WO2016081033A1 - Procédé de reformage à deux étages conçu pour un taux d'alimentation accru pour fabriquer un reformat - Google Patents

Procédé de reformage à deux étages conçu pour un taux d'alimentation accru pour fabriquer un reformat Download PDF

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Publication number
WO2016081033A1
WO2016081033A1 PCT/US2015/042582 US2015042582W WO2016081033A1 WO 2016081033 A1 WO2016081033 A1 WO 2016081033A1 US 2015042582 W US2015042582 W US 2015042582W WO 2016081033 A1 WO2016081033 A1 WO 2016081033A1
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stage
reforming
reformate
catalyst
naphtha
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PCT/US2015/042582
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Stephen Joseph Miller
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Chevron U.S.A. Inc.
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Publication of WO2016081033A1 publication Critical patent/WO2016081033A1/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
    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
    • 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
    • C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • 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
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/543—Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • Described herein is a two-stage reforming process using a unique configuration which allows the reforming unit to operate at a higher feed rate as compared to conventional reforming configurations.
  • two-stage reforming process refers to a reforming processing wherein a naphtha feedstock is subjected to reforming conditions in one or more reforming reactors containing conventional metallic reforming catalyst (first stage) to form an intermediate reformate having a target Research Octane Number (RON) which is greater than the naphtha feedstock RON.
  • the intermediate reformate is then subjected to reforming conditions in one or more reforming reactors containing one or more medium pore zeolite-based catalysts (second stage) to form a final reformate having a higher RON than the intermediate reformate RON.
  • Catalytic reforming is a petroleum refining process for upgrading light hydrocarbon feedstocks, frequently referred to as naphtha feedstocks. Products from catalytic reforming are referred to as reformates, and can include high Research
  • Octane Number (RON) gasoline useful as an automobile fuel blend stock aromatics (for example benzene, toluene, xylenes and ethylbenzene), and hydrogen. Reformers often function as the sole hydrogen source for refinery operations.
  • paraffins to aromatics [0006] Less desirable reactions which commonly occur include hydrocracking of paraffins and naphthenes to produce coke and gaseous hydrocarbons such as ethane and propane. Due to these less desirable reactions, an important objective of catalytic reforming is to rearrange the structure of the hydrocarbon molecules to form higher octane products without any significant change in the carbon number distribution of the naphtha feedstock.
  • the reforming reactions are typically catalyzed by metallic reforming catalysts composed of porous supports, such as alumina, that have dehydrogenation promoting metal such as platinum (Pt/Al 2 O 3 -Cl) or bimetallic species such as platinum-rhenium (Pt-Re/Al 2 0 3 -Cl).
  • dehydrogenation promoting metal such as platinum (Pt/Al 2 O 3 -Cl) or bimetallic species such as platinum-rhenium (Pt-Re/Al 2 0 3 -Cl).
  • Figure 1 is a flow scheme for a typical semi-regenerative three-reactor reforming unit. This three-reactor reforming unit would be considered the first stage in the unique two-stage process described herein below.
  • a naphtha feedstock 1 and hydrogen 2 are preheated in a first heater 3, and the heated naphtha feedstock 4 is introduced into the first reforming reactor 5 and subjected to reforming conditions to upgrade the RON of the feedstock 4.
  • Each reforming reactor is generally provided with a fixed bed or beds of reforming catalyst.
  • the reformed first intermediate reformate 6 from the first reforming reactor 5 is heated in a second heater 7, and the heated reformed first intermediate reformate 8 is passed to a second reforming reactor 9 for further reforming to a higher RON.
  • the reformed second intermediate reformate 10 from the second reforming reactor 9 is then heated in a third heater 1 1, and the heated second intermediate reformate 12 is passed to a penultimate third reforming reactor 13.
  • the reformate products 14 from the third reforming reactor 13 undergo separation in a distillation column 15 to separate the higher-RON reformate product 16 (and optionally aromatics products) from the light ends and hydrogen gas 17, which is recycled back to the first stage reforming reactor 5 or piped off for use in other refinery operations.
  • the reforming configuration illustrated in Figure 1 has a disadvantage.
  • the entire effluent from each stage passed to the next stage.
  • the addition of reforming units allows refiners to potentially lengthen the time between catalyst regeneration cycles, or more tailor the reformate product slate, the addition of reforming units does not allow the refiner to increase the feed rate, and therefore the reformate production rate, of the reforming unit for the case where feed rate is limited by factors such as feed pump size or furnace size.
  • Described herein is a two-stage reforming process using a unique configuration which allows the reforming unit to operate at higher naphtha feed rates as compared to conventional reforming configurations.
  • a naphtha feedstock undergoes a distillation step prior to the first reforming stage (e.g., the three-reactor reformer of Figure 1).
  • the distillation step separates the naphtha feedstock into (1) a top light C 6 and C 7 fraction, or in the alternative a C 7 fraction, and (2) a Cs+ fraction. These top light fractions typically accounts for between 5 and 25 percent of the overall naphtha feedstock.
  • the C 8 + fraction undergoes reforming in the first reforming stage at a first stage reforming pressure, which contains at least one conventional metallic reforming catalyst, under conditions sufficient to convert the C 8 + fraction into a first
  • the first reforming stage may contain more than one reforming reactor (collectively referred to as the "first stage" of the reforming unit), around which the C 6 /C 7 fraction (or in the alternative the C 7 fraction) is bypassed.
  • the light top C 6 /C 7 or C 7 fraction bypasses the first stage reformer reactor(s) and is combined with the intermediate reformate stream from the first stage reactor(s).
  • the combined stream undergoes reforming in a second stage at a lower second stage reforming pressure, which contains a medium pore zeolite -based reforming catalyst described herein, under conditions sufficient to produce a final reformate having a higher RON than the intermediate feedstock.
  • the final reformate undergoes distillation to separate hydrogen and other products, such as benzene and the like, from the final reformate.
  • Operation of the reforming unit as described above tailors the feedstock to each stage that portion of the feedstock the catalyst in each stage are best suited for reforming. It has been found the medium pore zeolite -based catalysts in the second stage are best suited for reforming the C 6 /C 7 portion of the naphtha feedstock. By removing the C 6 /C 7 portion of the naphtha feedstock from the first stage, the first stage can operate at a higher feed rate, thereby allowing the refiner to operate the first stage at high feed rates because there is less material to reform. The increased feed rate results in increased reformate product production.
  • Figure 1 is a block flow diagram of a conventional semi-regenerative three- reactor reforming process.
  • Figure 2 is a block flow diagram of the unique two-stage reforming process described herein. DETAILED DESCRIPTION
  • Two-stage reforming process refers to a reforming processing wherein a naphtha feedstock is subjected to reforming conditions in one or more reforming reactors containing conventional metallic reforming catalyst (first stage) to form an intermediate reformate. The intermediate reformate is then subjected to reforming conditions in one or more reforming reactors containing one or more zeolite -based catalysts (second stage) to form a final reformate.
  • Periodic Table refers to the version of IUPAC Periodic Table of the Elements dated June 22, 2007, and the numbering scheme for the Periodic Table
  • Hydroprocessing refers to a process in which a carbonaceous feedstock is brought into contact with hydrogen and a catalyst, at a higher temperature and pressure, for the purpose of removing undesirable impurities and/or converting the feedstock to a desired product.
  • Nephtha means a mixture of hydrocarbons containing at least some compounds with between 6 and 12 carbon atoms.
  • Paraffin means a saturated straight or branched chain hydrocarbon (i.e., an alkane).
  • distillation column and “fractionator” are synonymous and refer to a distillation column or columns for separating a feedstock into one or more fractions according to boiling point.
  • feed rate to a catalytic reaction zone is reported as the volume of feed per volume of catalyst per hour.
  • the feed rate as disclosed herein is reported in reciprocal hours (i.e. hr "1 ) which is also referred to as liquid hourly space velocity (LHSV).
  • C x fraction and "C x feedstock” where x is an integer between 6 and 12 for naphtha feedstocks, means the fraction or feedstock contains at least 80% C x hydrocarbons, including linear, branched and cyclic variations, as determined by standard gas chromatography. By way of example, a C 8 fraction would contain at least 80% Cs hydrocarbons.
  • “Hydrocarbonaceous” means a compound or substance that contains hydrogen and carbon atoms, but which can include heteroatoms such as oxygen, sulfur or nitrogen.
  • Si0 2 /Al 2 0 3 Ratio (a) Si0 2 /Al 2 0 3 Ratio (SAR): determined by ICP elemental analysis.
  • a SAR of infinity represents the case where there is no aluminum in the zeolite, i.e., the mole ratio of silica to alumina is infinity. In that case the molecular sieve is comprised of essentially all of silica.
  • FIG. 2 is a flow scheme for an improved two-stage reforming process for making reformate from a naphtha feedstock. While only two reactors are illustrated for each of the first and second stages, it is recognized that each stage could consist of multiple reactors, each containing their respective catalysts (metallic reforming catalyst for the first stage, medium-pore zeolite reforming catalyst in the second stage).
  • the refining equipment used in the refining process described below will consist of conventional process equipment typically used in commercial reforming units for recovery of reformate and any other products, and hydrogen, including feed heater and heat exchangers, gas separators, pumps, caustic scrubbers, flash drums, suction traps, acid washes, fractionators and separators, and the like.
  • Each reforming stage will typically be accomplished using a bed reactor or reactors which can include one or more fixed or moving catalyst beds of the same, or different, of the reforming catalysts described below.
  • the naphtha boiling range feedstock used in the unique process described herein can be a mostly C 5 to C 12 full range naphtha fraction boiling within the range of 50° to 550°F (10 to 288°C).
  • the C 5 /C 6 portion of the naphtha feedstock is stripped upstream from the reforming unit, for separate upgrading to higher octane products using processes such as UOP's PENEX process.
  • Table 1 lists the typical physical properties for a naphtha feedstock suitable for manufacturing reformate using the unique two-stage reforming process described herein.
  • the naphtha feedstock is a C 6 to C 12 naphtha fraction, allowing for the co-production of benzene.
  • the naphtha feedstock is a C 7 to C 12 naphtha fraction.
  • the naphtha feed can include, for example, straight run naphthas, paraffmic raffinates from aromatic extraction or adsorption, C 6 -Ci 0 paraffin-rich feeds, bio- derived naphtha, naphtha from hydrocarbon synthesis processes, including Fischer Tropsch and methanol synthesis processes, as well as naphtha products from other refinery processes, such as hydrocracking or conventional reforming.
  • the reformer feed may comprise at least a portion of the product generated in a preceding reactor.
  • a naphtha feedstock 18 is subjected to separation in a distillation column 19 prior to being subjected to reforming conditions.
  • the distillation column 19 separates the naphtha feedstock 18 into a C 6 /C 7 fraction 20a, and a C 8 + fraction 21.
  • the C 5 /C 6 components of the naphtha feedstock 18 are removed (not illustrated) upstream from the reforming unit, and the distillation column 19 separates the naphtha feedstock 18 a C 7 fraction 20b and a C 8 + fraction 21.
  • Each of these top light fractions (20a/20b) typically account for between 5 and 25 percent of the overall naphtha feedstock 18.
  • the C 8 + fraction 21 is combined with fresh make-up hydrogen 22 and heated in a first heater 23.
  • the heated hydrogen rich Cg+ fraction 24 undergoes reforming in a first stage reformer ("first stage") 25 containing conventional metallic reforming catalyst, at a first stage pressure and under reforming conditions sufficient to convert the hydrogen rich C 8 + fraction 24 into a first intermediate reformate 26 having a higher RON than the naphtha feedstock 18.
  • first stage reformer
  • Figure 2 illustrates the first stage as consisting of only one reactor (reformer 25), the first stage operation could consist of multiple reactors connected in series, collectively representing the first stage, each reactor containing conventional metallic reforming catalyst and possibly operated under varying conditions (e.g. temperature and pressure), depending on the target RON for the intermediate reformate 26.
  • the selection of the first stage catalyst and reforming conditions will depend on the naphtha feedstock 18 characteristics (paraffmic, iso-paraffmic, naphthenic and aromatic content) as well as target reformate specifications.
  • a refiner with ordinary skill in the art will readily be able to select a suitable catalyst and first stage reforming conditions to meet the refinery's target reformate product slate.
  • Table 2 illustrates the typical reforming conditions in the first stage reformer 25. It should be understood the liquid hour space velocity (LHSV) selected for operation of the first stage operation will be less than if the C 6 /C 7 fraction (20a) were not removed from the naphtha feedstock, while at the same time producing an intermediate reformate 26 having the same target RON.
  • LHSV liquid hour space velocity
  • the C 6 /C 7 fraction (20a) (or C 7 fraction (20b) in an alternate embodiment) by-passes the first stage reformer 25 and is combined with the intermediate reformate stream 26 from the first stage reformer 25. If the first stage consists of multiple reactors, the intermediate reformate 26 would be the effluent from the last reactor forming the first stage.
  • the combined stream is heated in a second stage furnace 27 (or multiple furnaces if multiple reactors in the second stage), and the heated combined
  • intermediate reformate stream 28 undergoes reforming, at a lower second stage pressure, in the second stage reformer 29 ("second stage") containing at least one medium pore zeolite -based reforming catalyst described herein below, under reforming conditions sufficient to convert the combined intermediate reformate stream 28 into a final reformate stream 30 having a higher RON than the intermediate reformate stream 28.
  • Figure 2 illustrates the second stage as consisting of only one reactor (reformer 29), the second stage operation could consist of multiple reactors connected in series collectively representing the second stage, each reactor containing the medium-pore zeolite reforming catalyst described below, with each reactor containing the medium pore reforming catalyst and possibly operated under varying conditions (e.g. temperature and pressure), depending on the target reformate product specifications.
  • the final reformate stream 30 undergoes separation in a product distillation unit 31 to separate the product reformate 32 from hydrogen 33, which can be recycled back to the front end of the second stage reformer 29 or piped off for use in other refinery operations. Where a C 6 component is reformed in the second stage, the reforming process will yield benzene 34 as a product.
  • the process can be operated at a higher feed rate, resulting in a higher yield of reformate product 32.
  • the reforming catalysts may be employed in the form of pills, pellets, granules, broken fragments, or various special shapes, disposed as a fixed bed within a reaction zone, and the charging stock may be passed through either upward, downward or radial flow.
  • the reforming catalysts can be used in moving beds or in fluidized-solid processes, in which the charging stock is passed upward through a turbulent bed of finely divided catalyst.
  • a fixed bed system or a dense-phase, moving bed system are often used due to less catalyst attrition and other operational advantages.
  • the second stage reforming catalyst contains at least one medium pore molecular sieve.
  • the molecular sieve is a porous inorganic oxide characterized by a crystalline structure which provides pores of a specified geometry, depending on the particular structure of each molecular sieve.
  • the phrase "medium pore,” as used herein means having a crystallographic free diameter in the range of from about 4.5 to about 7.1 A when the porous inorganic oxide is in the calcined form.
  • the medium pore molecular sieves used in the unique process described herein are generally one-, two or three-dimensional (1-D, 2-D or 3-D structures, with the pores characterized as being 10-, 1 1- or 12-ring structures.
  • the classification of intrazeolite channels as 1-D, 2-D and 3-D is set forth by R. M. Barrer in Zeolites, Science and Technology, edited by F. R. Rodrigues, L. D. Rollman and C. Naccache, NATO ASI Series, 1984 which classification is incorporated in its entirety by reference (see particularly page 75).
  • the medium pore molecular sieve is a high silica ZSM-5 zeolite such as silicalite.
  • Silicalite has a crystal structure which is nominally based on that of ZSM-5.
  • Various references disclosing ZSM-5 are provided in U.S. Patent No. 4,401,555 to Miller. These references include U.S. Patent No. 4,061,724 to Grose et al; U.S. Pat. Reissue No. 29,948 to Dwyer et al.; Flanigan et al., Nature, 271 , 512-516 (Feb. 9, 1978) which discusses the physical and adsorption characteristics of high silica ZSM- 5; Bibby et al., Nature, 280, 664-665 (Aug.
  • a ZSM-5 useful in the present process has a specific gravity at 77°F of 1.99 ( ⁇ 0.05) g/cc, as measured by water displacement.
  • this ZSM-5 has a specific gravity of 1.70% ( ⁇ 0.05) g/cc.
  • values obtained by measurement of the as synthesized form and the calcined form (11 12° F in air for one hour) are 1.48% ( ⁇ 0.01) and 1.39% ( ⁇ 0.01), respectively.
  • the ZSM-5 for use in the second stage of the process described herein has a high silica-to-alumina (SAR) molar ratio.
  • the ZSM-5 useful in the unique process described herein is a high silica ZSM-5 zeolite with a molar ratio of Si0 2 :M 2 0 3 of at least 40: 1 , preferably at least 200: 1 and more preferably at least 500: 1 , where M is selected from Al, B, or Ga.
  • the Si0 2 :M 2 0 mole ratio is at least 1000: 1.
  • the second stage reforming catalyst consists of an all- zeolite extrudate, wherein the extrudate is formed by forming a reaction mixture, shaping the reaction mixture (e.g. into an extrudate), and heating the shaped reaction mixture substantially in the absence of an external water phase to form a crystallized extrudate.
  • the manufacture of such extrudates is disclosed in U.S. Patent Nos.
  • the size of the ZSM-5 crystallites in the second stage catalyst can vary.
  • the ZSM-5 is characterized as having an average crystallite size less than about 10 microns.
  • the average crystallite size is less than about 5 microns and more typically the average crystallite size is less than about 1 micron.
  • the ZSM-5 crystallites are between 20 and 40 nm.
  • the ZSM-5 second stage catalyst is characterized as having at least 80% crystallinity, more preferably at least 90% crystallinity, most preferably at least 95% crystallinity. Strong acidity is undesirable in the catalyst because it promotes cracking, resulting in lower selectivity.
  • the ZSM-5 catalyst preferably contains an alkali metal and/or an alkaline earth metal.
  • the alkali or alkaline earth metals are preferably incorporated into the catalyst during or after synthesis of the molecular sieve.
  • the medium pore molecular sieve has less than 5,000 ppm alkali.
  • Such medium pore silicate molecular sieves are disclosed, for example, in U.S. Patent No. 4,061,724 and in U.S. Patent No. 5,182,012. These patents are incorporated herein by reference, particularly with respect to the description, preparation and analysis of silicates having the specified silica to alumina molar ratios, having a specified crystallite size, having a specified crystallinity and having a specified alkali metal content.
  • ZSM-5 is more particularly described in U.S. Patent No. 3,702,886 and U.S. Patent Reexamination No. 29,948, the entire contents of which are incorporated herein by reference.
  • the crystalline molecular sieve may be in the form of a borosilicate, where boron replaces at least a portion of the aluminum of the more typical aluminosilicate form of the silicate. Borosilicates are described in U.S. Patent Nos. 4,268,420;
  • the second stage catalyst contains one or more elements from Group 6 and Groups 8 through 10 of the Periodic Table, e.g., nickel, ruthenium, rhodium, palladium, iridium or platinum. Iridium, palladium, and particularly platinum are believed to be more selective with regard to dehydrocyclization and are more stable under the dehydrocyclization reaction conditions than other Group 8 - 10 metals.
  • the percentage of the metal, such as platinum, in the catalyst is between 0.1 wt. % and 5 wt. %, more preferably from 0.3 wt. % to 2.5 wt. %.
  • the metal(s) can be incorporated into the final stage catalyst using any method known in the art such as ion exchange, homogeneous deposition precipitation, redox chemistry, chemical vapor deposition, and impregnation.
  • the second stage catalyst can optionally include promoter metals such as tin and/or rhenium.
  • the promoter metal can be incorporated into the final stage catalyst using any method known in the art such as ion exchange, homogeneous deposition precipitation, redox chemistry, chemical vapor deposition, and
  • the catalyst includes sufficient promoter metal to provide a promoter to metal ratio between 0.5: 1 and 10: 1 , more preferably between 1 : 1 and 6: 1 , most preferably between 2: 1 and 5: 1.
  • the second stage catalyst can be dried and/or calcined and/or sulfided.
  • the second stage catalyst is sulfided prior to use. This involves converting the metal components in the catalyst to their sulfided form.
  • the sulfiding can be done by means of processes known to the skilled person, for example, by contacting the catalyst with a sulfur source such as elemental sulfur, sulfur containing compounds, or with a mixture of hydrogen and hydrogen sulfide.
  • the final stage catalyst comprises platinum and is sulfided with DMDS (dimethyldisulfide) prior to use.
  • the second stage catalyst can further comprise one or more inorganic oxide matrix components such as amorphous alumina.
  • inorganic oxide matrix components which may be employed in formulating the second stage catalyst, include, but are not limited to, amorphous silicas, aluminas, silica-aluminas, silica-zirconias, silica-magnesias, silica-thorias, silica-berylias, silica-alumina-thorias, silica-alumina- zirconias, alumina-borias, alumina-titanias and mixtures thereof.
  • the matrix may be in the form of a sol, hydrogel or gel and is typically an alumina, silica, or silica-alumina component.
  • the matrix may itself provide a catalytic effect, such as that observed for catalytically active silica/aluminas, or it may be essentially inert.
  • the matrix may act as a "binder" in some instances although in some instances the second catalyst may be spray dried or formed without the need of a binder.
  • the effluent from the second stage is an upgraded product, in that the RON has been increased during reaction in the second stage as compared to the RON of the naphtha feedstock.
  • the second stage effluent comprises hydrocarbons and hydrogen generated during reaction in the second stage and at least some of the hydrogen, if any, which is added to the feed upstream of the second stage.
  • the effluent hydrocarbons may be characterized as a mixture of C 4 - hydrocarbons and C 5 + hydrocarbons, the distinction relating to the molecular weight of the hydrocarbons in each group.
  • the C 5 + hydrocarbons in the effluent have a combined RON of at least 92.
  • These C 5 + hydrocarbons may include one or more of a high octane gasoline blending stock, benzene, toluene, xylene and ethylbenzene.
  • the reformate is useful as a fuel or as a blend stock for a fuel.
  • the reformate which is produced in the second reforming stage has an increased RON relative to that of the intermediate reformate which is the feed to the second reforming stage.
  • the RON of the final C 5 + reformate is at least 92, typically at least 98.
  • the final C 5 + reformate boils in the range from about 70°F to about 280°F.
  • the final C 5 + reformate boils in the range from about 100°F to about 330°F.
  • the final reformate comprises at least 70 vol% C 6 -C hydrocarbons.
  • the final C 5 + reformate boils in the range from about 100°F to about 280°F. In some such embodiments, the final C 5 + reformate comprises at least 70 vol% C 6 -C 8 hydrocarbons.
  • a final light stream may also be recovered from the final effluent. In such cases, the final light stream boils in the range of about 70° to about 140°F. In some such embodiments, the final light stream comprises at least 70 vol% C 5 hydrocarbons.

Abstract

L'invention concerne un procédé de reformage à deux étages à l'aide d'une configuration unique qui permet à l'unité de reformage de fonctionner à un plus haut taux d'alimentation de naphta par rapport aux configurations de reformage classiques. Dans le procédé de reformage unique de l'invention, une charge d'alimentation de naphta subit une étape de distillation avant la première étape de reformage. L'étape de distillation sépare la charge de naphta en un courant de C7 à chaîne légère supérieur , qui représente classiquement entre 5 et 20 pour cent de la charge d'alimentation globale, et un courant de C8+. Le courant de C8+ subit un reformage dans un premier étage constitué d'au moins un réacteur contenant un catalyseur de reformage métallique classique, dans des conditions suffisantes pour convertir le courant de C8+ en un premier reformat intermédiaire. Le courant de C7 contourne le premier étage et est combiné avec le reformat intermédiaire, et reformé dans le deuxième étage, à une pression plus basse que dans le premier étage, sur un catalyseur de reformage contenant une zéolite à pores moyens.
PCT/US2015/042582 2014-11-20 2015-07-29 Procédé de reformage à deux étages conçu pour un taux d'alimentation accru pour fabriquer un reformat WO2016081033A1 (fr)

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