EP2370551A2 - Composition de carburant diesel - Google Patents

Composition de carburant diesel

Info

Publication number
EP2370551A2
EP2370551A2 EP09796393A EP09796393A EP2370551A2 EP 2370551 A2 EP2370551 A2 EP 2370551A2 EP 09796393 A EP09796393 A EP 09796393A EP 09796393 A EP09796393 A EP 09796393A EP 2370551 A2 EP2370551 A2 EP 2370551A2
Authority
EP
European Patent Office
Prior art keywords
diesel fuel
fuel composition
less
composition according
chemical shifts
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP09796393A
Other languages
German (de)
English (en)
Inventor
Nobuhiro Okabe
Yoriko Sakamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP2370551A2 publication Critical patent/EP2370551A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • the present invention relates to a diesel fuel composition. More specifically, it relates to a diesel fuel composition with superior oxidation stability while being constituted essentially only of paraffins.
  • FT fuels Fischer-Tropsch fuels
  • FT fuels are fuels obtained by synthesis from raw materials such as natural gas, coal or biomass, using the Fischer-Tropsch process via synthesis gas, a mixture of carbon monoxide and hydrogen. They are often used under names corresponding to the raw material.
  • GTL is often used, if coal is the raw material the name CTL may be used, and if biomass is the raw material, the name BTL may be used.
  • GTL is also sometimes used as a generic name for fuels obtained by the Fischer-Tropsch process, but in the present invention the term FT fuels is used for fuels obtained by the Fischer-Tropsch process and FT fuels are deemed to include GTL, CTL and BTL.
  • these FT fuels are expected to be used as alternatives to petroleum because they are synthesised from raw materials such as natural gas, coal and biomass and also, because they do not contain sulphur or aromatic hydrocarbons, they are expected to be used as diesel fuels which are better for the environment, in that they limit the emission of sulphur oxides and particulate matter (PM) from engines. They have already been made available commercially in some areas, as reported for example In “The marketability of liquid fuels from natural gas (GTL)", [Energy Economics], November 2001 issue.
  • oxidation stability is an important indicator for evaluation of the qualitative stability of a diesel fuel, and it is desirable for a diesel fuel to have superior oxidation stability.
  • diesel engines have been equipped with common rail fuel injection systems as a means of reducing particulates (or particulate matter, referred to below as PM) in exhaust gases.
  • oxidation stability of diesel fuels it is widely and generally known that oxidation stability can be improved by the addition of amine-based and phenol-based anti-oxidants of various kinds, and there have been attempts to add oxidation stabilisers also to the fractions corresponding to the diesel oils of FT fuels (referred to below as FT diesel oils) .
  • FT diesel oils fractions corresponding to the diesel oils of FT fuels
  • JP-A-2008-214369 JP-A-2008-214369.
  • the amount of anti-oxidant required in order to obtain the desired effect becomes large for fuels that have poor oxidation stability and production costs are raised.
  • the amount of anti-oxidant increases, there are problems in that the anti-oxidant is prone to separate out at lower temperatures, or conversely, if the amount added is small, problems in that, after the effect of the anti-oxidant has been used up during oxidation, the oxidation stability will deteriorate significantly and there may be a deleterious impact such as corrosion of metallic elements of the vehicle's fuel system.
  • JP-A-2008-266617 has, therefore, proposed maintaining the oxidation stability of diesel fuels without adding anti-oxidants .
  • at least one kind of polycyclic aromatic compound selected from the group comprised of anthracenes and dialkylnaphthalenes is blended with an FT diesel oil to ensure oxidation stability.
  • the diesel fuel composition according to the present invention essentially comprises only paraffins, and is characterised in that
  • OI 0.247X - 0.001Y - 0.053
  • X is the proportion ⁇ %) of the total peak area of the peak group at chemical shifts of 1.45 to 2.25 ppm relative to the total peak area of the peak group at chemical shifts of 1.00 to 1.45 ppm in proton nuclear magnetic resonance ( 1 H-NMR) spectra
  • Y is the content (mass % ⁇ of normal paraffins with 18 or fewer carbons.
  • the normal paraffins with 18 or fewer carbons are less than 12% by mass, if the proportion of the total peak area of the peak group at chemical shifts of 1.45 to 2.25 ppm relative to the total peak area of the peak group at chemical shifts of 1.00 to 1.45 ppm is 6.5% or more in proton nuclear magnetic resonance ( 1 H-NMR) spectra, or if the oxidation index OI is 1.10 or more, because then the oxidation stability is impaired. To increase the oxidation stability even further, it is preferable if the oxidation index OI is less than 0.9, and more preferably less than 0,7.
  • the diesel fuel composition relating to the present invention may also be such that the increase in the total acid number between before and after an oxidation stability test is not more than 1.3 mg KOH/g.
  • the preferred increase in the total acid number between before and after an oxidation stability test is 1.0 mg KOH/g, but more preferably 0.9 mg KOH/g.
  • an oxidation stability test in the present invention is an oxidation test performed as in ASTM D2274 under conditions of oxygen bubbling for 16 hours but with the test temperature changed to 115°C.
  • paraffins are essentially composed only of paraffins.
  • the main constituent does not contain styrene compounds or diene compounds, or condensed polycyclic aromatics. Containing compositions of other than paraffins as impurities is tolerated.
  • an FT diesel oil in which the total mass or volume of isoparaffins and normal paraffins is not less than 99% of the whole, excluding tiny impurities, is a diesel fuel composition constituted essentially only of paraffins suitable for the present invention.
  • suitable additives within a range that does not go beyond the scope of the present invention, for example a range that does not cause the problems of cost or separation in the prior art.
  • lubricity improvers to prevent wear of, for example, fuel feed-pump parts. It is also possible to use, as the lubricity improvers, any known lubricity improvers provided they are miscible in paraffins.
  • Typical lubricity improvers are commercial acid-based lubricity improvers which have fatty acids as their main constituent, and ester-based lubricity improvers which have as their main constituent glycerin mono fatty acid esters. These compounds may be used singly or in combinations of two or more kinds.
  • the fatty acids used in these lubricity improvers are preferably those that have as their main constituent a mixture of unsaturated fatty acids of approximately 12 to 22 carbons, but preferably about 18 carbons, that is oleic acid, linolic acid and linolenic acid.
  • the lubricity improver may be added so that the wear scar WS 1.4 value in an HFRR (High Frequency Reciprocating Rig) of the fuel composition after addition of the lubricity improver is not more than 500 ⁇ m, but preferably not more than 460 ⁇ m, and the amount thereof is usually 50 to 1000 ppm.
  • the WS 1.4 value in an HFRR here refers to the value obtained in accordance with the Japanese Petroleum Institute standard JPI-5S-50-98 "Gas oil ⁇ Method for testing lubricity".
  • additives such as amine salts of alkenyl succinate derivatives, metal deactivators such as salicylidene derivatives, de-icing agents such as polyglycol ethers, rust inhibitors such as aliphatic amines and alkenyl succinate esters, anti-static agents such as anionic and cationic amphoteric surfactants, and silicone-based defoaming agents.
  • detergents such as amine salts of alkenyl succinate derivatives, metal deactivators such as salicylidene derivatives, de-icing agents such as polyglycol ethers, rust inhibitors such as aliphatic amines and alkenyl succinate esters, anti-static agents such as anionic and cationic amphoteric surfactants, and silicone-based defoaming agents.
  • detergents such as amine salts of alkenyl succinate derivatives, metal deactivators such as salicylidene derivatives, de-icing agents such as polyglycol ethers,
  • Low-temperature flow characteristics are required of diesel fuel compositions, to take account of use during winter or in cold regions. From the standpoint of improving these low-temperature flow characteristics, it is generally preferable if there are more iso-paraffins. On the other hand, from the standpoint of oxidation stability it is preferable to have more normal paraffins. In other words, low-temperature flow characteristics and oxidation stability show opposing behaviours in the composition. However, because it is possible to improve low-temperature flow characteristics by means of additives, it is possible to achieve improvement in oxidation stability while taking low-temperature flow characteristics into account by suitable use of additives .
  • Typical low-temperature fluidity improvers are commercial low-temperature fluidity improvers such as ethylene-vinyl acetate copolymers, ethylene-alkylacrylate copolymers, alkenyl succinamides, chlorinated polyethylenes, or polyalkyl acrylates. These compounds may be used singly or in combinations of two or more kinds. Of these, ethylene-vinyl acetate copolymers and alkenyl succinamides are especially preferred.
  • the amount of the low temperature fluidity improver for example a suitable amount may be blended in so as to satisfy the pour points and cold filter plugging points specified in JIS K 2204, which is the JIS standard for diesel fuel, but normally the amount will be 50 to 1000 ppm.
  • the pour point here refers to the pour point obtained in accordance with JIS K 2269 "Testing methods for pour point and cloud point of crude oil and petroleum products", and the cold filter plugging point refers to the cold filter plugging point obtained by JIS K 2288 "Petroleum products - Diesel fuel - Determination of cold filter plugging point”.
  • diesel fuel composition according to the present invention
  • the following base materials were used to produce diesel fuel compositions comprising hydrocarbon fuel oils and FT fuels comprised only of polykerosene (paraffin) base materials, being oil mixtures with adjusted distillation characteristics and compositions.
  • Table 1 shows the characteristics of the base materials
  • Tables 2 and 3 show the characteristics and compositions of the diesel fuel compositions obtained.
  • Table 3 also shows an FT fuel of the prior art as a reference example.
  • Base material A base material B (synthetic paraffins) : Taking as the raw materials by-product gases (butane and butylene fractions) which have as their main constituent light hydrocarbons with a carbon number of 4 obtained, for example, from fluid catalytic cracking apparatus and thermal cracking apparatus during petroleum refining, an oligomerisation treatment was carried out by means of the IFP/Axens Polynaphtha process, and after conversion selectively to hydrocarbon fractions of 10 to 24 carbons, paraffin base materials with differing distillation characteristics and compositions were obtained via desulphurisation, hydrogenation treatment of olefins and the distillation process.
  • by-product gases butane and butylene fractions
  • Base material C base material D, base material E, base material F, base material G (FT fuels) : natural gas was partially oxidised by means of the SMDS (Shell Middle Distillate Synthesis) process, and after synthesising the syngas derived from carbon monoxide and hydrogen (CO + H2) to a waxy straight-chain alkyl hydrocarbon by means of a Fischer-Tropsch reaction, hydrocracking and isomerisation were carried out over a catalyst, and base materials being mixtures of normal paraffins and isoparaffins with differing distillation characteristics and compositions were obtained.
  • SMDS Shell Middle Distillate Synthesis
  • the type of column in the gas chromatography was HP5 (length: 30m, inside diameter: 0.32mm, liquid layer thickness: 0.25 ⁇ m) , and the analysis conditions were as follows.
  • OI 0.247X - 0.001Y - 0.053
  • X is the proportion (% ⁇ of the total peak area of the peak group at chemical shifts of 1.45 to 2.25 ppm relative to the total peak area of the peak group at chemical shifts of 1.00 to 1.45 ppm in proton nuclear magnetic resonance ( 1 H-HMR) spectra
  • Y is the content (mass %) of normal paraffins with 18 or fewer carbons) .

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)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

Une composition de carburant diesel qui comprend essentiellement des paraffines, et qui se caractérise en ce que 1) les paraffines normales avec 18 carbones au maximum ne constituent pas moins de 12 % en masse, et (2) la proportion de la zone de pics totale du groupe de pics aux déplacements chimiques de 1,45 à 2,25 ppm par rapport à la zone de pics totale du groupe de pics aux déplacements chimiques de 1,00 à 1,45 ppm est inférieure à 6,5 % dans le spectre de résonance magnétique nucléaire du proton (1H-NMR), et qui possède un indice d'oxydation OI inférieur à 1,10. OI est représenté par l'équation OI = 0.247X - 0.001Y - 0.053, dans laquelle X est la proportion (%) de la zone de pics totale du groupe de pics aux déplacements chimiques de 1,45 à 2,25 ppm par rapport à la zone de pics totale du groupe de pics aux déplacements chimiques de 1,00 à 1,45 ppm dans le spectre de résonance magnétique nucléaire du protons (1H-NMR), et Y et le contenu (% en masse) des paraffines normales avec 18 carbones au maximum.
EP09796393A 2008-12-26 2009-12-24 Composition de carburant diesel Withdrawn EP2370551A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008332630A JP2010150479A (ja) 2008-12-26 2008-12-26 軽油燃料組成物
PCT/EP2009/067914 WO2010072838A2 (fr) 2008-12-26 2009-12-24 Composition de carburant diesel

Publications (1)

Publication Number Publication Date
EP2370551A2 true EP2370551A2 (fr) 2011-10-05

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP09796393A Withdrawn EP2370551A2 (fr) 2008-12-26 2009-12-24 Composition de carburant diesel

Country Status (5)

Country Link
US (1) US20120046506A1 (fr)
EP (1) EP2370551A2 (fr)
JP (1) JP2010150479A (fr)
CN (1) CN102307973A (fr)
WO (1) WO2010072838A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010168537A (ja) * 2008-12-26 2010-08-05 Showa Shell Sekiyu Kk 軽油燃料組成物
CN104152190B (zh) * 2014-03-31 2016-03-23 刘锦超 一种生物柴油添加剂及其制备方法
FR3081879B1 (fr) * 2018-05-29 2020-11-13 Total Marketing Services Composition de carburant et procede de fonctionnement d’un moteur a combustion interne
CN110819395A (zh) * 2019-11-22 2020-02-21 湖南红宝科技开发有限公司 一种低温甲醇柴油
CN111879806B (zh) * 2020-07-23 2024-08-06 中蓝晨光成都检测技术有限公司 一种核磁共振氢谱鉴别掺烷烃增塑剂有机硅产品的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU765274B2 (en) * 1998-10-05 2003-09-11 Sasol Technology (Pty) Ltd. Process for producing middle distillates and middle distillates produced by that process
US20070187292A1 (en) * 2001-10-19 2007-08-16 Miller Stephen J Stable, moderately unsaturated distillate fuel blend stocks prepared by low pressure hydroprocessing of Fischer-Tropsch products
WO2003104361A2 (fr) * 2002-06-07 2003-12-18 Sasol Technology (Pty) Ltd Carburant de synthese a emission reduite de matieres particulaires et un procede de fonctionnement d'un moteur a combustion par compression utilisant un tel carburant en combinaison avec des catalyseurs d'oxydation
JP5072010B2 (ja) * 2006-05-17 2012-11-14 Ｊｘ日鉱日石エネルギー株式会社 軽油組成物
JP5105853B2 (ja) * 2006-12-18 2012-12-26 Ｊｘ日鉱日石エネルギー株式会社 低硫黄燃料組成物
JP2008214369A (ja) 2007-02-28 2008-09-18 Showa Shell Sekiyu Kk ディーゼルエンジン用燃料組成物
JP5227626B2 (ja) 2007-03-22 2013-07-03 Ｊｘ日鉱日石エネルギー株式会社 フィッシャートロプシュ合成により製造された燃料油基材を含有する燃料組成物

Non-Patent Citations (1)

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Title
See references of WO2010072838A2 *

Also Published As

Publication number Publication date
WO2010072838A3 (fr) 2010-08-26
US20120046506A1 (en) 2012-02-23
CN102307973A (zh) 2012-01-04
JP2010150479A (ja) 2010-07-08
WO2010072838A2 (fr) 2010-07-01

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