WO2008124912A1 - Procede de valorisation de petrole brut lourd - Google Patents

Procede de valorisation de petrole brut lourd Download PDF

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Publication number
WO2008124912A1
WO2008124912A1 PCT/CA2007/000599 CA2007000599W WO2008124912A1 WO 2008124912 A1 WO2008124912 A1 WO 2008124912A1 CA 2007000599 W CA2007000599 W CA 2007000599W WO 2008124912 A1 WO2008124912 A1 WO 2008124912A1
Authority
WO
WIPO (PCT)
Prior art keywords
thfa
hco
distillate
distillation
mixture
Prior art date
Application number
PCT/CA2007/000599
Other languages
English (en)
Inventor
George A. Constable
Norman L. Carlson
Gerard A. Heelan
Klaus H. Oehr
Original Assignee
Tru Oiltech Inc.
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 Tru Oiltech Inc. filed Critical Tru Oiltech Inc.
Priority to PCT/CA2007/000599 priority Critical patent/WO2008124912A1/fr
Publication of WO2008124912A1 publication Critical patent/WO2008124912A1/fr

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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
    • C10G7/00—Distillation of hydrocarbon 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/06—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by pressure distillation

Definitions

  • the present method relates to the field of upgrading heavy hydrocarbons, especially heavy crude oil (HCO), such as high sulphur containing heavy oil (i.e. "sour heavy crude oil”), to a light crude oil (LCO).
  • HCO heavy crude oil
  • sour heavy crude oil high sulphur containing heavy oil
  • LCO light crude oil
  • Crude oil contains a number of different chemical components. In general terms, it consists primarily of hydrocarbon compounds, with varying amounts of impurities such as sulphur, nitrogen and oxygen. Heavy crude oil has a lower hydrogen-to-carbon ratio than lighter crude oil, therefore the density (or specific gravity) of heavy crude oil is greater than that of light crude oil.
  • Viscosity is the resistance of fluid to flow.
  • Heavy oil is generally any crude oil with an API gravity ranging from about 10° to 20° at standard conditions and with a gas-free viscosity ranging from about 100 to 10,000 centipoises at original reservoir temperature.
  • Ultra heavy oil such as tar sand oil, also known as bitumen, is any crude oil with an API gravity less than about 10° and a gas- free viscosity greater than 10,000 centipoises.
  • a significant problem with heavy oil is the difficulty and expense entailed in increasing the volume of light hydrocarbons distilled from a heavy oil feedstock. Typically, this is done by increasing the hydrogen-to-carbon ratio. This can be accomplished by either removing carbon or by adding hydrogen. Carbon is typically removed by coking, solvent deasphalting, or catalytic cracking. Hydrogen is typically added by hydrotreating or hydrocracking. Hydrocracking processes are known which utilize a catalyst in a hydrogen environment to convert heavy distillates into lighter distillates such as gasoline or jet fuels. Such processes typically include adding to heavy oil feedstock or distillate a source of donor hydrogen such as hydrogen gas. Unfortunately, typical heavy-oil feedstocks have relatively high metal content (100 parts per million or higher) thus limiting the application of hydrocracking because the metals contaminate the catalyst.
  • THFA tetrahydrofurfuryl alcohol
  • U.S. Patent No. 4,360,420 issued to Fletcher et al., discloses a method of re-refining used oil by low pressure evaporation or distillation, followed by solvent extraction of the distillate with THFA (see col. 2, lines 18-27 of Fletcher et al.).
  • U.S. Patent No. 4,360,420 issued to Fletcher et al., discloses a method of re-refining used oil by low pressure evaporation or distillation, followed by solvent extraction of the distillate with THFA (see col. 2, lines 18-27 of Fletcher et al.).
  • 7,094,331 issued to Kiser, discloses the use of 0.5 to 5 % by weight dihydric alcohols as non-distillation additives to reduce heavy hydrocarbon viscosity. Neither of these patents describe methods for upgrading a heavy or crude oil to a light crude oil compatible with hydrotreaters.
  • the present invention is a method of upgrading heavy crude oil, especially high sulphur HCO, via the addition of THFA.
  • the present invention relates to the use of THFA as a cracking additive, the use of THFA as a distillation additive, and to hydrocarbon distillates and light crude oils produced by distillation of HCO in the presence of THFA.
  • HCO refers to heavy hydrocarbons and includes heavy oil, ultra heavy oil, bitumen, sour crude oil and oil refinery heavy hydrocarbon residues.
  • the THFA is used as a combination distillation and cracking additive.
  • THFA is a monohydric alcohol-ether, which in the present invention is added to HCO to form an HCO-THFA mixture.
  • the HCO-THFA mixture is heated and distilled to form a lower density, lower acidity, ash-free distillate called light gas oil (LGO), containing less sulphur and having lower viscosity than the feed HCO.
  • LGO light gas oil
  • Subsequent distillation of the LGO residue can be performed under vacuum to produce a vacuum gas oil (VGO).
  • the distillate is essentially a light crude oil (LCO) containing THFA.
  • LCO is used herein to refer to light crude oil and includes light gas oil (LGO) and vacuum gas oil (VGO).
  • the distillate is an ash-free LCO that has a lower olefin content than conventional distillates.
  • the distillate of the present invention has higher value than its HCO feed and can be used, for example, as a fuel in a gas-turbine for producing electricity, steam, or electricity plus steam, (with or without all or a portion of its THFA removed). Furthermore, the distillate of the present invention (with or without all or a portion of its THFA removed) can be easily upgraded (e.g. with hydrotreaters) to reduce its sulphur content and to further increase its API gravity, since it is heavy metal-free and therefore will not foul hydrotreater catalysts.
  • THFA is able to form small amounts of organoperoxide (THFAP) under aeration, especially at elevated temperatures. Organoperoxides are able to decompose under heat to create free radicals which are believed to enhance thermal cracking of molecules such as those in HCO. It is believed that a functionality of THFA is to generate HCO free radicals conducive to enhanced thermal cracking before or during distillation when the THFA is exposed to oxygen alone or in combination with HCO. This is indicated by lower maximum boiling point of the Sample 1 distillate than of the Sample 2 distillate (i.e. 320 0 C vs. 342°C).
  • the THFA- HCO mixture can be aerated prior to distillation as described above, the THFA-HCO mixture can be aerated during the distillation, the distillate (containing THFA) can be aerated, THFA can be aerated prior to mixing with HCO, etc.
  • Sample 1 distillate had the following characteristics, relative to the undistilled HCO feed:
  • Sample 3 having the same HCO used in Example 1 , was distilled in similar fashion to Example 1 above, to determine the effect of THFA on distillate density (e.g. American Petroleum Institute "API" gravity") and viscosity.
  • Sample 3 consisting of a THFA-HCO mixture having 10 parts by weight THFA per 90 parts by weight HCO, was heated for 2 hours at 150 0 C with aeration and stirring, followed by atmospheric pressure distillation. The results are as follows:
  • API gravity of Sample 3 distillate vs. undistilled HCO feed (i.e. API gravity of 9.3 for undistilled HCO feed vs. API gravity of 27.0 for Sample 3).
  • Samples 4 and 5 Two samples (Samples 4 and 5) of HCO (this time bitumen from Athabasca, Alberta, Canada), were distilled via atmospheric pressure distillation (760 mm mercury pressure) followed by vacuum distillation (0.67 mm mercury pressure) in which distilled gases during the atmospheric pressure distillation were collected in a Tedlar® bag. Samples 4 and 5 were not subjected to 2 hour aeration, stirring or heating at 150 0 C. Sample 4 had 10 parts by weight THFA per 90 parts by weight HCO, and Sample 5 had no THFA. Distillations were carried out using the apparatus described in the American Society of Testing Materials (ASTM) method D86. Sample 4 was stirred with a magnetic Teflon®- coated stirrer bar, during the atmospheric distillation.
  • ASTM American Society of Testing Materials
  • Atmospheric pressure distillation time for Sample 4 was 528 seconds (time from start of producing distillate to the end of producing distillate).
  • the initial and final boiling points for atmospheric pressure distillate of Sample 5 were 296°C and 374°C, respectively.
  • the initial and final boiling points for atmospheric pressure distillate of Sample 4 were 176°C and 38O 0 C, respectively.
  • Sample 4 distillate had the following characteristics, relative to the undistilled HCO feed:
  • THFA can be removed from the distillate, as from LCO, by distillation since its boiling point of 178 0 C is lower than that of the majority of LCO components. Most of the LCO components have boiling points higher than THFA. With respect to the distillate of Sample 4, it is estimated that less than about 5% of the distillate boils below the THFA boiling point, and that about 95% of the distillate boils above the THFA boiling point. Therefore it is possible to obtain high THFA recovery by distillation alone.
  • THFA is also water soluble, therefore an alternative for removing THFA from the distillate would be to remove the THFA by water extraction.
  • THFA THFA
  • distillation feedstock having THFA content that is higher or lower than the 10 wt% specifically discussed herein would result in similar enhancements in LCO or LCO quality including yield, sulphur content, olefin content, etc., although quantitatively the results are expected to be sensitive to THFA dose.
  • the present invention is scaled up to industrial scale, and as the present invention is optimized for various applications (e.g.
  • the present invention is not limited to doses of 10 wt%, and that the scope of the invention includes THFA doses higher and lower than 10 wt%. It is important to note that the distillates produced from Samples 1 , 3 and 4 above are free of heavy metals. Therefore they can be upgraded (with or without the THFA contained therein) to reduce sulphur content and to further increase API gravity, since they will not foul hydrotreater catalysts.
  • the THFA and HCO were mixed and then added to the distillation vessel together.
  • the invention need not necessarily be carried out in this manner. It is also possible to add the THFA and HCO to the distillation vessel separately. For example, pump THFA and HCO separately into the distillation vessel.

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

L'invention concerne un procédé de valorisation du pétrole brut lourd, tel que le pétrole lourd, le pétrole ultra-lourd, le bitume, le pétrole brut corrosif lourd et les résidus d'hydrocarbures lourds de raffinage du pétrole, par l'addition d'alcool tétrahydrofurfurylique (THFA). De manière correspondante, la présente invention porte sur l'utilisation de THFA comme additif de craquage, sur l'utilisation de THFA comme additif de distillation et sur des distillats d'hydrocarbures obtenus par distillation de pétrole brut lourd en présence de THFA.
PCT/CA2007/000599 2007-04-11 2007-04-11 Procede de valorisation de petrole brut lourd WO2008124912A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CA2007/000599 WO2008124912A1 (fr) 2007-04-11 2007-04-11 Procede de valorisation de petrole brut lourd

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CA2007/000599 WO2008124912A1 (fr) 2007-04-11 2007-04-11 Procede de valorisation de petrole brut lourd

Publications (1)

Publication Number Publication Date
WO2008124912A1 true WO2008124912A1 (fr) 2008-10-23

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Country Status (1)

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WO (1) WO2008124912A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104419443A (zh) * 2013-09-09 2015-03-18 中国石油化工股份有限公司 一种烃油蒸馏方法
WO2015142858A1 (fr) * 2014-03-18 2015-09-24 Quanta Associates, L.P. Traitement du pétrole brut lourd et du diluant
US20160010004A1 (en) * 2013-02-15 2016-01-14 Rival Technologies Inc. Method of Upgrading Heavy Crude Oil
US10113122B2 (en) 2015-08-31 2018-10-30 University Of New Brunswick Process for upgrading heavy hydrocarbon liquids
WO2019084672A1 (fr) * 2017-11-02 2019-05-09 Rival Technologies Inc. Valorisation de pétrole brut lourd avant craquage thermique
US10308878B2 (en) 2016-10-07 2019-06-04 Ying Zheng Catalytic process for co-processing of cellulosic biomass and heavy petroleum fuels

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302325A (en) * 1980-10-28 1981-11-24 Delta Central Refining, Inc. Solvent extraction process for rerefining used lubricating oil
US4360420A (en) * 1980-10-28 1982-11-23 Delta Central Refining, Inc. Distillation and solvent extraction process for rerefining used lubricating oil
US4399025A (en) * 1980-10-28 1983-08-16 Delta Central Refining, Inc. Solvent extraction process for rerefining used lubricating oil
US4877513A (en) * 1987-12-11 1989-10-31 Hydrocarbon Sciences, Inc. Oil characteristic improvement process and device therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302325A (en) * 1980-10-28 1981-11-24 Delta Central Refining, Inc. Solvent extraction process for rerefining used lubricating oil
US4360420A (en) * 1980-10-28 1982-11-23 Delta Central Refining, Inc. Distillation and solvent extraction process for rerefining used lubricating oil
US4399025A (en) * 1980-10-28 1983-08-16 Delta Central Refining, Inc. Solvent extraction process for rerefining used lubricating oil
US4877513A (en) * 1987-12-11 1989-10-31 Hydrocarbon Sciences, Inc. Oil characteristic improvement process and device therefor

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160010004A1 (en) * 2013-02-15 2016-01-14 Rival Technologies Inc. Method of Upgrading Heavy Crude Oil
US9988584B2 (en) 2013-02-15 2018-06-05 Rival Technologies Inc. Method of upgrading heavy crude oil
CN104419443A (zh) * 2013-09-09 2015-03-18 中国石油化工股份有限公司 一种烃油蒸馏方法
CN104419443B (zh) * 2013-09-09 2016-01-20 中国石油化工股份有限公司 一种烃油蒸馏方法
WO2015142858A1 (fr) * 2014-03-18 2015-09-24 Quanta Associates, L.P. Traitement du pétrole brut lourd et du diluant
US9751072B2 (en) 2014-03-18 2017-09-05 Quanta, Associates, L.P. Treatment of heavy crude oil and diluent
US9925513B2 (en) 2014-03-18 2018-03-27 Quanta Associates, L.P. Treatment of heavy crude oil and diluent
US10113122B2 (en) 2015-08-31 2018-10-30 University Of New Brunswick Process for upgrading heavy hydrocarbon liquids
US10308878B2 (en) 2016-10-07 2019-06-04 Ying Zheng Catalytic process for co-processing of cellulosic biomass and heavy petroleum fuels
WO2019084672A1 (fr) * 2017-11-02 2019-05-09 Rival Technologies Inc. Valorisation de pétrole brut lourd avant craquage thermique

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