EP3541894A1 - Process and system for conversion of crude oil to petrochemicals and fuel products integrating steam cracking, fluid catalytic cracking, and conversion of naphtha into chemical rich reformate - Google Patents
Process and system for conversion of crude oil to petrochemicals and fuel products integrating steam cracking, fluid catalytic cracking, and conversion of naphtha into chemical rich reformateInfo
- Publication number
- EP3541894A1 EP3541894A1 EP17812154.7A EP17812154A EP3541894A1 EP 3541894 A1 EP3541894 A1 EP 3541894A1 EP 17812154 A EP17812154 A EP 17812154A EP 3541894 A1 EP3541894 A1 EP 3541894A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zone
- naphtha
- stream
- fraction
- oil
- 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.)
- Granted
Links
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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/06—Vacuum distillation
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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
- C10G2400/06—Gasoil
Definitions
- the phrase "a significant portion” with respect to a particular stream or plural streams means at least about 75 wt% and up to 100 wt%, or the same values of another specified unit. [36] The phrase "a substantial portion” with respect to a particular stream or plural streams means at least about 90, 95, 98 or 99 wt% and up to 100 wt%, or the same values of another specified unit.
- A refers to Arab Light crude oil, characterized by an API gravity of greater than or equal to about 30°, 32°, 34°, 36° or 38°, and in certain embodiments in the range of about 30°- 38°, 30°- 36°, 30°- 35°, 32°- 38°, 32°- 36°, 32°- 35°, 33°- 38°, 33°- 36° or 33°- 35°.
- naphthenic hydrocarbons or “naphthenes” or “cycloalkanes” are used herein having their established meanings and accordingly relates to types of alkanes that have one or more rings of carbon atoms in the chemical structure of their molecules.
- wild naphtha is used herein to refer to naphtha products derived from hydroprocessing units such as distillate hydroprocessing units, diesel hydroprocessing units and/or gas oil hydroprocessing units.
- reformate or “chemical reformate” as used herein refer to a mixture of hydrocarbons that are rich in aromatics, and are intermediate products in the production of chemicals and/or gasoline, and include hydrocarbons boiling in the range of about 30-200, 40-200, 30-185, 40-185, 30-170 or 40- 170°C.
- C# hydrocarbons or “C#”, is used herein having its well-known meaning, that is, wherein "#” is an integer value, and means hydrocarbons having that value of carbon atoms.
- C#+ hydrocarbons or “C#+” refers to hydrocarbons having that value or more carbon atoms.
- C#- hydrocarbons or “C#-” refers to hydrocarbons having that value or less carbon atoms.
- ranges are also set forth, for instance, C1-C3 means a mixture comprising CI, C2 and C3.
- BTX refers to the well-known acronym for benzene, toluene and xylenes.
- make-up hydrogen is used herein with reference to hydroprocessing zones to refer to hydrogen requirements of the zone that exceed recycle from conventionally integrated separation vessels; in certain embodiments as used herein all or a portion of the make-up hydrogen in any given hydroprocessing zone or reactor within a zone is from gases derived from the steam cracking zone(s) and the reforming zone(s) in the integrated processes and systems.
- crude to chemicals conversion refers to conversion of crude oil into petrochemicals including but not limited to lower olefins such as ethylene, propylene, butylenes (including isobutylene), butadiene, MTBE, butanols, benzene, ethylbenzene, toluene, xylenes, and derivatives of the foregoing.
- lower olefins such as ethylene, propylene, butylenes (including isobutylene), butadiene, MTBE, butanols, benzene, ethylbenzene, toluene, xylenes, and derivatives of the foregoing.
- the term "crude to chemicals conversion ratio” as used herein refers to the ratio, on a mass basis, of the influent crude oil before desalting, to petrochemicals.
- C4 Raffinate 1 or “C4 RafF-1” refers to the mixed C4s stream leaving the butadiene extraction unit, that is, mixed C4s from the crude C4 except butadiene.
- C4 Raffinate 2 or “C4 Raff-2” refers to the mixed C4s stream leaving the MTBE unit, that is, mixed C4s from the crude C4 except butadiene and isobutene.
- C4 Raffinate 3 or “C4 Raff-3” refers to the mixed C4s stream leaving the C4 distillation unit, that is, mixed C4s from the crude C4 except butadiene, isobutene, and butane- 1.
- pyrolysis gasoline and its abbreviated form “py-gas” are used herein having their well-known meaning, that is, thermal cracking products in the range of C5 to C9, for instance having an end boiling point of about 204.4°C (400°F), in certain embodiments up to about 148.9°C (300°F).
- pyrolysis oil and its abbreviated form “py-oil” are used herein having their well-known meaning, that is, a heavy oil fraction, C10+, that is derived from steam cracking.
- light pyrolysis oil and its acronym “LPO” as used herein in certain embodiments refer to pyrolysis oil having an end boiling point of about 440, 450, 460 or 470°C.
- LCO light cycle oil
- the distillation cut for this stream is, for example, in the range of about 220-330°C.
- LCO is used sometimes in the diesel blends depending on the diesel specifications, or it can be utilized as a cutter to the fuel oil tanks for a reduction in the viscosity and sulfur contents.
- HCO heavy cycle oil
- the distillation cut for this stream is, for example, in the range of about 330-510°C.
- HCO is used sometimes in an oil flushing system within the process. Additionally, HCO is used to partially vaporize the debutanizer bottoms and then is recycled back as a circulating reflux to the main fractionator in the fluid catalytic cracking unit.
- cycle oil is used herein to refer to a mixture of LCO and HCO.
- the integrated process for producing petrochemicals and fuel products from a crude oil feed includes an initial separation step to separate from a crude oil feed in an atmospheric distillation zone at least a first atmospheric distillation zone fraction comprising straight run naphtha; a second atmospheric distillation zone fraction comprising at least a portion of the middle distillates, and a third atmospheric distillation zone fraction comprising atmospheric residue.
- a first vacuum distillation zone fraction comprising vacuum gas oil is separated from the third atmospheric distillation zone fraction in a vacuum distillation zone.
- a distillate hydroprocessing (“DHP") zone such as a diesel hydrotreater
- DHP distillate hydroprocessing
- first DHP fraction comprises naphtha
- second DHP fraction is used for diesel fuel production
- the first vacuum distillation zone fraction is processed in a fluid catalytic cracking zone to produce at least a first fluid catalytic cracking fraction corresponding to light olefins, a portion of which are recovered as petrochemicals, a second fluid catalytic cracking fraction corresponding to fluid catalytic cracking naphtha and a third fluid catalytic cracking fraction corresponding to cycle oil.
- the light components such as LPG from the atmospheric distillation zone, and an aromatics extraction zone raffinate, are processed in a mixed feed steam cracking zone. All or a portion of the straight run naphtha is passed to a catalytic reforming zone to produce chemical rich reformate as additional feed to the aromatics extraction zone.
- the products from the mixed feed steam cracking zone include a mixed product stream containing H 2 , methane, ethane, ethylene, mixed C3s, and mixed C4s, a pyrolysis gasoline stream and a pyrolysis oil stream.
- Pyrolysis gasoline is treated in a py-gas hydroprocessing zone to produce hydrotreated pyrolysis gasoline that is routed to an aromatics extraction complex to recover aromatic petrochemicals and a raffinate, including pyrolysis gasoline raffinate that is recycled to the steam cracking complex.
- fluid catalytic cracking naphtha is also hydroprocessed and passed to the aromatics extraction complex to produce additional aromatic petrochemicals and additional raffinate that is routed to the steam cracking complex.
- FIGs. 1, 2 and 3 schematically depict embodiments of processes and systems for conversion of crude oil to petrochemicals and fuel products, including a mixed feed steam cracking zone, a chemical reforming zone and a high olefinic fluid catalytic cracking (HOFCC) zone 700.
- FIGs. 1 and 2 show operations upstream of a mixed feed steam cracking zone (MFSC) 230
- FIG. 3 shows operations downstream of the crude oil conversion zone and including the mixed feed steam cracking zone 230.
- the integrated processes and systems include a vacuum gas oil hydroprocessing zone, which can operate as a vacuum gas oil hydrocracker 320 as shown in FIG. 1 or as a vacuum gas oil hydrotreater 300 as shown in FIG. 2.
- a crude oil feed 102 in certain embodiments AXL or AL, is separated into fractions in a crude complex 100 typically including an atmospheric distillation zone (CDU) 110, a saturated gas plant 150 and a vacuum distillation zone 160.
- the crude oil feed 102 in certain embodiments having LPG and light naphtha removed, is separated into fractions the atmospheric distillation zone 110.
- light products for instance, light hydrocarbons with fewer than six carbons, are passed to the mixed feed steam cracking zone 230.
- C2-C4 hydrocarbons 152 including ethane, propane and butanes are separated from the light ends and LPG 112 from the atmospheric distillation zone 110 via the saturated gas plant 150.
- other light products are routed to the saturated gas plant 150 shown in dashed lines as stream 156, such as light gases from refinery units within the integrated system and in certain embodiments, light gases from outside of the battery limits.
- Off- gases from the fluid catalytic cracking unit after passing through an unsaturated gas plant, can be integrated with off-gases from the saturated gas plant 150 for common handling of the fuel gases.
- the separated C2-C4 hydrocarbons 152 are routed to the mixed feed steam cracking zone 230.
- Off-gases 154 from the saturated gas plant 150 and off-gases 208 from the mixed feed steam cracking zone 230 are removed and recovered as is typically known, for instance to contribute to a fuel gas ("FG") system.
- FG fuel gas
- Straight run naphtha 136 from the atmospheric distillation zone 110 is passed to a catalytic reforming zone 400 to produce chemical rich reformate 426.
- all, a substantial portion or a significant portion of the straight run naphtha 136 is routed to the catalytic reforming zone 400.
- Remaining naphtha can be routed to the mixed feed steam cracking zone 230 (as shown in dashed lines) and/or added to a gasoline pool.
- the straight run naphtha stream 136 contains naphtha from other sources as described herein and sometimes referred to as wild naphtha, for instance, naphtha range hydrocarbons from one or more of the integrated distillate, gas oil and/or residue hydroprocessing units.
- Middle distillates are used to produce diesel and/or kerosene, and additional feed to the mixed feed steam cracking zone 230.
- at least three different middle distillate cuts are processed for production of fuel products and petrochemicals (via the steam cracker). In one example using the arrangements shown in FIGs.
- a first atmospheric distillation zone middle distillate fraction 116 in certain embodiments referred to a kerosene fraction, contains light kerosene range hydrocarbons
- a second atmospheric distillation zone middle distillate fraction 122 in certain embodiments referred as a diesel fraction
- a third atmospheric distillation zone middle distillate fraction 126 in certain embodiments referred to as an atmospheric gas oil fraction, contains heavy AGO range hydrocarbons.
- a first middle distillate fraction 116 contains kerosene range hydrocarbons
- a second middle distillate fraction 122 contains medium AGO range hydrocarbons
- a third middle distillate fraction 126 contains heavy AGO range hydrocarbons.
- a first middle distillate fraction 116 contains light kerosene range hydrocarbons and a portion of heavy kerosene range hydrocarbons
- a second middle distillate fraction 122 contains a portion of heavy kerosene range hydrocarbons and a portion of medium AGO range hydrocarbons
- a third middle distillate fraction 126 contains a portion of medium AGO range hydrocarbons and heavy AGO range hydrocarbons.
- a first middle distillate fraction 116 can be processed in a kerosene sweetening process 170 to produce kerosene fuel product 172, for instance, jet fuel compliant with Jet A or Jet A-l specifications, and optionally other fuel products (not shown).
- all or a portion of the first middle distillate fraction 116 is not used for fuel production, but rather is used as a feed for distillate hydroprocessing so as to produce additional feed for the mixed feed steam cracking zone 230.
- a second middle distillate fraction 122 is processed in a distillate hydroprocessing zone such as a diesel hydrotreating zone 180, to produce wild naphtha 184 and a diesel fuel fraction 182, for instance, compliant with Euro V diesel standards.
- a distillate hydroprocessing zone such as a diesel hydrotreating zone 180
- wild naphtha 184 and a diesel fuel fraction 182 for instance, compliant with Euro V diesel standards.
- all or a portion of the first middle distillate fraction 116 can be treated with the second middle distillate fraction 122, as denoted by dashed lines.
- all, a substantial portion, a significant portion or a major portion of the wild naphtha 184 is routed to the mixed feed steam cracking zone 230 alone, or in combination with other wild naphtha fractions from within the integrated process; any portion that is not passed to the mixed feed steam cracking zone 230 can be routed to the crude complex 100 and/or directly to the catalytic reforming zone 400 and/or to a gasoline pool.
- all, a substantial portion, a significant portion or a major portion of the wild naphtha 184 is passed to the crude complex 100, alone, or in combination with other wild naphtha fractions from within the integrated process; any portion that is not passed to the crude complex 100 can be routed to the mixed feed steam cracking zone 230 and/or directly to the catalytic reforming zone 400 and/or to a gasoline pool.
- all, a substantial portion, a significant portion or a major portion of the wild naphtha 184 is passed to the catalytic reforming zone 400, alone, or in combination with other wild naphtha fractions from within the integrated process; any portion that is not passed to the catalytic reforming zone 400 can be routed to the mixed feed steam cracking zone 230 and/or to the crude complex 100 and/or to a gasoline pool.
- wild naphtha 184 is routed through the crude complex 100
- all or a portion of the liquefied petroleum gas produced in the vacuum gas oil hydroprocessing zone can be passed with the wild naphtha.
- all, a substantial portion, a significant portion or a major portion of the third middle distillate fraction 126 is routed to the vacuum gas oil hydroprocessing zone in combination with the vacuum gas oil stream 162; any portion that is not passed to the vacuum gas oil hydroprocessing zone can be routed to the high olefinic fluid catalytic cracking zone 700, bypassing the vacuum gas oil hydroprocessing zone.
- all, a substantial portion, a significant portion or a major portion of the third middle distillate fraction 126 is routed to the high olefinic fluid catalytic cracking zone 700, bypassing the vacuum gas oil hydroprocessing zone; any portion that is not passed to the high olefinic fluid catalytic cracking zone 700 can be routed to the vacuum gas oil hydroprocessing zone.
- vacuum gas oil hydroprocessing is in a vacuum gas oil hydrocracking zone 320 that can operate under mild, moderate or severe hydrocracking conditions, and generally produces a hydrocracked naphtha fraction 326, a diesel fuel fraction 322, and an unconverted oil fraction 324.
- the diesel fuel fraction 322 is recovered as fuel, for instance, compliant with Euro V diesel standards, and can be combined with the diesel fuel fraction 182 from the diesel hydrotreating zone 180.
- vacuum gas oil hydroprocessing is in a vacuum gas oil hydrotreating zone 300 that can operate under mild, moderate or severe hydrotreating conditions, and generally produces a hydrotreated gas oil fraction 304, naphtha and some middle distillates.
- Naphtha range products can be separated from products within the vacuum gas oil hydrotreating zone 300 as a hydrotreated naphtha stream 306.
- a cracked distillates stream 308 containing hydrotreated distillates are routed to diesel hydrotreating zone 180 for further hydroprocessing and/or separation into diesel hydrotreating zone 180 products.
- all, a substantial portion, a significant portion or a major portion of the wild naphtha fraction from the vacuum gas oil hydroprocessing zone, streams 326 or 306, is routed to the mixed feed steam cracking zone 230, alone, or in combination with other wild naphtha fractions from within the integrated process; any portion that is not passed to the mixed feed steam cracking zone 230 can be routed to the crude complex 100 and/or directly to the catalytic reforming zone 400 and/or to the gasoline pool.
- all, a substantial portion, a significant portion or a major portion of the wild naphtha fraction from the vacuum gas oil hydroprocessing zone is passed to the crude complex 100, alone, or in combination with other wild naphtha fractions from within the integrated process; any portion that is not passed to the crude complex 100 can be routed to the mixed feed steam cracking zone 230 and/ directly to the catalytic reforming zone 400 and/or to the gasoline pool.
- Heavy product from the vacuum gas oil hydroprocessing zone is routed to the high olefinic fluid catalytic cracking zone 700.
- heavy product is the hydrotreated gas oil fraction 304 that contains the portion of the vacuum gas oil hydrotreater 300 effluent that is at or above the AGO, H-AGO or VGO boiling range.
- heavy product is the unconverted oil fraction 324. All, a substantial portion, a significant portion or a major portion of heavy product from the vacuum gas oil hydroprocessing zone is routed to high olefinic fluid catalytic cracking zone 700.
- the remainder (if any) can be passed to the optional vacuum residue treating zone 800 and/or passed to the mixed feed steam cracking zone 230.
- any remainder can be recycled and further processed (cracked to extinction in VGO hydrocracking) and/or bled from the system and/or passed to the optional residue treating zone 800.
- the high olefinic fluid catalytic cracking zone 700 is configured to produce light olefin product 704 and high olefinic fluid catalytic cracking naphtha 706. It should be appreciated that the light olefin product 704 can be recovered from the high olefinic fluid catalytic cracking zone 700 as is known, or recovered in combination with the olefins recovery zone 270 and/or the mixed feed steam cracking zone 230 as described herein. Off-gases from the high olefinic fluid catalytic cracking zone 700 can be integrated with the fuel gas system. In certain embodiments (not shown in FIG.
- certain gases after treatment in an unsaturated gas plant, can be routed to the separation units associated with the mixed feed steam cracking zone 230, and/or LPGs can be routed to the mixed feed steam cracking zone 230. All, a substantial portion, a significant portion or a major portion of the gases containing light olefins (a C2- stream and a C3+ stream) are routed through the unsaturated gas plant. The remainder, if any, can be routed to the mixed feed steam cracking zone 230 and/or the olefins recovery train 270.
- all or a portion of the high olefinic fluid catalytic cracking naphtha 706 can be processed as described below (and in conjunction with FIG. 3) in a naphtha hydrotreatment and recovery center 610/620, to increase the quantity of raffinate as additional feed to the mixed feed steam cracking zone 230.
- all or a portion of the high olefinic fluid catalytic cracking naphtha 706 is hydrotreated and recovered for fuel production and incorporation into a gasoline pool (not shown).
- a portion of the high olefinic fluid catalytic cracking naphtha 706 that is not recovered for fuel production can be processed in the naphtha hydrotreatment and recovery center 610/620, as shown in dashed lines, to increase the quantity of raffinate as additional feed to the mixed feed steam cracking zone 230.
- all or a portion of the high olefinic fluid catalytic cracking naphtha 706 is hydrotreated in a fluid catalytic cracking naphtha hydrotreating zone 670, and the hydrotreated fluid catalytic cracking naphtha stream 672 is directly routed to the mixed feed steam cracking zone 230. Any portion of the high olefinic fluid catalytic cracking naphtha 706 that is not routed to the to the mixed feed steam cracking zone 230, shown in dashed lines, is recovered for fuel production (not shown).
- components of the hydrotreated fluid catalytic cracking naphtha stream 672 that are not cracked in the mixed feed steam cracking zone 230, including aromatics, increase the pyrolysis gasoline 212 from the mixed feed steam cracking zone 230, which are routed to the py-gas hydrotreatment and recovery center 600/620.
- all, a substantial portion, a significant portion or a major portion of the hydrotreated fluid catalytic cracking naphtha stream 672 is routed to the mixed feed steam cracking zone 230; the remainder, if any, can be routed to aromatics extraction 620 and/or recovered for fuel production and incorporation into a gasoline pool and/or passed to the chemical reforming zone 400.
- all, a substantial portion, a significant portion or a major portion of the hydrotreated fluid catalytic cracking naphtha stream 672 is routed to the chemical reforming zone 400, the remainder, if any, can be routed to aromatics extraction 620 and/or recovered for fuel production and incorporation into a gasoline pool and/or passed to the mixed feed steam cracking zone 230.
- Other products from the high olefinic fluid catalytic cracking zone 700 include cycle oil, such as light cycle oil 708 and heavy cycle oil 710.
- all or a portion of the light cycle oil 708 is routed to the distillate hydroprocessing zone 180, thereby increasing the yield of the diesel fuel fraction 182 and wild naphtha 184 that is passed to the mixed feed steam cracking zone 230. In certain embodiments, all, a substantial portion, a significant portion or a major portion of the light cycle oil 708 is passed to the distillate hydroprocessing zone 180, and any remaining portion can be routed to the vacuum gas oil processing zone. Heavy cycle oil stream 710 can be routed to a fuel oil pool or used as feedstock for production of carbon black.
- the mixed feed steam cracking zone 230 which operates as a high severity or low severity thermal cracking process, converts its feed primarily into ethylene 202, propylene 204, mixed C4s 206, pyrolysis gasoline 212, pyrolysis oil 218, and off-gases 208 that can be passed to an integrated fuel gas system. Further, hydrogen 210 is recovered from the cracked products and can be recycled to hydrogen users within the complex limits. Not shown are the ethane and propane recycle, which are typical in steam cracking operations, although it is appreciated that in certain embodiments all or a portion of the ethane and propane can be diverted.
- all, a substantial portion, a significant portion or a major portion of ethane is recycled to the mixed feed steam cracking zone 230, and all, a substantial portion, a significant portion or a major portion of propane is mixed feed steam cracking zone 230.
- hydrogen for all hydrogen users in the integrated process and system is derived from hydrogen 210 recovered from the cracked products, and no outside hydrogen is required once the process has completed start-up and reached equilibrium. In further embodiments excess hydrogen can be recovered.
- SHU selective hydrogenation unit
- MTBE methyl tertiary butyl ether
- a second raffinate 516 (“C4 Raff-2”) from the SHU and MTBE zone 510 is routed to a C4 distillation unit 520 for separation into a 1-butene product stream 522 and an alkane stream 524 (a third raffinate "C4-Raff-3") containing residual C4s, all, a substantial portion, a significant portion or a major portion of which is recycled to the mixed feed steam cracking zone 230 although it is appreciated that in certain embodiments all or a portion of the residual C4s can be diverted.
- Separation of the ethylene 202, propylene 204 and the mixed C4s stream 206 occurs in a suitable arrangement of known separation steps for separating steam cracking zone effluents, including compression stage(s), depropanizer, debutanizer, demethanizer and deethanizer.
- Pyrolysis gasoline 212 from the steam cracking zone 230 is fed to the naphtha hydrotreatment and recovery center 610/620.
- select hydrocarbons having 5-12 carbons are recovered from untreated pyrolysis gasoline and high olefinic fluid catalytic cracking naphtha ("FCCN") 706, and the remainder is subsequently hydrotreated for aromatics recovery.
- FCCN high olefinic fluid catalytic cracking naphtha
- diolefins and olefins in the pyrolysis gasoline are saturated. All, a substantial portion or a significant portion of the pyrolysis gasoline 212 from the steam cracking zone 230 is passed to the naphtha hydrotreatment and recovery center 610/620.
- Hydrotreated pyrolysis gasoline and fluid catalytic cracking naphtha are routed to the aromatics extraction zone 620.
- the naphtha hydrotreating zone 610 and the aromatics extraction zone 620 high olefinic fluid catalytic are shown for simplicity in a single schematic block 610/620 in FIGs. 3, 4, 5, 6, 7, 8 and 11.
- the naphtha hydrotreating zone 610 operates to hydrotreat pyrolysis gasoline 212 prior to aromatics recovery.
- modes of operation are provided in which the chemical rich reformate 426 can serve as feed to the aromatics extraction zone 620 and/or as gasoline blending components.
- a producer can vary the quantity of feed to tailor the desired outputs. Accordingly, 0-100% of the chemical rich reformate 426 can be routed to the aromatics extraction zone 620, and the remainder (if any) is directed to a gasoline blending pool (not shown).
- the quantity can be determined, for instance, based upon demand for aromatic petrochemicals, demand for gasoline, and/or minimum ranges for which the unit is operated depending on design capacity.
- the aromatics extraction zone 620 includes, for instance, one or more extractive distillation units, and operates to separate the hydrotreated pyrolysis gasoline and fluid catalytic cracking naphtha into an aromatics stream 622 containing high-purity benzene, toluene, xylenes and C9 aromatics, which are recovered for chemical markets.
- C5 raffinate 644 and non-aromatics 646 (for instance, C6-C9) are recycled to the mixed feed steam cracking zone 230. In certain embodiments, all, a substantial portion or a significant portion of the C5 raffinate 644 and non-aromatics 646 are passed to the mixed feed steam cracking zone 230.
- a heavy aromatics stream 642 (for instance, C10-C12) can be used as an aromatic solvent, an octane boosting additive or as a cutter stock into a fuel oil pool.
- ethylbenzene 628 can be recovered.
- pyrolysis oil 218 can be blended into the fuel oil pool.
- pyrolysis oil 218 can be fractioned (not shown) into light pyrolysis oil and heavy pyrolysis oil.
- light pyrolysis oil can be blended with the first middle distillate stream 116 and/or the second middle distillate stream 122, for processing to produce diesel fuel product and/or additional feed to the mixed feed steam cracking zone 230.
- light pyrolysis oil derived from pyrolysis oil 218 can be processed in the vacuum gas oil hydroprocessing zone. In additional embodiments, light pyrolysis oil derived from pyrolysis oil 218 can be blended into the fuel oil pool. In further embodiments, light pyrolysis derived from pyrolysis oil 218 can be processed in the residue treating zone 800. In certain embodiments, all, a substantial portion, a significant portion or a major portion of light pyrolysis oil can be passed to the diesel hydrotreating zone 180 and/or the vacuum gas oil hydroprocessing zone; any remainder can be blended into the fuel oil pool. Heavy pyrolysis oil can be blended into the fuel oil pool, used as a carbon black feedstock and/or processed in the optional residue treating zone 800. In certain embodiments, all, a substantial portion, a significant portion or a major portion of the pyrolysis oil 218 (light and heavy) can be processed in the optional residue treating zone 800.
- FIG. 6 schematically depicts further embodiments of processes and systems for conversion of crude oil to petrochemicals and fuel products, with metathesis conversion of C4 and C5 olefins to produce additional propylene.
- the process operates as described with respect to any of FIGs. 1, 2, 4 or 5 upstream of the steam cracking operations and with respect to the fluid catalytic cracking operations.
- the butadiene extraction train can optionally operate in a manner similar to that in FIG. 3 shown as the stream 524 from a diverter (in dashed lines) from the C4 distillation unit 520 directly to the mixed feed steam cracking zone 230.
- mixed C4 raffinate stream 532 (“C4 Raff 3") from the C4 distillation unit 520 and C5 raffinate 540 from the naphtha hydrotreatment and recovery center 610/620 are routed to the metathesis unit 530 for metathesis conversion to additional propylene 534.
- all, a substantial portion, a significant portion or a major portion of the cracked C5s from the py-gas hydrotreater can be routed to the metathesis unit 530 prior to aromatics extraction.
- a portion 536 of the ethylene mixed feed steam cracking product 202 can be routed to the metathesis unit 530.
- ethylene for the metathesis unit 530 is supplied from outside the complex limits, instead of or in addition to the portion 536 of the ethylene mixed feed steam cracking product.
- pyrolysis gasoline 212 from the steam cracking zone 230 is routed to the naphtha hydrotreatment and recovery center 610/620 where select hydrocarbons having 5-12 carbons can be recovered from untreated pyrolysis gasoline and fluid catalytic cracking naphtha, and the remainder is subsequently hydrotreated for aromatics recovery.
- a py-gas hydrotreating unit HTU
- diolefins and olefins in the pyrolysis gasoline are saturated.
- aromatics extraction step aromatics are separated from hydrotreated pyrolysis gasoline and fluid catalytic cracking naphtha.
- aromatic extraction can separate the hydrotreated pyrolysis gasoline and fluid catalytic cracking naphtha into high-purity benzene, toluene, xylenes and C9 aromatics.
- C6-C9 aromatics stream 622, BTX is recovered for chemical markets
- C6-C9 non-aromatics stream 646 is recycled to the mixed feed steam cracking zone 230
- C10-C12 products stream 642 may be used as an aromatic solvent or as an octane boosting additive.
- ethylbenzene 628 can be recovered.
- C5 raffinate is routed to the metathesis unit 530 as shown as stream 540, and/or recycled to the mixed feed steam cracking zone 230 (as in the embodiment of FIG. 3) via stream 644, shown in dashed lines in FIG. 6.
- an optional diverter is shown, indicated as a diverter and stream in dashed lines, to bypass the metathesis conversion process, to therefore divert all, a substantial portion, a significant portion or a major portion of the C4 Raff-3 524 to the mixed feed steam cracking zone 230.
- flow can be directed to the metathesis conversion unit 530.
- flow of the C4 Raff-3 524 can be directed to the mixed feed steam cracking zone 230 and the metathesis conversion unit 530. In this manner, a producer can vary the quantity of feed to tailor the desired outputs.
- FIG. 7 schematically depicts further embodiments of processes and systems for conversion of crude oil to petrochemicals and fuel products. The process operates as described with respect to FIGs. 1, 2, 4 or 5 upstream of the steam cracking operations and with respect to the fluid catalytic cracking operations.
- an additional step is provided to convert a mixture of butenes into mixed butanols suitable as a gasoline blending oxygenate and for octane enhancement.
- Suitable processes to convert a mixture of butenes into mixed butanols are described in one or more of commonly owned patent publications US20160115107A1, US20150225320A1, US20150148572A1, US20130104449A1, US20120245397A1 and commonly owned patents US9447346B2, US9393540B2, US9187388B2, US8558036B2, all of which are incorporated by reference herein in their entireties.
- a particularly effective conversion process known as "SuperButolTM” technology is integrated, which is a one- step process that converts a mixture of butenes into mixed butanol liquids.
- the butadiene extraction train can optionally operate in a manner similar to that in FIG. 3 shown as the stream 524 from a diverter (in dashed lines) from the C4 distillation unit 520 directly to the mixed feed steam cracking zone 230.
- a crude C4 processing center 550 is integrated for selective recovery of various alkene and diene pyrolysis chemicals having four carbons, and in certain processing arrangements hydrating a portion of those C4's in a butanol production unit (such as a "SuperButolTM" unit) to produce high value fuel additives.
- the mixed butanols production zone 550 operates to convert butenes to butanols from undervalued refinery/petrochemical mixed olefin streams.
- the butanols provide an alternative option for oxygenates in gasoline blends.
- the crude C4 processing center 550 includes the conversion reaction of butenes to butanols, for instance, in one or more high pressure catalytic reactors followed by gravity separation of butenes and butanols from water, and subsequent separation of the butanols product from butenes by distillation.
- Process stages include butenes and water make-up and recycle, butanol reaction, high pressure separation, low pressure separation, debutenizer distillation (product column) and an aqueous distillation column.
- FIG. 7 depicts a stream 552 containing butenes from the C4 distillation step routed to a crude C4 processing zone such as a butanol production unit 550 to convert the mixture of butenes into mixed butanol liquids 554.
- a crude C4 processing zone such as a butanol production unit 550 to convert the mixture of butenes into mixed butanol liquids 554.
- all, a substantial portion, a significant portion or a major portion of stream 552 is routed to the butanol production unit 550.
- Alkanes 556 are recycled to the mixed feed steam cracking zone 230.
- pyrolysis gasoline 212 from the steam cracking zone 230 is routed to the naphtha hydrotreatment and recovery center 610/620 where select hydrocarbons having 5-12 carbons can be recovered from untreated pyrolysis gasoline and fluid catalytic cracking naphtha, and the remainder is subsequently hydrotreated for aromatics recovery. C5s are recycled to the mixed feed steam cracking zone 230.
- diolefins and olefins in the pyrolysis gasoline are saturated. Hydrotreated pyrolysis gasoline from the py-gas hydrotreating unit is routed to aromatics extraction.
- aromatics are separated from hydrotreated pyrolysis gasoline and fluid catalytic cracking naphtha.
- aromatic extraction can separate the hydrotreated pyrolysis gasoline and fluid catalytic cracking naphtha into high-purity benzene, toluene, xylenes and C9 aromatics.
- C6-C9 aromatics stream 622 can be recovered for chemical markets, C5 raffinate 644 and non- aromatics 646 (for instance, C6-C9) can be recycled to the mixed feed steam cracking zone 230, and heavy aromatic 642 (for instance, C10-C12) products can be used as an aromatic solvent or as an octane boosting additive.
- ethylbenzene 628 can be recovered.
- an optional diverter is shown, indicated as a diverter and stream in dashed lines, to bypass the process for conversion of a mixture of butenes into mixed butanols, to therefore divert all, a substantial portion, a significant portion or a major portion of the C4 Raff-3 524 to the mixed feed steam cracking zone 230.
- flow can be directed to the mixed butanols production zone 550 for conversion of a mixture of butenes into mixed butanols.
- flow of the C4 Raff-3 524 can be directed to the mixed feed steam cracking zone 230 and the mixed butanols production zone 550.
- a producer can vary the quantity of feed to tailor the desired outputs. Accordingly, 0-100% of the third C4 raffinate stream 524 can be routed to mixed butanols production zone 550, and the remainder (if any) is directed to the mixed feed steam cracking zone 230.
- the quantity can be determined, for instance, based upon demand for ethylene, demand for mixed butanols, and/or minimum ranges for which the unit is operated depending on design capacity
- the butadiene extraction train can optionally operate in a manner similar to that in FIG. 3 shown as the stream 524 from a diverter (in dashed lines) from the C4 distillation unit 520 directly to the mixed feed steam cracking zone 230 as an optional mode of operation.
- the configuration in FIG. 8 integrates selective recovery of various alkene and diene pyrolysis chemicals having four carbons, metathesis conversion to produce additional propylene, and/or conversion of a mixture of butenes into mixed butanols suitable as a gasoline blending oxygenate and for octane enhancement.
- ethylene for the metathesis unit 530 is supplied from outside the complex limits, instead of or in addition to the portion 536 of the ethylene product 202.
- a stream 538, having a mixture of mostly saturated C4/C5 from metathesis unit, is recycled to the mixed feed steam cracking zone.
- pyrolysis gasoline 212 from the steam cracking zone 230 is routed to the naphtha hydrotreatment and recovery center 610/620 where select hydrocarbons having 5-12 carbons can be recovered from untreated pyrolysis gasoline and fluid catalytic cracking naphtha, and the remainder is subsequently hydrotreated for aromatics recovery.
- a py-gas hydrotreating unit diolefins and olefins in the pyrolysis gasoline are saturated.
- Hydrotreated pyrolysis gasoline from the py-gas hydrotreating unit is routed to aromatics extraction.
- aromatics extraction step aromatics are separated from hydrotreated pyrolysis gasoline and fluid catalytic cracking naphtha.
- aromatic extraction can separate the hydrotreated pyrolysis gasoline and fluid catalytic cracking naphtha into high-purity benzene, toluene, xylenes and C9 aromatics.
- C6-C9 aromatics stream 622, BTX can be recovered for chemical markets, non-aromatics 646 (for instance, C6-C9) can be recycled to the mixed feed steam cracking zone 230, and heavy aromatics 642 (for instance, C10-C12) products can be used as an aromatic solvent or as an octane boosting additive.
- ethylbenzene 628 can be recovered.
- 540 can be routed to the metathesis unit 530 as shown, and/or optionally recycled to the mixed feed steam cracking as shown in dashed lines, stream 644.
- all or a portion of the cracked C5s from the py-gas hydrotreater can be routed to the metathesis unit 530 prior to aromatics extraction.
- an optional diverter is shown, indicated as a diverter and stream in dashed lines, to bypass the metathesis conversion process and the process for conversion of a mixture of butenes into mixed butanols, to therefore divert all, a substantial portion, a significant portion or a major portion of the C4 Raff-3 524 to the mixed feed steam cracking zone 230.
- An optional valve also can be provided to direct flow of the C4 Raff-3 to one or both of the metathesis conversion unit 530 and/or the mixed butanols production zone 550 for conversion of a mixture of butenes into mixed butanols.
- flow of the C4 Raff-3 524 can be directed to each of the mixed feed steam cracking zone 230, the metathesis conversion unit 530 (as stream 532), and the mixed butanols production zone 550 (as stream 552).
- a producer can vary the quantity of feed to tailor the desired outputs. Accordingly, all, a substantial portion, a significant portion or a major portion of the third C4 raffinate stream can be routed to the metathesis conversion unit 530, and the remainder (if any) is directed to the mixed feed steam cracking zone 230 and/or the mixed butanols production zone 550.
- all, a substantial portion, a significant portion or a major portion of the third C4 raffinate stream is routed to the metathesis conversion unit 530, and the remainder (if any) is directed to the mixed feed steam cracking zone 230.
- all, a substantial portion, a significant portion or a major portion of the third C4 raffinate stream is routed to the metathesis conversion unit 530, and the remainder (if any) is directed to the mixed butanols production zone 550 for production of mixed butanols.
- FIGs. 9 and 11 schematically depict further embodiments of processes and systems for conversion of crude oil to petrochemicals and fuel products.
- a crude oil feed 102 in certain embodiments AXL or AL, is fed to an atmospheric distillation zone 110 of a crude complex 100. All or a portion of straight run naphtha 136 is passed to a catalytic reforming zone 400 to produce chemical rich reformate 426.
- Lighter products 152 are routed to a mixed feed steam cracking zone 230.
- Middle distillate fractions 116 and 122 are used to produce kerosene and diesel, and wild naphtha 184 as additional feed to the mixed feed steam cracking zone 230.
- all or a portion of a third middle distillate fraction 126 is routed to a vacuum gas oil hydroprocessing zone, which can operate as a vacuum gas oil hydrocracker as shown in FIG. 9 or as a vacuum gas oil hydrotreater as shown in FIG. 10.
- all or a portion of the third middle distillate fraction 126 is routed to the high olefinic fluid catalytic cracking zone 700, bypassing the vacuum gas oil hydroprocessing zone.
- the third middle distillate fraction 126 can be divided between the vacuum gas oil hydroprocessing zone and the high olefinic fluid catalytic cracking zone 700.
- the atmospheric residue fraction 114 is further distilled in a vacuum distillation zone 160.
- VGO 162 from the vacuum distillation zone 160 is routed to a vacuum gas oil hydroprocessing zone, which can operate as a high severity vacuum gas oil hydrotreater or a mild vacuum gas oil hydrocracker.
- the heaviest fraction 168 from the vacuum distillation zone 160, vacuum residue can be sent to a fuel oil ("FO") pool or optionally processed in a residue treatment zone 800, shown in dashed lines.
- FO fuel oil
- a vacuum gas oil hydrotreater 300 can operate under mild, moderate or severe hydrotreating conditions, and generally produces cracked products 308 and hydrotreated gas oil 304. Cracked products 308 from the vacuum gas oil hydrotreater 300 are routed to the diesel hydrotreating zone 180. Hydrotreated gas oil 304 from the vacuum gas oil hydrotreater 300 is routed to a high olefinic fluid catalytic cracking zone 700 configured to produce maximum light olefin product 704.
- the light olefin product 704 can be recovered from the high olefinic fluid catalytic cracking zone 700 as is known, or recovered in combination with the olefins recovery zone 270 and/or the mixed feed steam cracking zone 230 as described herein.
- the hydrotreated gas oil fraction 304 generally contains the portion of the vacuum gas oil hydrotreater 300 effluent that is at or above the AGO, H-AGO or VGO range.
- a vacuum gas oil hydrocracker 320 can operate under mild, moderate or severe hydrocracking conditions, and generally produces a hydrocracked naphtha product 326, a diesel fuel fraction 322, and an unconverted oil fraction 324.
- Hydrocracked naphtha 326 from the vacuum gas oil hydrocracker 320 is routed to the mixed feed steam cracking zone 230.
- the unconverted oil fraction 324 is routed to the high olefinic fluid catalytic cracking zone 700.
- the diesel fuel fraction 322 is recovered as fuel, for instance, compliant with Euro V diesel standards, and can be combined with the diesel fuel fraction 182 from the diesel hydrotreating zone 180.
- an aromatics recovery center 620 is included, in which aromatics are separated from pyrolysis gasoline 212 and hydrotreated pyrolysis gasoline can be obtained.
- C6-C9 aromatics 622 are recovered for chemical markets, C6-C9 non-aromatics 646 are recycled to the mixed feed steam cracking zone 230, and C10-C12 products 642 can be used as an aromatic solvent or used as gasoline blenders as an octane boosting additive.
- high olefinic fluid catalytic cracking naphtha 706 is hydrotreated and fed to the aromatics extraction, the light naphtha and middle naphtha are fed to the mixed feed steam cracking zone 230.
- the C5 and C9 streams from the high olefinic fluid catalytic cracker can be recycled to the mixed feed steam cracking zone 230.
- all or a portion of the high olefinic fluid catalytic cracking naphtha 706 is used as a gasoline blendstock, rather being used in its entirety as feed to the mixed feed steam cracking zone; any remainder of the of the high olefinic fluid catalytic cracking naphtha 706 can be used as feed to the mixed feed steam cracking zone 230.
- pyrolysis oil 218 from the steam cracking zone 230 can be passed to a catalytic hydrogen addition process, such as a residue hydrocracking or conditioning process
- pyrolysis oil 218 is split into light and heavy fractions, whereby the light fraction is fed to the gas oil hydroprocessing zone and the heavy fraction is fed to the catalytic hydrogen addition process, such as a residue hydrocracking or conditioning process.
- all or a portion of the hydrotreated gas oil fraction or unconverted oil fraction from the gas oil hydroprocessing zone is passed to an isodewaxing unit and a hydrofmishing unit, for instance, to enable production of group III lube oils or lube oil feedstocks.
- FIGs. 12, 13 and 21 schematically depict embodiments of processes and systems for conversion of crude oil to petrochemicals and fuel products including a mixed feed steam cracking zone and a high olefinic fluid catalytic cracking zone 700.
- FIGs. 12 and 13 show operations upstream of the mixed feed steam cracking zone 230 while FIG. 21 shows operations downstream of and including the mixed feed steam cracking zone 230.
- a crude oil feed 102 is passed to a crude complex 100.
- the crude complex 100 generally includes an atmospheric distillation zone 110, a saturated gas plant 150 and a vacuum distillation zone 160.
- the atmospheric distillation unit is used in well-known arrangements.
- Intermediate streams obtained from the feed 102 via separation in the crude complex 100 include: off-gas 154, obtained within the crude complex 100 via the saturated gas plant 150, and which is passed to a fuel gas system; a light ends stream 152, obtained within the crude complex 100 via the saturated gas plant 150, and which is passed to the mixed feed steam cracking zone 230; one or more straight run naphtha stream(s), in this embodiment a light naphtha stream 138 and a heavy naphtha stream 140, with all or a portion of the light naphtha stream 138 being passed to the mixed feed steam cracking zone 230, and all or a portion of the heavy naphtha stream 140 passed to a catalytic reforming zone 400 to produce chemical rich reformate 426; a first middle distillate stream 118, such as a light kerosene stream, that is passed to a kerosene sweetening zone 170, such as a mercaptan oxidation zone; a second middle distillate stream 120, such as a heavy
- the intermediate streams from the crude complex 100 are used in an efficient manner in the integrated process and system herein.
- the light ends stream 152, and a portion of the straight run naphtha stream(s), in this embodiment light naphtha 138, are routed to the mixed feed steam cracking zone 230 as feed for conversion into light olefins and other valuable petrochemicals.
- all, a substantial portion or a significant portion of the light naphtha 138 is routed to the mixed feed steam cracking zone 230, and the remainder (if any) passed to a catalytic reforming zone 400.
- All or a portion of the heavy naphtha 140 from the atmospheric distillation zone 110 is passed to the catalytic reforming zone 400 to produce chemical rich reformate 426, which can be routed as additional feed to the aromatics extraction zone 620 or used for gasoline blending.
- all, a substantial portion or a significant portion of the heavy naphtha 140 is routed to the catalytic reforming zone 400, and the remainder (if any) passed to the mixed feed steam cracking zone 230.
- Either or both of the straight run naphtha streams, light naphtha 138 and heavy naphtha 140 can optionally be steam- stripped in a side stripper prior to routing to the mixed feed steam cracking zone 230.
- Components of the crude complex not shown but which are well-known can include feed / product and pump-around heat exchangers, crude charge heaters, crude tower(s), product strippers, cooling systems, hot and cold overhead drum systems including re-contactors and off-gas compressors, and units for water washing of overhead condensing systems.
- the atmospheric distillation zone 110 can include well-known design features. Furthermore, in certain embodiments, naphtha, kerosene and atmospheric gas oil products from the atmospheric distillation column are steam -stripped in side strippers, and atmospheric residue is steam-stripped in a reduced-size can section inside the bottom of the atmospheric distillation column.
- the feed to the atmospheric distillation zone 110 is primarily the crude feed 102, although it shall be appreciated that wild naphtha, LPGs and off-gas streams from the diesel hydrotreating zone 180; and in certain embodiments from the vacuum gas oil hydroprocessing step and/or an optional residue treating zone, can be routed to the atmospheric distillation zone 110 where they are fractionated before being passed to the cracking complex.
- a desalting unit (not shown) is typically included upstream of the distillation zone 110. A substantial amount of the water required for desalting can be obtained from a sour water stripper within the integrated process and system.
- the straight run naphtha, or the heavy naphtha is separated into a normal paraffin (n-paraffin) rich stream and a non-normal rich stream containing branched paraffins.
- a separation zone 402 shown in dashed lines as optional, which can be, for instance, based on technology commercially available from Honeywell UOP, US (MaxEneTM).
- the n-paraffin rich stream bypasses the catalytic reforming zone and is routed to the mixed feed steam cracking zone 230, enabling an increase in the combined yield of ethylene and propylene.
- Processing of the n-paraffin rich stream in the mixed feed steam cracking zone 230 can also reduce coking which can facilitate increases in throughput or extended run times between de-coking cycles.
- the stream rich in non-normal paraffins also has significant benefits when processed in the catalytic reformer, including improved selectivity and reduced coke formation on the catalyst, which can facilitate increases in throughput.
- a schematic process flow diagram of a catalytic reforming zone 400 is shown in FIGs. 14 and 15, and in certain embodiments combined with the units of FIG. 16.
- a naphtha hydrotreating zone 410 is integrated with a catalytic reforming reaction zone 414 for the processing of a straight run naphtha stream 136 (FIG. 14) or a heavy naphtha stream 140 (FIG. 15), to produce chemical rich reformate 426 for chemical recovery, as a gasoline blend component, or both for chemical recovery and as a gasoline blend component.
- all, a substantial portion, a significant portion or a major portion of the chemical rich reformate 426 is passed to the aromatics extraction zone 620, and any remainder can be blended in a gasoline pool.
- the naphtha feed 136 or 140 (or in certain embodiments the stream rich in non- normal paraffins from an optional separation zone 402) is hydrotreated in the naphtha hydrotreating zone 410 to produce a hydrotreated naphtha stream 412.
- the feed to the naphtha hydrotreating zone 410 is heavy naphtha stream 140
- light naphtha 138 can be routed to the mixed feed steam cracking unit 230.
- the feed to the naphtha hydrotreating zone 410 can also be a full range naphtha including light naphtha (for instance, both the heavy naphtha stream 140 combined with which can be the light naphtha stream 138 described in other embodiments).
- Hydrotreating occurs in the presence of an effective amount of hydrogen obtained from recycle within the naphtha hydrotreating zone 410 (not shown), recycle reformer hydrogen 406, and if necessary make-up hydrogen 408 (shown in dashed lines).
- Effluent off-gases are recovered from the naphtha hydrotreating zone 410 and are passed the olefins recovery train, the saturated gas plant as part of the other gases stream 156, and/or directly to a fuel gas system.
- Liquefied petroleum gas is recovered from the naphtha hydrotreating zone 410 and is routed to the mixed feed steam cracking zone, the olefins recovery train and/or the saturated gas plant.
- all or a portion of any necessary make-up hydrogen 408 is derived from the steam cracker hydrogen stream 210 from the olefins recovery train 270.
- hydrogen gas recovered from the catalytic reforming reaction zone 414 provides sufficient hydrogen to maintain the hydrogen requirements of naphtha hydrotreating zone 410 when the reactions reach equilibrium.
- there is a net hydrogen gain in the catalytic reforming zone so that hydrogen can be added, for instance, to the other hydrogen users in the integrated process, and/or to the fuel gas that is used to operate the various heating units within the integrated process.
- a suitable naphtha hydrotreating zone 410 can include, but is not limited to, systems based on technology commercially available from Honeywell UOP, US; Chevron Lummus Global LLC (CLG), US; Axens, IFP Group Technologies, FR; Shell Global Solutions, US, Haldor Topsoe A/S, DK; GTC Technology US, LLC, US; or Exxon Mobil Corporation, US.
- the naphtha hydrotreating zone 410 is operated under conditions, and utilizes catalyst(s), effective for removal of a significant amount of the sulfur and other known contaminants. Accordingly, the naphtha hydrotreating zone 410 subjects feed to hydrotreating conditions to produce a hydrotreated straight run naphtha stream 412 effective as feed to the catalytic reforming reaction zone 414.
- the naphtha hydrotreating zone 410 operates under conditions of, e.g., temperature, pressure, hydrogen partial pressure, liquid hourly space velocity (LHSV), catalyst selection/loading that are effective to remove at least enough sulfur, nitrogen, olefins and other contaminants needed to meet requisite product specifications.
- LHSV liquid hourly space velocity
- hydrotreating in conventional naphtha reforming systems generally occurs under relatively mild conditions that are effective to remove sulfur and nitrogen to less than 0.5 ppmw levels.
- the naphtha hydrotreating zone 410 operating conditions include:
- a reactor inlet temperature in the range of from about 355-400, 355-375, 355- 385, 370-400 or 360-390;
- a reactor outlet temperature in the range of from about 400-450, 400-430, 410-450, 420-450 or 410-430
- a start of run (SOR) reaction temperature °C
- WABT weighted average bed temperature
- reaction inlet pressure in the range of from about 48-60, 48-52, 48-55, 50-55 or 50-60;
- reaction outlet pressure in the range of from about 40-51, 40-44, 40- 48, 45-51 or 45-48;
- a hydrogen partial pressure (barg) (outlet) in the range of from about 24-34, 24- 30, 27-34 27-30 or 27-32;
- a hydrogen treat gas feed rate up to about 645, 620, 570, 500 or 530, in certain embodiments from about 413-640, 413-570, 413-542, 465-620, 465-570, 465- 542, 491-620, 491-570 or 491-542;
- a quench gas feed up to about 99, 90, 85, 78 or 70, in certain embodiments from about 57-90, 57-78, 57-75, 64-85, 64-78, 64-75, 68-85, 68-78 or 68- 75; and;
- a make-up hydrogen feed rate up to about 125, 110 or 102, in certain embodiments from about 78-120, 78-110, 78-102, 87-120, 87-110, 87-102, 92-120, 92- 110, 92-102 or 95-100.
- Effective straight run naphtha reactor catalyst include those possessing hydrotreating functionality and which generally contain one or more active metal component of metals or metal compounds (oxides or sulfides) selected from the Periodic Table of the Elements IUPAC Groups 6-10.
- the active metal component is one or more of cobalt, nickel, tungsten and molybdenum.
- the active metal component is typically deposited or otherwise incorporated on a support, such as amorphous alumina, amorphous silica alumina, zeolites, or combinations thereof.
- a hydrogen to hydrocarbon molar ratio in the range of from about 2: 1-5: 1.
- Cyclic and CCR process designs include online catalyst regeneration or replacement, and accordingly the lower pressure ranges as indicated above are suitable.
- CCRs can operate in the range of about 5 bar, while semi regenerative systems operate at the higher end of the above ranges, with cyclic designs typically operating at a pressure higher than CCRs and lower than semi regenerative systems.
- An effective quantity of reforming catalyst is provided.
- Such catalyst include mono-functional or bi-functional reforming catalyst which generally contain one or more active metal component of metals or metal compounds (oxides or sulfides) selected from the Periodic Table of the Elements IUPAC Groups 8-10.
- a bi-functional catalyst has both metal sites and acidic sites.
- the active metal component can include one or more of platinum, rhenium, gold, palladium, germanium, nickel, silver, tin, iridium or halides.
- the active metal component is typically deposited or otherwise incorporated on a support, such as amorphous alumina, amorphous silica alumina, zeolites, or combinations thereof.
- platinum or platinum alloy supported on alumina or silica or silica-alumina are the reforming catalyst.
- Effective liquid hourly space velocity values (h "1 ) on a fresh feed basis relative to the hydrotreating catalysts, are in the range of from about 0.5-4, 0.5-2, .5-3, 1-3, 1- 4, 1-2, 1.5-4 or 1.5 - 3.
- Suitable reforming catalysts used in the reforming reaction zone 414 have an expected lifetime in the range of about 6-18, 12-26, 18-54 or 24-72 months.
- the relatively benzene-lean heavy reformate bottom fraction 436 comprises about 40-80 V% of the total reformate and has a benzene content generally in the range of from about 0.3-1 vol%, which is sufficiently low to be passed to a gasoline pool 444 without further processing.
- the light reformate top fraction 432 which includes about 10-25 vol% of the total reformate, contains about 5-30 vol% benzene and is recovered or blended with other product pools.
- the heart cut fraction 434 which contains a majority of the benzene content of total reformate stream 426, can be passed to a hydrogenation unit 438, also referred to as a benzene saturation unit, or directly to the aromatics extraction unit. Hydrogenation reactions occur in the presence of a predetermined amount of hydrogen gas 440 for conversion reactions including conversion of benzene to cyclohexane, and for the production of a benzene-lean and in certain embodiments an essentially benzene-free, gasoline blending component 442.
- all, a substantial portion, a significant portion or a major portion of the benzene-lean heavy reformate bottom fraction 436 is passed to the aromatics extraction zone, and any remainder can be passed to the gasoline pool; all, a substantial portion, a significant portion or a major portion of light reformate top fraction 432 is passed to the mixed feed steam cracking zone 230, and any remainder can be passed to the gasoline pool; and all, a substantial portion, a significant portion or a major portion of the benzene-lean blending component 442 can be routed to the mixed feed steam cracking zone 230, and any remainder can be passed to the gasoline pool.
- Effective liquid hourly space velocity values (h "1 ), on a fresh feed basis relative to the benzene saturation unit catalysts, are in the range of from about 0.1-10.0, 0.1-5.0, 0.1-2.0, 0.3-10.0, 0.3-5.0, 0.3-2.0, 0.5-10.0, 0.5-5.0, 0.5-2.0 or 0.8-1.2.
- Suitable hydrotreating catalysts used in the benzene saturation unit 438 have an expected lifetime in the range of about 28-44, 34-44, 28-38 or 34-38 months.
- FIG. 17 another embodiment of a catalytic reforming system 414 is schematically depicted.
- a series of reactors 414 are provided.
- a feedstock, hydrotreated naphtha 412, is heat exchanged with a hot reformate stream 416 to increase the temperature of the feed.
- the heated feedstock is treated in a series of reaction zones containing reformer reactors 414, shown in the exemplary embodiment as zones A-D, although fewer or more zones can be used.
- the hot reformate stream 416 contains hot product hydrogen and reformate.
- the reforming reactions are endothermic resulting in the cooling of reactants and products, requiring heating of effluent, typically by direct -fired furnaces 446, prior to charging as feed to a subsequent reforming reactor 414.
- catalyst particles are deactivated by the formation of coke on the catalyst which reduces the available surface area and active sites for contacting the reactants.
- Treated kerosene is recovered as a kerosene fuel product 172, for instance, jet fuel compliant with Jet A or Jet A-l specifications, and optionally other fuel products.
- all or a portion of the first middle distillate fraction 116 is not used for fuel production, but rather is used as a feed for distillate hydroprocessing so as to produce additional feed for the mixed feed steam cracking zone 230.
- a suitable kerosene sweetening zone 170 can include, but is not limited to, systems based on MeroxTM technology (Honeywell UOP, US), Sweetn'K technology (Axens, IFP Group Technologies, FR) or ThiolexTM technology (Merichem Company ,US). Processes of these types are well-established commercially and appropriate operating conditions are well known to produce kerosene fuel product 172 and disulfide oils as by-product. In certain kerosene sweetening technologies impregnated carbon is utilized as catalyst to promote conversion to disulfide oil. In certain embodiments, common treatment of sour water from the kerosene sweetening zone 170 and other unit operations is employed to maximize process integration.
- the kerosene product passes downward through one of two parallel clay filters for removal of solids, moisture, emulsions and surfactants, to ensure that the kerosene product meets haze, color stability and water separation specifications, for instance, compliant with Jet A specifications.
- the second middle distillate stream 120 and the third middle distillate stream 128 are processed in a diesel hydrotreating zone 180 in the presence of an effective amount of hydrogen obtained from recycle within the diesel hydrotreating zone 180 and make-up hydrogen 186.
- all or a portion of the make-up hydrogen 186 is derived from a steam cracker product hydrogen 210 stream from the olefins recovery train 270.
- Liquefied petroleum gas can be recovered from the diesel hydrotreating zone 180 and routed to the mixed feed steam cracking zone, the olefins recovery train and/or the saturated gas plant.
- the hydrotreated naphtha fraction 184 is routed through the crude complex 100, alone, or in combination with other wild naphtha fractions from within the integrated process.
- all or a portion of the liquefied petroleum gas produced in the diesel hydrotreating zone 180 can be passed with the hydrotreated naphtha fraction 184.
- all, a substantial portion or a significant portion of the wild naphtha 184 is routed to the mixed feed steam cracking zone 230 (directly or through the crude complex 100).
- the diesel hydrotreating zone 180 can optionally process other fractions from within the complex (not shown).
- all or a portion of the disulfide oil can be additional feed to the diesel hydrotreating zone 180.
- all or a portion of the first middle distillate fraction 116 can be additional feed to the diesel hydrotreating zone 180.
- all or a portion of distillates from the vacuum gas oil hydroprocessing zone, and/or all or a portion of distillates from the optional vacuum residue treatment zone can be routed to the diesel hydrotreating zone 180. Any portion of distillates not routed to the diesel hydrotreating zone 180 can be passed to the crude complex 100 or routed to the mixed feed steam cracking zone 230. Further, all or a portion of light pyrolysis oil can be routed to the diesel hydrotreating zone 180.
- the diesel hydrotreating zone 180 also processes at least a portion of the light cycle oil 708 from the high olefinic fluid catalytic cracking zone 700. Any portion of the light cycle oil 708 not routed to the diesel hydrotreating zone 180 can optionally be passed to a fuel oil pool and/or processed in the integrated gas oil hydroprocessing zone. For example, no more than 0-30, 0-25, 0-20, 5-30, 5-25, 5-20, 10- 30, 10-25, or 10-20 wt% of the total light cycle oil 708 from the high olefinic fluid catalytic cracking zone 700 can be routed to the diesel hydrotreating zone 180.
- the diesel hydrotreating zone 180 can contain one or more fixed-bed, ebullated- bed, slurry -bed, moving bed, continuous stirred tank (CSTR) or tubular reactors, in series and/or parallel arrangement.
- the diesel hydrotreating zone 180 contains a layered bed reactor with three catalyst beds and having inter-bed quench gas, and employs a layered catalyst system with the layer of hydrodewaxing catalyst positioned between beds of hydrotreating catalyst.
- Additional equipment including exchangers, furnaces, feed pumps, quench pumps, and compressors to feed the reactor(s) and maintain proper operating conditions, are well known and are considered part of the diesel hydrotreating zone 180.
- equipment, including pumps, compressors, high temperature separation vessels, low temperature separation vessels and the like to separate reaction products and provide hydrogen recycle within the diesel hydrotreating zone 180 are well known and are considered part of the diesel hydrotreating zone 180.
- the diesel hydrotreating zone 180 operating conditions include:
- a reactor inlet temperature in the range of from about 296-453, 296-414, 296- 395, 336-453, 336-414, 336-395, 355-453, 355-414, 355-395 or 370-380;
- an end of run (EOR) reaction temperature (°C), as a WABT in the range of from about 311-476, 311-434, 311-414, 352-476, 352-434, 352-414, 373-476, 373-434, 373- 414 or 390-396;
- reaction inlet pressure in the range of from about 48-72, 48-66, 48-63, 54-72, 54-66, 54-63, 57-72, 57-66 or 57-63;
- reaction outlet pressure in the range of from about 44-66, 44-60, 44-58, 49-66, 49-60, 49-58, 52-66, 52-60 or 52-58;
- a hydrogen partial pressure (barg) in the range of from about 32-48, 32- 44, 32-42, 36-48, 36-44, 36-42, 38-48, 38-44 or 38-42;
- a hydrogen treat gas feed rate (standard liters per liter of hydrocarbon feed, SLt/Lt) up to about 400, 385, 353 or 337, in certain embodiments from about 256-385, 256-353, 256-337, 289-385, 289-353, 289-337, 305-385, 305-353 or 305-337;
- a hydrogen quench gas feed rate up to about 100, 85, 78 or 75, in certain embodiments from about 57-85, 57-78, 57-75, 64-85, 64-78, 64-75, 68-85, 68-78, or 68- 75;
- a make-up hydrogen feed rate up to about 110, 108, 100 or 95, in certain embodiments from about 70-108, 70-100, 70-95, 80-108, 80-100, 80-95, 85-108, 85-100 or 85-95.
- An effective quantity of hydrotreating catalyst is provided in the diesel hydrotreating zone 180, including those possessing hydrotreating functionality and which generally contain one or more active metal component of metals or metal compounds (oxides or sulfides) selected from the Periodic Table of the Elements IUPAC Groups 6- 10.
- the active metal component is one or more of Co, Ni, W and Mo.
- the active metal component is typically deposited or otherwise incorporated on a support, such as amorphous alumina, amorphous silica alumina, zeolites, or combinations thereof.
- the catalyst used in the diesel hydrotreating zone 180 can include one or more catalyst selected from Co/Mo, Ni/Mo, NiAV, and Co/Ni/Mo.
- Co/Mo hydrodesulfurization catalyst is suitable.
- Effective liquid hourly space velocity values (h "1 ), on a fresh feed basis relative to the hydrotreating catalysts, are in the range of from about 0.1-10.0, 0.1- 5.0, 0.1-2.0, 0.3-10.0, 0.3-5.0, 0.3-2.0, 0.5-10.0, 0.5-5.0, 0.5-2.0 or 0.8-1.2.
- Suitable hydrotreating catalysts used in the diesel hydrotreating zone 180 have an expected lifetime in the range of about 28-44, 34-44, 28-38 or 34-38 months.
- each train contains feed/effluent heat exchangers, feed heater, a reactor and the hot separator.
- Each reactor contains three catalyst beds with inter-bed quench gas.
- a layered catalyst system is used with the layer of hydrodewaxing catalyst positioned between beds of hydrotreating catalyst.
- the trains recombine after the hot separators. Tops from the hot separators are combined and passed to a cold separator. Bottoms from the hot separators and from the cold separator are passed to a product stripper to produce stabilized ultra low sulfur diesel and wild naphtha. Tops from the cold separator are subjected to absorption and amine scrubbing. Recycle hydrogen is recovered, and passed (along with make-up hydrogen) to the reaction zone as treat gas and quench gas.
- VGO 162 from the vacuum distillation zone 160 is/are processed in a gas oil hydroprocessing zone 300 (FIG. 12]) or 320 (FIG. 13]) in the presence of an effective amount of hydrogen obtained from recycle within the gas oil hydroprocessing zone and make-up hydrogen 302.
- all or a portion of the make-up hydrogen 302 is derived from the steam cracker hydrogen stream 210 from the olefins recovery train 270. In certain embodiments (not shown in FIGs.
- the severity of the gas oil hydroprocessing operation can be used to moderate the relative yield of olefin and aromatic chemicals from the overall complex and improve the economic threshold of cracking heavy feeds.
- This application of a gas oil hydroprocessing zone, as a chemical yield control mechanism, is uncommon in the industry, where fuels products are typically the product objectives.
- the naphtha fraction 306 is routed to the mixed feed steam cracking zone 230.
- the hydrotreated naphtha fraction 306 is routed through the crude complex 100, alone, or in combination with other wild naphtha fractions from within the integrated process.
- all or a portion of the liquefied petroleum gas produced in the gas oil hydrotreating zone 300 can be passed with the hydrotreated naphtha fraction 306.
- Hydrotreated gas oil 304 is routed to the high olefinic fluid catalytic cracking zone 700.
- all or a portion of the hydrotreated distillates and naphtha from the gas oil hydrotreating zone 300 are passed to the diesel hydrotreating zone 180.
- a suitable gas oil hydrotreating zone 300 can include, but is not limited to, systems based on technology commercially available from Honeywell UOP, US; Chevron Lummus Global LLC (CLG), US; Axens, IFP Group Technologies, FR; or Shell Global Solutions, US.
- the catalyst used in the gas oil hydrotreating zone 300 includes one or more beds selected from Co/Mo, Ni/Mo, Ni/W, and Co/Ni/Mo. Combinations of one or more beds of Co/Mo, Ni/Mo, Ni/W and Co/Ni/Mo, can also be used. The combinations can be composed of different particles containing a single active metal species, or particles containing multiple active species. In certain embodiments, a combination of Co/Mo catalyst and Ni/Mo catalyst are effective for hydrodesulfurization and hydrodenitrifi cation. One or more series of reactors can be provided, with different catalysts in the different reactors of each series.
- a reactor outlet temperature in the range of from about 338-516, 338-471, 338-449, 382-516, 382-471, 382-449, 404-516, 404-471, 404-449 or 422-430;
- reaction outlet pressure in the range of from about 85-127, 85-117, 85- 111, 96-127, 96-117, 96-111, 100-127, 100-117 or 100-111
- hydrogen partial pressure barg (outlet) in the range of from about 63-95, 63- 87, 63-83, 71-95, 71-87, 71-83, 75-95, 75-87, 75-83 or 77-81 ;
- a hydrogen treat gas feed rate up to about 525, 510, 465 or 445, in certain embodiments from about 335-510, 335-465, 335-445, 380-510, 380-465, 380-445, 400- 510, 400-465 or 400-445;
- a make-up hydrogen feed rate up to about 220, 200, 180 or 172, in certain embodiments from about 130-200, 130-180, 130-172, 148-200, 148-180, 148- 172, 155-200, 155-180 or 155-172; and
- An effective quantity of catalyst is provided in gas oil hydrotreating zone 300, including those possessing hydrotreating functionality, for hydrodesulfurization and hydrodenitrifi cation.
- Such catalyst generally contain one or more active metal component of metals or metal compounds (oxides or sulfides) selected from the Periodic Table of the Elements IUPAC Groups 6-10.
- the active metal component is one or more of Co, Ni, W and Mo.
- the active metal component is typically deposited or otherwise incorporated on a support, such as amorphous alumina, amorphous silica alumina, zeolites, or combinations thereof.
- a reactor outlet temperature in the range of from about 480-516, 480-489, 489-495 or 495-516;
- exemplary products from the gas oil hydrotreating zone 300 operating under conditions effective for feed conditioning and to maximize targeted conversion to petrochemicals in the steam cracker complex include 20-30, 22-28, 23-27 or 24-26 wt% of effluent (relative to the feed to the gas oil hydrotreating zone 300) boiling at or below the atmospheric residue end boiling point, such as 370°C, including LPG, kerosene, naphtha, and atmospheric gas oil range components.
- the remaining bottoms fraction is the hydrotreated gas oil fraction, all or a portion of which can be effectively integrated as feed to the gas oil steam cracking zone 250 as described herein.
- Bottoms from the cold separator and tops from the hot flash drum are passed to a low pressure flash drum to remove off-gases.
- Hot flash liquid bottoms and low pressure flash bottoms are passed to a stripper to recover hydrotreated gas oil and wild naphtha.
- Tops from the cold separator are subjected to absorption and amine scrubbing.
- Recycle hydrogen is recovered, and passed (along with make-up hydrogen) to the reaction zone as treat gas and quench gas.
- FIG. 13 depicts a hydrocracking mode of operation for treatment of the vacuum gas oil.
- Hydrocracking processes are used commercially in a large number of petroleum refineries. They are used to process a variety of feeds boiling above the atmospheric gas oil range (for example, in the range of about 370 to 520°C) in conventional hydrocracking units and boiling above the vacuum gas oil range (for example, above about 520°C) in residue hydrocracking units.
- hydrocracking processes split the molecules of the feed into smaller, i.e., lighter, molecules having higher average volatility and economic value.
- hydrocracking processes typically improve the quality of the hydrocarbon feedstock by increasing the hydrogen-to-carbon ratio and by removing organosulfur and organonitrogen compounds. The significant economic benefit derived from hydrocracking processes has resulted in substantial development of process improvements and more active catalysts.
- Three major hydrocracking process schemes include single-stage once through hydrocracking, series-flow hydrocracking with or without recycle, and two-stage recycle hydrocracking.
- Single-stage once through hydrocracking is the simplest of the hydrocracker configuration and typically occurs at operating conditions that are more severe than hydrotreating processes, and less severe than conventional higher pressure hydrocracking processes. It uses one or more reactors for both treating steps and cracking reaction, so the catalyst must be capable of both hydrotreating and hydrocracking. This configuration is cost effective, but typically results in relatively low product yields (for example, a maximum conversion rate of about 50 wt%).
- Single stage hydrocracking is often designed to maximize mid-distillate yield over a single or dual catalyst systems.
- Dual catalyst systems can be used in a stacked-bed configuration or in two different reactors.
- the effluents are passed to a fractionator column to separate the H 2 S, NH 3 , light gases (C 1-C4), naphtha and diesel products, boiling in the temperature range including and below atmospheric gas oil range fractions (for instance in the temperature range of 36-370°C).
- the hydrocarbons boiling above the atmospheric gas oil range (for instance 370°C) are typically unconverted oils. Any portion of these unconverted oils that are not recycled are drawn from a bottoms fraction in a gas oil hydrocracking zone 320 as a hydrogen-rich bleed stream and is effectively integrated as feed to the high olefinic fluid catalytic cracking zone 700 as described herein.
- unconverted oils can be processed in a lube oil production unit (not shown).
- the gas oil hydrocracking zone 320 operates under mild, moderate or severe hydrocracking conditions, and generally produces off-gas and light ends (not shown), a wild naphtha stream 326, a diesel fuel fraction 322, and an unconverted oil fraction 324.
- Effluent off-gases are recovered from the gas oil hydrotreating zone 300 and are passed to the olefins recovery train, the saturated gas plant as part of the other gases stream 156, and/or directly to a fuel gas system.
- Liquefied petroleum gas can be recovered from the gas oil hydrocracking zone 320 and routed to the mixed feed steam cracking zone, the olefins recovery train and/or the saturated gas plant.
- the naphtha fraction 326 is routed to the mixed feed steam cracking zone 230.
- the naphtha fraction 326 is routed through the crude complex 100, alone, or in combination with other wild naphtha fractions from within the integrated process.
- all or a portion of the liquefied petroleum gas produced in the gas oil hydrocracking zone 320 can be passed with the naphtha fraction 326.
- the unconverted oil fraction 324 is routed to the high olefinic fluid catalytic cracking zone 700.
- the diesel fuel fraction 322 is recovered as fuel, for instance, compliant with Euro V diesel standards, and can be combined with the diesel fuel fraction 182 from the diesel hydrotreating zone 180.
- Vacuum gas oil hydrocracker 320 can operate under mild, moderate or severe conditions, depending on factors including the feedstock and the desired degree of conversion
- the gasoil hydrocracking zone 320 can operate under mild, moderate or severe conditions, depending on factors including the feedstock and the desired degree of conversion. Such conditions are effective for removal of a significant amount of the sulfur and other known contaminants, and for conversion of the feed(s) into a major proportion of hydrocracked products and minor proportions of off-gases, light ends and unconverted product that is passed to the high olefinic fluid catalytic cracking zone 700.
- a suitable vacuum gas oil hydrocracker zone 320 can include, but is not limited to, systems based on technology commercially available from Honeywell UOP, US; Chevron Lummus Global LLC (CLG), US; Axens, IFP Group Technologies, FR; or Shell Global Solutions, US.
- the gas oil hydrocracking zone 320 can contain one or more fixed-bed, ebullated- bed, slurry-bed, moving bed, continuous stirred tank (CSTR) or tubular reactors, in series and/or parallel arrangement. Additional equipment, including exchangers, furnaces, feed pumps, quench pumps, and compressors to feed the reactor(s) and maintain proper operating conditions, are well known and are considered part of the gas oil hydrocracking zone 320. In addition, equipment, including pumps, compressors, high temperature separation vessels, low temperature separation vessels and the like to separate reaction products and provide hydrogen recycle within the gas oil hydrocracking zone 320, are well known and are considered part of the gas oil hydrocracking zone 320.
- Two-stage recycle hydrocracking uses two reactors and unconverted bottoms from the fractionation column are passed to the second reactor for further cracking. Since the first reactor accomplishes both hydrotreating and hydrocracking, the feed to second reactor is virtually free of ammonia and hydrogen sulfide. This permits the use of high performance zeolite catalysts which are susceptible to poisoning by sulfur or nitrogen compounds.
- Effective hydrocracking catalyst generally contain about 5-40 wt% based on the weight of the catalyst, of one or more active metal component of metals or metal compounds (oxides or sulfides) selected from the Periodic Table of the Elements IUPAC Groups 6-10.
- the active metal component is one or more of Mo, W, Co or Ni.
- the active metal component is typically deposited or otherwise incorporated on a support, such as amorphous alumina, amorphous silica alumina, zeolites, or combinations thereof.
- Pt group metals such as Pt and/or Pd, may be present as a hydrogenation component, generally in an amount of about 0.1 -2 wt% based on the weight of the catalyst.
- Suitable hydrocracking catalyst have an expected lifetime in the range of about 18-30, 22-30, 18-26 or 22-26 months.
- Exemplary products from the gas oil hydrocracking zone 320 include 27-99, 27- 90, 27-82, 27-80, 27-75, 27-52, 27-48, 30-99, 30-90, 30-82, 30-80, 30-75, 30-52, 30-48, 48-99, 48-90, 48-82, 48-80, 48-75, 48-52, 78-99, 78-90, 78- 85, 80-90 or 80-99 wt% of effluent (relative to the feed to the gas oil hydrocracking zone 320) boiling at or below the atmospheric residue end boiling point, such as 370°C, including LPG, kerosene, naphtha, and atmospheric gas oil range components.
- the atmospheric residue end boiling point such as 370°C, including LPG, kerosene, naphtha, and atmospheric gas oil range components.
- FIG. 18 schematically depicts an embodiment of a once-through single reactor hydrocracking zone 330 including a reaction zone 332 and a fractionating zone 342, which can as a mild conversion or partial conversion hydrocracker.
- Reaction zone 332 generally includes one or more inlets in fluid communication with a source of initial feedstock 334 and a source of hydrogen gas 338.
- One or more outlets of reaction zone 332 that discharge effluent stream 340 is in fluid communication with one or more inlets of the fractionating zone 342 (typically including one or more high pressure and/or low pressure separation stages therebetween for recovery of recycle hydrogen, not shown).
- Fractionating zone 342 includes one or more outlets for discharging gases 344, typically H 2 , H 2 S, H 3 , and light hydrocarbons (C 1-C4); one or more outlets for recovering product 346, such as middle distillates naphtha and diesel products boiling in the temperature range including and below atmospheric gas oil range fractions (for instance in the temperature range of 36-370°C); and one or more outlets for discharging bottoms 348 including hydrocarbons boiling above the atmospheric gas oil range (for instance 370°C).
- the temperature cut point for bottoms 348 (and correspondingly the end point for the products 346) is a range corresponding to the upper temperature limit of the desired gasoline, kerosene and/or diesel product boiling point ranges for downstream operations.
- Hydrogen stream 338 is an effective quantity of hydrogen to support the requisite degree of hydrocracking, feed type, and other factors, and can be any combination including, recycle hydrogen 336 from optional gas separation subsystems (not shown) associated with reaction zone 332, and/or derived from fractionator gas stream 344 and make-up hydrogen 302, if necessary.
- a reaction zone can contain multiple catalyst beds and can receive one or more quench hydrogen streams between the beds (not shown).
- Gas stream 344 typically containing H 2 , H 2 S, H 3 , and light hydrocarbons (C 1 - C 4 ), is discharged and recovered and can be further processed. Effluent off-gases are passed to the olefins recovery train, the saturated gas plant as part of the other gases stream 156, and/or directly to a fuel gas system. Liquefied petroleum gas can be recovered and routed to the mixed feed steam cracking zone, the olefins recovery train and/or the saturated gas plant.
- One or more cracked product streams 346 are discharged via appropriate outlets of the fractionator and can be further processed and/or blended in downstream refinery operations to produce gasoline, kerosene and/or diesel fuel, or other petrochemical products.
- fractionating zone 342 can operate as a flash vessel to separate heavy components at a suitable cut point, for example, a range corresponding to the upper temperature range of the desired gasoline, kerosene and/or diesel products for downstream operations.
- a suitable cut point is in the range of 350 to 450°C, 360 to 450°C, 370 to 450°C, 350 to 400°C, 360 to 400°C, 370 to 400°C, 350 to 380°C, or 360 to 380°C.
- the stream above that cut point is routed to the high olefinic fluid catalytic cracking zone 700 as described herein.
- a suitable once-through single reactor hydrocracking zone 330 can include, but is not limited to, systems based on technology commercially available from Honeywell UOP, US; Chevron Lummus Global LLC (CLG), US; Axens, IFP Group Technologies, FR; or Shell Global Solutions, US.
- a reactor inlet temperature in the range of from about 329-502, 329-460, 329- 440, 372-502, 372-460, 372-440, 394-502, 394-460, 394-440 or 412-420;
- a reactor outlet temperature in the range of from about 338-516, 338-471, 338-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- a start of run (SOR) reaction temperature as a weighted average bed temperature (WABT), in the range of from about 310-475, 310-435, 310-415, 350-475, 350-435, 350- 415, 370-475, 370-435, 370-415 or 390-397;
- an end of run (EOR) reaction temperature as a WABT, in the range of from about 338-516, 338-471, 338-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- reaction inlet pressure in the range of from about 108-161, 108-148, 108- 141, 121-161, 121-148, 121-141, 128-161, 128-148, 128-141 or 131-137;
- reaction outlet pressure in the range of from about 100-150, 100-137, 100-130, 112-150, 112-137, 112-130, 118-150, 118-137 or 118-130;
- make-up hydrogen rate up to about 225, 215, 200 or 190, in certain embodiments from about 143-215, 143-200, 143-190, 161-215, 161-200, 161-190, 170- 215, 170-200 or 170-190; and
- liquid hourly space velocity values (h "1 ), on a fresh feed basis relative to the hydrocracking catalysts, are in the range of from about 0.1 -10.0, 0.1-5.0, 0.1-2.0, 0.3- 10.0, 0.3-5.0, 0.3-2.0, 0.4-10.0, 0.4-5.0 or 0.5-3.0.
- operating conditions for the reactor(s) in hydrocracking zone 330 using a once-through (single stage without recycle) configuration and operating in a partial conversion mode include:
- a reactor inlet temperature in the range of from about 340-502, 340-460, 340- 440, 372-502, 372-460, 372-440, 394-502, 394-460, 394-440 or 412-420;
- a reactor outlet temperature in the range of from about 350-516, 350-471, 350-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- a start of run (SOR) reaction temperature as a weighted average bed temperature (WABT), in the range of from about 310-475, 310-435, 310-415, 350-475, 350-435, 350- 415, 370-475, 370-435, 370-415 or 390-397;
- an end of run (EOR) reaction temperature as a WABT, in the range of from about 338-516, 338-471, 338-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- reaction inlet pressure in the range of from about 100-165, 100-150, 100- 140, 120-165, 120-140, 130-165, 130-150, or 130-140;
- a hydrogen quench gas feed rate up to about 614, 558, 553 or 520, in certain embodiments from about 457-558, 457-533, 457-520, 482-558, 482-533, 482- 520, 495-558, 495-533, or 495-520;
- Gas stream 344 typically containing H 2 , H 2 S, H 3 , and light hydrocarbons (C 1 - C 4 ), is discharged and recovered and can be further processed.
- Effluent off-gases are passed to the olefins recovery train, the saturated gas plant as part of the other gases stream 156, and/or directly to a fuel gas system.
- Liquefied petroleum gas can be recovered and routed to the mixed feed steam cracking zone, the olefins recovery train and/or the saturated gas plant.
- One or more cracked product streams 346 are discharged via appropriate outlets of the fractionator and can be further processed and/or blended in downstream refinery operations to produce gasoline, kerosene and/or diesel fuel, or other petrochemical products.
- a diesel fraction 362 derived from the one or more cracked product streams 346 can be integrated with the recycle streams to the reactors. This integration adds to the flexibility of the configuration between production of diesel fuel or petrochemicals from the product streams 346.
- All or a portion of the fractionator bottoms stream 348 from the reaction effluent is recycled to the first or second reaction zones 352 and/or 358 (streams 364a and/or 364b).
- a portion of the fractionator bottoms from the reaction effluent is removed as bleed stream 368.
- Bleed stream 368 can be about 0-10 vol%, 1-10 vol%, 1-5 vol% or 1-3 vol% of the fractionator bottoms 348.
- This stream 368 is routed to the high olefinic fluid catalytic cracking zone 700 as described herein.
- stream 364a recycled to zone 352 comprises 0 to 100 vol%, in certain embodiments 0 to about 80 vol%, and in further embodiments 0 to about 50 vol% of stream 348
- stream 364b recycled to zone 358 comprises 0 to 100 vol%, in certain embodiments 0 to about 80 vol%, and in further embodiments 0 to about 50 vol% of stream 348.
- recycle of the unconverted oil increases the yield of products suitable as feed to the mixed feed steam cracking zone 230.
- a suitable series flow hydrocracking zone 350 can include, but is not limited to, systems based on technology commercially available from Honeywell UOP, US; Chevron Lummus Global LLC (CLG), US; Axens, IFP Group Technologies, FR; or Shell Global Solutions, US.
- the reactor arrangement in the series flow hydrocracking zone 350 can contain one or more fixed-bed, ebullated-bed, slurry-bed, moving bed, continuous stirred tank (CSTR), or tubular reactors, which can be in parallel arrangement. Additional equipment, including exchangers, furnaces, feed pumps, quench pumps, and compressors to feed the reactor(s) and maintain proper operating conditions, are well known and are considered part of the series flow hydrocracking zone 350. In addition, equipment, including pumps, compressors, high temperature separation vessels, low temperature separation vessels and the like to separate reaction products and provide hydrogen recycle within the series flow hydrocracking zone 350, are well known and are considered part of the series flow hydrocracking zone 350.
- operating conditions for the first reactor(s) in hydrocracking zone 350 using once-through series configuration operating in a partial conversion mode of operation include:
- a reactor inlet temperature in the range of from about 340-502, 340-460, 340- 440, 372-502, 372-460, 372-440, 394-502, 394-460, 394-440 or 412-420;
- a reactor outlet temperature in the range of from about 350-516, 350-471, 350-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- a start of run (SOR) reaction temperature as a weighted average bed temperature (WABT), in the range of from about 310-475, 310-435, 310-415, 350-475, 350-435, 350- 415, 370-475, 370-435, 370-415 or 390-397;
- an end of run (EOR) reaction temperature as a WABT, in the range of from about 338-516, 338-471, 338-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- reaction inlet pressure in the range of from about 100-165, 100-150, 100- 140, 120-165, 120-140, 130-165, 130-150, or 130-140;
- reaction outlet pressure in the range of from about 92-150, 92-137, 92- 130, 112-150, 112-127, 112-130, 118-140, 118-130;
- a hydrogen partial pressure (barg) in the range of from about 80-120, 80- 106, 80-101, 90-120, 90-106, 90-101, 100-120, or 100-115; a hydrogen treat gas feed rate (SLt/Lt) up to about 668, 607, 580 or 566, in certain embodiments from about 497-607, 497-580, 497-566, 525-607, 525-580, 525-566, 538- 607, 538-580, or 538-566;
- a hydrogen quench gas feed rate up to about 819, 744, 711 or 694, in certain embodiments from about 609-744, 609-711, 609-694, 643-744, 643-711, 643- 694, 660-744, 660-711, or 660-694;
- make-up hydrogen rate up to about 271, 246, 235 or 224, in certain embodiments from about 182-246, 182-235, 182-224, 192-246, 192-235, 192-224, 203- 246, 203-235, or 203-224; and
- liquid hourly space velocity values (h "1 ), on a fresh feed basis relative to the hydrocracking catalysts, are in the range of from about 0.1-10.0, 0.1-5.0, 0.1-2.0, 0.3- 10.0, 0.3-5.0, 0.3-2.0, 0.4-10.0, 0.4-5.0, 0.4-2.0 or 0.5-1.5.
- partial conversion hydrocracking using once- through configuration operating conditions include:
- a reactor inlet temperature in the range of from about 340-502, 340-460, 340- 440, 372-502, 372-460, 372-440, 394-502, 394-460, 394-440 or 412-420;
- a reactor outlet temperature in the range of from about 350-516, 350-471, 350-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- a start of run (SOR) reaction temperature as a weighted average bed temperature (WABT), in the range of from about 310-475, 310-435, 310-415, 350-475, 350-435, 350- 415, 370-475, 370-435, 370-415 or 390-397;
- reaction inlet pressure in the range of from about 90-150, 90-130, 90-140, 110-150, 110-130, 110-145, or 130-150;
- a hydrogen treat gas feed rate up to about 890, 803, 767 or 748, in certain embodiments from about 657-803, 657-767, 657-748, 694-803, 694-767, 694-748, 712- 803, 712-767, or 712-748;
- exemplary products from the partial conversion hydrocracker using once-through configuration include 48-82, 50-80, 48-75 or 50-75 wt% of effluent boiling at or below the atmospheric residue end boiling point, such as 370°C, including LPG, kerosene, naphtha, and atmospheric gas oil range components.
- the remaining bottoms fraction is the unconverted oil fraction, all or a portion of which can be effectively integrated as feed to the high olefinic fluid catalytic cracking zone 700 as described herein.
- First reaction zone 372 generally includes one or more inlets in fluid communication with a source of initial feedstock 334 and a source of hydrogen gas 338. One or more outlets of the first reaction zone 372 that discharge effluent stream 374 are in fluid communication with one or more inlets of the fractionating zone 342 (optionally having one or more high pressure and low pressure separation stages therebetween for recovery of recycle hydrogen, not shown).
- the fractionating zone 342 bottoms outlet is in fluid communication with the one or more inlets of the second reaction zone 382 for recycle stream 348a derived from the bottoms stream 348.
- Recycle stream 348a can be all or a portion of the bottoms stream 348.
- a portion 348b is in fluid communication with one or more inlets of the first reaction zone 372.
- Second reaction zone 382 generally includes one or more inlets in fluid communication with the fractionating zone 342 bottoms outlet portion 348a of bottoms 348, and a source of hydrogen gas 384.
- One or more outlets of the second reaction zone 382 that discharge effluent stream 386 are in fluid communication with one or more inlets of the fractionating zone 342 (optionally having one or more high pressure and low pressure separation stages therebetween for recovery of recycle hydrogen, not shown).
- Gas stream 344 typically containing H 2 , H 2 S, NH 3 , and light hydrocarbons (C 1 - C 4 ), is discharged and recovered and can be further processed. Effluent off-gases are passed to the olefins recovery train, the saturated gas plant as part of the other gases stream 156, and/or directly to a fuel gas system. Liquefied petroleum gas can be recovered and routed to the mixed feed steam cracking zone, the olefins recovery train and/or the saturated gas plant.
- One or more cracked product streams 346 are discharged via appropriate outlets of the fractionator and can be further processed and/or blended in downstream refinery operations to produce gasoline, kerosene and/or diesel fuel, or other petrochemical products.
- a diesel fraction 376 derived from the one or more cracked product streams 346 can be integrated with the feed to the second stage reactor 382. This integration adds to the flexibility of the configuration between production of diesel fuel or petrochemicals from the product streams 346.
- fractionating zone 342 can operate as a flash vessel to separate heavy components at a suitable cut point, for example, a range corresponding to the upper temperature range of the desired gasoline, kerosene and/or diesel products for downstream operations.
- a suitable cut point is in the range of 350 to 450°C, 360 to 450°C, 370 to 450°C, 350 to 400°C, 360 to 400°C, 370 to 400°C, 350 to 380°C, or 360 to 380°C.
- the stream above that cut point is routed to the high olefinic fluid catalytic cracking zone 700 as described herein.
- bleed stream 368 a portion of the fractionator bottoms from the reaction effluent is removed as bleed stream 368.
- Bleed stream 368 can be about 0-10 vol%, 1-10 vol%, 1-5 vol% or 1-3 vol% of the fractionator bottoms 348.
- Second reaction zone 382 operates under conditions effective for production of the reaction effluent stream 386, which contains converted, partially converted and unconverted hydrocarbons.
- the second stage the reaction effluent stream 386 is passed to the fractionating zone 342, optionally through one or more gas separators to recovery recycle hydrogen and remove certain light gases [263]
- a suitable two-stage hydrocracking zone 370 can include, but is not limited to, systems based on technology commercially available from Honeywell UOP, US; Chevron Lummus Global LLC (CLG), US; Axens, IFP Group Technologies, FR; or Shell Global Solutions, US.
- a reactor inlet temperature in the range of from about 340-502, 340-460, 340- 440, 372-502, 372-460, 372-440, 394-502, 394-460, 394-440 or 412-420;
- an end of run (EOR) reaction temperature as a WABT, in the range of from about 338-516, 338-471, 338-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- reaction inlet pressure in the range of from about 100-180, 100-160, 100- 141, 121-180, 121-160, 121-141, 128-180, 128-160, 128-141 or 131-180;
- reaction outlet pressure in the range of from about 90-170, 90-137, 90- 130, 112-170, 112-137, 112-130, 118-150, 118-137 or 118-170;
- a hydrogen partial pressure (barg) in the range of from about 90-137, 90- 106, 90-120, 100-137, 100-106, or 100-120;
- a hydrogen quench gas feed rate up to about 1100, 980, 935 or 913, in certain embodiments from about 801 -980, 801-935, 801-913, 846-980, 846-935, 846- 913, 868-980, 868-935, or 868-913;
- operating conditions for the second stage reactor(s) in hydrocracking zone 370 using a two-stage with recycle configuration operating in a full conversion mode of operation include:
- operating conditions for the reactor(s) in the first stage reaction zone of the two-stage hydrocracking zone 370 include:
- a reactor inlet temperature in the range of from about 340-502, 340-460, 340- 440, 372-502, 372-460, 372-440, 394-502, 394-460, 394-440 or 412-420;
- an end of run (EOR) reaction temperature as a WABT, in the range of from about 338-516, 338-471, 338-450, 382-516, 382-471, 382-450, 400-516, 400-471, 400-450 or 422-430;
- a hydrogen treat gas feed rate up to about 910, 823, 785 or 767, in certain embodiments from about 673-823, 673-785, 673-767, 711-823, 711-785, 711-767, 729- 823, 729-785, or 729-767;
- a hydrogen quench gas feed rate up to about 980, 882, 842 or 822, in certain embodiments from about 721-882, 721-842, 721-822, 761-882, 761-842, 761- 822, 781-882, 781-842, or 781-822;
- make-up hydrogen rate up to about 451, 410, 392 or 374, in certain embodiments from about 303-410, 303-392, 303-374, 321-410, 321-392, 321-374, 338- 410, 338-392, or 338-374;
- Embodiments of systems and processes incorporating certain vacuum residue hydroprocessing zones are disclosed in United States Patent Application Number [SA3106 AFS 215,409] filed on November 17, 2017, entitled “Process and System for Conversion of Crude Oil to Petrochemicals and Fuel Products Integrating Vacuum Residue Hydroprocessing," and United States Patent Application Number [SA3107 AFS 215,410] filed on November 17, 2017, entitled “Process and System for Conversion of Crude Oil to Petrochemicals and Fuel Products Integrating Vacuum Residue Conditioning and Base Oil Production,” which are commonly owned and are incorporated by reference herein in their entireties.
- the hydrotreated gas oil fraction 304 is routed to the high olefinic fluid catalytic cracking zone 700.
- the fourth middle distillate stream 130 is also routed the high olefinic fluid catalytic cracking zone 700, bypassing the vacuum gas oil hydrotreating zone 300.
- the fourth middle distillate stream 130 is subjected to hydrotreating prior to passage to the high olefinic fluid catalytic cracking zone 700, for instance with the other feeds to the vacuum gas oil hydrotreating zone 300.
- the high olefinic fluid catalytic cracking zone 700 can have one or more risers / reactors, a disengager / stripper and one or more regenerators. If plural reactors are implemented, propylene yield and selectivity can be maximized.
- a fluid catalytic cracking unit configured with a riser reactor that operates under conditions that promote formation of light olefins, particularly propylene, and that minimize light olefin-consuming reactions including hydrogen-transfer reactions.
- FIG. 21a is a simplified schematic illustration of a riser fluid catalytic cracking unit.
- a fluid catalytic cracking unit 720 includes a riser reactor.
- Fluid catalytic cracking unit 720 includes a reactor/separator 724 having a riser portion 726, a reaction zone 728 and a separation zone 730.
- Fluid catalytic cracking unit 720 also includes a regeneration vessel 732 for regenerating spent catalyst.
- regeneration zone 732 the coked catalyst comes into contact with a stream of oxygen-containing gas, such as pure oxygen or air, which enters regeneration zone 732 via a conduit 740.
- the regeneration zone 732 is operated in a configuration and under conditions that are known in typical fluid catalytic cracking operations. For instance, regeneration zone 732 can operate as a fluidized bed to produce regeneration off-gas comprising combustion products which is discharged through a conduit 742.
- the hot regenerated catalyst is transferred from regeneration zone 732 through conduit 734 to the bottom portion of the riser 726 for admixture with the hydrocarbon feedstock and noted above.
- reaction temperature of from about 480-650, 480-620, 480-600, 500-650, 500-620, or 500-600;
- reaction pressure of from about 1-20, 1-10, or 1-3;
- reaction vapor of hydrocarbon cracked products, unreacted feed and catalyst mixture quickly flows through the remainder of reaction zone 768 and into the rapid separation zone 770 at the bottom portion of reactor/separator 764.
- Cracked and uncracked hydrocarbons are directed through a conduit or pipe 776 to a conventional product recovery section known in the art to yield as fluid catalytic cracking products light olefins, gasoline and cycle oil, with a maximized propylene yield.
- a quench injection can be provided near the bottom of reaction zone 768 immediately before the separation zone 770. This quench injection quickly reduces or stops the cracking reactions and can be utilized for controlling cracking severity to achieve the product slate.
- reaction temperature of from about 550-650, 550-630, 550-620, 580-650, 580-630, 580-620, 590-650, 590-630, 590-620;
- a preferred shaped selective catalyst additive can be employed, such as those used in fluid catalytic cracking processes to produce light olefins and increase fluid catalytic cracking gasoline octane is ZSM-5 zeolite crystal or other pentasil type catalyst structure.
- This ZSM-5 additive can be mixed with the cracking catalyst zeolites and matrix structures in conventional fluid catalytic cracking catalyst and is particularly suitable to maximize and optimize the cracking of the crude oil fractions in the downflow reaction zones.
- the cracked naphtha hydrotreating zone 670 operates under conditions effective to ensure removal of substantially all nitrogen, since nitrogen is a limiting contaminant in the aromatics extraction and subsequent processes. Due to the high temperature conditions effective for nitrogen removal, saturation of aromatics occurs, for instance, in the range of about 15% saturation, ahead of recovery. Effluents from the cracked naphtha hydrotreating zone 670 are a hydrotreated fluid catalytic cracking naphtha stream 672, and fuel gas.
- a suitable cracked naphtha hydrotreating zone 670 can include, but is not limited to, systems based on technology commercially available from Honeywell UOP, US; Chevron Lummus Global LLC (CLG), US; or Axens, IFP Group Technologies, FR.
- the fluid catalytic cracking naphtha hydrotreating zone 670 can contain one or more fixed-bed, ebullated-bed, slurry-bed, moving bed, continuous stirred tank (CSTR) or tubular reactors, in series and/or parallel arrangement. Additional equipment, including exchangers, furnaces, feed pumps, quench pumps, and compressors to feed the reactor(s) and maintain proper operating conditions, are well known and are considered part of the fluid catalytic cracking naphtha hydrotreating zone 670.
- CSTR continuous stirred tank
- a reactor inlet temperature in the range of from about 293-450, 293-410, 293- 391, 332-450, 332-410, 332-391, 352-450, 352-410, 352-391 or 368-374;
- reaction inlet pressure in the range of from about 44-66, 44-60, 44-58, 49-66, 49-60, 49-58, 52-66, 52-60, 52-58 or 53-56;
- a hydrogen partial pressure (barg) in the range of from about 22-33, 22- 30, 22-29, 25-33, 25-30, 25-29, 26-33, 26-30 or 26-29; a hydrogen treat gas feed rate (SLt/Lt) up to about 640, 620, 570 or 542, in certain embodiments from about 413-620, 413-570, 413-542, 465-620, 465-570, 465-542, 491- 620, 491-570 or 491-542;
- a hydrogen quench gas feed rate up to about 95, 85, 78 or 75, in certain embodiments from about 57-85, 57-78, 57-75, 64-85, 64-78, 64-75, 68-85, 68-78 or 68- 75;
- a make-up hydrogen feed rate up to about 120, 110 or 102, in certain embodiments from about 78-120, 78-110, 78-102, 87-120, 87-110, 87-102, 92-120, 92- 110, 92-102 or 95-100.
- An effective quantity of hydrotreating catalyst is provided in the fluid catalytic cracking naphtha hydrotreating zone 670, including those possessing hydrotreating functionality and which generally contain one or more active metal component of metals or metal compounds (oxides or sulfides) selected from the Periodic Table of the Elements IUPAC Groups 6-10.
- the active metal component is one or more of Co, Ni, W and Mo.
- the active metal component is typically deposited or otherwise incorporated on a support, such as amorphous alumina, amorphous silica alumina, zeolites, or combinations thereof.
- the catalyst used in the fluid catalytic cracking naphtha hydrotreating zone 670 includes one or more catalyst selected from Co/Mo, Ni/Mo, Ni/W, and Co/Ni/Mo. Combinations of one or more of Co/Mo, Ni/Mo, Ni/W and Co/Ni/Mo, can also be used. The combinations can be composed of different particles containing a single active metal species, or particles containing multiple active species. In certain embodiments, Co/Mo hydrodesulfurization catalyst is suitable.
- Effective liquid hourly space velocity values (h "1 ), on a fresh feed basis relative to the hydrotreating catalysts, are in the range of from about 0.1-10.0, 0.1-5.0, 0.1-2.0, 0.3-10.0, 0.3-5.0, 0.3-2.0, 0.5-10.0, 0.5-5.0, 0.5-2.0 or 0.8-1.2.
- Suitable hydrotreating catalysts used in the fluid catalytic cracking naphtha hydrotreating zone 670 have an expected lifetime in the range of about 28-44, 34-44, 28-38 or 34-38 months.
- the mixed feed steam cracking zone 230 which operates as high severity or low severity thermal cracking process, generally converts LPG, naphtha and heavier hydrocarbons primarily into a mixed product stream 220 containing mixed C1-C4 paraffins and olefins.
- the mixed feed steam cracking zone 230 processes straight-run liquids from the crude unit, propane (from outside battery limits and/or recycled) and various recycle streams from chemical production and recovery areas within the integrated process and system.
- a suitable mixed feed steam cracking zone 230 can include, but is not limited to, systems based on technology commercially available from Linde AG, DE; TechnipFMC pic, UK; Chicago Bridge & Iron Company N. V. (CB&I), NL; or KBR, Inc, US.
- Plural feeds to the mixed feed steam cracking zone 230 include: light ends 152, light naphtha 138 and heavy naphtha 140 (or a full range straight run naphtha 136 as shown in other embodiments) from the crude complex 100; a LPG stream 634 from a transalkylation zone 630; a C3+ stream 716 recovered from the high olefinic fluid catalytic cracking zone 700; a recycle stream 282 from the methyl acetylene/propadiene (MAPD) saturation and propylene recovery zone 280, described below; C4 raffinate 524 from the 1-butene recovery zone 520 described below; C5s stream 676 from the fluid catalytic cracking naphtha hydrotreating ("FCCN HT") zone 670; C5s stream 606 from the py-gas hydrotreating zone 600; wild naphtha 184 from the diesel hydrotreating zone 180 described above (in certain embodiments via the crude complex); naphtha from the vacuum gas oil hydroprocess
- the products from the mixed feed steam cracking zone 230 include a quenched cracked gas stream 220 containing mixed C1-C4 paraffins and olefins that is routed to the olefins recovery zone 270, a raw pyrolysis gasoline stream 212 that is routed to a py-gas hydrotreating zone 600 to provide feed 604 to the aromatics extraction zone 620, and a pyrolysis fuel oil stream 218.
- the mixed feed steam cracking zone 230 operates under parameters effective to crack the feed into desired products including ethylene, propylene, butadiene, and mixed butenes. Pyrolysis gasoline and pyrolysis oil are also recovered. In certain embodiments, the steam cracking furnace(s) are operated at conditions effective to produce an effluent having a propylene-to-ethylene weight ratio of from about 0.3-0.8, 0.3-0.6, 0.4-0.8 or 0.4- 0.6.
- the mixed feed steam cracking zone 230 generally comprises one or more trains of furnaces.
- a typical arrangement includes reactors that can operate based on well-known steam pyrolysis methods, that is, charging the thermal cracking feed to a convection section in the presence of steam to raise the temperature of the feedstock, and passing the heated feed to the pyrolysis reactor containing furnace tubes for cracking.
- the mixture is heated to a predetermined temperature, for example, using one or more waste heat streams or other suitable heating arrangement.
- the feed mixture is heated to a high temperature in a convection section and material with a boiling point below a predetermined temperature is vaporized.
- the heated mixture (in certain embodiments along with additional steam) is passed to the pyrolysis section operating at a further elevated temperature for short residence times, such as 1-2 seconds or less, effectuating pyrolysis to produce a mixed product stream.
- separate convection and radiant sections are used for different incoming feeds to the mixed feed steam cracking zone 230 with conditions in each optimized for the particular feed.
- steam cracking in the mixed feed steam cracking zone 230 is carried out using the following conditions: a temperature (°C) in the convection section in the range of about 400-600, 400-550, 450-600 or 500-600; a pressure (barg) in the convection section in the range of about 4.3 -4.8, 4.3-4.45, 4.3-4.6, 4.45-4.8, 4.45-4.6 or 4.6-4.8; a temperature (°C) in the pyrolysis section in the range of about 700-950, 700- 900, 700-850, 750-950, 750-900 or 750-850; a pressure (barg) in the pyrolysis section in the range of about 1.0-1.4, 1.0-1.25, 1.25-1.4, 1.0-1.15, 1.15-1.4 or 1.15-1.25; a steam-to- hydrocarbon ratio in the in the convection section in the range of about 0.3 : 1-2: 1, 0.3 : 1- 1.5: 1, 0.5:
- cracked gas from the furnaces is cooled in transfer line exchangers (quench coolers), for example, producing 1800 psig steam suitable as dilution steam.
- Quenched cracked gas enters a primary fractionator associated with the mixed feed steam cracker 230 that removes pyrolysis fuel oil bottoms from lighter components.
- the primary fractionator enables efficient recovery of pyrolysis fuel oil.
- Pyrolysis fuel oil is stripped with steam in a fuel oil stripper to control product vapor pressure, and cooled.
- secondary quench is carried out by direct injection of pyrolysis fuel oil as quench oil into liquid furnace effluents.
- the stripped and cooled pyrolysis fuel oil can be sent to a fuel oil pool or product storage.
- the olefins recovery zone 270 operates to produce on-specification light olefin (ethylene and propylene) products from the mixed product stream 220.
- cooled gas intermediate products from the steam cracker is fed to a cracked gas compressor, caustic wash zone, and one or more separation trains for separating products by distillation.
- the distillation train includes a cold distillation section, wherein lighter products such as methane, hydrogen, ethylene, and ethane are separated in a cryogenic distillation/separation operation.
- the mixed C2 stream from the steam cracker contains acetylenes that are hydrogenated to produce ethylene in an acetylene selective hydrogenation unit.
- This system can also include ethylene, propane and/or propylene refrigeration facilities to enable cryogenic distillation.
- Deethanizer bottoms contain C3s from which propylene product 204, in certain embodiments polymer-grade propylene product, is recovered as the overhead of a C3 splitter, with propane 282 from the C3 splitter bottoms recycled to the mixed feed steam cracking zone 230.
- the stream 206 in operation of the butadiene extraction zone 500, is preheated and vaporized into a first extractive distillation column, for instance having two sections.
- NMP or DMF solvent separates the 1,3 -butadiene from the other C4 components contained in stream 504. Rich solvent is flashed with vapor to a second extractive distillation column that produces a high purity 1,3 butadiene stream as an overhead product. Liquid solvent from the flash and the second distillation column bottoms are routed to a primary solvent recovery column. Bottoms liquid is circulated back to the extractor and overhead liquid is passed to a secondary solvent recovery or solvent polishing column.
- the C4 raffinate stream 516 from the methyl tertiary butyl ether zone 510 is passed to the C4 distillation unit 520 for butene-1 recovery.
- a selective hydrogenation zone can also be included (not shown).
- raffinate from the methyl tertiary butyl ether zone 510 is selectively hydrogenated in a selective hydrogenation unit to produce butene-1.
- Other co-monomers and paraffins are also co- produced.
- the selective hydrogenation zone operates in the presence of an effective amount of hydrogen obtained from recycle within the selective hydrogenation zone and make-up hydrogen; in certain embodiments, all or a portion of the make-up hydrogen for the selective hydrogenation zone is derived from the steam cracker hydrogen stream 210 from the olefins recovery train 270.
- a suitable selective hydrogenation zone can include, but is not limited to, systems based on technology commercially available from Axens, IFP Group Technologies, FR; Haldor Topsoe A/S, DK; Clariant International Ltd, CH; Chicago Bridge & Iron Company N.V. (CB&I), NL; Honeywell UOP, US; or Shell Global Solutions, US.
- Isobutane product 526 can optionally be recovered in the overhead (shown in dashed lines), 1-butene product 522 is recovered as a sidecut, and n-butane is recovered as the bottoms stream. Bottoms from both splitters is recovered as all or a portion of the recycle stream 524.
- a depentanizing step associated with the aromatics extraction zone 620 separates all or a portion of the C5s from the hydrotreated naphtha stream 604, for instance, as additional feed to the mixed feed steam cracking zone 230 and/or as feed to a metathesis unit 530.
- the first reaction stage of the py-gas hydrotreating zone 600 operating conditions include:
- isobutylene 544 can also be recovered (shown in dashed lines) and routed to the methyl tertiary butyl ether zone 510. In embodiments that operate without separation of isobutylene, it is included within stream 542.
- the computer system can include one or more processors typically connected to one or more memory devices, which can comprise, for example, any one or more of a disk drive memory, a flash memory device, a RAM memory device, or other device for storing data.
- the memory is typically used for storing programs and data during operation of the system.
- the memory can be used for storing historical data relating to the parameters over a period of time, as well as operating data.
- Software including programming code that implements embodiments of the invention, can be stored on a computer readable and/or writeable nonvolatile recording medium, and then typically copied into memory wherein it can then be executed by one or more processors. Such programming code can be written in any of a plurality of programming languages or combinations thereof.
- the disclosed processes and systems create new outlets for direct conversion of crude oil, for instance, light crudes such as Arab Extra Light (AXL) or Arab Light (AL) crude oil. Additionally, the disclosed processes and systems offer novel configurations that, compared to known processes and systems, requires lower capital expenditure relative to conventional approaches of chemical production from fuels or refinery byproducts and that utilize refining units and an integrated chemicals complex. The disclosed processes and systems substantially increase the proportion of crude oil that is converted to high purity chemicals that traditionally command high market prices. Complications resulting from advancing the threshold of commercially proven process capacities are minimized or eliminated using the processes and systems described herein. [358] The disclosed processes and systems utilize different commercially proven units arranged in novel configurations.
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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
Claims
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662424883P | 2016-11-21 | 2016-11-21 | |
| US201762450060P | 2017-01-24 | 2017-01-24 | |
| US201762450058P | 2017-01-24 | 2017-01-24 | |
| US201762450018P | 2017-01-24 | 2017-01-24 | |
| US15/710,799 US20180142167A1 (en) | 2016-11-21 | 2017-09-20 | Process and system for conversion of crude oil to chemicals and fuel products integrating steam cracking and fluid catalytic cracking |
| PCT/US2017/062614 WO2018094353A1 (en) | 2016-11-21 | 2017-11-20 | Process and system for conversion of crude oil to petrochemicals and fuel products integrating steam cracking, fluid catalytic cracking, and conversion of naphtha into chemical rich reformate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3541894A1 true EP3541894A1 (en) | 2019-09-25 |
| EP3541894B1 EP3541894B1 (en) | 2024-01-10 |
Family
ID=62145873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17812154.7A Active EP3541894B1 (en) | 2016-11-21 | 2017-11-20 | Process for conversion of crude oil to petrochemicals and fuel products integrating steam cracking, fluid catalytic cracking, and conversion of naphtha into chemical rich reformate |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP3541894B1 (en) |
| JP (1) | JP2020500966A (en) |
| KR (1) | KR20190086707A (en) |
| CN (1) | CN110214170B (en) |
| WO (1) | WO2018094353A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11279891B2 (en) * | 2020-03-05 | 2022-03-22 | Saudi Arabian Oil Company | Systems and processes for direct crude oil upgrading to hydrogen and chemicals |
| US20230398533A1 (en) * | 2020-11-13 | 2023-12-14 | Shell Usa Inc. | Methods for replacing a spent catalyst of a reactor train of an operating hydroprocessing system |
| CN112500891A (en) * | 2020-12-23 | 2021-03-16 | 北京石油化工工程研究院 | Heavy oil processing method and system |
| CN116554927B (en) * | 2022-01-28 | 2024-10-11 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin and aromatic hydrocarbon by heavy oil |
| CN114674780B (en) * | 2022-03-16 | 2025-02-11 | 中国石油化工股份有限公司 | A method for blending light crude oil |
| US11820950B1 (en) * | 2022-06-16 | 2023-11-21 | Saudi Arabian Oil Company | Conversion of whole crude to value added petrochemicals in an integrated reactor process |
| US11866663B1 (en) * | 2023-02-02 | 2024-01-09 | Saudi Arabian Oil Company | Multi-zone catalytic cracking of crude oils |
| US11939539B1 (en) * | 2023-06-09 | 2024-03-26 | Saudi Arabian Oil Company | Multi-zone catalytic cracking of crude oils |
| CN119912975B (en) * | 2023-10-30 | 2025-11-14 | 中国石油化工股份有限公司 | A crude oil processing method and system for producing all chemical products |
| FR3160183A1 (en) * | 2024-03-14 | 2025-09-19 | IFP Energies Nouvelles | Process for the production of petrochemical bases comprising fluid catalytic cracking, oligomerization, fixed bed hydrocracking, catalytic reforming and steam cracking |
| FR3160184A1 (en) * | 2024-03-14 | 2025-09-19 | IFP Energies Nouvelles | Process for the production of petrochemical bases comprising fluid catalytic cracking, oligocracking, fixed bed hydrocracking, catalytic reforming and steam cracking |
| FR3160185A1 (en) * | 2024-03-14 | 2025-09-19 | IFP Energies Nouvelles | Process for the production of petrochemical bases comprising fluid catalytic cracking, fixed bed hydrocracking, catalytic reforming and steam cracking |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702292A (en) * | 1970-03-10 | 1972-11-07 | Du Pont | Composite hydrocarbon refinery apparatus and process arrangement |
| CN1031646C (en) | 1992-10-22 | 1996-04-24 | 中国石油化工总公司 | Method for Catalytic Conversion of Petroleum Hydrocarbons |
| US6538169B1 (en) | 2000-11-13 | 2003-03-25 | Uop Llc | FCC process with improved yield of light olefins |
| US20020195373A1 (en) | 2001-06-07 | 2002-12-26 | Takashi Ino | Heavy oil fluid catalytic cracking process |
| US6656346B2 (en) | 2001-06-07 | 2003-12-02 | King Fahd University Of Petroleum And Minerals | Fluid catalytic cracking process for heavy oil |
| US8558036B2 (en) | 2010-11-15 | 2013-10-15 | Saudi Arabian Oil Company | Dual phase catalysts system for mixed olefin hydrations |
| US8629080B2 (en) | 2011-03-21 | 2014-01-14 | Saudi Arabian Oil Company | Hydrated niobium oxide nanoparticle containing catalysts for olefin hydration |
| US8999013B2 (en) | 2011-11-01 | 2015-04-07 | Saudi Arabian Oil Company | Method for contemporaneously dimerizing and hydrating a feed having butene |
| KR101876612B1 (en) | 2011-12-05 | 2018-07-09 | 사우디 아라비안 오일 컴퍼니 | Hydrophilic Membrane Integrated Olefin Hydration Process |
| US10155707B2 (en) | 2012-09-05 | 2018-12-18 | Saudi Arabian Oil Company | Olefin hydration process using oscillatory baffled reactor |
| US9187388B2 (en) | 2012-09-05 | 2015-11-17 | Saudi Arabian Oil Company | Olefin hydration process using oscillatory baffled reactor |
| JP6810606B2 (en) * | 2013-07-02 | 2021-01-06 | サウディ ベーシック インダストリーズ コーポレイション | Improved ethylene yield methods and equipment for converting crude oil to petrochemicals |
| ES2702179T3 (en) * | 2013-07-02 | 2019-02-27 | Sabic Global Technologies Bv | Process and installation for the conversion of crude oil into petrochemical products that have improved BTX performance |
| CN105358661A (en) * | 2013-07-02 | 2016-02-24 | 沙特基础工业公司 | Process and facility for converting crude oil to petrochemicals with improved propylene yield |
| US11046900B2 (en) * | 2013-07-02 | 2021-06-29 | Saudi Basic Industries Corporation | Process for upgrading refinery heavy residues to petrochemicals |
| KR102308545B1 (en) * | 2013-07-02 | 2021-10-05 | 사우디 베이식 인더스트리즈 코포레이션 | Method of producing aromatics and light olefins from a hydrocarbon feedstock |
| US20150148572A1 (en) | 2013-11-27 | 2015-05-28 | Saudi Arabian Oil Company | Process for the Dimerization/Oligomerization of Mixed Butenes Over an Ion-Exchange Resin Catalyst |
| US9447346B2 (en) | 2013-12-11 | 2016-09-20 | Saudi Arabian Oil Company | Two-step process for production of RON-enhanced mixed butanols and diisobutenes |
| US9732018B2 (en) | 2014-02-11 | 2017-08-15 | Saudi Arabian Oil Company | Process for production of mixed butanols and diisobutenes as fuel blending components |
-
2017
- 2017-11-20 WO PCT/US2017/062614 patent/WO2018094353A1/en not_active Ceased
- 2017-11-20 JP JP2019527360A patent/JP2020500966A/en not_active Withdrawn
- 2017-11-20 EP EP17812154.7A patent/EP3541894B1/en active Active
- 2017-11-20 CN CN201780078195.3A patent/CN110214170B/en not_active Expired - Fee Related
- 2017-11-20 KR KR1020197017067A patent/KR20190086707A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018094353A1 (en) | 2018-05-24 |
| EP3541894B1 (en) | 2024-01-10 |
| CN110214170B (en) | 2021-12-07 |
| KR20190086707A (en) | 2019-07-23 |
| WO2018094353A9 (en) | 2018-08-02 |
| JP2020500966A (en) | 2020-01-16 |
| CN110214170A (en) | 2019-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10894926B2 (en) | System for conversion of crude oil to petrochemicals and fuel products integrating steam cracking, fluid catalytic cracking, and conversion of naphtha into chemical rich reformate | |
| US10913908B2 (en) | System for conversion of crude oil to petrochemicals and fuel products integrating steam cracking and fluid catalytic cracking | |
| US10760012B2 (en) | System for conversion of crude oil to petrochemicals and fuel products integrating steam cracking and conversion of naphtha into chemical rich reformate | |
| US10800977B2 (en) | System for conversion of crude oil to petrochemicals and fuel products integrating delayed coking of vacuum residue | |
| EP3541894B1 (en) | Process for conversion of crude oil to petrochemicals and fuel products integrating steam cracking, fluid catalytic cracking, and conversion of naphtha into chemical rich reformate | |
| US10760011B2 (en) | System for conversion of crude oil to petrochemicals and fuel products integrating vacuum gas oil hydrocracking and steam cracking | |
| EP3541893B1 (en) | Process for conversion of crude oil to petrochemicals and fuel products integrating vacuum gas oil hydrotreating and steam cracking | |
| EP3541898A1 (en) | Process and system for conversion of crude oil to petrochemicals and fuel products integrating solvent deasphalting of vacuum residue | |
| US11066611B2 (en) | System for conversion of crude oil to petrochemicals and fuel products integrating vacuum gas oil hydrotreating and steam cracking |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20190619 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) | ||
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
| 17Q | First examination report despatched |
Effective date: 20210908 |
|
| P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230529 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20230929 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SAUDI ARABIAN OIL COMPANY |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602017078388 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1648895 Country of ref document: AT Kind code of ref document: T Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240510 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240411 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240410 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240410 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240410 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240510 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240411 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240510 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240510 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602017078388 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| 26N | No opposition filed |
Effective date: 20241011 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20241120 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20241120 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20241130 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20241130 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20241120 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20241130 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20241120 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20251022 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20251022 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20251022 Year of fee payment: 9 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20171120 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20171120 |