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WO2002032570A2 - Catalyseur d'hydrodemetallation et procede de fabrication correspondant - Google Patents

Catalyseur d'hydrodemetallation et procede de fabrication correspondant Download PDF

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Publication number
WO2002032570A2
WO2002032570A2 PCT/US2001/032432 US0132432W WO0232570A2 WO 2002032570 A2 WO2002032570 A2 WO 2002032570A2 US 0132432 W US0132432 W US 0132432W WO 0232570 A2 WO0232570 A2 WO 0232570A2
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Prior art keywords
catalyst
amount
pores
metal
alumina
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Ceased
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PCT/US2001/032432
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English (en)
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WO2002032570A3 (fr
Inventor
Opinder Kishan Bhan
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Shell Internationale Research Maatschappij BV
Shell USA Inc
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Shell Internationale Research Maatschappij BV
Shell Oil Co
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Priority to AU2002215374A priority Critical patent/AU2002215374A1/en
Publication of WO2002032570A2 publication Critical patent/WO2002032570A2/fr
Publication of WO2002032570A3 publication Critical patent/WO2002032570A3/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • C10G45/06—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 nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • This invention relates to a catalyst for removal of metals from heavy hydrocarbon oils and fractions and a method of making such catalyst.
  • Petroleum feedstocks are characterized by relatively high levels of contaminants, including sulfur, nitrogen, Conradson carbon residue, aromatic compounds and metals such as nickel, vanadium and iron.
  • contaminants including sulfur, nitrogen, Conradson carbon residue, aromatic compounds and metals such as nickel, vanadium and iron.
  • hydrotreating process promotes reactions such as hydrodesulfurization (HDS), hydrodenitrogenation (HDN), Conradson carbon removal, hydrodemetallation (HD ) and aromatics saturation, accompanied by a conversion to lower boiling products.
  • HDS hydrodesulfurization
  • HDN hydrodenitrogenation
  • HD Conradson carbon removal
  • hydrodemetallation HD
  • aromatics saturation accompanied by a conversion to lower boiling products.
  • sulfur and nitrogen components are converted into hydrogen sulfide and ammonia, metals are deposited onto the catalyst as metal sulfides.
  • Some researchers have taught catalysts based on a support having a bimodal pore size distribution.
  • Japanese patent application JP 1 1 128744 teaches a catalyst preparation method where molybdenum is impregnated on a ⁇ -alumina support having a bimodal pore structure in such a way that a concentration gradient exists between the molybdenum on the particle surface and internally.
  • Other researchers have taught catalysts that appear to be directed at fulfilling the need for a catalyst that is effective at promoting hydrodemetallation.
  • U.S. Patent No. 5,002,919 teaches a catalyst comprising a support having a unimodal pore size distribution on which a metal that promotes hydrogenation has been deposited.
  • U.S. Patent No. 5,322,829 also teaches a catalyst comprising a support having a unimodal pore size distribution on which Group IVB and Group VIII metals have been deposited. Disclosure of the Invention
  • a catalyst having a bimodal pore structure prepared by mixing alumina with fines produced by crushing commercial hydroprocessing or hydrocracking catalyst comprising at least 20 wt.% alumina and metal from Group VIB of the Periodic Table and, optionally, a Group VIII metal and/or phosphorus followed by mulling with water and, optionally, an acid, extruding, drying and calcining at the proper temperature is highly effective at removing metals from heavy oil fractions and maintains its effectiveness for much longer periods than catalysts presently available.
  • the present invention provides for such a catalyst comprising a support comprising alumina having a bimodal pore size distribution, a catalytically active amount of metal from Group VIB of the Periodic Table and, optionally, a metal from Group VI II and/or phosphorus distributed uniformly throughout the catalyst particle as well as on its surface.
  • This catalyst has been found to be particularly effective at removing metals from heavy oil fractions containing high concentrations of nickel and vanadium while exhibiting good stability, i.e.. the ability to exhibit activity equivalent to or close to its initial activity, even when the amount of metals removed (i.e., deposited on the catalyst) is nearly equivalent to the weight of fresh catalyst.
  • the present invention also provides for a process for manufacturing such catalyst comprising: 1) mixing between 60 % and 90 % alumina powder with the balance fines derived from crushing catalyst comprising alumina, metal from Group
  • the present invention provides for a catalyst made by the process of the present invention and for a process for removing metals from a heavy oil fraction comprising contacting such heavy oil fraction with the catalyst of the present invention in the presence of hydrogen at elevated temperature and pressure.
  • Figure 3 shows the reaction rate constant at two operating temperatures, 370°C and 395°C, versus weight percentage of vanadium deposited, calculated on a fresh catalyst weight basis for removal of vanadium from whole Boscan crude by the catalyst of the present invention in a hydrotreating process as compared to that of catalysts prepared in a similar manner but calcined at higher and lower temperatures.
  • Figure 4. shows the concentration of molybdenum across the cross section of a conventional catalyst particle.
  • Figure 5. shows the concentration of molybdenum across the cross section of a catalyst particle of the present invention.
  • Figure 6. is a TEM photograph of the surface of a catalyst particle of the present invention.
  • Figure 7. is a TEM photograph of the surface of a catalyst particle prepared following the procedure of the present invention but calcined at 815°C.
  • Figure 8. is a TEM photograph of the surface of a commercial catalyst particle calcined at 815°C.
  • Figure 9 shows the reaction rate constant at 370°C, 385°C and 400°C versus weight percentage of vanadium deposited, calculated on a fresh catalyst weight basis for removal of vanadium from Heavy Arabian long residuum by Catalysts D, E and F.
  • Figure 10. shows the reaction rate constant at two operating temperatures
  • the catalyst of the present invention comprises an alumina support having a bimodal pore size distribution, a uniform distribution across the catalyst cross- section of a catalytically active amount of metal from Group VIB of the Periodic Table Group and optionally, a metal from Group VIII and/or phosphorus.
  • Support having a bimodal pore size distribution, a uniform distribution across the catalyst cross- section of a catalytically active amount of metal from Group VIB of the Periodic Table Group and optionally, a metal from Group VIII and/or phosphorus.
  • the alumina support should have a bimodal pore size distribution, which is accomplished by mixing alumina powder and fines from crushed hydrotreating or hydrocracking catalyst.
  • This bimodal distribution provides a) a sufficient number of macropores, i.e., pores of at least 1000 A in diameter, to allow large macro-molecular species in the hydrocarbon fraction (such as asphaltenes) that contain the bulk of the metals and organic metal complexes to enter the catalyst interior and to provide sufficient pore volume for effective deposition of metals without blocking the pore mouths; and b) a sufficiently high concentration of micropores, i.e., pores no larger than 350 ⁇ in diameter, to maintain high surface area, where sulfur-containing molecules are converted to H 2 S.
  • At least 50 % of the pores should be micropores, preferably at least 60 % and at least 20 % should be macropores, preferably at least 30 %.
  • Gamma phase alumina is preferred for the support. Pore volume distribution is determined by mercury intrusion at high pressures.
  • the total pore volume of the support should be between 0.6 and 1.2 cc/g.
  • the support surface area should be between about 80 m /g and about 350
  • alumina in the support is essential, supports comprising zeolites and other inorganic oxides, such as alumina-silica, alumina- boria, alumina-titania, and alumina-magnesia, may be used so long as the percentage of alumina in the support comprises at least 64 wt. % of the support material.
  • a critical element of the present invention is the even distribution of a catalytically active amount of a Group VIB metal throughout each catalyst particle.
  • Catalyst prepared by conventional methods such as by impregnating a support with a solution containing the desired metal followed by drying and calcining, invariably exhibits a gradient in the concentration of metal across the catalyst particle's cross section.
  • a typical concentration gradient for a conventionally prepared catalyst is shown in Figure 4 for molybdenum. This scan, showing "PP as a function of location on the particle diameter ("Point”) illustrates the decrease in Mo concentration from the particle surface towards the particle's interior.
  • PI is defined as the actual amount of metal loading present on catalyst at time “t” divided by the maximum amount of deposition that is possible in the absence of any diffusion restrictions and infinite time. The PI for this particle is 0.69.
  • Figure 5 shows the concentration profile for Mo across the cross section of a catalyst particle of the present invention. Figure 5 illustrates that the concentration of Mo is almost uniform throughout the catalyst particle, having a PI of 0.987.
  • Catalyst of the present invention should have a PI for the Group VIB metal of at least about 0.8, preferably at least about 0.9. Suitable metals from Group VIB are tungsten and molybdenum in an amount such that the Group VIB metal represents between about 0.5 wt.% and about 10 wt. % of the finished catalyst. Between about 2 wt. % and about 6 wt.% of molybdenum is preferred. If present, any of the metals from Group VIII are acceptable, with cobalt and nickel being preferred.
  • Phosphorus aids hydrogenation. Its presence in the finished catalyst is also optional and largely depends on whether the catalyst that is crushed to make fines contains it. When present, phosphorus increases the hydrogenation activity of the catalyst while reducing the metals-removal activity. If present, the amount of phosphorus should be between about 0.1 wt. % and about 2 wt.% of the finished catalyst.
  • the catalyst of the present invention may be prepared by crushing commercial hydroprocessing or hydrocracking catalyst comprising alumina- containing supports comprising alumina, zeolites or other inorganic oxides, such as alumina-silica, alumina-boria, alumina-titania, and alumina-magnesia impregnated with a Group VIB metal and, optionally, a Group VIII metal and/or phosphorus to yield catalyst fines having a particle size distribution such that the median particle diameter is between about 2 ⁇ m and about 50 ⁇ m, preferably between about 5 ⁇ m and about 15 ⁇ m.
  • median particle size of the fines is too large, i.e., above about 100 ⁇ m, catalyst strength and activity will be impaired.
  • Suitable metals concentrations in the fines are between about 2 wt. % and about 20 wt. % of Group VIB metal, preferably molybdenum, up to about 10 wt. % Group VIII metal and up to about 4 wt. % phosphorus.
  • fines produced during the manufacture of a commercial catalyst may be collected and milled to produce the recommended median particle size.
  • the catalyst fines are then mixed with alumina powder in a ratio such that the alumina powder comprises between about 60 wt.% and 90 wt.% of the mixture, preferably between about 70 wt.% and 80 wt.%.
  • the proportion of fines is determined by the concentration of metals in the commercial catalyst used to produce the fines, the metals loading desired in the finished catalyst and the pore size distribution desired in the finished catalyst.
  • the mixture is then mulled with water or, preferably, an aqueous acid solution by techniques well known to those skilled in the art. Any inorganic acid. except phosphoric acid which should be avoided, or organic acid, such as acetic or lactic is suitable, with nitric acid being preferred.
  • the aqueous acid solution should contain no more than about 6 % acid, with acid concentrations between about 0.2 % and about 2 % being preferred.
  • the mixture is formed into catalyst particles of the desired shape and size. Extrusion of the mixture is preferred.
  • the catalyst particles are then dried and calcined by methods known to those skilled in the art. During calcination, the metals originally contained in the catalyst fines migrate to the remaining alumina, dispersing uniformly throughout the entire particle surface. The temperature at which calcination is performed is important, however. If the catalyst particles are calcined at too low a temperature, below about 370°C, the metals will not properly disperse. If, however, the calcination temperature is above about 790°C, alumina changes phase resulting in drastically reduced surface area and very wide pores, thereby dramatically reducing catalyst strength and catalyst activity. Therefore, calcination temperatures between about 540°C and 730°C are preferred, and temperatures between about 650°C and 705°C particularly preferred.
  • calcination is accomplished by transporting the catalyst particles through a kiln wherein the particles are exposed to increasingly higher temperatures as they progress. Normally, this procedure will expose the particles to low temperatures initially (about 425°C) and progressively to temperatures that, at the outlet of the oven, reach up to 900°C.
  • the preferred calcination temperature (650°C to 705°C) referred to above is meant to apply to the temperature to which the catalyst particles are exposed "on average". Particular care must be taken to insure that the catalyst particles, while being exposed to temperatures during calcination within the range described above, spend as little time as practical at temperatures above 790°C. The importance of this practice is illustrated by reference to Figures 6 -8.
  • Figure 6 is a photograph of a section of the surface of a catalyst particle at an enlargement of 47,600 taken by Transmission Electron Microscopy (TEM). This photograph shows a very finely grained surface with no distinguishable crystals of alumina. In contrast.
  • Figure 7 shows a photograph (taken under the same conditions) of catalyst made by the procedure of the present invention that has been calcined at a temperature of 815°C. In this photograph, easily distinguishable crystals of alumina with metal can be discerned, indicating that the alumina in the presence of metals has experienced a phase transformation, thereby producing a mediocre catalyst.
  • Figure 8 shows the surface of a conventionally prepared catalyst of the same nominal composition calcined at 815°C. No noticeable phase transformation has occurred.
  • Hydrodemetallation of heavy hydrocarbon fractions may be achieved by contacting such feed with the catalyst of the present invention in the presence of hydrogen at elevated temperature and pressure.
  • the preferred operating conditions are between about 6,996 kPa (1 ,000 psig) and about 20,786 kPa (3,000 psig), between about 315°C and about 455°C, a hydrogen treat gas rate between about 178.1 and 1 ,781 m 3 per m 3 (1,000 and 10,000 SCF per bairel) of feed and sufficient catalyst to result in a liquid hourly space velocity (LHSV) of between about 0.1 hr "1 and about 2 hr "1 .
  • LHSV liquid hourly space velocity
  • the catalyst of the present invention be employed in the lead or first bed of a multi-bed system to permit removal of metals by a catalyst that is particularly well-adapted for such, thereby permitting the use of another catalyst less resistant to rapid deactivation from metals contamination in subsequent beds.
  • This example describes the preparation of a catalyst of the present invention and the characteristics of such catalyst.
  • a mixture comprising 70 wt.% alumina powder and 30 wt.% fines from crushed commercial hydroprocessing catalyst was prepared. The mixture was mulled in a 1 % aqueous solution of nitric acid for 35 minutes, extruded into 1.2 mm trilobe cylinders, dried at 100°C (212°F) for 3 hours and calcined at 677°C for 2 hours.
  • Analysis of the resulting catalyst, designated Catalyst A showed it to have the following metals concentrations uniformly distributed throughout the catalyst and pore size distribution determined by Hg intrusion under pressure: Metals: wt. % Ni: 0.96 wt. % Mo: 5.4 wt. % P: 0.48
  • This example compares the performance of catalyst of the present invention to that of a commercial hydrometallation catalyst when used to treat whole Boscan crude.
  • Catalyst A from Example 1 was compared to that of a commercial hydrometallation catalyst comprising an alumina support impregnated with 4 wt. % Mo.
  • Each catalyst was used to treat whole Boscan crude oil containing 5.3 wt.% S, 1 1 1 wppm Ni and 1360 wppm V at 370°C and at 395°C at a liquid hourly space velocity (LHSV) of 0.5 h " '.
  • LHSV liquid hourly space velocity
  • the results of these tests are shown as graphs of the reaction rate constants for conversion of vanadium versus weight percentage of vanadium deposited, calculated on afresh catalyst weight basis, on Figure 1. Vanadium removal proceeds at 1.5 order of reaction.
  • V 0 the square root of the vanadium concentration leaving the reactor
  • V; the square root of the vanadium concentration entering the reactor.
  • Figure 1 shows that Catalyst A exhibits much higher activity for removal of vanadium at the normal hydrotreating temperature of 395°C than the conventional catalyst and equivalent activity at a lower operating temperature of 370°C. Figure 1 also shows that this improvement in performance increases as run length increases, indicating that Catalyst A not only has a higher activity for removal of vanadium but also is more stable.
  • Example 3 shows that
  • This example compares the performance of catalyst of the present invention to that of a commercial hydrometallation catalyst when used to treat Ba Ceiro long residuum.
  • Catalyst A from Example 1 was compared to that of a commercial hydrometallation catalyst comprising an alumina support impregnated with 4 wt. % Mo.
  • LHSV liquid hourly space velocity
  • This example illustrates the importance of calcining the catalyst of the present invention at the proper temperature.
  • Catalysts B and C were prepared following the same procedure described in Example 1 except that Catalyst B was calcined at 732°C and Catalyst C at
  • This example describes the preparation of a catalyst impregnated with 2.3 wt.%) Ni and 4 wt.% Mo.
  • Catalyst E contained 4.0 wt. % Mo and had a pore volume distribution as follows:
  • An aqueous solution comprising 225.5 g of in 196.91 g deionized water and 35.52 g H 2 O was prepared.
  • a solution containing 180.0 g of glacial acetic acid and 95.0 g of deionized water was prepared. 3,992.55 g of ⁇ -alumina were added to a muller. With the muller running, the Mo solution was added and mulled for 3 minutes. Then the acid solution and 3,952.1 g of deionized water was added and mulled for 55 minutes.
  • a portion of the mulled material was extruded into 1/20 inch trilobe extrudates, dried for several hours at 125DC and calcined at 732DC for 2 hours.
  • the resulting catalyst, designated Catalyst F contained 4.0 wt. % Mo and had a pore volume distribution as follows:
  • Example 8 (Comparative) This example compares the performance of Catalysts D, E and F from
  • Catalyst D provided inferior vanadium removal activity compared to Catalyst E (i.e., without Ni). This was particularly true at the high operating temperature of 400°C, at which Catalyst D deactivated more quickly than Catalyst E; and 2) Catalyst E provided superior vanadium removal activity at all temperatures relative to Catalyst F, showing that simple co- mulling of Mo with alumina produces a less effective catalyst than the catalyst of the present invention.
  • Example 9

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur d'hydrodémétallation d'un courant d'hydrocarbures lourds comprenant des particules de support d'alumine, présentant une distribution bimodale des tailles de pores, et des quantités catalytiquement actives d'un métal du groupe VIB distribuées uniformément dans les particules et à leur surface, 20 % au moins du volume total des pores contenu dans le catalyseur étant sous forme de pores d'un diamètre d'au moins 1000 Å et 50 % au moins du volume total des pores contenu dans le catalyseur étant sous forme de pores possédant un diamètre de 350 Å au plus. L'invention concerne aussi un procédé de fabrication d'un tel catalyseur et un procédé d'élimination de métaux contenus dans un courant d'hydrocarbures lourds au moyen de ce catalyseur.
PCT/US2001/032432 2000-10-19 2001-10-16 Catalyseur d'hydrodemetallation et procede de fabrication correspondant Ceased WO2002032570A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002215374A AU2002215374A1 (en) 2000-10-19 2001-10-16 Hydrodemetallation catalyst and method for making same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69272600A 2000-10-19 2000-10-19
US09/692,726 2000-10-19

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WO2002032570A2 true WO2002032570A2 (fr) 2002-04-25
WO2002032570A3 WO2002032570A3 (fr) 2002-08-29

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AU (1) AU2002215374A1 (fr)
WO (1) WO2002032570A2 (fr)

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WO2002043862A3 (fr) * 2000-11-28 2003-02-13 Shell Oil Co Alumine possedant une nouvelle structure de pores, son procede d'elaboration et catalyseurs fabriques a base de cette alumine
WO2009022890A1 (fr) * 2007-08-07 2009-02-19 Instituto Mexicano Del Petroleo Catalyseur pour la première étape d'hydrodémétallisation dans un système d'hydrotraitement à l'aide de plusieurs réacteurs afin d'améliorer le pétrole lourd et extra-lourd
WO2009126973A3 (fr) * 2008-04-10 2010-10-07 Shell Oil Company Catalyseurs ayant des distributions sélectionnées de tailles des pores, procédé de préparation de tels catalyseurs, procédés de production d’un produit brut, produits obtenus par de tels procédés et utilisations des produits obtenus
US7820036B2 (en) 2006-08-03 2010-10-26 Shell Oil Company Highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
US7824541B2 (en) 2006-08-03 2010-11-02 Shell Oil Company Catalyst and process for the manufacture of ultra-low sulfur distillate product
US8734634B2 (en) 2008-04-10 2014-05-27 Shell Oil Company Method for producing a crude product, method for preparing a diluted hydrocarbon composition, crude products, diluents and uses of such crude products and diluents
US8912375B2 (en) 2008-09-10 2014-12-16 Haldor Topsoe A/S Hydroconversion process and catalyst
CN104549329A (zh) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 加氢脱金属催化剂的制备方法
US9101918B2 (en) 2006-09-29 2015-08-11 Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg Catalyst with bimodal pore size distribution and the use thereof
CN110773188A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773179A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种氧化铝载体及其制备方法
CN110773183A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773187A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773190A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773209A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN112547079A (zh) * 2019-09-25 2021-03-26 中国石油化工股份有限公司 一种重油加氢处理催化剂及其应用
US11498060B2 (en) 2013-10-17 2022-11-15 Shell Usa, Inc. Ultra-stable heavy hydrocarbon hydroprocessing catalyst and methods of making and use thereof
CN116020498A (zh) * 2021-10-27 2023-04-28 中国石油化工股份有限公司 加氢催化剂的制备方法、由该方法制备的催化剂及应用

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US4526675A (en) * 1983-05-26 1985-07-02 Standard Oil Company (Indiana) Hydrocarbon conversion method
US4846961A (en) * 1986-12-05 1989-07-11 Union Oil Company Of California Hydroprocessing catalyst with a Ni-P-Mo
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WO2002043862A3 (fr) * 2000-11-28 2003-02-13 Shell Oil Co Alumine possedant une nouvelle structure de pores, son procede d'elaboration et catalyseurs fabriques a base de cette alumine
KR100855411B1 (ko) * 2000-11-28 2008-08-29 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 새로운 세공 구조를 갖는 알루미나와 그 제조방법 및이로부터 제조된 촉매
US8883673B2 (en) 2006-08-03 2014-11-11 Shell Oil Company Catalyst and process for the manufacture of ultra-low sulfur distillate product
US8530373B2 (en) 2006-08-03 2013-09-10 Shell Oil Company Catalyst and process for the manufacture of ultra-low sulfur distillate product
US7820036B2 (en) 2006-08-03 2010-10-26 Shell Oil Company Highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
US7824541B2 (en) 2006-08-03 2010-11-02 Shell Oil Company Catalyst and process for the manufacture of ultra-low sulfur distillate product
US7871513B1 (en) 2006-08-03 2011-01-18 Shell Oil Company Highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
US9101918B2 (en) 2006-09-29 2015-08-11 Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg Catalyst with bimodal pore size distribution and the use thereof
WO2009022890A1 (fr) * 2007-08-07 2009-02-19 Instituto Mexicano Del Petroleo Catalyseur pour la première étape d'hydrodémétallisation dans un système d'hydrotraitement à l'aide de plusieurs réacteurs afin d'améliorer le pétrole lourd et extra-lourd
US8734634B2 (en) 2008-04-10 2014-05-27 Shell Oil Company Method for producing a crude product, method for preparing a diluted hydrocarbon composition, crude products, diluents and uses of such crude products and diluents
WO2009126973A3 (fr) * 2008-04-10 2010-10-07 Shell Oil Company Catalyseurs ayant des distributions sélectionnées de tailles des pores, procédé de préparation de tels catalyseurs, procédés de production d’un produit brut, produits obtenus par de tels procédés et utilisations des produits obtenus
US8450538B2 (en) 2008-04-10 2013-05-28 Shell Oil Company Hydrocarbon composition
US8912375B2 (en) 2008-09-10 2014-12-16 Haldor Topsoe A/S Hydroconversion process and catalyst
US11498060B2 (en) 2013-10-17 2022-11-15 Shell Usa, Inc. Ultra-stable heavy hydrocarbon hydroprocessing catalyst and methods of making and use thereof
CN104549329A (zh) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 加氢脱金属催化剂的制备方法
CN110773188A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773183A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773187A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773190A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773209A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种重油加氢脱沥青质催化剂及其制备与应用
CN110773179A (zh) * 2018-07-31 2020-02-11 中国石油化工股份有限公司 一种氧化铝载体及其制备方法
CN112547079A (zh) * 2019-09-25 2021-03-26 中国石油化工股份有限公司 一种重油加氢处理催化剂及其应用
CN116020498A (zh) * 2021-10-27 2023-04-28 中国石油化工股份有限公司 加氢催化剂的制备方法、由该方法制备的催化剂及应用

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WO2002032570A3 (fr) 2002-08-29
AR030905A1 (es) 2003-09-03
AU2002215374A1 (en) 2002-04-29

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