US3546103A - Hydrogenation catalysts on charcoal in guard chamber for removing metals from petroleum residua - Google Patents

Hydrogenation catalysts on charcoal in guard chamber for removing metals from petroleum residua Download PDF

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Publication number
US3546103A
US3546103A US796213A US3546103DA US3546103A US 3546103 A US3546103 A US 3546103A US 796213 A US796213 A US 796213A US 3546103D A US3546103D A US 3546103DA US 3546103 A US3546103 A US 3546103A
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United States
Prior art keywords
catalyst
charcoal
metals
feed
percent
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US796213A
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English (en)
Inventor
Glen P Hamner
Ralph B Mason
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C

Definitions

  • This invention relates to a method for the removal of metals and coke precursors from heavy feeds to a hydrodesulfurization process.
  • the above disadvantages are overcome by first contacting the feedstock in a guard chamber containing a hydrodesulfurization catalyst supported on a charcoal or activated carbon base at elevated temperature and pressure in the presence of hydrogen so that a considerable proportion of the metals and coke precursors are deposited thereon and thereafter passing the thus treated feedstock to a hydrodesulfurization zone under generally more severe conditions than prevails in the first stage whereby the activity of the catalyst is increased and the catalyst life is extended because of reduced metal deposition.
  • the charcoal base can be easily removed by burning or steam gasification to form desirable gas products leaving 3,546,103 Patented Dec.
  • the charcoal or activated carbon base suitable for use in this invention may be any solid type of carbon capable of supporting metallic catalyst. However it is preferred to use activated carbon which is made by the destructive distillation of carbonaceous material under controlled conditions. The specific area of such a carbon may range from 600 to 2000 square meters per gram.
  • sulfactive hydrogenation catalyst may be used in conjunction with the charcoal or activated carbon base.
  • Suitable catalysts include one or more of the oxides or sulfides of a metal of Group VIII in combination with metals of Group II-B and VI-B, such as Ni-W, Ni-Mo, Co-Mo, Co-W, Zn-Mo, Zn-W or mixtures thereof.
  • a typical catalyst contains about 0.1 to 20% by weight of a Group VIII metal such as nickel and about 0.1 to 20% by weight of a Group VI-B metal such as tungsten.
  • the reaction conditions used in the first stage can vary over wide ranges depending on the particular feed. Generally the conditions include pressures of from about 500 to 1500 p.s.i.g., a temperature of about 650 to 950 F., a feed rate of 0.5 to 20 volumes of feed per volume of catalyst per hour (v./v./hr.) and 1000 to 10,000 s.c.f. per barrel of hydrogen.
  • the subsequent hydrodesulfurization reaction is accomplished over catalysts which are preferably more active than those used for the preliminary treatment.
  • the active metallic components in the catalyst are a Group VI-B oxide or sulfide, specifically an oxide or sulfide of molybdenum, tungsten, or their mixtures and a Group VIII metal oxide or sulfide, specifically an oxide or sulfide of nickel or cobalt.
  • Suitable catalysts consist of 1 to 15 wt. percent of nickel or cobalt (as oxide) preferably 2 to 10 wt. percent, 5 to 25 wt. percent of tungsten or molybdenum (as oxide), preferably 10 to 20 wt.
  • a particularly suitable catalyst consists of 3.5 wt. percent of C00" and 12.5 wt. percent M00 on alumina containing about 2.0 wt. percent silica and having a maximum surface area in pores having a diameter of 30 to 70 A. as described in application Ser. No. 648,604 filed June 26, 1967, which was issued as U.S. Patent 3,509,044 on April 28, 1970, to Adams and House and the subject matter of which is incorporated herein by reference.
  • the reaction conditions in the hydrodesulfurization step may range between 500-825 F., preferably 650-800, 500-2500 p.s.i.g., preferably 800-1800 p.s.i.g., a space velocity of 0.2 to 5.0 v./v./hr., preferably 0.5-2.0, and a hydrogen rate of 500-7500 s.c.f. per barrel, preferably 1000-5000.
  • the feed stock is preferably a petroleum residium 30 to of which boils above 900 F. and which is obtained from crude oils by distillation or treating or by some other type of separation.
  • the residuum may be a blend of high boiling materials such as atmospheric bottoms, vacuum bottoms, deasphalted oil visbreaker bottoms, gas oil cuts and the like. All of these materials contain about 25 p.p.m. or more each of nickel or vanadium measured as the oxides NiO and V 0
  • the following example is included to illustrate the effectiveness of the instant process for the preliminary 3 treatment of petroleum residuum prior to hydrodesulfurization thereof without limiting the same.
  • a process for the removal of metals and coke precursors from a hydrocarbon residuum containing the same which comprises contacting said residuum at 65095 0 E, 500-1500 p.s.i.g., a feed rate of 0.5 to volumes of residuum per volume of catalyst per hour and in the presence of 1000 to 10,000 standard cubic feet of hydrogen per barrel of feed and a catalyst comprising an oxide or sulfide of a metal of Group II-B or VI-B together with a Group VIII metal on charcoal for a period of time to remove a substantial quantity of the metals.
  • a process for the two-stage treatment of a hydrocarbon residuum containing a substantial quantity of metals and coke precursors which comprises pretreating said residuum in a first stage with a contact material comprising an oxide or sulfide of a metal of Group II or VI- B together with a Group VIII metal on charcoal at 650 950 F., 500-1500 p.s.i.g., a feed rate of 0.5 to 20 volumes of feed per volume of catalyst per hour and in the presence of 1000 to 10,000 standard cubic feet of hydrogen per barrel of feed for a period of time to remove a substantial quantity of the metals and coke precursors and subsequently contacting the thus pretreated feed in a second stage with a hydrodesulfurizing catalyst comprising an oxide or sulfide of a Group VI-B and a Group VIII metal on alumina at a temperature of 500-825 F., a pressure of 500-2500 p.s.i.g., a space velocity of 0.2 to 5.0 v.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
US796213A 1969-02-03 1969-02-03 Hydrogenation catalysts on charcoal in guard chamber for removing metals from petroleum residua Expired - Lifetime US3546103A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US79621369A 1969-02-03 1969-02-03

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JP (1) JPS4949008B1 (enrdf_load_stackoverflow)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770618A (en) * 1967-06-26 1973-11-06 Exxon Research Engineering Co Hydrodesulfurization of residua
US3833498A (en) * 1973-07-18 1974-09-03 Gulf Research Development Co Process for reducing the arsenic content of gaseous hydrocarbon streams by the use of selective activated carbon
US3923635A (en) * 1974-06-17 1975-12-02 Exxon Research Engineering Co Catalytic upgrading of heavy hydrocarbons
US3997473A (en) * 1973-10-23 1976-12-14 American Cyanamid Company Hydrodesulfurization catalysts supported on carbon
US4038376A (en) * 1975-08-12 1977-07-26 Atlantic Richfield Company Process for the recovery of selenium from urethanes containing selenium or compounds thereof
US4052296A (en) * 1976-11-29 1977-10-04 Gulf Research & Development Company Hydrogenation process employing a zinc promoted catalyst
US4088567A (en) * 1976-12-03 1978-05-09 Chevron Research Company Solids removal and fluid catalytic cracking of a synthetic hydrocarbon stream derived from hydrocarbon-containing solids
US4102779A (en) * 1976-08-13 1978-07-25 Standard Oil Company (Indiana) Processes for treating a heavy petroleum hydrocarbon stream containing metals and asphaltenes
US4128505A (en) * 1975-12-22 1978-12-05 Mobil Oil Corporation Catalyst for hydrotreating
US4342641A (en) * 1980-11-18 1982-08-03 Sun Tech, Inc. Maximizing jet fuel from shale oil
US4568655A (en) * 1984-10-29 1986-02-04 Mobil Oil Corporation Catalyst composition comprising Zeolite Beta
US4696732A (en) * 1984-10-29 1987-09-29 Mobil Oil Corporation Simultaneous hydrotreating and dewaxing of petroleum feedstocks
US4743572A (en) * 1986-12-05 1988-05-10 Mobil Oil Corporation Magnesia-alumina-aluminum phosphate catalyst and catalyst product thereof
US4781817A (en) * 1986-12-04 1988-11-01 Mobil Oil Corporation Hydrogen bronze catalyst and improved resid upgrading processes using it
US4910181A (en) * 1986-12-04 1990-03-20 Mobil Oil Corporation Hydrogen bronze catalyst for demetallizing petroleum resids
US5124024A (en) * 1989-11-20 1992-06-23 Nova Husky Research Corporation Method for extending hydroconversion catalyst life
EP0696632A1 (en) 1994-08-09 1996-02-14 Texaco Development Corporation Hydrodearomatisation of hydrocarbon oils using phosphorus-treated carbon-supported metal sulphide catalysts
EP0696633A1 (en) 1994-08-09 1996-02-14 Texaco Development Corporation Process for hydrodearomatisation of hydrocarbon oils using carbon supported metal sulphide catalysts promoted by phosphate
US5556824A (en) * 1993-09-20 1996-09-17 Texaco Inc. Hydrodearomatization of hydrocarbons
EP0731156A3 (en) * 1995-03-09 1996-11-27 Texaco Development Corp Process for hydrodesaromatization of hydrocarbon oils with metal sulphide catalysts on carbon supports and activated by zinc
US5651878A (en) * 1992-12-14 1997-07-29 Texaco Inc. Hydrodearomatization of Hydrocarbons
US5846503A (en) * 1990-12-17 1998-12-08 Mobil Oil Corporation Process for rejuvenating used alkanolamaine solutions
US20030070965A1 (en) * 1999-11-01 2003-04-17 Shih Stuart S. Method for the production of very low sulfur diesel

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4955833U (enrdf_load_stackoverflow) * 1972-08-24 1974-05-17

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB682387A (en) * 1949-06-22 1952-11-12 Anglo Iranian Oil Co Ltd Improvements relating to the removal of vanadium from petroleum products
US2687985A (en) * 1952-01-31 1954-08-31 Anglo Iranian Oil Co Ltd Removal of vanadium and sodium from petroleum hydrocarbons
US2755225A (en) * 1951-10-18 1956-07-17 British Petroleum Co Treatment of crude petroleum
US2766183A (en) * 1952-06-18 1956-10-09 British Petroleum Co Removal of vanadium and/or sodium from petroleum and petroleum products with fuller's earth
US2987467A (en) * 1958-05-26 1961-06-06 Hydrocarbon Research Inc Removal of sulfur and metals from heavy oils by hydro-catalytic treatment
US3367862A (en) * 1965-10-18 1968-02-06 Exxon Research Engineering Co Process for desulfurization by hydrolysis with metals on charcoal base catalysts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB682387A (en) * 1949-06-22 1952-11-12 Anglo Iranian Oil Co Ltd Improvements relating to the removal of vanadium from petroleum products
US2755225A (en) * 1951-10-18 1956-07-17 British Petroleum Co Treatment of crude petroleum
US2687985A (en) * 1952-01-31 1954-08-31 Anglo Iranian Oil Co Ltd Removal of vanadium and sodium from petroleum hydrocarbons
US2766183A (en) * 1952-06-18 1956-10-09 British Petroleum Co Removal of vanadium and/or sodium from petroleum and petroleum products with fuller's earth
US2987467A (en) * 1958-05-26 1961-06-06 Hydrocarbon Research Inc Removal of sulfur and metals from heavy oils by hydro-catalytic treatment
US3367862A (en) * 1965-10-18 1968-02-06 Exxon Research Engineering Co Process for desulfurization by hydrolysis with metals on charcoal base catalysts

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770618A (en) * 1967-06-26 1973-11-06 Exxon Research Engineering Co Hydrodesulfurization of residua
US3833498A (en) * 1973-07-18 1974-09-03 Gulf Research Development Co Process for reducing the arsenic content of gaseous hydrocarbon streams by the use of selective activated carbon
US3997473A (en) * 1973-10-23 1976-12-14 American Cyanamid Company Hydrodesulfurization catalysts supported on carbon
US3923635A (en) * 1974-06-17 1975-12-02 Exxon Research Engineering Co Catalytic upgrading of heavy hydrocarbons
US4038376A (en) * 1975-08-12 1977-07-26 Atlantic Richfield Company Process for the recovery of selenium from urethanes containing selenium or compounds thereof
US4128505A (en) * 1975-12-22 1978-12-05 Mobil Oil Corporation Catalyst for hydrotreating
US4102779A (en) * 1976-08-13 1978-07-25 Standard Oil Company (Indiana) Processes for treating a heavy petroleum hydrocarbon stream containing metals and asphaltenes
US4052296A (en) * 1976-11-29 1977-10-04 Gulf Research & Development Company Hydrogenation process employing a zinc promoted catalyst
US4088567A (en) * 1976-12-03 1978-05-09 Chevron Research Company Solids removal and fluid catalytic cracking of a synthetic hydrocarbon stream derived from hydrocarbon-containing solids
US4342641A (en) * 1980-11-18 1982-08-03 Sun Tech, Inc. Maximizing jet fuel from shale oil
US4568655A (en) * 1984-10-29 1986-02-04 Mobil Oil Corporation Catalyst composition comprising Zeolite Beta
US4696732A (en) * 1984-10-29 1987-09-29 Mobil Oil Corporation Simultaneous hydrotreating and dewaxing of petroleum feedstocks
US4910181A (en) * 1986-12-04 1990-03-20 Mobil Oil Corporation Hydrogen bronze catalyst for demetallizing petroleum resids
US4781817A (en) * 1986-12-04 1988-11-01 Mobil Oil Corporation Hydrogen bronze catalyst and improved resid upgrading processes using it
US4743572A (en) * 1986-12-05 1988-05-10 Mobil Oil Corporation Magnesia-alumina-aluminum phosphate catalyst and catalyst product thereof
US5124024A (en) * 1989-11-20 1992-06-23 Nova Husky Research Corporation Method for extending hydroconversion catalyst life
US5846503A (en) * 1990-12-17 1998-12-08 Mobil Oil Corporation Process for rejuvenating used alkanolamaine solutions
US5651878A (en) * 1992-12-14 1997-07-29 Texaco Inc. Hydrodearomatization of Hydrocarbons
US5556824A (en) * 1993-09-20 1996-09-17 Texaco Inc. Hydrodearomatization of hydrocarbons
EP0696632A1 (en) 1994-08-09 1996-02-14 Texaco Development Corporation Hydrodearomatisation of hydrocarbon oils using phosphorus-treated carbon-supported metal sulphide catalysts
EP0696633A1 (en) 1994-08-09 1996-02-14 Texaco Development Corporation Process for hydrodearomatisation of hydrocarbon oils using carbon supported metal sulphide catalysts promoted by phosphate
EP0731156A3 (en) * 1995-03-09 1996-11-27 Texaco Development Corp Process for hydrodesaromatization of hydrocarbon oils with metal sulphide catalysts on carbon supports and activated by zinc
US5676822A (en) * 1995-03-09 1997-10-14 Texaco Inc. Process for hydrodearomatization of hydrocarbon oils using carbon supported metal sulfide catalysts promoted by zinc
US20030070965A1 (en) * 1999-11-01 2003-04-17 Shih Stuart S. Method for the production of very low sulfur diesel

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Publication number Publication date
JPS4949008B1 (enrdf_load_stackoverflow) 1974-12-25

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