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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 for use in diesel engines and the like.
• 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. For example, for those where natural gas is the raw material the name 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.
• JP-A-2006-16541 proposes a fuel composition which compares favourably with existing diesel fuels and their function of causing rubber materials to swell (referred to below as rubber swellability) by incorporating an aromatic component in a GTL diesel oil.
• FT diesel oils do not give rise to the environmental problems associated with aromatics and sulphur, and that feature is attributable to their being formed only of paraffins.
• the aim of the present invention is to offer a diesel fuel composition with improved rubber swellability while being constituted essentially only of paraffins.
• the diesel fuel composition according to the present invention essentially comprises only paraffins, and the proportion of the content of paraffins of 15 or fewer carbons is made not less than 28% by volume, while the proportion of normal paraffins of 18 or more carbons is made not more than 11% by volume.
• the proportion of paraffins with 15 or fewer carbons is preferably not less than 40% by volume and more preferably not less than 50% by volume.
• the proportion of normal paraffins with 18 or more carbons is preferably not more than 8% by volume and more preferably not more than 5% by volume.
• essentially comprising only paraffins is that 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.
• the method of manufacturing fuels comprising only paraffins apart from the aforementioned Fischer-Tropsch process there are methods in which animal and plant oils and fats, being biomass raw materials, are hydrorefined. Of the fuels thus produced, those corresponding to diesel fuels are called, for example, second-generation biomass diesel fuels, and these second-generation biomass diesel fuels are also fuel compositions, essentially comprising only paraffins, suitable for the present invention.
• additives does not prevent a diesel fuel composition from essentially comprising only paraffins.
• Compositions in which additives have been added are also encompassed by the diesel fuel composition of the present invention.
• low-temperature fluidity improvers it is possible to add low-temperature fluidity improvers in order to prevent feed problems caused by separation of waxes at low temperatures, or plugging of the filters installed in the fuel systems of vehicles.
• low-temperature fluidity improvers it is possible to use any known low-temperature fluidity improvers provided they are miscible with paraffins.
• 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.
• ethylene-vinyl acetate copolymers and alkenyl succinamides are especially preferred.
• 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 TES 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”
• 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”.
• lubricity improvers in order to inhibit wear of, for example, fuel feed-pump parts.
• Any known lubricity improvers may be used as lubricity improvers provided they are miscible with FT oils.
• 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 concentration 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”.
• the 10% distillation temperature is not more than 250° C. and the 50% distillation temperature is not more than 300° C., and 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 in proton nuclear magnetic resonance spectra is not less than 2.5%, and it is even more preferable if the 10% distillation temperature is not more than 200° C. and the 50% distillation temperature is not more than 250° C.
• the value of Z as expressed by the following formula (1) is greater than ⁇ 3.5, and even more preferable if it is greater than ⁇ 1.5.
• A 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 spectra, %; B is the 10% distillation temperature, ° C.; C is the 50% distillation temperature, ° C.; and D is the 90% distillation temperature, ° C.
• the present invention it is possible to obtain a diesel fuel composition with improved rubber swellability, although essentially comprised only of paraffins, by ensuring that the proportion of paraffins with 15 or fewer carbons is not less than 28% by volume and that the proportion of normal paraffins with 18 or more carbons is not more than 11% by volume.
• paraffins have the nature of having poor rubber swellability, but experiments have revealed that the nature of having poor swellability is a characteristic of normal paraffins while isoparaffins tend rather to have high rubber swellability. It has also been discovered that the tendency of isoparaffins to cause swelling of rubber differs according to the number of carbons. The present invention is based on these novel findings.
• the rubber swellability of a diesel fuel composition essentially comprising only paraffins is influenced by the proportion of isoparaffins and the distillation characteristics. It was discovered that, provided 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 spectra, which show the hydrogen isotopes in paraffins, and the distillation characteristics (10%, 50% and 90% distillation temperatures) are within specified ranges, the rubber swellability of a diesel fuel composition essentially comprising only paraffins is further enhanced, and that the value obtained by a specified formula in which the variables are the aforementioned ratio of the peak total areas and the distillation characteristics is an indicator of rubber swellability of a diesel fuel composition essentially comprising only paraffins.
• the present invention is based on these novel findings.
• This confirmation experiment used three kinds of isoparaffin solvents, A, B and C, which have different distillation ranges, as shown in Table 1, and, for comparison, two kinds of normal paraffin solvents, D and E, which have different distillation ranges.
• Density at 15° C. measured in accordance with JIS K 2249 “Crude oil and petroleum products—Determination of density and density/mass/volume conversion tables”.
• the gas chromatography detector was a hydrogen flame ionisation detector (FID), so that the measurement sensitivity was proportionate to the number of carbons of the paraffins. Taking this sensitivity into account, therefore, the molar ratios were obtained from the area values and finally mass ratios were obtained.
• FID hydrogen flame ionisation detector
• the type of column in the gas chromatography was HP5 (length: 30 m, inside diameter: 0.32 mm, liquid layer thickness: 0.25 ⁇ m), and the analysis conditions were as follows.
• HNBR hydrogenated nitrile butadiene rubber
• diesel fuel compositions were obtained that were comprised of the regulated oil mixtures.
• the characteristics and make-up of the diesel fuel compositions obtained are shown in Tables 4 to 6.
• the SMDS process is a process in which natural gas is partially oxidised, and after synthesising heavy paraffins by means of Fischer-Tropsch synthesis, the heavy paraffin oil is hydrocracked and distilled so as to obtain naphtha, kerosene and gas oil fractions.
• Table 4 also shows, by way of a reference example, the characteristics of an FT diesel oil already made available commercially overseas.
• the present invention is not limited in any way by these Examples.
• Tables 7 and 8 show the difference between the percentage change in volume of rubber materials after the experiment of immersing them in each diesel fuel composition and the percentage change in volume of the reference example ( ⁇ percentage change in volume), together with the Z value obtained by means of Formula (1).
• Examples 1 to 12 all showed an increase in percentage volume change compared with the reference example, which was an FT diesel oil of the prior art. It was therefore confirmed, as can be seen from Tables 4 to 6 and these results, that it is possible to improve rubber swellability even when the diesel fuel composition is composed essentially only of paraffins, by ensuring that the proportion of paraffins with 15 or fewer carbons is not less than 28% by volume and that the proportion of normal paraffins with 18 or more carbons is not more than 11% by volume.
• Example 2 The ratio of total peak areas for Example 2, Example 3 and Example 12 was lower than for the Reference Example, but because the content of paraffins of 15 or fewer carbons and the content of normal paraffins of 18 or more carbons satisfy the conditions of the present invention, the percentage change in volume increased compared to the comparative examples and the reference example.
• the point that from the standpoint of increasing the percentage change in volume a high proportion of isoparaffins is preferable is as discussed above, but even though, for example, the ratio of total peak areas in proton nuclear magnetic resonance spectra of paraffins is lower than the comparative examples and reference example, it was confirmed that an increase in percentage volume change can be achieved provided the proportions of content of paraffins with 15 or fewer carbons and content of normal paraffins with 18 or more carbons satisfy the conditions of the present invention.

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

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• 2009
  • 2009-08-31 JP JP2009201044A patent/JP2010168537A/ja active Pending
  • 2009-12-24 WO PCT/EP2009/067918 patent/WO2010072839A2/en not_active Ceased
  • 2009-12-24 MY MYPI2011002973A patent/MY180301A/en unknown
  • 2009-12-24 US US13/141,843 patent/US20120138508A1/en not_active Abandoned
  • 2009-12-24 SG SG2011044641A patent/SG172241A1/en unknown
  • 2009-12-24 EP EP09796013A patent/EP2370550A2/en not_active Withdrawn
  • 2009-12-24 CA CA2747787A patent/CA2747787A1/en not_active Abandoned

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