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
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
  • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
• • 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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • 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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • 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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number

Definitions

• the present invention relates to diesel fuel compositions that are extremely stable against thermal degradation, sedimentation, and discoloration.
• the diesel fuel compositions of the present invention have been designed to be void or essentially void of certain heteroatomic compounds often present in diesel fuel and which have been discovered to cause the thermal degradation in the presence of nitrate-based cetane improver additives.
• the benefits of operating a diesel engine on a diesel fuel treated with a nitrate-based cetane improver are well known: improved cold starting, less combustion noise, smoother engine operation and reduced toxic pollutant emissions. It is known that diesel fuels containing nitrate-containing cetane improvers often exhibit instability in the form of discoloration and sedimentation when heated to high temperatures (>120°C). It is also known that organic nitrate cetane improvers (e.g. 2-ethylhexyl nitrate, commercially available from Ethyl Corporation as HiTEC® 4103 cetane improver, also known as DII-3) can worsen diesel fuel discoloration and sedimentation in the 150°C pad stability test (ASTM D6468).
• HiTEC® 4103 cetane improver also known as DII-3
• Discoloration and sedimentation induced by nitrate-based cetane improvers can be undesirable to the consumer and can also interfere with common petroleum industry tests (e.g., ASTM D189, "Conradson Carbon Residue of Petroleum Products” and ASTM D524, "Ramsbottom Carbon Residue of Petroleum Products”). It is therefore desired to have a diesel fuel composition which can demonstrate excellent thermal stability, i.e., lack of sedimentation and minimal discoloration upon heating to >120°C. It has been discovered that certain components in the diesel fuel are responsible for these undesired effects, and that by eliminating these certain components, an improved diesel fuel is produced.
• a feature of the present invention is to provide a diesel fuel composition exhibiting improved ignition quality, which can demonstrate excellent thermal stability, i.e., lack of sedimentation and minimal discoloration when heated.
• Another feature of the present invention is to provide a diesel fuel composition containing a major amount of a hydrocarbon boiling in the middle distillate boiling range, and a minor amount of a nitrate-containing cetane improver, wherein the composition is free of, or essentially free of, certain heteroatomic compounds.
• a further feature of the present invention is to provide a method of reducing the sedimentation and/or discoloration of a middle distillate fuel containing nitrate-based cetane improver.
• the present invention relates to a diesel fuel composition containing a major amount of a hydrocarbon fuel boiling in the middle distillate boiling range, and a minor amount of a nitrate-containing cetane improver, wherein the composition is free of, or essentially free of, one or more heteroatomic compounds selected from pyrroles, indoles, sulfides, disulfides, mercaptans, thioacids, sulfonic acids, and/or indolines.
• heteroatomic compound herein is meant one or more heteroatomic compounds selected from pyrroles, indoles, sulfides, disulfides, mercaptans, thioacids, sulfonic acids, and/or indolines.
• heteroatomic compound herein is meant a heteroatomic compound that in a diesel fuel containing nitrated cetane improver causes discoloration and/or sedimentation of the diesel fuel upon heating of the fuel.
• free of in the present invention is meant a deleterious heteroatomic compound level generally undetectable in terms of adverse effect on color and sediment formation of the diesel fuel. This level is generally a level of less than about 2 ppm of deleterious heteroatomic compound in the finished diesel fuel. Similarly, by “removing all of” herein is meant a remaining level, if any, of deleterious heteratomic compound of less than about 2 ppm.
• essentially free of in the present invention is meant a level of less than about 5 ppm of heteroatomic compound in the finished diesel fuel. Similarly, by “removing essentially all of” herein is meant a remaining level, if any, of heteratomic compound of less than about 5 ppm.
• nitrate-containing cetane improver chemical compounds that contain a nitrate group covalently bonded, ionically bonded, or generated in situ.
• nitrate-containing cetane improvers useful in the present invention include methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec -butyl nitrate, tert -butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, n -pentyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-e
• an improved diesel fuel is prepared by combining a major amount of a middle distillate fuel, and a minor amount of a nitrate-based cetane improver, and removing before or after the addition of the nitrate-based cetane improver all or essentially all of one or more the following heteroatomic compounds: pyrroles, indoles, sulfides, disulfides, mercaptans, thioacids, sulfonic acids, and/or indolines.
• middle distillate diesel fuel containing nitrate-based cetane improver has significantly improved thermal stability, i.e., reduced discoloration and reduced sedimentation, if the deleterious heteroatomic compounds of pyrroles, indoles, sulfides, disulfides, mercaptans, thioacids, sulfonic acids, and/or indolines are removed or essentially removed from the fuel, relative to the comparable diesel fuel from which these heteroatomic compounds have not been removed.
• the aforementioned deleterious heteroatomic species may be removed by any method known to those skilled in the art, including hydrotreatment, selective adsorption, or oxidation.
• the nitrate-based cetane improver can be present in the diesel fuel compositions of the present invention at a level of from about 100 ppm to about 10,000 ppm.
• heteroatomic compounds do not have an adverse or deleterious effect on sedimentation and discoloration of middle distillate fuel containing nitrate-based cetane improver.
• the heteroatomic compounds that do not have an adverse or deleterious effect on these properties of diesel fuel include anilines, pyridines, quinolines, amides, thiophenes, sulfoxides, phenols, carboxylic acids, nitriles, nitro compounds, aldehydes, esters, alcohols, peroxides, and carbazoles (see Table 1).
• a benefit of this particular invention over the prior art is that certain species that are hard to remove from the diesel fuel by desulfurization and/or denitrogenation can be left in the fuel because they have been discovered herein to be innocuous in terms of thermal stability of the resulting diesel fuel. For example, most nitrogen compounds and thiophenes are more difficult to remove by hydrogenation than sulfides, mercaptans, etc. However, since most nitrogen compounds and thiophenes do not cause thermal instability of the diesel fuel, they can be left in the fuel at substantial savings to the refiner.
• a low sulfur D-2 (ASTM D975) diesel fuel having the following properties:
• the present invention provides in another embodiment a diesel fuel meeting the requirements of ASTM D 975 for a low sulfur No. 2-D diesel and providing emission benefits at least equivalent to a diesel fuel as per Section 2282(g), Title 13, California Code of Regulations, said fuel containing from about 10 vol. % to about 30 vol.
• % aromatics and having (1) a Cetane number of at least 40 but less than 60, and preferably from 45 to 55; (2) a nitrogen content of no greater than 1000 ppmw; (3) a sulfur content of no greater than 50 ppmw; and (4) a total amount of nitrogen and sulfur from pyrroles, indoles, sulfides, disulfides, mercaptans, thioacids, sulfonic acids and/or indolines of no more than 5 ppm, preferably no more than 2 ppm.
• the amount of each of pyrroles, indoles, sulfides, disulfides, mercaptans, thioacids, sulfonic acids, and indolines is no more than 5 ppm, and in a more preferred embodiment, no more than 2 ppm.
• Fuel 9041 An ultralow-sulfur diesel fuel (Fuel 9041), with inspection data as listed in Table 2, was separately treated with enough of each of the additives listed in Table 1 to deliver 350 ppm of oxygen, nitrogen, or sulfur.
• Fuel 9041 contained very low amounts of sulfur and nitrogen, but was in all other properties typical for a No. 2 diesel fuel.
• the base fuel with no added heteroatomic compound was very stable in the presence of 2-EH nitrate, ensuring that any instability observed in subsequent experiments arose from the introduced heteroatomic species.
• the heteroatomic compounds were selected as representative of compounds that might typically be expected to be found in a diesel fuel.
• Half of each fuel composition was treated with 2500 ppmv of 2-EH nitrate.
• nitrate-free and nitrate-containing fuel compositions were subjected to 180-minute thermal stability testing at 150°C as described in pad stability test ASTM D6468. Inspection data for Fuel 9041 Aromatics, vol. % 33.6 Olefins, vol. % 2.1 Saturates, vol.
• ANNEX MIDDLE DISTILLATE FUELS
• Middle distillate fuels are used particularly in running diesel engines (especially for automobiles), aircraft engines and turbines.
• the great majority of such fuels have a boiling range of 140-360°C and most conform to the following distillation profile: initial b.p. 140-220°C 10% b.p. 190-240°C 50% b.p. 220-290°C 90% b.p. 260-340°C endpoint 280-360°C
• Such fuels are particularly preferred in connection with the present invention.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Combustion & Propulsion (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2001
  • 2001-12-18 US US10/020,411 patent/US20030110684A1/en not_active Abandoned
• 2002
  • 2002-11-15 CA CA002411933A patent/CA2411933C/en not_active Expired - Fee Related
  • 2002-12-12 JP JP2002360503A patent/JP3764721B2/ja not_active Expired - Fee Related
  • 2002-12-18 EP EP02258749A patent/EP1321504A3/de not_active Ceased

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