EP1838433A1 - Catalyseur de reformage comprenant un promoteur chelate - Google Patents

Catalyseur de reformage comprenant un promoteur chelate

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Publication number
EP1838433A1
EP1838433A1 EP05711584A EP05711584A EP1838433A1 EP 1838433 A1 EP1838433 A1 EP 1838433A1 EP 05711584 A EP05711584 A EP 05711584A EP 05711584 A EP05711584 A EP 05711584A EP 1838433 A1 EP1838433 A1 EP 1838433A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
tin
component
platinum
support
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05711584A
Other languages
German (de)
English (en)
Other versions
EP1838433A4 (fr
Inventor
Frank S. UOP LLC MODICA
Thomas K. UOP LLC MCBRIDE
Irina Z. Galperin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Publication of EP1838433A1 publication Critical patent/EP1838433A1/fr
Publication of EP1838433A4 publication Critical patent/EP1838433A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • 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
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • 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
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • 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
    • C10G2400/30—Aromatics

Definitions

  • This invention relates to a process for preparing a catalyst.
  • the process involves the use of a chelating ligand to form a tin chelate complex.
  • the invention also relates to a reforming process using the catalyst which provides increased selectivity to gasoline components and aromatic products.
  • Catalytic reforming involves a number of competing processes or reaction sequences. These include dehydrogenation of cyclohexanes to aromatics, dehydroisomerization of alky Icy clopentanes to aromatics, dehydrocyclization of an acyclic hydrocarbon to aromatics, hydrocracking of paraffins to light products boiling outside the gasoline range, dealkylation of alkylbenzenes and isomerization of paraffins. Some of the reactions occurring during reforming, such as hydrocracking which produces light paraffin gases, have a deleterious effect on the yield of products boiling in the gasoline range. Process improvements in catalytic reforming thus are targeted toward enhancing those reactions effecting a higher yield of the gasoline fraction at a given octane number.
  • Activity is a measure of the ability of the catalyst to convert hydrocarbon reactants to products at a designated severity level, with severity level representing a combination of reaction conditions: temperature, pressure, contact time, and hydrogen partial pressure.
  • Activity typically is characterized as the octane number of the pentanes and heavier (“C5 + ”) product stream from a given feedstock at a given severity level, or conversely as the temperature required to achieve a given octane number.
  • Stability refers to the rate of change of activity or selectivity per unit of time or of feedstock processed.
  • Activity stability generally is measured as the rate of change of operating temperature per unit of time or of feedstock to achieve a given C5 + product octane, with a lower rate of temperature change corresponding to better activity stability, since catalytic reforming units typically operate at relatively constant product octane
  • Selectivity stability is measured as the rate of decrease of C ⁇ + product or aromatics yield per unit of time or of feedstock.
  • Reforming catalysts containing tin as platinum-group (or Group VIII) modifiers, along with optional third metal promoters such as rhenium, indium, gallium, iridium, etc. are well known in the art.
  • US 6,153,090 discloses a process for catalytic reforming using a catalyst comprising at least one group VIII metal, at least one additional element selected from the group consisting of germanium, tin, lead, rhenium, gallium, indium, thallium, where the promoter element is added in the form of an organometallic carboxylate compound containing at least one organometallic bond such as tributyl tin acetate.
  • chelating ligands can be used to impregnate metals onto a support.
  • US 4,719,196 discloses preparing a catalyst using a solution containing ethylene diaminetetraacetic acid (EDTA), a noble metal and ammonia.
  • US 5,482,910 discloses a process for preparing a catalyst using a mixed solution comprising EDTA, a noble metal, and a promoter metal, such as an alkali earth metal.
  • US 6,015,485 and US 6,291,394 disclose a process for treating an existing catalyst with EDTA in order to create a bimodal mesopore structure with alumina at two different crystallite sizes.
  • a process for preparing catalysts which involves the use of a stannous tin chelate complex to impregnate the tin component.
  • the process involves preparing a tin solution containing a chelating ligand such as EDTA. This solution is heated and then used to impregnate a refractory oxide support such as alumina.
  • another solution can be used to impregnate platinum-group metals and any other desired promoter metals such as rhenium.
  • the impregnation with the tin chelate is performed at basic conditions, while the impregnation of the other components is performed at acidic conditions. After impregnation, calcination and reduction provide the desired catalyst.
  • This invention relates to an improved naphtha reforming process, a catalyst for carrying out the naphtha reforming process, and a process for preparing a naphtha reforming catalyst.
  • one aspect of the invention is a process for preparing a naphtha reforming catalyst comprising: a) preparing a first aqueous solution containing a chelating agent and a stannous tin compound; b) heating said first solution for a time of 5 minutes to 5 hours at a temperature of 40°C to 100 0 C; c) preparing a second aqueous solution containing a platinum-group compound and a rhenium compound; e) impregnating a solid refractory oxide support with said first solution to give a first impregnated solid support; g) impregnating said first impregnated solid support with said second solution to give a second impregnated solid support; h) calcining the second impregnated solid support at a temperature of 300
  • the invention also relates to a process for the catalytic reforming of a naphtha feedstock which comprises contacting the feedstock at reforming conditions with a catalyst comprising a particulate inorganic oxide support having dispersed thereon a stannous tin component, a platinum-group metal component, and a rhenium component; the catalyst characterized in that the tin component is deposited on the support by impregnation using a tin chelate complex and is uniformly distributed throughout the support.
  • the invention relates to a catalyst effective for naphtha reforming comprising a particulate refractory inorganic oxide support having dispersed thereon a stannous tin component in an amount of 0.01 to 5 mass-% on an elemental basis, a platinum component in an amount of 0.01 to 2 mass-% on an elemental basis, and a rhenium component in an amount of 0.05 to 5 mass-% on an elemental basis.
  • the catalyst is characterized in that the tin is uniformly distributed and the platinum-group metal is uniformly distributed; the tin being dispersed on the support with an impregnation using a tin chelate complex.
  • FIG. 1 presents plots of C5 + liquid yields as a function of catalyst life for various catalysts incorporating tin by different methods.
  • FIG. 2 presents plots of average reactor block temperatures corresponding to catalyst activity as a function of catalyst life for various tin incorporation methods.
  • the catalyst of the present invention has particular utility as a hydrocarbon conversion catalyst.
  • the catalyst is particularly suitable for catalytic reforming of gasoline- range feedstocks, and also may be used for, inter alia, dehydrocyclization, isomerization of aliphatics and aromatics, dehydrogenation, hydro-cracking, disproportionation, dealkylation, alkylation, transalkylation, and oligomerization.
  • hydrocarbon feedstock and a hydrogen-rich gas are preheated and charged to a reforming zone containing typically two to five reactors in series. Suitable heating means are provided between reactors to compensate for the net endothermic heat of reaction in each of the reactors.
  • Reactants may contact the catalyst in individual reactors in either upflow, downflow, or radial flow fashion, with the radial flow mode being preferred.
  • the catalyst is contained in a fixed-bed system or, preferably, in a moving-bed system with associated continuous catalyst regeneration.
  • Alternative approaches to reactivation of deactivated catalyst are well known to those skilled in the art, and include semi-regenerative operation in which the entire unit is shut down for catalyst regeneration and reactivation or swing-reactor operation in which an individual reactor is isolated from the system, regenerated and reactivated while the other reactors remain on-stream.
  • Reforming conditions applied in the reforming process of the present invention include a pressure selected within the range of 100 kPa to 7 MPa (abs).
  • Reforming temperature is in the range from 315° to 600°C, and preferably from 425° to 565°C.
  • the initial selection of the temperature within this broad range is made primarily as a function of the desired octane of the product reformate considering the characteristics of the charge stock and of the catalyst. Ordinarily, the temperature then is thereafter slowly increased during the run to compensate for the inevitable deactivation that occurs to provide a constant octane product.
  • the hydrocarbon feedstock that is charged to this reforming system preferably is a naphtha feedstock comprising naphthenes and paraffins that boil within the gasoline range.
  • the preferred feedstocks are naphthas consisting principally of naphthenes and paraffins, although, in many cases, aromatics also will be present.
  • the gasoline-range naphtha charge stock may be a full-boiling gasoline having an initial ASTM D-86 boiling point of from 40° to 80 0 C and an end boiling point within the range of from 160° to 220°C, or may be a selected fraction thereof which generally will be a higher-boiling fraction commonly referred to as a heavy naphtha ⁇ for example, a naphtha boiling in the range of 100° to 200°C. If the reforming is directed to production of one or more of benzene, toluene and xylenes, the boiling range may be principally or substantially within the range of 60° to 150 0 C.
  • the present invention relates to a process for preparing a catalyst.
  • the catalyst comprises a solid refractory oxide support having dispersed thereon a tin component, at least one platinum group metal component and optionally a modifier metal such as rhenium.
  • the support can be any of a number of well-known supports in the art including aluminas, silica/alumina, silica, titania, zirconia, and zeolites.
  • the aluminas which can be used as support include gamma alumina, theta alumina, delta alumina, and alpha alumina with gamma and theta alumina being preferred.
  • aluminas which contain modifiers such as tin, zirconium, titanium and phosphate.
  • the zeolites which can be used include: faujasites, zeolite beta, L-zeolite, ZSM-5, ZSM-8, ZSM-11, ZSM-12 and ZSM-35.
  • the supports can be formed in any desired shape such as spheres, pills, cakes, extrudates, powders, granules, etc. and they may be utilized in any particular size. [0020]
  • One way of preparing a spherical alumina support is by the well known oil drop method which is described in US 2,620,314.
  • the oil drop method comprises forming an aluminum hydrosol by any of the techniques taught in the art and preferably by reacting aluminum metal with hydrochloric acid; combining the hydrosol with a suitable gelling agent; and dropping the resultant mixture into an oil bath maintained at elevated temperatures.
  • the droplets of the mixture remain in the oil bath until they set and form hydrogel spheres.
  • the spheres are then continuously withdrawn from the oil bath and typically subjected to specific aging and drying treatments in oil and ammoniacal solutions to further improve their physical characteristics.
  • the resulting aged and gelled spheres are then washed and dried at a relatively low temperature of 80° to 260°C and then calcined at a temperature of 455° to 705°C for a period of 1 to 20 hours. This treatment effects conversion of the hydrogel to the corresponding crystalline gamma alumina If theta alumina is desired, then the hydrogel spheres are calcined at a temperature of 950° to 1100°C.
  • An alternative form of carrier material is a cylindrical extrudate, preferably pre- pared by mixing the alumina powder with water and suitable peptizing agents such as HCl until an extrudable dough is formed.
  • the amount of water added to form the dough is typically sufficient to give a loss on ignition (LOI) at 500 0 C of 45 to 65 mass-%, with a value of 55 mass-% being preferred.
  • the acid addition rate is generally sufficient to provide 2 to 7 mass-% of the volatile-free alumina powder used in the mix, with a value of 3 to 4 mass-% being preferred.
  • the resulting dough is extruded through a suitably sized die to form extrudate particles.
  • the refractory inorganic oxide comprises substantially pure alumina having an apparent bulk density of 0.6 to 1 g/cc and a surface area of 150 to 280 m ⁇ /g (preferably 185 to 235 m ⁇ /g, at a pore volume of 0.3 to 0.8 cc/g).
  • a Group IVA(IUPAC 14) metal component is an essential ingredient of the catalyst of the present invention.
  • germanium and tin are preferred and tin is especially preferred.
  • This component may be present as an elemental metal, as a chemical compound such as the oxide, sulfide, halide, oxychloride, etc., or as a physical or chemical combination with the porous carrier material and/or other components of the catalytic composite.
  • a substantial portion of the Group IVA(IUPAC 14) metal exists in the finished catalyst in an oxidation state above that of the elemental metal.
  • the Group IVA(IUPAC 14) metal component optimally is utilized in an amount sufficient to result in a final catalytic composite containing 0.01 to 5 mass-% metal, calculated on an elemental basis, with best results obtained at a level of 0.1 to 0.5 mass-% metal.
  • the Group IVA(IUPAC 14) metal or metals are dispersed onto the desired support as follows. First, an aqueous solution of a chelating ligand and at least one soluble, decomposable metal promoter compound is prepared to give a promoter metal chelate complex.
  • the metal compound is a tin compound. More preferably, the tin compound is a tin salt.
  • tin salts or water-soluble compounds of tin include without limitation stannous bromide, stannous chloride, stannous fluoride, stannous iodide, stannous sulfate, stannous tartrate, stannous oxalate, stannous acetate and the like compounds.
  • a tin salt in the form of a chloride compound, such as stannous or stannic chloride is particularly preferred since it facilitates the incorporation of both the tin component and at least a minor amount of a halogen component in a single step.
  • Highly preferred is a salt with stannous tin having a plus two oxidation state.
  • the chelating ligands which can be used in the process of this invention include amino acids which upon decomposing do not leave overly detrimental components on the support, e.g., sulfur.
  • amino acids include ethylenediaminetetraacetic acid ("EDTA"), nitrilotriacetic acid, N-methylaminodiacetic acid, iminodiacetic acid, glycine, alanine, sarcosine, ⁇ -aminoisobutyric acid, N,N-dimethylglycine, ⁇ , ⁇ -diaminopropionate, aspartate, glutamate, histidine, and methionine.
  • EDTA ethylenediaminetetraacetic acid
  • nitrilotriacetic acid N-methylaminodiacetic acid
  • iminodiacetic acid glycine
  • glycine alanine
  • sarcosine ⁇ -aminoisobutyric acid
  • the chelate-metal complex solution which is preferably a chelate-tin complex solution, is heated for a time of 5 minutes to 5 hours at a temperature of 40° to 100°C or its boiling point.
  • the ratio of chelating ligand to the metal salt will vary from 1 to 8 and preferably from 1.5 to 4.
  • the chelate-metal solution described above may also contain a basic compound selected from the group consisting of ammonium hydroxide and quaternary ammonium compounds having the formula NRjR2R3R4 + X " where Rj, R2, R3, R4 are each separately methyl, ethyl, propyl, butyl or t-butyl and X is hydroxide.
  • the purpose of adding one or more of these basic compounds is to adjust the pH of the solution in order to vary the distribution of the metals. Further, the distribution of the IVA(IUPAC 14) metal may be different from the distribution of the platinum-group or other promoter metal. For the present invention, it is preferred that the tin component and platinum-group components are uniformly distributed throughout the catalyst.
  • the chelate-metal complex solution is now used to deposit the metal onto the support by means well known in the art.
  • means include spray impregnation and evaporative impregnation.
  • Spray impregnation involves taking a small volume of the mixed solution and spraying it over the support while the support is moving. When the spraying is over, the wetted support can be transferred to other apparatus for drying or finishing steps.
  • evaporative impregnation involves the use of a steam-jacketed rotary dryer. In this method the support is immersed in the impregnating solution which has been placed in the dryer and the support is tumbled by the rotating motion of the dryer.
  • Evaporation of the solution in contact with the tumbling support is expedited by applying steam to the dryer jacket.
  • the impregnated support is then dried at a temperature of 60° to 300°C and then calcined at a temperature of 300° to 850°C for a time of 30 minutes to 18 hours to give the calcined catalyst.
  • the calcined catalyst is reduced by heating the catalyst under a reducing atmosphere, preferably dry hydrogen, at a temperature of 300° to 850°C for a time of 30 minutes to 18 hours.
  • the refractory oxide support is first impregnated with the tin chelate complex, and then impregnated with a platinum-group component.
  • the tin chelate complex is impregnated after the platinum- group component. Note that the impregnation steps may overlap as well, thus functioning effectively as a co-impregnation.
  • the support may be dried and/or calcined in between procedures as needed under the drying and calcination conditions listed hereinafter.
  • the calcination after the first distinct impregnation is sufficient to convert the tin to a tin-oxide compound.
  • An essential ingredient of the catalyst is a dispersed platinum-group component.
  • This platinum-group component may exist within the final catalytic composite as a compound such as an oxide, sulfide, halide, oxyhalide, etc., in chemical combination with one or more of the other ingredients of the composite or as an elemental metal. It is preferred that substantially all of this component is present in the elemental state and is uniformly dispersed within the support material. This component may be present in the final catalyst composite in any amount which is catalytically effective, but relatively small amounts are preferred. Of the platinum-group metals which can be dispersed on the desired support, preferred metals are rhodium, palladium, platinum, and platinum being most preferred.
  • Platinum generally comprises 0.01 to 2 mass-% of the final catalytic composite, calculated on an elemental basis. Excellent results are obtained when the catalyst contains 0.05 to 1 mass-% of platinum.
  • This platinum component may be incorporated into the catalytic composite in any suitable manner, such as coprecipitation or cogelation, ion-exchange, or impregnation, in order to effect a uniform dispersion of the platinum component within the carrier material.
  • the preferred method of preparing the catalyst involves the utilization of a soluble, decomposable compound of platinum to impregnate the carrier material. For example, this component may be added to the support by commingling the latter with an aqueous solution of chloroplatinic acid.
  • platinum may be employed in impregnation solutions and include ammonium chloroplatinate, bromoplatinic acid, platinum dichloride, platinum tetrachloride hydrate, platinum dichlorocarbonyl dichloride, dinitrodiaminoplatinum, etc.
  • a platinum chloride compound such as chloroplatinic acid
  • 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 distribution of the metallic component.
  • Rhenium is a metal promoter of the catalyst.
  • the platinum and rhenium components of the terminal catalytic composite may be composited with the refractory inorganic oxide in any manner which results in a preferably uniform distribution of these components such as coprecipitation, cogelation, coextrusion, ion exchange or impregnation. Alternatively, non-uniform distributions such as surface impregnation are within the scope of the present invention.
  • the preferred method of preparing the catalytic composite involves the utilization of soluble decomposable compounds of platinum and rhenium for impregnation of the refractory inorganic oxide in a relatively uniform manner.
  • the platinum and rhenium components may be added to the refractory inorganic oxide by commingling the latter with an aqueous solution of chloroplatinic acid and thereafter an aqueous solution of perrhenic acid.
  • Other water-soluble compounds or complexes of platinum and rhenium may be employed in the impregnation solutions.
  • Typical decomposable rhenium compounds which may be employed include ammonium perrhenate, sodium perrhenate, potassium perrhenate, potassium rhenium oxychloride, potassium hexachlororhenate (IV), rhenium chloride, rhenium heptoxide, and the like compounds.
  • the utilization of an aqueous solution of perrhenic acid is preferred in the impregnation of the rhenium component.
  • any procedure may be utilized in compositing the platinum component and rhenium component with the refractory inorganic oxide as long as such method is sufficient to result in relatively uniform distributions of these components. Accordingly, when an impregnation step is employed, the platinum component and rhenium component may be impregnated by use of separate impregnation solutions or, as is preferred, a single impregnation solution comprising decomposable compounds of platinum component and rhenium component.
  • hydrogen chloride, nitric acid, or the like acid may be also added to the impregnation solution or solutions in order to further facilitate uniform distribution of the platinum and rhenium components throughout the refractory inorganic oxide. Additionally, it is generally preferred to impregnate the refractory inorganic oxide after it has been calcined in order to minimize the risk of washing away valuable platinum and rhenium compounds; however, in some cases, it may be advantageous to impregnate refractory inorganic oxide when it is in a gelled, plastic dough or dried state.
  • oxidation and reduction steps may be employed between application of the separate impregnation solutions.
  • halogen adjustment steps may be employed between application of the separate impregnation solutions. Such halogenation steps will facilitate incorporation of the catalytic components and halogen component into the refractory inorganic oxide.
  • the dispersion of platinum component and rhenium component must be sufficient so that the platinum component comprises, on an elemental basis, from 0.01 to 2 mass-% of the finished catalytic composite. Additionally, there must be sufficient rhenium component present to comprise, on an elemental basis, from 0.01 to 5 mass-% of the finished composite.
  • a modifier metal selected from the group consisting of germanium, lead, indium, gallium, iridium, lanthanum, cerium, phosphorous, cobalt, nickel, iron and mixtures thereof may be added to the catalyst.
  • An optional step in the process of this invention involves halogenation, which is preferably oxychlorination, of the reduced catalyst described above. If such a step is desired, the catalyst is placed in a reactor and a gaseous stream containing a halogen, which is preferably chloride or chlorine, is flowed over the catalyst at a flow rate of 0.9 kg/hr to 18.1 kg/hr, at a temperature of 300° to 85O 0 C for atime of 10 minutes to 12 hours.
  • the gaseous stream can be a hydrogen chloride/chlorine stream, a water/HCl stream, a water/Cl2 stream or a chlorine stream.
  • the purpose of this step is to provide optimum dispersion of the Group VIII and provide a certain amount of halide, preferably chloride, on the final catalyst.
  • the halogen content of the final catalyst should be such that there is sufficient halogen to comprise, on an elemental basis, from 0.1 to 10 mass-% of the finished composite.
  • the catalytic composite may be subjected to a presulfiding step.
  • the optional sulfur component may be incorporated into the catalyst by any known technique.
  • tin is added in alumina-sol which, due to very high acidity, provided the excellent conditions for uniform tin distribution.
  • tin salts typically SnCl ⁇ water solution
  • the addition of tin in dough results usually in tin precipitation due to the buffering of solution pH to 4-5 by alumina and formation of tin clumps containing agglomerated tin.
  • +4 tin distribution on support prepared by impregnation of tin in the presence of 12% HCl was not quite uniform and had an increased concentration on the surface when analyzed using Scanning Electron Microscopy (SEM).
  • SEM Scanning Electron Microscopy
  • +4 tin could not be dissolved with EDTA and could not properly be distributed through a catalyst support when a precipitate formed.
  • the +4 tin was still skewed towards the surface and was unable to be uniformly distributed throughout the support.
  • a rough calculation showed that almost 66% of the +4 tin was present in the surface half a first 400 ⁇ m of the catalyst particle.
  • a catalyst support material was treated with a chelating agent according to the method of the US 3,994,832 patent by dissolving 6.17 grams of EDTA in 5 cubic centimeters of concentrated ammonium hydroxide and diluting the solution to 500 cubic centimeters with water. Approximately 500 cubic centimeters of 1/16 inch gamma-alumina spheres were then immersed in the solution contained in a steam jacketed rotary dryer. The spheres were tumbled in the solution for a 1 A hour at room temperature, after which steam was applied to the dryer jacket and the solution evaporated to dryness in contact with the tumbling spheres.
  • Tin was added to the support when as part of the forming process called extrusion, or preferably co-extrusion.
  • 2500 g of alumina powder (commercially available under the trade names Catapal B and/or Versal 250) was added to a mixer.
  • a solution was prepared using 60.8 g nitric acid (67.5% HNO3) with 220 g deionized water, followed by the addition of 5.91 g of tin tartrate, and the solution was stirred.
  • the solution was added to the alumina powder in the mixer, and mulled to make a dough suitable for extrusion.
  • the dough was extruded through a die plate to form extrudate particles.
  • the extrudate particles were dried at on a belt calciner operating with a first zone at 37O 0 C for 15 minutes and a second zone at 62O 0 C for 30 minutes. [0043] The extrudate particles were placed in a rotary evaporator and heated to 6O 0 C. A solution comprising deionized water, hydrochloric acid, chloroplatinic acid, and perrhenic acid was added to the rotary evaporator and temperature was raised to 100°C and the support rolled for 5 hours. Next the impregnated support was heated to a temperature of 525°C in dry air. When the temperature was reached, an air stream containing HCl and CI2 was flowed through the catalyst for 6 hours. Finally, the catalyst was reduced by flowing pure hydrogen over the catalyst at a temperature of 510°C for 2.5 hours.
  • a spherical alumina support was prepared by the well-known oil dropping method, per US 3,929,683.
  • a tin component was incorporated in the support by commingling a tin component precursor with the alumina hydrosol and thereafter gelling the hydrosol.
  • the catalyst particles were then dried at 600 0 C for 2 hours.
  • This support was placed in a rotary evaporator and heated to 6O 0 C.
  • a solution comprising deionized water, hydrochloric acid, chloroplatinic acid, and perrhenic acid was added to the rotary evaporator and temperature was raised to 100 0 C and the support rolled for 5 hours.
  • the impregnated support was heated to a temperature of 525°C in dry air. When the temperature was reached, an air stream containing HCl and CI2 was flowed through the catalyst for 6 hours. Finally, the catalyst was reduced by flowing pure hydrogen over the catalyst at a temperature of 510 0 C for 2.5 hours.
  • a tin-EDTA solution was prepared by combining in a flask 300 g of deionized water, 1.42 g of ammonium hydroxide (concentration 29.6% NH4OH), and 0.88 g of EDTA and stirred to dissolve EDTA. Then 0.3392 g of tin chloride (Sn Cl2*2H2 ⁇ ) was added while stirring the solution and heated to 60°C to dissolve.
  • a second solution was prepared by the addition to 300 g of deionized water of 14.21 g of hydrochloric acid (37.6% HCl) and 17.48 ml of chloroplatinic acid (HyPtC ⁇ solution with a Pt concentration 27.6 mg/ml). Next was added 14.65 ml of perrhenic acid (HRe ⁇ 4 solution with a Re concentration 32.8 mg/ml).
  • the catalyst was reduced by flowing pure hydrogen over the catalyst at a temperature of 510 0 C for 2.5 hours.
  • Analysis of the catalyst showed it to contain 0.25 mass-% Pt and 0.25 mass-% Re and 0.1 mass-% Sn.
  • the platinum, rhenium and tin were evenly distributed throughout the support. This catalyst was identified as Catalyst C.
  • Catalysts A, B, C with even and uniform metals distributions were tested for catalytic reforming ability in a pilot plant using a typical naphtha feedstock available from the western United States as follows. Process conditions were selected to achieve a research octane number (RONC) of 100. Pressure was 1379 kPa (200 psig), hydrogen to hydrocarbon mole ratio was 1.5, and liquid hourly space velocity was 2.5 hr"l. Catalyst life was measured by the prevailing industry standard using Barrels of feed Per Cubic Foot of catalyst, or BPCF, as shown in FIG. 1 and FIG. 2. First, FIG. 1 presents plots of C5 + liquid yields as a function of catalyst life. Second, FIG. 2 presents plots of average reactor block temperatures corresponding to catalyst activity as a function of catalyst life. The results from this test are summarized in the table below indicating equivalent start of run activity and yield at 12.5 BPCF. TABLE

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Abstract

L'invention concerne un procédé de préparation d'un catalyseur de reformage de naphte consistant à utiliser un ligand chélateur, tel que l'acide éthylènediaminetétraacétique (EDTA). La solution aqueuse du ligand chélateur et un composé d'étain sont utilisés pour imprégner un support, par exemple, des extrudats d'alumine. Un métal du groupe du platine est également un composant essentiel du catalyseur. Le rhénium peut également être un composant. L'invention concerne également un procédé de reformage mettant en oeuvre le catalyseur et possédant un rendement, une activité et une stabilité améliorés pour la conversion de naphte en essence et produits aromatiques de valeur.
EP05711584A 2005-01-18 2005-01-18 Catalyseur de reformage comprenant un promoteur chelate Withdrawn EP1838433A4 (fr)

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RU2747527C1 (ru) * 2020-10-28 2021-05-06 Общество с ограниченной ответственностью "Институт по проектированию предприятий нефтеперерабатывающей и нефтехимической промышленности" (ООО "Ленгипронефтехим") Способ каталитического риформинга с непрерывной регенерацией катализатора

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CN106238045A (zh) * 2010-12-17 2016-12-21 埃克森美孚化学专利公司 脱氢催化剂和方法
CN103443060B (zh) 2011-03-28 2016-01-20 埃克森美孚化学专利公司 脱氢方法
WO2013072289A1 (fr) * 2011-11-17 2013-05-23 Basf Se Procédé pour la production des catalyseurs contenant sn
US9040451B2 (en) 2011-11-17 2015-05-26 Basf Se Process for producing Sn-comprising catalysts

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CA2594803A1 (fr) 2006-07-27
CA2594803C (fr) 2012-11-27
EP1838433A4 (fr) 2009-03-04
NO20074221L (no) 2007-09-25
WO2006078240A1 (fr) 2006-07-27

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