EP1627028B1 - Procede d'amelioration de coupes gazoles et kerosenes de petrole brut - Google Patents

Procede d'amelioration de coupes gazoles et kerosenes de petrole brut Download PDF

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Publication number
EP1627028B1
EP1627028B1 EP04741581A EP04741581A EP1627028B1 EP 1627028 B1 EP1627028 B1 EP 1627028B1 EP 04741581 A EP04741581 A EP 04741581A EP 04741581 A EP04741581 A EP 04741581A EP 1627028 B1 EP1627028 B1 EP 1627028B1
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EP
European Patent Office
Prior art keywords
kerosene
fraction
petroleum
crude
fischer
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Expired - Lifetime
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EP04741581A
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German (de)
English (en)
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EP1627028A1 (fr
Inventor
Willem Bosch
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons

Definitions

  • Virgin naphtha fractions as distilled from Napthenic or Aromatic crudes are very suitable to prepare high octane motor gasoline components as they are easy convertable via Catalytic Reforming to high octane value reformates.
  • virgin kerosenes and virgin gasoils produced from Naphthenic and/or Aromatic crudes are being characterised by certain quality properties which makes them unsuitable to meet certain environmentally driven fuels specifications as required by an increasing number of legislators in various Regions and Markets.
  • Diesel quality gasoils produced from such naphthenic or aromatic crudes will typically feature a low cetane number (CN).
  • CN cetane number
  • the cetane number will be between 35-50 below the required international Cetane number specifications set for Diesel grades.
  • the minimum Cetane Number requirement in the European Diesel specification (EN 590) has been increased to minimum of 51 from year 2000 onwards to meet the European Diesel fuel and emissions requirements set in the EU Fuels Directive 98/70 for Euro III fuels.
  • EU Fuels Directive 98/70 for Euro III fuels.
  • Global car manufacturers want to increase Diesel fuel Cetane Number requirements even further to minimum 55 as published in their World Wide Fuel Charter in year 2002.
  • a disadvantage of blending with paraffinic crudes is that such crudes are not always available at the refinery location or only at a much higher price.
  • Another disadvantage is, that it is not always possible to find a paraffinic crude to blend which will meet both kerosene and gas oil properties and volume demands of distillates to the qualities respectively quantities as specified.
  • the object of the present invention is to obtain a process to prepare kerosene and gas oil from a naphthenic or aromatic crude wherein the product quality give away is being reduced and wherein special measures to reduce the naphthenic or aromatic hydrocarbon contents is not required.
  • Process to prepare a kerosene and a gasoil product from a crude petroleum source having a Watson characterisation factor K value of equal or below 12.0 by (a) isolation of a petroleum derived kerosene fraction and a petroleum derived gasoil fraction from said crude petroleum source, wherein the petroleum derived kerosene fraction has a smoke point of below 25 mm or below 19 mm if naphthalenes content of the kerosene fraction is below 3 %vol and the petroleum derived gas oil has a cetane number of below 50 or a density higher than 845 kg/m 3 , (b) adding a Fischer-Tropsch derived kerosene fraction to the petroleum derived kerosene fraction in an amount sufficient to obtain a mixture having a smoke point value of above 25 mm or above 19 mm if the naphthalenes content of the mixture is below 3 %vol and (c) adding a Fischer-Tropsch derived gas oil fraction to
  • the process according to the invention provides a simple method to obtain kerosene and gas oil products having desired properties while avoiding the need to co-processing a paraffinic crude.
  • Fischer-Tropsch products as blending components also facilitates the use of virgin kerosene and gas oil distilled from a naphthenic or aromatic crude type. This will thus reduce the need or even avoid hydroprocessing steps, which are normally applied to reduce the naphthenic or aromatics contents in these fractions.
  • the petroleum crude source feature a value of the Watson characterisation factor K of equal or below 12.0. These K-values are being calculated according to formulae and nomograms described in the API Technical Data Book (section 2 characterisation).
  • K-values are being calculated according to formulae and nomograms described in the API Technical Data Book (section 2 characterisation).
  • Examples of crude petroleum sources having such a low K value are West African crudes, for example Forcados and Nigerian Light, Far East crudes, for example Champion Export, Labuan and Miri Light, North Sea crudes for example Danish (DUC), Troll, Gryphon and Alba crudes and South American crudes, for example Tia Juana Pesado, Bachequero and Maya.
  • the petroleum derived fraction of the gas oil and kerosene products as obtained from the process according to the invention are for more than 50 wt%, more preferably more than 70 wt% and most preferably more than 90 wt% based on a crude having a K value equal or below 12.0.
  • a petroleum derived kerosene and gas oil is isolated, preferably by distillation. Such distillation is preferably carried out in an atmospheric distillation column by well known processes for the person skilled in refinery operations.
  • the fractions isolated by distillation and which have not been subjected to another conversion process are referred to as virgin distillate fractions.
  • the petroleum derived kerosene fraction will preferably have an ASTM D 86 distillation IBP of between 140 and 200 °C and a final boiling point of between 200 and max 300 °C.
  • the petroleum derived gas oil fraction should preferably have an ASTM D 86 IBP of between 250 and 300 °C and a FBP of between 340 and 380 °C.
  • Fischer-Tropsch derived kerosene and gas oil fractions are suitably obtained from the (hydrocracked) Fischer-Tropsch synthesis product.
  • Fischer-Tropsch derived kerosene and gas oils are described in EP-A-583836 , WO-A-9714768 , WO-A-9714769 , WO-A-011116 , WO-A-011117 , WO-A-0183406 , WO-A-0183648 , WO-A-0183647 , WO-A-0183641 , WO-A-0020535 , WO-A-0020534 , EP-A-1101813 , US-A-5766274 , US-A-5378348 , US-A-5888376 and US-A-6204426 .
  • the Fischer-Tropsch derived kerosene 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 kerosene or gas oil from the Fischer-Tropsch synthesis product. Some cyclic-paraffins may be present.
  • the Fischer-Tropsch derived kerosene will suitably have a smoke point of higher than 25 mm and preferably above 50 mm and the ASTM D 86 distillation curve which will for its majority be within the typical kerosene range: between about 150 and 200 °C, a density of about 740 kg/m 3 at 15 °C, and zero sulphur and aromatics levels (below detection limits).
  • 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 kerosene or gas oil from the Fischer-Tropsch synthesis product. Some cyclic-paraffins may be present.
  • the Fischer-Tropsch derived gas oil will suitably have a cetane number of higher than 60 and preferably above 70 and an ASTM D 86 distillation curve which will for its majority be within the typical gas oil range: between about 200 and 400 °C.
  • the Fischer-Tropsch gas oil will suitably have a T90 %vol of between 300-400 °C, a density of between about 0.76 and 0.79 g/cm 3 at 15 °C, and a viscosity between about 2.5 and 4.0 centistokes at 40 °C.
  • Blending can either be performed by so-called in-line blending, on-line blending or batch blending. This depends on the level of automation.
  • in batch blending the petroleum derived fraction and the Fischer-Tropsch derived fraction are first mixed and subsequently supplied to a storage vessel and than supplied to a ship, rail or road car or other means of transport of the final blend.
  • the desired product quality, i.e. smoke point or cetane number, of the feed to the storage vessel is measured and the quantity of the blending components is adjusted such that the property value is maintained within a pre-determined range in order to minimise quality give-away.
  • the invention will be illustrated with the following non-limiting examples.
  • the Examples are based on calculations using known blending rules.
  • a naphthenic crude having a UOPK value of 11.5 is distilled into a naphtha fraction, a kerosene fraction and a gas oil fraction.
  • the properties of the different fractions are listed in Table 1.
  • Table 1 Distillates properties of a typical Naphthenic crude Kerosene Gas oil Yield on naphthenic crude (%woc) 12.2 36.9
  • Final boiling point (°C) 235 350 Density (spec ⁇ 845 kg/m 3 Diesel EN 590) 840 887 Smoke point (spec >25 mm) 18 - Aromatics (%vol) 21 43 Sulphur (%wt) 0.02 0.07 Cetane number (spec >51 33 38.5
  • Example 1 is repeated.
  • an paraffinic crude having a Watson K characterisation factor value of 12.3 was distilled to obtain blending components to improve the kerosene and gas oil properties of the fractions listed in Table 1.
  • the amount of paraffinic crude that was used was enough to obtain a kerosene and gas oil mixture to adjust the respective fraction of Table 1 to meet the desired specification.
  • the properties of the blends are reported in Table 2.
  • Table 2 Distillates properties of Paraffinic and Naphthenic crudes and blend Naphthenic crude Paraffinic crude Crude Blend (31/69 %w/w N/P) Kero Gasoil Kero Gasoil Kero Gasoil Yield on paraffinic crude (%woc) 12.2 36.9 17.1 28.6 15.5 31.3
  • Initial boiling point (°C) 165 235 165 235 165 235
  • Final boiling point (°C) 235 350 235 350 235 350 235 350
  • Density (kg/m 3 ) (spec ⁇ 845 kg/m 3 Diesel EN 590) 840 887 790 826 0.806 0.845 Smoke point (spec >19 mm) 18 - 26 - 24
  • Aromatics (%vol) 21 43 16 14 17 24 Sulphur (%wt) 0.02 0.07 0.01 0.04 0.01 0.05 Cetane number (spec >51 33 38.5 52 62.8 47 55
  • a quality give away is observed for Smokepoint of the Kero
  • Example 1 is repeated. To the kerosene and gas oil fractions of Table 1 an amount of Fischer-Tropsch kerosene and gas oil (having the properties as listed in Table 3) respectively is added in an amount sufficient to meet the smoke point and cetane number specifications. The resulting properties are listed in Table 4.

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  • 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)
  • Fats And Perfumes (AREA)

Claims (6)

  1. Procédé de préparation d'un produit gasoil et kérosène à partir d'une source de pétrole brut ayant une valeur de facteur de caractérisation Watson K égal ou inférieur à 12.0. Ce procédé consiste :
    a) à isoler une fraction de kérosène dérivée du pétrole et une fraction de gasoil dérivée du pétrole à partir de cette source de pétrole brut, où la fraction de kérosène dérivée du pétrole a un point de fumée inférieur à 25 mm ou inférieur à 19 mm si le contenu de naphtalènes de la fraction de kérosène est inférieur à 3 % en volume et le gasoil dérivé du pétrole a un indice de cétane inférieur à 50 ou une densité supérieure à 845 kg/m3,
    b) à ajouter une fraction de kérosène dérivée par un procédé Fischer-Tropsch à la fraction de kérosène dérivée du pétrole en quantité suffisante pour obtenir un mélange ayant une valeur de point de fumée supérieure à 25 mm ou supérieure à 19 mm si le contenu de naphtalènes du mélange est inférieur à 3 % en volume et
    c) à ajouter une fraction de gasoil dérivée par un procédé Fischer-Tropsch à la fraction de gasoil dérivée de pétrole de telle manière que le mélange résultant ait une valeur d'indice de cétane supérieure à 51, où le rapport en poids de isoparaffine / paraffines normales dans le gasoil et kérosène dérivé par un procédé Fischer-Tropsch est supérieur à 0.3.
  2. Procédé selon la revendication 1, où le kérosène et le gasoil est isolé de la source de pétrole brut dans une raffinerie type distillation-reformage.
  3. Procédé selon n'importe laquelle des revendications de 1 à 2, où le kérosène et le gasoil de pétrole sont pour plus de 50 % en poids, sur la base d'un brut ayant une valeur Watson K égale ou inférieur à 12.0.
  4. Procédé selon n'importe laquelle des revendications de 1 à 3, où la fraction de kérosène dérivée du pétrole a un point d'ébullition de distillation initial (ASTM D86) atteignant des températures comprises entre 140 et 200 °C et un point d'ébullition final atteignant des températures comprises entre 200 à 300 °C.
  5. Procédé selon n'importe laquelle des revendications de 1 à 4, où la fraction de gasoil dérivée de pétrole a un point d'ébullition de distillation initial (ASTM D86) atteignant des températures comprises entre 250 à 300 °C et un point d'ébullition final atteignant des températures comprises entre 340 et 380 °C.
  6. Procédé selon n'importe laquelle des revendications de 1 à 5, où le kérosène dérivé par un procédé Fischer-Tropsch a un rapport en poids de isoparaffine / paraffine normale se situant entre 2 et 6.
EP04741581A 2003-05-22 2004-05-17 Procede d'amelioration de coupes gazoles et kerosenes de petrole brut Expired - Lifetime EP1627028B1 (fr)

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Application Number Priority Date Filing Date Title
EP04741581A EP1627028B1 (fr) 2003-05-22 2004-05-17 Procede d'amelioration de coupes gazoles et kerosenes de petrole brut

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP03076566 2003-05-22
EP04741581A EP1627028B1 (fr) 2003-05-22 2004-05-17 Procede d'amelioration de coupes gazoles et kerosenes de petrole brut
PCT/EP2004/050819 WO2004104142A1 (fr) 2003-05-22 2004-05-17 Procede de valorisation du kerosene et du gasoil de sources de petrole brut naphthenique et aromatique

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EP1627028A1 EP1627028A1 (fr) 2006-02-22
EP1627028B1 true EP1627028B1 (fr) 2007-12-12

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US (1) US20070021636A1 (fr)
EP (1) EP1627028B1 (fr)
JP (1) JP5478806B2 (fr)
CN (1) CN100362085C (fr)
AT (1) ATE380855T1 (fr)
DE (1) DE602004010648T2 (fr)
DK (1) DK1627028T3 (fr)
WO (1) WO2004104142A1 (fr)

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Publication number Publication date
EP1627028A1 (fr) 2006-02-22
US20070021636A1 (en) 2007-01-25
ATE380855T1 (de) 2007-12-15
JP5478806B2 (ja) 2014-04-23
JP2007502899A (ja) 2007-02-15
DE602004010648D1 (de) 2008-01-24
DK1627028T3 (da) 2008-03-17
CN100362085C (zh) 2008-01-16
CN1795258A (zh) 2006-06-28
WO2004104142A1 (fr) 2004-12-02
DE602004010648T2 (de) 2008-12-11

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