Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • 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
• • 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
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • 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
  • B01J21/12—Silica and alumina
• • 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
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the 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
  • 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
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/42—Platinum
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/084—Y-type faujasite
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
  • B01J29/088—Y-type faujasite
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
  • B01J29/12—Noble metals
  • B01J29/126—Y-type faujasite
• • 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
  • 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
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/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
  • 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
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/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
  • 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
  • B01J37/0211—Impregnation using a colloidal suspension
• • 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
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
  • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/37—Acid treatment
• • 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
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/02—Gasoline

Definitions

• the present invention relates to a catalyst for catalytic reforming of hydrocarbon oil containing a framework-substituted zeolite- Y in which zirconium atoms and/or hafnium atoms and/or titanium atoms form a part of a framework of an ultra-stable Y-type zeolite.
• Catalytic reforming is a major conversion process in petroleum refinery and petrochemical industries.
• the reforming process is a catalytic process which converts low octane naphtha that have been, e.g., distilled from crude oil, into higher octane reformate used in gasoline blending and aromatic rich reformates used for aromatic production.
• the process re-arranges or re-structures the hydrocarbon molecules in naphtha feedstocks and breaks some of the molecules into smaller molecules.
• Naphtha feeds to catalytic reforming include heavy straight run naphtha.
• U.S. Patent No. 4,698,322 to Santilli teaches a reformation catalyst containing (i) Pt, (ii) type L zeolite, and (iii) a "promoter” which can be Fe, Co, or Ti. The ratio of Pt to promoter is less than 10:1. This "promoter" is not inserted into the zeolite framework which, in any event, differs from USY zeolite. No binder is disclosed either.
• U.S. Patent No. 5,271,761 to Skeels teaches zeolite Y molecular sieves. The artisan recognizes that, while USY and zeolite Y both have an FAU framework, they differ in composition and properties.
• the '761 Patent also describes mole fractions of T1O2, AIO2, and SiCh, as well as Si/Ti ratios and (Si + Al)/Ti ratios, which are not within the ranges of those of the invention described herein.
• U.S. Patent No. 9,512,371 describes incorporating Ti into FAU zeolites, followed by their use as hydrocracking catalysts.
• the weight % ratio of Al/Si ranges from 0.14 - 0.35, which is well outside of the range of the present invention.
• catalytic hydrocracking may be viewed as the "opposite" of reforming processes, because in the former, large molecules are broken (“cracked") into smaller ones, while reformation converts the molecules by, e.g., dehydrogenation, isomerization, alkylation, and cracking reactions converting starting materials into high octane containing molecules.
• the literature on hydrocracking catalysts is enormous, and the inventors wish to draw attention to U.S. Patent No. 9,221,036, incorporated by reference in its entirety.
• the '036 patent teaches, inter alia, a hydrocracking catalyst in which a USY framework has been substituted, in part, by one or more of zirconium, titanium, and hafnium.
• the metal (Ti, Zr, and/or Hi), substitutes for part of the aluminum in the aluminum/silica framework, and essentially become part of the framework.
• Processes for making these catalysts and their use, are all described in the '036 patent. Examples 1 and 2, infra, are in fact taken from this Patent.
• Zeolite based catalysts provide sufficient acidity to function in cracking, which are desirable in hydrocracking. In contrast, these reactions are very undesirable in reforming reactions, so a goal of developing any new reforming catalyst is a reduction of acidity in the catalytic composition.
• characteristic metals which are used in hydrocracking are Ni, Mo, and W, alone or preferably, in combination. Such metals are avoided in reforming catalysts, which are characterized by the presence of noble metals.
• a further fundamental difference is the temperature at which hydrocracking and reforming reactions operate, with the latter type of reaction requiring temperatures of 500° C. or more, well above those used in hydrocracking.
• the invention includes a catalyst useful in reforming processes, wherein an ultra stable Y (“USY” hereafter) zeolite is framework substituted to incorporate one or more of zirconium, titanium, and hafnium into its framework, and also has impregnated therein a reforming process metal, such as Pt, Rh, or Pd.
• the reforming catalyst can include or comprise a metal such as V, Zn, Ga, Li, Ca, Mg, or a rare earth metal.
• the USY zeolite, base component of the catalysts of the invention contains from 0.1 to 5 mass % of one or more of Zr, Ti, and Hf, as calculated on their oxide basis.
• the reforming metal is present in an amount from 0.01 to 1 wt%, preferably from 0.1 to 0.4 wt% of the resulting catalyst composition.
• the amounts of the individual materials supplying Zr, Ti, and Hf is less than 0.1 wt%, but when combined, the total is at least 0.1 wt%.
• the catalytic compositions comprise a binder, e.g., an alumina binder, a USY zeolite, and the aforementioned metals.
• the amount of US Y-zeolite should not exceed 50 wt%, and is preferably 1-10, more preferably 1-5, and most preferably 2-3 wt% of the total composition.
• NaY NaY zeolite
• UD unit cell dimension
• SA specific surface area
• Na 2 O content 13.0% by mass
• HY hydrogen-Y zeolite
• HY was suspended in 400 L of water having a temperature of 60° C.
• 49.0 kg of ammonium sulfate was added thereto.
• the resulting mixture was stirred at 90° C. for 1 hour and washed with 200 L of water having a temperature of 60° C.
• the mixture was then dried at 130° C. for 20 hours, thereby affording about 37 kg of a Y zeolite (N3 ⁇ 4 95 Y) in which 95% of Na contained in the initial NaY was ion-exchanged with NH4.
• LiSY (a) ultra stable Y zeolite having a SiO 2 /AI 2 O 3 molar ratio of 5.2 and a Na 2 O content of 0.60% by mass.
• USY (b) was fired at 600° C. for 1 hour, thereby affording about 17 kg of ultra stable Y-type zeolite (hereinafter, also referred to as "USY (c)").
• USY (c) ultra stable Y-type zeolite
• USY (E) zirconium/titanium-substituted type zeolite
• This example presents a catalyst prepared in accordance with the invention.
• a catalyst support was prepared by combining 95 wt% of an alumina binder as a support, and 5 wt% of a framework inserted Ti-Zr-USY prepared in accordance with Example 2, supra. This support was then impregnated with Pt, by mixing 600g of the support with a solution of tetra-amine Pt containing 1.9 wt% Pt. (This solution was prepared by dissolving 63g of tetra-amine platinum in water). This served to impregnate the catalyst support with Pt. The product was then air dried at 120° C. for one hour, and calcined at 400° C. for one hour. Analysis showed that 0.2 wt% Pt had been impregnated in the support.
• the mixture as prepared may be mixed with a catalyst support (e.g., alumina, silica, or mixes thereof, or any catalyst support known to the art) and then extruded, at room temperature prior to drying and calcination.
• a catalyst support e.g., alumina, silica, or mixes thereof, or any catalyst support known to the art.
• the mixing and extrusion will be familiar to the skilled artisan, as well as by way of review of the ⁇ 36 Patent, supra.
• Example 3 The catalyst prepared in Example 3, was used in a pilot study, which took place over sixteen (16) days. The conditions were changed, so as to determine the impact of various parameters. The pilot plant was operated at 510° C, at a pressure range of 6-8 bars, a liquid hourly space velocity range of 1.0-1.5 h '1 and a hydrogen to hydrocarbon ratio range of 3.5-5.0. Table 1 shows the composition of the test feedstock. Table 2 refers to the final results. "Feed” refers, of course, to the composition of the feedstock. "Commercial” refers to a commercially available catalyst compared to the catalyst of Example 3.
• the reforming catalyst of the invention is a composition comprising an ultra stable (“US") Y type zeolite, with a framework in which part of the aluminum has been substituted with Zr and Ti, and to which a reforming metal has been added.
• the reforming metal is preferably added in an amount of from 0.01-1.0 wt% of the total weight of catalyst.
• "Reforming metals" as used herein includes the noble metals, i.e., Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au, with Pt and Pd being preferred.
• the framework of the zeolite may contain one or more of V, Zn, Ga, Li, Ca, Mg, and the rare earth elements.
• the actual amount of USY-zeolite in the catalyst is less than 50% by weight, but is preferably as low as 1-10 wt%, preferably 1-5 wt%, most preferably 2-3 wt%.
• the Zr, Ti, Hf and other optional metals used may be present in amounts ranging from 0.1-5% by mass of the zeolite base component.
• zeolite of the reforming catalyst include a crystal lattice constant of from 2.425 to 2.450 nm, preferably 2.430- 2.450 nm, a specific surface area of from 600 m 2 /g to 900 m 2 /g, and a molar ratio of SiO 2 to AI 2 O 3 , generally ranging from 5:1 to 100:1 and preferably from 20:1 to 100:1.
• These reforming catalysts preferably have a specific surface area of from 200 to 450 m 2 /g, and a pore volume of from 0.4 - 1.00 ml/g.
• the catalytic composition of the zeolite component in preferred embodiments, contains from 0.25 to 1.25 wt% of TiO 2 . Preferably, it contains from 0.75 to 1.0 wt% TiO 2 , and most preferably, 0.8 wt% TiO 2 (which corresponds to 0.01 mol% of TiO 2 ).
• the catalysts of the invention are made, essentially, by using the processes described in U.S. Patent No. 9,221,036, incorporated by reference supra, via, the USY zeolite of Example 2 is placed in suspension, preferably to form a suspension having a liquid/solid mass ratio of from 5 to 15, after which an acid is preferably added to bring the suspension to a pH of from 1 to 2, after which Zr and Ti are added and mixed, followed by neutralization.
• the resulting material is combined with a binder, such as an alumina binder, and impregnated with a noble metal by adding a solution of the noble metal thereto, followed by drying and calcining.
• the reforming catalyst of the invention is contacted to a hydrocarbon feedstock having a boiling point in the range of 36 - 250° C, at a reaction temperature of from 400° C. to 600° C, preferably 430° C. - 600° C, and most preferably 430-550° C, and a pressure of from 1 bar to 50 bars, an LHSV of from 0.5 to 5 h -1 , and a hydrogen to hydrocarbon feed ratio of from 1:1 to 50:1, preferably 1:1 to 30:1.
• Various methods may be used, such as a fixed bed reactor, a catalyst replacement reactor, a semi-regenerative fixed bed reactor, a cyclic fixed bed reformer, or a continuous reformer.

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• Chemical Kinetics & Catalysis (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
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• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Health & Medical Sciences (AREA)
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• 2018
  • 2018-01-23 US US15/877,788 patent/US10787618B2/en active Active
  • 2018-12-05 CN CN201880087089.6A patent/CN111684046B/zh not_active Expired - Fee Related
  • 2018-12-05 WO PCT/US2018/064001 patent/WO2019147345A1/en not_active Ceased
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