WO2002083303A1 - Procede de traitement d'un catalyseur et utilisation du catalyseur traite pour l'hydrogenation selective de composes a teneur en soufre - Google Patents

Procede de traitement d'un catalyseur et utilisation du catalyseur traite pour l'hydrogenation selective de composes a teneur en soufre Download PDF

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Publication number
WO2002083303A1
WO2002083303A1 PCT/US2002/012119 US0212119W WO02083303A1 WO 2002083303 A1 WO2002083303 A1 WO 2002083303A1 US 0212119 W US0212119 W US 0212119W WO 02083303 A1 WO02083303 A1 WO 02083303A1
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Prior art keywords
catalyst
sulfiding
silica
temperature
hydrogenation
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PCT/US2002/012119
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English (en)
Inventor
Yun-Feng Chang
Lawrence L. Murrell
Frits M. Dautzenberg
Jeroen Van Buijtenen
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Abb Lummus Global Inc.
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Publication of WO2002083303A1 publication Critical patent/WO2002083303A1/fr

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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
    • 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
    • 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
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof

Definitions

  • the present invention relates to a method for treating a hydrogenation catalyst and to the use of the treated catalyst in the selective hydrogenation of sulfur-containing compounds in an olefinic gasoline.
  • Gasoline stock may be produced by fluid catalytic cracking (FCC) or thermal cracking of higher boiling liquid hydrocarbon fractions.
  • FCC fluid catalytic cracking
  • Catalytically cracked gasoline currently forms a major part of the gasoline product pool in the United States.
  • the sulfur content of the gasoline is reduced, usually by hydrotreating, e.g., hydrodesulfurization, . in order to meet product specifications or to ensure compliance with environmental regulations, both of which are expected to become more stringent in the future, possibly permitting no more than about 300 ppmw sulfur in motor gasoline.
  • the newly enacted U.S. government regulation requires sulfur in motor gasoline to be at or below 30 ppmw by the year 2004. Low sulfur levels result in reduced emissions of CO, NO x and hydrocarbons .
  • Naphthas and other light fractions such as heavy cracked gasoline may be hydrodesulfurized by passing the feed over a hydrodesulfurization catalyst at elevated temperature and somewhat elevated pressure in a hydrogen atmosphere.
  • a hydrodesulfurization catalyst which has been widely used for this operation is a combination of a Group VIII and a Group VI element, e.g., a mixture of cobalt and molybdenum, on a substrate such as alumina, silica- alumina, crystalline aluminosilicate (zeolite), and the like.
  • the product may be fractionated, or simply flashed, to release by-product hydrogen sulfide and collect the now sweetened gasoline.
  • a method for treating a catalyst comprises : a) providing a catalyst for the selective hydrogenation of sulfur-containing compounds in an olefinic gasoline, the catalyst possessing a catalytically effective amount of at least one noble metal on an acidic amorphous silica-alumina support having a silica content of not more than about 40% by weight; and, b) contacting said catalyst with a sulfiding agent and ⁇ ydrogen under sulfiding conditions to provide an activated catalyst having a higher activity and selectivity for hydrogenation of sulfur-containing compounds than the unsulfided catalyst.
  • Treating the noble metal hydrogenation catalyst in accordance with the method of this invention increases catalyst activity and selectivity for hydrogenation of sulfur-containing compounds as opposed to hydrogenation of olefinic hydrocarbon components of the gasoline, thereby providing improved conversion of sulfur- containing compounds in the removal from gasoline stock with less reduction of octane number.
  • FIG. 1 is a graph illustrating the improved hydrogenation performance of sulfided PdPt/silica-alumina catalyst as opposed to untreated PdPt/silica-alumina catalyst .
  • the catalyst described herein is- useful for the selective hydrogenation of unsaturated organic sulfur- containing compounds such as thiophene or thiophene derivatives (methylthiophene, ethylthiophene, and the like) into corresponding saturated compounds (e.g., tetrahydrothiophene) , which have higher boiling points.
  • unsaturated organic sulfur- containing compounds such as thiophene or thiophene derivatives (methylthiophene, ethylthiophene, and the like) into corresponding saturated compounds (e.g., tetrahydrothiophene) , which have higher boiling points.
  • saturated sulfur-containing compounds are more easily removed from the olefinic gasoline by subsequent distillation, rendering a substantially sulfur free overhead product while concentrating the sulfur compounds in a bottom fraction that can subsequently be subjected to desulfurization.
  • Use of the catalyst described herein enables a larger fraction of the original gasoline feedstock to be separated as a substantially sulfur free overhead
  • the catalyst can be in the form of extrudates, pellets, spheres, granules, etc. More particularly, the catalyst includes a catalytically effective amount of at least one noble metal on an acidic amorphous silica-alumina support containing not more than about 40% silica by weight.
  • the noble metal is selected from platinum, palladium, rhodium, ruthenium, osmium and iridium and their mixtures.
  • the catalyst may also contain one or more non-noble metal components, e.g., Cu, Zn, Mn, Re, Ag, Sn, Au, Fe, Co, Ni, K, Ca, B, P, Mo, W, Cr, or Tc.
  • non-noble metal components e.g., Cu, Zn, Mn, Re, Ag, Sn, Au, Fe, Co, Ni, K, Ca, B, P, Mo, W, Cr, or Tc.
  • the acidic amorphous silica-alumina catalyst support utilized herein contains not more than about 40, preferably not more than about 30, and more preferably not more than about 15, weight percent of silica. Within the foregoing limits, the support contains at least that amount of silica which will provide surface acid sites on the support. This amount of silica will ordinarily constitute not less than about 0.1, and preferably not less than about 0.5, weight percent of the silica-alumina support.
  • the strong to weak acidity ratio (SWAR) of the silica-alumina support can advantageously range from about 0.1 to about 1.0, preferably from about 0.2 to about 0.8 and more preferably from about 0.25 to about 0.75.
  • the silica-alumina support herein contains not more than about 0.2% carbon, not more than about 0.01% iron oxide and not more than about 0.01% sodium oxide.
  • the support possesses an average particle size of from about 40 to about 60 ⁇ , a BET surface area of from about 10 m 2 /g to about 500 m 2 /g and a pore volume ranging from about 0.1 ml/g to about 0.90 ml/g.
  • Suitable acidic amorphous silica-alumina supports include the SIRALOX products available from Sasol GmbH, Hamburg, Germany which are supplied in powder, extrudate, pellet, tablet and microsphere forms, all of which are useful herein.
  • the silica in these products is substantially uniformly distributed throughout the silica-alumina matrix, an advantageous feature for the support employed in the catalyst of this invention.
  • the noble metal (s) can be loaded onto the support by any conventional method.
  • the support in the case of a PdPt combination, can be impregnated with aqueous solutions of platinumtetraamine nitrate, Pt (NH 3 ) 4 (N0 3 ) 2 and palladiumtetraamine nitrate, Pd (NH 3 ) 4 (N0 3 ) 2 and then dried and calcined to leave bimetallic PdPt deposited on the support.
  • the total loading of. noble metal can range from about 0.1% to about 5%, and preferably from about 0.5% to about 1.5% by weight based on total catalyst weight.
  • any ratio can be suitably employed.
  • the Pd/Pt weight ratio can range from about 1/5 to about 5/1, more preferably from about 1/4 to about 4/1 and most preferably from about 2/1 to about 3.5/1.
  • any of the optional non-noble metals referred to above can be present at levels, including their mixtures, of from about 0.05 to about 5, and preferably from about 0.1 to about 2, weight percent based on total catalyst weight.
  • the catalyst is treated prior to its use in hydrogenation by contacting the catalyst with an effective amount of a sulfiding agent and hydrogen under sulfiding conditions to produce an activated catalyst having a higher activity and selectivity for hydrogenation of sulfur-containing compounds than for hydrogenation of olefinic hydrocarbon components of the feed as compared with the unsulfided catalyst.
  • Sulfiding can be performed on a fresh catalyst or, alternatively, on a catalyst previously used in hydrodesulfurization.
  • the catalyst is contacted with hydrogen and a sulfiding feed including a sulfiding agent and a solvent. The nature of the solvent depends on the type of sulfiding agent used.
  • Preferred solvents for the sulfidation feed include hydrocarbons such as gasoline fractions containing one or more of hexane, heptane, octane and/or nonane, with or without aromatic components such as benzene, toluene, xylene and the like.
  • the sulfiding feed includes from about 0.05% to about 10% by weight of a sulfiding agent, and preferably from about' 0.5% to about 5.0% by weight of a sulfiding agent, which can be selected from sulfur, carbon disulfide, substituted or unsubstituted thiophenic compounds, e .g. , .
  • thiophene and compounds having the formula R-(S) n -R' (I) wherein n is an integer of from 1 to about 6, and R and R' are each individually selected from hydrogen and an organic group containing from 1 to about 10 carbon atoms, the organic group being selected from branched or straight chain alkyl groups, naphthenic groups, aryl groups and alkaryl groups.
  • One or more of the sulfiding agents can be incorporated into the sulfiding feed individually or combined.
  • sulfiding agents of formula (I) include hydrogen sulfide, methyl mercaptan, ethyl mercaptan, butyl mercaptan, dimethyl sulfide, dimethyl disulfide and organic polysulfides such as ditertbutyl polysulfide, ditertnonyl polysulfide and ditertdodecyl polysulfide, the. aforementioned polysulfides being available from Elf Aquitaine of Courbevoie, France, under the designations TPS-54, TPS-37 and TPS-32, respectively.
  • the sulfiding conditions include a temperature of from about 120°C to about 420°C, preferably from about 200°C to about 400°C, more preferably from about 250°C to about 350°C, and most preferably from about 330°C to about 350°C, a pressure of up to about 900 psig, preferably up to about 500 psig, more preferably from about 100 to about 400 psig, and a hydrogen flow of from about 1 cc/g-catalyst/min to about 100 cc/g-catalyst/min, preferably from about 2.5 to about 30 cc/g- catalyst/minute .
  • the feed rate of sulfiding feed can be from about 0.02 to about 5 g-feed/g-catalyst/min, preferably from about 0.05g feed/g-catalyst/min to about 3.5 g-feed/g- catalyst/min.
  • Sulfiding of the catalyst can be performed in situ or ex situ, i.e., in the same reactor in which the selective hydrogenation is to be performed or in a separate reactor.
  • the catalyst is pre-wetted with the sulfiding feed before heating. The temperature of the system is then raised at the rate of from about 0.1°C to about 10°C.
  • the catalyst is then held at that temperature for at least about 0.5 hours, preferably for a period of time ranging from about 2 hours to about 10 hours.
  • the temperature of the system is reduced to about 150°C while maintaining the sulfiding feed flow and hydrogen flow.
  • the sulfiding feed is then flushed out of the system.
  • the hydrogenation feed can be used for flushing the system which is then adjusted to the hydrogenation temperature and pressure.
  • the feed to the hydrogenation process of this invention is a sulfur-containing olefinic gasoline.
  • Feeds of this type include light naphthas typically having a boiling range of about C 6 to 330°F, full range naphthas typically having a boiling range of about C 5 to 420°F, heavier naphtha fractions boiling in the range of about 260°F to 412°F, or heavy gasoline fractions boiling at, or at least within, the range of about 330°F to 500°F, preferably about 330°F to 412°F.
  • the hydrogenation process can be operated upon the entire gasoline fraction obtained from the catalytic cracking unit or with just a part of it, depending on the amount and the nature of the sulfur compounds present.
  • the cut point between the treated and untreated fractions can vary according to the sulfur compounds present, but usually a cut point in the range of from about 100°F (38°C) to about 300°F (150°C) , more usually i • the range of about 200°F (93°C) to about 300°F (150°C) , will be suitable.
  • the exact cut point selected will depend on the sulfur specification for the gasoline product as well as on the type of sulfur compounds present. Lower cut points will typically be necessary for lower product sulfur specifications.
  • the sulfur which is present in components boiling below about 150°F (65°C) is mostly in the form of mercaptans which can be removed by extractive type processes such as Merox but hydrotreating is appropriate for the removal of thiophene and other cyclic sulfur compounds present in higher boiling components, e.g., component fractions boiling above about 180°F (82°C) .
  • Treatment of the lower boiling fraction in an extractive type process coupled with hydrotreating of the higher boiling component thus represents an embodiment of the present invention.
  • Higher cut points will be preferred in order to minimize the amount of feed which is passed to the hydrotreater and the final selection of cut point together with other process options such as the extractive type desulfurization will therefore be made in accordance with the product specifications, feed constraints and other factors.
  • the sulfur content of these catalytically cracked fractions will depend on the sulfur content of the feed to the cracker as well as on the boiling range of the selected fraction used as the feed in the process. Lighter fractions, for example, will tend to have lower sulfur contents than the higher boiling fractions. As a practical matter, the sulfur content of the olefinic gasoline feed herein will exceed 50 ppmw, will usually be in excess of 100 ppmw and in most cases will be in excess of about 500 ppmw. For the fractions which have 95 percent points over about 380°F (193°C) , the sulfur content may exceed about 1000 ppmw and may be as high as 4000 or 5000 ppmw or even higher, as shown below.
  • the nitrogen content is not as characteristic of the feed as the sulfur content and is preferably not greater than about 20 ppmw although higher nitrogen levels typically up to about 50 ppmw may be found in certain higher boiling feeds with 95 percent points in excess of about 380°F (193°C) .
  • the nitrogen level will, however, usually not be greater than 250 or 300 ppmw.
  • the feed to the selective hydrogenation step will be olefinic, with an olefin content of at least 5% by weight and more typically in the range of 10 to 20% by weight, e.g. 15-20% by weight.
  • the selective hydrogenation of the sulfur- containing compounds in the feed is carried out with the aforedescribed hydrogenation catalyst under conditions which result in the conversion of at least- some of the sulfur-containing compounds in the feed to less volatile saturated compounds to produce a product comprising a normally liquid fraction boiling in substantially the same boiling range as the feed to this step.
  • the sulfur-containing compound to be removed is thiophene, ' which boils at about 84.4°C.
  • the thiophene is converted by selective hydrogenation into tetrahydrothiophene, which boils at about 121°C.
  • the sulfur content of the product fraction is associated with higher boiling compounds which are more easily removed by subsequent distillation.
  • the temperature of the selective hydrogenation step is suitably from about 300°F to 850°F (about 150°C to 454°C), preferably about 350°F to 650°F (about 180°C to 427°C) with the exact selection dependent on the hydrogenation desired for a given feed and catalyst. These temperatures are average temperatures and will, of course, vary according to the feed and other reaction paramenters including, for example, hydrogen pressure and catalyst activity.
  • the hydrogenation can be performed in any one of a variety of reactor systems such as catalytic distillation, fixed bed, ebulliated bed, fluidized bed, moving bed, slurry reactor, and the like.
  • reactor systems such as catalytic distillation, fixed bed, ebulliated bed, fluidized bed, moving bed, slurry reactor, and the like.
  • the reactor may contain more than one bed.
  • low to moderate pressures may be used, typically from about 50 to 1500 psig (about 400 to 13000 kPa) , preferably about 200 to 800 psig (about 1700 to 7000 kPa) .
  • Pressures are total system pressure. Pressure will normally be chosen to maintain the desired aging rate -for the catalyst in use.
  • the space velocity for the hydrogenation step overall is typically about 0.1 to 50 LHSV (hr- 1 ) , preferably about 0.2 to about 30, e.g., 3 to 25, LHSV(hr- 1 ), based on the total feed and the total catalyst volume.
  • the hydrogen to hydrocarbon ratio in the feed is typically about 500 to 5000 SCF/Bbl (about 90 to 900 n.1.1 -1 .), usually about 1000 to 2500
  • Examples 1 and 3 are directed to the catalysts of the present invention in an unsulfided condition.
  • Examples 2 and 4 are directed to the sulfidation of the catalysts of Examples 1 and 3, respectively. With respect to Examples 1-4, the following methods, materials and equipment were employed.
  • a formulated gasoline feed illustrative of an FCC olefinic gasoline was used for the measurement of catalyst activity.
  • the formulated gasoline contained two olefins, i.e., octene-1 and 2, 4 , 4-trimethylpentene-l (TMP) , together with toluene, thiophene, pyridine and n- heptane.
  • TMP 4-trimethylpentene-l
  • the olefins were chosen to represent olefin distribution of typical cracked naphtha gasolines, i.e., from about 10 to about 20% by weight terminal olefins and from about 80 to about 90% by weight branched olefins.
  • Toluene was chosen to represent the aromatics contained in a typical olefinic gasoline.
  • Thiophene was used to represent organic sulfur components contained in cracked naphtha gasoline.
  • Pyridine was included to represent the basic components of an FCC gasoline.
  • the amount of total olefins was varied in the range of from about 10 to about 40 weight %.
  • the amount of aromatics was ' fixed to about 40 weight %.
  • the amount of sulfur in the feed was varied in the range of from about 500 to about 2500 ppm wt.
  • the amount of pyridine was varied in the range of from about 50 to about 250 ppm wt.
  • Catalyst in the form of pellets or small particles mixed with a diluent, e.g., silicon carbide, was loaded into the reactor.
  • the reactor was constructed of stainless steel (OD: V, wall thickness of 1/16", length: 8") .
  • Typical diluent to catalyst ratio was 5-15 wt/wt .
  • the catalyst was positioned in between two quartz wool plugs to prevent the catalyst from being carried away.
  • the reactants (olefinic gasoline feed and hydrogen) were fed from the bottom.
  • the liquid feed was delivered by an Eldex metering pump (Eldex Laboratories Inc., Napa, CA) .
  • Hydrogen was controlled by a Brooks mass flow controller (Brooks Instrument, Hatfield, PA) .
  • Reactor pressure was controlled by a Mighty-
  • Mite backpressure regulator (Grove Valve & Regulator Co., Oakland, CA) . Reaction products were analyzed by an online gas chromatography (GC) unit.
  • GC gas chromatography
  • the reactor was charged with 1 to 3g of catalyst.
  • the feed was introduced into the reactor at room temperature at a rate of from 0. Ig/min to 2g/min to first pre-wet the catalyst.
  • Hydrogen was introduced at a rate of from lOcc/min to 200cc/min and the reactor was pressurized to a hydrogenation reaction pressure of 440 psig.
  • the temperature was then increased at the rate of from about 0.2°C/min to 5°C/min until the reaction temperature of 215°C was reached.
  • the entire reactor and pre-heating feed line were immersed in a fluid bed sand bath to achieve uniform temperature control.
  • PdPt/silica-alumina catalyst of the present invention designated PdPt/SA-1
  • SA-1 silica-alumina support from Condea Vista Company
  • Silica-alumina SA-1 20g was impregnated by incipient wetness with a solution containing 0.1195g of platinumtetraamine nitrate (Alfa Aesar, 99.9% metal purity) and 0.5369g of palladiumtetraamine nitrate (Alfa Aesar, 99.9% metal purity) to give 0.3 wt% Pt and 0.9 wt% Pd.
  • the mixture was dried at 110°C for two hours before being calcined at 500°C in air for 3 hours. This gave 1.2%PdPt/SA-l .
  • Wafers of 1mm thick and 20-30 mm in diameter made by pressurizing the catalyst powder were crushed and sieved to have particles in the range of 0.6-1.2 mm. Catalyst particles in the size range of 0.6-1.2mm were used for the hydrogenation performance test.
  • the olefinic gasoline feed in the reactor was vented and the reactor then purged with nitrogen until it was dry.
  • the catalyst was then pre-wetted with a sulfiding feed containing 0.5% to 5.0% by weight of dimethyl disulfide in n-heptane.
  • the flow rate of sulfiding feed was 0.05 g-feed/g- catalyst/min to 0.5 g-feed/g-catalyst/min.
  • Hydrogen was then introduced into the reactor at a flow rate of from 5 cc/g-catalyst/min to 150 cc/g-catalyst/min and the temperature of the system raised at the rate of from 0.2°C/min to 5.0°C/min until the sulfiding temperature of 250°C to 350°C was reached.
  • the system pressure was 100 to 400 psig.
  • the sulfiding reaction was held at these conditions of temperature and pressure for from 4 to 12 hours .
  • PdPt/silica-alumina catalyst of the present invention was prepared by incipient wetness impregnation of a low silica silica- alumina from Condea Vista Company, designated SA-2, containing 10% of Si0 2 .
  • the SA-2 support 20g, was impregnated with a solution containing 0.1195g of platinumtetraamine nitrate (Alfa Aesar, 99.9% metal purity) and 0.5369g of palladiumtetraamine nitrate (Alfa Aesar, 99.9% metal purity) to give 0.3 wt% Pt and 0.9 wt% Pd.
  • the catalyst was tested for activity in the reactor described above. Both hydrogenation activity and selectivity were determined. The results are set forth below in Table 1 below.
  • EXAMPLE 4 The 1.2% PdPt/SA-2 catalyst of Example 3 was sulfided in accordance with the following procedure.
  • the olefinic gasoline feed in the reactor was vented and the reactor then purged with nitrogen until it was dry.
  • the catalyst was then pre-wetted with a sulfiding feed containing 0.5% to 5.0% by weight of dimethyl disulfide in n-heptane.
  • the flow rate of sulfiding feed was 0.05 g-feed/g- catalyst/min to 0.5 g-feed/g-catalyst/min.
  • Hydrogen was then introduced into the reactor at a flow rate of from 5 cc/g-catalyst/min to 150 cc/g-catalyst/min and the temperature of the system raised at the rate of from
  • the system was cooled down to below 200°C and the sulfiding feed was flushed out of the system at 100°-200°C.
  • the olefinic gasoline feed was introduced along with hydrogen and the reactor conditions were then adjusted for hydrogenation.
  • the catalyst designated 1.2% PdPt/SA-2-S, was then tested with respect to both HDS and HYD activity. The results are set forth below in Table 1.
  • Table 1 summarizes the HDS hydrogenation activity of the catalysts exemplified above (as measured by the hydrogenation of thiophene) as compared with the HYD hydrogenation activity (as measured by the hydrogenation of 2, 4, 4-trimethylpentene-l).
  • Example 2 1.2%PdPt/SA-l- 21.3 3.07 6.94 S (catalyst of Example 1 sulfided)
  • Example 4 1.2%PdPt/SA-2- 12.96 1.94 * 5.44 S (catalyst of Example 3 sulfided)
  • the sulfided 1.2% PtPd/SA-1-S catalyst of Example 2 was more than 55% more active with respect to hydrogenation of thiophene than the same catalyst in an unsulfided condition (Example 1) Moreover, the sulfided 1.2% PdPt/SA-1-S catalyst of Example 2 had a selectivity for hydrogenation of thiophene (k HDS /k HYD ) which was more than 79% better than that of the same PdPt/SA-1 catalyst in an unsulfided condition (Example 1) .
  • the sulfided 1.2% PdP ' t/SA-2-S catalyst of Example 4 was more than 31% more active with respect to hydrogenation of thiophene than the corresponding unsulfided 1.2% PdPt/SA-2 catalyst of Example 3.
  • the selectivity of the sulfided catalyst of Example 4 for the hydrogenation of thiophene was about 31% better than that of the corresponding unsulfided catalyst of Example 3.
  • FIG. 1 illustrates the performance of the tested catalysts for treating gasoline by charting the hydrogenation activity k HDS relative to the hydrogenation activity k HyD .
  • the unsulfided catalysts of Examples 1 and 3 lie on line A. Data points above line A indicate that the catalysts are more active and selective. The arrows indicate the improvement in activity and selectivity accomplished by the sulfiding method herein.
  • the data points for the sulfided catalysts of Examples 2 and 4 lie on line B, which is above line A, indicating the improved performance in hydrogenation achieved by sulfiding the PdPt/silica-alumina catalysts according to the present invention.

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Abstract

L'invention concerne un catalyseur destiné à l'hydrogénation sélective de composés à teneur en soufre contenus dans une essence oléfinique, telle qu'un naphta à craquage catalytique fluide comprenant au moins un métal noble sur un support silice-alumine amorphe acide qui ne contient pas plus de 40 % de silice. Ce catalyseur est traité par mise en contact dudit catalyseur avec un agent de sulfuration et avec de l'hydrogène dans des conditions de sulfuration de manière à produire un catalyseur sulfuré présentant une meilleure activité et une meilleure sélectivité pour l'hydrogénation de composés à teneur en soufre par rapport à l'hydrogénation de constituants hydrocarbures oléfiniques de l'essence.
PCT/US2002/012119 2001-04-16 2002-04-16 Procede de traitement d'un catalyseur et utilisation du catalyseur traite pour l'hydrogenation selective de composes a teneur en soufre WO2002083303A1 (fr)

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Cited By (1)

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CN106622268A (zh) * 2015-10-29 2017-05-10 中国石油化工股份有限公司 一种浆态床加氢催化剂及其制备方法

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WO1998035754A1 (fr) * 1997-02-13 1998-08-20 Engelhard Corporation Procede d'hydrogenation, d'hydro-isomerisation et/ou d'hydrodesulfuration d'une charge renfermant un contaminant sulfure
JPH11253805A (ja) * 1998-03-11 1999-09-21 Dainippon Ink & Chem Inc 予備硫化触媒の製造方法

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