WO2003087273A1 - Method to increase the cetane number of gas oil - Google Patents

Method to increase the cetane number of gas oil Download PDF

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Publication number
WO2003087273A1
WO2003087273A1 PCT/EP2003/003927 EP0303927W WO03087273A1 WO 2003087273 A1 WO2003087273 A1 WO 2003087273A1 EP 0303927 W EP0303927 W EP 0303927W WO 03087273 A1 WO03087273 A1 WO 03087273A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas oil
cetane number
fischer
derived gas
tropsch
Prior art date
Application number
PCT/EP2003/003927
Other languages
English (en)
French (fr)
Inventor
Richard Hugh Clark
Gautam Tavanappa Kalghatgi
Eleanor Mair Liney
Original Assignee
Shell Internationale Research Maatschappij B.V.
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 Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP03722483A priority Critical patent/EP1506272B1/en
Priority to AT03722483T priority patent/ATE470696T1/de
Priority to DE60332937T priority patent/DE60332937D1/de
Priority to JP2003584217A priority patent/JP2005522569A/ja
Priority to US10/511,127 priority patent/US20050256352A1/en
Priority to BR0308905-3A priority patent/BR0308905A/pt
Priority to AU2003229676A priority patent/AU2003229676A1/en
Publication of WO2003087273A1 publication Critical patent/WO2003087273A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition

Definitions

  • the invention is directed to a method to increase the cetane number of a gas oil product based on a petroleum derived gas oil by adding to the petroleum derived gas oil an amount of a Fischer-Tropsch derived gas oil.
  • petroleum derived gas oils have generally a lower cetane number than gas oils, derived from a Fischer-Tropsch process.
  • Fischer-Tropsch derived gas oil A problem with Fischer-Tropsch derived gas oil is that they are not widely available and that the cost of preparing such gas oils is believed to be higher than the cost of preparing petroleum derived gas oil for the foreseeable future. There is thus a continuous drive to minimize the amount of Fischer-Tropsch derived gas oil in such a blend while meeting the different final product specifications.
  • Fischer-Tropsch derived gas oil is less than the amount which would be added if linear blending is assumed.
  • the fraction x will be a value between 0 and 1 and preferably greater than 0.02.
  • the invention is in particular directed to blends wherein the fraction x of Fischer-Tropsch derived gas oil is less than 0.7 and more preferably less than 0.5 and most preferably between 0.05 and 0.3.
  • A is the cetane number of the petroleum derived gas oil and B the cetane number of the Fischer-Tropsch derived gas oil.
  • the cetane number of the petroleum derived gas oil and the Fischer-Tropsch derived gas oil as used in the method according the invention may be measured according the normal ASTM D613 method.
  • a more preferred method is by measuring the cetane number by near infrared spectroscopy (NIR) as for example described in detail in US-A-5349188. Such measurements will include the use of a correlation between the measured spectrum and the actual cetane number of the sample.
  • NIR near infrared spectroscopy
  • the underlying model is made by correlating the cetane number according to ASTM D613 of a wide variety of petroleum derived samples, Fischer-Tropsch derived gas oil samples and/or their blends with their near infrared spectral data.
  • the method according to the invention is embedded in an automated process control of the blending operation in for example a refinery environment.
  • a process control may use so-called quality estimators which will provide, by making use of a model, a real time prediction of the cetane number of the resulting blend from readily available raw process measurements, such as for example the cetane numbers as measured by NIR and the volumetric flows.
  • quality estimators is calibrated on-line by making use of for example the method described in detail in WO-A-0206905.
  • the Fischer-Tropsch derived gas oil may be any gas oil, which is prepared from the synthesis product of a Fischer-Tropsch synthesis.
  • the gas oil product may be obtained by fractionation of such a Fischer-Tropsch synthesis product or obtained from a hydroconverted (hydrocracking/hydroisomerisation) Fischer-Tropsch synthesis product.
  • Fischer-Tropsch derived gas oils are described in EP-A-583836, WO-A-9714768, WO-A-9714769, WO-A-011116, WO-A-011117, WO-A-0183406, O-A-0183648, WO-A-0183647, WO-A-0183641, WO-A-0020535, O-A-0020534, EP-A-1101813 and US-A-6204426.
  • the Fischer-Tropsch derived gas oil will consist of at least 90 wt%, more preferably at least 95 wt% of iso and linear paraffins.
  • the weight ratio of iso-paraffins to normal paraffins will suitably be greater than 0.3. This ratio may be up to 12. Suitably this ratio is between 2 and 6.
  • the actual value for this ratio will be determined, in part, by the hydroconversion process used to prepare the Fischer-Tropsch derived gas oil from the Fischer-Tropsch synthesis product. Some cyclic-paraffins may be present.
  • the Fischer-Tropsch derived gas oil has essentially zero content of sulphur and nitrogen (or amounts which are no longer detectable) .
  • the Fischer-Tropsch derived gas oil will suitably have a distillation curve which will for its majority be within the typical gas oil range: between about 150 and 400 °C.
  • the Fischer-Tropsch gas oil will suitably have a T90 wt% of between 340-400 °C, a density of between about
  • the petroleum derived gas oils are gas oils as obtained from refining and optionally (hydro) processing of a crude petroleum source.
  • the petroleum derived gas oil may be a single gas oil stream as obtained in such a refinery process or be a blend of several gas oil fractions obtained in the refinery process via different processing routes.
  • Examples of such different gas oil fractions as produced in a refinery are straight run gas oil, vacuum gas oil, gas oil as obtained in a thermal cracking process and light and heavy cycle oil as obtained in a fluid catalytic cracking unit and gas oil as obtained from a hydrocracker unit.
  • a petroleum derived gas oil may comprise some petroleum derived kerosene fraction.
  • the straight run gas oil fraction is the gas oil fraction, which has been obtained in the atmospheric distillation of the crude petroleum refinery feedstock. It has an Initial Boiling Point (IBP) of between 150 and 280 °C and a Final Boiling Point (FBP) of between 320 and 380 °C.
  • IBP Initial Boiling Point
  • FBP Final Boiling Point
  • the vacuum gas oil is the gas oil fraction as obtained in the vacuum distillation of the residue as obtained in the above referred to atmospheric distillation of the crude petroleum refinery feedstock.
  • the vacuum gas oil has an IBP of between 240 and 300 °C and a FBP of between 340 and 380 °C.
  • the thermal cracking process also produces a gas oil fraction, which may.be used in step (a) .
  • This gas oil fraction has an IBP of between 180 and 280 °C and a FBP of between 320 and
  • the light cycle oil fraction as obtained in a fluid catalytic cracking process will have an IBP of between 180 and 260 °C and a FBP of between 320 and 380 °C.
  • the heavy cycle oil fraction as obtained in a fluid catalytic cracking process will have an IBP of between 240 and 280 °C. and a FBP of between 340 and 380 °C.
  • These feedstocks may have a sulphur content of above 0.05 ' wt%. The maximum sulphur content will be about 2 wt%.
  • the Fischer-Tropsch derived gas oil comprises almost no sulphur it could still be necessary to lower the sulphur level of the petroleum derived gas oil in order to meet the current stringent low sulphur specifications.
  • the reduction of sulphur will be performed by processing these gas oil fractions in a hydrodesulphurisation (HDS) unit.
  • HDS hydrodesulphurisation
  • Gas oil as obtained in a fuels hydrocracker has suitably an IBP of between 150 and 280 °C and a FBP of between 320 and 380 °C-
  • the cetane number of the (blend of) petroleum derived gas oil (fractions) as described above is preferably greater than 40 and less than 70.
  • Other properties of the blend need to meet the required specifications. Examples of such properties are the Cloud Point, CFPP (cold filter plugging point) , Flash Point, Density, Di+-aromatics content, Poly Aromatics and/or distillation temperature for 95% recovery.
  • the final blended gas oil product comprising the Fischer-Tropsch and the petroleum derived gas oil will have a sulphur content of at most 2000 ppmw (parts per million by weight) sulphur, preferably no more than 500 ppmw, most preferably no more than 50 or even 10 ppmw.
  • the density of such a blend is typically less than 0.86 g/cm ⁇ at 15 °C, and preferably less than
  • the lower density of such a blend as compared to conventional gas oil blends results from the relatively low density of the Fischer-Tropsch derived gas oils.
  • the above fuel composition is suited as fuel in an indirect injection diesel engine or a direct injection diesel engine, for example of the rotary pump, in-line pump, unit pump, electronic unit injector or common rail type.
  • the final gas oil blend may be an additised (additive-containing) oil or an unadditised (additive- free) oil.
  • the fuel oil is an additised oil, it will contain minor amounts of one or more additives, e.g. one or more additives selected from detergent additives, for example those obtained from Infineum (e.g., F7661 and F7685) and Octel (e.g., OMA 4130D) ; lubricity enhancers, for example EC 832 and PARADYNE 655 (ex Infineum) , HITEC E580 (ex Ethyl Corporation), VELTRON 6010 (ex Infineum) (PARADYNE, HITEC and VELTRON are trademarks) and amide- based additives such as those available from the Lubrizol Chemical Company, for instance LZ 539 C; dehazers, e.g., alkoxylated phenol formaldehyde polymers such as those commercially available as NALCO EC5462A
  • the additive concentration of each such additional component in the additivated fuel composition is preferably up to 1 %w/w, more preferably in the range from 5 to 1000 ppmw, advantageously from 75 to 300 ppmw, such as from 95 to 150 ppmw.

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)
  • Combustion Methods Of Internal-Combustion Engines (AREA)
PCT/EP2003/003927 2002-04-15 2003-04-15 Method to increase the cetane number of gas oil WO2003087273A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP03722483A EP1506272B1 (en) 2002-04-15 2003-04-15 Method to increase the cetane number of gas oil
AT03722483T ATE470696T1 (de) 2002-04-15 2003-04-15 Methode zum erhöhen der cetanzahl von gasöl
DE60332937T DE60332937D1 (de) 2002-04-15 2003-04-15 Methode zum erhöhen der cetanzahl von gasöl
JP2003584217A JP2005522569A (ja) 2002-04-15 2003-04-15 ガス油のセタン価を増大させる方法
US10/511,127 US20050256352A1 (en) 2002-04-15 2003-04-15 Method to increase the cetane number of gas oil
BR0308905-3A BR0308905A (pt) 2002-04-15 2003-04-15 Método para aumentar o ìndice de cetano de um produto de gasóleo, e, produto de gasóleo
AU2003229676A AU2003229676A1 (en) 2002-04-15 2003-04-15 Method to increase the cetane number of gas oil

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP02252637.0 2002-04-15
EP02252637 2002-04-15

Publications (1)

Publication Number Publication Date
WO2003087273A1 true WO2003087273A1 (en) 2003-10-23

Family

ID=29225719

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/003927 WO2003087273A1 (en) 2002-04-15 2003-04-15 Method to increase the cetane number of gas oil

Country Status (9)

Country Link
US (1) US20050256352A1 (zh)
EP (1) EP1506272B1 (zh)
JP (1) JP2005522569A (zh)
CN (1) CN1276062C (zh)
AT (1) ATE470696T1 (zh)
AU (1) AU2003229676A1 (zh)
BR (1) BR0308905A (zh)
DE (1) DE60332937D1 (zh)
WO (1) WO2003087273A1 (zh)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005021688A1 (en) * 2003-09-03 2005-03-10 Shell Internationale Research Maatschappij B.V. Fuel compositions comprising fischer-tropsch derived fuel
WO2005105961A1 (en) 2004-04-28 2005-11-10 Sasol Technology (Pty) Ltd Crude oil derived and gas-to-liquids diesel fuel blends
WO2007020234A1 (en) * 2005-08-12 2007-02-22 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2007039460A1 (en) 2005-09-21 2007-04-12 Shell Internationale Research Maatschappij B.V. Process to blend a mineral derived hydrocarbon product and a fisher-tropsch derived hydrocarbon product
WO2007071747A1 (en) * 2005-12-22 2007-06-28 Shell Internationale Research Maatschappij B.V. Fuel composition
WO2007110448A1 (en) * 2006-03-29 2007-10-04 Shell Internationale Research Maatschappij B.V. Process to prepare an aviation fuel and an automotive gas oil
WO2008000778A1 (en) * 2006-06-28 2008-01-03 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2008052996A1 (en) * 2006-10-30 2008-05-08 Shell Internationale Research Maatschappij B.V. Fuel compositions
JP2008535990A (ja) * 2005-04-11 2008-09-04 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 船舶上で鉱物誘導生成物とフィッシャー−トロプシュ誘導生成物とをブレンドする方法
US7737311B2 (en) 2003-09-03 2010-06-15 Shell Oil Company Fuel compositions
US8173439B2 (en) 2006-12-20 2012-05-08 Roche Diagnostics Operations, Inc. Measurement system with optical referencing
EP3587538A4 (en) * 2017-02-22 2021-02-17 Oshima Shipbuilding Co., Ltd. FUEL COMPOSITION, VESSEL AND AUTOMATIC FUEL COMPOSITION CHANGEOVER

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JP4615913B2 (ja) * 2004-07-02 2011-01-19 出光興産株式会社 燃料油組成物
JP5102965B2 (ja) * 2006-03-31 2012-12-19 Jx日鉱日石エネルギー株式会社 金属加工油組成物
EP2006365B1 (en) * 2006-03-31 2018-02-21 Nippon Oil Corporation Use of a polyfunctional hydrocarbon oil composition
US8646312B2 (en) * 2006-12-01 2014-02-11 Petroleum Analyzer Company, Lp Method and system for measuring RON and MON values for light distillates
US7949471B2 (en) * 2006-12-01 2011-05-24 Petroleum Analyzer Company, Lp Method and system of measuring cetane values for middle distillate fuels
US9080111B1 (en) 2011-10-27 2015-07-14 Magellan Midstream Partners, L.P. System and method for adding blend stocks to gasoline or other fuel stocks
WO2018077976A1 (en) * 2016-10-27 2018-05-03 Shell Internationale Research Maatschappij B.V. Process for preparing an automotive gasoil

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US20020020107A1 (en) * 1999-07-02 2002-02-21 Bailey Brent K. Low molecular weight compression ignition fuel

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WO2000060029A1 (en) * 1999-04-06 2000-10-12 Sasol Technology (Pty) Ltd Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process
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WO2001083648A2 (en) * 2000-05-02 2001-11-08 Exxonmobil Research And Engineering Company Low emissions f-t fuel/cracked stock blends

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7737311B2 (en) 2003-09-03 2010-06-15 Shell Oil Company Fuel compositions
WO2005021688A1 (en) * 2003-09-03 2005-03-10 Shell Internationale Research Maatschappij B.V. Fuel compositions comprising fischer-tropsch derived fuel
JP2007535614A (ja) * 2004-04-28 2007-12-06 セイソル テクノロジー (プロプライエタリー) リミテッド 原油由来のディーゼル燃料及びガストゥーリキッドディーゼル燃料のブレンド
WO2005105961A1 (en) 2004-04-28 2005-11-10 Sasol Technology (Pty) Ltd Crude oil derived and gas-to-liquids diesel fuel blends
AU2005238539B2 (en) * 2004-04-28 2010-07-01 Sasol Technology (Pty) Ltd Crude oil derived and gas-to-liquids diesel fuel blends
JP2008535990A (ja) * 2005-04-11 2008-09-04 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 船舶上で鉱物誘導生成物とフィッシャー−トロプシュ誘導生成物とをブレンドする方法
US7837853B2 (en) 2005-04-11 2010-11-23 Shell Oil Company Process to blend a mineral and a Fischer-Tropsch derived product onboard a marine vessel
NO20081287A (no) * 2005-08-12 2008-05-06 Shell Int Research Brenselsammensetning og fremgangsmåte for å fremstille denne
US8076522B2 (en) * 2005-08-12 2011-12-13 Shell Oil Company Fuel compositions
NO344229B1 (no) * 2005-08-12 2019-10-14 Shell Int Research Brenselsammensetning og fremgangsmåte for å fremstille denne
WO2007020234A1 (en) * 2005-08-12 2007-02-22 Shell Internationale Research Maatschappij B.V. Fuel compositions
US20070135664A1 (en) * 2005-09-21 2007-06-14 Claire Ansell Process to blend a mineral derived hydrocarbon product and a fischer-tropsch derived hydrocarbon product
WO2007039460A1 (en) 2005-09-21 2007-04-12 Shell Internationale Research Maatschappij B.V. Process to blend a mineral derived hydrocarbon product and a fisher-tropsch derived hydrocarbon product
US7867377B2 (en) 2005-12-22 2011-01-11 Shell Oil Company Fuel composition
WO2007071747A1 (en) * 2005-12-22 2007-06-28 Shell Internationale Research Maatschappij B.V. Fuel composition
WO2007110448A1 (en) * 2006-03-29 2007-10-04 Shell Internationale Research Maatschappij B.V. Process to prepare an aviation fuel and an automotive gas oil
US8444718B2 (en) 2006-03-29 2013-05-21 Shell Oil Company Process to prepare an aviation fuel
WO2008000778A1 (en) * 2006-06-28 2008-01-03 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2008052996A1 (en) * 2006-10-30 2008-05-08 Shell Internationale Research Maatschappij B.V. Fuel compositions
US8173439B2 (en) 2006-12-20 2012-05-08 Roche Diagnostics Operations, Inc. Measurement system with optical referencing
EP3587538A4 (en) * 2017-02-22 2021-02-17 Oshima Shipbuilding Co., Ltd. FUEL COMPOSITION, VESSEL AND AUTOMATIC FUEL COMPOSITION CHANGEOVER

Also Published As

Publication number Publication date
AU2003229676A1 (en) 2003-10-27
CN1646667A (zh) 2005-07-27
DE60332937D1 (de) 2010-07-22
EP1506272A1 (en) 2005-02-16
CN1276062C (zh) 2006-09-20
US20050256352A1 (en) 2005-11-17
JP2005522569A (ja) 2005-07-28
BR0308905A (pt) 2005-01-04
EP1506272B1 (en) 2010-06-09
ATE470696T1 (de) 2010-06-15

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