WO2006028196A1 - Procédé pour la désulfuration d'une huile lourde - Google Patents

Procédé pour la désulfuration d'une huile lourde Download PDF

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Publication number
WO2006028196A1
WO2006028196A1 PCT/JP2005/016572 JP2005016572W WO2006028196A1 WO 2006028196 A1 WO2006028196 A1 WO 2006028196A1 JP 2005016572 W JP2005016572 W JP 2005016572W WO 2006028196 A1 WO2006028196 A1 WO 2006028196A1
Authority
WO
WIPO (PCT)
Prior art keywords
heavy oil
desulfurization
oil
catalyst
mass
Prior art date
Application number
PCT/JP2005/016572
Other languages
English (en)
Japanese (ja)
Inventor
Nobuo Aoki
Toshio Waku
Wataru Sahara
Yuichi Tanaka
Kazuaki Hayasaka
Hirofumi Konno
Original Assignee
Nippon Oil Corporation
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 Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to EP05778519A priority Critical patent/EP1798275A4/fr
Priority to CA002578864A priority patent/CA2578864A1/fr
Publication of WO2006028196A1 publication Critical patent/WO2006028196A1/fr
Priority to US11/681,991 priority patent/US20070151902A1/en

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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
    • 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
    • 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
    • C10G45/04—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
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils

Definitions

  • the present invention relates to a method for desulfurizing heavy oil continuously for a long period of time. More specifically, in the oil refining process, heavy oil such as atmospheric residual oil is desulfurized continuously for a long time without catalyst replacement.
  • Heavy oil such as atmospheric residue and vacuum residue produced in the oil refining process usually contains several percent by mass of sulfur and is difficult to produce as it is. Under the present circumstances, a desulfurization treatment is carried out using a catalyst to reduce the sulfur concentration. Since the product obtained from the desulfurization process of heavy oil is further subjected to secondary treatment to become various useful products such as gasoline, kerosene and light oil, the desulfurization process of heavy oil Plays an important role in today's oil refining (see Non-Patent Document 1, for example). If this desulfurization process is stopped, other processes will be affected, and the economics of the refinery will be greatly affected.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-180 0 109
  • Patent Document 2 Japanese Patent Laid-Open No. 1 1 1 1 5 1 4 4 1
  • Non-patent document 1 "Petroleum refining process", Japan Petroleum Institute, 1998, p. 88
  • An object of the present invention is to improve the economics of petroleum refining by dramatically increasing the catalyst life in desulfurization of heavy oil.
  • the present inventors have conducted an operation for decomposing heavy oil at a low decomposition rate in a heavy oil desulfurization step in a state where the concentration of heavy oil is diluted with a dilution medium. It has been found that the life of the desulfurization catalyst can be extended by including the operation, and the present invention has been completed.
  • the present invention is characterized by including an operation of decomposing heavy oil at a decomposition rate of 10% or less in a state where the concentration of heavy oil is diluted to 90% by mass or less with a dilution medium.
  • the present invention relates to a method for desulfurization of heavy oil.
  • the concentration of the heavy oil is 90 masses by the dilution medium. /.
  • the present invention relates to a desulfurization method for heavy oil, characterized in that the heavy oil is decomposed at a decomposition rate of 10% or less in the diluted state, the dilution medium is removed, and then desulfurized in a desulfurization step.
  • the heavy oil used in the present invention includes carbon and hydrogen having an initial boiling point of 300 ° C. or higher and a fraction having a boiling point of 360 ° C. or higher of 90% by mass or more as main constituent elements. Yes Heavy oil.
  • the type of heavy oil used in the present invention is not particularly limited, but examples of typical oils include atmospheric residual oil and reduced-pressure residual oil produced in an oil refining process.
  • the dilution medium used in the present invention is inactive against the heavy oil to be processed.
  • those which are compatible with the heavy oil to be treated at the decomposition temperature are preferable, and a dilution medium having a boiling point of 120 ° C. or lower is particularly preferable.
  • Examples of a preferable dilution medium include aromatic hydrocarbons such as benzene and toluene. With these dilution media, heavy oil can be diluted uniformly.
  • the concentration of heavy oil is 90% by mass or less, preferably 85% by mass or less, and particularly preferably 80% by mass or less by using these dilution media. If the concentration of heavy oil exceeds 90% by mass, a sufficient effect for extending the life of the catalyst cannot be obtained.
  • the lower limit is not particularly limited, but is 20 mass from the viewpoint of process efficiency. / 0 or more is preferable, and 30% by mass or more is more preferable.
  • the mixing temperature is preferably 60 ° C or higher.
  • the heavy oil is decomposed in such a state that the concentration of the heavy oil is diluted to 90% by mass or less with a dilution medium. It is essential that the decomposition process be performed at a low decomposition rate of 10% or less.
  • the cracking rate here means a fraction that is lighter than the raw material heavy oil produced by the cracking process (the fraction having a boiling point lower than the initial boiling point of the raw material heavy oil and does not include the dilution medium). This is the ratio (by mass) of the oil produced.
  • the decomposition rate is controlled to 10% or less, preferably 8% or less. When it is higher than 10%, the effect of extending the life of the desulfurization catalyst is insufficient.
  • the lower limit is not particularly limited, but is preferably 1% or more, more preferably 2% or more from the viewpoint of stable operation.
  • the heavy oil decomposition treatment in the present invention is usually carried out by thermal decomposition.
  • the temperature range used in the pyrolysis is preferably 400 to 60 ° C, more preferably 420 to 5400 ° C.
  • the range of LHSV is preferably 6 to 20 h 1 , more preferably 8 to 15 h 1 .
  • There is no particular limitation on the pressure and it can be carried out at normal to slightly pressurized pressure, but it is usually carried out at normal pressure.
  • the diluted medium is removed from the resulting product oil, and then the desulfurization process is performed in the desulfurization step.
  • the method for removing the dilution medium is not particularly limited, but the dilution medium is usually removed by atmospheric distillation.
  • the catalyst conditions for the desulfurization reaction there are no particular restrictions on the catalyst conditions for the desulfurization reaction, and any known catalyst conditions used for conventional heavy oil desulfurization reactions can be used.
  • the catalyst for example, a catalyst in which molybdenum or tungsten is supported on alumina.
  • Typical reaction conditions include a reaction temperature of 380 to 480 ° C, a reaction pressure of 5 to 20 MPa, and an LHSV of 0.1 to 2.0 h 1 .
  • the desulfurized product oil is further subjected to secondary treatment as before, and can be used as a base material for products such as gasoline, kerosene, light oil and heavy oil.
  • the desulfurization rate of the desulfurization catalyst is reduced, and the life of the catalyst can be extended.
  • vacuum residue (initial boiling point 580 ° C, sulfur content 4.3 mass%) is diluted with benzene to reduce the concentration of vacuum residue to 78 mass%.
  • LHSV 1 O h 1 was supplied.
  • the treated product oil contained 7.7 mass% of decomposition products with a boiling point of less than 580 ° C (decomposition rate 7.7%).
  • This product oil is supplied together with hydrogen to a reaction tower packed with a commercially available heavy oil desulfurization catalyst, and the sulfur content of the product oil after the reaction is reduced under LH S V0.2 h to reaction pressure 15 MPa. It was operated for 30 days while controlling the reaction temperature to be 4% by mass.
  • the reaction temperature gradually increases from 452.0 ° C at the start at a roughly constant rate, and opens at the end of the reaction. 1. 6 ° C higher than the beginning. During this period, the average deterioration rate of the catalyst was 0.053 ° CZ days.
  • Example 2 The same operation as in Example 1 was performed except that the dilution low-decomposition treatment in Example 1 was omitted.
  • the temperature rise for 30 days was 4.8 ° C, and the average catalyst degradation rate was 0.160 ° CZ days.
  • the treated product oil contained 9.7% by mass of decomposition products.
  • this treated oil was desulfurized in the same manner as in Example 1, the reaction temperature increased by 3.5 ° C in 30 days. During this period, the average deterioration rate of the catalyst was 0.1 1 7 ° C / day.
  • the treated product oil contained 14.7% by mass of decomposition products.
  • the reaction temperature increased by 4.6 ° C in 30 days.
  • the average deterioration rate of the catalyst was 0.1 53 ° CZ days.
  • Example 2 The same operation as in Example 1 was performed except that toluene was used instead of benzene in Example 1.
  • the treated product oil contained 8.7% by weight of decomposition products.
  • this treated product oil was desulfurized as in Example 1, the reaction temperature increased by 1.9 ° C in 30 days. During this period, the average deterioration rate of the catalyst was 0.063 ° 0 days.

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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Procédé pour la désulfuration d'une huile lourde, lequel comprend la dilution d'une huile lourde avec un milieu de dilution à une teneur inférieure ou égale à 90 % en poids et une opération consistant à soumettre l'huile lourde diluée résultante à un traitement de décomposition avec un taux de décomposition inférieur ou égal à 10 %. On peut utiliser le procédé ci-dessus pour prolonger la durée de vie d'un catalyseur dans un procédé pour la désulfuration d'une huile lourde.
PCT/JP2005/016572 2004-09-06 2005-09-02 Procédé pour la désulfuration d'une huile lourde WO2006028196A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP05778519A EP1798275A4 (fr) 2004-09-06 2005-09-02 Procédé pour la désulfuration d'une huile lourde
CA002578864A CA2578864A1 (fr) 2004-09-06 2005-09-02 Procede pour la desulfuration d'une huile lourde
US11/681,991 US20070151902A1 (en) 2004-09-06 2007-03-05 Process of desulfurization of heavy oil

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-258719 2004-09-06
JP2004258719A JP2006070230A (ja) 2004-09-06 2004-09-06 重質油の脱硫方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/681,991 Continuation US20070151902A1 (en) 2004-09-06 2007-03-05 Process of desulfurization of heavy oil

Publications (1)

Publication Number Publication Date
WO2006028196A1 true WO2006028196A1 (fr) 2006-03-16

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ID=36036477

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Application Number Title Priority Date Filing Date
PCT/JP2005/016572 WO2006028196A1 (fr) 2004-09-06 2005-09-02 Procédé pour la désulfuration d'une huile lourde

Country Status (7)

Country Link
US (1) US20070151902A1 (fr)
EP (1) EP1798275A4 (fr)
JP (1) JP2006070230A (fr)
KR (1) KR20070100872A (fr)
CN (1) CN101040033A (fr)
CA (1) CA2578864A1 (fr)
WO (1) WO2006028196A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5737981B2 (ja) * 2011-02-04 2015-06-17 独立行政法人石油天然ガス・金属鉱物資源機構 炭化水素油の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5153505A (en) * 1974-11-07 1976-05-12 Showa Oil Tankasuisono henkanhoho
JPS58201889A (ja) * 1982-03-18 1983-11-24 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ 炭化水素油留出物の製法
JPH01103697A (ja) * 1987-10-15 1989-04-20 Chiyoda Corp 複数種の重質炭化水素油を原料とする軽質化方法

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
GB758413A (en) * 1953-11-18 1956-10-03 Exxon Research Engineering Co Improvements in or relating to process for cracking gas oils to gasoline
US3444073A (en) * 1966-09-13 1969-05-13 Gulf Research Development Co Process of hydrogen treating asphaltic and maltene containing fractions
US3549519A (en) * 1968-10-28 1970-12-22 Universal Oil Prod Co Mixed-phase thermal cracking process
US4213846A (en) * 1978-07-17 1980-07-22 Conoco, Inc. Delayed coking process with hydrotreated recycle
US4176046A (en) * 1978-10-26 1979-11-27 Conoco, Inc. Process for utilizing petroleum residuum
FR2559497B1 (fr) * 1984-02-10 1988-05-20 Inst Francais Du Petrole Procede de conversion de residus petroliers lourds en hydrogene et hydrocarbures gazeux et distillables
US4661241A (en) * 1985-04-01 1987-04-28 Mobil Oil Corporation Delayed coking process
US5370787A (en) * 1988-07-25 1994-12-06 Mobil Oil Corporation Thermal treatment of petroleum residua with alkylaromatic or paraffinic co-reactant
US7309416B2 (en) * 2003-07-11 2007-12-18 Aspen Products Group, Inc. Methods and compositions for desulfurization of hydrocarbon fuels

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5153505A (en) * 1974-11-07 1976-05-12 Showa Oil Tankasuisono henkanhoho
JPS58201889A (ja) * 1982-03-18 1983-11-24 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ 炭化水素油留出物の製法
JPH01103697A (ja) * 1987-10-15 1989-04-20 Chiyoda Corp 複数種の重質炭化水素油を原料とする軽質化方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1798275A4 *

Also Published As

Publication number Publication date
CA2578864A1 (fr) 2006-03-16
JP2006070230A (ja) 2006-03-16
EP1798275A1 (fr) 2007-06-20
CN101040033A (zh) 2007-09-19
US20070151902A1 (en) 2007-07-05
KR20070100872A (ko) 2007-10-12
EP1798275A4 (fr) 2008-12-03

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