WO2026006184A1 - Catalyseur de reformage multimétallique et procédé de reformage catalytique - Google Patents

Catalyseur de reformage multimétallique et procédé de reformage catalytique

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Publication number
WO2026006184A1
WO2026006184A1 PCT/US2025/034804 US2025034804W WO2026006184A1 WO 2026006184 A1 WO2026006184 A1 WO 2026006184A1 US 2025034804 W US2025034804 W US 2025034804W WO 2026006184 A1 WO2026006184 A1 WO 2026006184A1
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Prior art keywords
catalyst
range
reforming
paragraph
metal
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Pending
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PCT/US2025/034804
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English (en)
Inventor
Dinesh ATTARDE
Sourabh Mishra
David S. Lafyatis
Pooja UPRETI
Yili SHI
Suhas Patil
Elie J. FAYAD
Ranganadham TPV
Takenouchi KENTA
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Honeywell UOP LLC
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UOP LLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B01J35/32—Bulk density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/24—Chlorinating
    • 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
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof

Definitions

  • Reforming may be defined as the total effect produced by dehydrogenation of cyclohexanes and dehydroisomerization of alkylcyclopentanes to yield aromatics, dehydrogenation of paraffins to yield olefins, dehydrocyclization of paraffins and olefins to yield aromatics, isomerization of n- paraffins, isomerization of alkylcycloparaffins to yield cyclohexanes, isomerization of substituted aromatics, and hydrocracking of paraffins.
  • a reforming feedstock can be a hydrocracker, straight run, FCC, or coker naphtha, and it can contain many other components such as a condensate or thermal cracked naphtha.
  • a catalyst must have the capability to perform its functions initially and for prolonged periods of time. This is typically measured by activity, selectivity, and stability. Activity is a measure of the catalyst's ability to convert hydrocarbon reactants into products at specified conditions.
  • Selectivity refers to the amount of desired product or products obtained relative to the amount of reactants charged or converted. Stability refers to the rate of change with time of the activity and selectivity parameters; the smaller the rate of change, the more stable the catalyst.
  • activity commonly refers to the amount of conversion that takes place for a given charge stock at a specified severity level and is typically measured by octane number of the C 5 + product stream.
  • Selectivity usually refers to the amount of C 5 + yield and other valuable products, relative to the amount of the charge, that is obtained at the particular activity or severity level. Stability is typically equated to the rate of change of activity with time, as measured by octane number of C 5 + product, and of selectivity as measured by C 5 + yield.
  • the catalyst should have superior activity, selectivity, and stability characteristics.
  • the problem is typically expressed in terms of shifting and stabilizing the C 5 + yield-octane relationship at the lowest possible severity level, with the C 5 + yield being representative of selectivity and octane being proportional to activity.
  • Multimetallic acidic reforming catalysts have been developed with excellent stability, regenerability, and which have a 1 wt% improvement in C5+ yield without activity loss in the start of run (SOR) phase at 98 RON.
  • the catalyst comprises a combination of a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising Al 2 O 3 , and a first metal of Groups 2 or 15, or a combination thereof; catalytically effective amounts of platinum and rhenium; at least one additional metal from Groups 1, 2, 3, 9, or 15 of the Periodic Table or combinations thereof; sulfur; and a halogen component.
  • the catalyst can be utilized to substantially improve the performance of a reforming process which operates on a low-octane gasoline fraction to produce a high- octane reformate.
  • One aspect of the invention is a catalyst.
  • the catalyst comprises a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising gamma Al 2 O 3 , and 0.01 to 3 wt% of a first metal of Group 2 or Group 15 of the Periodic Table, or a combination thereof.
  • the Group 2 and/or 15 metals are incorporated into the framework of the support.
  • the catalyst also includes 0.05 to 5 wt%, or 0.1 to 1.0 wt% Pt and 0.05 to 5 wt%, or 0.1 to 1.0 wt% Re; 0.01 to 2 wt% of at least one additional metal from Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; 0.03 to 1.0 wt% S; and 0.5 to 2 wt% of a halogen.
  • the catalyst has an average bulk density in a range of 0.25 – 1.50 g/cc, or 0.25-1.30 g/cc, or 0.25-1.25 g/cc, or 0.25-1.20 g/cc, or 0.25-1.10 g/cc, or 0.25-0.90 g/cc, or 0.25-0.80 g/cc, or 0.30 – 1.50 g/cc, or 0.30-1.30 g/cc, or 0.30-1.25 g/cc, or 0.30-1.20 g/cc, or 0.30-1.10 g/cc, or 0.30-0.90 g/cc, or 0.30-0.80 g/cc, or 0.40 – 1.50 g/cc, or 0.40-1.30 g/cc, or 0.40-1.25 g/cc, or 0.40-1.20 g/cc, or 0.40-1.10 g/cc, or 0.40-0.90 g/cc,
  • the surface area is in the range of 50-300 m 2 /g (BET), or 50-290 m 2 /g, or 50-280 m 2 /g, or 50-270 m 2 /g, or 50-260 m 2 /g, or 50-250 m 2 /g, or 75-300 m 2 /g, or 75- 290 m 2 /g, or 75-280 m 2 /g, or 75-270 m 2 /g, or 75-260 m 2 /g, or 75-250 m 2 /g, or 100-300 m 2 /g, or 100-290 m 2 /g, or 100-280 m 2 /g, or 100-270 m 2 /g, or 100-260 m 2 /g, or 100-250 m 2 /g, 125-300 m 2 /g, or 125-290 m 2 /g, or 125-280 m 2 /g, or 125-270 m
  • Any Group 2 or Group 15 metal can be included as the first metal in the support to improve yield and/or selectivity.
  • Suitable Group 2 and Group 15 metals include, but are not limited to, Mg and/or P.
  • the Group 2 and Group 15 metals are present in amounts in the range of 0.01 to 3 wt%, or 0.01 to 2 wt%, or 0.01 to 1 wt%, or 0.05 to 3 wt%, or 0.05 to 2 wt%, or 0.05 to 1 wt%.
  • the catalyst includes Pt and Re in the range of 0.05 to 5 wt%, or 0.1 to 1.0 wt% each.
  • the rhenium component may be incorporated into the catalytic composite in any suitable manner known to those skilled in the catalyst formulation art which results in a relatively uniform distribution of rhenium in the carrier material such as by coprecipitation, ion-exchange, or impregnation. In addition, it may be added at any stage of the preparation of the composite, either during preparation of the carrier material or thereafter, and the precise method of incorporation used is not deemed to be critical. However, best results are obtained when the rhenium component is relatively uniformly distributed throughout the carrier material in a relatively small particle size, and the preferred procedures are the ones known to result in a composite having this relatively uniform distribution.
  • One acceptable procedure for incorporating this component into the composite involves co-gelling or co-precipitating the rhenium component during the preparation of the preferred carrier material, alumina.
  • This procedure usually comprehends the addition of a soluble, decomposable compound of rhenium such as perrhenic acid or a salt thereof to the alumina hydrosol before it is gelled.
  • the resulting mixture is then finished by conventional gelling, aging, drying, and calcination steps as explained hereinbefore.
  • a preferred way of incorporating this component is an impregnation step wherein the porous carrier material is impregnated with a suitable rhenium-containing solution either before, during, or after the carrier material is calcined.
  • Preferred impregnation solutions are aqueous solutions of water soluble, decomposable rhenium compounds such as ammonium perrhenate, sodium perrhenate, potassium perrhenate, potassium rhenium oxychloride (K 2 ReOCl 5 ), potassium hexachlororhenate (IV), rhenium chloride, rhenium heptoxide, and the like compounds. Best results are ordinarily obtained when the impregnation solution is an aqueous solution of perrhenic acid.
  • This component can be added to the carrier material either prior to, simultaneously with, or after the other metallic components are combined therewith. Best results are usually achieved when this component is added simultaneously with the other metallic components.
  • Platinum should exist in the elemental metallic state. It may be incorporated in the catalytic composite in any suitable manner known to result in a relatively uniform distribution of this component in the carrier material such as coprecipitation or cogellation, ion exchange or impregnation.
  • the preferred method of preparing the catalyst involves the utilization of a soluble, decomposable compound of platinum group metal to impregnate the carrier material in a relatively uniform manner.
  • this component may be added to the support by commingling the latter with an aqueous solution of chloroplatinic or chloroiridic or chloropalladic acid.
  • Other water-soluble compounds or complexes of platinum group metals may be employed in impregnation solutions and include ammonium chloroplatinate, bromoplatinic acid, platinum trichloride, platinum tetrachloride hydrate, platinum dichlorocarbonyl dichloride, dinitrodiaminoplatinum, sodium tetranitroplatinate (II), palladium chloride, palladium nitrate, palladium sulfate, diamminepalladium (II) hydroxide, tetramminepalladium (II) chloride, hexamminerhodium chloride, rhodium carbonylchloride, rhodium trichloride hydrate, rhodium nitrate, sodium hexachlororhodate (III), sodium
  • a platinum, iridium, rhodium, or palladium chloride compound such as chloroplatinic, chloroiridic, or chloropalladic acid or rhodium trichloride hydrate
  • Hydrogen chloride or the like acid is also generally added to the impregnation solution in order to further facilitate the incorporation of the halogen component and the uniform distribution of the metallic components throughout the carrier material.
  • any metals of Groups 1, 2, 3, 9, or 15, or combinations thereof are included as an additional metal in the catalyst.
  • Suitable additional metals include, but are not limited to, Na, K, Mg, Ca, Ba, Bi, Y, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Sn, Sb, La, Hf, W, Ir, Au, Pb, Ce, or combinations thereof.
  • This additional metal is present in the range of 0.01 to 2 wt%, or 0.01 to 1 wt%, or 0.05 to 2 wt%, or 0.05 to 1 wt%, or 0.1 to 2 wt%, or 0.1 to 1%.
  • the additional metal improves the activity of the catalyst and reduces coke formation.
  • This additional metal may be incorporated into the catalyst in any suitable manner known to those skilled in the catalyst formulation art to result in a relatively uniform distribution in the carrier material such as coprecipitation, cogellation, ion exchange, impregnation, etc.
  • the catalyst includes 0.03 to 1.0 wt% S, or 0.05 to 0.8 wt% S.
  • the sulfur helps to maintain the initial activity of the catalyst, and thus, the C5+ yield. It can be added using any suitable process, such as cold sulfiding at room temperature or hot sulfiding. Any suitable sulfur compound can be used, including, but not limited to, H 2 S.
  • the catalyst also includes 0.05 to 2.0 wt% of a halogen, or 0.05-1.90, or 0.05-1.80, or 0.05-1.70, or 0.05-1.60, 0.10 to 2.0, or 0.10-1.90, or 0.10-1.80, or 0.10- 1.70, or 0.10-1.60,.or 0.50 to 2.0, or 0.50-1.90, or 0.50-1.80, or 0.50-1.70, or 0.50-1.60, or 0.90 to 2.0 wt% S, or 0.9-1.90, or 0.90-1.80, or 0.9-1.70, or 0.9-1.60.
  • Any suitable halogen can be used, including, but not limited to, Fl, Cl, Br, and I, or combinations thereof.
  • the halogen may be present in the form of the halide (e.g., as the chloride).
  • the halogen may be added in any suitable manner, either during preparation of the support or before or after the addition of the other components.
  • the halogen may be added, at any stage of the preparation of the carrier material or to the calcined carrier material, as an aqueous solution of a suitable, decomposable halogen- containing compound such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, ammonium chloride, etc.
  • the halogen component or a portion thereof may be added during the impregnation with the platinum, the rhenium; or the additional metal, for example, through the utilization of a mixture of chloroplatinic acid and hydrogen chloride.
  • the final catalyst generally will be dried at a temperature of about 93°C to about 315°C (about 200° to about 600° F) for a period of at least about 2 to about 24 hours or more, and calcined or oxidized at a temperature of about 371°C to about 593°C (about 700° to about 1100° F) in an air or oxygen atmosphere for a period of about 0.5 to about 10 hours in order to convert substantially all of the metallic components to the corresponding reducible oxide form.
  • the catalyst can have any suitable shape, including, but not limited to, spherical, cylindrical, trilobe, and quadra-lobe.
  • Another aspect of the invention comprises a catalytic reforming process.
  • the catalytic reforming process comprises contacting a feed stream comprising naphtha with a reforming catalyst in a catalytic reforming zone comprising a catalytic reforming reactor under catalytic reforming conditions to obtain a product stream.
  • the reforming catalyst is described above.
  • the contacting may be accomplished by using the catalyst in any suitable reactor system, such as in a fixed bed system, a moving bed system, a fluidized bed system, or a batch type operation.
  • the reforming zone will typically comprise a catalytic reforming zone containing one or more fixed beds or dense-phase moving beds of the catalyst.
  • the present catalyst may be used in all or less than all of the beds, with conventional catalysts being used in the remainder of the beds.
  • hydrocarbon distillates for example, straight-chain paraffins
  • charge stocks be treated by conventional catalytic pretreatment methods such as hydrorefining, hydrotreating, hydrodesulfurization, etc., to remove substantially all sulfurous, nitrogenous, and water-yielding contaminants therefrom and to saturate any olefins that may be contained therein.
  • the feed stream comprises a hydrotreated feed stream comprising hydrocarbons boiling in the gasoline range and having less than or equal to 1.0 ppmw S, or less than or equal to 0.5 ppmw S, or less than or equal to 0.3 ppmw S.
  • Example 1 A reference naphtha reforming catalyst, specifically for a fixed-bed semi- regenerative process was prepared.
  • the catalyst support ( ⁇ -Al 2 O 3, cylindrical extrudates) was wet-impregnated with Pt & Re solutions and dried at 100 °C for 12 hrs.
  • a catalyst support was prepared by incorporating Mg in the support (i.e., in ⁇ -Al 2 O 3 framework itself).
  • the multimetallic catalyst (Catalyst B) was pre-treated and sulfided as done in Example 1.
  • the catalyst B composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 wt. % Co, 0.2 wt.% Mg, 1.25 wt.% Cl, and 0.18 wt. % S.
  • Example 3 [0028] The multimetallic catalyst was similar to the catalyst in Example 2 except the catalyst extrudate was of trilobe shape.
  • the catalyst (Catalyst C) composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 wt. % Co, 0.2 wt.% Mg, 1.25 wt.% Cl, and 0.18 wt. % S.
  • Example 4 [0029] The multimetallic catalyst was similar to the catalyst in Example 2 except the magnesium content was decreased to zero.
  • the catalyst (Catalyst D) composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 % Co, 1.25 wt.% Cl and 0.18 wt. % S.
  • Example 5 [0030] The multimetallic catalyst was similar to the catalyst in Example 2 except the magnesium content was increased in the support.
  • the catalyst (Catalyst E) composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 wt. % Co, 0.4 wt.% Mg, 1.25 wt.% Cl, and 0.18 wt. % wt.% S.
  • Example 6 [0031] The multimetallic catalyst was similar to the catalyst in Example 4 except the cobalt content was increased.
  • the catalyst (Catalyst F) composition was 0.25 wt. % Pt, 0.40 wt.% Re, 1 wt. % Co, 1.25 wt.% Cl, and 0.18 wt. % S.
  • Catalyst E 1.4 wt.% higher C5+ yield was observed at 98 GC RON as compared to reference Catalyst A, but it showed a significant activity loss of 5 o C.
  • Catalyst F showed 0.4 wt. % C5+ yield benefit with 2.7 o C better activity as compared to reference Catalyst A.
  • Catalyst G had 1 wt.% higher C5+ yield with activity loss of 0.4 o C compared to reference Catalyst A.
  • Catalyst C performed better in terms of C5+ yield benefit while maintaining overall activity.
  • the amount of coke observed was approximately 35 % lower in the case of Catalyst C as compared to reference Catalyst A.
  • a first embodiment of the invention is a catalyst comprising (a) a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising Al 2 O 3 , and optionally 0.01 to 3 wt% of a first metal from Groups 2 or 15 of the Periodic Table, or a combination thereof; (b) 0.05 to 5.0 wt% Pt and 0.05 to 5.0 wt% Re; (c) 0.01 to 2 wt% of at least one additional metal from Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; (d) 0.03 to 1.0 wt% S; and (e) 0.5 to 2 wt% of a halogen; wherein the catalyst has an average bulk density in a range of 0.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the first metal comprises Mg.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the first metal comprises Mg present in an amount in a range of 0.05% to 1% wt%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the first metal comprises P.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the first metal comprises P present in an amount in a range of 0.05 to 1 wt%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the at least one additional metal comprises Co.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the halogen comprises Cl.
  • an embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst comprises (a) the support comprising the solid solution or the homogenous mixture of atoms in solid state having the single crystal structure, comprising gamma Al 2 O 3 , and 0.05 to 3 wt% Mg or P or the combination thereof; (b) 0.1% to 1.0 wt% Pt and 0.1 to 1.0 wt% Re; (c) 0.01 to 2 wt% Co; (d) 0.03 to 1.0 wt% S; and (e) 0.5%-2 wt% Cl.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the catalyst comprises 0.1% to 1.0 wt% Pt and 0.1 to 1.0 wt% Re.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst comprises 0.05 to 0.8 wt% S.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the Al 2 O 3 comprises gamma Al 2 O 3 .
  • a second embodiment of the invention is a catalytic reforming process comprising contacting a feed stream comprising hydrocarbons boiling in the gasoline range with a reforming catalyst in a catalytic reforming zone comprising a catalytic reforming reactor under catalytic reforming conditions to obtain a product stream; wherein the reforming catalyst comprises (a) a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising Al 2 O 3 , and optionally 0.01 to 3 wt% of a first metal from Groups 2 or 15 of the Periodic Table, or a combination thereof; (b) 0.05 to 5.0 wt% Pt and 0.05 to 5.0 wt% Re; (c) 0.01 to 2 wt% of at least one additional metal of Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; (d) 0.03 to 1.0 wt% S; and (e) 0.5 to 2 wt% of a halogen; wherein the reforming catalyst
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the first metal comprises Mg present in an amount in a range of 0.05% to 1% wt%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the first metal comprises P present in an amount in a range of 0.05 to 1 wt%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the at least one additional metal comprises Co.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the halogen comprises Cl.

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

Abstract

L'invention concerne des catalyseurs de reformage de naphta. Le catalyseur comprend un support comprenant une solution solide ou un mélange homogène d'atomes à l'état solide présentant une structure monocristalline comprenant AI2O3, et/ou 0,01 à 3 % en poids d'un premier métal du groupe 2 ou du groupe 15 du tableau périodique, ou une combinaison de ceux-ci. Ledit catalyseur comprend également 0,05 à 5,0 % en poids de Pt et 0,05 à 5,0 % en poids de Re ; 0,01 à 2 % en poids d'au moins un métal supplémentaire des groupes 1, 2, 3, 9 ou 15 du tableau périodique, ou des combinaisons de ceux-ci ; 0,03 à 1,0 % en poids de S ; et 0,5 à 2 % en poids d'un halogène. Le catalyseur présente une densité apparente moyenne dans une plage de 0,25 à 1,50 g/cc et une surface dans une plage de 50 à 300 m2/g. L'invention concerne également des procédés de reformage catalytique.
PCT/US2025/034804 2024-06-28 2025-06-23 Catalyseur de reformage multimétallique et procédé de reformage catalytique Pending WO2026006184A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4480048A (en) * 1982-05-24 1984-10-30 Societe Francaise Des Produits Pour Catalyse Pro-Catalyse Chez Institute Francais Du Petrole Catalysts for hydrocarbons conversion
US5227357A (en) * 1990-03-17 1993-07-13 China Petro-Chemical Corporation Method for preparing a catalyst for reforming naphtha
US6045689A (en) * 1995-06-16 2000-04-04 Institut Francais Du Petrole Process for catalytic conversion of hydrocarbons into aromatic compounds with a catalyst containing silicon
US6218334B1 (en) * 1995-06-16 2001-04-17 Institut Francais Du Petrole Catalysts which can be used in conversion reactions of hydrocarbons and containing silicon
US20180104676A1 (en) * 2015-05-27 2018-04-19 Jgc Catalysts And Chemicals Ltd. Hydrotreating catalyst for hydrocarbon oil, process for producing same, and hydrotreating method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4480048A (en) * 1982-05-24 1984-10-30 Societe Francaise Des Produits Pour Catalyse Pro-Catalyse Chez Institute Francais Du Petrole Catalysts for hydrocarbons conversion
US5227357A (en) * 1990-03-17 1993-07-13 China Petro-Chemical Corporation Method for preparing a catalyst for reforming naphtha
US6045689A (en) * 1995-06-16 2000-04-04 Institut Francais Du Petrole Process for catalytic conversion of hydrocarbons into aromatic compounds with a catalyst containing silicon
US6218334B1 (en) * 1995-06-16 2001-04-17 Institut Francais Du Petrole Catalysts which can be used in conversion reactions of hydrocarbons and containing silicon
US20180104676A1 (en) * 2015-05-27 2018-04-19 Jgc Catalysts And Chemicals Ltd. Hydrotreating catalyst for hydrocarbon oil, process for producing same, and hydrotreating method

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