone is a delayed coker, a fluid coker, a FlexicokerTM, a visbreaker or a catalytic hydrovisbreaker.
  • a system for cracking hydrocarbon feedstock containing vacuum resid comprising: a) a first thermal conversion zone operating at a temperature of less than 649°C selected from the group consisting of: a delayed coker, a fluid coker, a FlexicokerTM, a visbreaker or a catalytic hydrovisbreaker, said first thermal conversion zone in fluid communication with b) a steam cracking furnace having a vapor/liquid separator in fluid communication with said furnace.
  • a fluidized bed gasifier i) a transfer line reactor comprising a hydrocarbon feed inlet in fluid communication with a lower portion of said separator, and a pyrolysis product outlet line,
  • At least one cyclone separator having an inlet connected to said pyrolysis product outlet line, a cracked product outlet at a top portion of said cyclone separator, and a solids outlet at the bottom of said cyclone separator.
  • said fluidized coker further comprises a fluidized bed heater vessel, having recirculating solids conduits connecting lower portions of said heater vessel and said gasifier, and at least one gas conduit connected between an upper portion of said gasifier and the lower portion of said heater vessel.

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Abstract

La présente invention porte sur un procédé et un système pour le craquage d'une charge hydrocarbonée contenant un résidu sous vide, comprenant (a) la soumission d'un résidu sous vide à une première conversion thermique dans un réacteur de conversion thermique (tel qu'un cokéfacteur retardé, un cokéfacteur à lit fluidisé, un FlexicokerR, un viscoréducteur et un hydroviscoréducteur catalytique), où au moins 30 % en poids du résidu sous vide sont convertis en un matériau ayant un point d'ébullition inférieur à 1050°F (566°C) ; (b) l'introduction dudit résidu ayant subi une conversion thermique dans un séparateur vapeur/liquide, ledit séparateur étant intégré dans un four de vapocraquage, pour former une phase vapeur et une phase liquide ; (c) l'envoi de cette phase vapeur dans le four rayonnant se trouvant dans ledit four de vapocraquage ; et (d) la récupération d'au moins 30 % en poids d'oléfines à partir du matériau sortant du four rayonnant (par rapport au poids du matériau hydrocarboné total sortant du four rayonnant).
PCT/US2011/039776 2010-07-09 2011-06-09 Procédé intégré de vapocraquage WO2012005861A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013150467A3 (fr) * 2012-04-04 2014-02-20 Saudi Basic Industries Corporation Procédé de production de produits chimiques hydrocarbonés à partir d'huile brute
WO2019019539A1 (fr) * 2017-07-26 2019-01-31 天津大学 Procédé et appareil de préparation d'arène et d'oléfine au moyen d'une hydrogénation catalytique couplée à un craquage catalytique de biocarburant

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020242920A1 (fr) * 2019-05-24 2020-12-03 Eastman Chemical Company Huile de pyrolyse thermique dans un four craqueur alimenté en gaz
CN113891928A (zh) * 2019-05-24 2022-01-04 伊士曼化工公司 裂化热解油的c4-c7馏分

Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2655464A (en) * 1951-06-09 1953-10-13 Standard Oil Dev Co Residuum coking and cracking
US3487006A (en) 1968-03-21 1969-12-30 Lummus Co Direct pyrolysis of non-condensed gas oil fraction
US3617493A (en) 1970-01-12 1971-11-02 Exxon Research Engineering Co Process for steam cracking crude oil
US3671424A (en) 1969-10-20 1972-06-20 Exxon Research Engineering Co Two-stage fluid coking
US3898299A (en) 1972-11-08 1975-08-05 Bp Chem Int Ltd Production of gaseous olefins from petroleum residue feedstocks
US4065379A (en) 1975-01-22 1977-12-27 Shell Oil Company Process for the production of normally gaseous olefins
US4180453A (en) 1977-02-11 1979-12-25 Institut Francais Du Petrole Process for the steam-cracking of heavy feedstocks
US4210520A (en) 1977-05-12 1980-07-01 Linde Aktiengesellschaft Unsupported catalysts in the production of olefins
US4257871A (en) 1978-10-06 1981-03-24 Linde Aktiengesellschaft Use of vacuum residue in thermal cracking
US4411769A (en) * 1982-03-23 1983-10-25 Exxon Research & Engineering Co. Integrated two stage coking and steam cracking process and apparatus therefor
US4975181A (en) 1984-12-10 1990-12-04 Utah Tsao Process and apparatus for ethylene production
US5024751A (en) 1988-05-19 1991-06-18 Institut Francais Du Petrole Catalytic composition comprising a metal sulfide suspended in a liquid containing asphaltenes and hydrovisbreaking process of a hydrocarbon charge
US5413702A (en) 1992-02-21 1995-05-09 Mobil Oil Corporation High severity visbreaking of residual oil
US5580443A (en) * 1988-09-05 1996-12-03 Mitsui Petrochemical Industries, Ltd. Process for cracking low-quality feed stock and system used for said process
US6210561B1 (en) 1996-08-15 2001-04-03 Exxon Chemical Patents Inc. Steam cracking of hydrotreated and hydrogenated hydrocarbon feeds
WO2001066672A1 (fr) 2000-03-08 2001-09-13 Shell Internationale Research Maatschappij B.V. Pyrolyse de petrole brut et fractions de petrole brut renfermant du brai
US7090765B2 (en) 2002-07-03 2006-08-15 Exxonmobil Chemical Patents Inc. Process for cracking hydrocarbon feed with water substitution
US7097758B2 (en) 2002-07-03 2006-08-29 Exxonmobil Chemical Patents Inc. Converting mist flow to annular flow in thermal cracking application
US7138047B2 (en) 2002-07-03 2006-11-21 Exxonmobil Chemical Patents Inc. Process for steam cracking heavy hydrocarbon feedstocks
US20070023845A1 (en) 2005-07-26 2007-02-01 Fujitsu Limited Semiconductor device and method for fabricating the same
US7193123B2 (en) 2004-05-21 2007-03-20 Exxonmobil Chemical Patents Inc. Process and apparatus for cracking hydrocarbon feedstock containing resid to improve vapor yield from vapor/liquid separation
US20070090019A1 (en) * 2005-10-20 2007-04-26 Keusenkothen Paul F Hydrocarbon resid processing and visbreaking steam cracker feed
US7220887B2 (en) 2004-05-21 2007-05-22 Exxonmobil Chemical Patents Inc. Process and apparatus for cracking hydrocarbon feedstock containing resid
WO2007117920A2 (fr) 2006-03-29 2007-10-18 Shell Oil Company Procédé de production d'oléfines inférieures
WO2007117919A2 (fr) 2006-03-29 2007-10-18 Shell Oil Company Améliorations apportées à un procédé de production d'oléfines inférieures à partir de charges d'alimentation contenant des hydrocarbures lourds comprenant l'utilisation de deux séparateurs vapeur/ liquide
WO2009025640A1 (fr) 2007-08-21 2009-02-26 Exxonmobil Chemical Patents Inc. Procédé et appareil de craquage à la vapeur de charges d'hydrocarbures
US20090272671A1 (en) * 2008-04-30 2009-11-05 Keusenkothen Paul F Process and Apparatus for Using Steam Cracked Tar as Steam Cracker Feed
US7678264B2 (en) 2005-04-11 2010-03-16 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US20100300936A1 (en) * 2009-05-29 2010-12-02 Stell Richard C Method and Apparatus for Recycle of Knockout Drum Bottoms

Patent Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2655464A (en) * 1951-06-09 1953-10-13 Standard Oil Dev Co Residuum coking and cracking
US3487006A (en) 1968-03-21 1969-12-30 Lummus Co Direct pyrolysis of non-condensed gas oil fraction
US3671424A (en) 1969-10-20 1972-06-20 Exxon Research Engineering Co Two-stage fluid coking
US3617493A (en) 1970-01-12 1971-11-02 Exxon Research Engineering Co Process for steam cracking crude oil
US3898299A (en) 1972-11-08 1975-08-05 Bp Chem Int Ltd Production of gaseous olefins from petroleum residue feedstocks
US4065379A (en) 1975-01-22 1977-12-27 Shell Oil Company Process for the production of normally gaseous olefins
US4180453A (en) 1977-02-11 1979-12-25 Institut Francais Du Petrole Process for the steam-cracking of heavy feedstocks
US4210520A (en) 1977-05-12 1980-07-01 Linde Aktiengesellschaft Unsupported catalysts in the production of olefins
US4257871A (en) 1978-10-06 1981-03-24 Linde Aktiengesellschaft Use of vacuum residue in thermal cracking
US4411769A (en) * 1982-03-23 1983-10-25 Exxon Research & Engineering Co. Integrated two stage coking and steam cracking process and apparatus therefor
US4975181A (en) 1984-12-10 1990-12-04 Utah Tsao Process and apparatus for ethylene production
US5024751A (en) 1988-05-19 1991-06-18 Institut Francais Du Petrole Catalytic composition comprising a metal sulfide suspended in a liquid containing asphaltenes and hydrovisbreaking process of a hydrocarbon charge
US5580443A (en) * 1988-09-05 1996-12-03 Mitsui Petrochemical Industries, Ltd. Process for cracking low-quality feed stock and system used for said process
US5413702A (en) 1992-02-21 1995-05-09 Mobil Oil Corporation High severity visbreaking of residual oil
US6210561B1 (en) 1996-08-15 2001-04-03 Exxon Chemical Patents Inc. Steam cracking of hydrotreated and hydrogenated hydrocarbon feeds
US6632351B1 (en) 2000-03-08 2003-10-14 Shell Oil Company Thermal cracking of crude oil and crude oil fractions containing pitch in an ethylene furnace
WO2001066672A1 (fr) 2000-03-08 2001-09-13 Shell Internationale Research Maatschappij B.V. Pyrolyse de petrole brut et fractions de petrole brut renfermant du brai
US7090765B2 (en) 2002-07-03 2006-08-15 Exxonmobil Chemical Patents Inc. Process for cracking hydrocarbon feed with water substitution
US7097758B2 (en) 2002-07-03 2006-08-29 Exxonmobil Chemical Patents Inc. Converting mist flow to annular flow in thermal cracking application
US7138047B2 (en) 2002-07-03 2006-11-21 Exxonmobil Chemical Patents Inc. Process for steam cracking heavy hydrocarbon feedstocks
US7193123B2 (en) 2004-05-21 2007-03-20 Exxonmobil Chemical Patents Inc. Process and apparatus for cracking hydrocarbon feedstock containing resid to improve vapor yield from vapor/liquid separation
US7220887B2 (en) 2004-05-21 2007-05-22 Exxonmobil Chemical Patents Inc. Process and apparatus for cracking hydrocarbon feedstock containing resid
US7678264B2 (en) 2005-04-11 2010-03-16 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US20070023845A1 (en) 2005-07-26 2007-02-01 Fujitsu Limited Semiconductor device and method for fabricating the same
US20070090018A1 (en) 2005-10-20 2007-04-26 Keusenkothen Paul F Hydrocarbon resid processing
US20070090020A1 (en) * 2005-10-20 2007-04-26 Buchanan John S Resid processing for steam cracker feed and catalytic cracking
US20070090019A1 (en) * 2005-10-20 2007-04-26 Keusenkothen Paul F Hydrocarbon resid processing and visbreaking steam cracker feed
WO2007117920A2 (fr) 2006-03-29 2007-10-18 Shell Oil Company Procédé de production d'oléfines inférieures
WO2007117919A2 (fr) 2006-03-29 2007-10-18 Shell Oil Company Améliorations apportées à un procédé de production d'oléfines inférieures à partir de charges d'alimentation contenant des hydrocarbures lourds comprenant l'utilisation de deux séparateurs vapeur/ liquide
WO2009025640A1 (fr) 2007-08-21 2009-02-26 Exxonmobil Chemical Patents Inc. Procédé et appareil de craquage à la vapeur de charges d'hydrocarbures
US20090272671A1 (en) * 2008-04-30 2009-11-05 Keusenkothen Paul F Process and Apparatus for Using Steam Cracked Tar as Steam Cracker Feed
US20100300936A1 (en) * 2009-05-29 2010-12-02 Stell Richard C Method and Apparatus for Recycle of Knockout Drum Bottoms

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Handbook of Petroleum Refining Processes", 2004, MCGRAW-HILL
P.J. ELLIS, C.A. PAUL: "Topical Conference on Refinery Processing", 1998, GREAT LAKES CARBON CORPORATION, article "Tutorial: Delayed Coking Fundamentals", pages: 29A

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013150467A3 (fr) * 2012-04-04 2014-02-20 Saudi Basic Industries Corporation Procédé de production de produits chimiques hydrocarbonés à partir d'huile brute
US9550707B2 (en) 2012-04-04 2017-01-24 Saudi Basic Industries Corporation Process for production of hydrocarbon chemicals from crude oil
WO2019019539A1 (fr) * 2017-07-26 2019-01-31 天津大学 Procédé et appareil de préparation d'arène et d'oléfine au moyen d'une hydrogénation catalytique couplée à un craquage catalytique de biocarburant

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