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
  • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

• This invention relates to gasoline compositions, more particularly to gasoline compositions containing a nitrogen-containing detergent, to processes for their preparation, and to their use in operation of spark-ignition engines.
• UK Patent 437, 023 discloses a process for refining cracked hydrocarbons of substantially gasoline boiling range by the treatment with a solid active adsorbent such as fullers earth, clay or other suitable adsorptive catalysts, under conditions of elevated temperature and superatmospheric pressure adequate to maintain said hydrocarbons in substantially liquid phase, which comprises first removing from said hydrocarbons relatively unstable low boiling constituents, namely dissolved gases, propane, part or all of the butanes and their corresponding unsaturates, and reducing the vapour pressure of said hydrocarbons by submitting them to a stabilising fractionation and thereupon subjecting the stabilised hydrocarbons, whilst still hot, to said refining treatment.
• a solid active adsorbent such as fullers earth, clay or other suitable adsorptive catalysts
• US Patent 3,529,944 discloses a method for clarifying and stabilizing hydrocarbon liquids which are subject to oxidative deterioration, particularly jet fuels, which includes adding to the fuel a material which accelerates the oxidative deterioration of the fuel, such as a polyphenyl substituted lower alkane or lower alkylene, an alkanol ester of citric acid or acetoxy ethyl monobutylether; passing the hydrocarbon liquid through the solid, particulate, adsorbent media to remove microimpurities and the products of oxidative deterioration; and thereafter adding additional amounts of a stabilizing material to stabilize the hydrocarbon liquid against further oxidative deterioration.
• a material which accelerates the oxidative deterioration of the fuel such as a polyphenyl substituted lower alkane or lower alkylene, an alkanol ester of citric acid or acetoxy ethyl monobutylether
• Suitable adsorbent materials include various types of natural or synthetic clays, either treated or untreated, fullers earth, attapulgite, silica gel and adsorbent catalysts.
• jet fuels are treated by filtration through attapulgite clay. It is specifically taught (Column 6, lines 27 to 32) that the effectiveness of the filtration process can be greatly improved and the life of the filter substantially prolonged if certain promoting agents which apparently promote oxidation and speed up certain types of degradation are added prior to filtration.
• an antioxidant in the form of 2,6-ditertiary butyl paracresol is added to some jet fuels together with a mixed polyamine product known as "jet fuel additive 5" "JFA5" prior to adsorptive filtration.
• adsorbent-treated cat cracked gasoline is blended into a fuel composition for use in an internal combustion engine.
• adsorbents which are useful "for treating the cat cracked gasoline include many of the well known adsorbents such as silica, alumina, silica-alumina, charcoal, carbon black, magnesium silicate, aluminium silicate, zeolites, clay, fuller's earth, magnesia and the like".
• the adsorbent used is silica-gel.
• US Patent 5,951,851 relates to a process for removing elemental sulphur from fluids, particularly fuels such as gasoline, jet fuel, diesel, kerosene and fuel additives such as ethers.
• the process involves contacting the sulphur contaminated fluid with layered double hydroxide (or hydrotalcite) Mg 2 AlNO 3 ; mH 2 O or Mg 3 Al NO 3 ; mH 2 O, where m is the number of waters of hydration.
• layered double hydroxide or hydrotalcite
• Kao-tetraethylene glycol, Al 13 pillared montmorillonite, tetramethylammonium-montmorillonite, palygorskite-PF1-s, Kaolinite KGa-1, Kao-cellosolve and Iron (III) montmorillonite are ineffective in removing elemental sulphur, whilst the hydrotalcites Al 2 LiCl, Mg 2 AlNO 3 , Mg 2 FeNO 3 , Mg 3 FeNO 3 and Mg 3 AlNO 3 are particularly effective in removing elemental sulphur.
• Group (8) sepiolite, attapulgite and palygorskite, are described as fibrous clay minerals, and these have, as an important structural element, the amphibole double silica chain which is oriented parallel to the c axis.
• a gasoline composition comprising a major amount of a gasoline suitable for use in a spark-ignition engine, which gasoline comprises a blend of at least two hydrocarbon refinery components boiling within the gasoline boiling range, at least one of which hydrocarbon refinery components has been treated with a fibrous clay mineral of the sepiolite, attapulgite and palygorskite groups, and a minor amount of a nitrogen-containing detergent containing a hydrocarbyl group having a number average molecular weight (Mn) in the range 750 to 6000.
• Mn number average molecular weight
• the blend of at least two refinery components has been treated with the fibrous clay mineral.
• the nitrogen-containing detergent containing a hydrocarbyl group having a number average molecular weight (Mn) in the range 750 to 6000 may be an amine, e.g. a polyisobutylene mono-amine or polyamine, such as a polyisobutylene ethylene diamine, or N-polyisobutenyl-N',N'-dimethyl-1,3-diaminopropane, or amides, e.g. a polyisobutenyl succinimide, and are variously descsribed, for example, in US Patent 5,855,629 and WO 0132812.
• the nitrogen-containing detergent is a polyisobutylene monoamine or polyamine or a polyisobutenyl succinimide.
• a particularly preferred nitrogen-containing detergent is hydrocarbyl amine of formula R 1 -NH 2 and R 1 represents a group R 2 or a group R 2 -CH 2 - and R 2 represents a hydrocarbyl group having a number average molecular weight in the range 750 to 6000, preferably in the range 900 to 3000, more preferably 950 to 2000, and most preferably in the range 950 to 1350, e.g. a polybutenyl or polyisobutenyl group having a number average molecular weight in the range 950 to 1050.
• the nitrogen-containing detergents are known materials and may be prepared by known methods or by methods analogous to known methods.
• US Patent 4,832,702 describes the preparation of polybutenyl and polyisobutenyl amines from an appropriate polybutene or polyisobutene by hydroformylation and subsequent amination of the resulting oxo product under hydrogenating conditions.
• Suitable hydrocarbyl amines are obtainable from BASF A.G., under the trade mark "Kerocom”.
• the nitrogen-containing detergent may be present in a wide range of concentrations, but is preferably present at a concentration in the range 25 to 2500 ppmw, based on total composition, more preferably 50 to 1000 ppmw, conveniently 50 to 500 ppmw and advantageously 50 to 250 ppmw.
• Number average molecular weights e.g. of hydrocarbons such as polyalkenes, may be determined by several techniques which give closely similar results. Conveniently Mn may be determined by vapour phase osmometry (VPO) (ASTM D 3592) or by modern gel permeation chromatography (GPC), e.g. as described for example in W.W. Yau, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979. Where the formula of a compound is known, the number average molecular weight can be calculated as its formula weight.
• VPO vapour phase osmometry
• GPC gel permeation chromatography
• gasolines suitable for use in spark ignition engines are mixtures of hydrocarbons having boiling points in the range from 25°C to 232°C and comprising mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons.
• Preferred are gasoline blends having a saturated hydrocarbon content ranging from 40 to 80 per cent volume, an olefinic hydrocarbon content ranging from 0 to 30 per cent volume and an aromatic hydrocarbon content ranging from 10 to 60 per cent volume.
• the gasoline can be derived from straight run gasoline, polymer gasoline, natural gasoline, dimer- or trimerised olefins, synthetically produced aromatic hydrocarbon mixtures from thermally or catalytically reformed hydrocarbons, or from catalytically cracked or thermally cracked petroleum stocks, or mixtures thereof.
• the hydrocarbon composition and octane level of the gasoline are not critical.
• the octane level, (R+M)/2 will generally be above 85. Any conventional gasoline can be used.
• hydrocarbons can be supplemented by up to substantial amounts of conventional alcohols or ethers conventionally known for use in gasoline.
• the gasoline composition is preferably lead-free, and this may be required by law. Where permitted, lead-free anti-knock compounds and/or valve-seat recession protectant compounds (e.g. known potassium salts, sodium salts or phosphorous compounds) may be present.
• lead-free anti-knock compounds and/or valve-seat recession protectant compounds e.g. known potassium salts, sodium salts or phosphorous compounds
• Modern gasolines are inherently low-sulphur fuels, e.g. containing less than 200 ppmw sulphur.
• the gasoline composition may additionally contain one or more corrosion inhibitors, anti-oxidants, dyes, dehazers, metal deactivators, detergents other than a nitrogen-containing detergent containing a hydrocarbyl group having a number average molecular weight (Mn) in the range 750 to 6000 (e.g. a polyether amine), synthetic or mineral oil carriers e.g. a polyalphaolefin or a polyoxyalkylene compound, friction modifiers, diluents and markers.
• Mn number average molecular weight
• the present invention further provides a process for the preparation of a gasoline composition of the invention, which comprises treating at least one hydrocarbon refinery component boiling within the gasoline boiling range with a fibrous clay mineral of the sepiolite, attapulgite and palygorskite groups, before or after blending said at least one hydrocarbon refinery component with at least one other hydrocarbon refinery component boiling within the gasoline boiling range, to form a gasoline suitable for use in a spark-ignition engine, and bringing the gasoline suitable for use in spark-ignition engine into admixture with the nitrogen-containing detergent.
• the treatment with fibrous clay mineral is effected with the hydrocarbons in the liquid phase, very conveniently at ambient temperature.
• the treatment may very conveniently be effected at atmospheric pressure.
• a particular hydrocarbon refinery component or combination/components of a gasoline is at least predominantly responsible for deposit formation when used as fuel in a spark-ignition engine, that component or combination of components may be treated with the fibrous clay mineral before blending with at least the other hydrocarbon refinery component to form the gasoline, it is preferred to treat the fully pre-blended gasoline.
• the process of the invention preferably comprises blending at least two hydrocarbon refinery components boiling within the gasoline boiling range and treating the resulting mixture with a fibrous clay mineral of the sepiolite, attapulgite and palygorskite groups, to form a gasoline suitable for use in a spark-ignition engine, and bringing the gasoline into admixture with the nitrogen-containing detergent.
• the fibrous clay mineral of the sepiolite, attapulgite and palygorskite, groups must at least contain at least one mineral of the sepiolite, attapulgite and palygorskite groups.
• fullers earth is used in published literature on clays in a number of different ways, but in the context of the present invention "fullers earth” comprises at least one fibrous clay mineral of the sepiolite, attapulgite and palygorskite groups.
• One type of fullers earth may comprise a mixture of montmorillonite and palygorskite.
• the fibrous clay mineral is sepiolite, attapulgite or fullers earth, as will be illustrated in the examples which follow this description.
• the fibrous clay mineral may remove iron and/or copper ions from iron and/or copper compounds which may contaminate hydrocarbon refinery components.
• spent clay contains iron and/or copper, whilst containing negligible organic contaminants, it may be susceptible for disposal as land fill, without prior incineration.
• the present invention further provides a method of operating a spark-ignition engine, which comprises bringing into the combustion chambers of such engine a gasoline composition according to the invention giving improved engine cleanliness, e.g. reduced intake valve deposits.
• Base fuel blends were prepared from 50%v of an unleaded gasoline (95 ULG) of RON 95.7, MON 84.6, and having sulphur content (ASTM D 2622-94) of 483 ppmw, saturated hydrocarbon content of 49.1% v/v, aromatics content of 29.6% v/v and olefins content of 21.3% v/v (ASTM D6623-01 (procedure C), density at 15°C (DIN 51757/V4) 735.1 kg/m 3 , distillation (ISO 3405/88) IBP 24°C, 10% 41°C, 50% 100°C, 90% 175°C and FBP 218°C and 50% v of a heavy catalytically cracked (HCC) gasoline (the higher boiling fraction of a refinery stream produced by catalytic cracking of heavier hydrocarbons), by mixing at ambient temperature (20°C).
• HCC heavy catalytically cracked
• the HCC gasoline had distillation (ISO 3405/88) IBP 65.6°C, 10% 79.3°C, 50% 94.3°C, 90% 124°C and FBP 153.3°C, sulphur content (ASTM D 2622-94) 520 ppmw, RON 91.8 and MON 79.7.
• the resulting base fuel blends had properties as follows:- density at 15°C (DIN 51757/V4) 746.6 kg/m 3 , distillation (ISO 3405/88) IBP 40°C, 10% 68°C, 50% 98.5°C, 90% 145°C, FBP 195.5°C, RON 93.2, and MON 81.
• Base fuel at ambient temperature (20°C) was poured into the column, to a depth of 25 to 30 cm above the clay.
• Flow rate was adjusted to 1 litre/hour, and the column was regularly topped up with fuel. Total volume of 50 litres was passed through each column. The first litre of permeate was discarded, and subsequently 5 litre samples were collected. The 2 nd , 4 th , 6 th , 8 th and final samples were tested for Fe and Cu content.
• the final samples were also subjected to testing in an intake valve deposit simulator test, using a multiple inclined hot plate (MIHPT) rig, in comparison both with untreated base fuel and with portions of both untreated base fuel and of final samples into which were incorporated (by mixing at ambient temperature (20°C)) a standard detergent additive package (“DP”), at a concentration of 380 ppmw.
• MIHPT multiple inclined hot plate
• DP standard detergent additive package
• the clays which were employed were as follows:- Example 1 Attapulgite 30-60, ex Wilfrid Smith Limited (manufactured by Millwhite) Example 2 Fullers Earth 30-60, ex Aldrich Example 3 Sepiolite, ex Steetly Bentonite & Absorbents Ltd. Comparative A Talc, ex Aldrich Comparative B Kaolin, ex Aldrich Comparative C Vermiculite, ex Aldrich Comparative D Calcined Kaolin 22-60, ex Imerys. Comparative E Bentonite, ex Wilfrid Smith Limited (Manufactured by Cymbar) Comparative F Diatomaceous earth, ex Steetley Bentonite & Absorbents Ltd.
• This simulator test corresponds closely to that described in SAE Paper 890215, Daneshgari et al ., "The Influence of Temperature upon Gasoline Deposit Build-Up on the Intake Valves", Detroit, USA, 27 February to 3 March 1989.
• the test rig utilises four inclined plates in parallel.
• the plates are strips of sandblasted aluminium 50 cm long and 2.5 cm wide, having a central groove along their lengths 3 mm wide and 1 mm deep, mounted in the rig at an angle of 3 degrees relative to the horizontal.
• the temperature at the top end of each plate is maintained at 400°C and at the middle of each plate is maintained at 250°C.
• Gasoline samples containing test materials at a concentration of non-volatile matter of 100 parts per million by weight (ppmw) in base fuel, are prepared, and 100 ml portions of the gasoline samples are delivered at a rate of 0.6 ml/minute from glass syringes fitted with 20 gauge steel hypodermic Luer lock needles into the groove at the top end of each plate. Once delivery is complete, after about 2 hours and 40 minutes, the plates are allowed to cool to ambient temperature (20°C) and are washed with n-heptane until the run-off liquid is clear, and are then left to dry before assessment of any deposit present.
• ambient temperature (20°C)
• n-heptane washed with n-heptane until the run-off liquid is clear, and are then left to dry before assessment of any deposit present.
• a clear portion of the plate is moved under the camera and an image thereof captured.
• the section of the plate containing deposit is then moved beneath the camera and an image thereof is captured.
• the image analyser divides, pixel by corresponding pixel, the deposit image by the clean image and automatically measures the area and optical density of deposit at the pixels contained within overall measuring frame, and calculates an integrated optical density for the image, the numerical value of which is recorded as a test rating.

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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)

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Citations (4)

• 2004
  • 2004-12-02 BR BRPI0405407 patent/BRPI0405407A/pt not_active Application Discontinuation
  • 2004-12-02 EP EP04106249A patent/EP1538192B1/de not_active Expired - Lifetime
  • 2004-12-02 DE DE200460010223 patent/DE602004010223D1/de not_active Expired - Lifetime

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