US20050113250A1 - Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams - Google Patents

Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams Download PDF

Info

Publication number
US20050113250A1
US20050113250A1 US10/949,513 US94951304A US2005113250A1 US 20050113250 A1 US20050113250 A1 US 20050113250A1 US 94951304 A US94951304 A US 94951304A US 2005113250 A1 US2005113250 A1 US 2005113250A1
Authority
US
United States
Prior art keywords
catalyst
hydrotreating
catalyst system
metal
stacked bed
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.)
Abandoned
Application number
US10/949,513
Other languages
English (en)
Inventor
Gary Schleicher
Kenneth Riley
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.)
ExxonMobil Technology and Engineering Co
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 US10/949,513 priority Critical patent/US20050113250A1/en
Assigned to EXXONMOBIL RESEARCH & ENGINEERING CO. reassignment EXXONMOBIL RESEARCH & ENGINEERING CO. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RILEY, KENNETH L., SCHLEICHER, GARY P.
Publication of US20050113250A1 publication Critical patent/US20050113250A1/en
Priority to US12/384,076 priority patent/US7816299B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of 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
    • 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
    • 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
    • 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
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also 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
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/002—Apparatus for fixed bed hydrotreatment processes
    • 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
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1062—Lubricating oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1074—Vacuum distillates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/302—Viscosity
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • This invention relates to a hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams. More particularly, the present invention is directed at a stacked bed catalyst system comprising at least one first catalyst selected from conventional hydrotreating catalyst having an average pore diameter of greater than about 10 nm and at least one second catalyst comprising a bulk metal hydrotreating catalyst.
  • the American Petroleum Institute (API) requirements for Group II basestocks include a saturates content of at least 90%, a sulfur content of 0.03 wt. % or less and a viscosity index (VI) between 80 and 120.
  • API American Petroleum Institute
  • the Figure is a plot of the relative volume activity of various catalysts and catalyst systems versus the days the respective catalysts and catalyst systems were on stream.
  • the present invention is directed at a stacked bed catalyst system suitable for use in the hydrotreating of hydrocarbonaceous feedstocks.
  • the catalyst system comprises:
  • feedstock and “feedstream” as used herein are synonymous.
  • the present invention is directed at a stacked bed catalyst system suitable for use in the hydrotreating of hydrocarbonaceous feedstocks.
  • the catalyst system comprises at least one first catalyst selected from conventional hydrotreating catalysts having an average pore diameter of greater than about 10 nm and at least one second catalyst selected from bulk metal hydrotreating catalysts.
  • the stacked bed hydrotreating catalyst system is suitable for use in the hydrotreating of hydrocarbonaceous feedstocks.
  • the present invention is a stacked bed catalyst system comprising at least a first and second hydrotreating catalyst.
  • stacked bed it is meant that the first catalyst appears in a separate catalyst bed, reactor, or reaction zone, and the second hydrotreating catalyst appears in a separate catalyst bed, reactor, or reaction zone downstream, in relation to the flow of the lubricating oil feedstock, from the first catalyst.
  • the first hydrotreating catalyst is a supported catalyst.
  • Suitable hydrotreating catalysts for use as the first catalyst of the present catalyst system include any conventional hydrotreating catalyst.
  • Conventional hydrotreating catalyst as used herein is meant to refer to those which are comprised of at least one Group VIII metal, preferably Fe, Co and Ni, more preferably Co and/or Ni, and most preferably Ni; and at least one Group VI metal, preferably Mo and W, more preferably Mo, on a high surface area support material, preferably alumina.
  • the Group VIII metal is typically present in an amount ranging from about 2 to 20 wt. %, preferably from about 4 to 12%.
  • the Group VI metal will typically be present in an amount ranging from about 5 to 50 wt. %, preferably from about 10 to 40 wt.
  • All metals weight percents are on support.
  • On support we mean that the percents are based on the weight of the support. For example, if the support were to weigh 100 g. then 20 wt. % Group VIII metal would mean that 20 g. of Group VIII metal was on the support.
  • the average pore diameter of the first catalyst must have a specific size to be suitable for use herein.
  • a conventional catalyst as described above, but having an average pore diameter greater than 10 nm, as measured by water adsorption porosimetry, must be used as the first catalyst of the present stacked bed catalyst system. It is preferred that the average pore diameter of the first catalyst, i.e. the conventional hydrotreating catalyst, of the present stacked bed catalyst system be greater than 11 nm, more preferably greater than 12 nm.
  • the second hydrotreating catalyst is a bulk metal catalyst.
  • bulk metal it is meant that the catalysts are unsupported wherein the bulk catalyst particles comprise 30-100 wt. % of at least one Group VIII non-noble metal and at least one Group VIB metal, based on the total weight of the bulk catalyst particles, calculated as metal oxides and wherein the bulk catalyst particles have a surface area of at least 10 m 2 /g.
  • the bulk metal hydrotreating catalysts used herein comprise about 50 to about 100 wt. %, and even more preferably about 70 to about 100 wt. %, of at least one Group VIII non-noble metal and at least one Group VIB metal, based on the total weight of the particles, calculated as metal oxides.
  • the amount of Group VIB and Group VIII non-noble metals can easily be determined VIB TEM-EDX.
  • Bulk catalyst compositions comprising one Group VIII non-noble metal and two Group VIB metals are preferred. It has been found that in this case, the bulk catalyst particles are sintering-resistant. Thus the active surface area of the bulk catalyst particles is maintained during use.
  • the molar ratio of Group VIB to Group VIII non-noble metals ranges generally from 10:1-1:10 and preferably from 3:1-1:3. In the case of a core-shell structured particle, these ratios of course apply to the metals contained in the shell. If more than one Group VIB metal is contained in the bulk catalyst particles, the ratio of the different Group VIB metals is generally not critical. The same holds when more than one Group VIII non-noble metal is applied.
  • the molybenum:tungsten ratio preferably lies in the range of 9:1-1:9.
  • the Group VIII non-noble metal comprises nickel and/or cobalt.
  • the Group VIB metal comprises a combination of molybdenum and tungsten.
  • combinations of nickel/molybdenum/tungsten and cobalt/molybdenum/tungsten and nickel/cobalt/molybdenum/tungsten are used. These types of precipitates appear to be sinter-resistant. Thus, the active surface area of the precipitate is remained during use.
  • the metals are preferably present as oxidic compounds of the corresponding metals, or if the catalyst composition has been sulfided, sulfidic compounds of the corresponding metals.
  • the bulk metal hydrotreating catalysts used herein have a surface area of at least 50 m 2 /g and more preferably of at least 100 m 2 /g. It is also desired that the pore size distribution of the bulk metal hydrotreating catalysts be approximately the same as the one of conventional hydrotreating catalysts. More in particular, these bulk metal hydrotreating catalysts have preferably a pore volume of 0.05-5 ml/g, more preferably of 0.1-4 ml/g, still more preferably of 0.1-3 ml/g and most preferably 0.1-2 ml/g determined by nitrogen adsorption. Preferably, pores smaller than 1 nm are not present.
  • these bulk metal hydrotreating catalysts preferably have a median diameter of at least 50 nm, more preferably at least 100 nm, and preferably not more than 5000 ⁇ m and more preferably not more than 3000 ⁇ n. Even more preferably, the median particle diameter lies in the range of 0.1-50 ⁇ m and most preferably in the range of 0 5-50 ⁇ m.
  • the reaction stage containing the stacked bed hydrotreating catalyst system used in the present invention can be comprised of one or more fixed bed reactors or reaction zones each of which can comprise one or more catalyst beds of the same or different catalyst.
  • fixed beds are preferred.
  • Such other types of catalyst beds include fluidized beds, ebullating beds, slurry beds, and moving beds.
  • Interstage cooling or heating between reactors, reaction zones, or between catalyst beds in the same reactor can be employed since some olefin saturation can take place, and olefin saturation and the desulfurization reaction are generally exothermic.
  • a portion of the heat generated during hydrotreating can be recovered. Where this heat recovery option is not available, conventional cooling may be performed through cooling utilities such as cooling water or air, or through use of a hydrogen quench stream. In this manner, optimum reaction temperatures can be more easily maintained.
  • the stacked bed catalyst system of the present invention comprises about 5-95 vol. % of the first catalyst with the second catalyst comprising the remainder, preferably about 40-60 vol. %, more preferably about 5 to about 50 vol. %.
  • the second catalyst will comprise 50 vol. % also.
  • hydrocarbonaceous feedstream it is meant a primarily hydrocarbon material obtained or derived from crude petroleum oil, from tar sands, from coal liquefaction, shale oil and hydrocarbon synthesis.
  • hydrocarbonaceous feedstreams suitable for treatment with the present invention include those feedstreams boiling from the naphtha boiling range to heavy feedstocks, such as gas oils and resids, and also those derived from Fischer-Tropsch processes. Typically, the boiling range will be from about 40° C. to about 1000° C.
  • suitable feedstreams include vacuum gas oils; distillates including naphtha, diesel, kerosene, and jet fuel; heavy gas oils, raffinates, lube oils, etc.
  • Hydrocarbonaceous boiling range feedstreams suitable for treatment with the present invention include, among other things, nitrogen and sulfur contaminants.
  • the nitrogen content of such streams is about 50 to about 1000 wppm nitrogen, preferably about 75 to about 800 wppm nitrogen, and more preferably about 100 to about 700 wppm nitrogen.
  • the nitrogen appears as both basic and non-basic nitrogen species.
  • Non-limiting examples of basic nitrogen species may include quinolines and substituted quinolines, and non-limiting examples of non-basic nitrogen species may include carbazoles and substituted carbazoles.
  • the sulfur content of the hydrocarbonaceous boiling range feedstream will generally range from about 50 wppm to about 7000 wppm, more typically from about 100 wppm to about 5000 wppm, and most typically from about 100 to about 3000 wppm.
  • the sulfur will usually be present as organically bound sulfur. That is, as sulfur compounds such as simple aliphatic, naphthenic, and aromatic mercaptans, sulfides, di- and polysulfides and the like. Other organically bound sulfur compounds include the class of heterocyclic sulfur compounds such as thiophene, tetrahydrothiophene, benzothiophene and their higher homologs and analogs.
  • the hydrocarbonaceous feedstreams suitable for use herein also contain aromatics, which are typically present in an amount ranging from about 0.05 wt. %, to about 2.5 wt. %, based on the hydrocarbonaceous boiling range feedstream.
  • Preferred feedstocks suitable for treatment with the present invention are wax-containing feeds that boil in the lubricating oil range, typically having a 10% distillation point greater than 650° F. (343° C.) and an endpoint greater than 800° F. (426° C.), measured by ASTM D 86 or ASTM 2887.
  • These feedstocks can be derived from mineral sources, synthetic sources, or a mixture of the two.
  • Non-limiting examples of suitable lubricating oil feedstocks include those derived from sources such as oils derived from solvent refining processes such as raffinates, partially solvent dewaxed oils, deasphalted oils, distillates, vacuum gas oils, coker gas oils, slack waxes, foots oils and the like, dewaxed oils, automatic transmission fluid feedstocks, and Fischer-Tropsch waxes.
  • Automatic transmission fluid (“ATF”) feedstocks are lube oil feedstocks having an initial boiling point between about 200° C. and 275° C., and a 10% distillation point greater than about 300° C.
  • ATF feedstocks are typically 75-110N feedstocks.
  • feedstocks may also have high contents of nitrogen- and sulfur-contaminants.
  • Feeds containing up to 0.2 wt. % of nitrogen, based on feed and up to 3.0 wt. % of sulfur can be processed in the present process.
  • Feeds having a high wax content typically have high viscosity indexes of up to 200 or more.
  • Sulfur and nitrogen contents may be measured by standard ASTM methods D5453 and D4629, respectively.
  • hydrotreating refers to processes wherein a hydrogen-containing treat gas is used in the presence of a suitable catalyst that is primarily active for the removal of heteroatoms, such as sulfur, and nitrogen, and saturation of aromatics.
  • a hydrocarbonaceous feedstream is contacted with the stacked bed catalyst system in a reaction stage operated under effective hydrotreating conditions.
  • effective hydrotreating conditions it is meant those conditions effective at removing at least a portion of the sulfur contaminants from the hydrocarbonaceous feedstream.
  • Effective hydrotreating conditions generally include temperatures of from 150 to 400° C., a hydrogen partial pressure of from 1480 to 20786 kPa (200 to 3000 psig), a space velocity of from 0.1 to 10 liquid hourly space velocity (LHSV), and a hydrogen to feed ratio of from 89 to 1780 m 3 /m 3 ( 500 to 10000 scf/B).
  • the contacting of the hydrocarbonaceous feedstock with the stacked bed hydrotreating catalyst system produces a hydrotreated effluent comprising at least a gaseous product and a hydrotreated hydrocarbonaceous feedstock.
  • the hydrotreated effluent is stripped to remove at least a portion of the gaseous product from the hydrotreated effluent.
  • the means used to strip the hydrotreated effluent can be selected from any stripping method, process, or means known can be used. Non-limiting examples of suitable stripping methods, means, and processes include flash drums, fractionators, knock-out drums, steam stripping, etc.
  • a medium vacuum gas oil having the properties outlined in Table 1 was processed in an isothermal pilot plant over three catalysts systems at 1200 psig hydrogen partial pressure.
  • the catalyst systems and operating conditions are given in Table 2.
  • Catalyst B is a conventional hydrotreating catalyst having about 4.5 wt. % Group VI metal, about 23 wt. % Group VIII metal on an alumina support and has an average pore size of 14.0 nm.
  • the bulk metal hydrotreating catalyst was a commercial bulk metal hydrotreating catalyst marketed under the name Nebula by Akzo-Nobel.
  • the Nitrogen Removal Relative Volume Activity (“RVA”) for each catalyst system was calculated by simple first order kinetic modeling. As shown in Table 2, the 50/50 vol. % stacked bed catalyst system, with the large average pore size Catalyst B upstream of the bulk metal catalyst, showed higher nitrogen removal activity than either of the single catalyst systems demonstrated on their own.
  • the hydrotreating ability of different stacked beds of Catalyst B and Nebula were analyzed by hydrotreating different feedstreams over the stacked beds in the in two parallel reactor trains of the same isothermal pilot plant unit used in Example 1 above.
  • the feedstreams used were Medium Cycle Oils (“MCO”) from an FCC unit and blends of the MCO with a virgin feedstock were tested in two parallel reactor trains.
  • MCO Medium Cycle Oils
  • one reactor train consisted entirely of a conventional NiMo on Alumina hydrotreating catalyst, Catalyst C, with an average pore diameter of 7.5 nm.
  • the other reactor train contained a stacked bed system with 75-vol. % of Catalyst C followed by 25-vol. % of Catalyst A, a bulk multimetallic sulfide catalyst having an average pore diameter of 5.5 nm.
  • each of the two reactor trains was divided into two separate reactor vessels where the temperature of the first 75-volume % containing 75 vol. % of the catalyst loading of that reactor could be independently controlled from the last 25-volume % of catalyst.
  • the activity advantage for the stacked bed catalyst system containing begins to decrease from about 275% to about 225% and then was subsequently reduced over about 20 days to slightly less than 150%.
  • Example 2 was conducted in the same two reactor train pilot plant unit as described in Example 2 above. The operating conditions for the two trains were 1200 psig H 2 , liquid hourly space velocities of 2 vol./hr/vol., and 5000 SCF/B of hydrogen.
  • Example 5 As can be seen in Table 5, when a conventional catalyst having an average pore diameter of 14 nm was used in the first 75 vol. % of the reactor, the Nitrogen Removal Relative Volume Activity (“RVA”) for the catalyst system remained constant when the heavier feed was used. In comparing the results of Example 3 to those obtained in Example 2, one can see that when a catalyst having a pore volume of 7.5 nm preceded the bulk metal catalyst, the RVA of the catalyst system decreased. However, in Example 3, the heavier feed did not negatively impact the RVA of the catalyst system.
  • RVA Nitrogen Removal Relative Volume Activity

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)
  • Catalysts (AREA)
US10/949,513 2003-11-10 2004-09-24 Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams Abandoned US20050113250A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/949,513 US20050113250A1 (en) 2003-11-10 2004-09-24 Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams
US12/384,076 US7816299B2 (en) 2003-11-10 2009-03-31 Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US51873903P 2003-11-10 2003-11-10
US60846604P 2004-09-09 2004-09-09
US10/949,513 US20050113250A1 (en) 2003-11-10 2004-09-24 Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/384,076 Continuation-In-Part US7816299B2 (en) 2003-11-10 2009-03-31 Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams

Publications (1)

Publication Number Publication Date
US20050113250A1 true US20050113250A1 (en) 2005-05-26

Family

ID=34594919

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/949,513 Abandoned US20050113250A1 (en) 2003-11-10 2004-09-24 Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams
US10/949,482 Active 2025-01-31 US7597795B2 (en) 2003-11-10 2004-09-24 Process for making lube oil basestocks

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/949,482 Active 2025-01-31 US7597795B2 (en) 2003-11-10 2004-09-24 Process for making lube oil basestocks

Country Status (7)

Country Link
US (2) US20050113250A1 (ja)
EP (1) EP1685214B1 (ja)
JP (1) JP2007510798A (ja)
AU (1) AU2004288904A1 (ja)
CA (1) CA2543844C (ja)
NO (1) NO341109B1 (ja)
WO (1) WO2005047434A1 (ja)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007048594A1 (en) * 2005-10-26 2007-05-03 Albemarle Netherlands Bv Process for the preparation of a shaped bulk catalyst
WO2011082142A1 (en) 2009-12-29 2011-07-07 Exxonmobil Research And Engineering Company Hydroprocessing of biocomponent feedstocks with low purity hydrogen-containing streams
WO2012009516A2 (en) 2010-07-15 2012-01-19 Exxonmobil Research And Engineering Company Hydroprocessing of biocomponent feeds with low pressure hydrogen-containing streams
US10533141B2 (en) 2017-02-12 2020-01-14 Mag{tilde over (e)}mã Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US20220135888A1 (en) * 2020-11-05 2022-05-05 Jgc Catalysts And Chemicals Ltd. Hydrotreating Catalyst for Heavy Hydrocarbon Oil, Method for Producing the Same, and Method for Hydrotreating Heavy Hydrocarbon Oil
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050109679A1 (en) * 2003-11-10 2005-05-26 Schleicher Gary P. Process for making lube oil basestocks
EP1902117A2 (en) * 2005-07-01 2008-03-26 Shell Internationale Research Maatschappij B.V. Process to prepare a mineral derived residual deasphalted oil blend
US20070062847A1 (en) * 2005-09-16 2007-03-22 Hyde Evan P Integrated lubricant upgrading process using once-through, hydrogen-containing treat gas
US8366908B2 (en) * 2008-12-31 2013-02-05 Exxonmobil Research And Engineering Company Sour service hydroprocessing for lubricant base oil production
CN102906231B (zh) 2009-12-08 2015-11-25 埃克森美孚研究工程公司 使用本体催化剂加氢处理高氮进料的方法
US20120000829A1 (en) * 2010-06-30 2012-01-05 Exxonmobil Research And Engineering Company Process for the preparation of group ii and group iii lube base oils
CN103827269B (zh) 2011-07-29 2016-02-03 沙特阿拉伯石油公司 集成的选择性加氢裂化和流化催化裂化方法
US9394495B1 (en) 2013-09-18 2016-07-19 Thomas George Murray Post hydrotreatment finishing of lubricant distillates
US20180127666A1 (en) * 2013-09-18 2018-05-10 Thomas George Murray Properties of Hydroprocessed Base Oils
FR3075220A1 (fr) * 2017-12-19 2019-06-21 IFP Energies Nouvelles Procede d'hydrotraitement de distillats sous vide mettant en oeuvre un enchainement specifique de catalyseurs
JP7050544B2 (ja) 2018-03-27 2022-04-08 Ｅｎｅｏｓ株式会社 ワックス異性化油の製造方法
CN116064115A (zh) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 加氢生产环烷基橡胶填充油的工艺方法

Citations (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4019976A (en) * 1974-04-24 1977-04-26 Institut Francais Du Petrole Process for hydrogenating highly unsaturated heavy hydrocarbon cuts
US4145276A (en) * 1976-01-05 1979-03-20 Institut Francais Du Petrole Process for the 3-step catalytic treatment of highly unsaturated heavy fractions under hydrogen pressure
US4181602A (en) * 1977-12-21 1980-01-01 Standard Oil Company (Indiana) Process for the hydrotreating of heavy hydrocarbon streams
US4188284A (en) * 1977-12-21 1980-02-12 Standard Oil Company (Indiana) Process for the hydrotreating of heavy hydrocarbon streams
US4191635A (en) * 1977-12-21 1980-03-04 Standard Oil Company (Indiana) Process for the cracking of heavy hydrocarbon streams
US4211634A (en) * 1978-11-13 1980-07-08 Standard Oil Company (Indiana) Two-catalyst hydrocracking process
US4225421A (en) * 1979-03-13 1980-09-30 Standard Oil Company (Indiana) Process for hydrotreating heavy hydrocarbons
US4397827A (en) * 1979-07-12 1983-08-09 Mobil Oil Corporation Silico-crystal method of preparing same and catalytic conversion therewith
US4431525A (en) * 1982-04-26 1984-02-14 Standard Oil Company (Indiana) Three-catalyst process for the hydrotreating of heavy hydrocarbon streams
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
US4572778A (en) * 1984-01-19 1986-02-25 Union Oil Company Of California Hydroprocessing with a large pore catalyst
US4585747A (en) * 1984-06-27 1986-04-29 Mobil Oil Corporation Synthesis of crystalline silicate ZSM-48
US4642179A (en) * 1983-12-19 1987-02-10 Intevep, S.A. Catalyst for removing sulfur and metal contaminants from heavy crudes and residues
US4657663A (en) * 1985-04-24 1987-04-14 Phillips Petroleum Company Hydrotreating process employing a three-stage catalyst system wherein a titanium compound is employed in the second stage
US4686030A (en) * 1986-04-28 1987-08-11 Union Oil Company Of California Mild hydrocracking with a catalyst having a narrow pore size distribution
US4695365A (en) * 1986-07-31 1987-09-22 Union Oil Company Of California Hydrocarbon refining process
US4776945A (en) * 1984-11-30 1988-10-11 Shell Oil Company Single-stage hydrotreating process
US4855037A (en) * 1984-09-12 1989-08-08 Nippon Kokan Kabushiki Kaisha Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar
US4900707A (en) * 1987-12-18 1990-02-13 Exxon Research And Engineering Company Method for producing a wax isomerization catalyst
US4902404A (en) * 1988-07-05 1990-02-20 Exxon Research And Engineering Company Hydrotreating process with catalyst staging
US4925554A (en) * 1988-02-05 1990-05-15 Catalysts & Chemicals Industries Co., Ltd. Hydrotreating process for heavy hydrocarbon oils
US4975177A (en) * 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US5068025A (en) * 1990-06-27 1991-11-26 Shell Oil Company Aromatics saturation process for diesel boiling-range hydrocarbons
US5075269A (en) * 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
US5100855A (en) * 1990-03-30 1992-03-31 Amoco Corporation Mixed catalyst system for hyproconversion system
US5116484A (en) * 1990-10-31 1992-05-26 Shell Oil Company Hydrodenitrification process
US5232578A (en) * 1991-04-09 1993-08-03 Shell Oil Company Multibed hydrocracking process utilizing beds with disparate particle sizes and hydrogenating metals contents
US5246566A (en) * 1989-02-17 1993-09-21 Chevron Research And Technology Company Wax isomerization using catalyst of specific pore geometry
US5282958A (en) * 1990-07-20 1994-02-01 Chevron Research And Technology Company Use of modified 5-7 a pore molecular sieves for isomerization of hydrocarbons
US5474670A (en) * 1994-05-17 1995-12-12 Exxon Research And Engineering Company Stacked bed catalyst system for deep hydrodesulfurization
US5624547A (en) * 1993-09-20 1997-04-29 Texaco Inc. Process for pretreatment of hydrocarbon oil prior to hydrocracking and fluid catalytic cracking
US5888380A (en) * 1994-09-19 1999-03-30 Nippon Ketjen Co., Ltd. Hydroprocessing catalyst and use thereof
US5976354A (en) * 1997-08-19 1999-11-02 Shell Oil Company Integrated lube oil hydrorefining process
US6096189A (en) * 1996-12-17 2000-08-01 Exxon Research And Engineering Co. Hydroconversion process for making lubricating oil basestocks
US6162350A (en) * 1997-07-15 2000-12-19 Exxon Research And Engineering Company Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901)
US6290841B1 (en) * 1999-02-15 2001-09-18 Shell Oil Company Hydrotreating process using sulfur activated non-calcined catalyst
US6294077B1 (en) * 2000-02-02 2001-09-25 Mobil Oil Corporation Production of high viscosity lubricating oil stock with improved ZSM-5 catalyst
US6303534B1 (en) * 1998-05-26 2001-10-16 Exxonmobil Chemical Patents Inc. Silicoaluminophosphates having an AEL structure, and their preparation
US6310265B1 (en) * 1999-11-01 2001-10-30 Exxonmobil Chemical Patents Inc. Isomerization of paraffins
US20020040863A1 (en) * 1996-12-17 2002-04-11 Cody Ian A. Hydroconversion process for making lubricating oil basestockes
US6383366B1 (en) * 1998-02-13 2002-05-07 Exxon Research And Engineering Company Wax hydroisomerization process
US6582590B1 (en) * 1997-07-15 2003-06-24 Exxonmobil Research And Engineering Company Multistage hydroprocessing using bulk multimetallic catalyst
US6620313B1 (en) * 1997-07-15 2003-09-16 Exxonmobil Research And Engineering Company Hydroconversion process using bulk group VIII/Group VIB catalysts
US6758963B1 (en) * 1997-07-15 2004-07-06 Exxonmobil Research And Engineering Company Hydroprocessing using bulk group VIII/group vib catalysts
US6863803B1 (en) * 1997-07-15 2005-03-08 Exxonmobil Research And Engineering Company Production of low sulfur/low nitrogen hydrocrackates
US7232515B1 (en) * 1997-07-15 2007-06-19 Exxonmobil Research And Engineering Company Hydrofining process using bulk group VIII/Group VIB catalysts

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526988A3 (en) 1991-07-10 1993-03-31 Texaco Development Corporation Hydrotreatment process employing a mono-modal catalyst with specified pore size distribution
US5935417A (en) 1996-12-17 1999-08-10 Exxon Research And Engineering Co. Hydroconversion process for making lubricating oil basestocks
ES2160058B1 (es) 1999-06-17 2002-06-16 Univ Valencia Politecnica Sintesis de zeolitas.
US6645462B1 (en) 2000-11-03 2003-11-11 Exxon Mobil Oil Corporation Synthetic porous crystalline MCM-71, its synthesis and use
CN1307290C (zh) 2002-12-06 2007-03-28 阿尔伯麦尔荷兰有限公司 使用催化剂混合物的烃的加氢处理方法

Patent Citations (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4019976A (en) * 1974-04-24 1977-04-26 Institut Francais Du Petrole Process for hydrogenating highly unsaturated heavy hydrocarbon cuts
US4145276A (en) * 1976-01-05 1979-03-20 Institut Francais Du Petrole Process for the 3-step catalytic treatment of highly unsaturated heavy fractions under hydrogen pressure
US4181602A (en) * 1977-12-21 1980-01-01 Standard Oil Company (Indiana) Process for the hydrotreating of heavy hydrocarbon streams
US4188284A (en) * 1977-12-21 1980-02-12 Standard Oil Company (Indiana) Process for the hydrotreating of heavy hydrocarbon streams
US4191635A (en) * 1977-12-21 1980-03-04 Standard Oil Company (Indiana) Process for the cracking of heavy hydrocarbon streams
US4211634A (en) * 1978-11-13 1980-07-08 Standard Oil Company (Indiana) Two-catalyst hydrocracking process
US4225421A (en) * 1979-03-13 1980-09-30 Standard Oil Company (Indiana) Process for hydrotreating heavy hydrocarbons
US4397827A (en) * 1979-07-12 1983-08-09 Mobil Oil Corporation Silico-crystal method of preparing same and catalytic conversion therewith
US4431525A (en) * 1982-04-26 1984-02-14 Standard Oil Company (Indiana) Three-catalyst process for the hydrotreating of heavy hydrocarbon streams
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
US4642179A (en) * 1983-12-19 1987-02-10 Intevep, S.A. Catalyst for removing sulfur and metal contaminants from heavy crudes and residues
US4572778A (en) * 1984-01-19 1986-02-25 Union Oil Company Of California Hydroprocessing with a large pore catalyst
US4585747A (en) * 1984-06-27 1986-04-29 Mobil Oil Corporation Synthesis of crystalline silicate ZSM-48
US4855037A (en) * 1984-09-12 1989-08-08 Nippon Kokan Kabushiki Kaisha Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar
US4776945A (en) * 1984-11-30 1988-10-11 Shell Oil Company Single-stage hydrotreating process
US4657663A (en) * 1985-04-24 1987-04-14 Phillips Petroleum Company Hydrotreating process employing a three-stage catalyst system wherein a titanium compound is employed in the second stage
US4975177A (en) * 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US4686030A (en) * 1986-04-28 1987-08-11 Union Oil Company Of California Mild hydrocracking with a catalyst having a narrow pore size distribution
US4695365A (en) * 1986-07-31 1987-09-22 Union Oil Company Of California Hydrocarbon refining process
US4900707A (en) * 1987-12-18 1990-02-13 Exxon Research And Engineering Company Method for producing a wax isomerization catalyst
US4925554A (en) * 1988-02-05 1990-05-15 Catalysts & Chemicals Industries Co., Ltd. Hydrotreating process for heavy hydrocarbon oils
US4902404A (en) * 1988-07-05 1990-02-20 Exxon Research And Engineering Company Hydrotreating process with catalyst staging
US5075269A (en) * 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
US5246566A (en) * 1989-02-17 1993-09-21 Chevron Research And Technology Company Wax isomerization using catalyst of specific pore geometry
US5100855A (en) * 1990-03-30 1992-03-31 Amoco Corporation Mixed catalyst system for hyproconversion system
US5068025A (en) * 1990-06-27 1991-11-26 Shell Oil Company Aromatics saturation process for diesel boiling-range hydrocarbons
US5282958A (en) * 1990-07-20 1994-02-01 Chevron Research And Technology Company Use of modified 5-7 a pore molecular sieves for isomerization of hydrocarbons
US5116484A (en) * 1990-10-31 1992-05-26 Shell Oil Company Hydrodenitrification process
US5232578A (en) * 1991-04-09 1993-08-03 Shell Oil Company Multibed hydrocracking process utilizing beds with disparate particle sizes and hydrogenating metals contents
US5624547A (en) * 1993-09-20 1997-04-29 Texaco Inc. Process for pretreatment of hydrocarbon oil prior to hydrocracking and fluid catalytic cracking
US5474670A (en) * 1994-05-17 1995-12-12 Exxon Research And Engineering Company Stacked bed catalyst system for deep hydrodesulfurization
US5888380A (en) * 1994-09-19 1999-03-30 Nippon Ketjen Co., Ltd. Hydroprocessing catalyst and use thereof
US20020040863A1 (en) * 1996-12-17 2002-04-11 Cody Ian A. Hydroconversion process for making lubricating oil basestockes
US6096189A (en) * 1996-12-17 2000-08-01 Exxon Research And Engineering Co. Hydroconversion process for making lubricating oil basestocks
US6582590B1 (en) * 1997-07-15 2003-06-24 Exxonmobil Research And Engineering Company Multistage hydroprocessing using bulk multimetallic catalyst
US6162350A (en) * 1997-07-15 2000-12-19 Exxon Research And Engineering Company Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901)
US6620313B1 (en) * 1997-07-15 2003-09-16 Exxonmobil Research And Engineering Company Hydroconversion process using bulk group VIII/Group VIB catalysts
US6758963B1 (en) * 1997-07-15 2004-07-06 Exxonmobil Research And Engineering Company Hydroprocessing using bulk group VIII/group vib catalysts
US6863803B1 (en) * 1997-07-15 2005-03-08 Exxonmobil Research And Engineering Company Production of low sulfur/low nitrogen hydrocrackates
US7232515B1 (en) * 1997-07-15 2007-06-19 Exxonmobil Research And Engineering Company Hydrofining process using bulk group VIII/Group VIB catalysts
US5976354A (en) * 1997-08-19 1999-11-02 Shell Oil Company Integrated lube oil hydrorefining process
US6383366B1 (en) * 1998-02-13 2002-05-07 Exxon Research And Engineering Company Wax hydroisomerization process
US6303534B1 (en) * 1998-05-26 2001-10-16 Exxonmobil Chemical Patents Inc. Silicoaluminophosphates having an AEL structure, and their preparation
US6290841B1 (en) * 1999-02-15 2001-09-18 Shell Oil Company Hydrotreating process using sulfur activated non-calcined catalyst
US6310265B1 (en) * 1999-11-01 2001-10-30 Exxonmobil Chemical Patents Inc. Isomerization of paraffins
US6294077B1 (en) * 2000-02-02 2001-09-25 Mobil Oil Corporation Production of high viscosity lubricating oil stock with improved ZSM-5 catalyst

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007048594A1 (en) * 2005-10-26 2007-05-03 Albemarle Netherlands Bv Process for the preparation of a shaped bulk catalyst
WO2007048596A1 (en) * 2005-10-26 2007-05-03 Albemarle Netherlands Bv A bulk catalyst composition and a process preparing the bulk catalyst composition
US20080308462A1 (en) * 2005-10-26 2008-12-18 Albemarle Netherlands B.V. Bulk Catalyst Composition And A Process Preparing The Bulk Catalyst Composition
US20090014356A1 (en) * 2005-10-26 2009-01-15 Albemarle Netherlands B.V. Process For The Preparation Of A Shaped Bulk Catalyst
US7964528B2 (en) 2005-10-26 2011-06-21 Albemarle Netherlands, B.V. Process for the preparation of a shaped bulk catalyst
EA015110B1 (ru) * 2005-10-26 2011-06-30 Альбемарл Недерландс Бв Способ получения формованного сыпучего катализатора
EA015445B1 (ru) * 2005-10-26 2011-08-30 Альбемарл Недерландс Бв Сыпучая каталитическая композиция и способ приготовления сыпучей каталитической композиции
US8476184B2 (en) 2005-10-26 2013-07-02 Albemarle Corporation Bulk catalyst composition and a process preparing the bulk catalyst composition
EP3078417A1 (en) * 2005-10-26 2016-10-12 Albemarle Netherlands B.V. Bulk catalyst composition and process for preparing it
EP3085441A1 (en) * 2005-10-26 2016-10-26 Albemarle Netherlands B.V. Process for the preparation of a shaped bulk catalyst
WO2011082142A1 (en) 2009-12-29 2011-07-07 Exxonmobil Research And Engineering Company Hydroprocessing of biocomponent feedstocks with low purity hydrogen-containing streams
WO2012009516A2 (en) 2010-07-15 2012-01-19 Exxonmobil Research And Engineering Company Hydroprocessing of biocomponent feeds with low pressure hydrogen-containing streams
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11441084B2 (en) 2017-02-12 2022-09-13 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US10563132B2 (en) 2017-02-12 2020-02-18 Magēmā Technology, LLC Multi-stage process and device for treatment heavy marine fuel oil and resultant composition including ultrasound promoted desulfurization
US10584287B2 (en) 2017-02-12 2020-03-10 Magēmā Technology LLC Heavy marine fuel oil composition
US10533141B2 (en) 2017-02-12 2020-01-14 Mag{tilde over (e)}mã Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US10655074B2 (en) 2017-02-12 2020-05-19 Mag{hacek over (e)}m{hacek over (a)} Technology LLC Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil
US10836966B2 (en) 2017-02-12 2020-11-17 Magēmā Technology LLC Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil
US11136513B2 (en) 2017-02-12 2021-10-05 Magëmä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11203722B2 (en) 2017-02-12 2021-12-21 Magëmä Technology LLC Multi-stage process and device for treatment heavy marine fuel oil and resultant composition including ultrasound promoted desulfurization
US11912945B2 (en) 2017-02-12 2024-02-27 Magēmā Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US11345863B2 (en) 2017-02-12 2022-05-31 Magema Technology, Llc Heavy marine fuel oil composition
US10563133B2 (en) 2017-02-12 2020-02-18 Magëmä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US11447706B2 (en) 2017-02-12 2022-09-20 Magēmā Technology LLC Heavy marine fuel compositions
US11492559B2 (en) 2017-02-12 2022-11-08 Magema Technology, Llc Process and device for reducing environmental contaminates in heavy marine fuel oil
US11530360B2 (en) 2017-02-12 2022-12-20 Magēmā Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US11560520B2 (en) 2017-02-12 2023-01-24 Magēmā Technology LLC Multi-stage process and device for treatment heavy marine fuel oil and resultant composition and the removal of detrimental solids
US11884883B2 (en) 2017-02-12 2024-01-30 MagêmãTechnology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil
US11795406B2 (en) 2017-02-12 2023-10-24 Magemä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11661554B2 (en) * 2020-11-05 2023-05-30 Jgc Catalysts And Chemicals Ltd. Hydrotreating catalyst for heavy hydrocarbon oil, method for producing the same, and method for hydrotreating heavy hydrocarbon oil
US20220135888A1 (en) * 2020-11-05 2022-05-05 Jgc Catalysts And Chemicals Ltd. Hydrotreating Catalyst for Heavy Hydrocarbon Oil, Method for Producing the Same, and Method for Hydrotreating Heavy Hydrocarbon Oil

Also Published As

Publication number Publication date
WO2005047434A1 (en) 2005-05-26
AU2004288904A1 (en) 2005-05-26
NO20062678L (no) 2006-06-09
US20050109673A1 (en) 2005-05-26
US7597795B2 (en) 2009-10-06
CA2543844C (en) 2012-07-10
CA2543844A1 (en) 2005-05-26
NO341109B1 (no) 2017-08-28
JP2007510798A (ja) 2007-04-26
EP1685214A1 (en) 2006-08-02
EP1685214B1 (en) 2015-03-04

Similar Documents

Publication Publication Date Title
US20050113250A1 (en) Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams
AU657567B2 (en) A method of treatment of heavy hydrocarbon oil
KR102447300B1 (ko) 선박용 연료들의 제조를 위한 고정층 수소화 처리, 수소화 처리된 잔사유 분획물의 분리 및 접촉 분해 스텝을 포함하는 전환 프로세스
US5403470A (en) Color removal with post-hydrotreating
CN101300325B (zh) 在重油改质中循环活性浆液催化剂组合物的方法
US4729826A (en) Temperature controlled catalytic demetallization of hydrocarbons
AU2014212784A1 (en) Upgrading raw shale-derived crude oils to hydrocarbon distillate fuels
AU2003241412B2 (en) Multi-stage hydrodesulfurization of cracked naphtha streams with a stacked bed reactor
US7816299B2 (en) Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams
CN102344826B (zh) 一种生产催化原料与优质柴油的加氢组合方法
CA2544210C (en) A hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams
CN114437786B (zh) 一种劣质原料油的加氢裂化方法
CA2544208C (en) A process for making lube oil basestocks
Trambouze Engineering of hydrotreating processes
JPH1180753A (ja) 水素化処理反応器および該反応器を用いた超低硫黄重質油の製造方法
AU2015317031B2 (en) Production of high quality diesel fuel and lubricant from high boiling aromatic carbonaceous material
US3923637A (en) Hydrodesulfurization process with a portion of the feed added downstream

Legal Events

Date Code Title Description
AS Assignment

Owner name: EXXONMOBIL RESEARCH & ENGINEERING CO., NEW JERSEY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SCHLEICHER, GARY P.;RILEY, KENNETH L.;REEL/FRAME:015619/0020;SIGNING DATES FROM 20050113 TO 20050119

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION