EP0978552B1 - Procédé d'élimination de composés metalliques à partir d'huiles lourdes - Google Patents

Procédé d'élimination de composés metalliques à partir d'huiles lourdes Download PDF

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Publication number
EP0978552B1
EP0978552B1 EP99114579A EP99114579A EP0978552B1 EP 0978552 B1 EP0978552 B1 EP 0978552B1 EP 99114579 A EP99114579 A EP 99114579A EP 99114579 A EP99114579 A EP 99114579A EP 0978552 B1 EP0978552 B1 EP 0978552B1
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EP
European Patent Office
Prior art keywords
heavy
metal compounds
heavy oils
metal
fraction
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Expired - Lifetime
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EP99114579A
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German (de)
English (en)
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EP0978552A2 (fr
EP0978552A3 (fr
Inventor
Kjeld Andersen
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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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier
    • 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
    • C10G45/24—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 with hydrogen-generating compounds
    • C10G45/26—Steam or water

Definitions

  • the invention relates to a process for the catalytic removal of Metal compounds from heavy oils.
  • Heavy oils usually contain metal compounds, often in large quantities Amounts, especially vanadium and nickel. Based on these Metal compounds is based on the recovery of heavy oils in general limited use as a fuel.
  • the upper temperature limit must therefore generally be below 440 ° C in order to prevent excessive coke formation, which would lead to the reactor systems becoming blocked.
  • Methods for removing or concentrating metal compounds from heavy oils in the presence of water near the critical point are described, for example, in US Patents 3983027, 3453206, 3733259, 3586621, 4446012 or 4743357. In these processes, the metals from the unprocessed heavy oil are usually found in the heaviest part of the oil product that flows off after treatment in unconverted form. This can be determined from the refractive properties of the organometallic compounds.
  • US Pat. No. 4,444,012 describes a non-catalytic process in which Boscan heavy oil from Venezuela was used as a feed at a temperature of 410 ° C. and a pressure of 140 ⁇ 10 5 Pa (140 bar), which has a density (API) of 10.3 and had a vanadium and nickel content of 1500 and 100 ppm, respectively.
  • API density
  • the draining oil was separated into two fractions, one with a boiling point below 343 ° C and soluble in pentane, which made up 64.6% by weight of the starting fraction and was the light fraction after conversion , and a second fraction with a boiling point above 343 ° C., insoluble in pentane, which represented 22.2% by weight of the starting fraction and was called the heavy fraction.
  • the untreated heavy starting oil originally contained about 15% by weight, which corresponded to the definition as light fraction.
  • vanadium or nickel contents of 7.8 ppm or 1.2 ppm were found in the light fraction, while the heavy fraction had concentrated vanadium or nickel to 5900 ppm or 600 ppm.
  • US-A-4,381,993 describes a method for removing Impurities from hydrocarbons described in which the Hydrocarbons at a temperature between 260 and 455 ° C with a gas containing water and carbon monoxide in the presence of a Treated catalyst, which is a base metal component of group VIII of the periodic table, activated alumina and a Contains phosphorus component.
  • a Treated catalyst which is a base metal component of group VIII of the periodic table, activated alumina and a Contains phosphorus component.
  • a gas for Treatment of the hydrocarbons makes this process expensive.
  • carbon monoxide is toxic, so its use is a Represents a source of danger.
  • a method is proposed in which a catalyst containing a metal from group IVB and a metal from group IA of the periodic table at temperatures between 300 to 500 ° C. and a pressure between 101 ⁇ 10 5 Pa and 304 ⁇ 10 5 Pa (100 to 300 atm) is used and in which zirconium oxide impregnated with potassium carbonate in the form of granules or tablets is used as a fixed bed catalyst in the reactor.
  • Catalysts from compounds of group IVB and IA of the periodic table are known per se from EP 0 402 405, but for use in Gasification process for organic substances.
  • group IVB is preferably zirconium oxide, which is used in the relatively high Temperatures is stable.
  • the preferred compound from the group IA is potassium carbonate, but it can be replaced by other potassium salts.
  • Other metal compounds of group IA or group IVB can also be used use, the ratio of the group IA compounds to that Group IVB should be in the range of about 0.01: 1 to 0.5: 1.
  • the invention offers the advantage that effective metal removal takes place and no enrichment of the metal compounds in the heavy fraction of the draining oil takes place. The separate treatment and disposal of this Difficult phase is therefore eliminated.
  • the catalytic demetallization was carried out at a pressure of 225 ⁇ 10 5 Pa (225 bar) and a temperature of 480 ° C for a period of 30 minutes, the oil feed (LHSV) being 1000 ml / h.
  • the outflowing oil fraction was not separated, but from it Total fraction performed a metal analysis that contained vanadium or nickel of 6 ppm or 2 ppm.
  • the yield was more than 99% in terms of metal removal.
  • the vanadium and nickel determinations were carried out in a manner known per se by atomic absorption spectroscopy.
  • a residue from a petroleum distillation under atmospheric pressure and water in a weight ratio of 0.9: 1 was introduced.
  • the distillation residue had a density (API) of 12.6 and a vanadium content of 7.0 ppm and a nickel content of 2.0 ppm.
  • the demetalization was carried out at a pressure of 225.10 6 Pa (225 bar) and a temperature of 460 ° C over a period of 30 minutes.
  • the effluent fraction was not divided into a light and a heavy fraction separated, but made a metal analysis of the total fraction, which found a content of vanadium or nickel of 0.2 or 0.1 ppm.

Landscapes

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

Claims (2)

  1. Procédé d'élimination catalytique de composés métalliques d'huiles lourdes, selon lequel on utilise un catalyseur contenant un métal du groupe IVB et un métal du groupe IA de la classification périodique des éléments, à des températures comprises entre 300 et 500 °C et à une pression comprise entre 101·105 Pa et 304·105 Pa (100 à 300 atm), caractérisé en ce qu'il utilise de l'oxyde de zirconium imprégné de carbonate de potassium, se présentant sous forme de granulés ou de pastilles, en tant que catalyseur à lit fixe dans le réacteur.
  2. Procédé selon la revendication 1, caractérisé en ce que la conversion a lieu à des températures comprises entre 400 et 500 °C et à une pression comprise entre 151·105 Pa et 253·105 Pa (150 à 250 atm).
EP99114579A 1998-08-06 1999-07-24 Procédé d'élimination de composés metalliques à partir d'huiles lourdes Expired - Lifetime EP0978552B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19835479 1998-08-06
DE19835479A DE19835479B4 (de) 1998-08-06 1998-08-06 Verfahren zum katalytischen Entfernen von Metallverbindungen aus Schwerölen

Publications (3)

Publication Number Publication Date
EP0978552A2 EP0978552A2 (fr) 2000-02-09
EP0978552A3 EP0978552A3 (fr) 2000-04-05
EP0978552B1 true EP0978552B1 (fr) 2004-09-01

Family

ID=7876612

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Application Number Title Priority Date Filing Date
EP99114579A Expired - Lifetime EP0978552B1 (fr) 1998-08-06 1999-07-24 Procédé d'élimination de composés metalliques à partir d'huiles lourdes

Country Status (3)

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US (1) US6325921B1 (fr)
EP (1) EP0978552B1 (fr)
DE (2) DE19835479B4 (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3724438B2 (ja) * 2002-03-08 2005-12-07 株式会社日立製作所 超臨界水による重質油の処理方法と処理装置及び重質油処理装置を備えた発電システム
JP4098181B2 (ja) * 2003-08-05 2008-06-11 株式会社日立製作所 重質油の処理方法及び重質油類処理システム
US7435330B2 (en) * 2003-10-07 2008-10-14 Hitachi, Ltd. Heavy oil reforming method, an apparatus therefor, and gas turbine power generation system
DE602006019698D1 (de) * 2006-05-30 2011-03-03 Environmental Consulting Catalysts & Processes For A Sustainable Dev Verfahren zur Herstellung von leichten Kohlenwasserstoffen aus natürlichen Bitumen oder Schwerölen
US7922895B2 (en) 2006-06-14 2011-04-12 Conocophillips Company Supercritical water processing of extra heavy crude in a slurry-phase up-flow reactor system
US20070289898A1 (en) * 2006-06-14 2007-12-20 Conocophillips Company Supercritical Water Processing of Extra Heavy Crude in a Slurry-Phase Up-Flow Reactor System
US7842181B2 (en) 2006-12-06 2010-11-30 Saudi Arabian Oil Company Composition and process for the removal of sulfur from middle distillate fuels
JP5111072B2 (ja) * 2007-11-22 2012-12-26 三菱電機株式会社 液晶表示装置
BRPI0820362A2 (pt) 2007-11-28 2015-05-12 Saudi Arabian Oil Co Processo para melhorar a qualidade do petróleo bruto altamente ceroso através de água quente pressurizada.
US8142646B2 (en) 2007-11-30 2012-03-27 Saudi Arabian Oil Company Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds
WO2009105749A2 (fr) 2008-02-21 2009-08-27 Saudi Arabian Oil Company Catalyseur pour parvenir à une essence à faible teneur en soufre
US8394260B2 (en) * 2009-12-21 2013-03-12 Saudi Arabian Oil Company Petroleum upgrading process
US9005432B2 (en) 2010-06-29 2015-04-14 Saudi Arabian Oil Company Removal of sulfur compounds from petroleum stream
US9039889B2 (en) 2010-09-14 2015-05-26 Saudi Arabian Oil Company Upgrading of hydrocarbons by hydrothermal process
US9382485B2 (en) 2010-09-14 2016-07-05 Saudi Arabian Oil Company Petroleum upgrading process
US8535518B2 (en) 2011-01-19 2013-09-17 Saudi Arabian Oil Company Petroleum upgrading and desulfurizing process
US10752847B2 (en) 2017-03-08 2020-08-25 Saudi Arabian Oil Company Integrated hydrothermal process to upgrade heavy oil
US10703999B2 (en) 2017-03-14 2020-07-07 Saudi Arabian Oil Company Integrated supercritical water and steam cracking process
CA3024814C (fr) 2018-01-20 2023-04-25 Indian Oil Corporation Limited Un procede de conversion de petroles bruts a teneur elevee en acide
US10526552B1 (en) 2018-10-12 2020-01-07 Saudi Arabian Oil Company Upgrading of heavy oil for steam cracking process

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3453206A (en) 1966-06-24 1969-07-01 Universal Oil Prod Co Multiple-stage hydrorefining of petroleum crude oil
US3586621A (en) 1968-09-03 1971-06-22 Phillips Petroleum Co Hydrocarbon steam reforming,conversion and refining
US3733259A (en) * 1971-11-10 1973-05-15 Texaco Inc Treatment of heavy petroleum oils
US3983027A (en) 1974-07-01 1976-09-28 Standard Oil Company (Indiana) Process for recovering upgraded products from coal
US4381993A (en) * 1981-10-14 1983-05-03 Standard Oil Company (Indiana) Process for treating hydrocarbon feedstocks with CO and H2 O in the presence of steam stable catalysts
US4446012A (en) * 1982-12-17 1984-05-01 Allied Corporation Process for production of light hydrocarbons by treatment of heavy hydrocarbons with water
US4743357A (en) 1983-12-27 1988-05-10 Allied Corporation Catalytic process for production of light hydrocarbons by treatment of heavy hydrocarbons with water
DE3806732A1 (de) 1988-03-02 1989-11-09 Andersen Kjeld Methode zur vergasung von organischem material in synthesegas oder gasfoermigen oder fluessigen kohlenwasserstoffen oder zur entfernung von organischem material in abwasser
US5236882A (en) * 1991-01-22 1993-08-17 Mobil Oil Corp. Catalyst comprising a hydrogenation metal and a delaminated layered silicate

Also Published As

Publication number Publication date
DE19835479B4 (de) 2007-06-06
US6325921B1 (en) 2001-12-04
EP0978552A2 (fr) 2000-02-09
DE59910380D1 (de) 2004-10-07
EP0978552A3 (fr) 2000-04-05
DE19835479A1 (de) 2000-02-10

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