WO2017074641A1 - Amélioration de charges d'alimentation contenant des oléfines en composés d'intervalle de distillation du diesel - Google Patents

Amélioration de charges d'alimentation contenant des oléfines en composés d'intervalle de distillation du diesel Download PDF

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Publication number
WO2017074641A1
WO2017074641A1 PCT/US2016/054369 US2016054369W WO2017074641A1 WO 2017074641 A1 WO2017074641 A1 WO 2017074641A1 US 2016054369 W US2016054369 W US 2016054369W WO 2017074641 A1 WO2017074641 A1 WO 2017074641A1
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olefin
compounds
less
containing feed
effluent
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PCT/US2016/054369
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English (en)
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Mohsen N. Harandi
William S. BRAGAN
Thomas J. DOOLIN
Adam I. SMITH
Suriyanarayanan RAJAGOPALAN
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Exxonmobil Research And Engineering Company
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Publication of WO2017074641A1 publication Critical patent/WO2017074641A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G69/12—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 polymerisation or alkylation step
    • C10G69/126—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 polymerisation or alkylation step polymerisation, e.g. oligomerisation
    • 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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect

Definitions

  • U.S. Patent No. 5,482,617 discloses a process for desulfurization of hydrocarbon streams having at least 50 ppmw organic sulfur compounds, and C 5 + hydrocarbons including benzene.
  • the hydrocarbon stream is exposed to a fluidized bed of an acidic catalyst in the absence of added hydrogen at a pressure of 0.0 psig to 400 psig and a temperature of 400°F to 900°F.
  • U.S. Patent No. 6,372,949 discloses a one-step process for converting an oxygenate- containing feed to liquid boiling range C 5 + hydrocarbons.
  • the feed is contacted with a catalyst having a uni dimensional 10-ring zeolite at a temperature less than 350°C and a pressure above 40 psia.
  • a method for converting an olefm-containing feed to diesel boiling range compounds comprising; exposing an olefin-containing feed having an olefin content of at least about 10 wt% to a conversion catalyst under first effective conversion conditions to form an oligomerized olefin effluent comprising C 5 + olefinic compounds, wherein the first effective conversion conditions comprise a pressure of less than about 300 psig (2.1 MPa) and a temperature of from about 550°F (288°C) to about SOOT (427°C); and exposing at least a portion of the C 5+ olefinie compounds to effective fixed bed conversion conditions to form a product effluent comprising diesel boiling range compounds, wherein the effective fixed bed conversion conditions comprise a pressure of at least about 300 psig and a temperature of from about 400°F (204°C) to - z. - about 700°F (371°C), wherein the first effective conversion conditions comprise a pressure that
  • a method for converting an olefin-containing feed to diesel boiling range compounds comprising: exposing an olefin-containing feed having an olefin content of at least about 10 wt% to first effective conversion conditions comprising fluidized bed conditions to form an oligornenzed olefin effluent comprising C?+ olefinic compounds, wherein the effective conversion conditions in the first reaction vessel include a pressure of from about 50 psig to about 250 psig and a temperature of from about 550°F (288°C) to about SOOT (427°C); separating at least a portion of the oligomerized olefin effluent to form a first fraction comprising at least a portion of the C?+ olefinic compounds and a second fraction comprising compounds having three carbon atoms or less, and exposing the at least a portion of the C 5 + olefinic compounds to effective conversion conditions in a second reaction vessel to form
  • a diesel boiling range effluent comprising at least a first wt% of C 10 + oligomerized compounds and/or at least a second wt% of C 10 + olefins , the C 10+ oligomerized compounds and/or C 10 + olefins optionally being formed by oiigomerization of C2-5 olefins.
  • FIG. 1 schematically shows an example of a reaction system for converting an olefin- containing feed to a product effluent compri sing diesel boiling range compounds, according to an aspect of the invention.
  • the olefin-containing feed can include fuel gas, FCC naphtha, and/or olefinic naphtha.
  • the olefin-containing feed is exposed to a first set of conversion conditions in a first reaction vessel, which can include exposure to an acidic catalyst at a low pressure.
  • At least a portion of the effluent from this first set of conversion conditions can include oligomerized olefins (such as C 5 + olefins) and/or the effluent can exhibit a reduced sulfur content.
  • the effluent from this first set of conversion conditions can then be exposed to a second set of conversion conditions that can include exposure to an acidic catalyst at a higher pressure than the pressure in the first set of conversion conditions.
  • the product effluent from the second set of conditions which can include diesei boiling range compounds, can be optionally hydrotreated to enhance one or more of its properties.
  • this can provide a variety of advantages. For example, converting the olefins in fuel gas to a product effluent having diesei boiling range compounds can enhance refiner ⁇ ' economics, as fuel gas is typically utilized for low value purposes.
  • Converting FCC naphtha to a product having diesei boiling range compounds in the methods disclosed herein can allow for sulfur reduction of the FCC naphtha without any external hydrogen supply.
  • an existing reaction vessel e.g., an idle hydrotreating or reformer reactor, can be re-rated for use as the second reaction vessel, further enhancing refinery economics.
  • oligomerization catalysts are susceptible to coking and/or poisoning, such as by ammonia or other basic compounds. As coke and/or poison(s) form on the catalyst, the catalyst can become deactivated, leading to a reduced activity. The oligomerization process can also tend to be exothermic, which can pose problems for temperature control .
  • one or more of the above difficulties can be reduced or minimized by performing the processes described herein in a fluidized bed reactor or riser reactor. Alternatively, moving bed and fixed bed reactor systems can also be used.
  • a first fluidized bed oligomerization reactor can be operated at low pressure and under fluidized bed conditions.
  • the low pressure can facilitate using a feed with low molecular weight components, thus allowing Ci and/or C3 olefins to be used with high conversion per pass (such as 90+%) for formation of larger olefins.
  • the fluidized bed conditions can also allow for control of temperature within the reactor and/or allow for regeneration of catalyst to remove coke and/or temporary poisons.
  • a separation can be performed to remove low molecular weight components.
  • the remaining portion of the oligomerized effluent can then be passed to a second oligomerization stage for formation of diesei boiling range compounds.
  • the second oligomerization stage can be a fixed bed stage. Because the feed into the second oligomenzation stage is already partially reacted, the second stage can be operated at higher pressure while still having a reduced or minimized amount of coke and/or temporary poisons formation on the catalyst.
  • the combination of the first lower pressure oligomenzation stage and the second higher pressure oligomenzation stage can allow a variety of low value refiner ⁇ ' streams to be effectively converted to diesel boiling range compounds, such as fuel gas, flue gas from a cracking or coking process, or another olefin-containing stream.
  • At least a portion of the feed can correspond to a higher boiling range fraction that contains olefins, such as a cracked naphtha fraction.
  • a partially distilled naphtha fraction could be used as a portion of a feed, such as a fraction formed by separating a naphtha at a cut point of about 300°F or less, or about 250°F or less, or about 225°F or less.
  • the lower boiling portion from such a separation can be used as a feed while the higher boiling portion could be used for any convenient purpose, such as in a naphtha boiling range fuel.
  • diesel boiling range refers to an initial or T5 boiling point of at least about 350°F (177°C), and/or a final or T95 boiling point of less than about 700°F (371°C).
  • diesel boiling range compounds refers to one or more compounds that exhibit the diesel boiling range specified above.
  • nophtha boiling range refers to an initial or T5 boiling point of at least about 50°F (10°C), and/or a final or T95 boiling point of less than about 450T (232°C).
  • T5 boiling point refers to a temperature at which 5 wt.
  • T95 boiling point refers to a temperature at which 95 wt. % of the feed, effluent, product, stream, or composition of interest will boil.
  • the olefin-containing feed can be any hydrocarbon feed that contains olefins.
  • at least a portion of the olefin-containing feed can include one or more low value refinery streams, such as refiner ⁇ ' fuel gas or flue gas from a cracking or coking process.
  • at least a portion of the olefin-containing feed can include a higher boiling range fraction that contains olefins, such as a cracked naphtha fraction.
  • a partially distilled naphtha fraction could be used as a portion of a feed, such as a fraction formed by separating a naphtha at a cut point of about 300°F (149°C) or less, or about 250°F (121°C) or less, or about 225°F (107°C) or less.
  • the olefin-containing feed can include at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, or at least about 60 wt% olefins.
  • the olefm-containing feed can include less than about 100 wt%, less than about 90 wt%, less than about 80 wt%, or less than about 70 wt% olefins.
  • the olefm-containing feed can include at least about 5 wt%, at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, or at least about 70 wt% Ci -C 3 hydrocarbon compounds, with a portion being C2-C3 olefins, such as the olefin amounts listed above.
  • the olefin-contaimng feed can include less than about 100 wt3 ⁇ 4, less than about 90 wt%, less than about 80 wt%, or less than about 70 wt% C 1-C3 hydrocarbon compounds, with a portion being C2-C3 olefins, such as the olefin amounts listed above.
  • the olefm- containing feed can include C 1-C3 hydrocarbon compounds, with a portion being C2-C 3 olefins, such that the C 1-C3 hydrocarbon compounds are at least about 10 wt% greater, at least about 20 wt% greater, at least about 30 wt% greater, at least about 40 wt% greater, at least about 50 wt% greater, or at least about 60 wt3 ⁇ 4 greater than the amount (wt%) of C2-C3 olefins.
  • the olefm-containing feed can include at least about 5 wt%, at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt3 ⁇ 4, or at least about 70 wt% C 1 -C4 hydrocarbon compounds, with a portion being C2-C4 olefins, such as the olefin amounts listed above.
  • the olefm-containing feed can include less than about 100 wt%, less than about 90 wt%, less than about 80 wt%, or less than about 70 wt% C 1-C4 hydrocarbon compounds, with a portion being C2-C4 olefins, such as the olefin amounts listed above.
  • the olefin- containing feed can include C 1 -C4 hydrocarbon compounds, with a portion being C2 -C4 olefins, such that the C 1 -C 4 hydrocarbon compounds are at least about 10 wt3 ⁇ 4 greater, at least about 20 wt% greater, at least about 30 wt% greater, at least about 40 wt% greater, at least about 50 wt% greater, or at least about 60 wt% greater than the amount (wt%) of C2-C4 olefins,
  • the olefin-containing feed can include at least about 5 wt3 ⁇ 4, at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, or at least about 70 wt% C 1 -C5 hydrocarbon compounds, with a portion being C2-C5 olefins, such as the olefin amounts listed above.
  • the olefm-containing feed can include less than about 100 wt3 ⁇ 4, less than about 90 wt%, less than about 80 wt%, or less than about 70 wt% C 1-C 5 hydrocarbon compounds, with a portion being C2-C 5 olefins, such as the olefin amounts listed above.
  • the olefm-containing feed can include C 1 -C5 hydrocarbon compounds, with a portion being C2-C5 olefins, such that the C 1-C5 hydrocarbon compounds are at least about 10 wt% greater, at least about 20 wt% greater, at least about 30 wt% greater, at least about 40 wt% greater, at least about 50 wt% greater, or at least about 60 wt% greater than the amount (wt3 ⁇ 4) of C2-C 5 olefins.
  • the olefin-containing feed can include at least about 5 wt%, at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt3 ⁇ 4, at least about 50 wt%, at least about 60 wt%, or at least about 70 wt% C i-Cg hydrocarbon compounds, with a portion being C2-C9 olefins, such as the olefin amounts listed above.
  • the olefin-contaimng feed can include less than about 100 wt3 ⁇ 4, less than about 90 wt%, less than about 80 wt%, or less than about 70 wt% C 1-C hydrocarbon compounds, with a portion being C2-C9 olefins, such as the olefin amounts listed above.
  • the olefin-containing feed can include C1-C9 hydrocarbon compounds, with a portion being C2-C9 olefins, such that the C i-Cg hydrocarbon compounds are at least about 10 wt% greater, at least about 20 wt% greater, at least about 30 wt% greater, at least about 40 wt% greater, at least about 50 wt% greater, or at least about 60 wt% greater than the amount (wt%) of C 2 -Cg olefins.
  • the olefin-containing feed can include C5+ compounds in an amount of about 50 wt% or less, about 40 wt% or less, about 30 wt% or less, about 20 wt% or less, about 10 wt% or less, or about 5 wt% or less.
  • the olefin-containing feed can include C 5+ compounds in an amount of at least about 0.5 wt%, at least about 1 wt%, or at least about 2.5 wt%.
  • the olefin-containing feed can include one or more low value refinery streams, such as refinery fuel gas or flue gas from a cracking or coking process.
  • the one or more low value streams may be present in the olefin-containing feed in an amount of at least about 10 wt%, at least about 20 wt%, at least about 30 w ⁇ %, at least about 40 wt%, at least about 50 wt%, or at least about 60 wt%.
  • the one or more low value streams may be present in the olefin-containing feed in an amount of about 100 wt3 ⁇ 4 or less, about 99 wt% or less, about 95 wt% or less, about 90 wt% or less, about 80 wt% or less, or about 70 wt% or less.
  • the olefin-contaimng feed can include one or more naphtha fractions, such as fluid catalytic cracking ("FCC") naphtha or olefinic naphtha.
  • the one or more naphtha fractions may be present in the olefin-containing feed in an amount of at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, or at least about 60 wt%.
  • the one or more naphtha fractions may be present in the olefin-containing feed in an amount of about 100 wt% or less, about 99 wt% or less, about 95 wt% or less, about 90 wt% or less, about 80 wt% or less, or about 70 wt% or less.
  • naphtha fractions can include FCC naphtha (or cat naphtha), steam cracked naphtha, coker naphtha, or a combination thereof.
  • Olefinic naphtha refinery streams generally contain not only paraffins, naphthenes, and aromatics, but also unsaturates, such as open-chain and cyclic olefins, dienes, and cyclic hydrocarbons with olefinic side chains.
  • An olefinic naphtha feedstock can also have a diene concentration up to about 15 wt%, but more typically less than about 5 wt% based on the total weight of the feed,
  • the olefin-containing feed can include a hydrocarbon feed having a boiling point less than the boiling point of diesel boiling range compounds.
  • the olefin-containing feed can exhibit a final or T95 boiling point of less than about 3 SOT (177°C), less than about 325°F (163°C), less than about 300°F (149°C), less than about 275°F (135°C), or less than about 250°F (121°C).
  • the olefin-containing feed can have a sulfur content of at least about 100 wppm, or at least about 500 wppm, or at least about 1000 wppm, or at least about 1500 wppm.
  • the sulfur content can be about 7000 wppm or less, or about 6000 wppm or less, or about 5000 wppm or less, or about 3000 wppm or less.
  • the sulfur may be present as organically bound sulfur.
  • nitrogen can also be present in the olefin-containing feed.
  • the amount of nitrogen can be at least about 5 wppm, or at least about 10 wppm, or at least about 20 wppm, or at least about 40 wppm.
  • the nitrogen content can be about 250 wppm or less, or about 150 wppm or less, or about 100 wppm or less, or about 50 wppm or less,
  • the olefin-containing feed can be exposed to an acidic catalyst (such as a zeolite) under effective conversion conditions for olefinic oligomerization and/or sulfur removal.
  • an acidic catalyst such as a zeolite
  • the zeolite or other acidic catalyst can also include a hydrogenation functionality, such as a Group VIII metal or other suitable metal that can activate hydrogenation / dehydrogenation reactions.
  • the olefin-containing feed can be exposed to the acidic catalyst without providing substantial additional hydrogen to the reaction environment.
  • Added hydrogen refers to hydrogen introduced as an input flow to the process, as opposed to any hydrogen that might be generated in-situ during processing.
  • Exposing the feed to an acidic catalyst without providing substantial added hydrogen is defined herein as exposing the feed to the catalyst in the presence of a) less than about 100 SCF/bbl (about 17 nrVm 3 ) of added hydrogen, or less than about 50 SCF/bbl (about 10 m 3 /m 3 ); b) a partial pressure of less than about 50 psia (350 kPa) of hydrogen, or less than about 15 psia ( 00 kPa); or c) a combination thereof.
  • the acidic catalyst used in the processes described herein can be any alumina- containing catalyst, such as a zeolite-based catalyst.
  • the acidic catalyst can comprise an acidic zeolite in combination with a binder or matrix material such as alumina, silica, or silica- alumina, and optionally further in combination with a hydrogenation metal.
  • the acidic catalyst can correspond to a molecular sieve (such as a zeolite) in combination with a binder, and optionally a hydrogenation metal.
  • Molecular sieves for use in the catalysts can be medium pore size zeolites, such as those having the framework structure of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, or MCM-22. Such molecular sieves can have a 10-member ring as the largest ring size in the framework structure.
  • the medium pore size zeolites are a well- recognized class of zeolites and can be characterized as having a Constraint Index of I to 12. Constraint Index is determined as described in U.S. Pat. No. 4,016,218 incorporated herein by reference. Catalysts of this type are described in U.S. Pat. Nos. 4,827,069 and 4,992,067 which are incorporated herein by reference and to which reference is made for further details of such cataivsts, zeolites and binder or matrix materials.
  • catalysts based on large pore size framework structures such as the synthetic faujasites, especially zeolite Y, such as in the form of zeolite USY.
  • Zeolite beta may also be used as the zeolite component.
  • Other materials of acidic functionality which may be used in the catalyst include the materials identified as MCM-36 and MCM-49.
  • Still other materials can include other types of molecular sieves having suitable framework structures, such as siiicoaluminophosphates (SAPOs), aluminosilicates having other heteroatoms in the framework structure, such as Ga, Sn, or Zn, or siiicoaluminophosphates having other heteroatoms in the framework structure.
  • SAPOs siiicoaluminophosphates
  • aluminosilicates having other heteroatoms in the framework structure such as Ga, Sn, or Zn
  • siiicoaluminophosphates having other heteroatoms in the framework structure such as Ga, Sn, or Zn
  • the exposure of the olefin-containing feed to the acidic cataly st can be performed in any convenient manner, such as exposing the olefin-containing feed to the acidic cataiyst under fluidized bed conditions.
  • the particle size of the catalyst can be selected in accordance with the fluidization regime which is used in the process. Particle size distribution can be important for maintaining turbulent fluid bed conditions as described in U.S. Pat. No. 4,827,069 and incorporated herein by reference. Suitable particle sizes and distributions for operation of dense fluid bed and transport bed reaction zones are described in U.S. Pat, Nos. 4,827,069 and 4,992,607, both incorporated herein by reference. Particle sizes in both cases will normally be in the range of 10 to 300 microns, typically from 20 to 100 microns.
  • Acidic zeolite catalysts suitable for use as described herein can be those exhibiting high hydrogen transfer activity and having a zeolite structure of ZSM-5, ZSM-1 1, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, MCM-36, MCM-49, zeolite Y, and zeolite beta.
  • Such catalysts can be capable of oligomerizing olefins from the olefin-containing feed.
  • such catalysts can convert C2-C4 olefins, such as those present in a refinery fuel gas, to C5+ olefins.
  • Such catalysts can also be capable of converting organic sulfur compounds such as mercaptans to hydrogen sulfide without added hydrogen by utilizing hydrogen present in the hydrocarbon feed.
  • Group VIII metals such as nickel may be used as desulfurization promoters.
  • a fluid-bed reactor/regenerator can assist with maintaining catalyst activity in comparison with a fixed-bed system. Further, the hydrogen sulfide produced in accordance with the processes described herein can be removed using conventional amine based absorption processes.
  • ZSM-5 crystalline structure is readily recognized by its X-ray diffraction pattern, which is described in U.S. Pat. No. 3,702,866.
  • ZSM-11 is disclosed in U.S. Pat. No. 3,709,979
  • ZSM-12 is disclosed in U.S. Pat. No. 3,832,449
  • ZSM-22 is disclosed in U.S. Pat. No, 4,810,357
  • ZSM-23 is disclosed in U.S. Pat. Nos. 4,076,842 and 4, 104, 151, ZSM-35 is disclosed in U.S. Pat. No.4,016,245,
  • ZSM-48 is disclosed in U.S. Pat. No.4,375,573
  • MCM-22 is disclosed in U.S. Pat. No. 4,954,325.
  • the U.S. Patents identified in this paragraph are incorporated herein by reference.
  • zeolites having a coordinated metal oxide to silica molar ratio of 20: 1 to 200: 1 or higher may be used, it can be advantageous to employ aluminosilicate ZSM-5 having a silica:alumina molar ratio of about 25: 1 to 70: 1, suitably modified.
  • a typical zeolite catalyst component having Bransted acid sites can comprises, consist essentially of, or consist of crystalline aluminosilicate having the structure of ZSM-5 zeolite with 5 to 95 wt. % silica, clay and/or alumina binder.
  • siliceous zeolites can be employed in their acid forms, ion-exchanged or impregnated with one or more suitable metals, such as Ga, Pd, Zn, Ni, Co, Mo, P, and/or other metals of Periodic Groups III to VIII.
  • suitable metals such as Ga, Pd, Zn, Ni, Co, Mo, P, and/or other metals of Periodic Groups III to VIII.
  • the zeolite may include other components, generally one or more metals of group IB, ⁇ , IIIB, VA, VIA or VIIIA of the Periodic Table (IUPAC).
  • Useful hydrogenation components can include the noble metals of Group VIIIA, such as platinum, but other noble metals, such as palladium, gold, silver, rhenium or rhodium, may also be used.
  • Base metal hydrogenation components may also be used, such as nickel, cobalt, molybdenum, tungsten, copper or zinc.
  • the catalyst materials may include two or more catalytic components which components may be present in admixture or combined in a unitary multifunctional solid particle.
  • the gallosilicate, ferrosilicate and "silicalite” materials may be employed, ZSM-5 zeolites can be useful in the process because of their regenerability, long life and stability under the extreme conditions of operation.
  • the zeolite crystals have a crystal size from about 0.01 to over 2 microns or more, such as 0.02-1 micron.
  • the fluidized bed catalyst particles can contain about 25 wt% to about 40 wt3 ⁇ 4 H-ZSM-5 zeolite, based on total catalyst weight, contained within a silica-alumina matrix.
  • Typical Alpha values for the catalyst can be about 100 or less. Sulfur conversion to hydrogen sulfide can increase as the alpha value increases.
  • the olefin-containing feed may be exposed to the acidic catalyst by using a moving or fluid catalyst bed reactor.
  • the catalyst may be regenerated, such via continuous oxidative regeneration.
  • the extent of coke loading on the catalyst can then be continuously controlled by varying the severity and/or the frequency of regeneration.
  • a turbulent fluidized catalyst bed the conversion reactions are conducted in a vertical reactor column by passing hot reactant vapor upwardly through the reaction zone and/or reaction vessel at a velocity greater than dense bed transition velocity and less than transport velocity for the average catalyst particle.
  • a continuous process is operated by withdrawing a portion of coked catalyst from the reaction zone and/or reaction vessel, oxidatively regenerating the withdrawn catalyst and returning regenerated catalyst to the reaction zone at a rate to control catalyst activity and reaction severity to effect feedstock conversion.
  • Preferred fluid bed reactor systems are described in Avidan et al, U.S. Pat. No. 4,547,616; Harandi & Owen U. S. Pat. No. 4,751,338; and in Gould et al. U. S. Pat. No. 4,579,999, incorporated herein by reference.
  • other types of reactors can be used, such as fixed bed reactors, riser reactors, fluid bed reactors, and/or moving bed reactors.
  • the effective conversion conditions for exposing the olefin- containing feed to an acidic catalyst can include a temperature of about 500°F (177°C) to about 900°F (482°C), or about 550°F (260°C) to about 800°F (427°C), or about 650°F (343°C) to about 750°F (399°C); a pressure of about 50 psig (0.34 MPag) to about 350 psig (2.4 MPag), or about 100 psig (0.69 MPag) to about 300 psig (4.1 MPag), or about 100 psig (0,69 MPag) to about 200 psig (1.4 MPag), or a pressure of about 350 psig (2.4 MPag) or less, or a pressure of about 300 psig (4.1 MPag) or less; and a weight hourly space velocity of about 0.05 hr "1 to about 20 hr '1 , or about 0.05 to about 10 hr
  • temperatures of about 550°F (260°C) to about 700°F (371°C) can provide a beneficial combination of selectivity, reactivity, and run length. Temperatures below 550°F can result in unacceptabiy low reaction rates due to reduced reactivity for catalyzing the oligomerization reaction. Temperatures above about 700°F (371°C) can lead to increased formation of saturates, which are not as desirable for subsequently producing diesei boiling range fuel.
  • exposing an olefin-containing feed to the conversion conditions discussed above can produce an effluent that includes oligomenzed olefins.
  • this oligomerized olefin effluent can include an increased Cs+ content compared to the olefin- containing feed.
  • At least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% of the olefins from the olefin-containing feed can be incorporated into the oligomerized olefins in the oligomerized olefin effluent.
  • the oligomerized olefin effluent can have a reduced sulfur content compared to the olefin- contaimng feed.
  • the sulfur content of the oligomerized olefin effluent can be about 100 wppm or less, or about 75 wppm or less, or about 50 wppm or less, or about 30 wppm or less, or about 20 wppm or less, or about 10 wppm or less, or about 5 wppm or less.
  • exposing an olefin-containing feed to the conversion conditions discussed above can achieve at least about 50% desulfurization of the olefin-containing feed, or at l east about 70%, or at least about 75%, or at least about 80%, or at least about 85%.
  • the oligomerized olefin effluent prior to converting the oligomerized olefin effluent to a product having diesei boiling range compounds, can be fractionated or separated, e.g., to remove a lighter portion.
  • the oligomerized olefin effluent can be fractionated or separated, e.g., to remove a lighter portion.
  • at least a portion of the C 4 (or Cj or C 2 ) or lower carbon-containing species can be separated from the oligomerized olefin effluent.
  • any type of general separating process can be utilized to separate out a portion of the oligomerized olefin effluent, such as by adjusting the temperature and/or pressure, or exposing the oligomerized olefin effluent to a simple liquid-vapor separator and/or a distillation column having one or more trays.
  • the diesei fraction present in the first reactor effluent can be fractionated to prevent further reaction in the second stage. This can improve or maximize diesei yield and in particular can improve or maximize formation of a lighter distillate fraction which can reduce or minimize viscosity and pour point of diesei fuel.
  • a fractionation or separation process can remove compounds having four carbon atoms (C4) or less, compounds having three carbon atoms (C3) or less, or compounds having two carbon atoms (C?) or less from the oligomerized olefin effluent.
  • the subsequent conversion of the oligomerized olefin effluent to a product that includes diesei boiling range compounds may be more economically favorable.
  • cutting the lighter compounds from the oligomerized olefin effluent allows for the subsequent conversion step to have a higher olefin concentration in the feed to improve or maximize diesei production while still having a reduced or minimal amount of coking of the catalyst.
  • the oligomerized olefin effluent can be exposed to effective conversion conditions to form a product effluent with at least a portion being in the diesei boiling range.
  • the oligomerized olefin effluent can be exposed to an acidic catalyst, such as the acidic catalysts discussed above.
  • the oligomerized olefin effluent can be exposed to one or more catalyst beds of the acidic catalysts discussed above or other catalyst, in one or more fixed bed reactors.
  • Effective conversion conditions for exposing the olefin-containing feed to an acidic catalyst can include a temperature of about 350°F (177°C) to about 750°F (399°C), or about 400°F (204°C) to about 700°F (371°C), or about 500°F (260°C) to about 650°F (343°C), or about 450°F (232°C) to about 650°F (316°C); a pressure of about 200 psig (1.4 MPag) to about 1000 psig (6.9 MPag), or about 250 psig (1.7 MPag) to about 900 psig (6.2 MPag), or about 300 psig (4.1 MPag) to about 850 psig (5.9 MPag), or about 300 psig (4.1 MPag) to about 800 psig (5.5 MPag), or a pressure of at least about 250 psig (1.7 MPag), or a pressure of at least about 300 psig (4.1 MPag), or a pressure of at
  • the reactor is optionally but preferably a fixed bed reactor system. Considering the feed was previously partially oligomerized and its coke precursors and poisons at least substantially removed, the heat of reaction can be managed in a fixed bed reaction section.
  • the product effluent can include diesei boiling range compounds.
  • the product effluent can include compounds with 10 or more carbon atoms (C 10 + compounds).
  • the C 10 + compounds can be at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, at least about 95 wt% or at least about 99 wt% of the total weight of the product effluent.
  • the product effluent can exhibit an initial (or T5) boiling point of at least about 250°F (121°C), at least about 300°F (149°C), or at least about 350°F (177°C), and/or exhibit a final (or T95) boiling point of about 800°F (427°C) or less, about 75Q°F (399°C) or less, or about 700°F (371°C) or less.
  • the product effluent can have a boiling range (initial or T5 to T95 or final) of from about 250°F (121°C) to about SOOT (427°C), or from about 300°F (149°C) to about 750°F (399°C), or from about 350°F (177°C) to about 700°F (371°C).
  • the product effluent can have an aromatic content of less than about 20 wt%, less than about 15 wt%, less than about 10 wt , less than about 5 wt%, or less than about 1 wt%. Due to the nature of how the C io+ compounds are formed by oligomerization, a substantial percentage of the C 10 + compounds can correspond to olefins.
  • At least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% of the C 10 ⁇ compounds in the product effluent can be olefins.
  • the oligomerized C 10 + compounds in the product effluent can correspond to at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% of the weight of olefins in the olefin-containing feed.
  • At least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% of the olefins present in the olefin-containing feed can be incorporated into the oligomerized C 10 + compounds in the product effluent.
  • the oligomerized C 10 + compounds in the product effluent can correspond to at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, or at least about 80 wt% of the weight of oligomerized olefins in the oligomerized olefin effluent.
  • At least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, or at least about 80 wt% of the oligomerized olefins from the oligomerized olefin effluent can be incorporated into the oligomerized C 10 + compounds in the product effluent.
  • the product effluent can be treated in one or more hydroprocessing stages to improve properties of the product effluent.
  • the product effluent can be subjected to hydroprocessing for one or more of sulfur reduction, olefin saturation, and/or dewaxing, such as iso-dewaxing (i.e., by catalytic dewaxing in the presence of a catalyst that dewaxes primarily by isomerization).
  • the reaction conditions for sulfur reduction hydroprocessing can include an LHSV of 0,3 to 5.0 hr "1 , a total pressure from about 200 psig (1.4 MPag) to about 3000 psig (20.7 MPa), a treat gas containing at least about 80% hydrogen (remainder inert gas), and a temperature of from about 500°F (260°C) to about 800°F (427°C).
  • the reaction conditions include an LHSV of from about 0.5 to about 1 .5 hr "1 , a total pressure from about 700 psig (4.8 MPa) to about 2000 psig (13.8 MPa), and a temperature of from about 600°F (316°C) to about 700°F (399°C).
  • the treat gas rate can be from about 500 SCF/B (84 NnrVm 3 ) to about 10000 SCF/B (1685 m 3 /m 3 ) of hydrogen, depending on various factors including the nature of the feed being hydrotreated. Note that the above treat gas rates refer to the rate of hydrogen flow. If hydrogen is delivered as part of a gas stream having less than 100% hydrogen, the treat gas rate for the overall gas stream can be proportionally higher.
  • the hydroprocessing can reduce the sulfur content of the product effluent to a suitable level.
  • the sulfur content can be reduced sufficiently so that the product effluent can have about 500 wppm sulfur or less, or about 250 wppm or less, or about 100 wppm or less, or about 50 wppm or less, or about 20 wppm or less, or about 10 wppm or less, or about 5 wppm or less.
  • the sulfur content of the product effluent can be at least about 1 wppm sulfur, or at least about 5 wppm, or at least about 10 wppm.
  • the catalyst in a hydroprocessing treatment for reducing sulfur content can be a conventional hydrotreating catalyst, such as a catalyst composed of a Group VTB metal (Group 6 of IUPAC periodic table) and/or a Group VIII metal (Groups 8 - 10 of IUPAC periodic table) on a support.
  • Suitable metals include cobalt, nickel, molybdenum, tungsten, or combinations thereof.
  • Preferred combinations of metals include nickel and molybdenum or nickel, cobalt, and molybdenum.
  • Suitable supports include silica, silica-alumina, alumina, and titania.
  • the hydrotreated effluent can optionally but preferably be separated, such as by separating the gas phase effluent from a liquid phase effluent, in order to remove gas phase contaminants generated during hydroprocessing.
  • the entire hydrotreated effluent can be cascaded into another hydroprocessing stage, such as a stage for iso-dewaxing.
  • Hydrofinishing catalysts can include catalysts containing Group VI metals, Group VIII metals, and mixtures thereof.
  • preferred metals include at least one metal sulfide having a strong hydrogenation function.
  • the hydrofmishing catalyst can include a Group VIII noble metal, such as Pt, Pd, or a combination thereof.
  • the mixture of metals may also be present as bulk metal catalysts wherein the amount of metal is about 30 wt% or greater based on catalyst.
  • Suitable metal oxide supports include low acidic oxides such as silica, alumina, silica-aluminas or titania, preferably alumina.
  • the preferred hydrofmishing catalysts will comprise at least one metal having relatively strong hydrogenation function on a porous support.
  • Typical support materials include amorphous or crystalline oxide materials such as alumina, silica, and silica-alumina.
  • the support materials may also be modified, such as by halogenation, or in particular fluorination.
  • the metal content of the catalyst is often as high as about 20 wt% for non-noble metals.
  • a preferred hydrofmishing catalyst can include a crystalline material belonging to the M41 S class or family of catalysts.
  • the M41 S family of catalysts are mesoporous materials having high silica content. Examples include MCM-41, MCM-48 and MCM-50. A preferred member of this class is MCM-41.
  • Hydrofmishing conditions can include temperatures from about 125°C (257°F) to about 425°C (797°F), or about 180°C (356°F) to about 280°C (536°F); a total pressure from about 200 psig (1.4 MPa) to about 800 psig (5.5 MPa), or about 400 psig (2.8 MPa) to about 700 psig (4.8 MPa); and a liquid hourly space velocity from about 0. hr "1 to about 5 hr '1 LHSV, preferably about 0.5 hr '1 to about 1.5 hr "1 .
  • the treat gas rate can be selected to be similar to a catalytic dewaxing stage discussed below, similar to a hydroprocessing for sulfur reduction discussed above, or any- other convenient selection.
  • the product effluent (or an effluent of one or more of the hydroprocesses discussed above) can undergo a dewaxing hvdrotreatment, e.g., to improve one or more cold flow properties of a diesel fuel such as pour point or cloud point.
  • the product effluent can be exposed to a dewaxing catalyst under effective dewaxing conditions to produce a dewaxed effluent.
  • Suitable dewaxing catalysts can include molecular sieves such as crystalline aluminosilicates (zeolites). In some aspects, any conventional dewaxing catalyst can be used. In other aspects, the molecular sieve can comprise, consist essentially of, or be ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, zeolite Beta, or a combination thereof, for example ZSM-23 and/or ZSM-48, or ZSM-48 and/or zeolite Beta, Optionally, molecular sieves that are selective for dewaxing by isomerization as opposed to cracking can be used, such as ZSM-48, zeolite Beta, ZSM-23, or a combination thereof.
  • molecular sieves that are selective for dewaxing by isomerization as opposed to cracking can be used, such as ZSM-48, zeolite Beta, ZSM-23, or a combination thereof.
  • the molecular sieve can comprise, consist essentially of, or be a 10-member ring 1 -D molecular sieve.
  • examples include ElJ-1 , ZSM-35 (or ferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, ZSM-48, ZSM-23, and ZSM-22,
  • the molecular sieve includes EU-2, EU-1 1, ZBM-30, ZSM-48, or ZSM-23.
  • a zeolite having the ZSM-23 stmcture with a silica to alumina ratio of from about 20: 1 to about 40: 1 can sometimes be referred to as SSZ-32.
  • the dewaxing catalyst can include a binder for the molecular sieve, such as alumina, titania, silica, silica-alumina, zirconia, or a combination thereof, for example alumina and/or titania or silica and/or zirconia and/or titania.
  • a binder for the molecular sieve such as alumina, titania, silica, silica-alumina, zirconia, or a combination thereof, for example alumina and/or titania or silica and/or zirconia and/or titania.
  • the dewaxing catalysts can be catalysts with a low ratio of silica to alumina.
  • the ratio of silica to alumina in the zeolite can be less than about 200: 1 , such as less than about 110: 1, or less than about 100: 1 , or less than about 90: 1, or less than about 75: 1.
  • the ratio of silica to alumina can be from 50: 1 to 200: 1, such as 60: 1 to 160: 1, or 70: 1 to 100: 1.
  • the catalysts can further include a metal hydrogenation component.
  • the metal hydrogenation component is typically a Group VI and/or a Group VIII metal.
  • the metal hydrogenation component can be a Group VIII noble metal.
  • the metal hydrogenation component can be Pt, Pd, or a mixture thereof.
  • the metal hydrogenation component can be a combination of a non-noble Group VIII metal with a Group VI metal. Suitable combinations can include Ni, Co, or Fe with Mo or W, preferably Ni with Mo or W.
  • the metal hydrogenation component may be added to the catalyst in any convenient manner.
  • One technique for adding the metal hydrogenation component is by incipient wetness. For example, after combining a zeolite and a binder, the combined zeolite and binder can be extruded into catalyst particles. These catalyst particles can then be exposed to a solution containing a suitable metal precursor.
  • metal can be added to the catalyst by ion exchange, where a metal precursor is added to a mixture of zeolite (or zeolite and binder) prior to extrusion.
  • the amount of metal in the catalyst can be at least 0.1 wt.% based on catalyst, or at least 0.15 wt%, or at least 0.2 wt%, or at least 0.25 wt%, or at least 0.3 wt%, or at least 0.5 wt% based on catalyst.
  • the amount of metal in the catalyst can be 20 wt% or less based on catalyst, or 10 wt% or less, or 5 wt% or less, or 2.5 wt% or less, or 1 wt% or less.
  • the amount of metal can be from 0.1 to 5 wt%, preferably from 0.
  • the metal is a combination of a non-noble Group VIII metal with a Group VI metal
  • the combined amount of metal can be from 0,5 wt% to 20 wt%, or 1 wt% to 15 wt%, or 2,5 wt% to 10 wt%.
  • Process conditions in a catalytic dewaxing zone can include a temperature of from 200 to 450°C, preferably 270 to 400°C, an LHSV from about 0.2 h '1 to about 10 h '1 , such as from about 0.5 h "1 to about 5 h "1 , and a treat gas rate of from 35.6 m /m 3 (200 SCF/B) to 1781 m 3 /m 3 (10,000 SCF/B), preferably 178 m 3 /m 3 (1000 SCF/B) to 890,6 m 3 /m 3 (5000 SCF/B).
  • the dewaxing can be performed at a pressure of about 300 psig (2.1 MPag) to about 700 psig (4.8 MPag), or about 300 psig (2.1 MPag) to about 600 psig (4.2 MPag), or about 300 psig (2.1 MPag) to about 500 psig (3,5 MPag), or about 400 psig (2.8 MPag) to about 700 psig (4.8 MPag), or about 400 psig (2.8 MPag) to about 600 psig (4.2 MPag), or about 400 psig (2.8 MPag) to about 500 psig (3.5 MPag), or about 500 psig (3.5 MPag) to about 700 psig (4.8 MPag).
  • Catalytic dewaxing can be performed by exposing a feedstock to a dewaxing catalyst under effective (catalytic) dewaxing conditions.
  • Effective dewaxing conditions can include a temperature of at least about 500°F (260°C), or at least about 550°F (288°C), or at least about 600°F (316°C), or at least about 650°F (343°C).
  • the temperature can be about 750°F (399°C) or less, or about 700°F (371°C) or less, or about 650°F (343°C) or less.
  • the pressure can be at least about 200 psig (1.4 MPa), or at least about 500 psig (3.4 MPa), or at least about 750 psig (5.2 MPa), or at least about 1000 psig (6,9 MPa).
  • the pressure can be about 1500 psig (10.3 MPa) or less, or about 1200 psig (8.2 MPa) or less, or about 1000 psig (6.9 MPa) or less, or about 800 psig (5.5 MPa) or less.
  • the Liquid Hourly Space Velocity (LHSV) can be at least about 0.5 hr "1 , or at least about 1.0 hr "1 , or at least about 1.5 hr '1 .
  • the LHSV can be about 5.0 hr "1 or less, or about 3.0 hr "1 or less, or about 2,0 hr '1 or less.
  • the treat gas rate can be at least about 500 SCF/bbl (84 mVnr), at least about 750 SCF/bbl (126 nrVm 3 ), or at least about 1000 SCF/bbl (169 m 3 /m 3 ).
  • the treat gas rate can be about 4000 SCF/bbl (674 mVm 3 ) or less, or about 2000 SCF/bbl (337 mVm 3 ) or less, or about 1500 SCF/bbl (253 mVnr) or less, or about 1250 SCF/bbl (213 m 3 /m 3 ) or less.
  • the cloud point of a dewaxed effluent can be reduced relative to the dewaxing feedstock (e.g., the product effluent (or an effluent of one or more of the hydroprocesses discussed above)) by at least about 10°F (5°C), such as at least about 20°F (1 1°C), or at least about 30°F (17 C 'C).
  • the amount of cloud point reduction can depend on a variety of factors, including the sulfur content of the feedstock, the nitrogen content of the feedstock, and the selected effective dewaxing conditions.
  • FIG. 1 depicts one example of a reaction system 100 for upgrading an olefin-containing feed to diesel boiling range compounds.
  • an olefin-containing feed 102 can be exposed to conversion conditions in a first reaction vessel 104.
  • the olefin- containing feed 102 may be heated prior to entering the first reaction vessel 04.
  • the ol elm-containing feed 102 can include one or more of a refinery fuel gas, FCC naphtha, or oiefinie naphtha.
  • the olefin-containing feed 102 can be exposed to a conversion catalyst, such as one or more of the acidic catalysts discussed above.
  • the first reaction vessel 104 can be a fluidized bed reactor.
  • a portion 106 of the conversion catalyst in the first reaction vessel 104 can be sent to a regenerator 108 for regeneration.
  • the regenerated catalyst 110 can be returned to the first reaction vessel 104.
  • the effective conversion conditions in the first reaction vessel 104 may result in olefin oligomerization and/or reduction in the sulfur content of the olefin-containing feed.
  • the oligomerized olefin effluent 112 can be exposed to a separator 1 14 to separate out the lighter compounds, such as compounds 118 having 2 carbon atoms or less, prior to subjecting the remainder 116 of the oligomerized olefin effluent to reaction conditions in a second reaction vessel 120.
  • the second reaction vessel 120 may be a fixed bed reactor having one or more beds of a conversion catalyst, such as one or more of the acidic catalysts discussed above.
  • the conversion conditions in the second reaction vessel 120 can include a pressure that is greater than the pressure of that in the first reaction vessel 104.
  • the product effluent 122 can include diesel boiling range compounds.
  • at least a portion of the product effluent 122 can be exposed to one or more hydroprocessor(s) 124.
  • the hydroprocessor(s) 124 can be utilized to reduce the sulfur content of the product effluent, for oiefinie saturation, and/or for dewaxing, as discussed above. Additional Embodiments
  • Embodiment 1 A method for converting an olefin-containing feed to diesel boiling range compounds, comprising: exposing an olefin-containing feed having an olefin content of at least about 0 wt% to a conversion catalyst under first effective conversion conditions to form an oligomerized olefin effluent comprising C 5 + oiefinie compounds, wherein the first effective conversion conditions comprise a pressure of less than about 300 psig (2, 1 MPa) and a temperature of about 550°F (288 C, C) to about SOOT (427°C); and exposing at least a portion of the C?+ oiefinie compounds to effective fixed bed conversion conditions to form a product effluent comprising diesel boiling range compounds, wherein the effective fixed bed conversion conditions comprise a pressure of at least about 300 psig (2.
  • the first effective conversion conditions comprise a pressure that is at least about 50 psi (0.3 MPa) lower than the effective fixed bed conversion conditions.
  • Embodiment 2 The method of Embodiment 1, further comprising separating the oligomerized olefin effluent to form at least a first fraction comprising the at least a portion of the C 5 + olefmic compounds and a second fraction comprising compounds having three carbon atoms or less.
  • Embodiment 3 A method for converting an olefin-containing feed to diesel boiling range compounds, comprising: exposing an olefin-containing feed having an olefin content of at least about 10 wt% to first effective conversion conditions comprising fiuidized bed conditions to form an oligomerized olefin effluent comprising C 5+ oiefinic compounds, wherein the effective conversion conditions in the first reaction vessel include a pressure of from about 50 psig to about 250 psig and a temperature of from about 5 SOT (288 C 'C) to about 800°F (427 C 'C); separating at least a portion of the oligomerized olefin effluent to form a first fraction comprising at least a portion of the C 5 + oiefinic compounds and a second fraction comprising compounds having three carbon atoms or less; and exposing the at least a portion of the C 5 + oiefinic compounds to effective conversion conditions in a second
  • Embodiment 4 The method of any of the above embodiments, wherein the first effective conversion conditions comprise fiuidized bed conditions.
  • Embodiment 5 The method of any of the above embodiments, wherein the effective fixed bed conversion conditions comprise a pressure of about 300 psig (2.1 MPa) to about 800 psig (5.5 MPa), a temperature of about 450°F (232°C) to about 600°F (316°C), or a combination thereof.
  • Embodiment 6 The method of any of the above embodiments, wherein the olefin- containing feed comprises refinery fuel gas.
  • Embodiment 7 The method of any of the above embodiments, wherein the olefin- containing feed comprises FCC naphtha, oiefinic naphtha, or mixtures thereof,
  • Embodiment 8 The method of Embodiment 7, wherein the second fraction comprises compounds having four carbon atoms or less.
  • Embodiment 9 The method of any of the above embodiments, wherein at least about 60 wt% of the olefins present in the olefi n-containing feed are converted to compounds present in the product effluent comprising diesel boiling range compounds, or at least about 70 wt%, or at least about 80 wt%, or at least about 90 wt%.
  • Embodiment 10 The method of any of the above embodiments, wherein the aromatic content of the product effluent comprising diesel boiling range compounds is about 20 wt% or less, or 15 wt% or less, or 10 wt% or less.
  • Embodiment 1 The method of any of the above embodiments, further comprising hydrotreating at least a portion of the product effluent comprising diesel boiling range compounds,
  • the exposing the olefin-containing feed to first effective conversion conditions and/or effective fixed bed conversion conditions comprises exposing the olefin-containing feed to an acidic zeolite catalyst.
  • Embodiment 13 The method of any of the above embodiments, wherein the olefin- containing feed comprises about 50 wt% or less of Cs+ compounds, or about 40 wt% or less, or about 30 wt% or less, or about 20 wt% or less, or about 10 wt% or less, or about 5 wt% or less, wherein the olefin-containing feed comprises about 50 wt% or less of d+ olefinic compounds, or about 40 wt% or less, or about 30 wt% or less, or about 20 wt% or less, or about 10 wt% or less, or about 5 wt% or less, or a combination thereof,
  • Embodiment 14 The method of any of the above embodiments, wherein the olefin- containing feed comprises d -C 4 hydrocarbon compounds, at least a portion of the C 1 -C hydrocarbon compounds comprising C 2 -C 4 olefins, a weight percentage of the C 2 -C 4 olefins relative to the weight of the olefin-containing feed being at least about 10 wt% lower than a weight percentage of the d-C 4 hydrocarbon compounds, or at least about 20 wt% lower, or at least about 30 wt% lower, or at least about 40 wt% lower, or at least about 50 wt% lower, or at least about 60 wt% lower,
  • Embodiment 15 A system for converting an olefin-containing feed to diesel boiling range compounds, comprising: a fluidized bed reactor comprising a fluidized bed of an acidic molecular sieve, the fluidized bed being fluidized with an olefin-containing feed comprising d-C 4 hydrocarbon compounds, the olefin-containing feed having an olefin content of at least about 10 wt%, the bed being fluidized at a pressure of about 50 psig (0.3 MPa) to about 250 psig (1.7 MPa) and a temperature of about 550°F (288°C) to about 800°F (427°C); a separator in fluid communication with the fluidized bed reactor for performing a separation on an effluent from the fluidized bed reactor; and a fixed bed reactor in fluid communication with the separator to receive a separated fraction comprising C 5 + olefinic compounds, the fixed bed reactor comprising a fixed bed of a second acidic molecular sieve, the fixed bed reactor having
  • Embodiment 16 The system of Embodiment 15, wherein the fixed bed of a second acidic molecular sieve comprises the same molecular sieve as the fluidized bed of an acidic molecular sieve.
  • Embodiment 17 The system of Embodiment 1 5 or 16, wherein at least one of the fluidized bed of an acidic molecular sieve and the fixed bed of a second acidic molecular sieve comprises a zeolite.
  • Embodiment 18 The system of any of Embodiments 15 to 17, wherein the molecular sieve or the zeolite comprises a 10-member ring molecular sieve or zeolite,
  • Embodiment 19 A diesel boiling range effluent comprising at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% C 10 ⁇ oligomerized compounds, the C io+ oligomerized compounds being formed by oligomerization of C2-5 olefins.
  • Embodiment 20 The diesel boiling range effluent of Embodiment 19, wherein the diesel boiling range effluent comprises at least about 10 wt%, at least about 20 wt%, at least about 30 wt3 ⁇ 4, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% C 10 + olefins.
  • Embodiment 21 The diesel boiling range effluent of Embodiment 20, wherein the at least about 10 wt%, at least about 20 wt%, at least about 30 wt , at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% C io+ olefins comprise oligomerized olefins formed by oligomerization of C2-5 olefins.
  • Embodiment 22 The diesel boiling range effluent of any of Embodiments 19 - 21, wherein the at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 w ⁇ % C 10 + oligomerized compounds incorporate at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% of C2-5 olefins present in a feed for the oligomerization of the C2-5 olefins,

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  • 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 des systèmes et des procédés de production de composés d'intervalle de distillation du diesel à partir d'une charge d'alimentation contenant des oléfines. La charge contenant des oléfines peut inclure un gaz combustible de raffinerie et/ou une charge de naphta. La charge contenant des oléfines peut être exposée à un premier ensemble de conditions de conversion qui peuvent comprendre une faible pression pour produire un effluent d'oléfines oligomérisées. L'effluent d'oléfines oligomérisées peut être exposé à un second ensemble de conditions de conversion qui comprenent une pression supérieure au premier ensemble de conditions de conversion pour produire un effluent de produits qui inclut des composés d'intervalle de distillation du diesel.
PCT/US2016/054369 2015-10-28 2016-09-29 Amélioration de charges d'alimentation contenant des oléfines en composés d'intervalle de distillation du diesel WO2017074641A1 (fr)

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US11118115B2 (en) 2019-06-18 2021-09-14 Exxonmobil Research And Engineering Company Methods for methanol-to-gasoline conversion with methanol recycling
US11130915B2 (en) 2019-06-18 2021-09-28 Exxonmobil Research And Engineering Company Methods for methanol-to-gasoline conversion with forwarding methanol processing
US11603340B2 (en) 2019-09-17 2023-03-14 ExxonMobil Technology and Engineering Company Methods for methanol-to-gasoline conversion with post-processing of heavy gasoline hydrocarbons

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