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WO2003064022A1 - Valorisation de naphtas et de distillats derives du petrole et de fischer-tropsch - Google Patents

Valorisation de naphtas et de distillats derives du petrole et de fischer-tropsch Download PDF

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Publication number
WO2003064022A1
WO2003064022A1 PCT/US2002/039778 US0239778W WO03064022A1 WO 2003064022 A1 WO2003064022 A1 WO 2003064022A1 US 0239778 W US0239778 W US 0239778W WO 03064022 A1 WO03064022 A1 WO 03064022A1
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WO
WIPO (PCT)
Prior art keywords
distillate
naphtha
fischer
tropsch
blended
Prior art date
Application number
PCT/US2002/039778
Other languages
English (en)
Inventor
Dennis J. O'rear
Lawrence W. Jossens
Original Assignee
Chevron U.S.A. Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/059,224 external-priority patent/US7033552B2/en
Priority claimed from US10/059,383 external-priority patent/US20030141220A1/en
Priority claimed from US10/059,382 external-priority patent/US6863802B2/en
Priority claimed from US10/059,381 external-priority patent/US20030141221A1/en
Application filed by Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Priority to JP2003563703A priority Critical patent/JP4748939B2/ja
Priority to BR0215537-0A priority patent/BR0215537A/pt
Publication of WO2003064022A1 publication Critical patent/WO2003064022A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • C10G2400/02—Gasoline

Definitions

  • the present invention is directed to the conversion of remote natural gases into saleable transportation fuels and petroleum products. More specifically, this invention is directed to upgrading by, for example, hydrotreating, hydrocracking and hydrodewaxing Fischer-Tropsch and/or petroleum-derived naphthas and distillates for use in saleable transportation fuels and petroleum products.
  • the Fischer-Tropsch reaction is a well known reaction, and catalysts and conditions for performing Fischer-Tropsch reactions are well known to those of skill in the art, and are described, for example, in EP 0 921 184A1, the contents of which are hereby incorporated by reference in their entirety.
  • the Fischer-Tropsch process converts synthesis gas into linear hydrocarbons(n-paraffins, linear olefins and minor amounts of fatty acids).
  • naphtha can be used as a petrochemical feedstock for ethylene production, naphtha has not been found to be suitable for transportation fuels.
  • naphtha may be suitable as a fuel for fuel cell vehicles, because fuel cell vehicles have not yet become widely used, a need still exists for a process to convert naphtha so that it can be used in conventional transportation fuels.
  • products of the Fischer-Tropsch process in finished products, exhibit boiling ranges having unacceptable levels of oxygenates and olefins (alcohols and traces of acids).
  • the content of linear hydrocarbons in such products is so high that the resulting products exhibit unacceptable cold climate properties including, but not limited to, jet freeze point, diesel cloud point, and lube base stock pour point.
  • these products can be upgraded to obtain saleable transportation fuels and lube base stocks by employing various processes including, but not limited to, hydrotr eating, hydrocracking, hydrodewaxing, combinations thereof and the like.
  • the least expensive catalysts for hydrotreating, hydrocracking and hydrodewaxing use sulfided Group VI and VIII metals including, but not limited to, nickel, cobalt, molybdenum, tungsten, combinations thereof and the like.
  • Non- sulfided catalysts for hydrotreating, hydrocracking and hydrodewaxing are available but are based on expensive noble metals including, but not limited to, platinum, palladium, combinations thereof and the like.
  • Petroleum-derived hydrocarbon products produced along with a natural gas can include condensates, naphthas and distillates. These products have chemical compositions that are analogous to compositions of conventional petroleum products, and include a mixture of a variety of hydrocarbons including, but not limited to, linear paraffins, iso-paraffins, cyclo-paraffms, aromatics, mixtures thereof and the like. They also contain sulfur and nitrogen impurities that must be removed to obtain saleable products.
  • the process of the present invention addresses the above needs.
  • the process of the present invention produces at least one of saleable gasoline components, distillate fuel components and lube base stock components by, for example, hydrotreating, hydrocracking and hydrodewaxing (i.e., upgrading) Fischer-Tropsch and/or petroleum-derived naphthas and distillates.
  • the fuel components produced by the present invention have octane values sufficient for use in conventional transportation fuels and petrochemical feedstocks.
  • the present invention produces hydrogen by-product that can be used in hydrotreating, hydrocracking and hydrodewaxing processes to inexpensively upgrade Fischer-Tropsch products.
  • the present invention inexpensively provides at least a portion of the hydrogen needed for hyrdotreatment processes without having to employ expensive separation processes or separate hydrogen production facilities.
  • the present invention can combine Fischer-Tropsch naphthas and distillates with petroleum-derived naphthas and distillates to obtain blended naphthas and distillates having sulphur levels of at least about 1 ppm.
  • the present invention ensures that sulfided catalysts, used to hydrotreat naphthas and distillates, maintain adequate sulfur levels without having to add sulfur by introducing costly pure chemicals.
  • the present invention can upgrade (e.g. , hydrotreat, hydrocrack or hydrodewax) petroleum hydrocarbon products, including condensates, naphthas and distillates, to obtain saleable gasoline components and petroleum feedstock products.
  • a process according to the present invention for upgrading at least one of a Fischer-Tropsch naphtha and a Fischer-Tropsch distillate, to produce at least one of a gasoline component, a distillate fuel component, or a lube base stock component can include reforming a Fischer-Tropsch naphtha to produce hydrogen by-product and a gasoline component with a research octane rating of at least about 80.
  • the hydrogen by-product is then used to upgrade a Fischer-Tropsch distillate to produce distillate fuel components and/or lube base stock blending components.
  • a process, according to the present invention, for upgrading a Fischer- Tropsch naphtha can include hydrotreating Fischer-Tropsch naphtha to remove oxygenates producing hydrotreated Fischer-Tropsch naphtha.
  • the process can further include reforming the hydrotreated Fischer-Tropsch naphtha producing hydrogen by-product and a gasoline component having a research octane rating of at least about 80.
  • the hydrogen by-product is recirculated to hydrotreat said Fischer-Tropsch naphtha.
  • Another process, according to the present invention, for upgrading a Fischer-Tropsch naphtha to obtain a gasoline component can include mixing Fischer-Tropsch naphtha with petroleum-derived naphtha to obtain a blended naphtha having a sulfur level of at least about 1 ppm.
  • the blended naphtha is hydrotreated to produce hydrotreated blended naphtha.
  • the hydrotreated blended naphtha is reformed producing hydrogen by-product and a gasoline component having an research octane rating of at least about 80.
  • a process of the present invention for upgrading a Fischer-Tropsch distillate to produce at least one of a distillate fuel and a lube base stock component can include mixing Fischer-Tropsch distillate and petroleum-derived distillate to obtain a blended distillate having a sulfur level of at least about 1 ppm.
  • the blended distillate is hydrotreated producing hydrotreated blended distillate.
  • hydrotreated blended distillate is upgraded producing distillate fuel components and/or lube base stock blending components.
  • a plant of the present invention for upgrading at least one of a Fischer-Tropsch naphtha and a Fischer-Tropsch distillate to obtain at least one of a gasoline componenet, a distillate fuel or a lube base feedstock component can include a hydrocarbon source providing a hydrocarbon.
  • a separator separates hydrocarbon gas, hydrocarbon condensate and crude oil from the hydrocarbon.
  • a synthesis gas from the hydrocarbon gas.
  • a Fischer-Tropsch reactor positioned downstream from the synthesis gas generator conducts a Fischer-Tropsch process on the synthesis gas to obtain Fischer-Tropsch naphtha and Fischer-Tropsch distillate.
  • a naphtha reformer downstream from the hydrotreatment reactor reforms hydrotreated naphtha to obtain hydrogen by-product and a gasoline component including at least about 10% aromatics.
  • a distillate hydrotreatment reactor downstream from the Fischer- Tropsch reactor hydrotreats the Fischer-Tropsch distillate.
  • a distillate upgrader is downstream from the distillate hydrotreatment reactor and relative to the naphtha reformer so that hydrogen by-product from the reformer recirculates to the upgrader so that the upgrader can upgrade hydrotreated distillate to produce distillate fuel and/or a lube base feedstock component.
  • Figure 1 is a schematic view of a preferred embodiment of the present invention.
  • Figure 2 is a schematic view of another preferred embodiment of the present invention.
  • Figure 3 is a schematic view of another preferred embodiment of the present invention.
  • Fischer-Tropsch naphtha and optionally petroleum-derived naphtha, can be reformed to make aromatics and hydrogen by-product.
  • the resulting aromatics can increase the octane number of the naphtha to permit the naphtha to be used as a conventional gasoline or a blend stock in conventional gasoline.
  • the resulting aromatics can also be sold as valuable petrochemicals including, but not limited to, benzene, toluene and xylene.
  • reforming processes There are two classes of reforming processes: catalytic reforming and
  • AROMAX ® reforming The process of the present invention can employ either or both catalytic reforming or AROMAX ® reforming technologies to convert the Fischer-Tropsch naphthas into aromatics.
  • Catalytic reforming as described, for example, in Catalytic Reforming, by D. M. Little, PennWell Books (1985), is a well-known process.
  • AROMAX ® reforming is also a well-known process, and is described, for example, in Petroleum & Petrochemical International, Volume 12, No. 12, pages 65 to 68, as well as U.S. Patent No. 4,456,527 to Buss et al.
  • the feed to either of these reforming processes should have very low levels of heteroatoms (e.g., sulfur, nitrogen, and oxygen).
  • Fischer-Tropsch naphthas generally have very low levels of sulfur and nitrogen, but often have appreciable levels of oxygen in the form of alcohols and traces of acids and other oxygenates. These heteroatoms can be removed by use of a hydrotreater.
  • the preferred hydrotreating catalysts use inexpensive non-noble metals from Groups VI and VIII including, but not limited to, nickel, cobalt, molybdenum, tungsten, combinations thereof and the like. These non-noble metals are active when they are in the sulfided state.
  • the product is stripped to remove hydrogen sulfide and other light sulfur compounds, and is optionally treated with a sulfur adsorbent.
  • adsorbents guard beds
  • the hydrogen by-product from the reformer is used to upgrade the distillates by the use of hydrogen consuming processes that include, for example, hydrotreating, hydrocracking, and hydrodewaxing.
  • the present invention avoids the need for expensive separation processes or separate hydrogen production facilities to supply added hydrogen needed for distillate upgrading.
  • processes of the present invention can produce hydrogen byproduct for use in hydrogen-consumer upgrading processes, at least initially, it may be necessary in processes of the invention to provide hydrogen.
  • hydrogen produced in the reformer can be used in other operations, including the hydrotreatment of naphtha and/or distillate, provisions may need to be made to provide hydrogen at startup.
  • There are several solutions to this problem including, but not limited to, providing a separate source of hydrogen, such as from high pressure containers, making the hydrogen from electrolysis units, or providing a source of low-sulfur hydrotreated naphtha for the reformer for startup.
  • hydrogen byproduct is not being produced, it is understood that hydrogen is being provided to conduct, for example, hydrotreatment and/or upgrading processes.
  • the Fischer-Tropsch naphtha is mixed with a petroleum-derived naphtha to obtain a blended naphtha having a sulfur level above about 1 ppm, preferably above about 10 ppm.
  • This blended naphtha is then hydrotreated over an inexpensive sulfided hydrotreating catalyst to remove oxygenates from the Fischer-Tropsch naphtha and sulfur from the petroleum-derived naphtha.
  • the Fischer-Tropsch distillate is mixed with a petroleum-derived distillate to increase the sulfur level of the blended distillate to above about 1 ppm, preferably above about 10 ppm.
  • This blended distillate is then hydrotreated over an inexpensive sulfided hydrotreating catalyst to remove oxygenates from the Fischer-Tropsch distillate and sulfur from the petroleum-derived distillate. Without the presence of some type of sulfur compound in the feedstock, the sulfur in the sulfided hydrotreating catalyst would eventually be removed and the hydrotreating catalyst would suffer a loss in performance.
  • a Fischer-Tropsch naphtha and a Fischer-Tropsch distillate can be hydrotreated in one reactor together with a petroleum-derived naphtha, condensate, distillate or combinations thereof, provided that the sulfur content of the blend is greater than about 1 ppm, preferably greater than about 10 ppm.
  • processes, according to the present invention need not include both naphtha reformation and distillate upgrading processes. That is, it is within the scope of the present invention to have a process wherein naphtha reformation or distillate upgrading are performed separately. In such embodiments it may be necessary to provide hydrogen during start up and/or hydrogen to be used in upgrading processes including, but not limited to, hydrotreating, hydrocracking and hydrodewaxing processes.
  • hydrogen may be supplied initially to be used to hydrotreat the naphtha before reformation.
  • at least a portion of the hydrogen by-product generated during reformation can be recirculated to hydrotreat naphtha before reformation. The recirculation of hydrogen by-product generated during reformation may substantially limit the amount of hydrogen that needs to be added for hydrotreatment.
  • hydrogen may need to be supplied during both hydrotreatment and upgrading.
  • FIG. 1 A preferred embodiment of the present invention, wherein hydrogen generated during Fischer-Tropsch naphtha reformation is used for distillate upgrading, is depicted in Figure 1.
  • a methane-containing hydrocarbon gas feed stream 12 is obtained from a methane-containing terrestrial reservoir 11.
  • the hydrocarbon gas feed stream 12 enters a separator 13.
  • the separator 13 separates the hydrocarbon gas feed stream 12 into a heavier condensate stream 15, a crude oil fraction stream 14 and a methane-containing hydrocarbon gas exit stream 16.
  • the hydrocarbon gas exit stream 16 enters a synthesis gas generator 17.
  • a gaseous oxidant stream 18 also enters the synthesis gas generator 17.
  • At least a part of the methane-containing hydrocarbon exit gas 16 is converted by the synthesis gas generator 17 into a synthesis gas stream 19 (a gas mixture containing at least carbon monoxide and hydrogen) by use of the gaseous oxidant stream 18 (air, O2, enriched air, carbon dioxide and combinations thereof).
  • the synthesis gas stream 19 enters a Fischer-Tropsch reactor 20.
  • the Fischer-Tropsch reactor 20 converts the synthesis gas stream 19 into at least a Fischer-Tropsch naphtha stream 21 and a Fischer-Tropsch distillate stream 22.
  • the Fischer-Tropsch naphtha stream 21 enters a naphtha hydrotreatment reactor 23.
  • the Fischer-Tropsch distillate stream 22 enters a distillate hydrotreatment reactor 24.
  • the naphtha hydrotreatment reactor 23 treats the naphtha stream 21 to remove oxygenates to obtain a hydrotreated naphtha stream 25.
  • the distillate hydrotreatment reactor 24 treats the distillate stream 22 to remove oxygenates to obtain a hydrotreated distillate stream 26.
  • the hydrotreated naphtha stream 25 enters a naphtha reformer 27.
  • the hydrotreated distillate stream 26 enters a distillate upgrader 28 wherein the hydrotreated distillate is upgraded by, for example, hydrocracking and/or hydrodewaxing processes.
  • a hydrogen by-product stream 29 is generated.
  • the hydrogen by-product stream 29 enters the naphtha hydrotreatment reactor 23, the distillate hydrotreatment reactor 24 and the distillate upgrader 28 providing additional hydrogen for the hydrotreatment processes conducted therein.
  • a saleable distillate fuel or lube base stock components stream 32 exits the distillate upgrader 28.
  • the catalysts used for hydrotreating the naphtha and distillate, and used to upgrade the hydrotreated distillate either comprise a noble metal including, but not limited to, Pd, Pt, combinations thereof or the like, or a non-noble metal including, but not limited to, Ni, Co, W, Mo, combinations thereof or the like.
  • the non-noble metal catalysts are in a sulfided form, and preferably sulfur is added to the unit either continuously or periodically.
  • the sulfur can be added, for example, in the form of a chemical, such as dimethyldisulfide.
  • the hydrotreating catalyst is a noble metal (less preferred), it is preferably not sulfided.
  • Figure 2 Another preferred embodiment of the present invention, wherein hydrogen generated during Fischer-Tropsch naphtha reformation is used for distillate upgrading, is depicted in Figure 2.
  • a methane-containing hydrocarbon feed gas 42 is obtained from a methane-containing terrestrial reservoir 41.
  • a heavier condensate stream 45 and/or a crude oil fraction stream 44 are separated from the methane-containing hydrocarbon feed gas 42 in a separator 43.
  • a methane-containing hydrocarbon gas exit stream 46 exits the separator 43 and enters a synthesis gas generator 48.
  • a gaseous oxidant stream 49 also enters the synthesis gas generator 48.
  • a synthesis gas stream 50 exits the generator 48 and enters a Fischer-Tropsch reactor 53.
  • the Fischer-Tropsch reactor 53 generates at least a Fischer-Tropsch naphtha stream 54 and a Fischer- Tropsch distillate-containing stream 55.
  • the crude oil stream 44 and the condensate stream 45 enter a distillate reactor 47.
  • the petroleum-derived naphtha stream 51 mixes with the Fischer- Tropsch distillate stream 54 to produce a blended naphtha having more than about 1 ppm sulfur, preferably more than about 10 ppm sulfur.
  • the blended naphtha then enters a naphtha hydrotreatment reactor 56.
  • the petroleum-derived distillate stream 52 mixes with the Fischer-Tropsch distillate stream 55 to produce a blended distillate comprising more than about 1 ppm sulfur, preferably more than about 10 ppm sulfur.
  • the blended distillate enters a distillate hydrotreatment reactor 57.
  • the blended naphtha is hydrotreated to remove oxygenates.
  • a hydrotreated naphtha stream 58 exits the naphtha hydrotreatment reactor 56.
  • the hydrotreated naphtha stream 58 then enters a naphtha reformer 60.
  • the blended distillate is hydrotreated in the distillate hydrotreating reactor 57 to remove oxygenates, and a hydrotreated distillate stream 59 exits the distillate hydrotreatment reactor 57.
  • the hydrotreated distillate stream 59 enters a distillate upgrader 61.
  • a hydrogen byproduct stream 62 is generated.
  • a portion of the hydrogen by-product stream 62 is recirculated in a hydrogen recirculation stream 63 to provide additional hydrogen needed for the hydrotreatment processes being conducted within the naphtha and distillate hydrotreatment reactors 56, 57.
  • hydrogen from hydrogen by-product stream 62 enters the distillate upgrader 61 to provide additional hydrogen for upgrading processes (e.g., hydrocracking and hydrodewaxing processes) conducted therein for upgrading the blended distillate.
  • a saleable gasoline component stream 65 comprising at least about 10% aromatics, and having a research octane rating of at least about 80, preferably at least about 90, exits the naphtha reformer 60 following naphtha reformation.
  • a salable distillate fuel or lube base stock component stream 64 exits the distillate upgrader 61.
  • a methane-containing hydrocarbon feed gas 72 is obtained from a methane-containing terrestrial reservoir 71.
  • a heavier condensate stream 75 and/or crude oil fraction stream 76 are separated from the methane-containing hydrocarbon feed gas 72 in a separator 73.
  • a methane-containing hydrocarbon exit stream gas 74 exits the separator 73 and enters a synthesis gas generator 77.
  • a gaseous oxidant stream 78 also enters the synthesis gas generator 77.
  • a synthesis gas stream 79 exits the synthesis gas generator 77 and enters a Fischer-Tropsch reactor 80.
  • a Fischer-Tropsch product stream 81 exits the Fischer-Tropsch reactor 80.
  • the crude oil stream 76 and the condensate stream 75 exit the separator 73 and enter a distillate reactor 89.
  • At least a petroleum-derived naphtha stream 90 and a petroleum-derived distillate stream 91 exit the distillate reactor 89 and mix with the Fischer-Tropsch product stream 81 to obtain a blended product stream, comprising at least about 1 ppm sulfur, preferably at least about 10 ppm sulfur.
  • the blended product stream enters a hydrotreatment reactor 82, wherein oxygenates are removed from the Fischer-Tropsch distillate and naphtha and sulfur is removed from the petroleum-derived distillate and naphtha.
  • a hydrotreated product stream 82A exits the hyrotreatment reactor 82 and enters a distillate reactor 83. At least a blended naphtha stream 84 and a blended distillate stream 85 exit the distillate reactor 83.
  • the blended naphtha stream 84 enters a naphtha reformer 86 wherein the naphtha is reformed generating a hydrogen by-product stream 88 and a salable gasoline product stream 93.
  • the gasoline product stream 93 comprises at least about 10% aromatics and has a research octane rating of at least about 80, preferably at least about 90.
  • the blended distillate stream 85 exits the distillate reactor 83 and enters a distillate upgrader 87.
  • the hydrogen by-product stream 88 exiting the naphtha reformer enters the distillate upgrader 87 providing additional hydrogen needed for upgrading processes (e.g. , hydrocracking and hydrodewaxing processes) conducted therein to upgrade the distillate.
  • upgrading processes e.g. , hydrocracking and hydrodewaxing processes
  • a portion of the hydrogen by-product stream 88 is recirculated in a hydrogen recirculation stream 92 to the hydrotreatment reactor 82 to provide additional hydrogen needed for the hydrotreatment processes conducted therein for the removal of oxygenates and sulfur.
  • a saleable distillate fuel or lube base stock components stream 94 exits the distillate upgrader 87.
  • a Fischer-Tropsch naphtha and distillate product are blended to provide a mixture that contains approximately 1 weight % oxygen and less than about 10 ppm sulfur.
  • This mixture is hydrocracked over a sulfided nickel tungsten catalyst at 663 °F, 1.0 LHSV, 77% conversion, 1100 psig, and 10000 SCFB hydrogen recirculation gas rate.
  • the product at that time is fractionated and the 300-650°F diesel portion is isolated.
  • the sulfur content of the diesel fraction as determined by the Antek method, is about 3.2 ppm by weight.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé de valorisation d'au moins un naphta de Fischer-Tropsch (21) et un distillat de Fischer-Tropsch (22) pour produire au moins un constituant d'essence (30), un constituant de mazout léger ou de charge de base lubrifiante (32). Le procédé consiste à reformer un naphta de Fischer-Tropsch dans un réacteur (27) afin de produire un sous-produit d'hydrogène (31) et un constituant d'essence (30) présentant un indice d'octane recherche d'au moins environ 80. Le procédé consiste également à valoriser un distillat de Fischer-Tropsch dans un réacteur (28) à l'aide du sous-produit d'hydrogène afin de produire un mazout léger et/ou un constituant de charge de base lubrifiante (32).
PCT/US2002/039778 2002-01-31 2002-12-13 Valorisation de naphtas et de distillats derives du petrole et de fischer-tropsch WO2003064022A1 (fr)

Priority Applications (2)

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JP2003563703A JP4748939B2 (ja) 2002-01-31 2002-12-13 フィッシャー・トロプシュおよび石油由来のナフサおよび留出物のアップグレード化
BR0215537-0A BR0215537A (pt) 2002-01-31 2002-12-13 Processo e planta para beneficiar pelo menos um de uma nafta de fischer-tropsch e um destilado de fischer-tropsch, e, componentes de gasolina, de combustìvel destilado, e de matéria-prima básica de lubrificantes

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US10/059,224 US7033552B2 (en) 2002-01-31 2002-01-31 Upgrading Fischer-Tropsch and petroleum-derived naphthas and distillates
US10/059,383 US20030141220A1 (en) 2002-01-31 2002-01-31 Upgrading fischer-tropsch and petroleum-derived naphthas and distillates
US10/059,382 US6863802B2 (en) 2002-01-31 2002-01-31 Upgrading fischer-Tropsch and petroleum-derived naphthas and distillates
US10/059,382 2002-01-31
US10/059,381 2002-01-31
US10/059,381 US20030141221A1 (en) 2002-01-31 2002-01-31 Upgrading Fischer-Tropsch and petroleum-derived naphthas and distillates
US10/059,383 2002-01-31
US10/059,224 2002-01-31

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WO2014095815A1 (fr) * 2012-12-17 2014-06-26 Shell Internationale Research Maatschappij B.V. Procédé de condensation gaz-liquide intégré
WO2014095814A1 (fr) * 2012-12-17 2014-06-26 Shell Internationale Research Maatschappij B.V. Procédé de condensation gaz-liquide intégré

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EP1644465B1 (fr) 2003-06-23 2010-03-17 Shell Internationale Researchmaatschappij B.V. Procede de preparation d'une huile de base lubrifiante
EP1853682A1 (fr) * 2004-12-23 2007-11-14 Shell Internationale Research Maatschappij B.V. Procédé pour préparer une huile de base lubrifiante
EP2149594A1 (fr) * 2008-07-28 2010-02-03 Mohammadreza Pircheraghali Production d'essence selon un nouveau procédé mélangeant des découpes de matériaux de pétrole
JP5296477B2 (ja) * 2008-09-30 2013-09-25 Ｊｘ日鉱日石エネルギー株式会社 ナフサ留分水素化処理反応器のスタートアップ方法
JP2024010687A (ja) * 2022-07-13 2024-01-25 三菱重工業株式会社 燃料製造設備及び燃料製造方法

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Publication number Priority date Publication date Assignee Title
WO2014095815A1 (fr) * 2012-12-17 2014-06-26 Shell Internationale Research Maatschappij B.V. Procédé de condensation gaz-liquide intégré
WO2014095814A1 (fr) * 2012-12-17 2014-06-26 Shell Internationale Research Maatschappij B.V. Procédé de condensation gaz-liquide intégré

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JP4748939B2 (ja) 2011-08-17
GB2386904A (en) 2003-10-01
GB0301347D0 (en) 2003-02-19
JP2005516082A (ja) 2005-06-02
GB2386904B (en) 2005-02-23
AU2003200318B2 (en) 2008-08-14
AU2003200318A1 (en) 2003-08-14
BR0215537A (pt) 2004-12-21

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