EP1240276A1 - Nouveaux catalyseurs de phosphures d'un metal de transition - Google Patents

Nouveaux catalyseurs de phosphures d'un metal de transition

Info

Publication number
EP1240276A1
EP1240276A1 EP00966987A EP00966987A EP1240276A1 EP 1240276 A1 EP1240276 A1 EP 1240276A1 EP 00966987 A EP00966987 A EP 00966987A EP 00966987 A EP00966987 A EP 00966987A EP 1240276 A1 EP1240276 A1 EP 1240276A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
support
ranges
group
metal
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.)
Ceased
Application number
EP00966987A
Other languages
German (de)
English (en)
Other versions
EP1240276A4 (fr
Inventor
Shigeo T. Oyama
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.)
IFP Energies Nouvelles IFPEN
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to EP09011715A priority Critical patent/EP2218502A3/fr
Publication of EP1240276A1 publication Critical patent/EP1240276A1/fr
Publication of EP1240276A4 publication Critical patent/EP1240276A4/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • 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
    • 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
    • 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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • 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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins 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
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/392—Metal surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation

Definitions

  • This invention pertains to a catalyst composition and a method for hydrotreating hydrocarbon feedstocks, and more particularly to hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrogenation (HYD).
  • HDS hydrodesulfurization
  • HDN hydrodenitrogenation
  • HEAD hydrogenation
  • Phosphorus has been used in combination with transition metals on supports for use in hydrotreating hydrocarbon feedstocks.
  • the phosphorus is in the form of an oxide (phosphate) usually incorporated as an additive.
  • oxide usually incorporated as an additive.
  • the phosphorus can have multiple roles. For example, it can stabilize the surface area of the support, prevent the formation of compounds such as cobalt or nickel aluminate, alter acid-base properties, or aid in the dispersion of the metals in the catalyst.
  • Several references have utilized phosphorus as an oxide component.
  • U.S. Patent Number 4,600,703 describes a catalyst composed of Mo, Ni, and phosphorus oxide deposited on an alumina support and calcined at 450-650 °C.
  • U.S. Patent Number 4,600,703 describes a catalyst composed of Mo, Ni, and phosphorus oxide deposited on an alumina support and calcined at 450-650 °C.
  • Patent Number 4,520,128 describes a catalyst composed of a group 6 metal, a group 8 metal, and phosphorus oxide on an alumina support and calcined at 400-600 °C.
  • U.S. Patent Number 4,687,568 describes a catalyst consisting of Ni sulfide supported on a Zr compound to which is added a compound containing P and O.
  • U.S. Patent Number 4,707,246 describes a catalyst containing either Mo, zinc titanate, either Ni or Co supported on alumina to which is added a compound containing P and O.
  • Patent Number 4,392,985 to a catalyst composed of Mo promoted with Co is added P in the form of orthophosphoric acid, and then calcined at a temperature of at least 750 °F (400 °C).
  • U.S. Patent Number 4,388,222 to a catalyst composed of Mo promoted with Ni or Co is added P in the form of phosphoric acid, and is then calcined.
  • U.S. Patent Number 4,632,914 Mo, W, Co and Ni are supported on bauxite and to this is added orthophosphoric acid followed by calcination between 300-600 °C.
  • Patent Number 4,689,314 describe a catalyst constituted of a group 6 metal, a group 8 metal and P in the form of phosphoric acid which is calcined at 400-550 °C.
  • 5,322,616 describe a catalyst comprising an alumina support, a group 8 metal oxide, a group 6 metal oxide, and phosphorus oxide.
  • the phosphorus is added to the alumina support to form an aluminum phosphate, and on this are added Co and Mo oxides.
  • U.S. Patent Number 3,755,148, U.S. Patent Number 3,755,150, and U.S. Patent Number 3,755,196 describe supported catalysts containing Mo, Ni or Co with P added as orthophosphoric acid.
  • Patent Number 4,738,945 describe a catalyst prepared by adding Ni and either Mo or ⁇ V with P to an alumina obtained by precipitation and calcining between 300-900 °C.
  • U.S. Patent Number 4,717,705 describes a catalyst prepared by adding Co and either Mo or W with P to an alumina obtained by precipitation and calcining between 300-900 °C. After the calcination step the metals are converted to sulfides by a separate sulfidation step for example at 250-330 °C as described in U.S. Patent Number 4,689,314 or by exposure to a feed containing sulfur. In no case are phosphides formed at the conditions of preparation.
  • the phosphorous component in standard catalysts is found in oxidized form, essentially a phosphate compound. This oxidation occurs as a result of calcination (high temperature treatment in air or oxygen).
  • the presence of phosphate in the standard catalysts is well established by nuclear magnetic resonance (NMR) and x-ray photoelectron spectroscopy (XPS) studies.
  • NMR nuclear magnetic resonance
  • XPS x-ray photoelectron spectroscopy
  • the present invention is directed to a catalyst where the phosphorous component is in reduced form, in the form of a phosphide highly dispersed on a high surface area support.
  • the formation of the phosphide on the support is a result of high temperature reduction during preparation of the catalyst.
  • Catalysts prepared in accordance with the present invention produce a highly dispersed catalyst in which the surface area of the metal component is enhanced.
  • An object of this invention is to provide a transition metal phosphide catalyst highly dispersed on a high surface area support.
  • Another object of the present invention is to provide a transition metal phosphide catalyst for hydrotreating hydrocarbon feedstocks.
  • an object of the present invention is to provide a catalyst material that that is easy to prepare through the reduction of phosphate, and that is easy to regenerate through reduction or by oxidation followed by reduction.
  • the present invention includes a catalyst comprising a metal phosphide complex having the formula MP X , where M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, and W, and where x ranges from about 0.1 to about 10; and a high surface area support, where the metal phosphide complex is dispersed on the high surface area support. Further, in a preferred embodiment, x may range from about 0.5 and about .>.
  • the high surface area support may be selected from the group consisting of carbon, silica, alumina, titania, thoria, magnesia, zirconia, kaolin, bentonite, kieselguhr, zeolites, and combinations thereof.
  • the metal phosphide complex may be supported on the high surface area support in the range from about 1 to about 40% by weight of complex to support and preferably in the range from about 10 to about 30% by weight of complex to support.
  • the invention further includes a metal phosphide catalyst comprising a metal phosphide complex having the formula A a B b P y , where A and B are each selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, and W, where the sum of a and b is 1, the ratio of a to b is between about 0.01 and about 100, and y is between about 0.1 and about 10.
  • the ratio of a to b may range from about 0.1 to about 10. Further, the ratio of a to b may preferably range from about 0.2 and 5. Further, y may preferably range from about 0.5 and about 3.
  • the metal phosphide complex is dispersed on the high surface area support.
  • the present invention more generally includes a metal catalyst comprising at least one metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, and W, wherein at least a portion of the one metal is in the form of a phosphide; and a high surface area support wherein the at least one metal and said phosphide are highly dispersed on said high surface area support.
  • the catalysts of the present invention may also include a promoter selected from the group consisting of the alkali metals, alkaline earth metals, platinum group metals, rhenium, copper, halides, boron, carbon, nitrogen, aluminum, sulfur, gallium, germanium, arsenic, tin, antimony, bismuth, selenium and tellurium.
  • a promoter selected from the group consisting of the alkali metals, alkaline earth metals, platinum group metals, rhenium, copper, halides, boron, carbon, nitrogen, aluminum, sulfur, gallium, germanium, arsenic, tin, antimony, bismuth, selenium and tellurium.
  • the invention includes a method for hydrotreating a hydrocarbon feed comprising the step of exposing the hydrocarbon feed to a catalyst in an atmosphere containing hydrogen, where the catalyst comprises at least one metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, and W, wherein at least a portion of the one metal is in the form of a phosphide; and a high surface area support wherein the at least one metal and said phosphide are dispersed on said high surface area support.
  • the phosphide may have the formula MP X , where M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, and W, and where x ranges from about 0.1 and about 10. Further, x may preferably range from about 0.5 and about 3.
  • the phosphide may have the formula A a B b P y , where A and B are each selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, and W, wherein the sum of a and b is 1, the ratio of a to b ranges from about 0.01 to about 100, and y ranges from about 0.1 and about 10.
  • the ratio of a to b may preferably range from about 0.1 to about 10. Further, the ratio of a to b may preferably range from about 0.2 to 5, and y may preferably range from about 0.5 to about 3.
  • the invention includes a method of hydrotreating a hydrocarbon feed where the step of exposing the hydrocarbon feed to a catalyst is sufficient to remove nitrogen from the hydrocarbon feed.
  • the invention includes a method of hydrotreating a hydrocarbon feed where the step of exposing the hydrocarbon feed to a catalyst is sufficient to remove oxygen from the hydrocarbon feed.
  • the invention includes a method of hydrotreating a hydrocarbon feed where the step of exposing the hydrocarbon feed to a catalyst is sufficient to hydrogenate an unsaturated organic compound in the hydrocarbon feed.
  • the invention includes a method of hydrotreating a hydrocarbon feed where the step of exposing the hydrocarbon feed to a catalyst is sufficient to hydroisomerize an organic compound in the hydrocarbon feed.
  • the method of the present invention may include a hydrocarbon feed selected from the group consisting of middle distillates, kero, naptha, gas oil obtained by catalytic cracking, gas oil obtained by thermal cracking, straight-run gas oil, coker gas oil, vacuum gas oils, heavy gas oils, coal liquids, feeds extracted from tar sands, and feeds extracted from shale.
  • a hydrocarbon feed selected from the group consisting of middle distillates, kero, naptha, gas oil obtained by catalytic cracking, gas oil obtained by thermal cracking, straight-run gas oil, coker gas oil, vacuum gas oils, heavy gas oils, coal liquids, feeds extracted from tar sands, and feeds extracted from shale.
  • the method may include the step of processing the hydrocarbon feed in the presence of the catalyst at a temperature ranging from about 250 to about 450 °C, pressure ranging from about 5 to about 250 bar, space velocities ranging from about 0.1 to about 10 hr "1 , and H 2 /feed ratios ranging from about 1000 to about 15000 scf/barrel.
  • the invention includes a method for hydrodesulfurizing a hydrocarbon feed wherein the feed contains sulfur compounds that include sterically hindered, alkyl substituted heteroaromatic condensed rings.
  • the hydrodesulfurization process consists of exposing the hydrocarbon feed to a catalyst, wherein the catalyst comprises at least one metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, and W, wherein at least a portion of the one metal is in the form of a phosphide; and a high surface area support wherein the at least one metal and said phosphide are dispersed on said high surface area support.
  • the phosphide may have the formula MP X , where M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, and W, and where x ranges from about 0.1 and about 10. Further, x may preferably range from about 0.5 and about 3.
  • the phosphide may have the formula A a B b P y , where A and B are each selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo. Ta. and W, wherein the sum of a and b is 1, the ratio of a to b ranges from about 0.01 to about 100, and y ranges from about 0.1 and about 10.
  • the ratio of a to b may preferably range from about 0.1 to about 10. Further, the ratio of a to b may preferably range from about 0.2 to 5, and y may preferably range from about 0.5 to about 3.
  • Figure 1 shows X-ray diffraction patterns of fresh and spent 23 wt% MoP/Al 2 O 3 .
  • Figure 2 shows X-ray diffraction patterns of fresh and spent MoP/SiO .
  • Figure 3 shows X-ray diffraction patterns of fresh and spent WP/SiO 2 .
  • Figure 4 shows X-ray diffraction patterns of fresh and spent 8.6 wt% Ni 2 P/SiO 2 .
  • Figure 5 shows X-ray diffraction patterns of fresh and spent CoP/SiO 2 .
  • Figure 6 shows X-ray diffraction patterns of fresh and spent Fe P/SiO 2 .
  • Figure 7 shows X-ray diffraction patterns of NiMoP .
  • Figure 8 shows the reactivity of phosphides in hydroprocessing.
  • Figure 9 shows the X-ray diffraction patterns of WP before and after reaction.
  • Figure 10 shows a comparison of conversion of 4,6-dimethyldibenzothiophene.
  • the present invention is directed to a catalyst composition and a method for hydrotreating hydrocarbon feedstocks, more particularly hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeoxygenation, hydroisomerization, and hydrogenation (HYD).
  • the invention further relates to processes for the preparation and use of a catalyst composition.
  • hydrotreating refers to the removal of sulfur (HDS) and nitrogen (HDN) from hydrocarbon feedstocks.
  • HDS sulfur
  • HDN nitrogen
  • the removal of these components is important for producing clean burning fuels.
  • it is essential to remove these elements, since the catalysts used in subsequent processing, like cracking, hydrocracking, and reforming, are poisoned by the sulfur and nitrogen.
  • the present invention provides new types of catalysts for hydrotreating hydrocarbon feedstocks.
  • the catalysts are supported transition metal phosphides, a class of material in which the phosphorus forms a chemical compound with the metal component.
  • the metal source can be quite diverse and includes the ammonium salts, chlorides, nitrates, hydroxides, heteropoly compounds and other species.
  • the transition metals that may be used in the catalyst of the present invention includes, but is not limited to, Mo, W, Fe, Co, Ni, V, Nb, Cr, Mn, Ta, and other suitable transition metals.
  • the catalyst may be prepared according to the formula MP X where M is a metal and x may range from about 0.1 to about 10. Preferably x ranges from about 0.5 to about 3.
  • the metals may be combined in various ratios to form multimetallic phosphides according to the formula A a B b P y where A and B are metals and where the sum of a and b is 1, the ratio of a to b ranges from about 0.01 to about 100, and y ranges from about 0.1 to about 10.
  • the ratio of a to b ranges from about 0.1 to about 10 and most preferably the ratio of a to b ranges from about 0.2 to 5.
  • y preferably ranges from about 0.5 to about 3.
  • Mixed metal compositions can give rise to diverse substances with potentially very unique properties such as activity, or selectivity for the hydrotreating reactions.
  • the mixed metal composition includes Mo a C ⁇ bP y , Mo a Nb b Py, W a Ni b P y , and the like. It will be evident to those skilled in the art that a wide variety of multimetallic phosphides can be prepared where the catalyst contains three or more metal elements.
  • the phosphorus source can be similarly diverse, and includes phosphoric acid, phosphorous acid, and the various ammonium hydrogen phosphates.
  • the relative amounts of phosphorus (P) and metal (M) are given by molar percentages of 50 to 300 mol% which correspond to stoichiometries of MP 0.5 to MP .
  • the catalysts are in supported form, where the active metal phosphide is present on the support as either small particles or as a surface phase.
  • the metal phosphide may
  • the support be present on the support as particles ranging from lnm to about lO ⁇ m in size.
  • the metal phosphide is loaded on the support in the range from about 1 to about 40% by weight metal phosphide to support.
  • the metal phosphide is loaded on the support in the range of about 10 to about 30% by weight metal phosphide to support.
  • "high surface area support” is a support preferably having a surface area of at least about 50 m 2 /g.
  • the support has a surface area of at least about 100 m : /g (BET method) and a pore volume in the range of 0.25-1.3 cm 3 /g (mercury penetration method).
  • the supports include, but are not limited to, substances like silica, alumina, titania, thoria, magnesia, zirconia, kaolin, bentonite, kieselguhr, zeolites, carbon, other high surface area supports, and combinations thereof. Preference is given to alumina or silica or combinations thereof.
  • a preferred method of preparation for the catalysts involves the reduction of precursor phosphates in a stream of hydrogen.
  • One suitable method of preparing the catalyst is impregnating the supports with solutions of the metal and phosphorus components, and optionally drying at 25-200 °C and calcining in air or oxygen in the range of 350-750 °C so as to intimately mix the components.
  • the resulting material is then reduced in a hydrogen stream at temperatures between 300 °C and 1000 °C, preferably 400-700 °C.
  • the catalyst can be used as such by exposure to the desired feed. If the catalyst needs to be transported to another site it can be passivated in a stream of oxygen in an inert gas which can start at low concentrations (0.1%) and gradually go up (21%).
  • the catalyst treated in this manner can undergo re- reduction in hydrogen at temperatures from 300-700 °C, or be activated by direct contact with the feed.
  • the catalyst is typically formed as spheres or extrudates, which include symmetrical and asymmetrical polylobed particles.
  • alkali metals alkaline earth metals
  • platinum group metals platinum group metals
  • rhenium copper
  • halides as well as main group elements like boron, carbon, nitrogen, aluminum, sulfur, gallium germanium, arsenic, tin, antimony, bismuth, selenium and tellurium.
  • the catalysts of the present invention have high activity for hydrodesulfurization and hydrodenitrogenation of hydrocarbon feedstocks.
  • the activity based on an equivalent surface area, is higher than that of a commercial catalyst studied at the same conditions.
  • the conditions are typical of industrial processes and involve high temperature and pressure.
  • the catalyst of the present invention show high stability with no deactivation over a hundred hours of reaction time.
  • the present catalysts can be used in the hydrotreating of a wide variety of feeds. These include, but are not limited to middle distillates, kero, naptha, gas oil obtained by catalytic cracking, gas oil obtained by thermal cracking, straight-run gas oil, coker gas oil, vacuum gas oils, heavy gas oils, coal liquids, and feeds extracted from tar sands or shale.
  • the conventional process conditions are temperatures in the range of 250-450 °C, pressures in the range of 5-250 bar, space velocities in the range of 0.1-10 hr " , and H 2 /oil ratios in the range of 1000- 15000 scf/barrel.
  • Example 2 Preparation and characterization of MoP/SiO 2
  • the catalyst was prepared in the same manner as in example 1, except that the support used was SiO 2 (Cabosil L90).
  • the physical properties are listed in Table II and the x-ray diffraction patterns of the material are shown in Figure 2.
  • the XRD patterns of the supported catalysts show a large broad feature at 20°, but otherwise the pattern corresponds to that of MoP as shown by the reference. Table II. Physical characteristics of MoP/SiO catalysts
  • Example 3 Preparation and characterization of WP/SiO 2
  • the catalyst was prepared in the same manner as in example 1, except that the precursor used was ammonium paratungstate (Aldrich, 95%), and the support used was SiO 2 (Cabosil L90).
  • the physical properties are shown in Table III below and the x-ray diffraction pattern of the material is shown in Figure 3.
  • the XRD pattern of the supported catalysts show a large broad feature at 20 °, but otherwise the pattern corresponds to that of WP as shown by the reference spectrum from the powder diffraction files (pdf 29-1364). Table III. Physical characteristics of WP/SiO: catalysts
  • Ni P/SiO 2 Preparation and characterization of Ni P/SiO 2
  • ammonium phosphate Aldrich, 99%
  • nickel nitrate Aldrich, 19.8% Ni
  • An excess of phosphorus was used, so that molar ratios of Ni:P of 1 :1 and 1 :2 were used, corresponding to weight percents of 9.4 and 12.2%.
  • a precipitate formed which was dissolved by the addition of a few drops of nitric acid (Fisher, 69.4% assay). Water was added to form enough solution to carryout an incipient wetness impregnation of a silica (Cabosil L90) support.
  • Example 5 Preparation and characterization of CoP/SiO 2
  • the catalyst was prepared in the same manner as in example 4, except that the precursor was cobalt nitrate (Aldrich, 99%) and no nitric acid was needed to form a solution. Equimolar quantities of Co and P were used. The final temperature reduction was 690 °C.
  • the physical properties are listed in Table V below and the x-ray diffraction pattern of the material is shown in Figure 5. Table V. Physical characteristics of CoP/SiO catalysts
  • Example 8 Hydrotreating activities of MoP/Al 2 O 3 catalysts Hydrotreating of a model petroleum liquid consisting of quinoline (Aldrich, 99%), benzofuran (Adrich, 99%), dibenzothiophene (Aldrich, 99%), tetralin (Aldrich, 99%), and tetradecane (Fisher, 99%), was carried out in a pressurized three-phase trickle bed reactor. Analysis was performed with a gas chromatograph (Hewlett Packard, 5890A) on liquid product collected at 2-3 hours intervals. An amount of catalyst corresponding to
  • Example 9 Hydrotreating activities of MoP/SiO 2 , WP/SiO 2 , Ni 2 P/SiO 2 , CoP/SiO 2 , Fe 2 P/SiO 2 , and NiMoP 2 /SiO 2 catalysts
  • Example 10 The catalysts were tested for HDN, HDS, and hydrogenation (HYD) activity in a trickle bed reactor operated at 643 K (370 °C) and 3.1 Mpa (450 psig). These are standard conditions typically used in an industrial hydroprocessing unit.
  • the reactant feed consisted of quinoline (2000 ppm N), dibenzothiopene (3000 ppm S), tetralin (20 wt.%), and tetradecane (balance). An amount corresponding to 30 m 2 of catalyst was loaded in the reactor.
  • the overall activity of the phosphides was superior to or comparable to that of the sulfide. Also very attractive was the fact that the phosphides showed lower hydrogenation activity than the sulfide, indicating a more effective use of hydrogen, and no cracking.
  • Example 11 A pressing problem in hydrotreating is the removal of sulfur from refractory compounds like alkyl substituted dibenzothiophenes. This is the problem of deep HDS.
  • the conditions were the same as in Example 7 except that the feed contained 4,6-dimethyldibenzothiophene (500 ppm S), quinoline (200 ppm N), and the solvent was hexadecane.
  • the phosphide catalysts tested were Ni 2 P/SiO 2 and NiMoP 2 /SiO 2 . Comparison was made to a highly optimized commercial Ni-Mo-S/Al 2 O 3 catalyst (Criterion 424) which was sulfided in situ at 400 °C in 10% H 2 S H 2 before use. The conversions obtained in HDS are shown in Figure 10. The comparison is on the
  • the Ni 2 P catalyst has higher activity than the commercial catalyst. It will be readily understood by those persons skilled in the art that the present invention is susceptible to broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements, will be apparent from or reasonably suggested by the present invention and the foregoing description without departing from the substance or scope of the present invention.

Landscapes

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

Abstract

L'invention concerne un catalyseur de phosphures d'un métal de transition qui est actif pour hydrogéner des produits de départ d'hydrocarbures. Le catalyseur comprend un complexe de phosphures du métal de transition porté sur un support à zone superficielle élevée. Ledit support peut être sélectionné à partir du groupe renfermant du carbone, de la silice, de l'alumine, du dioxyde de titane, de la thorine, de la magnésie, de la zircone, du kaolin, de la bentonite, du kieselguhr, des permutites et des combinaisons correspondantes. Le complexe de phosphures du métal de transition peut comprendre un complexe de phosphures du métal mélangé. Le catalyseur renferme un complexe de phosphures du métal de formule MPx, où M est sélectionné parmi le groupe contenant V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, et W, et où x est compris entre environ 0,1 et 10, et un support d'oxyde, où le complexe de phosphures est dispersé sur le support à zone superficielle élevée. En outre, le catalyseur contient un catalyseur de phosphures de métal renfermant un complexe de phosphures de métal de formule AaBbPy, où A et B sont sélectionnés respectivement à partir du groupe contenant V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta, et W, où la somme de a et b est égale à 1, le taux de a par rapport à b est compris entre environ 0,01 et 100, et y est compris entre environ 0,1 et 10, et un support d'oxyde où le complexe de phosphures de métal est dispersé sur le support à zone superficielle élevée. Par ailleurs, cette invention a trait à un procédé d'hydrogénation d'une charge d'hydrocarbures au moyen d'un catalyseur de phosphures de métal de transition, ainsi qu'à un procédé d'hydrodésulfurisation, notamment d'hydrodésulfurisation profonde à l'aide des catalyseurs susmentionnés.
EP00966987A 1999-09-30 2000-09-28 Nouveaux catalyseurs de phosphures d'un metal de transition Ceased EP1240276A4 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09011715A EP2218502A3 (fr) 1999-09-30 2000-09-28 Catalyseurs de phosphures d'un métal de transition

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US15670199P 1999-09-30 1999-09-30
US156701P 1999-09-30
PCT/US2000/026603 WO2001023501A1 (fr) 1999-09-30 2000-09-28 Nouveaux catalyseurs de phosphures d'un metal de transition

Publications (2)

Publication Number Publication Date
EP1240276A1 true EP1240276A1 (fr) 2002-09-18
EP1240276A4 EP1240276A4 (fr) 2003-07-02

Family

ID=22560684

Family Applications (2)

Application Number Title Priority Date Filing Date
EP09011715A Withdrawn EP2218502A3 (fr) 1999-09-30 2000-09-28 Catalyseurs de phosphures d'un métal de transition
EP00966987A Ceased EP1240276A4 (fr) 1999-09-30 2000-09-28 Nouveaux catalyseurs de phosphures d'un metal de transition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP09011715A Withdrawn EP2218502A3 (fr) 1999-09-30 2000-09-28 Catalyseurs de phosphures d'un métal de transition

Country Status (3)

Country Link
EP (2) EP2218502A3 (fr)
AU (1) AU7725200A (fr)
WO (1) WO2001023501A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112609205A (zh) * 2020-11-30 2021-04-06 陕西科技大学 一种氮掺杂碳纤维负载锆诱导的过渡金属磷化物及制备方法

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7446075B1 (en) 2005-08-23 2008-11-04 Uop Llc Transition metal phosphides and hydrotreating process using the same
DE112007002462T5 (de) * 2006-10-18 2009-09-10 BDF IP Holdings Ltd., Vancouver Katalysatorträger für eine Brennstoffzelle
US20080099375A1 (en) * 2006-10-30 2008-05-01 Exxonmobil Research And Engineering Company Process for adsorption of sulfur compounds from hydrocarbon streams
CN101380586B (zh) * 2007-09-07 2011-08-03 中国科学院大连化学物理研究所 一种双组分磷化物肼分解催化剂及其制备和应用
US7935248B2 (en) * 2007-10-30 2011-05-03 The University Of New Brunswick Adsorbents for denitrogenation desulfurization of hydrocarbon oils and methods of producing
US8574337B2 (en) 2008-06-18 2013-11-05 Board Of Trustees Of The University Of Arkansas Renewable resource-based metal-containing materials and applications of the same
US8920688B2 (en) * 2008-06-18 2014-12-30 Board Of Trustees Of The University Of Arkansas Microwave-assisted synthesis of transition metal phosphide
US9095837B2 (en) 2008-06-18 2015-08-04 Broad of Trustees of the University of Arkansas Renewable resource-based metal oxide-containing materials and applications of the same
US8753603B2 (en) 2008-06-18 2014-06-17 Board Of Trustees Of The University Of Arkansas Microwave-assisted synthesis of carbon nanotubes from tannin, lignin, and derivatives
KR101192930B1 (ko) * 2009-04-01 2012-10-18 에스케이에너지 주식회사 바이오 디젤 제조용 금속 인 화합물 촉매 및 이를 이용한 바이오 디젤 제조방법
WO2011099686A1 (fr) 2010-02-11 2011-08-18 Sk Innovation Co., Ltd. Catalyseur pour la production de biodiesel hydrogéné (hbd) et son procédé de production
CN102631941B (zh) * 2012-03-07 2014-04-16 中国科学院山西煤炭化学研究所 一种合成乙醇的催化剂及制法和应用
CN102585876A (zh) * 2012-03-07 2012-07-18 天津大学 以金属磷化物催化剂由高级脂肪酸酯制烃的方法
US8877153B2 (en) 2012-06-06 2014-11-04 Exxonmobil Research And Engineering Company Adsorbent for ultradeep removal of sulfur compounds from distillate fuels
CN103521249B (zh) * 2012-07-05 2016-08-24 中国科学院大连化学物理研究所 一种用于合成气转化的磷化物催化剂和制备方法及其应用
CN102887809A (zh) * 2012-10-17 2013-01-23 天津大学 以负载型磷化镍催化剂正构烷烃加氢异构化的方法
CN104152171B (zh) * 2014-07-24 2015-11-18 大连理工大学 一种催化木质素衍生芳醚制备烷烃液体燃料的方法
CN104275202B (zh) * 2014-10-09 2017-02-15 山东华星石油化工集团有限公司 一种负载型柴油加氢处理催化剂及其应用
CN105642324B (zh) * 2014-12-04 2018-04-10 中国石油化工股份有限公司 一种非贵金属选择性加氢催化剂及其制备方法和应用
JP6302424B2 (ja) * 2015-03-10 2018-03-28 日本電信電話株式会社 リチウム空気二次電池
US9636664B1 (en) 2015-06-04 2017-05-02 Alliance For Sustainable Energy, Llc Metal phosphide catalysts and methods for making the same and uses thereof
CN105251521B (zh) * 2015-11-19 2017-12-15 中科合成油淮南催化剂有限公司 负载型过渡金属磷化物催化剂及其制备方法与应用
GB201607540D0 (en) * 2016-04-29 2016-06-15 Scg Chemicals Co Ltd And Scg Packaging Public Company Ltd Hydrcarbon production process
RU2637117C1 (ru) * 2016-11-03 2017-11-30 Федеральное государственное автономное образовательное учреждение высшего образования "Новосибирский национальный исследовательский государственный университет" (Новосибирский государственный университет, НГУ) Способ приготовления катализатора гидродеоксигенации алифатических кислородсодержащих соединений
CN108212184A (zh) * 2016-12-22 2018-06-29 中国石油天然气股份有限公司 烷烃异构化催化剂及其制备方法
CN106748613B (zh) * 2017-01-19 2019-10-22 黑龙江大学 一种负载型晶态磷化镍催化剂上正十六烷加氢异构化反应的方法
CN109722333B (zh) * 2017-10-27 2021-10-08 中国石油化工股份有限公司 提高废润滑油再生装置运转周期的方法
JP7421177B2 (ja) * 2019-01-30 2024-01-24 国立大学法人大阪大学 水素化触媒およびこれを用いた水素化有機化合物の製造方法
CN111822036B (zh) * 2019-04-15 2023-04-07 中国石油化工股份有限公司 加氢裂化催化剂及其制备方法
US11982006B2 (en) 2019-07-22 2024-05-14 King Fahd University Of Petroleum And Minerals Transition metal phosphide supported on carbon nanosheets
RU2744504C1 (ru) * 2020-07-27 2021-03-10 Федеральное государственное бюджетное учреждение науки «Федеральный исследовательский центр «Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук» (ИК СО РАН) Способ приготовления катализатора гидроочистки сырья каталитического крекинга
RU2744503C1 (ru) * 2020-07-27 2021-03-10 Федеральное государственное бюджетное учреждение науки «Федеральный исследовательский центр «Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук» (ИК СО РАН) Катализатор гидроочистки сырья каталитического крекинга
CN112742422B (zh) * 2021-01-20 2022-05-13 烟台大学 一种负载型催化剂及其在喹啉类化合物选择加氢中的应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617528A (en) * 1969-10-16 1971-11-02 Universal Oil Prod Co Hydrotreating process and catalyst
US5763721A (en) * 1996-12-12 1998-06-09 Phillips Petroleum Company Hydrodealkylation of C9+ aromatic compounds
US5834522A (en) * 1994-04-01 1998-11-10 Institut Francais Du Petrole Hydroisomerization treatment process for feeds from the fisher-tropsch process

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3224831A (en) * 1961-07-12 1965-12-21 Ethyl Corp Method of treating engine exhaust gas with an oxidation catalyst containing platinum and phosphorus
US3755148A (en) 1971-04-01 1973-08-28 Union Oil Co Hydrocarbon hydrogenation
US3755196A (en) 1971-04-01 1973-08-28 Union Oil Co Hydrotreating catalyst
US4003828A (en) 1975-07-23 1977-01-18 Exxon Research And Engineering Company Catalyst and process for removing sulfur and metal contaminants from hydrocarbon feedstocks
US4388222A (en) 1976-03-29 1983-06-14 Filtrol Corporation Ni/Co Mo P On titania-alumina hydrodesulfurizing catalyst
US4359406A (en) * 1977-06-17 1982-11-16 Exxon Research And Engineering Co. Highly dispersed supported group VIII metal-phosphorus compounds, and highly dispersed, supported group VIII metal-arsenic and a process for making said compounds
US4454246A (en) * 1977-06-17 1984-06-12 Exxon Research And Engineering Co. Highly dispersed supported group VIII noble metal phosphorus compounds
US4367137A (en) * 1980-12-04 1983-01-04 Uop Inc. Hydrocarbon conversion with an acidic multimetallic catalytic composite
US4392985A (en) 1981-07-27 1983-07-12 Union Oil Company Of California Hydrocarbon conversion catalyst and method of preparation
US4632914A (en) 1982-06-29 1986-12-30 Intevep, S.A. Method of preparing a hydrocracking catalyst
US4520128A (en) 1983-12-19 1985-05-28 Intevep, S.A. Catalyst having high metal retention capacity and good stability for use in the demetallization of heavy crudes and method of preparation of same
US4600703A (en) 1983-12-19 1986-07-15 Intevep, S.A. Catalyst for the hydrocracking of heavy vacuum gas oils, method of preparation of catalyst and process for use thereof in the mild hydrocracking of heavy vacuum gas oils
US4743574A (en) 1986-01-09 1988-05-10 Intevep, S.A. Catalyst for hydrotreatment of distillates of petroleum and method for the preparation of same
US4689314A (en) 1986-05-05 1987-08-25 Intevep, S.A. Method of preparation of mild hydrocracking catalyst for the production of middle distillates
US4687568A (en) 1986-09-19 1987-08-18 Phillips Petroleum Company Catalytic hydrofining of oil
US4716141A (en) 1986-10-28 1987-12-29 Shell Oil Company Hydrotreating catalysts prepared from hydrogels
US4717705A (en) 1986-10-28 1988-01-05 Shell Oil Company Hydrotreating catalysts prepared from hydrogels
US4707246A (en) 1986-11-14 1987-11-17 Phillips Petroleum Company Hydrotreating catalyst and process
US4941964A (en) 1988-03-14 1990-07-17 Texaco Inc. Hydrotreatment process employing catalyst with specified pore size distribution
US5462651A (en) 1994-08-09 1995-10-31 Texaco Inc. Hydrodearomatization of hydrocarbon oils using novel "phosphorus treated carbon" supported metal sulfide catalysts

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617528A (en) * 1969-10-16 1971-11-02 Universal Oil Prod Co Hydrotreating process and catalyst
US5834522A (en) * 1994-04-01 1998-11-10 Institut Francais Du Petrole Hydroisomerization treatment process for feeds from the fisher-tropsch process
US5763721A (en) * 1996-12-12 1998-06-09 Phillips Petroleum Company Hydrodealkylation of C9+ aromatic compounds

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
F. NOZAKI, R. ADACHI: "Chemical Composition of the Catalyst Prepared by Reduction of Nickel Orthophosphate in Hydrogen and Catalytic Activity for Partial Hydrogenation of 1,3-Butadiene" JOURNAL OF CATALYSIS, vol. 40, 1975, pages 166-172, XP009009980 *
J. GOPALAKRISHNAN, SONAL PANDEY, AND K. KASTHURI RANGAN: "Convenient Route for the Synthesis of Transition-Metal Pnictides by Direct Reduction of Phosphate, Arsenate, and Antimonate Precursors" CHEMISTRY OF MATERIALS, vol. 9, no. 10, 1997, pages 2113-2116, XP007908073 *
J. P. CARPENTER ET AL: J ORGANOMETALLIC CHEM, vol. 557, 1998, pages 121-130, XP004122372 *
LI W, DHANDAPANI B, OYAMA S T: "MOLYBDENUM PHOSPHIDE: A NOVEL CATALYST FOR HYDRODENITROGENATION" CHEMISTRY LETTERS, CHEMICAL SOCIETY OF JAPAN. TOKYO, JP, vol. 27, no. 3, 1998, pages 207-208, XP009010252 ISSN: 0366-7022 *
NOZAKI F, TOKUMI M: "Hydrogenation activity of metal phosphides and promoting effect of oxygen" JOURNAL OF CATALYSIS, ACADEMIC PRESS, NEW YORK, NY, US, vol. 79, 1983, pages 207-210, XP009009979 ISSN: 0021-9517 *
ROBINSON W.R.A.M. ET AL: "Phosphorus promotion of Ni (Co)-containing Mo-free catalysts in quinoline hydrodenitrogenation" JOURNAL OF CATALYSIS, ACADEMIC PRESS, vol. 161, 1996, pages 539-550, XP001147827 ISSN: 0021-9517 *
See also references of WO0123501A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112609205A (zh) * 2020-11-30 2021-04-06 陕西科技大学 一种氮掺杂碳纤维负载锆诱导的过渡金属磷化物及制备方法

Also Published As

Publication number Publication date
EP2218502A2 (fr) 2010-08-18
EP2218502A3 (fr) 2010-09-22
AU7725200A (en) 2001-04-30
EP1240276A4 (fr) 2003-07-02
WO2001023501A1 (fr) 2001-04-05

Similar Documents

Publication Publication Date Title
EP2218502A2 (fr) Catalyseurs de phosphures d'un métal de transition
CA2560925C (fr) Catalyseur pour le traitement d'hydrogeneration des hydrocarbures liquides, processus de production connexe et methode de traitement d'hydrogeneration des hydrocarbures
CA2509847C (fr) Catalyseur d'hydrotraitement pour carburant diesel, procede de production de ce catalyseur et procede d'hydrotraitement de carburant diesel
JP4156859B2 (ja) 軽油の水素化処理触媒及びその製造方法並びに軽油の水素化処理方法
JP5033631B2 (ja) 有機剤を含む前駆体から作製されるバルクＮｉ−Ｍｏ−Ｗ触媒
JP5039256B2 (ja) 低硫黄かつ低窒素の水素化分解生成物の製造方法
CA2470393C (fr) Catalyseur d'extraction d'arsenic et procede de fabrication de ce catalyseur
US10406509B2 (en) Nanoscale nickel phosphide catalysts for hydrotreatment
JP5060044B2 (ja) 炭化水素油の水素化処理触媒およびその製造方法、並びに炭化水素油の水素化処理方法
EP3065867B1 (fr) Procédé de préparation d'un catalyseur d'hydrotraitement
JPH08259960A (ja) 亜鉛により活性化された炭素担持金属硫化物触媒を使用する炭化水素油の水素化脱芳香族法
JPS6197036A (ja) シリカに支持された水素化処理触媒の製造方法および該製造方法により得られる解媒
JP4954095B2 (ja) 軽油の水素化処理触媒及びその製造方法並びに軽油の水素化処理方法
KR101976224B1 (ko) 수소화처리 촉매 및 이러한 촉매의 제조 방법 및 사용 방법
WO2012156294A1 (fr) Catalyseur d'hydrotraitement comprenant un composé de siliciure d'un métal du groupe viii et/ou du groupe vib
US20020037806A1 (en) Ex-situ presulfuration in the presence of a hydrocarbon molecule
US20230095045A1 (en) Low pressure hydroprocessing catalyst
JP2001062304A (ja) 軽油の水素化脱硫触媒の製造方法及び軽油の水素化処理方法
JP2023017723A (ja) クラストとしての活性相分布を有する水素化脱硫触媒
JPH07178B2 (ja) 炭化水素の水素化処理用触媒の製造方法
MXPA97001701A (en) Catalyst for hydrodesintegration of residual fractions of oil and procedure for its preparation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020423

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL PAYMENT 20020423;LT PAYMENT 20020423;LV PAYMENT 20020423;MK PAYMENT 20020423;RO PAYMENT 20020423;SI PAYMENT 20020423

RIC1 Information provided on ipc code assigned before grant

Ipc: 7B 01J 21/18 B

Ipc: 7B 01J 27/02 B

Ipc: 7B 01J 21/04 B

Ipc: 7B 01J 21/16 B

Ipc: 7B 01J 27/045 B

Ipc: 7B 01J 21/10 B

Ipc: 7C 10G 45/04 B

Ipc: 7B 01J 21/08 B

Ipc: 7B 01J 21/02 A

Ipc: 7B 01J 21/06 B

A4 Supplementary search report drawn up and despatched

Effective date: 20030519

17Q First examination report despatched

Effective date: 20041021

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: IFP

RIN1 Information on inventor provided before grant (corrected)

Inventor name: IFP

APBK Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNE

APBN Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2E

APBR Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3E

APAF Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: IFP ENERGIES NOUVELLES

RIN1 Information on inventor provided before grant (corrected)

Inventor name: IFP ENERGIES NOUVELLES

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

APBT Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9E

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20130122