EP0096483B1 - Traitement préalable d'un catalyseur frais contenant de l'iridium - Google Patents

Traitement préalable d'un catalyseur frais contenant de l'iridium Download PDF

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Publication number
EP0096483B1
EP0096483B1 EP83302771A EP83302771A EP0096483B1 EP 0096483 B1 EP0096483 B1 EP 0096483B1 EP 83302771 A EP83302771 A EP 83302771A EP 83302771 A EP83302771 A EP 83302771A EP 0096483 B1 EP0096483 B1 EP 0096483B1
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Prior art keywords
catalyst
temperature
hydrogen
oxygen
hours
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EP83302771A
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German (de)
English (en)
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EP0096483A1 (fr
Inventor
Sowmithri Krishnamurthy
George Robert Landolt
Hans Juergen Schoennagel
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ExxonMobil Oil Corp
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Mobil Oil Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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

Definitions

  • the present invention relates to a method for treating fresh iridium-containing reforming catalysts.
  • the treatment consists basically of a drying step at 200-600°F (93-316°C) for 2 to 24 hours, a calcination step at 700-1100°F (371-593°C) for 5 to 10 hours, and a water-free reduction step at 800-1100°F (427-593°C).
  • U.S. Patent No. 3,941,682 discloses a method of treating a catalyst which can be applied to either a spent or a fresh catalyst which comprises drying the catalyst at 220-250°F (104 ⁇ 121°C) followed by a calcination step at 500-700°F (260-371°C) optionally in the presence of both H 2 0 and HCI.
  • This patent notes that calcination temperatures in excess of 700°F (371°C) should be avoided.
  • the drying and calcination steps may be followed by contact with hydrogen chloride or reduction with hydrogen.
  • the present invention resides in a process for the treatment of a fresh iridium-containing reforming catalyst, comprising subjecting said catalyst to the following steps under essentially water-free conditions:
  • the present process is preferably carried out by treating a fresh catalyst prepared from hexachloroiridic acid with an oxygen-containing gas at elevated temperatures.
  • Preferred conditions range from temperatures of 750-1000°F (399-538°C), pressures of 0.1-500 psig (0.007-35 bar) and oxygen concentrations of 0.1-50 wt.% for 0.1 to 24 hours.
  • the oxygen treatment step is accomplished by treating the fresh catalyst with 0.1-21 wt.% of oxygen at temperatures of 850-950°F (454-510°C) for 0.25 to 2 hours at atmospheric pressure.
  • the next step in the treatment sequence involves the addition of a dry hydrogen halide, preferably hydrogen chloride, to the catalyst.
  • dry hydrogen halide is intended to mean that water is controlled to a level no greater than 1/30 the concentration of hydrogen halide. Preferably, water is present at a level no greater than 10 ppm (parts per million).
  • commercially available hydrogen chloride is suitable as is, i.e. no drying step is necessary.
  • the treatment with dry hydrogen halide is preferably carried out at temperatures ranging from 700-1000°F (371-538°C) and pressures ranging from about 0.1-500 psig (0.007-35 bar) for a period of time ranging from 0.5 to 24 hours utilizing at least 0.1 wt.% of hydrogen halide per weight of catalyst per hour.
  • the amount of hydrogen halide used is generally no greater than 10 wt.% per weight of catalyst per hour since higher amounts, although operabte, are not necessary to obtain the desired results.
  • hydrogen chloride with a concentration of about 3 vol.% in an inert gas is added at 1.5 wt.% of hydrogen chloride per weight of catalyst per hour at a temperature of 850 to 950°F (454 to 510°C) for 2 hours at atmospheric pressure.
  • oxygen and hydrogen halide treatment steps may also be accomplished simultaneously with the same results.
  • the final pretreatment step consists of treating the catalyst with a reducing agent, e.g. hydrogen.
  • a reducing agent e.g. hydrogen.
  • Suitable conditions include temperatures ranging from 400-1100°F (204-593°C) for periods of time ranging from 0.1 to 24 hours.
  • this procedure is performed at a temperature of 850-950°F (454 ⁇ 510°C) for 0.5 to 2 hours at atmospheric pressure.
  • this last step i.e. reduction with hydrogen, can be carried out either as a separate step in the pretreatment procedure or can be carried out as part of the reformer start-up procedure.
  • the hydrogen reduction step should, however, be performed after the oxygen and hydrogen halide treatments.
  • the treatment in step 1 (oxygen) and step 2 (hydrogen halide) is carried out by mixture of the same with an inert diluent such as nitrogen, neon, helium or argon.
  • an inert diluent such as nitrogen, neon, helium or argon.
  • the amount of inert gas is not critical and can range from 50 to 99.9 vol.% based on oxygen and can range from 90 to 99.9 vol.% based on the dry hydrogen halide.
  • the iridium-containing catalysts used herein comprise a porous carrier or support material in combination with iridium and other metals such as platinum and rhenium.
  • the support component of the catalyst is preferably a porous, adsorptive material having a surface area, as determined by the Brunauer-Emmit-Teller (BET) method, of 20-800, preferably 100-300 square meters per gram. This support material should be refractory at the temperature and pressure conditions utilized in any given hydrocarbon conversion process.
  • Useful support materials include: (a) silicon-based materials such as silica or silica gel, silicon carbide, clays, natural or synthetic silicates such as kieselguhr, kaolin, china clay or Attapulgus clay; (b) aluminosilicate zeolite materials such as naturally occurring or synthetic erionite, mordenite or faujasite, that may or may not have been previously converted to a hydrogen or ammonium form and reduced in sodium content by virtue of an exchange reaction with various metal cations, including rare earth metal cations; (c) refractory inorganic oxides, including alumina, titanium dioxide, zinc oxide magnesia, thoria, chromia, silica-alumina, alumina-titania, silica-zirconia and alumina- chromia; and (d) mixtures of one or more of the materials referred to above.
  • silicon-based materials such as silica or silica gel, silicon carbide, clays
  • Refractory inorganic oxide materials are preferred catalyst support materials.
  • alumina in particular the gamma or eta form
  • Alumina is the preferred catalyst support material when the catalyst is employed in naphtha reforming operations.
  • the support materials described above are known articles of commerce and can be prepared for use as catalyst constituents by many varied techniques. Typically, the support materials are prepared in the form of spheres, granules, powders, extrudates or pellets. It is possible to have all the metals of the iridium-containing catalyst on the same support in one particle, e.g. platinum and iridium on alumina, or as a mixture of separate particles, e.g. platinum on alumina mixed with iridium on alumina. When mixtures of separate particles are used, the supports can be the same or different.
  • the catalyst preferably contains greater than 0.1 wt.% iridium, based upon the dry weight of the total catalyst.
  • lesser quantities of iridium may be employed.
  • iridium and platinum may each be present on the catalyst in amounts varying from 0.01 to 5.0 wt.%, preferably in amounts varying from 0.1 to 1.0 wt.%, based upon the total weight of the dry catalyst.
  • Iridium/platinum naphtha reforming catalysts having maximum effectiveness normally contain 0.2 to 0.5 wt.% each, of iridium and platinum, based on total catalyst.
  • the iridium-containing catalysts may be prepared employing simple impregnation techniques well in the art. Such a catalyst may be prepared by impregnating a support material with a solution of a soluble iridium compound and soluble compounds of any additional metals to be incorporated in the catalyst. Generally, an aqueous solution of the metal compounds is used. The support material may be impregnated with the various metal-containing compounds either sequentially or simultaneously. The carrier material is impregnated with solutions of appropriate concentration to provide the desired quantity of metals in the finished catalyst.
  • compounds suitable for the impregnation onto the carrier include hexachloroiridic acid, iridium tribromide, iridium trichloride, and ammonium chloroiridate, with hexachloroiridic acid being preferred.
  • the preferred catalyst manufacturing technique involves contacting a previously prepared support, such as alumina, with an aqueous solution of hex- chloroiridic acid of appropriate concentration to provide the desired quantity of metal in the finished catalyst.
  • the composite catalyst is dried at a temperature varying from 220-250°F (104 ⁇ 121°C).
  • the catalyst may be dried in air at the above stated temperatures or may be dried by treating the catalyst in a flowing stream of inert gas, e.g. nitrogen.
  • the fresh catalyst is then subjected to the pretreatment steps described above.
  • the catalyst is dried in an oxygen-containing gas at a temperature of from 850°-950°F (454°-510°C) for 0.25 to 2 hours.
  • the drying step is followed by treatment with hydrogen chloride for 2 hours again at a temperature of from 850-950°F (424-510°C). If preferred, the foregoing steps may be accomplished simultanously.
  • the catalyst is next treated with reducing agent such as hydrogen for 0.5 to 2 hours also at a temperature of 850-950°F (454-510°C).
  • Iridium-containing reforming catalysts are used to improve the octane quality of naphthas and straight run gasolines. In addition they may be used to promote a wide variety of hydrocarbon conversion reactions such as hydrocracking, isomerization, dehydrogenation and cracking.
  • a substantially sulfur-free naphtha stream that typically contains 15 to 80 volume percent paraffins, 15 to 80 volume percent naphthenes and 2 to 20 percent aromatics and boiling at atmospheric pressure substantially between 80°F and 450°F (27°C and 232°C), preferably between 150°F and 375°F (66°C and 191°C), is contacted with the iridium-containing catalyst composite in the presence of hydrogen.
  • the reactions typically occur in the vapor phase at a temperature varying from about 650-1000°F (343-538°C), preferably about 750-980°F) (399-527°C).
  • Reaction zone pressures may vary from 1 to 50 atmospheres (0,98-49 bar), preferably from 5 to 30 atmospheres (4,9-29,4 bar).
  • the naphtha feed stream is conveniently passed over the catalyst composite at space velocities varying from 0.5 to 20 parts by weight of naphtha per hour per part by weight of catalyst (W/hr/W), preferably from 1 to 10 W/hr/W.
  • the hydrogen to hydrocarbon mole ratio within the reaction zone is conveniently maintained between 0.5 and 20, preferably between 1 and 10.
  • the hydrogen used may be in admixture with light gaseous hydrocarbons.
  • the catalyst is maintained as a fixed bed within a series of adiabatically operated reactors.
  • the catalyst may be used in a moving bed in which the naphtha charge stock, hydrogen and catalyst are passed in parallel through the reactor or in a fluidized system wherein the naphtha feed stock is passed upwardly through a turbulent bed of finely divided catalyst particles.
  • the catalyst may be simply slurried with the charge stock and the resulting mixture conveyed to the reaction zone for further reaction.
  • Figure 1 is a graph of inlet temperature versus days on stream for a naphtha reforming operation using a conventional bi-metallic catalyst and a tri-metallic catalyst pretreated according to one example of the invention
  • Figure 2 is a graph similar to Figure 1 but comparing the pretreated catalyst of said one example with a pretreated Pt-Re catalyst mixed with a fresh iridium component.
  • a deactivated reforming catalyst comprising: was regenerated in the following manner.
  • TPD of hydrogen is a technique used for estimating metal dispersions on reforming catalysts.
  • the procedure consists of chemisorbing hydrogen on the metals at room temperature and further desorbing it by applying heat at a programmed rate. By collecting the hydrogen desorbed and knowing the hydrogen to metal ratio, the metal dispersion can be calculated. Thus, a dispersion of 0.5 is equivalent to 50% of the total metal being exposed as surface metal. It has been found that a dispersion of at least 0.5 is necessary to effect reforming reactions.
  • pretreated iridium-containing catalysts have dispersions in the range of 0.6 to 1.0.
  • the nature of the desorption spectrum which is a plot of the rate of hydrogen release with respect to temperature as a function of temperature, provides additional information on the state of the metals on the support.
  • the resulting catalyst of Example 1 had a dispersion of less than 0.5.
  • the pretreatment procedure therefore does not work well with a deactivated or spent catalyst.
  • a fresh reforming catalyst comprising: was pretreated in the following manner.
  • a fresh reforming catalyst comprising: was pretreated in the following manner.
  • the resulting catalyst had a dispersion of greater than 0.5 which indicates that the pretreatment was successful.
  • a fresh reforming catalyst comprising: was pretreated in the following manner.
  • the resulting catalyst had a dispersion of less than 0.5.
  • the low dispersion clearly indicates the necessity of oxygen to effect the pretreatment.
  • the catalyst of Comparative Example 3 was treated in the same manner as Comparative Example 3 with the exceptions of substituting temperatures of 900°F (488°C) and 950°F (510°C) in steps 1-3.
  • the resulting catalysts also had a dispersion of less than 0.5 which indicates the necessity of oxygen to effect the pretreatment.
  • a fresh reforming catalyst comprising: was pretreated in the following manner.
  • the resulting catalyst again had a dispersion of less than 0.5.
  • a fresh reforming catalyst comprising:
  • the resulting catalyst had a dispersion of greater than 0.5. Therefore steps 1 and 2 of the pretreatment procedure can be accomplished sequentially (Example 1) or simultaneously.
  • a fresh reforming catalyst comprising: was pretreated as in Example 2 resulting in a dispersion of greater than 0.5 as determined by hydrogen chemisorption.
  • a commercial platinum-rhenium reforming catalyst (E603) having a composition of 0.35% platinum, and 0.35% rhenium was pretreated in a conventional manner using 5% oxygen in a nitrogen atmosphere for 2 hours at a temperature of 950°F (510°C) and subsequently treated with hydrogen for 1 hour at a temperature of 950°F (510°C).
  • the pretreated bi-metallic and tri-metallic catalysts were then evaluated at an octane severity of 98 R+O for the reforming of a C6 350°F (177°C) Arabian Light Naphtha having the following properties:
  • reaction conditions were 250 psig (18 bar), 2 WHSV and a total molar recycle ratio of 7.
  • a comparison of the inlet temperatures versus days on stream is shown in Figure 1.
  • the pretreated tri-metallic catalyst had improved stability as compared with the conventional bi-metallic catalyst.
  • a fresh reforming catalyst comprising: was pretreated in accordance with Example 2.
  • a platinum-rhenium catalyst was pretreated with 1.93% chlorine in nitrogen at 1.5 wt.% chlorine per weight of catalyst per hour for 2 hours at a temperature of 900°F (482°C). The iridium component was then added and the composite was treated in hydrogen for 1 hour at a temperature of 850°F (454°C).
  • the pretreated platinum-rhenium/fresh iridium catalyst and the platinum-rhenium/iridium catalyst pretreated in accordance with this invention were evaluated at an octane severity of 98 R+O for the reforming of C 6 350°F (177°C) Arabian Light Naphtha having the following properties.
  • reaction conditions were 250 psig (18 bar), 2 WHSV and a total molar recycle ratio of 7.
  • a comparison of the inlet temperature versus days on stream is shown in Figure 2.
  • the pretreated catalyst according to this invention had an octane advantage of 10°F (6°C) after 40 days on the stream.
  • a bi-metallic catalyst comprising: was pretreated in accordance with Example 2.
  • the pretreated catalyst had a dispersion of greater than 0.5 which indicates that the pretreatment procedure was successful.
  • the pretreated catalyst had a dispersion of greater than 0.5 which indicates that the pretreatment procedure was successful. Comparative Example 6
  • a fresh reforming catalyst comprising: was pretreated according to the procedure in Example 2 with the exception that the fresh catalyst was first reduced in hydrogen for 1 hour at 450°C.
  • the resulting catalyst had a dispersion less than 0.5 as determined by hydrogen chemisorption. Therefore, the prescribed pretreatment procedure is ineffective on a previously reduced reforming catalyst.
  • a fresh reforming catalyst comprising: was pretreated according to the procedure in Example 2 resulting in a dispersion of greater than 0.5 (0.7) as determined by hydrogen chemisorption.
  • the reduced catalyst was again subjected to the pretreatment procedure of Example 2.
  • the resulting catalyst had a dispersion of greater than 0.5 (0.8), which indicates the effectiveness of the multiple use of this procedure.
  • a fresh reforming catalyst comprising: was pretreated according to the procedure in Example 2 with the exception that oxygen- chlorine was used instead of oxygen/hydrogen chloride in step 1.
  • the resulting catalyst had a dispersion less than 0.5 as determined by hydrogen chemisorption which indicates the necessity of the presence of oxygen with a hydrogen halide to effect successful pretreatment.

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

Claims (10)

1. Un procédé pour le traitement d'un catalyseur de réformage contenant de l'iridium frais consistant à soumettre ce catalyseur aux étapes suivantes, dans des conditions essentiellement anhydres:
(1) traitement par de l'oxygène à une température élevée;
(2) traitement par un acide halohydrique à une température élevée; et
(3) après les étapes (1) et (2), traitement par un agent de réduction à une température élevée.
2. Le procédé selon la revendication 1, dans lequel ledit traitement par l'oxygène et l'acide halohydrique est combiné en une seule étape.
3. Le procédé selon la revendication 1 ou la revendication 2, dans lequel l'étape de traitement par l'oxygène comprend le traitement du catalyseur avec 0,1 à 50% en poids d'oxygène à une température de 399 à 538°C (750-1000°F) pendant 0,1 à 24 heures et sous une pression de 0,007-35 bar (0,1-500 psig).
4. Le procédé selon la revendication 1 ou la revendication 2, dans lequel l'étape de traitement par l'oxygène comprend le traitement dudit catalyseur avec 0,1 à 21% en poids d'oxygène à une température comprise entre 454°C et 510°C (850-950°F) pendant 0,25 à 2 heures.
5. Le procédé selon l'une quelconque des revendications précédentes, dans lequel le traitement à l'acide halohydrique comprend le traitement dudit catalyseur avec 0,1 à 10% en poids d'acide halohydrique par rapport au poids dudit catalyseur, par heure, pendant 0,5 à 24 heures à une température de 371 à 538°C (700-1000°F).
6. Le procédé selon l'une quelconque des revendications précédentes, dans lequel l'acide halohydrique est l'acide chlorhydrique.
7. Le procédé selon l'une quelconque des revendications précédentes, dans lequel ledit catalyseur est traité par un agent réducteur à une température comprise entre 204 et 593°C (400-1000°F) pendant 0,1 à 24 heures.
8. Le procédé selon l'une quelconque des revendications précédentes, dans lequel le catalyseur est traité par un agent réducteur à une température de 454 à 510°C (850-950°F) pendant 0,5 à 2 heures.
9. Le procédé selon l'une quelconque des revendications précédentes, dans lequel l'agent réducteur précité est de l'hydrogène.
10. Le procédé selon l'une quelconque des revendications précédentes, dans lequel ledit catalyseur peut également contenir du platine ou du platine et du rhénium.
EP83302771A 1982-06-04 1983-05-17 Traitement préalable d'un catalyseur frais contenant de l'iridium Expired EP0096483B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US38515882A 1982-06-04 1982-06-04
US385158 1982-06-04

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EP0096483A1 EP0096483A1 (fr) 1983-12-21
EP0096483B1 true EP0096483B1 (fr) 1986-06-04

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EP83302771A Expired EP0096483B1 (fr) 1982-06-04 1983-05-17 Traitement préalable d'un catalyseur frais contenant de l'iridium

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EP (1) EP0096483B1 (fr)
JP (1) JPS59334A (fr)
AU (1) AU1449583A (fr)
DE (1) DE3363909D1 (fr)
ES (1) ES522957A0 (fr)
PT (1) PT76801B (fr)
ZA (1) ZA833970B (fr)

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WO2021172134A1 (fr) * 2020-02-28 2021-09-02 市光工業株式会社 Appareil d'éclairage de véhicule

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998755A (en) * 1971-05-03 1976-12-21 Universal Oil Products Company Regeneration of a coke-deactivated, acidic bimetallic Pt-1r catalyst
US4172817A (en) * 1978-05-22 1979-10-30 Exxon Research & Engineering Co. Process for reactivating an iridium-containing catalyst
AU525445B2 (en) * 1978-08-16 1982-11-04 Mobil Oil Corp. Reforming catalyst of separate platinum-containing and iridium-containing particles

Also Published As

Publication number Publication date
ES8500313A1 (es) 1984-10-01
ES522957A0 (es) 1984-10-01
PT76801B (en) 1986-02-12
ZA833970B (en) 1984-02-29
EP0096483A1 (fr) 1983-12-21
JPS59334A (ja) 1984-01-05
PT76801A (en) 1983-07-01
DE3363909D1 (en) 1986-07-10
AU1449583A (en) 1983-12-08

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